EP0143969A1 - Procédé pour réaliser des impressions résistantes aux décharges sur des matières textiles hydrophobes - Google Patents

Procédé pour réaliser des impressions résistantes aux décharges sur des matières textiles hydrophobes Download PDF

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Publication number
EP0143969A1
EP0143969A1 EP84112741A EP84112741A EP0143969A1 EP 0143969 A1 EP0143969 A1 EP 0143969A1 EP 84112741 A EP84112741 A EP 84112741A EP 84112741 A EP84112741 A EP 84112741A EP 0143969 A1 EP0143969 A1 EP 0143969A1
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EP
European Patent Office
Prior art keywords
etching
printing paste
salts
acid
dyes
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
EP84112741A
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German (de)
English (en)
Other versions
EP0143969B1 (fr
Inventor
Ulrich Dr. Bühler
Theo Stahl
Konrad Dr. Mix
Kurt Roth
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.)
Sanofi Aventis Deutschland GmbH
Cassella Farbwerke Mainkur AG
Original Assignee
Cassella AG
Cassella Farbwerke Mainkur AG
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Publication of EP0143969A1 publication Critical patent/EP0143969A1/fr
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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
    • D06P5/00—Other features in dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form
    • D06P5/12—Reserving parts of the material before dyeing or printing ; Locally decreasing dye affinity by chemical means
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P5/00—Other features in dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form
    • D06P5/15—Locally discharging the dyes
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
    • D06P1/64—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 low-molecular-weight organic compounds without sulfate or sulfonate groups
    • D06P1/651—Compounds without nitrogen
    • D06P1/65168—Sulfur-containing compounds
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P5/00—Other features in dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form
    • D06P5/15—Locally discharging the dyes
    • D06P5/155—Locally discharging the dyes with reductants
    • 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
    • Y10S8/921—Cellulose ester or ether
    • 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

Definitions

  • the present invention relates to a method for producing etching reserve prints on textile materials which consist of hydrophobic fibers or contain these in conjunction with cellulose, in particular with cotton, or in conjunction with wool, one or more white-etchable disperse dyes and optionally one or more being present on the textile material etching-resistant disperse dyes are applied in the form of a dye liquor or printing paste and then carefully dried or dried and then an etching reserve printing paste is printed in the desired pattern, which may also contain one or more etching-resistant dispersing dyes, the order in which the etching reserve printing paste and printing paste are also reversed be and when using a printing paste drying or intermediate drying can also be omitted, and subsequent heat treatment at 100 to 230 ° C.
  • the known etching printing process is therefore modified in such a way that the textile material is first padded with a dye liquor containing disperse dye and then carefully dried or dried so that the dye is not yet fixed , ie Solution of the dye in which hydrophobic fiber takes place.
  • the desired pattern is then printed on the dried or dried-on padded fabric with the etching printing paste and the fabric treated in this way is then subjected to a heat treatment, the base dye immigrating into the polyester at the non-printed areas at the same time, i.e. is fixed, and the dye is destroyed at the areas printed with etching printing paste, i.e. no coloring takes place.
  • This process is also known as etching reserve pressure.
  • etching reserve printing which is simple in itself, involves a number of technical difficulties which often make its use more difficult. It is usually not easy to completely destroy the base dye with the etchant. If this does not succeed, a colored residue remains on the etched areas, the shade of which can vary between yellow-brown and dull violet or reddish gray tones and which soils the white background at the etched areas. This leads to white etch which appears to be unclean or, in the event that a colored etch is to be produced, to a falsification of the shade of the etchant-resistant dye.
  • etching printing pastes which contain relatively strong reducing or oxidizing agents, e.g. Alkali formaldehyde sulfoxylates, or even heavy metal salts, such as tin-2-chloride.
  • relatively strong reducing or oxidizing agents e.g. Alkali formaldehyde sulfoxylates, or even heavy metal salts, such as tin-2-chloride.
  • strong etching agents it is generally possible to achieve a perfect white etching print, but damage to the fiber material often occurs. Furthermore, these etchants are usually not cheap.
  • zinc-2-chloride is used, the hydrochloric acid that splits off causes severe corrosion in the dampers.
  • Japanese patent applications 56-165079, 56-159378, 57-029683, 57-029684 and 57-029685 describe the use of reducing sugars in the presence of alkali as an etchant.
  • DE-OS 31 13 732 relates to an etching or etching reserve printing process for textile materials made of hydrophobic fibers, in which a combination of an organic reducing agent with alkoxylated amines is used as the etching agent, alkyl sulfinates, reducing mono- or disaccharides and / or thiourea dioxide being used as the reducing agent becomes.
  • ingrain dyes In the field of the etching reserve printing of cellulose textiles with phthalocyanine condensation dyes (so-called ingrain dyes), it is known from DE-OS 31 32 416 to use water-soluble organic derivatives of thiocarbonic acid or thiophosphoric acid as etching agents. These substances prevent the formation of phthalocyanine dyes from the printed polyisoindolenine metal complexes.
  • disperse dyes for background coloring which can be etched pure white with the mildest possible agents.
  • Dyes which can be etched by aqueous alkalis are known from German Offenlegungsschriften 26 12 740, 26 12 741, 26 12 742, 26 12 790, 26 12 791, 26 12 792, 28 36 391, 30 21 269 and 30 35 912 , either destroying their chromophore or converting their carboxylic ester or sulfonamide groups into a salt-like structure, causing the dyes to lose their affinity for the fiber.
  • Such dyes by the processes described leads to fiber damage by saponification, which is particularly intolerable in the case of very light, thin qualities.
  • such dyes can generally only be prepared using special, complex processes and from preliminary products produced specifically for this type of dye. However, they also show defects in the application. After the etching, for example, they show a certain affinity for and contaminate hydrophilic accompanying tissues, or they tend to thermomigrate, or they have poor drawing properties and thus have only a low color yield on the fiber.
  • Their special structure also usually has a negative impact on the fastness to use, such as light fastness and heat-set fastness.
  • Compounds that can form a thiolate structure are e.g. the corresponding acids to the above thiolates in combination with inorganic or organic bases, which bring about a pH of at least 8 in water.
  • thermolyzable compounds are e.g. aromatic or aliphatic disulfides, which are optionally used in combination with inorganic or organic bases.
  • Suitable hydrolyzable compounds, especially in an alkaline medium are e.g. the alkyl or aryl esters of thiocarbonic acid, thiocarboxylic acid or thiophosphoric acid derivatives.
  • Monovalent alkane radicals representing R are branched or preferably straight-chain alkyl radicals; m-valent alkane radicals are those which differ from branched or preferably straight-chain alkanes by substitution of m hydrogen atoms deduce. If the carbon chain of the alkane radical is interrupted by a phenylene radical, the 1,3- and 1,4-phenylene radicals are preferred.
  • alkane residues interrupted by -O-, -S- or -NR - those interrupted by -O- are preferred. If the alkane chains are interrupted by -S- or -NR 2- , then preferably only one -S- or one - NR 2 group is present. This also applies if, in addition to the interruption by -S- or -NR 2- , the alkane chain has further interruptions by -O-.
  • m-valent radicals R which are derived from trialkylamines, are preferably trivalent. They correspond to the formula where R 4 in turn has the definition that applies to divalent radicals R.
  • the radicals R 4 are preferably divalent alkane radicals which are optionally substituted and, with a chain length> 3, can be interrupted once or more than once at a distance of at least 2 carbon atoms by -O-.
  • M-valent radicals R which are derived from polyalkylalkylene polyamines, correspond to the formula wherein R 5 is a direct bond or a radical R 4 .
  • etchants with a thiolate structure are also to be understood in the following as those compounds which are capable of forming a thiolate structure under suitable ambient conditions (e.g. corresponding acids, hydrolytically or thermolytically cleavable precursors).
  • Suitable etchants of the formula I to be used according to the invention can come from the series of thiocarbamates.
  • A is a C atom
  • B is an O atom
  • X is a group - NR 2 - .
  • etching agents of the formula I to be used according to the invention comes from the series of trithiocarbonic acid derivatives, where A is a C atom, B is an S atom and X is also an S atom.
  • etchants of the formula I to be used according to the invention are the salts of thio- or di-thiocarbonic acids, in which A is a C atom, B is an O or S atom and X is a direct bond.
  • Preferred etchants of formula I to be used according to the invention are compounds from the series of di-thiocarbaminates, where A is a C atom, B is an S atom and X is a group -NR 2- , and from the series of di-thiophosphorus acid esters, where A stands for POR 2 , B for an S atom and X for a 0 atom.
  • etchants of the formula I to be used according to the invention are compounds of the xanthate series, where A is a C atom, B is an S atom and X is an O atom.
  • alkane, cycloalkane or alkene radicals which stand for R as well as alkyl, alkenyl or cycloalkyl radicals which represent R 1 or R 2 are alkane or alkyl radicals having 1 to 12 carbon atoms, cycloalkane or cycloalkyl radicals with 5 or 6 carbon atoms or alkenyl or alkenyl radicals with 3 to 5 carbon atoms, which are replaced by fluorine, chlorine, bromine, hydroxy, alkoxy with 1 to 4 carbon atoms, phenoxy, phenyl, benzyl, phenethyl , Cyan, carboxyl, alkoxycarbonyl with a total of up to 8 carbon atoms or by an alkyl radical of the formula II can be substituted.
  • the number of the above-mentioned substituents attached to the hydrocarbon radicals representing R, R and R 2 depends on their structure. Simple substituents, such as halogen atoms, hydroxy, lower alkoxy, 1 to 6, preferably 1 to 3 identical or different, can be bonded to one of the hydrocarbon radicals. More extensive substituents, such as those which contain a phenyl nucleus, but also substituents with stronger neighboring group effects, such as cyan, carboxyl or alkoxycarbonyl, are generally only present once. Overall, simple substitution is preferred.
  • Optionally substituted aryl radicals which can represent R and R are phenyl, naphthyl-1 and naphthyl-2 radicals which are mono- to triple-fluorine, chlorine, bromine, alkyl having 1 to 4 carbon atoms, alkoxy 1 to 4 carbon atoms, nitro, cyano, carboxyl, alkoxycarbonyl with 1 to 4 carbon atoms, mono- or dialkylaminocarbonyl with 1 to 4 carbon atoms in each alkyl radical, hydroxysulfonyl, alkoxysulfonyl with 1 to 4 carbon atoms, alkylsulfonyl with 1 to 4 carbon atoms in the alkyl radical, phenylsulfonyl, mono- or dialkylaminosulfonyl can be substituted with 1 to 4 carbon atoms in each alkyl radical.
  • M-valent aromatic radicals which stand for R are 1,2-, 1,3- and 1,4-phenylene or 1,2-, 1,4-, 1,6- or 1,8-naphthylene.
  • the phenylene radicals, in particular the 1,3-phenylene radical and very particularly the 1,4-phenylene radical, are preferred.
  • Preferred monovalent radicals R or preferred radicals R and R 2 are alkyl radicals having 1 to 4 carbon atoms which are substituted, in particular monosubstituted, by hydroxy, alkoxy having 1 to 4 carbon atoms, phenoxy, phenyl, chlorine, bromine or cyano, could be.
  • Another preferred meaning of R 1 is hydrogen.
  • Preferred divalent radicals R are ethylene and polymethylene with 3 to 6 C atoms, which, if they have 2 or more C atoms, by phenylene or, if they have 4 or more C atoms, at a distance of at least 2 C atoms can be interrupted by 1 to 2 oxygen atoms, or the 1,4-phenylene radical.
  • Alkali or alkaline earth metals whose cation stands for MM ⁇ are e.g. Lithium, sodium, potassium, magnesium, calcium, strontium and barium.
  • Ammonium ions which stand for Me ⁇ can carry up to 2 radicals of R 1 and one radical of R 2 or can be derived from a 5- or 6-ring nitrogen heteroxy, such as pyridine, lutidine or pyrrolidine.
  • Preferred cations are the ammonium ion and ammonium ions which carry up to 3 alkyl radicals with 1 to 4 carbon atoms, which are optionally substituted by hydroxy, alkoxy with 1 to 4 carbon atoms.
  • the particularly preferred Me @ cations are the sodium or potassium ion.
  • salts of optionally substituted aliphatic or aromatic thiols of the general formula III can also be used in which R has the meanings mentioned above with the exception of hydrogen, can be used according to the invention.
  • Preferred salts of aliphatic thiols are the mono- and divalent salts of thioglycolic acid.
  • the sodium and potassium salts are particularly preferred.
  • Corresponding acids which can form compounds with a thiolate structure with inorganic or organic bases are, for example: Thiols, such as the thioglycolic acid esters, and preferably thioglycolic acid.
  • Inorganic bases in the sense of the above statements are e.g. the hyder oxides, oxides, or salts of weak acids, such as the carbonates, hydrogen carbonates, phosphates, hydrogen phosphates and acetates of the abovementioned metals, the cation of which can stand for Me ⁇ ; organic bases are e.g. the amines corresponding to the ammonium ions mentioned above.
  • Preferred etchants to be used according to the invention are also the salts of the hydrogen sulfide Hs ⁇ Me ⁇ and S 2 ⁇ Me ⁇ 2 and the polysulfanes Me ⁇ 2 S x with 2 to 4, preferably 2, S atoms.
  • etchants to be used according to the invention are disulfides, which can decompose thermally into compounds with a thiolate structure, in particular in the presence of bases, such as, for example, the thiurams of the general formula IV Compounds of the general formulas V and Va or, for example, di (hydroxycarbonylmethyl) disulfide.
  • Compounds which release compounds with thiolate structure by alkaline hydrolysis are e.g. Di- (hydroxycarbonylmethyl) tri-thiocarbonic acid ester or the inner salt of S-hydroxycarbonylmethyl-thiourea.
  • a prerequisite for the use of compounds which form a thiolate structure through neutralization, thermal decomposition or alkaline hydrolysis is that this formation has ended and the compound with the thiolate structure can still have a caustic effect on the dye by the process according to the invention before this is fixed on the fiber.
  • Combinations of salts of thiocyanic acid with compounds which have or can form a thiolate structure are combinations of e.g. Sodium, potassium or ammonium rhodanide with compounds of the formulas I to V, in particular with salts from the series of the di-thiocarbaminates, di-thiophosphoric acid esters, xanthates or thioglycolic acid. ,
  • etching agents to be used according to the invention can be used as a single substance. Because of their compatibility with one another, combinations of several etching agents according to the invention can also be used.
  • etchants to be used according to the invention can also be used in combination with inorganic or organic bases which produce a pH of at least 8 in water to provide the etching reserve for dyes which would not be completely etched by these bases alone, or in which these bases are in such large quantities would have to be used that fiber damage would result.
  • Suitable etching reserve printing pastes are all preparations which allow the abovementioned etching agents to be applied to the tissue and which, under the application conditions, ensure that the printing paste is dispensed as evenly as possible to the tissue and deliver a pressure which is as sharp as possible.
  • the compounds which have a thiolate structure or can form one are added to the printing pastes which are usually used.
  • the etching agents are expediently added from the starting components during the production of the printing pastes.
  • concentrations of the etchant in the etching reserve printing pastes of 0.1 to 250 g / kg, preferably 1 to 130 g / kg, are required in order to ensure, in the case of the application quantities of the etching reserve printing paste that are usually used, that the substrates to be printed on have the necessary properties the amount of etchant required for the etching is present. This amount depends on the depth of color of the coloring, the etchability of the dyes used and the activity of the etchant.
  • the etchant is used in the usual application quantities of the etching printing paste and at the specified concentrations in a molar ratio of etchant: caustic dyes of 1: (1 to 10,000).
  • the etching reserve printing pastes contain, in addition to the etching agents, water, thickening agents and auxiliaries (for example swelling agents, dispersing agents, fixing accelerators) and, if appropriate, etching-resistant dyes.
  • Suitable thickeners for etching reserve printing pastes to be used according to the invention are, for example: starch degradation products, such as dextrin; nonionic starch derivatives such as British gum; Gums such as gum arabic; Johanis bread kernel flour, in particular kernel flour ether, tragacanth; Guar derivatives, especially guar ethers, cellulose ethers carboxylic acids.
  • the etching reserve printing pastes can also contain other customary auxiliaries and additives, such as, for example, hydrotropic substances, and also additives which promote wetting, penetration and dye absorption.
  • nonionic detergents or solubilizers which are expediently contained in the etching reserve printing pastes, such as, for example, glycerol and / or polyglycols, such as polyethylene glycol, with an average molecular weight of 300 to 500, and / or polypropylene glycols, such as in, for example, are particularly favorable for the etching process DE-OS 29 51 312 are described, or products based on N, N-dialkyl-substituted lower carbonamides, such as N, N-di-cyanoethyl formamide.
  • etching-resistant disperse dyes can also be incorporated in the etching reserve printing pastes.
  • the etching reserve printing pastes used according to the invention preferably contain no reducing agents or oxidizing agents apart from the etching agents to be used according to the invention.
  • all disperse dyes can be etched, the chromophore of which is destroyed by the etching reserve printing pastes and / or which are converted by this etching reserve printing pastes into a form which does not absorb onto the hydrophobic fibers.
  • Dyes that can be etched by the method according to the invention are, in particular, mono- and disazo dyes.
  • Monoazo dyes which can be etched by the process according to the invention are, for example, those with carbocyclic or heterocyclic diazo and / or coupling components from the series of the anilines, naphthylamines, phenols, naphthols, 5- or 6-ring heterocycles, which can optionally be gas-condensed.
  • Suitable disazo dyes are, for example, those whose central component is anilines, naphthylamines or 5- or 6-ring hetero cyclic amines.
  • etchable azo dyes are: CI Disperse Yellow 7, 23, 68, 103 and 180; CI Disperse Orange 1, 3, 5, 13, 18, 19, 20, 21, 25, 29, 30, 33, 38, 44, 55, 61, 66, 71, 81, 96, 127, 128 and 130; CI Disperse Red 1, 2, 5, 7, 13, 17, 43, 50, 54, 56, 65, 73, 76, 82, 90, 134, 151, 160, 167, 168, 177, 180, 183, 184 , 202, 203, 279, 281, 311, 312 and 324; CI Disperse Violet 12, 13, 24, 48, 58, 63 and 33; CI Disperse Blue 79, 85, 94, 122, 125, 130, 139, 148, 149, 165, 165/1, 165/2, 171, 183, 284, 287, 290, 295 and 330; CI Disperse Brown 1, 4/1 and 19; CI Disperse Green 9.
  • the process according to the invention is suitable for textile materials which consist of hydrophobic fibers, for example polypropylene, polyacrylonitrile, polyamide, cellulose triacetate, but especially polyester fibers, but also for textile materials which mix these hydrophobic fibers with cellulose, in particular cotton, or in Mix with wool included.
  • Suitable polyester fibers are, for example, those based on polybutylene terephthalate, poly-1,4-cyclohexylene-dimethylene terephthalate, but especially polyethylene terephthalate, these polyesters, e.g. with a view to easier dyeability, can also be modified, for example by cocondensation of other components, e.g. other dicarboxylic acids and / or other diols.
  • the method according to the invention is also suitable for textile materials which predominantly use hydrophobic fibers alongside other fibers, such as e.g. Cellulose or cotton wool.
  • textile materials that dye when printing A or that provide a uniform product image when printed with disperse dyes.
  • the textile material can e.g. in the form of tangled nonwovens, felt, carpets, woven, knitted or knitted sheets or pieces.
  • the process according to the invention is carried out by applying the white-etchable disperse dyes to the textile material in the form of liquors or printing pastes.
  • the textile material When using a dye liquor, the textile material is impregnated, for example, in a manner known per se, for example padded or splashed.
  • the dye liquors or printing pastes can contain one or more of the white-etchable disperse dyes mentioned in addition to known customary dyeing or printing aids, such as, for example, dispersing agents, wetting agents, foam damping agents and padding aids.
  • the impregnated textile material is squeezed to a liquor absorption of 50 to 120%.
  • the textile materials treated in this way are then dried so carefully that no dye fixation takes place in the fiber.
  • the textile materials prepared in this way are then printed in the desired pattern using one of the abovementioned etching reserve printing pastes.
  • the impregnated and printed textile materials are then subjected to a heat treatment between 100 and 230 ° C. In the lower temperature range up to approx. 130 ° C, the heat is preferably supplied by compressed steam. For heat treatments that are carried out between 160 and 230 ° C., superheated steam or hot air is preferably used as the heat carrier.
  • the heat treatment is preferably carried out with superheated steam, ins especially at 170 to 200 ° C.
  • a special embodiment of the method according to the invention consists in that the dye liquor additionally contains, in addition to white-etchable dispersion dyes, one or more dispersion dyes which are resistant to the etching agents according to the invention and are therefore not destroyed. If one proceeds as above, then multicolored designs are obtained.
  • the white-etchable disperse dyes can also be printed on the textile material in the form of printing pastes and then overprinted in the desired pattern with the etching reserve printing paste.
  • a drying or intermediate drying between the two printing processes is not absolutely necessary, so that wet-wet work can also be carried out.
  • the textile prints are then fixed and completed as described above.
  • etching reserve printing pastes of the type mentioned which in turn contain one or more resistant dispersion dyes, are printed on the fund impregnated or printed with white-etchable dispersion dyes. With subsequent fixation and completion of the textile materials, as described above, multi-colored designs are also obtained here.
  • etching reserve printing paste which contains one or more etching agents of the type mentioned, in the desired pattern on the textile material and to print the textile material thus printed after drying or intermediate drying or without drying or intermediate drying, that is to say "wet-on-wet "to overprint with a printing paste that contains one or more white-etchable dyes.
  • the textile material treated in this way is subjected to the heat treatment already mentioned above in order to fix the dye at the points not covered with etching reserve printing paste and to destroy the dye at the places covered with etching reserve printing paste and, as already stated above, is completed.
  • the etching reserve printing paste additionally contains one or more etching-resistant dispersion dyes and / or the printing paste contains one or more etching-resistant dispersion dyes in addition to one or more white-etchable dispersion dyes.
  • the dyes are present in the padding liquors, printing pastes or in the etching reserve printing pastes in finely dispersed form, as is customary and known for disperse dyes.
  • the padding liquors or printing pastes which are to be used according to the invention are also prepared in a manner known per se by mixing the flatting or printing paste constituents with the necessary amount of water and liquid finely dispersed or solid redispersible settings of the dyes.
  • Etching-resistant disperse dyes which can be combined with the etchable dyes to produce multicolored designs, are, for example, anthraquinone, naphthalimide, nitro, quinophthalone or methine dyes or suitable caustic-resistant dyes are, for example, CI Disperse Yellow 54 and 58; CI Disperse Orange 146; CI Disperse Red 60, 91, 92 and 132; CI Vat Red 41; CI Disperse Violet 35; CI Disperse Blue 56 and 87.
  • parts by weight to parts by volume behave like kilograms to liters.
  • a polyester fabric is woven with a fleet of 20 parts by weight of the liquid commercial form of C.I. Disperse Blue 165, 3 parts by weight of citric acid, 20 parts by weight of an anti-migration agent based on polyacrylamide and 877 parts by weight of water at 20 to 30 ° C with a squeeze-off effect of 70% and carefully dried at 60 to 80 ° C.
  • a pattern is then overprinted with an etching reserve printing paste which contains 500 parts by weight of a 14% core meal ether thickener, 80 parts by weight of glycerin, 80 parts by weight of polyglycol 400 and 50 g of potassium xanthate to 1000 parts by weight.
  • a white etch on a blue background with a sharp stand and very good color fastness is obtained.
  • a polyester fabric is padded and dried as described in Example 1: Then with an etching reserve printing paste, the 375 parts by weight of a 14% core meal ether thickener, 125 parts by weight of a 5% starch ether thickener, 20 parts by weight of glycerin and 80 Ge contains parts by weight of polyglycol 400, 1 part by weight of thioglycolic acid and 40 parts by weight of potash per 1000 parts by weight, overprinted in a pattern. After fixing under superheated steam for 7 minutes at 175 ° C. and finishing as in Example 1, a white etch is obtained on a blue background with a sharp stand and very good coloristic properties.
  • a polyester fabric is, as described in Example 1, with a liquor, but instead of C.I. Disperse Blue 165 20 parts by weight of the liquid commercial form of C.I. Disperse Brown 1 contains, padded and dried. Then, as in Example 1, a padding liquor which, however, contains 2 parts by weight of sodium sulfide and 80 parts by weight of potash instead of potassium xanthate, is overprinted, fixed and aftertreated. This gives a white etching on a reddish-brown background with a sharp stand and very good coloristic properties.
  • a polyester fabric is printed in film with an etching reserve printing paste, which consists of 500 parts by weight of a 5% core meal thickener, 80 parts by weight glycerin, 80 parts by weight polyglycol 400, 80 parts by weight potassium xanthate, 20 parts by weight of a block aid based on fatty acid polyglycol ester and 220 parts by weight water.
  • an etching reserve printing paste which consists of 500 parts by weight of a 5% core meal thickener, 80 parts by weight glycerin, 80 parts by weight polyglycol 400, 80 parts by weight potassium xanthate, 20 parts by weight of a block aid based on fatty acid polyglycol ester and 220 parts by weight water.
  • the fabric is then overprinted "wet-on-wet" without intermediate drying using a printing ink consisting of 20 parts by weight of CI Disperse Blue 165/1, 300 parts by weight of a low-viscosity alginate thickener (10%) and 200 parts by weight of a starch ether (120%) , 5 parts by weight of a decalcifying agent based on polyphosphate, 3 parts by weight of citric acid in 1000 parts by weight.
  • steaming is carried out at 175 ° C. for 7 minutes, then reductively with 2 parts by weight of hydrosulfite and 3 volumes divide a 50% sodium hydroxide solution after 15 minutes at 80 ° C, rinsed, soaped and dried. You get a white pattern on a blue background.
  • a cellulose triacetate fabric is, as described in Example 1, with a liquor containing 30 parts by weight of the liquid commercial form of C.I. Contains Disperse Yellow 180 per 1000 parts by volume, padded and carefully dried. It is then overprinted with an etching reserve printing paste as in Example 1 and dried. After fixing with superheated steam for 7 minutes at 175 ° C, the pressure is rinsed, neutralized, soaped and dried. The printed areas appear white on a yellow background.
  • a polyester fabric is padded and dried as described in Example 1. Then, as in Example 1, with an etching paste which, however, instead of the potassium xanthate, 2 parts by weight of thioglycolic acid and 80 parts by weight of potash and an additional 40 parts by weight of the liquid commercial form of C.I. Disperse Red 303 contains, overprinted in a pattern. After fixing under superheated steam for 7 minutes at 175 ° C. and aftertreatment as in Example 1, a brilliant red etching on a blue background with a sharp stand and very good coloristic properties is obtained.
  • Example 2 A polyester fabric is padded and dried as described in Example 1. Then, as in Example 2, an etching reserve paste, which, however, contains 80 parts by weight of bis (isopropoxythiocarboayl) disulfide instead of the thioglycolic acid, is overprinted, fixed and aftertreated. This also gives a white etch on a blue background with a sharp stand and very good coloristic fastness properties.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Coloring (AREA)
EP84112741A 1983-10-28 1984-10-23 Procédé pour réaliser des impressions résistantes aux décharges sur des matières textiles hydrophobes Expired EP0143969B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3339158 1983-10-28
DE19833339158 DE3339158A1 (de) 1983-10-28 1983-10-28 Verfahren zur herstellung von aetzreservedrucken auf hydrophoben textilmaterialien

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EP0143969A1 true EP0143969A1 (fr) 1985-06-12
EP0143969B1 EP0143969B1 (fr) 1987-11-25

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EP84112741A Expired EP0143969B1 (fr) 1983-10-28 1984-10-23 Procédé pour réaliser des impressions résistantes aux décharges sur des matières textiles hydrophobes

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US (1) US4571246A (fr)
EP (1) EP0143969B1 (fr)
JP (1) JPS60110988A (fr)
KR (1) KR850003451A (fr)
DE (2) DE3339158A1 (fr)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE551775C (de) * 1927-05-24 1932-06-04 I G Farbenindustrie Akt Ges Verfahren zur Erzeugung von Zwei- oder Mehrfarbeneffekten auf mit Nitroanthrachinonen oder Substitutionsprodukten derselben gefaerbten Celluloseaethern, -estern oder dere n Umwandlungsprodukten
GB877028A (en) * 1959-08-27 1961-09-13 Ici Ltd Improved colouring process
EP0044601A1 (fr) * 1980-07-18 1982-01-27 Epec-Dinon Procédé d'impression par rongeage de matières polyesters
DE3128984A1 (de) * 1980-07-25 1982-03-18 CIBA-GEIGY AG, 4002 Basel "aetzreservedruckverfahren zum bedrucken von polyester enthaltenden fasermaterialien unter einsatz eines reduzierenden kohlenhydrate enthaltenden aetzmittels"
DE3132416A1 (de) * 1981-08-17 1983-02-24 Hoechst Ag, 6000 Frankfurt Verwendung von thiokohlensaeure- und -phosphorsaeurederivaten als reservemittel

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3113732A1 (de) * 1981-04-04 1982-10-21 Basf Ag, 6700 Ludwigshafen Verfahren zum bedrucken von synthesefasern
DE3209327A1 (de) * 1982-03-15 1983-09-15 Cassella Ag, 6000 Frankfurt Verfahren zur herstellung von aetzreservedrucken auf hydrophoben textilmaterialien

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE551775C (de) * 1927-05-24 1932-06-04 I G Farbenindustrie Akt Ges Verfahren zur Erzeugung von Zwei- oder Mehrfarbeneffekten auf mit Nitroanthrachinonen oder Substitutionsprodukten derselben gefaerbten Celluloseaethern, -estern oder dere n Umwandlungsprodukten
GB877028A (en) * 1959-08-27 1961-09-13 Ici Ltd Improved colouring process
EP0044601A1 (fr) * 1980-07-18 1982-01-27 Epec-Dinon Procédé d'impression par rongeage de matières polyesters
DE3128984A1 (de) * 1980-07-25 1982-03-18 CIBA-GEIGY AG, 4002 Basel "aetzreservedruckverfahren zum bedrucken von polyester enthaltenden fasermaterialien unter einsatz eines reduzierenden kohlenhydrate enthaltenden aetzmittels"
DE3132416A1 (de) * 1981-08-17 1983-02-24 Hoechst Ag, 6000 Frankfurt Verwendung von thiokohlensaeure- und -phosphorsaeurederivaten als reservemittel

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
CHEMICAL ABSTRACTS, Band 96, Nr. 14, April 1982, Seiten 74-75, Nr. 105737f, Columbus, Ohio, US; & JP - A - 81 165 079 (NIPPON KAYAKU CO., LTD.) 18.12.1981 *

Also Published As

Publication number Publication date
DE3339158A1 (de) 1985-05-09
JPS60110988A (ja) 1985-06-17
US4571246A (en) 1986-02-18
EP0143969B1 (fr) 1987-11-25
DE3467786D1 (en) 1988-01-07
KR850003451A (ko) 1985-06-17

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