CA1180974A - Foaming surfactant compositions - Google Patents
Foaming surfactant compositionsInfo
- Publication number
- CA1180974A CA1180974A CA000407146A CA407146A CA1180974A CA 1180974 A CA1180974 A CA 1180974A CA 000407146 A CA000407146 A CA 000407146A CA 407146 A CA407146 A CA 407146A CA 1180974 A CA1180974 A CA 1180974A
- Authority
- CA
- Canada
- Prior art keywords
- alkyl
- carbon atoms
- group
- sulfonate
- mixtures
- 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)
- Fire-Extinguishing Compositions (AREA)
- Cosmetics (AREA)
- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
FOAMING SURFACTANT COMPOSITIONS
Abstract of the Disclosures Foaming compositions containing an alkylpolysaccharide surfactant and a cosurfactant mixture consisting essentially of an alkylbenzene sulfonate with either an alkyl glyceryl ether sulfonate, an alpha-olefice sulfonate, an alkyl polyethoxylate carboxylate or mixtures thereof.
Abstract of the Disclosures Foaming compositions containing an alkylpolysaccharide surfactant and a cosurfactant mixture consisting essentially of an alkylbenzene sulfonate with either an alkyl glyceryl ether sulfonate, an alpha-olefice sulfonate, an alkyl polyethoxylate carboxylate or mixtures thereof.
Description
7'?~
FOAMI~G SURFACTANT COMPOSITIONS
Technical Field This invention relates to surfactant combinations which provide controllable aqueous foams. Such compositions can be used in any situation where foams are desirable, includ-ing the laundry, personal cleaning produets, dishwashing, fire fighting, 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,B65; 3,721,633; and 3,772,269. These patents also disclose processes for making alkylpolyglycoside surfactants and built liquid detergent compositions containing these sur~actants.
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;
3,346,558; 4,011,389; 4,223,129.
All percentages, parts and ratios used herein are by weight unless otherwise speeified.
Summary of the Invention This invention relates to the discov2ry of certain combinations of surfactants whieh provide unusual foams.
Specifically this invention relates to foaming 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, glucosyl, or galactosyl residue or mixtures thereof; R is a hydropnobic group selected from the group consisting of alkyl, alkyl phenyl, hydroxyalkyl phenyl or hydroxy-, alkyl ~roups or mixtures thereof in which sa;d allcyl;
~roups contain from about 8 to about 20 carbon atoms preferably from about 10 to about 16 carbon atoms, most preferably from about 12 to about 14 carbon ` atoms; R1 contains from 2 to 4 carbon atoms, preferably ethylene, propylene and/or glyceryl, t is from 0 to about 30, preferably 0 to about 10, most preferably 0;
wherein x is a number from ;-bout 1 . 5 to to about l O, preferably 1.5 to 4, most preferably 1.6 to 2.7; and
FOAMI~G SURFACTANT COMPOSITIONS
Technical Field This invention relates to surfactant combinations which provide controllable aqueous foams. Such compositions can be used in any situation where foams are desirable, includ-ing the laundry, personal cleaning produets, dishwashing, fire fighting, 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,B65; 3,721,633; and 3,772,269. These patents also disclose processes for making alkylpolyglycoside surfactants and built liquid detergent compositions containing these sur~actants.
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;
3,346,558; 4,011,389; 4,223,129.
All percentages, parts and ratios used herein are by weight unless otherwise speeified.
Summary of the Invention This invention relates to the discov2ry of certain combinations of surfactants whieh provide unusual foams.
Specifically this invention relates to foaming 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, glucosyl, or galactosyl residue or mixtures thereof; R is a hydropnobic group selected from the group consisting of alkyl, alkyl phenyl, hydroxyalkyl phenyl or hydroxy-, alkyl ~roups or mixtures thereof in which sa;d allcyl;
~roups contain from about 8 to about 20 carbon atoms preferably from about 10 to about 16 carbon atoms, most preferably from about 12 to about 14 carbon ` atoms; R1 contains from 2 to 4 carbon atoms, preferably ethylene, propylene and/or glyceryl, t is from 0 to about 30, preferably 0 to about 10, most preferably 0;
wherein x is a number from ;-bout 1 . 5 to to about l O, preferably 1.5 to 4, most preferably 1.6 to 2.7; and
(2) an anionic cosurfactant which is a sulfate, sulfonate and/or carboxylate or mixtures thereof neutralizecl with one or more cationic moieties (M) to complete the - formula,- preferably the - anionic cosurfactant has the formula R (SO3)y(COO)z~ q;
,vherein F< is an alkyl, alkylphenyl, 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 4, z is a number from 0 to about 4, y + z is at least 1, and 1~1 is a cationic moiety with q bein~ selected to complete the formula, wherein the ratio of (2) to (I) is from about l:lû to about 25 I0:1 (i.e., 0.1` to 10.0) e-xcept that when the cosurfactant is an alkylbenzene sulfonate, the ratio of (2) to (ll 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 O.S), and when the anionic cosurfactant does not contain sulfonate or carboxylate ~roup x must be from 1.5 to 3 and the alliylpoh~saccharide surfactant must have a free fatty alcohol content of less than about 2~ by ~vei3ht.
7'~
.~ ..
It has surprisingly been found tl1at the cosurfactan-ts inter act with the allcylpolysaccharide surfactant of this invention to provide a relatively stable foam which is readily rinsed.
The invention also relates to the process oF producing foams utilizing aqueous solutions containing from about 0.01~ to abou-t 95% of the mixed surfactants.
Description of the Preferred Embodiments The Alkylpolysaccharide Surfactant The alkylpolysaccharides are those having a hydrophobic group 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., galacto-side, glucoside, fructoside, glucosyl, fructosyl and/or galactosyl units). Mixtures of saccharicle moieties may be used in the alkyl polysaccharide surfactants. The number x indicates the number of saccharide units in a particular alkylpolysaccharide surfactant.
For a particular all;ylpolysaccharide molecule x can only assume integral values. In any physical sample of alkylpolysaccharicle surfactants there ~vill in general be molecules having different x values. Ti1e physical sample can be characterized by the average value of x and this average value can assume non-integral values.
I n 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 4-positions rather than at the 1-position, (thus giving e.g. a glucosyl or galactosyl as opposed to a glucoside or galactoside), However, attachment throucJh the 1-posieion, i.e., glucosides, galactosides, fructosicles, etc., is preferred. In the preferred product the additional saccharide units are predomin-ately attached to the previous saccharide unit's 2-position.
Attachment through the 3-, 4-, and 6-positions can also occur.
Optionally and less desirably there can be a polyalkoxide chain joining the hydrophobic moiety ( F<) and the polysaccharide-chain. The preferred alkoxide moiety is ethoxide.
Typical hydrophobic ~roups inclucl alkyl groups, either;
satura-ted or unsaturatecl, branched or unbranchecl containin~3 from about 8 to about 20, preferably from about 10 to about 16 carbori atoms. Preferably, the alkyl group is a straight chain sa-turated alkyl group~ The alkyl ~roup can contain up to 3 hydroxy groups and/or thè polyalkoxide cilain can con~ain up -to about 30, prcferably less tilan 10, most preferably 0, alkoxide moieties .
Suitable allcyl polysaccharides are decyl, dodecyl, tetradecyl, hexadecyi, and octadecyl, di-, tri-, tetra-, penta-, and hexaglu-cosides, galactosides, lactosides, fructosides, fructosyls, lac-tosyls, glucosyls and/or galactosyls and mixtures thereof.
-- - The alkylmonosaccharides are relatively less soluble in water - than the higher alkylpolysaccharides. When used in admixture with alkylpolysaccharides, the alkylmonosaccharides are solubili~ed to some extent. The use o~ allcylmonosaccharicles in aclrnixture with allcylpolysaccharides is a preferred mode of carrying out the invention. Suitable mixtures include coconut alkyl, di-, tri-, tetra-, and pentaglucosides ancl tallow alkyl tetra-, penta-, and 2 0 hexag 1 u cos ides .
The preferred alkyl polysaccharides are alkyi poly~lucosides having the formula R O(Cll~l2nO)t~z2)x wherein Z is derived from glucose, R is a hydrophobic group selected from the group consisting of allcyl, allcylphenyl, hydroxy-alkyl, hydroxyalkylphenyl, and mixtures tilereof in which said alkyl groups contain from abou-t 10 to about 18, preferably from 12 to 1 ~ 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 from 1.5 to ~, most preferably from 1.6 to 2.7. To prepare these compounds a long chain alcohol ( R20H) can be reacted ~,vith glucose, in the presence of an acid catalyst to for-m the desired glllcoside. Alternatively the alkylpolyglucosides can be prepared by a two step proc~dure in which a short chain alcohol ( C1 6) is ~5 reacted with glucose or a polyglucoside (x=2 to L~) to yield a ~8~)~7~
short chain alliyl ~lucoside (x=1 to ~1) which can in turn b~
reacted with a longer chain alcohol ~R OH) to displace the short cl-ain alcohol and obtain the desired allcylpolyglucoside. If this two step proce~ure is used, the short chain allcylglucoside con-tent of the final alkylpolyglucosid~ material should be less than 509~, preferably less than 10~, more preferably less than 5%, most preferably U~ of the alkylpoly~lucosid~.
The ar~ount ~f unreacted alcohol ~the free fatty alcohol content) in the desired alkylpolysaccharide surfactant is pre-LO ferably less than a~out 2~, more pre~er~bly less than about 0 . 5by wei~ht of ~he total of the alkyl polysaccharide plus unreacted alcohol. The amount of alkylmonosaccharide is about 20~6 to about 70~, preferably 30% to 60~, most preferably 30% to 50~ by weight of the total of the alkylpolysaccharide. For some uses it is ii desirable to l-lave ~he alkylmonosaccharide content less than about 0%.
As used herein, "alkylpolysaccharide surfactant" is intended to represent both the preferred glucose and galactose derived surfactants and the less preferred ,~C alkylpolysaccharide surfactants. Throughout this specification "alkylpolyglucoside" is used to include alkylpolyglucosidas because the stero chemistry o~ the saccharide moiety 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 neutrali~ed with a cationic moiety or moieties selected from the group consisting of alkali metal, e.g. sodium or potassium, alkaline earth metal, e.g. calcium or magnesium, ammonium, substituted ammonium, including mono-, di-, or tri-, ethanolammonium cations.
Mixutres of cations can be desirable. The anionic cosurfactants useful in the present invention all have
,vherein F< is an alkyl, alkylphenyl, 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 4, z is a number from 0 to about 4, y + z is at least 1, and 1~1 is a cationic moiety with q bein~ selected to complete the formula, wherein the ratio of (2) to (I) is from about l:lû to about 25 I0:1 (i.e., 0.1` to 10.0) e-xcept that when the cosurfactant is an alkylbenzene sulfonate, the ratio of (2) to (ll 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 O.S), and when the anionic cosurfactant does not contain sulfonate or carboxylate ~roup x must be from 1.5 to 3 and the alliylpoh~saccharide surfactant must have a free fatty alcohol content of less than about 2~ by ~vei3ht.
7'~
.~ ..
It has surprisingly been found tl1at the cosurfactan-ts inter act with the allcylpolysaccharide surfactant of this invention to provide a relatively stable foam which is readily rinsed.
The invention also relates to the process oF producing foams utilizing aqueous solutions containing from about 0.01~ to abou-t 95% of the mixed surfactants.
Description of the Preferred Embodiments The Alkylpolysaccharide Surfactant The alkylpolysaccharides are those having a hydrophobic group 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., galacto-side, glucoside, fructoside, glucosyl, fructosyl and/or galactosyl units). Mixtures of saccharicle moieties may be used in the alkyl polysaccharide surfactants. The number x indicates the number of saccharide units in a particular alkylpolysaccharide surfactant.
For a particular all;ylpolysaccharide molecule x can only assume integral values. In any physical sample of alkylpolysaccharicle surfactants there ~vill in general be molecules having different x values. Ti1e physical sample can be characterized by the average value of x and this average value can assume non-integral values.
I n 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 4-positions rather than at the 1-position, (thus giving e.g. a glucosyl or galactosyl as opposed to a glucoside or galactoside), However, attachment throucJh the 1-posieion, i.e., glucosides, galactosides, fructosicles, etc., is preferred. In the preferred product the additional saccharide units are predomin-ately attached to the previous saccharide unit's 2-position.
Attachment through the 3-, 4-, and 6-positions can also occur.
Optionally and less desirably there can be a polyalkoxide chain joining the hydrophobic moiety ( F<) and the polysaccharide-chain. The preferred alkoxide moiety is ethoxide.
Typical hydrophobic ~roups inclucl alkyl groups, either;
satura-ted or unsaturatecl, branched or unbranchecl containin~3 from about 8 to about 20, preferably from about 10 to about 16 carbori atoms. Preferably, the alkyl group is a straight chain sa-turated alkyl group~ The alkyl ~roup can contain up to 3 hydroxy groups and/or thè polyalkoxide cilain can con~ain up -to about 30, prcferably less tilan 10, most preferably 0, alkoxide moieties .
Suitable allcyl polysaccharides are decyl, dodecyl, tetradecyl, hexadecyi, and octadecyl, di-, tri-, tetra-, penta-, and hexaglu-cosides, galactosides, lactosides, fructosides, fructosyls, lac-tosyls, glucosyls and/or galactosyls and mixtures thereof.
-- - The alkylmonosaccharides are relatively less soluble in water - than the higher alkylpolysaccharides. When used in admixture with alkylpolysaccharides, the alkylmonosaccharides are solubili~ed to some extent. The use o~ allcylmonosaccharicles in aclrnixture with allcylpolysaccharides is a preferred mode of carrying out the invention. Suitable mixtures include coconut alkyl, di-, tri-, tetra-, and pentaglucosides ancl tallow alkyl tetra-, penta-, and 2 0 hexag 1 u cos ides .
The preferred alkyl polysaccharides are alkyi poly~lucosides having the formula R O(Cll~l2nO)t~z2)x wherein Z is derived from glucose, R is a hydrophobic group selected from the group consisting of allcyl, allcylphenyl, hydroxy-alkyl, hydroxyalkylphenyl, and mixtures tilereof in which said alkyl groups contain from abou-t 10 to about 18, preferably from 12 to 1 ~ 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 from 1.5 to ~, most preferably from 1.6 to 2.7. To prepare these compounds a long chain alcohol ( R20H) can be reacted ~,vith glucose, in the presence of an acid catalyst to for-m the desired glllcoside. Alternatively the alkylpolyglucosides can be prepared by a two step proc~dure in which a short chain alcohol ( C1 6) is ~5 reacted with glucose or a polyglucoside (x=2 to L~) to yield a ~8~)~7~
short chain alliyl ~lucoside (x=1 to ~1) which can in turn b~
reacted with a longer chain alcohol ~R OH) to displace the short cl-ain alcohol and obtain the desired allcylpolyglucoside. If this two step proce~ure is used, the short chain allcylglucoside con-tent of the final alkylpolyglucosid~ material should be less than 509~, preferably less than 10~, more preferably less than 5%, most preferably U~ of the alkylpoly~lucosid~.
The ar~ount ~f unreacted alcohol ~the free fatty alcohol content) in the desired alkylpolysaccharide surfactant is pre-LO ferably less than a~out 2~, more pre~er~bly less than about 0 . 5by wei~ht of ~he total of the alkyl polysaccharide plus unreacted alcohol. The amount of alkylmonosaccharide is about 20~6 to about 70~, preferably 30% to 60~, most preferably 30% to 50~ by weight of the total of the alkylpolysaccharide. For some uses it is ii desirable to l-lave ~he alkylmonosaccharide content less than about 0%.
As used herein, "alkylpolysaccharide surfactant" is intended to represent both the preferred glucose and galactose derived surfactants and the less preferred ,~C alkylpolysaccharide surfactants. Throughout this specification "alkylpolyglucoside" is used to include alkylpolyglucosidas because the stero chemistry o~ the saccharide moiety 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 neutrali~ed with a cationic moiety or moieties selected from the group consisting of alkali metal, e.g. sodium or potassium, alkaline earth metal, e.g. calcium or magnesium, ammonium, substituted ammonium, including mono-, di-, or tri-, ethanolammonium cations.
Mixutres of cations can be desirable. The anionic cosurfactants useful in the present invention all have
3~ detergent properties and are all water 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 unsaturated, 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.
9~
However in heavLer soil conditions, phenyl attachment at the 1- or 2-position is preferred.
` The preferred alkylbenzene sulfonates 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 sodium, potassium, ammonium, mono-, di-, or triethanolammon-ium, calcium or magnesium and mixtures thereof. Magnesium is the - 10 preferred cationic moiety. These same cations are preferred for other anionic surfactants and ingredients. The magnesium aikyl-benzene sulfonates where 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 greater than about 3 saccharide units. Suitable alkylbenzene sulfonates include Cll alkylbenzene sulfonates ~vith low 2-phenyl content.
The alkylbenzene sulfonate cosurfactant is desirable in the foaming compositions of the invent!on since the foams produced therewith are exceptionally stable, have a large volume, rinse quickly, and do not have a "slippery" feel. These co~positions are particularly desirable for industrial and comrlercial processes as discussed hereinafter. The volume of foam produced using the alkylbenzene sulfonate cosurfactant is larger than for any other 2~ cosurfactant.
Soap Other preferrecl cosurfactants for use in this invention are carboxylates, e.g. fatty acid soaps and si~ilar surfactants. The soaps can be saturated or unsaturated and can contain various 'Q substituen~s such as hydroxy groups and alpha-sulfonate groups.
Preferably, the hydrophobic portion of the soap is a straight chain saturated or unsaturatecl hyclrocarbon. The hydrophobic portion of the soap usually contains from about 6 to about 30 carbon atoms, preferably from about 10 ~o about 18 carbon atoms.
The use of carboxylate cosurfactants is especially valuable since the alkylpolysaccharide surfactants are exceptional lime soap dispersers.
The cationic moiety tM) for carboxylate cosurfactants is selected from the group consisting of alkali metal, for exa;nple, sodium or potassium, alkaline earth metal, for example, calcium or magnesium, ammoniumJ 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 use 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, sulfoni~m 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; 3,390,034; and 3J239~560.
Such cosurfactants are especially desirable for shampoos~
Another group of cosurfactants are the amphoteric 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) sulfonates, preferably with a more central hydro-philic group, containing from about 6 to about 30 carbon atoms. Compositions containing these cosur~actants produce the least volume of foam, if that is desired. The hydro-phobic group can contain up to C)974 about 10 hydroxy groups and/or ether linka~3es. Examples include;
C1LI 15 paraffin sulFonates and C1l~ 16 olefin sulfona-tes.
Still another cosurfactant is a soap structure containing up -to about 10 ether linkages in the chain and from about I to about 1~ carbon atoms between ether linkages with from about 6 to about 30 carbon atoms in a terminal portion containing no ether link-ages .
The preferred all<ylpolyglucosides that contain an average of from 1.5 to 4 ~lucoside units, preferably from 1.6 to 2.7 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~3ent cosurfact-ants, especially alkyl sulfate and alkyl polyether sulfate cosur-factants having the formula:
R O(CnH2nO)t 53 M
wherein R is an allcyl 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 definecl above, the cosurfactant being water soluble or dispersible.
A preferred foaming composition of the invention herein comprises (1 ) an alkylpolysaccharide surfactant having the formula RO(R1O)t(Z)X wherein Z is a moiety 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, hydroxyalkyl-phenyl or hydroxyalkyl groups or mi,ctures thereof in which said alkyl groups contain from about 8 to about 18 carbon atoms; Rl 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-ferably 1 . 6 to 2 . 7 and (2) a mixture of cosurfactants neutrali~ed with one ~r more cationic moieties consisting essentially of:
(a) from about 1~ to about 95~ pre-ferably about 10~6 to ~vg~
about 50~ of a water soluble allcylbenzene sulfonate~
cosurfactant in which the alkyl group contains from about 10 to about 13 carbon atoms, and (b) from about 5% to about 99%, preferably 50-90~ of a cosurfactant. selected from the group consisting of an allcyl glyceryl ether sulfollate in which -the alkyl group con-tains from about 8 to about 18 carbon atoms, an alpha-olefin sulfona-te 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 ~3roups, and mixtures thereof.
Such compositions have improved suds mileage as compared to compositions containing only the alkyl benzene sulfonate cosur-factant and the alkylpolysaccharide surfactant.
Another preferred embodiment of a foaming composition of the invention herein comprises 20 ~1 ) an all;ylpolysaccharide surfactant having the formula RO~R10)t~Z)X wherein Z is a moiety derivecl from a reducing saccharide containing from 5 to 6 carbon atoms and wherein R is a hydrophobic group selected from the group consisting of allcyl, alkylphenyl, hy-droxyalkylphenyl or hydroxyalkyl groups or rnixtures thereof in which said alkyl groups contain from about 8 to about 18 carbon atoms; R contains from 2 to about L~
carbon atoms; t is from 0 to about 30 and x is a number from about 1.5 to about 10;
30 ~2) an anionic cosurfactant selected from the group con-sisting of sulfates, sulfonates, carboxylates and mix-tures thereof neutralized with one or more cationic moieties ~1 to complete the formula, the ratio of (2) to (1) being from about 1:10 to about 10:1; and 3) from about 2% to about 106 of an auxiliary foam booster selected from the group consisting of:
(a) amides having the formula R7 -C-N- ~ R ) 2 wherein ~7 is an alkyl ~roup containing fron~ about 8 to about 18 carbon atoms, preferably about 12 to about 14 carbon atoms and each ~8 jS the same or different and is selected from -the group consisting of hydrogen, C1 3 allcyl, C1_3 alkanol, and -(C2H4O-)1_4H groups and mixtures thereof;
(b) amine oxides having the formula:
o R4(oR5)bN(R6)2 wherein R is an allcyl group containing from about 8 to about 18 carbon atoms, prefera~ly from 12 to 14 carbon atorns, each 1~ contains t-vo or three carbon atoms, b is from 0 to about 30, each R is - the same or different ancl is selected from the group consisting of Cl_3 allcyl, C1_3 -(C2H4O)1_6H groups and mixtures thereof and (c) mixtures thereof.
Such compositions provide superior grease/oil removal and suds mileage. i-Preferred anionic cosurfactants are alkylben2ene sulfonate, alpha-olefin sulfonate, alkylsulfates, alkylpolyethoxylate sulfates 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 comprise from 1% to about 956, preferably 56 to about 506 of an - al'cylpolysaccharide 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 16 to about 956, preferably from about 106 to ~:~L8(~7~
about 50% of an anionic cosurfactant neutralized with one or more~
cationic moieties and which is a mixture of ~1 ) from 1% to about 95~6, preferably from about 5% to about 50~ of an alkyl benzene sulfonate in which the alkyl 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 atoms, or mixtures thereof; and (2) from 1% to about ~5~g, 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 14 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 moieties are magnesium and wherein the auxiliary foam booster is an amide.
Another preferreci foaming composition oF the invention herein is an agglomerated light duty detergent granule composi-tion comprising ~1 ) from about 5% to about 60%, preferably from 1 0~s to about 20% of an alkylpolysaccharide surfactant having ti-e formula RO(R )t(~)x wilerein Z is a moiety derived from a reducing saccharide moiety containing from 5 to 6 carbon 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 8 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 from about 1 5 to about 10, preferably 1 5 to 4, most preFerably 1 6 to 2 7;
(23 from about 5~ to about 60~ of an alkyl benzene sul-fonate cosurfactant in which the alkyl group contains frorn about 10 -to about 13 carbon atoms, said alkyl 397~
benzene sulfonate neutralized with one or more cationic moieties ~M) to balance the formula;
t3~ from about 5~ to about 60~, 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 neutra-lized with one or more cationic moieties M to complete the formula.
,. .
- 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 unsaturated, 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.
9~
However in heavLer soil conditions, phenyl attachment at the 1- or 2-position is preferred.
` The preferred alkylbenzene sulfonates 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 sodium, potassium, ammonium, mono-, di-, or triethanolammon-ium, calcium or magnesium and mixtures thereof. Magnesium is the - 10 preferred cationic moiety. These same cations are preferred for other anionic surfactants and ingredients. The magnesium aikyl-benzene sulfonates where 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 greater than about 3 saccharide units. Suitable alkylbenzene sulfonates include Cll alkylbenzene sulfonates ~vith low 2-phenyl content.
The alkylbenzene sulfonate cosurfactant is desirable in the foaming compositions of the invent!on since the foams produced therewith are exceptionally stable, have a large volume, rinse quickly, and do not have a "slippery" feel. These co~positions are particularly desirable for industrial and comrlercial processes as discussed hereinafter. The volume of foam produced using the alkylbenzene sulfonate cosurfactant is larger than for any other 2~ cosurfactant.
Soap Other preferrecl cosurfactants for use in this invention are carboxylates, e.g. fatty acid soaps and si~ilar surfactants. The soaps can be saturated or unsaturated and can contain various 'Q substituen~s such as hydroxy groups and alpha-sulfonate groups.
Preferably, the hydrophobic portion of the soap is a straight chain saturated or unsaturatecl hyclrocarbon. The hydrophobic portion of the soap usually contains from about 6 to about 30 carbon atoms, preferably from about 10 ~o about 18 carbon atoms.
The use of carboxylate cosurfactants is especially valuable since the alkylpolysaccharide surfactants are exceptional lime soap dispersers.
The cationic moiety tM) for carboxylate cosurfactants is selected from the group consisting of alkali metal, for exa;nple, sodium or potassium, alkaline earth metal, for example, calcium or magnesium, ammoniumJ 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 use 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, sulfoni~m 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; 3,390,034; and 3J239~560.
Such cosurfactants are especially desirable for shampoos~
Another group of cosurfactants are the amphoteric 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) sulfonates, preferably with a more central hydro-philic group, containing from about 6 to about 30 carbon atoms. Compositions containing these cosur~actants produce the least volume of foam, if that is desired. The hydro-phobic group can contain up to C)974 about 10 hydroxy groups and/or ether linka~3es. Examples include;
C1LI 15 paraffin sulFonates and C1l~ 16 olefin sulfona-tes.
Still another cosurfactant is a soap structure containing up -to about 10 ether linkages in the chain and from about I to about 1~ carbon atoms between ether linkages with from about 6 to about 30 carbon atoms in a terminal portion containing no ether link-ages .
The preferred all<ylpolyglucosides that contain an average of from 1.5 to 4 ~lucoside units, preferably from 1.6 to 2.7 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~3ent cosurfact-ants, especially alkyl sulfate and alkyl polyether sulfate cosur-factants having the formula:
R O(CnH2nO)t 53 M
wherein R is an allcyl 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 definecl above, the cosurfactant being water soluble or dispersible.
A preferred foaming composition of the invention herein comprises (1 ) an alkylpolysaccharide surfactant having the formula RO(R1O)t(Z)X wherein Z is a moiety 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, hydroxyalkyl-phenyl or hydroxyalkyl groups or mi,ctures thereof in which said alkyl groups contain from about 8 to about 18 carbon atoms; Rl 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-ferably 1 . 6 to 2 . 7 and (2) a mixture of cosurfactants neutrali~ed with one ~r more cationic moieties consisting essentially of:
(a) from about 1~ to about 95~ pre-ferably about 10~6 to ~vg~
about 50~ of a water soluble allcylbenzene sulfonate~
cosurfactant in which the alkyl group contains from about 10 to about 13 carbon atoms, and (b) from about 5% to about 99%, preferably 50-90~ of a cosurfactant. selected from the group consisting of an allcyl glyceryl ether sulfollate in which -the alkyl group con-tains from about 8 to about 18 carbon atoms, an alpha-olefin sulfona-te 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 ~3roups, and mixtures thereof.
Such compositions have improved suds mileage as compared to compositions containing only the alkyl benzene sulfonate cosur-factant and the alkylpolysaccharide surfactant.
Another preferred embodiment of a foaming composition of the invention herein comprises 20 ~1 ) an all;ylpolysaccharide surfactant having the formula RO~R10)t~Z)X wherein Z is a moiety derivecl from a reducing saccharide containing from 5 to 6 carbon atoms and wherein R is a hydrophobic group selected from the group consisting of allcyl, alkylphenyl, hy-droxyalkylphenyl or hydroxyalkyl groups or rnixtures thereof in which said alkyl groups contain from about 8 to about 18 carbon atoms; R contains from 2 to about L~
carbon atoms; t is from 0 to about 30 and x is a number from about 1.5 to about 10;
30 ~2) an anionic cosurfactant selected from the group con-sisting of sulfates, sulfonates, carboxylates and mix-tures thereof neutralized with one or more cationic moieties ~1 to complete the formula, the ratio of (2) to (1) being from about 1:10 to about 10:1; and 3) from about 2% to about 106 of an auxiliary foam booster selected from the group consisting of:
(a) amides having the formula R7 -C-N- ~ R ) 2 wherein ~7 is an alkyl ~roup containing fron~ about 8 to about 18 carbon atoms, preferably about 12 to about 14 carbon atoms and each ~8 jS the same or different and is selected from -the group consisting of hydrogen, C1 3 allcyl, C1_3 alkanol, and -(C2H4O-)1_4H groups and mixtures thereof;
(b) amine oxides having the formula:
o R4(oR5)bN(R6)2 wherein R is an allcyl group containing from about 8 to about 18 carbon atoms, prefera~ly from 12 to 14 carbon atorns, each 1~ contains t-vo or three carbon atoms, b is from 0 to about 30, each R is - the same or different ancl is selected from the group consisting of Cl_3 allcyl, C1_3 -(C2H4O)1_6H groups and mixtures thereof and (c) mixtures thereof.
Such compositions provide superior grease/oil removal and suds mileage. i-Preferred anionic cosurfactants are alkylben2ene sulfonate, alpha-olefin sulfonate, alkylsulfates, alkylpolyethoxylate sulfates 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 comprise from 1% to about 956, preferably 56 to about 506 of an - al'cylpolysaccharide 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 16 to about 956, preferably from about 106 to ~:~L8(~7~
about 50% of an anionic cosurfactant neutralized with one or more~
cationic moieties and which is a mixture of ~1 ) from 1% to about 95~6, preferably from about 5% to about 50~ of an alkyl benzene sulfonate in which the alkyl 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 atoms, or mixtures thereof; and (2) from 1% to about ~5~g, 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 14 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 moieties are magnesium and wherein the auxiliary foam booster is an amide.
Another preferreci foaming composition oF the invention herein is an agglomerated light duty detergent granule composi-tion comprising ~1 ) from about 5% to about 60%, preferably from 1 0~s to about 20% of an alkylpolysaccharide surfactant having ti-e formula RO(R )t(~)x wilerein Z is a moiety derived from a reducing saccharide moiety containing from 5 to 6 carbon 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 8 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 from about 1 5 to about 10, preferably 1 5 to 4, most preFerably 1 6 to 2 7;
(23 from about 5~ to about 60~ of an alkyl benzene sul-fonate cosurfactant in which the alkyl group contains frorn about 10 -to about 13 carbon atoms, said alkyl 397~
benzene sulfonate neutralized with one or more cationic moieties ~M) to balance the formula;
t3~ from about 5~ to about 60~, 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 neutra-lized with one or more cationic moieties M to complete the formula.
(4) from about 5~ to about 30~ o~ a water soluble inorganic salt selected from the group consisting of sodium 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 foams.
These foams are relatively stable and, if not disturbed, can exist for several days, Furthermore, the foam has structural integrity and does not spread out. The foams prepared using mixtures of alkylbenzene sulfonate and the alkylpolysaccharide are unique in that they do not have a "slippery" feel. All of the foams rinse quickly.
- 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 fieldsunrelated 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,~00. 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 ~rom 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 ighting or fire prevention processes where a stable foam is used to extinguish a flame or sparks by cutting off the oxygen supply. This includes Eire fighting and foa~ing runways for crash-landings as disclosed in U~S. Patents 27514,310; 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 useful.
The compositions and processes of this invention are also especially valuable in the field of preparing gypsum board, plastic, and resin foams. The foams of this invention pro-vide a stable relatively thick structure permitting solid-ification of the resins, plastics, cellulosic particles, etc., into stable foam structures having light densities, thick cell walls and good structural integrity. Examples of forming processes which utilize foaming agents are described in U.S. Patents 3,669,898; 4,907,982; and 4,423,720.
The flotation of minerals so as to concentrate the mineral valuest e.g., in the foam (beneficiation), can be carried out advantageously using the compositions and processes of this invention. Such processes are described in U.S. 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 inventi~n involves making use of their exceptional stablility to provide temporary insulation for plants when freezing conditions are expected. An alkylbenzene sulfonate is the preEerred cosurfactant and the foam can be applied to the foliage etc., of the plants. Such a process is disclosed in U~S. Patent 3,669,898.
79~
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 cletergent
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 foams.
These foams are relatively stable and, if not disturbed, can exist for several days, Furthermore, the foam has structural integrity and does not spread out. The foams prepared using mixtures of alkylbenzene sulfonate and the alkylpolysaccharide are unique in that they do not have a "slippery" feel. All of the foams rinse quickly.
- 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 fieldsunrelated 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,~00. 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 ~rom 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 ighting or fire prevention processes where a stable foam is used to extinguish a flame or sparks by cutting off the oxygen supply. This includes Eire fighting and foa~ing runways for crash-landings as disclosed in U~S. Patents 27514,310; 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 useful.
The compositions and processes of this invention are also especially valuable in the field of preparing gypsum board, plastic, and resin foams. The foams of this invention pro-vide a stable relatively thick structure permitting solid-ification of the resins, plastics, cellulosic particles, etc., into stable foam structures having light densities, thick cell walls and good structural integrity. Examples of forming processes which utilize foaming agents are described in U.S. Patents 3,669,898; 4,907,982; and 4,423,720.
The flotation of minerals so as to concentrate the mineral valuest e.g., in the foam (beneficiation), can be carried out advantageously using the compositions and processes of this invention. Such processes are described in U.S. 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 inventi~n involves making use of their exceptional stablility to provide temporary insulation for plants when freezing conditions are expected. An alkylbenzene sulfonate is the preEerred cosurfactant and the foam can be applied to the foliage etc., of the plants. Such a process is disclosed in U~S. Patent 3,669,898.
79~
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 cletergent
5 compositions in washing dishes comprise from about 5% to about 50~, preferably from about 10~ to about 40~ 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, Cl_3 allcanolamines, C2_4 polyols, mixtures thereof, and the 10 balance water. It is a special advantage of the compositions of this invention that they can be made in concentrated form ~up to about 5096 by ~IYt. of the mixture of surfactants~ with only very low levels of organic solvents and without the addition of expen-sive hydrotropic materials. Additional suds boosters or builders 15 such as triall<yl 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 190 to about 95g~, preferably from about 5% to about 20% of the mixture of surfac-20 tants mentioned hereinbefore, from about 1% to about 5% of anall<anol amide, from about 0.5~ to about 3?6 of a polymeric thiclc-ener, and tlle balance water. It is a special advantaJe of the sharnpoos that they rinse quickly and readily.
Additional Ingredients -`
.. . . . .. .
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. In de-tergen-t compositions the compositions can contain any of the well known ingreclients including minor amounts of other surfactants, 30 detergency builders, soil suspending a~ents, brighteners, abras-ives, dyes, fabric conditioniny agents, hair conditioning agents, hydrotropes, solvents, fillers, clays, perfumes, etc. Suitable ingredients are disclosed in U.S. Patents 4,166,039--Wise;
4,157,978--Llenado; 4~056,481--Tate; 4,049,586--Collier;
4,035,257--Cherney; 4,019,g98--Benson et al; 4,000,080--Bartolotta et al; and 89983,078--Collins. The shampoo compositions of this invention can contain any of the additional ingredients known to the art to be suitable for use in shampoos. Bistings of suitable additional ingred-ients, including low levels of other surfactants can be found in U.S. Patents ~,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. For example, raising the pH to above about 8.5 by alkaline materials or incorporating the tertiary alco~
hols of the Jones et al, Canadian Patent 1,160,131 issued January 10, 1984. Such ingredients are desira~le for some consumers since the solutions do not have the normal "soapy"
feel associated with surractant 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 Premium Product Commercial Commercial of the Product Product Invention U.S. Crystal U.S.
White~ Palmolive~
F _~LA Weight % Weigh~ % Wei~
Sodium Cll 8 alkyl benzene sulfonate 10.5 18.0 18.0 C12-13 alk glucoside2_3 (~
free fatty alcohol) ~ .0 ., ,.~, ~`-' 7'~
m 14-15 all<yl polyethoxylate3 sulfate 5 . 5 12 . 0 Balance of formula inc. water 84. 0 70. 0 70 . 0 SUDSI NG
5 ~ Relative Volume of Sucls (ml) 110 125 220 0 . 2% solutions CONSUMER TEST
Overall preference, % lQ 18 23 Favorable sudsing 10 comments, % 7~1 85 ~0 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 consurners wore rubber ~31Oves during the -test. The differences are siynificant at 20 the 95~ conficlence level for the invention over the generic product .
The relative volume of suds in ml. is determined by the following test procedure:
100 ml of the test solution at 11 5F is placed in a 500 ml 25 graduated cyliner: the solution is agitated by repeated inversion of the graduated cylinder until the amount of suds in the cylinder does not increase with further agitation. Suds heic3ht is measured directly on the cylinder scale making allowance for the height of liquid remaining in the cyiinder. The test solution is 30 made by addin~ the test product to water having a hardness of 7 gr. per U.S. gallon (Ca/Mg = 3/1).
EXAI\/IPLE 11 -~
LAS Suds Boostin~
i~`lt. % of: A B C D E F G
SSodium C1 1 ~ alkyl-benzene sulfonate 0 20 40 50 60 80 100 Cl 2 15 alkylPIY2 3 glucoside 100 80 60 50 40 20 0 Relative Volume 10 of suds (ml) 140 220 280 300310 300 240 The suds (foam) were generated as described in Ex. I using 300 ppm of the surfactant mixtures in city water (~9 grains per gallon). The results clearly show the sudsing synergism for 15 ratios greater than about 1:2, i.e. for the foaminy composition of the invention herein.
EXAMPLE 11 i Soap Suds Boosting Wt. % of: A B C D E F
20 Sodium oleate 0 20 40 60 80 100 Cl 2-15 alkYIPIY2-3 glucoside 100 80 60 40 20 0 Relative Volume of suds (ml.) 160 270 280 300310 260 The suds werè generated as in Ex. I using 500 ppm. of the surfactant mixtures. This data clearly indicates the sudsing synergism for the foaming composition of the invention herein.
EXA~lPLE IV
Foamin~ with Soa,o Effect of ~lardness on Relative Volume of Suds ~rains hardness Sodium oleate 225 10 0 0 So~lium oleate plus C12_15 alkylpoly2_3 ~31ucoside ~3: 2 ratio) 360 100 55 10 The suds were generated as in Ex. I using 500 ppm. of the surfactant mixtures.
EXAMPLE V
Alkyl Poly~ucosid~ (C1~ 15 alkylpoly 3 ~lucoside) 15 Suds Boosting for the Following Representative Cosurfactants (3: 2 ratio; 500 ppm) % increase in foaming Sodium C11 8 allcylbenzene sulfonate - 100-150 Sodium oleate 50-75 20 3-1 N -coconuta Ikyl-N, N -dimethy I ~ -2-hydroxy-1-sulfonate 40-60 Sodium C14 15 olefin sulfonate 20-40 Sodium coconut alkyl sulfate 10-30 Sodium coconut alkyl polyethoxylate3 sulfate 0-20 The above data clearly demonstrate the criticality of utilizing a carboxylate or sul-Fonate anionic detergent cosurfactant for sudsing synergism with the allcyl polyglucoside surfactant.
EXAl\lPLE Vl Glucoside Chain Length Criticality 40: 60 wt- ratio of C12-15 all~yl polygl~Jcoside to sodium C12 allcylbenzene sulfonate (500 ppm. concentration) where the gluco-side portion is:
9~'~
Relative Volume of Suds ~ mi ) Monoglucoside 1 80 Diglucoside 240 Pentaglucoside 260 Decaglucoside 1 70 Sodium C1 1. 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, signiflcant synergism is obtained only with 1 . 5 or more glucoside units and preferably less than about 10, more prefer-- ably less than about 8 glucoside units.
EXAI~/lPLE Vl I
Allcylbenzene sulfonates ( LAS) ~lomologs/phenvl-position (3:2 ratio; 500 ppm) Relative Volume of Suds ( ml ) 20 Ex. I I's alkylpolygl-Jcoside plus:
Sodium C1 1 LAS, high 2-phenyl 210 Sodium C1 1 LAS, low 2-phenyl250 Sodium C12 LAS, high 2-phenyl225 Sodium C1 2 LAS, low 2-phenyl225 25 Sodium Cl L~ LAS, ~iigh 2-pheriyl 210 Sodium C1 4 LAS, low 2-phenyl215 As can be seen from the above, in general C~ QW 2-phenyl LAS is preferred for sudsing.
EXAMPLE Vl l l -~.
Suds Boos-ting of Alkyl Polyglucosides and Effect of Soil Rela-tive Volume of Suds ~ml) ~'~ithout Soii With Soil 0.5% 1.0 0.2% aqueous solution of a detergent composition 10 formulated with:
15% sodium C1 1 ~ alkyl-benzene sulfonate (C11 8 LAS~ - - 120 50 - - 25 11 . 8 LAS 12%
15Ex. Il's alkyl poly~lucoside 310, 130 70 ~6 C11.8 LAS 190 140 100 20% C1 1 8 LAS ~ 12%
Ex l's alkylpolyglucoside 380 170 100 20Test method of Ex. I rnodified by adding to the -test solu-tion the indicated amount of soil. % is wt. 96 of test solution.
The soil is a 44%/5G~ by weight mix-ture of Fluffo(~? and PREP~) both of which products are available in the United States from The Procter ~ Gamble Company.
25As can be seeh from the'~above, the benefit for the invention is even more remarkable when soil is present.
EXAl\lPLE IX
Relative \/olume of Suds lm!) No Soil 1% Soil Present 30 Generic commercial product (Crystal ~ ite(~))** 110 30 Premium commerical product E3 ~ Palmolive Liquic~) 120 100 Premium commercial product C
35 ( (~)) 125 120 8~7~
~ 21 --.
12~ Cll 8 LAS/8% Ex. Il's alkyl polyglucoside1~0 120 1&% C11 8 LAS/12% Ex. Il's alkyl polyglucoside240 150 24% Cll ~ LAS/16~ Ex. Il's allcyl polyglucoside300 180 Soil is added as described in Ex. Vl 1.
** ~
Crystal White~ is available from Colgate-Palmolive Co.
Palmolive Liquid~ is available from Colyate-Palmolive Co.
10 Joy~) is available from The Procter ~ Gamble Company.
Suds generated as in Ex. I usinq a test solution containing 0.2~ by wt. of the indicated commercial product or 0.2% of a product formulated with the surfactant 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 licluids.
EXAMPLE X
Wt. % of: A ~ C D E F
20 C11 8 LAS (Sodium) 20 40 6080 100 Sucrose monolaurate 100 80 6040 20 0 Relative Volume of suds (ml.) 30 100 150 190210 220 ~ !-300 ppm of surfactant mixture used in test solu-tion of Ex. I.
The above demonstrates that structures which are similar to the alkyl polyglucosides do not provide the benefits of this in-vention .
EXAMPLE Xl Shampoo Cocamido propyl betaine (30% aqueous ~olution) 50.00%
Ex. I's alkyl polyglucoside 5.006 Polyethylene glycol distearate 1. 00%
35 Preserva tive 03%
Distilled water q.s. lOO.OOQo EXAMPLE X l l Shampoo Alpha-olefin sulfonate ~40% aqueous solution~ 30.00 Ex. I's alkyl polyglucoside 3.00 Hydroxyethyl cellulose 0.80~
Perfume 1. 006 Preservative 0. 04~
Dis-tilled water - q.s. 100.006 EXAMPLE X l l l Paraffin Sulfonate Suds Boosting Wt. ~ of: A B C D E F_ Mixture of sodium C1 ~5 15 paraffin sulfonate 0 20 40 60 80 100 ~12-15 G"_5 100 80 60 40 20 0 Relative Vol. of Suds(ml) 185 250 275 275 235 210 Test Conditions:
l otal concentration of 300 ppm; water having 8 grains of 20 mixed hardness.
C12 1 5G4 5 is a notation for an allcyl polysaccharide surfactant in which there are 4-5 glucoside units and in which the alkyl group has 12-15 carbons.
EXAMPLE X IV
Sodium vs. Magnes~um Alkylbenzene Sulfonate -Relative Volume of Suds ~ml. ) *
Without Soil ~Vith Soil 0 . 6% 1 . 06 0.26 aqueous solution of a 30 cletergent composition with:
156 Ex. Il's alkyl poly-glucoside; 22~ Cl l 8 alkylbenzene sulfonate with the benzene group attached primarily to the center ,~
of the alkyl chain, sodium neutrali~ed 450 15075 15% Ex. Il's all<yl polyglucoside;
2 0 C11.8 alkylben~ene sulfonate with the benzene group attached primarily to the center of the alkyl chain, mac3nesium neutralized 450 200110 10 Premium product tJoy~)) 350 12075 Soil added to the -test solution as in E~. Vl l l .
EXAMPLE XV
The optimum alkylpolysaccharides, especially all<ylpolygluco-- sides have an HLB of from about 6 to about 27 and a critical 15 micelle concentration (CMC) of less than about 10UOppm, prefer-ably less than about 500. Short chain alkylpolysaccharides in which the alkyl group contains less than about 8 carbon atoms have unacceptably high CMC's and those all<ylpolysaccharides having more than about 4 saccharide units have unacceptably high 20 HLB's as is shown in the followincJ table in which the alkyl group and the glucoside chain length were varied.
it of Go Gl G2 G3 G~l G5 Glucosides o f 25 Carbons ` !---C4 HLB 5.1 12.4 17.9 23.3 28.8 34.2 C6 HLB 4.2 11.4 17,0 22.4 27.8 33.2 C8 HLB 3.2 10.5 16.0 21.4 26.9 32.3 Ci~llC ~7000 C1O HLB 2,2 9.6 15.0 20.4 26.0 31.4 CMC ~700 2000E
C12 HLB 1.3 8.6 14.1 19.5 25.0 30.4 CMC ~6.0 ~70 ~200 225E ~250 :~8~
-- 2~ --C14 ~ILE~ O.Ll 7.6 13.2 18.6 24.0 29.~i CMC ~6 ~2025-60E
C16 HLE30.0 6.7 12.2 17.6 23.1 28.5 CMC~0.3 ~0.6 ~4 C18 ~IL13 0.0 5.8 11.~ 16.6 22.2 27.6 CMC ~1 E=Estimated HLB determined accordirig to Davies: Proc. ~ International Congress, Surface Activity 1,426, Butterworths, London, 1957.
10 ppm As can be seen above, (1) longer pure glucoside chain lengtl s raise the HLE~ and lower the molecule's surface activity (high CMCj and- ~2) the shorter alkyl chain lengths ha~e extremely high CMC's even as the monoglucoside.
EXAMPLE XVI
The following formulas were prepared:
A B C
Magnesium linear C11 2 alkylbenzene sulfonate 22.4 22.4 22.4 20 C12 13 all~ylpolygluco-side (G1 7) (<2% free fatty a Icohol ) 14.9 14.9 14.9 C9 11 allcoxypropyldi-hydroxyethyl amine oxide - 4 25 C12 alkylclihYdrXY
ethyl amine oxide - - 4 Ethanol 5 5 5 Water balance balance balance Formulas A, 3 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 protein, carbohydrate and edible acid). Dinner plates are wasi1ed with ~ ml. of soil on 35 each plate and the suds height is measured after each five plates.
~< ~ )g7~
, .
30 plates in total are washed and the integral of the suds height~
taken over the number of plates washed is reported as the SD~V
grade ~SD~ = Suds During ~'~ashing).
,'\ B C
S SDW grade 24 28.S 28.4 This shows that the addition of a small amount of these amine oxides dramatically increases the amount of dishes that can be washed. Similar results are obtained when a fatty 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 alkylpolyglucoside IG2 2) (<2~ free fatty alcohol) are then mixed in. The mixture is transferred into a fluid bed dryer operated at room temperature (e.g., Aeromatic Inc., Model STREA-1 ), then 100 grams of a 50%
solution of said allcylpolycJlucoside is sprayed onto the powder.
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 at 30 in. of Hg vacuum at 50C for -ten hours to remove excess water.
In a similar manner 60 grams of a 50?6 solution of said alkyl-polyglucoside is sprayed onto 100 gram of Berkite and S0 grams of sodium dodecylbenzene sulfonate flakes are admixed with the product to give a light duty granule.
EXAMPLE XVI l l Ammonium C1t 2 linear alkyl benzene sulfonate was admixed with C12 alliylpolyglucoside G3 5 in a ratio of about 2:1. The mixture was used at a level of 400 ppm in city 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. Substieution of a sodium C12 16 alkyl glyceryl ether sulfonate for 25% and 40~ of the g7'~
mixture extencled the point at which there was no suds to 1 . 5 and 1.75 cgrams of soil per 200 ml. of wash? solution respectively~
Similar r esults are obtained when a sodium, potassium, ammonium, or monoethanolammonium C1 2-16 allcylpolyethoxy3 5~ acetate, or C1l~_16 olefin sulFonate or mixtures thereof is substituted for at least part of the alkyl glyceryl ether sulfonate.
EXAMPLE X I X
The following formula was prepared with alkylpolyglucosides having 0.3~ and 1% free fatty alcohol respectively.
Wt. %
Ammonium Cl l 2 linear alkyl benzene sulfonate 17 . 5 Magnesium Cl l 2 linear - alkyl benzene sulfonate 6.4 15 Amrnonium C1 2-13 allcyl poly-ethoxylate (0.8) sulfate6.1 C12_13 alkYIPIY~IUCside G1.7 Minors and water balance The SDI?`~ 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.
E~AMPLE XX
The following formulas were prepared:
% by weight ? ~A B C D
Ammonium/magnesium C11 2 linear alkyl benzene sulfonate 2~??.2 21.8 - -Ammoniumlmac?nesium Cl 2-15 30 olefin sulfonate - - 12.8 10.6 AmmoniUm/ma9nesium C1 2-13 alkyl sulfonate - - 19.2 15.9 Arnmonium Cl 2-13 alky polyethoxylate (0.8) 35 sulfate 6.5 5.8 C12 fatty acid diethanoi-amide - 3.8 - S .5 C12-13 alkylpoly5lucoside G 1 7 ~ f ree fa tty 5 ~alcohol <0.5%) 5.3 4.8 4 3,3 Minors and l,Yater balance A B C D
The SDW I ndex 79 89 97 107 The SDW index is -the SDW grade for each product as a 10 percentage of the SDIIV value of a standard commercial product.
The following are examples of particularly pre-ferred compo-sitions. The broad and preferred ranges of ingredients which can be used are given in the second and third columns, respec-- tively, in each example.
EXAI\/IPLE XX I
% by Weight Amrnonium C~ alkyl benzene sulfonate 17.5 10-35 12-25 Ma~nesium C11 4 alkyl 20benzene sul-fonate 6.4 0-11 3-9 Ammonium C12-13 alkyl poly-ethoxylate ~0.8) sulfates 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 EXA~IPLE XXI!
% by ~Yeisht AMmonium C12_13 alkyl sulfate 15.7 7-23 10-20 14-16 olefi sulfonate 10.4 4-19 6-13 7'~
MgC12 6~12 5.6 0-11 2-10 Coconut monoethanol amide 5 . 5 2-8 3-7 Cl2-13 alkyl polyglycoside (1.7) derived from glucose (<0.5% frce fatty alcohol) 5.9 2-t2 3-9 Ethanol 11. 0 0-10 0-10 H2O and minor components, e.g., perfume Balance The alkyl groups in the surfactants of Examples XXI and 10 XX l l can vary from about 10 to about 16 carbon atoms and the cations can be ammonium, sodium, potassium, monoethanolammonium, diethanolammonium, triethanolammonium, magnesium, or preferably, mixtures therof. Any of the preferred alkyl polyglycosides can be used and other known amine oxide and amide suds boosters l S disclosed herein can be used.
EXAMPLE XX l l l When a 2:1 mixture of an ammonium C11 2 alkylbenzene sulfonate and the C12 13 alkylpoly~3lucoside (2-4) (>2% free fatty alcohol) are tested under the conditions of Example l l the ini~ial 20 suds volur,le is good, but the SDW grade is not as good as some premium commercial products. Substitution of between 25~ and S0~ of the mixture with a sodium C12 16 alkyl glyceryl ether sulfonate, or sodium C1 4 16 olefin sulfonate, or sodium C1 2 13 alkyl polyethoxylate~3~ acetate increases the SD~V grade without 25 loweriny the initial 'sudsing e~cessively.
Known analytical techniques can be used to determine the structures of the alkylpolysaccharide surfactants herein; f~r example, to determine the qlycosidic chain length, the amount of butyl glucoside, the free fatty alcohol content~ and the level of 30 unreacted polysaccharide. ~lore 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 the hydrophobic portion of the molecule can be determined by 1 3C nmr.
97~
The alkylpolysaccharide surfactants are complex mixturesn~
Their components vary depending upon the nature of the starting ma-terials and the reaction by which they are prepared. Analyti-cal standards which are useful in calibrating instruments for 5 analyzing the components of a particular alkylpolysaccharide surfactant can be obtained from Calbiochem Behring Co. LaJolla, California. These standards include those for octylglucoside (Calbiochem #494559), decylglucoside ~Calbiochem #252715), dodecylmaltoside (Calbiochem ~32~i3555).
The HLBs of al~ylpolysaccharide 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 results indicated in the examples.
WHAT lS CLAIMED IS:
Shampoo compositions comprise from about 190 to about 95g~, preferably from about 5% to about 20% of the mixture of surfac-20 tants mentioned hereinbefore, from about 1% to about 5% of anall<anol amide, from about 0.5~ to about 3?6 of a polymeric thiclc-ener, and tlle balance water. It is a special advantaJe of the sharnpoos that they rinse quickly and readily.
Additional Ingredients -`
.. . . . .. .
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. In de-tergen-t compositions the compositions can contain any of the well known ingreclients including minor amounts of other surfactants, 30 detergency builders, soil suspending a~ents, brighteners, abras-ives, dyes, fabric conditioniny agents, hair conditioning agents, hydrotropes, solvents, fillers, clays, perfumes, etc. Suitable ingredients are disclosed in U.S. Patents 4,166,039--Wise;
4,157,978--Llenado; 4~056,481--Tate; 4,049,586--Collier;
4,035,257--Cherney; 4,019,g98--Benson et al; 4,000,080--Bartolotta et al; and 89983,078--Collins. The shampoo compositions of this invention can contain any of the additional ingredients known to the art to be suitable for use in shampoos. Bistings of suitable additional ingred-ients, including low levels of other surfactants can be found in U.S. Patents ~,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. For example, raising the pH to above about 8.5 by alkaline materials or incorporating the tertiary alco~
hols of the Jones et al, Canadian Patent 1,160,131 issued January 10, 1984. Such ingredients are desira~le for some consumers since the solutions do not have the normal "soapy"
feel associated with surractant 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 Premium Product Commercial Commercial of the Product Product Invention U.S. Crystal U.S.
White~ Palmolive~
F _~LA Weight % Weigh~ % Wei~
Sodium Cll 8 alkyl benzene sulfonate 10.5 18.0 18.0 C12-13 alk glucoside2_3 (~
free fatty alcohol) ~ .0 ., ,.~, ~`-' 7'~
m 14-15 all<yl polyethoxylate3 sulfate 5 . 5 12 . 0 Balance of formula inc. water 84. 0 70. 0 70 . 0 SUDSI NG
5 ~ Relative Volume of Sucls (ml) 110 125 220 0 . 2% solutions CONSUMER TEST
Overall preference, % lQ 18 23 Favorable sudsing 10 comments, % 7~1 85 ~0 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 consurners wore rubber ~31Oves during the -test. The differences are siynificant at 20 the 95~ conficlence level for the invention over the generic product .
The relative volume of suds in ml. is determined by the following test procedure:
100 ml of the test solution at 11 5F is placed in a 500 ml 25 graduated cyliner: the solution is agitated by repeated inversion of the graduated cylinder until the amount of suds in the cylinder does not increase with further agitation. Suds heic3ht is measured directly on the cylinder scale making allowance for the height of liquid remaining in the cyiinder. The test solution is 30 made by addin~ the test product to water having a hardness of 7 gr. per U.S. gallon (Ca/Mg = 3/1).
EXAI\/IPLE 11 -~
LAS Suds Boostin~
i~`lt. % of: A B C D E F G
SSodium C1 1 ~ alkyl-benzene sulfonate 0 20 40 50 60 80 100 Cl 2 15 alkylPIY2 3 glucoside 100 80 60 50 40 20 0 Relative Volume 10 of suds (ml) 140 220 280 300310 300 240 The suds (foam) were generated as described in Ex. I using 300 ppm of the surfactant mixtures in city water (~9 grains per gallon). The results clearly show the sudsing synergism for 15 ratios greater than about 1:2, i.e. for the foaminy composition of the invention herein.
EXAMPLE 11 i Soap Suds Boosting Wt. % of: A B C D E F
20 Sodium oleate 0 20 40 60 80 100 Cl 2-15 alkYIPIY2-3 glucoside 100 80 60 40 20 0 Relative Volume of suds (ml.) 160 270 280 300310 260 The suds werè generated as in Ex. I using 500 ppm. of the surfactant mixtures. This data clearly indicates the sudsing synergism for the foaming composition of the invention herein.
EXA~lPLE IV
Foamin~ with Soa,o Effect of ~lardness on Relative Volume of Suds ~rains hardness Sodium oleate 225 10 0 0 So~lium oleate plus C12_15 alkylpoly2_3 ~31ucoside ~3: 2 ratio) 360 100 55 10 The suds were generated as in Ex. I using 500 ppm. of the surfactant mixtures.
EXAMPLE V
Alkyl Poly~ucosid~ (C1~ 15 alkylpoly 3 ~lucoside) 15 Suds Boosting for the Following Representative Cosurfactants (3: 2 ratio; 500 ppm) % increase in foaming Sodium C11 8 allcylbenzene sulfonate - 100-150 Sodium oleate 50-75 20 3-1 N -coconuta Ikyl-N, N -dimethy I ~ -2-hydroxy-1-sulfonate 40-60 Sodium C14 15 olefin sulfonate 20-40 Sodium coconut alkyl sulfate 10-30 Sodium coconut alkyl polyethoxylate3 sulfate 0-20 The above data clearly demonstrate the criticality of utilizing a carboxylate or sul-Fonate anionic detergent cosurfactant for sudsing synergism with the allcyl polyglucoside surfactant.
EXAl\lPLE Vl Glucoside Chain Length Criticality 40: 60 wt- ratio of C12-15 all~yl polygl~Jcoside to sodium C12 allcylbenzene sulfonate (500 ppm. concentration) where the gluco-side portion is:
9~'~
Relative Volume of Suds ~ mi ) Monoglucoside 1 80 Diglucoside 240 Pentaglucoside 260 Decaglucoside 1 70 Sodium C1 1. 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, signiflcant synergism is obtained only with 1 . 5 or more glucoside units and preferably less than about 10, more prefer-- ably less than about 8 glucoside units.
EXAI~/lPLE Vl I
Allcylbenzene sulfonates ( LAS) ~lomologs/phenvl-position (3:2 ratio; 500 ppm) Relative Volume of Suds ( ml ) 20 Ex. I I's alkylpolygl-Jcoside plus:
Sodium C1 1 LAS, high 2-phenyl 210 Sodium C1 1 LAS, low 2-phenyl250 Sodium C12 LAS, high 2-phenyl225 Sodium C1 2 LAS, low 2-phenyl225 25 Sodium Cl L~ LAS, ~iigh 2-pheriyl 210 Sodium C1 4 LAS, low 2-phenyl215 As can be seen from the above, in general C~ QW 2-phenyl LAS is preferred for sudsing.
EXAMPLE Vl l l -~.
Suds Boos-ting of Alkyl Polyglucosides and Effect of Soil Rela-tive Volume of Suds ~ml) ~'~ithout Soii With Soil 0.5% 1.0 0.2% aqueous solution of a detergent composition 10 formulated with:
15% sodium C1 1 ~ alkyl-benzene sulfonate (C11 8 LAS~ - - 120 50 - - 25 11 . 8 LAS 12%
15Ex. Il's alkyl poly~lucoside 310, 130 70 ~6 C11.8 LAS 190 140 100 20% C1 1 8 LAS ~ 12%
Ex l's alkylpolyglucoside 380 170 100 20Test method of Ex. I rnodified by adding to the -test solu-tion the indicated amount of soil. % is wt. 96 of test solution.
The soil is a 44%/5G~ by weight mix-ture of Fluffo(~? and PREP~) both of which products are available in the United States from The Procter ~ Gamble Company.
25As can be seeh from the'~above, the benefit for the invention is even more remarkable when soil is present.
EXAl\lPLE IX
Relative \/olume of Suds lm!) No Soil 1% Soil Present 30 Generic commercial product (Crystal ~ ite(~))** 110 30 Premium commerical product E3 ~ Palmolive Liquic~) 120 100 Premium commercial product C
35 ( (~)) 125 120 8~7~
~ 21 --.
12~ Cll 8 LAS/8% Ex. Il's alkyl polyglucoside1~0 120 1&% C11 8 LAS/12% Ex. Il's alkyl polyglucoside240 150 24% Cll ~ LAS/16~ Ex. Il's allcyl polyglucoside300 180 Soil is added as described in Ex. Vl 1.
** ~
Crystal White~ is available from Colgate-Palmolive Co.
Palmolive Liquid~ is available from Colyate-Palmolive Co.
10 Joy~) is available from The Procter ~ Gamble Company.
Suds generated as in Ex. I usinq a test solution containing 0.2~ by wt. of the indicated commercial product or 0.2% of a product formulated with the surfactant 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 licluids.
EXAMPLE X
Wt. % of: A ~ C D E F
20 C11 8 LAS (Sodium) 20 40 6080 100 Sucrose monolaurate 100 80 6040 20 0 Relative Volume of suds (ml.) 30 100 150 190210 220 ~ !-300 ppm of surfactant mixture used in test solu-tion of Ex. I.
The above demonstrates that structures which are similar to the alkyl polyglucosides do not provide the benefits of this in-vention .
EXAMPLE Xl Shampoo Cocamido propyl betaine (30% aqueous ~olution) 50.00%
Ex. I's alkyl polyglucoside 5.006 Polyethylene glycol distearate 1. 00%
35 Preserva tive 03%
Distilled water q.s. lOO.OOQo EXAMPLE X l l Shampoo Alpha-olefin sulfonate ~40% aqueous solution~ 30.00 Ex. I's alkyl polyglucoside 3.00 Hydroxyethyl cellulose 0.80~
Perfume 1. 006 Preservative 0. 04~
Dis-tilled water - q.s. 100.006 EXAMPLE X l l l Paraffin Sulfonate Suds Boosting Wt. ~ of: A B C D E F_ Mixture of sodium C1 ~5 15 paraffin sulfonate 0 20 40 60 80 100 ~12-15 G"_5 100 80 60 40 20 0 Relative Vol. of Suds(ml) 185 250 275 275 235 210 Test Conditions:
l otal concentration of 300 ppm; water having 8 grains of 20 mixed hardness.
C12 1 5G4 5 is a notation for an allcyl polysaccharide surfactant in which there are 4-5 glucoside units and in which the alkyl group has 12-15 carbons.
EXAMPLE X IV
Sodium vs. Magnes~um Alkylbenzene Sulfonate -Relative Volume of Suds ~ml. ) *
Without Soil ~Vith Soil 0 . 6% 1 . 06 0.26 aqueous solution of a 30 cletergent composition with:
156 Ex. Il's alkyl poly-glucoside; 22~ Cl l 8 alkylbenzene sulfonate with the benzene group attached primarily to the center ,~
of the alkyl chain, sodium neutrali~ed 450 15075 15% Ex. Il's all<yl polyglucoside;
2 0 C11.8 alkylben~ene sulfonate with the benzene group attached primarily to the center of the alkyl chain, mac3nesium neutralized 450 200110 10 Premium product tJoy~)) 350 12075 Soil added to the -test solution as in E~. Vl l l .
EXAMPLE XV
The optimum alkylpolysaccharides, especially all<ylpolygluco-- sides have an HLB of from about 6 to about 27 and a critical 15 micelle concentration (CMC) of less than about 10UOppm, prefer-ably less than about 500. Short chain alkylpolysaccharides in which the alkyl group contains less than about 8 carbon atoms have unacceptably high CMC's and those all<ylpolysaccharides having more than about 4 saccharide units have unacceptably high 20 HLB's as is shown in the followincJ table in which the alkyl group and the glucoside chain length were varied.
it of Go Gl G2 G3 G~l G5 Glucosides o f 25 Carbons ` !---C4 HLB 5.1 12.4 17.9 23.3 28.8 34.2 C6 HLB 4.2 11.4 17,0 22.4 27.8 33.2 C8 HLB 3.2 10.5 16.0 21.4 26.9 32.3 Ci~llC ~7000 C1O HLB 2,2 9.6 15.0 20.4 26.0 31.4 CMC ~700 2000E
C12 HLB 1.3 8.6 14.1 19.5 25.0 30.4 CMC ~6.0 ~70 ~200 225E ~250 :~8~
-- 2~ --C14 ~ILE~ O.Ll 7.6 13.2 18.6 24.0 29.~i CMC ~6 ~2025-60E
C16 HLE30.0 6.7 12.2 17.6 23.1 28.5 CMC~0.3 ~0.6 ~4 C18 ~IL13 0.0 5.8 11.~ 16.6 22.2 27.6 CMC ~1 E=Estimated HLB determined accordirig to Davies: Proc. ~ International Congress, Surface Activity 1,426, Butterworths, London, 1957.
10 ppm As can be seen above, (1) longer pure glucoside chain lengtl s raise the HLE~ and lower the molecule's surface activity (high CMCj and- ~2) the shorter alkyl chain lengths ha~e extremely high CMC's even as the monoglucoside.
EXAMPLE XVI
The following formulas were prepared:
A B C
Magnesium linear C11 2 alkylbenzene sulfonate 22.4 22.4 22.4 20 C12 13 all~ylpolygluco-side (G1 7) (<2% free fatty a Icohol ) 14.9 14.9 14.9 C9 11 allcoxypropyldi-hydroxyethyl amine oxide - 4 25 C12 alkylclihYdrXY
ethyl amine oxide - - 4 Ethanol 5 5 5 Water balance balance balance Formulas A, 3 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 protein, carbohydrate and edible acid). Dinner plates are wasi1ed with ~ ml. of soil on 35 each plate and the suds height is measured after each five plates.
~< ~ )g7~
, .
30 plates in total are washed and the integral of the suds height~
taken over the number of plates washed is reported as the SD~V
grade ~SD~ = Suds During ~'~ashing).
,'\ B C
S SDW grade 24 28.S 28.4 This shows that the addition of a small amount of these amine oxides dramatically increases the amount of dishes that can be washed. Similar results are obtained when a fatty 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 alkylpolyglucoside IG2 2) (<2~ free fatty alcohol) are then mixed in. The mixture is transferred into a fluid bed dryer operated at room temperature (e.g., Aeromatic Inc., Model STREA-1 ), then 100 grams of a 50%
solution of said allcylpolycJlucoside is sprayed onto the powder.
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 at 30 in. of Hg vacuum at 50C for -ten hours to remove excess water.
In a similar manner 60 grams of a 50?6 solution of said alkyl-polyglucoside is sprayed onto 100 gram of Berkite and S0 grams of sodium dodecylbenzene sulfonate flakes are admixed with the product to give a light duty granule.
EXAMPLE XVI l l Ammonium C1t 2 linear alkyl benzene sulfonate was admixed with C12 alliylpolyglucoside G3 5 in a ratio of about 2:1. The mixture was used at a level of 400 ppm in city 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. Substieution of a sodium C12 16 alkyl glyceryl ether sulfonate for 25% and 40~ of the g7'~
mixture extencled the point at which there was no suds to 1 . 5 and 1.75 cgrams of soil per 200 ml. of wash? solution respectively~
Similar r esults are obtained when a sodium, potassium, ammonium, or monoethanolammonium C1 2-16 allcylpolyethoxy3 5~ acetate, or C1l~_16 olefin sulFonate or mixtures thereof is substituted for at least part of the alkyl glyceryl ether sulfonate.
EXAMPLE X I X
The following formula was prepared with alkylpolyglucosides having 0.3~ and 1% free fatty alcohol respectively.
Wt. %
Ammonium Cl l 2 linear alkyl benzene sulfonate 17 . 5 Magnesium Cl l 2 linear - alkyl benzene sulfonate 6.4 15 Amrnonium C1 2-13 allcyl poly-ethoxylate (0.8) sulfate6.1 C12_13 alkYIPIY~IUCside G1.7 Minors and water balance The SDI?`~ 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.
E~AMPLE XX
The following formulas were prepared:
% by weight ? ~A B C D
Ammonium/magnesium C11 2 linear alkyl benzene sulfonate 2~??.2 21.8 - -Ammoniumlmac?nesium Cl 2-15 30 olefin sulfonate - - 12.8 10.6 AmmoniUm/ma9nesium C1 2-13 alkyl sulfonate - - 19.2 15.9 Arnmonium Cl 2-13 alky polyethoxylate (0.8) 35 sulfate 6.5 5.8 C12 fatty acid diethanoi-amide - 3.8 - S .5 C12-13 alkylpoly5lucoside G 1 7 ~ f ree fa tty 5 ~alcohol <0.5%) 5.3 4.8 4 3,3 Minors and l,Yater balance A B C D
The SDW I ndex 79 89 97 107 The SDW index is -the SDW grade for each product as a 10 percentage of the SDIIV value of a standard commercial product.
The following are examples of particularly pre-ferred compo-sitions. The broad and preferred ranges of ingredients which can be used are given in the second and third columns, respec-- tively, in each example.
EXAI\/IPLE XX I
% by Weight Amrnonium C~ alkyl benzene sulfonate 17.5 10-35 12-25 Ma~nesium C11 4 alkyl 20benzene sul-fonate 6.4 0-11 3-9 Ammonium C12-13 alkyl poly-ethoxylate ~0.8) sulfates 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 EXA~IPLE XXI!
% by ~Yeisht AMmonium C12_13 alkyl sulfate 15.7 7-23 10-20 14-16 olefi sulfonate 10.4 4-19 6-13 7'~
MgC12 6~12 5.6 0-11 2-10 Coconut monoethanol amide 5 . 5 2-8 3-7 Cl2-13 alkyl polyglycoside (1.7) derived from glucose (<0.5% frce fatty alcohol) 5.9 2-t2 3-9 Ethanol 11. 0 0-10 0-10 H2O and minor components, e.g., perfume Balance The alkyl groups in the surfactants of Examples XXI and 10 XX l l can vary from about 10 to about 16 carbon atoms and the cations can be ammonium, sodium, potassium, monoethanolammonium, diethanolammonium, triethanolammonium, magnesium, or preferably, mixtures therof. Any of the preferred alkyl polyglycosides can be used and other known amine oxide and amide suds boosters l S disclosed herein can be used.
EXAMPLE XX l l l When a 2:1 mixture of an ammonium C11 2 alkylbenzene sulfonate and the C12 13 alkylpoly~3lucoside (2-4) (>2% free fatty alcohol) are tested under the conditions of Example l l the ini~ial 20 suds volur,le is good, but the SDW grade is not as good as some premium commercial products. Substitution of between 25~ and S0~ of the mixture with a sodium C12 16 alkyl glyceryl ether sulfonate, or sodium C1 4 16 olefin sulfonate, or sodium C1 2 13 alkyl polyethoxylate~3~ acetate increases the SD~V grade without 25 loweriny the initial 'sudsing e~cessively.
Known analytical techniques can be used to determine the structures of the alkylpolysaccharide surfactants herein; f~r example, to determine the qlycosidic chain length, the amount of butyl glucoside, the free fatty alcohol content~ and the level of 30 unreacted polysaccharide. ~lore 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 the hydrophobic portion of the molecule can be determined by 1 3C nmr.
97~
The alkylpolysaccharide surfactants are complex mixturesn~
Their components vary depending upon the nature of the starting ma-terials and the reaction by which they are prepared. Analyti-cal standards which are useful in calibrating instruments for 5 analyzing the components of a particular alkylpolysaccharide surfactant can be obtained from Calbiochem Behring Co. LaJolla, California. These standards include those for octylglucoside (Calbiochem #494559), decylglucoside ~Calbiochem #252715), dodecylmaltoside (Calbiochem ~32~i3555).
The HLBs of al~ylpolysaccharide 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 results indicated in the examples.
WHAT lS CLAIMED IS:
Claims (7)
1. A foaming composition comprising (I) an alkylpolysaccharide surfactant having the formula RO(R1O)t(Z)x where Z is a moiety derived from a reducing saccharide containing 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) a mixture of anionic cosurfactants neutralized with one or more cationic moieties consisting essentially of:
(a) from about 1% to about 95% of a water soluble alkylbenzene sulfonate in which the alkyl group contains from about 10 to about 13 carbon atoms, and (b) from about 5% to about 99% of a cosurfactant selected from the group consisting of an alkyl glyceryl ether sulfonate in which the alkyl group contained from about 8 to about 18 carbon atoms, an alpha-olefin sulfonate 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 con-tains from about 2 to about 6 ethoxylate groups, and mixtures thereof.
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) a mixture of anionic cosurfactants neutralized with one or more cationic moieties consisting essentially of:
(a) from about 1% to about 95% of a water soluble alkylbenzene sulfonate in which the alkyl group contains from about 10 to about 13 carbon atoms, and (b) from about 5% to about 99% of a cosurfactant selected from the group consisting of an alkyl glyceryl ether sulfonate in which the alkyl group contained from about 8 to about 18 carbon atoms, an alpha-olefin sulfonate 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 con-tains from about 2 to about 6 ethoxylate groups, and mixtures thereof.
2. The composition of Claim 1 wherein the cosurfactant (2) (b) is an alkyl glyceryl ether sulfonate and the cationic moiety is selected from the group consisting of sodium, potassium, ammon-ium, monoethanolammonium, diethanolammonium, triethanolammonium, calcium, magnesium and mixtures thereof.
3. The composition of Claim 1 wherein the cosurfactant (2) (b) is an alkyl polyethoxylate carboxylate.
4. The composition of Claim 1 wherein the cosurfactant (2) (b) is an alpha olefin sulfonate.
5. A composition according to Claim 1, 2 or 3 wherein x is a number of from 1.5 to 4.
6. The composition of Claim 1, 2 or 3 wherein x is a number from 1.6 to 2.7.
7. A light-duty liquid detergent composition comprising from about 5% to about 50% of the surfactant mixture of Claim 1 and from about 1% to about 50% of a solvent selected from the group consisting of C1-3 alkanols, C1-3 alkanol-amines, C2-4 polyols, and mixtures thereof, and the balance water.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US37169482A | 1982-04-26 | 1982-04-26 | |
| US371,694 | 1982-04-26 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1180974A true CA1180974A (en) | 1985-01-15 |
Family
ID=23465031
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000407146A Expired CA1180974A (en) | 1982-04-26 | 1982-07-13 | Foaming surfactant compositions |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JPS58186428A (en) |
| CA (1) | CA1180974A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012036560A1 (en) * | 2010-09-17 | 2012-03-22 | Elkem As | Slurry comprising manganomanganic oxide particles and dispersant and method for the production of such slurries |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2555037B2 (en) * | 1985-10-31 | 1996-11-20 | ザ、プロクタ−、エンド、ギヤンブル、カンパニ− | Liquid detergent composition |
| JPH0699711B2 (en) * | 1989-07-25 | 1994-12-07 | 花王株式会社 | Liquid detergent composition |
| JP2824192B2 (en) * | 1993-05-31 | 1998-11-11 | 花王株式会社 | Detergent composition |
| FR2911781B1 (en) * | 2007-01-26 | 2009-03-20 | Fabre Pierre Dermo Cosmetique | DERMATOLOGICAL EMULSION AND PREPARATION METHOD |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3721633A (en) * | 1969-10-06 | 1973-03-20 | Atlas Chem Ind | Aqueous built liquid detergents containing alkyl glycosides |
-
1982
- 1982-07-13 JP JP57121975A patent/JPS58186428A/en active Granted
- 1982-07-13 CA CA000407146A patent/CA1180974A/en not_active Expired
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012036560A1 (en) * | 2010-09-17 | 2012-03-22 | Elkem As | Slurry comprising manganomanganic oxide particles and dispersant and method for the production of such slurries |
| US8668772B2 (en) | 2010-09-17 | 2014-03-11 | Elkem As | Slurry of manganomanganic oxide particles and method for the production of slurry |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS58186428A (en) | 1983-10-31 |
| JPH0311810B2 (en) | 1991-02-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4536318A (en) | Foaming surfactant compositions | |
| CA1180973A (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 | |
| EP0070076B1 (en) | Foaming dishwashing liquid compositions | |
| EP0070077B1 (en) | Light-duty detergent granule composition | |
| EP0070075B1 (en) | Foaming dishwashing liquid compositions | |
| CA1335876C (en) | Detergent compositions | |
| US3755206A (en) | Detergent compositions | |
| US4555360A (en) | Mild detergent compositions | |
| DE3827778A1 (en) | PASTE-SHAPED DETERGENT AND CLEANING AGENT AND METHOD FOR PRODUCING THE SAME | |
| US5503779A (en) | High foaming light duty liquid detergent | |
| KR940010123B1 (en) | Detergent composition | |
| US5972867A (en) | High foaming, grease cutting light duty liquid detergent | |
| AU676899B2 (en) | High foaming nonionic surfactant based liquid detergent | |
| CA1180974A (en) | Foaming surfactant compositions | |
| JPH037718B2 (en) | ||
| CA1209010A (en) | Foaming surfactant compositions | |
| EP0848745A1 (en) | Foaming composition | |
| US6010992A (en) | Liquid detergent composition containing amine oxide and citric acid | |
| US6107263A (en) | High foaming, grease cutting light duty composition containing a C12 alkyl amido propyl dimethyl amine oxide | |
| CA1190450A (en) | Foaming surfactant compositions | |
| NO179952B (en) | Liquid detergent mixture |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEC | Expiry (correction) | ||
| MKEX | Expiry |