CA1209010A - Foaming surfactant compositions - Google Patents
Foaming surfactant compositionsInfo
- Publication number
- CA1209010A CA1209010A CA000407156A CA407156A CA1209010A CA 1209010 A CA1209010 A CA 1209010A CA 000407156 A CA000407156 A CA 000407156A CA 407156 A CA407156 A CA 407156A CA 1209010 A CA1209010 A CA 1209010A
- Authority
- CA
- Canada
- Prior art keywords
- alkyl
- group
- carbon atoms
- mixtures
- composition
- 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 sulfate, sulfonate and/or carboxylate cosurfactant with an amide and/or amine oxide auxilliary foam booster.
Abstract of the Disclosures Foaming compositions containing an alkylpolysaccharide surfactant and a sulfate, sulfonate and/or carboxylate cosurfactant with an amide and/or amine oxide auxilliary foam booster.
Description
lZO~10 FOAMII~JG SURFACTANT COMPOSITIONS
Keith ~. Jones and Ramon A. Llerlado Technical Field This invention relates to surfactant combinations ~Yhich provide controllable aqueous foams. Such compositions can be used in any situation where foams are desirable, including the laundry, personal cleaning products, dishwashing, fire fighting, oil well drilling, ore beneficiation, solution mining, washing hair, preparation of foamed solid ~tructures, etc.
Description of the Prior Art Alkylpolyglycoside:, which are surfactants have ~een dis-closed in U.S. Patents 3,598,865 3,721,633; and 3,772,269.
These patents also disclose processes for making alkylpolyglyco-side surfactants and built liquid detergent compositions containing these surfactants. U.S. Patent 3,219,656 discloses alkylmonoglu-cosides and suggests their utility as foam stabilizers for other surfactants. Vari:~us polyglycoside surfactant structures and processes for making them are disclosed in U.S. Patents 2,974,1~4;
3,640,9~8; 3,839,318; 3,314,936; 3,346,558; 4,011,3R9; 4,223,129.
All percentages, parts ancl ratios used herein arc by weight unless otherwise specified.
Sumrmary of the hlvention This invention relates to the discovery of certain combina-tions of surfactants which provide unusual foams. Specifically this invention relates to foaming compositions comprising (I) an alkylpolysaccharide surfactant having the formula RO( R ) tZx wherein Z is a moiety d~rived from a reclucing saccharide containing from 5 to 6 carbon atoms, preferably a glucose, galactose, glucosyl, or galactosyl resiclue or mixtures thereof; R is a hydro-phobic group selected from the group consisting of alkyl, alkyl phenyl, hyclroxyalky phenyl or hydroxy-"~
:~09~1~
alkyl groups or mixtures thereof in which said allcyl;
yroups 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: R 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 about 1.5 to to about 10, preferably 1 . 5 to 4, most preferably 1 . 6 to 2 . 7; and
Keith ~. Jones and Ramon A. Llerlado Technical Field This invention relates to surfactant combinations ~Yhich provide controllable aqueous foams. Such compositions can be used in any situation where foams are desirable, including the laundry, personal cleaning products, dishwashing, fire fighting, oil well drilling, ore beneficiation, solution mining, washing hair, preparation of foamed solid ~tructures, etc.
Description of the Prior Art Alkylpolyglycoside:, which are surfactants have ~een dis-closed in U.S. Patents 3,598,865 3,721,633; and 3,772,269.
These patents also disclose processes for making alkylpolyglyco-side surfactants and built liquid detergent compositions containing these surfactants. U.S. Patent 3,219,656 discloses alkylmonoglu-cosides and suggests their utility as foam stabilizers for other surfactants. Vari:~us polyglycoside surfactant structures and processes for making them are disclosed in U.S. Patents 2,974,1~4;
3,640,9~8; 3,839,318; 3,314,936; 3,346,558; 4,011,3R9; 4,223,129.
All percentages, parts ancl ratios used herein arc by weight unless otherwise specified.
Sumrmary of the hlvention This invention relates to the discovery of certain combina-tions of surfactants which provide unusual foams. Specifically this invention relates to foaming compositions comprising (I) an alkylpolysaccharide surfactant having the formula RO( R ) tZx wherein Z is a moiety d~rived from a reclucing saccharide containing from 5 to 6 carbon atoms, preferably a glucose, galactose, glucosyl, or galactosyl resiclue or mixtures thereof; R is a hydro-phobic group selected from the group consisting of alkyl, alkyl phenyl, hyclroxyalky phenyl or hydroxy-"~
:~09~1~
alkyl groups or mixtures thereof in which said allcyl;
yroups 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: R 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 about 1.5 to to about 10, preferably 1 . 5 to 4, most preferably 1 . 6 to 2 . 7; and
(2) an anionic cosurfactant which is a sulfate, sulfonate andlor carboxylate or mixtures thereof neutralizecl with one or more cationic moieties (M) to complete the - formula, preferably the anionic cosurfactant has the formula R (SO3)y(COO)zMq;
wherein R is an alkyl, alkylphenyl, hydroxyalkyl-phenyl or hydroxyalkyl, or raixtures 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 ~l is a cationic moiety with q being selected to complete the formula, wherein the ratio of (2) to (I) is from about l:lO to about I0:1 (i.e., 0.1 to 10.0) ~xcept that when the cosurfactant is an alkylbenzene sulfonate, the ratio of (2) to (I) is at least about 1:2 (i.e., at least about 0.5) ancl when y is 0 and z is one, the ratio of (2) to (I) is at least about 1:2 (i.e., at least about 0.5), and when the anionic cosurfactant does not contain sulfonate or carboxylate group x must be from 1. 5 to 3 and the all<ylpolysaccharide surfactant must have a free fatty alcohol content of less than about 2~ by weight.
~09~i~
It has surprisingly been found that the cosurfactants inter--~
act with the all<ylpolysaccharicle surfactan-t 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 about 95~ of the mixed surfactants.
Description of the Preferred Embodiments The Alkylpoiysaccharide Surfactant The alkylpolysaccharides are th~se having a hydrophobic group - /O containing from about 8 to about 20 carbon atoms, preferably fromabout 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, ri~ost preferably from 1.6 to 2.7 saccharide units (e.g., galacto-l ~ side, glucoside, fructoside, glucosyl, fructosyl and/or galactosyl units). Mix-tures of saccharide 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 alkylpolysaccharide molecule x can only assurne aO ir,tegral values. In any physical sample of alkylpolysaccharide surfactants there will in general be molecules having different x values. The physical sample can be characterized by the average value of x and this average value can assurne non-integral values.
In this specification the values of x are to be understood to be a~s averaye values. The hydrop!hobic 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 through the 1-position, i.e., glucosides, galactosides, fructosides, etc., is preferred. In the
wherein R is an alkyl, alkylphenyl, hydroxyalkyl-phenyl or hydroxyalkyl, or raixtures 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 ~l is a cationic moiety with q being selected to complete the formula, wherein the ratio of (2) to (I) is from about l:lO to about I0:1 (i.e., 0.1 to 10.0) ~xcept that when the cosurfactant is an alkylbenzene sulfonate, the ratio of (2) to (I) is at least about 1:2 (i.e., at least about 0.5) ancl when y is 0 and z is one, the ratio of (2) to (I) is at least about 1:2 (i.e., at least about 0.5), and when the anionic cosurfactant does not contain sulfonate or carboxylate group x must be from 1. 5 to 3 and the all<ylpolysaccharide surfactant must have a free fatty alcohol content of less than about 2~ by weight.
~09~i~
It has surprisingly been found that the cosurfactants inter--~
act with the all<ylpolysaccharicle surfactan-t 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 about 95~ of the mixed surfactants.
Description of the Preferred Embodiments The Alkylpoiysaccharide Surfactant The alkylpolysaccharides are th~se having a hydrophobic group - /O containing from about 8 to about 20 carbon atoms, preferably fromabout 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, ri~ost preferably from 1.6 to 2.7 saccharide units (e.g., galacto-l ~ side, glucoside, fructoside, glucosyl, fructosyl and/or galactosyl units). Mix-tures of saccharide 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 alkylpolysaccharide molecule x can only assurne aO ir,tegral values. In any physical sample of alkylpolysaccharide surfactants there will in general be molecules having different x values. The physical sample can be characterized by the average value of x and this average value can assurne non-integral values.
In this specification the values of x are to be understood to be a~s averaye values. The hydrop!hobic 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 through the 1-position, i.e., glucosides, galactosides, fructosides, etc., is preferred. In the
3 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 ( R) and the polysaccharide-chdin. The preferred all;oxide moiety is ethoxide.
~20~0iO
Typical hydrophobic groups inclucle alkyl ~roups, eithe saturated or unsaturated, branched or unbranchecl containincl from about 8 to about 20, prcferably from about 10 to about 16 carbon atoms. Preferably, the alkyl group is a straight chain saturated allcyl group. The alkyl group can contain up to 3 hydroxy groups and/or the polyalkoxide chain can con tain up to about 30, preferably less than lO, most prcferably 0, alkoxide moieties .
Suitable alkyl polysaccharides are decyl, dodecyl, tetradecyl, hexadecyl, and octadecyl, di-, tri-, tetra-, penta-, and hexaylu-cosides, galactosides, lactosides, fructosides, fructosyls, lac-tosyls, glucosyls and/or galactosyls and mExtures thereof.
The alkylmonosaccharides are relatively less soluble in water than the higher alkylpolysaccharides. When used in admixture with alkylpolysaccharides, the alkylmonosacchclrides are solubilized to some extent. The use of alkylmonosaccharides in admixture with alkylpolysaccharides 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 hexaglucosides.
The preferred alkyl polysaccharides are alkyl polyglucosides having the formula R (Cn~l2n)t~z2)x wherein Z is derived from glucose, R is a hydrophobic group 2~ selected from the group consisting of allcyl, alkylphenyl, hydroxy-alkyl, hydroxyalkylphenyl, and mixtures thereof in which said alkyl groups contain from about 10 to about 18, preferably from 12 to 14 carbon atoms; n is 2 or 3, preferably 2, t is from 0 to about 10, preferably 0; and x is from 1.5 to about 8, preferably from 1.5 to 4, most preferably from 1.6 to 2.7. To prepare these compounds a iony chain alcohol ( R2OI~) carl be reacted with glucose, in the presence of an acid catalyst to form the desired glucoside. Alternatively the alkylpolyglucosicles can be prepared by a two step procedure in which a short chain alcohol (Cl 6) is ~5 reacted with glucose or a polyglucoside (x=2 to L~) to yield a i20g~i~
short chain alkyl glucoside (x=1 to ~1) which can in turn b~
reacted with a longer chain alcohol ( R20H) to displa~e the short chaln alcohol and obtain the desired alkylpolyglucosicle. If this two step procedure is used, the short chain all~ylglucoside con-tent of the final alkylpolyglucoside material sho~lld be less than 50~, preferably less than 10%, more preferably less than 5%, mos~
preferably 0~6 of the alkylpolyglu~oside.
The amount of unreacted alcohol ~the free fatty alcohol content) in the desired alkylpolysaccharide surfac-tant is pre-iO ferably less than about 2%, more preferably less tha~ a~out 0 . 5~6by weight of the total of the alkyl polysac~haride plus unreacted alcohol. The amount of alkylmonosaccharide is about 20~ to about 70%, preferably 30g6 to 60~6, most preferably 30% to 5~% by weight of the total of the alkylpolysaccharide. For some uses it is :~ desirable to have the alkylmonosaccharide content less ~han about 10%.
As used herein, "alkylpolysaccharide surfactant" is intended to represent both the preferred glucose and g~lactose derived surfactants and the less preferred C alkylpolysaccharide surfactants. Throughout this specification "alkylpolyglucoside" is used to include alkylpolyglucosides because the stero chemistry of 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 neutralized with a cationic moiety or moieties selected from the group consisting of alkali metal, e.g. sodium or potassium, alkaline earth metal, e~s. 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.
~2~9~0 - 5a -Alkylbenzene Sul~onates 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.
1~09~10 However in heavier soil conditions, phenyl attachment at the 1- or 2-position is preferred.
The preferred alkylbenzene sulfonates contain a strai~ht 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 alkyl-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 15 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 invention since the foams produced 20 therewith are exceptionally stable, have a large volume, rinse quickly, and do not have a "slippery" feel. These compositions are particularly desirable for industrial and commercial processes as discussed hereinafter. The volume of foam produced using the alkylbenzene sulfonate cosurfactant is larger than for any other 2 ~ cosurfactant.
Soap .
Other preferred cosurfactants for use in this invention are carboxylates, e.g. fatty acid soaps and sir;lilar surfactants. The soaps can be saturated or unsaturated and can contain various '0 substituents such as hydroxy groups and alpha-sulfonate groups.
Preferably, the hydrophobic portion of the soap is a strai~ht chain saturated or unsaturated hydrocarbon. The hydrophobic portion of the soap usually contains from about 6 to about 30 carbon atoms, preferably from about 10 to about 18 carbon atoms.
~i The use of carboxylate cosurfactants is especially valuable since ~20~0 the alkylpolysaccharide surfactants are exceptional lime soap dispersers.
The cationic moiety (~1) for carboxylate cosurfactants is selected from the group consisting of allcali metal, for example, sodium or potassium, alkaline earth metal, for e~ample, calcium or magnesiurn, ammonium, or substituted ammonium, including mono-, di-, or triethanolammonium cations. Mixtures of cations can be desi rable .
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 pro-duces less foam volume than does the use of the preferred cosur-factants. However, the alkylpolysaccharide surfactant stabilizes the foams which are produced and allows the foams to be rinsed more quicl<ly.
One group of cosurfactants that are of interest because of their superior detergency are the zwitterionic detergents which contain both a cationic group, either ammonium, phosphonium, 2~) sulfonium or mixtures thereof and a sulfonate or carboxylate yroup. Preferably there are at least about four atoms separating the cationic and anionic groups. Suitable 2witterionic surfactants are disclosed in U.S. Patents 4,159,277; 3,928,251 3,925,26~;
3,929,678; 3,227,749; 3,539,521; 3,383,321; 3,390,094; and '5 3,239,s60. Such cosurfactants are especially desirable for shampoos.
Another group of cosurfactants are the amphoteric detersents which have the same general structure as the zwitterionic surfac-tants but with an amine group instead of the quaternary ammon-3C ium group.
Yet other cosurfactants are the alkyl (paraffin or olefin) sulfonates, preferably with a more central hydrophilic group, containing from about 6 to about 30 carbon atoms. Compositions containing. these cosurfactants produce the least volume of foam, ~5 if that is desired~ The hydrophobic group can contain up to 1~0~
about lO hyclroxy groups and/or ether linlcages. Examples include~
C1~ 5 paraffin sulfonates and C1 L~ 16 olefin sulfonate5 Still another cosurfactant is a soap structure containing up to about lO ether linkages in the chain and from about I to about 5 4 carbon atoms between ether lin' ages with from about 6 to about 30 carbon atoms in a terMinal portion containing no ether link-ages .
The preferred alkylpolyglucosides that contain an average of from 1.5 to 4 glucoside units, preferably from 1.6 to 2.7 - 10 glucoside uni-ts; less than about 50% short chain alkylpolyglu-cosides; less than about 10~6, preferably less than about 296, most preferably less than about 0.5% unreacted fatty alcohol~ increase the sudsing ability of conventional sulfate detergent cosurfact-ants, especially alkyl sulfate and alkyl polyether sulfate cosur-15 factant5 having the formula:
3 (~nH2n)t SO3 M
wherein R is an alkyl or hydroxyalkyl group containing from about 8 to about 18 carbon atoms, n is 2 or 3, t can vary from 0 to about 30, and M is a cationic moiety as defined above, the 20 cosurfactant being water soluble or dispersible.
A preferred foaming composition of the invention herein comprises (1 ) an alkylpolysaccharide surfactant having the formula RO(RlO)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 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 a 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 or more cationic moieties consisting essentially of:
(a~ from about 1 P~ to about 956 preferably about 10~ to ~20~0~0 about 506 nf a water soluble alkylbenzene 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 S .cosurfactant. selected from the group consisting of an alkyl glyceryl ether sulfonate in which the alkyl group contains 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 10atoms, an aikyl polyethoxylate carboxylate in which the alkyl group contains from about 10 to about 18 carbon atoms, and the polyethoxylate chain contains from about 2 to about 6 ethoxylate groups, and mixtures thereof.
15Such compositions have improved suds mileage as compared to compositions containing only the alkyl benzene sulfonate cosur-factant and the allcylpolysaccharide surfactant.
Another preferred embodiment of a foaming composition of the invention herein comprises ( 1 ) an alkylpolysaccharide surfactant having the formula RO(R )t(Z)x wherein Z is a moiety derived from a reducing saccharide containing from 5 to 6 carbon atoms and \,vherein R is a hydrophobic group selected from the ~roup co!nsisting of alkyl, alky!phenyl, hy-droxyalkylphenyl or hydroxyalkyl groups or mixtures thereof in which said alkyl groups contain from about 8 to about 18 carbon atoms; R contains from 2 to about 4 carbon atoms; t is from O to about 30; and x is a number from about 1 . 5 to about 10;
(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 M to complete the formula, the ratio of (2) to (1) being from about 1:10 to about tO:l, and ~20~0 (3) from about 2% to about 10~ of an auxiliary foam boos-ter~
selected from the group consistin~3 of:
(a) amides having the formula R7 -C-N- ( R8 ) wherein ~7 is an alkyl group containing from about 8 to about 18 carbon atoms, preferably about 12 to about 14 carbon atoms and each R8 is the same or different and is selected from the group consisting of hydrogen, C1 3 alkyl, C1 3 alkanol, and -(C2H4O-)1 4H groups and mixtures thereof;
(b) amine oxides having the formula:
R 4) bN ( R ) 2 wherein R is an alkyl group containing from about 8 to about 18 carbon atoms, preferably from 12 to 14 carbon atoms, each R contains t~ o or three car bon atoms, b is from 0 to about 30, each R is the same or different and is selected from the group consisting of C1_3 alkyl, C1_3 all<anol, and -(C2H40)1 6H groups and mixtures thereof; and lc) mixtures thereof.
Such compositions provide superior grease/oil removal and suds mi leage.
Preferred anionic cosurfactants are alkylbenzene 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 95%, preferably 5% to about 50% of an alkylpolysaccharide 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 1% to about 95%, preferably from about 10% to ~090~0 "
about 50~ of an anionic cosurfactant neu~ralized with one or more~
cationic moieties and which is a mixture of (1) from l~ to about 95~, preferably from about 5% to about 50% of an alkyl betlzene sulfona-te 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 95%, preferably from about 5% to about 50% of an alkyl polyethoxylate sulfate in which the alkyl group contains From about 8 to about 18 carbon atoms, preferably from 12 to 14 carbon atoms and from abou t one to about six ethoxylate moieties and wherein from about 1% to about 100%, preferably from about 10% to about 80g~ of the cationic moieties are magnesium: and wherein the auxiliary foam booster is an amide.
Another preferred 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 10% to about 20% of an alkylpolysaccharide surfactant having the formula RO(R )t(Z)x ~Jherein Z is a moiety derived from a reducin~ saccharide moiety containing from 5 to 6 carbon atoms and wherein R is a hydrophobic group se!ected 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;
(2) from about 5O to about 60% of an alkyl benzene sul-fonate cosurfactant in which the alkyl group contains from about 10 to about 13 carbon atorns, said alkyl ~20~
benzene sulfonate neutralized with one or more cationi~
moieties (1~/1) to balance the formula;
(3) from about 5~ to about 606, preferably from about 10~
to about 20~ of an alkylpolyethoxylate sul,ate 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 ~3roups, said aikylpolyethoxylate sulfate neutralized with one or more cationic moieties M to complete the formula.
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 ( R) and the polysaccharide-chdin. The preferred all;oxide moiety is ethoxide.
~20~0iO
Typical hydrophobic groups inclucle alkyl ~roups, eithe saturated or unsaturated, branched or unbranchecl containincl from about 8 to about 20, prcferably from about 10 to about 16 carbon atoms. Preferably, the alkyl group is a straight chain saturated allcyl group. The alkyl group can contain up to 3 hydroxy groups and/or the polyalkoxide chain can con tain up to about 30, preferably less than lO, most prcferably 0, alkoxide moieties .
Suitable alkyl polysaccharides are decyl, dodecyl, tetradecyl, hexadecyl, and octadecyl, di-, tri-, tetra-, penta-, and hexaylu-cosides, galactosides, lactosides, fructosides, fructosyls, lac-tosyls, glucosyls and/or galactosyls and mExtures thereof.
The alkylmonosaccharides are relatively less soluble in water than the higher alkylpolysaccharides. When used in admixture with alkylpolysaccharides, the alkylmonosacchclrides are solubilized to some extent. The use of alkylmonosaccharides in admixture with alkylpolysaccharides 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 hexaglucosides.
The preferred alkyl polysaccharides are alkyl polyglucosides having the formula R (Cn~l2n)t~z2)x wherein Z is derived from glucose, R is a hydrophobic group 2~ selected from the group consisting of allcyl, alkylphenyl, hydroxy-alkyl, hydroxyalkylphenyl, and mixtures thereof in which said alkyl groups contain from about 10 to about 18, preferably from 12 to 14 carbon atoms; n is 2 or 3, preferably 2, t is from 0 to about 10, preferably 0; and x is from 1.5 to about 8, preferably from 1.5 to 4, most preferably from 1.6 to 2.7. To prepare these compounds a iony chain alcohol ( R2OI~) carl be reacted with glucose, in the presence of an acid catalyst to form the desired glucoside. Alternatively the alkylpolyglucosicles can be prepared by a two step procedure in which a short chain alcohol (Cl 6) is ~5 reacted with glucose or a polyglucoside (x=2 to L~) to yield a i20g~i~
short chain alkyl glucoside (x=1 to ~1) which can in turn b~
reacted with a longer chain alcohol ( R20H) to displa~e the short chaln alcohol and obtain the desired alkylpolyglucosicle. If this two step procedure is used, the short chain all~ylglucoside con-tent of the final alkylpolyglucoside material sho~lld be less than 50~, preferably less than 10%, more preferably less than 5%, mos~
preferably 0~6 of the alkylpolyglu~oside.
The amount of unreacted alcohol ~the free fatty alcohol content) in the desired alkylpolysaccharide surfac-tant is pre-iO ferably less than about 2%, more preferably less tha~ a~out 0 . 5~6by weight of the total of the alkyl polysac~haride plus unreacted alcohol. The amount of alkylmonosaccharide is about 20~ to about 70%, preferably 30g6 to 60~6, most preferably 30% to 5~% by weight of the total of the alkylpolysaccharide. For some uses it is :~ desirable to have the alkylmonosaccharide content less ~han about 10%.
As used herein, "alkylpolysaccharide surfactant" is intended to represent both the preferred glucose and g~lactose derived surfactants and the less preferred C alkylpolysaccharide surfactants. Throughout this specification "alkylpolyglucoside" is used to include alkylpolyglucosides because the stero chemistry of 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 neutralized with a cationic moiety or moieties selected from the group consisting of alkali metal, e.g. sodium or potassium, alkaline earth metal, e~s. 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.
~2~9~0 - 5a -Alkylbenzene Sul~onates 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.
1~09~10 However in heavier soil conditions, phenyl attachment at the 1- or 2-position is preferred.
The preferred alkylbenzene sulfonates contain a strai~ht 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 alkyl-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 15 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 invention since the foams produced 20 therewith are exceptionally stable, have a large volume, rinse quickly, and do not have a "slippery" feel. These compositions are particularly desirable for industrial and commercial processes as discussed hereinafter. The volume of foam produced using the alkylbenzene sulfonate cosurfactant is larger than for any other 2 ~ cosurfactant.
Soap .
Other preferred cosurfactants for use in this invention are carboxylates, e.g. fatty acid soaps and sir;lilar surfactants. The soaps can be saturated or unsaturated and can contain various '0 substituents such as hydroxy groups and alpha-sulfonate groups.
Preferably, the hydrophobic portion of the soap is a strai~ht chain saturated or unsaturated hydrocarbon. The hydrophobic portion of the soap usually contains from about 6 to about 30 carbon atoms, preferably from about 10 to about 18 carbon atoms.
~i The use of carboxylate cosurfactants is especially valuable since ~20~0 the alkylpolysaccharide surfactants are exceptional lime soap dispersers.
The cationic moiety (~1) for carboxylate cosurfactants is selected from the group consisting of allcali metal, for example, sodium or potassium, alkaline earth metal, for e~ample, calcium or magnesiurn, ammonium, or substituted ammonium, including mono-, di-, or triethanolammonium cations. Mixtures of cations can be desi rable .
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 pro-duces less foam volume than does the use of the preferred cosur-factants. However, the alkylpolysaccharide surfactant stabilizes the foams which are produced and allows the foams to be rinsed more quicl<ly.
One group of cosurfactants that are of interest because of their superior detergency are the zwitterionic detergents which contain both a cationic group, either ammonium, phosphonium, 2~) sulfonium or mixtures thereof and a sulfonate or carboxylate yroup. Preferably there are at least about four atoms separating the cationic and anionic groups. Suitable 2witterionic surfactants are disclosed in U.S. Patents 4,159,277; 3,928,251 3,925,26~;
3,929,678; 3,227,749; 3,539,521; 3,383,321; 3,390,094; and '5 3,239,s60. Such cosurfactants are especially desirable for shampoos.
Another group of cosurfactants are the amphoteric detersents which have the same general structure as the zwitterionic surfac-tants but with an amine group instead of the quaternary ammon-3C ium group.
Yet other cosurfactants are the alkyl (paraffin or olefin) sulfonates, preferably with a more central hydrophilic group, containing from about 6 to about 30 carbon atoms. Compositions containing. these cosurfactants produce the least volume of foam, ~5 if that is desired~ The hydrophobic group can contain up to 1~0~
about lO hyclroxy groups and/or ether linlcages. Examples include~
C1~ 5 paraffin sulfonates and C1 L~ 16 olefin sulfonate5 Still another cosurfactant is a soap structure containing up to about lO ether linkages in the chain and from about I to about 5 4 carbon atoms between ether lin' ages with from about 6 to about 30 carbon atoms in a terMinal portion containing no ether link-ages .
The preferred alkylpolyglucosides that contain an average of from 1.5 to 4 glucoside units, preferably from 1.6 to 2.7 - 10 glucoside uni-ts; less than about 50% short chain alkylpolyglu-cosides; less than about 10~6, preferably less than about 296, most preferably less than about 0.5% unreacted fatty alcohol~ increase the sudsing ability of conventional sulfate detergent cosurfact-ants, especially alkyl sulfate and alkyl polyether sulfate cosur-15 factant5 having the formula:
3 (~nH2n)t SO3 M
wherein R is an alkyl or hydroxyalkyl group containing from about 8 to about 18 carbon atoms, n is 2 or 3, t can vary from 0 to about 30, and M is a cationic moiety as defined above, the 20 cosurfactant being water soluble or dispersible.
A preferred foaming composition of the invention herein comprises (1 ) an alkylpolysaccharide surfactant having the formula RO(RlO)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 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 a 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 or more cationic moieties consisting essentially of:
(a~ from about 1 P~ to about 956 preferably about 10~ to ~20~0~0 about 506 nf a water soluble alkylbenzene 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 S .cosurfactant. selected from the group consisting of an alkyl glyceryl ether sulfonate in which the alkyl group contains 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 10atoms, an aikyl polyethoxylate carboxylate in which the alkyl group contains from about 10 to about 18 carbon atoms, and the polyethoxylate chain contains from about 2 to about 6 ethoxylate groups, and mixtures thereof.
15Such compositions have improved suds mileage as compared to compositions containing only the alkyl benzene sulfonate cosur-factant and the allcylpolysaccharide surfactant.
Another preferred embodiment of a foaming composition of the invention herein comprises ( 1 ) an alkylpolysaccharide surfactant having the formula RO(R )t(Z)x wherein Z is a moiety derived from a reducing saccharide containing from 5 to 6 carbon atoms and \,vherein R is a hydrophobic group selected from the ~roup co!nsisting of alkyl, alky!phenyl, hy-droxyalkylphenyl or hydroxyalkyl groups or mixtures thereof in which said alkyl groups contain from about 8 to about 18 carbon atoms; R contains from 2 to about 4 carbon atoms; t is from O to about 30; and x is a number from about 1 . 5 to about 10;
(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 M to complete the formula, the ratio of (2) to (1) being from about 1:10 to about tO:l, and ~20~0 (3) from about 2% to about 10~ of an auxiliary foam boos-ter~
selected from the group consistin~3 of:
(a) amides having the formula R7 -C-N- ( R8 ) wherein ~7 is an alkyl group containing from about 8 to about 18 carbon atoms, preferably about 12 to about 14 carbon atoms and each R8 is the same or different and is selected from the group consisting of hydrogen, C1 3 alkyl, C1 3 alkanol, and -(C2H4O-)1 4H groups and mixtures thereof;
(b) amine oxides having the formula:
R 4) bN ( R ) 2 wherein R is an alkyl group containing from about 8 to about 18 carbon atoms, preferably from 12 to 14 carbon atoms, each R contains t~ o or three car bon atoms, b is from 0 to about 30, each R is the same or different and is selected from the group consisting of C1_3 alkyl, C1_3 all<anol, and -(C2H40)1 6H groups and mixtures thereof; and lc) mixtures thereof.
Such compositions provide superior grease/oil removal and suds mi leage.
Preferred anionic cosurfactants are alkylbenzene 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 95%, preferably 5% to about 50% of an alkylpolysaccharide 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 1% to about 95%, preferably from about 10% to ~090~0 "
about 50~ of an anionic cosurfactant neu~ralized with one or more~
cationic moieties and which is a mixture of (1) from l~ to about 95~, preferably from about 5% to about 50% of an alkyl betlzene sulfona-te 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 95%, preferably from about 5% to about 50% of an alkyl polyethoxylate sulfate in which the alkyl group contains From about 8 to about 18 carbon atoms, preferably from 12 to 14 carbon atoms and from abou t one to about six ethoxylate moieties and wherein from about 1% to about 100%, preferably from about 10% to about 80g~ of the cationic moieties are magnesium: and wherein the auxiliary foam booster is an amide.
Another preferred 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 10% to about 20% of an alkylpolysaccharide surfactant having the formula RO(R )t(Z)x ~Jherein Z is a moiety derived from a reducin~ saccharide moiety containing from 5 to 6 carbon atoms and wherein R is a hydrophobic group se!ected 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;
(2) from about 5O to about 60% of an alkyl benzene sul-fonate cosurfactant in which the alkyl group contains from about 10 to about 13 carbon atorns, said alkyl ~20~
benzene sulfonate neutralized with one or more cationi~
moieties (1~/1) to balance the formula;
(3) from about 5~ to about 606, preferably from about 10~
to about 20~ of an alkylpolyethoxylate sul,ate 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 ~3roups, said aikylpolyethoxylate sulfate neutralized with one or more cationic moieties M to complete the formula.
(4) from about 5% to about 80% of a water soluble inorganic salt selected from the group consisting of sodium and potassium sulfates, chlorides, carbonates, phosphates, and mixtures thereof.
The Processes =
Mixtures of all;ylbenzene sulfonate and/or the soap cosurfac-tant and the alkylpolysaccharide surfactant can be used at levels of from about 0.01~6 to about 95%, in ratios of cosurfactant to alkylpolysaccharide of from about l~:l to about l:lO, in water with a~itation to provide foams. These foams are relatively stable and, if not disturbed, can exist for several days. Furthermore, the foam has structural intcgrity and does not spread out. The foams prepared using mixtures of all<ylbenzene 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 ùse not only in soap bars, bubble baths, shaving creams, laundry, dishwashing, and washing hair, where a good volume of stable suds and quick rinsabiliey are desirable, but also in a large number of fields unrelated to deter~3ency.
The compositions and processes of this invention are particu-larly valuable for use in the "foam" or "mist" well drilling pro-ccsses 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 m,ethod can be found in U.S. Patents 3,303,896 3,111,178;
3,130,798; and 3,215,200; In 120~
such a process, the surfactants are present at a level of from about 0. 01~ to about 5%, preferably from about 0. 01~ to about 2%, most preferably from about 0 . 05~ to about 0 . 5%. The preferred cosurfactant is an alkylbenzene suifonate.
The compositions and processes of this invention are also of considerable value in fire fighting or fire prevention processes where a stable foam is used to extinguish a flame or sparks by cutting off the oxygen suppiy. This inclucies fire fighting and foaming runways for crash-landings as disclosed in U . S. Patents 2,514,310; 3,186,943; 3,422,011; 3,457,172; 3,479,285; and 3,541,010, Conc~ntrations of from about 0.1~ to ab~ut
The Processes =
Mixtures of all;ylbenzene sulfonate and/or the soap cosurfac-tant and the alkylpolysaccharide surfactant can be used at levels of from about 0.01~6 to about 95%, in ratios of cosurfactant to alkylpolysaccharide of from about l~:l to about l:lO, in water with a~itation to provide foams. These foams are relatively stable and, if not disturbed, can exist for several days. Furthermore, the foam has structural intcgrity and does not spread out. The foams prepared using mixtures of all<ylbenzene 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 ùse not only in soap bars, bubble baths, shaving creams, laundry, dishwashing, and washing hair, where a good volume of stable suds and quick rinsabiliey are desirable, but also in a large number of fields unrelated to deter~3ency.
The compositions and processes of this invention are particu-larly valuable for use in the "foam" or "mist" well drilling pro-ccsses 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 m,ethod can be found in U.S. Patents 3,303,896 3,111,178;
3,130,798; and 3,215,200; In 120~
such a process, the surfactants are present at a level of from about 0. 01~ to about 5%, preferably from about 0. 01~ to about 2%, most preferably from about 0 . 05~ to about 0 . 5%. The preferred cosurfactant is an alkylbenzene suifonate.
The compositions and processes of this invention are also of considerable value in fire fighting or fire prevention processes where a stable foam is used to extinguish a flame or sparks by cutting off the oxygen suppiy. This inclucies fire fighting and foaming runways for crash-landings as disclosed in U . S. Patents 2,514,310; 3,186,943; 3,422,011; 3,457,172; 3,479,285; and 3,541,010, Conc~ntrations of from about 0.1~ to ab~ut
5% are useful, The compositions and processes of this invention are also especially valuable in the field of preparing gypsum board, plas-tic, and resin foams. The foams of this invention provide a stable relatively thiclc structure permitting solidification of the resins, plastics, cellulosic particles, etc., into stable foam structures having light densities, thick cell walls and good struc-tural integrity. Examples of forming processes which utilize foaming agents are described in U.S. Patents 3,669,89a; 4,907,982 4, 423, 720; and 4, 423, 720.
The flotation of minerals so as to concentrate the mineral values, 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 invention involves making use of their exceptional stabiiity to provide temporary insulation for plants when freezing conditions are expected. An alkylbenzene sulfonate is the preferred cosur-factant and the foam can be applied to the foliacie etc., of the plants. Such a process is disclosed in U.S. Patent 3,669,898, ~o~
The range of utilities which are possible with the composi-`
tions and processes of this invention include all of the above and many more.
Typical compositions for use as light duty liquid detergent 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 alkanolamines, C2_4 polyols, mixtures thereof, and the balance water. It is a special advantage of the compositions of this invention that they can be made in concentrated form (up to about 50% by wt. of the mixture of surfactants) with only very iow levels of organic solvents and without the addition of expen-sive hydrotropic materials. Additional suds boosters or builders such as trialkyl amine oxides and fatty acid amides can also be used in amounts up to about 20%. Fatty alcohols should not be used .
Shampoo compositions comprise from about 1% to about 95%, preferably from about 5% to about 20% of the mixture of surfac-tants mentioned hereinbefore, from about 1~ to about 5% of an alkanol amide, from about 0. 5% to about 3% of a polymeric tnick-ener, and the balance water. It is a special advantage of the shampoos that they rinse quickly and readily.
Additional !ngredients , The compositions and processes of this invention can utilize other compatible ingredients, including other surfactants, in addition to the mixture of surfactants herein disclosed. In de-tergent compositions the compositions can contain any of the well known ingredients including minor amounts of other surfactants, detergency builders, soil suspending agents, brighteners, abras-ives, clyes, fabric conditioning a~3ents, hair conditioning agents, hydrotropes, solvents, fillers, clays, perfumes, etc. Suitable inyredients are disclosed in U.S. Patents 4,166,039--~llise;
4,157,978--Llenado 4,056,481--Tate; 4,04s,586--Collier;
120~)J 0 4,035,257--Cherney; 4,019,998--Benson et al; 4,000,080--Bartolotta et al; and 3,983,078--Collins. The shampoo compositions of this invention can contain any of the addi-tional ingredients known to the art to be suitable for use in shampoos. Listings of suitable additional ingredients, inlcuding low levels of other surfactants can be found in U.S. Patents 4,089,945; 3,987,161; and 3,962,418.
of special interest are ingredients which modify the feel of aqueous solutions containing the foaming compo-sitions of this invention. For example, raising the pH toabove about 8.5 by alkaline-materials or incorporating the tertiary alcohols of U.S. patent 4,371,461 of Jones et al.
Such ingregients are desirable for some consumers since the solutions do not have the normal "soapy" feel associated with surfactant solutions.
The following nonlimiting examples illustrate the foaming compositions of the present invention.
Relative Volume of Suds Com~arison and Consumer Preference A B C
Generic Premium Product Commercial Commercial of the Product Product invention U.S. Crystal ~.S.
White~ Palmolive~
FORMULA Wei~ht % Weight % Wei~ %
Sodium Cll 8alkyl benzene sulfonate10.5 18.0 18.0 Cl2-l3alkylpoly-9lUcoside2-3 (>2% free fatty alcohol) - - 12.0 , ~L209~
~ lG -5Ociium C14_l5 alkyl polyethoxylate3 sulfate 5.5 12.0 Balance of formula inc. water 84. 0 70 . 0 70. 0 SUDSI NG
_ Relative Volume of Suds(ml) 110 125 220 0. 2% solutions CONSUMER TEST
Overall preference, g~ 10 18 23 Favorable sudsing 10 comments, % 74 85 90 Favorable rinsing comments, % 3 6 10 The foaming composi tion of the invention is superior to a 15 representative generic product and at least equivalent to a representative premium commercial product and is preferred by consumers for rinsing reasons. The test involved 50 consumers washing soiled dishes in the test solutions. The consumers wore rubber gloves during the test. The differences are significant at 20 the 95% confidence level for the invention over the generic product .
The relative volume of suds in ml. is determined by the following test procedure:
100 ml of the test solution at 11 5F is piaced in a 500 ml 25 graduated cyliner the solut~on is agitated by repeated inversion of the graduated cylinder until the amount of suds in the cylinder does not increase with further agitation. Suds height is measured directly on the cylinder scale making allowance for the height of liquid remaining in the cylinder. The test solution is 30 made by adding the test product to water having a hardness of 7 gr. per U.S. gallon (Call~,ig = 3/1 ) .
~zo~o EXAMlPLE l l -~
LAS Suds Boosting ~Vt . % o f: A _ C D E F G__ 5Sodium C11 8 allcyl-benzene sulfonate 0 20 40 50 60 80 100 C12-l 5 alkYIPIY2-3 glucoside 10080 60 50 40 20 0 Relative Volume 10 of suds (ml) 140220 280 300 310300 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 foaming composition of the invention herein.
EXAMPLE l l l Soap Suds Boosting ~Yt. ~ of: A B C D E F
20 Sodium oleate 0 20 40 60 80 100 C12 15 alkYIPIY2-3 glucoside 10080 60 40 20 0 Relative Volume of suds (mi.) 160270 280 300 310260 The suds were 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.
~209~ 0 EXAlv1PLE IV
Foaming with Soap Effect of llardness on Relative Volume of Suds .. . ... .. _ ~rains hardness ... .
Sodium oleate 225 10 0 0 Sodium oleate pl~ls C12_15 all<ylpoly2_3 glucoside ~3:2 ratio) 360 100 55 10 The suds were generated as in Ex. I using 500 ppm. of the surfactant mixtures.
-- EXA~1PLE V
Alkyl Poly~31ucosidy (C~ alkylpoly 3 glucoside) 15 Suds Boosting for the Following Representa-tive Cosurfactants -(3:2 ratio 500 ppm) % increase in foaming Sodium C11 ~ alkylbenzene sulfonate 100-150 Sodium oleate 50-75 20 3- [ N-coconuta I kyl-N, N -d i methy 1] -2-hydroxy-1-sulfonate 40-60 Sodium C14 15 olefin sulfonate 20-40 Sodium coconut alkyl sulfate 1 0-30 Sodium coconut alkyl polyethoxylate3 sulfate 0-20 The above data clearly demonstrate the criticality of ueilizing a carboxylate or sulfonate anionic detergent cosur-Factant for sudsing synergism with the alkyl polyglucoside surfactan-t.
EXAMPLE Vl Glucoside Chain Length Criticality 40:60 wt. ratio of C12 15 alkyl polyglucoside to sodium C12 alkylbenzene sulfonate (500 ppm. concentration) where the ~luco-side portion is:
~20~g~0 Relative Volume of Suds ( ml ) Monoglucoside 180 Diglucosicle 240 Pentaglucoside 260 Decag lucoside 170 Sodium C11 8 alkylbenzene sulfonate alone 160 - 10 "Diglucoside" etc. indicates the average glucoside chain Ieng-th in the sample is two, etc. As can be seen from the above, significant synergism is obtained only with 1.5 or more glucoside units and preferably less than about 10, more prefer-ably less than about 8 glucoside units.
EXAMPLE Vl l All<ylbenzene sulfonates ( LAS) Homoiogs/phenyi-position (3:2 ratio; 500 ppm) . .
Relative Volume of Suds ( ml ) Ex. Il's alkylpolyglucoside plus:
Sodium C11 LAS, high 2-phenyl 210 Sodium C11 LAS, low 2 phenyl 250 Sodiurn C12 LAS, high 2-phenyl 225 Sodium C12 LAS, low 2-phenyl 225 Sodium C14 L~S, lligh 2-phenyl 210 Sodium C14 LAS, low 2-phenyl 215 As can be seen from the above~ in general C11, low 2-phenyl LAS is preferred for sudsing.
~'~0~10 EXAMPLE Vl 11 -, Suds Boostin~ of Alkyl Poly~lucosides and Effect of Soil Relative Volume of Suds (rn!?
Witl-lout Wit~l Soil 0.5% 1.0%
0.2~ aqueous solution of a detergent composition 10 formulated with:
15% sodium Cl 1 8 alkyl-benzene sulfonate ( Cl 1 . 8 L~S) 1 20 50 25 % Cll.8 LAS ~ 12%
Ex. Il's alkyl poly~lucoside 310 130 70 % C11.8 LAS 190 140 100 ~ C11.8 LAS ~ 12%
Ex. I's alkylpolyglucoside 380 170 100 20Test method of Ex. I modified by addin~3 to the test solu-tion the indicated amount of soil. % is wt. % of test solution.
The soil is a 44P6/56% by weight mixture of Fiuffo~) and PREP6~) both of which products are available irl the Uni-ted States from The Procter ~ Gamble Company.
25As can be seen from the above, the benefit for the invention is even more remarkable when soil is present.
EXAMPLE I X
Relative Volume of Suds (ml) *
No Soil 1% Soil Present 30 Generic commer~al product (Crystal ~Yhite )** 110 30 Prcmium commerical product B
( Palmolive Liquia~)) 120 100 Premium commercial product C
( J oy(~)) 12 5 12 0 12% Cll 8 LAS/8~ Ex. Il's alkyl polyglucoside 180 120 18% C11 8 LAS/12% Ex. Il's alkyl polyglucoside 240 150 24~6 C1 1 8 LASI 16% Ex. I l 's allcyl polyglucoside 300 180 *
Soil is added as described in Ex . Vl 1.
** ~
Crystal V~hite~Y is available from Colgate-Palmolive Co.
Palmolive Liquic~3 is available from Colyate-Palmolive Co.
10 Joy~3 is available from The Procter ~ Gamble Company.
Suds generated as in Ex. I using 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 liquids.
EXA~vlPLE X
Wt. % of: A B C D E F
20 C1 1 8 LAS (Sodium) 0 20 4060 80 100 Sucrose monolaurate 100 80 60L~0 20 0 Relative Volume of suds (r,~l.) 30 100 150 190 2tO 220 300 ppm of surfactant mixture used in test solution of Ex. I.
The above demonstrates that structures which are similar to the alkyl polyglucosides do not provide the benefits of this in-vention .
EXAMPI E Xl Shampoo Cocamido propyl betaine (30~ aqueous solution) 50.00%
Ex. I's alkyl polyglucoside 5.00%
Polyethylene glycol distearate 1 . 00~
35 Preservative - 03%
Distilled water q . s. 100. 00%
EXA~ PLE X 1 1 Shampoo Alpha-olefin sulfonate (40~ aqueoussolutiol1) 30.00%
Ex. I's alkyl polyglucoside 3.00%
S llydroxyethyl cellulose 0.80%
Perfume 1. OO~d Preservative 0.04%
Distilled water q.s. 100.û0%
EXAMPLE X l l l Paraffin Sulfonate Suds Boosting Wt. % of: A B C D E F
Mixture of sodium C14_15 15 paraffin sulfonate 0 20 40 60 80 100 *
C12-15 G4_5 100 80 60 40 20 o Relative Vol. of Suds (ml) 185 250 275 275 235 210 Test. Conditions:
Total concentration of 300 ppm, water having 8 grains of 20 mixed hardness.
C12 15G4 5 is a notation for an alkyl polysaccharide surfactant in which there are 4-5 glucoside units and in which the allcyl group has 12-15 carbons.
EXAMPLE XIV
Sodium vs. Magnesium Allcylbenzene Sulfonate -Relative Volume of Sua's ( ml .3 Without Soil Wi th Soil 0.6% 1.0%
0.2% aqueous solution of a 30 det2rgent composition witl1:
15g6 Ex. I l 's alkyl poly-glucoside; 22~i C11 8 alkylbenzene sulfonate with the benzene group attached 1~0~0 ' primarily to the center ;~
of the allcyl chain, sodium neutralized 450 150 75 15% Ex Il's alkyl polyglucoside;
22~ C11 8 alkylbenzene sulfonate with the benzene group attached primarily to the center of the alkyl chain, magnesium neutralized 450 200 110 10 Premium product (Joy~3) 350 120 75 Soil added to the test solution as in Ex Vlll EXAMPLE XV
The optimum alkylpolysaccharides, especially alkylpolygluco-sides have an HLB of from about 6 to about 27 and a critical **
15 micelle concentration (Cl\~C) of less than about 1000ppm, 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 alkylpolysaccharides having more than about 4 saccharide units have unacceptably high 20 HLB's as is shown in the following table in which the alkyl group and the glucoside chain length were varied ~ of Go G1 G2 G3 GL! G5 Glucosides # of 25 Carbons C4 HLe 5 112 417 923 3 28 834 2 C,~IC ~7000 CMC ~700 2000E
C12 HLB 1 3 8 614 119 5 25 0 30.4 CMC ~6 0~70 ~200 225E ~250 12()~0~
-- 2~ --C14 HLE:0,4 7.6 13.2 18,6 2~.0 29.4 CMC ~6 ~2025-60E
C16 HLB 0.0 6.7 12.2 17.6 23.1 28.5 CMC~0.3 ~0.6 ~4 S C18 HLB 0.0 5.~ 11.2 16.6 22.2 27.6 CMC ~1 E=Estimated HLB determined according to Davies:Proc. ~ International Congress, Surface Activity 1,426, Butterworths, London, 1957.
**
10 ppm As can be seen above, ~1) longer pure glucoside chain lengths raise the HLE~ and lower the molecule's surface activity (high CMC) and (2) the shorter alkyl chain lengths have extremely high CMC's even as the monoglucoside.
EXAMPLE XVI
The following formulas were prepared:
Magnesium linear C11 2 allcylbenzene sulfonate 22.4 22.4 22.4 20 C12 13 alkylpolygluco-side (G1 7) (<2% free fatty alcohol ) 14.9 14.9 14.9 Cg_1 l alkoxypropyldi-hydroxyethyl amine oxide - 4 25 C12 alkyldihydroxy ethyl amine oxide - - 4 Ethanol 5 5 5 Water balance balance balance Formulas A, B and C were compared by generating suds with a constant source of a~itation 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 edi~le acid). Dinner plates are washed with 4 ml. of soil on 35 each plate and the suds height is measured after each five plates.
lZ~ 0 30 plates in total are washed and the integral of the suds heigh~
taken over the number of plates washecl is reported as the SD~Y
grade (SDI,'1 = Suds During Washing), B C
5` SDl~l grade 24 28 . 8 28 . Ll This shows tllat the adcfition 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-- 10 panol amide is substi-tuted, at least in part for the specific amine oxides .
EXA~lPLE XVI I
105 grams of sodium dodecylbenzene sulfonate are mixed with 350 grams of anhydrous sodium sulfate. After the mixture is 15 ground into a fine powder, 70 9 of C12 13 alkylpolyglucoside (G2 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 alkylpolyglucoside is sprayed onto the powder.
20 7.5 milliliters of a 1% polar blue solution are sprayed onto the powder and a small portion of perfume is then added. The resulting granule is dried in a vacuum oven at 30 in. of ~Ig vacuum at 50C for ten hours to remove excess water.
In a similar manner 60 grams of a 50% solution of said alkyl-25 polyglucoside is sprayed onto 100 gram of Berkite and 50 grams of sodium dodecylbenzene sulfonate flakes are admixed with the product to give a light duty granule.
EXAMPLE XVI l l Ammonium C1 1 2 linear alkyl benzene sulfonate was admixed 30 with C12 alkylpolyglucoside G3 5 in a ratio of about 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. Substitution of a sodium 35 C12_~6 alkyl glyceryl ether sulfonate for 25~6 and 40% of the ~2090~
mixture extended the point at which there was no suds to 1. 5 and 1.75 grams of soil per 200 mi . of wash solution respectively .
Similar results are obtained when a sodium, potassium, ammonium, or monoethanolammonium C1 2-16 alkylpolyethoxy3 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
~he following formula was prepared with alkylpolyglucosides having 0 . 3% and 1% free fatty alcohol respectively.
Wt. ~6 Ammonium C11 2 iinear alkyl benzene sulfonate 17. 5 Magnesium C1 1 2 linear alkyl benzene sulfor:ate 6.4 15 Ammonium C1 2-13 alkyl poly-ethoxylate (0.8) sulfate 6.1 C12 13 alkYIPIYglUCside G1.7 Minors and water balance The SDW values for the low and high alcohol samples were 20 12.9 and 12.2 respecively with an LSDo 05 at 0.6. See Ex. XVI
for test method.
EXAMPLE XX
The following formulas were prepared:
% by welc~
A B C D
Ammoniumlmagnesium Cl 1 2 linear alkyl benzene sulfonate 24.2 21. 8 - -Ammoniuml magnesium C1 2-1 5 olefin sulfonate - - 12.8 10.
Ammonium/ magnesium C1 2-1 3 alkyl sulfonate - - 19 . 2 15.9 Ammonium C1 2 1 3 alkyl pol ye thoxy I ate ( 0 . 8 ) sulfate 6.5 5.8 ~o9~o C12 fatty acid diethanol~
amide - 3, 8 - 5 . 5 C12-l3 al~cylpolygl~lcoside C1 7 (free fatty alcohol '0.5%) 5.3 4.8 4 3.3 Minors and water balance A B C D
The SDVJ i ndex 79 89 97 107 The SI~W index is the SDW grade for each product as a 10 percentaye of the SDW value of a stanclard commercial product.
The following are examples of particularly preferred 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.
EXAMPLE XXI
% by Weig ht Ammonium Cl 1 4 alkyl benzene sulfonate 17.5 10-35 12-25 Magnesium C1 1 4 alkyl benzene sulfonate 6 . 4 0-11 3-9 12-13 a Icyl poly ethoxylate (0.8) suifates 6.1 2-11 3-9 C12-13 alkyl polyglucoside (1.7) derived from glucose ('0. 5~ free fatty alcohol J 5.0 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., perfurne Palance EXAMPLE XXI I
.
% by ~Yeight Arnmonium C1 2-13 alkyl sulfate 15 . 7 7-23 10-20 Sodium Cl 4-16 oiefin 35 sulfonate 10.4 4-19 6-13 1~0~0~
gC12 6~12 5.6 0-11 2-10 Coconut monoethanol amide 5.5 2-8 3-7 C12-13 all<yl polyglycoside (1.7) derived from ~lucose 5('0.5% free fatty alcohol) 5.9 2-12 3-9 Ethanol 4.0 0-lO 0-10 ~120 and minor components, e.g., perfume Balance The alkyl groups in the surfactants of Examples XXI and - 10 XXII can vary from about 10 to about 16 carbon atoms and the cations can be 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 disclosed herein can be used.
EXAMPLE XXIII
When a 2:1 mixture of an ammonium C1 1 2 alkylbenzene sulfonate and the C12_13 all<ylpolyglucoside (2-4) (>2% free fatty alcohol ) are tested under the conditions of Example 11 the initial suds volume is good, but the SD~V grade is not as good as some premium commercial products. Substitution of between 25% and 50% of the mixture with a sodium C1 2-~ 6 alkyl glyceryl ether sulfonate, or sodium C14_16 olefin sulfonate, or sodium C12_13 alkyl polyethoxylate(3) acetate increases the SD~`~ grade without lowering the initial sudsing excessively.
Known analytical techniques can be used to determine the structures of the all<ylpolysaccharide surfactants herein; for example, to determine the glycosidic chain length, the amount of butyl glucoside, the free fatty alcohol content, and the level of 30 unreacted polysaccharide. More specifically, gas or liquid chromatography can be used to determine the unreacted alcohol content and the unreacted polysaccharide content respective1y.
-Proton nmr can be used to determine the average glycosidic chain length. Ihe 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.
1~0~0~
Tlle alkylpolysaccharide surfactants are complex mixtures.
Their components vary depending upon the nature of the starting materials and the reac-tion by which they are prepared. Analyti-cal standards which are useful in calibrating irlstruments for 5 analyzing the components of a particular alkylpolysaccharide surfactant can be obtained from Calbiochem Behrin~ Co. LaJolla, California. These standards include those for octylglucoside (Calbiochem #494559), decylglucoside ~Calbiochem #252715), dodecylmaltoside ~Calbiochem #3243555).
The HLBs of alkylpolysaccharide surfactants useful in the foaming compositions of this invention have the values given in EXAMPLE XV; the CMCs will approximate those values given in the same example. Alkylpolysaccharide surfactants having the structures specified in the claims and characterized by one or 15 more of the standard analytical techniques will give the results indicated in the examples.
WHAT IS CLAIMED IS:
The flotation of minerals so as to concentrate the mineral values, 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 invention involves making use of their exceptional stabiiity to provide temporary insulation for plants when freezing conditions are expected. An alkylbenzene sulfonate is the preferred cosur-factant and the foam can be applied to the foliacie etc., of the plants. Such a process is disclosed in U.S. Patent 3,669,898, ~o~
The range of utilities which are possible with the composi-`
tions and processes of this invention include all of the above and many more.
Typical compositions for use as light duty liquid detergent 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 alkanolamines, C2_4 polyols, mixtures thereof, and the balance water. It is a special advantage of the compositions of this invention that they can be made in concentrated form (up to about 50% by wt. of the mixture of surfactants) with only very iow levels of organic solvents and without the addition of expen-sive hydrotropic materials. Additional suds boosters or builders such as trialkyl amine oxides and fatty acid amides can also be used in amounts up to about 20%. Fatty alcohols should not be used .
Shampoo compositions comprise from about 1% to about 95%, preferably from about 5% to about 20% of the mixture of surfac-tants mentioned hereinbefore, from about 1~ to about 5% of an alkanol amide, from about 0. 5% to about 3% of a polymeric tnick-ener, and the balance water. It is a special advantage of the shampoos that they rinse quickly and readily.
Additional !ngredients , The compositions and processes of this invention can utilize other compatible ingredients, including other surfactants, in addition to the mixture of surfactants herein disclosed. In de-tergent compositions the compositions can contain any of the well known ingredients including minor amounts of other surfactants, detergency builders, soil suspending agents, brighteners, abras-ives, clyes, fabric conditioning a~3ents, hair conditioning agents, hydrotropes, solvents, fillers, clays, perfumes, etc. Suitable inyredients are disclosed in U.S. Patents 4,166,039--~llise;
4,157,978--Llenado 4,056,481--Tate; 4,04s,586--Collier;
120~)J 0 4,035,257--Cherney; 4,019,998--Benson et al; 4,000,080--Bartolotta et al; and 3,983,078--Collins. The shampoo compositions of this invention can contain any of the addi-tional ingredients known to the art to be suitable for use in shampoos. Listings of suitable additional ingredients, inlcuding low levels of other surfactants can be found in U.S. Patents 4,089,945; 3,987,161; and 3,962,418.
of special interest are ingredients which modify the feel of aqueous solutions containing the foaming compo-sitions of this invention. For example, raising the pH toabove about 8.5 by alkaline-materials or incorporating the tertiary alcohols of U.S. patent 4,371,461 of Jones et al.
Such ingregients are desirable for some consumers since the solutions do not have the normal "soapy" feel associated with surfactant solutions.
The following nonlimiting examples illustrate the foaming compositions of the present invention.
Relative Volume of Suds Com~arison and Consumer Preference A B C
Generic Premium Product Commercial Commercial of the Product Product invention U.S. Crystal ~.S.
White~ Palmolive~
FORMULA Wei~ht % Weight % Wei~ %
Sodium Cll 8alkyl benzene sulfonate10.5 18.0 18.0 Cl2-l3alkylpoly-9lUcoside2-3 (>2% free fatty alcohol) - - 12.0 , ~L209~
~ lG -5Ociium C14_l5 alkyl polyethoxylate3 sulfate 5.5 12.0 Balance of formula inc. water 84. 0 70 . 0 70. 0 SUDSI NG
_ Relative Volume of Suds(ml) 110 125 220 0. 2% solutions CONSUMER TEST
Overall preference, g~ 10 18 23 Favorable sudsing 10 comments, % 74 85 90 Favorable rinsing comments, % 3 6 10 The foaming composi tion of the invention is superior to a 15 representative generic product and at least equivalent to a representative premium commercial product and is preferred by consumers for rinsing reasons. The test involved 50 consumers washing soiled dishes in the test solutions. The consumers wore rubber gloves during the test. The differences are significant at 20 the 95% confidence level for the invention over the generic product .
The relative volume of suds in ml. is determined by the following test procedure:
100 ml of the test solution at 11 5F is piaced in a 500 ml 25 graduated cyliner the solut~on is agitated by repeated inversion of the graduated cylinder until the amount of suds in the cylinder does not increase with further agitation. Suds height is measured directly on the cylinder scale making allowance for the height of liquid remaining in the cylinder. The test solution is 30 made by adding the test product to water having a hardness of 7 gr. per U.S. gallon (Call~,ig = 3/1 ) .
~zo~o EXAMlPLE l l -~
LAS Suds Boosting ~Vt . % o f: A _ C D E F G__ 5Sodium C11 8 allcyl-benzene sulfonate 0 20 40 50 60 80 100 C12-l 5 alkYIPIY2-3 glucoside 10080 60 50 40 20 0 Relative Volume 10 of suds (ml) 140220 280 300 310300 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 foaming composition of the invention herein.
EXAMPLE l l l Soap Suds Boosting ~Yt. ~ of: A B C D E F
20 Sodium oleate 0 20 40 60 80 100 C12 15 alkYIPIY2-3 glucoside 10080 60 40 20 0 Relative Volume of suds (mi.) 160270 280 300 310260 The suds were 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.
~209~ 0 EXAlv1PLE IV
Foaming with Soap Effect of llardness on Relative Volume of Suds .. . ... .. _ ~rains hardness ... .
Sodium oleate 225 10 0 0 Sodium oleate pl~ls C12_15 all<ylpoly2_3 glucoside ~3:2 ratio) 360 100 55 10 The suds were generated as in Ex. I using 500 ppm. of the surfactant mixtures.
-- EXA~1PLE V
Alkyl Poly~31ucosidy (C~ alkylpoly 3 glucoside) 15 Suds Boosting for the Following Representa-tive Cosurfactants -(3:2 ratio 500 ppm) % increase in foaming Sodium C11 ~ alkylbenzene sulfonate 100-150 Sodium oleate 50-75 20 3- [ N-coconuta I kyl-N, N -d i methy 1] -2-hydroxy-1-sulfonate 40-60 Sodium C14 15 olefin sulfonate 20-40 Sodium coconut alkyl sulfate 1 0-30 Sodium coconut alkyl polyethoxylate3 sulfate 0-20 The above data clearly demonstrate the criticality of ueilizing a carboxylate or sulfonate anionic detergent cosur-Factant for sudsing synergism with the alkyl polyglucoside surfactan-t.
EXAMPLE Vl Glucoside Chain Length Criticality 40:60 wt. ratio of C12 15 alkyl polyglucoside to sodium C12 alkylbenzene sulfonate (500 ppm. concentration) where the ~luco-side portion is:
~20~g~0 Relative Volume of Suds ( ml ) Monoglucoside 180 Diglucosicle 240 Pentaglucoside 260 Decag lucoside 170 Sodium C11 8 alkylbenzene sulfonate alone 160 - 10 "Diglucoside" etc. indicates the average glucoside chain Ieng-th in the sample is two, etc. As can be seen from the above, significant synergism is obtained only with 1.5 or more glucoside units and preferably less than about 10, more prefer-ably less than about 8 glucoside units.
EXAMPLE Vl l All<ylbenzene sulfonates ( LAS) Homoiogs/phenyi-position (3:2 ratio; 500 ppm) . .
Relative Volume of Suds ( ml ) Ex. Il's alkylpolyglucoside plus:
Sodium C11 LAS, high 2-phenyl 210 Sodium C11 LAS, low 2 phenyl 250 Sodiurn C12 LAS, high 2-phenyl 225 Sodium C12 LAS, low 2-phenyl 225 Sodium C14 L~S, lligh 2-phenyl 210 Sodium C14 LAS, low 2-phenyl 215 As can be seen from the above~ in general C11, low 2-phenyl LAS is preferred for sudsing.
~'~0~10 EXAMPLE Vl 11 -, Suds Boostin~ of Alkyl Poly~lucosides and Effect of Soil Relative Volume of Suds (rn!?
Witl-lout Wit~l Soil 0.5% 1.0%
0.2~ aqueous solution of a detergent composition 10 formulated with:
15% sodium Cl 1 8 alkyl-benzene sulfonate ( Cl 1 . 8 L~S) 1 20 50 25 % Cll.8 LAS ~ 12%
Ex. Il's alkyl poly~lucoside 310 130 70 % C11.8 LAS 190 140 100 ~ C11.8 LAS ~ 12%
Ex. I's alkylpolyglucoside 380 170 100 20Test method of Ex. I modified by addin~3 to the test solu-tion the indicated amount of soil. % is wt. % of test solution.
The soil is a 44P6/56% by weight mixture of Fiuffo~) and PREP6~) both of which products are available irl the Uni-ted States from The Procter ~ Gamble Company.
25As can be seen from the above, the benefit for the invention is even more remarkable when soil is present.
EXAMPLE I X
Relative Volume of Suds (ml) *
No Soil 1% Soil Present 30 Generic commer~al product (Crystal ~Yhite )** 110 30 Prcmium commerical product B
( Palmolive Liquia~)) 120 100 Premium commercial product C
( J oy(~)) 12 5 12 0 12% Cll 8 LAS/8~ Ex. Il's alkyl polyglucoside 180 120 18% C11 8 LAS/12% Ex. Il's alkyl polyglucoside 240 150 24~6 C1 1 8 LASI 16% Ex. I l 's allcyl polyglucoside 300 180 *
Soil is added as described in Ex . Vl 1.
** ~
Crystal V~hite~Y is available from Colgate-Palmolive Co.
Palmolive Liquic~3 is available from Colyate-Palmolive Co.
10 Joy~3 is available from The Procter ~ Gamble Company.
Suds generated as in Ex. I using 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 liquids.
EXA~vlPLE X
Wt. % of: A B C D E F
20 C1 1 8 LAS (Sodium) 0 20 4060 80 100 Sucrose monolaurate 100 80 60L~0 20 0 Relative Volume of suds (r,~l.) 30 100 150 190 2tO 220 300 ppm of surfactant mixture used in test solution of Ex. I.
The above demonstrates that structures which are similar to the alkyl polyglucosides do not provide the benefits of this in-vention .
EXAMPI E Xl Shampoo Cocamido propyl betaine (30~ aqueous solution) 50.00%
Ex. I's alkyl polyglucoside 5.00%
Polyethylene glycol distearate 1 . 00~
35 Preservative - 03%
Distilled water q . s. 100. 00%
EXA~ PLE X 1 1 Shampoo Alpha-olefin sulfonate (40~ aqueoussolutiol1) 30.00%
Ex. I's alkyl polyglucoside 3.00%
S llydroxyethyl cellulose 0.80%
Perfume 1. OO~d Preservative 0.04%
Distilled water q.s. 100.û0%
EXAMPLE X l l l Paraffin Sulfonate Suds Boosting Wt. % of: A B C D E F
Mixture of sodium C14_15 15 paraffin sulfonate 0 20 40 60 80 100 *
C12-15 G4_5 100 80 60 40 20 o Relative Vol. of Suds (ml) 185 250 275 275 235 210 Test. Conditions:
Total concentration of 300 ppm, water having 8 grains of 20 mixed hardness.
C12 15G4 5 is a notation for an alkyl polysaccharide surfactant in which there are 4-5 glucoside units and in which the allcyl group has 12-15 carbons.
EXAMPLE XIV
Sodium vs. Magnesium Allcylbenzene Sulfonate -Relative Volume of Sua's ( ml .3 Without Soil Wi th Soil 0.6% 1.0%
0.2% aqueous solution of a 30 det2rgent composition witl1:
15g6 Ex. I l 's alkyl poly-glucoside; 22~i C11 8 alkylbenzene sulfonate with the benzene group attached 1~0~0 ' primarily to the center ;~
of the allcyl chain, sodium neutralized 450 150 75 15% Ex Il's alkyl polyglucoside;
22~ C11 8 alkylbenzene sulfonate with the benzene group attached primarily to the center of the alkyl chain, magnesium neutralized 450 200 110 10 Premium product (Joy~3) 350 120 75 Soil added to the test solution as in Ex Vlll EXAMPLE XV
The optimum alkylpolysaccharides, especially alkylpolygluco-sides have an HLB of from about 6 to about 27 and a critical **
15 micelle concentration (Cl\~C) of less than about 1000ppm, 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 alkylpolysaccharides having more than about 4 saccharide units have unacceptably high 20 HLB's as is shown in the following table in which the alkyl group and the glucoside chain length were varied ~ of Go G1 G2 G3 GL! G5 Glucosides # of 25 Carbons C4 HLe 5 112 417 923 3 28 834 2 C,~IC ~7000 CMC ~700 2000E
C12 HLB 1 3 8 614 119 5 25 0 30.4 CMC ~6 0~70 ~200 225E ~250 12()~0~
-- 2~ --C14 HLE:0,4 7.6 13.2 18,6 2~.0 29.4 CMC ~6 ~2025-60E
C16 HLB 0.0 6.7 12.2 17.6 23.1 28.5 CMC~0.3 ~0.6 ~4 S C18 HLB 0.0 5.~ 11.2 16.6 22.2 27.6 CMC ~1 E=Estimated HLB determined according to Davies:Proc. ~ International Congress, Surface Activity 1,426, Butterworths, London, 1957.
**
10 ppm As can be seen above, ~1) longer pure glucoside chain lengths raise the HLE~ and lower the molecule's surface activity (high CMC) and (2) the shorter alkyl chain lengths have extremely high CMC's even as the monoglucoside.
EXAMPLE XVI
The following formulas were prepared:
Magnesium linear C11 2 allcylbenzene sulfonate 22.4 22.4 22.4 20 C12 13 alkylpolygluco-side (G1 7) (<2% free fatty alcohol ) 14.9 14.9 14.9 Cg_1 l alkoxypropyldi-hydroxyethyl amine oxide - 4 25 C12 alkyldihydroxy ethyl amine oxide - - 4 Ethanol 5 5 5 Water balance balance balance Formulas A, B and C were compared by generating suds with a constant source of a~itation 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 edi~le acid). Dinner plates are washed with 4 ml. of soil on 35 each plate and the suds height is measured after each five plates.
lZ~ 0 30 plates in total are washed and the integral of the suds heigh~
taken over the number of plates washecl is reported as the SD~Y
grade (SDI,'1 = Suds During Washing), B C
5` SDl~l grade 24 28 . 8 28 . Ll This shows tllat the adcfition 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-- 10 panol amide is substi-tuted, at least in part for the specific amine oxides .
EXA~lPLE XVI I
105 grams of sodium dodecylbenzene sulfonate are mixed with 350 grams of anhydrous sodium sulfate. After the mixture is 15 ground into a fine powder, 70 9 of C12 13 alkylpolyglucoside (G2 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 alkylpolyglucoside is sprayed onto the powder.
20 7.5 milliliters of a 1% polar blue solution are sprayed onto the powder and a small portion of perfume is then added. The resulting granule is dried in a vacuum oven at 30 in. of ~Ig vacuum at 50C for ten hours to remove excess water.
In a similar manner 60 grams of a 50% solution of said alkyl-25 polyglucoside is sprayed onto 100 gram of Berkite and 50 grams of sodium dodecylbenzene sulfonate flakes are admixed with the product to give a light duty granule.
EXAMPLE XVI l l Ammonium C1 1 2 linear alkyl benzene sulfonate was admixed 30 with C12 alkylpolyglucoside G3 5 in a ratio of about 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. Substitution of a sodium 35 C12_~6 alkyl glyceryl ether sulfonate for 25~6 and 40% of the ~2090~
mixture extended the point at which there was no suds to 1. 5 and 1.75 grams of soil per 200 mi . of wash solution respectively .
Similar results are obtained when a sodium, potassium, ammonium, or monoethanolammonium C1 2-16 alkylpolyethoxy3 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
~he following formula was prepared with alkylpolyglucosides having 0 . 3% and 1% free fatty alcohol respectively.
Wt. ~6 Ammonium C11 2 iinear alkyl benzene sulfonate 17. 5 Magnesium C1 1 2 linear alkyl benzene sulfor:ate 6.4 15 Ammonium C1 2-13 alkyl poly-ethoxylate (0.8) sulfate 6.1 C12 13 alkYIPIYglUCside G1.7 Minors and water balance The SDW values for the low and high alcohol samples were 20 12.9 and 12.2 respecively with an LSDo 05 at 0.6. See Ex. XVI
for test method.
EXAMPLE XX
The following formulas were prepared:
% by welc~
A B C D
Ammoniumlmagnesium Cl 1 2 linear alkyl benzene sulfonate 24.2 21. 8 - -Ammoniuml magnesium C1 2-1 5 olefin sulfonate - - 12.8 10.
Ammonium/ magnesium C1 2-1 3 alkyl sulfonate - - 19 . 2 15.9 Ammonium C1 2 1 3 alkyl pol ye thoxy I ate ( 0 . 8 ) sulfate 6.5 5.8 ~o9~o C12 fatty acid diethanol~
amide - 3, 8 - 5 . 5 C12-l3 al~cylpolygl~lcoside C1 7 (free fatty alcohol '0.5%) 5.3 4.8 4 3.3 Minors and water balance A B C D
The SDVJ i ndex 79 89 97 107 The SI~W index is the SDW grade for each product as a 10 percentaye of the SDW value of a stanclard commercial product.
The following are examples of particularly preferred 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.
EXAMPLE XXI
% by Weig ht Ammonium Cl 1 4 alkyl benzene sulfonate 17.5 10-35 12-25 Magnesium C1 1 4 alkyl benzene sulfonate 6 . 4 0-11 3-9 12-13 a Icyl poly ethoxylate (0.8) suifates 6.1 2-11 3-9 C12-13 alkyl polyglucoside (1.7) derived from glucose ('0. 5~ free fatty alcohol J 5.0 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., perfurne Palance EXAMPLE XXI I
.
% by ~Yeight Arnmonium C1 2-13 alkyl sulfate 15 . 7 7-23 10-20 Sodium Cl 4-16 oiefin 35 sulfonate 10.4 4-19 6-13 1~0~0~
gC12 6~12 5.6 0-11 2-10 Coconut monoethanol amide 5.5 2-8 3-7 C12-13 all<yl polyglycoside (1.7) derived from ~lucose 5('0.5% free fatty alcohol) 5.9 2-12 3-9 Ethanol 4.0 0-lO 0-10 ~120 and minor components, e.g., perfume Balance The alkyl groups in the surfactants of Examples XXI and - 10 XXII can vary from about 10 to about 16 carbon atoms and the cations can be 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 disclosed herein can be used.
EXAMPLE XXIII
When a 2:1 mixture of an ammonium C1 1 2 alkylbenzene sulfonate and the C12_13 all<ylpolyglucoside (2-4) (>2% free fatty alcohol ) are tested under the conditions of Example 11 the initial suds volume is good, but the SD~V grade is not as good as some premium commercial products. Substitution of between 25% and 50% of the mixture with a sodium C1 2-~ 6 alkyl glyceryl ether sulfonate, or sodium C14_16 olefin sulfonate, or sodium C12_13 alkyl polyethoxylate(3) acetate increases the SD~`~ grade without lowering the initial sudsing excessively.
Known analytical techniques can be used to determine the structures of the all<ylpolysaccharide surfactants herein; for example, to determine the glycosidic chain length, the amount of butyl glucoside, the free fatty alcohol content, and the level of 30 unreacted polysaccharide. More specifically, gas or liquid chromatography can be used to determine the unreacted alcohol content and the unreacted polysaccharide content respective1y.
-Proton nmr can be used to determine the average glycosidic chain length. Ihe 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.
1~0~0~
Tlle alkylpolysaccharide surfactants are complex mixtures.
Their components vary depending upon the nature of the starting materials and the reac-tion by which they are prepared. Analyti-cal standards which are useful in calibrating irlstruments for 5 analyzing the components of a particular alkylpolysaccharide surfactant can be obtained from Calbiochem Behrin~ Co. LaJolla, California. These standards include those for octylglucoside (Calbiochem #494559), decylglucoside ~Calbiochem #252715), dodecylmaltoside ~Calbiochem #3243555).
The HLBs of alkylpolysaccharide surfactants useful in the foaming compositions of this invention have the values given in EXAMPLE XV; the CMCs will approximate those values given in the same example. Alkylpolysaccharide surfactants having the structures specified in the claims and characterized by one or 15 more of the standard analytical techniques will give the results indicated in the examples.
WHAT IS CLAIMED IS:
Claims (12)
1. A foaming composition comprising (1) an alkylpolysaccharide surfactant having the formula RO(R'O)t(Z)x wherein Z is a moiety derived from a reducing saccharide containing from 5 to 6 carbon atoms and wherein $ is an alkyl, alkylphenyl, hydroxy alkylphenyl or hydroxyalkyl 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;
an anioic cosurfactant selected from the group con-sisting of sufates, sulfonates, carboxylates and mix-tures thereof neutralized with one or more cationic moieties, the ratio of (2) to (1) being from about 1:10 to about 10:1; and from about 2% to about 10% of an auxiliary foam booster selected from the group consisting of:
(a) amides having the formula wherein R7 is an alkyl group containing from about 8 to about 18 carbon atoms and each R8 is the same or different and is selected from the group consisting of hydrogen, C1-3 alkyl, C1-3 alkanol, and -(C2H4O-)1-4H groups and mixtures thereof;
(b) amine oxides having the formula:
wherein R4 is an alkyl group containing from about 8 to about 18 carbon atoms, each R5 contains from two or three carbon atoms, b is from 0 to about 30, each R6 is the same or different and is selected from the group consisting of C1-3 alkyl, C1-3 alkanol, and -(C3H4O)1-6 groups and mixtures thereof; and (c) mixtures thereof.
an anioic cosurfactant selected from the group con-sisting of sufates, sulfonates, carboxylates and mix-tures thereof neutralized with one or more cationic moieties, the ratio of (2) to (1) being from about 1:10 to about 10:1; and from about 2% to about 10% of an auxiliary foam booster selected from the group consisting of:
(a) amides having the formula wherein R7 is an alkyl group containing from about 8 to about 18 carbon atoms and each R8 is the same or different and is selected from the group consisting of hydrogen, C1-3 alkyl, C1-3 alkanol, and -(C2H4O-)1-4H groups and mixtures thereof;
(b) amine oxides having the formula:
wherein R4 is an alkyl group containing from about 8 to about 18 carbon atoms, each R5 contains from two or three carbon atoms, b is from 0 to about 30, each R6 is the same or different and is selected from the group consisting of C1-3 alkyl, C1-3 alkanol, and -(C3H4O)1-6 groups and mixtures thereof; and (c) mixtures thereof.
2. The composition of Claim I wherein the cosurfactant is selec-ted from the group consisting of alkylbenzelle sulfonates, alpha-olefin sulfonates, alkyl sulfates, alkyl polyethoxylate sulfates, and paraffin sulfonates and mixtures thereof 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 2 wherein the cosurfactant is an alkylbenzene sulfonate.
4. The composition of Claim 3 wherein the phenyl portion of the alkylbenzene sulfonate is attached near the middle of the alkyl chain and at least about 10% of the cations are magnesium.
5 . The composition of Claim 2 wherein the cosurfactant is an alpha-olefin sulfonate.
6. The composition of Claim 2 wherein the cosurfactant is a paraffin sulfonate.
7. The composition of Claim I wherein the cosurfactant is a mixture of (1) from about 5% to about 50% of an alkyl benzene sul-fonate 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 about 5% to about 50% of an alkyl polyethoxylate sulfate in which the alkyl group contains from about 10 to about 18 carbon atoms and from about one to about six ethoxylate moieties and from about 10% to about 80%
of the cationic moieties are magnesium.
of the cationic moieties are magnesium.
8. A composition according to Claim 1, 2 or 7 wherein x is a number of from 1.5 to 4.
9. The composition of Claim 1, 2 or 7 wherein x is a number from 1.6 to 2.7.
10. A light-duty liquid detergent composition comprising from about 5% to about 50% of a 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 alkanolamines, C2-4 polyols, and mixtures thereof, and the balance water.
11. The composition of Claim 10 wherein the cosurfactant is selected from the group consisting of alkylbenzene sulfonates, alpha-olefin sulfonates, and paraffin sulfonates and the cationic moieties are selected from the group consisting of sodium, potas-sium, ammonium, monoethanolammonium, diethanolammonium, trieth-anolammonium, magnesium and mixtures thereof.
12. The composition of Claim 11 wherein at least 10% of the cationic moieties are magnesium.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US37169582A | 1982-04-26 | 1982-04-26 | |
| US371,695 | 1982-04-26 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1209010A true CA1209010A (en) | 1986-08-05 |
Family
ID=23465036
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000407156A Expired CA1209010A (en) | 1982-04-26 | 1982-07-13 | Foaming surfactant compositions |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JPS58186429A (en) |
| CA (1) | CA1209010A (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB8810820D0 (en) * | 1988-05-06 | 1988-06-08 | Unilever Plc | Detergent compositions |
| JPH0699711B2 (en) * | 1989-07-25 | 1994-12-07 | 花王株式会社 | Liquid detergent composition |
| JP2724220B2 (en) * | 1989-10-17 | 1998-03-09 | 花王株式会社 | Foam composition |
| DE69518393T2 (en) | 1994-11-28 | 2001-01-25 | Kao Corp | Detergent composition |
| JP2000026889A (en) * | 1998-07-07 | 2000-01-25 | Kao Corp | Detergent composition |
| JP4503346B2 (en) * | 2004-04-27 | 2010-07-14 | 花王株式会社 | Foaming agent for bubble shield 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 JP57121976A patent/JPS58186429A/en active Granted
- 1982-07-13 CA CA000407156A patent/CA1209010A/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| JPS58186429A (en) | 1983-10-31 |
| JPH0311811B2 (en) | 1991-02-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4565647A (en) | Foaming surfactant compositions | |
| US4536318A (en) | Foaming surfactant compositions | |
| US4663069A (en) | Light-duty liquid detergent and shampoo compositions | |
| US4599188A (en) | Foaming surfactant compositions | |
| US4536317A (en) | Foaming surfactant compositions | |
| CA1180973A (en) | Foaming surfactant compositions | |
| EP0070076B1 (en) | Foaming dishwashing liquid compositions | |
| EP0070075B1 (en) | Foaming dishwashing liquid compositions | |
| EP0070077B1 (en) | Light-duty detergent granule composition | |
| US4483787A (en) | Concentrated aqueous detergent compositions | |
| EP0341071A2 (en) | Detergent compositions | |
| US5503779A (en) | High foaming light duty liquid detergent | |
| US5780417A (en) | Light duty liquid cleaning compositions | |
| CA1209010A (en) | Foaming surfactant compositions | |
| US5972867A (en) | High foaming, grease cutting light duty liquid detergent | |
| JPH037718B2 (en) | ||
| US5773406A (en) | Foaming composition | |
| CA1180974A (en) | Foaming surfactant compositions | |
| US6010992A (en) | Liquid detergent composition containing amine oxide and citric acid | |
| WO1998036041A1 (en) | Improved light-duty liquid performance of ether sulfate using alkyl polyglycoside | |
| CA1190450A (en) | Foaming surfactant compositions | |
| EP0508507A1 (en) | Liquid dishwashing composition | |
| NO179952B (en) | Liquid detergent mixture | |
| KR19990054319A (en) | Detergent Composition Containing Alkyl Glucosulfate | |
| JPH06172784A (en) | Detergent composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEX | Expiry |