CA1087062A - Liquid detergent compositions - Google Patents
Liquid detergent compositionsInfo
- Publication number
- CA1087062A CA1087062A CA258,964A CA258964A CA1087062A CA 1087062 A CA1087062 A CA 1087062A CA 258964 A CA258964 A CA 258964A CA 1087062 A CA1087062 A CA 1087062A
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- Prior art keywords
- soap
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- accordance
- alcohol
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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
- C11D10/00—Compositions of detergents, not provided for by one single preceding group
- C11D10/04—Compositions of detergents, not provided for by one single preceding group based on mixtures of surface-active non-soap compounds and soap
-
- 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
- C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic compounds
-
- 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
- C11D1/66—Non-ionic compounds
- C11D1/72—Ethers of polyoxyalkylene glycols
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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
ABSTRACT OF THE DISCLOSURE
Heavy duty liquid detergent compositions containing a mixture of particular nonionic surfactants and anionic surfactants in specific ratios and particular soaps are formulated into highly concentrated, stable liquid detergents having excellent pretreatment performance sudsing characteristics and reduced gel formation upon exposure to air.
Heavy duty liquid detergent compositions containing a mixture of particular nonionic surfactants and anionic surfactants in specific ratios and particular soaps are formulated into highly concentrated, stable liquid detergents having excellent pretreatment performance sudsing characteristics and reduced gel formation upon exposure to air.
Description
1~387~16Z
~AC~GROUND OF THE INVENTIO~
The present invention relates to concentrated heavy duty liquid detergent compositions. Such compositions contain a nonionic surfactant component, an anionic surfactant component, and a soap.
Heavy duty liquid detergent compositions are well known in the art. Usually such compositions (see, for example, U.S. Patent 2,908,651; 2,920,045; 3,272,753; 3,393,154; and Belgian Patents 613,165 and 665,532) contain a synthetic organic detergent component which is generally anionic, ;~
nonionic, or mixed anionic-nonionic in nature; an inorganic builder salt; and a solvent, usually water and/or alcohol.
The compositions frequently contain a hydrotrope or solubilizing agent to permit the addition of sufficient quantities oE
surfactant and builder salt to provide a reasonable volume usage/perEormance ratio. While such liquid detergent compositions have been found effective for some types of home laundering, the presence of inorganic builder salts in such compositions may be undesirable from an ecological standpoint 20 in improperly treated sewage.
Several attempts have been made to ormulate essentially builder- Eree, hydrotrope-free liquid de tergent compositions.
For example, U.S. Patent 3,528,925 disaloses substantiall~
anhydrous liquid detergent compositions which consist of an alkyl aryl sulEonic acid, a nonionic surface active agent and an alkanolamine component. U.S. Patent 2,875,153 discloses liquid detergent compositions containing a nonionic surfactant component and a sodium soap component. U.S~ Patent 2,543,744 discloses a low-foaming dishwashing composition comprising 30 a nonionic, water-soluble, synthetic detergent and a water~
b,~ "
, :
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soluhle soap in t~e form of an alkali metal, ammonium or amîne salt. All of these detergent compositions are ;
effective for certain types o~ washing operations, but none of the commercially available compositions of this kind are highly effective both as pretreatment and heavy duty washing agents for cleaning ~oth natural and synthetic fabrics.
U.S. Patent 3,663,445 relates to liquid cleaning and defatting compositions containing a nonionic surfactant, an alkanolamine-neutralized anionic surfactant and alkanolamine. ~;
Belgian Patent 794,713, granted July 30, 1973, entitled LIQUI-D DETERGENT COMPOSITIONS, relates to detergent mixtures comprisîng a high ratio of nonionic to anionic surfactant and free alkanolamine. Belgian Patent 817,267, granted January 6, 1975 and entitled LIQUID DETERGENT COMPOSITIONS, relates to specific nonionic detergents in formulas of the type disclosed in Belgian Patent 7~4,713.
U.S. Patents 3,709,838; 3,697,451; 3,554,916; 3,239,468;
~AC~GROUND OF THE INVENTIO~
The present invention relates to concentrated heavy duty liquid detergent compositions. Such compositions contain a nonionic surfactant component, an anionic surfactant component, and a soap.
Heavy duty liquid detergent compositions are well known in the art. Usually such compositions (see, for example, U.S. Patent 2,908,651; 2,920,045; 3,272,753; 3,393,154; and Belgian Patents 613,165 and 665,532) contain a synthetic organic detergent component which is generally anionic, ;~
nonionic, or mixed anionic-nonionic in nature; an inorganic builder salt; and a solvent, usually water and/or alcohol.
The compositions frequently contain a hydrotrope or solubilizing agent to permit the addition of sufficient quantities oE
surfactant and builder salt to provide a reasonable volume usage/perEormance ratio. While such liquid detergent compositions have been found effective for some types of home laundering, the presence of inorganic builder salts in such compositions may be undesirable from an ecological standpoint 20 in improperly treated sewage.
Several attempts have been made to ormulate essentially builder- Eree, hydrotrope-free liquid de tergent compositions.
For example, U.S. Patent 3,528,925 disaloses substantiall~
anhydrous liquid detergent compositions which consist of an alkyl aryl sulEonic acid, a nonionic surface active agent and an alkanolamine component. U.S. Patent 2,875,153 discloses liquid detergent compositions containing a nonionic surfactant component and a sodium soap component. U.S~ Patent 2,543,744 discloses a low-foaming dishwashing composition comprising 30 a nonionic, water-soluble, synthetic detergent and a water~
b,~ "
, :
1087~Z
soluhle soap in t~e form of an alkali metal, ammonium or amîne salt. All of these detergent compositions are ;
effective for certain types o~ washing operations, but none of the commercially available compositions of this kind are highly effective both as pretreatment and heavy duty washing agents for cleaning ~oth natural and synthetic fabrics.
U.S. Patent 3,663,445 relates to liquid cleaning and defatting compositions containing a nonionic surfactant, an alkanolamine-neutralized anionic surfactant and alkanolamine. ~;
Belgian Patent 794,713, granted July 30, 1973, entitled LIQUI-D DETERGENT COMPOSITIONS, relates to detergent mixtures comprisîng a high ratio of nonionic to anionic surfactant and free alkanolamine. Belgian Patent 817,267, granted January 6, 1975 and entitled LIQUID DETERGENT COMPOSITIONS, relates to specific nonionic detergents in formulas of the type disclosed in Belgian Patent 7~4,713.
U.S. Patents 3,709,838; 3,697,451; 3,554,916; 3,239,468;
2,947,702; 2,551,634; British Patents 900,000; 842,813;
759,877; and Canadian Patent 615,583 disclose a variety of detergent compositions containing mixed nonionic-anionic surfactants, both with and without alkanolamines.
As can be seen Erom the. Eoregoin~, a substantial eEfort has been expended in developing low-built anA builder-Eree detergent compositions in li~uid Eorm. Yet, there are several problems associated with the art-disclosed compositions which render them less than optimal for wide-scale use.
~ irst, man~ of the prior art compositions are Eormulated at either too high or too low a ratio of nonionic:anionic surfactant to permit the formulation of stable highly concentrated detergent compositions.
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Second, many of th.e prior art compositions are formulated to provïde satisfactory through-the-wash fabric cleaning perormance, ~ut do not provide optimal pre-wash treatment o~ greasv stains and oily soil found in collars .
and cuffs of fabrics. Most users of liquid laundr~ detergent compositions expect t~.at superior fa~ric cleansing can be secured by applying the liquid product directly, at full :
strength, to heavily soiled areas of the fabric prior to laundering. Accordingly, it is desira~le to provide a liquid `.
detergent having optimal pre-treatment cleaning benefits as well as optimal through-the-wash. cleaning performance.
Finally,.t~e prior art ~see U.S. Patent 3,663,445 discloses that surfactant compositions containing high concentrations of ethylene oxide-~ased nonionic surfactants and alkanolamines must contain fatty acid salts to provide the desired product stability and/or performance characteristics.
However, this art does not teach the preferred ingredients and ratios required for the stable, concentrated, low sudsing compositions of this invention.
It has now ~een found that certain ethylene oxide-based nonionic surfactants can be used at high concentrations in liquid detergent compositions, in combination with certain anionic surfactant mixtures to give stable compositions with acceptable .low-suds.in~ charac-terlstics.
It is an o~ject of this inv2ntion to provide liquid detergent compositions which provide both good pre-wash and through-the-wash fabric cleansing.
These and other objects are obtained herein, as will be seen rom the following disclosure.
759,877; and Canadian Patent 615,583 disclose a variety of detergent compositions containing mixed nonionic-anionic surfactants, both with and without alkanolamines.
As can be seen Erom the. Eoregoin~, a substantial eEfort has been expended in developing low-built anA builder-Eree detergent compositions in li~uid Eorm. Yet, there are several problems associated with the art-disclosed compositions which render them less than optimal for wide-scale use.
~ irst, man~ of the prior art compositions are Eormulated at either too high or too low a ratio of nonionic:anionic surfactant to permit the formulation of stable highly concentrated detergent compositions.
~8706~
Second, many of th.e prior art compositions are formulated to provïde satisfactory through-the-wash fabric cleaning perormance, ~ut do not provide optimal pre-wash treatment o~ greasv stains and oily soil found in collars .
and cuffs of fabrics. Most users of liquid laundr~ detergent compositions expect t~.at superior fa~ric cleansing can be secured by applying the liquid product directly, at full :
strength, to heavily soiled areas of the fabric prior to laundering. Accordingly, it is desira~le to provide a liquid `.
detergent having optimal pre-treatment cleaning benefits as well as optimal through-the-wash. cleaning performance.
Finally,.t~e prior art ~see U.S. Patent 3,663,445 discloses that surfactant compositions containing high concentrations of ethylene oxide-~ased nonionic surfactants and alkanolamines must contain fatty acid salts to provide the desired product stability and/or performance characteristics.
However, this art does not teach the preferred ingredients and ratios required for the stable, concentrated, low sudsing compositions of this invention.
It has now ~een found that certain ethylene oxide-based nonionic surfactants can be used at high concentrations in liquid detergent compositions, in combination with certain anionic surfactant mixtures to give stable compositions with acceptable .low-suds.in~ charac-terlstics.
It is an o~ject of this inv2ntion to provide liquid detergent compositions which provide both good pre-wash and through-the-wash fabric cleansing.
These and other objects are obtained herein, as will be seen rom the following disclosure.
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1~7~ ~ `
The present invention provides liquid detergent compositions comprising: (:a~ from about 28% to about 44%
by weight of a nonionic surfac-tant produced by the condensation .
of from a~out 4 to about 11 moles of ethylene oxide with one mole of a C13 to C16 alcohol; ~1 an anionic surfactant mixture present in a quantity sufficient to provide a weight ratio of nonionic surfactant to the anionic surfactant mixture in its ~ -free ac;d form of from a~out 1:1 to about 2.3:1 (preferably from a~out 1.3:1 to about 2:1); said anionic surfactant mixture consisting o ~i) an alkyl benzene sulfonate having from about 9 to about 15 carbon atoms in the alkyl chain; and (ii) from :
about 0.2~ to about 5% ~y weight, and preferably from 1.5% to 5%, of a saturated fatty acid soap containing from about 16 to about 24 car~on atoms in the fatty acid moiety of said soap; the cations of the sulfonate and soap being selected from the group consisting of mono-ethanolamine, triethanolamine, potassium, and sodium cations and mixtures thereof, and said anionic surfactant mixture containing sulfonate and soap in quantities sufficient to provide a weight ratio of the acid form of the sulfonate to the acid form of the soap of from about 3:1 to a~out 80:1, preferably from 4:1 to 70:1.
In other execution oE this invention the weight rat.io o:E the acid form of the sulfonate to the acid form of the soap is from 3:1 to 10:1, preferably from 4:1 to 8:1.
DESCRIPTION OF THE INvENrrIoN
The individual components of the instant detergent compositions are described in detail belo~.
1~7~ ~ `
The present invention provides liquid detergent compositions comprising: (:a~ from about 28% to about 44%
by weight of a nonionic surfac-tant produced by the condensation .
of from a~out 4 to about 11 moles of ethylene oxide with one mole of a C13 to C16 alcohol; ~1 an anionic surfactant mixture present in a quantity sufficient to provide a weight ratio of nonionic surfactant to the anionic surfactant mixture in its ~ -free ac;d form of from a~out 1:1 to about 2.3:1 (preferably from a~out 1.3:1 to about 2:1); said anionic surfactant mixture consisting o ~i) an alkyl benzene sulfonate having from about 9 to about 15 carbon atoms in the alkyl chain; and (ii) from :
about 0.2~ to about 5% ~y weight, and preferably from 1.5% to 5%, of a saturated fatty acid soap containing from about 16 to about 24 car~on atoms in the fatty acid moiety of said soap; the cations of the sulfonate and soap being selected from the group consisting of mono-ethanolamine, triethanolamine, potassium, and sodium cations and mixtures thereof, and said anionic surfactant mixture containing sulfonate and soap in quantities sufficient to provide a weight ratio of the acid form of the sulfonate to the acid form of the soap of from about 3:1 to a~out 80:1, preferably from 4:1 to 70:1.
In other execution oE this invention the weight rat.io o:E the acid form of the sulfonate to the acid form of the soap is from 3:1 to 10:1, preferably from 4:1 to 8:1.
DESCRIPTION OF THE INvENrrIoN
The individual components of the instant detergent compositions are described in detail belo~.
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~4~871[)62 ~:
;':
The Nonionic Surfactant T~e instant compositions contain as an essential ~
ingredient about 28% to about 44~, preferably from a~out ~`
35~ to a~out 40%, ~y weight of a nonionic surfactarit derived by the condensation of ethylene oxide with an alcohol havîng a carbon content of from C13 to about C16. Ethylene oxide condensates having more than about 16 carbon atoms in the alkyl chain of the alcohol portion of the molecule are not suitable for t~e purposes of this invention. As noted hereinabove, alcohols having a hydrocarbon content C13 and ;~
greater are preferred from the standpoint of cleaning and sudsing characteristics.
The nonionic surfactants employed herein contain fromabout 4 ~avg.~ moles of ethylene oxide to about 11 (avg.) moles of et~ylene oxide per mole of alcohol in the condensate.
However, it is not always sufficient to describe the nonionic surfactants merely in terms of their alkyl carbon content and ethylene oxide content. The preferred nonionic surfactants ~;
are those descri~ed in Belgian Patent 817,267, i.e., those having an HLB of from about 10 to about 14, preferably from about 11 to about 13.
The individual nonionic surEactants employ~d in the compositions herein are commonly thought o~ as an constituting a hydrocarbyl chain (derived from the alcohol) condensed with an alkylene oxide chain. The hydrocarbyl portion of such materials y.ives rise to their lipophilic characteristics, whereas the ethylene oxide portion determines their hydrophilic characteristics. The overall hydrophilic-lipoPhilic characteristics of a given hydrocarbyl-ethylene oxide condensate " ' _5_ ~ , : . ,, , , . .,, . .. , . .. , . , ~
~8~;2 are reflected in the ~alance of these two factors, i.e., the hydrophilic-lipophilic balance ~HLB~. The H~B of the ethoxylated nonionics herein can be experimentally determined in well-known fashion, or can ~e calculated in the manner set forth in Decker, "Emulsions Theory and Practice" Reinhold 1965, pp. 233 and 248.
Accordingly, the preferred nonionic materials herein can be descri~ed as condensates of an alcohol having a carbon content of from Cl3 to about C16 condensed with from about 4 ~avg.) moles to about ll (avg.) moles of ethylene oxide per mole of alcohol, and further characterized by an HLB
within the range of from about lO to about 14, preferably from about ll to about 13. Nonionic surfactants falling within these ranges are highly preferred herein from the standpoint of optimal pre-treatment cleansing, optimal through-the-wash cleansing, sudsing characteristics and product stability.
EIighly preferred nonionic surfactants for use herein are alcohol ethylene oxide condensates wherein the alcohol contains from 14 to 15 carbon atoms and wherein the condensate contaîns from 6 to 9 moles of ethylene oxide (hydrophilic) per mole o alcohol ~lipophilic~. ~uch materlals are commonly abbreviated as Cl~ l5EO6 9 The nonionic sur~actant~ cmployecl in the pxesent compositions can be prepared by a variety of methods well known in the art. In general terms, such nonionic surfactants are prepared by condensing ethylene oxide with an alcohol under conditions of acidic or basic catalysis.
The nonionic surfactants herein include the ethylene 3a oxïde condensates of both primary and secondary alcohols;
the condensates of primary alcohols are preferred. Non-limiting, , . ~ . .
~7~6Z :
specific examples of nonionic surfactants having the requisite car~on content of the hydrocarbyl portion of the molecule, the requisite ethylene oxide content and the requisite HLB are as ~ollows:
n-C13H27~E~4; n~C13H27(EO~5; n C14H29( ~5 1~ 29 6 14 29 ~7; C14H29~E]lo; n~ClsH31(EO)6; n-Cl H (EO) ;
2-C H l(EO~7; n~C15~I31(EO~8; 2 C15H31~ 8 15 31 2-C H31~E~g; n-C16H33(EO~g; and 2 C16H33( ~9 It îs to ~e recognized that mixtures of the foregoing nonionic surfactants are also useful herein and are readily available from commercial alcohol mixtures. Moreover, the degree of ethoxylation can vary somewhat, inasmuch as average fractional degrees of ethoxylation occur. For example, n-C15~31(EO)7 can contain small quantities o n-C15H31(EO)O
and n-ClsH31(E~14 Such commercial mixtures ~alling within the limits disclosed herein are useful in the present detergent compositions.
The preferred nonionic surfactants are the C14 15(EO)6 9 materials disclosed hereinabove and are commercially available as mixtures under the trademarks "Dobanol 45-7" and "Dobanol 45-9" from the Shell Chemical Co. "Dobanol 45-7" is a Vi9 COUS
liquid at ambient temperatures and is preferred herein.
"Dobanol 45-9" is a solid at room temperature, but is useful in the liquid detergent compositions of this invention inasmuch as it readily dissolves therein.
The presence of the nonionic surfactant in the instant liquid detergent compositions in the essential specified concentrations and proportions provides the necessary oily stain removal in ~oth pre-treatment application and through-3a the-wash utilization o~ the instant invention. The selected nonionic surfactants herein also contribute to the sudsing ~`
_7-~087062 ~
characteristics and p~ys~cal sta~ility of the liquid detergent compos;t;ons.
T~e mixture of anionic surfactant salts is employed hereIn in a quantity suf~icient to provide a weighk ratio ;~
of nonionic surfactant to anionic surfactant mixture of from about 1:1 to a~out 2.3:1, prefera~ly from a~out 1.3:1 to 2:1 based on the free acid from of the anionic surfactants.
The non-soap component of the anionic surfactant mixture consists of a mono- or tri-ethanolaminer potassium, sodium salt or mixtures of such salts of a straight or branched chain alkyl ~enzene sulfonic acid in which the alkyl group contains from about ~ to about 15 carbon atoms. Preferred surfactants of this type are those in which the alkyl chain is linear and averages about 12 carbon atom.s in length. Examples of alkyl benzene sulfonates useful in the instant invention include mono-et~anolamine decyl benzene sulfonate, sodium undecyl benzene sulfonate, triethanolamine dodecyl benzene sulfonate, monoethanolamine tridecyl benzene sulfonate, triethanolarnine tridecyl benzene sulfonate, triethanolamine tetradecyl benzene sulfonate and potassium tetrapropylene ;~
benzene sulfonate. Examples of commercially available alkyl benzene sulfonic acids useful in preparing the sulfonates of the instant invention include "Conoco"* S~ 515, SA 597 and SA 697 all marketed by th~ Continental Oil Company and "Calsoft LAS 99"** marketed by the Pilot Chemical Company.
The soap component of the anionic surfactant mixture consists of mono- or triethanolamine or potassium or sodium soaps of saturated fatty acids containing from about 16 to about 24 carbon atoms and preferably from about 18 to about 24 carbon atoms. Suitable fatty acids can be obtained from *Trademark **Trademark ....~
~L~I 370GZ
natural sources such as, for example, plant or animal esters (:e.g., palm oil, coconut oil, babassu oil, saf10wer oil, tall oil, castor oil, tallow, whale and fish oils, grease, lard, and mixtures thereof~. The fatty acids also can ~e sYnthetically prepared ~e.g., by the oxidation of petroleum or hy ~ydrogenation of carbon monoxide via the Fischer-Tropsch process~. Examples of suitable soaps for use in the instant invention include monoethanolamine eicosinate, sodium palmitate, triethanolamine myristate, triethanolamine palmitate, monoethanolamine stearate and potassium behenate.
Preferred soaps include the mono- or triethanolamine or potassium or sodium soaps of mixtures o fatty acids derived from hydrogenated tallow, hydrogenated rapeseed oil or hydrogenated fish oil. A highly preferred soap for use in the instant invention is the triethanolamine soap of "Hyfac"*, a hydrogenated fish oil fatty acid marketed by Emery Industries, Inc.
Within the anionic surfactant mixture, the two components thereof are present in quantities sufficient to provide a weight ratio of the acid form of the sulfonate (an alkyl benzene sulfonic acid) to the acid form o the soap (a fatty acid) of from a~out 3:1 to about 80:1, preferably rom about `
4:1 to 70:1. :~n another execut.ion oE this :Lnventioll the weight ratio o the acid form of the sulfonate in the acid orm of the soap is from 3:1 to 10:1, preferably from 4:1 to 8:1. If the fatty ac~d is a hydrogenated fish oil having from 18 to 24 carbon atoms, the acid sulfonate to fatty ~ ;
acid weight ratio is most preferably in the range from 30:1 to 70:1. These ratios provide acceptable low sudsing characteristics.
*Trademark _g_ 1~870~
Alkanolamine An optional component of the liquid detergent composition of the present invention is an alkanolamine compound. The alkanolamine useful herein is selected from ' the group consisting of monoethanolamine, triethanolamine, and mixtures thereof. Mixtures of these alkanolamine compounds are produced ~y the reaction o~ ethylene oxide with ammonia. -The pure compounds can be separated from this mixture by standard distillation procedures.
. ~ .
10- The alkanolamine component of the present invention, if present, serves up to three purposes. As will be discussed more fully hereinafter, in one method for preparing the instant compositions t~e alkanolamine neutralizes the free acid form of the anionic surfactant to provide the corresponding alkanolamine salt. In addition, the excess alkanolamine beyond that necessary to form the anionic surfactant salt contributes to the stability of the highly concentrated composition, to detergency performance and buffers the pH
of the washing liquors within the range from about 7 to about 9. It is preferred that the compositions of this invention contain at least 0.5% by weight of the total composition o~
free alkanolamine, i.e., an excess over that needed to neutralize the anionic sur~actant mixture.
Stable liquid detergent compositions containing nonionic, anionic and soap components can be formulated by prepar:Lng each component separately and thoroughly mixing them together in any order. In one method for preparing the instant compositions, the anionic and optional alkanolamine components are formulated sîmultaneously by over-neutralizing the alkyl benzene sulfonic acid and fatty acid with alkanolamine.
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This method forms the requisite alkanolamine alkyl benzene sulfonate and soap and provides the free alkanolamine component of the instant composition. Preferably, the compositïons contain from 0.5~ to about 4% by weight of free alkanolamine, most prefera~ly triethanolamine.
The Solvent The liquid detergent compositions of the instant invention contain a solvent which is a water-alcohol mixture.
Such a solvent can ~e employed to the extent of from about 20~ to 45% by weight of the total detergent composition.
In preferred compositions, the solvent comprises from about 30% to 40% by welght of the total composition. Use of such a solvent in the compositions herein has several advantages.
First, the physical stability of the detergent compositions can be improved by dilution with such solvents in that clear points can thereby be lowered. The diluted compositions do not cloud at the low temperatures which are commonly encountered during shipping or storing of commercially marketed detergent compositions.
Secondly, addition of the water-alcohol mixture serves to regulate the gelling tendency which li~uid deter~ent compo~ltlons oE ~he InstAnt kypc exh~blt upon dilution with water.
The weight ratio o~ water to alcohol preferably is maintalned above about 1.1. High alcohol (particularly ethanoll concentrations in the water-alcohol mixtures used in the instant invention are ~re~erably avoided because of flammability pro~lems which may arise at such higher alcohol levels.
1al87~62 Any alcohol containing ~rom 1 to about 5 carbon atoms can ~e employed in the water-alcohol diluent used to prepare the instant detergent composi`tions. Examples of operable alco~ols include methanol, ethanol, propanol, is~propanol, butanol, isobutanol, and pentanol; ethanol is highly ;
preferred for general use.
Optional Components An optional component which can be added to the detergent comPositions of the instant invention is an electrolyte. As pointed out in U.S. Patents 2,580,173 and 3,440,171, electrolytes lessen the gel formation which tends to occur with alkanolamine-neutralized surfactants. Such electrolytes, when used herein in combinakion with a water-alcohol solvent at a weight percent o~ the total composition o~ from about 0.5~ to 5%, prePerably from about 1% to about 3%, of said electrolyte, completely eliminate gelation of the anionic surfactant without the need for excessively high alcohol levels.
Other optional components include brighteners, fluorescers, enzymes1 bleaching agents, anti-microbial agents, corrosion inhibitors, perfumes and coloring agents. Such components preferably comprise no more than about 3~ by weight of the total composition.
Utilization of nonionic surfactant to anionic surfactant (~ree acid basis) ratios of from about 1:1 to about 2.3:1 in combination with utilization of higher saturated soaps is critical to formation of detergent compositions having the unexpected performance and stability characteristics of the instant invention. Higher ratios do not provide the maximum stability in such concentrated formulas and lower or unsaturated - :. . .. .
~08t7~6Z :
fatty acids do not keep the suds down.
Employment of alkanolamine salts and excess alkanolamine also contribute to the effectiveness of the instant detergent compositionsO
The compositions of the înstant invention are ~.
specifically designed to prov;de optlmum cleaning benefits when used in either of the two modes commonly employed with lîqu;d detergent compositions. First, the compositions herein ~
can ~e used as pre-treatment agents which are applied in :
concentrated form directly onto fabric stains prior to fabric washing. Second, th.e instant compositions are also useful as detergents for conventional through-the-wash fabric laundering operations. For through-the-wash fabric laundering, a concentration of the instant compositions in the range o~
from 0.2% to about 0.6%, preferably from about 0.3~ to about ;~
0.5~ by weight of the laundering liquor is preferred. OE ' course, this can be adjusted, depending on the soil load and the desires of the user.
With regard to pre-treatment efficacy, the instant compositions containing the herein specified compon~n~s and component ratios provide oily stain removal ~rom polyamide, polyester or polyester/cotton ~abrics which is superio.r to sim.i~ar p.re-tr~atment pa.r:Eormance atta.ined ~ uti~.ization of conventional built anionic detergent compositions and which is, in fact, comparable in oily stain removal with that attained with pure nonionic surfactants which are known to be particularly useful in such pre-treatment stain removal.
Through-the-wash detergency performance of the instant compositions is, in fact, comparable with that attained with conventional built granular anionic detergent .
compositions.
: -13 : :
~L~87~)62 The ~ollowing examples illustrate the liquid detergent , compositions of t~e instant invention, The abbreviations for the nonionic surfactants emplo~ed, e.g., C14(EO)6, are standard for such materials and describe the carbon content of the alcoholic lipophilic portion of the molecule and the ethylene oxide content of the hydrophilic portion of the molecule.
~87~;2 ~ ~
EXAMPI~S I - IV
Component I II III IV
C14 15 synthetic alcohol polyethoxylate (7) 38 35 - - ;
("Dobanol 45-7"1 C14 15 synthetic alcohol polyethoxylate ~4~ 33 ("Dobanol 45-4"1 C14 15 synthetic alcohol polyethoxylate ~9) - - 40 - .`
("iDobanol 45-9")3 Cll 12 linear alkyl ~enzene sulfonic acid 19 23 17 18 :
Long chain C12_22 fatty acids 2.8 3.5 - 3 .
("Hyfac"4 fatty acids) Tallow fatty acids - - 4.5 _ -;~ . r:
Triethanolamine 6.9 - 11 12 Monoethanolamine - 4.0 KOH 1.5 1.5 Ethanol 8.0 8.0 10 15 Potassium acetate - - 2 - '~
"Brightener DMSX" ~Di~a-Geigy) _______--0.23--------Water ~ miscellaneous --------balance------ :~
Nonionic/anionic 1.74 1.32 1.86 1.57 Sul~onic acid/atty acid 6.78 6.57 3.77 6 1. Trademark 2. Trademark 3. Trademark 4. Trademark
~4~871[)62 ~:
;':
The Nonionic Surfactant T~e instant compositions contain as an essential ~
ingredient about 28% to about 44~, preferably from a~out ~`
35~ to a~out 40%, ~y weight of a nonionic surfactarit derived by the condensation of ethylene oxide with an alcohol havîng a carbon content of from C13 to about C16. Ethylene oxide condensates having more than about 16 carbon atoms in the alkyl chain of the alcohol portion of the molecule are not suitable for t~e purposes of this invention. As noted hereinabove, alcohols having a hydrocarbon content C13 and ;~
greater are preferred from the standpoint of cleaning and sudsing characteristics.
The nonionic surfactants employed herein contain fromabout 4 ~avg.~ moles of ethylene oxide to about 11 (avg.) moles of et~ylene oxide per mole of alcohol in the condensate.
However, it is not always sufficient to describe the nonionic surfactants merely in terms of their alkyl carbon content and ethylene oxide content. The preferred nonionic surfactants ~;
are those descri~ed in Belgian Patent 817,267, i.e., those having an HLB of from about 10 to about 14, preferably from about 11 to about 13.
The individual nonionic surEactants employ~d in the compositions herein are commonly thought o~ as an constituting a hydrocarbyl chain (derived from the alcohol) condensed with an alkylene oxide chain. The hydrocarbyl portion of such materials y.ives rise to their lipophilic characteristics, whereas the ethylene oxide portion determines their hydrophilic characteristics. The overall hydrophilic-lipoPhilic characteristics of a given hydrocarbyl-ethylene oxide condensate " ' _5_ ~ , : . ,, , , . .,, . .. , . .. , . , ~
~8~;2 are reflected in the ~alance of these two factors, i.e., the hydrophilic-lipophilic balance ~HLB~. The H~B of the ethoxylated nonionics herein can be experimentally determined in well-known fashion, or can ~e calculated in the manner set forth in Decker, "Emulsions Theory and Practice" Reinhold 1965, pp. 233 and 248.
Accordingly, the preferred nonionic materials herein can be descri~ed as condensates of an alcohol having a carbon content of from Cl3 to about C16 condensed with from about 4 ~avg.) moles to about ll (avg.) moles of ethylene oxide per mole of alcohol, and further characterized by an HLB
within the range of from about lO to about 14, preferably from about ll to about 13. Nonionic surfactants falling within these ranges are highly preferred herein from the standpoint of optimal pre-treatment cleansing, optimal through-the-wash cleansing, sudsing characteristics and product stability.
EIighly preferred nonionic surfactants for use herein are alcohol ethylene oxide condensates wherein the alcohol contains from 14 to 15 carbon atoms and wherein the condensate contaîns from 6 to 9 moles of ethylene oxide (hydrophilic) per mole o alcohol ~lipophilic~. ~uch materlals are commonly abbreviated as Cl~ l5EO6 9 The nonionic sur~actant~ cmployecl in the pxesent compositions can be prepared by a variety of methods well known in the art. In general terms, such nonionic surfactants are prepared by condensing ethylene oxide with an alcohol under conditions of acidic or basic catalysis.
The nonionic surfactants herein include the ethylene 3a oxïde condensates of both primary and secondary alcohols;
the condensates of primary alcohols are preferred. Non-limiting, , . ~ . .
~7~6Z :
specific examples of nonionic surfactants having the requisite car~on content of the hydrocarbyl portion of the molecule, the requisite ethylene oxide content and the requisite HLB are as ~ollows:
n-C13H27~E~4; n~C13H27(EO~5; n C14H29( ~5 1~ 29 6 14 29 ~7; C14H29~E]lo; n~ClsH31(EO)6; n-Cl H (EO) ;
2-C H l(EO~7; n~C15~I31(EO~8; 2 C15H31~ 8 15 31 2-C H31~E~g; n-C16H33(EO~g; and 2 C16H33( ~9 It îs to ~e recognized that mixtures of the foregoing nonionic surfactants are also useful herein and are readily available from commercial alcohol mixtures. Moreover, the degree of ethoxylation can vary somewhat, inasmuch as average fractional degrees of ethoxylation occur. For example, n-C15~31(EO)7 can contain small quantities o n-C15H31(EO)O
and n-ClsH31(E~14 Such commercial mixtures ~alling within the limits disclosed herein are useful in the present detergent compositions.
The preferred nonionic surfactants are the C14 15(EO)6 9 materials disclosed hereinabove and are commercially available as mixtures under the trademarks "Dobanol 45-7" and "Dobanol 45-9" from the Shell Chemical Co. "Dobanol 45-7" is a Vi9 COUS
liquid at ambient temperatures and is preferred herein.
"Dobanol 45-9" is a solid at room temperature, but is useful in the liquid detergent compositions of this invention inasmuch as it readily dissolves therein.
The presence of the nonionic surfactant in the instant liquid detergent compositions in the essential specified concentrations and proportions provides the necessary oily stain removal in ~oth pre-treatment application and through-3a the-wash utilization o~ the instant invention. The selected nonionic surfactants herein also contribute to the sudsing ~`
_7-~087062 ~
characteristics and p~ys~cal sta~ility of the liquid detergent compos;t;ons.
T~e mixture of anionic surfactant salts is employed hereIn in a quantity suf~icient to provide a weighk ratio ;~
of nonionic surfactant to anionic surfactant mixture of from about 1:1 to a~out 2.3:1, prefera~ly from a~out 1.3:1 to 2:1 based on the free acid from of the anionic surfactants.
The non-soap component of the anionic surfactant mixture consists of a mono- or tri-ethanolaminer potassium, sodium salt or mixtures of such salts of a straight or branched chain alkyl ~enzene sulfonic acid in which the alkyl group contains from about ~ to about 15 carbon atoms. Preferred surfactants of this type are those in which the alkyl chain is linear and averages about 12 carbon atom.s in length. Examples of alkyl benzene sulfonates useful in the instant invention include mono-et~anolamine decyl benzene sulfonate, sodium undecyl benzene sulfonate, triethanolamine dodecyl benzene sulfonate, monoethanolamine tridecyl benzene sulfonate, triethanolarnine tridecyl benzene sulfonate, triethanolamine tetradecyl benzene sulfonate and potassium tetrapropylene ;~
benzene sulfonate. Examples of commercially available alkyl benzene sulfonic acids useful in preparing the sulfonates of the instant invention include "Conoco"* S~ 515, SA 597 and SA 697 all marketed by th~ Continental Oil Company and "Calsoft LAS 99"** marketed by the Pilot Chemical Company.
The soap component of the anionic surfactant mixture consists of mono- or triethanolamine or potassium or sodium soaps of saturated fatty acids containing from about 16 to about 24 carbon atoms and preferably from about 18 to about 24 carbon atoms. Suitable fatty acids can be obtained from *Trademark **Trademark ....~
~L~I 370GZ
natural sources such as, for example, plant or animal esters (:e.g., palm oil, coconut oil, babassu oil, saf10wer oil, tall oil, castor oil, tallow, whale and fish oils, grease, lard, and mixtures thereof~. The fatty acids also can ~e sYnthetically prepared ~e.g., by the oxidation of petroleum or hy ~ydrogenation of carbon monoxide via the Fischer-Tropsch process~. Examples of suitable soaps for use in the instant invention include monoethanolamine eicosinate, sodium palmitate, triethanolamine myristate, triethanolamine palmitate, monoethanolamine stearate and potassium behenate.
Preferred soaps include the mono- or triethanolamine or potassium or sodium soaps of mixtures o fatty acids derived from hydrogenated tallow, hydrogenated rapeseed oil or hydrogenated fish oil. A highly preferred soap for use in the instant invention is the triethanolamine soap of "Hyfac"*, a hydrogenated fish oil fatty acid marketed by Emery Industries, Inc.
Within the anionic surfactant mixture, the two components thereof are present in quantities sufficient to provide a weight ratio of the acid form of the sulfonate (an alkyl benzene sulfonic acid) to the acid form o the soap (a fatty acid) of from a~out 3:1 to about 80:1, preferably rom about `
4:1 to 70:1. :~n another execut.ion oE this :Lnventioll the weight ratio o the acid form of the sulfonate in the acid orm of the soap is from 3:1 to 10:1, preferably from 4:1 to 8:1. If the fatty ac~d is a hydrogenated fish oil having from 18 to 24 carbon atoms, the acid sulfonate to fatty ~ ;
acid weight ratio is most preferably in the range from 30:1 to 70:1. These ratios provide acceptable low sudsing characteristics.
*Trademark _g_ 1~870~
Alkanolamine An optional component of the liquid detergent composition of the present invention is an alkanolamine compound. The alkanolamine useful herein is selected from ' the group consisting of monoethanolamine, triethanolamine, and mixtures thereof. Mixtures of these alkanolamine compounds are produced ~y the reaction o~ ethylene oxide with ammonia. -The pure compounds can be separated from this mixture by standard distillation procedures.
. ~ .
10- The alkanolamine component of the present invention, if present, serves up to three purposes. As will be discussed more fully hereinafter, in one method for preparing the instant compositions t~e alkanolamine neutralizes the free acid form of the anionic surfactant to provide the corresponding alkanolamine salt. In addition, the excess alkanolamine beyond that necessary to form the anionic surfactant salt contributes to the stability of the highly concentrated composition, to detergency performance and buffers the pH
of the washing liquors within the range from about 7 to about 9. It is preferred that the compositions of this invention contain at least 0.5% by weight of the total composition o~
free alkanolamine, i.e., an excess over that needed to neutralize the anionic sur~actant mixture.
Stable liquid detergent compositions containing nonionic, anionic and soap components can be formulated by prepar:Lng each component separately and thoroughly mixing them together in any order. In one method for preparing the instant compositions, the anionic and optional alkanolamine components are formulated sîmultaneously by over-neutralizing the alkyl benzene sulfonic acid and fatty acid with alkanolamine.
:' --10--"
., , , . ., ~ , ,. . ; :
~ 7~;Z ~
This method forms the requisite alkanolamine alkyl benzene sulfonate and soap and provides the free alkanolamine component of the instant composition. Preferably, the compositïons contain from 0.5~ to about 4% by weight of free alkanolamine, most prefera~ly triethanolamine.
The Solvent The liquid detergent compositions of the instant invention contain a solvent which is a water-alcohol mixture.
Such a solvent can ~e employed to the extent of from about 20~ to 45% by weight of the total detergent composition.
In preferred compositions, the solvent comprises from about 30% to 40% by welght of the total composition. Use of such a solvent in the compositions herein has several advantages.
First, the physical stability of the detergent compositions can be improved by dilution with such solvents in that clear points can thereby be lowered. The diluted compositions do not cloud at the low temperatures which are commonly encountered during shipping or storing of commercially marketed detergent compositions.
Secondly, addition of the water-alcohol mixture serves to regulate the gelling tendency which li~uid deter~ent compo~ltlons oE ~he InstAnt kypc exh~blt upon dilution with water.
The weight ratio o~ water to alcohol preferably is maintalned above about 1.1. High alcohol (particularly ethanoll concentrations in the water-alcohol mixtures used in the instant invention are ~re~erably avoided because of flammability pro~lems which may arise at such higher alcohol levels.
1al87~62 Any alcohol containing ~rom 1 to about 5 carbon atoms can ~e employed in the water-alcohol diluent used to prepare the instant detergent composi`tions. Examples of operable alco~ols include methanol, ethanol, propanol, is~propanol, butanol, isobutanol, and pentanol; ethanol is highly ;
preferred for general use.
Optional Components An optional component which can be added to the detergent comPositions of the instant invention is an electrolyte. As pointed out in U.S. Patents 2,580,173 and 3,440,171, electrolytes lessen the gel formation which tends to occur with alkanolamine-neutralized surfactants. Such electrolytes, when used herein in combinakion with a water-alcohol solvent at a weight percent o~ the total composition o~ from about 0.5~ to 5%, prePerably from about 1% to about 3%, of said electrolyte, completely eliminate gelation of the anionic surfactant without the need for excessively high alcohol levels.
Other optional components include brighteners, fluorescers, enzymes1 bleaching agents, anti-microbial agents, corrosion inhibitors, perfumes and coloring agents. Such components preferably comprise no more than about 3~ by weight of the total composition.
Utilization of nonionic surfactant to anionic surfactant (~ree acid basis) ratios of from about 1:1 to about 2.3:1 in combination with utilization of higher saturated soaps is critical to formation of detergent compositions having the unexpected performance and stability characteristics of the instant invention. Higher ratios do not provide the maximum stability in such concentrated formulas and lower or unsaturated - :. . .. .
~08t7~6Z :
fatty acids do not keep the suds down.
Employment of alkanolamine salts and excess alkanolamine also contribute to the effectiveness of the instant detergent compositionsO
The compositions of the înstant invention are ~.
specifically designed to prov;de optlmum cleaning benefits when used in either of the two modes commonly employed with lîqu;d detergent compositions. First, the compositions herein ~
can ~e used as pre-treatment agents which are applied in :
concentrated form directly onto fabric stains prior to fabric washing. Second, th.e instant compositions are also useful as detergents for conventional through-the-wash fabric laundering operations. For through-the-wash fabric laundering, a concentration of the instant compositions in the range o~
from 0.2% to about 0.6%, preferably from about 0.3~ to about ;~
0.5~ by weight of the laundering liquor is preferred. OE ' course, this can be adjusted, depending on the soil load and the desires of the user.
With regard to pre-treatment efficacy, the instant compositions containing the herein specified compon~n~s and component ratios provide oily stain removal ~rom polyamide, polyester or polyester/cotton ~abrics which is superio.r to sim.i~ar p.re-tr~atment pa.r:Eormance atta.ined ~ uti~.ization of conventional built anionic detergent compositions and which is, in fact, comparable in oily stain removal with that attained with pure nonionic surfactants which are known to be particularly useful in such pre-treatment stain removal.
Through-the-wash detergency performance of the instant compositions is, in fact, comparable with that attained with conventional built granular anionic detergent .
compositions.
: -13 : :
~L~87~)62 The ~ollowing examples illustrate the liquid detergent , compositions of t~e instant invention, The abbreviations for the nonionic surfactants emplo~ed, e.g., C14(EO)6, are standard for such materials and describe the carbon content of the alcoholic lipophilic portion of the molecule and the ethylene oxide content of the hydrophilic portion of the molecule.
~87~;2 ~ ~
EXAMPI~S I - IV
Component I II III IV
C14 15 synthetic alcohol polyethoxylate (7) 38 35 - - ;
("Dobanol 45-7"1 C14 15 synthetic alcohol polyethoxylate ~4~ 33 ("Dobanol 45-4"1 C14 15 synthetic alcohol polyethoxylate ~9) - - 40 - .`
("iDobanol 45-9")3 Cll 12 linear alkyl ~enzene sulfonic acid 19 23 17 18 :
Long chain C12_22 fatty acids 2.8 3.5 - 3 .
("Hyfac"4 fatty acids) Tallow fatty acids - - 4.5 _ -;~ . r:
Triethanolamine 6.9 - 11 12 Monoethanolamine - 4.0 KOH 1.5 1.5 Ethanol 8.0 8.0 10 15 Potassium acetate - - 2 - '~
"Brightener DMSX" ~Di~a-Geigy) _______--0.23--------Water ~ miscellaneous --------balance------ :~
Nonionic/anionic 1.74 1.32 1.86 1.57 Sul~onic acid/atty acid 6.78 6.57 3.77 6 1. Trademark 2. Trademark 3. Trademark 4. Trademark
5. Trademark ~87~
The foregoing compositions are stable (i.e., do not ~ -separate or otherwïse degrade on storage and are satisfactory or use after ~eing su~jected to a freeze-thaw cycle~, clear, liquid detergents which do not gel upon dilution with water. ~ ;
ThQ compositions provide satisfactorily low sudsing in wash ~
~ater of varyîng temperature and hardness. The foregoing ~-compositions provide both excellent pre-treatment and through-the-wash fa~ric detergency. "
The foregoing compositions are stable (i.e., do not ~ -separate or otherwïse degrade on storage and are satisfactory or use after ~eing su~jected to a freeze-thaw cycle~, clear, liquid detergents which do not gel upon dilution with water. ~ ;
ThQ compositions provide satisfactorily low sudsing in wash ~
~ater of varyîng temperature and hardness. The foregoing ~-compositions provide both excellent pre-treatment and through-the-wash fa~ric detergency. "
Claims (10)
1. A liquid detergent composition consisting essentially of:
(a) about 28% to about 44% by weight of a nonionic surfactant produced by the condensation of from about 4 to about 11 moles of ethylene oxide with one mole of C13 to C16 alcohol;
(b) an anionic surfactant mixture present in a quantity sufficient to provide a weight ratio of nonionic surfactant to the anionic surfactant mixture in its free acid form of from about 1:1 to about 2.3:1; said anionic surfactant mixture consisting of (i) an alkylbenzene sulfonate having from about 9 to about 15 carbon atoms in the alkyl chain; and (ii) from about 0.2% to about 5% by weight of saturated fatty acid soap containing from about 16 to about 24 carbon atoms in the fatty acid moiety of said soap;
the cations of the sulfonate and soap being selected from the group consisting of monoethanolamine, triethanolamine, potassium, and sodium cations and mixtures thereof, and said anionic surfactant mixture containing sulfonate and soap in quantities sufficient to provide a weight ration of the acid from of the sulfonate to the acid form of the soap of from about 3:1 to 80:1.
(a) about 28% to about 44% by weight of a nonionic surfactant produced by the condensation of from about 4 to about 11 moles of ethylene oxide with one mole of C13 to C16 alcohol;
(b) an anionic surfactant mixture present in a quantity sufficient to provide a weight ratio of nonionic surfactant to the anionic surfactant mixture in its free acid form of from about 1:1 to about 2.3:1; said anionic surfactant mixture consisting of (i) an alkylbenzene sulfonate having from about 9 to about 15 carbon atoms in the alkyl chain; and (ii) from about 0.2% to about 5% by weight of saturated fatty acid soap containing from about 16 to about 24 carbon atoms in the fatty acid moiety of said soap;
the cations of the sulfonate and soap being selected from the group consisting of monoethanolamine, triethanolamine, potassium, and sodium cations and mixtures thereof, and said anionic surfactant mixture containing sulfonate and soap in quantities sufficient to provide a weight ration of the acid from of the sulfonate to the acid form of the soap of from about 3:1 to 80:1.
2. A composition in accordance with Claim 1 which contains in addition from about 20% to about 45% by weight of a solvent, said solvent being a mixture of water and an alcohol containing from 1 to about 4 carbon atoms; said mixture having a water to alcohol weight ratio greater than about 1.1.
3. A composition in accordance with Claim 1 wherein the anionic surfactant mixture contains sulfonate and soap in quantities sufficient to provide a weight ratio of the acid form of the sulfonate to the acid form of the soap of from about 4:1 to 70:1.
4. A composition in accordance with Claim 1 wherein the ratio of nonionic surfactant to anionic surfactant in the free acid form is from about 1.3:1 to about 2:1.
5. A composition in accordance with Claim 2 wherein the alcohol is ethanol.
6. A composition in accordance with Claim 3 which contains in addition from about 0.5% to about 5% by weight of an electrolyte.
7. A composition in accordance with Claim 4 wherein the electrolyte is potassium hydroxide.
8. A composition in accordance with Claim 1 wherein the saturated fatty acid soap represents from about 1.5%
to about 5% by weight, and the weight ratio of the acid form of the sulfonate to the acid form of the soap is from about 3:1 to 10:1.
to about 5% by weight, and the weight ratio of the acid form of the sulfonate to the acid form of the soap is from about 3:1 to 10:1.
9. A composition in accordance with Claim 8 which contains in addition from about 20% to about 45% by weight of a solvent, said solvent being a mixture of water and an alcohol containing from 1 to about 4 carbon atoms, said mixture having a water to alcohol weight ratio greater than about 1.1.
10. A composition in accordance with Claim 9 wherein the ratio of the nonionic surfactant to the anionic surfactant in the free acid form is from about 1,3:1 to about 2:1.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB33717/75 | 1975-08-13 | ||
| GB3371775A GB1548389A (en) | 1975-08-13 | 1975-08-13 | Liquid detergent compositions |
| GB3663375 | 1975-09-05 | ||
| GB36633/75 | 1975-09-05 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1087062A true CA1087062A (en) | 1980-10-07 |
Family
ID=26261989
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA258,964A Expired CA1087062A (en) | 1975-08-13 | 1976-08-12 | Liquid detergent compositions |
Country Status (4)
| Country | Link |
|---|---|
| CA (1) | CA1087062A (en) |
| DE (1) | DE2635913A1 (en) |
| FR (1) | FR2320983A1 (en) |
| NL (1) | NL7608961A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2847437C2 (en) * | 1978-11-02 | 1983-10-06 | Henkel Kgaa, 4000 Duesseldorf | Process for the production of washing liquors |
| DE2847438A1 (en) * | 1978-11-02 | 1980-05-22 | Henkel Kgaa | LIQUID, REFRIGERABLE DETERGENT CONCENTRATE |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE794713A (en) * | 1972-01-31 | 1973-07-30 | Procter & Gamble | LIQUID DETERGENT COMPOSITIONS |
-
1976
- 1976-08-10 DE DE19762635913 patent/DE2635913A1/en not_active Withdrawn
- 1976-08-12 NL NL7608961A patent/NL7608961A/en not_active Application Discontinuation
- 1976-08-12 CA CA258,964A patent/CA1087062A/en not_active Expired
- 1976-08-12 FR FR7624635A patent/FR2320983A1/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| FR2320983A1 (en) | 1977-03-11 |
| NL7608961A (en) | 1977-02-15 |
| FR2320983B1 (en) | 1980-05-23 |
| DE2635913A1 (en) | 1977-03-03 |
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