Classifications

• • 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
• • 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
  • D01F2/02—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof from solutions of cellulose in acids, bases or salts
• • 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
  • D01F2/02—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof from solutions of cellulose in acids, bases or salts
  • D01F2/04—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof from solutions of cellulose in acids, bases or salts from cuprammonium solutions
• • 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
  • D01F2/06—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof from viscose
• • 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
  • D01F2/06—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof from viscose
  • D01F2/08—Composition of the spinning solution or the bath
  • D01F2/10—Addition to the spinning solution or spinning bath of substances which exert their effect equally well in either
• • 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
  • D06P1/52—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 using compositions containing synthetic macromolecular substances
  • D06P1/5264—Macromolecular compounds obtained otherwise than by reactions involving only unsaturated carbon-to-carbon bonds
  • D06P1/5278—Polyamides; Polyimides; Polylactames; Polyalkyleneimines
• • 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
  • D06P3/6008—Natural or regenerated cellulose using acid dyes
• • 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
  • D06P3/66—Natural or regenerated cellulose using reactive dyes
• • 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
• • 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
  • D06P5/30—Ink jet printing

Definitions

• the present invention is in the field of textile dyeing viscose fibers.
• Viscose fibers also called regenerated cellulose fibers, essentially have the same dyeing properties as cotton fibers.
• alkaline dispensing agents and electrolytes are required for dyeing cellulosic natural or regenerated fibers in order to achieve satisfactory fixing results with reactive dyes.
• Regenerated fibers based on cellulose that can be dyed without salt or alkali will therefore be of increasing importance for the future.
• One possibility is to modify the viscose fibers so that their chemical behavior resembles that of animal fibers, such as wool or silk, and that they can be dyed with anionic dyes under neutral conditions without further salt or alkali additions.
• DE-A-1 469 062 also describes aminalized fibers.
• the additives are aminoethyl and diethylaminoethyl celluloses in high concentration, coloring is done exclusively with acid dyes.
• EP-A-0 284 010, EP-A-0 359 188 and EP-A-0 546 476 describe various compounds containing amino groups as agents for pretreating the surface of textiles containing cellulose fibers before the dyeing process.
• the disadvantage of such processes is an additional process step and yellowing of the fabric.
• the object of the present invention was to provide modified viscose fibers in order to dye textiles made from such fibers salt-free and alkali-free with reactive dyes and to avoid the disadvantages of the prior art mentioned.
• the fibers of the invention can be dyed with reactive dyes without the addition of alkali and salts. Coloring with acid dyes is also easily possible.
• these fibers when spun by the viscose process, have higher tensile strengths and elongations at break compared to conventional viscose fibers, both in the dry and in the wet state.
• the polyethyleneimine of formula (I) used is a molecule in which there are -NH2,> NH and -N ⁇ building blocks which are linked to one another by ethylene groups. In total, the polyethyleneimine contains about 50 to 600 ethyleneimine units. In conventional commercial products, primary, secondary and tertiary nitrogen functions are in a number ratio of approximately 1: 2: 1. In principle, all known bifunctional alkylating agents can be used for the reaction with the polyethyleneimine of the formula (I).
• Preferred for the reaction with polyethyleneimine are those bifunctional alkylating agents in which A are groups of the formula -CH2-Y, which are linked to one another via a bridge member of the formula (IV), or those in which one of the radicals A is a group of the formula - Is CH2-Y, which is bonded directly to an epoxy group.
• bifunctional alkylating agents are epichlorohydrin, glycid, 1,3-dichloropropan-2-ol, ⁇ , ⁇ '-dichloro-diethyl ether, ⁇ , ⁇ '-dichlorodiethylamine, ⁇ , ⁇ '-dichloro-diethyl sulfide, ⁇ , ⁇ '-Dichlorodiethylsulfoxide, ⁇ , ⁇ '-dichlorodiethylsulfone, ⁇ , ⁇ '-disulfatoethyl ether, ⁇ , ⁇ '-diphenylsulfonyloxyethyl ether, meta- or para-diepoxyethylbenzene, meta- or para-diepoxypropylbenzene, Diepoxybutane, diepoxy-2-methylbutane and diepoxypropylamine.
• the polyethyleneimine and the bifunctional alkylating agent are reacted with one another in a weight ratio of from 100: 0.01 to 100: 2, preferably from 100: 0.1 to 100: 1.
• reaction products to be used according to the invention from an epihalohydrin with NH3 or an amine of the formula (V) are obtained by reacting an epihalohydrin, preferably epichlorohydrin, with ammonia or an amine of the formula (V) at temperatures of about 60 to 70 ° C. in water or a lower alcohol as a solvent.
• These amines can optionally also be quaternized with C1-C4 alkyl groups, preferably C1-C3 alkyl groups.
• the quaternization can be carried out using alkyl halides, preferably alkyl chlorides, or dialkyl sulfonates by known methods.
• Examples of amines which correspond to the formula (V) listed above are: monomethyl-, -ethyl-, -propyl-, -isoproyl-, -butyl-, -isobutylamine, monooxethyl-, monooxypropylamine, ethylenediamine, diaminopropanes, diaminobutanes, Diaminohexanes, 3,3'-diaminodipropyl ether, piperazine, monooxethyl and di-oxethyl ethylene diamine, diethylene triamine, dipropylene triamine and triethylene tetramine. The preparation of these compounds is described in detail in US-A-3 544 363.
• EP-A2-0 363 745 Water-soluble, organic polybases are described in EP-A2-0 363 745.
• the minimum molecular weights of the modifiers according to the invention for sufficient incorporation into the fibers are 400, excellent results are obtained with molecular weights over 1000.
• the amount of the modifier incorporated in the viscose fibers according to the invention is advantageously 0.1 to 20% by weight, preferably 1 to 10% by weight, based on the total weight of the modified viscose fibers according to the invention.
• the content of amino groups is decisive for the amount of the modifier to be used.
• the fibers according to the invention are produced by the viscose spinning process
• the cellulose is first broken down under alkaline conditions (alkali cellulose), then reacted with carbon disulphide, dissolved in water or dilute alkali and then the modifier is added to this viscose solution.
• the modifier is added directly to the alkalizing solution and the modified alkali cellulose is then reacted with carbon disulfide to form the xanthate.
• the addition of the modifier during alkalizing increases the reactivity of the cellulose for xanthation. This enables the production of a better filterable spinning solution and a reduction in the use of CS2 or lye.
• the reaction with carbon disulphide expediently takes place at temperatures of 15 to 30 ° C.
• the modified cellulose fibers according to the invention are obtained by subsequent spinning in an acidic spinning bath.
• the fibers according to the invention are produced from solution by other customary processes known to those skilled in the art for producing cellulosic fibers, such as, for example, the cupro process, the lyocell process and the process using low-substituted cellulose ethers, the cellulose is dissolved in a suitable organic solvent with which Modifier added and spun into fibers directly from the solution. It is most advantageous to meter in immediately before the spinning, and the mixing and homogeneous distribution can be carried out by known mixing systems with the aid of static or dynamic mixing systems. However, metering can also take place in any preliminary stage in the manufacture of spinning mass.
• the advantage of the modifier according to the invention lies in the simple technical application, since it can be used directly or as an aqueous preparation with a content of over 50%. On the one hand, this enables high embeddings and on the other hand prevents negative effects on physical fiber properties due to thinning effects.
• the modifiers according to the invention are particularly suitable for use with viscose fibers since, in addition to the dyeing behavior, the physical properties of the fibers also improve.
• the spinning solutions can be processed further using the known methods for fiber production. Serious changes to the procedures are not necessary.
• the process changes known from the use of modifiers such as, for example, increased drawing, can be used successfully.
• the filterability of the viscose shows no deterioration in comparison with free samples, so that no clogging of the spinneret is observed in the course of the spinning process. If the modifier is added during the alkalization, an improvement in the filterability is observed.
• the Deformation of the viscose is carried out by customary and known methods, such as, for example, using spinnerets, a subsequent precipitation bath and, if appropriate, further post-treatment baths.
• the modified cellulose regenerate fibers produced according to the invention can be dyed with reactive dyes after processing into woven and knitted fabrics using a wide variety of processes, such as exhaust, padding and modern printing processes, including ink-jet processes, without the use of additional electrolyte salt or alkali.
• the fibers according to the invention are significantly more affine than conventional viscose fibers, but hardly differ from the conventional viscose fibers in the properties otherwise desired, such as handle.
• Both the fibers according to the invention after the viscose process and the fibers spun from solution can be dyed with reactive dyes without additional alkali and salt, and with acid dyes.
• the cellulose fibers according to the invention spun after the viscose process are furthermore distinguished by improved dry and wet strengths.
• the textile modified fiber material that is used for subsequent dyeing processes can be present in all processing states, such as yarn, flake, sliver and piece goods (fabric).
• the dyeing of the modified textile fiber materials according to the invention is carried out analogously to known dyeing methods and printing processes for dyeing or printing fiber materials with water-soluble textile dyes and using the temperature ranges and customary amounts of dye known to be used for this, but with the exception that for the dyebaths, padding liquors, printing pastes or ink Jet formulations an addition of alkaline compounds, such as those usually used to fix fiber-reactive Dyes are used, is not necessary and furthermore, the usual additions of electrolyte salts can be dispensed with.
• the dyeing process can be, for example, the various exhaust processes, such as dyeing on the jigger and on the reel runner or dyeing from a long or short liquor, dyeing in jet dyeing machines, dyeing by padding-cold dwelling or padding-hot steam fixing .
• Conventional printing techniques including ink jet printing and transfer printing, can be considered as printing processes.
• the dyes used to dye the modified cellulose are generally anionic in nature.
• Particularly suitable are the fiber-reactive textile dyes, which can react with hydroxyl groups, for example of cellulose, or amino and thiol groups, for example of wool and silk, of synthetic polymers, such as polyamides, or also the celluloses aminated according to the invention, and are capable of forming a covalent bond.
• the sulfatoethylsulfonyl, vinylsulfonyl, chlorotriazinyl and fluorotriazinyl group and combinations of these reactive groups may be mentioned in particular as fiber-reactive components on the textile dyes.
• Suitable reactive dyes for dyeing or printing viscose fibers modified according to the invention are all water-soluble, preferably anionic dyes which preferably have one or more sulfo and / or carboxy groups and which contain fiber-reactive groups.
• Suitable dyes can be the class of azo development dyes, direct dyes, vat dyes and acid dyes, copper complex, cobalt complex and chromium complex azo dyes, copper and nickel phthalocyanine dyes, anthraquinone, copper formazane, azomethine, nitroaryl, dioxazine -, Triphendioxazin-, Phenazin- and stilbene dyes belong.
• Such dyes have been described in numerous publications, for example in EP-A-0 513 656, and are well known to those skilled in the art.
• a viscose spinning mass is produced as described in Example 1 with a reaction product of polyethyleneimine (molecular weight 3000 to 5000) and epichlorohydrin. After degassing, the spinning mass is spun into fibers using a conventional viscose spinning process in a sulfuric acid, sodium and zinc sulfate-containing bath, stretched, cut, washed, prepared and dried in acid baths. After weaving, a textile viscose fabric is obtained which can be further processed directly in a dyeing process using the block method.
• an aqueous dye solution containing 20 parts of the dye of the formula in 1000 parts by volume known from EP-A-0 158 233, Example 1, and 3 parts of a commercially available nonionic wetting agent dissolved, by means of a pad with a liquor absorption of 80%, based on the weight of the fabric, applied to the fabric at 25 ° C.
• the fabric padded with the dye solution is wound on a dock, wrapped in a plastic film and left for 4 hours at 40 to 50 ° C and then with cold and hot water, which may contain a commercially available surfactant, and then again with cold water if necessary rinsed and dried.
• a strong, uniformly colored yellow coloration is obtained which has good general fastness properties, in particular good fastness to rubbing and light.
• a viscose spinning mass is produced as described in Example 1 with a reaction product of polyethyleneimine (molecular weight 3000 to 5000) and epichlorohydrin. After degassing, spinning, stretching, cutting, washing and drying, a fiber is obtained which can be dyed using a conventional pull-out method.
• 20 parts of the pretreated viscose fiber are treated in a dyeing machine with 200 parts of an aqueous liquor, which - based on the weight of the dry goods - 1.5% of the reactive dye of the formula known from EP-A-0 061 151, example 4, in a commercially available form and composition.
• the fiber is dyed with this liquor at 60 ° C. for 30 minutes.
• the dyeing thus produced is further processed by rinsing and soaping in the customary manner. The result is a lively orange color with the good fastness properties customary for reactive dyes.
• a viscose spinning mass is produced as described in Example 1 with a reaction product of polyethyleneimine (molecular weight 3000 to 5000) and epichlorohydrin.
• a fiber material made of modified viscose is produced from an alkali cellulose produced according to the information in Example 4 using the process steps customary for spinning viscose, and is reactively dyed in a pull-out process without salt and alkali additives.
• a viscose spinning mass as described in Example 1 is produced using a polybase prepared according to Example 1 of EP-A2-0 363 745 from polyethyleneimine, a diethylenetriamine-adipic acid condensation product (1: 1) and ethanolic epichlorohydrin. After degassing, spinning, stretching, cutting, washing and drying, a fiber is obtained which can be dyed using a conventional pull-out method.
• 20 parts of the pretreated viscose fiber are treated in a dyeing machine with 200 parts of an aqueous liquor, which - based on the weight of the dry goods - 1.5% of the reactive dye of the formula known from EP-A-0 061 151, example 4, in commercial form and Contains texture.
• the fiber is dyed with this liquor at 60 ° C. for 30 minutes.
• the dyeing thus produced is further processed by rinsing and soaping in the customary manner. The result is a lively orange color with the good fastness properties customary for reactive dyes.

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• Engineering & Computer Science (AREA)
• Textile Engineering (AREA)
• Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• General Chemical & Material Sciences (AREA)
• Manufacturing & Machinery (AREA)
• Coloring (AREA)
• Artificial Filaments (AREA)
• Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)

Applications Claiming Priority (2)

Publications (1)

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Family Applications (1)

Country Status (8)

Cited By (4)

Families Citing this family (7)

Citations (18)

• 1994
  • 1994-06-30 DE DE4422865A patent/DE4422865A1/de not_active Withdrawn
• 1995
  • 1995-06-19 EP EP95109423A patent/EP0692558A1/de not_active Withdrawn
  • 1995-06-28 CN CN95107737A patent/CN1120080A/zh active Pending
  • 1995-06-28 FI FI953197A patent/FI953197A/sv not_active Application Discontinuation
  • 1995-06-29 JP JP7164232A patent/JPH08113821A/ja not_active Withdrawn
  • 1995-06-29 CA CA002152976A patent/CA2152976A1/en not_active Abandoned
  • 1995-06-29 KR KR1019950018100A patent/KR960001221A/ko not_active Application Discontinuation
  • 1995-06-30 BR BR9503023A patent/BR9503023A/pt not_active Application Discontinuation

Patent Citations (18)

Non-Patent Citations (3)

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