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
  • 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
  • D06P1/5207—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
  • D06P1/525—Polymers of unsaturated carboxylic acids or functional 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
  • 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
  • D06P1/5207—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
  • D06P1/5214—Polymers of unsaturated compounds containing no COOH groups or functional derivatives thereof
  • D06P1/5242—Polymers of unsaturated N-containing compounds

Definitions

• components (a), (b), (c) or (d) as dyeing or printing aids, as well as the fiber materials dyed or printed according to the process form further objects of the present invention.
• Preferred auxiliaries used in the process according to the invention contain either quaternary ammonium salts
• Suitable copolymers in the reaction product (a) are those of maleic anhydride and isopropylene, preferably of maleic anhydride and ethylene and in particular of maleic anhydride and styrene.
• Maleic anhydride on the one hand and propylene, ethylene or styrene on the other hand are preferably used in these copolymers in equimolar proportions.
• N, N-disubstituted 1,2-ethylenediamine or especially 1,3-propylenediamine is used, in which the substituents together with the nitrogen atom e.g. form a pyrrolidine, piperidine or preferably morpholine ring, or in which the substituents are n-propyl, preferably ethyl or in particular methyl.
• the starting components are used in a molar ratio of styrene: vinylpyridine from 1: 1 to 1:10, preferably 1: 3 to 1: 6, and in particular 1: 5.
• methyl chloride is never used alone, but always in a mixture with, for example, benzyl chloride, while, for example, n-dodecyl chloride is always used alone.
• Benzyl chloride especially used alone but also in a mixture with sodium chloroacetate, is the quaternizing agent of primary interest.
• a tertiary monoamine or amine mixture is used, two of which, together with the nitrogen atom, e.g. form a pyrrolidine, piperidine, preferably pyridine or morpholine ring or of which two substituents are preferably ethyl and in particular methyl groups, while the third substituent is alkenyl, preferably alkyl and in particular substituted by alkyl or alkylene having 1 to 4, preferably 1 or 2, carbon atoms or is unsubstituted aryl, this third substituent having a total of at most 18, preferably 2 to 18, in particular 4 to 12 carbon atoms.
• tertiary monoamines of this type are N, N-dimethyl- or N, N-diethyl-naphthylamine, -benzylamine, -aniline, furthermore N-methyl- or N-ethylpyridine, -piperidine, or -morpholine, especially dimethylbenzylamine comes into consideration.
• the auxiliaries used according to the invention contain (a) reaction products of a copolymer of maleic anhydride and ethylene, in particular of maleic anhydride and styrene, with N, N-diethyl- or N, N-dimethyl-ethylenediamine, with N- (3-amino -n-propyl) -morpholine or preferably with N, N-diethyl or in particular N, N-dimethyl-n-propylenediamine or homopolymers (b) from unsubstituted 4-vinyl pyridine, the reaction products (a) preferably with n-dodecyl chloride, with l-chloromechyl-2-methylbenzene, with 1-chloromethylnaphthalene, with mixtures of benzyl chloride and 1-chloromethylnaphthalene, chloroacetamide, sodium chloroacetate or methyl chloride or in particular with benzyl
• quaternary ammonium salt is the reaction product of a copolymer of maleic anhydride and styrene with N, N-dimethyl-n-propylenediamine, quaternized with benzyl chloride, which is of primary interest.
• Preferred quaternary ammonium salts have repeating units that have the formula correspond, wherein R 3 and R 4 e j methyl, Aet h y l, n-propyl or n-butyl or together with the nitrogen atom to which they are connected, form a pyrrolidine, piperidine or morpholine radical, Q 2 an Represents substituents of one of the given formulas (4) to (8) or a mixture of at least one of the formulas (4) to (8) with alkyl or alkenyl having at most 4 carbon atoms, preferably with ethyl or methyl, and A,.
• E 1 and X 1 ⁇ have the meanings given, or especially the formula correspond, wherein E2 is hydrogen or phenyl and A, R 3 , R 4 , Q 2 and X 1 ⁇ have the meanings given, or in particular of the formula correspond, in which Q 3 -CN, - CO - NH2 or phenyl, A ethylene or n-propylene, X 2 ⁇ chlorine or bromine and R 5 and R 6 each represent methyl, ethyl or n-propyl or R 3 and R 6 together form a morpholine residue with the nitrogen atom to which they are attached.
• Quaternary ammonium salts which are of primary interest have recurring units which correspond to the formula correspond in which A is ethylene or n-propylene and R 5 and R 6 are each methyl or ethyl.
• quaternary ammonium salts have repeating units that are of the formula correspond, wherein Q 2 , X 1 ⁇ , Y 1 , Y 2 , n, p and q have the meanings given. or especially the formula correspond in which Q 2 , X 1 , Y 1 , Y 2 , p and q have the meanings given or in particular of the formula correspond in which X 2 8 and Q 3 have the meanings given.
• quaternary ammonium salts which are also preferred, have recurring units that of the formula correspond in which D is ethylene or methylene, T 2 alkyl or optionally substituted by methyl or ethyl aryl with a total of at most 18 carbon atoms and v 1 or 2, and R 3 , R 4 and X 1 ⁇ have the meanings given or preferably one of the formula or correspond in which T 3 is alkyl having 1 to 12 carbon atoms or optionally substituted by ethyl or preferably methyl, benzyl, phenyl or naphthyl and D, R 5 , R 6 , X 1 ⁇ and v have the meanings given or in particular one of the formulas or correspond, wherein T4 is naphthyl, benzyl or phenyl, R 5 and R 6 are each ethyl or methyl and X 2 ⁇ bromine or chlorine.
• auxiliaries used according to the invention contain, as examples of individual, specific ammonium salts, those which have recurring units which correspond to the formulas listed below:
• the quaternary ammonium salts with recurring units of the formula (30) and in particular (22) are of primary interest here.
• the molecular weight of the quaternary ammonium salts in the auxiliaries used according to the invention, which have recurring units of the formulas (1), (2) or (3), is generally from 1500 to 1,000,000. Accordingly, the quaternary ammonium salts generally have 4 - 3000, preferably 8 to 3000 repeating units of the formulas (1), (2) or (3) and in particular 1800 to 2200 repeating units of the formula (30) or 7 to 36 repeating units of one of the formulas (22) to (29) or (31 ) to (35).
• German Offenlegungsschrift 2 604 910 British Patent 855 028 in J. Macromol. Sci.-Chem. A4 (6), pages 1327 to 1417 (October 1970), in J. Polymer Science Vol IV, pages 97 to 133 (1949) and Vol. XXV, pages 201 to 215 (1957).
• German Offenlegungsschrift 2 609 910 discloses or British Patent 855 028 and pages 1327 to 1417 by J. Macromol. Sci.-Chem. A4 (6), quaternary ammonium salts, the units of which at least partially match the units of the formulas (1) or (2) where n is 1, while Vol.
• the quaternary ammonium salts which have recurring units of the formula (1) are generally prepared in such a way that the unsaturated compound of the formula where E 1 has the meaning given, copolymerized with maleic anhydride, preferably in equimolar amounts at elevated temperatures, for example 70 to 100 ° C., in the presence of an inert solvent, preferably an aromatic hydrocarbon such as toluene or xylene mixture and a catalyst such as an azo compound or a peroxide , then the copolymer preferably without its isolation with a generally equimolar amount of a diamine of the formula wherein A, R 1 and R 2 have the meanings given, at elevated temperature, for example 110 to 140 ° C, and the reaction product is preferably isolated and finally with an equimolar amount of a quaternizing agent of the formula wherein X 1 and Q have the meanings given, preferably in an inert, polar solvent, for example an alkanol such as isopropanol or an
• the quaternary ammonium salts having repeating units of the likely formula (2), wherein n is 1, are usually prepared by using the unsaturated compound of the formula wherein Y 1 , Y 2 , p and q have the meanings given, preferably in water in the presence of a dispersant and a catalyst of the type mentioned above at an elevated temperature, for example 40 to 60 ° C, the homopolymer preferably by reprecipitation in a water-soluble solvent , for example cleaning an alkanol such as ethanol and then quaternizing as mentioned above with a quaternizing agent of the formula (4 4 ).
• n in formula (2) is 2, the procedure is analogous but with the difference that styrene is used as comonomer in addition to the compound of formula (45), the molar ratio of styrene: compound of formula (45) being 1: 1 is up to 1:10.
• the quaternary ammonium salts which have repeating units of the formula (3), are as a rule prepared that one the unsaturated compound of the formula wherein X is halogen, homopolymerized and the homopolymer with generally an equimolar amount of a tertiary amine of the formula , wherein R 1 , R 2 and T have the meanings given, preferably in an inert, polar solvent, for example an optionally etherified alkanol such as isopropanol or 1-methoxy-2-ethanol or an amide such as dimethylformamide at elevated temperature, for example 60 to 90 ° C, quaternized.
• an inert, polar solvent for example an optionally etherified alkanol such as isopropanol or 1-methoxy-2-ethanol or an amide such as dimethylformamide at elevated temperature, for example 60 to 90 ° C, quaternized.
• auxiliaries since they contain quaternized compounds, are generally water-soluble and are preferably used according to the invention as dilute, aqueous solutions. However, they can also contain dispersants, as are usually used in dyeing and printing, or organic solvents.
• the auxiliaries used in the process according to the invention are 0.01 to 5, preferably 0.05 to 2 and in particular 0.1 to 1 percent of the quaternary ammonium salts, the repeating units of the formula (1), (2) or (3), calculated as pure ammonium salt, based on the weight of the fiber material to be dyed or printed.
• synthetic synthetic materials come as organic fiber materials that are dyed or printed according to the invention and natural fibers, ie natural or in particular synthetic fibers on their own or mixtures of synthetic and natural fibers. Mixtures of different synthetic fibers are also possible.
• These textile fiber materials are available in a wide variety of processing states, for example as cables, slats, threads, yarns, packages, fabrics, knitted fabrics, non-woven arricles, or finished garments.
• Textile materials made from natural fibers include those made of cellulosic materials, especially cotton, also wool and silk, while the textile materials made of synthetic fibers, e.g. those made of high molecular weight polyesters, such as polyethylene terephthalate or polycyclohexanedimethylene terephthalate, made of polyamides, such as polyhexamethylene diamine adipate, poly- ⁇ -caprolactam or poly- ⁇ -aminoundecanoic acid, made of polyolefins, polyacrylonitriles or acrylonitrile mixed chlorinated polymers, vinyl acetate from vinyl acetate, also from vinyl acetate, from vinyl acetate, from vinyl acetate, from vinyl acetate, from 1/2 acetate and cellulose triacetate are.
• polyesters such as polyethylene terephthalate or polycyclohexanedimethylene terephthalate
• polyamides such as polyhexamethylene diamine adipate, poly- ⁇ -caprolactam
• fibers made from polyacrylonitrile or from modified, cationically dyeable polyester or polyamide are particularly suitable for being dyed or printed according to the invention, the fast-drawing fibers being of particular importance.
• Modified polyester and polyamide fibers are e.g. in Teintures et Apprets 144, pages 163 to 167 (1974).
• Fast-drawing polyacrylonitrile fibers are the focus of interest and are e.g. in Melliand Textilberichte 12 1968, pages 1436 to 1443, in J.Soc. Dyers and Colors, May 1971, pages 149 to 155 and Feb. 1978, pages 49 to 52, in Teintex 5 1973, pages 281 to 296, in man-made fibers / textiles. May 1974, pages 391 to 396 and Jan. 1974, pages 52 to 60.
• Polyacrylonitrile fiber materials are to be understood here as fibers from acrylonitrile copolymers, also called modacrylic fibers, for their production other than acrylonitrile as well
• Vinyl compounds for example vinyl chloride, vinyl acetate, vinylidene chloride, vinyl chloride canide and acrylic acid alkyl ester, have been used, provided that the proportion of these other vinyl compounds is not more than 20 percent, based on the weight of the materials.
• the dye preparations are in the form of aqueous and / or organic solutions or dispersions or as printing pastes or inks which, in addition to a dye, contain further additives, e.g. Contain acids, salts, urea and other auxiliaries such as oxyalkylation products of fatty amines, fatty alcohols, alkylphenols, fatty acids and fatty acid amides.
• further additives e.g. Contain acids, salts, urea and other auxiliaries such as oxyalkylation products of fatty amines, fatty alcohols, alkylphenols, fatty acids and fatty acid amides.
• Cationic dyes in particular are used in the dyeing preparations, in particular for dyeing polyacrylonitrile fibers. These dyes belong to the most diverse groups. Suitable dyes are e.g. Di- and triphenylmethane dyes, rhodamine dyes and azo or anthraquinone dyes containing onium groups, furthermore thiazine, oxazine, methine and azomethine dyes.
• the cationic dyes are e.g. in Color Index, 3rd edition (1971), Volume 1, under the heading "Basic dyes”.
• Direct dyes into consideration. These dyes also belong to the most diverse groups and are e.g. also described in Color Index, Volume 2, under the heading "Direct dyes”.
• the fiber materials are treated with the auxiliary before, during or after dyeing or printing.
• the fiber material is preferably dyed in the presence of the auxiliary, the auxiliary being used primarily as a retarding and leveling agent for the cationic dyes used and the fiber material being treated with the auxiliary with a preparation which simultaneously contains the dye and the auxiliary contains in the so-called "all-in process".
• the aqueous preparation as a means for carrying out the color process according to the invention, which contains a cationic dye and the auxiliary, forms a further subject of the present invention.
• the already grained or printed pasermats are post-treated with the auxiliary, an improvement in the wetness of the dyeing or the printing being achieved.
• the aid is also used as a wet fastness improver.
• This application is particularly suitable for the aftertreatment of callclosic fiber materials dyed or printed with direct dyes.
• the dyeing of the polyacrylonitrile textile materials is carried out in the usual way, e.g. after the exhaust process, carried out by placing the material to be dyed in an aqueous liquor heated to about 50 to 60 ° C., which contains a cationic dye, the auxiliary, additions of salts such as sodium acetate and sodium sulfate, especially in the so-called “all-in process” as well as acids, such as acetic acid or formic acid, then brings the temperature of the dyebath to approximately 100 ° C. in the course of about 30 minutes, and then holds the dyebath at this temperature until it is exhausted.
• the basic dye can also only be added to the dye bath subsequently, e.g. when the temperature of the bath has risen to about 60 ° C.
• the material to be dyed can also be pretreated at a temperature of 40 to 100 ° C. with a liquor which removes the usual salts and acids and the auxiliary used according to the invention but not yet a dye, only then add the dye and dye at 100 ° C.
• the aid used according to the invention When inserting the aid in the course of dyeing, e.g. between the additions of different dyes, a particularly favorable shading can be achieved.
• the dyeings produced with the aid used according to the invention are notable for very good levelness without any significant loss in the dye yield on the fibers. An increased wet fastness of the dyeings or prints of cellulose-containing fiber mixtures with the auxiliary is also possible.
• the presence of the auxiliaries forms on more than one class of dye and on corresponding fiber types, i.e. on fiber mixtures, as well as the good compatibility of the auxiliary with most common non-ionic, cationic textile auxiliaries, e.g. also textile finishing agents, further advantages of the present invention.
• the specific viscosity of a 1% strength solution of the copolymer obtained in dimethylformamide at 20 ° C. is 0.35, which corresponds to an average molecular weight of the copolymer of 3400.
• copolymer of ethylene and maleic anhydride in a molar ratio of 1: 1 the specific viscosity of which as a 1% solution in dimethylformamide at 25 ° C. is 0.1, which corresponds to an average molecular weight of the copolymer of 1000.
• the copolymer A 1 from styrene and maleic anhydride which is in the form of a suspension, is diluted with 295 parts of a xylene mixture and heated to 130.degree. At this temperature, 53 parts of 3-dimethylamino-l-propylamine (0.517 mol) are added to the suspension within one hour. The reaction mixture is then heated to the reflux temperature of approximately 140 ° C., and the water formed by the reaction is distilled off azeotropically. About 9 parts (0.5 mol) of water are obtained. The reaction mixture, now in the form of a clear solution, is cooled to 70 ° C. and by distillation of the xylene mixture concentrated under reduced pressure at this temperature. A viscous, concentrated xylene solution of the reaction product is obtained in practically quantitative yield.
• reaction products B 2 to B 10 are prepared in accordance with Table II below, 0.5 mol of the corresponding copolymer being used in each case:
• the reaction product B 1 is dissolved in 300 parts of isopropanol. 63 parts of benzyl chloride (0.5 mol) are added to this solution. The tion solution is heated to the reflux temperature of about 80 ° C. and held until a sample of the reaction solution is soluble in water and has a pH of less than 7, which usually takes 4 hours. With the addition of water, the solvents (isopropanol and xylene mixture) are removed from the reaction solution by distillation under reduced pressure. A 10 to 30% strength aqueous solution of the quaternized copolymer which is suitable for further handling and has an average of 17 recurring units of the formula (12) is obtained.
• the brown, water-soluble powder obtained is 28 parts of a quaternization product which has a degree of quaternization of 86% and 8 to 3000 units of the formulas (38) and (39), 95% of the units of the formula (38) and 5% of the units of the Correspond to formula (39).
• Example 1 5 g of a polyacrylonitrile fabric (ORLON 42, registered trademark of DUPONT) with a basis weight of 138 g / m 2 are treated in a dyeing machine for 10 minutes at 98 ° C. using the exhaust process with 200 ml of an aqueous liquor whose pH Value was set to 4.0 with 80% acetic acid and contains 0.017 g of a 30% aqueous solution of the quaternizing product C 2 (0.1% pure substance based on the weight of the fabric). The fabric in the liquor is constantly moved in the dyeing machine.
• ORLON 42 registered trademark of DUPONT
• the liquor is then at 98 ° C a dye mixture from 0.007 g of the yellow dye of the formula 0.006 g of the red dye of the formula and 0.010 g of the blue dye of the formula added.
• the fabric is then dyed at 98 ° C for 60 minutes.
• the liquor is slowly cooled to 60 ° C and the fabric is rinsed and dried.
• the gray color obtained is characterized by excellent levelness and good coloration without loss of good wet fastness
• Example 2 A 1 kg muff (winding body without metal spool) of a pre-shrunk, double high-rise yarn (Tex 38x2) made of polyacrylonitrile (EUROACRYL, registered trademark of ANIC) is in a dyeing machine for 10 minutes at 70 ° C after the pull-out process at 30 1 of an aqueous liquor, the pH of which was adjusted to 4.0 with 80% acetic acid, the 6.66 g of a 30% aqueous solution of the quaternizing product C 15 (0.2% pure substance based on the weight of the yarn) and 2 g of the blue dye of formula (50) contains.
• the liquor is constantly circulated through the muff. The liquor temperature is then heated to 98 ° C. within 30 minutes. The muff is colored at this temperature for 60 minutes. After this time, the liquor temperature is slowly cooled to 60 ° C and the muff is rinsed and dried.
• Example 3 10 g of the polyacrylonitrile fabric specified in Example 1 are printed in places with a printing paste which have the following composition:
• the fabric printed in this way is dried and steamed at 102 ° C. for 24 minutes.
• the printed and steamed fabric is treated in a dyeing machine for 10 minutes at 70 ° C. after the exhaust process with 200 ml of an aqueous liquor, the pH of which has been adjusted to 4.0 with 80% acetic acid, the 0.002 g of the blue dye of the formula contains.
• the fabric in the liquor is constantly moved in the dyeing machine.
• the liquor temperature is then raised to 98 ° C. within 30 minutes.
• the fabric is dyed at this temperature for 60 minutes. After this time, the liquor temperature is slowly cooled to 60 ° C and the fabric is rinsed and dried.
• Pronounced two-tone effects are obtained on the fabric by the areas printed with the quaternization product C 15 being light blue, while the areas not printed are colored dark blue.
• Example 4 100 g of a mercerized, bleached cotton fabric with a basis weight of 125 g / m 2 are introduced in a dyeing machine into 2 l of an aqueous liquor at 50 ° C., the 3 g of the red dye of the formula contains.
• the liquor temperature is raised to 98 ° C within 30 minutes.
• the fabric is calcined at this temperature with the addition in portions of a total of 20 g Glauber's salt. dyed, the fabric in the dyeing apparatus in the liquor being constantly moved. After this time, the liquor is slowly cooled to 40 ° C and the fabric is rinsed and dried.
• the dyed fabric is aftertreated for 20 minutes at 40 ° C. in the exhaust process with 2 l of an aqueous liquor which contains 13.3 g of the quaternizing product C 17 as a 30% aqueous solution (4% pure substance based on the fabric weight). The fabric is then dewatered and dried.
• the red color obtained of the fabric aftertreated with the quaternizing product C 17 has excellent waterfastness (waterfastness under heavy use) in DIN Test No. 54006, while the red dyeing of the fabric before the aftertreatment is insufficiently waterfast.

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• Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Engineering & Computer Science (AREA)
• Textile Engineering (AREA)
• Coloring (AREA)
• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

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• 1979
  • 1979-12-21 DK DK552779A patent/DK552779A/da unknown
  • 1979-12-21 EP EP79810185A patent/EP0013540A1/de not_active Withdrawn
  • 1979-12-26 US US06/107,115 patent/US4243390A/en not_active Expired - Lifetime
  • 1979-12-28 AU AU54244/79A patent/AU5424479A/en not_active Abandoned
  • 1979-12-28 ZA ZA00797055A patent/ZA797055B/xx unknown
  • 1979-12-28 BR BR7908619A patent/BR7908619A/pt unknown
  • 1979-12-28 ES ES487614A patent/ES487614A0/es active Granted
  • 1979-12-29 JP JP17404679A patent/JPS5593883A/ja active Pending

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