Classifications

• • 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
• • 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
• • 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
  • D06P1/0004—General aspects of dyeing
  • D06P1/0008—Dyeing processes in which the dye is not specific (waste liquors)
• • 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
  • D06P1/30—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 sulfur 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
  • 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
  • D06P3/66—Natural or regenerated cellulose using reactive dyes

Definitions

• the dyeing of textile materials can be carried out according to known processes in that the textile material is drawn out with a dyeing liquor containing a reactive dye, usually at elevated temperature and in most commercial reactive dye types in the presence of Alkali, is treated, or continuous or discontinuous processes, such as the so-called pad-steam process, or the cold retention process can be used.
• the textile material is first padded with a reactive dye liquor, the alkali required for fixing being usually applied in a separate impregnation step.
• the dye fixation is then carried out by a steaming process, in the cold residence process by docking the impregnated goods and staying for several hours at room temperature.
• Other fixation options such as The treatment of the goods, which have been sealed with an alkali-free reactive dye liquor, using sodium hydroxide solution / water glass solution has become known and is practiced industrially.
• U.S. Patent 4,806,126 describes a process for dyeing cellulosic fibers with reactive dyes in which the presence of alkali is not required.
• the fixation of the dyes on the fibers is achieved in this process by pretreating the fibers with a reaction product of polyethyleneimine and a bifunctional alkylating agent before dyeing.
• the invention relates to a process for the uneven dyeing of cellulose fibers in the absence of alkali or a reducing agent, characterized in that the cellulose fibers are treated with a liquor which contains a wetting agent, an optionally quaternized reaction product of polyethyleneimine with a bifunctional alkylating agent and an anionic surfactant, dries and dyes with reactive, direct or water-soluble sulfur dyes without the addition of alkali.
• the auxiliary device required for the pretreatment is known from US Pat. No. 4,588,413.
• the aid is used there exclusively for the aftertreatment of dyeings with reactive dyes. Pretreatment with this auxiliary and subsequent dyeing without alkali or reducing agent is not described there.
• a method exclusively for the aftertreatment of reactive dyeings with compounds of a similar structure is also described in GB-PS 2 006 279.
• the polyethyleneimine required to produce the pretreatment agent to be used according to the invention corresponds to formula I.
• polyethyleneimine used is a molecule in which -NH2, and> NH and -N ⁇ building blocks are present, which are linked together by ethylene groups.
• the polyethyleneimine contains about 50 to 600 ethyleneimine units.
• primary, secondary and tertiary nitrogen functions are in a numerical ratio of approximately 1: 2: 1.
• bifunctional alkylating agents can be used for the reaction with the ethyleneimine of the formula I.
• Such known bifunctional alkylating agents correspond to formula II A - Z - A (II)
• A is the residue of an alkylating agent and Z is either a direct bond or a divalent bridge member.
• Those preferred for the reaction with polyethyleneimine to auxiliaries to be used according to the invention are those bifunctional alkylating agents in which A are groups of the formula -CR2-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 -CH2-Y which is directly attached to an epoxy group is bound.
• bifunctional alkylating agents are epichlorohydrin, glycid, 1,3-dichloropropan-2-ol, ⁇ , ⁇ '-dichloro-diethyl ether, ⁇ , ⁇ '-dichloro-diethylamine, ⁇ , ⁇ '-dichloro-diethyl sulfide, ⁇ , ⁇ '-dichloro-diethylsulfoxide, ⁇ , ⁇ '-dichloro-diethylsulfone, ⁇ , ⁇ '-disulfatoethyl ether, ⁇ , ⁇ '-diphenylsulfonyloxyethyl ether, meta- or para-diepoxyethylbenzo, meta- or para-diepoxypropylbenzene, diepoxybutane, diepoxy-2 -methylbutane, diepoxypropylamine.
• the polyethyleneimine and the bifunctional alkylating agent are reacted with one another in a weight ratio of 100: 0.01 to 100: 2.0, preferably from 100: 0.1 to 100: 1.0.
• this reaction involves the installation of crosslinking bridging links between the polyethyleneimine chains.
• An external indication of this is that the viscosity of the aqueous solutions increases significantly when the non-crosslinked polyethyleneimine is transferred to the product crosslinked by the bifunctional alkylating agent.
• the polyethyleneimine can be reacted with the bifunctional alkylating agents without a solvent.
• the reaction can be carried out in the temperature range between -10 and about 100 ° C.
• the reaction is essentially completed in about 1 to 2 hours.
• the reaction mixture In order to obtain aids to be used according to the invention which have particularly narrow-tolerance specifications, i.e. In order to achieve particularly good reproducibility of the production process, it is advantageous, after the main reaction has ended, for the reaction mixture to have a defined pH between 9 and 10 for several hours, usually 2 to 6 hours, at elevated temperature, advantageously between 60 and 100 ° C afterwards.
• reaction products of polyethyleneimine used according to the invention with a bifunctional alkylating agent can optionally also be quaternized with C1-C4, preferably C1-C3 alkyl groups.
• the quaternization can be carried out using alkyl halides, preferably alkyl chlorides, or dialkyl sulfates by known methods.
• wetting or padding aids are, for example, propylene oxide / ethylene oxide block polymers with a proportion of 40-80% by weight of ethylene oxide, but especially ethoxylated nonylphenol.
• anionic surfactants for example sec. Alkanesulfonates, alkyl sulfates, alkyl ether sulfates, fatty acids, alkylbenzenesulfonates, olefin sulfonates, di-alkyl sulfosuccinates or di-alkyl phosphates.
• the presence of the anionic surfactants is of crucial importance for the process according to the invention, because the anionic surfactants form agglomerates and precipitates with the optionally quaternized reaction products of polyethyleneimine with a bifunctional alkylating agent, which deposit on the fibers in an uneven form and thus ensure an uneven coloring .
• the pretreatment with the auxiliary, together with the nonionic wetting agent and the anionic surfactant is carried out from an aqueous liquor by customary methods by padding or in the exhaust process at temperatures of about 20 to 70 ° C., preferably 40 to 60 ° C.
• the liquor is adjusted to a weakly acidic pH, preferably pH 6.
• the amount of auxiliary is about 5 to 100 g / l, preferably 30 to 80 g / l.
• the amount of wetting agent is preferably 0.5 to 4 g / l and the amount of anionic surfactant is approximately 1 to 80 g / l.
• the pretreatment liquor is then squeezed off and the goods are dried.
• Raw or pretreated cotton or mixed fabrics containing cotton are suitable as textile materials.
• the goods pretreated in this way are then dyed using customary processes and on customary dyeing units with direct dyes, reactive dyes or sulfur dyes containing sulfo groups, for example using the cold residence process or an exhaust process.
• the Fleet ratio can be about 1: 3 to 1:40. It is important, however, that, in contrast to the previously customary procedure, no alkali and no reducing agent is used in the present case.
• Suitable reactive dyes in this process are all known types of reactive dyes which contain groups which are reactive towards the hydroxyl groups of cellulose and which, under the dyeing conditions described according to the invention, preferably react by reaction with the polymers described and fixed on the cellulose material.
• the reactive groups are, for example, groups with easily removable substituents which leave an electrophilic radical, such as reactive groups of the vinylsulfone type, groups of the ring systems quinoxaline, phthalazine, triazine, pyrimidine or pyridazone substituted with halogen atoms or reactive groups substituted with alkylsulfonyl radicals in the case of sulfonylpyrimzthiazonyl or sulfonylcarbonyl sulfonyl or sulfonyl sulfonyl .
• dyes are sulfatoethylsulfone ⁇ -with the reactive groups, ⁇ -chloroethyl, ⁇ -Thiosulfatoethylsulfon, ⁇ -Phosphatoethylsulfon, Chlortriazinylamino, Dichlortriazinylamino, Chlortriazinyldiamino, Dichlorpyridazinylamino, Trichlorpyridazinylamino, Dichlorpyridazinylcarbonylamino, 2-chloro-benzothiazole-6-yl-amino, 2, To mention 3-dichloroquinoxalin-6-yl-carbonylamino or 4-chloro-5-methyl-2-methylsulfonylpyrimid-3-yl-amino.
• Suitable basic dye bodies of the reactive dyes are, for example, water-soluble azo, disazo, formazan, anthraquinone, dioxazine or phthalocyanine dyes.
• Water-soluble azo and disazo reactive dyes which can also be metal complex reactive dyes, are preferably used.
• the goods are finished by rinsing, possibly soaping and drying.
• the process according to the invention can be carried out not only with reactive dyes, but also in the same way with other types of dyes which contain anionic, for example sulfo groups, such as, for example, direct dyes and water-soluble sulfur dyes. Similar effects and fastness properties are achieved with these dyes as with the reactive dyes.
• pigment dyes such as vat and sulfur vat dyes can also be used in the process.
• a variant of the method according to the invention is that it is not a finished fabric that is pretreated and dyed, but only the warp yarns, expediently in combination with a sizing treatment.
• the warp yarn made of cellulose is treated according to customary methods with a size liquor which, in addition to the usual wetting agent, contains an anionic size and the pretreatment agent described above.
• the amount of sizing agent is usually 10 to 100, preferably 20 to 40 g / l.
• the warp yarn is then dried and woven with a white weft yarn. When this fabric is over-dyed using customary methods, but in the absence of alkali, a denim fabric is obtained which has an interesting fashionable effect due to the uneven dyeing of the warp yarn.
• anionic surfactant is replaced by an anionic size agent.
• anionic sizing agents are carboxymethyl cellulose, carboxymethyl starch, degraded starches, polysaccharides, galactomanes, acrylates or polyesters.
• the brilliance of the dyeings can be increased significantly and the weft thread, which has not been dyed or, depending on the dye shade, slightly soiled, can become white, so that a dyeing with high brilliance and white weft yarn is obtained.
• the use of optical brighteners in the wash liquor further increases the brilliance of the dyeings and the weft yarns.
• Cotton warp yarns are treated as follows on a sizing machine in the trough provided: 30 g / l sodium carboxymethyl cellulose (CMC) 3 g / l non-ionic wetting agent (nonylphenol + 10 EO) 100 g / l polyethyleneimine condensation product according to the example in Table 1, last line of patent application EP 0 133 933.
• the sodium carboxymethyl cellulose used has a viscosity of 300 mPa ⁇ s in a 2% strength aqueous solution at 20 ° C., measured in a falling ball viscometer (commercial product Tylose C 300).
• CMC size a mixture of CMC and modified starch can also be used.
• so-sized cotton chains are woven with raw white cotton weft and the fabric obtained is padded with a solution on a cold dwelling system consisting of dyeing pad and docking device
• the goods padded in this way are wrapped airtight on the dock with a polyethylene film and left to rotate for up to 24 hours.
• cotton warp yarns are treated as follows in the trough provided: 60 g / l carboxymethyl starch (CMS) 3 g / l non-ionic wetting agent (nonylphenol + 10 EO) 80 g / l of a reaction product of polyethylene lmin with a bifunctional alkylating agent quaternized with dimethyl sulfate / commercial product: (R) Solidogen FFL) Fleet absorption 100 - 130% (high-performance crushing unit).
• CMS carboxymethyl starch
• non-ionic wetting agent nonylphenol + 10 EO
• R Solidogen FFL
• the cotton chains which are so simply sized, are woven with raw white cotton weft.
• the tissue obtained is padded on a dyeing pad with an aqueous solution which 40 g / l CI Solubilized Sulfur Red 11 3 g / l wetting agent (ethoxylated nonylphenol) contains.
• Cotton warp yarns are treated as follows on a sizing machine in the trough provided: 50 g / l polyvinyl alcohol (PVA) 3 g / l wetting agent (nonylphenol + 10 EO) 20 g / l alkanesulfonate (commercial product: (R) Hostapur SAS) 100 g / l polyethyleneimine condensation product according to the example in Table 1, last line of patent application EP 0 133 933.
• the yarn runs at a speed of 60 m / min.,
• the temperature of the sizing liquor is 80 - 90 ° C.
• the yarns run over drying cylinders and are dried at approx. 130 ° C.
• the so-sized cotton chains are woven with raw white cotton weft and the fabric obtained is processed into garments.
• the items of clothing eg men's trousers, are washed on a paddle dyeing machine in a 1:40 liquor ratio at 30 ° C for 40 min. treated with an aqueous bath containing 1% by weight of Blue 77 reactive.
• a bleached cotton fabric is placed on a 2- or 3-roll pad with a solution that 60 g / l of the polyethyleneimine condensation product 3 g / l of a wetting agent (nonylphenol + 10 EO) and 14 g / l of degraded starch contains, cold padded and dried.
• the 30 ° C warm liquor for this auxiliary block is 30 min. set up before use and kept in motion during this waiting period with a slowly running agitator (approx. 60 rpm) in order to achieve agglomeration of the aids.
• the dyeing is lingered and treated according to Example 1.
• a yellow color is obtained with light and dark spots and good fastness properties.

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• Engineering & Computer Science (AREA)
• Textile Engineering (AREA)
• Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Coloring (AREA)

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Family Applications (1)

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Cited By (2)

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• 1988
  • 1988-09-13 DE DE3831139A patent/DE3831139A1/de not_active Withdrawn
• 1989
  • 1989-09-06 EP EP19890116417 patent/EP0359104A3/fr not_active Withdrawn
  • 1989-09-11 PT PT91686A patent/PT91686A/pt unknown
  • 1989-09-11 KR KR1019890013100A patent/KR900005012A/ko not_active Withdrawn
  • 1989-09-11 TR TR89/0810A patent/TR24109A/xx unknown
  • 1989-09-12 JP JP1234828A patent/JPH02104780A/ja active Pending
  • 1989-09-12 AU AU41215/89A patent/AU4121589A/en not_active Abandoned
  • 1989-09-12 ZA ZA896932A patent/ZA896932B/xx unknown
  • 1989-09-12 BR BR898904594A patent/BR8904594A/pt unknown

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