CA2004812A1 - Detergent composition comprising betaine and ether sulphate - Google Patents
Detergent composition comprising betaine and ether sulphateInfo
- Publication number
- CA2004812A1 CA2004812A1 CA002004812A CA2004812A CA2004812A1 CA 2004812 A1 CA2004812 A1 CA 2004812A1 CA 002004812 A CA002004812 A CA 002004812A CA 2004812 A CA2004812 A CA 2004812A CA 2004812 A1 CA2004812 A1 CA 2004812A1
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- CA
- Canada
- Prior art keywords
- composition
- betaine
- alkyl
- ether sulfate
- carbon atoms
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
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
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/0005—Other compounding ingredients characterised by their effect
- C11D3/0094—High foaming compositions
-
- 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
- C11D1/88—Ampholytes; Electroneutral compounds
- C11D1/94—Mixtures with anionic, cationic or non-ionic 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
- 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
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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)
- Crystallography & Structural Chemistry (AREA)
- Detergent Compositions (AREA)
Abstract
ABSTRACT
DETERGENT COMPOSITION COMPRISING
BETAINE AND ETHER SULFATE
A light duty liquid detergent, especially suitable for hand dishwashing. The detergent comprises an essentially binary active system of (i) amidoalkyl betaines or amidoalkylsulo-betaines and (ii) alkyl ether sulfates in a weight ratio of 1:4 to 1:1, preferably 1:3 to 1:1, together with hydrotropes and water and certain optional ingredients. The light duty liquids have excellent mildness and foaming properties and do not require large amounts of surfactants.
DETERGENT COMPOSITION COMPRISING
BETAINE AND ETHER SULFATE
A light duty liquid detergent, especially suitable for hand dishwashing. The detergent comprises an essentially binary active system of (i) amidoalkyl betaines or amidoalkylsulo-betaines and (ii) alkyl ether sulfates in a weight ratio of 1:4 to 1:1, preferably 1:3 to 1:1, together with hydrotropes and water and certain optional ingredients. The light duty liquids have excellent mildness and foaming properties and do not require large amounts of surfactants.
Description
~o~a~
DETER&ENT COMPOSITION COMPRISING
BETAINE AND ETHER SULFATE
5 BACKGROUND OiF THE INVENTION
Two particularly important characteri tics of hand dishwashing detergent liquids are mildness, which is significant due to the exposure of the hands to the detergent formulations, and foamability. Foamability is important because the amount of foam generated during washing is related to the ability of a formulation to : clean dishes and eating utensils effectively.
; 15 Among the surfactants included to promote mildness in some light duty liquid detergent formulations are certain betaine surfactants and linear ether sulfates. However, such formulations have tended generally to include high levels of total surfactant high levels of the costly betaine surfactants and/or one or more extra surfactants in addition to the betaine and ether sulfates.
, :, ` ` ` ' ~ .
-- 2 - C607~
Rubin et al., US Patent No ~ 375 421 discloses high viscosity aqueous compositions including alkylamidobetaines and selected salts such as certain sulfates, carbonates, citrates, tartrates and succinates.
The inclusion of micelle-forming anionic surfactants are said to produce a synergistic, viscosity-building effect.
Among the numerous types of anionics mentioned for use in their invention are included sodium, potassium, calcium, .
;
~ 3 - C6074 magne~ium and am~onium alco~ol ethoxy sulfate6. In Examples 6~B
and 6-C, hand dishwashing preparations are disclosed which include cocoamido betaine, ammonium alcohol ethoxy sulfate, lauryl dimethyl amine oxide and either sodium citrate or sodlum sulfate. The ratio of betaine to ether sulfate i~ ~uch greater than l:l. Rubin et al. indicate that the par~icular type of betaine is important and that ~ost betaines are not thickened in the presence of salts. It is said that only alkylamidobetaine~ -are thickened under the described conditions.
Chirash et al., U.S. Patent No. 4,772,425 discloses light duty li~uid abrasive-containing dishwashing'compositions which include at least one sulfated or sulfonated anionic surfactant, a betaine, a clay stabilizing agent and a minor amount of a solubilizer such as ethanol as a preferred optional ingredient. Preferably, the formulation includes a ternary sur-factant system of an alkyl benzyl su1fonate or alkane sulfonate, an alkyl ethenoxy ether sulfate and a betaine, the clay, and 2 to 9% alcohol Several of the examplified compositions of Chirash include ether sulfate and betaine suractants and ethanol. For instance, a composition including 17% sodium dodecylbenzene sulfonate, 13% ammonium alkyl trièthenoxyether sulfate, ~%
cocamidopropyl dimethyl betaine, 5.5% ethanol and water is disclosed. In example 6, 6.5% ether sulfate, 2% amidoal~yl ~oc~
betaine, 8.5% sodium dodecylbenzene sul~onate and 4% alcohol are included. The examples including ether sulfate and b~taine appear to possess ternary surfactant systems.
Verdicchio et al., U.S. Patent No. 3,950,417 disclo3e~
high lathering detergent compositions, especially useful as shampo~s, which comprise a surfactant betaine, an a~ionic surfac-tant and a nonionic surfactant. The preferred molar ratio of surfactant betaine to anionic surfactant falls between about 0.9 and about 1.1. The preferred betaines are said to be surfactant amidocarboxybetaines and amidosulfobetaines. Alcohol ether sul-fates are used as anionics and are said to be the preferredanionics. The examples generally include a nonionic surfactant in a~dition to the betaines and the anionic surfactant such as ether sulfates. In addition to use as shampoos, the compofiitions are said to be useful as cleansers for cleaning other parts of the human body, animals, inanimate objects and the like.
Nishimura et al., U.S. Patent No. 4,166,048 discloses hi~h foami~g detergent compositions which are said to have a vcry mild action on the skin. The compositions include certain polyoxyethylene alkyl ether su~,fate salt mixtures and a betaine-type amphoteric surfactant of the~formula Rl~R~)NI(CH2COO-~R3 wherein Rl is alkyl having 8 to 20 carbon atoms. The weight of the betaine type amphoteric surfactant is 0.01 to 2 times, espe-cially 0.03 to 0.5 times the weight of the polyoxyethylepe alkyl ether sulfate salt mixture.
, The ether sulfate salts of the '048 patent may include monovalent metal ions, ~referably Na or ~ or divale~t metal ions, preferably Ca or Mg. Solubilizing agent-~ such a~ et~anol, pro-pylene glycol, glycerin and xylene sulonic acid salt~ ~ay be included. In some of the examples, the compo~ition iB te~ted or washing power on dishes. Small amounts of ammonium chlvride ar~
included in some of tne examples.
The Lonzaine C Product Information Bulletin dlsclo~es that Lonzane C is a mild, hicih oaming s~rfactant of the amide betaine structure. Lonzaine C is said to contain`5% NaCl.
Lonzaine C is said to have outstandin~ conditioning, foaming, and viscosity potentiating properties.- Lonzaine C, in comb~nation with most anionic surfactants, is said to potentiate vi3cosity to permit formulations rangin~ from viscous liguids to ringing gels.
Shampoo formulations including a 30% solutio~ of Lonzaine C (14~), Barlox C, a 40% solution o~ ~odium alpha olefin sulfonate (22%), citric acid, water and optionally polymer JR 125 are disclosed. Lonzaine C is said to be useul in light duty liquids and is said to exhibit toleranc,e toward high levels o~
builder, electrolytes, alkali and acids.
The Stepan bulletin for Amphosol CA (cocoamidopropyl betaine) gives a shampoo formulation including Amphosol CA, a~
amine oxide, an alpha olefin sulfonate, citric acid and water.
In three other formulas, the anionic is respectively sodium ~0~ 2 - 6 - c6074 lauryl sulfa~e, another alcohol ~ulfate salt and slpha olefin sulfonate. It is said that a wide Yariety of visco~itie ~an be attained by addition of NaCl (~om 0 to a gel).
Pancheri et al., U.S. Patent No. 4,772,423 di~clo~
liquid detergents said to have high sudsing c~aracteristic and said to be suitable for washing tableware. The detergents com-prise 5 to 50% anionic surfactant, a polmeric surfactant, detergency builders and water and may also include other surfactants, of which betaine surfactants are highly preferre~l.
1~ The betaine is present at from 0.5 to lS~, preferably from 1 to 10%. The ratio of anionic to betaine is from about 1 to 80, preferably from 1 to 40 more preerably from about 2 to 40. The preferred anionic surfactants are alkylpolyethoxylate sulfates having from 0.5 to 10 ethylene oxide groups. The anionics may be salts of sodium, potassium, ammonium, monoethanolammonium, diethanolammonium, trietha~olammonium and other cations. Alcohols and hydrotropes such as sodium xylene sulonate may be included, as may water-soluble inor~anic builders. Alkyl ether sulfates and alkylamido betaines are included together in various examples, ~enerally with an addi-tional surfactant.
Lamb et. al., U.S. Patent No. 4,671,894 disclo~es liquid dishwashing de~ergents comprising 4 to ~0% alXyl ~ulfate, 5 to 20~o alkylbenzene sulfonate, 1 to 10% of a nonionic surfactant, 5 ,' .
' ' ; :
`
to 24% alkyl et~oxy sulfate, 0.25 to 10% of a zwitterionlc sur-factant such a~ an alkyl betaine, an alkylamidobeta~ne or a sulfobetaine, and a hydrotrope-water system which may include ethanol, urea, and/or a lower alkyl benzene sulfonate. In exam-ple D, 9.9% ammonium alkyl ethoxy sulfate, 2.2S~ amidopropylbetaine, ethanol, alkylbenzene sulfonate, alkyl ~ulfate and water are included. In comparative Example M, alkylbenzene sulfonate is omitted and a marked decline in suds mileage is said to be obtained.
Klisch et al., U.S. Patent No. 4,554,098 discloses good foaming liquid detergents having reduced skin ir~tatin~ proper-ties which include 8 to 30% alkyl ether sulfate, a ~upplementary, non-soap anionic detergent, 1 to 8% of a zwitterionic surfactant which may be a betaine, an amidobetaine or a sulfobetaine and a solubilizer which is selected from a group including alcohols, lower alkyl benzene sulfonate salts, urea and mixture3 thereof.
The formulations are said to be suitable as hand dishwashing li~uids.
Example 5 of Klisch includes 16% ammonium alkyl ether ~o sulate salt, 6% sodium alkyl ether sulfate salt, 4%
amidobetaine, 3% monoethanolamide, 5.4% sodium xylene sulfonate and 9.5% ethanol. Example 35 includes 13% ammonium alkyl et~er sulfate, 2% ammonium lauryl sulfate, 4.5~ amidobetaine, 1.5%
monoethanolamide, 9.2% ethanol, and 4.2% sodium xylene s~lonate.
Zoo ~8~2 - 8 - c6074 . ~ .
Bissett et. al., U.s. Patent No. 4,5~8,360 disclos~s miid, foaming detergent compo-qitions comprising 5 to 99% of a mild, foaming anionic surfactant selected from a group i~cluding alkyl ether sulfates, 1 to 30% of a surfactant which may be a betaine or an amidobetaine and 0.5 to 20% of an amine oxide 6uds booster. The ratio of anionic detergent to the ~etaine i~ rom 1:1 to 20:1, preferably 3:1 to 10:1. Detergency builders, 501-vents such as ethanol and water, and hydrotropes ~uch as sodium xylene s~lfonate may be included. In Example lII, 27% al~:yl 0 ether sulfate, 5~ amine oxide, and 10% cetyl dimethyl betaine are pres~nt.
Carter et. al., U.S. Patent No. 4,088,612 disclose~ COM-positions which include certain sulfobetai~es and an anion~c sur~
factant in a molar ratio of not less than 1 to 2 parts. ~mong the anionics lis~ed are ether sulfates. In Table II a fo~mula-tion including hexadecyl pyridino sulfobetaines and sodium lauryl ethylene oxide (BEC) ether sulfate in a 1:1 molar ratio i8 given.
Compositions including sulfobetaines and ether sulfates are al~o given in Table I. Hydrotropes such as alkali metal aryl sulfonates, organic solvents such as lower alcohols, and salts such as sodium sulfate may be included.
European Patent Application 036,625 discloses li~uid f cleaning compositions said to be useful for washing di~hes by hand. The compositions include by weight 4-20% of a ~ixture of :, , ,. . .
' ' ' ' , . ~
' ' 8~Z
_ 9 _ C6074 sulated ethylene oxide/alkanol adducts, and ~i~ionally 2-5% ~us-face active be~aines in addition to one or more anionic t~n~ide~, optionally nonionic tensides, solvents and other ingredient Example 4 appears to include 9% alkylbenzene sulfonate, ~% al~yl ether sulfate, 2% alkyamidopropyldimethylcarboxymethylbetaine and 10% ethanol. Example 6 appears to include 10%
alkylbenzenesulfonate, 10% alkylsulfonate, 5% alkyl e~her sulfate, 5% amidobetaine and 8% isopropanol. Example 9 appear~ .
to include 5% alkyl ether sulfate, 2% betaine, 3% alkylsul~ate, 5% nonionic and 4% isopropanol.
It has now ~een found that light duty liquid detergent formulations having a ratio of amido- and/or amido sul~obetaine surfactants to linear ether sulfate within the range defined below exhibit excellent mildness and foaming without the need for additional surfactants or excessive amounts of betaine ox of total surfactant.
SUMMARY OF THE INVENTION
_ The invention comprises aqueous light duty liquid deter-20 gent formulations, especially suitable for use in hand dishwashing, which include a) an essentially-binary active system consisting essentially of i) a betaine surfactant which may be an alkylamidobetaine or a amidosulfobetaine or mixtures thereof and ii~ an alkyl ether sulfate surfactant, wherein the weight ratio of i) to ii) is in the range of 1:4 to 1:1, b) from 1 ko 12% of a 2al~
- 10 - c6074 -hydrotrope and c) from O to 12% of electrolyte~. Pre~rably tha - range of i) to ii) is from 1:3 to 1:1, even more preferab~y 1:2 to 1:1.5.
The light duty liquid deter~ent of t~ ve~tion has been found to have excellent mildness and foaming propertieA, and is particularly suitable for use as a hand dishwashing li~uid.
Moreover, the liquid of the invention does not require large amounts of the betaine or of total surfactant and US25 an essen-tially binary active system, thus eliminating th~ need ~or addi-tional surfactants.
1o DETAILED DESCRIPTION OF THE INVENTION
The betaine surfactan~s useful in th~ invention are zwitterionic surfactants and are either al~ylamidobetaines or alkylamidosulfobetaines.
The alkylamidobetaines usef~l in the present invention are given by the following formula:
o (CH2)y(CH3) R CNH(CH2)xl(~)c~2cO2(-) (CH2)Z(CH3) where R is an al~yl or alkenyl ch~in containing 9 to 17 carbon atoms, x is an integer of 2 to 4, y is an integer of O to 3, and z is an integer of O to 3. The preferred value o x is 3. The preferred values of y and z are both 0. R is preferably a fatty .
-. ~ , .
2~
group which ~ontains ll to I3 carbon atom5, moS~ preferably in ~
straight chain. The preferable ~ource of the R group ie coconut oil. The preferred amidobetaine may be represented by the fol-lowing formula:
Il I
RCN}l ( CH2 ) 3 1 ( ~ ) CH2~2 ( - ) wherein R is an alkyl or alkenyl group containing 9 to l3 carbon atoms.
Examples of the alkylamidobetaine~ useful i~ t~e preQ~nt invention include cocoamidomethylbetaine, laurylamidopropyl-betaine, and cetylamidomethylbetaine.
Alkylamidobetaines useful in the pre~ent invention are commercially available from, e.g., Lonza Incorporated und~r the trademark Lonzaine C; from the Miranol Chemical Company under th~ ~' trademark Mirataine CB; and from the Stepan Chemical CoO under the trademark Amphosol CA.
The alkylamidosulfobetaines useful in the invention have the following formula:
R5-C-NHR4-N(I)CH- Rl-SO3~-) R3 y X
wherein Rl is an alkylene radical having from l to about 3 car~on atoms, X is hydrogen, methyl or hydroxy, Y is hydrogen or methyl, ~, ~ "
. .
: ~
.2 - 12 - c6074 R2 and R3 are independently selected from metbyl, ethyl and hydroxyethyl radicals, R4 is an alkylene radical havin~ from a~out 2 to about 6 carbon atoms and R5 icii an alkyl radical havlng from about 10 to about 18 carbon atoms.
Representative amidosulfobetaine surfactant~ include cocoamidomethylsulfopropylbetaine, stearylamidodimethylsulfopro-pylbetaine, and laurylamidobis-(2-hydroxyethyl)-s~lfopro~yl-betaine.
In preferred sul~obetaine surfactants, R2 and R3 are methyl. R1 is preferably ethylene. R4 is preferàbly an alkylene radical having 2 to 4 carbon atoms. R5 pre~erably i8 a stra~ght chain. Convenient sources of alkyl radicals having from 10 to 18 carbon atoms are tallow fatty alcohol and coconut ~atty alcohol.
Particularly preferred a~idosulfobetaines are hydroxysultai~ss such as cocamidopropyl hydroxysultaine, the formula of which i~
RC-NH(CH2)3-N(l~CH2CHCH2503(-) C~3 0~
where RC0 represents the coconut acid radical. Cocamidopropyl-hydroxysultaine is available from Lon~a Inc. as Lonz~ine rs and Lonzaine JS and from Miranol as Miratalne CBS.
The ~etaine surfactanti~ will generally be pxesent in the compositions of the inventions at levels rangin~ from 2-13% by weight, p~eerably 3-9%.
.
, ~ .
By e~sentlally bin~ry actiYe aystem . it 1~ mean that no more than about 1% of ~u~factants other than the ether sulfate and amidobetaine or amidosulfobetainc are included.
The alkyl ether sulfate surfactants used in the present formulations have the formula:
RO~CnH2nO)qS03X
or RO(CnH(2n~1)0)qS03X
where R is an alkyl or hydroxyalkyl group containing about 8 to about 18 carbon atom , n is 2 or 3 and q can vary;~rom 1 to ab~ut 30. Ether sulfates wherein R is rom C12 to Cls are preferred.
Preferably q range~ from 1 to 3, especially 3. ~ is preerably 2. X is a cation preferably selected rom the group con3isting of alkali metal, especially sodium and potassium, i~n~, alkal~ne earth metal, e.g., calcium and magnesium, ions, ammonium or 8ub-stituted ammonium ions such as mono-, di- or triethanolammonium cations. Mixtures of cations may be u~ed. Ammonium ion~ are especia~ly prefer~ed. The alkyl ether sulfates will ~enerally be present in the compositions of the invention at levels o~ ~rom 6 to 22%, preferably 6 to 20%, and especially 10 to 18%o Neodol 25-3A (ex Shell), which includes an ether sul~ate wherein R i6 a mixture of C12-Cls alcohol, X is ammonium and the alcohols are ethoxylated with 3EO groups may be used as ~ source - of the ether sulfat~. Other source of alkyl ~thor Yulf~tes suitable f or use in the compo~itions of the inYention ~ncl~de Pareth 23-3 (ex Shell) which include~ ammonlum alkyl et~er ~ul~
fates in which R is a mixture of C12 and C13 alco~ol~ and wher~ln the alcohols are ethoxylated with 3 EO ~roups.
The total percent by weight of sur~actants in the formu-lations of the invention is preferably no ~igher than 30k, more preferably no higher than 25%, e~pecially up to 21%. Pref~r~bly the surfactants comprise at least 16% of the composition.
The hydrotropes used herein are preferably 6electad ~rom the group consisting of alkanols and lower alkyl ~Cl-C3) ben~ene sulfonates and mixtures thereof. Alkanols containing ~ro~ ona to six carbon atoms, particularly ethyl alcohol, a~d mixtu~e~
thereo~ can be used as solvents. Isopropanol i~ another appro-priate alcohol. The preferred lower alkyl benzene sulfonatea are sodium and potassium xylene, toluene, and cume~e ~u1~onate3 and mixtures thereof. Especially preferred hydrotrope ~ystems for alkylamidobetaines comprise miXtUre-Q of ~thyl alcohol and sodlum xylene sulfonate. The preferred hydrotrope for al~ylamidosulfobetaines is ethanol.
The hydrotropes can tot~l from l to 12% by weight o the formulation. For sodium xylene sulfonate and other lower alkyl benzene sulfonate hydrotropes, the preferred range is from 0.5 t~
: ' ' ~
'' ' .
DETER&ENT COMPOSITION COMPRISING
BETAINE AND ETHER SULFATE
5 BACKGROUND OiF THE INVENTION
Two particularly important characteri tics of hand dishwashing detergent liquids are mildness, which is significant due to the exposure of the hands to the detergent formulations, and foamability. Foamability is important because the amount of foam generated during washing is related to the ability of a formulation to : clean dishes and eating utensils effectively.
; 15 Among the surfactants included to promote mildness in some light duty liquid detergent formulations are certain betaine surfactants and linear ether sulfates. However, such formulations have tended generally to include high levels of total surfactant high levels of the costly betaine surfactants and/or one or more extra surfactants in addition to the betaine and ether sulfates.
, :, ` ` ` ' ~ .
-- 2 - C607~
Rubin et al., US Patent No ~ 375 421 discloses high viscosity aqueous compositions including alkylamidobetaines and selected salts such as certain sulfates, carbonates, citrates, tartrates and succinates.
The inclusion of micelle-forming anionic surfactants are said to produce a synergistic, viscosity-building effect.
Among the numerous types of anionics mentioned for use in their invention are included sodium, potassium, calcium, .
;
~ 3 - C6074 magne~ium and am~onium alco~ol ethoxy sulfate6. In Examples 6~B
and 6-C, hand dishwashing preparations are disclosed which include cocoamido betaine, ammonium alcohol ethoxy sulfate, lauryl dimethyl amine oxide and either sodium citrate or sodlum sulfate. The ratio of betaine to ether sulfate i~ ~uch greater than l:l. Rubin et al. indicate that the par~icular type of betaine is important and that ~ost betaines are not thickened in the presence of salts. It is said that only alkylamidobetaine~ -are thickened under the described conditions.
Chirash et al., U.S. Patent No. 4,772,425 discloses light duty li~uid abrasive-containing dishwashing'compositions which include at least one sulfated or sulfonated anionic surfactant, a betaine, a clay stabilizing agent and a minor amount of a solubilizer such as ethanol as a preferred optional ingredient. Preferably, the formulation includes a ternary sur-factant system of an alkyl benzyl su1fonate or alkane sulfonate, an alkyl ethenoxy ether sulfate and a betaine, the clay, and 2 to 9% alcohol Several of the examplified compositions of Chirash include ether sulfate and betaine suractants and ethanol. For instance, a composition including 17% sodium dodecylbenzene sulfonate, 13% ammonium alkyl trièthenoxyether sulfate, ~%
cocamidopropyl dimethyl betaine, 5.5% ethanol and water is disclosed. In example 6, 6.5% ether sulfate, 2% amidoal~yl ~oc~
betaine, 8.5% sodium dodecylbenzene sul~onate and 4% alcohol are included. The examples including ether sulfate and b~taine appear to possess ternary surfactant systems.
Verdicchio et al., U.S. Patent No. 3,950,417 disclo3e~
high lathering detergent compositions, especially useful as shampo~s, which comprise a surfactant betaine, an a~ionic surfac-tant and a nonionic surfactant. The preferred molar ratio of surfactant betaine to anionic surfactant falls between about 0.9 and about 1.1. The preferred betaines are said to be surfactant amidocarboxybetaines and amidosulfobetaines. Alcohol ether sul-fates are used as anionics and are said to be the preferredanionics. The examples generally include a nonionic surfactant in a~dition to the betaines and the anionic surfactant such as ether sulfates. In addition to use as shampoos, the compofiitions are said to be useful as cleansers for cleaning other parts of the human body, animals, inanimate objects and the like.
Nishimura et al., U.S. Patent No. 4,166,048 discloses hi~h foami~g detergent compositions which are said to have a vcry mild action on the skin. The compositions include certain polyoxyethylene alkyl ether su~,fate salt mixtures and a betaine-type amphoteric surfactant of the~formula Rl~R~)NI(CH2COO-~R3 wherein Rl is alkyl having 8 to 20 carbon atoms. The weight of the betaine type amphoteric surfactant is 0.01 to 2 times, espe-cially 0.03 to 0.5 times the weight of the polyoxyethylepe alkyl ether sulfate salt mixture.
, The ether sulfate salts of the '048 patent may include monovalent metal ions, ~referably Na or ~ or divale~t metal ions, preferably Ca or Mg. Solubilizing agent-~ such a~ et~anol, pro-pylene glycol, glycerin and xylene sulonic acid salt~ ~ay be included. In some of the examples, the compo~ition iB te~ted or washing power on dishes. Small amounts of ammonium chlvride ar~
included in some of tne examples.
The Lonzaine C Product Information Bulletin dlsclo~es that Lonzane C is a mild, hicih oaming s~rfactant of the amide betaine structure. Lonzaine C is said to contain`5% NaCl.
Lonzaine C is said to have outstandin~ conditioning, foaming, and viscosity potentiating properties.- Lonzaine C, in comb~nation with most anionic surfactants, is said to potentiate vi3cosity to permit formulations rangin~ from viscous liguids to ringing gels.
Shampoo formulations including a 30% solutio~ of Lonzaine C (14~), Barlox C, a 40% solution o~ ~odium alpha olefin sulfonate (22%), citric acid, water and optionally polymer JR 125 are disclosed. Lonzaine C is said to be useul in light duty liquids and is said to exhibit toleranc,e toward high levels o~
builder, electrolytes, alkali and acids.
The Stepan bulletin for Amphosol CA (cocoamidopropyl betaine) gives a shampoo formulation including Amphosol CA, a~
amine oxide, an alpha olefin sulfonate, citric acid and water.
In three other formulas, the anionic is respectively sodium ~0~ 2 - 6 - c6074 lauryl sulfa~e, another alcohol ~ulfate salt and slpha olefin sulfonate. It is said that a wide Yariety of visco~itie ~an be attained by addition of NaCl (~om 0 to a gel).
Pancheri et al., U.S. Patent No. 4,772,423 di~clo~
liquid detergents said to have high sudsing c~aracteristic and said to be suitable for washing tableware. The detergents com-prise 5 to 50% anionic surfactant, a polmeric surfactant, detergency builders and water and may also include other surfactants, of which betaine surfactants are highly preferre~l.
1~ The betaine is present at from 0.5 to lS~, preferably from 1 to 10%. The ratio of anionic to betaine is from about 1 to 80, preferably from 1 to 40 more preerably from about 2 to 40. The preferred anionic surfactants are alkylpolyethoxylate sulfates having from 0.5 to 10 ethylene oxide groups. The anionics may be salts of sodium, potassium, ammonium, monoethanolammonium, diethanolammonium, trietha~olammonium and other cations. Alcohols and hydrotropes such as sodium xylene sulonate may be included, as may water-soluble inor~anic builders. Alkyl ether sulfates and alkylamido betaines are included together in various examples, ~enerally with an addi-tional surfactant.
Lamb et. al., U.S. Patent No. 4,671,894 disclo~es liquid dishwashing de~ergents comprising 4 to ~0% alXyl ~ulfate, 5 to 20~o alkylbenzene sulfonate, 1 to 10% of a nonionic surfactant, 5 ,' .
' ' ; :
`
to 24% alkyl et~oxy sulfate, 0.25 to 10% of a zwitterionlc sur-factant such a~ an alkyl betaine, an alkylamidobeta~ne or a sulfobetaine, and a hydrotrope-water system which may include ethanol, urea, and/or a lower alkyl benzene sulfonate. In exam-ple D, 9.9% ammonium alkyl ethoxy sulfate, 2.2S~ amidopropylbetaine, ethanol, alkylbenzene sulfonate, alkyl ~ulfate and water are included. In comparative Example M, alkylbenzene sulfonate is omitted and a marked decline in suds mileage is said to be obtained.
Klisch et al., U.S. Patent No. 4,554,098 discloses good foaming liquid detergents having reduced skin ir~tatin~ proper-ties which include 8 to 30% alkyl ether sulfate, a ~upplementary, non-soap anionic detergent, 1 to 8% of a zwitterionic surfactant which may be a betaine, an amidobetaine or a sulfobetaine and a solubilizer which is selected from a group including alcohols, lower alkyl benzene sulfonate salts, urea and mixture3 thereof.
The formulations are said to be suitable as hand dishwashing li~uids.
Example 5 of Klisch includes 16% ammonium alkyl ether ~o sulate salt, 6% sodium alkyl ether sulfate salt, 4%
amidobetaine, 3% monoethanolamide, 5.4% sodium xylene sulfonate and 9.5% ethanol. Example 35 includes 13% ammonium alkyl et~er sulfate, 2% ammonium lauryl sulfate, 4.5~ amidobetaine, 1.5%
monoethanolamide, 9.2% ethanol, and 4.2% sodium xylene s~lonate.
Zoo ~8~2 - 8 - c6074 . ~ .
Bissett et. al., U.s. Patent No. 4,5~8,360 disclos~s miid, foaming detergent compo-qitions comprising 5 to 99% of a mild, foaming anionic surfactant selected from a group i~cluding alkyl ether sulfates, 1 to 30% of a surfactant which may be a betaine or an amidobetaine and 0.5 to 20% of an amine oxide 6uds booster. The ratio of anionic detergent to the ~etaine i~ rom 1:1 to 20:1, preferably 3:1 to 10:1. Detergency builders, 501-vents such as ethanol and water, and hydrotropes ~uch as sodium xylene s~lfonate may be included. In Example lII, 27% al~:yl 0 ether sulfate, 5~ amine oxide, and 10% cetyl dimethyl betaine are pres~nt.
Carter et. al., U.S. Patent No. 4,088,612 disclose~ COM-positions which include certain sulfobetai~es and an anion~c sur~
factant in a molar ratio of not less than 1 to 2 parts. ~mong the anionics lis~ed are ether sulfates. In Table II a fo~mula-tion including hexadecyl pyridino sulfobetaines and sodium lauryl ethylene oxide (BEC) ether sulfate in a 1:1 molar ratio i8 given.
Compositions including sulfobetaines and ether sulfates are al~o given in Table I. Hydrotropes such as alkali metal aryl sulfonates, organic solvents such as lower alcohols, and salts such as sodium sulfate may be included.
European Patent Application 036,625 discloses li~uid f cleaning compositions said to be useful for washing di~hes by hand. The compositions include by weight 4-20% of a ~ixture of :, , ,. . .
' ' ' ' , . ~
' ' 8~Z
_ 9 _ C6074 sulated ethylene oxide/alkanol adducts, and ~i~ionally 2-5% ~us-face active be~aines in addition to one or more anionic t~n~ide~, optionally nonionic tensides, solvents and other ingredient Example 4 appears to include 9% alkylbenzene sulfonate, ~% al~yl ether sulfate, 2% alkyamidopropyldimethylcarboxymethylbetaine and 10% ethanol. Example 6 appears to include 10%
alkylbenzenesulfonate, 10% alkylsulfonate, 5% alkyl e~her sulfate, 5% amidobetaine and 8% isopropanol. Example 9 appear~ .
to include 5% alkyl ether sulfate, 2% betaine, 3% alkylsul~ate, 5% nonionic and 4% isopropanol.
It has now ~een found that light duty liquid detergent formulations having a ratio of amido- and/or amido sul~obetaine surfactants to linear ether sulfate within the range defined below exhibit excellent mildness and foaming without the need for additional surfactants or excessive amounts of betaine ox of total surfactant.
SUMMARY OF THE INVENTION
_ The invention comprises aqueous light duty liquid deter-20 gent formulations, especially suitable for use in hand dishwashing, which include a) an essentially-binary active system consisting essentially of i) a betaine surfactant which may be an alkylamidobetaine or a amidosulfobetaine or mixtures thereof and ii~ an alkyl ether sulfate surfactant, wherein the weight ratio of i) to ii) is in the range of 1:4 to 1:1, b) from 1 ko 12% of a 2al~
- 10 - c6074 -hydrotrope and c) from O to 12% of electrolyte~. Pre~rably tha - range of i) to ii) is from 1:3 to 1:1, even more preferab~y 1:2 to 1:1.5.
The light duty liquid deter~ent of t~ ve~tion has been found to have excellent mildness and foaming propertieA, and is particularly suitable for use as a hand dishwashing li~uid.
Moreover, the liquid of the invention does not require large amounts of the betaine or of total surfactant and US25 an essen-tially binary active system, thus eliminating th~ need ~or addi-tional surfactants.
1o DETAILED DESCRIPTION OF THE INVENTION
The betaine surfactan~s useful in th~ invention are zwitterionic surfactants and are either al~ylamidobetaines or alkylamidosulfobetaines.
The alkylamidobetaines usef~l in the present invention are given by the following formula:
o (CH2)y(CH3) R CNH(CH2)xl(~)c~2cO2(-) (CH2)Z(CH3) where R is an al~yl or alkenyl ch~in containing 9 to 17 carbon atoms, x is an integer of 2 to 4, y is an integer of O to 3, and z is an integer of O to 3. The preferred value o x is 3. The preferred values of y and z are both 0. R is preferably a fatty .
-. ~ , .
2~
group which ~ontains ll to I3 carbon atom5, moS~ preferably in ~
straight chain. The preferable ~ource of the R group ie coconut oil. The preferred amidobetaine may be represented by the fol-lowing formula:
Il I
RCN}l ( CH2 ) 3 1 ( ~ ) CH2~2 ( - ) wherein R is an alkyl or alkenyl group containing 9 to l3 carbon atoms.
Examples of the alkylamidobetaine~ useful i~ t~e preQ~nt invention include cocoamidomethylbetaine, laurylamidopropyl-betaine, and cetylamidomethylbetaine.
Alkylamidobetaines useful in the pre~ent invention are commercially available from, e.g., Lonza Incorporated und~r the trademark Lonzaine C; from the Miranol Chemical Company under th~ ~' trademark Mirataine CB; and from the Stepan Chemical CoO under the trademark Amphosol CA.
The alkylamidosulfobetaines useful in the invention have the following formula:
R5-C-NHR4-N(I)CH- Rl-SO3~-) R3 y X
wherein Rl is an alkylene radical having from l to about 3 car~on atoms, X is hydrogen, methyl or hydroxy, Y is hydrogen or methyl, ~, ~ "
. .
: ~
.2 - 12 - c6074 R2 and R3 are independently selected from metbyl, ethyl and hydroxyethyl radicals, R4 is an alkylene radical havin~ from a~out 2 to about 6 carbon atoms and R5 icii an alkyl radical havlng from about 10 to about 18 carbon atoms.
Representative amidosulfobetaine surfactant~ include cocoamidomethylsulfopropylbetaine, stearylamidodimethylsulfopro-pylbetaine, and laurylamidobis-(2-hydroxyethyl)-s~lfopro~yl-betaine.
In preferred sul~obetaine surfactants, R2 and R3 are methyl. R1 is preferably ethylene. R4 is preferàbly an alkylene radical having 2 to 4 carbon atoms. R5 pre~erably i8 a stra~ght chain. Convenient sources of alkyl radicals having from 10 to 18 carbon atoms are tallow fatty alcohol and coconut ~atty alcohol.
Particularly preferred a~idosulfobetaines are hydroxysultai~ss such as cocamidopropyl hydroxysultaine, the formula of which i~
RC-NH(CH2)3-N(l~CH2CHCH2503(-) C~3 0~
where RC0 represents the coconut acid radical. Cocamidopropyl-hydroxysultaine is available from Lon~a Inc. as Lonz~ine rs and Lonzaine JS and from Miranol as Miratalne CBS.
The ~etaine surfactanti~ will generally be pxesent in the compositions of the inventions at levels rangin~ from 2-13% by weight, p~eerably 3-9%.
.
, ~ .
By e~sentlally bin~ry actiYe aystem . it 1~ mean that no more than about 1% of ~u~factants other than the ether sulfate and amidobetaine or amidosulfobetainc are included.
The alkyl ether sulfate surfactants used in the present formulations have the formula:
RO~CnH2nO)qS03X
or RO(CnH(2n~1)0)qS03X
where R is an alkyl or hydroxyalkyl group containing about 8 to about 18 carbon atom , n is 2 or 3 and q can vary;~rom 1 to ab~ut 30. Ether sulfates wherein R is rom C12 to Cls are preferred.
Preferably q range~ from 1 to 3, especially 3. ~ is preerably 2. X is a cation preferably selected rom the group con3isting of alkali metal, especially sodium and potassium, i~n~, alkal~ne earth metal, e.g., calcium and magnesium, ions, ammonium or 8ub-stituted ammonium ions such as mono-, di- or triethanolammonium cations. Mixtures of cations may be u~ed. Ammonium ion~ are especia~ly prefer~ed. The alkyl ether sulfates will ~enerally be present in the compositions of the invention at levels o~ ~rom 6 to 22%, preferably 6 to 20%, and especially 10 to 18%o Neodol 25-3A (ex Shell), which includes an ether sul~ate wherein R i6 a mixture of C12-Cls alcohol, X is ammonium and the alcohols are ethoxylated with 3EO groups may be used as ~ source - of the ether sulfat~. Other source of alkyl ~thor Yulf~tes suitable f or use in the compo~itions of the inYention ~ncl~de Pareth 23-3 (ex Shell) which include~ ammonlum alkyl et~er ~ul~
fates in which R is a mixture of C12 and C13 alco~ol~ and wher~ln the alcohols are ethoxylated with 3 EO ~roups.
The total percent by weight of sur~actants in the formu-lations of the invention is preferably no ~igher than 30k, more preferably no higher than 25%, e~pecially up to 21%. Pref~r~bly the surfactants comprise at least 16% of the composition.
The hydrotropes used herein are preferably 6electad ~rom the group consisting of alkanols and lower alkyl ~Cl-C3) ben~ene sulfonates and mixtures thereof. Alkanols containing ~ro~ ona to six carbon atoms, particularly ethyl alcohol, a~d mixtu~e~
thereo~ can be used as solvents. Isopropanol i~ another appro-priate alcohol. The preferred lower alkyl benzene sulfonatea are sodium and potassium xylene, toluene, and cume~e ~u1~onate3 and mixtures thereof. Especially preferred hydrotrope ~ystems for alkylamidobetaines comprise miXtUre-Q of ~thyl alcohol and sodlum xylene sulfonate. The preferred hydrotrope for al~ylamidosulfobetaines is ethanol.
The hydrotropes can tot~l from l to 12% by weight o the formulation. For sodium xylene sulfonate and other lower alkyl benzene sulfonate hydrotropes, the preferred range is from 0.5 t~
: ' ' ~
'' ' .
3.5 wt%, preferably l.S to 3.5%. The preer~el range for ethanol is from l to 10%, especially 3 to 8%.
Among the optional ingredients which may be present in the light duty li~uid detergent compositions of the invention a~e neutral salts. Particularly preferred neutral salts include the alkalï metal sulfates, particularly sodium sulate, and the alkali metal chlorides, particularly sodium chlorlde~ The ne~-tral salts comprise from 0 to 12%, preferably from ~.5 to 12% of the present .:ompo~itions. Sodium chloride is preferably pres nt within the range of 0.25 to 2 wt% whereas sodium 6ul~ate will generally b~ present at from 0 to 5 wt%, especially 0.25 to 5 wt %. Compositions may include both sodium chloride and 60dium sulfa~e. Other examples of neutral salts which may be included in the formulations of the invention are sodium, pota#3ium, ammonium, zinc, monoethanolammonium, diethanolammonium and triethanolammonium sulfates, chlorides, bromides, iodides, fornates, oretates, citrates, succinates and tartrates The compositions of the invention are ormulated gener-ally to have a viscosity of from 150 to 3500 cps. Where less ciscous liquids are desired, the viscosity will range from 150 Up to 1000 cps, preferably 300-400 cps. The viscosity of high vis-cosity liquids will preferably be within the rango of 1000-2500 cps, preferably about 2500 cps. The present invention yields an clear, stable, highly viscous liguid within the 1000-2S00 cps .
.
.
range. Such hig~er visco~ity formulation0 can oe used ~dvanta-ge~usly in direct application washing where~n the l~uid iQ
applied to the dishware or utenRil itself (e.g., squ~rted onto the utensil or onto a sponge and applied to the ute~sil) instead of after dilution wi~h dishwater. In general, the viscosity o the compositions is adjusted by varying the levels o~ neutral salts and hydrotropes.
Water will generally comprise fro~ 40 to 80% by weight of the compositions, preferably 49 to 77~.
The compositions of the invention may include variou~
other ingredients typically found in light duty detergents including colorants and dyes such as D&C Yellow #lO and FD~C
Green #3, perfu~es and preservatives.
The pH of the compositions will generally range from 6 to 7.5, preferably about 7.
The compositions of the invention are stable and gener-ally clear, although they may be opacified if desired.
The light duty liquid detergent of the invention does not generally include a polymeric surfactant, cationic polymer~, a clay or an abrasive, although inclusion of such ingredients may be appropriate in certain circumstances. Also, the detergent of the invention does not include alkanolamide or aminc oxide surfactants.
- 17 - c6074 While t~e liqht duty liguid detergent compo~ition~ o the invention are primarily adapted to usc as h~nd d~shwash~ng detergent~, their u~e i~ not limited thereto. For in~tance, it may be ~ppropriate to utilize the formulations as shampoos, ~u~
ble hath compositions, liguid soaps and th~ like.
The compositions of the invention may be pr~pared ~n the following manner. The require~ amount of alkyl ether ~ulate active solution is poured into a mixin~ vessel fitted with an overhead stirrer. With the mixer operating at high spe~d, any sodium xylene sulfonate solution is slowly added Once tho ~lu-tion is ho~ogeneous, water i9 slowly added to th~ cente~ o~ t~e vortex to minimize gelation. If electrolyte i~ reguir~d in the form-~lation, it should be dissolved in the water beforehand.
Once all the water has been added, mixing is continued until no gel par~icles are visible. The betaine solution i~ then added with mixing, followed by any color and fragrance. The entlre process is carried out at room temperature.
Unless otherwise indicated, all percentage~ given her~i~
are by weight.
Z0~74~ L~
- 18 - c6074 EXAMPLES
Exam~le l The following dishwashing li~uid was prepared i~ accordance wit~
t~e process described above.
Component Ammonium Cl2-Cls alcohol ethoxylated withlS.4%
3 moles ethylene oxide, sulfated 8 6%
Cocoamidopropylbetaine Ethanol l 4;0 Sodium chloride Sodium xylene sulfonate to 100%
Water, color, fragrance The viscosity of the product was 2000-2500 cps. The product was clear and stable.
Example 2 Mildness An occlusive patch test was c~nducted to evaluate formu~
lationR for mildness potential. Ivory Liguid Di~hwashi~ deter-gen~ was used as a standard. In the ocolusive patch te~t, 2%
solutions of a formulation are attached to the forearm using plastic discs. The discs are left on t~e arm for 24 hours, then the skin is evaluated 24 hours after removal o~ the di5cs. ~h~
lower the score, the less irritating the ~ormula~ion. The ~ol-lowing formulations were tested.
2~ L8 ~2 . .
Com~nent A B C D E
Sodium lauryl sulfate 14 Ammonium C12-C15 -- 13.5 19 15 19 alcohol ~ 3 E0, Sulfated ~from Neodol 25-3A) Cocoamidopropylbetaine 8 7.5 6 10 --Cocoamidopropylhydroxy~ 6 sultaine Ethanol -- 3-4 4-75 3-75 4-75 Sodium Chloride 1.3 1.25 1.0 1.67 ~.85 Sodium xylene sulfonate1.5 1.5 1.5 1.5 --Water 75.2 72.85 67.75 68.08 69.40 Formulation Irritation A (Comparison) 1.233 B 0.6 C 0.6 D 0.633 E 0.6 Ivory Liquid 0.7 There are no significant differences between ~ormula-tions B,C,D and E in accordance with the invention and Ivory Li~uid.
Example 3 Dispersibility A six foot clear ty~on tube with an internal diameter of 3 cm was suspended vertically. The tube was calibrated, its end capped and filled with 40 degree C tap water. A 75 ul aliguot of ~00 ~8~2 light duty liquid was injected onto ths water ~urf~co usln~ a positive displacement pipette. The LDL dropl~t was followed vls-ually and the point where the drop could no lonqer be ~een was recorded. Thrçe trials were performed for each LDL. F~esh 40 5 degree C tap water was used for each formulatio~. The larger ~e distance reported, the poorer the dispersability.
Formulation:
Component (wt/~ 1 2 3 4 5 Ammonium C12-C15 13.5 13.513.5 13.5 13.5 alcohol ethoxylated 10 with 3 moles Ethylene oxide, sulfated cocoamidopropyl betaine 7.5 7.5 7.5 7.5 7.5 Ethanol 3.~ 3.4 3.4 3.4 8.2 Sodium chloride 1.25 1.2511.25 1.25 1.25 Sodium sulfate -- 4.0 -- 8.0 --15 Sodium xylene sulfonate 0.5 2.5 -- __ __ Water 73.85 67.8564.35 66.35 69.55 Viscosi~y (cps) 2000 20002000 2000 2000 Formulation Dispersion Distance ~inche~) 3 did not disper~e 4 did not disperse ` 30 Commercial Dishwashing Liquid I 33 Commercial Dishwashing Liquid II 49 Viscosities were measured with a Brookfield viscometer using a 25numher 3 spindle. Thi~ example demonstrates the preferred embod--.
: ' ~
q20~f~8 LZ
iment of a h~gh v~Scosity LES~betaine mixtur~ ~ ~ch pO38~8S~
dispersability equal to that of marketed products. The hlg~er viscosity provides an advantage in direct application washing.
Formulations l, 2 and 5 containing sufficient hydrotrope ~uch that the LDL is dispersed in this test are preferred. It is especially preferred that the LDL disperse within 40, pre~erably within 35, inches in this test.
Example Piston Plunger Test The piston plun~er is used to determine t~e relative abilities of LDLs to resist foam depletion in the presenca of food soil. In the test, foam is generated and food ~oil i~
added in lO gram increments. The agitation/soil addition cycl~s continue until the foam is depleted. The weight of the soil added is then determined and used as a relative measure of LDL
efficacY-Ragu Cri~co Shorten~n~ Soll A Food Soil Including A Food Soil Incl~ding Crisco Shortening Ragu Spag~etti Sauc~
Example o~ Cleaning Performance 1 The piston plunger method u~in~ the Ragu spag~tti ~oll wa~ utilized to determine the performance o th~ ollow~ng formulations. The experiments were conducted at 40C.
ComPonent 1 2 Ammonium C12-Cls alcohol 13.5% 19~3Xo 3EO, sulfated 10 7 : Cocoamidopropylbetaine 7 5 Sodium chloride 1.25% . %
Sodium xylene sul~onate 73 85% 62 9%
_ .
: Formulation Trial 1 Trial 2 Tr~l 3 1 384g 42~g 356 2 435~ 533~ 405 Commercial Dishwashing Liguid I 363g 380g 289~
Commercial Dishwashing Llguid II 422g 463~ 371g The performance of formu~lation 1 121% total actlve~ i~
superior to that of Commercial Dishwashing 1i~uid I. The per-forma~ce of formulation 2 (30% total active~ i~ superior to t~at of Commercial Dishwashin~ Liquid II. Both Commercial D~ehwashing Liquid I and Commercial Dishwashing Liguid II Liguid~ contain greater than 30% total actives.
, .
': ' ' :; : ' :
' 20~48~X
Cleanlng Performance II
Effect of LES/betaine Ratio Evaluation was via piston plunger using Ragu~ ~paghekti sauc0 soil. The experi~ent was conducted at 40C.
Com~onent 1 2 3 4 Ammonium Cl~-C1s alcohol 3 E0, sulfated 19.5% 16.5% 13.5% 10.5%
Cocoamidopropylbetaine 1.5% 4.5% 7.5% 10.5%
Ethanol . 4.9% 4.15% 3.4% 2.6%
Sodium chloride 0.25% 0.75% 1.25% 1.75%
Sodium sulfate 4.0% 4.0% ~.0% 4.3%
Sodium xylene sulfonate 1.5% 1.5% 1.5% 1.5%
Water 68.35~ 68.6% 68.85~ 69.1~%
Formulation Trial 1 Trial 2 Trial 3 1 246g 280g 264g 2 317g 351g 342g 3 339g 341g 386g 4 321g 362g 372~
Ivory Liquid Detergent 383g 429g 425g Commercial Dishwashing Liquid II 370g 403g 413g Commercial Dishwashing Liquid ~ 313g 320g 326g At a ratio of 4 LES~1 betaine and a total of 21%
actives, equal performance to Commercial Dishwashin~ Liquid I i~
attained. At smaller ratios of LES/betaine (below 2:1), and a total actives content of 21%, superior performance to Commercial Dishwashing Liquid I was observed - 24 - C6~74 Cleaning Performance III
Comparison of 24~ total active formulations to Ivory (R) ~iguid (33-34% total actives). The piston plunger test using the Crisco (R) shortening soil at 40 degrees C was used.
Component 1 2 3 Ammonium C12-C1s alcohol 3 E0, sulfated 15.4% 18.0% 15.4%
Cocoamidopropylbetaine8.~% 6.0% --Cocoamidopropylhydroxysultaine -- -- 8.5%
Ethanol 3.8~ 4.6% 3.8~
Sodium chloride 1.4~ 1.15% 1.0%
Sodium sulfate 4.6% ~.0% 1.0%
Sodium xylene sulfonate1.7% 1.5% -- -Water 64.5% 64.75% 70.2%
Viscosity (cps) 2000 2000 ~000 FormulationWei~ht of Soil to Deplete Foam 2 23gg 3 237g Ivory Liquid Detergent250g Cleaning Performance IV
The plates washing test was used to evalùate the exam-ples from "Cleaning Performance III".
Plates Washing Test Soiled dishes are prepared by spreading 5 mls of Crisco (R) shortening soil on sach dish with a spatula. They are ~hen stacked. Meanwhile, water containing the appropriate amount of hardness i5 heated to 115 degrees F.
, :
' ' , : ':
~o~
One gallon of the warm water i9 added to a wa6~ ~a~in ~long wlt~
the appropriate amount of LDL. Foam i3 then generated by u~ing a Mixette electric hand mi~er at high speeds for 20 econds.
Plates washing then proceeds using a standard wash cloth and washing regime. The operator submerges the plate and washes the front surface with six circular stokes. The plate i5 inverted, and the bacX surface is washed with three circular stro~es. The plate is then removed from the wash solution, tipped a~ainst the basin's edge at a 4S degree angle for 3 seconds (to allow foam drainage), and st~cked. The process continues until half the water's surface is no longer covered with foam, as judged by an independent observer. The number of plates washed is then counted and used as a relative measure of performance.
Formulation Plates Wash_ l 36 Ivory Liqui~ 34 Both the piston plunger and plates washing test demon-strate that the preferred embodiment at 24% total active~ level provides parity performance to a leading product containing 34%
total actives.
. ~ .. ,
Among the optional ingredients which may be present in the light duty li~uid detergent compositions of the invention a~e neutral salts. Particularly preferred neutral salts include the alkalï metal sulfates, particularly sodium sulate, and the alkali metal chlorides, particularly sodium chlorlde~ The ne~-tral salts comprise from 0 to 12%, preferably from ~.5 to 12% of the present .:ompo~itions. Sodium chloride is preferably pres nt within the range of 0.25 to 2 wt% whereas sodium 6ul~ate will generally b~ present at from 0 to 5 wt%, especially 0.25 to 5 wt %. Compositions may include both sodium chloride and 60dium sulfa~e. Other examples of neutral salts which may be included in the formulations of the invention are sodium, pota#3ium, ammonium, zinc, monoethanolammonium, diethanolammonium and triethanolammonium sulfates, chlorides, bromides, iodides, fornates, oretates, citrates, succinates and tartrates The compositions of the invention are ormulated gener-ally to have a viscosity of from 150 to 3500 cps. Where less ciscous liquids are desired, the viscosity will range from 150 Up to 1000 cps, preferably 300-400 cps. The viscosity of high vis-cosity liquids will preferably be within the rango of 1000-2500 cps, preferably about 2500 cps. The present invention yields an clear, stable, highly viscous liguid within the 1000-2S00 cps .
.
.
range. Such hig~er visco~ity formulation0 can oe used ~dvanta-ge~usly in direct application washing where~n the l~uid iQ
applied to the dishware or utenRil itself (e.g., squ~rted onto the utensil or onto a sponge and applied to the ute~sil) instead of after dilution wi~h dishwater. In general, the viscosity o the compositions is adjusted by varying the levels o~ neutral salts and hydrotropes.
Water will generally comprise fro~ 40 to 80% by weight of the compositions, preferably 49 to 77~.
The compositions of the invention may include variou~
other ingredients typically found in light duty detergents including colorants and dyes such as D&C Yellow #lO and FD~C
Green #3, perfu~es and preservatives.
The pH of the compositions will generally range from 6 to 7.5, preferably about 7.
The compositions of the invention are stable and gener-ally clear, although they may be opacified if desired.
The light duty liquid detergent of the invention does not generally include a polymeric surfactant, cationic polymer~, a clay or an abrasive, although inclusion of such ingredients may be appropriate in certain circumstances. Also, the detergent of the invention does not include alkanolamide or aminc oxide surfactants.
- 17 - c6074 While t~e liqht duty liguid detergent compo~ition~ o the invention are primarily adapted to usc as h~nd d~shwash~ng detergent~, their u~e i~ not limited thereto. For in~tance, it may be ~ppropriate to utilize the formulations as shampoos, ~u~
ble hath compositions, liguid soaps and th~ like.
The compositions of the invention may be pr~pared ~n the following manner. The require~ amount of alkyl ether ~ulate active solution is poured into a mixin~ vessel fitted with an overhead stirrer. With the mixer operating at high spe~d, any sodium xylene sulfonate solution is slowly added Once tho ~lu-tion is ho~ogeneous, water i9 slowly added to th~ cente~ o~ t~e vortex to minimize gelation. If electrolyte i~ reguir~d in the form-~lation, it should be dissolved in the water beforehand.
Once all the water has been added, mixing is continued until no gel par~icles are visible. The betaine solution i~ then added with mixing, followed by any color and fragrance. The entlre process is carried out at room temperature.
Unless otherwise indicated, all percentage~ given her~i~
are by weight.
Z0~74~ L~
- 18 - c6074 EXAMPLES
Exam~le l The following dishwashing li~uid was prepared i~ accordance wit~
t~e process described above.
Component Ammonium Cl2-Cls alcohol ethoxylated withlS.4%
3 moles ethylene oxide, sulfated 8 6%
Cocoamidopropylbetaine Ethanol l 4;0 Sodium chloride Sodium xylene sulfonate to 100%
Water, color, fragrance The viscosity of the product was 2000-2500 cps. The product was clear and stable.
Example 2 Mildness An occlusive patch test was c~nducted to evaluate formu~
lationR for mildness potential. Ivory Liguid Di~hwashi~ deter-gen~ was used as a standard. In the ocolusive patch te~t, 2%
solutions of a formulation are attached to the forearm using plastic discs. The discs are left on t~e arm for 24 hours, then the skin is evaluated 24 hours after removal o~ the di5cs. ~h~
lower the score, the less irritating the ~ormula~ion. The ~ol-lowing formulations were tested.
2~ L8 ~2 . .
Com~nent A B C D E
Sodium lauryl sulfate 14 Ammonium C12-C15 -- 13.5 19 15 19 alcohol ~ 3 E0, Sulfated ~from Neodol 25-3A) Cocoamidopropylbetaine 8 7.5 6 10 --Cocoamidopropylhydroxy~ 6 sultaine Ethanol -- 3-4 4-75 3-75 4-75 Sodium Chloride 1.3 1.25 1.0 1.67 ~.85 Sodium xylene sulfonate1.5 1.5 1.5 1.5 --Water 75.2 72.85 67.75 68.08 69.40 Formulation Irritation A (Comparison) 1.233 B 0.6 C 0.6 D 0.633 E 0.6 Ivory Liquid 0.7 There are no significant differences between ~ormula-tions B,C,D and E in accordance with the invention and Ivory Li~uid.
Example 3 Dispersibility A six foot clear ty~on tube with an internal diameter of 3 cm was suspended vertically. The tube was calibrated, its end capped and filled with 40 degree C tap water. A 75 ul aliguot of ~00 ~8~2 light duty liquid was injected onto ths water ~urf~co usln~ a positive displacement pipette. The LDL dropl~t was followed vls-ually and the point where the drop could no lonqer be ~een was recorded. Thrçe trials were performed for each LDL. F~esh 40 5 degree C tap water was used for each formulatio~. The larger ~e distance reported, the poorer the dispersability.
Formulation:
Component (wt/~ 1 2 3 4 5 Ammonium C12-C15 13.5 13.513.5 13.5 13.5 alcohol ethoxylated 10 with 3 moles Ethylene oxide, sulfated cocoamidopropyl betaine 7.5 7.5 7.5 7.5 7.5 Ethanol 3.~ 3.4 3.4 3.4 8.2 Sodium chloride 1.25 1.2511.25 1.25 1.25 Sodium sulfate -- 4.0 -- 8.0 --15 Sodium xylene sulfonate 0.5 2.5 -- __ __ Water 73.85 67.8564.35 66.35 69.55 Viscosi~y (cps) 2000 20002000 2000 2000 Formulation Dispersion Distance ~inche~) 3 did not disper~e 4 did not disperse ` 30 Commercial Dishwashing Liquid I 33 Commercial Dishwashing Liquid II 49 Viscosities were measured with a Brookfield viscometer using a 25numher 3 spindle. Thi~ example demonstrates the preferred embod--.
: ' ~
q20~f~8 LZ
iment of a h~gh v~Scosity LES~betaine mixtur~ ~ ~ch pO38~8S~
dispersability equal to that of marketed products. The hlg~er viscosity provides an advantage in direct application washing.
Formulations l, 2 and 5 containing sufficient hydrotrope ~uch that the LDL is dispersed in this test are preferred. It is especially preferred that the LDL disperse within 40, pre~erably within 35, inches in this test.
Example Piston Plunger Test The piston plun~er is used to determine t~e relative abilities of LDLs to resist foam depletion in the presenca of food soil. In the test, foam is generated and food ~oil i~
added in lO gram increments. The agitation/soil addition cycl~s continue until the foam is depleted. The weight of the soil added is then determined and used as a relative measure of LDL
efficacY-Ragu Cri~co Shorten~n~ Soll A Food Soil Including A Food Soil Incl~ding Crisco Shortening Ragu Spag~etti Sauc~
Example o~ Cleaning Performance 1 The piston plunger method u~in~ the Ragu spag~tti ~oll wa~ utilized to determine the performance o th~ ollow~ng formulations. The experiments were conducted at 40C.
ComPonent 1 2 Ammonium C12-Cls alcohol 13.5% 19~3Xo 3EO, sulfated 10 7 : Cocoamidopropylbetaine 7 5 Sodium chloride 1.25% . %
Sodium xylene sul~onate 73 85% 62 9%
_ .
: Formulation Trial 1 Trial 2 Tr~l 3 1 384g 42~g 356 2 435~ 533~ 405 Commercial Dishwashing Liguid I 363g 380g 289~
Commercial Dishwashing Llguid II 422g 463~ 371g The performance of formu~lation 1 121% total actlve~ i~
superior to that of Commercial Dishwashing 1i~uid I. The per-forma~ce of formulation 2 (30% total active~ i~ superior to t~at of Commercial Dishwashin~ Liquid II. Both Commercial D~ehwashing Liquid I and Commercial Dishwashing Liguid II Liguid~ contain greater than 30% total actives.
, .
': ' ' :; : ' :
' 20~48~X
Cleanlng Performance II
Effect of LES/betaine Ratio Evaluation was via piston plunger using Ragu~ ~paghekti sauc0 soil. The experi~ent was conducted at 40C.
Com~onent 1 2 3 4 Ammonium Cl~-C1s alcohol 3 E0, sulfated 19.5% 16.5% 13.5% 10.5%
Cocoamidopropylbetaine 1.5% 4.5% 7.5% 10.5%
Ethanol . 4.9% 4.15% 3.4% 2.6%
Sodium chloride 0.25% 0.75% 1.25% 1.75%
Sodium sulfate 4.0% 4.0% ~.0% 4.3%
Sodium xylene sulfonate 1.5% 1.5% 1.5% 1.5%
Water 68.35~ 68.6% 68.85~ 69.1~%
Formulation Trial 1 Trial 2 Trial 3 1 246g 280g 264g 2 317g 351g 342g 3 339g 341g 386g 4 321g 362g 372~
Ivory Liquid Detergent 383g 429g 425g Commercial Dishwashing Liquid II 370g 403g 413g Commercial Dishwashing Liquid ~ 313g 320g 326g At a ratio of 4 LES~1 betaine and a total of 21%
actives, equal performance to Commercial Dishwashin~ Liquid I i~
attained. At smaller ratios of LES/betaine (below 2:1), and a total actives content of 21%, superior performance to Commercial Dishwashing Liquid I was observed - 24 - C6~74 Cleaning Performance III
Comparison of 24~ total active formulations to Ivory (R) ~iguid (33-34% total actives). The piston plunger test using the Crisco (R) shortening soil at 40 degrees C was used.
Component 1 2 3 Ammonium C12-C1s alcohol 3 E0, sulfated 15.4% 18.0% 15.4%
Cocoamidopropylbetaine8.~% 6.0% --Cocoamidopropylhydroxysultaine -- -- 8.5%
Ethanol 3.8~ 4.6% 3.8~
Sodium chloride 1.4~ 1.15% 1.0%
Sodium sulfate 4.6% ~.0% 1.0%
Sodium xylene sulfonate1.7% 1.5% -- -Water 64.5% 64.75% 70.2%
Viscosity (cps) 2000 2000 ~000 FormulationWei~ht of Soil to Deplete Foam 2 23gg 3 237g Ivory Liquid Detergent250g Cleaning Performance IV
The plates washing test was used to evalùate the exam-ples from "Cleaning Performance III".
Plates Washing Test Soiled dishes are prepared by spreading 5 mls of Crisco (R) shortening soil on sach dish with a spatula. They are ~hen stacked. Meanwhile, water containing the appropriate amount of hardness i5 heated to 115 degrees F.
, :
' ' , : ':
~o~
One gallon of the warm water i9 added to a wa6~ ~a~in ~long wlt~
the appropriate amount of LDL. Foam i3 then generated by u~ing a Mixette electric hand mi~er at high speeds for 20 econds.
Plates washing then proceeds using a standard wash cloth and washing regime. The operator submerges the plate and washes the front surface with six circular stokes. The plate i5 inverted, and the bacX surface is washed with three circular stro~es. The plate is then removed from the wash solution, tipped a~ainst the basin's edge at a 4S degree angle for 3 seconds (to allow foam drainage), and st~cked. The process continues until half the water's surface is no longer covered with foam, as judged by an independent observer. The number of plates washed is then counted and used as a relative measure of performance.
Formulation Plates Wash_ l 36 Ivory Liqui~ 34 Both the piston plunger and plates washing test demon-strate that the preferred embodiment at 24% total active~ level provides parity performance to a leading product containing 34%
total actives.
. ~ .. ,
Claims (11)
1. An aqueous liquid detergent comprising a) an essentially binary active system consisting of (i) a betaine surfactant selected from:
A) alkylamidobetaines having the formula:
where R is an alkyl or alkenyl chain containing 9 to 17 carbon atoms, x is an integer of 2 to 4, y is an integer of 0 to 3 and z is an integer of 0 to 3 and B) alkylamidosulfobetaines of formula:
wherein R1 is an alkylene radical having from 1 to about 3 carbon atoms, X is hydrogen, methyl or hydroxy, Y is hydrogen or methyl, R and R are each independently selected from methyl, ethyl and hydroxyethyl radicals, R is an alkylene radical having from about 2 to about 6 carbon atoms and R5 is an alkyl radical having from about 10 to about 18 carbon atoms, and mixtures thereof and (ii) an alkyl ether sulfate surfactant of formula:
RO(CnH2nO)q -S03X or RO(CnH(2n+1)0)q- S03X
wherein R is higher alkyl group of from 8 to 18 carbon atoms, X is a member selected from the group consisting of alkali metal ions, alkaline earth metal ions, ammonium ions and ammonium ions substituted with from one to three lower alkyl or alkanol groups and q is from 1 to 3, and mixtures thereof, the weight ratio of (i) to (ii) being in the range of 1:4 to 1:1, b) from 1 to 12% by weight of a hydrotrope, c) from O to 12% by weight of electrolytes and d) water.
A) alkylamidobetaines having the formula:
where R is an alkyl or alkenyl chain containing 9 to 17 carbon atoms, x is an integer of 2 to 4, y is an integer of 0 to 3 and z is an integer of 0 to 3 and B) alkylamidosulfobetaines of formula:
wherein R1 is an alkylene radical having from 1 to about 3 carbon atoms, X is hydrogen, methyl or hydroxy, Y is hydrogen or methyl, R and R are each independently selected from methyl, ethyl and hydroxyethyl radicals, R is an alkylene radical having from about 2 to about 6 carbon atoms and R5 is an alkyl radical having from about 10 to about 18 carbon atoms, and mixtures thereof and (ii) an alkyl ether sulfate surfactant of formula:
RO(CnH2nO)q -S03X or RO(CnH(2n+1)0)q- S03X
wherein R is higher alkyl group of from 8 to 18 carbon atoms, X is a member selected from the group consisting of alkali metal ions, alkaline earth metal ions, ammonium ions and ammonium ions substituted with from one to three lower alkyl or alkanol groups and q is from 1 to 3, and mixtures thereof, the weight ratio of (i) to (ii) being in the range of 1:4 to 1:1, b) from 1 to 12% by weight of a hydrotrope, c) from O to 12% by weight of electrolytes and d) water.
2. A composition as claimed in claim 1, wherein the alkyl ether sulfate salt is an ammonium salt.
3. A composition as claimed in claim 1 or claim 2 wherein the hydrotrope is selected from ethanol, isopropanol, C1 and C3 aromatic sulfonates and urea.
4. A composition as claimed in any one of claims 1 to 3 wherein the alkyl ether sulfate is a liner alkyl ether sulfate.
5. A composition as claimed in any one of claims 1 to 4 wherein the weight ratio of (i) to (ii) is from about 1:3 to about 1:1.5.
6. A composition as claimed in any one of claims 1 to 5 wherein the betaine surfactant is present at from 2 to 13% by weight.
7. A composition as claimed in any one of claims 1 to 6 wherein the alkyl ether sulfate is present at from 6 to 22% by weight.
8. A composition as claimed in any one of claims 1 to 7 comprising no greater than 30% total surfactant.
9. A composition as claimed in any one of claims 1 to 8 wherein the electrolytes are selected from neutral salts of the group of sodium chloride, sodium sulfate and mixtures thereof.
10. A method for the preparation of a composition according to any one of claims 1 to 9 which comprises mixing together the surfactants, hydrotrope and an appropriate quantity of water.
11. The aqueous liquid detergent composition as claimed in claim 1 and substantially as described herein.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US28254388A | 1988-12-12 | 1988-12-12 | |
| US282543 | 1988-12-12 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2004812A1 true CA2004812A1 (en) | 1990-06-12 |
Family
ID=23082000
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002004812A Abandoned CA2004812A1 (en) | 1988-12-12 | 1989-12-06 | Detergent composition comprising betaine and ether sulphate |
Country Status (7)
| Country | Link |
|---|---|
| EP (1) | EP0373851A3 (en) |
| JP (1) | JPH02212600A (en) |
| AU (1) | AU613545B2 (en) |
| BR (1) | BR8906417A (en) |
| CA (1) | CA2004812A1 (en) |
| NO (1) | NO894963L (en) |
| ZA (1) | ZA899474B (en) |
Families Citing this family (27)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5540865A (en) * | 1990-01-29 | 1996-07-30 | The Procter & Gamble Company | Hard surface liquid detergent compositions containing hydrocarbylamidoalkylenebetaine |
| US5342549A (en) * | 1990-01-29 | 1994-08-30 | The Procter & Gamble Company | Hard surface liquid detergent compositions containing hydrocarbyl-amidoalkylenebetaine |
| US5336445A (en) * | 1990-03-27 | 1994-08-09 | The Procter & Gamble Company | Liquid hard surface detergent compositions containing beta-aminoalkanols |
| US5540864A (en) * | 1990-12-21 | 1996-07-30 | The Procter & Gamble Company | Liquid hard surfce detergent compositions containing zwitterionic detergent surfactant and monoethanolamine and/or beta-aminoalkanol |
| SE469428B (en) * | 1991-11-21 | 1993-07-05 | Berol Nobel Ab | LIQUID DISCHARGE COMPOSITION CONTAINING ANIONIC TENSID AND A COMBINATION OF THREE TYPES OF AMPOTATED SOCIETIES |
| WO1993015173A1 (en) * | 1992-01-23 | 1993-08-05 | The Procter & Gamble Company | Liquid hard surface detergent compositions containing zwitterionic and cationic detergent surfactants and monoethanolamine and/or beta-aminoalkanol |
| US5536451A (en) * | 1992-10-26 | 1996-07-16 | The Procter & Gamble Company | Liquid hard surface detergent compositions containing short chain amphocarboxylate detergent surfactant |
| EP0598335A3 (en) * | 1992-11-13 | 1996-01-10 | Albright & Wilson | Novel cleaning compositions. |
| ATE318304T1 (en) | 1993-10-08 | 2006-03-15 | Novozymes As | AMYLASE VARIANTS |
| AU8132894A (en) * | 1993-11-12 | 1995-05-29 | Procter & Gamble Company, The | Liquid hard surface detergent compositions containing amphoteric detergent surfactant and perfume |
| US5531933A (en) * | 1993-12-30 | 1996-07-02 | The Procter & Gamble Company | Liquid hard surface detergent compositions containing specific polycarboxylate detergent builders |
| US5534198A (en) * | 1994-08-02 | 1996-07-09 | The Procter & Gamble Company | Glass cleaner compositions having good filming/streaking characteristics and substantive modifier to provide long lasting hydrophilicity |
| US5665364A (en) * | 1995-07-24 | 1997-09-09 | The Procter & Gamble Company | Compositions for topical delivery of active ingredients |
| US5607980A (en) * | 1995-07-24 | 1997-03-04 | The Procter & Gamble Company | Topical compositions having improved skin feel |
| WO1998005745A2 (en) * | 1996-08-08 | 1998-02-12 | Colgate-Palmolive Company | Light duty liquid cleaning compositions |
| BR9704210A (en) * | 1997-07-31 | 1999-02-02 | Unilever Nv | Detergent composition and dish washing process |
| AU4118500A (en) * | 1999-04-20 | 2000-11-02 | Unilever Plc | Low viscosity shower gels and pump spray delivery |
| WO2006069794A2 (en) | 2004-12-30 | 2006-07-06 | Rhodia Chimie | Herbicidal composition comprising an aminophosphate or aminophosphonate salt, a betaine and an amine oxide |
| AU2006315513B2 (en) | 2005-11-14 | 2013-06-13 | Specialty Operations France | Agricultural adjuvant compositions, pesticide compositions, and methods for using such compositions |
| WO2008066611A2 (en) | 2006-10-16 | 2008-06-05 | Rhodia Inc. | Agricultural adjuvant compositions. pesticide compositions. and methods for using such compositions |
| DE102007005942A1 (en) * | 2007-02-01 | 2008-08-07 | Henkel Ag & Co. Kgaa | Hand dishwashing detergent with native surfactant combination |
| FR2913351B1 (en) * | 2007-03-08 | 2010-11-26 | Rhodia Recherches Et Tech | USE OF BETAINE AS A DRAINAGE REDUCTION AGENT FOR FOAM |
| FR2914647B1 (en) | 2007-04-05 | 2011-10-21 | Rhodia Recherches Et Tech | COPOLYMER COMPRISING BETAINIC UNITS AND HYDROPHOBIC AND / OR AMPHIPHILIC UNITS, PREPARATION METHOD, AND USES. |
| JP5601785B2 (en) * | 2009-03-25 | 2014-10-08 | 株式会社マンダム | Hair cleaning composition |
| US8748344B2 (en) | 2009-07-14 | 2014-06-10 | Rhodia Operations | Agricultural adjuvant compositions, pesticide compositions, and methods for using such compositions |
| BR112013003347B1 (en) | 2010-08-10 | 2018-03-20 | Rhodia Operations | AGRICULTURAL PESTICIDES COMPOSITIONS AND METHOD FOR CONTROLING A TARGET PEST |
| EP3146032B1 (en) | 2014-05-21 | 2018-10-31 | Colgate-Palmolive Company | Aqueous liquid dishwashing composition |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4166048A (en) * | 1975-09-22 | 1979-08-28 | Kao Soap Co., Ltd. | High foaming detergent composition having low skin irritation properties |
| GB2013235B (en) * | 1977-07-26 | 1982-02-03 | Albright & Wilson | Concentrated aqueous surfactant compositions |
| US4186113A (en) * | 1978-04-03 | 1980-01-29 | Johnson & Johnson | Low irritating detergent compositions |
| US4375421A (en) * | 1981-10-19 | 1983-03-01 | Lever Brothers Company | Viscous compositions containing amido betaines and salts |
| JPS6086198A (en) * | 1983-10-19 | 1985-05-15 | 株式会社資生堂 | Detergent composition |
| GB8428149D0 (en) * | 1984-11-07 | 1984-12-12 | Procter & Gamble Ltd | Liquid detergent compositions |
| DE3512535A1 (en) * | 1985-04-06 | 1986-10-16 | Henkel KGaA, 4000 Düsseldorf | METHOD FOR MANUAL CLEANING OF OBJECTS WITH HARD SURFACES |
| US4726915A (en) * | 1986-03-10 | 1988-02-23 | Johnson & Johnson Baby Products Company | Detergent compositions |
| JPH0832913B2 (en) * | 1987-03-31 | 1996-03-29 | 川研ファインケミカル株式会社 | Method for producing amphoteric surfactant |
| JP2567277B2 (en) * | 1988-10-27 | 1996-12-25 | 川研ファインケミカル株式会社 | Liquid detergent composition |
| GB8905551D0 (en) * | 1989-03-10 | 1989-04-19 | Unilever Plc | Detergent compositions |
-
1989
- 1989-12-06 CA CA002004812A patent/CA2004812A1/en not_active Abandoned
- 1989-12-08 AU AU46062/89A patent/AU613545B2/en not_active Ceased
- 1989-12-11 EP EP19890312894 patent/EP0373851A3/en not_active Withdrawn
- 1989-12-11 NO NO89894963A patent/NO894963L/en unknown
- 1989-12-11 JP JP1321233A patent/JPH02212600A/en active Pending
- 1989-12-12 ZA ZA899474A patent/ZA899474B/en unknown
- 1989-12-12 BR BR898906417A patent/BR8906417A/en not_active Application Discontinuation
Also Published As
| Publication number | Publication date |
|---|---|
| BR8906417A (en) | 1990-08-28 |
| JPH02212600A (en) | 1990-08-23 |
| AU613545B2 (en) | 1991-08-01 |
| NO894963L (en) | 1990-06-13 |
| NO894963D0 (en) | 1989-12-11 |
| EP0373851A3 (en) | 1991-03-06 |
| AU4606289A (en) | 1990-07-19 |
| EP0373851A2 (en) | 1990-06-20 |
| ZA899474B (en) | 1991-08-28 |
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