EP0157443B1 - Detergenszusammensetzung, die ein semipolares nichtionisches Detergens, ein alkalische Erdmetalle enthaltendes anionisches Detergens und ein Amidoalkylbetan-Detergens enthält - Google Patents

Detergenszusammensetzung, die ein semipolares nichtionisches Detergens, ein alkalische Erdmetalle enthaltendes anionisches Detergens und ein Amidoalkylbetan-Detergens enthält Download PDF

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Publication number
EP0157443B1
EP0157443B1 EP19850200329 EP85200329A EP0157443B1 EP 0157443 B1 EP0157443 B1 EP 0157443B1 EP 19850200329 EP19850200329 EP 19850200329 EP 85200329 A EP85200329 A EP 85200329A EP 0157443 B1 EP0157443 B1 EP 0157443B1
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Prior art keywords
carbon atoms
detergent
alkyl
anionic
composition
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Expired
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EP19850200329
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English (en)
French (fr)
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EP0157443A1 (de
Inventor
Lowell Watson Bernardino
Edward William Kuhl
Mark Hsiang K. Mao
Eugene Joseph Pancheri
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Procter and Gamble Co
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Procter and Gamble Co
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    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/88Ampholytes; Electroneutral compounds
    • C11D1/90Betaines
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/88Ampholytes; Electroneutral compounds
    • C11D1/94Mixtures with anionic, cationic or non-ionic compounds
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02Anionic compounds
    • C11D1/12Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/14Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • C11D1/143Sulfonic acid esters
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02Anionic compounds
    • C11D1/12Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/14Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • C11D1/146Sulfuric acid esters
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02Anionic compounds
    • C11D1/12Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/22Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic compounds
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02Anionic compounds
    • C11D1/12Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/29Sulfates of polyoxyalkylene ethers
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66Non-ionic compounds
    • C11D1/75Amino oxides
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66Non-ionic compounds
    • C11D1/755Sulfoxides
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66Non-ionic compounds
    • C11D1/79Phosphine oxides

Definitions

  • This invention relates to a detergent composition especially formulated for the removal of greasy soils. More particularly, it relates to a detergent composition containing a semi-polar nonionic detergent, an alkaline earth metal, preferably magnesium, salt of an anionic detergent and an amidoalkylbetaine.
  • Detergent compositions containing a wide variety of water-soluble organic detergents or mixtures thereof have been formulated. Recognizably, certain water-soluble organic detergents are better at removing one type of soil than other detergents. For example, anionic detergents are noted for their ability to remove carbohydrate and protein type stains, while nonionic detergents are especially useful in the removal of grease and oil stains.
  • anionic detergents are noted for their ability to remove carbohydrate and protein type stains
  • nonionic detergents are especially useful in the removal of grease and oil stains.
  • Various mixtures of detergents have been tried in order to find the optimum combination for removing a wide variety of stains as is normally encountered on soiled articles. (See for example, U.S. Patents 2,691,636, 3,085,982, 3,177,598, 3,179,599, 3,196,166 and 3,223,647 for various organic detergent combinations.)
  • a detergent composition especially effective in the removal of greasy soil is formulated using a semi-polar nonionic detergent, an alkaline earth metal salt of certain anionic detergents, and an amidoalkylbetaine.
  • a detergent composition especially effective in removing greasy soils comprises, by weight of the composition,
  • the detergent compositions of this invention contain a water-soluble semi-polar nonionic detergent, an alkaline earth metal salt of an anionic detergent, and an amidoalkylbetaine as essential ingredients. Descriptions of these detergents follow.
  • the Semi-polar nonionic detergents useful herein are water-soluble amine oxides having one alkyl or hydroxyalkyl moiety of 8 to 28 carbon atoms, preferably 8 to 16 carbon atoms and two alkyl moieties selected from the group consisting of alkyl groups and hydroxyalkyl groups containing 1 to 3 carbon atoms.
  • Examples of such materials include dimethyloctylamine oxide, diethyldecylamine oxide, bis-(2-hydroxyethyl)dodecylamine oxide, dimethyldodecylamine oxide, dipropyl- tetradecylamine oxide, methylethylhexadecylamine oxide, and dimethyl-2-hydroxyoctadecylamine oxide.
  • the amine oxide is present in an amount of from 2% to 10% more preferably from 1% to 8% and most particularly from 2% to 6% by weight of the composition.
  • the composition comprises at least 10%, preferably at least 15% of the alkaline earth metal, preferably magnesium, salt of an organic anionic detergent.
  • the composition may comprise the sodium, potassium, ammonium and/or substituted ammonium salts of an organic anionic detergent.
  • Especially preferred salts are the magnesium salts.
  • the anionic detergent salts which are useful in the present invention are selected from the following classes of anionic detergents:
  • the above-described anionic detergents are all available commercially.
  • the acid form of the anionic detergent can be converted to the alkaline earth metal salt form either prior to admixture with the semi-polar nonionic detergent or thereafter. This conversion can be accomplished either by direct neutralization with an alkaline earth metal base or by ion exchange between, e.g., an alkali metal, ammonium or alkanolammonium salt of the anionic detergent and a non-toxic, water-soluble alkaline earth metal salt.
  • a source of magnesium or calcium ions is added to the detergent mixture under desirable reaction conditions to form the desired salts.
  • Calcium and magnesium chlorides, calcium and magnesium sulfates, calcium and magnesium acetates or calcium and magnesium hydroxides and oxides are examples of magnesium and calcium sources. Magnesium chloride and magnesium sulfate are preferred. Magnesium oxide or hydroxide is most preferred.
  • the cation of the anionic detergent is important in that the alkaline earth metal salts of the herein described anionic detergent perform better in terms of suds persistence, especially in the presence of grease, than the alkali metal, ammonium or alkanolammonium salts of said anionic detergents when in combination with the semi-polar nonionic detergent and the betaine detergent.
  • a mixture of cations may be desirable for optimum physical properties or sudsing across a range of conditions and soils, provided sufficient amounts of the anionic surfactant are in the alkaline earth metal form to provide the desired grease removal.
  • Up to about 25% of the above anionic detergents can be in the form of their sodium, potassium, ammonium, mono-, di- or triethanolammonium salts, especially ammonium, monoethanolammonium, or triethanolammonium.
  • the amidoalkylbetaine surfactant is essential to the improved performance.
  • the suds persistence (mileage) is less when the amidoalkylbetaine is combined with alkali metal anionic and semi-polar nonionic detergent mixtures.
  • Overall superior performance requires all three essential ingredients.
  • betaines examples include coconutacylamidopropyldimethylbetaine; C 12 - 14 acylamidopropylbetaine; C s acylamidohexyldiethylbetaine; C 16 - 18 acylamidodimethylbetaine; C 12 - 14 acylamido- pentanediethylbetaine; and C 12 - 16 acylmethylamidodimethylbetaine.
  • Preferred betaines are the C 10 - 18 acylamidopropane (or ethane) dimethyl (or diethyl) betaines.
  • Suitable amidoalkylbetains are disclosed in U.S. Patents 3,950,417; 4,137,191; and 4,375,421 and British Patent GB 2,103,236.
  • the level of betaine in the product is preferably more than 1 %, desirably 4 to 6%, where maximum grease handling is desired.
  • alkyl (and acyl) groups for the above detergents can be derived from either natural or synthetic sources, e.g., they can be derived from naturally occurring fatty acids; olefins such as those prepared by Ziegler, or Qxo processes; or from olefins separated from petroleum either with or without "cracking".
  • alkyl sulfates and alkyl ether sulfates include those derived from Neodol 23 (Trade Mark) which is a synthetic alcohol prepared by an Oxo process and containing about 42 weight percent of dodecanol and about 54 weight percent of tridecanol.
  • Ratios of semi-polar nonionic detergent and betaine to anionic detergent (salt basis) of from 1:20 to 1:2, preferably from 1:15 to 1:3 provide very satisfactory grease removal.
  • the degree of grease removal obtained from the detergent mixture is greater than that achieved by the individual detergents alone when used under normal conditions.
  • the detergent compositions of this invention are formulated in powder, granular, tablet, paste, or, preferably, liquid form. Regardless of the form of the composition, it is especially effective in the removal of greasy soils.
  • a preferred detergent composition containing the above-described detergents is in a liquid form.
  • Such liquid compositions are especially useful for the hand washing of soiled cooking utensils and tableware.
  • the liquid compositions may contain from 11% to 60%, preferably from 11 % to 50% for concentrated products designed for dilution prior to use, of the semi-polar nonionic, anionic, and betaine detergent mixture.
  • the balance of the formula comprises water.
  • All manner of known additives can be included in the liquid composition. For example, suds boosters, organic solvents, e.g., C l -C. alkanols (preferably ethanol), perfumes, dyes, and hydrotropes can be added for their known functions.
  • An especially preferred liquid detergent composition also contains a source of alkalinity for increased greasy soil removal.
  • Sodium hydroxide, potassium hydroxide, ammonium hydroxide, and mono-, di- or trialkanolamines wherein said alkanol moieties contain from one to five, preferably two to three carbon atoms, in either a linear or branched configuration are suitable bases. Normally, the higher chain length branched alkanolamines are mono- or di-substituted. Common alkanolamines are mono- and diisopropanolamines and mono-, di- and triethanolamines. Sufficient base is added to the composition to raise its pH to above 7.0, but below about 9.0.
  • Such a composition has not only increased greasy soil removal ability, but also the removal is accelerated.
  • Ammonia, di- and triethanolamines and mixtures thereof are preferred sources of alkalinity because of the resultant compositions' physical characteristics, i.e., the compositions have good fluidity and viscosity.
  • a liquid detergent composition having the following formulation is most preferred:
  • the balance of the composition comprises inert filler salts.
  • a suitable inert filler salt is sodium sulfate.
  • Various additives, e.g., suds suppressors, dyes, perfume, soil anti-redeposition agents, and water can also be included in the granular or tableted composition.
  • liquid detergent compositions of this invention are preferably prepared by neutralizing the acid forms of the anionic detergent with the aforementioned sources of alkalinity, magnesium hydroxide, magnesium oxide, and/or adding a soluble alkaline earth metal source, preferably magnesium sulfate or magnesium chloride, to give the finished formula.
  • the following detergent compositions are formulated on a weight percent basis.
  • compositions A-F When compositions A-F are tested for their ability to remove grease from a soiled surface, the results will show that the compositions of this invention, i.e. compositions B, D, and F will remove more grease and have better suds mileage than the similar compositions wherein the magnesium cation and betaine are not employed.
  • compositions A, B and C This base formula was compared to compositions A, B and C in which 5% C 12 - 14 acylamidopropyl betaine was added.
  • Mg salts were replaced by ammonium salts and in B the amine oxide was removed. Water was removed or added to maintain the given percentages.
  • a preweighed 250 ml polypropylene cup has 3 ml of a melted beef grease applied to its inner bottom surface. After the grease has solidified, the cup is reweighed. Then a 0.4% aqueous solution of the composition to be tested is added to the cup to completely fill it. The aqueous solution has a temperature of 45°C. After 15 minutes, the cup is emptied and rinsed with distilled water. The cup is dried and then weighed to determine the amount of grease removal. The results of tests performed on the above compositions are reported as follows on a % grease removal basis.
  • the amine oxide and the magnesium anionic detergent and/or betaine are essential for optimum grease removal.
  • both the magnesium anionic detergent and the betaine are required for both improved suds mileage and improved grease removal.

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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)
  • Detergent Compositions (AREA)

Claims (6)

1. Detergenszusammensetzung, besonders wirksam zur Entfernung von fettigem Schmutz, worin der Anteil des organischen Detergens dieser Zusammensetzung eine Mischung umfaßt aus:
a) 0,5 bis 10 Gewichtsprozent eines semipolaren organischen nichtionischen Detergens, welches wasserlösliche Aminoxide mit einer Alkyl- oder Hydroxyalkylkette mit 8-28 Kohlenstoffatomen und zwei Alkylketten, ausgewählt aus Alkyl- und Hydroxyalkylgruppen mit 1-3 Kohlenstoffatomen, enthält,
b) 10-50 Gewichtsprozent eines Erdalkalisalzes eines anionischen Detergens, das ausgewählt wird aus (1) linearen Alkylbenzolsulfonaten mit 9 bis 15 Kohlenstoffatomen in der Alkylkette, (2) Alkylsulfaten mit 8-22 Kohlenstoffatomen, (3) Alkylethersulfaten mit 8-22 Kohlenstoffatomen in der Alkylkette und 1 bis 30 Ethylenoxid-Einheiten, und (4) deren Mischungen,
dadurch gekennzeichnet, daß diese Zusammensetzung weiterhin enthält:
c) 0,5 bis 6% eines Acylamidoalkylbetains der allgemeinen Formel
Figure imgb0008
worin R eine Alkylgruppe mit 7 bis 21 Kohlenstoffatomen, vorzugsweise mit 9 bis 17 Kohlenstoffatomen,
R1 Wasserstoff oder eine Alkylgruppe mit 1 bis 6 Kohlenstoffatomen,
R2 eine Alkylengruppe mit 1 bis 10 Kohlenstoffatomen, jeder Rest R3 eine Alkyl- oder Hydroxyalkylgruppe mit 1 bis 6 Kohlenstoffatomen oder eine ethoxylierte Hydroxyalkylgruppe mit 1 bis 10 Ethylenoxid-Einheiten, und
R4 eine Alkylengruppe mit 1 bis 6 Kohlenstoffatomen bedeuten.
2. Detergenszusammensetzung gemäß Anspruch 1, worin die langen Alkylketten im Aminoxid und in den anionischen Detergentien 8 bis 16 Kohlenstoffatome enthalten, und im Acylamidoalkylbetain der Rest R 9 bis 17 Kohlenstoffatome enthält, R1 Wasserstoff bedeutet, R2 2 bis 6, vorzugsweise 3 Kohlenstoffatome enthält, R3 1 bis 3 Kohlenstoffatome und R4 ein Kohlenstoffatom enthält.
3. Detergenszusammensetzung gemäß Anspruch 1 oder 2, worin das Verhältnis von Aminoxid und Betaindetergens zum Gesamtgewicht des anionischen Detergens 1:20 bis 1:2 beträgt.
4. Detergenszusammensetzung gemäß Anspruch 3, worin das Verhältnis von Aminoxid und Betaindetergens zum Gesamtgewicht des anionischen Detergens 1:15 bis 1:3 beträgt.
5. Detergenszusammensetzung nach einem der Ansprüche 1-3 in flüssiger Form, worin die Zusammensetzung 11 bis 45% dieser Mischung enthält und der Rest Wasser oder Mischungen aus Wasser und CI-C5-Alkanolen enthält.
6. Detergenszusammensetzung gemäß Anspruch 5, worin diese Mischung, bezogen auf das Gewicht der Zusammensetzung, enthält:
a) 2 bis 6% eines wasserlöslichen Aminoxids mit einem Alkylrest mit 8-16 Kohlenstoffatomen und zwei Alkylgruppen mit 1 bis 3 Kohlenstoffatomen,
b) 10 bis 30% eines Magnesiumalkylsulfats mit 12-16 Kohlenstoffatomen,
c) 0 bis 20% eines Alkylethersulfats, erhalten aus einem Alkohol mit 12-16 Kohlenstoffatomen und mit 1-12 Molen Ethylenoxid ethoxyliert, wobei das Gegenion ausgewählt wird aus Calcium, Magnesium, Ammonium oder einem Ethanolammoniumrest oder deren Mischungen,
d) 1 bis 6% eines C12-16-Acylamidopropylbetains,
e) 0 bis 15% eines Ammonium- oder Ethanolammoniumhydroxids, -sulfats oder -chlorids.
EP19850200329 1984-03-19 1985-03-07 Detergenszusammensetzung, die ein semipolares nichtionisches Detergens, ein alkalische Erdmetalle enthaltendes anionisches Detergens und ein Amidoalkylbetan-Detergens enthält Expired EP0157443B1 (de)

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US59109784A 1984-03-19 1984-03-19
US591097 1984-03-19

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EP0157443B1 true EP0157443B1 (de) 1988-05-18

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Families Citing this family (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4555360A (en) * 1984-06-22 1985-11-26 The Procter & Gamble Company Mild detergent compositions
LU86839A1 (fr) * 1987-04-10 1988-12-13 Oreal Composition cosmetique detergente et moussante,retardant le regraissage des cheveux
US5540865A (en) * 1990-01-29 1996-07-30 The Procter & Gamble Company Hard surface liquid detergent compositions containing hydrocarbylamidoalkylenebetaine
US5342549A (en) * 1990-01-29 1994-08-30 The Procter & Gamble Company Hard surface liquid detergent compositions containing hydrocarbyl-amidoalkylenebetaine
US5336445A (en) * 1990-03-27 1994-08-09 The Procter & Gamble Company Liquid hard surface detergent compositions containing beta-aminoalkanols
US5540864A (en) * 1990-12-21 1996-07-30 The Procter & Gamble Company Liquid hard surfce detergent compositions containing zwitterionic detergent surfactant and monoethanolamine and/or beta-aminoalkanol
JPH07503271A (ja) * 1992-01-23 1995-04-06 ザ、プロクター、エンド、ギャンブル、カンパニー 双性イオン洗剤界面活性剤と陽イオン洗剤界面活性剤とモノエタノールアミンおよび/またはβ‐アミノアルカノールとを含有する液体硬質表面用洗剤組成物
US5536451A (en) * 1992-10-26 1996-07-16 The Procter & Gamble Company Liquid hard surface detergent compositions containing short chain amphocarboxylate detergent surfactant
JP2540435B2 (ja) * 1993-06-21 1996-10-02 花王株式会社 硬質表面用洗浄剤組成物
ES2143030T3 (es) * 1993-11-12 2000-05-01 Procter & Gamble Composiciones detergentes liquidas para superficies duras, que contienen tensioactivo detergente anfotero y perfume.
US5531933A (en) * 1993-12-30 1996-07-02 The Procter & Gamble Company Liquid hard surface detergent compositions containing specific polycarboxylate detergent builders
US5534198A (en) * 1994-08-02 1996-07-09 The Procter & Gamble Company Glass cleaner compositions having good filming/streaking characteristics and substantive modifier to provide long lasting hydrophilicity
DE19534369C2 (de) * 1995-09-15 2000-06-15 Cognis Deutschland Gmbh Wäßrige Handgeschirrspülmittel
GB2321253B (en) * 1997-01-16 2000-10-18 Mcbride Robert Ltd Liquid detergent formulation
ES2551227T3 (es) 2010-10-29 2015-11-17 The Procter & Gamble Company Composición limpiadora líquida espesada para superficies duras

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4122043A (en) * 1973-12-19 1978-10-24 Polytrol Chemical Corporation Amidobetaine containing detergent composition non-toxic to aquatic life
US4133779A (en) * 1975-01-06 1979-01-09 The Procter & Gamble Company Detergent composition containing semi-polar nonionic detergent and alkaline earth metal anionic detergent
US4137191A (en) * 1977-02-14 1979-01-30 Inolex Corporation Low-irritant surfactant composition
US4375421A (en) * 1981-10-19 1983-03-01 Lever Brothers Company Viscous compositions containing amido betaines and salts

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EP0157443A1 (de) 1985-10-09
CA1239324A (en) 1988-07-19

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