EP1583814B1 - Waschmittel - Google Patents

Waschmittel Download PDF

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Publication number
EP1583814B1
EP1583814B1 EP03789338A EP03789338A EP1583814B1 EP 1583814 B1 EP1583814 B1 EP 1583814B1 EP 03789338 A EP03789338 A EP 03789338A EP 03789338 A EP03789338 A EP 03789338A EP 1583814 B1 EP1583814 B1 EP 1583814B1
Authority
EP
European Patent Office
Prior art keywords
laundry detergent
detergent composition
sodium
surfactants
graft polymer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP03789338A
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English (en)
French (fr)
Other versions
EP1583814A1 (de
Inventor
Christopher David Unilever R & D Gibbs
Alyn James Unilever R & D Parry
Susanne Henning Unilever R & D Rogers
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Unilever PLC
Unilever NV
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Unilever PLC
Unilever NV
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Publication of EP1583814A1 publication Critical patent/EP1583814A1/de
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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
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0036—Soil deposition preventing compositions; Antiredeposition agents
    • 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
    • C11D3/37—Polymers
    • C11D3/3788—Graft polymers

Definitions

  • the present invention relates to laundry detergent compositions containing certain graft polymers that can reduce redeposition of soil onto fabrics during the wash process.
  • Laundry detergent compositions conventionally contain sodium carboxymethyl cellulose (SCMC) as an antiredeposition agent.
  • SCMC sodium carboxymethyl cellulose
  • US 4 235 735 discloses cellulose acetates with a defined degree of substitution as antiredeposition agents in laundry detergent compositions.
  • cellulosic materials have also been used in laundry detergent compositions for a variety of benefits, for example, soil release, and fabric care benefits.
  • WO 00/18861A and WO 00/18862A disclose cellulosic compounds having a benefit agent attached, so that the benefit agent will be deposited on the fibres of the washed textiles during the laundry process.
  • the present invention provides the use of a graft polymer having a locust bean gum backbone and grafts of an aromatic sulphonic acid to improve the antiredeposition properties of a laundry detergent composition.
  • the graft polymer which is used in accordance with the invention to improve the antiredeposition properties of a laundry detergent composition is a polymer having a backbone of locust bean gum.
  • Locust bean gum is a naturally occurring galactomannan polysaccharide having a beta-1,4-linked backbone.
  • the total number of sugar units is preferably from 50 to 7000, and the preferred molecular weight is from 10 000 to 1 000 000.
  • At least one sugar unit of the polysaccharide has been substituted with groups derived from an aromatic sulphonic acid, preferably styrene 4-sulphonic acid.
  • the preferred graft polymer used in accordance with the invention is locust bean gum - graft - poly(4-styrenesulphonic acid).
  • the graft polymer may be prepared by any suitable process.
  • the polymer is prepared by the "living polymerisation” technique of atom transfer radical polymerisation (ATRP), as described and claimed in our International Patent Application WO-A-03010267 .
  • ATRP atom transfer radical polymerisation
  • the laundry detergent composition is a laundry detergent composition
  • the graft polymer is suitably incorporated in laundry detergent compositions in an amount of from 0.1 to 10 wt%, preferably from 0.5 to 5 wt%.
  • Laundry detergent compositions utilising the graft polymer may suitably comprise:
  • the organic detergent surfactant is the organic detergent surfactant
  • Detergent-active compounds may be chosen from soap and non-soap anionic, cationic, nonionic, amphoteric and zwitterionic detergent-active compounds, and mixtures thereof.
  • suitable detergent-active compounds are available and are fully described in the literature, for example, in "Surface-Active Agents and Detergents", Volumes I and II, by Schwartz, Perry and Berch.
  • the preferred detergent-active compounds that can be used are soaps and synthetic non-soap anionic and nonionic compounds:
  • the total amount of surfactant present is suitably within the range of from 5 to 60 wt%, preferably from 5 to 40 wt%.
  • Anionic surfactants are well-known to those skilled in the art. Examples include-alkylbenzene sulphonates, particularly linear alkylbenzene sulphonates having an alkyl chain length of C 8 -C 15 ; primary and secondary alkylsulphates, particularly C 8 -C 20 primary alkyl sulphates; alkyl ether sulphates; olefin sulphonates; alkyl xylene sulphonates; dialkyl sulphosuccinates; and fatty acid ester sulphonates.
  • Sodium salts are generally preferred.
  • Nonionic surfactants that may be used include the primary and secondary alcohol ethoxylates, especially the C B -C 20 aliphatic alcohols ethoxylated with an average of from 1 to 20 moles of ethylene oxide per mole of alcohol, and more especially the C 10 -C 15 primary and secondary aliphatic alcohols ethoxylated with an average of from 1 to 10 moles of ethylene oxide per mole of alcohol.
  • Non-ethoxylated nonionic surfactants include alkanolamides, alkylpolyglycosides, glycerol monoethers, and polyhydroxyamides (glucamide).
  • Cationic surfactants that may be used include quaternary ammonium salts of the general formula R 1 R 2 R 3 R 4 N + X - wherein the R groups are long or short hydrocarbyl chains, typically alkyl, hydroxyalkyl or ethoxylated alkyl groups, and X is a solubilising anion (for example, compounds in which R 1 is a C 8 -C 22 alkyl group, preferably a C 8 -C 10 or C 12 -C 14 alkyl group, R 2 is a methyl group, and R 3 and R 4 , which may be the same or different, are methyl or hydroxyethyl groups); and cationic esters (for example, choline esters).
  • R 1 is a C 8 -C 22 alkyl group, preferably a C 8 -C 10 or C 12 -C 14 alkyl group
  • R 2 is a methyl group
  • R 3 and R 4 which may be the same or different, are methyl or
  • Amphoteric and zwitterionic surfactants that may be used include alkyl amine oxides, betaines and sulphobetaines.
  • the detergent surfactant (a) most preferably comprises an anionic sulphonate or sulphonate surfactant optionally in admixture with one or more cosurfactants selected from ethoxylated nonionic surfactants, non-ethoxylated nonionic surfactants, ethoxylated sulphate anionic surfactants, cationic surfactants, amine oxides, alkanolamides and combinations thereof.
  • Surfactants are preferably present in a total amount of from 5 to 60 wt%, more preferably from 10 to 40 wt%.
  • the invention encompasses both built and unbuilt laundry detergent compositions.
  • Preferred inorganic builders are alkali metal aluminosilicates, more especially crystalline alkali metal aluminosilicates (zeolites), preferably in sodium salt form.
  • Zeolite builders may suitably be present in a total amount of from 5 to 60 wt%, preferably from 10 to 50 wt%.
  • the zeolites may be supplemented by other inorganic builders, for example, amorphous aluminosilicates, or layered silicates such as SKS-6 ex Clariant.
  • the zeolites may be supplemented by organic builders, for example, polycarboxylate polymers such as polyacrylates and acrylic/maleic copolymers; monomeric polycarboxylates such as citrates, gluconates, oxydisuccinates, glycerol mono-, di- and trisuccinates, carboxymethyloxysuccinates, carboxymethyloxymalonates, dipicolinates, hydroxyethyliminodiacetates, alkyl- and alkenylmalonates and succinates; and sulphonated fatty acid salts.
  • polycarboxylate polymers such as polyacrylates and acrylic/maleic copolymers
  • monomeric polycarboxylates such as citrates, gluconates, oxydisuccinates, glycerol mono-, di- and trisuccinates, carboxymethyloxysuccinates, carboxymethyloxymalonates, dipicolinates, hydroxyethyliminodiacetates, alkyl- and
  • compositions of the invention may contain phosphate builders, for example, sodium tripolyphosphate.
  • organic builders are citrates, suitably used in amounts of from 1 to 30 wt%, preferably from 2 to 15 wt%; and acrylic polymers, more especially acrylic/maleic copolymers, suitably used in amounts of from 0.5 to 15 wt%, preferably from 1 to 10 wt%.
  • Builders both inorganic and organic, are preferably present in alkali metal salt, especially sodium salt, form.
  • Builders are suitably present in total amounts of from 10 to 80 wt%, more preferably from 20 to 60 wt%. Builders may be inorganic or organic.
  • a built composition in accordance with the invention may most preferably comprise from 10 to 80 wt% of a detergency builder (b) selected from zeolites, phosphates, and citrates.
  • a detergency builder selected from zeolites, phosphates, and citrates.
  • the laundry detergent composition will generally comprises other detergent ingredients well known in the art.
  • These may suitably be selected from bleach ingredients, enzymes, sodium carbonate, sodium silicate, sodium sulphate, foam controllers, foam boosters, perfumes, fabric conditioners, soil release polymers, dye transfer inhibitors, photobleaches, fluorescers and coloured speckles.
  • Detergent compositions in accordance with the invention may also suitably contain a bleach system.
  • a bleach system Preferably this will include a peroxy bleach compound, for example, an inorganic persalt or an organic peroxyacid, capable of yielding hydrogen peroxide in aqueous solution.
  • Preferred inorganic persalts are sodium perborate monohydrate and tetrahydrate, and sodium percarbonate, the latter being especially preferred.
  • the sodium percarbonate may have a protective coating against destabilisation by moisture.
  • the peroxy bleach compound is suitably present in an amount of from 5 to 35 wt%, preferably from 10 to 25 wt%.
  • the peroxy bleach compound may be used in conjunction with a bleach activator (bleach precursor) to improve bleaching action at low wash temperatures.
  • the bleach precursor is suitably present in an amount of from 1 to 8 wt%, preferably from 2 to 5 wt%.
  • Preferred bleach precursors are peroxycarboxylic acid precursors, more especially peracetic acid precursors and peroxybenzoic acid precursors; and peroxycarbonic acid precursors.
  • An especially preferred bleach precursor is N,N,N',N'-tetracetyl ethylenediamine (TAED).
  • a bleach stabiliser may also be present.
  • Suitable bleach stabilisers include ethylenediamine tetraacetate (EDTA), diethylenetriamine pentaacetate (DTPA), ethylenediamine disuccinate (EDDS), and the polyphosphonates such as the Dequests (Trade Mark), ethylenediamine tetramethylene phosphonate (EDTMP) and diethylenetriamine pentamethylene phosphate (DETPMP).
  • compositions of the invention in particulate form may contain alkali metal, preferably sodium, carbonate, in order to increase detergency and ease processing.
  • alkali metal preferably sodium, carbonate
  • Sodium carbonate may suitably be present in amounts ranging from 1 to 60 wt%, preferably from 2 to 40 wt%.
  • sodium silicate may also be present.
  • the amount of sodium silicate may suitably range from 0.1 to 5 wt%.
  • the laundry detergent composition may be of any suitable form, for example, powder, tablet, liquid, gel, paste or bar.
  • the laundry detergent composition is a granular or particulate composition, especially a powder or a tablet; or a liquid.
  • Particulate detergent compositions are suitably prepared by spray-drying a slurry of compatible heat-insensitive ingredients in a spray-drying tower, and then spraying on or postdosing those ingredients unsuitable for processing via the slurry.
  • the skilled detergent formulator will have no difficulty in deciding which ingredients should be included in the slurry and which should not.
  • the spray-dried detergent composition may be subjected to post-tower densification using, for example, a high-speed mixer/granulator.
  • particulate detergent compositions may be prepared by wholly non-tower mixing and granulation processes. In both cases a high-speed mixer/granulator may advantageously be used.
  • LiCl lithium chloride
  • DMSO N,N-dimethylsulphoxide
  • the average degree of substitution (DS) is 1 ester group for every 15 Locust Bean Gum sugar rings.
  • the reaction was stirred for 2 hours at ambient temperature.
  • the contents of the flask was then diluted with demineralised water and the solution passed through a bed of silica on a sinter funnel, yielding a water-white, clear solution. This was added to a threefold volume of methanol, causing the product to precipitate. This was collected on a filter and dried in vacuo at 40°C to constant weight, yielding 8g of white, crystalline powder.
  • the method involved the use of a tergotometer and multiple washing in order to simulate the redeposition process that occurs with repeated washing either under difficult wash conditions or with low efficiency wash products.
  • Test formulations were used to wash pre-soiled "test cloths” together with clean fabrics (redeposition monitors) under standard conditions.
  • the soiled fabrics were used to supply soil to the system and also to measure the cleaning efficiency of the formulations.
  • the clean fabrics were used to "collect” soil from the liquor and were used to quantify the level of soil redeposition.
  • the test cloths and redeposition monitors were dried and their reflectance measured.
  • a new batch of test cloths was then washed together with the redeposition monitors from the original wash cycle and the process repeated to give information on the level of redeposition after two wash cycles. This process was then repeated for a third, fourth (etc) wash cycle:
  • This protocol allows both the detergency and the redeposition process to be followed as a function of cycle number.
  • the reflectance value falls with successive cycles as more soil is present in the system: the smaller the reflectance decrease, the better the antiredeposition properties of the formulation.
  • a stock solution was prepared, using water of 40 degrees French hardness, containing 2 g/l of the following notional formulation (equivalent to 1.77 g/l of the specified ingredients the rest comprising other detergent ingredients such as water, enzyme, fluorescer, perfume etc.
  • Ingredient Weight% Sodium linear alkylbenzene sulphonate LAS (100%) 26.00
  • Sodium carbonate 10.85 Sodium alkaline silicate (48%) as 100% by weight 4.66 (Water to 100)
  • Example Comparative Example A Formulation as above Comparative Example B Formulation as above plus 1.5 wt% of sodium carboxymethyl cellulose
  • Example 2 Formulation as above plus 1.5 wt% of the polymer of Example 1
  • the soiled test cloths were 7.5 cm x 7.5 cm squares as follows: Fabric Soil Cotton Nut oil and iron oxide (black) Cotton Kaolin and sebum Polyester Kaolin and sebum Cotton Carbon black and mineral oil
  • the clean test cloths were 10 cm x 10 cm squares of the following fabrics:
  • the tergotometer pots containing the test formulations, soiled and clean test cloths at 25°C were agitated at 90 rpm for 15 minutes.
  • the fabric bundles were then removed from the pots and rinsed twice in water (40 degrees French hard). the fabrics were then dried in the dark for at least 12 hours.
  • the reflectance values of the redeposition monitors were measured (full spectrum with ultraviolet) excluded) before and after the wash.
  • Example 4 non-phosphate heavy duty laundry powder
  • Non-phosphate tablet Phosphate tablet Na linear alkylbenzene sulphonate 9.33 9.48 Nonionic surfactant 4.1 4.19 Soap 0.73 0.29 Sodium tripolyphosphate - 51.00 zeolite MAP (anhydrous basis) 20.86 - Na citrate 2.5 - Na acetate 26.43 - Na carbonate 3.1 - Na disilicate (as 100%) 2.0 3.48 Antifoam granule (100%) 0.3 0.425 Na percarbonate (100%) 13.35 12.46 Tetraacetyl ethylenediamine (100%) 4.2 2.35 Ethylenediamine tetramethylene phosphonate 0.34 0.46 Polyvinyl pyrrolidone (100%) 0.19 0.143 Soil release polymer. (sulphonated polyester) 0.25 0.11 Polymer of Example 1 1.5 1.5 Enzymes (protease, lipase, cellulase), fluorescer, perfume, minor ingredients, water to 100 to 100 to 100 to 100 to 100 to

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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 (9)

  1. Verwendung eines Pfropfpolymers mit einem Johannisbrotbaumgummigerüst und Pfropfungen von einer aromatischen Sulfonsäure, um die Antiwiederablagerungseigenschaften einer Wäschewaschmittelzusammensetzung zu verbessern.
  2. Verwendung nach Anspruch 1, dadurch gekennzeichnet, dass das Pfropfpolymer Johannisbrotbaumgummi-Pfropf-Poly(4-styrolsulfonsäure) ist.
  3. Verwendung nach Anspruch 1 oder Anspruch 2, dadurch gekennzeichnet, dass das Pfropfpolymer in der Wäschewaschmittelzusammensetzung in einer Menge von 0,1 bis 10 Gewichtsprozent vorliegt.
  4. Verwendung nach einem vorangehenden Anspruch, dadurch gekennzeichnet, dass die Wäschewaschmittelzusammensetzung umfasst:
    (a) 5 bis 60 Gewichtsprozent von einem organischen Waschmitteltensid, ausgewählt aus anionischen, nichtionischen, kationischen, zwitterionischen und amphoteren Tensiden und Kombinationen davon,
    (b) gegebenenfalls 0 bis 80 Gewichtsprozent eines Waschmittelbuilders,
    (c) 0,1 bis 10 Gewichtsprozent des Johannisbrotbaumgummipfropfpolymers,
    (d) gegebenenfalls andere Waschmittelbestandteile auf 100 Gewichtsprozent.
  5. Verwendung nach Anspruch 4, dadurch gekennzeichnet, dass das organische Waschmitteltensid (a) ein anionisches Sulfonat oder Sulfonattensid, gegebenenfalls in Anmischung mit einem oder mehreren Co-Tensiden, ausgewählt aus ethoxylierten nichtionischen Tensiden, nichtethoxylierten nichtionischen Tensiden, ethoxylierten anionischen Sulfattensiden, kationischen Tensiden, Aminoxiden, Alkanolamiden und Kombinationen davon, umfasst.
  6. Verwendung nach Anspruch 4 oder Anspruch 5, dadurch gekennzeichnet, dass die Wäschewaschmittelzusammensetzung 10 bis 80 Gewichtsprozent von einem Waschmittelbuilder (b), ausgewählt aus Zeolithen, Phosphaten und Citraten, umfasst.
  7. Verwendung nach einem der Ansprüche 4 bis 6, dadurch gekennzeichnet, dass die Wäschewaschmittelzusammensetzung andere Waschmittelbestandteile (d), ausgewählt aus Bleichmittelbestandteilen, Enzymen, Natriumcarbonat, Natriumsilikat, Natriumsulfat, Schaumbekämpfungsmitteln, Schaumverstärkungsmitteln, Parfüms, Textilkonditionierern, Schmutzlösemitteln, Farbstoffübertragungsinhibitoren, Photobleichmitteln, Fluoreszenzmitteln und gefärbten Sprenkeln, umfasst.
  8. Verwendung nach einem vorangehenden Anspruch, dadurch gekennzeichnet, dass die Wäschewaschmittelzusammensetzung eine granuläre oder teilchenförmige Zusammensetzung ist.
  9. Verwendung nach einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, dass die Wäschewaschmittelzusammensetzung eine Flüssigkeit ist.
EP03789338A 2003-01-16 2003-12-18 Waschmittel Expired - Lifetime EP1583814B1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
GBGB0301020.4A GB0301020D0 (en) 2003-01-16 2003-01-16 Detergent composition
GB0301020 2003-01-16
PCT/EP2003/014521 WO2004063316A1 (en) 2003-01-16 2003-12-18 Detergent compositions

Publications (2)

Publication Number Publication Date
EP1583814A1 EP1583814A1 (de) 2005-10-12
EP1583814B1 true EP1583814B1 (de) 2007-07-11

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ID=9951277

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Application Number Title Priority Date Filing Date
EP03789338A Expired - Lifetime EP1583814B1 (de) 2003-01-16 2003-12-18 Waschmittel

Country Status (10)

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EP (1) EP1583814B1 (de)
AR (1) AR043333A1 (de)
AT (1) ATE366791T1 (de)
AU (1) AU2003293934A1 (de)
BR (1) BR0317955B1 (de)
CL (1) CL2004000057A1 (de)
DE (1) DE60314910T2 (de)
ES (1) ES2289350T3 (de)
GB (1) GB0301020D0 (de)
WO (1) WO2004063316A1 (de)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB0508882D0 (en) * 2005-04-29 2005-06-08 Unilever Plc Polymers for laundry applications

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6031511A (ja) * 1983-07-29 1985-02-18 Kohjin Co Ltd 新規な高吸収性ポリマーの製造方法
DE4003172A1 (de) * 1990-02-03 1991-08-08 Basf Ag Pfropfcopolymerisate von monosacchariden, oligosacchariden, polysacchariden und modifizierten polysacchariden, verfahren zu ihrer herstellung und ihre verwendung
DE4343993A1 (de) * 1993-12-22 1995-06-29 Stockhausen Chem Fab Gmbh Pfropf-Copolymerisate von ungesättigten Monomeren und Polyhydroxyverbindungen, Verfahren zu ihrer Herstellung und ihre Verwendung
US5977275A (en) * 1998-02-17 1999-11-02 National Starch And Chemical Investment Holding Corporation Polymers having pendant polysaccharide moieties and uses thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
None *

Also Published As

Publication number Publication date
AU2003293934A1 (en) 2004-08-10
WO2004063316A1 (en) 2004-07-29
GB0301020D0 (en) 2003-02-19
EP1583814A1 (de) 2005-10-12
DE60314910D1 (de) 2007-08-23
ES2289350T3 (es) 2008-02-01
AR043333A1 (es) 2005-07-27
BR0317955A (pt) 2005-11-29
BR0317955B1 (pt) 2013-09-24
DE60314910T2 (de) 2007-11-08
ATE366791T1 (de) 2007-08-15
CL2004000057A1 (es) 2005-02-18

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