WO1993017084A1 - Compositions detersives aqueuses contenant des ions calcium pour surfaces dures - Google Patents

Compositions detersives aqueuses contenant des ions calcium pour surfaces dures Download PDF

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Publication number
WO1993017084A1
WO1993017084A1 PCT/US1993/001156 US9301156W WO9317084A1 WO 1993017084 A1 WO1993017084 A1 WO 1993017084A1 US 9301156 W US9301156 W US 9301156W WO 9317084 A1 WO9317084 A1 WO 9317084A1
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WO
WIPO (PCT)
Prior art keywords
weight
alkyl
composition
composition according
feel
Prior art date
Application number
PCT/US1993/001156
Other languages
English (en)
Inventor
Nakamura (Okabe), Yuko
Mayumi Daiki
Ryohei Ohtani
Original Assignee
The Procter & Gamble Company
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Priority claimed from JP4074509A external-priority patent/JP2871941B2/ja
Application filed by The Procter & Gamble Company filed Critical The Procter & Gamble Company
Priority to EP93905000A priority Critical patent/EP0626995B1/fr
Priority to KR1019940702886A priority patent/KR950700396A/ko
Priority to US08/290,711 priority patent/US5635464A/en
Priority to SK980-94A priority patent/SK281088B6/sk
Priority to AU36157/93A priority patent/AU668919B2/en
Priority to DE69320794T priority patent/DE69320794T2/de
Priority to BR9305919A priority patent/BR9305919A/pt
Publication of WO1993017084A1 publication Critical patent/WO1993017084A1/fr
Priority to NO943024A priority patent/NO943024L/no
Priority to FI943800A priority patent/FI943800A/fi

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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, 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.
  • compositions which comprise alkyl ether alkoxy sulfate salts and water soluble polyvalent salts of magnesium, calcium, iron, or aluminum 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.
  • 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: (1) 3 - 35% by weight of a surfactant system selected from the group consisting of anionic, nonionic, amphoteric surfactants, and mixtures thereof, comprising:
  • composition amine oxide with an alkyl chain of Cg_i6 d. 0 - 10% by weight of the composition amine oxide with an alkyl chain of Cg_i6;
  • 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 composition.
  • 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 - 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 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 CIQ-1 a * an avera g e 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 ⁇ o-16 m ⁇ 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.
  • alkyl ethoxy sulfate having 0 moles of ethylene oxide per molecule.
  • 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 0 - 10% preferably 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 0 - 10% preferably 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 H O
  • 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 feel 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:
  • 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 Cio-16 an ⁇ " a n 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 C _20i c. 2 - 5 by weight of the composition amine oxide with an alkyl chain of Cg_ ⁇ g;
  • 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
  • Polyhydroxy fatty acid amide is an optional surfactant in the present invention, having the formula
  • R 5 -C-N-Z wherein 4 is H, C ⁇ hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl, or a mixture thereof, preferably C ⁇ _ alkyl, more preferably methyl; and -5 is C5.
  • 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
  • R6 (C m H 2m O) p (glucosyl) q
  • R ⁇ is selected from the group consisting of alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof in which the alkyl groups are C ⁇ o-18- preferably C 2- ⁇ 4, 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- ⁇ osition.
  • 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
  • R 7 CO-N-R 9 -N + R 1 !COO-
  • R? is a C7.21 alkyl group, or alkylaryl group, preferably Cg. ⁇
  • R is hydrogen or a C . alkyl group, preferably C1.3
  • R is a CI.JQ alkylene group, preferably C2-6, most preferably C3
  • each R 0 is a C ⁇ ._ alkyl or hydroxy alkyl group, preferably C ⁇ _, most preferably methyl or an ethoxylated hydroxy alkyl containing from about 1 to about 10 ethylene oxide units
  • ! 1 is an C j.g 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 HC1 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 and examples 1 - 9 are all prepared according to this method.
  • 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.
  • (+) the sample has a better feel (less slippery)
  • (+) the sample has a worse feel (more slippery)
  • 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.

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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

Une composition détersive aqueuse pour surfaces dures présente une meilleure sensation de toucher de la solution, et comprend 3 à 35 % en poids d'un système de tensio-actifs choisis dans le groupe constitué par des tensio-actifs anioniques, non ioniques, amphotères, ainsi que des mélanges de ceux-ci et 0,01 à 0,5 % en poids d'ion calcium.
PCT/US1993/001156 1992-02-19 1993-02-08 Compositions detersives aqueuses contenant des ions calcium pour surfaces dures WO1993017084A1 (fr)

Priority Applications (9)

Application Number Priority Date Filing Date Title
EP93905000A EP0626995B1 (fr) 1992-02-19 1993-02-08 Compositions detersives aqueuses contenant des ions calcium pour surfaces dures
KR1019940702886A KR950700396A (ko) 1992-02-19 1993-02-08 칼슘이온을 함유한 수성 경질 표면 세척제 조성물(aqueous hard surface detergent compositions containing calcium ions)
US08/290,711 US5635464A (en) 1992-02-19 1993-02-08 Aqueous hard surface detergent compositions containing calcium ions
SK980-94A SK281088B6 (sk) 1992-02-19 1993-02-08 Vodorozpustný detergentný prostriedok na povrchové čistenie
AU36157/93A AU668919B2 (en) 1992-02-19 1993-02-08 Aqueous hard surface detergent compositions containing calcium ions
DE69320794T DE69320794T2 (de) 1992-02-19 1993-02-08 Kalziumionen enthaltende, waessrige waschmittelzusammensetzungen fuer harte oberflaechen
BR9305919A BR9305919A (pt) 1992-02-19 1993-02-08 Composições detergentes aquosas para superficie dura contendo ions de cálcio
NO943024A NO943024L (no) 1992-02-19 1994-08-16 Vandige detergentblandinger inneholdende kalsiumioner for harde flater
FI943800A FI943800A (fi) 1992-02-19 1994-08-18 Vesipohjaiset kovien pintojen pesuainekoostumukset, jotka sisältävät kalsiumioneja

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP6960792 1992-02-19
JP4/69607 1992-02-19
JP4/74509 1992-03-30
JP4074509A JP2871941B2 (ja) 1992-02-19 1992-03-30 カルシウムイオンを含有する硬質表面用水性洗剤組成物

Publications (1)

Publication Number Publication Date
WO1993017084A1 true WO1993017084A1 (fr) 1993-09-02

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ID=26410782

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1993/001156 WO1993017084A1 (fr) 1992-02-19 1993-02-08 Compositions detersives aqueuses contenant des ions calcium pour surfaces dures

Country Status (19)

Country Link
EP (1) EP0626995B1 (fr)
CN (1) CN1052505C (fr)
AU (1) AU668919B2 (fr)
BR (1) BR9305919A (fr)
CA (1) CA2130466C (fr)
CZ (1) CZ197494A3 (fr)
DE (1) DE69320794T2 (fr)
ES (1) ES2119890T3 (fr)
FI (1) FI943800A (fr)
HU (1) HUT68839A (fr)
MA (1) MA22805A1 (fr)
MX (1) MX9300834A (fr)
MY (1) MY109586A (fr)
NO (1) NO943024L (fr)
NZ (1) NZ249400A (fr)
RU (1) RU2114907C1 (fr)
SK (1) SK281088B6 (fr)
TR (1) TR27773A (fr)
WO (1) WO1993017084A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000043476A2 (fr) * 1999-01-20 2000-07-27 The Procter & Gamble Company Compositions de detergents vaisselle contenant des melanges de tensioactifs a rupture de cristallinite

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2296688A1 (fr) * 1975-01-06 1976-07-30 Procter & Gamble Composition detergente contenant un detergent non ionique semi-polaire et un detergent anionique a base d'un metal alcalino-terreux
GB2058823A (en) * 1979-09-17 1981-04-15 Unilever Ltd Dishwashing compositions
GB2078246A (en) * 1980-06-26 1982-01-06 Procter & Gamble Liquid detergent compositions
EP0062371A1 (fr) * 1981-04-03 1982-10-13 THE PROCTER & GAMBLE COMPANY Compositions détergentes liquides
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
GB2205578A (en) * 1987-05-08 1988-12-14 Kao Corp Liquid detergent
EP0399752A2 (fr) * 1989-05-22 1990-11-28 The Procter & Gamble Company Détergent doux, liquide ou sous forme de gel pour laver la vaisselle et contenant comme agent tensio-actif un alkyl-éthoxy carboxylate
WO1992006161A1 (fr) * 1990-09-28 1992-04-16 The Procter & Gamble Company Compositions detergentes contenant des tensioactifs anioniques, des amides d'acides gras polyhydroxy et un agent ameliorant le pouvoir moussant a selection critique

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2296688A1 (fr) * 1975-01-06 1976-07-30 Procter & Gamble Composition detergente contenant un detergent non ionique semi-polaire et un detergent anionique a base d'un metal alcalino-terreux
GB2058823A (en) * 1979-09-17 1981-04-15 Unilever Ltd Dishwashing compositions
GB2078246A (en) * 1980-06-26 1982-01-06 Procter & Gamble Liquid detergent compositions
EP0062371A1 (fr) * 1981-04-03 1982-10-13 THE PROCTER & GAMBLE COMPANY Compositions détergentes liquides
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
GB2205578A (en) * 1987-05-08 1988-12-14 Kao Corp Liquid detergent
EP0399752A2 (fr) * 1989-05-22 1990-11-28 The Procter & Gamble Company Détergent doux, liquide ou sous forme de gel pour laver la vaisselle et contenant comme agent tensio-actif un alkyl-éthoxy carboxylate
WO1992006161A1 (fr) * 1990-09-28 1992-04-16 The Procter & Gamble Company Compositions detergentes contenant des tensioactifs anioniques, des amides d'acides gras polyhydroxy et un agent ameliorant le pouvoir moussant a selection critique

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000043476A2 (fr) * 1999-01-20 2000-07-27 The Procter & Gamble Company Compositions de detergents vaisselle contenant des melanges de tensioactifs a rupture de cristallinite
WO2000043476A3 (fr) * 1999-01-20 2000-11-30 Procter & Gamble Compositions de detergents vaisselle contenant des melanges de tensioactifs a rupture de cristallinite

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MX9300834A (es) 1994-07-29
HU9402400D0 (en) 1994-11-28
HUT68839A (en) 1995-08-28
NO943024D0 (no) 1994-08-16
RU2114907C1 (ru) 1998-07-10
DE69320794T2 (de) 1999-04-29
NZ249400A (en) 1997-02-24
EP0626995A1 (fr) 1994-12-07
TR27773A (tr) 1995-08-09
DE69320794D1 (de) 1998-10-08
CA2130466C (fr) 1998-12-15
MY109586A (en) 1997-02-28
CN1076477A (zh) 1993-09-22
SK98094A3 (en) 1995-01-12
NO943024L (no) 1994-08-16
CZ197494A3 (en) 1995-01-18
MA22805A1 (fr) 1993-10-01
RU94040384A (ru) 1996-06-20
FI943800A0 (fi) 1994-08-18
AU668919B2 (en) 1996-05-23
AU3615793A (en) 1993-09-13
ES2119890T3 (es) 1998-10-16
BR9305919A (pt) 1997-08-26
CA2130466A1 (fr) 1993-09-02
FI943800A (fi) 1994-08-18
EP0626995B1 (fr) 1998-09-02
CN1052505C (zh) 2000-05-17
SK281088B6 (sk) 2000-11-07

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