CA2168307A1 - Pourable detergent concentrates which maintain or increase in viscosity after dilution with water - Google Patents
Pourable detergent concentrates which maintain or increase in viscosity after dilution with waterInfo
- Publication number
- CA2168307A1 CA2168307A1 CA 2168307 CA2168307A CA2168307A1 CA 2168307 A1 CA2168307 A1 CA 2168307A1 CA 2168307 CA2168307 CA 2168307 CA 2168307 A CA2168307 A CA 2168307A CA 2168307 A1 CA2168307 A1 CA 2168307A1
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- Prior art keywords
- concentrate
- viscosity
- surfactants
- composition
- weight
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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
- C11D1/66—Non-ionic compounds
- C11D1/72—Ethers of polyoxyalkylene glycols
- C11D1/721—End blocked ethers
-
- 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
- C11D1/29—Sulfates of polyoxyalkylene ethers
-
- 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
- C11D1/83—Mixtures of non-ionic with anionic 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
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/0008—Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
- C11D17/0026—Structured liquid compositions, e.g. liquid crystalline phases or network containing non-Newtonian phase
-
- 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
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/0008—Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
- C11D17/003—Colloidal solutions, e.g. gels; Thixotropic solutions or pastes
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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)
- Dispersion Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Detergent Compositions (AREA)
Abstract
Aqueous detergent concentrates containing a mixture of two or more surfactants having a differing resistance to electrolytic salting out in the form of micellar solutions and having pourable viscosities are converted into lamellar solutions upon dilution with water where the dispersion contains a viscosity promoting electrolyte present at a narrow range of concentration. Transformation from the micellar phase to the lamellar phase produces an increase in viscosity such that the diluted concentrate has a viscosity equal to or higher than the viscosity of the original concentrate.
Description
~ 307 IR Fl286 POURA RT T- DETFR('IT-~NT CON~NTRATE~
WT~TCH MAINTAIN OR INCREASE TN VISCOSITY AFTFT~
DTT UTION WITH WATER
BACKGROUND OFT~ INVF~TION
Field of ~he Invention 15 This inYention relates to ~queous detergent concentrates adapted to bc diluted by ~he consumer prior fO use.
Descri~tion of Rel~t~d Art 20 There is a trend in the household products and personal care ir l ~ 5 to provide products in concentrated form which are adapted to be di~uted with water by the consumer prior to use. This approach reduces the bull~ of p~ in~ which needs to be disposed of by the consumer and teduces the shipping and handling costs associated with 25 distribution of such products.
Aqueous liquid concentrates such ~s laundry, fine fabric and dishwasher d~ ,c,.~ are normally provided with a high content of active ingredients such that, when diluted by the consumer per 30 p~ in~ e the diluted product will contain an amount of active ;- c.~ c normally present in a non- - ' product.
However, the provision of ~ ~ r d~d liquids gives rise to a number of problems, including viscosity conttol and stability.
(~n- dll.;i liquids tend to e~hibit a higher viscosity due to the high content of surfactants, builders, electrolytes and other present in the: ~- dlC. Collcc,,lldt~,s having viscosities in e~cess of 10,000 cps (mPas~ tend to be difficult to pour from the p~
_ _ _ _ _ _ _ _ .
30~
container, while pourable UllCt:~lLLCltes tend to have insufficient viscosity on the other hand when dyyluyLiately diluted by the ~ :r -r, thereby reducinq c-- -r appeal.
Also, surfactants present at high levels in such 5 coY~Centrates tend to form closely spaced, ~ J~ d la -Fl~r structures which tend to contact one another after periods of storage, resulting in a flocculation rh~r which destabilizes the suspension and leads to a marked increase in product viscosity.
One approach to dealing with poor post-dilution viscosity is to include in the liquid concentrate formulation one or more organic or inorganic th i ~-kPn i nq agents such as swelling clays, alumina, gums, polymeric materials or 15 cellulosic polymers. However, the use of such th;~k~ning additives tends to worsen the problem of ullC~:IILL~e pourability and imparts only a minimal viscosity increase to the diluted u..c~nLLi~te.
WT~TCH MAINTAIN OR INCREASE TN VISCOSITY AFTFT~
DTT UTION WITH WATER
BACKGROUND OFT~ INVF~TION
Field of ~he Invention 15 This inYention relates to ~queous detergent concentrates adapted to bc diluted by ~he consumer prior fO use.
Descri~tion of Rel~t~d Art 20 There is a trend in the household products and personal care ir l ~ 5 to provide products in concentrated form which are adapted to be di~uted with water by the consumer prior to use. This approach reduces the bull~ of p~ in~ which needs to be disposed of by the consumer and teduces the shipping and handling costs associated with 25 distribution of such products.
Aqueous liquid concentrates such ~s laundry, fine fabric and dishwasher d~ ,c,.~ are normally provided with a high content of active ingredients such that, when diluted by the consumer per 30 p~ in~ e the diluted product will contain an amount of active ;- c.~ c normally present in a non- - ' product.
However, the provision of ~ ~ r d~d liquids gives rise to a number of problems, including viscosity conttol and stability.
(~n- dll.;i liquids tend to e~hibit a higher viscosity due to the high content of surfactants, builders, electrolytes and other present in the: ~- dlC. Collcc,,lldt~,s having viscosities in e~cess of 10,000 cps (mPas~ tend to be difficult to pour from the p~
_ _ _ _ _ _ _ _ .
30~
container, while pourable UllCt:~lLLCltes tend to have insufficient viscosity on the other hand when dyyluyLiately diluted by the ~ :r -r, thereby reducinq c-- -r appeal.
Also, surfactants present at high levels in such 5 coY~Centrates tend to form closely spaced, ~ J~ d la -Fl~r structures which tend to contact one another after periods of storage, resulting in a flocculation rh~r which destabilizes the suspension and leads to a marked increase in product viscosity.
One approach to dealing with poor post-dilution viscosity is to include in the liquid concentrate formulation one or more organic or inorganic th i ~-kPn i nq agents such as swelling clays, alumina, gums, polymeric materials or 15 cellulosic polymers. However, the use of such th;~k~ning additives tends to worsen the problem of ullC~:IILL~e pourability and imparts only a minimal viscosity increase to the diluted u..c~nLLi~te.
- 2~ Hydrophilic polymeric materials have also been used in liguid detergent ~_UIl- ~llLLc.tes as viscosity control agents.
For example, U.S. Patent 4,715,969 discloses that the addition of less than about 0.5% by weight of a polyacrylate polymer, e.g., sodium polyacrylate, having a 25 molecular weight ~rom about l, 000 to 5, 000, to aqueous detergent compositions containing primarily anionic surfactants will stabilize the viscosity of the composition and prevent a major increase in viscosity after a period of storage of the formulated composition. Also, EPO 301,883 30 fliq~loc~s similar compositions containing from about 0.1 to 20S by weight of a viscosity reducing, water soluble polymer such as polyethylene glycol, dextran or a dextran sul f onate .
5 While these and other approaches tend to enhance te pourability, they do not solve the problem of poor post-dilution viscosity.
~lB8307 . 3 Accordingly, it is an object of the invention to provide a liquid detergent concentrate which exhibits a sufficiently low viscosity such that it is pourable as a free flowing li~uid from its packaging container and which also exhibits S ~ viscosity after appropriate dilution with water which is preferably at lea6t equal to the viscosity of the original, unailuted concentrate.
S~ARY oF T~TF IN~tENT~ON
The present invention provides pourable aqueous detergent u u..- enLL~lte compositions comprisinq a n~ l 1 Ar dispersion of a mixture of at least two surfactants having differing resistance to electrolytic salting out and a dissolved 15 electrolyte salt, which co~uel.~L~lte has a viscosity of less than about 2500 cps (mPas) and which contains the electrolyte salt at a u u~l~.6llLL~tion such that, upon dilution of the concentrate with a designated amount of water, the m;c~llAr surfactant dispersion is converted at - 2Q least partially or totally into a l~ r phase dispersion, thereby providing a diluted uu..~ LL~te having a viscosity in excess of 200 cps, and more preferably a viscosity at least egual to and generally higher than the viscosity of the undiluted concentrate.
The invention also provide a method for preparing a diluted detergent concentrate having a viscosity at least about equal to and generally higher than the viscosity of the lln~ uted cu..cJ-.LL~,te comprising:
a) providing a detergent ~ullC~I.LL~lte composition comprising an aqueous mic-~llAr dispersion of a mixture of at least two surfactants having differing resistance to electrolytic salting out and a dissolved electrolyte salt, which 35 u..- e..LLc.te has a viscosity of less than about 2500 Cp8 (mPas), and b) diluting the ~ul~c~--LL~te with sufficient water such that ~16~3~7 said ~ Ul~ Pl-LLaLe is at least partially converted into a Ar phase di5persion, thereby providing a diluted ate having a viscosity in excess of 200 cps, more preferably a viscosity at least egual to the viscosity of 5 the undiluted ::v..cenLL~te.
RRT~ ES~RTPTION OF THE DRAWINGS
Figure 1 is a graph plotting viscosity characteristics of 10 a dispersed surfactant system in the micDllAr and 1 -llAr phases as a function of electrolyte ~_vllu_~lLLation.
Figure 2 is a graph plotting viscosity ~nh~nf --L of a detergent concentrate of the invention as a function of the 15 degree of dilution with water.
DETAILED ~ES~ RTPTION OF THE INVENTION
When surfactants are solubilized in electrolyte-free water, - 20 they exhibit different phase aLLU~L~L~S in accordance with ~ulluc:llLLation and degree Or water solubility. At cu..c~llLLc.tions of less than about 30-40 wt%, surfactants usually form the micellar isotropic solution "L" phase.
mese micelles are aggregates of surfactant molecules, too 25 small to be visible through an optical microscope. These mic~lle~ tend to form spherical shapes at lower uullc~llLLc.tions and become cylindrical in shape at higher C- llC~ Lations within this range. Mir~llAr solutions look and behave in most cases ag true clear solutions with very 30 low viscosity, e.g., generally less than about 200 cps.
When the surfactant ~ ol~cel.LL-tion in water is increased up to about 50 to 60 wt%, many surfactants form a wax-liXe or gel-like "M" phase, also referred to as the liquid crystal 35 phase, in which the cylindrical a~-~Le ~ates are arranged very close ~n~eth~r in a h~ .. .A 1 structure. At this phase, the ~;~p-~r~Rion is; ~;le and unpourable due to the fact that mobility of the cylindrical aggregates is limited 21~83~
only along the cylinder lengths.
At eu..cel-L-i~tions above about 60 wt% and below about 80 wt9~, surfactants form a more mobile "G" or "L alpha"
5 l~ qr phase. ri -llAr phases are anisotropic phases composed of successive bilayers of surfactant arranged in riqr~ and separated by a liquid medium, usually an aqueous medium. T~r~ qr phase solutions are less viscous than i~ phase solutions even though they contain less water.
10 This reduction in viscosity is due to the ease with which the parallel layers can slide over each other during shear.
ri -llAr phase solutions are, however, generally more viscous than micellar phase solutions.
15 At still higher concentrations, surfactants form a hydrated solid. Some surfactants such as the non-ionics tend to form a liquid phase containing dispersed water droplets of micelle size.
20 Further ~liccllcsion of the properties of various surfactants dispersed in water as a function of ~ùl.~ e..L.cltion is found in U.S. Patents 3,893,955, 4,243,549 and 4,753,754.
The present invention is grounded on the discovery that 25 ~;cP~ r dispersions of certain combinations of surfactants having differing resistance to electrolytic salting out can be converted at relatively low surfactant concentrations into and out of 1 l l iir phase dispersions as a function of the ~,..ce-.L.~ltion of water soluble electrolyte added to the 30 dispersion. This rh~- is illustrated in ~igure 1 which '- L~ltes the development of a ~ -llAr, more viscous phase within a m;cPlli~r sur~actant ~licpc~rRirn containing a certain ~ ,I.c~ tion range of electrolyte, and reversion to the m;cPllilr phase above and below that 35 ~ el.L-~tion range.
Thus, conce..L,~.ted micellar phase detergents containing up to about 60 wt% of surfactants and containing a water 8~
soluble electrolyte at a ~ ul.-, l,L-c-tion in excess of the ~ UIlC~ Lc~tion which promotes conversion of the micelle phase to the 7 i - l l A r phase can be diluted with water to the point where the electrolyte iu.~cel~LLlltion falls within 5 the l i - l l Ar phase-promoting concentratiOn ranqe for the particular system. Dilution levels of the u ullc~llLL~Le may generally range from about 0 . 5 to abcut 5 volumes of water per volume of uul~c~lL-~ste. Conversion of the micelle dispersion into a li llAr dispersion produces an increase 10 in viscosity of the detergent composition which at least equals, and normally will exceed, the viscosity of the undLluted, micellar phase concentrate. In effect, li llAr phase development which normally occur5 at surfactant uullu~llL~tions of about 60 to 80 wt% is created in the 15 m;c~llAr phase, where the surfactant ~ull~-:llLLc~tion is considerably lower, by careful control of the cull i~llLL~,tion of electrolyte present in the dispersion. Thus, viscosity a~nhAr L is achieved without the presence of 1~hirl~an;nq adjuvants in the cù~ce~LL~,te formulation.
me combination of surfactants which may be used in the present invention may be selected from anionic, non-ionic, cationic and amphoteric species, including mixtures containing different species or mixtures of different 25 surfactants within the same species.
Suitable anionic surfactants include the water-soluble alkali metal salts having alkyl radicals con~A;n;n7 from about 8 to about 22 carbon atomq, the term alkyl being used 30 to include the alkyl portion of higher acyl radicals.
EYamples of suitable synthetic anionic detergent _ '~
are sodium and potassium alkyl sulphates, ~re~ lly those obtained by sulphating higher (Ca-C18) i~lcnholq pLuduced, ~or example, from tallow or coconut oil; sodium and 35 potassium alkyl (C9-C20~ benzene sulfonates, particularly sodium linear secnn~l~ry alkyl (C10-C15) benzene sulfonates;
sodium alkyl glycerol ether sulfates, ~qren;Ally those ethers of the higher A 1 cnhnlq derived from tallow or 21~830~
coconut oil and synthetic alcohols derived from petroleum;
sodium coconut oil fatty monoglyceride sulfates and sulfonates; sodium and potassium salts of sulfuric acid esters of higher (C8-C18) fatty alcohol-alkylene oxide, 5 particularly ethylene oxide reaction products; the reaction prudu~;L~i of fatty acids such as coconut fatty acids esterified with isethionic acid and neutralized with sodium hydroxide: sodium and potassium salts of fatty acid amides of methyl taurine; alkane oslll fonates such as those 10 derived from reacting alpha-olefins (Cl-Cz0) with sodium bisulfite and those derived from reacting paraffins with SO2 and C12 and then hydrolyzing with a base to produce a random sulfonate: and olefin sulfonates which term is used to describe the material made by reacting olefins, 15 particularly C10-C20 alpha-olefins, with SO~ and then neutralizing and hydrolyzing the reaction product. me preferred anionic surfactants are (C10-C18) alkyl polyethoxy ~l-ll Eo) sulfates and mixtures thereof having differing water solubilities.
Suitable nonionic surfactants include, in particular, the reaction products of ~ '- having a hydrophobic group and a reactive hydrogen a~-om, for example aliphatic Alcnhnlc, acids, amides and alkyl phenols with alkylene 25 oxides, ~spe~ iAlly ethylene oxide, either alone or with propylene oxide. Specific nonionic surfactant ~ '-are alkyl (C6-C18) primary or secon~l~ry linear or branched alcohols cnn~ n~o~ with ethylene oxide, and products made by ~ tion of ethylene oxide with the reaction 30 l~rud~ L; of propylene oxide and ethylono~ m;n~. Other so-called n~n;~n;~ surfactant ~ '- include long chain tertiary amine oxides, long-chain tertiary rhnsrhin~
oxides, dialkyl sulfoxides, fatty (C~-Cl8) esters of glycerol, sorbitan and the like, alkyl polyglycosides, 35 ethoxylated glycerol esters, ethyoxylated sorbitans and ethoxylated phosphate esters.
me preferred non-ionic surfactant ~_ __ - are those of ~68~
the ethoxylated and mixed ethyoxylated-propyloXylated ~C6-C1~) fatty alcohol type, containing 2-ll EO groups.
Examples of amphoteric surfactants which can be used in the 5 compositions of the present invention are betaines and those which can be broadly described as derivatives of aliphatic secQr~ ry and tertiary amines in which the aliphatic radical can be straight chain or branched and wherein one of the aliphatic substituents contains from 10 about 8 to about 18 carbon atoms and one contains an anionic water solubilizing group, e.g., carboxy, sulfonate, sulfate, phosphate, or phosphonate. Examples of ~
falling within this def inition are sodium 3-dodecyl ~tm; nnpropionate~ sodium 3-dodecyl~mi nnpropane 15 sulfonate, N-alkyltaurines, such as prepared by reacting dodecylamine with sodium isothionate, N-higher alkyl aspartic acids and the products sold under the trade name "!~iranol " .
20 Examples of betaines useful herein include the high alkyl betaines such as coco dimethyl caL~u~y yl betaine, lauryl dimethyl carboxymethyl betaine, lauryl dimethyl alpha . aLl,u,.ye~hyl betaine, oetyl dimethyl caLl,u~y ~llyl betaine, lauryl bis(2 hy~llv~y~:Lllyl) c2rboxy methyl betaine, 25 stearyl bis-(2-11y~Lu~.y~Lu~yl) caL,.U.cy L~.yl betaine, oleyl dimethyl gamma-caLLv,~y~Lu~yl betaine, lauryl bis-(2-ilydLu~y~Luyyl) alpha-carboxyethyl betaine, etc. The sulfo-he~ i n~ may be represented by coco dimethyl sulfopropyl betaine, steary-l dimethyl sulfopropyl betaine, lauryl bis-30 (2 ~-y-lLu~y~Lhyl) sulfopropyl betaine, amino betaine Ami~os~l fnhet:~in~s, and the like.
Other suitable betaines include l-(lauryl, dimethyl; ;n) acetate-l-(myristyl dimethylammonio) propane-3-sulfonate, 35 l-(myristyl dimethylamino)-2-hyd~u,~y~Lu~ane-3-sulfonate, coco~m; cloethyl he~ i ne and roco~m; ~lopropylbetaine .
Cationic surfactants which maybe used include mono CZs-C24 21~8~0~
alkyl or alkenyl onium salts, ecr~riAl ly mono-or polyammonium salts, imidazolinium salts, pyridinium salts or mixtures thereof. FcreriAl ly preferred cationics include the following:
stearyldimethylbenzyl ammonium chloride;
dodecyltrimethylammonium chloride; nonylbenzylethyl~ yl ammonium Nitrate, tetradecylpyridinium bromide;
laurylpyridinium chloride; cetylpyridinium chloride;
10 laurylisoauinolium bromide; ditallow (hydrogenated) dimethyl ammonium chloride; dilauryldimethyl ammonium chloride; and stearalkonium chloride.
A more detailed illustration of the various surfactants and 15 classes of surfactants mentioned may be found in the text Sllrface Active Aaents, Vol. II, by schwartz, Perry and Berch (Interscience Publishers, 1958), in a series of annual publications entitled McCutcheon's Deteraents and F~lllcifier5 issued in 1969, or in Tenside-Tas~henhuch~ H.
- 20 Stache, 2nd Ed. Carl Hanser Verlag, Munich and Vienna, 1981 .
In order to achieve the objectives of this invention, the surfactant or at least one of a combination of two or more 25 surfactants used must possess a hiqh resistance to salting out in the presence of an electrolyte such as potassium citrate or sodium chloride. By "high salting out resistance" is meant that a 10% by weight aaueous solution of a particular surfactant should remain as a clear 30 isotropic, stable solution where the aaueous solution contains about 4% by weight of dissolved citrate electrolyte .
Conversely, a surfactant of low electrolyte resistance iEi 35 one where a 10% by weight aqueous solution would form a cloudy, turbid or two phase solution in the presence of 4%
by weight or less of potassium citrate.
_ _ _ _ _ _ _ _ _ _ _ _ _ _, _ 2~8~7 Thus, high salting out resistant surfactants which can be used alone or as a mixture in the composition of this invention include Cl2 - C1~ fatty alcohol ether sulfates (AEOS) with 2 or 3 moles of ethylene oxide, preferably 2 5 moles of ethylene oxide and mixtures thereof. Some other high salting out resistant surfactantS, e.g. betaines and AEOS surfactants having 4 or greater EO groups cannot be used as the sole surfactant because they do not provide the desired viscosity boost at relatively low electrolytic l0 levels.
Low salting out resistant surfactants which cannot be used as the sole surfactant include linear alkyl benzene sulfonates (LAS) or the alkyl sulfates, since these tend to 15 salt out in the presence of only 1% by weight electrolyte Other surfactants which can not be used alone include AEOS
surfactants having a high EO content, e.g. 4 moles or greater and betaines, because, although they have a high resistance to electrolytic salting out, they do not exhibit - 2~0 a substantial viscosity boost when diluted with water.
In a more preferred ~ L of the invention, the surfactants comprise a mixture of two or more surfactants, at least one of which has a high salting out resistance and 25 at least one other of which has a low salting out resistance. Such a combination provides the desired balance of electrolytic stability afforded by the electrolyte-resistant surfactant combined with a higher boost in viscosity provided by the non-electrolyte 30 resistant surfactant when the surfactant phase is converted from the micpllAr phase to the li 11i~r phase upon dilution with water.
Specific combinations of surfactants which may be used 35 include AEOS (2EO) or AEOS (3EO) mixed with AEOS > (4EO);
AEOS (2EO) blended with AEOS (3EO) (4:1 to 1:4 blend ratios); a mixture of a betaine, e.g.
cocni~mi-~n~ropylbetaine, with linear alkyl benzene sulfonate 2~68307 . --(3 : 1 to 1: 1 blend ratios?; a blend of C8 to C13 alkyl sulfates or sulfonates with AEOS (2 or 3EO) at 2:1 to 1:2 blend ratios; a ternary blend of C8 to C18 alkyl sulfate or sulfonate with a Cl3 - C15 fatty ethoxy alcohol (6-10 EO~
5 and AEOS (2-3EO), blended at about equal parts of each surfactant; a ternary blend of a betaine, e.q.
ro~ oAmi~-proplybetaine, with a C~3 - C,5 fatty ethoxy alcohol (6-lOEO) and AEOS (2-3EO) and like co~binations.
10 When combined, such surfactants exhibit the desired balance of properties and stability required for the present invention. Accordingly, some trial and error may be required to determine the oetimum surfactant combination.
Surfactants may be combined in the relative weight ratios 15 of about 4 :1 to 1: 4 respectively.
A particularly preferred surfactant combination comprises a mixture of an anionic alkyl polyethoxy sulfate (AEOS) wherein the alkyl group contains from about 10 to 18 carbon - 20 atoms and the polyethyoxy is of 2 to 7 ethylene oxide groups, more preferably 2 or 3 ethylene oxide groups and a non-ionic ethoxylated fatty alcohol wherein the fatty alcohol contains from about 6 to 18 carbon atoms and containing 2-11 ethylene oxide groups, used in the relative 25 proportion of 3 :1 to 1: 3 .
The surfactant combination may be present in the Le at a level of from about 10 to 60% by weight, more preferably from about 10 to 35~ by weight.
Electrolytes which may be used in the present invention include one of a mixture of water soluble organic and inorganic salts. Suitable inorganics include alkali or i~lkAl in~ earth metal chlorides, sulfates, phosphates, 35 acetates and nitrates such as sodium, magnesium, lithium or calcium chloride, potassium bromide, calcium sulfate and the like. Organic salts include the citrates, formates and salts of ethylene diamine tetraacetic acid. A preferred 2~8307 electrolyte is sodium or potassium citrate since it also contributes as a builder in detergent compositions in the amount used.
5 $he amount of electrolyte present in any given concentrate is detprm; nPd by first evaluating the ~u..~ie-.L~ ation in a diluted product containing a given combination of surfactants where conversion from the micellar into the li -11Ar phase is achieved, and than multiplying that level 10 of u~.~el~LLGtion by the dilution factor as hereinafter described. Generally spPilk;n~, the concentrate will normally contain electrolyte at a level in the range of from about 1 to about 309~ by weight.
~5 The detergent composition of the invention may be used in numerous applications such as heavy duty laundry detergents, dish detergents, household cleaners, sh 9, body douche and body lotions. Accordingly they may contain the usual quantities of one or more adjuvants such as - 20 rhosrhl~rous and non-phosphorous containing builders, fluorescent brighteners, dyes, peL r, - -, viscosity regulators, shampoo adjuvants, enzymes, bleaches, batericidies, fungicides, anti-foam agents, preservatives, stabilizers and skin conditioners. The adjuvants should 25 not, however, be of a type which will promote instability of the product on standing.
For the ~u~os~s of this invention, all references to viscosity are viscosity measured at a product temperature 30 of 2SC using a Brookfield RV$-DVll vi~ :~ ~ at 10 rpm, with a #l spindle from 0 to 1000 mPas (cps) and a #2 spindle from 1000 to 4000 mPas (cps).
$he following eYampleS are illustrative of the invention.
F le 1 A stock fine fabric detergent formulation was prepared by 21~83û7 mixing the following ingredients (as 100% active ingredients by weight) and in the following proportions in a high shear mixer:
5 D~ ni7ed water 89.43%
NI--7EO* 3 . 70 AEOS--3EO** 3 . 80 Coco amino betaine 1. 50 Foam control - myristic acid 0.10 Foam control - lauric acid 0. 70 Fraqrance o . 35 Protein cosmetic 0 . 01 Opacifier 0.38 Preservative o. 03 Dye 0. 0001 *NI-7EO is C13 - C1s fatty alcohol with 7EO.
**AEOS-3EO i5 Clz - Cl~ fatty alcohol ether sulfate with 3EO .
20 The resulting product was a clear micellar dispersion having a viscosity of about 12 cps (12 mPas). Ph was adjusted to about 7 . 4 to 7 . 6 by addition of potassium hydroxide (50% j . The product had a total active ingredient content of about 10. 5%, of which about 9% is 2 5 surf actant content .
EX312~le 2 A series of ten additional solutions (A-J) having the 30 composition of Example 1 were prepared except that a combination of citric acid and potassium hydroxide (50%) at about a 1. 0 to 0 . 9 weight ratio was added at appropriate weight levels to form solutions containing about 1, 2, 3, 4, 5, 6, 7, 8, 9 and 10% by weight, respectively, of 35 potassium citrate electrolyte. Ph of each was adjusted to 7 . 4 - 7 . 6 as above . Viscosity mea~uL- Ls were as follows:
` 14 EXAMP~E ~TFCT~OLyTE CONf'rNTRATION (WT~6) VISCoSITy (CPS) o 12 2~I 8 175 15 Microscopic examination of the samples showed the development of a lamellar phase at electrolyte col.~en~Lc.tions in the range of from about 3-7~6 by weight, wi~ peak lam~llar phase development at about 4-596 by weight electrolyte concentration. Above and below these - 20 electrolyte concentrations, the solutions were essentially clear, isotropic, micPllAr solutions. These data are plotted in Figure 1.
These data suggest that concentrated versions of the 25 formulations described above may be prepared by simply increasing the concentration of the active ingredients, including electrolyte, up to but below the point where stable, pourable mir-llAr phase dispersions having a viscosity of 200 cps or lesg can no longer be formed. Upon 30 dilution of these micPl 1 Ar ...,l~. ,..LLates with an appropriate amount of water to the point where the electrolyte CUI~ LGtion best promotes viscosity ~nhAnl l, in this case about 4 to 5% by weight conc~ -LGtion, a diluted product having a viscosity at least equal to or higher than 35 the original viscosity of the ~ LGte will be obtained.
This is illustrated by the following Example.
.
21~83~
~Yi~mnle 3 A concentrate having approximately double the concentration of active ingredients of Example 2E, which contained about 5 5% by weight electrolyte, was prepared as described above.
The ~ U.~cel~L,-te had the following composition:
Doinni70-1 water 67.9%
NI-7Eo 7 . 4 0 AEûS-3EO 9 Coco amino betaine 3 .
Foam control - myristic acid 0.10 Foam control - lauric acid 1. 50 Citric acid (anhy) 5-XOH (50%) 4.40 Fragrance O . 70 Protein cosmetic 0. 01 ûpaci f ier O . 7 5 Preservative O . 07 - 20 Dye 0. 0002 The pH of the concentrate was adjusted to 7.4 to 7.6 using 50% KoH as above. The concentrate had a viscoisity of lOO-150 cps and formed a clear, isotropic micellar dispersion.
25 Total active ingredients were about 31.2% by weight, of which about 19 . 4% by weight is surfactant and about 9% by weight is potassium citrate electrolyte.
Portions of the ~_o~ L~lte were then diluted with varying 30 amounts o~ tap water ais illustrated in Figure 2. The uu"ce"LLate developed a marked increase in viscosity with increasing dilution up to a maximum value in the ~ r phase and then began to drop again with the reformation of a micolli~r solution. The twice diluted product (one volume 35 water per volume of ~ u..cel.LLate) exhibited a viscosity in the range of 600-800 cps.
~ ~8307 Accordingly, pourable deterqent ~ ul-ce--LLa-es having a viscosity of 200 Cp5 and less are readily converted, by simple mixing, into water diluted ~;u..~ -LLa~es having a viscosity in excess of 400 cps which have rnnci~orable appeal to the ~ r,
For example, U.S. Patent 4,715,969 discloses that the addition of less than about 0.5% by weight of a polyacrylate polymer, e.g., sodium polyacrylate, having a 25 molecular weight ~rom about l, 000 to 5, 000, to aqueous detergent compositions containing primarily anionic surfactants will stabilize the viscosity of the composition and prevent a major increase in viscosity after a period of storage of the formulated composition. Also, EPO 301,883 30 fliq~loc~s similar compositions containing from about 0.1 to 20S by weight of a viscosity reducing, water soluble polymer such as polyethylene glycol, dextran or a dextran sul f onate .
5 While these and other approaches tend to enhance te pourability, they do not solve the problem of poor post-dilution viscosity.
~lB8307 . 3 Accordingly, it is an object of the invention to provide a liquid detergent concentrate which exhibits a sufficiently low viscosity such that it is pourable as a free flowing li~uid from its packaging container and which also exhibits S ~ viscosity after appropriate dilution with water which is preferably at lea6t equal to the viscosity of the original, unailuted concentrate.
S~ARY oF T~TF IN~tENT~ON
The present invention provides pourable aqueous detergent u u..- enLL~lte compositions comprisinq a n~ l 1 Ar dispersion of a mixture of at least two surfactants having differing resistance to electrolytic salting out and a dissolved 15 electrolyte salt, which co~uel.~L~lte has a viscosity of less than about 2500 cps (mPas) and which contains the electrolyte salt at a u u~l~.6llLL~tion such that, upon dilution of the concentrate with a designated amount of water, the m;c~llAr surfactant dispersion is converted at - 2Q least partially or totally into a l~ r phase dispersion, thereby providing a diluted uu..~ LL~te having a viscosity in excess of 200 cps, and more preferably a viscosity at least egual to and generally higher than the viscosity of the undiluted concentrate.
The invention also provide a method for preparing a diluted detergent concentrate having a viscosity at least about equal to and generally higher than the viscosity of the lln~ uted cu..cJ-.LL~,te comprising:
a) providing a detergent ~ullC~I.LL~lte composition comprising an aqueous mic-~llAr dispersion of a mixture of at least two surfactants having differing resistance to electrolytic salting out and a dissolved electrolyte salt, which 35 u..- e..LLc.te has a viscosity of less than about 2500 Cp8 (mPas), and b) diluting the ~ul~c~--LL~te with sufficient water such that ~16~3~7 said ~ Ul~ Pl-LLaLe is at least partially converted into a Ar phase di5persion, thereby providing a diluted ate having a viscosity in excess of 200 cps, more preferably a viscosity at least egual to the viscosity of 5 the undiluted ::v..cenLL~te.
RRT~ ES~RTPTION OF THE DRAWINGS
Figure 1 is a graph plotting viscosity characteristics of 10 a dispersed surfactant system in the micDllAr and 1 -llAr phases as a function of electrolyte ~_vllu_~lLLation.
Figure 2 is a graph plotting viscosity ~nh~nf --L of a detergent concentrate of the invention as a function of the 15 degree of dilution with water.
DETAILED ~ES~ RTPTION OF THE INVENTION
When surfactants are solubilized in electrolyte-free water, - 20 they exhibit different phase aLLU~L~L~S in accordance with ~ulluc:llLLation and degree Or water solubility. At cu..c~llLLc.tions of less than about 30-40 wt%, surfactants usually form the micellar isotropic solution "L" phase.
mese micelles are aggregates of surfactant molecules, too 25 small to be visible through an optical microscope. These mic~lle~ tend to form spherical shapes at lower uullc~llLLc.tions and become cylindrical in shape at higher C- llC~ Lations within this range. Mir~llAr solutions look and behave in most cases ag true clear solutions with very 30 low viscosity, e.g., generally less than about 200 cps.
When the surfactant ~ ol~cel.LL-tion in water is increased up to about 50 to 60 wt%, many surfactants form a wax-liXe or gel-like "M" phase, also referred to as the liquid crystal 35 phase, in which the cylindrical a~-~Le ~ates are arranged very close ~n~eth~r in a h~ .. .A 1 structure. At this phase, the ~;~p-~r~Rion is; ~;le and unpourable due to the fact that mobility of the cylindrical aggregates is limited 21~83~
only along the cylinder lengths.
At eu..cel-L-i~tions above about 60 wt% and below about 80 wt9~, surfactants form a more mobile "G" or "L alpha"
5 l~ qr phase. ri -llAr phases are anisotropic phases composed of successive bilayers of surfactant arranged in riqr~ and separated by a liquid medium, usually an aqueous medium. T~r~ qr phase solutions are less viscous than i~ phase solutions even though they contain less water.
10 This reduction in viscosity is due to the ease with which the parallel layers can slide over each other during shear.
ri -llAr phase solutions are, however, generally more viscous than micellar phase solutions.
15 At still higher concentrations, surfactants form a hydrated solid. Some surfactants such as the non-ionics tend to form a liquid phase containing dispersed water droplets of micelle size.
20 Further ~liccllcsion of the properties of various surfactants dispersed in water as a function of ~ùl.~ e..L.cltion is found in U.S. Patents 3,893,955, 4,243,549 and 4,753,754.
The present invention is grounded on the discovery that 25 ~;cP~ r dispersions of certain combinations of surfactants having differing resistance to electrolytic salting out can be converted at relatively low surfactant concentrations into and out of 1 l l iir phase dispersions as a function of the ~,..ce-.L.~ltion of water soluble electrolyte added to the 30 dispersion. This rh~- is illustrated in ~igure 1 which '- L~ltes the development of a ~ -llAr, more viscous phase within a m;cPlli~r sur~actant ~licpc~rRirn containing a certain ~ ,I.c~ tion range of electrolyte, and reversion to the m;cPllilr phase above and below that 35 ~ el.L-~tion range.
Thus, conce..L,~.ted micellar phase detergents containing up to about 60 wt% of surfactants and containing a water 8~
soluble electrolyte at a ~ ul.-, l,L-c-tion in excess of the ~ UIlC~ Lc~tion which promotes conversion of the micelle phase to the 7 i - l l A r phase can be diluted with water to the point where the electrolyte iu.~cel~LLlltion falls within 5 the l i - l l Ar phase-promoting concentratiOn ranqe for the particular system. Dilution levels of the u ullc~llLL~Le may generally range from about 0 . 5 to abcut 5 volumes of water per volume of uul~c~lL-~ste. Conversion of the micelle dispersion into a li llAr dispersion produces an increase 10 in viscosity of the detergent composition which at least equals, and normally will exceed, the viscosity of the undLluted, micellar phase concentrate. In effect, li llAr phase development which normally occur5 at surfactant uullu~llL~tions of about 60 to 80 wt% is created in the 15 m;c~llAr phase, where the surfactant ~ull~-:llLLc~tion is considerably lower, by careful control of the cull i~llLL~,tion of electrolyte present in the dispersion. Thus, viscosity a~nhAr L is achieved without the presence of 1~hirl~an;nq adjuvants in the cù~ce~LL~,te formulation.
me combination of surfactants which may be used in the present invention may be selected from anionic, non-ionic, cationic and amphoteric species, including mixtures containing different species or mixtures of different 25 surfactants within the same species.
Suitable anionic surfactants include the water-soluble alkali metal salts having alkyl radicals con~A;n;n7 from about 8 to about 22 carbon atomq, the term alkyl being used 30 to include the alkyl portion of higher acyl radicals.
EYamples of suitable synthetic anionic detergent _ '~
are sodium and potassium alkyl sulphates, ~re~ lly those obtained by sulphating higher (Ca-C18) i~lcnholq pLuduced, ~or example, from tallow or coconut oil; sodium and 35 potassium alkyl (C9-C20~ benzene sulfonates, particularly sodium linear secnn~l~ry alkyl (C10-C15) benzene sulfonates;
sodium alkyl glycerol ether sulfates, ~qren;Ally those ethers of the higher A 1 cnhnlq derived from tallow or 21~830~
coconut oil and synthetic alcohols derived from petroleum;
sodium coconut oil fatty monoglyceride sulfates and sulfonates; sodium and potassium salts of sulfuric acid esters of higher (C8-C18) fatty alcohol-alkylene oxide, 5 particularly ethylene oxide reaction products; the reaction prudu~;L~i of fatty acids such as coconut fatty acids esterified with isethionic acid and neutralized with sodium hydroxide: sodium and potassium salts of fatty acid amides of methyl taurine; alkane oslll fonates such as those 10 derived from reacting alpha-olefins (Cl-Cz0) with sodium bisulfite and those derived from reacting paraffins with SO2 and C12 and then hydrolyzing with a base to produce a random sulfonate: and olefin sulfonates which term is used to describe the material made by reacting olefins, 15 particularly C10-C20 alpha-olefins, with SO~ and then neutralizing and hydrolyzing the reaction product. me preferred anionic surfactants are (C10-C18) alkyl polyethoxy ~l-ll Eo) sulfates and mixtures thereof having differing water solubilities.
Suitable nonionic surfactants include, in particular, the reaction products of ~ '- having a hydrophobic group and a reactive hydrogen a~-om, for example aliphatic Alcnhnlc, acids, amides and alkyl phenols with alkylene 25 oxides, ~spe~ iAlly ethylene oxide, either alone or with propylene oxide. Specific nonionic surfactant ~ '-are alkyl (C6-C18) primary or secon~l~ry linear or branched alcohols cnn~ n~o~ with ethylene oxide, and products made by ~ tion of ethylene oxide with the reaction 30 l~rud~ L; of propylene oxide and ethylono~ m;n~. Other so-called n~n;~n;~ surfactant ~ '- include long chain tertiary amine oxides, long-chain tertiary rhnsrhin~
oxides, dialkyl sulfoxides, fatty (C~-Cl8) esters of glycerol, sorbitan and the like, alkyl polyglycosides, 35 ethoxylated glycerol esters, ethyoxylated sorbitans and ethoxylated phosphate esters.
me preferred non-ionic surfactant ~_ __ - are those of ~68~
the ethoxylated and mixed ethyoxylated-propyloXylated ~C6-C1~) fatty alcohol type, containing 2-ll EO groups.
Examples of amphoteric surfactants which can be used in the 5 compositions of the present invention are betaines and those which can be broadly described as derivatives of aliphatic secQr~ ry and tertiary amines in which the aliphatic radical can be straight chain or branched and wherein one of the aliphatic substituents contains from 10 about 8 to about 18 carbon atoms and one contains an anionic water solubilizing group, e.g., carboxy, sulfonate, sulfate, phosphate, or phosphonate. Examples of ~
falling within this def inition are sodium 3-dodecyl ~tm; nnpropionate~ sodium 3-dodecyl~mi nnpropane 15 sulfonate, N-alkyltaurines, such as prepared by reacting dodecylamine with sodium isothionate, N-higher alkyl aspartic acids and the products sold under the trade name "!~iranol " .
20 Examples of betaines useful herein include the high alkyl betaines such as coco dimethyl caL~u~y yl betaine, lauryl dimethyl carboxymethyl betaine, lauryl dimethyl alpha . aLl,u,.ye~hyl betaine, oetyl dimethyl caLl,u~y ~llyl betaine, lauryl bis(2 hy~llv~y~:Lllyl) c2rboxy methyl betaine, 25 stearyl bis-(2-11y~Lu~.y~Lu~yl) caL,.U.cy L~.yl betaine, oleyl dimethyl gamma-caLLv,~y~Lu~yl betaine, lauryl bis-(2-ilydLu~y~Luyyl) alpha-carboxyethyl betaine, etc. The sulfo-he~ i n~ may be represented by coco dimethyl sulfopropyl betaine, steary-l dimethyl sulfopropyl betaine, lauryl bis-30 (2 ~-y-lLu~y~Lhyl) sulfopropyl betaine, amino betaine Ami~os~l fnhet:~in~s, and the like.
Other suitable betaines include l-(lauryl, dimethyl; ;n) acetate-l-(myristyl dimethylammonio) propane-3-sulfonate, 35 l-(myristyl dimethylamino)-2-hyd~u,~y~Lu~ane-3-sulfonate, coco~m; cloethyl he~ i ne and roco~m; ~lopropylbetaine .
Cationic surfactants which maybe used include mono CZs-C24 21~8~0~
alkyl or alkenyl onium salts, ecr~riAl ly mono-or polyammonium salts, imidazolinium salts, pyridinium salts or mixtures thereof. FcreriAl ly preferred cationics include the following:
stearyldimethylbenzyl ammonium chloride;
dodecyltrimethylammonium chloride; nonylbenzylethyl~ yl ammonium Nitrate, tetradecylpyridinium bromide;
laurylpyridinium chloride; cetylpyridinium chloride;
10 laurylisoauinolium bromide; ditallow (hydrogenated) dimethyl ammonium chloride; dilauryldimethyl ammonium chloride; and stearalkonium chloride.
A more detailed illustration of the various surfactants and 15 classes of surfactants mentioned may be found in the text Sllrface Active Aaents, Vol. II, by schwartz, Perry and Berch (Interscience Publishers, 1958), in a series of annual publications entitled McCutcheon's Deteraents and F~lllcifier5 issued in 1969, or in Tenside-Tas~henhuch~ H.
- 20 Stache, 2nd Ed. Carl Hanser Verlag, Munich and Vienna, 1981 .
In order to achieve the objectives of this invention, the surfactant or at least one of a combination of two or more 25 surfactants used must possess a hiqh resistance to salting out in the presence of an electrolyte such as potassium citrate or sodium chloride. By "high salting out resistance" is meant that a 10% by weight aaueous solution of a particular surfactant should remain as a clear 30 isotropic, stable solution where the aaueous solution contains about 4% by weight of dissolved citrate electrolyte .
Conversely, a surfactant of low electrolyte resistance iEi 35 one where a 10% by weight aqueous solution would form a cloudy, turbid or two phase solution in the presence of 4%
by weight or less of potassium citrate.
_ _ _ _ _ _ _ _ _ _ _ _ _ _, _ 2~8~7 Thus, high salting out resistant surfactants which can be used alone or as a mixture in the composition of this invention include Cl2 - C1~ fatty alcohol ether sulfates (AEOS) with 2 or 3 moles of ethylene oxide, preferably 2 5 moles of ethylene oxide and mixtures thereof. Some other high salting out resistant surfactantS, e.g. betaines and AEOS surfactants having 4 or greater EO groups cannot be used as the sole surfactant because they do not provide the desired viscosity boost at relatively low electrolytic l0 levels.
Low salting out resistant surfactants which cannot be used as the sole surfactant include linear alkyl benzene sulfonates (LAS) or the alkyl sulfates, since these tend to 15 salt out in the presence of only 1% by weight electrolyte Other surfactants which can not be used alone include AEOS
surfactants having a high EO content, e.g. 4 moles or greater and betaines, because, although they have a high resistance to electrolytic salting out, they do not exhibit - 2~0 a substantial viscosity boost when diluted with water.
In a more preferred ~ L of the invention, the surfactants comprise a mixture of two or more surfactants, at least one of which has a high salting out resistance and 25 at least one other of which has a low salting out resistance. Such a combination provides the desired balance of electrolytic stability afforded by the electrolyte-resistant surfactant combined with a higher boost in viscosity provided by the non-electrolyte 30 resistant surfactant when the surfactant phase is converted from the micpllAr phase to the li 11i~r phase upon dilution with water.
Specific combinations of surfactants which may be used 35 include AEOS (2EO) or AEOS (3EO) mixed with AEOS > (4EO);
AEOS (2EO) blended with AEOS (3EO) (4:1 to 1:4 blend ratios); a mixture of a betaine, e.g.
cocni~mi-~n~ropylbetaine, with linear alkyl benzene sulfonate 2~68307 . --(3 : 1 to 1: 1 blend ratios?; a blend of C8 to C13 alkyl sulfates or sulfonates with AEOS (2 or 3EO) at 2:1 to 1:2 blend ratios; a ternary blend of C8 to C18 alkyl sulfate or sulfonate with a Cl3 - C15 fatty ethoxy alcohol (6-10 EO~
5 and AEOS (2-3EO), blended at about equal parts of each surfactant; a ternary blend of a betaine, e.q.
ro~ oAmi~-proplybetaine, with a C~3 - C,5 fatty ethoxy alcohol (6-lOEO) and AEOS (2-3EO) and like co~binations.
10 When combined, such surfactants exhibit the desired balance of properties and stability required for the present invention. Accordingly, some trial and error may be required to determine the oetimum surfactant combination.
Surfactants may be combined in the relative weight ratios 15 of about 4 :1 to 1: 4 respectively.
A particularly preferred surfactant combination comprises a mixture of an anionic alkyl polyethoxy sulfate (AEOS) wherein the alkyl group contains from about 10 to 18 carbon - 20 atoms and the polyethyoxy is of 2 to 7 ethylene oxide groups, more preferably 2 or 3 ethylene oxide groups and a non-ionic ethoxylated fatty alcohol wherein the fatty alcohol contains from about 6 to 18 carbon atoms and containing 2-11 ethylene oxide groups, used in the relative 25 proportion of 3 :1 to 1: 3 .
The surfactant combination may be present in the Le at a level of from about 10 to 60% by weight, more preferably from about 10 to 35~ by weight.
Electrolytes which may be used in the present invention include one of a mixture of water soluble organic and inorganic salts. Suitable inorganics include alkali or i~lkAl in~ earth metal chlorides, sulfates, phosphates, 35 acetates and nitrates such as sodium, magnesium, lithium or calcium chloride, potassium bromide, calcium sulfate and the like. Organic salts include the citrates, formates and salts of ethylene diamine tetraacetic acid. A preferred 2~8307 electrolyte is sodium or potassium citrate since it also contributes as a builder in detergent compositions in the amount used.
5 $he amount of electrolyte present in any given concentrate is detprm; nPd by first evaluating the ~u..~ie-.L~ ation in a diluted product containing a given combination of surfactants where conversion from the micellar into the li -11Ar phase is achieved, and than multiplying that level 10 of u~.~el~LLGtion by the dilution factor as hereinafter described. Generally spPilk;n~, the concentrate will normally contain electrolyte at a level in the range of from about 1 to about 309~ by weight.
~5 The detergent composition of the invention may be used in numerous applications such as heavy duty laundry detergents, dish detergents, household cleaners, sh 9, body douche and body lotions. Accordingly they may contain the usual quantities of one or more adjuvants such as - 20 rhosrhl~rous and non-phosphorous containing builders, fluorescent brighteners, dyes, peL r, - -, viscosity regulators, shampoo adjuvants, enzymes, bleaches, batericidies, fungicides, anti-foam agents, preservatives, stabilizers and skin conditioners. The adjuvants should 25 not, however, be of a type which will promote instability of the product on standing.
For the ~u~os~s of this invention, all references to viscosity are viscosity measured at a product temperature 30 of 2SC using a Brookfield RV$-DVll vi~ :~ ~ at 10 rpm, with a #l spindle from 0 to 1000 mPas (cps) and a #2 spindle from 1000 to 4000 mPas (cps).
$he following eYampleS are illustrative of the invention.
F le 1 A stock fine fabric detergent formulation was prepared by 21~83û7 mixing the following ingredients (as 100% active ingredients by weight) and in the following proportions in a high shear mixer:
5 D~ ni7ed water 89.43%
NI--7EO* 3 . 70 AEOS--3EO** 3 . 80 Coco amino betaine 1. 50 Foam control - myristic acid 0.10 Foam control - lauric acid 0. 70 Fraqrance o . 35 Protein cosmetic 0 . 01 Opacifier 0.38 Preservative o. 03 Dye 0. 0001 *NI-7EO is C13 - C1s fatty alcohol with 7EO.
**AEOS-3EO i5 Clz - Cl~ fatty alcohol ether sulfate with 3EO .
20 The resulting product was a clear micellar dispersion having a viscosity of about 12 cps (12 mPas). Ph was adjusted to about 7 . 4 to 7 . 6 by addition of potassium hydroxide (50% j . The product had a total active ingredient content of about 10. 5%, of which about 9% is 2 5 surf actant content .
EX312~le 2 A series of ten additional solutions (A-J) having the 30 composition of Example 1 were prepared except that a combination of citric acid and potassium hydroxide (50%) at about a 1. 0 to 0 . 9 weight ratio was added at appropriate weight levels to form solutions containing about 1, 2, 3, 4, 5, 6, 7, 8, 9 and 10% by weight, respectively, of 35 potassium citrate electrolyte. Ph of each was adjusted to 7 . 4 - 7 . 6 as above . Viscosity mea~uL- Ls were as follows:
` 14 EXAMP~E ~TFCT~OLyTE CONf'rNTRATION (WT~6) VISCoSITy (CPS) o 12 2~I 8 175 15 Microscopic examination of the samples showed the development of a lamellar phase at electrolyte col.~en~Lc.tions in the range of from about 3-7~6 by weight, wi~ peak lam~llar phase development at about 4-596 by weight electrolyte concentration. Above and below these - 20 electrolyte concentrations, the solutions were essentially clear, isotropic, micPllAr solutions. These data are plotted in Figure 1.
These data suggest that concentrated versions of the 25 formulations described above may be prepared by simply increasing the concentration of the active ingredients, including electrolyte, up to but below the point where stable, pourable mir-llAr phase dispersions having a viscosity of 200 cps or lesg can no longer be formed. Upon 30 dilution of these micPl 1 Ar ...,l~. ,..LLates with an appropriate amount of water to the point where the electrolyte CUI~ LGtion best promotes viscosity ~nhAnl l, in this case about 4 to 5% by weight conc~ -LGtion, a diluted product having a viscosity at least equal to or higher than 35 the original viscosity of the ~ LGte will be obtained.
This is illustrated by the following Example.
.
21~83~
~Yi~mnle 3 A concentrate having approximately double the concentration of active ingredients of Example 2E, which contained about 5 5% by weight electrolyte, was prepared as described above.
The ~ U.~cel~L,-te had the following composition:
Doinni70-1 water 67.9%
NI-7Eo 7 . 4 0 AEûS-3EO 9 Coco amino betaine 3 .
Foam control - myristic acid 0.10 Foam control - lauric acid 1. 50 Citric acid (anhy) 5-XOH (50%) 4.40 Fragrance O . 70 Protein cosmetic 0. 01 ûpaci f ier O . 7 5 Preservative O . 07 - 20 Dye 0. 0002 The pH of the concentrate was adjusted to 7.4 to 7.6 using 50% KoH as above. The concentrate had a viscoisity of lOO-150 cps and formed a clear, isotropic micellar dispersion.
25 Total active ingredients were about 31.2% by weight, of which about 19 . 4% by weight is surfactant and about 9% by weight is potassium citrate electrolyte.
Portions of the ~_o~ L~lte were then diluted with varying 30 amounts o~ tap water ais illustrated in Figure 2. The uu"ce"LLate developed a marked increase in viscosity with increasing dilution up to a maximum value in the ~ r phase and then began to drop again with the reformation of a micolli~r solution. The twice diluted product (one volume 35 water per volume of ~ u..cel.LLate) exhibited a viscosity in the range of 600-800 cps.
~ ~8307 Accordingly, pourable deterqent ~ ul-ce--LLa-es having a viscosity of 200 Cp5 and less are readily converted, by simple mixing, into water diluted ~;u..~ -LLa~es having a viscosity in excess of 400 cps which have rnnci~orable appeal to the ~ r,
Claims (25)
1. An aqueous detergent concentrate composition comprising a micellar dispersion of a mixture of at least two surfactants having differing resistance to electrolytic salting out and a dissolved electrolyte salt, said concentrate having a viscosity of less than about 2500 cps and said electrolyte salt present in said concentrate at a level such that, upon dilution of said concentrate with a specific amount of water, said micellar surfactant dispersion is converted at least partially into a lamellar phase dispersion providing a diluted concentrate having a viscosity in excess of 200 cps.
2. The composition of claim 1 wherein said diluted concentrate has a viscosity at least equal to the viscosity of said concentrate.
3. The composition of claim 1 wherein at least one of said surfactants is resistant to salting out (maintains a clear isotropic solution when dissolved in water at a level of 10% by weight containing 4% by weight potassium citrate electrolyte) and at least one other of said surfactants is not resistant to salting out (does not maintain a clear isotropic solution when dissolved in water at a level of 10% by weight containing 4% by weight of potassium citrate).
4. The composition of claim 3 wherein said concentrate has a viscosity in the range of about 100 to 200 cps.
5. The composition of claim 4 wherein said diluted concentrate has a viscosity in excess of 400 cps.
6. The composition of claim 1 wherein said surfactants comprise a mixture of anionic and non-ionic surfactants.
7. The composition of claim 6 wherein said anionic surfactant comprises an alkyl polyethoxy sulfate wherein the alkyl group contains from about 10 to 18 carbon atoms and the polyethoxy is 1 to 11 ethylene oxide groups.
8. The composition of claim 6 wherein said non-ionic surfactant comprises an ethoxylated fatty alcohol wherein the fatty alcohol contains about 6 to 18 carbon atoms and the polyethoxy is of 2 to 11 ethylene oxide groups.
9. The composition of claim 3 wherein said concentrate contains said surfactants at a level of from about 10 to about 60% by weight.
10. The composition of claim 3 wherein said concentrate contains said electrolyte salt at a level of from about 1 to about 30% by weight.
11. The composition of claim 10 wherein said electrolyte salt is an alkali metal citrate.
12. The composition of claim 3 which is free of added thickening agents.
13. A method for preparing a diluted detergent concentrate having a viscosity at least equal to the viscosity of the undiluted concentrate comprising:
a) providing a detergent concentrate comprising an aqueous micellar dispersion of a mixture of at least two surfactants having differing resistance to electrolytic salting out and a dissolved electrolyte salt, said concentrate having a viscosity of less than about 2500 cps, and b) diluting said concentrate with sufficient water such that said concentrate is at least partially converted into a lamellar phase dispersion, providing a diluted concentrate having a viscosity in excess of 200 cps.
a) providing a detergent concentrate comprising an aqueous micellar dispersion of a mixture of at least two surfactants having differing resistance to electrolytic salting out and a dissolved electrolyte salt, said concentrate having a viscosity of less than about 2500 cps, and b) diluting said concentrate with sufficient water such that said concentrate is at least partially converted into a lamellar phase dispersion, providing a diluted concentrate having a viscosity in excess of 200 cps.
14. The method of claim 13 wherein at least one of said surfactants is resistant to salting out (maintains a clear isotropic solution when dissolved in water at a level of 10% by weight containing 4% by weight potassium citrate electrolyte) and at least one other of said surfactants is not resistant to salting out (does not maintain a clear isotropic solution when dissolved in water at a level of 10% by weight containing 4% by weight of potassium citrate).
15. The method of claim 14 wherein said concentrate is diluted with from about 0.5 to about 5 volumes of water per volume of concentrate.
16. The method of claim 14 wherein said concentrate has a viscosity in the range of about 100 to 200 cps and said diluted concentrate has a viscosity in excess of 200 cps.
17. The method of claim 16 wherein said diluted concentrate has a viscosity in excess of 400 cps.
18. The method of claim 14 wherein said surfactants comprise a mixture of anionic and non-ionic surfactants.
19. The method of claim 14 wherein said anionic surfactant comprises an alkyl polyethoxy sulfate wherein the alkyl group contains from about 10 to 18 cargon atoms and the polyethoxy is 1 to 11 ethylene oxide groups.
20. The method of claim 14 wherein said non-ionic surfactant comprises an ethoxylated fatty alcohol wherein the fatty alcohol contains about 6 to 18 carbon atoms and the polyethoxy is of 2 to 11 ethylene oxide groups.
21. The method of claim 14 wherein said concentrate contains said surfactants at a level of from about 10 to about 60% by weight.
22. The method of claim 14 wherein said concentrate contains said electrolyte salt at a level of form about 1 to about 30% by weight.
23. The method of claim 22 wherein said electrolyte salt is an alkali metal citrate.
24. The method of claim 14 wherein said diluted concentrate has a viscosity at least equal to the viscosity of said concentrate.
25. An aqueous detergent concentrate composition comprising a miscellar dispersion of surfactant consisting essentially of C10 to C18 alkyl diethoxy sulfate, a C10 to C18 alkyl triethoxy sulfate or a mixture thereof, and a dissolved electrolyte salt, said concentrate having a viscosity of less than about 2500 cps and said electrolyte salt present in said concentrate at a level such that, upon dilution of said concentrate with a specific amount of water, said micellar surfactant dispersion is converted at least partially into a lamellar phase dispersion providing a diluted concentrate having a viscosity in excess of 200cps.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US38047795A | 1995-01-30 | 1995-01-30 | |
| US08/380,477 | 1995-01-30 | ||
| US49607195A | 1995-06-28 | 1995-06-28 | |
| US08/496,071 | 1995-06-28 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2168307A1 true CA2168307A1 (en) | 1996-07-31 |
Family
ID=27009005
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 2168307 Abandoned CA2168307A1 (en) | 1995-01-30 | 1996-01-29 | Pourable detergent concentrates which maintain or increase in viscosity after dilution with water |
Country Status (8)
| Country | Link |
|---|---|
| EP (1) | EP0724013A1 (en) |
| AU (1) | AU702446B2 (en) |
| BR (1) | BR9600236A (en) |
| CA (1) | CA2168307A1 (en) |
| NO (1) | NO960377L (en) |
| NZ (1) | NZ280841A (en) |
| SG (1) | SG54105A1 (en) |
| TR (1) | TR199600075A2 (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5922664A (en) * | 1995-01-30 | 1999-07-13 | Colgate-Palmolive Co. | Pourable detergent concentrates which maintain or increase in viscosity after dilution with water |
| DE19731398A1 (en) | 1997-07-22 | 1999-01-28 | Henkel Ecolab Gmbh & Co Ohg | Use of enzyme-containing solutions for cleaning fermentation and storage tanks |
| DE19752163A1 (en) | 1997-11-26 | 1999-05-27 | Henkel Kgaa | Thickened liquid detergent composition(s) |
| DE19752165A1 (en) | 1997-11-26 | 1999-05-27 | Henkel Kgaa | Thickened liquid detergent composition(s) |
| DE10023438A1 (en) * | 2000-05-12 | 2001-11-22 | Henkel Kgaa | Aqueous concentrate containing surfactant, used in concentrated or diluted form for washing up and cleaning hard surfaces, contains electrolyte combination of aromatic carboxylic and inorganic acids or salts |
| JP3255637B1 (en) * | 2001-01-23 | 2002-02-12 | 花王株式会社 | Liquid detergent composition |
| DE10136001A1 (en) | 2001-07-24 | 2003-02-13 | Henkel Kgaa | Automatic dishwashing detergent with low viscosity surfactants |
| DE10136000A1 (en) | 2001-07-24 | 2003-02-13 | Henkel Kgaa | Automatic dishwashing detergent with surfactants with low dynamic surface tension |
| DE10136002A1 (en) | 2001-07-24 | 2003-02-13 | Henkel Kgaa | Automatic dishwashing detergent with surfactants with a certain diffusion coefficient |
| US6617293B2 (en) * | 2001-08-06 | 2003-09-09 | 3M Innovative Properties Company | Thickening on dilution liquid soap |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB8412045D0 (en) * | 1984-05-11 | 1984-06-20 | Unilever Plc | Detergent compositions |
| EP0314232A3 (en) * | 1987-10-27 | 1990-07-04 | Unilever N.V. | Thickening gels |
| GB8803036D0 (en) * | 1988-02-10 | 1988-03-09 | Unilever Plc | Liquid detergents |
| GB8821763D0 (en) * | 1988-09-16 | 1988-10-19 | Unilever Plc | Liquid detergents |
| US5035826A (en) * | 1989-09-22 | 1991-07-30 | Colgate-Palmolive Company | Liquid crystal detergent composition |
| IN180345B (en) * | 1990-04-10 | 1998-01-24 | Albright & Wilson U K Ltd | |
| US5399285A (en) * | 1992-10-30 | 1995-03-21 | Diversey Corporation | Non-chlorinated low alkalinity high retention cleaners |
| US5965503A (en) * | 1993-05-04 | 1999-10-12 | Novo Nordisk A/S | Cleaning gel for hard surfaces containing one or more surfactants, an electrolyte, and an enzyme |
| AU676066B2 (en) * | 1993-06-01 | 1997-02-27 | Ecolab Inc. | Thickened hard surface cleaner |
| GB9314410D0 (en) * | 1993-07-13 | 1993-08-25 | Jeyes Group Plc | Cleansing compositions |
-
1996
- 1996-01-16 EP EP96200101A patent/EP0724013A1/en not_active Withdrawn
- 1996-01-17 NZ NZ28084196A patent/NZ280841A/en unknown
- 1996-01-18 SG SG1996000276A patent/SG54105A1/en unknown
- 1996-01-22 AU AU42113/96A patent/AU702446B2/en not_active Ceased
- 1996-01-26 BR BR9600236A patent/BR9600236A/en not_active Application Discontinuation
- 1996-01-29 CA CA 2168307 patent/CA2168307A1/en not_active Abandoned
- 1996-01-29 NO NO960377A patent/NO960377L/en unknown
- 1996-01-30 TR TR96/00075A patent/TR199600075A2/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| BR9600236A (en) | 1997-12-23 |
| AU4211396A (en) | 1996-08-08 |
| AU702446B2 (en) | 1999-02-18 |
| EP0724013A1 (en) | 1996-07-31 |
| TR199600075A2 (en) | 1996-08-21 |
| NZ280841A (en) | 1997-04-24 |
| SG54105A1 (en) | 1998-11-16 |
| NO960377L (en) | 1996-07-31 |
| NO960377D0 (en) | 1996-01-29 |
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Legal Events
| Date | Code | Title | Description |
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| FZDE | Dead |