EP3246462B1 - Farbtransferhemmendes material - Google Patents

Farbtransferhemmendes material Download PDF

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Publication number
EP3246462B1
EP3246462B1 EP15710823.4A EP15710823A EP3246462B1 EP 3246462 B1 EP3246462 B1 EP 3246462B1 EP 15710823 A EP15710823 A EP 15710823A EP 3246462 B1 EP3246462 B1 EP 3246462B1
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EP
European Patent Office
Prior art keywords
cellulose
colour transfer
laundering
colour
particles
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Not-in-force
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EP15710823.4A
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English (en)
French (fr)
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EP3246462A1 (de
Inventor
Guadalupe BORJA RODRÍGUEZ
Esther DELGADO RODRÍGUEZ
Janina SERRA COMELLAS
Mirko FACCINI
David Amantia
Rosa Escudero Moreno
Miguel OSSET HERNÁNDEZ
Laurent Aubouy
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Leitat Technological Centre
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Leitat Technological Centre
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    • 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
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0021—Dye-stain or dye-transfer inhibiting compositions
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/0007—Electro-spinning
    • D01D5/0015—Electro-spinning characterised by the initial state of the material
    • D01D5/003—Electro-spinning characterised by the initial state of the material the material being a polymer solution or dispersion
    • D01D5/0038—Electro-spinning characterised by the initial state of the material the material being a polymer solution or dispersion the fibre formed by solvent evaporation, i.e. dry electro-spinning
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/10—Other agents for modifying properties
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F2/00—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof
    • D01F2/24—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof from cellulose derivatives
    • D01F2/28—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof from cellulose derivatives from organic cellulose esters or ethers, e.g. cellulose acetate
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
    • D06M13/46—Compounds containing quaternary nitrogen atoms
    • D06M13/463—Compounds containing quaternary nitrogen atoms derived from monoamines
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
    • D06P1/655—Compounds containing ammonium groups
    • D06P1/66—Compounds containing ammonium groups containing quaternary ammonium groups
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P5/00—Other features in dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form
    • D06P5/22—Effecting variation of dye affinity on textile material by chemical means that react with the fibre
    • D06P5/225—Aminalization of cellulose; introducing aminogroups into cellulose
    • 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
    • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/10—Objects to be cleaned
    • C11D2111/12—Soft surfaces, e.g. textile
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/02—Natural fibres, other than mineral fibres
    • D06M2101/04—Vegetal fibres
    • D06M2101/06—Vegetal fibres cellulosic

Definitions

  • the present invention relates to additives for the laundering of clothing, and in particular to a material which is suitable for colour transfer inhibition during laundering.
  • coloured articles of clothing may lose some of the colourant substances contained therein during laundering, which are transferred to the water used for this purpose, and may be transferred therefrom to other articles present, which may be of a lighter colour or white, giving rise to an undesired colouring of these last.
  • a traditional method to prevent this colour transfer between laundered clothing consists of simply laundering the articles of clothing separately in the washing machine, in accordance with their colour.
  • performing this separation is irksome, entails difficulties in the optimisation of the number of washes, and an undesired dyeing cannot always be avoided thus.
  • This separation also entails an increase in laundering time, and a greater water and electricity consumption.
  • the North American patent US4380453 describes the use of a substrate intended for the application of or impregnation with a colourant-collecting substance, for example a quaternary ammonium compound of the glycidyl ammonium type, such as glycidyltrimethylammonium chloride, or a derivative of trisubstituted 2-hydroxy-3-halopropyl ammonium.
  • a colourant-collecting substance for example a quaternary ammonium compound of the glycidyl ammonium type, such as glycidyltrimethylammonium chloride, or a derivative of trisubstituted 2-hydroxy-3-halopropyl ammonium.
  • the substrate acts to adsorb the colourants which become dissociated from the dyed materials, and thus to prevent the colouring of other materials present in the washer tub.
  • a cellulose textile material which may be woven, non-woven, rope, a ball, knitted or otherwise.
  • the French patent application FR-A-2761702 also relates to the same problem of colour transfer during the laundering process.
  • Said application proposes the use of finely-divided lignocellulose substances to gather the colourants which are released from the fabrics during laundering.
  • a description is made of the use of micronised steam-treated wood powder and micronised straw. It is also set forth that said substances are not added to the detergent formula, but are added separately to the washer tub, for example, within a bag whose mesh is adapted to the granulometry of the lignocellulose substances in such a way as to prevent the egress of the same into the tub, as it would be difficult to avoid their redeposition on the clothing.
  • the European patent application EP-A-1621604 also puts forward the problem of colour transfer during laundering, and proposes a colourant-collecting material comprising a selected woven or non-woven, synthetic or natural, or paper substrate, and an additive comprised of one of the following polymers: proteins, chitin, chitosan, cationic heterocyclic polymers, polyvinylamine, polyethylenimine, acrylic polymers, vinylic polymers, polyamine N-oxide, and blends of the same.
  • the additive is incorporated in the substrate by means of impregnation or pulverisation.
  • the object of the present invention is a colour transfer-inhibiting material.
  • a procedure for the preparation of said material is also part of the object of the invention.
  • a laundering procedure including the use of said material is also part of the object of the invention.
  • a composition comprising said material is also part of the object of the invention.
  • the anti-colour transfer efficacy is represented in ordinates, according to a numerical scale from 0 to 5, 5 indicating maximum efficacy.
  • Each of the materials tested is represented in abscissas.
  • the object of the present invention is a colour transfer-inhibiting material consisting of a cellulose substrate, functionalised by means of a quaternary ammonium compound with the formula (I): where:
  • the authors of the present invention have developed a new material, prepared from a substrate formed by microcrystalline cellulose particles which, surprisingly, present colour transfer-inhibiting properties superior to those of the products described in the state of the art, particularly regarding the commercial products where the cellulose medium is not nanostructured but has the form of a common textile material of the towelling type.
  • the material developed is suited to be used as an additive in the laundering of clothing in order to prevent the undesired dyeing of items.
  • the colour transfer-inhibiting material in accordance with the present invention, is characterised in that it contains a cellulose substrate in particle form, which presents specific physio-chemical characteristics, entirely dissimilar to the textile cellulose materials commonly used as a medium in colour transfer-inhibiting products, and which confer to said material considerably superior colour transfer-inhibiting properties.
  • the cellulose substrate employed in the present invention is in the form of microcrystalline cellulose particles.
  • the particles of cellulose are cellulose microparticles or nanoparticles; that is to say, their average size is in the order of micrometers (or microns), habitually between 1 ⁇ m and 1000 ⁇ m, or in the order of nanometers, habitually between 1 nm and 1000 nm.
  • cellulose microparticles and nanoparticles are not always well-defined, as the particles are not usually granular, i.e. they do not have an approximately spherical shape but are fibrillar, typically defined in accordance with their average thickness (T) and their average length (L), so that cellulose particles are usually classified as nanoparticles if at least one of said dimensions, particularly the thickness, is less than 1 ⁇ m.
  • fibrillar-shaped particles they are also habitually characterised by means of the "aspect ratio" parameter, this being the ratio between the length and thickness of said fibres.
  • the particles of cellulose have an average size of between 0.01 ⁇ m and 400 ⁇ m, and preferably between 0.05 ⁇ m and 200 ⁇ m.
  • Said average size of the cellulose particles whose shape, as was mentioned above, is irregular, habitually refers to its equivalent average diameter; that is, the diameter of a sphere of a volume equivalent to that of the particle.
  • the term "average size" is used interchangeably to refer to the average diameter or the equivalent average diameter.
  • the average size of the cellulose particles may be determined by means of the usual analytical procedures for the measurement of average particle size, which are well-known to the expert in the field, such as screening methods, the electric current-sensitive area method (Coulter counter), by laser light dispersion, or by means of the use of electronic microscopy, particularly the Scanning Electron Microscope (SEM) or Transmission Electron Microscope (TEM).
  • SEM Scanning Electron Microscope
  • TEM Transmission Electron Microscope
  • La ciencia del dise ⁇ o de las formas farmacéuticas [The science of pharmaceutical dosage form design], second edition, Elsevier, Madrid, 2004, Chapter 10, pp 154-167 , the most usual parameters and methods used for the definition and measurement of particle sizes are described.
  • the particles of cellulose which act as the substrate of the colour transfer-inhibiting material, are microcrystalline cellulose.
  • the particles of cellulose employed as a medium are microcrystalline cellulose.
  • Microcrystalline cellulose is a crystalline, powdery substance, obtained by means of the controlled hydrolysis of ⁇ -cellulose, whose characteristics are well known and are described, for example, in the book by R.C. Rowe, P.J. Sheskey and P.J. Weller, Handbook of pharmaceutical excipients, fourth edition, Pharmaceutical Press, 2003 .
  • Microcrystalline cellulose presents an average particle size which usually varies between 20 ⁇ m and 300 ⁇ m, depending on the different suppliers and procedures used for the obtaining of the same.
  • a microcrystalline cellulose with an average particle size of between 40 ⁇ m and 150 ⁇ m is used, and more preferably, between 50 ⁇ m and 120 ⁇ m; still more preferably, between 70 ⁇ m and 100 ⁇ m.
  • Microcrystalline cellulose particles are granular, with an approximately spherical shape, with an aspect ratio usually between approximately 1 and 3.
  • Microcrystalline cellulose may be obtained commercially from a number of suppliers, for example from the company FMC Biopolymer, under the generic brand name of AVICEL® or from the company Acros Organics, which distributes microcrystalline cellulose with an average particle size of 50 ⁇ m to 90 ⁇ m; the company Sigma-Aldrich also distributes microcrystalline cellulose under the name Cellulose Microcrystalline 310697, with an average particle size of 20 ⁇ m; likewise, the company JRS (J. Rettenmaier & Söhne) markets microcrystalline cellulose under the brand names VIVAPUR® and HEWETEN®, with different particle sizes, for example the so-called HEWETEN® 102, with an average particle size of 90 ⁇ m.
  • FMC Biopolymer under the generic brand name of AVICEL® or from the company Acros Organics, which distributes microcrystalline cellulose with an average particle size of 50 ⁇ m to 90 ⁇ m
  • Sigma-Aldrich also distributes microcrystalline cellulose under the name Cellulose Microcrystalline
  • the cellulose particles employed as a medium are powdered cellulose.
  • Powdered cellulose is a powder obtained by the reduction in size of ⁇ -cellulose by mechanical means, and whose characteristics are specified, for example, in the aforementioned book by R.C. Rowe; they present a usual particle size of between 20 ⁇ m and 250 ⁇ m.
  • Cellulose in powdered form may be obtained commercially, for example, from the company J. Rettenmaier & Söhne, under the generic brand name ARBOCEL®, according to the ARBOCEL® M80 or ARBOCEL® A300 varieties, for example.
  • the cellulose particles employed as a medium are microfibrillated cellulose.
  • Microfibrillated cellulose features dimensions which habitually vary between 0.01 ⁇ m and 4 ⁇ m average thickness, poreferably between 0.01 ⁇ m and 0.1 ⁇ m, and between 1 ⁇ m and 100 ⁇ m average length. They usually have an aspect ratio of up to 100 (maximum).
  • microfibrillated cellulose may be characterised by the average diameter or equivalent average diameter of the particles, which is usually between 0.05 ⁇ m and 15 ⁇ m.
  • Microfibrillated cellulose is obtained from cellulose, or from microcrystalline cellulose, by a mechanical homogenisation treatment under high pressure, optionally combined with a chemical or enzymatic treatment. Microfibrillated cellulose usually has a thickness of less than 1 ⁇ m; for this reason, it is usually described as nanocellulose, or cellulose nanoparticles.
  • Microfibrillated cellulose is well-known to the expert in the field, and may be obtained commercially, in different sizes, from various suppliers, in particular from the company J. Rettenmaier & Söhne, for example, that known under the brand name ARBOCEL® UFC 100, whose fibres have a length of approximately 8 ⁇ m.
  • the cellulose particles employed as a medium are nanocrystalline cellulose.
  • Nanocrystalline cellulose is a highly crystalline form of cellulose, presented in the shape of needles, and obtained by means of the hydrolysis of cellulose with a strong acid under controlled conditions, for example, as described in the article by Habibi et al., Cellulose nanocrystals: chemistry, self-assembly, and applications, Chem. Rev., 2010, 110, pp3479-3500 .
  • Nanocrystalline cellulose presents usual dimensions of between 3 nm and 5nm in thickness and up to 200 nm in length.
  • the particles of cellulose employed as a medium are prepared by means of the pulverisation of cellulose nanofibres obtained by electrospinning.
  • the particles thus obtained, in the form of fibres or filaments generally have an average diameter of between 0.1 ⁇ m and 1 ⁇ m, but preferably between 0.3 ⁇ m and 0.8 ⁇ m, and an average length of between 2 ⁇ m and 100 ⁇ m, more preferably between 3 ⁇ m and 80 ⁇ m, and more preferably still between 4 ⁇ m and 50 ⁇ m.
  • cellulose nanofibres for example, a cellulose acetate solution may be used in a solvent or a blend of solvents; for example, a blend of acetone and dimethylacetamide.
  • the cellulose acetate may be obtained commercially; e.g. the Sigma-Aldrich company distributes cellulose acetate with an average molecular weight (Mn) of 30,000.
  • Suitable conditions for performing the electrospinning of cellulose acetate are, for example: a voltage of 30 kV, a flowrate of between 3 and 4 mL/h, a distance of 12 cm to the collector and a rotation velocity of 500 rpm.
  • the cellulose acetate nanofibres obtained are hydrolysed, usually with a sodium hydroxide solution, in order to deacetylise the product and to obtain cellulose nanofibres.
  • the solid obtained is filtered and dried, preferably at a temperature between 40 oC and 80 oC, and more preferably between 55 oC and 65 oC, during a period of usually between 0.5 and 3 hours, and preferably of approximately 1 hour.
  • the nanofibres obtained by means of this electrospinning process are pulverised, for example in an IKA A 11 basic mill, to obtain cellulose particles.
  • the pulverisation stage may be performed on the cellulose acetate nanofibres obtained directly from the electrospinning process and/or subsequent to the hydrolysis stage, once the cellulose has been deacetylised.
  • the cellulose medium employed in the colour transfer-inhibiting material is cellulose nanofibres, prepared by electrospinning, but unpulverised.
  • the colour transfer-inhibiting material consists of a microcrystalline cellulose medium, functionalised by means of a quaternary ammonium compound, characterised in that it has great affinity for colourants or dyes.
  • the quaternary ammonium compound employed in the material which is the object of the present invention is a product with the formula (I): where:
  • a C 1-6 alkyl group refers to a saturated hydrocarbonated group possessing between 1 and 6 carbon atoms, which may be linear or branched, and includes, among others, the methyl, ethyl, n- propyl, isopropyl, sec-butyl, tert -butyl, n-pentyl, 1-methylbutyl or n-hexyl groups.
  • a C 1-20 alkyl group refers to a saturated hydrocarbonated group possessing between 1 and 20 carbon atoms, which may be linear or branched, and includes, among others, the methyl, ethyl, n-propyl, isopropyl, sec-butyl, tert -butyl, n-pentyl, 1-methylbutyl, n-hexyl, n-octyl, n-decyl, n-dodecyl, n-tetradecyl, n-hexadecyl or n-octadecyl groups.
  • a C 8 -C 18 n-alkyl group refers to a saturated linear hydrocarbonated group possessing between 8 and 18 carbon atoms, and is formed by the n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl and n-octadecyl groups.
  • the oxiranyl group refers to the radical:
  • the 2-chloro-hydroxyethyl group refers to the radical:
  • the tetrafluoroborate anion refers to the BF 4 - group
  • the trifluoromethanesulphonate (or triflate) is the SO 3 (CF 3 ) - anion
  • the nitrate group corresponds to the NO 3 - anion.
  • the compound with formula (I) is characterised in that n is 1, R 2 , R 3 and R 4 are selected from the group formed by methyl, ethyl, n-propyl and isopropyl, and X is selected from the group formed by Cl, Br and I. In a still more preferred embodiment, R 2 , R 3 and R 4 are methyl and X is Cl.
  • R 1 is oxiranyl
  • the quaternary ammonium compound with formula (I) is characterised in that:
  • the compound with formula (I) is characterised in that n is 1, R 1 is oxiranyl, R 2 , R 3 and R 4 are methyl and X is selected between Cl, Br and I; more preferably, X is Cl.
  • the product with formula (I) is glycidyltrimethylammonium chloride ( CAS number 3033-77-0 ), which is commercially available from various suppliers, for example Sigma-Aldrich (Switzerland) or from SKW Quab Chemicals (product Quab® 151).
  • the compound with formula (I) is characterised in that n is 1, R 1 is 2-chloro-1-hydroxyethyl, R 2 , R 3 and R 4 are methyl and X is selected between Cl, Br and I; more preferably, X is Cl.
  • the product with formula (I) is 3-Chloro-2-hydroxypropyltrimethyl ammonium chloride ( CAS number 3327-22-8 ), which may be obtained from the Sigma-Aldrich company, or from the company SKW Quab Chemicals (product Quab® 188).
  • the compound with formula (I) is characterised in that n is 1, R 1 is 2-chloro-1-hydroxyethyl, R 2 and R 3 are methyl, R 4 is selected from a C 8 -C 18 n-alkyl; more preferably, it is selected between n-octyl, n-dodecyl, n-hexadecyl and n-octadecyl, and X is selected between Cl, Br and I; more preferably, X is Cl.
  • the compound with formula (I) is usually a blend of at least two compounds, with different R 4 , in different proportions.
  • the cellulose medium is functionalised with the quaternary ammonium product with formula (I). This means that said product binds to the cellulose due to a reaction with the hydroxyl groups present in the same, so as to form functionalised cellulose particles or nanofibres, in accordance with the structure below, where the circle represents the cellulose medium:
  • a procedure for the preparation of the material of the present invention also constitutes part of the invention.
  • a procedure consisting of the following stages, for example, may be employed:
  • any alkalising agent may be used, such as alkaline hydroxides or alkaline carbonates.
  • alkaline hydroxides or alkaline carbonates Preferably, sodium hydroxide should be employed as an alkalising agent.
  • the concentration of sodium hydroxide is preferably between 2% and 10%, more preferably between 3% and 5%, and still more preferably between 4% and 4.5%; the concentration of the quaternary ammonium compound with formula (I) is preferably between 2% and 15%, more preferably between 5% and 10%, and still more preferably between 8% and 9%; and the concentration of cellulose is preferably between 1% and 10%, more preferably between 3% and 5%, and still more preferably between 4% and 4.5%; all these percentages are expressed by weight.
  • the molar ratio between the cellulose material / sodium hydroxide / compound with formula (I) is preferably between the following values: 1 / (3-10) / (1.5-5), more preferably between 1 / (4.0-4.5) / (2.0-2.5), and still more preferably said molar ratio is 1 / 4.1 / 2.1.
  • stage (a) the combination is kept stirred at ambient temperature, for example between 10 minutes and 3 hours, preferably between 15 minutes and 1.5 hours, by means of mechanical stirring at, for example, between 600 and 1500 rpm, or by means of magnetic stirring.
  • stage (b) of the process the majority of the solution is eliminated by means of filtration, and the soaked cellulose material is placed in an oven at a temperature between 60 oC and 110 oC, preferably at 100 oC, during a period of preferably between 15 minutes and 24 hours.
  • stage (c) the functionalised cellulose obtained is washed repeatedly with water until the pH of the water used in the washing is approximately neutral.
  • the resulting material is then dried at a temperature between 60 oC and 80 oC, during a period of time of preferably between 12 and 24 hours.
  • stage (a) Two alternative procedures may be followed in stage (a).
  • an aqueous solution is prepared of the alkalising agent, preferably sodium hydroxide, with the quaternary ammonium compound with formula (I), and the cellulose particles are added to said solution, subsequently stirring the combination during a period of time preferably between 10 minutes and 3 hours, more preferably between 15 minutes and 1.5 hours.
  • the alkalising agent preferably sodium hydroxide
  • a blend may first be prepared by adding the cellulose material to an aqueous solution of the alkalising agent, preferably sodium hydroxide, stirring during a period of time preferably between 5 minutes and 1.5 hours; the quaternary ammonium compound with formula (I) is then added, stirring once again, preferably during between 5 minutes and 1.5 hours.
  • the alkalising agent preferably sodium hydroxide
  • Example 11 the efficacy of the material of the invention in the prevention of inter-fabric colour transfer was assessed, according to a test performed in a Lini-Test apparatus which simulated the washing conditions within a washing machine, and in which coloured fabrics and white fabrics were placed, together with a detergent without anti-colour transfer additives and the material of the invention, or three commercial products, as well as said detergent as a reference. Fabrics dyed with different colourants were tested, and white cotton and polyamide fabrics.
  • the material of the invention is suited to be incorporated as an additive during the laundering of clothing, typically for the automatic wash provided by any commercially available type of washing machine. Said material may be added, for example, at the start of the main wash program, together with the detergent, or alternatively immediately before or after adding the detergent.
  • the quantity of the material of the invention added to the washing machine is usually between 1 g and 50 g per each Kg of clothing, although this quantity may be varied according to needs.
  • a procedure for the washing of textiles and comprising the use of said material also forms part of the object of the invention.
  • Said procedure consists of following the habitual washing process of each washing machine, according to any of the programs available, at any temperature, and with any duration, and is characterised by the action of adding the colour transfer-inhibiting material which is the object of the present invention during the wash; this is preferably added together with the detergent, or alternatively immediately before or after adding the detergent, so that it may operate during the main washing stage, which is when the risk of colour transfer is greatest.
  • the product of the invention in the form of fine, functionalised cellulose particles, acts in the washer tub, adsorbing the colourant which may be released by coloured articles of clothing, and is eliminated simply during rinsing, leaving no residue and without damaging the clothing. It is therefore unnecessary to eliminate the anti-transfer product on completion of the wash, as is the case with other commercial products of the towelling type.
  • the material of this invention may be added to any suitable composition for use in the laundering of clothing; for example, to a laundering additive or a detergent compound.
  • the material of this invention may be added to a detergent compound, in such a way that a detergent containing a colour transfer-inhibiting product is obtained.
  • Suitable detergent compounds for the addition of the colour transfer-inhibiting product in accordance with the present invention may be, without limit, any type of detergent compound which is suited for the laundering of textile articles, and which are well-known by an expert in the field; for example, as described in the book by J.J. Garcia Dom ⁇ nguez, Tensioactivos y Detergencia, Editorial Dossat, Madrid, 1986 (ISBN 84-237-0687-7 ); or the book by G. Jakobi and A. Lschreib, Detergents and Textile Washing. Principles and Practice. VCH Verlagsgesellschaft, Weinheim, 1987 (ISBN 3-527-26811-1 ).
  • a combination for the laundering of clothing including the colour transfer-inhibiting material of the present invention also forms part of the object of the invention.
  • a solution was prepared, at 22% by weight, of cellulose acetate (Sigma Aldrich 180955, average molecular weight M n , 30.000) in a blend of the solvents acetone and dimethylacetamide at a proportion of 1:1 by weight.
  • cellulose acetate Sigma Aldrich 180955, average molecular weight M n , 30.000
  • the resulting solution was subjected to an electrospinning process in the commercial equipment model NF-103 of the company MECC Co. Ltd.
  • nanofibres were deacetylised; to this end they were submerged in 3.5 L of a solution of NaOH 0.3 M for 1 hour, and the deacetylation was monitored by infrared spectroscopy (IR/ATR, Infrared / Attenuated Total Reflection ); to this end, a commercial apparatus model IRAffinity-1 was used, with a MiracleTM ATR accessory belonging to the company SHIMADZU.
  • nanofibres were filtered, washed with water, and dried overnight at a temperature of 60 oC.
  • the cellulose nanofibres thus obtained were characterised using a Scanning Electron Microscope (SEM), specifically using an apparatus model JSM-6010-LV belonging to the company JEOL.
  • SEM Scanning Electron Microscope
  • the diameter of said fibres was 452 nm ⁇ 130 nm.
  • Preparative example 2 Preparation of cellulose particles by pulverisation of cellulose nanofibres obtained by means of electrospinning (Comparative)
  • the size of said particles was characterised using the Scanning Electron Microscope, observing that the particles prepared from the nanofibres had an approximate length of between 4 and 20 ⁇ m.
  • microcrystalline cellulose Invention
  • ACROS ORGANICS Microcrystalline cellulose
  • Comparative Albocel, Product UFC 100, average particle size between 6-12 ⁇ m (d 50 )
  • Preparative Preparative
  • Procedure 1 An aqueous solution of NaOH and glycidyltrimethylammonium chloride was prepared in a receptacle and the particles of cellulose were added to said solution, in such a way that the proportion by weight of the cellulose particles was 4.2% in all cases, the proportion by weight of NaOH was 4.3%, and the concentration of glycidyltrimethylammonium chloride was 8.3%; this represented a molar cellulose / NaOH / glycidyltrimethylammonium chloride ratio of 1 / 4.1 / 2.1. The combination was mechanically stirred at 1000 rpm for 1 hour at ambient temperature.
  • the particles of cellulose were filtered in order to eliminate the majority of the solution, leaving the soaked cellulose material, and immediately said material was arranged in an oven at 100 oC for 30 minutes. Subsequently, the final product was washed repeatedly in water until the water from the washes displayed a neutral pH. The resulting material was dried at 80 oC for 20 hours.
  • Procedure 2 An aqueous solution of NaOH was prepared in a receptacle, the particles of cellulose were added and the combination was mechanically stirred at 1000 rpm for 30 minutes at ambient temperature. Next, the glycidyltrimethylammonium chloride was added, and the combination was mechanically stirred at 1000 rpm for another 15 minutes at ambient temperature. As in the previous procedure, the proportion by weight of the cellulose particles in all cases was 4.2%, the proportion by weight of NaOH was 4.3%, and the concentration of glycidyltrimethylammonium chloride was 8.3%; this represented a molar cellulose / NaOH / glycidyltrimethylammonium chloride ratio of 1 / 4.1 / 2.1.
  • Example 6 (Comparative) Microfibrillated Cellulose Proc. 1 0.410
  • Example 7 (Comparative) Microfibrillated Cellulose Proc. 2 0.440 Reference Example A -- -- 0.60 Reference Example B -- -- 0.441 Reference Example C -- -- 0.194-2.802*
  • Example 9 Test of colourant adsorption capacity of the material of the invention: kinetic trial
  • a test was performed in order to assess the adsorption capacity of Direct Red 83 colourant ( CAS 15418-16-3 ) by the material which is the object of the present invention, in comparison with commercial products, according to contact time (or kinetic trial).
  • the quantity of colourant adsorbed was determined, expressed as mg of colourant per gramme of material, after different periods of time (1, 5, 10, 15, 30, 45 and 60 minutes).
  • Example 10 Test of colourant adsorption capacity of the material of the invention: trial at 60 minutes
  • Example 9 A procedure analogous to that described in Example 9 was followed, placing 10 mg of the material to be tested in contact with 10 mL of a solution of Direct Red 83 colourant with a concentration of 500 ppm.
  • Example 3 Comparative
  • Example 5 Invention
  • Example 7 Comparative
  • Example 11 Test of the efficacy of the materials of the invention as anti-colour transfer agents
  • the colour acceptor fabrics used in the test were:
  • acceptor fabrics were pre-washed three times at 60 oC using a cotton program and a detergent without optical whiteners.
  • the colour donor fabrics employed in the test were: Direct Orange 39 ( CAS 1325-54- 8 ), Direct Red 83 ( CAS 15418-16-3 ), Direct Black 22 ( CAS 6473-13-8 ) and Acid Blue 113 ( CAS 3351-05-1 ), all of these commercially available, for example via EMPA or WFK. 0.3 g of each donor fabric was used for the tests.
  • a Lini-Test Atlas apparatus For the performance of the test a Lini-Test Atlas apparatus was employed. Said apparatus consists of a water bath in which a device with 8 hermetically closed receptacles rotates at a speed of (40 ⁇ 2) rpm. Each receptacle contained a donor fabric and an acceptor fabric of each type, together with 100 mL of the solution of the product to be tested.
  • the pre-prepared receptacles were inserted. At this time, the bath continued to be heated at a rate of 2 oC/min until reaching 60 oC, and this temperature was maintained constant for 20 minutes. On completion of the testing time, the acceptor fabrics were removed and were rinsed under running water. The fabrics were air-dried, avoiding direct light.
  • the fabrics were assessed spectrophotometrically at the commencement and on completion of the test, in order to calculate the quantity of colour accepted (dyeing) by each specimen.
  • the assessment of anti-transfer efficacy was based on a numerical assessment assigned on the basis of a scale of greys according to the UNE EN ISO 105-A04 standard. The values range from 0 (black) to 5 (white). The higher the value, the better the prevention of colour transfer.
  • Table 4 summarises the results obtained in the test on the materials in accordance with Examples 4 and 5 (Invention), and Examples 3, 6 and 7 (Comparative) compared with the commercial products (Reference Examples A, B and C) and with the commercial detergent without any anti-colour transfer additive ( Det ). The transfer of colour from each donor fabric was tested independently for each type of acceptor fabric (cotton and polyamide). TABLE 4 Donor fabric (acceptor fabric) Comparisons Material of the invention Det A B C 3 Comp. 4 Inv. 5 Inv. 6 Comp. 7 Comp.
  • Figures 3, 4 , 5 and 6 depict graphically the results from Table 4 for the three direct colourants on cotton, and for the acid colourant on polyamide. In all of these it is possible to observe the superiority of the material of the invention in comparison with the rest of products assessed.

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

Claims (9)

  1. Ein einen Farbübergang hemmendes Material, das aus einem Zellulosesubstrat besteht, das mit einer quaternären Ammoniumverbindung der Formel (I) funktionalisiert ist:
    Figure imgb0007
     wobei:
    n zwischen 1 und 20 beträgt;
    R1 zwischen Oxiranyl und 2-Chlor-1-Hydroxyethyl ausgewählt ist;
    R2 und R3 unabhängig voneinander aus C1-6-Alkylgruppen und Benzyl ausgewählt sind;
    R4 aus C1-20-Alkylgruppen ausgewählt ist; und
    X aus der Gruppe ausgewählt ist, die durch Cl, Br, I, Tetrafluorborat, Trifluormethansulphonat und Nitrat gebildet ist;
    und wobei das Zellulosesubstrat aus Partikeln einer mikrokristallinen Zellulose besteht.
  2. Material gemäß Anspruch 1, dadurch gekennzeichnet, dass die mikrokristalline Zellulose einen durchschnittlichen Partikeldurchmesser zwischen 40 µm und 150 µm aufweist.
  3. Material gemäß Anspruch 1 oder 2, dadurch gekennzeichnet, dass bei der Verbindung der Formel (I) n 1 ist, R2, R3 und R4 aus der Gruppe ausgewählt sind, die durch Methyl, Ethyl, n-Propyl und Isopropyl gebildet ist, und X aus der durch Cl, Br und I gebildeten Gruppe ausgewählt ist.
  4. Material gemäß Anspruch 3, dadurch gekennzeichnet, dass R2, R3 und R4 Methyl sind und X Cl ist.
  5. Material gemäß Anspruch 4, dadurch gekennzeichnet, dass die Verbindung der Formel (I) Glycidyltrimethylammoniumchlorid ist.
  6. Ein Verfahren zur Herstellung des einen Farbübergang hemmenden Materials gemäß einem der Ansprüche 1 bis 5, das folgende Schritte aufweist:
    a) Herstellen einer wässrigen Suspension des Zellulosesubstrats zusammen mit der quaternären Ammoniumverbindung mit der Formel (I) bei einem alkalischen pH-Wert zwischen 12 und 14 und unter ständigem Rühren der Kombination;
    b) Filtern und Beaufschlagen des resultierenden eingeweichten Zellulosematerials mit einer Temperatur zwischen 60°C und 110°C;
    c) Waschen des resultierenden Materials mit Wasser, bis ein neutraler pH-Wert erreicht ist, und anschließendes Trocknen bei einer Temperatur zwischen 60°C und 80°C.
  7. Verwendung des Materials gemäß einem der Ansprüche 1 bis 5, um einen Farbübergang während des Waschens von Kleidung zu hemmen.
  8. Ein Verfahren zum Waschen von Textilien, das die Verwendung des Materials gemäß einem der Ansprüche 1 bis 5 aufweist.
  9. Eine Zusammensetzung zum Waschen von Kleidung, die das Material gemäß einem der Ansprüche 1 bis 5 aufweist.
EP15710823.4A 2015-01-15 2015-01-15 Farbtransferhemmendes material Not-in-force EP3246462B1 (de)

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US10421932B2 (en) 2016-07-21 2019-09-24 The Procter & Gamble Company Cleaning composition with insoluble quaternized cellulose particles and non-anionic performance polymers
US10421931B2 (en) 2016-07-21 2019-09-24 The Procter & Gamble Company Cleaning composition with insoluble quaternized cellulose particles and an external structurant

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US4380453A (en) 1980-02-06 1983-04-19 Dixie Yarns, Inc. Extraneous dye or colorant scavenging system in laundry
DE3606729A1 (de) * 1986-03-01 1987-09-03 Henkel Kgaa Wasch- und reinigungsmittel mit verringertem chemikalienbedarf
FR2761702B1 (fr) 1997-04-08 1999-05-28 Bernard Jacques George Dubreux Procede de lavage de tissus en bain aqueux permettant d'eviter ou limiter le transfert de teintures
AU2001281109A1 (en) 2000-08-04 2002-02-18 Cuno, Incorporated Charge-modified dye absorption media
ES2315827T3 (es) 2004-07-29 2009-04-01 Orlandi S.P.A. Material rescatador de color.
ATE545694T1 (de) 2007-12-04 2012-03-15 Atlantichem Gmbh Mittel zum verhindern von verfärbungen beim waschen von textilien
CN102844422B (zh) * 2010-04-22 2016-01-20 荷兰联合利华有限公司 涉及织物调理剂的改进
JP5150792B2 (ja) * 2011-03-11 2013-02-27 Ｄｉｃ株式会社 変性セルロースナノファイバー、その製造方法及びこれを用いた樹脂組成物
ES2575802T3 (es) * 2012-02-13 2016-07-01 Henkel Ag & Co. Kgaa Agente de lavado o de limpieza protector del color

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* Cited by examiner, † Cited by third party
Title
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