CA1334571C - Liquid detergent compositions containing binary anionic surfactant system - Google Patents
Liquid detergent compositions containing binary anionic surfactant systemInfo
- Publication number
- CA1334571C CA1334571C CA000523227A CA523227A CA1334571C CA 1334571 C CA1334571 C CA 1334571C CA 000523227 A CA000523227 A CA 000523227A CA 523227 A CA523227 A CA 523227A CA 1334571 C CA1334571 C CA 1334571C
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/04—Carboxylic acids or salts thereof
- C11D1/08—Polycarboxylic acids containing no nitrogen or sulfur
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/37—Mixtures of compounds all of which are anionic
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/123—Sulfonic acids or sulfuric acid esters; Salts thereof derived from carboxylic acids, e.g. sulfosuccinates
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Detergent Compositions (AREA)
Abstract
Homogeneous concentrated liquid detergent compositions are disclosed, containing a binary anionic surfactant system.
The binary anionic surfactant system is represented by a mixture, in well-defined ratios, of an alk(en)yl succinate and a specific class of sulfonated surface-active agents with a critical micellar concentration in the range of from 10-5 to 10-3 mole/l.
The binary anionic surfactant system is represented by a mixture, in well-defined ratios, of an alk(en)yl succinate and a specific class of sulfonated surface-active agents with a critical micellar concentration in the range of from 10-5 to 10-3 mole/l.
Description
LIQUID DETERGENT COMPOSITIONS CONTAINING BINARY
ANIONIC SURFACTANT SYSTEM
Technical Field The present invention relates to homogeneous, concentrated, liquid detergent composition6 containing a binary anionic 6urfactant 6ystem, together with desirable detergent ingredients. The binary anionic surfactant sy6tem i6 represented by a mixture, in well-defined ratios, of an alk(en)yl 6uccinate and a specific class of 6ulfonated urface-active agents, 6aid 6ulfonated 6urface-active agents having a critical micellar concentration in the range of from 10-5 to 10-3 mole/l.
Preferred 6ulfon~ted surface-active agent6 for use in the binary sy6tem of the invention are linear alkyl arene 6ulfonates, containing from 13 to 17 carbon atoms in their alkyl group, and dialkyl sulfosuccinates, having from 9 to 12 carbon atoms in each alkyl group.
The compo~itions of the invention exhibit excellent cleaning propertie~ on a}l type of ~tains.
-- 2 _ 1 334 57 Backqround of the invention The prior art relative to concentrated homogeneous heavy duty liquid detergent composition6 i6 crowded and diver6e.
As an example U.S. Patent 4.285.841 di6closes` builder-free 5 concentrated homogeneou6 liquid composition6 containing a combination of anionic 6ynthetic surface-active compounds, nonionic 6urface-active compounds and fatty acids.
The 6uccinate ingredient i6 well-known in the detergent art and ha6 been di6clo6ed in combination with all kinds of 10 detergent execution6.
Succinate derivatives have been u6ed for 6everal purpose6 a6 6urfactants in U.S. Patent 2.283.214, as builders in U.S. Patent 2.562.758, a6 6ud6-boosters in U.K.
Patent 1.293.753, and a6 ingredient6 of liquid cleaners in 15 U.S. Patent 4.277.378.
Linear alkyl-arene sulfonate6, 6uch a6 linear ortho-xylene sulfonates, are known 6urfactant6, mainly for Enhanced Oil Becovery Applications. In European Patent O 111 354, their use in detergents i6 mentioned.
Dialkyl sulfo6uccinate6 are al60 known as 6urfactants;
they have been di6clo6ed frequently in high-foaming dishwashing composition6; U.K. Patent6 2.130.235 and 2.130.238, di6close combination of dialkyl sulfosuccinates with linear alkyl sulfonate6 and ethoxylated nonionic 6urfactants-Copending Briti6h Patent Application N 8511303di6close6 liquid detergent compo6ition6 containing a ternary 6urfactant 6y6tem of 6uccinate6, anionic 6urface-active ~ agents and nonionic 6urface-active agents.
Copending British Patent Application N 8520489 relates to liquid detergent compo6ition6 containing a mixture of citrate6 and 6uccinates as detergency builder6.
However, the incorporation of high levels of alk(en)yl 6uccinates in concentrated liquid detergent compositions is ~ 3 ~ 1 3 3 4 57 1 known to adver6ely affect overall detergency benefits, 6uch a6 grea6y 6tain removal performance.
It i6 a major objective of the pre6ent invention to provide liquid detergent compositions containing high levels 5 of alk(en)yl succinate6, which exhibit excellent cleaning benefit6 on all type6 of 6tain6, e6pecially on grea6y 6tains.
The above and other objectives can now be met by means of a combination, in well-defined ratio6, of alk(en)yl 6uccinates and 6ulfonated 6urface-active agent6 having a narrowly-defined critical micelle concentration. Linear alkyl-arene 6ulfonate6 containing from 13 to 17 carbon atoms in their alkyl group, and di-alkyl 6ulfo6uccinates having from 9 to 12 carbon atoms in each alkyl group, are e6pecially u6eful in that respect.
Summary of the invention The present invention relate6 to homogeneous concentrated aqueou6 liquid detergent compo6itions containing le66 than 50% by weight of water, and a binary anionic 6urfactant 6y6tem, together with conventional additives, characterized in that, (a) the binary anionic 6urfactant 6ystem represent6 from 12%
to 50% by weight of the composition:
(b) the anionic 6urfactant sy6tem i6 repre6ented by a mixture of (1) an alk(en)yl 6uccinate having the formula I
Rl CH CH COOH
I
COOH
~ 4 ~ 1 3 34 5 ~ 1 wherein Rl i6 an alkten)yl radical, having from 10 to 20 C-atom6, and R2 i6 hydrogen or Cl-C4 alkyl; and (2) a 6ulfonated 6urface-active agent having a critical micelle concentration in the range of from 10 3 to 10-5 mole/l;
the weight ratio of 6ulfonate to 6uccinate being in the range from 2:1 to 1:4.
Preferred 6ulfonated 6urface-active agent6 are:
- linear alkyl-arene 6ulfonate6 containing from 13 to 17 carbon atom6 in the alkyl group; and - di-alkyl 6ulfo6uccinate6, having from 9 to 12 carbon atoms in each alkyl group.
Most preferred are C13-C14 linear alkyl ortho-xylene 6ulfonate and di-Clo alkyl 6ulfo6uccinate Detailed de6cription of the invention Unle66 6tated to the contrary, the 'Ipercent-indications 6tand for "percent by weight~ of t.he compo6itions.
The anionic 6urfactant binary mixture amount6 to from 12% to 50% preferably from 15% to 35% of the total compo6ition and i6 repre6ented by a binary compo6ition of:
(1) an alk(en)yl 6uccinate having the formula:
Rl CH CH COOH
COOH
wherein Rl i6 an al~(en)yl radical, having from 10 to 20 C-atom6, and R2 i6 hydrogen or Cl-C4 alkyl; and (2) a sulfona~ed 6urface-active agent having a critical micellar concentration in the range of from 10 5 to 10-3 mole/l;
(1) The alk(en)yl 6uccinate ha6 the formula referred to hereinbefore wherein Rl i6 either a 6aturated or un6atu-rated radical having from 10 to 20 carbon atom6, preferably an un6aturated derivative having from 12 to 16 carbon atoms in the alkenyl moiety. R2 can be hydrogen or Cl-C4 alkyl, although hydrogen i6 preferred. The term6 "6ucci-nate" and "6uccinic acidll are used interchangeably. Sui-table 6uccinic acid 6alt6 include the 60dium, pota66ium, lithium, ammonium, mono-, di- and tri-alkanol amine 6alt6 and mixture6 thereof.
Preferred 6uccinic acid derivative6 for u6e herein include 2-dodecenyl6uccinic acid, 2-tetradecenyl6uccinic acid, 2-hexadecenyl6uccinic acid, decyl 6uccinic acid, dodecyl 6uccinic acid and tetradecyl 6uccinic acid and the water-601uble salt6 thereof. The alkyl or alkenyl chain attached to 6uccinic acid can be either 6traight or branched. Preferred are the 6traight-chain alk(en)yl moietie6. For any practical purpo6e, the alk(en)yl 6uccinates are used at level6 above 4% of the total compo6ition.
(2) The 6ulfonated 6urface-active agent for u6e in the pre6ent invention mu6t have a critical micelle concentration, mea6ured on the 60dium 6alt form, in the range of from 10-5 to 10-3 mole/l.
The critical micellar concentration (hereinafter referred to a6 cmc) of a compound i6 the concentration above which the molecule6 of the compound begin to aggregate to form micelle6.
Several method6 of determination of the cmc have been 30 ~ de6cribed in the literature. The method u6ed in the context of the pre6ent invention i6 the 6urface-ten6ion-log concentration plot method, which can be found e.g. in "Critical Micelle Concentration6 of Aqueou6 Surfactant Sy6tem6~, by P. Mukerjee and ~.J. My6el6, publi6hed by the United State6 Department of Commerce. The cmc i6 determined with the aid of solutions in distilled water. The temperature of measurement i8 6uperior to the Kraft temperature.
Particularly suitable for use herein are sulfonated 6urface-active agent6 inclusive of:
A. Linear alkyl arene 6ulfonate6 containing from 13 to 17 carbon atoms in the alkyl group, preferably toluene or xylene derived 6ulfonate6. E6pecially are C13_14 linear orthoxylene 6ulfonate C13 14 linear paraxylene 6ulfonate, and C14 linear toluene 6ulfonate;
B. Di-alkyl 6ulfosuccinates, having from 9 to 12 carbon atoms in each alkyl group. Particularly preferred are di-Clo alkyl 6ulfo6uccinates.
The sulfonate component can be represented by individual 6ulfonates having the 6pecified cmc~s or by mixtures of 6ulfonate 6urfactant6 provided the 6ulfonate mixture has a cmc within the claimed range. It i6 po6sible that 6pecific sulfonate mixtures meet the cmc requirement even though the individual sulfonates of the mixture can have cmc's which are outside of the claimed range.
Consequently, conventional sulfonate surface-active agent6 such as water-soluble salts of alkylbenzene sulfonic acid containing from 10 to 18 carbon atoms in the alkyl groups can be present in the above mixtures.
The weight ratio of sulfonate to succinate surfactant in the binary mixture is in the range from 2:1 to 1:4.
In addition to the binary anionic 6urfactant 6ystem, the compo6ition6 therein can contain, a6 an optional but preferred ingredient, a nonionic 6urface-active agent.
The nonionic surfactant can be present at levels of from 3% to 3s%, preferably from ~% to 20% of the total composition.
The nonionic surfactant comlonent contains a hydrophobic organic radical conden~ed with an ethylene oxide hydrophilic _ 7 - ~ 3345 7 1 moiety. All ethoxylated nonionic 6urfactants which are known to be ~uitable for use in detergent application can be used in the compo~itions of this invention. Preferred nonionic specie6 herein are polyethoxylate6 ~erived from primary and ~econdary aliphatic alcohol6 having from 8 to 24 carbon atoms, and having a HLB (hydrophilic lipophilic balance) in the range from about 8 to 15. These preferred ethoxylates frequently contain from 2 to about 14 moles of ethylene oxide per mole of hydrophobic moiety. The hydrocarbyl chain (hydrophobic moiety) can be represented by linear or branched fatty alcohols.
A preferred class of nonionic ethoxylates is represented by the condensation product of a fatty alcohol having from 12 to 15 carbon atoms and from about 4 to 10 moles of ethylene oxide per mole of fatty alcohol. Suitable species of this clas6 of ethoxylates include: the condensation product of C12-C15 oxo-alcohols and 7 moles of ethylene oxide per mole of alcohol; the condensation product of C13 15 oxoalcohols and 5 moles of ethylene oxide; the condensation product of narrow cut C14-C15 oxo-alcohols and 7 or 9 moles of ethylene oxide per mole of fatty (oxo)alcohol; the condensation product of a narrow cut C12-C13 fatty (oxo)alcohol and 6.5 moles of ethylene oxide per mole of fatty alcohol; and the condensation products of a C10-Cl4 coconut fatty alcohol with a degree of ethoxylation (moles E0/mole fatty alcohol) in the range from 5 to 8. The fatty oxo alcohols while mainly linear can have, depending upon the proces6ing conditions and rav material olefins, a certain degree of branching, particularly 6hort chain such as methyl branching. A degree of branching in the range from 15S to 50% (weight %) is frequently found in commercial oxo-alcohol6.
Nonionic ethoxylated components can al60 be represented by a mixture of Z separately ethoxylated nonionic surfactant6 having a different degree of ethoxylation.
The compositions herein contain less than 50%, usually from 15% to 40% water.
The claimed compositions have a pH, measured in 1%
aqueous solution at 20C, in the range from about 7 to about 9. This pH range implies that the anionic surfactant component, i.e., the binary mixture of sulfonate and succinate, particularly the succinate, is substantially completely (i.e., more than 90%) neutralized in the claimed compo6ition as is.
In addition to the es6ential ingredients described hereinbefore, the compositions herein frequently contain a series of optional ingredients which are used for their known functionality in conventional quantities.
Example6 of the like optional ingredients can include fatty acids, saturated and/or un6aturated, and the corresponding soaps, synthetic anionic surfactant6 which are different from sulfonates (non-sulfonate anionics), water-insoluble solvents, enzymes, enzyme stabilizer6, polyacids, polyaminopolyalkylene ethoxylate polymers, suds regulants, brighteners, perfumes, dyes, antioxidants, bactericides, corrosion inhibitors, fabric-softening agents, phase regulants and the like.
Suitable fatty acids, saturated or unsaturated, have from 10 to 18 carbon atoms in the alkyl chain. Preferred are unsaturated species having from 14 to 18 carbon atoms in the alkyl chain, most preferably oleic acid. The corresponding soaps can equally be used. The optional fatty acid/soaps are used in levels up to 10%, preferably from 1%
to 8%, (of the composition). The fatty acids/soaps, among 30~ others, act as suds modifiers/regulants.
Synthetic non-6ulfonate anionic6 can also be used in the composition in relatively minor levels. Examples of suitable non-sulfonate anionics include the salts of sulfated fatty alcohols having from 12 to 20 carbon atoms in the alcohol chain.
- 9 - 1 33 4 ~ 7 1 Water-insoluble 601vents 6uch as terpene~, phthalic acid ester6 and liquid paraffins can al~o be used in levels generally below 5%.
Detergent enzymes generally aid and augment the removal of ~pecific ~tain~. Suitable enzymes can be repre~ented by proteases, amylase~, lipa~es, glucose-oxidase6, cellulase, or mixtures thereof. Proteases and amylase~ are preferred in the claimed liquid concentrated compo6itions. They are frequently employed in a level from about 0.01% to about 1%.
All generally known enzyme stabilizing ~ystems can be used in the compositions herein in the art establi~hed level. Examples of ~uitable 6tabilizing ~y6tems include ~hort Cl 4 chain carboxylic acid, particularly formic acid in combination with low level of calcium, boric acid and the water-~oluble 6alt~ thereof pos~ibly in combination with polyols.
Another preferred optional ingredient i~ represented by a polyacid or mixture of polyacids in an amount from about 0.05% to about 4%. Suitable polyacid6 are those having one pK value of at least 5. Preferred polyacid 6pecies for use herein can be represented by citric acid, and organo-pho6phonic acids, particularly alkylene-polyamino-polyalkylene phosphonic acids such as ethylene diamine tetramethylenephosphonic acid, and diethylene triaminepentamethylenephosphonic acid or the 6alt~ thereof. Suitable polyamino-polyalkylene ethoxylate polymers, di~closed in publi~hed European Patent Application N 112 593, are present at level~ of from 0.2 to 1.2%.
Non-fatty acid detergent 6ud~ regulant~ can al60 be used. Preferred 6pecies include alkylated poly~iloxanes 6uch a~ dimethylpolysiloxane also frequently termed 6ilicone. The 6ilicone6 are frequently u~ed in a level not exceeding O.St, most preferably between 0.01% to 0.2%.
The compositions herein can al~o contain known antioxidant~ for their known utility, frequently radical _ 10- 1334571 6cavengecs, in the art e6tabli6hed level6 i.e. 0.01% to 0.25% (by reference to total compo6ition). The6e antioxidant6 are frequently introduced in conjunction with un6aturated organic acids. While many suitable antioxidants are readily known and available for that purpo6e, e6pecially preferred for u6e in the compo6ition6 herein are: 2,6 ditertiary butyl-p-cre601, more commonly known a~ butylated hydroxytoluene, BHT, and 2-tertiarybutyl-4-hydroxyanisole.
Other 6uitable antioxidant6 are:
ANIONIC SURFACTANT SYSTEM
Technical Field The present invention relates to homogeneous, concentrated, liquid detergent composition6 containing a binary anionic 6urfactant 6ystem, together with desirable detergent ingredients. The binary anionic surfactant sy6tem i6 represented by a mixture, in well-defined ratios, of an alk(en)yl 6uccinate and a specific class of 6ulfonated urface-active agents, 6aid 6ulfonated 6urface-active agents having a critical micellar concentration in the range of from 10-5 to 10-3 mole/l.
Preferred 6ulfon~ted surface-active agent6 for use in the binary sy6tem of the invention are linear alkyl arene 6ulfonates, containing from 13 to 17 carbon atoms in their alkyl group, and dialkyl sulfosuccinates, having from 9 to 12 carbon atoms in each alkyl group.
The compo~itions of the invention exhibit excellent cleaning propertie~ on a}l type of ~tains.
-- 2 _ 1 334 57 Backqround of the invention The prior art relative to concentrated homogeneous heavy duty liquid detergent composition6 i6 crowded and diver6e.
As an example U.S. Patent 4.285.841 di6closes` builder-free 5 concentrated homogeneou6 liquid composition6 containing a combination of anionic 6ynthetic surface-active compounds, nonionic 6urface-active compounds and fatty acids.
The 6uccinate ingredient i6 well-known in the detergent art and ha6 been di6clo6ed in combination with all kinds of 10 detergent execution6.
Succinate derivatives have been u6ed for 6everal purpose6 a6 6urfactants in U.S. Patent 2.283.214, as builders in U.S. Patent 2.562.758, a6 6ud6-boosters in U.K.
Patent 1.293.753, and a6 ingredient6 of liquid cleaners in 15 U.S. Patent 4.277.378.
Linear alkyl-arene sulfonate6, 6uch a6 linear ortho-xylene sulfonates, are known 6urfactant6, mainly for Enhanced Oil Becovery Applications. In European Patent O 111 354, their use in detergents i6 mentioned.
Dialkyl sulfo6uccinate6 are al60 known as 6urfactants;
they have been di6clo6ed frequently in high-foaming dishwashing composition6; U.K. Patent6 2.130.235 and 2.130.238, di6close combination of dialkyl sulfosuccinates with linear alkyl sulfonate6 and ethoxylated nonionic 6urfactants-Copending Briti6h Patent Application N 8511303di6close6 liquid detergent compo6ition6 containing a ternary 6urfactant 6y6tem of 6uccinate6, anionic 6urface-active ~ agents and nonionic 6urface-active agents.
Copending British Patent Application N 8520489 relates to liquid detergent compo6ition6 containing a mixture of citrate6 and 6uccinates as detergency builder6.
However, the incorporation of high levels of alk(en)yl 6uccinates in concentrated liquid detergent compositions is ~ 3 ~ 1 3 3 4 57 1 known to adver6ely affect overall detergency benefits, 6uch a6 grea6y 6tain removal performance.
It i6 a major objective of the pre6ent invention to provide liquid detergent compositions containing high levels 5 of alk(en)yl succinate6, which exhibit excellent cleaning benefit6 on all type6 of 6tain6, e6pecially on grea6y 6tains.
The above and other objectives can now be met by means of a combination, in well-defined ratio6, of alk(en)yl 6uccinates and 6ulfonated 6urface-active agent6 having a narrowly-defined critical micelle concentration. Linear alkyl-arene 6ulfonate6 containing from 13 to 17 carbon atoms in their alkyl group, and di-alkyl 6ulfo6uccinates having from 9 to 12 carbon atoms in each alkyl group, are e6pecially u6eful in that respect.
Summary of the invention The present invention relate6 to homogeneous concentrated aqueou6 liquid detergent compo6itions containing le66 than 50% by weight of water, and a binary anionic 6urfactant 6y6tem, together with conventional additives, characterized in that, (a) the binary anionic 6urfactant 6ystem represent6 from 12%
to 50% by weight of the composition:
(b) the anionic 6urfactant sy6tem i6 repre6ented by a mixture of (1) an alk(en)yl 6uccinate having the formula I
Rl CH CH COOH
I
COOH
~ 4 ~ 1 3 34 5 ~ 1 wherein Rl i6 an alkten)yl radical, having from 10 to 20 C-atom6, and R2 i6 hydrogen or Cl-C4 alkyl; and (2) a 6ulfonated 6urface-active agent having a critical micelle concentration in the range of from 10 3 to 10-5 mole/l;
the weight ratio of 6ulfonate to 6uccinate being in the range from 2:1 to 1:4.
Preferred 6ulfonated 6urface-active agent6 are:
- linear alkyl-arene 6ulfonate6 containing from 13 to 17 carbon atom6 in the alkyl group; and - di-alkyl 6ulfo6uccinate6, having from 9 to 12 carbon atoms in each alkyl group.
Most preferred are C13-C14 linear alkyl ortho-xylene 6ulfonate and di-Clo alkyl 6ulfo6uccinate Detailed de6cription of the invention Unle66 6tated to the contrary, the 'Ipercent-indications 6tand for "percent by weight~ of t.he compo6itions.
The anionic 6urfactant binary mixture amount6 to from 12% to 50% preferably from 15% to 35% of the total compo6ition and i6 repre6ented by a binary compo6ition of:
(1) an alk(en)yl 6uccinate having the formula:
Rl CH CH COOH
COOH
wherein Rl i6 an al~(en)yl radical, having from 10 to 20 C-atom6, and R2 i6 hydrogen or Cl-C4 alkyl; and (2) a sulfona~ed 6urface-active agent having a critical micellar concentration in the range of from 10 5 to 10-3 mole/l;
(1) The alk(en)yl 6uccinate ha6 the formula referred to hereinbefore wherein Rl i6 either a 6aturated or un6atu-rated radical having from 10 to 20 carbon atom6, preferably an un6aturated derivative having from 12 to 16 carbon atoms in the alkenyl moiety. R2 can be hydrogen or Cl-C4 alkyl, although hydrogen i6 preferred. The term6 "6ucci-nate" and "6uccinic acidll are used interchangeably. Sui-table 6uccinic acid 6alt6 include the 60dium, pota66ium, lithium, ammonium, mono-, di- and tri-alkanol amine 6alt6 and mixture6 thereof.
Preferred 6uccinic acid derivative6 for u6e herein include 2-dodecenyl6uccinic acid, 2-tetradecenyl6uccinic acid, 2-hexadecenyl6uccinic acid, decyl 6uccinic acid, dodecyl 6uccinic acid and tetradecyl 6uccinic acid and the water-601uble salt6 thereof. The alkyl or alkenyl chain attached to 6uccinic acid can be either 6traight or branched. Preferred are the 6traight-chain alk(en)yl moietie6. For any practical purpo6e, the alk(en)yl 6uccinates are used at level6 above 4% of the total compo6ition.
(2) The 6ulfonated 6urface-active agent for u6e in the pre6ent invention mu6t have a critical micelle concentration, mea6ured on the 60dium 6alt form, in the range of from 10-5 to 10-3 mole/l.
The critical micellar concentration (hereinafter referred to a6 cmc) of a compound i6 the concentration above which the molecule6 of the compound begin to aggregate to form micelle6.
Several method6 of determination of the cmc have been 30 ~ de6cribed in the literature. The method u6ed in the context of the pre6ent invention i6 the 6urface-ten6ion-log concentration plot method, which can be found e.g. in "Critical Micelle Concentration6 of Aqueou6 Surfactant Sy6tem6~, by P. Mukerjee and ~.J. My6el6, publi6hed by the United State6 Department of Commerce. The cmc i6 determined with the aid of solutions in distilled water. The temperature of measurement i8 6uperior to the Kraft temperature.
Particularly suitable for use herein are sulfonated 6urface-active agent6 inclusive of:
A. Linear alkyl arene 6ulfonate6 containing from 13 to 17 carbon atoms in the alkyl group, preferably toluene or xylene derived 6ulfonate6. E6pecially are C13_14 linear orthoxylene 6ulfonate C13 14 linear paraxylene 6ulfonate, and C14 linear toluene 6ulfonate;
B. Di-alkyl 6ulfosuccinates, having from 9 to 12 carbon atoms in each alkyl group. Particularly preferred are di-Clo alkyl 6ulfo6uccinates.
The sulfonate component can be represented by individual 6ulfonates having the 6pecified cmc~s or by mixtures of 6ulfonate 6urfactant6 provided the 6ulfonate mixture has a cmc within the claimed range. It i6 po6sible that 6pecific sulfonate mixtures meet the cmc requirement even though the individual sulfonates of the mixture can have cmc's which are outside of the claimed range.
Consequently, conventional sulfonate surface-active agent6 such as water-soluble salts of alkylbenzene sulfonic acid containing from 10 to 18 carbon atoms in the alkyl groups can be present in the above mixtures.
The weight ratio of sulfonate to succinate surfactant in the binary mixture is in the range from 2:1 to 1:4.
In addition to the binary anionic 6urfactant 6ystem, the compo6ition6 therein can contain, a6 an optional but preferred ingredient, a nonionic 6urface-active agent.
The nonionic surfactant can be present at levels of from 3% to 3s%, preferably from ~% to 20% of the total composition.
The nonionic surfactant comlonent contains a hydrophobic organic radical conden~ed with an ethylene oxide hydrophilic _ 7 - ~ 3345 7 1 moiety. All ethoxylated nonionic 6urfactants which are known to be ~uitable for use in detergent application can be used in the compo~itions of this invention. Preferred nonionic specie6 herein are polyethoxylate6 ~erived from primary and ~econdary aliphatic alcohol6 having from 8 to 24 carbon atoms, and having a HLB (hydrophilic lipophilic balance) in the range from about 8 to 15. These preferred ethoxylates frequently contain from 2 to about 14 moles of ethylene oxide per mole of hydrophobic moiety. The hydrocarbyl chain (hydrophobic moiety) can be represented by linear or branched fatty alcohols.
A preferred class of nonionic ethoxylates is represented by the condensation product of a fatty alcohol having from 12 to 15 carbon atoms and from about 4 to 10 moles of ethylene oxide per mole of fatty alcohol. Suitable species of this clas6 of ethoxylates include: the condensation product of C12-C15 oxo-alcohols and 7 moles of ethylene oxide per mole of alcohol; the condensation product of C13 15 oxoalcohols and 5 moles of ethylene oxide; the condensation product of narrow cut C14-C15 oxo-alcohols and 7 or 9 moles of ethylene oxide per mole of fatty (oxo)alcohol; the condensation product of a narrow cut C12-C13 fatty (oxo)alcohol and 6.5 moles of ethylene oxide per mole of fatty alcohol; and the condensation products of a C10-Cl4 coconut fatty alcohol with a degree of ethoxylation (moles E0/mole fatty alcohol) in the range from 5 to 8. The fatty oxo alcohols while mainly linear can have, depending upon the proces6ing conditions and rav material olefins, a certain degree of branching, particularly 6hort chain such as methyl branching. A degree of branching in the range from 15S to 50% (weight %) is frequently found in commercial oxo-alcohol6.
Nonionic ethoxylated components can al60 be represented by a mixture of Z separately ethoxylated nonionic surfactant6 having a different degree of ethoxylation.
The compositions herein contain less than 50%, usually from 15% to 40% water.
The claimed compositions have a pH, measured in 1%
aqueous solution at 20C, in the range from about 7 to about 9. This pH range implies that the anionic surfactant component, i.e., the binary mixture of sulfonate and succinate, particularly the succinate, is substantially completely (i.e., more than 90%) neutralized in the claimed compo6ition as is.
In addition to the es6ential ingredients described hereinbefore, the compositions herein frequently contain a series of optional ingredients which are used for their known functionality in conventional quantities.
Example6 of the like optional ingredients can include fatty acids, saturated and/or un6aturated, and the corresponding soaps, synthetic anionic surfactant6 which are different from sulfonates (non-sulfonate anionics), water-insoluble solvents, enzymes, enzyme stabilizer6, polyacids, polyaminopolyalkylene ethoxylate polymers, suds regulants, brighteners, perfumes, dyes, antioxidants, bactericides, corrosion inhibitors, fabric-softening agents, phase regulants and the like.
Suitable fatty acids, saturated or unsaturated, have from 10 to 18 carbon atoms in the alkyl chain. Preferred are unsaturated species having from 14 to 18 carbon atoms in the alkyl chain, most preferably oleic acid. The corresponding soaps can equally be used. The optional fatty acid/soaps are used in levels up to 10%, preferably from 1%
to 8%, (of the composition). The fatty acids/soaps, among 30~ others, act as suds modifiers/regulants.
Synthetic non-6ulfonate anionic6 can also be used in the composition in relatively minor levels. Examples of suitable non-sulfonate anionics include the salts of sulfated fatty alcohols having from 12 to 20 carbon atoms in the alcohol chain.
- 9 - 1 33 4 ~ 7 1 Water-insoluble 601vents 6uch as terpene~, phthalic acid ester6 and liquid paraffins can al~o be used in levels generally below 5%.
Detergent enzymes generally aid and augment the removal of ~pecific ~tain~. Suitable enzymes can be repre~ented by proteases, amylase~, lipa~es, glucose-oxidase6, cellulase, or mixtures thereof. Proteases and amylase~ are preferred in the claimed liquid concentrated compo6itions. They are frequently employed in a level from about 0.01% to about 1%.
All generally known enzyme stabilizing ~ystems can be used in the compositions herein in the art establi~hed level. Examples of ~uitable 6tabilizing ~y6tems include ~hort Cl 4 chain carboxylic acid, particularly formic acid in combination with low level of calcium, boric acid and the water-~oluble 6alt~ thereof pos~ibly in combination with polyols.
Another preferred optional ingredient i~ represented by a polyacid or mixture of polyacids in an amount from about 0.05% to about 4%. Suitable polyacid6 are those having one pK value of at least 5. Preferred polyacid 6pecies for use herein can be represented by citric acid, and organo-pho6phonic acids, particularly alkylene-polyamino-polyalkylene phosphonic acids such as ethylene diamine tetramethylenephosphonic acid, and diethylene triaminepentamethylenephosphonic acid or the 6alt~ thereof. Suitable polyamino-polyalkylene ethoxylate polymers, di~closed in publi~hed European Patent Application N 112 593, are present at level~ of from 0.2 to 1.2%.
Non-fatty acid detergent 6ud~ regulant~ can al60 be used. Preferred 6pecies include alkylated poly~iloxanes 6uch a~ dimethylpolysiloxane also frequently termed 6ilicone. The 6ilicone6 are frequently u~ed in a level not exceeding O.St, most preferably between 0.01% to 0.2%.
The compositions herein can al~o contain known antioxidant~ for their known utility, frequently radical _ 10- 1334571 6cavengecs, in the art e6tabli6hed level6 i.e. 0.01% to 0.25% (by reference to total compo6ition). The6e antioxidant6 are frequently introduced in conjunction with un6aturated organic acids. While many suitable antioxidants are readily known and available for that purpo6e, e6pecially preferred for u6e in the compo6ition6 herein are: 2,6 ditertiary butyl-p-cre601, more commonly known a~ butylated hydroxytoluene, BHT, and 2-tertiarybutyl-4-hydroxyanisole.
Other 6uitable antioxidant6 are:
4,4~thiobi6(6-ter-butyl-mcre601) and 2-methyl-4,6-dinonyl phenol.
Soil relea6e polymer6 can al60 be incorporated in the compo~ition6 herein. Suitable 6pecie6 of 6uch release polymers are described in Canadian Patent Application Serial Number 498,176, filed December 16, 1985.
The pha6e regulant i6 a further optional ingredient in the compo~ition6 herein. Thi6 component together with water can con6titute the 601vent matrix for the claimed concentrated liquid compo6ition6. Suitable ingredient cla6ses include lower aliphatic alcohol6 having from 2 to 6 carbon atom6 and from 1 to 3 hydroxyl group6, ether6 of diethyleneglycol and lower aliphatic monoalcohol6 having from 1 to 4 carbon atom6. Specific example6 of phase regulant6 are: ethanol; n-propanol; i60propanol; butanol;
1,2-propanediol; 1,3-propanediol; monomethyl-, ethyl-, propyl-, and monobutyl ethers of di-ethylene glycol.
The claimed invention i6 illu6trated and clarified with the aid of the following example6.
Concentrated liquid detergent composition6 are prepared by mixing the individual ingredient6 li6ted hereinafter in the stated proportion6.
Inqredient6 Comp.A Comp.B Ex.l Ex.2 Dodecylbenzene 6ulfonic acid10.3 10.3 Ethoxylated C13_15 alcohol con-den6ed with 7 moles of ethylene oxide per mole of fatty alcohol 11.6 11.6 11.6 11.6 C13_14 linear ortho xylene 6ul-fonic acid (1) - - 11.8 Di-i60decyl 6ulfo6uccinate Na 6alt * (2) - - - 12.0 Topped Whole Cut fatty acid ** 10.7 - - -2-Dodecenyl 6uccinate - 15.0 15.0 15.0 Citric acid 0.9 0-9 0-9 0-9 Oleic acid 3.9 3.9 3.9 3.9 Diethylenetriamine pentame-thylene pho6phonic acid 0.85 0.85 0.8 0.8 Triethanolamine 5.0 5.0 6.3 6.3 Coconut alkyl 6ulfate TEA 6alt 3.9 3.9 3.9 3.9 Soil relea6e polymer *** - 0.5 Ethanol 6.2 9.0 9.0 9.0 1,2-Propanediol 1.5 Formate (Na) 1.0 1.0 1.0 1.0 Enzymes 0.43 0.69 0.15 0.15 Water, NaOH CaC12 and minor6balance to 100 pH 7.7 7.6 7.6 7.6 (1) cmc t~urface ten6ion-log concentration plot method) =
4.7 10-4 mole/l (2) cmc (6urface tension-log concentration plot method) =
1.9 10-4 mole/l 70% by weight 601ution in propylene glycol ~* Fatty acid chain di6tribution:50t lauric, 20%
myri6tic, 15% palmitic, 10% oleic, 2% 6tearic *~ Prepared by e6terifying 1,4 phtalic acid (chloride) with 1,2-propane diol and ethoxylating the polymer with ethylene oxide. The re6ulting polymer mix i5 fractionated in cold (15C) ethanol to provide a cold-ethanol 601uble fraction with an average ethoxylation value in the range from lZ-43.
The above compo6ition6 were u6ed for comparative laundry te6t6. A MIELE W423 washing machine wa6 used thereby 6electing a main-wa6h 6tep.
Cotton and polye6ter/cotton (polycotton) 6trip6 6tained a6 indicated below were u6ed to mea6ure the comparative performance. Additional te6ting parameter6 were, temperature 60C, product u6age 180 g/18 1. of city water having an average water hardne66 of about 3 mmole6/l.;
laundering treatment in pre6ence of 3 kg6 60iled clothes (no-pretreatment on te6t 6trip6); 6tain6 : grea6y type, i.e., ma~e-up, lip6tick, and dirty motor oil (DM0).
After having been 6ubjected to the above washing treatment the dried 6tained cotton 6trips were vi6ually graded by two expert judge6 thereby using a 0-4 6cale whereby:
0 = 6ee no difference between the 6watche6 1 = believe there i6 a difference between the 6watches 2 = there i6 a difference between the 6watche6 3 = am 6ure there i6 a difference between the 6watches 4 = very important differeVnce between the ~watches.
The 6tain removal reading6 were pooled and averaged on 8 replicate6 with the following re6ult6. The 6watches treated with prior art compo6ition A were u6ed for reference purpo~es:
Type of Comp.B v6.Comp.A Ex.l vs.Comp.A Ex.2 V6.Comp.A
6tains Cotton/Poly- Cotton/Poly- Cotton/Poly-cotton cotton cotton GREASY -1.1*/-1.0* +0.8*/+0.7* +0.1/+1.0*
. Makeup -2.4*/-2.6* +1.8*/+1.4* +0.9/+1.2*
. Lipstick -2.3*/-2.1* +0.2/-0.2 -O.l/+l.O*
. DMO -1.5*/+0.8* -0.3/+0.8* -1.5*/+1.0*
* Readings stati6tically significant at 95% confidence limit.
The above data shows significant performance superiority on greasy stain6 of the composition6 of Examples 1 and 2 in accordance with this invention V6. a commercial heavy duty liquid, termed compo6ition A. The performance superiority is equally applicable V6. a 6uccinate containing liquid detergent, termed composition B.
On other types of 6tains (bleachable, enzymatic, particulate) the performance of the composition6 of Examples 1 and 2 i6 at least as good as the performance of composition B, with composition A as a reference.
Soil relea6e polymer6 can al60 be incorporated in the compo~ition6 herein. Suitable 6pecie6 of 6uch release polymers are described in Canadian Patent Application Serial Number 498,176, filed December 16, 1985.
The pha6e regulant i6 a further optional ingredient in the compo~ition6 herein. Thi6 component together with water can con6titute the 601vent matrix for the claimed concentrated liquid compo6ition6. Suitable ingredient cla6ses include lower aliphatic alcohol6 having from 2 to 6 carbon atom6 and from 1 to 3 hydroxyl group6, ether6 of diethyleneglycol and lower aliphatic monoalcohol6 having from 1 to 4 carbon atom6. Specific example6 of phase regulant6 are: ethanol; n-propanol; i60propanol; butanol;
1,2-propanediol; 1,3-propanediol; monomethyl-, ethyl-, propyl-, and monobutyl ethers of di-ethylene glycol.
The claimed invention i6 illu6trated and clarified with the aid of the following example6.
Concentrated liquid detergent composition6 are prepared by mixing the individual ingredient6 li6ted hereinafter in the stated proportion6.
Inqredient6 Comp.A Comp.B Ex.l Ex.2 Dodecylbenzene 6ulfonic acid10.3 10.3 Ethoxylated C13_15 alcohol con-den6ed with 7 moles of ethylene oxide per mole of fatty alcohol 11.6 11.6 11.6 11.6 C13_14 linear ortho xylene 6ul-fonic acid (1) - - 11.8 Di-i60decyl 6ulfo6uccinate Na 6alt * (2) - - - 12.0 Topped Whole Cut fatty acid ** 10.7 - - -2-Dodecenyl 6uccinate - 15.0 15.0 15.0 Citric acid 0.9 0-9 0-9 0-9 Oleic acid 3.9 3.9 3.9 3.9 Diethylenetriamine pentame-thylene pho6phonic acid 0.85 0.85 0.8 0.8 Triethanolamine 5.0 5.0 6.3 6.3 Coconut alkyl 6ulfate TEA 6alt 3.9 3.9 3.9 3.9 Soil relea6e polymer *** - 0.5 Ethanol 6.2 9.0 9.0 9.0 1,2-Propanediol 1.5 Formate (Na) 1.0 1.0 1.0 1.0 Enzymes 0.43 0.69 0.15 0.15 Water, NaOH CaC12 and minor6balance to 100 pH 7.7 7.6 7.6 7.6 (1) cmc t~urface ten6ion-log concentration plot method) =
4.7 10-4 mole/l (2) cmc (6urface tension-log concentration plot method) =
1.9 10-4 mole/l 70% by weight 601ution in propylene glycol ~* Fatty acid chain di6tribution:50t lauric, 20%
myri6tic, 15% palmitic, 10% oleic, 2% 6tearic *~ Prepared by e6terifying 1,4 phtalic acid (chloride) with 1,2-propane diol and ethoxylating the polymer with ethylene oxide. The re6ulting polymer mix i5 fractionated in cold (15C) ethanol to provide a cold-ethanol 601uble fraction with an average ethoxylation value in the range from lZ-43.
The above compo6ition6 were u6ed for comparative laundry te6t6. A MIELE W423 washing machine wa6 used thereby 6electing a main-wa6h 6tep.
Cotton and polye6ter/cotton (polycotton) 6trip6 6tained a6 indicated below were u6ed to mea6ure the comparative performance. Additional te6ting parameter6 were, temperature 60C, product u6age 180 g/18 1. of city water having an average water hardne66 of about 3 mmole6/l.;
laundering treatment in pre6ence of 3 kg6 60iled clothes (no-pretreatment on te6t 6trip6); 6tain6 : grea6y type, i.e., ma~e-up, lip6tick, and dirty motor oil (DM0).
After having been 6ubjected to the above washing treatment the dried 6tained cotton 6trips were vi6ually graded by two expert judge6 thereby using a 0-4 6cale whereby:
0 = 6ee no difference between the 6watche6 1 = believe there i6 a difference between the 6watches 2 = there i6 a difference between the 6watche6 3 = am 6ure there i6 a difference between the 6watches 4 = very important differeVnce between the ~watches.
The 6tain removal reading6 were pooled and averaged on 8 replicate6 with the following re6ult6. The 6watches treated with prior art compo6ition A were u6ed for reference purpo~es:
Type of Comp.B v6.Comp.A Ex.l vs.Comp.A Ex.2 V6.Comp.A
6tains Cotton/Poly- Cotton/Poly- Cotton/Poly-cotton cotton cotton GREASY -1.1*/-1.0* +0.8*/+0.7* +0.1/+1.0*
. Makeup -2.4*/-2.6* +1.8*/+1.4* +0.9/+1.2*
. Lipstick -2.3*/-2.1* +0.2/-0.2 -O.l/+l.O*
. DMO -1.5*/+0.8* -0.3/+0.8* -1.5*/+1.0*
* Readings stati6tically significant at 95% confidence limit.
The above data shows significant performance superiority on greasy stain6 of the composition6 of Examples 1 and 2 in accordance with this invention V6. a commercial heavy duty liquid, termed compo6ition A. The performance superiority is equally applicable V6. a 6uccinate containing liquid detergent, termed composition B.
On other types of 6tains (bleachable, enzymatic, particulate) the performance of the composition6 of Examples 1 and 2 i6 at least as good as the performance of composition B, with composition A as a reference.
Claims (8)
1. A homogeneous concentrated aqueous liquid detergent composition containing less than 50% by weight of water, and from 12% to 50% by weight of the composition of a binary anionic surfactant system represented by a mixture of (1) an alk(en)yl succinate having the formula wherein R1 is an alk(en)yl radical, having from 10 to 20 C-atoms, and R2 is hydrogen or C1-C4 alkyl; and (2) a sulfonated surface-active agent having a critical micelle concentration in the range of from 10-3 to 10-5 mole/l;
the weight ratio of sulfonate to succinate being in the range from 2:1 to 1:4.
the weight ratio of sulfonate to succinate being in the range from 2:1 to 1:4.
2. The composition in accordance with Claim 1 wherein the sulfonated surface-active agent is selected from linear alkyl xylene sulfonates containing from 13 to 17 carbon atoms in the alkyl group, linear alkyl toluene sulfonates containing from 13 to 17 carbon atoms in the alkyl group, and dialkyl sulfosuccinates having from 9 to 12 carbon atoms in each alkyl group, and mixtures thereof.
3. The composition in accordance with Claim 2 wherein the sulfonated surface-active agent is selected from C13-15 linear ortho xylene sulfonates and di-C10 alkyl sulfosuccinates.
4. The composition in accordance with Claim 1 wherein the binary anionic surfactant system represents from 15% to 35% by weight of the total composition.
5. The composition in accordance with Claim 1 which in addition contains from 3% to 35% by weight of a nonionic surfactant.
6. The composition in accordance with Claim 1 which in addition contains from 1% to 8% by weight of a fatty acid having from 10 to 18 carbon atoms in the alkyl chain.
7. The composition in accordance with Claim 1 wherein the alkenyl succinate has from 12 to 16 carbon atoms in the alkenyl moiety and R2 is hydrogen.
8. The composition in accordance with Claim 6 wherein the fatty acid is represented by oleic acid.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB858528521A GB8528521D0 (en) | 1985-11-20 | 1985-11-20 | Liquid detergent compositions |
| GB8528521 | 1985-11-20 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1334571C true CA1334571C (en) | 1995-02-28 |
Family
ID=10588475
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000523227A Expired - Fee Related CA1334571C (en) | 1985-11-20 | 1986-11-18 | Liquid detergent compositions containing binary anionic surfactant system |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP0223306B1 (en) |
| JP (1) | JPH0739591B2 (en) |
| AT (1) | ATE74377T1 (en) |
| CA (1) | CA1334571C (en) |
| DE (1) | DE3684668D1 (en) |
| GB (1) | GB8528521D0 (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2245000B (en) * | 1987-09-17 | 1992-06-03 | Colgate Palmolive Co | Liquid detergent composition |
| JPH01287017A (en) * | 1988-05-11 | 1989-11-17 | Kao Corp | Low-irritant washing agent composition |
| JPH02113100A (en) * | 1988-10-21 | 1990-04-25 | Kao Corp | Liquid detergent composition |
| EP0430330A3 (en) * | 1989-11-24 | 1991-12-18 | The Procter & Gamble Company | Suspending liquid detergent compositions |
| JPH04189637A (en) * | 1990-06-19 | 1992-07-08 | Teikoku Kuromu Kk | Load tightening belt for truck |
| FR2780732B1 (en) * | 1998-07-06 | 2000-09-08 | Ceca Sa | NON-FOAMING DETERGENT COMPOSITIONS FOR CONCENTRATED ALKALINE MEDIA |
| JP7124658B2 (en) * | 2018-11-15 | 2022-08-24 | 日油株式会社 | Detergent composition for poorly water-soluble substances |
| TW202233818A (en) | 2020-12-25 | 2022-09-01 | 日商花王股份有限公司 | Method for treating textile product |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2642400A (en) * | 1950-05-10 | 1953-06-16 | Monsanto Chemicals | Surface-active composition |
| US3579453A (en) * | 1968-11-12 | 1971-05-18 | Rohm & Haas | Alkali-soluble surfactant consisting of substituted succinic acid-nonionic ethoxylate blends |
| NZ206209A (en) * | 1982-11-16 | 1986-01-24 | Unilever Plc | Foaming liquid detergents containing sulphosuccinic acid esters and polyethoxy sulphates |
| NZ206212A (en) * | 1982-11-16 | 1986-04-11 | Unilever Plc | Foaming liquid detergent compositions containing sulphosuccinic acid esters and alkyl ether sulphates |
-
1985
- 1985-11-20 GB GB858528521A patent/GB8528521D0/en active Pending
-
1986
- 1986-11-14 EP EP86202001A patent/EP0223306B1/en not_active Expired - Lifetime
- 1986-11-14 AT AT86202001T patent/ATE74377T1/en active
- 1986-11-14 DE DE8686202001T patent/DE3684668D1/en not_active Expired - Fee Related
- 1986-11-18 CA CA000523227A patent/CA1334571C/en not_active Expired - Fee Related
- 1986-11-20 JP JP61277776A patent/JPH0739591B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| EP0223306A3 (en) | 1989-05-03 |
| JPH0739591B2 (en) | 1995-05-01 |
| JPS62195096A (en) | 1987-08-27 |
| ATE74377T1 (en) | 1992-04-15 |
| EP0223306A2 (en) | 1987-05-27 |
| EP0223306B1 (en) | 1992-04-01 |
| DE3684668D1 (en) | 1992-05-07 |
| GB8528521D0 (en) | 1985-12-24 |
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