EP0509277A1 - Procédé de teinture de la cellulose avec des colorants au soufre - Google Patents

Procédé de teinture de la cellulose avec des colorants au soufre Download PDF

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Publication number
EP0509277A1
EP0509277A1 EP92105100A EP92105100A EP0509277A1 EP 0509277 A1 EP0509277 A1 EP 0509277A1 EP 92105100 A EP92105100 A EP 92105100A EP 92105100 A EP92105100 A EP 92105100A EP 0509277 A1 EP0509277 A1 EP 0509277A1
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EP
European Patent Office
Prior art keywords
grafted
cellulose
alkyl
polymer
formula
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.)
Ceased
Application number
EP92105100A
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German (de)
English (en)
Inventor
Karl-Heinz Dr. Keil
Thomas Dr. Martini
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.)
Hoechst AG
Original Assignee
Cassella AG
Hoechst AG
Cassella Farbwerke Mainkur AG
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 Cassella AG, Hoechst AG, Cassella Farbwerke Mainkur AG filed Critical Cassella AG
Publication of EP0509277A1 publication Critical patent/EP0509277A1/fr
Ceased legal-status Critical Current

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Classifications

    • 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
    • D06M14/00—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials
    • D06M14/02—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials on to materials of natural origin
    • D06M14/04—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials on to materials of natural origin of vegetal origin, e.g. cellulose or derivatives thereof
    • 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
    • D06M14/00—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials
    • D06M14/18—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials using wave energy or particle radiation
    • D06M14/20—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials using wave energy or particle radiation on to materials of natural origin
    • D06M14/22—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials using wave energy or particle radiation on to materials of natural origin of vegetal origin, e.g. cellulose or derivatives thereof
    • 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
    • D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
    • D06P3/58—Material containing hydroxyl groups
    • D06P3/60—Natural or regenerated cellulose
    • D06P3/6025—Natural or regenerated cellulose using vat or sulfur dyes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S8/00—Bleaching and dyeing; fluid treatment and chemical modification of textiles and fibers
    • Y10S8/916—Natural fiber dyeing
    • Y10S8/918—Cellulose textile

Definitions

  • the invention relates to a process for dyeing cellulose with non-reduced anionic sulfur dyes.
  • non-reduced anionic sulfur dyes are in particular the so-called water-soluble sulfur dyes.
  • Cellulose can be mixed with sulfur dyes e.g. can be dyed by the pull-out process from a long or short liquor or by a large number of processes on dyeing machines and dyeing machines.
  • Semi-continuously e.g. can be dyed on pad-roll systems or by the pad-docking method or by the cold dwell process.
  • Sulfur dyes can also be colored continuously, e.g. according to the pad steam process or the thermosol continuous process, among others
  • water-insoluble sulfur dyes are first converted into the soluble, fiber-affine leuco form by reduction, usually with sodium sulfide or sodium sulf hydrate, and are applied to the fiber in this form and then oxidized.
  • the sulfur dyes are modified by reaction with alkali sulfite or alkali bisulfite and are marketed as so-called water-soluble sulfur dyes.
  • These water-soluble sulfur dyes contain thiosulfuric acid derivatives (colored salts) of sulfur dyes.
  • the water-soluble sulfur dyes can be dissolved in water without a reducing agent and only become fiber-affine after the addition of reducing agents and alkali.
  • the fastness properties of dyeings with sulfur dyes can be improved by the process of EP-A2-0277580 in that the cellulose is treated with a polymer before, during or after the dyeing process, which contains 16 2/3 to 100 mol% e.g. Contains dimethyl diallyl ammonium chloride.
  • the sulfur dyes are applied in the usual way in this process. When using water-soluble sulfur dyes, this means that after they have been dissolved in water, they are firstly added by adding a reducing agent, e.g.
  • electrolyte salts such as Glauber's salt or table salt, are added to accelerate the drawing up.
  • the sulfur dyes After being drawn onto the fiber, the sulfur dyes, as usual, must be converted into an insoluble form by oxidation on the fiber. For this purpose, oxidation is carried out in particular in piece dyeing with bichromate acetic acid.
  • Other oxidizing agents are e.g. Hydrogen peroxide, e.g. in connection with ammonium acetate, also alkali salts of hypochlorous acid, ammonium persulfate, alkali chlorites, polythionates, alkali bromites, potassium iodate, chloramine T, etc.
  • R1 and R2 can be the same or different.
  • R3 and R4 can also be the same or different.
  • the number 2 or 3 is preferred for m, the number 0 is preferred for n.
  • the group -NH- is preferred for X.
  • the monovalent anion X ⁇ can be, for example, a monovalent residue of a mineral, sulfonic or carboxylic acid, or a residue of a polybasic mineral, sulfonic or carboxylic acid equivalent to a monovalent anion.
  • a monovalent anion for X ⁇ can be, for example, nitrate, hydrogen sulfate, benzenesulfonate, fluoride, chloride, bromide, iodide, acetate, propionate or another residue of a carboxylic acid.
  • a part of a multivalent anion equivalent to a monovalent anion can be, for example, 1/2 equivalent of sulfate or 1/3 equivalent of phosphate.
  • X ⁇ is preferably a halogen anion , such as bromide or iodide, in particular chloride.
  • R6 and R7 can be the same or different.
  • R8 and R9 can also be the same or different.
  • Alkyl radicals and hydroxyalkyl radicals can be straight-chain or branched.
  • alkyl radicals representing R1, R2, R5, R6, R7 or R10 are: methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, isobutyl, pentyl, hexyl.
  • cycloalkyl radicals are cyclopentyl, cyclohexyl, cycloheptyl. Cyclohexyl is preferred.
  • hydroxyalkyl radicals examples are: 2-hydroxyethyl, 2- or 3-hydroxypropyl 2-, 3- or 4-hydroxybutyl, 2-methyl-3-hydroxypropyl.
  • Examples of such five- or six-membered radicals are: pyrrolidinyl, piperidino, pyrrolyl, pyridinyl, piperazinyl, morpholino, thiomorpholino.
  • the alkyl can be straight-chain or branched.
  • phenalkyl radicals are benzyl, phenethl, 3-phenylpropyl, 2-phenylpropyl, 3- or 4-phenylbutyl, of which benzyl is preferred.
  • phenyl (OCH2CH2) p radicals are: phenyl- (OCH2CH2) -, phenyl- (OCH2CH2) 2-, phenyl- (OCH2CH2) 4.
  • the monovalent anion Y ⁇ can have one of the meanings given for X ⁇ and can also be identical to X ⁇ .
  • Particularly suitable and preferred compounds of the formula I are, for example:
  • Particularly suitable and preferred compounds of the formula Ia are the compounds given above in quaternized form, in particular when three identical radicals are bonded to the quaternary nitrogen, for example in the following compounds of the formula Ia:
  • Suitable substituents for R13 are in particular (C1 to C4) alkyl and (C2 to C4) hydroxyalkyl, these radicals also being straight-chain or branched. In the event of a substitution, the radical R 13 is preferably mono- or disubstituted. R 12 is preferably hydrogen.
  • the 5-membered heterocyclic radical representing R13 can be saturated or unsaturated and e.g. is one of the following radicals: imidazolyl, imidazolinyl, pyrrolyl, pyrrolinyl, pyrrolidinyl, indolyl.
  • N-vinyl-imidazole 1-vinyl-2-imidazoline, 2-vinyl-4- (or 5) -methyl-2-imidazoline, 1-vinyl-2-methyl-imidazole, 1-vinyl-4- (2- hydroxymethyl) imidazole, N-vinyl pyrrole, 2-isopropenyl-2-imidazoline, 1-vinyl-2,4-dimethylimidazole.
  • the 6-membered heterocyclic radical representing R13 can be saturated or unsaturated, for example a pyridinyl or quinolinyl radical.
  • Suitable 6-ring compounds of the formula III are, for example, 2-vinylpyridine, 3-vinylpyridine, 4-vinylpyridine, 3-isopropenylpyridine, 2-vinylquinoline, 2-methyl-3-vinyl-8-hydroxyquinoline, 2-vinyl-quinoline, 2-methyl-3-vinylisoquinoline, 1-methyl-5-vinyl-isoquinoline, 2-isopropenylquinoline.
  • Vinyl pyridine and its derivatives are particularly preferred.
  • the polymer grafted onto the cellulose can consist of monomer units of one or more compounds of the formula I, Ia, II, IIa and / or III. It can also contain other polymerizable monomers.
  • the polymer grafted onto the cellulose contains e.g. 20 to 100 mol%, preferably 40 to 100 mol% and very particularly preferably 80 to 100 mol% of one or more compounds of the formula I, Ia, II, IIa and / or III.
  • the division between the monomers of the formulas I, Ia, II, IIa and / or III is arbitrary.
  • the grafted-on polymer normally contains only one of the compounds I, Ia, II, IIa and / or III D.h. cellulose with a grafted-on homopolymer which consists of polymerized monomer units of the formulas I, Ia, II, IIa and / or III is preferred.
  • R14, R15 are hydrogen, (C1 to C6) alkyl, (C5 to C7) cycloalkyl, (C2 to C4) hydroxyalkyl or R14 and R15 together with the nitrogen atom to which they are attached, a five- or
  • Examples of compounds of the formula IV are: acrylamide and methacrylamide.
  • Examples of compounds of formula V are (C1 to C6) alkyl esters, especially the methyl and ethyl esters of acrylic and methacrylic acid.
  • the grafting of the mono- or copolymer onto the cellulose is carried out in such a way that one or more monomers of the formula I, Ia, II, IIa and / or III, if appropriate in the presence of one or more monomers, in particular of the formula IV and / or V, be polymerized.
  • Suitable solvents are water mixed with a water-miscible solvent.
  • Suitable water-miscible solvents are, for example, lower alcohols, such as, for example, methanol, ethanol, n-propanol, i-propanol, n-butanol, tert-butanol, glycols and diols, such as, for example, ethylene glycol, propylene glycol, 1,3-propanediol, di and polyglycols such as, for example, diethylene glycol, triethylene glycol, glycol ethers, such as, for example, diethylene glycol mono-methyl ether, diethylene glycol mono-ethyl ether, Ethylene glycol mono-methyl ether, Ethylene glycol mono-ethyl ether, Ethylene glycol mono-n-propyl ether, Ethylene glycol mono-n-butyl ether,
  • the homo- or copolymerization in the presence of the cellulose can also be carried out in a mixture of different solvents which contains water. If one or more components are used in the form of aqueous solutions, additional water is normally not required. Water in a mixture with alcohols, in particular those with 1 to 4 carbon atoms, and in a mixture with diols or glycols is preferred. It may be expedient to add organic solvent or solvent mixture once or in particular several times during the homo- or copolymerization.
  • an acid preferably an organic acid, in particular formic acid, acetic acid, glycolic acid and / or citric acid, is generally used for this pH adjustment.
  • the homo- or copolymerization is carried out in the presence of the cellulose at normal temperature or, in particular, at elevated temperature, for example at temperatures from 40 to 100 ° C., preferably 60 to 90 ° C., very particularly preferably at temperatures from 65 to 85 ° C., and in Usually started, for example by adding suitable initiators, by elevated temperature, by the action of high-energy rays, for example UV rays, by microwaves or the action of ultrasound.
  • Suitable initiators are radical-forming substances, such as benzoyl peroxide tert-butyl hydroperoxide, cumene peroxide, methyl ethyl ketone peroxide, lauryl peroxide, tert-butyl perbenzoate, di-butyl perphthalate, azodiisobutyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile), 2-phenyl-azo-2,4-dimethyl-4-methoxy -valeronitrile, 2-cyano-2-propyl-azoformamide, azodiisobutyramide, dimethyl, diethyl or di-n-butyl-azobis-methyl valerate, tert-butyl-perneodecanoate, di-isononanoyl-peroxide, tert.-amyl-perpivalate, Di -2-ethylhexyl peroxydicarbonate, dilauroyl
  • Based on the amount of monomers 0.01 to 2% by weight, preferably 0.1 to 1% by weight, of initiator is used. It is expedient to carry out the polymerization or copolymerization or the grafting in the absence of oxygen. This can be done in a manner known per se by purging or passing through an inert gas, such as nitrogen.
  • the monomer components are used in amounts such that the polymer grafted onto the cellulose contains at least 20 mol%, preferably at least 40 mol% and very particularly preferably at least 80 mol% of one or more compounds of the formula I, Ia, II, IIa and / or III in copolymerized form.
  • the grafting can be carried out, for example, in such a way that the cellulose to be grafted is introduced into the polymerization vessel together with the solution of the monomer (s) and the homopolymerization or copolymerization is carried out. Under these conditions, the homo- or copolymerization is normally complete after about 30 minutes to about 4 hours, in many cases after 30 minutes to 2 1/2 hours.
  • the cellulose is removed from the polymerization container, e.g. by squeezing, freed, rinsed with water and dried.
  • the grafting of the cellulose can also be carried out in such a way that the monomer solution e.g. applied to the cellulose by padding, slapping, soaking or spraying and then the homo- or copolymerization, at normal temperature or elevated temperature, is expediently triggered by the action of high-energy jets or ultrasound. It is often sufficient if irradiation or sonication is carried out for about 0.5 to 10 minutes and the cellulose is then stored in a moist condition for 2 to 36 hours, preferably 10 to 24 hours, and then dried after rinsing.
  • the cellulose e.g. as cellulose fiber, e.g. as linen, jute, ramie fiber or as regenerated cellulose fiber, preferably as cotton fiber, is present, in all processing states, as a yarn, flake, sliver, piece goods grafted with the polymer or copolymer mentioned.
  • a cellulose which is modified in the above manner i.e. has been grafted and onto which 0.5 to 40% by weight, preferably 2 to 25% by weight and very particularly preferably 4 to 15% by weight, based on cellulose, polymer has been grafted.
  • Cellulose which is present, for example, as cotton or cellulose or as a cellulose component in blended fabrics, for example cellulose / polyester blended fabrics and which has been modified or grafted in the manner mentioned, can be mixed with sulfur dyes, which can be dissolved without the addition of reducing agents, ie in particular with so-called.
  • water-soluble sulfur dyes without the use of a pre-reduction or reducing agents and electrolyte salts and without the use of special specific oxidizing agents at normal temperature (room temperature) or slightly elevated temperature up to approx. 60 to 75 o C, for example. So-called.
  • Water-soluble sulfur dyes are, in particular, thiosulfur dye derivatives of sulfur dyes ("colored" salts of sulfur dyes).
  • the fastness to use obtained, in particular the light fastness and the fastness to rubbing are good with good fixation yields and in many cases exceed the fastnesses obtained for the water-soluble sulfur dyes in the processes of EP-A-0277580.
  • the dye concentration for a given liquor intake which is normally 100 to 200%, depends on the desired depth of dyeing.
  • the dye liquors usually contain 10 to 50 g / l of the water-soluble sulfur dye.
  • the water-soluble sulfur dyes if they are in the form of a powder, are normally dissolved in warm, but possibly also in boiling, as soft as possible. Since no reducing agents are required, these dye solutions are insensitive to the effects of oxidation and are therefore very durable. Liquid water-soluble sulfur dyes are diluted with water that is as soft as possible.
  • Dyeing can be carried out using various methods, e.g. after the jigger pull-out process, on the reel runner or in dyeing machines from a long or short liquor. Yarn, flake and sliver are e.g. dyed on apparatus in which the fleet circulates. Piece goods are appropriately dyed in jet dyeing machines.
  • the liquor ratio is adapted to the dyeing process and is normally 1: 3 to 1:20.
  • the dyeing temperature is generally lower than in the previously known processes for dyeing sulfur dyes. In the inventive method such as dyeing temperatures from room temperatures to about 60 are applied to 75 o C, so that the cold pad-batch is highly suitable.
  • Sulfur dyes which are water-soluble without the addition of reducing agents are in particular the so-called water-soluble sulfur dyes.
  • these so-called water-soluble sulfur dyes are obtained, in particular, by modification of the actual sulfur dyes with sulfite and / or bisulfite and, in particular, are thiosulfuric acid derivatives or multicolored salts of sulfur dyes Melting together with elemental sulfur or by prolonged boiling with polysulfide in water or alcohols).
  • the so-called water-soluble sulfur dyes were named C.I. in the Color Index. Solubilised Sulfur listed. Of these C.I.
  • Solubilized Sulfur Dyestuffs are particularly suitable for the following: Black 1, Brown 1, Blue 2, Blue 7, Brown 12, Red 11, Brown 15, Blue 11, Green 3, Brown 46, Red 6, Brown 93, Blue 10, Brown 16 , Brown 51, Brown 52, Green 2, Green 19, Green 9, Green 24, Yellow 5, Yellow 20, Brown 60, Yellow 19, Brown 21, Brown 10.
  • Auxiliaries such as wetting and / or padding aids, can be present in the dyeing liquors in concentrations customary in the prior art.
  • washing can be replaced by rinsing with water.
  • the washing or rinsing can be carried out at normal temperature or a slightly elevated temperature of, for example, 50 to 60 ° C. Then it is dried, for example, at temperatures of 50 to 60 o C.
  • the use of a special oxidizing agent is not necessary.
  • the method according to the invention offers considerable ecological and economic advantages by saving chemicals (omission of reducing agents, electrolyte salts, oxidizing agents) and energy. In addition, good fastness properties are achieved.
  • Examples 1 to 10 relate to the preparation of the grafted substrates to be used in the process according to the invention, and Examples 11 to 14 relate to the dyeing carried out by the process according to the invention.
  • a 2.8 g, 8 x 30 cm cotton cloth is attached to a 5 liter 3-neck flask equipped with an anchor stirrer, nitrogen inlet tube and reflux condenser. Then: 1000 ml of distilled water, 113.3 g of table salt, 573 mg of ethylenediaminetetraacetic acid disodium salt, 2372.5 g dimethyl diallyl ammonium chloride submitted as a 61% aqueous solution, the flask 3 times evacuated and inerted with nitrogen and heated to 80 o C under 380 - 400 mbar.
  • a further 118 g of an aqueous ammonium persulfate solution are then metered in and the mixture is polymerized at 80 to 83 ° C. for 2 h.
  • the cotton cloth is then removed from the reaction flask, squeezed off, rinsed twice with 500 ml of water, squeezed out in between and dried at 100 ° C. for 5 minutes.
  • the absorption of polymer is 5.3%.
  • a pH of 8.5 to 9.0 is adjusted with 231 g of glacial acetic acid, 960 g of water are added and 2060 mg of 2,2'-azobis (2-amidino-propane) dihydrochloride) are added as initiator and then the flask 3 times evacuated, inerted with nitrogen and heated to 79 to 80 o C.
  • the active substance concentration of polymer is 25%.
  • the K value of a 1% aqueous solution is: 112600.
  • Example 2 When Example 2 is repeated, the cotton cloth is replaced by a 3.4 g heavy, 8 x 47 cm large cellulose cloth. The absorption of polymer is 2.95%.
  • Example 3 When Example 3 is repeated, the cotton cloth is replaced by a 5.7 g, equally large, polyester / cotton 65/35 cloth. The absorption of polymer is 3.4%.
  • a solution is released in a 3 liter three-necked flask equipped with an anchor stirrer, gas inlet tube and reflux condenser 200 g distilled water 56.7 g of table salt 287 mg disodium ethylenediaminetetraacetic acid salt 250 g ethanol 1210 g of dimethyl diallylammonium chloride as 61% aqueous Submitted solution.
  • a solution 200 ml water, 18.1 g of table salt 206.18 g dimethylaminopropyl methacrylamide 63.9 g ethanol 81.4 mg disodium ethylenediaminotetraacetic acid salt is adjusted to a pH of 8.5 to 9.0 with glacial acetic acid and applied to a cotton cloth via a padder and squeezed off.
  • the fleet pick-up after squeezing is 114.4%.
  • the damp cloth is then subjected to a microwave treatment (30 seconds 90 watts and then 4 times 30 seconds 720 watts).
  • the damp cloth is left to stand at room temperature for 24 hours and then dried for 5 minutes at 100 ° C.
  • the absorption of polymer is 29.5%.
  • Example 6 The monomer solution specified in Example 6 is in the applied in a manner specified in Example 6 to a cotton cloth and squeezed off. The damp cloth is then exposed to UV radiation to initiate the polymerization and grafting.
  • the aftertreatment of the cloth is carried out as indicated in Example 6.
  • the absorption of polymer is 30.8%.
  • the polymerization and grafting begins with an increase in temperature to 84 o C.
  • 64.5 g, 54.2 g, 118.4 g and 453 g of ethanol are added in succession added at intervals of 10 to 15 minutes and after adding the last portion for 1 h 77 to 80 o C stirred.
  • the cloth is then removed and treated as in Example 1.
  • the absorption of polymer is 14.6%.
  • the viscosity of the solution is measured in the DIN cup / nozzle ⁇ 6 mm / 44.6 sec.
  • the cloth is removed and treated as in Example 1.
  • the absorption of polymer is 4.7%.
  • a cotton cloth treated according to Example 10 is dyed with 2.5%, based on the weight of the goods, of the commercial dye Solubilised Sulfur Blue 7 at a liquor ratio of 1:20 35 min at 60 ° C. No salts and no reducing agents are used to carry out the dyeing.
  • the dyed goods are rinsed cold with water and then dried.
  • the light fastness obtained is 4 and the dry rub fastness 5.
  • Example 10-treated and dried cotton cloth is dyed without the addition of salts and reducing agents with 2.5% of the commercial product CI Solubilized Sulfur Red 11 by pad application, stored for 12 hr. At room temperature, cold-rinsed with water and dried at 50 ° C.
  • the fastness properties obtained are 3 to 4 for the light fastness and 5 for the rub fastness.
  • Example 8 A according to Example 8 - Part A treated cotton cloth is dyed with 2.5%, based on weight, of the commercial dye CI Solubilised Blue 7 by Foulardim Weggntechnik, 12 hours stored at room temperature, cold-rinsed with water and dried at 50 ° C..
  • the fastness properties of the dye obtained are 3 to 4 for light fastness and 5 for rubbing fastness.
  • a cotton cloth treated according to Example 8 - Part B is dyed with 2.5%, based on the weight of the commercial material CI Solubilized Sulfur Red 11, of padding, stored for 12 hours at room temperature, rinsed cold with water and dried at 50 ° C.
  • the light fastness of the dyed material is 3 to 4 and the fastness to rubbing dry 5.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • Coloring (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Graft Or Block Polymers (AREA)
EP92105100A 1991-04-15 1992-03-25 Procédé de teinture de la cellulose avec des colorants au soufre Ceased EP0509277A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE4112228 1991-04-15
DE4112228A DE4112228A1 (de) 1991-04-15 1991-04-15 Verfahren zum faerben von cellulose mit schwefelfarbstoffen

Publications (1)

Publication Number Publication Date
EP0509277A1 true EP0509277A1 (fr) 1992-10-21

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EP92105100A Ceased EP0509277A1 (fr) 1991-04-15 1992-03-25 Procédé de teinture de la cellulose avec des colorants au soufre

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US (1) US5230711A (fr)
EP (1) EP0509277A1 (fr)
JP (1) JPH05140879A (fr)
DE (1) DE4112228A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009019567A2 (fr) * 2007-08-03 2009-02-12 Next Technology Tecnotessile Societa' Nazionale Diricerca R.L. Appareil de brassage de boissons comprenant un système de distribution à pompe

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE69403319T2 (de) * 1993-02-01 1997-08-28 Ciba Geigy Ag Strahlungsinduzierte fixierung von farbstoffen
BR9407551A (pt) * 1993-09-16 1996-12-31 Ciba Geigy Ag Termofixaçao de corantes na presença de composto polimerizável e um iniciador
EP0952168A4 (fr) 1996-07-16 2000-05-24 Toray Industries Polymere greffe et moulages realises a partir de celui-ci pour fournitures medicales
CA2276680C (fr) * 1997-11-04 2006-05-16 Toray Industries, Inc. Polymere greffe et moulages realises a partir de celui-ci pour fournitures medicales
CN107604695B (zh) * 2017-09-26 2019-12-10 河北科技大学 一种用于硫化染料染色的复合氧化剂及其使用方法
RU2692388C1 (ru) * 2018-10-05 2019-06-24 федеральное государственное автономное образовательное учреждение высшего образования "Российский государственный университет нефти и газа (национальный исследовательский университет) имени И.М. Губкина" Способ получения радиационно-сшитого полимерного материала

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3514385A (en) * 1966-07-19 1970-05-26 Du Pont Process for radiation grafting onto a partially swollen cellulosic substrate
EP0265768A2 (fr) * 1986-10-27 1988-05-04 National Starch and Chemical Investment Holding Corporation Traitement de tissu pour augmenter son affinité pour les colorants

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL301450A (fr) * 1962-12-06
SE382049B (sv) * 1970-12-10 1976-01-12 Basf Ag Foretring av foreningar med alkoholiska hydroxylgrupper for framstellning av n-karbazol, n-pyrrolidon- och n-dihydrooxazinderivat
JPS54131091A (en) * 1978-03-30 1979-10-11 Toppan Printing Co Ltd Printing of cellulose fiber structure or cellulose fiber containing blended structure

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3514385A (en) * 1966-07-19 1970-05-26 Du Pont Process for radiation grafting onto a partially swollen cellulosic substrate
EP0265768A2 (fr) * 1986-10-27 1988-05-04 National Starch and Chemical Investment Holding Corporation Traitement de tissu pour augmenter son affinité pour les colorants

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
WORLD PATENTS INDEX Derwent Publications Ltd., London, GB; AN 68-11046Q & SU-A-193 020 (KAUSKANSKII) *
WORLD PATENTS INDEX Derwent Publications Ltd., London, GB; AN 79-84808B & JP-A-54 131 091 (TOPPAN PRINTING KK) 11. Oktober 1979 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009019567A2 (fr) * 2007-08-03 2009-02-12 Next Technology Tecnotessile Societa' Nazionale Diricerca R.L. Appareil de brassage de boissons comprenant un système de distribution à pompe
WO2009019567A3 (fr) * 2007-08-03 2009-06-04 Next Technology Tecnotessile S Appareil de brassage de boissons comprenant un système de distribution à pompe

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DE4112228A1 (de) 1992-10-22
JPH05140879A (ja) 1993-06-08
US5230711A (en) 1993-07-27

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