EP4073216A1 - Composition détergente - Google Patents

Composition détergente

Info

Publication number
EP4073216A1
EP4073216A1 EP20803594.9A EP20803594A EP4073216A1 EP 4073216 A1 EP4073216 A1 EP 4073216A1 EP 20803594 A EP20803594 A EP 20803594A EP 4073216 A1 EP4073216 A1 EP 4073216A1
Authority
EP
European Patent Office
Prior art keywords
detergent composition
fabric
composition according
acid
quaternary ammonium
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP20803594.9A
Other languages
German (de)
English (en)
Other versions
EP4073216B1 (fr
Inventor
Anshul Gupta
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Unilever Global IP Ltd
Unilever IP Holdings BV
Original Assignee
Unilever Global IP Ltd
Unilever IP Holdings BV
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 Global IP Ltd, Unilever IP Holdings BV filed Critical Unilever Global IP Ltd
Publication of EP4073216A1 publication Critical patent/EP4073216A1/fr
Application granted granted Critical
Publication of EP4073216B1 publication Critical patent/EP4073216B1/fr
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/10—Carbonates ; Bicarbonates
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D10/00—Compositions of detergents, not provided for by one single preceding group
    • C11D10/04—Compositions of detergents, not provided for by one single preceding group based on mixtures of surface-active non-soap compounds and soap
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/001—Softening compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/22—Carbohydrates or derivatives thereof
    • C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
    • C11D3/227—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin with nitrogen-containing groups
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/26—Organic compounds containing nitrogen
    • C11D3/33—Amino carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/36—Organic compounds containing phosphorus
    • C11D3/361—Phosphonates, phosphinates or phosphonites
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/36—Organic compounds containing phosphorus
    • C11D3/362—Phosphates or phosphites
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/36—Organic compounds containing phosphorus
    • C11D3/364—Organic compounds containing phosphorus containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3769—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D9/00—Compositions of detergents based essentially on soap
    • C11D9/04—Compositions of detergents based essentially on soap containing compounding ingredients other than soaps
    • C11D9/06—Inorganic compounds
    • C11D9/08—Water-soluble compounds
    • C11D9/10—Salts
    • C11D9/12—Carbonates
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D9/00—Compositions of detergents based essentially on soap
    • C11D9/04—Compositions of detergents based essentially on soap containing compounding ingredients other than soaps
    • C11D9/22—Organic compounds, e.g. vitamins
    • C11D9/26—Organic compounds, e.g. vitamins containing oxygen
    • C11D9/262—Organic compounds, e.g. vitamins containing oxygen containing carbohydrates
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D9/00—Compositions of detergents based essentially on soap
    • C11D9/04—Compositions of detergents based essentially on soap containing compounding ingredients other than soaps
    • C11D9/22—Organic compounds, e.g. vitamins
    • C11D9/30—Organic compounds, e.g. vitamins containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D9/00—Compositions of detergents based essentially on soap
    • C11D9/04—Compositions of detergents based essentially on soap containing compounding ingredients other than soaps
    • C11D9/22—Organic compounds, e.g. vitamins
    • C11D9/34—Organic 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.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Molecular Biology (AREA)
  • Emergency Medicine (AREA)
  • Detergent Compositions (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

Abstract

La présente invention concerne une composition détergente. Plus particulièrement, l'invention concerne un adoucissement dans la composition de lessive de lavage. On observe, dans une composition détergente à base de carbonate, que les propriétés d'adoucissement d'un composant adoucissant le tissu sur le tissu diminuent après de multiples lavages. Il serait par conséquent souhaitable d'améliorer davantage les bénéfices d'adoucissement sur le tissu durant le lavage. Il existe en outre un besoin de fournir des compositions détergentes adoucissantes tout en conservant les performances de nettoyage. Ainsi, un objet de la présente invention consiste à fournir une composition détergente capable de conférer une douceur et une performance de nettoyage améliorées à des tissus traités pendant le cycle de lavage d'un processus de lessive. Les présents inventeurs ont découvert que la présence d'un agent chélatant et d'un savon neutralisé conduisait à une amélioration significative des bénéfices d'adoucissement du tissu dans une composition détergente à base de carbonate contenant un polymère cationique tout en conservant de bonnes performances de nettoyage.
EP20803594.9A 2019-12-11 2020-11-13 Composition de détergent Active EP4073216B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP19215248 2019-12-11
PCT/EP2020/082020 WO2021115724A1 (fr) 2019-12-11 2020-11-13 Composition détergente

Publications (2)

Publication Number Publication Date
EP4073216A1 true EP4073216A1 (fr) 2022-10-19
EP4073216B1 EP4073216B1 (fr) 2023-08-09

Family

ID=68886839

Family Applications (1)

Application Number Title Priority Date Filing Date
EP20803594.9A Active EP4073216B1 (fr) 2019-12-11 2020-11-13 Composition de détergent

Country Status (4)

Country Link
EP (1) EP4073216B1 (fr)
BR (1) BR112022011360A2 (fr)
WO (1) WO2021115724A1 (fr)
ZA (1) ZA202206435B (fr)

Family Cites Families (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3958581A (en) 1972-05-17 1976-05-25 L'oreal Cosmetic composition containing a cationic polymer and divalent metal salt for strengthening the hair
ZA734721B (en) 1972-07-14 1974-03-27 Procter & Gamble Detergent compositions
CA1018893A (en) 1972-12-11 1977-10-11 Roger C. Birkofer Mild thickened shampoo compositions with conditioning properties
AT330930B (de) 1973-04-13 1976-07-26 Henkel & Cie Gmbh Verfahren zur herstellung von festen, schuttfahigen wasch- oder reinigungsmitteln mit einem gehalt an calcium bindenden substanzen
US4605509A (en) 1973-05-11 1986-08-12 The Procter & Gamble Company Detergent compositions containing sodium aluminosilicate builders
DE2433485A1 (de) 1973-07-16 1975-02-06 Procter & Gamble Zur verwendung in waschmitteln geeignete aluminosilikat-ionenaustauscher
EP0026529B2 (fr) 1979-09-29 1992-08-19 THE PROCTER & GAMBLE COMPANY Compositions détergentes
DE3413571A1 (de) 1984-04-11 1985-10-24 Hoechst Ag, 6230 Frankfurt Verwendung von kristallinen schichtfoermigen natriumsilikaten zur wasserenthaertung und verfahren zur wasserenthaertung
DE3526405A1 (de) 1985-07-24 1987-02-05 Henkel Kgaa Schichtsilikate mit beschraenktem quellvermoegen, verfahren zu ihrer herstellung und ihre verwendung in wasch- und reinigungsmitteln
CA2001927C (fr) 1988-11-03 1999-12-21 Graham Thomas Brown Aluminosilicates et detergents
YU221490A (sh) 1989-12-02 1993-10-20 Henkel Kg. Postupak za hidrotermalnu izradu kristalnog natrijum disilikata
CA2255011A1 (fr) * 1996-05-17 1997-11-27 Stuart Clive Askew Composition detergente
AU3923500A (en) 1999-03-25 2000-10-09 Procter & Gamble Company, The Laundry detergent compositions with certain cationically charged dye maintenancepolymers
US6642200B1 (en) 1999-03-25 2003-11-04 The Procter & Gamble Company Fabric maintenance compositions comprising certain cationically charged fabric maintenance polymers
DE10153551A1 (de) * 2001-10-30 2003-05-22 Henkel Kgaa Im wesentlichen sedimentfrei dispergierbares Wasch- oder Reinigungsmittel
US20050187130A1 (en) * 2004-02-23 2005-08-25 Brooker Alan T. Granular laundry detergent composition comprising an anionic detersive surfactant, and low levels of, or no, zeolite builders and phosphate builders
US9427391B2 (en) 2006-01-09 2016-08-30 The Procter & Gamble Company Personal care compositions containing cationic synthetic copolymer and a detersive surfactant
US20080045438A1 (en) 2006-08-21 2008-02-21 D/B/A Unilever, A Corporation Of New York Softening laundry detergent
DE602006007142D1 (de) * 2006-09-19 2009-07-16 Unilever Nv Waschmitteltablette
GB0618542D0 (en) * 2006-09-21 2006-11-01 Unilever Plc Laundry compositions
CN108697591B (zh) 2016-02-18 2022-06-17 国际香料和香精公司 聚脲胶囊组合物
CN109563443B (zh) * 2016-08-10 2021-01-26 荷兰联合利华有限公司 洗衣组合物
US10640731B2 (en) * 2017-12-01 2020-05-05 The Procter & Gamble Company Particulate laundry softening wash additive

Also Published As

Publication number Publication date
EP4073216B1 (fr) 2023-08-09
ZA202206435B (en) 2023-11-29
BR112022011360A2 (pt) 2022-08-23
WO2021115724A1 (fr) 2021-06-17

Similar Documents

Publication Publication Date Title
JP5969042B2 (ja) シールド塩類を含有する表面処理組成物
CA2748531C (fr) Composition detergente hautement alcaline a effet antitartre ameliore
CN101784649B (zh) 清洁产品
US10844323B2 (en) Formulations, the production and use thereof, and suitable components
RU2676769C2 (ru) Композиции, их получение и применение, и подходящие компоненты
JP5377536B2 (ja) 自動食器洗いシステムのためのスケール低減添加剤
WO2018028933A1 (fr) Détergent liquide stable comprenant un polymère facilitant l'élimination des taches au lavage (« soil release »)
ES2445441T3 (es) Composición detergente que contiene pirrolidona
AU3232499A (en) Isotropic liquid detergent
EP3622049A1 (fr) Composition de détergent pour lave-vaisselle sans phosphate
EP4073216B1 (fr) Composition de détergent
EP4073215B1 (fr) Composition de détergent
WO2018028935A1 (fr) Détergent liquide stable comprenant un polymère facilitant l'élimination des taches au lavage (« soil release »)
WO2018028936A1 (fr) Détergent liquide stable comprenant un polymère facilitant l'élimination des taches au lavage (« soil release »)
US10844326B2 (en) Formulations and production and use thereof
WO2021102080A1 (fr) Polymères inhibiteurs de redéposition et compositions détergentes les contenant
WO2018028934A1 (fr) Détergent liquide stable comprenant un polymère facilitant l'élimination des taches au lavage (« soil release »)
EP4077612B1 (fr) Polymères inhibiteurs de redéposition et compositions détergentes les contenant
US8740993B2 (en) Method for reduced encrustation of textiles using a polymer comprising maleic acid, vinyl acetate, and alkyl acrylate
WO2023144110A1 (fr) Composition de lessive
WO2020109227A1 (fr) Grosses particules
EP4392512A1 (fr) Composition détergente
WO2024100226A1 (fr) Composition de nettoyage
US20210230515A1 (en) Formulations, the production and use thereof, and suitable components
WO2023025761A1 (fr) Composition de détergent

Legal Events

Date Code Title Description
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: UNKNOWN

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE INTERNATIONAL PUBLICATION HAS BEEN MADE

PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE

17P Request for examination filed

Effective date: 20220602

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

DAV Request for validation of the european patent (deleted)
DAX Request for extension of the european patent (deleted)
GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: GRANT OF PATENT IS INTENDED

INTG Intention to grant announced

Effective date: 20230331

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE PATENT HAS BEEN GRANTED

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 602020015590

Country of ref document: DE

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG9D

REG Reference to a national code

Ref country code: NL

Ref legal event code: MP

Effective date: 20230809

REG Reference to a national code

Ref country code: AT

Ref legal event code: MK05

Ref document number: 1597540

Country of ref document: AT

Kind code of ref document: T

Effective date: 20230809

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20231110

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20231209

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20230809

Ref country code: RS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20230809

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20231211

Ref country code: NO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20231109

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20230809

Ref country code: LV

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20230809

Ref country code: LT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20230809

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20231209

Ref country code: HR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20230809

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20231110

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20230809

Ref country code: AT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20230809

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: TR

Payment date: 20231110

Year of fee payment: 4

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: PL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20230809

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20230809

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SM

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20230809

Ref country code: RO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20230809

Ref country code: ES

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20230809

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20230809

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20230809

Ref country code: CZ

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20230809

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20230809

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 602020015590

Country of ref document: DE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20230809

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MC

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20230809