EP2473590B2 - Procédé de traitement d'un tissu - Google Patents

Procédé de traitement d'un tissu Download PDF

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Publication number
EP2473590B2
EP2473590B2 EP10742151.3A EP10742151A EP2473590B2 EP 2473590 B2 EP2473590 B2 EP 2473590B2 EP 10742151 A EP10742151 A EP 10742151A EP 2473590 B2 EP2473590 B2 EP 2473590B2
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EP
European Patent Office
Prior art keywords
acid
polymer
fabric
composition
cellulose
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.)
Not-in-force
Application number
EP10742151.3A
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German (de)
English (en)
Other versions
EP2473590B1 (fr
EP2473590A1 (fr
Inventor
Aravindakshan Perincheery
Sameer Keshav Barne
Abhishek Rastogi
Archana Sinha
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Unilever PLC
Unilever NV
Original Assignee
Unilever PLC
Unilever NV
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Application filed by Unilever PLC, Unilever NV filed Critical Unilever PLC
Priority to EP10742151.3A priority Critical patent/EP2473590B2/fr
Publication of EP2473590A1 publication Critical patent/EP2473590A1/fr
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0036—Soil deposition preventing compositions; Antiredeposition agents
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—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
    • 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
    • C11D3/225—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin etherified, e.g. CMC
    • 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
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3707—Polyethers, e.g. polyalkyleneoxides
    • 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
    • C11D3/3753—Polyvinylalcohol; Ethers or esters thereof
    • 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
    • C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
    • C11D3/3765—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in liquid 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
    • C11D3/37—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
    • C11D3/3776—Heterocyclic compounds, e.g. lactam

Definitions

  • the present invention relates to a process for treatment of a fabric. It further relates to a composition and a kit for treatment of a fabric.
  • the invention will be described hereinafter with reference to this application. However, it will be appreciated that the invention is not limited to this particular field of use.
  • US2006046950A (Penninger and Bastmaschine, 2006 ) teaches a detergent composition for cleaning textile materials comprising a combination of a soil release-capable alkyl or hydroxyalkyl cellulose derivative and a hygroscopic polymer selected from the class consisting of polypeptides, hydrogels, polyvinyl alcohol, the polyalkylene glycols, the homopolymers of acrylic acid, methacrylic acid, and maleic acid, copolymers of acrylic acid, methacrylic acid, and maleic acid and mixtures of the homo and copolymers.
  • the use of the hygroscopic polymers in combination with the cellulose derivatives is said to result in improved cleaning performance.
  • EP0256696 (Unilever, 1988 ) teaches that improvement in soil suspension is achieved by adding mixture of vinyl pyrrolidone polymer and a nonionic cellulose ether to a detergent composition.
  • GB994353 (Domestos, 1965 ) teaches that mixtures of certain polymeric materials, when incorporated into unbuilt detergent compositions based on synthetic surface active agents, provide enhanced anti-redeposition as compared to activity of individual polymers alone when added alone to same detergent compositions.
  • the cleaning compositions essentially comprise of a surfactant and the pH of wash liquor is alkaline or neutral.
  • US4007305 (Kakar et al, 1977 ) addresses the problem of providing satisfactory nondurable finishes to textiles which impart optimum soil release and soil repellent properties.
  • the textiles must be treated with an alkaline aqueous medium having pH value of 7.5-11 and containing water soluble hydrophilic soil release polymer having carboxylic acid groups and a dispersed hydrophobic soil repellent fluorochemical.
  • one of the objects of the present invention is to provide a process for reducing soiling of fabrics that can be easily used in the household. Another object of the present invention is to provide a process of treatment of a fabric for reducing soiling of fabrics. Yet another object of the present invention is to provide a process for treatment of a fabric that improves efficacy of subsequent cleaning.
  • Yet another object of the present invention is to provide a process for reducing soiling of fabrics that allows enhanced deposition of benefit agents, such as perfume and fluorescer.
  • Yet another object of the present invention is to provide a process for treatment of a fabric which is effective on various types of fabrics such as cotton, polyester and polycotton.
  • Yet another object of the present invention is to provide a process for treatment of a fabric which is relatively easy to practice in household.
  • composition comprising a carboxylic acid polymer that has been neutralised at least partially to the salt form and a second polymer, capable of forming hydrogen bonds with the first polymer in the present of an acid, provides both a secondary cleaning benefit and good storage stability, without forming polymer-polymer complex when it is in the solid formulation and give a complex when dispersed in water.
  • the present inventors also have been found that a liquid composition of two polymers dispersed in a solvent in presence of a stabilizer provides a stable preformed complex at high concentration with very good storage stability and it provides a secondary cleaning benefit.
  • the present invention provides a liquid fabric treatment composition
  • a liquid fabric treatment composition comprising base composition comprising a mixture of polymer A and a stabilizer wherein the polymer A is selected from the group of homopolymers and copolymers of carboxylic acid wherein the polymer A is atleast partially neutralised;, a polymer B selected from the group of homopolymers and copolymers of alkylene oxides having a molecular 10 mass greater than 2x104 D, vinyl pyrrolidone; and/or the group of homopolymers and copolymers of vinyl alcohol, saccharides, hydroxyalkyl cellulose; and a pH adjustment agent selected from organic acids, selected from citric acid, formic acid, oxalic acid, phtalic acid ascorbic acid, glutamic acid, salicylic acid, tartaric acid, pyroglutamic acid, malic acid, maleic acid, malonic acid, succinic acid, glutaric acid, adipic acid, propane 1,2,3 tricarbox
  • the present invention provides a wash or rinse liquor 20 comprising between 0.02 and 40 g/l of the composition according to the invention, having a pH ⁇ 6
  • the present invention provides a process for washing fabric comprising the steps in sequence of contacting the fabric with a wash or rinse liquor 25 comprising between 0.02 and 40 g/l of the composition according to the invention; leaving the fabric to dry; leaving the fabric for soil and/or dirt to deposit onto the fabric; washing the fabric with a conventional washing detergent in a conventional way.
  • the present invention provides a process for preparing the liquid composition according to the invention comprising the steps of: (a) preparing solution of polymer A and polymer B separately with or without the stabilizer (b) adding the stabilizer if it is not added while preparing the solution of polymer A and polymer B and then (c) Mixing the both solution and stirring it with the pH adjustment agent.
  • storage stability here we mean, that such a formulation in powder form exhibit no complex formation between the interacting polymers and it readily forms the complex when dispersed in water and in liquid form the complex will be well dispersed and not precipitated in the composition.
  • secondary cleaning benefit is meant that a fabric treated with the composition exhibits benefits such as reduction in soiling, ease of subsequent cleaning and/or enhanced deposition of benefit agents.
  • the present invention thus aims for a composition in form of a liquid and process for the application of a sacrificial layer of polymeric material onto a fabric surface, before dirt and/or soil is deposited onto the fabric.
  • a sacrificial layer of polymeric material onto a fabric surface
  • dirt and/or soil are removed by dissolution of the sacrificial layer of the polymeric material from the fabric surface.
  • This is also referred to in the art as a secondary cleaning benefit or next-time-cleaning-benefit.
  • the complex disperses into an aqueous solvent and does not dissolve, like the individual polymers.
  • the dispersed complex in turn is thought to bind or precipitate onto a fabric surface, thus forming a layer.
  • the complex is thought to disintegrate when in alkaline conditions, such as the conditions in a laundry main wash, thereby removing the layer and soil or stains deposited onto the layer from the fabric.
  • the fabric that can be treated includes synthetic as well as natural textiles. Fabrics may be made of cotton and other cellulosic materials, polycotton, polyester, silk or nylon. It is envisaged that the method of the present invention can be used to treat garments and other clothing and apparel materials that form typical wash load in household laundry.
  • the household materials that can be treated according to the process of the present invention include, but are not limited to, bedspreads, blankets, carpets, curtains and upholstery.
  • the process of the present invention is described primarily for treatment of a fabric, it is envisaged that the process of the present invention can be advantageously used to treat other materials such as jute, leather, denim and canvass. It is envisaged that the process of the present invention can be used to treat articles such as shoes, rain-wear and jackets.
  • composition according to the invention comprises a polymer A and a polymer B.
  • Polymers A and B are selected such that they form a complex due to the formation of hydrogen bonds.
  • the polymers may be homo polymers or co polymers. Wherein by copolymer of monomer X is meant any polymer that contains the monomer X and at least one further monomer.
  • Polymer A has a plurality of carboxyl groups.
  • the polymer A has a molecular mass preferably from 300 to 10 9 D.
  • Polymer A has a molecular mass of preferably from 2x10 3 to 10 7 D more preferably from 5x10 4 to 10 6 D and most preferably from 9x10 4 to 5x10 5 D.
  • the particle size is preferably less than 200 ⁇ m, preferably less than 100 ⁇ m, more preferably 30 less than 50 ⁇ m still more preferably less than 10 ⁇ m, or even less than 5 ⁇ m.
  • Polymer A is at least partially neutralised in the Sodium (Na + ) form, preferably at least 10%w of polymer A is neutralised, more preferably at least 20%, still more preferably at least 50%.
  • Polymer A is preferably water soluble or water dispersible, most preferably polymer A is water soluble.
  • Polymer A is preferably a polyacrylic acid.
  • the concentration of polymer A in a fabric cleaning or fabric rinse composition is preferably between 0.01 and 25% by weight, more preferably at least 0.1%, or even at least 1%, but preferably not more than 20%, more preferably less than 15%.
  • the amount of polymer A relative to the fabric surface area is preferably from 0.5 to 200 ⁇ g/cm 2 of fabric surface area, more preferably from 1 to 100 ⁇ g/cm 2 , and most preferably from 2 to 50 ⁇ g/cm 2 of fabric surface area.
  • fabric surface area refers to surface area of one side of the fabric.
  • polymer B has a monomeric unit comprising a group that can form hydrogen bonds with the carboxyl groups of polymer A.
  • Poly-vinyl alcohol and, hydroxyethyl cellulose are generally not water soluble.
  • the particle size is set such that the particles are easily dispersible in water or and aqueous solution (i.e. a wash or rinse liquor).
  • the particle size is preferably less than 200 ⁇ m, more preferably less than 100 ⁇ m, even more preferably less than 50 ⁇ m still more preferably less than 10 ⁇ m, or even less than 5 ⁇ m.
  • the two polymers A and B when dissolved in water, form a complex with a solubility lower than each of the polymers A and B, which helps in enhanced deposition and other benefits.
  • Polymer B has a molecular mass preferably from 10 3 to 10 9 D.
  • Homopolymers of vinyl pyrrolidone or vinyl alcohol preferably have a molecular mass of between 10 3 and 10 7 D, more preferably from 10 4 to 10 6 D and most preferably from 30,000 to 500,000 D.
  • Commercially available polyvinyl pyrrolidone can be used, one example of which is LUVISKOL® (BASF).
  • Polyethylene oxide preferably has a molecular mass greater than 2x10 4 D.
  • the molecular mass is preferably from 2x10 4 to 10 6 D, more preferably from 3x10 4 to 5x10 5 D and most preferably from 5x10 4 to 2x10 5 D.
  • the polymer B is water soluble.
  • the polymer B is selected from a class consisting of homopolymers of vinyl pyrrolidone or alkylene oxide.
  • the concentration of polymer B in a fabric cleaning or fabric rinse composition is preferably between 0.01 and 20% by weight, more preferably at least 0.1%, or even at least 1%, but preferably not more than 15%, more preferably less than 10%.
  • the amount of polymer B relative to the fabric surface area is preferably from 0.5 to 200 ⁇ g/cm 2 of fabric surface area, more preferably from 1 to 100 ⁇ g/cm 2 , and most preferably from 2 to 50 ⁇ g/cm 2 of fabric surface area.
  • fabric surface area refers to surface area of one side of the fabric.
  • the most preferred combinations of the polymer A and polymer B are PAA-PVP, PAA-PEO, PEG-PAA, Starch-graft-polymethacrylic acid-Polyethylene Oxide.
  • the present invention provides a liquid fabric treatment composition.
  • the stabilizers are preferably selected from polyvinyl alcohol, silicone, Carboxymethyl cellulose, ethyl cellulose, methyl cellulose, methyl hydroxypropyl cellulose.
  • the stabiliser may be selected from surfactants such as anionic, cationic, non-ionic especially ethoxylated fatty alcohols. However these surfactant stabilizers are typically less preferred.
  • polyvinyl alcohol PVA
  • PVA polyvinyl alcohol
  • the polymers of the invention are best applied to the fabric at acidic pH and removed at alkaline pH.
  • a normal washing process is done at alkaline pH, generally pH between 8 and 11.
  • alkaline high pH washing liquor from the main wash to the rinse step. This carry over is typically in the order of 1:10 and cause the rinse liquor to be alkaline.
  • composition of the invention further comprises a pH adjustment agent or a buffer.
  • Suitable pH adjustment agents are, organic and inorganic acids. Such acids are preferably in solid form and have a high water solubility, most preferably they are fully soluble in water.
  • Suitable inorganic acids are boric acid, sodium dihydrogen phosphate, aluminium chloride, aluminium sulphate, cupric sulphate etc.
  • Suitable organic acids in the context of the present invention are citric acid, formic acid, oxalic acid, phtalic acid ascorbic acid, glutamic acid, salicylic acid, tartaric acid, pyroglutamic acid, malic acid, maleic acid, malonic acid, succinic acid, glutaric acid, adipic acid, propane 1,2,3 tricarboxylic acid, butane 1,2,3,4 tetra carboxylic acid.
  • the anhydrides of all the abovementioned acids may also be used for this purpose.
  • the wash liquor or rinse liquor wherein the composition of the invention is dissolved preferably has a pH of less than 6, preferably less than 5 and more preferably less than 4.
  • Aqueous medium has pH preferably greater than 2 and more preferably greater than 3.
  • the polymers may be also chosen in such a way that when the polymers are added to the aqueous medium, pH of the aqueous medium is less than 6.
  • an acidic ingredient is added to aqueous medium to ensure that the pH of the aqueous medium is less than 6.
  • Acidic ingredients that reduce pH of resulting aqueous medium to less than 6 are well known to a person skilled in the art and any suitable acidic ingredient may be chosen.
  • the aqueous medium may comprise an electrolyte.
  • the electrolyte is preferably present in a concentration from 0.001 to 5%, more preferably from 0.01 to 1%, and most preferably from 0.04 to 0.2% by weight of the aqueous medium.
  • Electrolytes that can be used according to the present invention include water soluble ionic salts.
  • the cation of the salt includes an alkali metal, alkaline earth metal or trivalent metal cation.
  • the anion of the salt includes chloride, sulphate, nitrate and phosphate.
  • Some examples of electrolytes include chlorides, sulphates or nitrates of sodium, potassium, magnesium or calcium. Calcium salts are particularly preferred.
  • the invention may further comprise natural or synthetic clays, preferably kaolin (kaolinite), bentonite or attapulgate.
  • natural or synthetic clays preferably kaolin (kaolinite), bentonite or attapulgate.
  • the aqueous medium comprises no more than 200 ppm anionic surfactant.
  • the aqueous medium comprises no more than 100 ppm, more preferably 5 less than 50 ppm anionic surfactant. It is particularly preferred that the aqueous medium is substantially free of anionic surfactant.
  • the aqueous medium may further comprise at least one benefit agent.
  • the benefit agent that can be included in the aqueous medium includes, but not limited to ingredients such as perfume, fluorescer, deodorant, antibacterial agent, shading dye and bluing agent.
  • ingredients such as perfume, fluorescer, deodorant, antibacterial agent, shading dye and bluing agent.
  • composition according to the invention may be applied to a fabric in different ways.
  • One way of applying the composition is by adding the composition to the rinse water of a manual or automatic washing process.
  • the fabric may be added to the rinse water either before or after addition of the composition.
  • the composition may be applied by use of a trigger spray dispenser.
  • the invention provides a process for washing fabric comprising the steps in sequence of: contacting the fabric with a wash or rinse liquor comprising between 0.02 and 40 g/l of the liquid composition according to the invention; leaving the fabric to dry; leaving the fabric for soil and / or dirt to deposit onto the fabric; washing the fabric with a conventional washing detergent in a conventional way.
  • the wash liquor preferably comprises at least 0.1 g/l of the total liquid composition, more preferably at least 0.25 g/l, still more preferably more than 19 g/l, but typically less than 20 g/l, more preferably less than 10 g/l, and even less than 5 g/l.
  • the conventional washing process may be any washing process, such as machine wash in an automatic or semi-automatic vertical axis or horizontal axis washing machine or a hand wash process.
  • the detergent may be any conventional washing detergent composition, typically comprising surfactant and builder and optionally perfume, optical brighteners, building aids, etc.
  • the composition comprises preferably 5-95%, more preferably 10-90% and most preferably 20-80% by weight polymer A.
  • the composition comprises preferably 5-95%, more preferably 10-90% and most preferably 20-80% by weight polymer B.
  • the liquid composition of the present invention is preferably prepared by first preparing the solution of polymer A and polymer B separately with or without the stabilizer. After that the stabilizer has been added if it is not added while preparing the solution of polymer A and 15 polymer B. Then followed by mixing both solution and stirring it with the pH adjustment agent.
  • the solvent is selected from water or a mixture of water and lower alcohol.
  • the preferable lower alcohol is selected from methanol, ethanol, iso-propanol etc.
  • the preferred ratio of water to lower alcohol is 6:4 more preferably 9:1 and most preferably 10:0.
  • the polymers may be chosen in such a way that pH of 1 % aqueous solution of the composition is less than 6.
  • an acidic ingredient is present in the composition at 0.1-10% by weight of the composition to ensure that the pH of 1 % aqueous solution of the composition is less than 6.
  • Acidic ingredients that reduce pH of resulting aqueous medium to less than 6 are well known to a person skilled in the art and any suitable acidic ingredient may be chosen.
  • Example 1 Dispersibility of the formulations
  • compositions according to the invention (1 and 2) are compared with comparative compositions outside the scope of the invention, with respect to the required dissolution or dispersion time and the uniformity of the solution or dispersion.
  • compositions (1, 2 and A-D) 100 ml deionized water was taken in a 250 ml glass beaker and stirred over a magnetic stirrer at controlled speed. The formulation was added to water with continuous stirring and the required time to form a dissolution/dispersion was noted as well as the nature of the dispersion (especially uniformity and/or for lumps remaining). Table 2: dissolution results Comp.
  • Amount Time Remarks (mg / 100ml dispersion) (for full dissolution/dispersion) (for full dissolution/dispersion)
  • a PAA 1) 180 >40 min Few lumps remaining B PAA 180 15 min lumps Soda 2) 30 C PAA 180 >40 lumps Citric Acid 70 D
  • compositions according to the invention show fast dissolution and a uniform dispersion of the polymer complex, whilst the comparative compositions A-D show either long dissolution times, or do not show a uniform dispersion.
  • Table 3 best mode solid formulations Example composition 3 (g/l) % PAA 0.15 7.3 PEO 0.10 4.9 Soda 0.15 7.3 NaCl 0.75 37 Citric acid 0.65 32 Kaolin 0.25 12 Total 2.05 100
  • the cotton, poly cotton and polyester fabric swatches (commercially available from WFK, Germany) were soaked in this dispersion for 30 minutes, and dried in air overnight. The swatches were 10x10 cm.
  • a composite soil was prepared by sonicating a mixture containing 100 ml triolein, 4 mg carbon soot and 4 mg iron oxide for 1 hour. A homogeneous soil dispersion was obtained.
  • the fabric swatches were soiled with composite soil and aged for a day at room temperature (ca 24°C). The swatches were then washed in surf XL (ex Unilever) by hand wash procedure.
  • Table 4 best mode liquid formulations Composition 9 (Liquid) % wt PAA (100k) 5 PVA(125k) 5 PEG (20k) 2.5 Citric Acid 10 Perfume 1 Water to 100
  • compositions according to the invention are compared to comparative compositions.
  • Polymer formulations (as specified in the table below) were prepared according to the method of example 1. The dispersion was checked for lump formation and uniformity.
  • Desized cotton, polycotton and polyester fabric swatches of 10 x 10 cm were pretreated by soaking into the polymer composition (dispersion) at a liquid to cloth ratio of 5:1 and soaked for 20 minutes.
  • the fabrics used had a mass of 1.5 g each (i.e. for 100 cm 2 ), resulting in a total of 18.75 ⁇ g of total polymer per cm 2 of fabric (one side), in the examples where polymer was present.
  • Fabrics were soiled with 0.3 ml of composite soil dispersion (see example 2) applied to about 20 cm 2 area and kept for ageing for 16 hours.
  • the fabric swatches were than washed by hand wash, in 1.5 g/l Surf XL wash liquor, at a wash liquor to cloth ratio of 5:1.
  • the fabric swatches were soaked in the liquor for 30 minutes.
  • the soaked fabrics were washed by a handwash protocol by brushing 5 times on both side of the fabrics. After brushing the fabrics were rinsed three times with clean water and dried in air.
  • the reflectance of the soil region was measured before and after washing using a reflectometer; the cleaning performance is indicated as the difference ("Delta R") between the reflectance (at 460 nm) before and after washing, as is a commonly known procedure in the art.
  • 3 g/l detergent product is representative for normal hand wash and horizontal axis machine wash. 1.5 g/l is included because the fabrics that are pre-treated with the compositions of the invention are washed with only half of the standard main wash dosage.
  • compositions G - M Comparative compositions (compositions G - M)
  • Examples 4-8 show compositions according to the invention.
  • the dose of the composition in case to liquid formulation is 2g/lit of rinse liquor. After the fabric treated with the composition of the invention, it is then soiled by composite soil and then usual detergency test was done on the fabric.

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

Claims (9)

  1. Composition liquide pour le traitement d'un tissu comprenant une composition de base comprenant
    a. un mélange de polymère A et d'un stabilisant dans lequel le polymère A est choisi dans le groupe d'homopolymères et de copolymères d'acide carboxylique où le polymère A est au moins partiellement neutralisé,
    b. un polymère B choisi dans :
    i. le groupe d'homopolymères et de copolymères d'oxydes d'alkylène présentant une masse moléculaire supérieure à 2x104 D, de vinylpyrrolidone ; et/ou
    ii. le groupe d'homopolymères et de copolymères d'alcool vinylique, de saccharides, d'hydroxyalkylcellulose ; et
    c. 0,1-10 % en poids d'un agent d'ajustement du pH choisi parmi des acides organiques, choisis parmi l'acide citrique, l'acide formique, l'acide oxalique, l'acide phtalique, l'acide ascorbique, l'acide glutamique, l'acide salicylique, l'acide tartarique, l'acide pyroglutamique, l'acide malique, l'acide maléique, l'acide malonique, l'acide succinique, l'acide glutarique, l'acide adipique, l'acide propane 1,2,3-tricarboxylique, l'acide butane 1,2,3,4-tétracarboxylique et leurs anhydrides, des acides inorganiques et/ou des tampons,
    dans laquelle la combinaison de polymère A et de polymère B est choisie parmi une des combinaisons suivantes :
    • poly(acide acrylique) et polyvinylpyrrolidone
    • poly(acide acrylique) et poly(oxyde d'éthylène)
    • poly(acide acrylique) et polyéthylène glycol
    • poly(acide acrylique) et poly(alcool vinylique)
    • carboxyméthylcellulose de sodium et poly(oxyde d'éthylène)
    • poly(acide acrylique) et hydroxyéthylcellulose
    • poly(acide méthacrylique) greffé par de l'amidon et poly(oxyde d'éthylène)
    • poly(acide méthacrylique) greffé par de l'amidon et polyvinylpyrrolidone
    • poly(acide acrylique) g-pluronique et poly(oxyde d'éthylène)
    • poly(acide acrylique) g-pluronique et polyvinylpyrrolidone
    • carboxyméthylcellulose de sodium et hydroxyéthylcellulose
    • carboxyméthylcellulose de sodium et poly(alcool vinylique)
    et dans laquelle le complexe de polymère A et de polymère B est préformé ;
    et dans laquelle le pH d'une solution aqueuse à 1 % de la composition est inférieur à 6 ;
    et comprenant de plus un solvant choisi parmi l'eau ou un mélange d'eau et d'alcool inférieur.
  2. Composition liquide pour le traitement d'un tissu selon la revendication 1, dans laquelle l'agent d'ajustement du pH dans la composition de base est un acide organique.
  3. Composition liquide pour le traitement d'un tissu selon la revendication 1 ou 2, dans laquelle la composition de base comprend de plus un sel d'électrolyte ou de l'argile ou les deux.
  4. Composition liquide pour le traitement d'un tissu comprenant la composition de base selon l'une quelconque des revendications précédentes, dans laquelle le stabilisant est choisi parmi le poly(alcool vinylique), un silicone, la carboxyméthylcellulose, l'éthylcellulose, la méthylcellulose, la méthylhydroxypropylcellulose et des tensioactifs.
  5. Composition liquide pour le traitement d'un tissu selon l'une quelconque des revendications précédentes, dans laquelle le polymère A est présent dans une concentration de 0,01 à 25 % en poids de la composition totale.
  6. Composition liquide pour le traitement d'un tissu selon l'une quelconque des revendications précédentes, dans laquelle le polymère B est présent dans une concentration de 0,01 à 20 % en poids de la composition totale.
  7. Liqueur de lavage ou de rinçage comprenant de 0,02 à 40 g/l de la composition selon l'une quelconque des revendications 1 à 5, présentant un pH de <6.
  8. Procédé pour le lavage d'un tissu comprenant les étapes successives consistant :
    a. à mettre le tissu en contact avec une liqueur de lavage ou de rinçage comprenant de 0,02 à 40 g/l de la composition selon l'une quelconque des revendications 2 à 6 ;
    b. à laisser le tissu sécher ;
    c. à laisser le tissu pour que de la terre et/ou de la saleté se dépose sur le tissu ;
    d. à laver le tissu avec un détergent de lavage classique de manière classique.
  9. Procédé de préparation de la composition liquide pour le traitement d'un tissu selon l'invention comprenant les étapes :
    a. de préparation d'une solution de polymère A et de polymère B séparément avec ou sans le stabilisant.
    b. d'addition du stabilisant s'il n'est pas ajouté tout en préparant la solution de polymère A et de polymère B,
    de mélange des deux solutions et d'agitation de celles-ci ensemble avec l'agent d'ajustement du pH.
EP10742151.3A 2009-09-02 2010-08-12 Procédé de traitement d'un tissu Not-in-force EP2473590B2 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP10742151.3A EP2473590B2 (fr) 2009-09-02 2010-08-12 Procédé de traitement d'un tissu

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
IN2007MU2009 2009-09-02
EP09173666 2009-10-21
IN1621MU2010 2010-05-26
EP10742151.3A EP2473590B2 (fr) 2009-09-02 2010-08-12 Procédé de traitement d'un tissu
PCT/EP2010/061744 WO2011026718A1 (fr) 2009-09-02 2010-08-12 Composition et procédé pour le traitement d'un tissu

Publications (3)

Publication Number Publication Date
EP2473590A1 EP2473590A1 (fr) 2012-07-11
EP2473590B1 EP2473590B1 (fr) 2014-11-26
EP2473590B2 true EP2473590B2 (fr) 2018-01-17

Family

ID=42931960

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Application Number Title Priority Date Filing Date
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Country Status (12)

Country Link
EP (1) EP2473590B2 (fr)
CN (1) CN102575197B (fr)
AR (1) AR078146A1 (fr)
AU (1) AU2010291392B2 (fr)
BR (1) BR112012003018A2 (fr)
CA (1) CA2770869A1 (fr)
CL (1) CL2012000538A1 (fr)
EA (1) EA022063B1 (fr)
ES (1) ES2531418T5 (fr)
MX (1) MX2012002748A (fr)
WO (1) WO2011026718A1 (fr)
ZA (1) ZA201200792B (fr)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BR112015011323A2 (pt) 2012-11-21 2017-07-11 Unilever Nv composição de reforço para prover um benefício de limpeza, composição detergente para roupas e composição de tratamento de tecido.
CN107532113A (zh) * 2015-05-20 2018-01-02 荷兰联合利华有限公司 用于处理基底的组合物和方法

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB994353A (en) † 1960-06-13 1965-06-02 Domestos Ltd Improvements in detergent compositions
US3716488A (en) † 1970-09-04 1973-02-13 Stevens & Co Inc J P Textile fabric cleaning compositions
EP0781836A1 (fr) † 1995-12-29 1997-07-02 Colgate-Palmolive Company Composition détergente ayant un pouvoir nettoyant amélioré dans un milieu acide ou neutre
DE10032589A1 (de) † 2000-07-07 2002-01-24 Henkel Kgaa Wäßriges Bleichmittel
US20030008804A1 (en) † 2001-06-05 2003-01-09 Qiu Xu Starch graft copolymer, detergent builder composition including the same, and production method thereof
US20060111261A1 (en) † 2004-11-19 2006-05-25 The Procter & Gamble Company Acidic laundry detergent compositions
US7229505B2 (en) † 2001-09-14 2007-06-12 Clean Control Corporation Methods and compositions for surfactant-free cleaning
JP2009263466A (ja) † 2008-04-24 2009-11-12 Kao Corp 液体洗浄剤組成物
JP5398051B2 (ja) † 2008-06-23 2014-01-29 花王株式会社 洗剤組成物

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3689435A (en) 1970-07-27 1972-09-05 Gaf Corp Detergency compositions containing a synergistic mixture of pvp and pva
US4007305A (en) 1974-12-23 1977-02-08 Basf Wyandotte Corporation Method of imparting nondurable soil release and soil repellency properties to textile materials
GB8618635D0 (en) 1986-07-30 1986-09-10 Unilever Plc Detergent composition
DE4318902C2 (de) * 1993-06-07 1996-10-24 Benckiser Gmbh Joh A Wasserlösliches, wasserenthärtendes Mittel
DE19714657C1 (de) * 1997-04-09 1999-01-07 Benckiser Nv Wasserlöslicher, wasserenthärtender Builder
GB2342358A (en) * 1998-10-09 2000-04-12 Procter & Gamble Detergent compositions comprising cationic polymers
EP1001011B2 (fr) * 1998-11-11 2010-06-23 The Procter & Gamble Company Composition de blanchiment comprenant acide benzoique alkoxylé
EP1010751B1 (fr) * 1998-12-14 2005-04-20 The Procter & Gamble Company Compositions de blanchiment
GB2379223A (en) * 2001-08-31 2003-03-05 Reckitt Benckiser Inc Cleaning composition comprising citric acid
US6608022B1 (en) * 2003-01-27 2003-08-19 Colgate-Palmolive Company Cleaning compositions in the form of a tablet
ES2286602T3 (es) 2003-02-10 2007-12-01 Henkel Kommanditgesellschaft Auf Aktien Antecedentes de la invencion.
US20080045438A1 (en) * 2006-08-21 2008-02-21 D/B/A Unilever, A Corporation Of New York Softening laundry detergent

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB994353A (en) † 1960-06-13 1965-06-02 Domestos Ltd Improvements in detergent compositions
US3716488A (en) † 1970-09-04 1973-02-13 Stevens & Co Inc J P Textile fabric cleaning compositions
EP0781836A1 (fr) † 1995-12-29 1997-07-02 Colgate-Palmolive Company Composition détergente ayant un pouvoir nettoyant amélioré dans un milieu acide ou neutre
DE10032589A1 (de) † 2000-07-07 2002-01-24 Henkel Kgaa Wäßriges Bleichmittel
US20030008804A1 (en) † 2001-06-05 2003-01-09 Qiu Xu Starch graft copolymer, detergent builder composition including the same, and production method thereof
US7229505B2 (en) † 2001-09-14 2007-06-12 Clean Control Corporation Methods and compositions for surfactant-free cleaning
US20060111261A1 (en) † 2004-11-19 2006-05-25 The Procter & Gamble Company Acidic laundry detergent compositions
JP2009263466A (ja) † 2008-04-24 2009-11-12 Kao Corp 液体洗浄剤組成物
JP5398051B2 (ja) † 2008-06-23 2014-01-29 花王株式会社 洗剤組成物

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
Priodoc. EP 09173666 †
Priodoc. IN 1621/MUM/2010 †
Priodoc. IN 2007/MUM/2009 †

Also Published As

Publication number Publication date
AU2010291392B2 (en) 2013-07-11
EA201200401A1 (ru) 2012-08-30
EA022063B1 (ru) 2015-10-30
CN102575197A (zh) 2012-07-11
EP2473590B1 (fr) 2014-11-26
MX2012002748A (es) 2012-04-19
BR112012003018A2 (pt) 2016-04-19
CA2770869A1 (fr) 2011-03-10
EP2473590A1 (fr) 2012-07-11
ES2531418T5 (es) 2018-04-13
AR078146A1 (es) 2011-10-19
ES2531418T3 (es) 2015-03-13
WO2011026718A1 (fr) 2011-03-10
AU2010291392A1 (en) 2012-02-23
CL2012000538A1 (es) 2012-10-19
ZA201200792B (en) 2013-05-29
CN102575197B (zh) 2013-10-30

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