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EP0626995B1 - Aqueous hard surface detergent compositions containing calcium ions - Google Patents

Aqueous hard surface detergent compositions containing calcium ions Download PDF

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Publication number
EP0626995B1
EP0626995B1 EP93905000A EP93905000A EP0626995B1 EP 0626995 B1 EP0626995 B1 EP 0626995B1 EP 93905000 A EP93905000 A EP 93905000A EP 93905000 A EP93905000 A EP 93905000A EP 0626995 B1 EP0626995 B1 EP 0626995B1
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EP
European Patent Office
Prior art keywords
composition
weight
alkyl
group
hard surface
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.)
Expired - Lifetime
Application number
EP93905000A
Other languages
German (de)
French (fr)
Other versions
EP0626995A1 (en
Inventor
Nakamura (Okabe), Yuko
Mayumi Daiki
Ryohei Ohtani
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Procter and Gamble Co
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Procter and Gamble Co
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Filing date
Publication date
Priority claimed from JP4074509A external-priority patent/JP2871941B2/en
Application filed by Procter and Gamble Co filed Critical Procter and Gamble Co
Publication of EP0626995A1 publication Critical patent/EP0626995A1/en
Application granted granted Critical
Publication of EP0626995B1 publication Critical patent/EP0626995B1/en
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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

Definitions

  • the present invention relates to an aqueous hard surface detergent composition containing calcium ion which provides improved solution feel without deteriorating storage stability of the composition.
  • the composition is particularly useful for dishwashing liquids, more particularly under soft water conditions.
  • Anionic surfactants such as alkyl ethoxy sulfates with short ethylene oxide chains, alkyl sulfates, alkyl benzene sulfonates, a-olefin sulfonates, and alkyl ethoxy carboxylates are known to be very effective for hard surface cleaning, but are also known to have more or less unfavorable "slippery" feel in use. This undesirable attribute is a problem to hard surface cleaning compositions, especially for dishwashing purposes.
  • Kokoku 46-43550 (Kao Corporation) teaches a liquid detergent composition which is mild to skin and has good detergency comprising alkaline earth metal salts of certain alkyl alkylene-oxy sulfate and certain alkyl alkylene-oxy carboxylates.
  • compositions comprising calcium and magnesium salts of anionic surfactants including alkyl ether sulfates and amine oxides, C 1-5 alkanols and water, wherein the weight ratio of amine oxide to anionic surfactant is 1:100 to 1:2. Up to about 25% of the anionic surfactants can be monovalent salts.
  • compositions which comprise alkyl ether alkoxy sulfate salts and water soluble polyvalent salts of magnesium, calcium, iron, or aluminium of 5 - 50% by weight of the surfactant. Examples show compositions comprising at least 70% of the anionic surfactant in which magnesium and calcium ions help detergency.
  • U.S. Patent 4,681,704 (The Procter & Gamble Company) teaches a detergent composition with effective grease removal comprising 10 - 50% alkaline earth metal salt preferably magnesium, of anionic surfactants, 0.5 - 10% amine oxides, and 0.5 - 15% betaines.
  • GB 2 205 578 discloses liquid detergent compositions having a pH 4 to 6 . 5, anionic surfactant, amine oxide, fatty acid alkanolamide and polypropylene oxide adduct of polyhydric alcohol having improved detergency, foaming power and stability.
  • GB 2058823 discloses liquid dishwashing compositions comprising calcium or magnesium sensitive anionic surfactant, source of magnesium or calcium ions, hydrotrope, alkyl phosphate ester and pH controller providing anti-resoiling benefits.
  • compositions of the above mentioned disclosures use alkaline earth metals mainly for their cleaning benefits, and do not disclose or suggest the improvement to solution feel benefits contributed by calcium ions.
  • compositions of the above mentioned disclosures have high divalent ion levels, so that they would be unstable upon storage in the context of the present invention, namely, would form undesirable precipitates of calcium.
  • Preferred compositions and examples shown in the above disclosures also have high surfactant levels, and thus the amount of calcium needed to reduce or eliminate the "slippery feel" of the composition would place the composition into a phase where calcium is believed to easily precipitate.
  • the present invention relates to an aqueous hard surface detergent composition which provides improved solution feel comprising :
  • 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 from 0.01% to 0.5% by weight of calcium ion to said composition.
  • Said aqueous hard surface detergent composition comprises from 3% to 35% by weight of the composition 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 of alkyl ethoxy sulfate with an alkyl group of C 10-16 and an average of 1 - 10 moles of ethylene oxide per molecule; (b) optionally other anionic surfactants selected from the group consisting of alkyl benzene sulfonate, alpha-olefin sulfonate, alkyl ethoxy carboxylate, and mixtures thereof; (c) 0% to 9% by
  • compositions of the present invention have 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.
  • compositions of the present invention comprise 15% to 35%, preferably 20% to 30% by weight of a 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 system is the sum of anionic surfactants, diethanol amide, and amine oxide.
  • 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 C 10-16 and an average of 1 - 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 C 10-16 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.
  • alkyl sulfate is dealt as an alkyl ethoxy sulfate having 0 moles of ethylene oxide per molecule. 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.
  • compositions of the present invention 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 surfactants are chosen in order to obtain optimum balance of detergency, solution feel, and storage stability.
  • compositions of the present invention can contain nonionic surfactants such as diethanol amides and amine oxides 0 - 9%, preferably 4 - 7% by weight of diethanol amide and 2 - 5% by weight of amine oxide is contained in the composition.
  • nonionic surfactants such as diethanol amides and amine oxides 0 - 9%, preferably 4 - 7% by weight of diethanol amide and 2 - 5% by weight of amine oxide is contained in the composition.
  • These two surfactants 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 comprising diethanol amide and/or amine oxide.
  • Diethanol amide useful in the present invention has the formula wherein R 1 is selected from an alkyl chain of C 8-20 , preferably C 12-14 .
  • Amine oxide useful in the present invention has the formula wherein R 2 is selected from an alkyl chain of C 8-20 preferably C 12-14 .
  • Calcium ions are added to the composition at levels of 0.01 -0.5%, preferably 0.1 - 0.5%, most preferably 0.1 - 0.3%. At lower calcium levels, no effect on solution fed will be observed. At higher calcium levels, storage stability will not be good. That is, it is known that calcium ions are relatively easily precipitated at high temperature conditions, and thus are apt to deteriorate storage stability when added at high levels. Calcium ions are further known to contribute to detergency, particularly to grease removal. By selecting 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.
  • compositions of the present invention must have less than 35% total surfactants to avoid precipitation of the calcium which is present at a level sufficient to improve solution feel. If the surfactant level is too high, the maximum amount of calcium that can be added without forming calcium precipitation would not be sufficient to improve solution feel to the composition.
  • the calcium ions can be incorporated in the composition in any convenient way, so long as the salts containing calcium ions are soluble in water and do not precipitate under ordinary use conditions.
  • a suitable way of incorporating calcium ions is by adding them as salts selected from the group consisting of chloride, hydroxide, oxide, acetate, nitrate, formate, and mixtures thereof. Chloride salts are most preferred.
  • calcium ions can also be incorporated as counter-ions of anionic surfactants, such as by neutralizing the acid form of anionic surfactants with calcium oxide or calcium hydroxide, without affecting the benefits thereof.
  • composition of the present invention comprises:
  • compositions of the present invention can optionally contain components in addition to those already disclosed herein.
  • Optional surfactants useful in the composition of the present invention are those such as monoethanol amides, polyhydroxy fatty acid amides, alkyl polyglucosides, and alkyl ethoxylates.
  • Monoethanol amide is an optional surfactant in the present invention, having the formula wherein R 3 is selected from an alkyl chain of C 8-20 , preferably C 12-14 .
  • Polyhydroxy fatty acid amide is an optional surfactant in the present invention, having the fomula wherein R 4 is H, C 1-4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl, or a mixture thereof, preferably C 1-4 alkyl, more preferably methyl; and R 5 is C 5-31 hydrocarbyl, preferably straight-chain C 10-16 alkyl; and Z is polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain, or an alkoxylated derivative (preferably ethoxylated or propoxylated) thereof.
  • Z preferably will be derived from a reducing sugar in a reductive amination reaction; more preferably Z is glycityl.
  • Suitable reducing sugars include glucose, fructose, maltose, lactose, galactose, mannose, and xylose.
  • Alkyl polyglucoside is an optional surfactant in the present invention, having the formula R 6 O(C m H 2m O) p (glucosyl) q wherein R 6 is selected from the group consisting of alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof in which the alkyl groups are C 10-18 , preferably C 12-14 , m is 2 or 3, preferably 2; p is from 0 to about 10, preferably 0; and q is 1.3 - 10, preferably 1.3 - 3, most preferably 1.3 - 2.7.
  • the alcohol or alkylpolyethoxy alcohol is formed first and then reacted with glucose, or a source of glucose, to form the glucoside (attachment at the 1-position).
  • the additional glycosyl units can then be attached between their 1-position and the preceding glycosyl units 2-, 3-, 4-and/or 6-position, preferably predominately the 2-position.
  • Alkyl ethoxylate is an optional surfactant in the present invention.
  • Such alkyl ethoxylates are aliphatic alcohols with 1 - 25 moles of ethylene oxide.
  • the alkyl chain of the aliphatic alcohol can either be straight or branched, primary or secondary, and generally contains 8- 22 carbon atoms.
  • Particularly preferred are the condensation products of alcohols having an alkyl group containing 8 - 20 carbon atoms with 2 - 10 moles of ethylene oxide per mole of alcohol.
  • Most preferred are the condensation products of alcohols having an alkyl group containing 8 - 14 carbon atoms with 6 - 10 moles of ethylene oxide per mole of alcohol.
  • Amphoteric surfactants optionally included in the present invention are betaines having the formula wherein R 7 is a C 7-21 alkyl group, or alkylaryl group, preferably C 9-17 ; R 8 is hydrogen or a C 1-6 alkyl group, preferably C 1-3 ; R 9 is a C 1-10 alkylene group, preferably C 2-6 , most preferably C 3 ; each R 10 is a C 1-6 alkyl or hydroxy alkyl group, preferably C 1-3 , most preferably methyl or an ethoxylated hydroxy alkyl containing from about 1 to about 10 ethylene oxide units; and R 11 is an C 1-6 alkylene group, preferably methyl.
  • Magnesium ions at a level of 0.1 - 1% are preferably included in the composition of the present invention to improve detergency without affecting good solution feel and good storage stability of the composition.
  • compositions of the present invention can also comprise 4 - 8% by weight of a hydrotrope selected from the group consisting of sodium and ammonium salts of cumene sulfonates, toluene sulfonates, xylene sulfonates, sulfo succinates, and mixtures thereof.
  • a hydrotrope selected from the group consisting of sodium and ammonium salts of cumene sulfonates, toluene sulfonates, xylene sulfonates, sulfo succinates, and mixtures thereof.
  • Other desirable ingredients include solvents, preservatives, dyes, and perfumes.
  • Solvents useful in the present invention include water and lower molecular weight alcohols, such as ethanol. Ethanol is also known to reduce the viscosity of the product, if necessary 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 formulated in the composition of the present invention to make products attractive to the consumer. These components are typically present at levels not more than 1% respectively.
  • Components which are preferably not included in the composition are those which generate precipitation upon binding with calcium ions. Examples are those which include sulfate, carboxylate, and fatty acid anions.
  • compositions of the present invention are not intended to be limiting thereof. All percentages and ratios are based on weight unless otherwise specified.
  • liquid detergent compositions herein described can be made conveniently by one skilled in the art.
  • Surfactants hydrotropes, calcium salts, and optionally magnesium salts are added in an appropriate amount of water and are blended.
  • the order of adding the components is not important. If necessary, the pH of the mixture is adjusted with HCl to a safe level for household products, and viscosity is adjusted with alcohol. Perfume, dye, and preservatives are optionally added, and the composition is balanced with water.
  • the standard product, the comparative examples 2,5,6 and 8, and examples 1, 3, 4, 7 according to the present invention are all prepared according to this method.
  • the sample is placed in a 100 ml glass container, and stored in rooms with established temperatures of-5°C and 40°C respectively.
  • the condition of the product after 2 weeks is evaluated as follows.
  • Examples 1, 3, 4, and 7 which are compositions of the present invention have both improved solution feel and good storage stability.
  • Standard product 1 2 3 4 5 6 7 8 Sodium C 12-14 alkyl ethoxy (5 ave.) sulfate 11.7 11.7 - - - - - - - - - Ammonium C 12-14 alkyl ethoxy (3 ave.) sulfate - - 12.0 12.0 12.0 12.0 12.0 12.0 12.0 C 12-14 alkyl dimethyl amine oxide 3.1 3.1 3.0 3.0 3.0 3.0 3.0 3.0 3.0 C 12 alkyl diethanol amide 4.4 4.4 4.5 4.5 4.5 4.5 4.5 4.5 4.5 4.5 4.5 4.5 4.5 4.5 4.5 C 12 - 14 alkyl N-methyl glucoamide - - 5.0 5.0 5.0 5.0 - - - C 12 alkyl ethoxy (3 ave.) alcohol 2.3 2.3 - - - - -

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Description

TECHNICAL FIELD
The present invention relates to an aqueous hard surface detergent composition containing calcium ion which provides improved solution feel without deteriorating storage stability of the composition. The composition is particularly useful for dishwashing liquids, more particularly under soft water conditions.
BACKGROUND
Anionic surfactants such as alkyl ethoxy sulfates with short ethylene oxide chains, alkyl sulfates, alkyl benzene sulfonates, a-olefin sulfonates, and alkyl ethoxy carboxylates are known to be very effective for hard surface cleaning, but are also known to have more or less unfavorable "slippery" feel in use. This undesirable attribute is a problem to hard surface cleaning compositions, especially for dishwashing purposes.
There is therefore a considerable demand for a hard surface detergent composition which has good detergency and good storage stability while having good solution feel when cleaning and rinsing, particularly for dishwashing purposes. As defined herein, good solution feel is best defined as the absence 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 important attribute for commercial liquid detergent products. Those wash solutions which have good solution feel on hands and objects to be cleaned allow easy handling of the objects, and provide good rinsing characters. Such benefits are most appreciated for dishwashing purposes.
Many attempts have been made to improve solution feel using various technology. These attempts are usually directed towards the use of nonionic-type surfactants, and other suds enhancing-type and solvent-type components. 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 alkaline 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 magnesium salts of anionic surfactants including alkyl ether sulfates and amine oxides, C1-5 alkanols and water, wherein the weight ratio of amine oxide to anionic surfactant is 1:100 to 1:2. Up to about 25% of the anionic surfactants can be monovalent salts.
U.S. Patent 2,766,212 (General Aniline and Film Corporation) teaches compositions which comprise alkyl ether alkoxy sulfate salts and water soluble polyvalent salts of magnesium, calcium, iron, or aluminium of 5 - 50% by weight of the surfactant. Examples show compositions comprising at least 70% of the anionic surfactant in which magnesium and calcium ions help detergency.
U.S. Patent 4,681,704 (The Procter & Gamble Company) teaches a detergent composition with effective grease removal comprising 10 - 50% alkaline earth metal salt preferably magnesium, of anionic surfactants, 0.5 - 10% amine oxides, and 0.5 - 15% betaines. GB 2 205 578 discloses liquid detergent compositions having a pH 4 to 6.5, anionic surfactant, amine oxide, fatty acid alkanolamide and polypropylene oxide adduct of polyhydric alcohol having improved detergency, foaming power and stability. GB 2058823 discloses liquid dishwashing compositions comprising calcium or magnesium sensitive anionic surfactant, source of magnesium or calcium ions, hydrotrope, alkyl phosphate ester and pH controller providing anti-resoiling benefits.
However, the above mentioned disclosures use alkaline earth metals mainly for their cleaning benefits, and do not disclose or suggest the improvement to solution feel benefits contributed by calcium ions. Further, the compositions of the above mentioned disclosures have high divalent ion levels, so that they would be unstable upon storage in the context of the present invention, namely, would form undesirable precipitates of calcium. Preferred compositions and examples shown in the above disclosures also have high surfactant levels, and thus the amount of calcium needed to reduce or eliminate 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.
OBJECT OF INVENTION
It is an object of the present invention to provide a clear aqueous hard surface detergent composition which has improved solution feel in use without deteriorating storage stability of the composition.
It is also an object of the present invention to provide a liquid hard surface detergent composition which has balanced good quality in detergency, solution feel, and storage stability.
It is further an object of the present invention to provide 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 composition.
DETAIL DESCRIPTION
The present invention relates to an aqueous hard surface detergent composition which provides improved solution feel comprising :
  • (1) 3 - 35% by weight of said composition 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 C10-16 and an average of 1 - 10 moles of ethylene oxide per molecule;
  • b. optionally other anionic surfactants selected from the group consisting of alkyl benzene sulfonates, α-olefin sulfonates, alkyl ethoxy carboxylates, and mixtures thereof;
  • c. 0% to 9% by weight of the composition of diethanol amide with an alkyl chain of C8-20;
  • d. 2% to 5% by weight of the composition of amine oxide with an alkyl chain of C8-16; and
  • (2) 0.1% to 0.3% by weight of calcium ion,
    • said composition excluding the presence of C12/14 alkylamidohydroxy sulfobetaine wherein preferably at least 20% by weight of a surfactant system comprises the total of component a, b, c and d.
    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 from 0.01% to 0.5% by weight of calcium ion to said composition. Said aqueous hard surface detergent composition comprises from 3% to 35% by weight of the composition 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 of alkyl ethoxy sulfate with an alkyl group of C10-16 and an average of 1 - 10 moles of ethylene oxide per molecule; (b) optionally other anionic surfactants selected from the group consisting of alkyl benzene sulfonate, alpha-olefin sulfonate, alkyl ethoxy carboxylate, and mixtures thereof; (c) 0% to 9% by weight of the composition of diethanol amide with an alkyl chain of C8-20; (d) 0% to 10% by weight of the composition of amine oxide with an alkyl chain of C8-16.
    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% to 35%, preferably 20% to 30% by weight of a 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 system 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 C10-16 and an average of 1 - 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 C10-16 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 per molecule. 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 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 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 surfactants such as diethanol amides and amine oxides 0 - 9%, preferably 4 - 7% by weight of diethanol amide and 2 - 5% by weight of amine oxide is contained in the composition. These two surfactants 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 comprising diethanol amide and/or amine oxide.
    Diethanol amide useful in the present invention has the formula
    Figure 00060001
    wherein R1 is selected from an alkyl chain of C8-20, preferably C12-14.
    Amine oxide useful in the present invention has the formula
    Figure 00060002
    wherein R2 is selected from an alkyl chain of C8-20 preferably C12-14.
    Calcium
    It has been found that by incorporating low levels of calcium ions, balanced benefits in solution feel and storage stability are obtained. The effect of the addition of low levels of calcium ion into dishwashing compositions is particularly beneficial under low hardness water conditions, where the amount of calcium inuoduced from tap water is low.
    Calcium ions are added to the composition at levels of 0.01 -0.5%, preferably 0.1 - 0.5%, most preferably 0.1 - 0.3%. At lower calcium levels, no effect on solution fed will be observed. At higher calcium levels, storage stability will not be good. That is, it is known that calcium ions are relatively easily precipitated at high temperature conditions, and thus are apt to deteriorate storage stability when added at high levels. Calcium ions are further known to contribute to detergency, particularly to grease removal. By selecting 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 compositions of the present invention must have less than 35% total surfactants to avoid precipitation of the calcium which is present at a level sufficient to improve solution feel. If the surfactant level is too high, the maximum amount of calcium that can be added without forming calcium precipitation would not be sufficient to improve solution feel to the composition.
    The calcium ions can be incorporated in the composition in any convenient way, so long as the salts containing calcium ions are soluble in water and do not precipitate under ordinary use conditions. A suitable way of incorporating calcium ions is by adding them as salts selected from the group consisting of chloride, hydroxide, oxide, acetate, nitrate, formate, and mixtures thereof. Chloride salts are most preferred.
    Alternately, calcium ions can also be incorporated as counter-ions of anionic surfactants, such as by neutralizing the acid form of anionic surfactants with calcium oxide or calcium hydroxide, without affecting the benefits thereof.
    The preferred composition of the present invention comprises:
  • (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 of the surfactant system alkyl ethoxy sulfate with an alkyl group of C10-16 and an average of 2.5 - 3.5 ethylene oxide per molecule;
  • 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 magnesium ion.
    • Optional Components
    The compositions of the present invention can optionally contain components in addition to those already disclosed herein.
    Optional surfactants useful in the composition of the present invention are those such as monoethanol amides, polyhydroxy fatty acid amides, alkyl polyglucosides, and alkyl ethoxylates.
    Monoethanol amide is an optional surfactant in the present invention, having the formula
    Figure 00080001
    wherein R3 is selected from an alkyl chain of C8-20, preferably C12-14.
    Polyhydroxy fatty acid amide is an optional surfactant in the present invention, having the fomula
    Figure 00080002
    wherein R4 is H, C1-4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl, or a mixture thereof, preferably C1-4 alkyl, more preferably methyl; and R5 is C5-31 hydrocarbyl, preferably straight-chain C10-16 alkyl; and Z is polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain, or an alkoxylated derivative (preferably ethoxylated or propoxylated) thereof. Z preferably will be derived from a reducing sugar in a reductive amination reaction; more preferably Z is glycityl. Suitable reducing sugars include glucose, fructose, maltose, 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 selected from the group consisting of alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof in which the alkyl groups are C10-18, 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, preferably 1.3 - 3, most preferably 1.3 - 2.7. To prepare these compounds the alcohol or alkylpolyethoxy alcohol is formed first and then reacted with glucose, or a source of glucose, to form the glucoside (attachment at the 1-position). The additional glycosyl units can then be attached between their 1-position and the preceding glycosyl units 2-, 3-, 4-and/or 6-position, preferably predominately the 2-position.
    Alkyl ethoxylate is an optional surfactant in the present invention. Such alkyl ethoxylates are aliphatic alcohols with 1 - 25 moles of ethylene oxide. The alkyl chain of the aliphatic alcohol can either be straight or branched, primary or secondary, and generally contains 8- 22 carbon atoms. Particularly preferred are the condensation products of alcohols having an alkyl group containing 8 - 20 carbon atoms with 2 - 10 moles of ethylene oxide per mole of alcohol. Most preferred are the condensation products of alcohols having an alkyl group containing 8 - 14 carbon atoms with 6 - 10 moles of ethylene oxide per mole of alcohol.
    Amphoteric surfactants optionally included in the present invention are betaines having the formula
    Figure 00100001
    wherein R7 is a C7-21 alkyl group, or alkylaryl group, preferably C9-17; R8 is hydrogen or a C1-6 alkyl group, preferably C1-3; R9 is a C1-10 alkylene group, preferably C2-6, most preferably C3; each R10 is a C1-6 alkyl or hydroxy alkyl group, preferably C1-3, most preferably methyl or an ethoxylated hydroxy alkyl containing from about 1 to about 10 ethylene oxide units; and R11 is an C1-6 alkylene group, preferably methyl.
    Magnesium ions at a level of 0.1 - 1% are preferably included in the composition of the present invention to improve detergency without affecting good solution feel and good storage stability of the composition.
    The compositions of the present invention can also comprise 4 - 8% by weight of a hydrotrope selected from the group consisting of sodium and ammonium salts of cumene sulfonates, toluene sulfonates, xylene sulfonates, sulfo succinates, and mixtures thereof. Such components are utilized in the interests 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 molecular weight alcohols, such as ethanol. Ethanol is also known to reduce the viscosity of the product, if necessary 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 formulated in the composition of the present invention to make products attractive to the consumer. These components are typically present at levels not more than 1% respectively.
    Components which are preferably not included in the composition are those which generate precipitation upon binding with calcium ions. Examples are those which include sulfate, carboxylate, and fatty acid anions.
    EXAMPLES
    The following examples illustrate the compositions of the present invention, but are not intended to be limiting thereof. All percentages and ratios are based on weight unless otherwise specified.
    Preparation
    The liquid detergent compositions herein described can be made conveniently by one skilled in the art. Surfactants hydrotropes, calcium salts, and optionally magnesium salts are added in an appropriate amount of water and are blended. In the present invention, the order of adding the components is not important. If necessary, the pH of the mixture is adjusted with HCl to a safe level for household products, and viscosity is adjusted with alcohol. Perfume, dye, and preservatives are optionally added, and the composition is balanced with water. The standard product, the comparative examples 2,5,6 and 8, and examples 1, 3, 4, 7 according to the present invention are all prepared according to this method.
    Experimentation 1. Solution feel
    • 500g each of 6% solutions of the standard product the comparative compositions and compositions of the present invention are prepared in a 1 liter beaker, and a porcelain 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 panelists, and the average score is obtained. Evaluation scale
      0=
      There is no difference
      ± 1=
      I think there is a difference
      ± 2=
      I know there is a difference
      ± 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 100 ml glass container, and stored in rooms with established temperatures of-5°C and 40°C respectively. The condition of the product after 2 weeks is evaluated as follows.
  • clear and no change compared to before the test - O
  • precipitated, or cloudy   - X
    • According to Table 1, it is understood that Examples 1, 3, 4, and 7 which are compositions of the present invention have both improved solution feel and good storage stability.
    Standard product 1 2 3 4 5 6 7 8
    Sodium C12-14 alkyl ethoxy (5 ave.) sulfate 11.7 11.7 - - - - - - -
    Ammonium C12-14 alkyl ethoxy (3 ave.) sulfate - - 12.0 12.0 12.0 12.0 12.0 12.0 12.0
    C12-14 alkyl dimethyl amine oxide 3.1 3.1 3.0 3.0 3.0 3.0 3.0 3.0 3.0
    C12 alkyl diethanol amide 4.4 4.4 4.5 4.5 4.5 4.5 4.5 4.5 4.5
    C12-14 alkyl N-methyl glucoamide - - 5.0 5.0 5.0 5.0 - - -
    C12 alkyl ethoxy (3 ave.) alcohol 2.3 2.3 - - - - - - -
    C9-1 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•7H2O) - - 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 2.5 4.2 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
    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 (7)

    1. An aqueous hard surface detergent composition which provides improved solution feel comprising 3% - 35% by weight of the composition of a surfactant system selected from the group consisting of anionic, nonionic, amphoteric surfactants, and mixtures thereof, comprising:
      a) at least 20% by weight of the alkyl ethoxy sulfate with an alkyl group of C10-16 and an average of 1 - 10 moles of ethylene oxide per molecule;
      b) optionally other anionic surfactants selected from the group consisting of alkyl benzene sulfonate, alpha-olefin sulfonate, alkyl ethoxy carboxylate, and mixtures thereof;
      c) diethanol amide with an alkyl chain of C8-20;
      d) amine oxide with an alkyl chain of C8-16; and
      wherein said composition contains 0% - 9% by weight of said diethanol amide, 2% - 5% by weight of said amine oxide, at least 3% by weight of said alkyl ethoxy sulfate, and 0.1% to 0.3% by weight of calcium ions, and wherein said composition excludes the presence of C12-14 alkylamidohydroxysulfobetaine.
    2. A composition according to claim 1 wherein said surfactant system comprises at least 35% by weight of the alkyl ethoxy sulfate.
    3. A composition according to claim 2 comprising 20 - 30% of the surfactant system.
    4. A composition according to any of claims 1-3, wherein the alkyl ethoxy sulfate has an average of 2-5 moles, more preferably 2.5 - 3.5 moles, of ethylene oxide per molecule.
    5. A composition according to any of claims 1-4, comprising 4 - 7% of said diethanol amide.
    6. A composition according to any of claims 1-5, comprising 0.1 1 % by weight of magnesium ion.
    7. 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, said composition comprising from 3% to 35% by weight of the composition 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 of alkyl ethoxy sulfate with an alkyl group of C10-16 and an average of 1 - 10 moles of ethylene oxide per molecule;
      b) optionally other anionic surfactants selected from the group consisting of alkyl benzene sulfonate, alpha-olefin sulfonate, alkyl ethoxy carboxylate, and mixtures thereof;
      c) 0% to 9% by weight of the composition of diethanol amide with an alkyl chain of C8-20;
      d) 0% - 10% by weight of the composition of amine oxide with an alkyl chain of C8-16;
      by adding from 0.01% - 0.5% by weight of calcium ion to said composition.
    EP93905000A 1992-02-19 1993-02-08 Aqueous hard surface detergent compositions containing calcium ions Expired - Lifetime EP0626995B1 (en)

    Applications Claiming Priority (5)

    Application Number Priority Date Filing Date Title
    JP6960792 1992-02-19
    JP69607/92 1992-02-19
    JP4074509A JP2871941B2 (en) 1992-02-19 1992-03-30 Aqueous detergent composition for hard surfaces containing calcium ions
    JP74509/92 1992-03-30
    PCT/US1993/001156 WO1993017084A1 (en) 1992-02-19 1993-02-08 Aqueous hard surface detergent compositions containing calcium ions

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    EP0626995B1 true EP0626995B1 (en) 1998-09-02

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    JP2002535441A (en) * 1999-01-20 2002-10-22 ザ、プロクター、エンド、ギャンブル、カンパニー Dishwashing detergent composition comprising a crystal disintegrating surfactant mixture
    RU2399657C1 (en) * 2009-02-10 2010-09-20 Открытое акционерное общество "Нэфис Косметикс" - Казанский химический комбинат им. М. Вахитова Liquid detergent

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    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
    ATE14142T1 (en) * 1981-04-03 1985-07-15 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
    MA21850A1 (en) * 1989-05-22 1990-12-31 Procter & Gamble DETERGENT COMOSITION FOR LIQUID DISHWASHER OR IN THE FORM OF DOMESTIC GEL CONTAINING A TENSIO - ACTIVE AGENT BASED ON ALCOYL - ETHOXY - CARBOXYLATE.
    FI931367L (en) * 1990-09-28 1993-04-26 Procter & Gamble TVAETTMEDELSKOMPOSITIONER, SOM INNEHAOLLER POLYHYDROXIFETTSYRAAMIDER OCHEN SKUMFOERSTAERKARE

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