WO1997023450A1 - Sequestrants du type monosuccinate cysteique et compositions detergentes les contenant - Google Patents

Sequestrants du type monosuccinate cysteique et compositions detergentes les contenant Download PDF

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Publication number
WO1997023450A1
WO1997023450A1 PCT/EP1996/005375 EP9605375W WO9723450A1 WO 1997023450 A1 WO1997023450 A1 WO 1997023450A1 EP 9605375 W EP9605375 W EP 9605375W WO 9723450 A1 WO9723450 A1 WO 9723450A1
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WO
WIPO (PCT)
Prior art keywords
group
mixtures
ammonium
composition
weight
Prior art date
Application number
PCT/EP1996/005375
Other languages
English (en)
Inventor
Eddie Nelson Gutierrez
Shang-Ren Wu
Original Assignee
Unilever Plc
Unilever N.V.
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 US08/576,669 external-priority patent/US5663427A/en
Application filed by Unilever Plc, Unilever N.V. filed Critical Unilever Plc
Priority to AU10977/97A priority Critical patent/AU1097797A/en
Publication of WO1997023450A1 publication Critical patent/WO1997023450A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
    • C07C309/01—Sulfonic acids
    • C07C309/02—Sulfonic acids having sulfo groups bound to acyclic carbon atoms
    • C07C309/03—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
    • C07C309/17—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton containing carboxyl groups bound to the carbon skeleton
    • C07C309/18—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton containing carboxyl groups bound to the carbon skeleton containing amino groups bound to the same carbon skeleton
    • 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
    • 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 improved laundry detergent composition. Specially, it relates to a new compound, cysteic monosuccinic acid (CMS), which can be used as a builder. CMS can be used as a replacement for all or part of the builders currently used in many existing laundry
  • detergent compositions which include reduced levels of phosphorous-containing components and are at least partially biodegradable, but which still exhibit excellent cleaning and stain removal performance.
  • compositions is desirable for enhanced stain removal, there is generally believed to be an efficacy/biodegradability trade-off with these compounds.
  • detergency builders containing an aluminosilicate or organic detergency builder and from about 0.5% to about 10% by weight of the chelant, HEDTA.
  • U.S. Patent No. 4,397,776 discloses liquid laundry detergent compositions having chelating agents which include
  • aminopolycarboxylates such as NTA, EDTA, DTPA and HEDTA.
  • U.S. Patent No. 3,920,564 discloses softener/detergent formulations containing surfactants, quaternary ammonium or diamine fabric softeners, and a builder salt selected from aminopolycarboxylates and/or sodium citrate. Examples of suitable aminopolycarboxylates include NTA, EDTA and HEDTA.
  • U.S. Patent No. 3,151,084 discloses detergent compositions in which solubility is said to be improved by the addition of 0.25% to 4% of a mixture of EDTA and a solubilizing agent selected from salts of N,N-di(2-hydroxyethyl) glycin , lminodiacetic acid, NTA and HEDTA. None of the patents disclose detergent compositions which contain CMS.
  • U.S. Patent No. 5,183,590 discloses N-(hydroxysuccinyl)cysteic acid as a corrosion inhibitor for aqueous systems.
  • the present invention provides a compound of the formula:
  • M is selected from the group consisting of Na, K, Li, ammonium, substituted ammonium and mixtures thereof.
  • M is sodium
  • the present invention provides a process for preparing a compound of the formula:
  • M is selected from the group consisting of Na, K, Li, ammonium, substituted ammonium and mixtures thereof
  • M is selected from the group consisting of Na, K, Li, ammonium and substituted ammonium at a temperature of about 25°C to about 100°C for about 1 to 5 hours at a pH of about 8.0 to 8.6 to form said compound.
  • M is selected from the group consisting of Na, K, Li, ammonium, substituted ammonium and mixtures thereof
  • M is selected from the group consisting of Na, K, Li, ammonium and substituted ammonium with: b. cysteic acid salts of the formula
  • M is selected from the group consisting of Na, K, Li, ammonium and substituted ammonium at a temperature of about
  • the present invention provides a laundry detergent composition
  • a laundry detergent composition comprising: (a) from about 1% to about 75% by weight of a detergent surfactant selected from the group consisting of anionic surfactants, nonionic surfactants, zwitteriomc surfactants, ampholytic surfactants, cationic surfactants, and mixtures thereof; and
  • the amount of detergent surfactant included in the detergent compositions of the present invention can vary from about 1% to about 75% by weight of the composition depending upon the particular surfactant(s) used, the type of composition to be formulated (e.g. granular, liquid, concentrate) and the effects desired.
  • the detergent surfactant(s) comprises from about 10% to about 60% by weight of the composition.
  • the detergent surfactant can be nonionic, anionic, ampholytic, zwitteriomc or cationic. Mixtures of these surfactants can also be used.
  • CMS monosuccinic acid
  • the detergent compositions of the invention contain, as an essential component, from about 5% to about 80%, preferably from about 20% to about 60% by weight, of cysteic monosuccinic acid, or the alkali metal, alkaline earth metal, ammonium or substituted ammonium salts thereof, or mixtures thereof.
  • Preferred CMS compounds for granular detergent compositions are the free acid form and the sodium salt thereof. Examples of such preferred sodium salts of CMS include NaCMS , Na 2 CMS and Na 4 CMS.
  • Preferred CMS compounds for liquid detergent compositions are the free acid and the ammonium or potassium salts thereof.
  • the structure of the acid form of CMS is as follows:
  • CMS cysteic monosuccinate
  • the former method generates CMS and disodium maleate and fumarate is byproducts after the saponification of the methyl esters, while the latter generates sodium bromide as an impurity. Both reaction schemes are shown as follows:
  • cystine d, l or ld can be reacted with Br succinic acid salts to generate a disulphide structure which can be oxidized to CMS as follows:
  • WR Grace has patented CMHS (cysteic monohydroxysuccinate) prepared from disodium cysteate and disodium epoxysuccinate. Both molecules are similar except that the WR Grace compound contains a hydroxy group adjacent to the sulfonate group.
  • CMHS cysteic monohydroxysuccinate
  • Detergent compositions of the present invention may also contain inorganic and/or organic detergent builders to assist in mineral hardness control. These builders comprise from about 5% to about 80% by weight of the compositions. Built liquid formulations preferably comprise from about 10% to about 30% by weight of detergent builder, while built granular formulations preferably
  • Suitable detergent builders include crystalline
  • aluminosilicate ion exchange materials having the formula:
  • Amorphous hydrated aluminosilicate materials useful herein have the empirical formula:
  • M z (ZAlO 2 •YSiO 2 ) wherein M is sodium, potassium, ammonium or substituted ammonium, Z is from about 0.5 to about 2, and Y is 1; this material has a magnesium ion exchange capacity of at least about 50 milligram equivalents of CaCO 3 hardness per gram of anhydrous aluminosilicate.
  • Aluminosilicate ion exchange materials useful herein are commercially available. These aluminosilicates can be crystalline or amorphous in structure and can be naturally-occurring aluminosilicates or synthetically derived. A method for producing aluminosilicate ion exchange materials is disclosed in U.S. Patent No. 3,985,669, Krummel et al, issued October 12, 1976, incorporated herein by reference.
  • Preferred synthetic crystalline aluminosilicate ion exchange materials useful herein are available under the designations Zeolite A, Zeolite P (B) and Zeolite X.
  • the crystalline aluminosilicate ion exchange material has the formula:
  • detergency builders useful in the present invention include the alkali metal silicates, alkali metal carbonates, phosphates, polyphosphates, phosphonates, polyphosphonic acids, C 10 -C 18 alkyl monocarboxylic acids, polycarboxylic acids, alkali metal ammonium or substituted ammonium salts thereof and mixtures thereof.
  • alkali metal salts of the above, especially sodium are preferred.
  • Useful water-soluble, nonphosphorous organic builders include the various alkali metal, ammonium and substituted ammonium polyacetates, carboxylates, polycarboxylates and
  • polycarboxylate builders are the sodium, potassium, lithium, ammonium and substituted ammonium salts of ethylenediamine tetraacetic acid, nitrilotriacetic acid, oxydisuccinic acids, mellitic acid, carboxymethyloxysuccinic acid, benzene
  • the organic detergent builder is a polycarboxylic acids and citric acid.
  • component which may be used herein does not include CMS or its salts.
  • Optional ingredients which can be included in detergent composition of the present invention, in their conventional art-established levels for use include solvents,
  • hydrotropes solubilising agents, processing aids, soil-suspending agents, corrosion inhibitors, dyes, fillers, optical brighteners, germicides, pH-adjusting agents
  • compositions of the invention are particularly useful in liquid compositions of the invention.
  • These clay soil removal/anti redeposition agents are usually included at from about 0.1% to about 10% by weight of the composition.
  • One group of preferred clay soil removal/anti-redeposition agents are the ethoxylated amines disclosed in U.S. Patent No. 4,597,898.
  • Soil release agents such as those disclosed in the art to reduce oily staining of polyester fabrics, may also be used in the compositions of the present invention.
  • U.S Patent No. 3,962,152 discloses copolymers of ethylene terephthalate and polyethylene oxide terephthalate as soil release agents. Cellulose ethers and various other soil release agents are also useful.
  • Detergent Formulations Granular detergent compositions embodying the present
  • inventions can be formed by conventional techniques, i.e., by slurrying the individual components in water and then
  • formulations preferably comprise from about 5% to about 40% by weight of detergent surfactant selected from the group consisting of anionic surfactants, nonionic surfactants, and mixtures thereof.
  • Liquid compositions of the present invention can contain water and other solvents.
  • Low molecular weight primary or secondary alcohols exemplified by methanol, ethanol, propanol and isopropanol are suitable.
  • Monohydric alcohols are preferred for solubilising the surfactant, but polyols containing from about 2 to about 6 carbon atoms and from about 2 to about 6 hydroxy groups can be used and can provide improved enzyme stability (if enzymes are included in the composition).
  • polyols include propylene glycol, glycerine and 1,2-propanediol. Ethanol is a particularly preferred alcohol.
  • the liquid compositions preferably comprise from about 10% to about 60% by weight of detergent surfactant, about 10% to about 30% of CMS or salts thereof as a builder.
  • CMS include the alkali metal silicates, alkali metal carbonates, polyphosphonic acids, C 10 -C 18 alkyl
  • liquid compositions containing from about 10% to about 28% by weight of detergency builders selected from the group consisting of C 10 -C 18 monocarboxylic acids, polycarboxylic acids and mixtures thereof.
  • preferred liquid compositions contain from about 10% to about 18% by weight of a C 10 -C 18 monocarboxylic (fatty) acid and from about 0.2% to about 10% by weight of a polycarboxylic acid, preferably citric acid, and provide a solution pH of from about 6 to about 10 at 1.0% by weight concentration in water.
  • Preferred liquid compositions are substantially free of inorganic phosphates or phosphonates. As used in this context “substantially free” means that the liquid
  • compositions contain less than about 0.5% by weight of an inorganic phosphate or phosphate containing compound.
  • the detergent compositions of the invention are particularly suitable for laundry use, but are also suitable for the cleaning of hard surfaces and for dishwashing.
  • typical laundry wash water solutions comprise from about 0.1% to about 2% by weight of the detergent compositions of the invention.
  • Fabrics to be laundered are agitated in these solutions to effect cleaning and stain removal.
  • EXAMPLE 1 Two g (0.02 mol) maleic anhydride are dissolved in 10 ml methanol, and the solution neutralised to pH 8 with sodium hydroxide. The solution is evaporated to dryness and the solid is dissolved in 15 CM 3 water, followed by the addition of 3.8 g (0.02 mol) cysteic acid monohydrate disodium salt. The mixture is stirred at pH8 for 10-12 hr. The product is contaminated with fumarate, maleate and cysteate and
  • Cysteic acid, 9.3 g (0.05 mol) and bromosuccinic acid (0.01 mol) are dissolved in 100 ml water and 12 g (0.3 mol) sodium hydroxide in 50 ml water added to pH 8.5.
  • the solution is heated to 50°C and 3 g of NaOH added to maintain the pH below 9.2.
  • the solution is evaporated down to 75 ml, followed by the addition of methanol to precipitate a viscous residue.
  • the residue is triturated 5X with methanol/water to afford 12.4 g solid after drying.
  • purified CMS 1 g of solid is acidified and extracted with acetone, several times the residue is extracted into methanol and neutralised to pH 8 in water.
  • This composition employing CMS as a builder is expected to have good cleaning properties.

Abstract

l'invention concerne l'acide monosuccinique-cystéique, ses sels alcaling et alcalins-terreux, ses sels d'ammonium et ses sels d'ammonium substitués utiles dans les compositions détergentes comme adjuvants de détergence. On produit ces composés en faisant réagir un monoalkyle maléate avec un sel de l'acide cystéique ou en faisant réagir un bromosuccinate avec un sel de l'acide cystéique. Les composés sont facilement biodégradables et ont de bonnes propriétés d'adjuvant pour des compositions détergentes. Une composition détergente contenant de 5 % environ en poids à 80 % environ en poids du composé a une bonne détergence, en particulier, un fort pouvoir détachant.
PCT/EP1996/005375 1995-12-21 1996-11-28 Sequestrants du type monosuccinate cysteique et compositions detergentes les contenant WO1997023450A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU10977/97A AU1097797A (en) 1995-12-21 1996-11-28 Cysteic monosuccinate sequestrants and detergent compositions containing them

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US58003395A 1995-12-21 1995-12-21
US08/580,033 1995-12-21
US08/576,669 US5663427A (en) 1995-12-21 1995-12-21 Cysteic monosuccinic acid and its salts
US08/576,669 1995-12-21

Publications (1)

Publication Number Publication Date
WO1997023450A1 true WO1997023450A1 (fr) 1997-07-03

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Application Number Title Priority Date Filing Date
PCT/EP1996/005375 WO1997023450A1 (fr) 1995-12-21 1996-11-28 Sequestrants du type monosuccinate cysteique et compositions detergentes les contenant

Country Status (2)

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AU (1) AU1097797A (fr)
WO (1) WO1997023450A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2261313A2 (fr) 2005-11-07 2010-12-15 Reckitt Benckiser N.V. Composition

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3151084A (en) * 1961-03-13 1964-09-29 Swift & Co Solubilizer for synthetic detergent
EP0509382A2 (fr) * 1991-04-17 1992-10-21 Hampshire Chemical Corporation Stabilisateurs de blanchiment biodégradables pour détergents
EP0513948A2 (fr) * 1991-05-15 1992-11-19 Hampshire Chemical Corporation Compositions de nettoyage pour surfaces dures contenant des agents de chelation biodégradable
US5472642A (en) * 1994-12-22 1995-12-05 Lever Brothers Company, Division Of Conopco Inc. Diaminoalkyl di(sulfosuccinates) and their use as builders

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3151084A (en) * 1961-03-13 1964-09-29 Swift & Co Solubilizer for synthetic detergent
EP0509382A2 (fr) * 1991-04-17 1992-10-21 Hampshire Chemical Corporation Stabilisateurs de blanchiment biodégradables pour détergents
EP0513948A2 (fr) * 1991-05-15 1992-11-19 Hampshire Chemical Corporation Compositions de nettoyage pour surfaces dures contenant des agents de chelation biodégradable
US5472642A (en) * 1994-12-22 1995-12-05 Lever Brothers Company, Division Of Conopco Inc. Diaminoalkyl di(sulfosuccinates) and their use as builders

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2261313A2 (fr) 2005-11-07 2010-12-15 Reckitt Benckiser N.V. Composition
US9441189B2 (en) 2005-11-07 2016-09-13 Reckitt Benckiser Finish B.V. Composition
US9920283B2 (en) 2005-11-07 2018-03-20 Reckitt Benckiser Finish B.V. Composition
EP3327109A1 (fr) 2005-11-07 2018-05-30 Reckitt Benckiser Finish B.V. Composition
US10240109B2 (en) 2005-11-07 2019-03-26 Reckitt Benckiser Finish B.V. Composition

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Publication number Publication date
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