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EP0613976A1 - Agent for textile wet finishing processes - Google Patents

Agent for textile wet finishing processes Download PDF

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Publication number
EP0613976A1
EP0613976A1 EP94810113A EP94810113A EP0613976A1 EP 0613976 A1 EP0613976 A1 EP 0613976A1 EP 94810113 A EP94810113 A EP 94810113A EP 94810113 A EP94810113 A EP 94810113A EP 0613976 A1 EP0613976 A1 EP 0613976A1
Authority
EP
European Patent Office
Prior art keywords
acrylamide
weight
dyes
copolymer
homo
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.)
Granted
Application number
EP94810113A
Other languages
German (de)
French (fr)
Other versions
EP0613976B1 (en
Inventor
Martin Dr. Kuhn
Philippe Ouziel
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.)
BASF Schweiz AG
Original Assignee
Ciba Geigy AG
Ciba Spezialitaetenchemie Holding 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
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Publication of EP0613976A1 publication Critical patent/EP0613976A1/en
Application granted granted Critical
Publication of EP0613976B1 publication Critical patent/EP0613976B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime 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
    • 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
    • D06P1/0036—Dyeing and sizing in one process
    • 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
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters 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
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/285—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acid amides or imides
    • 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
    • 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
    • D06P1/5257—(Meth)acrylic acid
    • 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
    • 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
    • Y10S8/92—Synthetic fiber dyeing
    • Y10S8/922—Polyester fiber
    • 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
    • Y10S8/929—Carpet dyeing

Definitions

  • the present invention relates to the use of specific polymers as textile auxiliaries, in particular as wrinkle preventing agents in the exhaust dyeing process.
  • Modern piece dyeing takes place preferably in closed equipment such as HT reel runners, fully and partially flooded jet dyeing machines or softstream dyeing machines.
  • closed equipment such as HT reel runners, fully and partially flooded jet dyeing machines or softstream dyeing machines.
  • wrinkles are to be expected, which can lead to uneven dyeings.
  • the cause of such irregularities is, on the one hand, the different access of the dye liquor in the running fold compared to the exposed tissue surface and, on the other hand, the changed dye absorption of the fiber deformed by kinking due to a change in crystallinity associated therewith.
  • This problem is countered by using auxiliary agents such as e.g. from the Textile Aids Catalog 1991, Konradin Verlag D-7022 Leinfelden-Echterdingen, pages 103-107.
  • the known anti-wrinkle agents are unable to meet the requirements placed on them in full. There is therefore a need for new anti-wrinkle agents with improved properties.
  • the present invention accordingly relates to the use of acrylamide homopolymers or copolymers in an amount of ⁇ 0.04 g per liter of dyeing liquor as an anti-wrinkle agent in exhaust dyeing processes.
  • the acrylamide homopolymers and copolymers are preferably used in the form of an aqueous preparation.
  • the polymer used as an anti-wrinkle agent is, for example, an acrylamide homopolymer or a copolymer of acrylamide and acrylic acid.
  • the preferred homo- and copolymers consist of 70 to 100% by weight of acrylamide and 0 to 30% by weight of acrylic acid, in each case based on the weight of the monomers. It is particularly preferred to use acrylamide / acrylic acid copolymers, and in particular those with an acrylamide content of> 70% by weight, based on the weight of the monomers.
  • a particularly preferred embodiment of the present invention relates to the use of copolymers of 75 to 90% by weight of acrylamide and 10 to 25% by weight of acrylic acid, in each case based on the weight of the monomers.
  • the homo- and copolymers used according to the invention have an average molecular weight of e.g. 800,000 to approximately 15 million, preferably 1 to 10 million and particularly preferably 1.5 to 3 million.
  • the homopolymers and copolymers used according to the invention are known per se or can be obtained by known methods; they can be converted into easy-to-use aqueous preparations by simply adding or mixing the polymers in water.
  • the amounts used in which the polymers according to the invention are added to the finishing liquor, in particular the dye baths are advantageously between 0.0005 and 0.04 g / l liquor, preferably between 0.0005 and 0.03 g / l liquor and particularly preferably between 0.005 and 0.02 g / l liquor. Amounts of ⁇ 0.4 g / l liquor are impractical because they can give rise to a smear layer on the fabric to be dyed, which is very difficult to remove.
  • the dyeings in the presence of the acrylamide homo- and copolymers according to the invention by an exhaust process are carried out in a manner known per se to the person skilled in the art using a wide variety of fiber materials.
  • Suitable cellulose fiber material is that of regenerated or in particular natural cellulose, such as Cellulose, viscose silk, hemp, linen, jute or preferably cotton.
  • Cellulose fiber materials are usually dyed with substantive dyes, vat dyes, leuco vat dye esters or, above all, reactive dyes.
  • the usual direct dyes are suitable as noun dyes, for example the "Direct Dyes” mentioned in Color Index 3rd Edition, (1971) Vol. 2 on pages 2005 to 2478.
  • vat dyes are higher fused and heterocyclic benzoquinones or naphthoquinones, sulfur dyes and in particular anthraquinones or indigo dyes.
  • vat dyes which can be used according to the invention are listed in the Color Index 3rd Edition (1971) Vol. 3 on pages 3649 to 3837 under the names "Sulfur Dyes” and "Vat Dyes”.
  • the leuco vat dye esters are e.g. from vat dyes of the indigo, antharaquinone or indanthrene series by reduction e.g. with iron powder and subsequent esterification e.g. available with chlorosulfonic acid and are referred to in the Color Index 3rd Edition, 1971, Vol. 3 as "Solubilized Vat Dyes".
  • Reactive dyes are understood to be the usual dyes which form a chemical bond with the cellulose, e.g. the "Reactive Dyes” listed in the Color Index, in volume 3 (3rd edition, 1971) on pages 3391-3560 and in volume 6 (revised 3rd edition, 1975) on pages 6268-6345.
  • Synthetic polyamide fiber materials in particular textile materials, which can be dyed in the presence of the new copolymers, are e.g. those from adipic acid and hexamethylenediamine (polyamide 6,6), from ⁇ -caprolactam (polyamide 6), from ⁇ -aminoundecanoic acid (polyamide 11), from ⁇ -aminoonanthic acid (polyamide 7), from ⁇ -aminopelargonic acid (polyamide 8) or from sebacic acid and hexamethylene diamine (polyamide 6, 10) to mention.
  • adipic acid and hexamethylenediamine polyamide 6,6
  • polyamide 6 ⁇ -caprolactam
  • polyamide 11 from ⁇ -aminoundecanoic acid
  • polyamide 7 from ⁇ -aminoonanthic acid
  • polyamide 8 from sebacic acid and hexamethylene diamine
  • Synthetic or natural polyamide fiber materials are usually dyed with anionic dyes.
  • the anionic dyes are, for example, salts of heavy metal-containing or preferably metal-free azomethine, mono-, dis- or polyazo dyes including the formazan dyes and the anthraquinone, xanthene, nitro, triphenylmethane, naphthoquinoneimine and phthalocyanine dyes.
  • the ionic character of these dyes can be achieved by metal complex formation alone and / or preferably acidic, salt-forming substituents, such as carboxylic acid groups, sulfuric acid and phosphonic acid ester groups, phosphonic acid groups or preferably sulfonic acid groups.
  • These dyes can also have so-called reactive groups in the molecule, which form a covalent bond with the material to be colored.
  • the so-called acidic metal-free dyes are preferred.
  • the latter preferably contain only a single sulfonic acid group and optionally a further, but not a salt-forming, water-solubilizing group such as the acid amide or alkylsulfonyl group.
  • the 1: 1 or preferably 1: 2 metal complex dyes are also of particular interest.
  • the 1: 1 metal complex dyes preferably have one or two sulfonic acid groups. As metal they contain a heavy metal atom, e.g. Copper, nickel or especially chrome.
  • the 1: 2 metal complex dyes contain a heavy metal atom as the central atom, e.g. a cobalt atom or in particular a chromium atom. Two complex-forming components are connected to the central atom, at least one of which is a dye molecule, but preferably both are dye molecules. The two dye molecules involved in the complex formation can be the same or different from one another.
  • the 1: 2 metal complex dyes can e.g. contain two azomethine molecules, a disazo dye and a monoazo dye, or preferably two monoazo dye molecules.
  • the azo dye molecules can have water solubilizing groups, e.g. Acid amide, alkylsulfonyl or the above acidic groups. Preference is given to 1: 2 cobalt or 1: 2 chromium complexes of monoazo dyes which have acid amide, alkylsulfonyl or a total of a single sulfonic acid group.
  • Linear polyester fibers are to be understood as synthetic fibers which are obtained, for example, by condensation of terephthalic acid with ethylene glycol or of isophthalic acid or terephthalic acid with 1,4-bis (hydroxymethyl) cyclohexane, as well as copolymers of terephthalic and isophthalic acid and ethylene glycol.
  • the linear polyester used so far almost exclusively in the textile industry consists of Terephthalic acid and ethylene glycol.
  • the disperse dyes to be used for dyeing polyester fiber materials which are only sparingly soluble in water and are largely in the form of a fine dispersion in the dye liquor, can belong to a wide variety of dye classes, for example acridone, azo, anthraquinone and coumarin -, methine, perinone, naphthoquinone imine, quinophthalone, styryl or nitro dyes. Mixtures of disperse dyes can also be used.
  • acrylamide homopolymers and copolymers according to the invention can also be used advantageously in the dyeing of polyacrylonitrile fibers with cationic dyes, since there are no interfering interactions and, in particular, no precipitation occurs. Both migrating and non-migrating dyes can be used as cationic dyes.
  • Particularly suitable as migrating cationic dyes are those with a more or less delocalized positive charge, the cation weight of which is less than 310, the parachor of which is less than 750 and the log P of which is less than 3.2.
  • the Parachor is according to the article by OR Quayle [Chem. Rev. 53 , 439 (1953)] and log P means the relative lipophilicity, the calculation of which by C. Hanach et al [J. Med. Chem. 16 , 1207 (1973)].
  • Non-migrating cationic dyes are, in particular, those whose cation weight is greater than 310 and whose parachor is greater than 750.
  • the cationic, migrating and non-migrating dyes can belong to different classes of dyes.
  • they are salts, for example chlorides, sulfates or metal halides, for example zinc chloride double salts of azo dyes such as monoazo dyes or hydrazone dyes, anthraquinone, diphenylmethane, triphenylmethane, methine, azomethine, coumarin, ketoneimine, cyanine, xanthene, Azine, oxazine or thiazine dyes.
  • azo dyes such as monoazo dyes or hydrazone dyes, anthraquinone, diphenylmethane, triphenylmethane, methine, azomethine, coumarin, ketoneimine, cyanine, xanthene, Azine, oxazine or thiazine dyes.
  • cationic dyes can be used.
  • Dye combinations of at least 2 or preferably 3 migrating or non-migrating cationic dyes are particularly preferred for producing level dichromia or trichromatic dyeings, mixtures of migrating and non-migrating cationic dyes can be used.
  • the fiber materials can also be used as a mixed fabric among themselves or with other fibers, e.g. Mixtures of polyacrylonitrile / polyester, polyamide / polyester, polyester / cotton, polyester / viscose, polyacrylonitrile / wool and polyester / wool can be used.
  • Fiber blends of polyester and cotton are usually dyed with combinations of disperse dyes and vat dyes, sulfur dyes, leuco vat ester dyes, direct dyes or reactive dyes, the polyester content being pre-, simultaneously or post-dyed with disperse dyes.
  • Polyester / wool mixed fiber materials are preferably dyed according to the invention with commercially available mixtures of anionic dyes and disperse dyes.
  • the textile material to be dyed can be in various forms. Piece goods, such as knitted or woven fabrics, are preferred.
  • Preparations according to the invention can also be used for whitening undyed synthetic fiber materials with optical brighteners dispersed in water.
  • the optical brighteners can belong to any brightener class. In particular, they are coumarins, triazolcoumarins, benzocoumarins, oxazines, pyrazines, pyrazolines, diphenylpyrazolines, stilbenes, styrylstilbenes, triazolylstilbenes, bisbenzoxazolylethylenes, stilbene-bis-benzoxazoles, phenylstilbenbenzoxazoles, thiophene-bis-benzoxazole, benzoxazole, benzoxazole, benzoxazole, benzoxazole, benzoxazole, benzoxazole, benzoxazole, benzophenazazole and naphthalimides.
  • Mixtures of optical brighteners can also be used.
  • the amount of dyes or optical brighteners to be added to the liquor depends on the desired color strength; In general, amounts of 0.01 to 10, preferably 0.2 to 5% by weight, based on the textile material used, have proven successful.
  • the dyebaths or brightener liquors can, in addition to the dyes or optical brighteners and the inventive preparations of copolymers, wool protection agents, oligomer inhibitors, oxidizing agents, Contain antifoams, emulsifiers, leveling agents, retarders and preferably dispersants.
  • the dispersants are used primarily to achieve a good fine distribution of the disperse dyes.
  • the dispersants generally used for dyeing with disperse dyes are suitable.
  • Preferred dispersants are sulfated or phosphated adducts of 15 to 100 moles of ethylene oxide or preferably propylene oxide with polyhydric aliphatic alcohols containing 2 to 6 carbon atoms, such as e.g. Ethylene glycol, glycerol or pentaerythritol or amines having 2 to 9 carbon atoms and having at least two amino groups or an amino group and a hydroxyl group and alkylsulfonates having 10 to 20 carbon atoms in the alkyl chain, alkylbenzenesulfonates having a straight-chain or branched alkyl chain having 8 to 20 carbon atoms in the alkyl chain, such as e.g.
  • Lignin sulfonates polyphosphates and preferably formaldehyde condensation products of aromatic sulfonic acids, formaldehyde and optionally mono- or bifunctional phenols, such as e.g. from cresol, ⁇ -naphtholsulfonic acid and formaldehyde, from benzenesulfonic acid, formaldehyde and naphthalenic acid, from naphthalenesulfonic acid and formaldehyde or from naphthalenesulfonic acid, dihydroxydiphenyl sulfone and formaldehyde.
  • the disodium salt of di- (6-sulfonaphthyl-2-) methane is preferred.
  • anionic dispersants can also be used.
  • the anionic dispersants are normally in the form of their alkali metal salts, ammonium salts or amino salts. These dispersants are preferably used in an amount of 0.1 to 5 g / l of liquor.
  • the dyebaths or brightener liquors can, in addition to the auxiliaries already mentioned, also conventional additives, advantageously electrolytes such as salts, for example sodium sulfate, ammonium sulfate, sodium or ammonium phosphates or polyphosphates, metal chlorides or nitrates such as sodium chloride, calcium chloride, Magnesium chloride or calcium nitrate, ammonium acetate or Sodium acetate and / or acids, for example mineral acids such as sulfuric acid or phosphoric acid, or organic acids, suitably lower aliphatic carboxylic acids such as formic, acetic or oxalic acid, and also alkalis or alkali donors and / or complexing agents.
  • salts for example sodium sulfate, ammonium sulfate, sodium or ammonium phosphates or polyphosphates
  • metal chlorides or nitrates such as sodium chloride, calcium chloride, Magnesium chloride or calcium nitrate
  • the acids primarily serve to adjust the pH of the liquors used according to the invention, which is generally 3 to 6.5, preferably 4.5 to 6.
  • the preparations When using reactive dyes, the preparations usually contain fixing alkalis.
  • a mixture of water glass and a 30% aqueous sodium hydroxide solution has proven particularly useful as an alkali.
  • the pH of the dye liquors containing alkali is generally 7.5 to 12.5, preferably 8.5 to 11.5.
  • the dyeing or lightening is advantageously carried out from an aqueous liquor using the exhaust process.
  • the liquor ratio can accordingly be chosen within a wide range, e.g. 1: 4 to 1: 100, preferably 1: 6 to 1:50.
  • the temperature at which dyeing or lightening is at least 70 ° C and is usually not higher than 140 ° C. It is preferably in the range from 80 to 135 ° C.
  • Linear polyester fibers and cellulose triacetate fibers are preferably dyed by the so-called high-temperature process in closed and expediently also pressure-resistant apparatus at temperatures above 100 ° C., preferably between 110 and 135 ° C., and optionally under pressure.
  • Circulation devices such as cross-winding or tree dyeing machines, reel runners, nozzle or drum dyeing machines, muff dyeing machines, paddles or jiggers are suitable as closed vessels, for example.
  • Cellulose-2 1/2 acetate fibers are preferably dyed at temperatures of 80-85 ° C.
  • the material to be dyed is cellulose fiber material or synthetic polyamide fiber material alone
  • the dyeing is expediently carried out at a temperature of 20 to 106 ° C., preferably 30 to 95 ° C. for cellulose fibers and 80 to 95 ° C. for polyamide fibers.
  • polyester-cotton fiber materials are preferably dyed at temperatures above 106 ° C., expediently at 110 to 135 ° C. These mixed fiber materials can be dyed in the presence of carriers or carrier mixtures, which act as a dyeing accelerator for dyeing the polyester portion with disperse dyes.
  • the dyeing process can be carried out by either briefly treating the material to be dyed first with the preparation according to the invention and then dyeing it, or preferably treating it simultaneously with the preparation and the dye.
  • the dyeings are completed by cooling the dye liquor to 40 to 70 ° C., rinsing the dyeings with water and, if appropriate, cleaning in a customary manner in an alkaline medium under reductive conditions. The dyeings are then rinsed again and dried. If carriers are used, the dyeings are used to improve the lightfastness, advantageously after heat treatment, e.g. Thermosolieren, subjected, which is preferably carried out at 160 to 180 ° C and for 30 to 90 seconds.
  • vat dyes for the cellulose portion the goods are treated in the usual way first with hydrosulfite at a pH of 6 to 12.5 and then with oxidizing agent and finally washed out.
  • the so-called friction test can advantageously be used as a measure of the ability of a polymer to prevent the formation of wrinkles.
  • a strip of tissue e.g. a strip made of cotton or cotton / polyester
  • the determined value represents the standard (friction value 100%).
  • the tissue strip is then immersed in an aqueous solution of the polymer to be determined and the measurement is repeated.
  • the values obtained with and without polymer are set in relation to each other and the friction value of the polymer is given in percent of the value obtained with pure water. Friction values of, for example, ⁇ 70% indicate a clearly wrinkle-reducing effect of the polymer in question.
  • the fastness of the dyeings such as Light fastness, fastness to rubbing and wet fastness are not negatively influenced by the use of the auxiliary mixture. Furthermore, no troublesome foaming occurs when the textile material is dyed in the presence of the preparations according to the invention.
  • the percentages are by weight unless otherwise specified.
  • the amounts of the dyes relate to commercial, i.e. Coucher goods and the components of the auxiliary mixture on pure substance.
  • 100 g of a bleached cotton cretonne fabric are dyed in 2 liters of water on a laboratory jet dyeing machine with the following additives: 0.25 g of a dye of the formula 0.3 g of a dye of the formula 4 g of a 1% strength solution of the polymer according to Example 16 (copolymer of approx. 15% acrylic acid and 85% acrylamide, molecular weight approx. 2 million).
  • additives are first dissolved or dispersed in water and added to the dyebath at 50 ° C.
  • the dye liquor is then heated to 98 ° C. over a period of 30 minutes with constant circulation and movement of the substrate.
  • 20 g of Glauber's salt are added to the dye liquor.
  • the fabric is then dyed at 98 ° C. for a further 30 minutes, whereupon the dyebath is cooled to 60 ° C. and the fabric is warm and rinsed cold and dried. A wrinkle-free level and gray coloration is obtained.
  • the use of the preparation according to the invention results in a significant reduction in the friction value compared to a dyeing liquor without the addition of this preparation.
  • the preparation containing the copolymer has no retarding effect and does not change the shade.
  • 100 g of a polyester staple fabric are treated on a reel at 30 ° C with 2 liters of an aqueous dyeing liquor 0.25 g of a dye of the formula 0.35 g of a dye of the formula 0.15 g of a dye of the formula 2 g of a 1% strength solution of the polymer according to Example 16 (copolymer of approx. 15% acrylic acid and 85% acrylamide, molecular weight approx. 2 million).
  • 2 g ammonium sulfate contains and is adjusted to pH 5.5 with formic acid. After a lead time of 10 minutes at 30 ° C, the temperature is increased to 130 ° C, after which the fabric is dyed at this temperature for a further 60 minutes. Then the liquor is cooled to 60 ° C., the fabric is rinsed and dried. A wrinkle-free, level brown color is obtained.
  • 100 g of a polyamide 6.6 stack fabric are treated on a laboratory jet dyeing machine at 40 ° C. in 2 liters of water with the following additives: 6 g of a 1% strength aqueous solution of the polymer according to Example 21 (polyacrylamide homopolymer, molecular weight approx. 10 million); 2 g of a condensation product of 1 mol of fatty amine and 70 mol of ethylene oxide;
  • the liquor is adjusted to 5.5 with acetic acid. After a lead time of 15 minutes at 40 ° C 1 g of a dye of the formula metered into the liquor, whereupon the liquor is circulated for a further 5 minutes. The liquor is then heated to 98 ° C. over a period of 30 minutes and dyed at this temperature for 30 minutes.
  • the liquor is then cooled to 60 ° C. in the course of 15 minutes and the fabric is rinsed and dried. A wrinkle-free, level blue color is obtained. There is no change in nuance.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Coloring (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

Abstract

The present invention relates to the use of an acrylamide homo- or copolymer in an amount of < 0.04 g per litre of dyeing liquor as crease preventative in exhaust dyeing processes.

Description

Die vorliegende Erfindung betrifft die Verwendung von spezifischen Polymeren als Textilhilfsmittel, insbesondere als Faltenverhinderungsmittel im Ausziehfärbeverfahren.The present invention relates to the use of specific polymers as textile auxiliaries, in particular as wrinkle preventing agents in the exhaust dyeing process.

Die moderne Stückfärberei findet vorzugsweise in geschlossenen Apparaturen wie HT-Haspelkufen, voll- und teildurchfluteten Jet-Färbemaschinen oder Softstream-Färbemaschinen statt. Beim Färben von Geweben und Gewirken mit diesen Maschinen hat man mit Faltenbildung zu rechnen, was zu unegalen Färbungen führen kann. Ursache solcher Unegalitäten ist zum einen der unterschiedliche Zutritt der Färbeflotte in der Lauffalte gegenüber der ausliegenden Gewebefläche und zum anderen die veränderte Farbstoffaufnahme der durch Knick deformierten Faser über eine damit einhergehende Kristallinitätsveränderung. Man begegnet diesem Problem, indem man den Färbebädern Hilfsmittel, wie sie z.B. aus dem Textilhilfsmittelkatalog 1991, Konradin Verlag D-7022 Leinfelden-Echterdingen, Seiten 103 - 107 bekannt sind, zusetzt. Die bekannten Lauffaltenverhinderungsmittel vermögen jedoch die an sie gestellten Anforderungen nicht im vollen Umfang zu erfüllen. Es besteht daher ein Bedarf nach neuen Faltenverhinderungsmitteln mit verbesserten Eigenschaften.Modern piece dyeing takes place preferably in closed equipment such as HT reel runners, fully and partially flooded jet dyeing machines or softstream dyeing machines. When dyeing fabrics and knitted fabrics with these machines, wrinkles are to be expected, which can lead to uneven dyeings. The cause of such irregularities is, on the one hand, the different access of the dye liquor in the running fold compared to the exposed tissue surface and, on the other hand, the changed dye absorption of the fiber deformed by kinking due to a change in crystallinity associated therewith. This problem is countered by using auxiliary agents such as e.g. from the Textile Aids Catalog 1991, Konradin Verlag D-7022 Leinfelden-Echterdingen, pages 103-107. However, the known anti-wrinkle agents are unable to meet the requirements placed on them in full. There is therefore a need for new anti-wrinkle agents with improved properties.

Es wurde nun überraschend gefunden, dass sich spezifische Homo- und Copolymere hervorragend als Faltenverhinderungsmittel eignen und Unegalitäten während der Jet-Färbung oder bei der Färbung auf der Haspelkufe effektiv vorbeugen.It has now surprisingly been found that specific homopolymers and copolymers are outstandingly suitable as anti-wrinkle agents and effectively prevent unevenness during jet dyeing or during dyeing on the reel runner.

Gegenstand der vorliegenden Erfindung ist dementsprechend die Verwendung von Acrylamid-Homo- oder -Copolymeren in einer Menge von < 0,04 g pro Liter Färbeflotte als Faltenverhinderungsmittel in Ausziehfärbeverfahren.The present invention accordingly relates to the use of acrylamide homopolymers or copolymers in an amount of <0.04 g per liter of dyeing liquor as an anti-wrinkle agent in exhaust dyeing processes.

Die Acrylamid-Homo- und -Copolymere werden vorzugsweise in Form einer wässrigen Zubereitungen eingesetzt.The acrylamide homopolymers and copolymers are preferably used in the form of an aqueous preparation.

Bei dem als Faltenverhinderungsmittel verwendeten Polymer handelt es sich z.B. um ein Acrylamid-Homopolymer oder um ein Copolymer aus Acrylamid und Acrylsäure. Die bevorzugten Homo- und Copolymere bestehen aus 70 bis 100 Gew.-% Acrylamid und 0 bis 30 Gew.-% Acrylsäure, jeweils bezogen auf das Gewicht der Monomeren. Besonders bevorzugt ist die Verwendung von Acrylamid/Acrylsäure-Copolymeren und hierbei insbesondere von solchen mit einem Acrylamidgehalt von > 70 Gew.-%, bezogen auf das Gewicht der Monomeren. Eine besonders bevorzugte Ausführungsform der vorliegenden Erfindung betrifft die Verwendung von Copolymeren aus 75 bis 90 Gew.-% Acrylamid und 10 bis 25 Gew.-% Acrylsäure, jeweils bezogen auf das Gewicht der Monomeren.The polymer used as an anti-wrinkle agent is, for example, an acrylamide homopolymer or a copolymer of acrylamide and acrylic acid. The preferred homo- and copolymers consist of 70 to 100% by weight of acrylamide and 0 to 30% by weight of acrylic acid, in each case based on the weight of the monomers. It is particularly preferred to use acrylamide / acrylic acid copolymers, and in particular those with an acrylamide content of> 70% by weight, based on the weight of the monomers. A particularly preferred embodiment of the present invention relates to the use of copolymers of 75 to 90% by weight of acrylamide and 10 to 25% by weight of acrylic acid, in each case based on the weight of the monomers.

Die erfindungsgemäss verwendeten Homo- und Copolymere weisen ein mittleres Molekulargewicht von z.B. 800000 bis ca. 15 Millionen, vorzugsweise 1 bis 10 Millionen und besonders bevorzugt 1,5 bis 3 Millionen auf.The homo- and copolymers used according to the invention have an average molecular weight of e.g. 800,000 to approximately 15 million, preferably 1 to 10 million and particularly preferably 1.5 to 3 million.

Die erfindungsgemäss verwendeten Homo- und Copolymere sind an sich bekannt oder können nach bekannten Methoden erhalten werden; sie können durch einfaches Zugeben bzw. Vermischen der Polymere in Wasser in einfach zu handhabende wässrige Zubereitungen überführt werden. Vorteilhaft verwendet man wässrige Lösungen bzw. Dispersionen der Acrylamid-Homo- oder -Copolymeren mit einem Trockengehalt von z.B. 0,05 bis 10 Gew.-% und vorzugsweise 0,5 bis 3 Gew.-%.The homopolymers and copolymers used according to the invention are known per se or can be obtained by known methods; they can be converted into easy-to-use aqueous preparations by simply adding or mixing the polymers in water. Aqueous solutions or dispersions of the acrylamide homo- or copolymers with a dry content of e.g. 0.05 to 10% by weight and preferably 0.5 to 3% by weight.

Die Einsatzmengen, in denen die Polymere erfindungsgemäss der Veredelungsflotte, insbesondere den Färbebädern, zugesetzt werden, bewegen sich zweckmässigerweise zwischen 0,0005 und 0,04 g/l Flotte, bevorzugt zwischen 0,0005 und 0,03 g/l Flotte und besonders bevorzugt zwischen 0,005 und 0,02 g/l Flotte. Einsatzmengen von ≧ 0,4 g/l Flotte sind unpraktikabel, weil sie zur Bildung einer Schmierschicht auf dem zu färbenden Gewebe Anlass geben können, welche nur sehr schwer wieder entfernbar ist.The amounts used in which the polymers according to the invention are added to the finishing liquor, in particular the dye baths, are advantageously between 0.0005 and 0.04 g / l liquor, preferably between 0.0005 and 0.03 g / l liquor and particularly preferably between 0.005 and 0.02 g / l liquor. Amounts of ≧ 0.4 g / l liquor are impractical because they can give rise to a smear layer on the fabric to be dyed, which is very difficult to remove.

Die Färbungen in Gegenwart der erfindungsgemässen Acrylamid-Homo- und Copolymeren nach einem Ausziehverfahren erfolgen in an sich üblicher dem Fachmann bekannter Weise unter Verwendung verschiedenster Fasermaterialien.The dyeings in the presence of the acrylamide homo- and copolymers according to the invention by an exhaust process are carried out in a manner known per se to the person skilled in the art using a wide variety of fiber materials.

Als Cellulosefasermaterial kommt solches aus regenerierter oder insbesondere natürlicher Cellulose in Betracht, wie z.B. Zellwolle, Viskoseseide, Hanf, Leinen, Jute oder vorzugsweise Baumwolle.Suitable cellulose fiber material is that of regenerated or in particular natural cellulose, such as Cellulose, viscose silk, hemp, linen, jute or preferably cotton.

Cellulosefasermaterialien werden in der Regel mit substantiven Farbstoffen, Küpenfarbstoffen, Leukoküpenfarbstoffestern oder vor allem Reaktivfarbstoffen gefärbt.Cellulose fiber materials are usually dyed with substantive dyes, vat dyes, leuco vat dye esters or, above all, reactive dyes.

Als Substantivfarbstoffe sind die üblichen Direktfarbstoffe geeignet, beispielsweise die in Colour Index 3rd Edition, (1971) Vol. 2 auf den Seiten 2005 bis 2478 genannten "Direct Dyes".The usual direct dyes are suitable as noun dyes, for example the "Direct Dyes" mentioned in Color Index 3rd Edition, (1971) Vol. 2 on pages 2005 to 2478.

Bei den Küpenfarbstoffen handelt es sich um höher annellierte und heterocyclische Benzochinone oder Naphthochinone, um Schwefelfarbstoffe und insbesondere um Anthrachinoide oder indigoide Farbstoffe. Beispiele von erfindungsgemäss verwendbaren Küpenfarbstoffen sind im Colour Index 3rd Edition (1971) Vol. 3 auf den Seiten 3649 bis 3837 unter der Bezeichnung "Sulphur Dyes" und "Vat Dyes" aufgeführt.The vat dyes are higher fused and heterocyclic benzoquinones or naphthoquinones, sulfur dyes and in particular anthraquinones or indigo dyes. Examples of vat dyes which can be used according to the invention are listed in the Color Index 3rd Edition (1971) Vol. 3 on pages 3649 to 3837 under the names "Sulfur Dyes" and "Vat Dyes".

Die Leukoküpenfarbstoffester sind z.B. aus Küpenfarbstoffen der Indigo-, Antharachinon- oder Indanthren-Reihe durch Reduktion z.B. mit Eisenpulver und anschliessende Veresterung z.B. mit Chlorsulfonsäure erhältlich und sind im Colour Index 3rd Edition, 1971, Vol. 3 als "Solubilised Vat Dyes" bezeichnet.The leuco vat dye esters are e.g. from vat dyes of the indigo, antharaquinone or indanthrene series by reduction e.g. with iron powder and subsequent esterification e.g. available with chlorosulfonic acid and are referred to in the Color Index 3rd Edition, 1971, Vol. 3 as "Solubilized Vat Dyes".

Unter Reaktivfarbstoffen werden die üblichen Farbstoffe verstanden, welche mit der Cellulose eine chemische Bindung eingehen, z.B. die im Colour Index, im Band 3 (3. Auflage, 1971) auf den Seiten 3391-3560 und in Band 6 (revidierte 3. Auflage, 1975) auf den Seiten 6268-6345 aufgeführten "Reactive Dyes".Reactive dyes are understood to be the usual dyes which form a chemical bond with the cellulose, e.g. the "Reactive Dyes" listed in the Color Index, in volume 3 (3rd edition, 1971) on pages 3391-3560 and in volume 6 (revised 3rd edition, 1975) on pages 6268-6345.

Als synthetische Polyamidfasermaterialien, insbesondere Textilmaterialien, die in Gegenwart der neuen Mischpolymerisate gefärbt werden können, sind z.B. solche aus Adipinsäure und Hexamethylendiamin (Polyamid 6,6), aus ε-Caprolactam (Polyamid 6), aus ω-Aminoundecansäure (Polyamid 11), aus ω-Aminoönanthsäure (Polyamid 7), aus ω-Aminopelargonsäure (Polyamid 8) oder aus Sebazinsäure und Hexamethylendiamin (Polyamid 6, 10) zu erwähnen.Synthetic polyamide fiber materials, in particular textile materials, which can be dyed in the presence of the new copolymers, are e.g. those from adipic acid and hexamethylenediamine (polyamide 6,6), from ε-caprolactam (polyamide 6), from ω-aminoundecanoic acid (polyamide 11), from ω-aminoonanthic acid (polyamide 7), from ω-aminopelargonic acid (polyamide 8) or from sebacic acid and hexamethylene diamine (polyamide 6, 10) to mention.

Synthetische oder natürliche Polyamidfasermaterialien werden in der Regel mit anionischen Farbstoffen gefärbt.Synthetic or natural polyamide fiber materials are usually dyed with anionic dyes.

Bei den anionischen Farbstoffen handelt es sich beispielsweise um Salze schwermetallhaltiger oder vorzugsweise metallfreier Azomethin-, Mono-, Dis- oder Polyazofarbstoffe einschliesslich der Formazanfarbstoffe sowie der Anthrachinon-, Xanthen-, Nitro-, Triphenylmethan-, Naphthochinonimin- und Phthalocyaninfarbstoffe. Der ionische Charakter dieser Farbstoffe kann durch Metallkomplexbildung allein und/oder vorzugsweise durch saure, salzbildende Substituenten, wie Carbonsäuregruppen, Schwefelsäure- und Phosphonsäureestergruppen, Phosphonsäuregruppen oder vorzugsweise Sulfonsäuregruppen bedingt sein. Diese Farbstoffe können im Molekül auch sogenannte reaktive Gruppierungen, welche mit dem zu färbenden Material eine kovalente Bindung eingehen, aufweisen. Bevorzugt sind die sogenannten sauren metallfreien Farbstoffe. Letztere enthalten vorzugsweise nur eine einzige Sulfonsäuregruppe und gegebenenfalls eine weitere, jedoch keine salzbildende, wasserlöslichmachende Gruppe wie die Säureamid- oder Alkylsulfonylgruppe.The anionic dyes are, for example, salts of heavy metal-containing or preferably metal-free azomethine, mono-, dis- or polyazo dyes including the formazan dyes and the anthraquinone, xanthene, nitro, triphenylmethane, naphthoquinoneimine and phthalocyanine dyes. The ionic character of these dyes can be achieved by metal complex formation alone and / or preferably acidic, salt-forming substituents, such as carboxylic acid groups, sulfuric acid and phosphonic acid ester groups, phosphonic acid groups or preferably sulfonic acid groups. These dyes can also have so-called reactive groups in the molecule, which form a covalent bond with the material to be colored. The so-called acidic metal-free dyes are preferred. The latter preferably contain only a single sulfonic acid group and optionally a further, but not a salt-forming, water-solubilizing group such as the acid amide or alkylsulfonyl group.

Von besonderem Interesse sind auch die 1:1- oder vorzugsweise 1:2-Metallkomplexfarbstoffe. Die 1:1 -Metallkomplexfarbstoffe weisen vorzugsweise eine oder zwei Sulfonsäuregruppen auf. Als Metall enthalten sie ein Schwermetallatom, wie z.B. Kupfer, Nickel oder insbesondere Chrom.The 1: 1 or preferably 1: 2 metal complex dyes are also of particular interest. The 1: 1 metal complex dyes preferably have one or two sulfonic acid groups. As metal they contain a heavy metal atom, e.g. Copper, nickel or especially chrome.

Die 1:2-Metallkomplexfarbstoffe enthalten als Zentralatom ein Schwermetallatom, wie z.B. ein Kobaltatom oder insbesondere ein Chromatom. Mit dem Zentralatom sind zwei komplexbildende Komponenten verbunden, von denen mindestens eine ein Farbstoffmolekül ist, vorzugsweise jedoch beide Farbstoffmoleküle sind. Dabei können die beiden an der Komplexbildung beteiligten Farbstoffmoleküle gleich oder voneinander verschieden sein. Die 1:2-Metallkomplexfarbstoffe können z.B. zwei Azomethinmoleküle, einen Disazofarbstoff und einen Monoazofarbstoff oder vorzugsweise zwei Monoazofarbstoffmoleküle enthalten. Die Azofarbstoffmoleküle können wasserlöslichmachende Gruppen aufweisen, wie z.B. Säureamid-, Alkylsulfonyl- oder die obengenannten sauren Gruppen. Bevorzugt sind 1:2-Kobalt- oder 1:2-Chromkomplexe von Monoazofarbstoffen, die Säureamid-, Alkylsulfonyl- oder insgesamt eine einzige Sulfonsäuregruppe aufweisen.The 1: 2 metal complex dyes contain a heavy metal atom as the central atom, e.g. a cobalt atom or in particular a chromium atom. Two complex-forming components are connected to the central atom, at least one of which is a dye molecule, but preferably both are dye molecules. The two dye molecules involved in the complex formation can be the same or different from one another. The 1: 2 metal complex dyes can e.g. contain two azomethine molecules, a disazo dye and a monoazo dye, or preferably two monoazo dye molecules. The azo dye molecules can have water solubilizing groups, e.g. Acid amide, alkylsulfonyl or the above acidic groups. Preference is given to 1: 2 cobalt or 1: 2 chromium complexes of monoazo dyes which have acid amide, alkylsulfonyl or a total of a single sulfonic acid group.

Es können Mischungen der anionischen Farbstoffe eingesetzt werden.Mixtures of the anionic dyes can be used.

Als Polyesterfasermaterial, das in Gegenwart des Mischpolymerisates gefärbt bzw. optisch aufgehellt werden kann, sind z.B. Celluloseesterfasern, wie Cellulose-2 1/2-acetatfasern und -triacetatfasern und besonders lineare Polyesterfasern zu erwähnen. Unter linearen Polyesterfasern sind dabei Synthesefasern zu verstehen, die z.B. durch Kondensation von Terephthalsäure mit Ethylenglykol oder von Isophthalsäure oder Terephthalsäure mit 1,4-Bis(hydroxymethyl)-cyclohexan erhalten werden, sowie Mischpolymere aus Terephthal- und Isophthalsäure und Ethylenglykol. Der in der Textilindustrie bisher fast ausschliesslich eingesetzte lineare Polyester besteht aus Terephthalsäure und Ethylenglykol.Examples of polyester fiber material which can be dyed or optically brightened in the presence of the copolymer are cellulose ester fibers, such as cellulose 2 1/2 acetate fibers and triacetate fibers and particularly linear polyester fibers. Linear polyester fibers are to be understood as synthetic fibers which are obtained, for example, by condensation of terephthalic acid with ethylene glycol or of isophthalic acid or terephthalic acid with 1,4-bis (hydroxymethyl) cyclohexane, as well as copolymers of terephthalic and isophthalic acid and ethylene glycol. The linear polyester used so far almost exclusively in the textile industry consists of Terephthalic acid and ethylene glycol.

Die für das Färben von Polyesterfasermaterialien zu verwendenden Dispersionsfarbstoffe, die in Wasser nur sehr wenig löslich sind und in der Farbflotte zum grössten Teil in Form einer feinen Dispersion vorliegen, können den verschiedensten Farbstoffklassen angehören, beispielsweise den Acridon-, Azo-, Anthrachinon-, Cumarin-, Methin-, Perinon-, Napthochinonimin-, Chinophthalon-, Styryl- oder Nitrofarbstoffen. Es können auch Mischungen von Dispersionsfarbstoffen eingesetzt werden.The disperse dyes to be used for dyeing polyester fiber materials, which are only sparingly soluble in water and are largely in the form of a fine dispersion in the dye liquor, can belong to a wide variety of dye classes, for example acridone, azo, anthraquinone and coumarin -, methine, perinone, naphthoquinone imine, quinophthalone, styryl or nitro dyes. Mixtures of disperse dyes can also be used.

Die erfindungsgemässen Acrylamid-Homo- und -Copolymere können auch vorteilhaft beim Färben von Polyacrylnitrilfasern mit kationischen Farbstoffen eingesetzt werden, da es hierbei zu keinen störenden Wechselwirkungen kommt und insbesondere keine Ausfällungen auftreten. Als kationische Farbstoffe können sowohl migrierende als auch nicht-migrierende Farbstoffe eingesetzt werden.The acrylamide homopolymers and copolymers according to the invention can also be used advantageously in the dyeing of polyacrylonitrile fibers with cationic dyes, since there are no interfering interactions and, in particular, no precipitation occurs. Both migrating and non-migrating dyes can be used as cationic dyes.

Als migrierende kationische Farbstoffe sind insbesondere solche mit einer mehr oder weniger delokalisierten positiven Ladung geeignet, deren Kationgewicht kleiner als 310, deren Parachor kleiner als 750 und deren log P kleiner als 3,2 ist. Der Parachor wird gemäss dem Artikel von O.R. Quayle [Chem. Rev. 53, 439 (1953)] berechnet und log P bedeutet die relative Lipophilie, deren Berechnung von C. Hanach et al [J. Med. Chem. 16, 1207 (1973)] beschrieben wurde.Particularly suitable as migrating cationic dyes are those with a more or less delocalized positive charge, the cation weight of which is less than 310, the parachor of which is less than 750 and the log P of which is less than 3.2. The Parachor is according to the article by OR Quayle [Chem. Rev. 53 , 439 (1953)] and log P means the relative lipophilicity, the calculation of which by C. Hanach et al [J. Med. Chem. 16 , 1207 (1973)].

Nicht-migrierende kationische Farbstoffe sind insbesondere diejenigen, deren Kationgewicht grösser als 310 und deren Parachor grösser als 750 ist.Non-migrating cationic dyes are, in particular, those whose cation weight is greater than 310 and whose parachor is greater than 750.

Die kationischen, migrierenden und nichtmigrierenden Farbstoffe können verschiedenen Farbstoffklassen angehören. Insbesondere handelt es sich um Salze, beispielsweise Chloride, Sulfate oder Metallhalogenide, beispielsweise Zinkchloriddoppelsalze von Azofarbstoffen wie Monoazofarbstoffen oder Hydrazonfarbstoffen, Anthrachinon-, Diphenylmethan-, Triphenylmethan-, Methin-, Azomethin-, Cumarin-, Ketonimin-, Cyanin-, Xanthen-, Azin-, Oxazin- oder Thiazinfarbstoffen.The cationic, migrating and non-migrating dyes can belong to different classes of dyes. In particular, they are salts, for example chlorides, sulfates or metal halides, for example zinc chloride double salts of azo dyes such as monoazo dyes or hydrazone dyes, anthraquinone, diphenylmethane, triphenylmethane, methine, azomethine, coumarin, ketoneimine, cyanine, xanthene, Azine, oxazine or thiazine dyes.

Es können Mischungen der kationischen Farbstoffe eingesetzt werden. Besonders bevorzugt sind Farbstoffkombinationen von mindestens 2 oder vorzugsweise 3 migrierenden oder nicht-migrierenden kationischen Farbstoffen zur Herstellung egaler Dichromie- oder Trichromiefärbungen, wobei auch Gemische aus migrierenden und nichtmigrierenden kationischen Farbstoffen verwendet werden können.Mixtures of the cationic dyes can be used. Dye combinations of at least 2 or preferably 3 migrating or non-migrating cationic dyes are particularly preferred for producing level dichromia or trichromatic dyeings, mixtures of migrating and non-migrating cationic dyes can be used.

Die Fasermaterialien können auch als Mischgewebe unter sich oder mit anderen Fasern, z.B. Mischungen aus Polyacrylnitril/Polyester, Polyamid/Polyester, Polyester/Baumwolle, Polyester/Viskose, Polyacrylnitril/Wolle und Polyester/Wolle, verwendet werden.The fiber materials can also be used as a mixed fabric among themselves or with other fibers, e.g. Mixtures of polyacrylonitrile / polyester, polyamide / polyester, polyester / cotton, polyester / viscose, polyacrylonitrile / wool and polyester / wool can be used.

Fasermischungen aus Polyester und Baumwolle werden in der Regel mit Kombinationen von Dispersionsfarbstoffen und Küpenfarbstoffen, Schwefelfarbstoffen, Leukoküpenesterfarbstoffen, Direktfarbstoffen oder Reaktivfarbstoffen gefärbt, wobei der Polyesteranteil mit Dispersionsfarbstoffen vor-, gleichzeitig oder nachgefärbt wird.Fiber blends of polyester and cotton are usually dyed with combinations of disperse dyes and vat dyes, sulfur dyes, leuco vat ester dyes, direct dyes or reactive dyes, the polyester content being pre-, simultaneously or post-dyed with disperse dyes.

Polyester/Wolle-Mischfasermaterialien werden erfindungsgemäss vorzugsweise mit handelsüblichen Mischungen von anionischen Farbstoffen und Dispersionsfarbstoffen gefärbt.Polyester / wool mixed fiber materials are preferably dyed according to the invention with commercially available mixtures of anionic dyes and disperse dyes.

Das zu färbende Textilmaterial kann sich in verschiedenen Aufmachungsformen befinden. Vorzugsweise kommt Stückware, wie Gewirke oder Gewebe, in Betracht.The textile material to be dyed can be in various forms. Piece goods, such as knitted or woven fabrics, are preferred.

Erfindungsgemässe Zubereitungen können auch beim Weisstönen ungefärbter synthetischer Fasermaterialien mit in Wasser dispergierten optischen Aufhellern eingesetzt werden. Die optischen Aufheller können beliebigen Aufhellerklassen angehören. Insbesondere handelt es sich um Cumarine, Triazolcumarine, Benzocumarine, Oxazine, Pyrazine, Pyrazoline, Diphenylpyrazoline, Stilbene, Styrylstilbene, Triazolylstilbene, Bisbenzoxazolylethylene, Stilben-bis-Benzoxazole, Phenylstilbenbenzoxazole, Thiophen-bis-Benzoxazole, Naphthalin-bis-Benzoxazole, Benzofurane, Benzimidazole und Naphthalimide.Preparations according to the invention can also be used for whitening undyed synthetic fiber materials with optical brighteners dispersed in water. The optical brighteners can belong to any brightener class. In particular, they are coumarins, triazolcoumarins, benzocoumarins, oxazines, pyrazines, pyrazolines, diphenylpyrazolines, stilbenes, styrylstilbenes, triazolylstilbenes, bisbenzoxazolylethylenes, stilbene-bis-benzoxazoles, phenylstilbenbenzoxazoles, thiophene-bis-benzoxazole, benzoxazole, benzoxazole, benzoxazole, benzoxazole, benzoxazole, benzoxazole, benzophenazazole and naphthalimides.

Es können auch Mischungen von optischen Aufhellern verwendet werden.Mixtures of optical brighteners can also be used.

Die Menge der der Flotte zuzusetzenden Farbstoffe oder optischen Aufheller richtet sich nach der gewünschten Farbstärke; im allgemeinen haben sich Mengen von 0,01 bis 10, vorzugsweise 0,2 bis 5 Gew.-%, bezogen auf das eingesetzte Textilmaterial, bewährt.The amount of dyes or optical brighteners to be added to the liquor depends on the desired color strength; In general, amounts of 0.01 to 10, preferably 0.2 to 5% by weight, based on the textile material used, have proven successful.

Die Färbebäder oder Aufhellerflotten können je nach dem zu behandelnden Textilmaterial neben den Farbstoffen bzw. optischen Aufhellern und den erfindungsgemässen Zubereitungen von Mischpolymerisaten Wollschutzmittel, Oligomereninhibitoren, Oxidationsmittel, Antischaummittel, Emulgatoren, Egalisiermittel, Retarder und vorzugsweise Dispergiermittel enthalten.Depending on the textile material to be treated, the dyebaths or brightener liquors can, in addition to the dyes or optical brighteners and the inventive preparations of copolymers, wool protection agents, oligomer inhibitors, oxidizing agents, Contain antifoams, emulsifiers, leveling agents, retarders and preferably dispersants.

Die Dispergiermittel dienen vor allem zur Erzielung einer guten Feinverteilung der Dispersionsfarbstoffe. Es kommen die beim Färben mit Dispersionsfarbstoffen allgemein gebräuchlichen Dispergatoren in Frage.The dispersants are used primarily to achieve a good fine distribution of the disperse dyes. The dispersants generally used for dyeing with disperse dyes are suitable.

Als Dispergiermittel kommen vorzugsweise sulfatierte oder phosphatierte Anlagerungsprodukte von 15 bis 100 Mol Ethylenoxid oder vorzugsweise Propylenoxid an mehrwertige, 2 bis 6 Kohlenstoffatome aufweisende aliphatische Alkohole, wie z.B. Ethylenglykol, Glycerin oder Pentaerythrit oder an mindestens zwei Aminogruppen oder eine Aminogruppe und eine Hydroxylgruppe aufweisende Amine mit 2 bis 9 Kohlenstoffatomen sowie Alkylsulfonate mit 10 bis 20 Kohlenstoffatomen in der Alkylkette, Alkylbenzolsulfonate mit geradkettiger oder verzweigter Alkylkette mit 8 bis 20 Kohlenstoffatomen in der Alkylkette, wie z.B. Nonyl- oder Dodecylbenzolsulfonat, 1,3,5,7-Tetramethyloctylbenzolsulfonat oder Sulfobernsteinsäureester, wie Natriumdioctylsulfosuccinat, in Betracht.Preferred dispersants are sulfated or phosphated adducts of 15 to 100 moles of ethylene oxide or preferably propylene oxide with polyhydric aliphatic alcohols containing 2 to 6 carbon atoms, such as e.g. Ethylene glycol, glycerol or pentaerythritol or amines having 2 to 9 carbon atoms and having at least two amino groups or an amino group and a hydroxyl group and alkylsulfonates having 10 to 20 carbon atoms in the alkyl chain, alkylbenzenesulfonates having a straight-chain or branched alkyl chain having 8 to 20 carbon atoms in the alkyl chain, such as e.g. Nonyl or dodecylbenzenesulfonate, 1,3,5,7-tetramethyloctylbenzenesulfonate or sulfosuccinic acid esters such as sodium dioctylsulfosuccinate.

Besonders günstig haben sich als anionische Dispergiermittel Ligninsulfonate, Polyphosphate und vorzugsweise Formaldehyd-Kondensationsprodukte aus aromatischen Sulfonsäuren, Formaldehyd und gegebenenfalls mono- oder bifunktionellen Phenolen, wie z.B. aus Kresol, β-Naphtholsulfonsäure und Formaldehyd, aus Benzolsulfonsäure, Formaldehyd und Naphthalinsäure, aus Naphthalinsulfonsäure und Formaldehyd oder aus Naphthalinsulfonsäure, Dihydroxydiphenylsulfon und Formaldehyd erwiesen. Bevorzugt ist das Dinatriumsalz des Di-(6-sulfonaphthyl-2-)methans.Lignin sulfonates, polyphosphates and preferably formaldehyde condensation products of aromatic sulfonic acids, formaldehyde and optionally mono- or bifunctional phenols, such as e.g. from cresol, β-naphtholsulfonic acid and formaldehyde, from benzenesulfonic acid, formaldehyde and naphthalenic acid, from naphthalenesulfonic acid and formaldehyde or from naphthalenesulfonic acid, dihydroxydiphenyl sulfone and formaldehyde. The disodium salt of di- (6-sulfonaphthyl-2-) methane is preferred.

Es können auch Gemische von anionischen Dispergiermitteln zum Einsatz kommen. Normalerweise liegen die anionischen Dispergiermittel in Form ihrer Alkalimetallsalze, Ammoniumsalze oder Aminosalze vor. Diese Dispergiermittel werden vorzugsweise in einer Menge von 0,1 bis 5 g/l Flotte verwendet.Mixtures of anionic dispersants can also be used. The anionic dispersants are normally in the form of their alkali metal salts, ammonium salts or amino salts. These dispersants are preferably used in an amount of 0.1 to 5 g / l of liquor.

Die Färbebäder oder Aufhellerflotten können je nach dem zu verwendenden Farbstoff und Substrat zusätzlich zu den bereits genannten Hilfsmitteln auch übliche Zusätze, zweckmässig Elektrolyte wie Salze, z.B. Natriumsulfat, Ammoniumsulfat, Natrium- oder Ammoniumphosphate oder -polyphosphate, Metallchloride oder -nitrate wie Natriumchlorid, Calciumchlorid, Magnesiumchlorid bzw. Calciumnitrat, Ammoniumacetat oder Natriumacetat und/oder Säuren, z.B. Mineralsäuren wie Schwefelsäure oder Phosphorsäure, oder organische Säuren, zweckmässig niedere aliphatische Carbonsäuren wie Ameisen-, Essig- oder Oxalsäure sowie auch Alkalien oder Alkalispender und/oder Komplexbildner, enthalten.Depending on the dye and substrate to be used, the dyebaths or brightener liquors can, in addition to the auxiliaries already mentioned, also conventional additives, advantageously electrolytes such as salts, for example sodium sulfate, ammonium sulfate, sodium or ammonium phosphates or polyphosphates, metal chlorides or nitrates such as sodium chloride, calcium chloride, Magnesium chloride or calcium nitrate, ammonium acetate or Sodium acetate and / or acids, for example mineral acids such as sulfuric acid or phosphoric acid, or organic acids, suitably lower aliphatic carboxylic acids such as formic, acetic or oxalic acid, and also alkalis or alkali donors and / or complexing agents.

Die Säuren dienen vor allem der Einstellung des pH-Wertes der erfindungsgemäss verwendeten Flotten, der in der Regel 3 bis 6,5, vorzugsweise 4,5 bis 6, beträgt.The acids primarily serve to adjust the pH of the liquors used according to the invention, which is generally 3 to 6.5, preferably 4.5 to 6.

Bei Verwendung von Reaktivfarbstoffen enthalten die Zubereitungen in der Regel Fixieralkalien.When using reactive dyes, the preparations usually contain fixing alkalis.

Als alkalisch reagierende Verbindung zur Fixierung der Reaktivfarbstoffe werden beispielsweise Natriumcarbonat, Natriumbicarbonat, Natriumhydroxid, Dinatriumphosphat, Trinatriumphosphat, Borax, wässeriges Ammoniak oder Alkalispender wie z.B. Natriumtrichloracetat, eingesetzt. Als Alkali hat sich insbesondere eine Mischung aus Wasserglas und einer 30 %-igen wässerigen Natriumhydroxidlösung sehr gut bewährt.Sodium carbonate, sodium bicarbonate, sodium hydroxide, disodium phosphate, trisodium phosphate, borax, aqueous ammonia or alkali donors such as e.g. Sodium trichloroacetate. A mixture of water glass and a 30% aqueous sodium hydroxide solution has proven particularly useful as an alkali.

Der pH-Wert der Alkali enthaltenden Färbeflotten beträgt in der Regel 7,5 bis 12,5 vorzugsweise 8,5 bis 11,5.The pH of the dye liquors containing alkali is generally 7.5 to 12.5, preferably 8.5 to 11.5.

Die Färbungen bzw. Aufhellungen erfolgen mit Vorteil aus wässeriger Flotte nach dem Ausziehverfahren. Das Flottenverhältnis kann dementsprechend innerhalb eines weiten Bereiches gewählt werden, z.B. 1:4 bis 1:100, vorzugsweise 1:6 bis 1:50. Die Temperatur, bei der gefärbt bzw. aufgehellt wird, beträgt mindestens 70°C und ist in der Regel nicht höher als 140°C. Vorzugsweise liegt sie im Bereich von 80 bis 135°C.The dyeing or lightening is advantageously carried out from an aqueous liquor using the exhaust process. The liquor ratio can accordingly be chosen within a wide range, e.g. 1: 4 to 1: 100, preferably 1: 6 to 1:50. The temperature at which dyeing or lightening is at least 70 ° C and is usually not higher than 140 ° C. It is preferably in the range from 80 to 135 ° C.

Lineare Polyesterfasern und Cellulosetriacetatfasern färbt man vorzugsweise nach dem sogenannten Hochtemperaturverfahren in geschlossenen und zweckmässigerweise auch druckbeständigen Apparaturen bei Temperaturen von über 100°C, bevorzugt zwischen 110 und 135°C, und gegebenenfalls unter Druck. Als geschlossene Gefässe eignen sich beispielsweise Zirkulationsapparaturen wie Kreuzspul- oder Baumfärbeapparate, Haspelkufen, Düsen- oder Trommelfärbemaschinen, Muff-Färbeapparate, Paddeln oder Jigger.Linear polyester fibers and cellulose triacetate fibers are preferably dyed by the so-called high-temperature process in closed and expediently also pressure-resistant apparatus at temperatures above 100 ° C., preferably between 110 and 135 ° C., and optionally under pressure. Circulation devices such as cross-winding or tree dyeing machines, reel runners, nozzle or drum dyeing machines, muff dyeing machines, paddles or jiggers are suitable as closed vessels, for example.

Cellulose-2 1/2-acetatfasern färbt man vorzusweise bei Temperaturen von 80-85°C.Cellulose-2 1/2 acetate fibers are preferably dyed at temperatures of 80-85 ° C.

Wenn das zu färbende Material Cellulosefasermaterial oder synthetisches Polyamidfasermaterial allein ist, erfolgt die Färbung zweckmässig bei einer Temperatur von 20 bis 106°C, vorzugsweise von 30 bis 95°C für Cellulosefasern und 80 bis 95°C für Polyamidfasern.If the material to be dyed is cellulose fiber material or synthetic polyamide fiber material alone, the dyeing is expediently carried out at a temperature of 20 to 106 ° C., preferably 30 to 95 ° C. for cellulose fibers and 80 to 95 ° C. for polyamide fibers.

Die Färbung der Polyester-Baumwollfasermaterialien erfolgt vorzugsweise bei Temperaturen von über 106°C, zweckmässig bei 110 bis 135°C. Diese Mischfasermaterialien können in Gegenwart von Carrier oder Carriergemischen gefärbt werden, welche als Färbebeschleuniger für das Färben des Polyesteranteils mit Dispersionsfarbstoffen wirken.The polyester-cotton fiber materials are preferably dyed at temperatures above 106 ° C., expediently at 110 to 135 ° C. These mixed fiber materials can be dyed in the presence of carriers or carrier mixtures, which act as a dyeing accelerator for dyeing the polyester portion with disperse dyes.

Das Färbeverfahren kann so durchgeführt werden, dass man das Färbegut entweder zuerst mit der erfindungsgemässen Zubereitung kurz behandelt und anschliessend färbt oder vorzugsweise gleichzeitig mit der Zubereitung und dem Farbstoff behandelt.The dyeing process can be carried out by either briefly treating the material to be dyed first with the preparation according to the invention and then dyeing it, or preferably treating it simultaneously with the preparation and the dye.

Die Fertigstellung der Färbungen erfolgt durch Abkühlen der Färbeflotte auf 40 bis 70°C, Spülen der Färbungen mit Wasser und gegebenenfalls durch Reinigung auf übliche Weise in alkalischem Medium unter reduktiven Bedingungen. Die Färbungen werden dann wiederum gespült und getrocknet. Bei einer allfälligen Verwendung von Carriern werden die Färbungen zwecks Verbesserung der Lichtechtheit, vorteilhafterweise nach einer Hitzebehandlung, z.B. Thermosolieren, unterworfen, die vorzugsweise bei 160 bis 180°C und während 30 bis 90 Sekunden durchgeführt wird. Bei Verwendung von Küpenfarbstoffen für den Celluloseanteil wird die Ware auf übliche Weise zuerst mit Hydrosulfit bei einem pH-Wert von 6 bis 12,5 und dann mit Oxydationsmittel behandelt und schliesslich ausgewaschen.The dyeings are completed by cooling the dye liquor to 40 to 70 ° C., rinsing the dyeings with water and, if appropriate, cleaning in a customary manner in an alkaline medium under reductive conditions. The dyeings are then rinsed again and dried. If carriers are used, the dyeings are used to improve the lightfastness, advantageously after heat treatment, e.g. Thermosolieren, subjected, which is preferably carried out at 160 to 180 ° C and for 30 to 90 seconds. When using vat dyes for the cellulose portion, the goods are treated in the usual way first with hydrosulfite at a pH of 6 to 12.5 and then with oxidizing agent and finally washed out.

Man erhält unter Verwendung der erfindungsgemässen Polymeren gleichmässige und farbkräftige Ausfärbungen, die sich durch gute Farbausbeuten auszeichnen. Insbesondere werden egale Färbungen erzielt, wobei das Material faltenfrei (Monsantobild 2-4) ist, ein ruhiges Warenbild zeigt und einen angenehmen, weichen Griff besitzt.Using the polymers according to the invention, uniform and vivid colorations are obtained which are distinguished by good color yields. In particular, level dyeings are achieved, whereby the material is wrinkle-free (Monsanto picture 2-4), shows a calm fabric appearance and has a pleasant, soft feel.

Als Mass für die Fähigkeit eines Polymers zur Verhinderung der Faltenbildung kann vorteilhaft der sogenannte Friktionstest herangezogen werden. Bei diesem Test wird zunächst ein Gewebestreifen, z.B. ein aus Baumwolle oder Baumwolle/Polyester bestehender Streifen, mit Wasser befeuchtet, auf die Oberfläche einer mit konstanter Geschwindigkeit rotierenden Walze gebracht und mit einem Kraftmesser die Kraft ermittelt, die notwendig ist, um den Gewebestreifen in einer festgelegten Position zu halten. Der ermittelte Wert stellt den Standard dar (Friktionswert 100 %). Der Gewebestreifen wird dann in eine wässrige Lösung des zu bestimmenden Polymers getaucht und die Messung wiederholt. Die mit und ohne Polymer erhaltenen Werte werden in Relation zueinander gesetzt und der Friktionswert des Polymers in Prozent vom mit reinem Wasser erhaltenen Wert angegeben. Friktionswerte von z.B. ≦ 70 %, zeigen einen deutlich faltenvermindernden Effekt des betreffenden Polymers an.The so-called friction test can advantageously be used as a measure of the ability of a polymer to prevent the formation of wrinkles. In this test, a strip of tissue, e.g. a strip made of cotton or cotton / polyester, is first moistened with water, placed on the surface of a roller rotating at a constant speed, and the force required to force the strip of tissue in one is determined using a dynamometer specified position hold. The determined value represents the standard (friction value 100%). The tissue strip is then immersed in an aqueous solution of the polymer to be determined and the measurement is repeated. The values obtained with and without polymer are set in relation to each other and the friction value of the polymer is given in percent of the value obtained with pure water. Friction values of, for example, ≦ 70% indicate a clearly wrinkle-reducing effect of the polymer in question.

Zudem werden die Echtheiten der Färbungen, wie z.B. Lichtechtheit, Reibechtheit und Nassechtheiten durch den Einsatz des Hilfsmittelgemisches nicht negativ beeinflusst. Ferner tritt beim Färben des Textilmaterials in Gegenwart der erfindungsgemässen Zubereitungen kein störendes Schäumen auf.In addition, the fastness of the dyeings, such as Light fastness, fastness to rubbing and wet fastness are not negatively influenced by the use of the auxiliary mixture. Furthermore, no troublesome foaming occurs when the textile material is dyed in the presence of the preparations according to the invention.

In den folgenden Beispielen beziehen sich die Prozentsätze, wenn nichts anderes angegeben ist, auf das Gewicht. Die Mengen beziehen sich bei den Farbstoffen auf handelsübliche, d.h. coupierte Ware und bei den Komponenten des Hilfsmittelgemisches auf Reinsubstanz.In the following examples, the percentages are by weight unless otherwise specified. The amounts of the dyes relate to commercial, i.e. Coupé goods and the components of the auxiliary mixture on pure substance.

HilfsmittelbeispieleAid examples

Figure imgb0001
Figure imgb0001
Figure imgb0002
Figure imgb0002
Figure imgb0003
Figure imgb0003

AnwendungsbeispieleExamples of use Beispiel 24:Example 24:

100 g eines gebleichten Baumwoll Cretonne Gewebes werden in 2 Liter Wasser auf einer Laborjetfärbemaschine mit folgenden Zusätzen gefärbt:
   0,25 g eines Farbstoffes der Formel

Figure imgb0004

   0,3 g eines Farbstoffes der Formel
Figure imgb0005
   4 g einer 1%igen Lösung des Polymers gemäss Beispiel 16 (Copolymer aus ca. 15 % Acrylsäure und 85 % Acrylamid, Molekulargewicht ca. 2 Millionen).100 g of a bleached cotton cretonne fabric are dyed in 2 liters of water on a laboratory jet dyeing machine with the following additives:
0.25 g of a dye of the formula
Figure imgb0004
0.3 g of a dye of the formula
Figure imgb0005
4 g of a 1% strength solution of the polymer according to Example 16 (copolymer of approx. 15% acrylic acid and 85% acrylamide, molecular weight approx. 2 million).

Diese Zusätze werden zuerst in Wasser gelöst bzw. dispergiert und dem Färbebad bei 50°C zugegeben. Danach wird die Färbeflotte bei ständiger Zirkulation und Bewegung des Substrates im Verlauf von 30 Minuten auf 98°C aufgeheizt. Nach 15 Minuten werden 20 g Glaubersalz der Färbeflotte zugegeben. Hiernach wird das Gewebe weitere 30 Minuten bei 98°C gefärbt, worauf das Färbebad auf 60°C abgekühlt und das Gewebe warm und kalt gespült und getrocknet wird. Man erhält eine faltenfreie egale und graue Färbung. Der Einsatz der erfindungsgemässen Zubereitung erbringt eine deutliche Herabsetzung des Friktionswertes gegenüber einer Färbeflotte ohne den Zusatz dieser Zubereitung. Die das Mischpolymerisat enthaltende Zubereitung wirkt nicht retardierend und verändert auch nicht die Nuance.These additives are first dissolved or dispersed in water and added to the dyebath at 50 ° C. The dye liquor is then heated to 98 ° C. over a period of 30 minutes with constant circulation and movement of the substrate. After 15 minutes, 20 g of Glauber's salt are added to the dye liquor. The fabric is then dyed at 98 ° C. for a further 30 minutes, whereupon the dyebath is cooled to 60 ° C. and the fabric is warm and rinsed cold and dried. A wrinkle-free level and gray coloration is obtained. The use of the preparation according to the invention results in a significant reduction in the friction value compared to a dyeing liquor without the addition of this preparation. The preparation containing the copolymer has no retarding effect and does not change the shade.

Verfährt man wie oben beschrieben und verwendet anstelle 4 g der 1 %igen Lösung des Polymers gemäss Beispiel 16 8 g einer 0,1 %igen Lösung des Acrylamid/Acrylsäure- Copolymers gemäss Beispiel 8, werden ähnlich gute Ergebnisse erhalten.If the procedure is as described above and instead of 4 g of the 1% solution of the polymer according to Example 16 8 g of a 0.1% solution of the acrylamide / acrylic acid copolymer according to Example 8, similarly good results are obtained.

Beispiel 25:Example 25:

100 g eines Polyesterstapelgewebes werden auf einer Haspelkupe bei 30°C mit 2 Liter einer wässrigen Färbeflotte behandelt, die
   0,25 g eines Farbstoffes der Formel

Figure imgb0006

   0,35 g eines Farbstoffes der Formel
Figure imgb0007
   0,15 g eines Farbstoffes der Formel
Figure imgb0008
   2 g einer 1 %igen Lösung des Polymers gemäss Beispiel 16 (Copolymer aus ca. 15 % Acrylsäure und 85 % Acrylamid, Molekulargewicht ca. 2 Millionen).
   2 g Ammoniumsulfat
enthält und mit Ameisensäure auf pH 5,5 gestellt ist. Nach einer Vorlaufzeit von 10 Minuten bei 30°C wird die Temperatur auf 130°C erhöht, worauf das Gewebe bei dieser Temperatur weitere 60 Minuten gefärbt wird. Alsdann kühlt man die Flotte auf 60°C ab, spült und trocknet das Gewebe. Man erhält eine faltenfreie, egale braune Färbung.100 g of a polyester staple fabric are treated on a reel at 30 ° C with 2 liters of an aqueous dyeing liquor
0.25 g of a dye of the formula
Figure imgb0006
0.35 g of a dye of the formula
Figure imgb0007
0.15 g of a dye of the formula
Figure imgb0008
2 g of a 1% strength solution of the polymer according to Example 16 (copolymer of approx. 15% acrylic acid and 85% acrylamide, molecular weight approx. 2 million).
2 g ammonium sulfate
contains and is adjusted to pH 5.5 with formic acid. After a lead time of 10 minutes at 30 ° C, the temperature is increased to 130 ° C, after which the fabric is dyed at this temperature for a further 60 minutes. Then the liquor is cooled to 60 ° C., the fabric is rinsed and dried. A wrinkle-free, level brown color is obtained.

Aehnliche Ergebnisse werden erhalten, wenn man anstelle des Polymers gemäss Beispiel 16 eine äquivalente Menge des Polymers gemäss einem der Beispiele 2 bis 15, 17 bis 20, 22 oder 23 verwendet.Similar results are obtained if, instead of the polymer according to Example 16, an equivalent amount of the polymer according to one of Examples 2 to 15, 17 to 20, 22 or 23 is used.

Beispiel 26:Example 26:

100 g eines Polyamid-6,6-Stapelgewebes werden auf einem Labor-Jet-Färbeapparat bei 40°C in 2 Liter Wasser mit folgenden Zusätzen behandelt:
   6 g einer 1 %igen wässrigen Lösung des Polymers gemäss Beispiel 21 (Polyacrylamid-Homopolymer, Molekulargewicht ca. 10 Millionen);
   2 g eines Kondensationsproduktes aus 1 Mol Fettamin und 70 Mol Ethylenoxid;100 g of a polyamide 6.6 stack fabric are treated on a laboratory jet dyeing machine at 40 ° C. in 2 liters of water with the following additives:
6 g of a 1% strength aqueous solution of the polymer according to Example 21 (polyacrylamide homopolymer, molecular weight approx. 10 million);
2 g of a condensation product of 1 mol of fatty amine and 70 mol of ethylene oxide;

Die Flotte wird mit Essigsäure auf 5,5 gestellt. Nach einer Vorlaufzeit von 15 Minuten bei 40°C wird
   1 g eines Farbstoffes der Formel

Figure imgb0009

der Flotte zudosiert, worauf man die Flotte weitere 5 Minuten zirkulieren lässt. Danach erwärmt man die Flotte im Verlaufe von 30 Minuten auf 98°C und färbt 30 Minuten bei dieser Temperatur.The liquor is adjusted to 5.5 with acetic acid. After a lead time of 15 minutes at 40 ° C
1 g of a dye of the formula
Figure imgb0009
metered into the liquor, whereupon the liquor is circulated for a further 5 minutes. The liquor is then heated to 98 ° C. over a period of 30 minutes and dyed at this temperature for 30 minutes.

Anschliessend kühlt man die Flotte im Verlauf von 15 Minuten auf 60°C ab und spült und trocknet das Gewebe. Man erhält eine faltenfreie, egale blaue Färbung. Eine Nuancenänderung tritt nicht ein.The liquor is then cooled to 60 ° C. in the course of 15 minutes and the fabric is rinsed and dried. A wrinkle-free, level blue color is obtained. There is no change in nuance.

Aehnliche Ergebnisse werden erhalten, wenn man anstelle des Polymers gemäss Beispiel 21 eine äquivalente Menge des Polymers gemäss Beispiel 1 verwendet.Similar results are obtained if, instead of the polymer according to Example 21, an equivalent amount of the polymer according to Example 1 is used.

Claims (12)

Verwendung von Acrylamid-Homo- oder -Copolymeren in einer Menge von < 0,04 g pro Liter Färbeflotte als Faltenverhinderungsmittel in Ausziehfärbeverfahren.Use of acrylamide homopolymers or copolymers in an amount of <0.04 g per liter of dye liquor as an anti-wrinkle agent in exhaust dyeing processes. Verwendung gemäss Anspruch 1, dadurch gekennzeichnet, dass die Acrylamid-Homo- oder -Copolymeren in Form einer wässrigen Zubereitung vorliegen.Use according to claim 1, characterized in that the acrylamide homo- or copolymers are in the form of an aqueous preparation. Verwendung gemäss Anspruch 1 oder 2, dadurch gekennzeichnet, dass das Acrylamid-Homo- oder -Copolymer ein Molekulargewicht von 800000 bis 15 Millionen aufweist.Use according to claim 1 or 2, characterized in that the acrylamide homo- or copolymer has a molecular weight of 800,000 to 15 million. Verwendung gemäss einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass das Acrylamid-Homo- oder -Copolymer ein Homo- oder Copolymer aus 70 bis 100 Gew.-% Acrylamid und 0 bis 30 Gew.-% Acrylsäure, jeweils bezogen auf das Gewicht der Monomeren, ist.Use according to one of claims 1 to 3, characterized in that the acrylamide homo- or copolymer is a homo- or copolymer of 70 to 100% by weight of acrylamide and 0 to 30% by weight of acrylic acid, in each case based on the weight of the monomers. Verwendung gemäss einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, dass das Acrylamid-Homo- oder -Copolymer ein Acrylamid/Acrylsäure-Copolymer mit einem Acrylamidgehalt von > 70 Gew.-%, bezogen auf das Gewicht der Monomeren, ist.Use according to one of claims 1 to 4, characterized in that the acrylamide homo- or copolymer is an acrylamide / acrylic acid copolymer with an acrylamide content of> 70% by weight, based on the weight of the monomers. Verwendung gemäss Anspruch 5, dadurch gekennzeichnet, dass das Acrylamid/Acrylsäure-Copolymer aus 75 bis 90 Gew.-% Acrylamid und 10 bis 25 Gew.-% Acrylsäure, jeweils bezogen auf das Gewicht der Monomeren, besteht.Use according to claim 5, characterized in that the acrylamide / acrylic acid copolymer consists of 75 to 90% by weight of acrylamide and 10 to 25% by weight of acrylic acid, each based on the weight of the monomers. Verwendung gemäss Anspruch 4, 5 oder 6, dadurch gekennzeichnet, dass das Acrylamid/Acrylsäure-Homo- oder -Copolymer ein Molekulargewicht von 800000 bis 15 Millionen und bevorzugt 1,5 bis 3 Millionen aufweist.Use according to claim 4, 5 or 6, characterized in that the acrylamide / acrylic acid homo- or copolymer has a molecular weight of 800,000 to 15 million and preferably 1.5 to 3 million. Verwendung gemäss einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, dass man 0,0005 bis 0,03 g/l Flotte und bevorzugt 0,005 bis 0,02 g/l Flotte des Acrylamid-Homo- oder -Copolymers einsetzt.Use according to one of claims 1 to 7, characterized in that 0.0005 to 0.03 g / l liquor and preferably 0.005 to 0.02 g / l liquor of the acrylamide homo- or copolymer are used. Verwendung der Acrylamid-Homo- oder -Copolymere gemäss einem der Ansprüche 1 bis 7 als Faltenfreimittel für das Färben von Cellulosefasern, synthetische Polyamidfasern oder Polyesterfasern enthaltende textile Fasermaterialien.Use of the acrylamide homo- or copolymers according to one of claims 1 to 7 as wrinkle-free agents for dyeing cellulose fibers, synthetic polyamide fibers or textile fiber materials containing polyester fibers. Verwendung gemäss Anspruch 9, dadurch gekennzeichnet, dass es sich bei den textilen Fasermaterialien um Polyesterfasern enthaltende textile Fasermaterialien handelt, die mit Dispersionsfarbstoffen bei einer Temperatur von 80 bis 135 °C und vorzugsweise 110 bis 135 °C gefärbt werden.Use according to claim 9, characterized in that the textile fiber materials are textile fiber materials containing polyester fibers, which are dyed with disperse dyes at a temperature of 80 to 135 ° C and preferably 110 to 135 ° C. Verwendung der Acrylamid-Homo- oder -Copolymere gemäss einem der Ansprüche 1 bis 7 als Faltenfreimittel für das Färben von Polyacrylnitrilfasern mit kationischen Farbstoffen.Use of the acrylamide homo- or copolymers according to one of claims 1 to 7 as wrinkle-free agents for dyeing polyacrylonitrile fibers with cationic dyes. Verfahren zur Verhinderung von Lauffalten beim Färben von Geweben und Gewirken in geschlossenen Apparaturen, dadurch gekennzeichnet, dass man das Färbegut in Gegenwart einer wässrigen Zubereitung eines Acrylamid-Homo- oder -Copolymers gemäss einem der Ansprüche 1 oder 3 bis 7 färbt.Process for preventing creases in the dyeing of fabrics and knitted fabrics in closed apparatus, characterized in that the dyeing material is dyed in the presence of an aqueous preparation of an acrylamide homopolymer or copolymer according to one of claims 1 or 3 to 7.
EP94810113A 1993-03-02 1994-02-23 Use of acryl amide polymers as anti-crease Expired - Lifetime EP0613976B1 (en)

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EP0613976B1 (en) 2001-06-13
JPH06280165A (en) 1994-10-04
JP3522819B2 (en) 2004-04-26
DE59409777D1 (en) 2001-07-19
AU5647994A (en) 1994-09-08
ZA941416B (en) 1994-09-28
AU670483B2 (en) 1996-07-18
US5445655A (en) 1995-08-29
TW267198B (en) 1996-01-01
CA2116629A1 (en) 1994-09-03

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