CA2130466C - Aqueous hard surface detergent compositions containing calcium ions - Google Patents
Aqueous hard surface detergent compositions containing calcium ionsInfo
- Publication number
- CA2130466C CA2130466C CA002130466A CA2130466A CA2130466C CA 2130466 C CA2130466 C CA 2130466C CA 002130466 A CA002130466 A CA 002130466A CA 2130466 A CA2130466 A CA 2130466A CA 2130466 C CA2130466 C CA 2130466C
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- hard surface
- feel
- composition
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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
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/04—Water-soluble compounds
- C11D3/046—Salts
-
- 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
- C11D1/86—Mixtures of anionic, cationic, and 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
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
- C11D3/2075—Carboxylic acids-salts thereof
-
- 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
-
- 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
- C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
- C11D1/143—Sulfonic acid esters
-
- 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
- C11D1/38—Cationic compounds
- C11D1/52—Carboxylic amides, alkylolamides or imides or their condensation products with alkylene oxides
- C11D1/523—Carboxylic alkylolamides, or dialkylolamides, or hydroxycarboxylic amides (R1-CO-NR2R3), where R1, R2 or R3 contain one hydroxy group per alkyl group
-
- 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
- C11D1/38—Cationic compounds
- C11D1/52—Carboxylic amides, alkylolamides or imides or their condensation products with alkylene oxides
- C11D1/525—Carboxylic amides (R1-CO-NR2R3), where R1, R2 or R3 contain two or more hydroxy groups per alkyl group, e.g. R3 being a reducing sugar rest
-
- 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
- C11D1/75—Amino oxides
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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)
- Health & Medical Sciences (AREA)
- Emergency Medicine (AREA)
- Inorganic Chemistry (AREA)
- Detergent Compositions (AREA)
- Cosmetics (AREA)
Abstract
An aqueous hard surface detergent composition which provides improved solution f eel comprising 3-35 % by weight of a surfactant system selected from the group consisting of anionic, nonionic, ampho teric surfactants, and mixtures thereof and 0.01-0.5 % by weight calcium ion.
Description
Wo 93/17084pcr/us93/ol156 AQUEOUS HARD SURFACE DETERGENT COMPOSITIONS
CONTAINING CALCIUM IONS
TECHNICAL FIELD
The present invention relates to an aqueous hard surface detergent composition con~ g G~irium ion which provides improved solution feel without deteriorating storage stability of the composition. The CG~..pGS;lion isparticularly useful for dishwashing liquids, more particularly under soft water conditions.
BACKGROUND
Anionic swf~ct~ntc such as alkyl ethoxy sulfates with short ethylene oxide chains, alkyl sl~lf~tes, alkyl benzene sulfonates, a-olefin sulfonates, and alkyl ethoxy carboxylates are known to be very effective for hard surface cle~nine but are also known to have more or less unfavorable "slippery" feel in use. This undeii.~lc attribute is a proble,.. to hard surface cle~ning compositions, espeçislly for d;~ aslfing purposes.
There is th~ ,fole a considerable demqrld for a hard surface delerg~nl composition which has good detergency and good storage stability while having good solution feel when cle~ning and rinsing, particularly for dishwashing purposes. As defined herein, good solution feel is best defined as the ~I-se-~ce of "slippery" or "slimy" feel, or a "draggy" kind of feel which one feels when the composition is in use. "Good solution feel" is an hllpGllanl attribute for co--..--~ ,;al liquid d~le-g~--l products. Those wash solutions which have good solution feel on hands and objects to be cleaned allow easy hqn~iing of the objects, and provide good rinsing characters. Such bencrlls are most apprecialed for dishwashing purposes.
Many attempts have been made to improve solution feel using various technology. These all~-"pts are usually directed towards the use of nonionic-type surf~ct~nts, and other suds e~-h~l-ri~-g-type and solvent-type con.l)onenls.
WO 93/17084 PCr/US93/01 _ 213046~
CONTAINING CALCIUM IONS
TECHNICAL FIELD
The present invention relates to an aqueous hard surface detergent composition con~ g G~irium ion which provides improved solution feel without deteriorating storage stability of the composition. The CG~..pGS;lion isparticularly useful for dishwashing liquids, more particularly under soft water conditions.
BACKGROUND
Anionic swf~ct~ntc such as alkyl ethoxy sulfates with short ethylene oxide chains, alkyl sl~lf~tes, alkyl benzene sulfonates, a-olefin sulfonates, and alkyl ethoxy carboxylates are known to be very effective for hard surface cle~nine but are also known to have more or less unfavorable "slippery" feel in use. This undeii.~lc attribute is a proble,.. to hard surface cle~ning compositions, espeçislly for d;~ aslfing purposes.
There is th~ ,fole a considerable demqrld for a hard surface delerg~nl composition which has good detergency and good storage stability while having good solution feel when cle~ning and rinsing, particularly for dishwashing purposes. As defined herein, good solution feel is best defined as the ~I-se-~ce of "slippery" or "slimy" feel, or a "draggy" kind of feel which one feels when the composition is in use. "Good solution feel" is an hllpGllanl attribute for co--..--~ ,;al liquid d~le-g~--l products. Those wash solutions which have good solution feel on hands and objects to be cleaned allow easy hqn~iing of the objects, and provide good rinsing characters. Such bencrlls are most apprecialed for dishwashing purposes.
Many attempts have been made to improve solution feel using various technology. These all~-"pts are usually directed towards the use of nonionic-type surf~ct~nts, and other suds e~-h~l-ri~-g-type and solvent-type con.l)onenls.
WO 93/17084 PCr/US93/01 _ 213046~
Generally, these compositions have sacrificed detergency to obtain the improved solution feel.
Kokoku 46-43550 (Kao Corporation) teaches a liquid detergent composition which is mild to skin and has good detergency comprising ~Ik~line earth metal salts of certain alkyl alkylene-oxy sulfate and certain alkyl alkylene-oxy carboxylates.
Kokai 51-125405 (The Procter & Gamble Company) teaches compositions comprising calcium and nl~gnesi~m salts of anionic surf~rt~nts inrluding alkyl ether sulfates and amine oxides, Cl 5 alk~no!e and water, wherein the weight ratio of amine oxide to anionic surfactant is 1:100 to 1:2.
Up to about 25% ofthe anionic surf~t~nts can be monovalent salts.
U.S. Patent 2,766,212 (General Aniline and Film Colpo~alion) teaches compositio~e which co"~p.ise alkyl ether alkoxy sulfate salts and water soluble polyvalent salts of ...~es; ~m, c~lc;~'m~ iron, or al~ u ~ of 5 - 50% by weight of the surfactant. Examples show CQlnpOSitione colllpli;.ing at least 70% of the anionic surfactant in which .~a~,~c,:~"- and c~lr;~lm ions help detergency.
U.S. Patent 4,681,704 (The Procter & Gamble Company) teaches a detergent co",i)osilion with effective grease removal co"""i~i"g 10 - 50%
k~line earth metal salt, preferably ...~ ; lm of anionic surf~rt~nte, 0.5 -10% amine oxides, and 0.5 - 15% b~laines.
However, the above mentioned diecl~sures use alk~line earth metals mainly for their cle~ning be~ s, and do not ~lierlose or s~ggest the improvement to solutio~ feel ben~fitc contributed by c~lci~-m ions. Further, theco,nl)ositions ofthe above mentioned dicclQs~lres have high divalent ion levels,so that they would be unstable upon storage in the context of the present invention, namely, would form undesirable p,c~,;p;l~les of c~1r;um ~rcf~ ;d cG."pos;lions and examples shown in the above disclosures also have high surfactant levels, and thus the amount of calcium needed to reduce or el;~ te 3 ~ 6 ~
the "slippery feel" of the composition would place the composition into a phase where calcium is believed to easily precipitate.
Here, it has been found that by using calcium ions at a certain low level, a composition which provides improved solution feel without deteriorating storage stability is obtained.
SUMMARY OF THE INVENTION
The present invention relates to an aqueous hard surface detergent composition which provides improved solution feel comprising:
(1) 3 - 35% by weight of a surfactant system selected from the group consisting of anionic, nonionic, amphoteric surfactants, and mixtures thereof, comprising:
a. at least 3% by weight of the composition and at least 20% by weight of the surfactant system alkyl ethoxy sulfate with an alkyl group of Cl0 l6 and an average of 1 - 10 moles of ethylene oxide per molecule;
b. other anionic surfactants selected from the group consisting of alkyl benzene sulfonates, a-olefin sulfonates, alkyl ethoxy carboxylates, and mixtures thereof;
c. 0 - 9% by weight of the composition diethanol amide with an alkyl chain of C8-20;
d. 0 - 10% by weight of the composition amine oxide with an alkyl chain of C8 ,6; and (2) 0.01 - 0.5% by weight calcium ion;
wherein at least 20% by weight of the surfactant system comprises the total of component a, b, c, and d.
t .~?
J
~ 1! 3 ~ ~ 6 ~
-More particularly, the invention relates to an aqueous hard surface detergent composition which provides improved solution feel comprising: (1) 20 - 30% by weight of a surfactant system selected from the group consisting of anionic, nonionic, amphoteric surfactants, and mixtures thereof, comprising:
a. at least 35% by weight alkyl ethoxy sulfate with an alkyl group of Cl0 ~6 andan average of 2.5 - 3.5 moles of ethylene oxide per molecule; b. diethanol amidewith an alkyl chain of C8 20; and c. amine oxide with an alkyl chain of C8 ~6; (2) 0.1 - 0.3% by weight calcium ion; and (3) 0.1 - 0.5% by weight magnesium ion;
wherein the composition contains 4 - 7% by weight of the diethanol amide, and 2 - 5% by weight the amine oxide.
The present invention also relates to a method of improving the solution feel of an aqueous hard surface detergent composition or a wash solution of an aqueous hard surface detergent composition by adding calcium ion to said composltlon.
The composition has less of an unacceptable slippery feel, and is easy to handle when cleaning and rinsing. The compositions of the present invention have good storage stability, that is, the composition is stable in ordinary use conditions, more specifically, it does not generate precipitation or gel in the temperature range of from -5~C to 40~C.
Anionic Surfactant The compositions of the present invention comprise 15 - 35%, preferably 20 - 30% by weight surfactant system selected from the group consisting of anionic, nonionic, amphoteric surfactants, and mixtures thereof. At least 20%, preferably at least 40%, more preferably at least 60%, by weight of the surfactant is the sum of anionic surfactants, diethanol amide, and amine oxide. Among the anionic surfactants, at least 3%, preferably at least 8%, more preferably at least 12%, of the composition is alkyl ethoxy sulfate with an alkyl group of Cl0 l6 and 7~ '' ~ ~ 3~4~
Kokoku 46-43550 (Kao Corporation) teaches a liquid detergent composition which is mild to skin and has good detergency comprising ~Ik~line earth metal salts of certain alkyl alkylene-oxy sulfate and certain alkyl alkylene-oxy carboxylates.
Kokai 51-125405 (The Procter & Gamble Company) teaches compositions comprising calcium and nl~gnesi~m salts of anionic surf~rt~nts inrluding alkyl ether sulfates and amine oxides, Cl 5 alk~no!e and water, wherein the weight ratio of amine oxide to anionic surfactant is 1:100 to 1:2.
Up to about 25% ofthe anionic surf~t~nts can be monovalent salts.
U.S. Patent 2,766,212 (General Aniline and Film Colpo~alion) teaches compositio~e which co"~p.ise alkyl ether alkoxy sulfate salts and water soluble polyvalent salts of ...~es; ~m, c~lc;~'m~ iron, or al~ u ~ of 5 - 50% by weight of the surfactant. Examples show CQlnpOSitione colllpli;.ing at least 70% of the anionic surfactant in which .~a~,~c,:~"- and c~lr;~lm ions help detergency.
U.S. Patent 4,681,704 (The Procter & Gamble Company) teaches a detergent co",i)osilion with effective grease removal co"""i~i"g 10 - 50%
k~line earth metal salt, preferably ...~ ; lm of anionic surf~rt~nte, 0.5 -10% amine oxides, and 0.5 - 15% b~laines.
However, the above mentioned diecl~sures use alk~line earth metals mainly for their cle~ning be~ s, and do not ~lierlose or s~ggest the improvement to solutio~ feel ben~fitc contributed by c~lci~-m ions. Further, theco,nl)ositions ofthe above mentioned dicclQs~lres have high divalent ion levels,so that they would be unstable upon storage in the context of the present invention, namely, would form undesirable p,c~,;p;l~les of c~1r;um ~rcf~ ;d cG."pos;lions and examples shown in the above disclosures also have high surfactant levels, and thus the amount of calcium needed to reduce or el;~ te 3 ~ 6 ~
the "slippery feel" of the composition would place the composition into a phase where calcium is believed to easily precipitate.
Here, it has been found that by using calcium ions at a certain low level, a composition which provides improved solution feel without deteriorating storage stability is obtained.
SUMMARY OF THE INVENTION
The present invention relates to an aqueous hard surface detergent composition which provides improved solution feel comprising:
(1) 3 - 35% by weight of a surfactant system selected from the group consisting of anionic, nonionic, amphoteric surfactants, and mixtures thereof, comprising:
a. at least 3% by weight of the composition and at least 20% by weight of the surfactant system alkyl ethoxy sulfate with an alkyl group of Cl0 l6 and an average of 1 - 10 moles of ethylene oxide per molecule;
b. other anionic surfactants selected from the group consisting of alkyl benzene sulfonates, a-olefin sulfonates, alkyl ethoxy carboxylates, and mixtures thereof;
c. 0 - 9% by weight of the composition diethanol amide with an alkyl chain of C8-20;
d. 0 - 10% by weight of the composition amine oxide with an alkyl chain of C8 ,6; and (2) 0.01 - 0.5% by weight calcium ion;
wherein at least 20% by weight of the surfactant system comprises the total of component a, b, c, and d.
t .~?
J
~ 1! 3 ~ ~ 6 ~
-More particularly, the invention relates to an aqueous hard surface detergent composition which provides improved solution feel comprising: (1) 20 - 30% by weight of a surfactant system selected from the group consisting of anionic, nonionic, amphoteric surfactants, and mixtures thereof, comprising:
a. at least 35% by weight alkyl ethoxy sulfate with an alkyl group of Cl0 ~6 andan average of 2.5 - 3.5 moles of ethylene oxide per molecule; b. diethanol amidewith an alkyl chain of C8 20; and c. amine oxide with an alkyl chain of C8 ~6; (2) 0.1 - 0.3% by weight calcium ion; and (3) 0.1 - 0.5% by weight magnesium ion;
wherein the composition contains 4 - 7% by weight of the diethanol amide, and 2 - 5% by weight the amine oxide.
The present invention also relates to a method of improving the solution feel of an aqueous hard surface detergent composition or a wash solution of an aqueous hard surface detergent composition by adding calcium ion to said composltlon.
The composition has less of an unacceptable slippery feel, and is easy to handle when cleaning and rinsing. The compositions of the present invention have good storage stability, that is, the composition is stable in ordinary use conditions, more specifically, it does not generate precipitation or gel in the temperature range of from -5~C to 40~C.
Anionic Surfactant The compositions of the present invention comprise 15 - 35%, preferably 20 - 30% by weight surfactant system selected from the group consisting of anionic, nonionic, amphoteric surfactants, and mixtures thereof. At least 20%, preferably at least 40%, more preferably at least 60%, by weight of the surfactant is the sum of anionic surfactants, diethanol amide, and amine oxide. Among the anionic surfactants, at least 3%, preferably at least 8%, more preferably at least 12%, of the composition is alkyl ethoxy sulfate with an alkyl group of Cl0 l6 and 7~ '' ~ ~ 3~4~
an average of I - 10 moles, more preferably 2 - 5 moles, of ethylene oxide per molecule.
The anionic surfactants are selected from said alkyl ethoxy sulfates, alkyl sulfates, alkyl benzene sulfonates, a-olefin sulfonates, alkyl ethoxy carboxylates, and mixtures thereof.
Alkyl ethoxy sulfate, particularly having an alkyl group of Cl0 l6 and an average of 1 - 10 moles, preferably 2 - 5 moles, more preferably 2.5 - 3.5 moles, of ethylene oxide per molecule, provides good detergency and less negative effect on solution feel. Furthermore, compositions including a considerable amount of such alkyl ethoxy sulfates are susceptible to the effect of improved solution feel due to calcium ions. The average number of moles of ethylene oxide per molecule of the alkyl ethoxy sulfates can change the character of the surfactant. Here, alkyl sulfate is dealt as an alkyl ethoxy sulfate having 0 moles of ethylene oxide permolecule. Generally, it is known that the longer the ethylene oxide chain contribute less to poor solution feel, but have poorer detergency performance. Those which have less than an average ethylene oxide chain of 1 moles per molecule by themselves will contribute to poor solution feel.
The salts for the anionic surfactant component can be alkali metal, alkali earth metal, amines, or ammonium salts, preferably sodium or ammonium salts.
Alkali earth metal salts of these surfactants are known for good detergency and sudsing. Some or all of the calcium ion of the present composition can be introduced as calcium salts of the anionic surfactant.
Other Surfactants The compositions of the present invention may also comprise, for the balance of the surfactant system, other anionic surfactants, nonionic surfactant and amphoteric surfactants. These surfactants are formulated in the compositions of the present invention to enhance detergency, and to enhance and stabilize suds. The species and levels of the other anionic, nonionic and amphoteric ~,..-WO 93/17084 PCr/US93/01-2~3~4~6 surfactants are chosen in order to obtain optimum balance of detergency, solution feel, and storage stability.
The compositions of the present invention can contain nonionic surf~-,t~nts such as dieth~nol amides and amine oxides. 0 - 9%, I)rerelably 4 -7% by weight of dieth~nol amide and 0 - 10% ~,erel~bly 2 - 5% by weight of amine oxide is contained in the composition. These two surf~ct~nts are known to provide good detergency and good storage stability, but can negatively effect solution feel. The use of calcium ion to improve solution feel is particularly useful in composition con~l;sing diethanol an~ide and/or amine oxide.
Diethanol amide useful in the present invention has the formula HO
l 11 (c2H5oH)2-N-c-Rl I
wherein Rl is sPI~ ,Led from an alkyl chain of Cg 20, pr~,f~.~bly C12 14.
Amine oxide useful in the present invention has the foll.wla o 1~ II
R2N(OC2H5)2 wherein R2 is s~ lectçd from an alkyl chain of Cg 2o, pr~r~-~bly C12 14.
Calcium It has been found that by incol~olal;ng low levels of c~lr,ivm ions, nced benefits in solutiQn feel and storage stability are ob~ained. The effect of the addition of low levels of c~rium ion into dishwashing compositions is particularly benefisi~l under low hardness water conditions, where the ~mo~nt of calcium introduced from tap water is low.
Calri~m ions are added to the co".~)os;lion at levels of 0.01 - 0.5%, preferably 0.1 - 0.~%, most preferably 0.1 - 0.3%. At lower c~lci--m levels, no effect on solution feel will be observed. At higher calri~-m levels, storage ~'0 93/17084 21 3 0 ~ 6 6 PCI/US93/011~6 _ ,.
stability will not be good. That is, it is known that calcium ions are relatively easily p,c;ci~ila~ed at high te",pe,a~-lre conditions, and thus are apt to deteriorate storage stability when added at high levels. C~lrium ions are further known to contribute to detergency, particularly to grease removal. By selectin~ a calcium level in the above range, a composition having all three important benefits are obtained; good solution feel, good grease removal, and good storage stability.
The co""~)Gs;lions of the present invention must have less than 35%
total surf~ct~nts to avoid p~ ecip;lalion of the calcium which is present at a level suffirient to improve solution feel. If the surfactant level is too high? the m~Yimum amount of calcium that can be added without fo.",ing c~lrium p, ~cipilalion would not be sufficiçnt to improve solution feel to the composltion.
The calcium ions can be inco,~o,aled in the co"",os;lion in any convenient way, so long as the salts CQ~ g cs~lri~lm ions are soluble in water and do not p,.~ e under oldh~y use conditions. A suitable way of il~co.~,G,ali.,g c~lrium ions is by adding them as salts selected from the groupcon~ g of chloride, hydroxide, oxide, ~cet~te, nitrate, formate, and mixtures thereof. Chloride salts are most pn,f~" cd.
Alternately, calcium ions can also be incorporated as counter-ions of anionic surfactants? such as by neutralizing the acid forrn of anionic surfi-ct~nt.c with r~lcium oxide or calcium hydroxide, without aa~ling the benefits thereo~
The p,~,fe.,ed composition ofthe present invention co"~.,ises:
(1) 20 - 30% by weight of a surfactant system selected from the group con.~;cl;.~ of anionic, nonionic, amphoteric sull~cl~"~, and mixtures thereof, c~"-~ lg.
a. at least 35% by weight of the surfactant system alkyl ethoxy sulfate with an alkyl group of C10-l6 and an average of 2.5 - 3.5 ethylene oxide per molecllle;
Wo 93/17084 PCr/US93/0 2~3a46G -8-b. 4 - 7% by weight of the composition diethanol amide with an alkyl chain of C8-20;
c. 2 - 5 by weight of the composition amine oxide with an alkyl chain of C8-16;
(2) 0.1 - 0.3% by weight calcium ion; and (3) 0.1 - 1% by weight m~gnPcium ion.
Optional Co",pone"ls The compositions of the present invention can optionally contain components in addition to those already disclosed herein.
Optional surf~t~ntc useful in the composition of the present invention are those such as monoeth~nol arnides, polyhydroxy fatty acid arnides, alkyl polyglucosidçc, and alkyl ethoxylates.
MOnG~Ih~nOI amide is an optional su,rac~al-t in the present invention, having the formula HO
l 11 (c2H5oH)-N-c-R3 wherein R3 is sçlçcted from an alkyl chain of Cg 20, pleI~Iably C12 14.
Polyhydroxy fatty acid arnide is an optional surfactant in the present invention, having the formula o R4 Il I .
wherein R4 is H, Cl 4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl, or a mixture thereof, preferably Cl 4 alkyl, more preferably methyl; and R5 is Cs 31 hydrocarbyl, prel~,~bly straight-chain C10 16 alkyl; and Z is WO 93/17084 213 0 ~ 6 6 PCI/US93/01156 polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls directly co~-necled to the chain, or an alkoxylated derivative (preferably ethoxylated or propoxylated) thereof. Z preferably will be derived from a reduçing sugar in a reductive amination reaction; more p,erelably Z is glycityl. Suit?ble reducing sugars include glucose, fructose, mq-ltose, lactose,galactose, mannose, and xylose.
Alkyl polyglucoside is an optional surfactant in the present invention, having the formula R6o(cmH2mo)p(glucosyl)q wherein R6 is selecled from the group con~ .g of alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof in which the alkyl groups are C10-l8~ preferably C12 14, m is 2 or 3, preferably 2; p is from 0 to about 10, preferably 0; and q is 1.3 - 10, plere(ably 1.3 - 3, most prerc,~bly 1.3 - 2.7. To prepare these compounds the alcohol or alkylpolyethoxy alcohol is formed first and then reacted with glUCOSf~ or a source of g~uGOSç, to form the g1~lcos;de (attr-hment at the l-position). The nd~itionql glycosyl units can then be attached ~ ~cn their l-pGS;l;On and the pl ece(~ glycosyl units 2-, 3-, 4-and/or 6-position, prer~,.ably predo...;.~ely the 2-pos;lion.
Alkyl ethoxylate is an optional surfactant in the present invention. Such alkyl ethoxylates are aliphatic alcohols with I - 25 moles of ethylene oxide.
The alkyl chain of the aliphatic alcohol can either be straight or b,iu~ched, primary or secondary, and generally co,.l~;l-C 8 - 22 carbon atoms. Particularlypreft,,cd are the con~1fnC~l;on products of-q-lcohols having an alkyl group con~ ;ng 8 - 20 carbon atoms with 2 - 10 moles of ethylene oxide per mole of alcohol. Most ptérelled are the conden~-qtiorl products of alcohols having an alkyl group cQI.~ ;ng 8 - 14 carbon atoms with 6 - 10 moles of ethylene oxide per mole of alcohol.
Amphoteric surf~ct~nt~ optionally included in the present invention are wO 93/17084 PCr/US93/01~
2~3o~6~
betaines having the formula R8 (R10)2 R7Co-N-R9-N+Rl lcoo-wherein R7 is a C7 21 alkyl group, or alkylaryl group, prel~,~bly Cg 17; R8 is hydrogen or a Cl 6 alkyl group, plefe,~bly Cl 3; R9 is a Cl 1o alkylene group, preferably C2 6, most preferably C3; each R10 is a C1 6 alkyl or hydroxy alkyl group, preferably C 1_3, most preferably methyl or an ethoxylated hydroxy alkyl co,.~ g from about 1 to about 10 ethylene oxide units; and R11 is an C 1 -6 alkylene group, preferably methyl.
~ nPsj-lm ions at a level of 0.1 - 1% are ple~lably inrluded in the composition of the present invention to improve detergency without ~-;I;np good solution feel and good storage stability of the co",?o~;lion.
The compositionc of the present invention can also comprise 4 - 8% by weight of a hydrGIIope selected from the group conC;~ of sodium and a".l"onium salts of cllm~ne sulfon~t~c~ toluene sulronales, xylene s~lron~
sulfo succ~ lec~ and mixtures thereo~ Such cGnl?onenls are utilized in the inlere~ls of achieving a desired product phase stability and viscosity.
Other desirable ingredients include solvents, preservatives, dyes, and perfumes.
Solvents useful in the present invention include water and lower rnoleclJI~r weight ~lcoholc such as ethanol. Ethanol is also known to reduce the viscosity of the product, if n~cecc~y for formulation. Solvents other than water are typically present at levels of 2 - 10% by weight.
Preservatives, dyes, and perfumes can be, and usually will be forrn~ ted in the composition of the present invention to make products attractive to the consumer. These co",?on~ s are typically present at levels not more than 1% resl)eclively.
Components which are preferably not incl~lded in the composition are those which generate plc~;l)ilation upon binding with calcium ions. Fysn~pl~s are those which include sulfate, carboxylate, and fatty acid anions.
EXAMPLES
The following e~n.llec illustrate the compositions of the present invention, but are not interlded to be limiting thereof. All per~ie.-lsges and ratios are based on weight unless otherwise specified.
P, epa, ~lion The liquid delergcnt compositions herein des~i,il,ed can be made conveniently by one skilled in the art. Surfs-ctsntc hyd,ul~opes, calcium salts,and optionally tt.~gn~si~-m salts are added in an approp,iate amount of water and are blended. In the present invention, the order of adding the co"")on~,.ds is not important. If l~ecçsC~ ~, the pH of the mixture is -s~dj~sted with HCI to a safe level for ho~sPhold products, and viscosity is adjl~sted with alcohol.
Perfume, dye, and preservatives are optionally added, and the co"~,ûsilion is ~slsnced with water. The standard product and c~a. ,Jles 1 - 9 are all p,epa,~d accord;ng to this Inetllod EA~;I i"~e.,la~ion 1. Solution feel - 500g each of 6% solutions of the standard product and compositions of the present invention are prepared in a 1 liter beaker, and a pûrcelain crucible is soaked in the solution - One hand is soaked in the sample solution and the other hand is soaked in the general standard product solution at the same time, and the feel of the crucible is evaluated according to the scale as shown below.
- Evaluation is done by three special psnelicts and the average score is Wo 93/17084 PCr/US93/01_ 21~66 12-obtained.
Evaluation scale O= There is no diIrerence I= I think there is a difference ~ 2= I know there is a dia~rence + 3= I know there is a big difference 4= I know there is a very big difference (+): the sample has a better feel (less slippery) the sample has a worse feel (more slippery) For those which have higher points than the composition with the same surfactant system without calcium it is evaluated that the "solution feel was improved".
2. Storage Stability The sample is placed in a lO0 ml glass co~ , and stored in rooms with e~ t~ ed t~..":c.~lules of-5~C and 40~C r~ec~ ely. The cor~ition of the product after 2 weeks is evaluated as follows.
clear and no change co"",a, ed to before the test - O
p, ec;~ e~l or cloudy - X
AccG,ding to Table 1, it is understood that FY~ IeS 1, 3, 4, and 7 which are compositions of the present invention have both improved solution feel and good storage stability.
)VO 93/17084 2 1 3 0.~ 6 6 - PCI/US93/01156 Standard 1 2 3 4 5 6 7 8 product Sodium C,2-l4 alkyl ethoxy (5 ave.) sulfate 11.7 11.7 - - - - - - -AmmOniUm C12-14 alkyl ethoxy (3 ave.) sulfate - - 12.0 12.0 12.012.0 12.0 12.0 12.0 Cl2-~4 alkyl dimethyl amine oxide 3.1 3.13.0 3.0 3.0 3.0 3.0 3.0 3.0 Cl2 alkyl diethanol amide 4.4 4-4 4-5 4-5 4-5 4-5 4-5 4-5 4-5 Cl2-l4 alkyl N-methyl glucoamide - - 5.0 5.0 5.0 5.0 Cl2 alkyl ethoxy (3 ave.) alcohol 2.3 2.3 C9-ll alkyl ethoxy (8 ave.~ alcohol - - 1.5 1.5 1.5 1.5 1.5 1.5 1.5 Sodium toluene sulfonate 2.3 2.3 Sodium cumene sulfonate - - 5-0 5.0 5.0 5.0 5.0 5.0 5.0 Mg++(MgC12-7H20) - - 0.7 0.5 0.36 0.1 0.7 0.5 0.1 Ca+ +(CaC12) - 0.3 - 0.2 0.14 0.6 - 0.2 0.6 Ethanol 2.5 2.54.2 4.2 4.2 4.2 2.8 2.8 2.8 Water and other minors bal~ bal bal bal bal bal bal bal bal Solution feel(point) Std+2.0 -1.38 -0.88+0.75+0.75 -1.38 -0.5 +0.13 (comparison example) - Std - ex.2 ex.2 ex.2 - ex.6 ex.6 (improved points) - +2.0 - +0.5 +2.13+2.13 - +0.88+ 1.25 (evaluation) - 0 - 0 0 0 - 0 0 bal = balance WO 93/l708~,-!L3Q 4G6 PCI/US93/01 (continuedJ
Standard 1 2 3 4 5 6 7 8 product Storage stability (-5~C) 0 0 0 0 0 X 0 0 X
(40~C) 0 0 0 0 0 X 0 0 X
The anionic surfactants are selected from said alkyl ethoxy sulfates, alkyl sulfates, alkyl benzene sulfonates, a-olefin sulfonates, alkyl ethoxy carboxylates, and mixtures thereof.
Alkyl ethoxy sulfate, particularly having an alkyl group of Cl0 l6 and an average of 1 - 10 moles, preferably 2 - 5 moles, more preferably 2.5 - 3.5 moles, of ethylene oxide per molecule, provides good detergency and less negative effect on solution feel. Furthermore, compositions including a considerable amount of such alkyl ethoxy sulfates are susceptible to the effect of improved solution feel due to calcium ions. The average number of moles of ethylene oxide per molecule of the alkyl ethoxy sulfates can change the character of the surfactant. Here, alkyl sulfate is dealt as an alkyl ethoxy sulfate having 0 moles of ethylene oxide permolecule. Generally, it is known that the longer the ethylene oxide chain contribute less to poor solution feel, but have poorer detergency performance. Those which have less than an average ethylene oxide chain of 1 moles per molecule by themselves will contribute to poor solution feel.
The salts for the anionic surfactant component can be alkali metal, alkali earth metal, amines, or ammonium salts, preferably sodium or ammonium salts.
Alkali earth metal salts of these surfactants are known for good detergency and sudsing. Some or all of the calcium ion of the present composition can be introduced as calcium salts of the anionic surfactant.
Other Surfactants The compositions of the present invention may also comprise, for the balance of the surfactant system, other anionic surfactants, nonionic surfactant and amphoteric surfactants. These surfactants are formulated in the compositions of the present invention to enhance detergency, and to enhance and stabilize suds. The species and levels of the other anionic, nonionic and amphoteric ~,..-WO 93/17084 PCr/US93/01-2~3~4~6 surfactants are chosen in order to obtain optimum balance of detergency, solution feel, and storage stability.
The compositions of the present invention can contain nonionic surf~-,t~nts such as dieth~nol amides and amine oxides. 0 - 9%, I)rerelably 4 -7% by weight of dieth~nol amide and 0 - 10% ~,erel~bly 2 - 5% by weight of amine oxide is contained in the composition. These two surf~ct~nts are known to provide good detergency and good storage stability, but can negatively effect solution feel. The use of calcium ion to improve solution feel is particularly useful in composition con~l;sing diethanol an~ide and/or amine oxide.
Diethanol amide useful in the present invention has the formula HO
l 11 (c2H5oH)2-N-c-Rl I
wherein Rl is sPI~ ,Led from an alkyl chain of Cg 20, pr~,f~.~bly C12 14.
Amine oxide useful in the present invention has the foll.wla o 1~ II
R2N(OC2H5)2 wherein R2 is s~ lectçd from an alkyl chain of Cg 2o, pr~r~-~bly C12 14.
Calcium It has been found that by incol~olal;ng low levels of c~lr,ivm ions, nced benefits in solutiQn feel and storage stability are ob~ained. The effect of the addition of low levels of c~rium ion into dishwashing compositions is particularly benefisi~l under low hardness water conditions, where the ~mo~nt of calcium introduced from tap water is low.
Calri~m ions are added to the co".~)os;lion at levels of 0.01 - 0.5%, preferably 0.1 - 0.~%, most preferably 0.1 - 0.3%. At lower c~lci--m levels, no effect on solution feel will be observed. At higher calri~-m levels, storage ~'0 93/17084 21 3 0 ~ 6 6 PCI/US93/011~6 _ ,.
stability will not be good. That is, it is known that calcium ions are relatively easily p,c;ci~ila~ed at high te",pe,a~-lre conditions, and thus are apt to deteriorate storage stability when added at high levels. C~lrium ions are further known to contribute to detergency, particularly to grease removal. By selectin~ a calcium level in the above range, a composition having all three important benefits are obtained; good solution feel, good grease removal, and good storage stability.
The co""~)Gs;lions of the present invention must have less than 35%
total surf~ct~nts to avoid p~ ecip;lalion of the calcium which is present at a level suffirient to improve solution feel. If the surfactant level is too high? the m~Yimum amount of calcium that can be added without fo.",ing c~lrium p, ~cipilalion would not be sufficiçnt to improve solution feel to the composltion.
The calcium ions can be inco,~o,aled in the co"",os;lion in any convenient way, so long as the salts CQ~ g cs~lri~lm ions are soluble in water and do not p,.~ e under oldh~y use conditions. A suitable way of il~co.~,G,ali.,g c~lrium ions is by adding them as salts selected from the groupcon~ g of chloride, hydroxide, oxide, ~cet~te, nitrate, formate, and mixtures thereof. Chloride salts are most pn,f~" cd.
Alternately, calcium ions can also be incorporated as counter-ions of anionic surfactants? such as by neutralizing the acid forrn of anionic surfi-ct~nt.c with r~lcium oxide or calcium hydroxide, without aa~ling the benefits thereo~
The p,~,fe.,ed composition ofthe present invention co"~.,ises:
(1) 20 - 30% by weight of a surfactant system selected from the group con.~;cl;.~ of anionic, nonionic, amphoteric sull~cl~"~, and mixtures thereof, c~"-~ lg.
a. at least 35% by weight of the surfactant system alkyl ethoxy sulfate with an alkyl group of C10-l6 and an average of 2.5 - 3.5 ethylene oxide per molecllle;
Wo 93/17084 PCr/US93/0 2~3a46G -8-b. 4 - 7% by weight of the composition diethanol amide with an alkyl chain of C8-20;
c. 2 - 5 by weight of the composition amine oxide with an alkyl chain of C8-16;
(2) 0.1 - 0.3% by weight calcium ion; and (3) 0.1 - 1% by weight m~gnPcium ion.
Optional Co",pone"ls The compositions of the present invention can optionally contain components in addition to those already disclosed herein.
Optional surf~t~ntc useful in the composition of the present invention are those such as monoeth~nol arnides, polyhydroxy fatty acid arnides, alkyl polyglucosidçc, and alkyl ethoxylates.
MOnG~Ih~nOI amide is an optional su,rac~al-t in the present invention, having the formula HO
l 11 (c2H5oH)-N-c-R3 wherein R3 is sçlçcted from an alkyl chain of Cg 20, pleI~Iably C12 14.
Polyhydroxy fatty acid arnide is an optional surfactant in the present invention, having the formula o R4 Il I .
wherein R4 is H, Cl 4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl, or a mixture thereof, preferably Cl 4 alkyl, more preferably methyl; and R5 is Cs 31 hydrocarbyl, prel~,~bly straight-chain C10 16 alkyl; and Z is WO 93/17084 213 0 ~ 6 6 PCI/US93/01156 polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls directly co~-necled to the chain, or an alkoxylated derivative (preferably ethoxylated or propoxylated) thereof. Z preferably will be derived from a reduçing sugar in a reductive amination reaction; more p,erelably Z is glycityl. Suit?ble reducing sugars include glucose, fructose, mq-ltose, lactose,galactose, mannose, and xylose.
Alkyl polyglucoside is an optional surfactant in the present invention, having the formula R6o(cmH2mo)p(glucosyl)q wherein R6 is selecled from the group con~ .g of alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof in which the alkyl groups are C10-l8~ preferably C12 14, m is 2 or 3, preferably 2; p is from 0 to about 10, preferably 0; and q is 1.3 - 10, plere(ably 1.3 - 3, most prerc,~bly 1.3 - 2.7. To prepare these compounds the alcohol or alkylpolyethoxy alcohol is formed first and then reacted with glUCOSf~ or a source of g~uGOSç, to form the g1~lcos;de (attr-hment at the l-position). The nd~itionql glycosyl units can then be attached ~ ~cn their l-pGS;l;On and the pl ece(~ glycosyl units 2-, 3-, 4-and/or 6-position, prer~,.ably predo...;.~ely the 2-pos;lion.
Alkyl ethoxylate is an optional surfactant in the present invention. Such alkyl ethoxylates are aliphatic alcohols with I - 25 moles of ethylene oxide.
The alkyl chain of the aliphatic alcohol can either be straight or b,iu~ched, primary or secondary, and generally co,.l~;l-C 8 - 22 carbon atoms. Particularlypreft,,cd are the con~1fnC~l;on products of-q-lcohols having an alkyl group con~ ;ng 8 - 20 carbon atoms with 2 - 10 moles of ethylene oxide per mole of alcohol. Most ptérelled are the conden~-qtiorl products of alcohols having an alkyl group cQI.~ ;ng 8 - 14 carbon atoms with 6 - 10 moles of ethylene oxide per mole of alcohol.
Amphoteric surf~ct~nt~ optionally included in the present invention are wO 93/17084 PCr/US93/01~
2~3o~6~
betaines having the formula R8 (R10)2 R7Co-N-R9-N+Rl lcoo-wherein R7 is a C7 21 alkyl group, or alkylaryl group, prel~,~bly Cg 17; R8 is hydrogen or a Cl 6 alkyl group, plefe,~bly Cl 3; R9 is a Cl 1o alkylene group, preferably C2 6, most preferably C3; each R10 is a C1 6 alkyl or hydroxy alkyl group, preferably C 1_3, most preferably methyl or an ethoxylated hydroxy alkyl co,.~ g from about 1 to about 10 ethylene oxide units; and R11 is an C 1 -6 alkylene group, preferably methyl.
~ nPsj-lm ions at a level of 0.1 - 1% are ple~lably inrluded in the composition of the present invention to improve detergency without ~-;I;np good solution feel and good storage stability of the co",?o~;lion.
The compositionc of the present invention can also comprise 4 - 8% by weight of a hydrGIIope selected from the group conC;~ of sodium and a".l"onium salts of cllm~ne sulfon~t~c~ toluene sulronales, xylene s~lron~
sulfo succ~ lec~ and mixtures thereo~ Such cGnl?onenls are utilized in the inlere~ls of achieving a desired product phase stability and viscosity.
Other desirable ingredients include solvents, preservatives, dyes, and perfumes.
Solvents useful in the present invention include water and lower rnoleclJI~r weight ~lcoholc such as ethanol. Ethanol is also known to reduce the viscosity of the product, if n~cecc~y for formulation. Solvents other than water are typically present at levels of 2 - 10% by weight.
Preservatives, dyes, and perfumes can be, and usually will be forrn~ ted in the composition of the present invention to make products attractive to the consumer. These co",?on~ s are typically present at levels not more than 1% resl)eclively.
Components which are preferably not incl~lded in the composition are those which generate plc~;l)ilation upon binding with calcium ions. Fysn~pl~s are those which include sulfate, carboxylate, and fatty acid anions.
EXAMPLES
The following e~n.llec illustrate the compositions of the present invention, but are not interlded to be limiting thereof. All per~ie.-lsges and ratios are based on weight unless otherwise specified.
P, epa, ~lion The liquid delergcnt compositions herein des~i,il,ed can be made conveniently by one skilled in the art. Surfs-ctsntc hyd,ul~opes, calcium salts,and optionally tt.~gn~si~-m salts are added in an approp,iate amount of water and are blended. In the present invention, the order of adding the co"")on~,.ds is not important. If l~ecçsC~ ~, the pH of the mixture is -s~dj~sted with HCI to a safe level for ho~sPhold products, and viscosity is adjl~sted with alcohol.
Perfume, dye, and preservatives are optionally added, and the co"~,ûsilion is ~slsnced with water. The standard product and c~a. ,Jles 1 - 9 are all p,epa,~d accord;ng to this Inetllod EA~;I i"~e.,la~ion 1. Solution feel - 500g each of 6% solutions of the standard product and compositions of the present invention are prepared in a 1 liter beaker, and a pûrcelain crucible is soaked in the solution - One hand is soaked in the sample solution and the other hand is soaked in the general standard product solution at the same time, and the feel of the crucible is evaluated according to the scale as shown below.
- Evaluation is done by three special psnelicts and the average score is Wo 93/17084 PCr/US93/01_ 21~66 12-obtained.
Evaluation scale O= There is no diIrerence I= I think there is a difference ~ 2= I know there is a dia~rence + 3= I know there is a big difference 4= I know there is a very big difference (+): the sample has a better feel (less slippery) the sample has a worse feel (more slippery) For those which have higher points than the composition with the same surfactant system without calcium it is evaluated that the "solution feel was improved".
2. Storage Stability The sample is placed in a lO0 ml glass co~ , and stored in rooms with e~ t~ ed t~..":c.~lules of-5~C and 40~C r~ec~ ely. The cor~ition of the product after 2 weeks is evaluated as follows.
clear and no change co"",a, ed to before the test - O
p, ec;~ e~l or cloudy - X
AccG,ding to Table 1, it is understood that FY~ IeS 1, 3, 4, and 7 which are compositions of the present invention have both improved solution feel and good storage stability.
)VO 93/17084 2 1 3 0.~ 6 6 - PCI/US93/01156 Standard 1 2 3 4 5 6 7 8 product Sodium C,2-l4 alkyl ethoxy (5 ave.) sulfate 11.7 11.7 - - - - - - -AmmOniUm C12-14 alkyl ethoxy (3 ave.) sulfate - - 12.0 12.0 12.012.0 12.0 12.0 12.0 Cl2-~4 alkyl dimethyl amine oxide 3.1 3.13.0 3.0 3.0 3.0 3.0 3.0 3.0 Cl2 alkyl diethanol amide 4.4 4-4 4-5 4-5 4-5 4-5 4-5 4-5 4-5 Cl2-l4 alkyl N-methyl glucoamide - - 5.0 5.0 5.0 5.0 Cl2 alkyl ethoxy (3 ave.) alcohol 2.3 2.3 C9-ll alkyl ethoxy (8 ave.~ alcohol - - 1.5 1.5 1.5 1.5 1.5 1.5 1.5 Sodium toluene sulfonate 2.3 2.3 Sodium cumene sulfonate - - 5-0 5.0 5.0 5.0 5.0 5.0 5.0 Mg++(MgC12-7H20) - - 0.7 0.5 0.36 0.1 0.7 0.5 0.1 Ca+ +(CaC12) - 0.3 - 0.2 0.14 0.6 - 0.2 0.6 Ethanol 2.5 2.54.2 4.2 4.2 4.2 2.8 2.8 2.8 Water and other minors bal~ bal bal bal bal bal bal bal bal Solution feel(point) Std+2.0 -1.38 -0.88+0.75+0.75 -1.38 -0.5 +0.13 (comparison example) - Std - ex.2 ex.2 ex.2 - ex.6 ex.6 (improved points) - +2.0 - +0.5 +2.13+2.13 - +0.88+ 1.25 (evaluation) - 0 - 0 0 0 - 0 0 bal = balance WO 93/l708~,-!L3Q 4G6 PCI/US93/01 (continuedJ
Standard 1 2 3 4 5 6 7 8 product Storage stability (-5~C) 0 0 0 0 0 X 0 0 X
(40~C) 0 0 0 0 0 X 0 0 X
Claims (2)
1. An aqueous hard surface detergent composition which provides improved solution feel comprising:
(1) 20 - 30% by weight of a surfactant system selected from the group consisting of anionic, nonionic, amphoteric surfactants, and mixtures thereof, comprising:
a. at least 35% by weight alkyl ethoxy sulfate with an alkyl group of C10-16 and an average of 2.5 - 3.5 moles of ethylene oxide per molecule;
b. diethanol amide with an alkyl chain of C8-20; and c. amine oxide with an alkyl chain of C8-16;
(2) 0.1 - 0.3% by weight calcium ion; and (3) 0.1 - 0.5% by weight magnesium ion;
wherein the composition contains 4 - 7% by weight of the diethanol amide, and 2 - 5% by weight the amine oxide.
(1) 20 - 30% by weight of a surfactant system selected from the group consisting of anionic, nonionic, amphoteric surfactants, and mixtures thereof, comprising:
a. at least 35% by weight alkyl ethoxy sulfate with an alkyl group of C10-16 and an average of 2.5 - 3.5 moles of ethylene oxide per molecule;
b. diethanol amide with an alkyl chain of C8-20; and c. amine oxide with an alkyl chain of C8-16;
(2) 0.1 - 0.3% by weight calcium ion; and (3) 0.1 - 0.5% by weight magnesium ion;
wherein the composition contains 4 - 7% by weight of the diethanol amide, and 2 - 5% by weight the amine oxide.
2. A method of cleaning a hard surface comprising contacting a hard surface with a cleaning effective amount of an aqueous hard surface detergent composition according to Claim 1.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4-69607 | 1992-02-19 | ||
| JP6960792 | 1992-02-19 | ||
| JP4/74509 | 1992-03-30 | ||
| JP4074509A JP2871941B2 (en) | 1992-02-19 | 1992-03-30 | Aqueous detergent composition for hard surfaces containing calcium ions |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2130466A1 CA2130466A1 (en) | 1993-09-02 |
| CA2130466C true CA2130466C (en) | 1998-12-15 |
Family
ID=26410782
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002130466A Expired - Fee Related CA2130466C (en) | 1992-02-19 | 1993-02-08 | Aqueous hard surface detergent compositions containing calcium ions |
Country Status (19)
| Country | Link |
|---|---|
| EP (1) | EP0626995B1 (en) |
| CN (1) | CN1052505C (en) |
| AU (1) | AU668919B2 (en) |
| BR (1) | BR9305919A (en) |
| CA (1) | CA2130466C (en) |
| CZ (1) | CZ197494A3 (en) |
| DE (1) | DE69320794T2 (en) |
| ES (1) | ES2119890T3 (en) |
| FI (1) | FI943800A (en) |
| HU (1) | HUT68839A (en) |
| MA (1) | MA22805A1 (en) |
| MX (1) | MX9300834A (en) |
| MY (1) | MY109586A (en) |
| NO (1) | NO943024L (en) |
| NZ (1) | NZ249400A (en) |
| RU (1) | RU2114907C1 (en) |
| SK (1) | SK281088B6 (en) |
| TR (1) | TR27773A (en) |
| WO (1) | WO1993017084A1 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000043476A2 (en) * | 1999-01-20 | 2000-07-27 | The Procter & Gamble Company | Dishwashing detergent compositions containing mixtures of crystallinity-disrupted surfactants |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA1052223A (en) * | 1975-01-06 | 1979-04-10 | David S. Lambert | Detergent composition containing semi-polar nonionic detergent and alkaline earth metal anionic detergent |
| GB2058823B (en) * | 1979-09-17 | 1983-06-22 | Unilever Ltd | Dishwashing compositions |
| US4316824A (en) * | 1980-06-26 | 1982-02-23 | The Procter & Gamble Company | Liquid detergent composition containing alkyl sulfate and alkyl ethoxylated sulfate |
| DE3264512D1 (en) * | 1981-04-03 | 1985-08-08 | Procter & Gamble | Liquid detergent compositions |
| GB2123847A (en) * | 1982-06-28 | 1984-02-08 | Procter & Gamble | Liquid detergent compositions |
| US4507219A (en) * | 1983-08-12 | 1985-03-26 | The Proctor & Gamble Company | Stable liquid detergent compositions |
| US4681704A (en) * | 1984-03-19 | 1987-07-21 | The Procter & Gamble Company | Detergent composition containing semi-polar nonionic detergent alkaline earth metal anionic detergent and amino alkylbetaine detergent |
| JPS63277300A (en) * | 1987-05-08 | 1988-11-15 | Kao Corp | Liquid detergent composition |
| ES2106729T3 (en) * | 1989-05-22 | 1997-11-16 | Procter & Gamble | DETERGENT COMPOSITION FOR DISHWASHERS, LIQUID OR IN GEL, OF LIGHT ACTION, CONTAINING AN ALKYL-ETHOXI-CARBOXYLATE SURFACTANT. |
| HU213365B (en) * | 1990-09-28 | 1997-05-28 | Procter & Gamble | Detergent composition containing polyhydroxy fatty acid amides and suds enhancing agent |
-
1993
- 1993-02-08 ES ES93905000T patent/ES2119890T3/en not_active Expired - Lifetime
- 1993-02-08 WO PCT/US1993/001156 patent/WO1993017084A1/en not_active Application Discontinuation
- 1993-02-08 BR BR9305919A patent/BR9305919A/en not_active Application Discontinuation
- 1993-02-08 SK SK980-94A patent/SK281088B6/en unknown
- 1993-02-08 CA CA002130466A patent/CA2130466C/en not_active Expired - Fee Related
- 1993-02-08 AU AU36157/93A patent/AU668919B2/en not_active Ceased
- 1993-02-08 DE DE69320794T patent/DE69320794T2/en not_active Expired - Fee Related
- 1993-02-08 EP EP93905000A patent/EP0626995B1/en not_active Expired - Lifetime
- 1993-02-08 NZ NZ249400A patent/NZ249400A/en unknown
- 1993-02-08 CZ CZ941974A patent/CZ197494A3/en unknown
- 1993-02-08 RU RU94040384A patent/RU2114907C1/en active
- 1993-02-08 HU HU9402400A patent/HUT68839A/en unknown
- 1993-02-13 MY MYPI93000236A patent/MY109586A/en unknown
- 1993-02-15 TR TR00125/93A patent/TR27773A/en unknown
- 1993-02-17 MX MX9300834A patent/MX9300834A/en not_active IP Right Cessation
- 1993-02-18 MA MA23098A patent/MA22805A1/en unknown
- 1993-02-19 CN CN93102957A patent/CN1052505C/en not_active Expired - Fee Related
-
1994
- 1994-08-16 NO NO943024A patent/NO943024L/en unknown
- 1994-08-18 FI FI943800A patent/FI943800A/en not_active Application Discontinuation
Also Published As
| Publication number | Publication date |
|---|---|
| MY109586A (en) | 1997-02-28 |
| ES2119890T3 (en) | 1998-10-16 |
| AU3615793A (en) | 1993-09-13 |
| TR27773A (en) | 1995-08-09 |
| SK98094A3 (en) | 1995-01-12 |
| HU9402400D0 (en) | 1994-11-28 |
| RU94040384A (en) | 1996-06-20 |
| AU668919B2 (en) | 1996-05-23 |
| MA22805A1 (en) | 1993-10-01 |
| BR9305919A (en) | 1997-08-26 |
| EP0626995B1 (en) | 1998-09-02 |
| EP0626995A1 (en) | 1994-12-07 |
| HUT68839A (en) | 1995-08-28 |
| FI943800A0 (en) | 1994-08-18 |
| CN1052505C (en) | 2000-05-17 |
| DE69320794D1 (en) | 1998-10-08 |
| NO943024D0 (en) | 1994-08-16 |
| CN1076477A (en) | 1993-09-22 |
| CZ197494A3 (en) | 1995-01-18 |
| NO943024L (en) | 1994-08-16 |
| WO1993017084A1 (en) | 1993-09-02 |
| CA2130466A1 (en) | 1993-09-02 |
| SK281088B6 (en) | 2000-11-07 |
| RU2114907C1 (en) | 1998-07-10 |
| DE69320794T2 (en) | 1999-04-29 |
| NZ249400A (en) | 1997-02-24 |
| FI943800A (en) | 1994-08-18 |
| MX9300834A (en) | 1994-07-29 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EEER | Examination request | ||
| MKLA | Lapsed |