WO2021115724A1 - Detergent composition - Google Patents

Detergent composition Download PDF

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Publication number
WO2021115724A1
WO2021115724A1 PCT/EP2020/082020 EP2020082020W WO2021115724A1 WO 2021115724 A1 WO2021115724 A1 WO 2021115724A1 EP 2020082020 W EP2020082020 W EP 2020082020W WO 2021115724 A1 WO2021115724 A1 WO 2021115724A1
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WO
WIPO (PCT)
Prior art keywords
detergent composition
fabric
composition according
acid
quaternary ammonium
Prior art date
Application number
PCT/EP2020/082020
Other languages
French (fr)
Inventor
Anshul Gupta
Original Assignee
Unilever Ip Holdings B.V.
Unilever Global Ip Limited
Conopco, Inc., D/B/A Unilever
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
Application filed by Unilever Ip Holdings B.V., Unilever Global Ip Limited, Conopco, Inc., D/B/A Unilever filed Critical Unilever Ip Holdings B.V.
Priority to EP20803594.9A priority Critical patent/EP4073216B1/en
Priority to BR112022011360A priority patent/BR112022011360A2/en
Publication of WO2021115724A1 publication Critical patent/WO2021115724A1/en
Priority to ZA2022/06435A priority patent/ZA202206435B/en

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Classifications

    • 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
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02Inorganic compounds ; Elemental compounds
    • C11D3/04Water-soluble compounds
    • C11D3/10Carbonates ; Bicarbonates
    • 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
    • C11D10/00Compositions of detergents, not provided for by one single preceding group
    • C11D10/04Compositions of detergents, not provided for by one single preceding group based on mixtures of surface-active non-soap compounds and soap
    • 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
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005Other compounding ingredients characterised by their effect
    • C11D3/001Softening compositions
    • 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
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/20Organic compounds containing oxygen
    • C11D3/22Carbohydrates or derivatives thereof
    • C11D3/222Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
    • C11D3/227Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin with nitrogen-containing groups
    • 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
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/26Organic compounds containing nitrogen
    • C11D3/33Amino carboxylic acids
    • 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
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/36Organic compounds containing phosphorus
    • C11D3/361Phosphonates, phosphinates or phosphonites
    • 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
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/36Organic compounds containing phosphorus
    • C11D3/362Phosphates or phosphites
    • 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
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/36Organic compounds containing phosphorus
    • C11D3/364Organic compounds containing phosphorus containing nitrogen
    • 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
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/37Polymers
    • C11D3/3746Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3769(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines
    • 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
    • C11D9/00Compositions of detergents based essentially on soap
    • C11D9/04Compositions of detergents based essentially on soap containing compounding ingredients other than soaps
    • C11D9/06Inorganic compounds
    • C11D9/08Water-soluble compounds
    • C11D9/10Salts
    • C11D9/12Carbonates
    • 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
    • C11D9/00Compositions of detergents based essentially on soap
    • C11D9/04Compositions of detergents based essentially on soap containing compounding ingredients other than soaps
    • C11D9/22Organic compounds, e.g. vitamins
    • C11D9/26Organic compounds, e.g. vitamins containing oxygen
    • C11D9/262Organic compounds, e.g. vitamins containing oxygen containing carbohydrates
    • 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
    • C11D9/00Compositions of detergents based essentially on soap
    • C11D9/04Compositions of detergents based essentially on soap containing compounding ingredients other than soaps
    • C11D9/22Organic compounds, e.g. vitamins
    • C11D9/30Organic compounds, e.g. vitamins containing nitrogen
    • 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
    • C11D9/00Compositions of detergents based essentially on soap
    • C11D9/04Compositions of detergents based essentially on soap containing compounding ingredients other than soaps
    • C11D9/22Organic compounds, e.g. vitamins
    • C11D9/34Organic compounds, e.g. vitamins containing phosphorus

Definitions

  • the present invention relates to a detergent composition. More particularly, the invention is directed to fabric softening in the wash laundry detergent composition.
  • Textile fabrics including clothes, have traditionally been cleaned with laundry detergents. After cleaning, fabrics may often feel harsh. Consumers prefer fabrics to be clean and with a soft feel.
  • Laundry detergent composition which simultaneously achieves detergency and softness of the fabric during the laundering process by incorporating fabric softening component that impart a fabric softening benefit to the laundered fabric is described in the following references.
  • US 2008/0045438 A1 (Unilever, 2008) is directed to a liquid laundry composition which deliver both effective softening and effective cleaning containing a solubilized cationic polymer and a solubilized soap blend.
  • EP 1903100 B1 (Unilever, 2009) discloses a detergent tablet composition having a combination of cationic polymer and mixed sodium-potassium soap for providing softness benefits.
  • phosphate builders and zeolite builders are preferred for providing good softening benefits and cleaning performance
  • detergent composition with low levels of phosphate builders are desired as they are environmentally friendly and low levels of zeolite in detergent composition are preferred as zeolites have a tendency to form undesirable cloudy wash liquor upon contact with water and may also form undesirable deposits on fabrics.
  • Yet another object of the invention is to provide a detergent composition which achieves improved fabric softening performance in the presence of alkaline builder salts.
  • a still further object of the present invention is to provide a detergent composition which achieves improved cleaning and fabric softening performance at lower concentration of fabric softening agent.
  • a need remains for carbonate built solid laundry detergent composition which includes cationic polymer for improving softening delivered on fabrics in the wash cycle of washing machines or during hand wash, without compromising on the cleaning performance.
  • a solid detergent composition comprising: i) a chelating agent; ii) a neutralised soap; iii) a cationically substituted quaternary ammonium polymer; and, iv) 15wt.% to 40wt.% carbonate-based builder.
  • a method for softening fabric comprising, in no particular order, the steps of: i) providing a fabric in a washing machine or in a hand wash container; ii) contacting the fabric during a wash cycle of said washing machine or hand wash process with the composition according to the first aspect; iii) optionally allowing the article or articles to dry or mechanically tumble-drying them.
  • a chelating agent, cationically substituted quaternary ammonium polymer and neutralised soap in a carbonate built solid detergent composition having from 15wt.% to 40wt.% carbonate- based builder, to provide softening benefit on fabric treated with the composition.
  • a solid detergent composition which includes a chelating agent, a cationically substituted quaternary ammonium polymer and a neutralised soap.
  • the detergent composition according to the present invention provides a through the wash fabric softening that is convenient for the consumer to dose to the washing machine.
  • the detergent composition according to the present invention preferably includes from 0 wt.% to 4 wt.% phosphate builder.
  • the detergent composition according to the present invention is a non-phosphate built laundry detergent formulation, i.e., preferably it contains less than 4 wt.%, still preferably less than 3 wt.%, further preferably less than 2 wt.%, more preferably contains less than 1 wt.% of phosphate builder material.
  • the term 'phosphate' includes diphosphate or triphosphate species.
  • the detergent composition is predominantly carbonate built, i.e.
  • the weight% of sodium carbonate is greater than the weight % of the sum of other builder material present, preferably the amount of other builder material is less than 30 wt.%, more preferably less than 15 wt.%, still preferably less than 10 wt.%, still further preferably less than 5% of the weight% level of sodium carbonate.
  • composition of the present invention can be made via a variety of conventional methods known in the art. These methods include but is not limited to homogenous mixing of ingredients, including dry-mixing; compaction techniques such as agglomerating, extrusion, tabletting; spray-drying a slurry of the ingredients, or a mixture of one or more of these techniques.
  • compaction techniques such as agglomerating, extrusion, tabletting
  • spray-drying a slurry of the ingredients, or a mixture of one or more of these techniques.
  • the various components added to the detergent composition of the present invention may also made by for various conventional methods for example compaction, including extrusion and agglomerating, or spray-drying.
  • the detergent composition is preferably prepared by the technique of slurry making and spray drying.
  • the composition is in the form of a solid detergent composition.
  • they are main wash detergent composition. It can take the form of a detergent composition for the main wash, which may be dilutable or non-dilutable.
  • the detergent composition herein can take a variety of physical solid forms which includes forms such as powder, particulate, granule, ribbon, noodle, paste, tablet, flake, pastille and bar, and preferably the composition is in the form of powder, granules or a tablet, still preferably the detergent composition is in the form of a powder or particulate. Further preferably the composition is in the form of a spray-dried powder or particulate.
  • composition of the present invention preferably has a density of more than 350 grams/litre, more preferably more than 450 grams/litre or even more than 570 grams/litre.
  • the detergent composition according to the present invention usually has an alkaline pH, generally in the region of pH 9 to 12.5 when measured with a 1wt% dilution in de- ionised water at 25°C, which is achieved by the presence of sodium carbonate and other alkaline salts especially sodium silicates such as the meta-, neutral or alkaline silicates, preferably at levels up to about 35 wt.% of the composition. More preferably the detergent composition has a pH from 9 to 11, still preferably from 9 to 10.5. Most preferably the pH is from 10.3 to 10.8.
  • detergent composition includes a chelating agent.
  • the chelating agent is selected from the group consisting of amino carboxylates, phosphonates or mixtures thereof.
  • Chelating agent as used herein includes those chemicals which interact with divalent ions, cations and anions, having tendency to precipitate in their saturated aqueous solutions. Chelating agents through threshold inhibition act as catalyst to delay the precipitation reaction of these ions in their saturated aqueous solutions.
  • chelating agent comprises the catalyst, a cation of calcium and / or magnesium ions and carbonate anions. Throughout this document the terms chelating agent and crystal growth inhibitor are used interchangeably.
  • Useful amino carboxylate chelating agents includes, but are not limited to, the following: N-(1,2-dicarboxy- ethyl)-D,L-aspartic acid (IDS), N-(2- hydroxyethyl)iminodiacetic acid (EDG), aspartic acid-N- monoacetic acid (ASMA), aspartic acid- N,N-diacetic acid (ASDA), aspartic acid-N- mono- propionic acid (ASMP), iminodisuccinic acid (IDA), N- (2-sulfomethyl) aspartic acid (SMAS), N- (2-sulfoethyl) aspartic acid (SEAS), N- (2- sulfomethyl) glutamic acid (SMGL), N- (2- sulfoethyl) glutamic acid (SEGL), N- methyliminodiacetic acid (MIDA), a- alanine-N,N- diacetic acid (a - ALDA) , se
  • the preferred chelating agent may contain an amino group and may be, e.g., an amino-polycarboxylate or a phosphonate. It may be a monomeric molecule comprising one, two or three amino groups (typically secondary or tertiary amino groups), and it may contain two, three, four or five carboxyl groups or even more carboxyl groups.
  • the chelating agents may be phosphorus containing or without phosphorus.
  • Suitable chelating agents includes those based on carboxylate groups includes EDTA (ethylene diamine tetraacetate), NTA (2,2',2"-nitrilotriacetate), citrate, 2-hydroxypropan- 1,2,3-tricarboxylate, DTPA (diethylenetriaminepentaacetic acid), MGDA (methylglycinediacetic acid OT N,N'-bis(carboxymethyl)alanine), EGTA (ethylene glycol tetraacetic acid), EDDS (ethylenediamine- N,W-disuccinic acid),, GLDA (L-Glutamic acid, N, N-diacetic acid),
  • the composition preferably may also include other polycarboxylates such as PAA [poly(acrylic acid)], PAA/PMA [copoly(acrylic acid/maleic acid)], or mixtures thereof.
  • Another group of preferred chelating agents includes phosphonates.
  • Aminoalkane and/or hydroxyalkane phosphonates are preferably used as phosphonates.
  • Suitable examples of these phosphonate chelating agent includes HEDP (l-hydroxyethylidene- 1,1-diphosphonic acid), EDTMP [ethylenediamine tetra(methylene phosphonic acid], EDTMPA (ethylenediaminetetramethylene- tetraphosphonic acid), DTPMP (diethylenetriamine penta (methylene phosphonic acid), DTMPA (diethylenetriaminepenta(methylenephosphonic acid)) nitrilotris(methylenephosphonic acid) (NTMP), 2-phosphonobutane-1,2,4-tricarboxylic acid (PBTC), ethylenediamine tetramethylene phosphonate (EDTMP), and the higher homologs thereof.
  • HEDP l-hydroxyethylidene- 1,1-
  • the chelating agents may contain nitrogen such as in EDTA, NTA, DTPA, PDTA, GLDA, MGDA, EDDS, EDTMP, EDTMPA, and DTPMP or ASMA, ASDA, ASMP, IDA, SMAS, SEAS, SMGL, SEGL, MIDA, a-ALDA, SEDA, ISDA, PHDA, ANDA, SLDA, TUDA, SMDA, HEDTA, DEG, ATMP, or mixtures thereof.
  • nitrogen such as in EDTA, NTA, DTPA, PDTA, GLDA, MGDA, EDDS, EDTMP, EDTMPA, and DTPMP or ASMA, ASDA, ASMP, IDA, SMAS, SEAS, SMGL, SEGL, MIDA, a-ALDA, SEDA, ISDA, PHDA, ANDA, SLDA, TUDA, SMDA, HEDTA, DEG, ATMP, or mixtures thereof.
  • Particularly preferred chelating agents includes but are not limited to the following: ethylene- diamine- tetra- acetic acid (EDTA), diethylene triamine penta methylene phosphonic acid (DTMPA, DTPMP), hydroxy-ethane diphosphonic acid (HEDP), ethylenediamine N,N- disuccinic acid (EDDS), methyl glycine di-acetic acid (MGDA), diethylene triamine penta acetic acid (DTPA), propylene diamine tetraacetic acid (PDTA), 2-hydroxypyridine-N-oxide (HPNO), methyl glycine diacetic acid (MGDA), glutamic acid N,N-diacetic acid (N,N-dicarboxymethyl glutamic acid tetrasodium salt (GLDA) and nitrilotriacetic acid (NTA) or mixtures thereof.
  • the chelating agent may be present in their acid form or a salt, preferably the chelating agents may be present as a
  • Especially preferred chelating agent includes diethylenetriamine pentacetic acid (DTPA), ethylenediamine-N, N’-disuccinic acid (EDDS) and 1,1 hydroxyethane diphosphonic acid (HEDP) or the alkali metal, potassium, alkaline earth metal, ammonium or substituted ammonium salts thereof, or mixtures thereof.
  • the most preferred chelating agent is a phosphonate.
  • the phosphonate chelating agent includes HEDP in its acid form or salt form with alkali metal, potassium, alkaline earth metal, ammonium or substituted ammonium.
  • the chelating agent is preferably present in an amount from 0.1 wt.% to 10 wt.%, still preferably from 0.1 wt.% to 5 wt.%, preferably from 0.1 wt.% to 3 wt.%, more preferably from 0.1 wt.% to 1 wt.%.
  • the detergent composition comprises at least 0.2 wt.% chelating agent based on the weight of the detergent composition, still preferably at least 0.3 wt.%, still preferably at least 0.5 wt.%, most preferably at least 0.6 wt.%, but typically not more than 3 wt.%, still preferably not more than 2 wt.%, most preferably not more than 1 wt.% of the chelating agent according to the present invention.
  • Neutralised soap :
  • Disclosed solid detergent composition includes a neutralized soap.
  • Soaps are the fatty acid salts having the general formula (I) R 3 CO-OX .
  • R 3 CO is a linear or branched, saturated or unsaturated acyl group containing 6 to 22 and preferably 12 to 18 carbon atoms
  • X is alkali and/or alkaline earth metal, ammonium, alkylammonium or alkanolammonium.
  • Typical examples are the sodium, potassium, magnesium, ammonium and triethanolammonium salts of caproic acid, caprylic acid, 2-ethylhexanoic acid, capric acid, lauric acid, isotridecanoic acid, myristic acid, palmitic acid, palmitoleic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, petroselic acid, linoleic acid, linolenic acid, elaeostearic acid, arachic acid, gadoleic acid, behenic acid and erucic acid and technical mixtures thereof. Cocofatty acid or palm kernel oil fatty acid in the form of their salts are preferably used.
  • soaps Water-soluble salts of the higher fatty acids (i.e. "soaps") containing from about 8 to about 24 carbon atoms and preferably from about 10 to about 20 carbon atoms are useful, still preferred are those with 10 to 12 carbon atoms, and those with 16 to 18 carbon atoms.
  • the soaps are either sodium, potassium, ammonium and alkanolammonium salts of higher fatty acids. Soaps can be made by direct saponification of fats and oils or by the neutralization of free fatty acids. Particularly useful are the sodium and potassium salts of the mixtures of fatty acids derived from coconut oil and tallow, i.e., sodium or potassium tallow and coconut soap.
  • the neutralized soap is preferably present in an amount from 5 wt.% to 30 wt.%, preferably from 8 wt.% to 25 wt.%, more preferably from 10 wt.% to 20 wt.%.
  • the detergent composition comprises at least 8 wt.% neutralized soap based on the weight of the detergent composition, still preferably at least 9 wt.%, still preferably at least 9.5 wt.%, most preferably at least 10 wt.%, more preferably at least 12 wt.% but typically not more than 25 wt.%, still preferably not more than 20 wt.%, most preferably not more than 15 wt.% of the neutralized soap.
  • Cationically substituted quaternary ammonium polymer Cationically substituted quaternary ammonium polymer:
  • Disclosed detergent composition includes a cationically substituted quaternary ammonium polymer.
  • the cationically substituted quaternary ammonium polymer provides the benefit of a deposition aid.
  • the cationically substituted quaternary ammonium polymer may preferably be selected from the list of Polyquaternium as named under the International Nomenclature for Cosmetic Ingredients and including those ranging from Polyquaternium 1 to Polyquaternium 101 as provided in Table 2 of WO2017/143174 A1 and incorporated herein by reference.
  • the cationically substituted quaternary ammonium polymer is selected from the group consisting of Polyquaternium 4, Polyquaternium 7, Polyquaternium 10, Polyquaternium 16, Polyquaternium 22, Polyquaternium 24, Polyquaternium 29, Polyquaternium 37, Polyquaternium 43, Polyquaternium 53, Polyquaternium 63, Polyquaternium 67, Polyquaternium 69, Polyquaternium 72 and Polyquaternium 90.
  • the polymer is a polysaccharide, preferably a natural polysaccharide.
  • the polysaccharide is selected from the group consisting of cellulose, guar gum, chitosan, alginates, starch, xanthan, dextrans, arabic gum, galactomannan, carrageenan, hyaluronates and combinations thereof.
  • these polysaccharides can be employed with cationic modification and alkoxy-cationic modifications such as cationic hydroxethyl or cationic hydroxypropyl.
  • Cationic polysaccharides have a molecular weight from about 1 ,000 to about 2 million, preferably from 20 about 100,000 to about 800,000.
  • Cationic starches refer to starch that has been chemically modified to provide the starch with a net positive charge in aqueous solution at pH 3. This chemical modification includes, but is not limited to, the addition of amino and/or ammonium group(s) into the starch molecules.
  • Non-limiting examples of these ammonium groups may include substituents such as trimethylhydroxypropyl ammonium chloride, dimethylstearylhydroxypropyl ammonium chloride, or dimethyldodecylhydroxypropyl ammonium chloride.
  • the cationic starches may comprise amylase, amylopectin, or maltodextrin.
  • the cationic starch may comprise one or more additional modifications.
  • these modifications may include cross-linking, stabilization reactions, phophorylations, hydrolyzations, cross-linking.
  • Stabilization reactions may include alkylation and esterification.
  • Suitable cationic starches for use in the present compositions are commercially-available from Cerestar under the trade name C*BOND ® and from National Starch and Chemical Company under the trade name CATO ® 2A.
  • Cationic galactomannans include cationic guar gums or cationic locust bean gum.
  • a cationic guar gum is a quaternary ammonium derivative of Hydroxypropyl Guar such as those sold under the trade name Jaguar C13 and Jaguar Excel available from Rhodia, Inc of Cranbury NJ and N-Hance by Aqualon, Wilmington, DE.
  • suitable polymers include cationic guar gum derivatives, quaternary nitrogen-containing cellulose ethers, synthetic polymers, copolymers of etherified cellulose, guar and starch. Suitable cationic polymers are described in U.S. Pat. Nos. 3,962,418; 3,958,581; and U.S. Publication No. 2007/0207109A 1.
  • the cationically substituted quaternary ammonium polysaccharide is selected from cationically modified hydroxyethyl cellulose, cationically modified hydroxypropyl cellulose, cationically and hydrophobically modified hydroxyethyl cellulose, cationically and hydrophobically modified hydroxypropyl cellulose, or a mixture thereof, more preferably cationically modified hydroxyethyl cellulose, cationically and hydrophobically modified hydroxyethyl cellulose, or a mixture thereof.
  • the cationically substituted quaternary ammonium polymer preferably has a cationic charge density more than about 0.05 meq/g (meq meaning milliequivalents), to 23 meq/g, preferably from about 0.1 meq/g to about 4 meq/g, even more preferably from about 0.1 meq/g to about 2 meq/g and most preferably from 0.1 meq/g to about 1 meq/g.
  • the above referenced cationic charge densities can be at the pH of intended use, which can be a pH from 3 to 12, optionally about 8 to 10.
  • Cationic charge density of a polymer refers to the ratio of the number of positive charges on the polymer to the molecular weight of the polymer. Charge density is calculated by dividing the number of net charges per repeating unit by the molecular weight of the repeating unit.
  • the positive charges may be located on the backbone of the polymers and/or the side chains of polymers.
  • the charge density relates to the degree of cationic substitution and can be expressed with nitrogen content of the cationic polymer.
  • Preferred are cationically substituted quaternary ammonium polymer having a nitrogen content % from 0.01 to 2.2%, more preferred are cationically substituted quaternary ammonium polymers having a nitrogen content from 0.2 to 1.6%, and most preferred are cationically substituted quaternary ammonium polymers having a nitrogen content from 0.3 to 1.4%.
  • the weight-average molecular weight of the cationically substituted quaternary ammonium polymer may be from about 500 to about 5,000,000, or from about 1 ,000 to about 2,000,000, or from about 5000 to about 1 ,000,000 Daltons, as determined by size exclusion chromatography relative to polyethyleneoxide standards with Rl detection. In one aspect, the weight-average molecular weight of the cationically substituted quaternary ammonium polymer may be from about 100,000 to about 800,000 Daltons. Without wishing to be bound by theory, it is believed that polymers that are too high in mass can entrap soils and prevent them from being removed.
  • the use of cationically substituted quaternary ammonium polymers with a weight average molecular weight of less than about 850,000 daltons is preferred, and even more preferred those with weight average molecular weight of less than 500,000 daltons.
  • the preferred minimum average molecular weight is about 10,000 daltons, because smaller molecules are believed to be too small to give an effective softening benefit.
  • the composition includes other polymers which are cationic or amphoteric, polysaccharides, proteins and synthetic polymers.
  • cationic cellulosic polymers with substituted anhydroglucose units that correspond to the general Structural Formula as follows: wherein R 1 , R 2 , R 3 are each independently selected from H, CH 3 , Cs-24 alkyl (linear or branched), n is from about 1 to 10;
  • R x is selected from the group consisting of H, CH 3 , Cs-24 alkyl (linear or branched),
  • Z is a water soluble anion, preferably a chlorine ion and/or a bromine ion;
  • R 5 is H, CH 3 , CH 2 CH 3 or mixtures thereof;
  • R 7 is CH 3 , CH2CH 3 , a phenyl group, Cs-24 alkyl (linear or branched), or mixture thereof; and
  • R 8 and R 9 are each independently CH 3 , CH2CH 3 , a phenyl group, or mixtures thereof: with the provisio that at least one of R 1 , R 2 and R 3 per anhydroglucose unit is
  • each polymer has at least one group.
  • the charge density of the cationic celluloses herein is preferably from about 0.5 % to about 60%, more preferably from about 15 1% to about 20%, and most preferably from about 2% to about 10%.
  • Alkyl substitution on the anhydroglucose rings of the polymer ranges from about 0.01% to 5% per glucose unit, more preferably from about 0.05% to 2% per glucose unit, of the polymeric material.
  • the cationic cellulose may lightly cross-linked with a dialdehyde such as glyoxyl to prevent forming lumps, nodules or other agglomerations when added to water at ambient temperatures.
  • the ratio of un-quaternised to quaternized sugar units (n:y) is preferably in the range from 3 to 30, more preferably from 4 to 25, most preferably from 5 to 20.
  • the level of nitrogen in the polymer of formula (I) is in the range from 0.1 to 1.5%, more preferably from 0.3 to 1.3% and most preferably from 0.5 to 1.1% by weight.
  • the molecular weight of the cationically substituted quaternary ammonium polysaccharide of formula (I) is from 1,000 to 1,000,000 kDa, preferably from 5,000 to 750,000 kDa, more preferably from 10,000 to 5000, 000 kDa. Mixtures of polymers may be used. The polymers are linear in structure.
  • the cationically substituted quaternary ammonium polymer is a cationically substituted quaternary ammonium polysaccharide.
  • Preferred example of cationic polysaccharide is a cationic cellulose derivative.
  • cationic hydroxyalkyl cellulose examples include those with the I NCI name Polyquaternium 10 such as those sold under the trade names Ucare Polymer JR 30M, JR 400, JR 125, LR 400 and LK 400, Polymer PK polymers; Polyquaternium 67 such as those sold under the trade name Soltcat SK TM, all of which are marketed by Dow Chemicals, Midlad Ml, and Polyquaternium 4 such as those sold under the trade name Celquat H200 and Celquat L-20025 available from National Starch and Chemical Company, Bridgewater, NJ.
  • Polyquaternium 10 such as those sold under the trade names Ucare Polymer JR 30M, JR 400, JR 125, LR 400 and LK 400, Polymer PK polymers
  • Polyquaternium 67 such as those sold under the trade name Soltcat SK TM, all of which are marketed by Dow Chemicals, Midlad Ml
  • Polyquaternium 4 such as those sold under the trade name Celquat H200 and Cel
  • polysaccharides include Hydroxyethyl cellulose or hydoxypropylcellulose quaternized with glycidyl C12-C22 alkyl dimethyl ammonium chloride.
  • suitable polysaccharides include the polymers with the I NCI names Polyquaternium 24 such as those sold under the trade name Quaternium LM 200 by Dow Chemicals of Midland, ML.
  • Most preferably the example of polyquaternium 10 is UCARETM Polymer, for example types JR-400 and LR-400 (all ex Dow,) and their copolymers. The most preferred is UCARETM Polymer LR-400.
  • Suitable optional cationic polymers preferably includes those produced by polymerization of ethylenically unsaturated monomers using a suitable initiator or catalyst, such as those disclosed in WO 00/56849 and USPN 6,642,200.
  • Suitable cationic polymers may be selected from the group consisting synthetic polymers made by polymerizing one or more cationic monomers selected from the group consisting of N,N-dialkylaminoalkyl acrylate, N,N-dialkylaminoalkyl methacrylate, N,N- dialkylaminoalkyl acrylamide, N,N-dialkylaminoalkylmethacrylamide, quaternized N, N dialkylaminoalkyl acrylate quaternized N,N-dialkylaminoalkyl methacrylate, quaternized N,N-dialkylaminoalkyl aeryl amide, quaternized N,N-5 dialkylaminoalkyl methacrylamide, Methacryloamid
  • the polymer may optionally be branched or cross-linked by using branching and crosslinking monomers.
  • Branching and crosslinking monomers include ethylene glycoldiacrylate divinylbenzene, and butadiene.
  • a suitable polyethyleneinine useful herein is that sold under the tradename Lupasol ® by BASF, 20 AG, Lugwigschaefen, Germany.
  • the optional cationic polymer may be also selected from the group consisting of polyethylene imine and its derivatives, poly(acrylamide-codiallyldimethylanunonium chloride), poly(acrylamide-methacrylamidopropyltrimethyl ammonium chloride), poly(acrylamide-co-N,N-dimethyl aminoethyl acrylate) and its quaternized derivatives, poly(acrylamide-co-N,N-dimethyl anunoethyl methacrylate) and its quaternized derivative, poly(hydroxyethylacrylate-co-dimethyl aminoethyl methacrylate), poly(hydroxpropylacrylate-co-dimethyl aminoethyl methacrylate), poly(hydroxpropylacrylatediallyldimethylammonium chloride-co-acrylic acid), co- methacrylamidopropyltrimethylammonium chloride), poly(acrylamide-copoly(acrylamide methacrylamidopropyltrimethyl am
  • the detergent composition may include optional cationic polymer such as polyethyleneimine or a polyethyleneimine derivative, a cationic acrylic based polymer, a cationic polyacrylamide, polyacrylamide and polymethacrylamidoproply trimethylammonium cation, poly(acrylamide- N-dimethyl aminoethyl acrylate) and its quaternized derivatives, poly(acrylamide-co- methacrylamidopropyltrimethyl ammonium chloride).
  • additional cationic polymer includes those sold under the tradename SEDIPUR, available from BTC Specialty Chemicals, a BASF Group, Florham Park, 15 N.J. and those sold under the tradename RHEOVIS CDE, available from Ciba
  • the cationic polymer can be provided in a powder form.
  • the cationic polymer can be provided in an anhydrous state.
  • the cationic polymer is contained in a co-granule.
  • the co-granule comprises a binder, in addition to the cationic polymer. More preferably the co-granule also comprises either an organic or an inorganic salt.
  • Preferred binder materials are polyethylene glycol, soaps, and fatty acids.
  • a preferred organic salt is sodium citrate, and a preferred inorganic salt is sodium sulphate.
  • the cationically substituted quaternary ammonium polymer is preferably present in an amount from 0.001 wt.% to 5 wt.%, preferably from 0.01 wt.% to 5 wt.%, more preferably from 0.05 wt.% to 5 wt.%, most preferably from 0.05 wt.% to 3 wt.%.
  • the detergent composition comprises at least 0.005 wt.% cationically substituted quaternary ammonium polymer based on the weight of the detergent composition, still preferably at least 0.01 wt.%, still preferably at least 0.05 wt.%, most preferably at least 1 wt.%, more preferably at least 2 wt.% but typically not more than 4.5 wt.%, still preferably not more than 4 wt.%, most preferably not more than 3 wt.% of the cationically substituted quaternary ammonium polymer.
  • Disclose detergent composition is carbonate built solid composition.
  • carbonate(s) refers to alkali metal or ammonium salts of carbonate, bicarbonate, and/or sesquicarbonate.
  • the carbonate is selected from the group consisting of carbonate salts of sodium, potassium and lithium, more preferably, salts of sodium or potassium and most preferably, salts of sodium.
  • the carbonate includes at least one of sodium carbonate, sodium bicarbonate.
  • the detergent composition according to the present invention includes from 15 wt.% to 40 wt.% carbonate-based builder.
  • the detergent composition preferably includes from
  • the detergent composition comprises at least 8 wt.% carbonate builder based on the weight of the detergent composition, still preferably at least 10 wt.%, still preferably at least 15 wt.%, most preferably at least 18 wt.%, still more preferably at least 20 wt.%, but typically not more than 35 wt.% , still preferably not more than 30 wt.%, most preferably not more than 28 wt.% of the carbonate based builder.
  • the composition typically comprises one or more detersive synthetic non-soap surfactants.
  • suitable detersive surfactant is chosen from anionic surfactant, nonionic surfactant, cationic surfactant, zwitterionic surfactant, amphoteric surfactant and mixtures thereof.
  • surface-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.
  • Suitable detersive surfactants may be linear or branched, substituted or un-substituted, and may be derived from petrochemical material or biomaterial.
  • Suitable anionic surfactant includes sulphonate and sulphate detersive surfactants.
  • sulphonate detersive surfactants include methyl ester sulphonate, alpha olefin sulphonates, alkyl benzene sulphonates, especially alkyl benzene sulphonates, preferably Cio to C alkyl benzene sulphonate.
  • Suitable alkyl benzene sulphonate is obtainable, preferably obtained, by sulphonating commercially available linear alkyl benzene (LAB); suitable LAB includes low 2-phenyl LAB, other suitable LAB includes high 2-phenyl LAB, such as those supplied by Sasol under the tradename Hyblene®.
  • the alkyl benzene sulphonates may be linear or branched, substituted or un-substituted, and may be derived from petrochemical material or biomaterial.
  • sulphate detersive surfactants include alkenyl sulfate, alkyl ether sulfate, alkyl ethoxy sulfate, sodium lauryl ether sulfate (SLES), primary alcohol sulphate, alkenyl sulfate, alkyl sulphate, preferably Cs to Cie alkyl sulphate, or predominantly C12 alkyl sulphate.
  • the alkyl sulphate may be linear or branched, substituted or un- substituted, and may be derived from petrochemical material or biomaterial.
  • the sulphate detersive surfactant is alkyl alkoxylated sulphate, preferably alkyl ethoxylated sulphate, preferably a Cs to Cis alkyl alkoxylated sulphate, preferably a Cs to Cis alkyl ethoxylated sulphate, preferably the alkyl alkoxylated sulphate has an average degree of alkoxylation of from 0.5 to 20. preferably from 0.5 to 10, preferably the alkyl alkoxylated sulphate is a Cs to Cis alkyl ethoxylated sulphate having an average degree of ethoxylation of from 0.5 to 10, preferably from 0.5 to 5.
  • the alkyl alkoxylated sulphate may be linear or branched, substituted or un-substituted, and may be derived from petrochemical material or biomaterial.
  • anionic detersive surfactants include alkyl ether carboxylates.
  • Suitable anionic detersive surfactants may be in salt form, suitable counter-ions include sodium, calcium, magnesium, amino alcohols, and any combination thereof.
  • a preferred counterion is sodium.
  • Suitable anionic surfactants comprising one or more anionic groups selected from sulfonate and sulfate.
  • anionic surfactants include and combinations thereof. More preferably, anionic surfactants selected from sodium dodecyl benzene sulfonate (Na-LAS), sodium dodecyl sulfate (SDS), sodium lauryl ether sulfate (SLES), methyl ester sulfate (MES), primary alcohol sulfate (PAS), alpha olefin sulfonate and combinations thereof.
  • compositions of the invention may for example contain linear alkylbenzene sulphonate, particularly linear alkylbenzene sulphonates having an alkyl chain length of CstoCis. It is preferred if the level of linear alkylbenzene sulphonate is from 0 wt% to 30 wt%, more preferably 1 wt% to 25 wt%, most preferably from 2 wt% to 15 wt%.
  • compositions of the invention may also contain non-ionic surfactant.
  • Nonionic surfactants that may be used include the primary and secondary alcohol ethoxylates, especially the Cs to C20 aliphatic alcohols ethoxylated with an average of from 1 to 20 moles of ethylene oxide per mole of alcohol, and more especially the C10 to C15 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 alkylpolyglycosides, glycerol monoethers, and polyhydroxyamides (glucamide).
  • the level of non-ionic surfactant is from 0 wt% to 30 wt%, preferably from 1 wt% to 25 wt%, most preferably from 2 wt% to 15 wt%. It is also possible to include certain mono-alkyl cationic surfactants which can be used in main-wash compositions for fabrics.
  • Cationic surfactants that may be used include quaternary ammonium salts of the general formula RIR 2 R S R 4 N + X wherein the R groups are long or short hydrocarbon chains, typically alkyl, hydroxyalkyl or ethoxylated alkyl groups, and X is a counter-ion (for example, compounds in which Ri is a CstoC22 alkyl group, preferably a Cs to C10 or C12 to C M alkyl group, R2IS a methyl group, and R3 and R 4 , which may be the same or different, are methyl or hydroxyethyl groups); and cationic esters (for example, choline esters).
  • RIR 2 R S R 4 N + X wherein the R groups are long or short hydrocarbon chains, typically alkyl, hydroxyalkyl or ethoxylated alkyl groups, and X is a counter-ion
  • Ri is a CstoC22 alkyl group, preferably a Cs
  • surfactant surface-active compound
  • amount present will depend on the intended use of the detergent composition.
  • surfactant systems may be chosen, as is well known to the skilled formulator, for handwashing products and for products intended for use in different types of washing machine.
  • the total amount of surfactant present will also depend on the intended end use and may be as high as 60 wt.%, for example, in a composition for washing fabrics by hand.
  • Detergent compositions suitable for use in most automatic fabric washing machines generally contain anionic non-soap surfactant, or non-ionic surfactant, or combinations of the two in any suitable ratio, optionally together with soap.
  • compositions for machine washing of fabrics an amount of from 5 wt.% to 40 wt.% is generally appropriate.
  • the compositions will comprise at least 2 wt.% surfactant e.g. 2 wt.% to 60 wt.%, preferably 15 wt.% to 40 wt.% most preferably 25 wt.% to 35 wt.%.
  • composition according to the present invention may also contain one or more additional detergency builders.
  • Inorganic builders that may be present in addition to carbonate- based builder (sodium carbonate), includes crystalline and amorphous aluminosilicates, for example, zeolites as disclosed in GB 1473201 (Henkel), amorphous aluminosilicates as disclosed in GB 1473202 (Henkel) and mixed crystalline/amorphous aluminosilicates as disclosed in GB 1470250 (Procter & Gamble); and layered silicates as disclosed in EP 164514B (Hoechst).
  • the compositions of the invention preferably contain an alkali metal, preferably sodium, aluminosilicate builder.
  • the alkali metal aluminosilicate may be either crystalline or amorphous or mixtures thereof, having the general formula: 0.8 to 1.5 Na 2 0.AI 2 0 3 . 0.8 to 6 Si0 2 . These materials contain some bound water and are required to have a calcium ion exchange capacity of at least 50 mg CaO/g.
  • the preferred sodium aluminosilicates contain 1.5 to 3.5 Si0 2 units (in the formula above). Both the amorphous and the crystalline materials can be prepared readily by reaction between sodium silicate and sodium aluminate, as amply described in the literature. Suitable crystalline sodium aluminosilicate ion-exchange detergency builders are described, for example, in GB 1429143 (Procter & Gamble).
  • the preferred sodium aluminosilicates of this type are the well-known commercially available zeolites A and X, and mixtures thereof.
  • the zeolite may be the commercially available zeolite 4A now widely used in laundry detergent powders.
  • the zeolite builder incorporated in the compositions of the invention is maximum aluminium zeolite P (zeolite MAP) as described and claimed in EP 384070A (Unilever).
  • Zeolite MAP is defined as an alkali metal aluminosilicate of the zeolite P type having a silicon to aluminium ratio not exceeding 1.33, preferably within the range of from 0.90 to 1.33, and more preferably within the range of from 0.90 to 1.20.
  • zeolite MAP having a silicon to aluminium ratio not exceeding 1.07, more preferably about 1.00.
  • the calcium binding capacity of zeolite MAP is generally at least 150 mg CaO per g of anhydrous material.
  • Zeolites are preferably present in the composition in an amount ranging from 0 wt.% to 5 wt.% of the composition.
  • the detergent composition has less than 4 wt.%, still preferably less than 3 wt.%, further preferably less than 2 wt.%, still further preferably less than 1 wt.% of zeolite in the composition.
  • the composition may even be substantially free of zeolite builder; substantially free means "no deliberately added"..
  • organic builders such as citrates, suitable used in amounts of from 1wt.% to 30 wt.%, preferably 5 wt.% to 30 wt%, preferably from 5 wt.% to 15 wt.%, still preferably from 5 wt.% to 10 wt.% are used.
  • the amount of citric acid and citrates in the composition is from 1 wt.% to 5 wt.%.
  • Water-soluble, non-phosphorus organic builders useful herein include the various alkali metal, ammonium and substituted ammonium polyacetates, carboxylates, polycarboxylates and polyhydroxy sulfonates.
  • Suitable non-phosphorus, inorganic builders include the silicates, aluminosilicates, borates and carbonates, such as sodium and potassium carbonate, bicarbonate, sesquicarbonate, tetraborate decahydrate, and silicates having a weight ratio of S1O2 to alkali metal oxide of from about 0.5 to about 4.0, or from about 1.0 to about 2.4.
  • the detergents may contain layer silicates.
  • Typical examples are crystalline, layered sodium silicates corresponding to the general formula NaMSi x C> 2x+i .yH 2 0, where M is sodium or hydrogen, x is a number of 1.9 to 4 and y is a number of 0 to 20, preferred values for x being 2, 3 or 4.
  • Crystalline layer silicates such as these are described, for example, in European patent application EP 0 164514 A1.
  • Preferred crystalline layer silicates corresponding to the above formula are those in which M is sodium and x assumes the value 2 or 3.
  • Both b- and delta-sodium disilicates I ⁇ ShOs.ykhO are particularly preferred, b -sodium disilicate being obtainable, for example, by the process described in International patent application WO 91/08171.
  • Other suitable layered silicates are known, for example, from patent applications DE 2334899 M, EP 0026529 M and DE 3526405 M. The suitability of these layered silicates is not limited to a particular composition or structural formula.
  • Amorphous sodium silicates with a modulus (Na 2 0:Si0 2 ratio) of 1:2 to 1:3.3, preferably 1 :2 to 1 :2.8 and more preferably 1 :2 to 1 :2.6 which dissolve with delay and exhibit multiple wash cycle properties may also be used.
  • Compacted amorphous silicates, compounded amorphous silicates and overdried X-ray- amorphous silicates are particularly preferred.
  • the term "silicate(s)" as used herein refers to alkali metal silicates.
  • the silicate used is selected from the group consisting of silicate salts of sodium, potassium and lithium (more preferably, salts of sodium or potassium; most preferably, salts of sodium).
  • the silicate used in the composition is sodium disilicate.
  • the builder used in the composition of the present invention includes a silicate.
  • the composition preferably, comprises 0 wt.% to 20 wt% preferably, 0.1 wt.% to 10 wt.%, more preferably, 1 wt.% to 10 wt.%, most preferably 2 wt.% to 10 wt.% of the silicate(s).
  • compositions preferably include one or more detergent enzymes which provide cleaning performance and/or fabric care benefits.
  • suitable enzymes include hemicellulases, peroxidases, proteases, cellulases, xylanases, lipases, phospholipases, esterases, cutinases, pectinases, keratanases, reductases, oxidases, phenoloxidases, lipoxygenases, ligninases, pullulanases, tannases, pentosanases, malanases, 11-glucanases, arabinosidases, hyaluronidase, chondroitinase, laccase, and amylases, or mixtures thereof.
  • a typical combination may be a cocktail of conventional applicable enzymes like mannanase, protease, lipase, cutinase and/or cellulase in conjunction with amylase.
  • Enzymes can be used at their recommended levels, for example at levels recommended by suppliers such as Novozymes and Genencor. Typical levels in the compositions are from about 0.0001 wt.% to about 5 wt.%. When enzymes are present, they can be used at very low levels, e.g., from about 0.001% or lower; or they can be used in heavy-duty laundry detergent formulations at higher levels, e.g., about 0.1% and higher.
  • the detergent composition according to the present may be enzyme-free. By the term “enzyme-free” it means that there is no deliberately added enzyme in the composition.
  • composition according to the present invention may also include from 0.0001 to 10 wt.%, preferably at least 0.01 wt.%, still preferably at least 0.05 wt.% by weight of the composition of a dye-transfer inhibiting agent. But typically, not more than 2 wt.%, preferably not more than 1wt.% of one or more dye transfer inhibiting agents such as polyvinylpyrrolidone polymers, polyamine N-oxide polymers, copolymers of Nvinylpyrrolidone and N-vinylimidazole, polyvinyloxazolidones and polyvinylimidazoles or mixtures thereof.
  • the detergent composition according to the present invention may preferably include an optical brightener also known as
  • optical brightener also known as
  • useful brighteners include: derivatives of stilbene or 4,4'-diaminostilbene, biphenyl, fivemembered heterocycles such as triazoles, pyrazolines. oxazoles, imidiazoles, etc., or sixmembered heterocycles (coumarins, naphthalamide, s-triazine, etc.).
  • Cationic, anionic, nonionic, amphoteric and zwitterionic brighteners can be used.
  • Suitable brighteners include those commercially marketed under the trade name Tinopal-UNPA- GX by Ciba Specialty Chemicals Corporation (High Point, NC). Perfume:
  • Preferred compositions include a perfume.
  • the detergent composition may deliver high-quality and long lasting perfume impact on clothes.
  • perfume is used to indicate any odoriferous material that is subsequently released into the aqueous wash solution and/or onto fabrics contacted therewith.
  • the perfume will most often be liquid at ambient temperatures.
  • a wide variety of chemicals are known for perfume uses, including materials such as aldehydes, ketones, and esters.
  • the perfumes herein can be relatively simple in their compositions or can comprise highly sophisticated complex mixtures of chemical components, all chosen to provide any desired odour.
  • the perfume may be of the encapsulated type, such as, shear sensitive encapsulates which deposit on fabrics during the rinse process and are capable of undergoing rupture, later, to release the perfume.
  • the perfume may be a perfume microcapsule, or a moisture-activated perfume microcapsule, comprising a perfume carrier and an encapsulated perfume composition, wherein said perfume carrier may be selected from the group consisting of cyclodextrins, starch microcapsules, porous carrier microcapsules, and mixtures thereof; and wherein said encapsulated perfume composition may comprise low volatile perfume ingredients, high volatile perfume ingredients, and mixtures thereof.
  • the perfume may additionally include a pro-perfume.
  • Pro-perfumes may comprise nonvolatile materials that release or convert to a perfume material as a result of, e.g., simple hydrolysis, or may be pH-change-triggered pro-perfumes (e.g.
  • Fabric Hueing agent may be enzymatically releasable pro-perfumes or light-triggered pro-perfumes.
  • the pro-perfumes may exhibit varying release rates depending upon the pro-perfume chosen.
  • the composition may preferably include a fabric hueing agent (sometimes referred to as shading, bluing or whitening agents).
  • the hueing agent provides a blue or violet shade to fabric.
  • Hueing agents can be used either alone or in combination to create a specific shade of hueing and/or to shade different fabric types. This may be provided for example by mixing a red and green-blue dye to yield a blue or violet shade.
  • Hueing agents may be selected from any known chemical class of dye, including but not limited to acridine, anthraquinone (including polycyclic quinones), azine, azo (e.g., monoazo, disazo, trisazo, tetrakisazo, polyazo), including premetallized azo, benzodifurane and benzodifuranone, carotenoid, coumarin, cyanine, diazahemicyanine, diphenylmethane, fonnazan, hemicyanine, indigoids, methane, naphthalimides, naphthoquinone, nitro and nitroso, oxazine, phthalocyanine, pyrazoles, stilbene, styryl, triarylmethane, triphenylmethane, xanthenes and mixtures thereof.
  • acridine including but not limited to acridine, anthraquinone (including polycyclic quinones
  • Suitable fabric hueing agents include dyes, dye-clay conjugates, and organic and inorganic pigments.
  • Suitable dyes include small molecule dyes and polymeric dyes.
  • Suitable small molecule dyes include small molecule dyes selected from the group consisting dyes falling into the Colour Index (C.l.) classifications of Acid, Direct, Basic, Reactive or hydrolysed Reactive, Solvent or Disperse dyes for example that are classified as Blue, Violet, Red, Green or Black, and provide the desired shade either alone or in combination.
  • suitable small molecule dyes include small molecule dyes selected from the group consisting of Colour Index (Society of Dyers and Colourists, Bradford, UK) numbers Direct Violet dyes such as 9, 35, 48, 51, 66, and 99, Direct Blue dyes such as 1, 71, 80 and 279, Acid Red dyes such as 17, 73, 52, 88 and 150, Acid Violet dyes such as 15, 17, 24, 43, 49 and 50, Acid Blue dyes such as 15, 17, 25, 29, 40, 45, 75, 80, 83, 90 and 113, Acid Black dyes such as 1 , Basic Violet dyes such as 1, 3, 4, 10 19, 35, 38, and 48, Basic Blue dyes such as 3, 16, 22, 47, 65, 66, 67, 71, 75 and 159, Disperse or Solvent dyes, and mixtures thereof.
  • Colour Index Society of Dyers and Colourists, Bradford, UK
  • Direct Violet dyes such as 9, 35, 48, 51, 66, and 99
  • Direct Blue dyes such as 1, 71, 80 and 279
  • suitable small molecule dyes include small molecule dyes selected from the group consisting of C. I. numbers Acid Violet 17, Acid Blue 80, Acid Violet 50, Direct Blue 71, Direct Violet 51, Direct Blue 1, Acid Red 88, Acid Red 150, Acid Blue 29, Acid Blue 113 or mixtures thereof. Process for treating the fabric
  • the detergent composition disclosed herein enable consumers to achieve softening through the wash, in particular the wash sub-cycle of a washing machine.
  • consumers only need to dose the detergent composition, for example the wash basin, prior to or shortly after the start of the washing machine. This can be more convenient to consumers than using a liquid fabric care composition that is separately dispensed into the wash basin after the wash sub cycle is completed, for example prior to, during, or in between rinse cycles.
  • a method for softening fabric comprising, in no particular order, the steps of: (i) providing a fabric in a washing machine or in a hand wash container; (ii) contacting the fabric during a wash cycle of said washing machine or hand wash process with the composition according to the first aspect; (iii) optionally allowing the article or articles to dry or mechanically tumble drying them.
  • the process for treating a fabric involves the steps of providing the fabric in a washing machine.
  • the fabric is contacted during the wash sub-cycle of the washing machine with a composition according to the first aspect of the present invention.
  • a fabric laundering process typically includes a washing step, a rinsing step and a drying step.
  • the washing step employs water and detergent composition comprising anionic surfactant along with other active ingredients to form a wash liquor.
  • the fabric is rinsed one or more times as part of the rinsing step.
  • a typical cycle of operation involves a wash cycle and a rinse cycle.
  • water fills the wash basin either fully or partially.
  • the wash cycle removes or loosens soil from the fabric and suspends that soil in the wash liquor.
  • the wash liquor is drained at the end of the wash cycle.
  • the rinse cycle of a washing machine follows the wash cycle and has a main purpose of rinsing soil, and optionally some benefit agents provided to the wash cycle from the fabric.
  • chelating agent neutralized soap, cationically substituted quaternary ammonium polymer in a carbonate built detergent composition having from 15 wt.% to 40 wt.% carbonate based builder, to provide softening benefit on fabric treated with the composition.
  • a spray-dried solid detergent composition was prepared according to the formulation given in Table 1.
  • the composition was prepared by the slurry route where a solution of the anionic surfactant, sodium carbonate and fillers were prepared and then dried into a solid form in a spray drier. The remaining ingredients were post dosed to obtain the composition as shown in Table 1.
  • the spray-dried solid detergent composition shown in Table 1 was poured in the powder-dispensing drawer of a Samsung automatic top loading machine at a dosage of 3 grams per litre in the wash stage. Approximately 2.7 Kgs of a fabric ballast was added into the washing machine. The fabric consisted of 100% clean polyester. 35 litres water was filled in the washing machine and the ballast was washed by selecting the fuzzy cycle of the washing machine at a wash water temperature of 28°C. The water has a hardness of 24°FH with a Ca:Mg ratio of 2:1. The main wash was followed by 2 rinse cycles. The washed fabric was line dried after each wash.
  • the fabric was washed 15 times, and the softness of the washed and dried fabric was evaluated after 5,10 and 15 washes.
  • the above washing process was similarly conducted for the control.
  • the control composition used for the present study was prepared by adding 1.1 wt% silicone (30% active content) and 0.166 wt% cationic polymer (90% active content) to commercially available Surf Excel Top Load matic liquid.
  • the washed fabric was evaluated by a panel of 15 trained sensory panellists. The panellists assessed the softness of the fabric and scored the softness intensity on a scale from 1 to 10. Where 1 denotes lowest softness score and 10 denotes highest level of softness score. The results were recorded and provided in Table 2 below. Table 1
  • Example 2 The results show that the fabric washed with the detergent composition (Ex 1) according to the present invention showed improved softness as compared to the fabric washed with the conventional marketed detergent composition (Control). The effect is more pronounced after 15 washes, as compared to 5 washes.
  • Example 2
  • compositions were prepared according to the formulation given in Table 3.
  • the composition was prepared by the slurry route where a solution of the anionic surfactant, sodium carbonate and fillers were prepared and then dried into a solid form in a spray drier. The remaining ingredients were post dosed to obtain the composition as shown in Table 3.
  • compositions were evaluated for softness using the method as described above in Example 1.
  • the fabric was washed 15 times, and the softness of the washed and dried fabric was evaluated after 10 and 15 washes.
  • the above washing process was similarly conducted for each composition provided in Table 3.
  • the washed fabric was evaluated by a panel of 15 trained sensory panellists.
  • the panellists assessed the softness of the fabric and scored the softness intensity on a scale from 1 to 10. Where 1 denotes lowest softness score and 10 denotes highest level of softness score. The results were recorded and provided in Table 3.

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Abstract

The present invention relates to a detergent composition. More particularly, the invention is directed to a softening in the wash laundry composition. It is seen that in a carbonate-built detergent composition, the softening properties of a fabric softening component on the fabric reduces over multiple washes and there is a desire to further improve the softening benefits on fabric in wash. Moreover, there is a need to provide softening detergent compositions while maintaining the cleaning performance. It is thus an object of the present invention to provide a detergent composition capable of imparting improved softness and cleaning performance to fabrics treated during the wash cycle of a laundering process. It is found by the present inventors that the presence of a chelating agent and a neutralized soap leads to significantly enhanced fabric softening benefits in a carbonate-built laundry detergent composition having a cationic polymer whilst maintaining good cleaning performance.

Description

DETERGENT COMPOSITION
Field of the invention
The present invention relates to a detergent composition. More particularly, the invention is directed to fabric softening in the wash laundry detergent composition.
Background of the invention
Textile fabrics, including clothes, have traditionally been cleaned with laundry detergents. After cleaning, fabrics may often feel harsh. Consumers prefer fabrics to be clean and with a soft feel.
To prevent harshness experienced after multiple wash cycles, technologies have been developed to improve the softness of fabrics. Various materials providing fabric softening benefit to the laundered fabric are known. The commonly used fabric softening compounds includes clay and silicone. Such softening compounds added in rinse-added conditioner compositions or main-wash laundry detergent composition are widely available commercially.
Laundry detergent composition which simultaneously achieves detergency and softness of the fabric during the laundering process by incorporating fabric softening component that impart a fabric softening benefit to the laundered fabric is described in the following references.
US 2008/0045438 A1 (Unilever, 2008) is directed to a liquid laundry composition which deliver both effective softening and effective cleaning containing a solubilized cationic polymer and a solubilized soap blend.
More recently, EP 1903100 B1 (Unilever, 2009) discloses a detergent tablet composition having a combination of cationic polymer and mixed sodium-potassium soap for providing softness benefits.
Previously published documents disclose detergent composition containing soap, cationic polymer or combinations thereof for delivering softening benefits to fabric. However, it is seen that in a carbonate-built detergent composition, the softening properties of a fabric softening component on the fabric is undermined over multiple washes and opportunity to further improve the softening benefits on fabric in wash remains. Moreover, there is a need to provide softening detergent compositions while maintaining the cleaning performance. It is further desired to provide such a carbonate- built detergent composition which preferably has low levels of phosphate builder and zeolite builder. Although phosphate builders and zeolite builders are preferred for providing good softening benefits and cleaning performance, detergent composition with low levels of phosphate builders are desired as they are environmentally friendly and low levels of zeolite in detergent composition are preferred as zeolites have a tendency to form undesirable cloudy wash liquor upon contact with water and may also form undesirable deposits on fabrics.
It is thus an object of the present invention to provide a detergent composition capable of imparting improved fabric softness and cleaning performance during the wash cycle of a laundering process.
Yet another object of the invention is to provide a detergent composition which achieves improved fabric softening performance in the presence of alkaline builder salts.
A still further object of the present invention is to provide a detergent composition which achieves improved cleaning and fabric softening performance at lower concentration of fabric softening agent.
A need remains for carbonate built solid laundry detergent composition which includes cationic polymer for improving softening delivered on fabrics in the wash cycle of washing machines or during hand wash, without compromising on the cleaning performance.
Summary of the invention
It is found by the present inventors that the presence of a chelating agent and a neutralized soap leads to significantly enhanced fabric softening benefits in a carbonate-built laundry detergent composition having a cationic polymer whilst maintaining good cleaning performance. It is further found that the fabric softening benefits is efficiently delivered in the composition having carbonate-based builders. According to a first aspect of the invention, disclosed is a solid detergent composition comprising: i) a chelating agent; ii) a neutralised soap; iii) a cationically substituted quaternary ammonium polymer; and, iv) 15wt.% to 40wt.% carbonate-based builder.
According to a second aspect of the invention, disclosed is a method for softening fabric comprising, in no particular order, the steps of: i) providing a fabric in a washing machine or in a hand wash container; ii) contacting the fabric during a wash cycle of said washing machine or hand wash process with the composition according to the first aspect; iii) optionally allowing the article or articles to dry or mechanically tumble-drying them. According to a third aspect of the present invention disclosed is use of a chelating agent, cationically substituted quaternary ammonium polymer and neutralised soap in a carbonate built solid detergent composition having from 15wt.% to 40wt.% carbonate- based builder, to provide softening benefit on fabric treated with the composition. Detailed description of the invention
According to a first aspect of the present invention, disclosed is a solid detergent composition which includes a chelating agent, a cationically substituted quaternary ammonium polymer and a neutralised soap. The detergent composition according to the present invention provides a through the wash fabric softening that is convenient for the consumer to dose to the washing machine. Detergent composition
The detergent composition according to the present invention preferably includes from 0 wt.% to 4 wt.% phosphate builder. Preferably the detergent composition according to the present invention is a non-phosphate built laundry detergent formulation, i.e., preferably it contains less than 4 wt.%, still preferably less than 3 wt.%, further preferably less than 2 wt.%, more preferably contains less than 1 wt.% of phosphate builder material. In this art the term 'phosphate' includes diphosphate or triphosphate species. The detergent composition is predominantly carbonate built, i.e. the weight% of sodium carbonate is greater than the weight % of the sum of other builder material present, preferably the amount of other builder material is less than 30 wt.%, more preferably less than 15 wt.%, still preferably less than 10 wt.%, still further preferably less than 5% of the weight% level of sodium carbonate.
The composition of the present invention can be made via a variety of conventional methods known in the art. These methods include but is not limited to homogenous mixing of ingredients, including dry-mixing; compaction techniques such as agglomerating, extrusion, tabletting; spray-drying a slurry of the ingredients, or a mixture of one or more of these techniques. The various components added to the detergent composition of the present invention may also made by for various conventional methods for example compaction, including extrusion and agglomerating, or spray-drying. The detergent composition is preferably prepared by the technique of slurry making and spray drying.
The composition is in the form of a solid detergent composition. Preferably they are main wash detergent composition. It can take the form of a detergent composition for the main wash, which may be dilutable or non-dilutable. The detergent composition herein can take a variety of physical solid forms which includes forms such as powder, particulate, granule, ribbon, noodle, paste, tablet, flake, pastille and bar, and preferably the composition is in the form of powder, granules or a tablet, still preferably the detergent composition is in the form of a powder or particulate. Further preferably the composition is in the form of a spray-dried powder or particulate.
The composition of the present invention preferably has a density of more than 350 grams/litre, more preferably more than 450 grams/litre or even more than 570 grams/litre.
The detergent composition according to the present invention usually has an alkaline pH, generally in the region of pH 9 to 12.5 when measured with a 1wt% dilution in de- ionised water at 25°C, which is achieved by the presence of sodium carbonate and other alkaline salts especially sodium silicates such as the meta-, neutral or alkaline silicates, preferably at levels up to about 35 wt.% of the composition. More preferably the detergent composition has a pH from 9 to 11, still preferably from 9 to 10.5. Most preferably the pH is from 10.3 to 10.8.
Chelating agent:
According to the first aspect of the present invention disclosed detergent composition includes a chelating agent. Preferably the chelating agent is selected from the group consisting of amino carboxylates, phosphonates or mixtures thereof.
Chelating agent as used herein includes those chemicals which interact with divalent ions, cations and anions, having tendency to precipitate in their saturated aqueous solutions. Chelating agents through threshold inhibition act as catalyst to delay the precipitation reaction of these ions in their saturated aqueous solutions. In the present context the term "chelating agent" comprises the catalyst, a cation of calcium and / or magnesium ions and carbonate anions. Throughout this document the terms chelating agent and crystal growth inhibitor are used interchangeably.
Useful amino carboxylate chelating agents includes, but are not limited to, the following: N-(1,2-dicarboxy- ethyl)-D,L-aspartic acid (IDS), N-(2- hydroxyethyl)iminodiacetic acid (EDG), aspartic acid-N- monoacetic acid (ASMA), aspartic acid- N,N-diacetic acid (ASDA), aspartic acid-N- mono- propionic acid (ASMP), iminodisuccinic acid (IDA), N- (2-sulfomethyl) aspartic acid (SMAS), N- (2-sulfoethyl) aspartic acid (SEAS), N- (2- sulfomethyl) glutamic acid (SMGL), N- (2- sulfoethyl) glutamic acid (SEGL), N- methyliminodiacetic acid (MIDA), a- alanine-N,N- diacetic acid (a - ALDA) , serine-N,N-diacetic acid (SEDA), isoserine-N,N-diacetic acid (ISDA), phenylalanine-N,N-diacetic acid (PHDA) , anthranilic acid- N ,N - diacetic acid (AND A), sulfanilic acid-N, N-diacetic acid (SLDA) , taurine-N, N-diacetic acid (TUDA), sulfomethyl- N, N-diacetic acid (SMDA), N-(hydroxyethyl)-ethylidenediaminetriacetate (HEDTA), diethanolglycine (DEG), aminotris(methylenephosphonic acid) (ATMP).
The preferred chelating agent may contain an amino group and may be, e.g., an amino-polycarboxylate or a phosphonate. It may be a monomeric molecule comprising one, two or three amino groups (typically secondary or tertiary amino groups), and it may contain two, three, four or five carboxyl groups or even more carboxyl groups. The chelating agents may be phosphorus containing or without phosphorus. Suitable chelating agents includes those based on carboxylate groups includes EDTA (ethylene diamine tetraacetate), NTA (2,2',2"-nitrilotriacetate), citrate, 2-hydroxypropan- 1,2,3-tricarboxylate, DTPA (diethylenetriaminepentaacetic acid), MGDA (methylglycinediacetic acid OT N,N'-bis(carboxymethyl)alanine), EGTA (ethylene glycol tetraacetic acid), EDDS (ethylenediamine- N,W-disuccinic acid),, GLDA (L-Glutamic acid, N, N-diacetic acid), The composition preferably may also include other polycarboxylates such as PAA [poly(acrylic acid)], PAA/PMA [copoly(acrylic acid/maleic acid)], or mixtures thereof.
Another group of preferred chelating agents includes phosphonates. Aminoalkane and/or hydroxyalkane phosphonates are preferably used as phosphonates. Suitable examples of these phosphonate chelating agent includes HEDP (l-hydroxyethylidene- 1,1-diphosphonic acid), EDTMP [ethylenediamine tetra(methylene phosphonic acid], EDTMPA (ethylenediaminetetramethylene- tetraphosphonic acid), DTPMP (diethylenetriamine penta (methylene phosphonic acid), DTMPA (diethylenetriaminepenta(methylenephosphonic acid)) nitrilotris(methylenephosphonic acid) (NTMP), 2-phosphonobutane-1,2,4-tricarboxylic acid (PBTC), ethylenediamine tetramethylene phosphonate (EDTMP), and the higher homologs thereof. Among the hydroxyalkane phosphonates, 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance. The chelating agents may contain nitrogen such as in EDTA, NTA, DTPA, PDTA, GLDA, MGDA, EDDS, EDTMP, EDTMPA, and DTPMP or ASMA, ASDA, ASMP, IDA, SMAS, SEAS, SMGL, SEGL, MIDA, a-ALDA, SEDA, ISDA, PHDA, ANDA, SLDA, TUDA, SMDA, HEDTA, DEG, ATMP, or mixtures thereof.
Particularly preferred chelating agents includes but are not limited to the following: ethylene- diamine- tetra- acetic acid (EDTA), diethylene triamine penta methylene phosphonic acid (DTMPA, DTPMP), hydroxy-ethane diphosphonic acid (HEDP), ethylenediamine N,N- disuccinic acid (EDDS), methyl glycine di-acetic acid (MGDA), diethylene triamine penta acetic acid (DTPA), propylene diamine tetraacetic acid (PDTA), 2-hydroxypyridine-N-oxide (HPNO), methyl glycine diacetic acid (MGDA), glutamic acid N,N-diacetic acid (N,N-dicarboxymethyl glutamic acid tetrasodium salt (GLDA) and nitrilotriacetic acid (NTA) or mixtures thereof. The chelating agent may be present in their acid form or a salt, preferably the chelating agents may be present as a sodium, ammonium or potassium salt.
Especially preferred chelating agent includes diethylenetriamine pentacetic acid (DTPA), ethylenediamine-N, N’-disuccinic acid (EDDS) and 1,1 hydroxyethane diphosphonic acid (HEDP) or the alkali metal, potassium, alkaline earth metal, ammonium or substituted ammonium salts thereof, or mixtures thereof. The most preferred chelating agent is a phosphonate. The phosphonate chelating agent includes HEDP in its acid form or salt form with alkali metal, potassium, alkaline earth metal, ammonium or substituted ammonium. In the detergent composition according to the present invention, the chelating agent is preferably present in an amount from 0.1 wt.% to 10 wt.%, still preferably from 0.1 wt.% to 5 wt.%, preferably from 0.1 wt.% to 3 wt.%, more preferably from 0.1 wt.% to 1 wt.%.
Preferably the detergent composition comprises at least 0.2 wt.% chelating agent based on the weight of the detergent composition, still preferably at least 0.3 wt.%, still preferably at least 0.5 wt.%, most preferably at least 0.6 wt.%, but typically not more than 3 wt.%, still preferably not more than 2 wt.%, most preferably not more than 1 wt.% of the chelating agent according to the present invention. Neutralised soap:
Disclosed solid detergent composition includes a neutralized soap. Soaps are the fatty acid salts having the general formula (I) R3CO-OX . Formula (I) where R3CO = is a linear or branched, saturated or unsaturated acyl group containing 6 to 22 and preferably 12 to 18 carbon atoms
X is alkali and/or alkaline earth metal, ammonium, alkylammonium or alkanolammonium.
Typical examples are the sodium, potassium, magnesium, ammonium and triethanolammonium salts of caproic acid, caprylic acid, 2-ethylhexanoic acid, capric acid, lauric acid, isotridecanoic acid, myristic acid, palmitic acid, palmitoleic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, petroselic acid, linoleic acid, linolenic acid, elaeostearic acid, arachic acid, gadoleic acid, behenic acid and erucic acid and technical mixtures thereof. Cocofatty acid or palm kernel oil fatty acid in the form of their salts are preferably used.
Water-soluble salts of the higher fatty acids (i.e. "soaps") containing from about 8 to about 24 carbon atoms and preferably from about 10 to about 20 carbon atoms are useful, still preferred are those with 10 to 12 carbon atoms, and those with 16 to 18 carbon atoms. The soaps are either sodium, potassium, ammonium and alkanolammonium salts of higher fatty acids. Soaps can be made by direct saponification of fats and oils or by the neutralization of free fatty acids. Particularly useful are the sodium and potassium salts of the mixtures of fatty acids derived from coconut oil and tallow, i.e., sodium or potassium tallow and coconut soap.
In the detergent composition according to the present invention, the neutralized soap is preferably present in an amount from 5 wt.% to 30 wt.%, preferably from 8 wt.% to 25 wt.%, more preferably from 10 wt.% to 20 wt.%.
Preferably the detergent composition comprises at least 8 wt.% neutralized soap based on the weight of the detergent composition, still preferably at least 9 wt.%, still preferably at least 9.5 wt.%, most preferably at least 10 wt.%, more preferably at least 12 wt.% but typically not more than 25 wt.%, still preferably not more than 20 wt.%, most preferably not more than 15 wt.% of the neutralized soap. Cationically substituted quaternary ammonium polymer:
Disclosed detergent composition includes a cationically substituted quaternary ammonium polymer. The cationically substituted quaternary ammonium polymer provides the benefit of a deposition aid. The cationically substituted quaternary ammonium polymer may preferably be selected from the list of Polyquaternium as named under the International Nomenclature for Cosmetic Ingredients and including those ranging from Polyquaternium 1 to Polyquaternium 101 as provided in Table 2 of WO2017/143174 A1 and incorporated herein by reference.
Preferably the cationically substituted quaternary ammonium polymer is selected from the group consisting of Polyquaternium 4, Polyquaternium 7, Polyquaternium 10, Polyquaternium 16, Polyquaternium 22, Polyquaternium 24, Polyquaternium 29, Polyquaternium 37, Polyquaternium 43, Polyquaternium 53, Polyquaternium 63, Polyquaternium 67, Polyquaternium 69, Polyquaternium 72 and Polyquaternium 90.
Preferably the polymer is a polysaccharide, preferably a natural polysaccharide. Preferably the polysaccharide is selected from the group consisting of cellulose, guar gum, chitosan, alginates, starch, xanthan, dextrans, arabic gum, galactomannan, carrageenan, hyaluronates and combinations thereof. Preferably these polysaccharides can be employed with cationic modification and alkoxy-cationic modifications such as cationic hydroxethyl or cationic hydroxypropyl. Cationic polysaccharides have a molecular weight from about 1 ,000 to about 2 million, preferably from 20 about 100,000 to about 800,000. Cationic starches refer to starch that has been chemically modified to provide the starch with a net positive charge in aqueous solution at pH 3. This chemical modification includes, but is not limited to, the addition of amino and/or ammonium group(s) into the starch molecules. Non-limiting examples of these ammonium groups may include substituents such as trimethylhydroxypropyl ammonium chloride, dimethylstearylhydroxypropyl ammonium chloride, or dimethyldodecylhydroxypropyl ammonium chloride. The cationic starches may comprise amylase, amylopectin, or maltodextrin. The cationic starch may comprise one or more additional modifications. For example, these modifications may include cross-linking, stabilization reactions, phophorylations, hydrolyzations, cross-linking. Stabilization reactions may include alkylation and esterification. Suitable cationic starches for use in the present compositions are commercially-available from Cerestar under the trade name C*BOND® and from National Starch and Chemical Company under the trade name CATO® 2A. Cationic galactomannans include cationic guar gums or cationic locust bean gum. An example of a cationic guar gum is a quaternary ammonium derivative of Hydroxypropyl Guar such as those sold under the trade name Jaguar C13 and Jaguar Excel available from Rhodia, Inc of Cranbury NJ and N-Hance by Aqualon, Wilmington, DE. Other suitable polymers include cationic guar gum derivatives, quaternary nitrogen-containing cellulose ethers, synthetic polymers, copolymers of etherified cellulose, guar and starch. Suitable cationic polymers are described in U.S. Pat. Nos. 3,962,418; 3,958,581; and U.S. Publication No. 2007/0207109A 1.
More preferably the cationically substituted quaternary ammonium polysaccharide is selected from cationically modified hydroxyethyl cellulose, cationically modified hydroxypropyl cellulose, cationically and hydrophobically modified hydroxyethyl cellulose, cationically and hydrophobically modified hydroxypropyl cellulose, or a mixture thereof, more preferably cationically modified hydroxyethyl cellulose, cationically and hydrophobically modified hydroxyethyl cellulose, or a mixture thereof.
The cationically substituted quaternary ammonium polymer preferably has a cationic charge density more than about 0.05 meq/g (meq meaning milliequivalents), to 23 meq/g, preferably from about 0.1 meq/g to about 4 meq/g, even more preferably from about 0.1 meq/g to about 2 meq/g and most preferably from 0.1 meq/g to about 1 meq/g. The above referenced cationic charge densities can be at the pH of intended use, which can be a pH from 3 to 12, optionally about 8 to 10. Cationic charge density of a polymer refers to the ratio of the number of positive charges on the polymer to the molecular weight of the polymer. Charge density is calculated by dividing the number of net charges per repeating unit by the molecular weight of the repeating unit. The positive charges may be located on the backbone of the polymers and/or the side chains of polymers.
The charge density relates to the degree of cationic substitution and can be expressed with nitrogen content of the cationic polymer. Preferred are cationically substituted quaternary ammonium polymer having a nitrogen content % from 0.01 to 2.2%, more preferred are cationically substituted quaternary ammonium polymers having a nitrogen content from 0.2 to 1.6%, and most preferred are cationically substituted quaternary ammonium polymers having a nitrogen content from 0.3 to 1.4%.
The weight-average molecular weight of the cationically substituted quaternary ammonium polymer may be from about 500 to about 5,000,000, or from about 1 ,000 to about 2,000,000, or from about 5000 to about 1 ,000,000 Daltons, as determined by size exclusion chromatography relative to polyethyleneoxide standards with Rl detection. In one aspect, the weight-average molecular weight of the cationically substituted quaternary ammonium polymer may be from about 100,000 to about 800,000 Daltons. Without wishing to be bound by theory, it is believed that polymers that are too high in mass can entrap soils and prevent them from being removed. In a preferred embodiment of the present invention, the use of cationically substituted quaternary ammonium polymers with a weight average molecular weight of less than about 850,000 daltons is preferred, and even more preferred those with weight average molecular weight of less than 500,000 daltons. The preferred minimum average molecular weight is about 10,000 daltons, because smaller molecules are believed to be too small to give an effective softening benefit.
Preferably the composition includes other polymers which are cationic or amphoteric, polysaccharides, proteins and synthetic polymers.
Particularly preferred are cationic cellulosic polymers with substituted anhydroglucose units that correspond to the general Structural Formula as follows:
Figure imgf000013_0001
wherein R1, R2, R3are each independently selected from H, CH3, Cs-24 alkyl (linear or branched),
Figure imgf000013_0004
n is from about 1 to 10;
Rxis selected from the group consisting of H, CH3, Cs-24 alkyl (linear or branched),
OH R7
I I +
— CH-JCHCHT N- RJ Z
Figure imgf000013_0002
or mixture thereof, wherein Z is a water soluble anion, preferably a chlorine ion and/or a bromine ion; R5 is H, CH3, CH2CH3 or mixtures thereof; R7 is CH3, CH2CH3, a phenyl group, Cs-24 alkyl (linear or branched), or mixture thereof; and R8and R9are each independently CH3, CH2CH3, a phenyl group, or mixtures thereof: with the provisio that at least one of R1 , R2and R3per anhydroglucose unit is
OH R
I I + 9
— CH2CHCH2-N- R- z
Figure imgf000013_0003
J « and each polymer has at least one group.
The charge density of the cationic celluloses herein (as defined by the number of cationic charges per 100 anhydroglucose units) is preferably from about 0.5 % to about 60%, more preferably from about 15 1% to about 20%, and most preferably from about 2% to about 10%. Alkyl substitution on the anhydroglucose rings of the polymer ranges from about 0.01% to 5% per glucose unit, more preferably from about 0.05% to 2% per glucose unit, of the polymeric material. The cationic cellulose may lightly cross-linked with a dialdehyde such as glyoxyl to prevent forming lumps, nodules or other agglomerations when added to water at ambient temperatures. Particularly preferred are the cationically substituted quaternary ammonium polysaccharide which has the formula (I)
Figure imgf000014_0001
where, x is from 0 to 3 and the ratio of y:n is in the range from 0.01 to 0.5 (i.e. n:y is from 100 to 2), provided that y =n, are excluded.
The ratio of un-quaternised to quaternized sugar units (n:y) is preferably in the range from 3 to 30, more preferably from 4 to 25, most preferably from 5 to 20. The level of nitrogen in the polymer of formula (I) is in the range from 0.1 to 1.5%, more preferably from 0.3 to 1.3% and most preferably from 0.5 to 1.1% by weight.
The molecular weight of the cationically substituted quaternary ammonium polysaccharide of formula (I) is from 1,000 to 1,000,000 kDa, preferably from 5,000 to 750,000 kDa, more preferably from 10,000 to 5000, 000 kDa. Mixtures of polymers may be used. The polymers are linear in structure.
Most preferably the cationically substituted quaternary ammonium polymer is a cationically substituted quaternary ammonium polysaccharide. Preferred example of cationic polysaccharide is a cationic cellulose derivative. Preferably a quaternary ammonium salt of modified cellulose, still preferably a quaternary ammonium salt of hydroxy cellulose. Examples of cationic hydroxyalkyl cellulose include those with the I NCI name Polyquaternium 10 such as those sold under the trade names Ucare Polymer JR 30M, JR 400, JR 125, LR 400 and LK 400, Polymer PK polymers; Polyquaternium 67 such as those sold under the trade name Soltcat SK TM, all of which are marketed by Dow Chemicals, Midlad Ml, and Polyquaternium 4 such as those sold under the trade name Celquat H200 and Celquat L-20025 available from National Starch and Chemical Company, Bridgewater, NJ. Other suitable polysaccharides include Hydroxyethyl cellulose or hydoxypropylcellulose quaternized with glycidyl C12-C22 alkyl dimethyl ammonium chloride. Examples of such polysaccharides include the polymers with the I NCI names Polyquaternium 24 such as those sold under the trade name Quaternium LM 200 by Dow Chemicals of Midland, ML. Most preferably the example of polyquaternium 10 is UCARE™ Polymer, for example types JR-400 and LR-400 (all ex Dow,) and their copolymers. The most preferred is UCARE™ Polymer LR-400.
One group of suitable optional cationic polymers preferably includes those produced by polymerization of ethylenically unsaturated monomers using a suitable initiator or catalyst, such as those disclosed in WO 00/56849 and USPN 6,642,200. Suitable cationic polymers may be selected from the group consisting synthetic polymers made by polymerizing one or more cationic monomers selected from the group consisting of N,N-dialkylaminoalkyl acrylate, N,N-dialkylaminoalkyl methacrylate, N,N- dialkylaminoalkyl acrylamide, N,N-dialkylaminoalkylmethacrylamide, quaternized N, N dialkylaminoalkyl acrylate quaternized N,N-dialkylaminoalkyl methacrylate, quaternized N,N-dialkylaminoalkyl aeryl amide, quaternized N,N-5 dialkylaminoalkyl methacrylamide, Methacryloamidopropyl-pentamethyl-1,3-propylene-2-olammonium dichloride, N , N , N , N', N', N", N"-heptamethyl-N"-3-(1 -oxo-2-methyl-2- propenyl)aminopropyl-9- oxo-g-azo-decane-1, 4, 10-triammonium trichloride, vinylamine and its derivatives, allylamine and its derivatives, vinyl imidazole, quaternized vinyl imidazole and diallyl dialkyl ammonium chloride and combinations thereof, and optionally a second monomer selected from the group consisting of acrylamide, N,N- dialkyl acrylamide, methacrylamide, N.Ndialkylmethacrylamide, C1-C12 alkyl acrylate, C1-C12 hydroxyalkyl acrylate, polyalkylene glyol acrylate, C1-C12 alkyl methacrylate, Ci- C12 hydroxyalkyl methacrylate, polyalkylene glycol methacrylate, vinyl acetate, vinyl alcohol, vinyl formamide, vinyl acetamide, vinyl alkyl ether, vinyl pyridine, vinyl pyrrolidone, vinyl imidazole, vinyl caprolactam, and derivatives, acrylic acid, methacrylic acid, maleic acid, vinyl sullonic acid, styrene sullonic acid, acrylamidopropylmethane sulfonic acid (AMFS) and their salts. The polymer may optionally be branched or cross-linked by using branching and crosslinking monomers. Branching and crosslinking monomers include ethylene glycoldiacrylate divinylbenzene, and butadiene. A suitable polyethyleneinine useful herein is that sold under the tradename Lupasol® by BASF, 20 AG, Lugwigschaefen, Germany. The optional cationic polymer may be also selected from the group consisting of polyethylene imine and its derivatives, poly(acrylamide-codiallyldimethylanunonium chloride), poly(acrylamide-methacrylamidopropyltrimethyl ammonium chloride), poly(acrylamide-co-N,N-dimethyl aminoethyl acrylate) and its quaternized derivatives, poly(acrylamide-co-N,N-dimethyl anunoethyl methacrylate) and its quaternized derivative, poly(hydroxyethylacrylate-co-dimethyl aminoethyl methacrylate), poly(hydroxpropylacrylate-co-dimethyl aminoethyl methacrylate), poly(hydroxpropylacrylatediallyldimethylammonium chloride-co-acrylic acid), co- methacrylamidopropyltrimethylammonium chloride), poly(acrylamide-copoly(acrylamide methacrylamidopropyltrimethyl ammonium chloride-co-acrylic acid), poly(diallyldimethyl ammonium chloride), poly(vinylpyrrolidone-co-dimethylaminoethyl methacrylate), poly(ethyl methacrylate-co-quaternized dimethylaminoethyl methacrylate), poly(ethyl methacrylate-co-oleyl methacrylate-co-diethylaminoethyl methacrylate), poly(diallyldimethylanunonium chloride-co-acrylic acid), poly(vinyl pyrrol idone-co- quaternized vinyl imidazole) and poly(acrylamide-co-Methacryloamidopropyl- pentamethy1-1,3-propylene-2-ol-ammonium dichloride).
Preferably the detergent composition may include optional cationic polymer such as polyethyleneimine or a polyethyleneimine derivative, a cationic acrylic based polymer, a cationic polyacrylamide, polyacrylamide and polymethacrylamidoproply trimethylammonium cation, poly(acrylamide- N-dimethyl aminoethyl acrylate) and its quaternized derivatives, poly(acrylamide-co- methacrylamidopropyltrimethyl ammonium chloride). Other additional cationic polymer includes those sold under the tradename SEDIPUR, available from BTC Specialty Chemicals, a BASF Group, Florham Park, 15 N.J. and those sold under the tradename RHEOVIS CDE, available from Ciba
Specialty Chemicals, a BASF group, Florham Park, N.J., or as disclosed in USPA 2006/0252668.
The cationic polymer can be provided in a powder form. The cationic polymer can be provided in an anhydrous state. In a preferred embodiment of the present invention, the cationic polymer is contained in a co-granule. Preferably the co-granule comprises a binder, in addition to the cationic polymer. More preferably the co-granule also comprises either an organic or an inorganic salt. Preferred binder materials are polyethylene glycol, soaps, and fatty acids. A preferred organic salt is sodium citrate, and a preferred inorganic salt is sodium sulphate.
In the detergent composition according to the present invention, the cationically substituted quaternary ammonium polymer is preferably present in an amount from 0.001 wt.% to 5 wt.%, preferably from 0.01 wt.% to 5 wt.%, more preferably from 0.05 wt.% to 5 wt.%, most preferably from 0.05 wt.% to 3 wt.%.
Preferably the detergent composition comprises at least 0.005 wt.% cationically substituted quaternary ammonium polymer based on the weight of the detergent composition, still preferably at least 0.01 wt.%, still preferably at least 0.05 wt.%, most preferably at least 1 wt.%, more preferably at least 2 wt.% but typically not more than 4.5 wt.%, still preferably not more than 4 wt.%, most preferably not more than 3 wt.% of the cationically substituted quaternary ammonium polymer.
Carbonate based builder
Disclose detergent composition is carbonate built solid composition. The term “carbonate(s)” as used herein refers to alkali metal or ammonium salts of carbonate, bicarbonate, and/or sesquicarbonate. Preferably, the carbonate is selected from the group consisting of carbonate salts of sodium, potassium and lithium, more preferably, salts of sodium or potassium and most preferably, salts of sodium. Most preferably, the carbonate includes at least one of sodium carbonate, sodium bicarbonate.
The detergent composition according to the present invention includes from 15 wt.% to 40 wt.% carbonate-based builder. The detergent composition preferably includes from
12 wt.% to 35 wt.% carbonate-based builder, still preferably from 20 wt.% to 35 wt.% still preferably from 20 wt.% to 30 wt.% carbonate-based builder.
Preferably the detergent composition comprises at least 8 wt.% carbonate builder based on the weight of the detergent composition, still preferably at least 10 wt.%, still preferably at least 15 wt.%, most preferably at least 18 wt.%, still more preferably at least 20 wt.%, but typically not more than 35 wt.% , still preferably not more than 30 wt.%, most preferably not more than 28 wt.% of the carbonate based builder. Further ingredients
Surfactants:
In the case of a detergent composition for laundering fabrics, the composition typically comprises one or more detersive synthetic non-soap surfactants. In the detergent composition of the present invention, suitable detersive surfactant is chosen from anionic surfactant, nonionic surfactant, cationic surfactant, zwitterionic surfactant, amphoteric surfactant and mixtures thereof. Many suitable surface-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. Suitable detersive surfactants may be linear or branched, substituted or un-substituted, and may be derived from petrochemical material or biomaterial.
Suitable anionic surfactant includes sulphonate and sulphate detersive surfactants. Examples of such sulphonate detersive surfactants include methyl ester sulphonate, alpha olefin sulphonates, alkyl benzene sulphonates, especially alkyl benzene sulphonates, preferably Cio to C alkyl benzene sulphonate. Suitable alkyl benzene sulphonate (LAS) is obtainable, preferably obtained, by sulphonating commercially available linear alkyl benzene (LAB); suitable LAB includes low 2-phenyl LAB, other suitable LAB includes high 2-phenyl LAB, such as those supplied by Sasol under the tradename Hyblene®. The alkyl benzene sulphonates may be linear or branched, substituted or un-substituted, and may be derived from petrochemical material or biomaterial.
Examples of sulphate detersive surfactants include alkenyl sulfate, alkyl ether sulfate, alkyl ethoxy sulfate, sodium lauryl ether sulfate (SLES), primary alcohol sulphate, alkenyl sulfate, alkyl sulphate, preferably Cs to Cie alkyl sulphate, or predominantly C12 alkyl sulphate. The alkyl sulphate may be linear or branched, substituted or un- substituted, and may be derived from petrochemical material or biomaterial.
Preferably the sulphate detersive surfactant is alkyl alkoxylated sulphate, preferably alkyl ethoxylated sulphate, preferably a Cs to Cis alkyl alkoxylated sulphate, preferably a Cs to Cis alkyl ethoxylated sulphate, preferably the alkyl alkoxylated sulphate has an average degree of alkoxylation of from 0.5 to 20. preferably from 0.5 to 10, preferably the alkyl alkoxylated sulphate is a Cs to Cis alkyl ethoxylated sulphate having an average degree of ethoxylation of from 0.5 to 10, preferably from 0.5 to 5. more preferably from 0.5 to 3 and most preferably from 0.5 to 1.5. The alkyl alkoxylated sulphate may be linear or branched, substituted or un-substituted, and may be derived from petrochemical material or biomaterial.
Other suitable anionic detersive surfactants include alkyl ether carboxylates. Suitable anionic detersive surfactants may be in salt form, suitable counter-ions include sodium, calcium, magnesium, amino alcohols, and any combination thereof. A preferred counterion is sodium.
Suitable anionic surfactants comprising one or more anionic groups selected from sulfonate and sulfate. Examples of such anionic surfactants include and combinations thereof. More preferably, anionic surfactants selected from sodium dodecyl benzene sulfonate (Na-LAS), sodium dodecyl sulfate (SDS), sodium lauryl ether sulfate (SLES), methyl ester sulfate (MES), primary alcohol sulfate (PAS), alpha olefin sulfonate and combinations thereof. The compositions of the invention may for example contain linear alkylbenzene sulphonate, particularly linear alkylbenzene sulphonates having an alkyl chain length of CstoCis. It is preferred if the level of linear alkylbenzene sulphonate is from 0 wt% to 30 wt%, more preferably 1 wt% to 25 wt%, most preferably from 2 wt% to 15 wt%.
The compositions of the invention may also contain non-ionic surfactant. Nonionic surfactants that may be used include the primary and secondary alcohol ethoxylates, especially the Cs to C20 aliphatic alcohols ethoxylated with an average of from 1 to 20 moles of ethylene oxide per mole of alcohol, and more especially the C10 to C15 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 alkylpolyglycosides, glycerol monoethers, and polyhydroxyamides (glucamide).
It is preferred if the level of non-ionic surfactant is from 0 wt% to 30 wt%, preferably from 1 wt% to 25 wt%, most preferably from 2 wt% to 15 wt%. It is also possible to include certain mono-alkyl cationic surfactants which can be used in main-wash compositions for fabrics. Cationic surfactants that may be used include quaternary ammonium salts of the general formula RIR2RSR4N+X wherein the R groups are long or short hydrocarbon chains, typically alkyl, hydroxyalkyl or ethoxylated alkyl groups, and X is a counter-ion (for example, compounds in which Ri is a CstoC22 alkyl group, preferably a Cs to C10 or C12 to CM alkyl group, R2IS a methyl group, and R3 and R4, which may be the same or different, are methyl or hydroxyethyl groups); and cationic esters (for example, choline esters). The choice of surface-active compound (surfactant), and the amount present, will depend on the intended use of the detergent composition. In fabric washing compositions, different surfactant systems may be chosen, as is well known to the skilled formulator, for handwashing products and for products intended for use in different types of washing machine.
The total amount of surfactant present will also depend on the intended end use and may be as high as 60 wt.%, for example, in a composition for washing fabrics by hand. Detergent compositions suitable for use in most automatic fabric washing machines generally contain anionic non-soap surfactant, or non-ionic surfactant, or combinations of the two in any suitable ratio, optionally together with soap.
In compositions for machine washing of fabrics, an amount of from 5 wt.% to 40 wt.% is generally appropriate. Typically, the compositions will comprise at least 2 wt.% surfactant e.g. 2 wt.% to 60 wt.%, preferably 15 wt.% to 40 wt.% most preferably 25 wt.% to 35 wt.%.
Builders:
The composition according to the present invention may also contain one or more additional detergency builders.
Inorganic builders that may be present in addition to carbonate- based builder (sodium carbonate), includes crystalline and amorphous aluminosilicates, for example, zeolites as disclosed in GB 1473201 (Henkel), amorphous aluminosilicates as disclosed in GB 1473202 (Henkel) and mixed crystalline/amorphous aluminosilicates as disclosed in GB 1470250 (Procter & Gamble); and layered silicates as disclosed in EP 164514B (Hoechst). The compositions of the invention preferably contain an alkali metal, preferably sodium, aluminosilicate builder. The alkali metal aluminosilicate may be either crystalline or amorphous or mixtures thereof, having the general formula: 0.8 to 1.5 Na20.AI203. 0.8 to 6 Si02. These materials contain some bound water and are required to have a calcium ion exchange capacity of at least 50 mg CaO/g. The preferred sodium aluminosilicates contain 1.5 to 3.5 Si02 units (in the formula above). Both the amorphous and the crystalline materials can be prepared readily by reaction between sodium silicate and sodium aluminate, as amply described in the literature. Suitable crystalline sodium aluminosilicate ion-exchange detergency builders are described, for example, in GB 1429143 (Procter & Gamble). The preferred sodium aluminosilicates of this type are the well-known commercially available zeolites A and X, and mixtures thereof.
The zeolite may be the commercially available zeolite 4A now widely used in laundry detergent powders. However, according to a preferred embodiment of the invention, the zeolite builder incorporated in the compositions of the invention is maximum aluminium zeolite P (zeolite MAP) as described and claimed in EP 384070A (Unilever). Zeolite MAP is defined as an alkali metal aluminosilicate of the zeolite P type having a silicon to aluminium ratio not exceeding 1.33, preferably within the range of from 0.90 to 1.33, and more preferably within the range of from 0.90 to 1.20.
Especially preferred is zeolite MAP having a silicon to aluminium ratio not exceeding 1.07, more preferably about 1.00. The calcium binding capacity of zeolite MAP is generally at least 150 mg CaO per g of anhydrous material.
Zeolites are preferably present in the composition in an amount ranging from 0 wt.% to 5 wt.% of the composition. Preferably the detergent composition has less than 4 wt.%, still preferably less than 3 wt.%, further preferably less than 2 wt.%, still further preferably less than 1 wt.% of zeolite in the composition. The composition may even be substantially free of zeolite builder; substantially free means "no deliberately added"..
Optionally, organic builders such as citrates, suitable used in amounts of from 1wt.% to 30 wt.%, preferably 5 wt.% to 30 wt%, preferably from 5 wt.% to 15 wt.%, still preferably from 5 wt.% to 10 wt.% are used. Preferably the amount of citric acid and citrates in the composition is from 1 wt.% to 5 wt.%. Water-soluble, non-phosphorus organic builders useful herein include the various alkali metal, ammonium and substituted ammonium polyacetates, carboxylates, polycarboxylates and polyhydroxy sulfonates. Suitable non-phosphorus, inorganic builders include the silicates, aluminosilicates, borates and carbonates, such as sodium and potassium carbonate, bicarbonate, sesquicarbonate, tetraborate decahydrate, and silicates having a weight ratio of S1O2 to alkali metal oxide of from about 0.5 to about 4.0, or from about 1.0 to about 2.4.
In addition, the detergents may contain layer silicates. Typical examples are crystalline, layered sodium silicates corresponding to the general formula NaMSixC>2x+i.yH20, where M is sodium or hydrogen, x is a number of 1.9 to 4 and y is a number of 0 to 20, preferred values for x being 2, 3 or 4. Crystalline layer silicates such as these are described, for example, in European patent application EP 0 164514 A1. Preferred crystalline layer silicates corresponding to the above formula are those in which M is sodium and x assumes the value 2 or 3. Both b- and delta-sodium disilicates I ^ShOs.ykhO are particularly preferred, b -sodium disilicate being obtainable, for example, by the process described in International patent application WO 91/08171. Other suitable layered silicates are known, for example, from patent applications DE 2334899 M, EP 0026529 M and DE 3526405 M. The suitability of these layered silicates is not limited to a particular composition or structural formula.
Amorphous sodium silicates with a modulus (Na20:Si02 ratio) of 1:2 to 1:3.3, preferably 1 :2 to 1 :2.8 and more preferably 1 :2 to 1 :2.6 which dissolve with delay and exhibit multiple wash cycle properties may also be used. Compacted amorphous silicates, compounded amorphous silicates and overdried X-ray- amorphous silicates are particularly preferred. The term "silicate(s)" as used herein refers to alkali metal silicates. Preferably, the silicate used is selected from the group consisting of silicate salts of sodium, potassium and lithium (more preferably, salts of sodium or potassium; most preferably, salts of sodium). More preferably, the silicate used in the composition (if any) is sodium disilicate. Preferably, the builder used in the composition of the present invention includes a silicate. Preferably, when the builder used in composition of the present invention includes a silicate, the composition preferably, comprises 0 wt.% to 20 wt% preferably, 0.1 wt.% to 10 wt.%, more preferably, 1 wt.% to 10 wt.%, most preferably 2 wt.% to 10 wt.% of the silicate(s).
Builders, both inorganic and organic, are preferably present in alkali metal salt, especially sodium salt, form. Enzymes:
The compositions preferably include one or more detergent enzymes which provide cleaning performance and/or fabric care benefits. Examples of suitable enzymes include hemicellulases, peroxidases, proteases, cellulases, xylanases, lipases, phospholipases, esterases, cutinases, pectinases, keratanases, reductases, oxidases, phenoloxidases, lipoxygenases, ligninases, pullulanases, tannases, pentosanases, malanases, 11-glucanases, arabinosidases, hyaluronidase, chondroitinase, laccase, and amylases, or mixtures thereof. A typical combination may be a cocktail of conventional applicable enzymes like mannanase, protease, lipase, cutinase and/or cellulase in conjunction with amylase. Enzymes can be used at their recommended levels, for example at levels recommended by suppliers such as Novozymes and Genencor. Typical levels in the compositions are from about 0.0001 wt.% to about 5 wt.%. When enzymes are present, they can be used at very low levels, e.g., from about 0.001% or lower; or they can be used in heavy-duty laundry detergent formulations at higher levels, e.g., about 0.1% and higher. The detergent composition according to the present may be enzyme-free. By the term “enzyme-free” it means that there is no deliberately added enzyme in the composition. Dye-transfer inhibiting agents:
The composition according to the present invention may also include from 0.0001 to 10 wt.%, preferably at least 0.01 wt.%, still preferably at least 0.05 wt.% by weight of the composition of a dye-transfer inhibiting agent. But typically, not more than 2 wt.%, preferably not more than 1wt.% of one or more dye transfer inhibiting agents such as polyvinylpyrrolidone polymers, polyamine N-oxide polymers, copolymers of Nvinylpyrrolidone and N-vinylimidazole, polyvinyloxazolidones and polyvinylimidazoles or mixtures thereof. Brighteners:
The detergent composition according to the present invention may preferably include an optical brightener also known as Non-limiting examples of useful brighteners include: derivatives of stilbene or 4,4'-diaminostilbene, biphenyl, fivemembered heterocycles such as triazoles, pyrazolines. oxazoles, imidiazoles, etc., or sixmembered heterocycles (coumarins, naphthalamide, s-triazine, etc.). Cationic, anionic, nonionic, amphoteric and zwitterionic brighteners can be used. Suitable brighteners include those commercially marketed under the trade name Tinopal-UNPA- GX by Ciba Specialty Chemicals Corporation (High Point, NC). Perfume:
Preferred compositions include a perfume. In such a case, the detergent composition may deliver high-quality and long lasting perfume impact on clothes.
As used herein the term "perfume" is used to indicate any odoriferous material that is subsequently released into the aqueous wash solution and/or onto fabrics contacted therewith.
The perfume will most often be liquid at ambient temperatures. A wide variety of chemicals are known for perfume uses, including materials such as aldehydes, ketones, and esters. The perfumes herein can be relatively simple in their compositions or can comprise highly sophisticated complex mixtures of chemical components, all chosen to provide any desired odour. Likewise, the perfume may be of the encapsulated type, such as, shear sensitive encapsulates which deposit on fabrics during the rinse process and are capable of undergoing rupture, later, to release the perfume. The perfume may be a perfume microcapsule, or a moisture-activated perfume microcapsule, comprising a perfume carrier and an encapsulated perfume composition, wherein said perfume carrier may be selected from the group consisting of cyclodextrins, starch microcapsules, porous carrier microcapsules, and mixtures thereof; and wherein said encapsulated perfume composition may comprise low volatile perfume ingredients, high volatile perfume ingredients, and mixtures thereof. The perfume may additionally include a pro-perfume. Pro-perfumes may comprise nonvolatile materials that release or convert to a perfume material as a result of, e.g., simple hydrolysis, or may be pH-change-triggered pro-perfumes (e.g. triggered by a pH drop) or may be enzymatically releasable pro-perfumes or light-triggered pro-perfumes. The pro-perfumes may exhibit varying release rates depending upon the pro-perfume chosen. Fabric Hueing agent:
The composition may preferably include a fabric hueing agent (sometimes referred to as shading, bluing or whitening agents). Typically, the hueing agent provides a blue or violet shade to fabric. Hueing agents can be used either alone or in combination to create a specific shade of hueing and/or to shade different fabric types. This may be provided for example by mixing a red and green-blue dye to yield a blue or violet shade. Hueing agents may be selected from any known chemical class of dye, including but not limited to acridine, anthraquinone (including polycyclic quinones), azine, azo (e.g., monoazo, disazo, trisazo, tetrakisazo, polyazo), including premetallized azo, benzodifurane and benzodifuranone, carotenoid, coumarin, cyanine, diazahemicyanine, diphenylmethane, fonnazan, hemicyanine, indigoids, methane, naphthalimides, naphthoquinone, nitro and nitroso, oxazine, phthalocyanine, pyrazoles, stilbene, styryl, triarylmethane, triphenylmethane, xanthenes and mixtures thereof.
Suitable fabric hueing agents include dyes, dye-clay conjugates, and organic and inorganic pigments. Suitable dyes include small molecule dyes and polymeric dyes. Suitable small molecule dyes include small molecule dyes selected from the group consisting dyes falling into the Colour Index (C.l.) classifications of Acid, Direct, Basic, Reactive or hydrolysed Reactive, Solvent or Disperse dyes for example that are classified as Blue, Violet, Red, Green or Black, and provide the desired shade either alone or in combination. In another aspect, suitable small molecule dyes include small molecule dyes selected from the group consisting of Colour Index (Society of Dyers and Colourists, Bradford, UK) numbers Direct Violet dyes such as 9, 35, 48, 51, 66, and 99, Direct Blue dyes such as 1, 71, 80 and 279, Acid Red dyes such as 17, 73, 52, 88 and 150, Acid Violet dyes such as 15, 17, 24, 43, 49 and 50, Acid Blue dyes such as 15, 17, 25, 29, 40, 45, 75, 80, 83, 90 and 113, Acid Black dyes such as 1 , Basic Violet dyes such as 1, 3, 4, 10 19, 35, 38, and 48, Basic Blue dyes such as 3, 16, 22, 47, 65, 66, 67, 71, 75 and 159, Disperse or Solvent dyes, and mixtures thereof. In another aspect, suitable small molecule dyes include small molecule dyes selected from the group consisting of C. I. numbers Acid Violet 17, Acid Blue 80, Acid Violet 50, Direct Blue 71, Direct Violet 51, Direct Blue 1, Acid Red 88, Acid Red 150, Acid Blue 29, Acid Blue 113 or mixtures thereof. Process for treating the fabric
The detergent composition disclosed herein enable consumers to achieve softening through the wash, in particular the wash sub-cycle of a washing machine. By providing softening through the wash sub-cycle, consumers only need to dose the detergent composition, for example the wash basin, prior to or shortly after the start of the washing machine. This can be more convenient to consumers than using a liquid fabric care composition that is separately dispensed into the wash basin after the wash sub cycle is completed, for example prior to, during, or in between rinse cycles. For instance, it can be inconvenient for the consumer to manually dispense fabric softening composition after completion of the wash sub-cycle since the consumer must monitor the progress of the sub-cycles of the washing machine, interrupt progress of the cycles of the washing machine, open the washing machine, and dispensing fabric softening composition into the wash basin. It can further be inconvenient to use auto-dispensing feature of modern upright and high efficiency machines since that requires loading the fabric softening composition to a location other than where detergent composition is dispensed. In addition, use of two different compositions one for cleaning and another for softening the fabric is perceived as an inconvenience as the consumer has to store them separately and each time dispense them separately. According to a second aspect of the invention, disclosed is a method for softening fabric comprising, in no particular order, the steps of: (i) providing a fabric in a washing machine or in a hand wash container; (ii) contacting the fabric during a wash cycle of said washing machine or hand wash process with the composition according to the first aspect; (iii) optionally allowing the article or articles to dry or mechanically tumble drying them.
The process for treating a fabric involves the steps of providing the fabric in a washing machine. The fabric is contacted during the wash sub-cycle of the washing machine with a composition according to the first aspect of the present invention.
Typically, a fabric laundering process includes a washing step, a rinsing step and a drying step. The washing step employs water and detergent composition comprising anionic surfactant along with other active ingredients to form a wash liquor. After washing, the fabric is rinsed one or more times as part of the rinsing step.
In a washing machine a typical cycle of operation involves a wash cycle and a rinse cycle. In the wash cycle of the washing machine, water fills the wash basin either fully or partially. The wash cycle removes or loosens soil from the fabric and suspends that soil in the wash liquor. Typically, the wash liquor is drained at the end of the wash cycle. The rinse cycle of a washing machine follows the wash cycle and has a main purpose of rinsing soil, and optionally some benefit agents provided to the wash cycle from the fabric. Use of the detergent composition
According to a third aspect of the present invention disclosed is the use of chelating agent, neutralized soap, cationically substituted quaternary ammonium polymer in a carbonate built detergent composition having from 15 wt.% to 40 wt.% carbonate based builder, to provide softening benefit on fabric treated with the composition.
The invention will now be described by way of example only and with reference to the following non-limiting examples. In the examples and throughout this specification all percentages are percentages by weight unless indicated otherwise. Examples
Example 1 :
A spray-dried solid detergent composition was prepared according to the formulation given in Table 1. The composition was prepared by the slurry route where a solution of the anionic surfactant, sodium carbonate and fillers were prepared and then dried into a solid form in a spray drier. The remaining ingredients were post dosed to obtain the composition as shown in Table 1.
Softness evaluation: The above prepared composition was evaluated as follows.
The spray-dried solid detergent composition shown in Table 1 was poured in the powder-dispensing drawer of a Samsung automatic top loading machine at a dosage of 3 grams per litre in the wash stage. Approximately 2.7 Kgs of a fabric ballast was added into the washing machine. The fabric consisted of 100% clean polyester. 35 litres water was filled in the washing machine and the ballast was washed by selecting the fuzzy cycle of the washing machine at a wash water temperature of 28°C. The water has a hardness of 24°FH with a Ca:Mg ratio of 2:1. The main wash was followed by 2 rinse cycles. The washed fabric was line dried after each wash.
The fabric was washed 15 times, and the softness of the washed and dried fabric was evaluated after 5,10 and 15 washes. The above washing process was similarly conducted for the control. The control composition used for the present study was prepared by adding 1.1 wt% silicone (30% active content) and 0.166 wt% cationic polymer (90% active content) to commercially available Surf Excel Top Load matic liquid. The washed fabric was evaluated by a panel of 15 trained sensory panellists. The panellists assessed the softness of the fabric and scored the softness intensity on a scale from 1 to 10. Where 1 denotes lowest softness score and 10 denotes highest level of softness score. The results were recorded and provided in Table 2 below. Table 1
Figure imgf000029_0001
* HEDP "cationic hydroxyalkyl cellulose sold under the trade name LR 400
Table 2
Figure imgf000029_0002
The results show that the fabric washed with the detergent composition (Ex 1) according to the present invention showed improved softness as compared to the fabric washed with the conventional marketed detergent composition (Control). The effect is more pronounced after 15 washes, as compared to 5 washes. Example 2:
Different spray-dried solid detergent compositions were prepared according to the formulation given in Table 3. The composition was prepared by the slurry route where a solution of the anionic surfactant, sodium carbonate and fillers were prepared and then dried into a solid form in a spray drier. The remaining ingredients were post dosed to obtain the composition as shown in Table 3. Softness evaluation:
The above prepared compositions were evaluated for softness using the method as described above in Example 1. The fabric was washed 15 times, and the softness of the washed and dried fabric was evaluated after 10 and 15 washes. The above washing process was similarly conducted for each composition provided in Table 3.
The washed fabric was evaluated by a panel of 15 trained sensory panellists. The panellists assessed the softness of the fabric and scored the softness intensity on a scale from 1 to 10. Where 1 denotes lowest softness score and 10 denotes highest level of softness score. The results were recorded and provided in Table 3.
Figure imgf000030_0001
* HEDP
"cationic hydroxyalkyl cellulose sold under the trade name LR 400 (cationically substituted quaternary ammonium polymer) The results show that the fabric softness benefits after multiple washes is higher in the in a carbonate-built solid laundry detergent composition according to the present invention which includes a chelating agent, soap and the cationically substituted quaternary ammonium polymer. The comparative examples with chelating agent and cationic polymer (Comp A) but without soap, or with chelating agent and soap but without cationic polymer (Comp B) or with soap and cationic polymer but without HEDP (Comp C) give inferior fabric softness benefits in a carbonate built detergent composition which fabric softness benefit also decreases over multiple washes.

Claims

Claims
1 A solid detergent composition comprising: i. a chelating agent; ii. a neutralised soap; iii. a cationically substituted quaternary ammonium polymer; and, iv. 15 wt.% to 40 wt.% carbonate-based builder.
2 A detergent composition according to claim 1 wherein the chelating agent is selected from amino carboxylates, phosphonates preferably from the group amino alkane phosphonate, hydroxy alkane phosphonate or mixtures thereof.
3 A detergent composition according to claim 1 or 2 wherein the chelating agent is a hydroxy diphosphonic acid or a salt thereof.
4 A detergent composition according to any claim 3 wherein the hydroxy diphosphonic acid is 1-hydroxy ethylidene-1,1-diphosphonic acid (HEDP).
5 A detergent composition according to any one of the preceding claims wherein the cationically substituted quaternary ammonium polymer is a cationic polysaccharide.
6 A detergent composition according to claim 5 wherein the cationic polysaccharide is a cationic cellulose derivative.
7 A detergent composition according to claim 5 or 6 wherein the cationically substituted quaternary ammonium is a quaternary ammonium salt of modified cellulose, preferably a quaternary ammonium salt of hydroxy cellulose.
8 A detergent composition according to any one of the preceding claims, wherein the average molecular weight of the cationic polymer is from 10,000 to 850,000 Daltons, more preferably from 10,000 to 500,000 Daltons. A detergent composition according to any one of the preceding claims, wherein the cationically substituted quaternary ammonium is present in an amount from 0.05 wt.% to 5 wt.%, preferably from 0.1 wt.% to 3 wt.%. A detergent composition according to any one of the preceding claims wherein the chelating agent is present in an amount from 0.3 wt.% to 3 wt.%. A detergent composition according to any one of the preceding claims wherein the neutralised soap is present in an amount ranging from 8 wt.% to 20 wt.%. A detergent composition according to any one of the preceding claims wherein the composition comprises a detersive surfactant preferably selected from non-soap anionic surfactant, non-ionic surfactant, zwitterionic surfactant, amphoteric surfactant or a mixture thereof. A detergent composition according to any one of the preceding claims wherein the composition is in a free-flowing solid particulate or powder form. A method for softening fabric comprising, in no particular order, comprising the steps of: i. providing a fabric in a washing machine or in a hand wash container; ii. contacting the fabric during a wash cycle of said washing machine or hand wash process with the composition according to any one of the preceding claims 1 to 13; iii. optionally allowing the article or articles to dry or mechanically tumble-drying them. Use of a chelating agent, cationically substituted quaternary ammonium and neutralised soap in a detergent composition having 5 wt.% to 40 wt.% carbonate- based builder, to provide softening benefit on fabric treated with the composition.
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