EP0513948B1 - Reinigungsmittel für harte Oberflächen, biologisch abbaubare Chelatbildner enthaltend - Google Patents

Reinigungsmittel für harte Oberflächen, biologisch abbaubare Chelatbildner enthaltend Download PDF

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Publication number
EP0513948B1
EP0513948B1 EP92250105A EP92250105A EP0513948B1 EP 0513948 B1 EP0513948 B1 EP 0513948B1 EP 92250105 A EP92250105 A EP 92250105A EP 92250105 A EP92250105 A EP 92250105A EP 0513948 B1 EP0513948 B1 EP 0513948B1
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EP
European Patent Office
Prior art keywords
acid
composition
cooh
chelating agent
accordance
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EP92250105A
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English (en)
French (fr)
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EP0513948A2 (de
EP0513948A3 (en
Inventor
Richard Paul Woodbury
Judithann Ruth Hartman
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Hampshire Chemical Corp
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Hampshire Chemical Corp
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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
    • C11D3/43—Solvents
    • 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
    • C11D3/26—Organic compounds containing nitrogen
    • C11D3/33—Amino carboxylic acids
    • 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
    • C11D3/34—Organic compounds containing sulfur
    • C11D3/349—Organic compounds containing sulfur additionally containing nitrogen atoms, e.g. nitro, nitroso, amino, imino, nitrilo, nitrile groups containing compounds or their derivatives or thio urea
    • 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
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/32—Organic compounds containing nitrogen
    • C11D7/3245—Aminoacids
    • 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
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/34—Organic compounds containing sulfur
    • 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
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/50—Solvents
    • C11D7/5004—Organic solvents
    • C11D7/5022—Organic solvents containing oxygen
    • 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
    • C11D3/34—Organic compounds containing sulfur
    • C11D3/3472—Organic compounds containing sulfur additionally containing -COOH groups or derivatives thereof

Definitions

  • the present invention relates to hard-surface cleaning compositions containing a binary mixture of an organic solvent and a biodegradable chelating agent.
  • Iminodisuccinic acid salts have been described as a detergency builder in U.S. Patent 3,697,453.
  • Water soluble salts of N,N-di(carboxymethyl)-aspartic acid have also been disclosed as a builder in U.S. Patent 3,637,511.
  • none of these references disclosed the use of these compounds in hard-surface cleaning compositions.
  • the present invention relates to hard-surface cleaning compositions containing an organic solvent having a boiling point equal to or above 90°C, and a nonphosphorus-containing, biodegradable chelating agent.
  • the chelants useful in the present invention have the following formula: in which
  • substituted ammonium refers to an ammonium radical substituted with one or more alkyl groups having up to about 6 carbon atoms, preferably from about 1 to 4 carbon atoms.
  • Preferred chelants of Formula I include those compounds in which X and Y are both COOH or a sodium, potassium, ammonium or substituted ammonium salt thereof; and Z, Z', and Z" are, independently, hydrogen or COOH or a sodium, potassium, ammonium or substituted ammonium salt thereof.
  • chelants in accordance with the invention include, for example, cysteic acid N,N-diacetic acid; cysteic acid N-monoacetic acid; alanine-N-monoacetic acid; N-(3-hydroxysuccinyl)aspartic acid; and N-[2-(3-hydroxysuccinyl)]-L-serine.
  • Exemplary of the most preferred chelants are B-alanine-N,N-diacetic acid; aspartic acid N,N-diacetic acid; iminodisuccinic acid; aspartic acid N-monoacetic acid; and their potassium, sodium or ammonium salts.
  • the compounds of Formula I may be readily prepared by the use of steps generally described in the literature or by methods analogous or similar thereto and within the skill of the art.
  • the chelants of Formula I may be prepared by reacting an alkali metal salt of an appropriately substituted amino carboxylic acid with an alkali metal salt of an appropriately substituted carboxylic acid in an alkaline aqueous system in a manner as described in U.S. Patent No. 3,683,014 and U.S. Patent No. 3,637,511 to yield the corresponding appropriately substituted organic acid salt.
  • Treatment of the organic salt with a mineral acid (e.g., HCl) or an acidic ion-exchange resin liberates the free acid to afford a compound of Formula I.
  • Compounds of Formula I may also be prepared in a manner as described in U.S. Patent No. 4,827,014.
  • the chelants used according to the invention are prepared by reacting a compound of the formula where X is a substituent within the meaning of Formula I, with an appropriately substituted amine and, if as the case may be amide, ester or nitrile groups are present, hydrolyzing these groups in the presence of and acid or base, to yield a free acid or a salt conforming to Formula I.
  • compounds of Formula I may be prepared by reacting the appropriate mercaptocarboxylic acid with maleic acid in an aqueous solution under neutral, acidic or basic conditions.
  • Chelants in accordance with the invention may also be prepared by method analogous to the procedure described in European Patent No. 89,115,896.3, Publication No. 0,356,972 A2 where an appropriately substituted imino carboxylic acid or its alkali metal or ammonium salt is reacted with acrylic acid in a non-basic or an alkaline or nitrogen basic aqueous medium to yield a compound of Formula I.
  • Chelants of Formula I may also be prepared in the manner as described in U.S. Patent No. 3,929,874, wherein an appropriately substituted amine is reacted with epoxysuccinic acid in a basic aqueous medium to yield a compound of Formula I.
  • Alkyliminodiacetic acids are available commercially but may be prepared cheaply and easily by the method for the preparation of methyliminodiacetic acid as described by G. J. Berchet in Organic Synthesis, Vol. 11, pages 397-398, which method is described in Example VI below.
  • Organic solvents suitable for use in combination with the above-described chelating agents must have a boiling point equal to or above 90°C, in order to give the unexpected soil-release benefits derivable from the solvent-chelating agent combination.
  • C 1 -C 3 aliphatic alcohols such as isopropanol (B.P. 82°C) are not suitable for use in the present invention.
  • organic solvents which are effective in the present context are: C 6 -C 9 alkyl aromatic solvents, especially the C 6 -C 9 alkyl benzenes, alpha-olefins, like 1-decene or 1-dodecene, benzyl alcohol, n-hexanol, phthalic acid esters.
  • a type of solvent especially suitable for the compositions herein comprises diols having from 6 to 16, preferably 8 to 12, carbon atoms in their molecular structure.
  • Preferred diol solvents have a solubility in water of from about 0.1 to 20 g/100 g of water at 20°C.
  • the most preferred diol solvents are 2,2,4-trimethyl-1,3-pentanediol, and 2-ethyl-1,3-hexanediol.
  • Glycol ethers are another class of particularly preferred solvents. In this category, are: water-soluble CARBITOL® solvents or water-soluble CELLOSOLVE® solvents.
  • Water soluble CARBITOL® solvents are compounds of the 2-(2-alkoxyethoxy)ethanol class wherein the alkoxy group is derived from ethyl, propyl, butyl pentyl hexyl; a preferred water-soluble carbitol is 2-(2-butoxyethoxy)ethanol also known as butyl carbitol. Preferred are also hexyl carbitol and 2-methyl pentyl carbitol.
  • Water-soluble CELLOSOLVE® solvents are compounds of the 2-alkoxyethoxy ethanol class, wherein the alkoxy group is preferably butyl or hexyl.
  • Mixtures of the above solvents can also be used, like butyl carbitol and/or benzyl alcohol together with diols and/or glycol ethers.
  • the organic solvent is present in an amount of from 1% to 20% by weight of the total composition, preferably from 1% to 10%.
  • the benefits of the present compositions are derived from the combination of the specific chelating agents and organic solvents described hereinabove. They are particularly noticeable in terms of calcium soap-soil removal from surfaces such as bathtub surfaces.
  • the weight ratio or organic solvent to chelating agent is in the range from 2:3 to 2:1, preferably 1:1 to 2:1.
  • the chelant is present in an amount of from 1% to 30% by weight of the total cleaning composition, preferably about 1% to 15% by weight of the total cleaning composition.
  • compositions of the invention can contain additional ingredients, which are often highly desirable.
  • the compositions herein will usually contain a surface-active agent.
  • Water-soluble detersive surfactants useful herein include well-known synthetic anionic, nonionic, cationic, emphoteric and zwitterionic surfactants and mixtures thereof. Typical of these are the alkyl benzene sulfates and sulfonates, paraffin sulfonates, olefin sulfonates, alkoxylated (especially ethoxylated) alcohols and alkyl phenols, amine oxides, sulfonates of fatty acids and of fatty acids esters, and the like, which are well-known in the detergency art.
  • detersive surfactants contain an alkyl group in the C 10 -C 18 range; the anionic detersive surfactants are most commonly used in the form of their sodium, potassium or triethanolammonium salts.
  • the nonionics generally contain from 3 to 17 ethylene oxide groups per mole of hydrophobic moiety.
  • Cationic surfactants will generally be represented by quaternary ammonium compounds such as ditallow dimethyl ammonium chloride, and will be preferably used in combination with nonionic surfactants.
  • compositions of the present invention are: C 12 -C 16 alkyl benzene sulfonates, C 12 -C 18 paraffin-sulfonates and the ethoxylated alcohols of the formula RO(CH 2 CH 2 O) n with R being a C 12 -C 15 alkyl chain and n being a number from 6 to 10, and the ethoxylated alcohol sulfates of formula RO-(CH 2 CH 2 O) n -SO 3 M, with R being a C 12 -C 18 alkyl chain on a number from 2 to 8, and M is H or an alkalimetal ion.
  • Anionic surfactants are frequently present at levels from 0.3% to 8% of the composition.
  • Nonionic surfactants are used at levels between 0.1% to 6% by weight of the composition. Mixtures of the like surfactants can also be used.
  • detergency builders which may be used in addition to the chelating agent herein; compounds classifiable and well-known in the art as detergent builders include the nitrilotriacetates (NTA), polycarboxylates, citrates, water-soluble phosphates such as tri-polyphosphate and sodium ortho- and pyrophosphates, silicates, ethylene diamine tetraacetate (EDTA), amino-polyphosphonates (DEQUEST), phosphates and mixtures thereof.
  • NTA nitrilotriacetates
  • EDTA ethylene diamine tetraacetate
  • DEQUEST amino-polyphosphonates
  • Highly desirable ingredients for use herein are represented by conventional detergent hydrotropes.
  • suitable hydrotropes are urea, monoethanolamine, diethanolamine, triethanolamine and the sodium potassium, ammonium and alkanol ammonium salts of xylene-, toluene-, ethylbenzene- and isopropyl-benzene sulfonates.
  • the hard-surface cleaning compositions of the invention may also contain an abrasive material.
  • the abrasives suitable herein are selected from water-insoluble, non-gritty materials well-known in the literature for their relatively mild abrasive properties. It is highly preferred that the abrasives used herein not be undesirably "scratchy". Abrasive materials having a Mohs hardness in the range of about 7, or below, are typically used; abrasives having a Mohs hardness of 3, or below, can be used to avoid scratches on aluminum or stainless steel finishes.
  • Suitable abrasives herein include inorganic materials, especially such materials as calcium carbonate and diatomaceous earth, as well as materials such as Fuller's earth, magnesium carbonate, China clay, actapulgite, calcium hydroxyapatite, calcium orthophosphate, dolomite and the like.
  • the aforesaid inorganic materials can be qualified as "strong abrasives”.
  • Organic abrasives such as urea-formaldehyde, methyl methacrylate melamine-formaldehyde resins, polyethylene spheres and polyvinylchloride can be advantageously used in order to avoid scratching on certain surfaces, especially plastic surfaces.
  • abrasives typically have a particle size range of 10-1000 microns and are used at concentrations of 5% to 30% in the compositions. Thickeners are frequently added to suspend the abrasives.
  • Thickeners will preferably be included in the compositions of the inventions, mainly in order to suspend the abrasive; high levels of thickener are detrimental to the performance because they are difficult to rinse from the cleaned surfaces. Accordingly, the level will be kept under 2%, preferably from 0.2% to 1.5%.
  • Common thickeners such as the polyacrylates, xanthan gums, carboxymethyl celluloses, swellable smectite clays, and the like, can be used herein.
  • Soaps can be included in the compositions herein, the soaps prepared from coconut oil fatty acids being preferred.
  • Optional components are also represented by ingredients typically used in commercial products to provide aesthetic or additional product performance benefits.
  • Typical ingredients include perfumes, dyes, optical brighteners, soil suspending agents, detersive enzymes, gel-control agents, thickeners, freeze-thaw stabilizers, bactericides, preservatives, and the like.
  • the hard-surface cleaning compositions herein will advantageously be prepared in the form of an aqueous liquid compositions, including concentrates, containing as essential ingredients a surface-active agent, and the solvent-chelating agent binary mixture according to the invention.
  • Liquid formulations at normal dilution usually contain 2-6% surfactant and 8-12% solvent/chelating agent binary mixture.
  • Concentrated liquid formulations usually contain 6-10% surfactant and 16-24% solvent/chelating agent binary mixture.
  • the compositions herein will be in the form of a creamy scouring cleanser, containing an abrasive material, surface-active agent, and the solvent/chelating agent binary mixture of the invention.
  • the pH of such compositions will be neutral or in the alkaline range, generally in the range of pH 5-11.
  • a major function of a chelant in a hard surface cleaner is to solubilized soap scum (Ca +2 and Mg +2 salts of soap) by chelating the calcium and magnesium ions.
  • solubilized soap scum Ca +2 and Mg +2 salts of soap
  • the ability of chelants in accordance with the invention to solubilize soap scum in the presence of solvent-based hard surface cleaner was tested by dipping a glass microscope slide coated with soap scum into the cleaner and visually observing whether the soil had been removed.
  • a soiled slide was dipped into a beaker containing hard surface cleaner for 5 seconds with gentle agitation. The slide was then removed, dipped into distilled water for 5 seconds, and air dried. Visual observation was used to determine soil removal. Three replicates were preformed with each chelant.
  • the biodegradability of chelating agents described hereinabove was determined using the Sturm CO 2 Evolution Test ( J. Amer. Oil Chem. Soc. , 50, 159(1973)).
  • the Sturm Test measures the ultimate biodegradation of soluble organic materials.
  • the term "ultimate biodegradation" is defined herein to indicate the complete mineralization of material to CO 2 generated from the degradation of the chelating agent was trapped using a series of three barium hydroxide traps. The barium hydroxide reacted with the CO 2 to form barium carbonate and the amount of CO 2 evolved was determined by titrating the unreacted barium hydroxide with hydrochloric acid.
  • the test was conducted in a two liter flask with the final volume of the test solution being one liter (Final volume equals the volume of the medium plus the volume of the test sample solution plus the volume of the inoculum).
  • a stock solution of the test compound was prepared at a concentration of 1000 mg/l and the pH adjusted to 7.0 if the initial pH was outside a 4.0-10.0 pH range.
  • the inoculum was prepared by taking unacclimated sludge and homogenizing it for two minutes, at room temperature, using a Waring Blender at medium speed. The homogenized sample was transferred to a beaker and left to settle for 15-30 minutes. The supernatant was carefully decanted and 10 ml of this solution was added to each test flask. Immediately prior to the beginning of the test, the viability of the test organisms was determined. There must be a least 1 x 10 6 microorganisms per milliliter before this inoculum can be used. The inoculum was used the day it was prepared.
  • test flask was charged with 980 ml of test medium and then purged for twenty-four hours using CO 2 free air. Following the removal of residual CO 2 , the test flasks were connected to a series of three barium hydroxide traps each containing 100 ml of 0.024 N barium hydroxide. The milliliters of the test sample stock suction was added to each flask followed by the addition of 10 ml of the inoculum prepared above.
  • the head space of each flask was aerated with CO 2 free air at a flow rate of 50-100 cc/min for the duration of the test. Every 2-3 days the first barium hydroxide trap (nearest to the test flask) was titrated using 0.05N standardized HCL and the amount of CO 2 evolved was determined. The remaining two barium hydroxide traps were moved forward to positions one and two and a new barium hydroxide trap was placed in position three. The length of the test was typically 26-30 days.
  • Each test also included a sample of glucose which was used as a control to guarantee the activity of the microorganisms.
  • Each chelating agent tested was degraded as described hereinabove with the exception that AspDA was degraded using acclimated microorganisms.
  • the microorganisms were acclimated in a bench scale semicontinuous activate sludge system. The initial activated sludge was adjusted to a suspended solids level of 2500-3000 mg/l. The activated sludge was exposed to increasing levels of test material over a five day period (4, 8, 12, 16, and 20 mg/l) and the maintained at 20 mg/l for an additional five days. The acclimated microorganisms were then treated as described above prior to the start of the Sturm test.

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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)
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  • Emergency Medicine (AREA)
  • Detergent Compositions (AREA)

Claims (9)

  1. Zusammensetzung zur Reinigung harter Oberflächen enthaltend ein organisches Lösungsmittel mit einem Siedepunkt von 90°C oder mehr und einen Chelatbildner ausgewählt unter einer Verbindung mit der Formel:
    Figure 00220001
    in der
    m
    NR' oder Schwefel ist;
    x
    SO3H oder COOH ist;
    Y
    Wasserstoff, SO3H oder COOH ist;
    R und R'
    unabhängig voneinander Wasserstoff, -CH(Z)CH2(Z'), -CH(Z)CH(Z') (Z") oder -CH2COOH sind; und
    Z, Z' und Z"
    unabhängig voneinander Wasserstoff, OH, SO3H oder COOH sind; oder ein Natrium-, Kalium-, Ammonium- oder substituiertes Ammoniumsalz davon, in einer zur Reinigung harter Oberflächen ausreichenden Menge.
  2. Zusammensetzung nach Anspruch 1, in der X und Y beide COOH oder ein Natrium-, Kalium- oder Ammonium- oder ein substituiertes Ammoniumsalz davon sind; und Z, Z' und Z" unabhängig voneinander Wasserstoff oder COOH oder ein Natrium-, Kalium-, Ammonium- oder substituiertes Ammoniumsalz davon sind.
  3. Zusammensetzung nach Anspruch 1, in der das organische Lösungsmittel in einer Menge von 1 bis 20 % der Gesamtzusammensetzung vorhanden ist und der Chelatbildner in einer Menge von 1 bis 30 % der Gesamtzusammensetzung vorhanden ist.
  4. Zusammensetzung nach Anspruch 3, in der das Gewichtsverhältnis von organischem Lösungsmittel zu Chelatbildner von 2:3 bis 2:1 beträgt.
  5. Zusammensetzung nach Anspruch 3, in der das Gewichtsverhältnis von organischem Lösungsmittel zu Chelatbildner von 1:1 bis 2:1 beträgt.
  6. Zusammensetzung nach Anspruch 1, in der das organische Lösungsmittel aus der Gruppe von Benzylalkohol, Glycolethern, und Diolen mit 6 bis 16 Kohlenstoffatomen in ihrer Molekülstruktur ausgewählt ist.
  7. Zusammensetzung nach Anspruch 5, in der das organische Lösungsmittel aus der Gruppe von Butoxypropanol, Butoxypropoxypropanol, 2-(2-Butoxyethoxy)ethanol, Benzylalkohol und 2,2,4,-Trimethyl-1,3-pentandiol ausgewählt ist.
  8. Zusammensetzung nach Anspruch 1, in der der Chelatbildner unter Asparaginsäure-N,N-diessigsäure; Asparagin-N-monoessigsäure, Iminodibernsteinsäure, Carboxymethylmercaptobernsteinsäure, β-Alanin-N,N-diessigsäure oder Cysteinsäure-N,N-diessigsäure ausgewählt ist.
  9. Zusammensetzung nach Anspruch 1, welche zusätzlich ein Scheuermittel enthält.
EP92250105A 1991-05-15 1992-05-04 Reinigungsmittel für harte Oberflächen, biologisch abbaubare Chelatbildner enthaltend Revoked EP0513948B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US70141791A 1991-05-15 1991-05-15
US701417 1991-05-15

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EP0513948A2 EP0513948A2 (de) 1992-11-19
EP0513948A3 EP0513948A3 (en) 1993-04-21
EP0513948B1 true EP0513948B1 (de) 1998-08-12

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EP (1) EP0513948B1 (de)
AT (1) ATE169668T1 (de)
DE (1) DE69226557T2 (de)
DK (1) DK0513948T3 (de)
ES (1) ES2119796T3 (de)

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US5804548A (en) 1995-03-30 1998-09-08 The Procter & Gamble Company Dry cleaning process and kit
US5912408A (en) 1995-06-20 1999-06-15 The Procter & Gamble Company Dry cleaning with enzymes

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EP0698660B1 (de) * 1994-08-22 2001-09-26 Kao Corporation Reinigungsmittel für harte Oberflächen
US5531934A (en) * 1994-09-12 1996-07-02 Rohm & Haas Company Method of inhibiting corrosion in aqueous systems using poly(amino acids)
DE4445820A1 (de) * 1994-12-21 1996-06-27 Hoechst Ag Verfahren zum Entwickeln bestrahlter, strahlungsempfindlicher Aufzeichnungsmaterialien
US5632780A (en) * 1995-03-30 1997-05-27 The Procter & Gamble Company Dry cleaning and spot removal proces
US5630847A (en) 1995-03-30 1997-05-20 The Procter & Gamble Company Perfumable dry cleaning and spot removal process
US5547476A (en) * 1995-03-30 1996-08-20 The Procter & Gamble Company Dry cleaning process
US5591236A (en) 1995-03-30 1997-01-07 The Procter & Gamble Company Polyacrylate emulsified water/solvent fabric cleaning compositions and methods of using same
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US5630848A (en) 1995-05-25 1997-05-20 The Procter & Gamble Company Dry cleaning process with hydroentangled carrier substrate
US5687591A (en) 1995-06-20 1997-11-18 The Procter & Gamble Company Spherical or polyhedral dry cleaning articles
DE19528059A1 (de) * 1995-07-31 1997-02-06 Bayer Ag Wasch- und Reinigungsmittel mit Iminodisuccinaten
AU1097797A (en) * 1995-12-21 1997-07-17 Unilever Plc Cysteic monosuccinate sequestrants and detergent compositions containing them
EP0783034B1 (de) 1995-12-22 2010-08-18 Mitsubishi Rayon Co., Ltd. Chelatbildendes Mittel und dieses enthaltendes Waschmittel
JP3581469B2 (ja) * 1995-12-25 2004-10-27 大三工業株式会社 洗浄剤組成物
DE19620644A1 (de) 1996-05-22 1997-11-27 Ciba Geigy Ag Verwendung von stickstoffhaltigen Komplexbildnern zur Desodorierung und antimikrobiellen Behandlung der Haut und textilen Fasermaterialien
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US5912408A (en) 1995-06-20 1999-06-15 The Procter & Gamble Company Dry cleaning with enzymes

Also Published As

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DE69226557D1 (de) 1998-09-17
EP0513948A2 (de) 1992-11-19
ES2119796T3 (es) 1998-10-16
DK0513948T3 (da) 1998-10-26
EP0513948A3 (en) 1993-04-21
DE69226557T2 (de) 1999-05-06
ATE169668T1 (de) 1998-08-15

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