EP0143969B1 - Process for the production of discharge resist prints on hydrophobic textile materials - Google Patents

Description

The present invention relates to a method for producing etching reserve prints on textile materials which consist of hydrophobic fibers or predominantly contain hydrophobic fibers, e.g. B. in connection with cellulose, in particular with cotton, or in connection with wool, one or more white-etchable disperse dyes and optionally one or more etch-resistant disperse dyes being applied in the form of a liquor or printing paste and then carefully dried or dried and then one Etching reserve printing paste is printed in the desired pattern, which optionally additionally contains one or more etching-resistant disperse dyes, the order of printing on the etching reserve printing paste and the printing paste being reversed and, if a printing paste is used, drying or intermediate drying can be omitted, and subsequent heat treatment at 100 to 230 ° C.

It has always been a problem in textile printing to produce white or colored, sharply defined patterns on a deep-colored background. The direct printing of the textile material completely fails, particularly when producing filigree-like patterns on a dark background. To produce such patterns, it is known to print an etching printing paste in the desired pattern on a deep background color produced with a white-etchable dye and then to destroy the dye at the point printed with the etching printing paste by means of dry or wet heat treatment. After washing out the prints obtained in this way, the desired pattern is obtained in white on a dark background. It is also known to add dyes that are resistant to the etchant to the etching printing pastes. In this case, at the same time as the background color is destroyed, the textile material is colored at the printed areas by the indestructible dye. In this case you get colored prints on a dark background. Colored prints on a dark background can also be obtained if the dark background is made with a mixture of an etchable and a different colored, non-etchable dye.

A problem arises in the transfer of these known methods to textile materials which consist of hydrophobic synthetic fibers in that the etching of polyester fibers stained with disperse dyes, for example, is very difficult. Disperse dyes that are once fixed in the polyester fiber, i.e. are largely removed from access by aqueous agents and thus also from attack by aqueous etching printing pastes. In the production of etching prints on textile materials containing hydrophobic fibers or consisting of hydrophobic fibers, 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.

The process of 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.

In order to overcome this difficulty, etching printing pastes are used which contain relatively strong reducing or oxidizing agents, such as e.g. B. alkali formaldehyde sulfoxylates, or even heavy metal salts, such as tin-2-chloride. With such strong etching agents it is usually possible to achieve a perfect white etching print, but damage to the fiber material often occurs. Furthermore, these etchants are usually not cheap. When zinc-2-chloride is used, the hydrochloric acid that splits off causes severe corrosion in the dampers.

One suggestion to avoid the use of reducing metal salts or at least to reduce their proportion in etching printing pastes is to use organic compounds as etching agents which have a reducing effect on the organic dyes, such as thiourea, isothiourea or their selenium analogs. However, since the caustic effect of these compounds is generally not sufficient, metal salts with their disadvantages mentioned at the outset must be added in the preferred embodiments of the process.

JP-A-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.

A similar process is described in DE-A-31 28 984: Here, a combination of reducing sugars with polyhydric alcohols is used as the etchant, with u.a. is also called thioglycol, and optionally used with salts of thiocyanic acid. In addition to the inadequate etching effect of the reducing sugars in many cases, one of the main deficiencies of these etchants is that the prints produced with them have a fuzzy state, so the limitation of the etching pattern is not sharp, which is particularly intolerable in the case of filigree patterns.

DE-A-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 as reducing agents is used.

In the field of etching reserve printing of cellulose textiles with phthalocyanine condensation dyes (so-called Ingrain dyes), it is known from DE-A-31 32 416 to use water-soluble organic derivatives of thiocarbonic acid or thiophosphoric acid as the etching agent. These substances prevent the formation of the phthalocyanine dyes from the printed polyisoindolenine-metal complexes.

In order to avoid the use of metallic reducing agents and to be able to use less effective reducing agents, it has also already been proposed to use such disperse dyes for background coloring which can be etched with white agents which are as mild as possible. Dyes are known from DE-A-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 which are etched by aqueous alkalis can either destroy their chromophore or convert their carbonic ester or sulfonamide groups into a salt-like structure, whereby the dyes lose their affinity for the fiber. The use of such dyes by the processes described leads to fiber damage by saponification, which is particularly intolerable in the case of very light, thin qualities. In addition, 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. B. lightfastness and thermosetting fastness.

It has now surprisingly been found that conventional disperse dyes from the Azo series are also suitable as white-etchable dyes for the etching reserve print on hydrophobic textile materials if an etching reserve printing paste is used in the process described at the outset which uses one or more salts of the hydrogen sulfide or the polysulfanes as an etchant and / or contains one or more compounds which have or can form a thiolate structure, optionally in combination with thiourea and / or salts of thiocyanic acid.

Compounds with a thiolate structure are those which have at least one thiolate structure (-S ^e ) or a thiostructure (= S) capable of tautomerism, such as. B. salts of thio derivatives of carbonic or phosphoric acid, salts of aromatic or aliphatic thio- or di-thiocarboxylic acids or salts of thiols.

Compounds that can form a thiolate structure are e.g. B. the corresponding acids to the above thiolates in combination with inorganic or organic bases, which produce a pH of at least 8 in water.

Compounds which decompose into fission products containing thiolate groups by thermolysis or by hydrolysis can also be used as the etching reserve according to the invention. Suitable thermolyzable compounds are e.g. B. 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. B. the alkyl or aryl esters of thiocarbonic acid, thiocarboxylic acid or thiophosphoric acid derivatives.

worin

• A ein Kohlenstoffatom oder eine der Gruppen P-NR¹R², POR² oder PSR²;
• B Sauerstoff, Schwefel oder eine Gruppe = NR2;
• X eine direkte Bindung, Sauerstoff, Schwefel oder eine Gruppe -NR^2-;
• R Wasserstoff, einen m-wertigen, gegebenenfalls substituierten Alkanrest, der durch einen 1,2-, 1,3- oder 1,4-Phenylenrest oder, sofern seine Kettenlänge >3 ist, durch -O-, -S- oder -NR^2- einmal oder mehrfach im Abstand von mindestens 2 C-Atomen oder durch zweiwertige Reste der Formeln
  
  einmal oder zweimal im Abstand von mindestens 2 C-Atomen unterbrochen sein kann; einen m-wertigen, gegebenenfalls substituierten Cycloalkanrest oder Alkenrest; einen m-wertigen Rest eines Trialkylamins oder Polyalkyl-alkylenpolyamins, dessen Alkylgruppen, sofern ihre Kettenlänge >3 ist, durch -O-, -S- oder -NR^2- einmal oder mehrfach im Abstand von mindestens 2 C-Atomen unterbrochen sein können;
• R¹ Wasserstoff, einen gegebenenfalls substituierten Alkylrest, der, sofern seine Kettenlänge >3 ist, durch -O-, -S- oder -NR^{3 -} einmal oder mehrfach im Abstand von mindestens 2 C-Atomen oder durch zweiwertige Reste der Formeln .
  
  einmal oder zweifach unterbrochen sein kann; einen gegebenenfalls substituierten Cycloalkylrest oder Alkenylrest bedeuten;
• R² eine der für R¹ genannten Bedeutungen hat und zusätzlich auch für gegebenenfalls substituiertes Aryl oder Heteroaryl steht;
• R^l und R² gemeinsam mit einem N-Atom, an das sie gebunden sind, einen N-Pyrrolidin-, N-Piperidin-, N-Piperazin-, N-Morpholin- oder N-Thiomorpholinrest bilden;
• R³ Wasserstoff oder gegebenenfalls durch Halogen, -OH oder Alkoxy substituiertes Alkyl, Alkenyl oder Cycloalkyl bedeutet und gegebenenfalls
• R-X- auch gemeinsam für Cyan stehen;
• m eine Zahl von 1 bis 3 ist und

Derivatives of carbonic or phosphoric acid which are suitable as etching reserve agents according to the invention and which have at least one thiolate structure or a thiostructure capable of tautomerism are those of the formula I.

wherein

• A is a carbon atom or one of the groups P-NR ¹ R ² , POR ² or PSR ² ;
• B oxygen, sulfur or a group = NR2;
• X is a direct bond, oxygen, sulfur or a group -NR ^2- ;
• R is hydrogen, an m-valent, optionally substituted alkane radical which is replaced by a 1,2-, 1,3- or 1,4-phenylene radical or, if its chain length> 3, by -O-, -S- or -NR ^2- once or several times at a distance of at least 2 carbon atoms or by divalent radicals of the formulas
  
  can be interrupted once or twice at a distance of at least 2 carbon atoms; an m-valent, optionally substituted cycloalkane radical or alkene radical; an m-valent radical of a trialkylamine or polyalkylalkylene polyamine, the alkyl groups of which, provided that their chain length is> 3, can be interrupted once or more than once by a distance of at least 2 C atoms by -O-, -S- or -NR ^2- ;
• R ^{1 is} hydrogen, an optionally substituted alkyl radical which, if its chain length is> 3, by -O-, -S- or -NR ^{3 -} one or more times at a distance of at least 2 carbon atoms or by divalent radicals of the formulas.
  
  can be interrupted once or twice; is an optionally substituted cycloalkyl radical or alkenyl radical;
• R ^{2 has} one of the meanings given for R ¹ and additionally also represents optionally substituted aryl or heteroaryl;
• R ¹ and R ² together with an N atom to which they are attached form an N-pyrrolidine, N-piperidine, N-piperazine, N-morpholine or N-thiomorpholine residue;
• R ^{3 is} hydrogen or alkyl, alkenyl or cycloalkyl optionally substituted by halogen, -OH or alkoxy and optionally
• RX- also stand together for cyan;
• m is a number from 1 to 3 and

Me⊕ represents an equivalent of a cation or alkali or alkaline earth metal or an optionally substituted ammonium ion.

ableiten. Sofern die Kohlenstoffkette des Alkanrestes durch einen Phenylenrest unterbrochen ist, sind die 1,3-und 1,4-Phenylenreste bevorzugt.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.

unterbrochen, so sind auch hier die 1,3- und 1,4-Stellungen in den Phenylenresten bevorzugt und ferner die einfache Unterbrechung.Is the alkane residue by residues of the formula

interrupted, the 1,3- and 1,4-positions in the phenylene radicals are also preferred here and furthermore the simple interruption.

Of the alkane radicals interrupted by -O-, -S- or -NR ^2- , those interrupted by -0- 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-.

• -CH₂CH₂-O-CH₂CH_z-NR^2-CH₂CH₂-O-CH₂CH₂-oder
• -CH₂CH₂-0-CH₂CH₂-S-CH₂CH₂-0-CH₂CH₂-bevorzugt.

So of such interrupted alkane chains such. B. those of the formulas

• -CH ₂ CH ₂ -O-CH ₂ CH _z -NR ^2- CH ₂ CH ₂ -O-CH ₂ CH ₂ -or
• -CH ₂ CH ₂ -0-CH ₂ CH ₂ -S-CH ₂ CH ₂ -0-CH ₂ CH ₂ -preferred.

worin R⁴ wiederum die für zweiwertige Reste R geltende Definition hat. Vorzugsweise sind die Reste R⁴ zweiwertige Alkanreste, die gegebenenfalls substituiert sind und, bei einer Kettenlänge >3 einfach oder mehrfach im Abstand von mindestens 2 C-Atomen durch -O- unterbrochen sein können.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 R ⁴ radicals are preferably divalent alkane radicals, which are optionally substituted and, with a chain length> 3, can be interrupted once or more than once by a distance of at least 2 C atoms by -O-.

worin R⁵ eine direkte Bindung oder ein Rest R⁴ ist.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 .

In order to simplify the description, “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 (for example corresponding acids, hydrolytically or thermolytically cleavable precursors).

Suitable etching agents of formula 1 to be used according to the invention can come from the series of thiocarbamates. In this case, A is a C atom, B is an O atom, X is a group -NR ^2- .

Another group of 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.

Further groups of etching agents of formula I to be used according to the invention belong to the series of cyanodithio formic acid (A = C atom; B = S atom; RX- means a cyano group) or the series of trithiophosphoric acid esters (A = POR ¹ ; B = S atom) ; X = S atom).

Another group of etching agents of formula 1 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 a 0 or S atom and X is a direct bond.

Preferred etchants of the formula to be used according to the invention are compounds from the series of the 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 the di-thiophosphoric acid esters, where A stands for POR ² , B for an S atom and X for an O atom.

Particularly preferred etching agents of formula 1 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.

In the above-mentioned groups of etchants, the symbols R, R ¹ and R ^{2 have} the meanings mentioned above.

substituiert sein können.

• In der obigen Formel bedeuten
• D und D' unabhängig voneinander lineare oder verzweigte Alkylenreste mit 2 bis 6 C-Atomen,
• R⁶ Wasserstoff, Alkyl mit 1 bis 8 C-Atomen, Cycloalkyl mit 5 oder 6 C-Atomen, Alkenyl mit 3 bis 5 C-Atomen, Phenyl, Benzyl, Phenethyl oder Cyanethyl,
• r die Zahlenwerte 0 bis 10 und
• t die Zahlenwerte 0 und 1, wobei die Summe von r und t > 1 ist.

Optionally substituted, m-valent 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.

• In the above formula mean
• D and D 'independently of one another are linear or branched alkylene radicals having 2 to 6 C atoms,
• R ^{6 is} hydrogen, alkyl having 1 to 8 carbon atoms, cycloalkyl having 5 or 6 carbon atoms, alkenyl having 3 to 5 carbon atoms, phenyl, benzyl, phenethyl or cyanoethyl,
• r the numerical values 0 to 10 and
• t the numerical values 0 and 1, the sum of r and t> 1.

The number of the above-mentioned substituents attached to the hydrocarbon radicals representing RR ² and R ³ 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 ² are phenyl, naphthyl-1 and naphthyl-2 radicals which are mono- to triple-fluorine, chlorine, bromine, alkyl having 1 to 4 carbon atoms, alkoxy with 1 to 4 C atoms, nitro, cyan, carboxyl, alkoxycarbonyl with 1 to 4 C atoms, mono- or dialkylaminocarbonyl with 1 to 4 C atoms in each alkyl radical, hydroxysulfonyl, alkoxysulfonyl with 1 to 4 C atoms, alkylsulfonyl with 1 to 4 C atoms in the alkyl radical, phenylsulfonyl, mono- or dialkylaminosulfonyl with 1 to 4 C atoms in each alkyl radical can be substituted.

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 ¹ and R ^{2 are.} Alkyl radicals having 1 to 4 carbon atoms, which are substituted by hydroxy, alkoxy having 1 to 4 carbon atoms, phenoxy, phenyl, chlorine, bromine or cyano, in particular simple can be substituted. 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, for whose cation Me ⁹ stands, are, for. B. 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.

Very particularly preferred cations Me ⁹ are the sodium or potassium ion.

in der R die oben genannten Bedeutungen mit Ausnahme von Wasserstoff hat, erfindungsgemäß eingesetzt werden.In addition to the etching agents of the formula I, 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 that can form compounds with thiolate structure with inorganic or organic bases are, for. B. thiols, such as the thioglycolic acid ester, and preferably thioglycolic acid.

Inorganic bases in the sense of the above statements are, for. B. the hydroxides, oxides, or salts of weak acids, such as the carbonates, hydrogen carbonates, phosphates, hydrogen phosphates and acetates of the above metals, the cation of which can represent Me ¢; organic bases are e.g. B. the amines corresponding to the above-mentioned ammonium ions.

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.

Another class of etchants to be used according to the invention are disulfides, which can decompose thermally in particular in the presence of bases into compounds having a thiolate structure, such as, for example, B. the thiurams of the general formula IV

oder z. B. Di-(hydroxycarbonylmethyl)-disulfid.Compounds of the general formulas V and Va

or z. B. Di- (hydroxycarbonylmethyl) disulfide.

Compounds which release compounds with thiolate structure by alkaline hydrolysis are e.g. B. di (hydroxycarbonylmethyl) tri-thiocarbonic acid ester or the inner salt of S-hydroxycarbonylmethylthiourea.

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. B. sodium, potassium or ammonium rhodanide with compounds of the formulas I to V, in particular with salts from the series of di-thiocarbaminates, di-thiophosphoric acid esters, xanthates or thioglycolic acid.

The 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.

The 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. To produce the etching reserve printing pastes to be used according to the invention, 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. As a rule, 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. As a rule, 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).

As usual, the etching reserve printing pastes contain, in addition to the etching agents, water, thickening agents and auxiliaries (e.g. 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 ether carboxylic acids. Furthermore, the etching reserve printing pastes can also contain other conventional auxiliaries and additives, such as. B. hydrotropic substances, as well as additives that promote wetting, penetration and dye absorption. The presence of nonionic detergents or solubilizers, which are expediently contained in the etching reserve printing pastes, such as e.g. B. glycerol and / or polyglycols, such as polyethylene glycol, with an average molecular weight of 300 to 500, and / or polypropylene glycols, as z. B. are described in DE-A-29 51 312, or products based on N, N-dialkyl-substituted lower carbonamides, such as. B. N, N-di-cyanoethyl formamide. To achieve colored designs, 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.

According to the method 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 method according to the invention are e.g. B. those with carbocyclic or heterocyclic diazo and / or coupling components from the series of anilines, naphthylamines, phenols, naphthols, 5- or 6-ring heterocycles, which may optionally be gas-condensed. Suitable disazo dyes are e.g. B. those whose central component is derived from anilines, naphthylamines or 5- or 6-ring heterocyclic amines. Examples of etchable azo dyes are: C.I. Disperse Yellow 7, 23, 68, 103 and 180; C.I. 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; C.I. 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; C.I. Disperse Violet 12, 13, 24, 48, 58, 63 and 33; C.I. Disperse Blue 79, 85, 94, 122,125, 130,139,148,149,165,165 / 1,165 / 2,171,183, 284, 287, 290, 295 and 330; C.I. Disperse Brown 1.4 / 1 and 19; C.I. 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. Examples of suitable polyester fibers are those based on polybutylene terephthalate, poly-1,4-cyclohexylene-dimethylene terephthalate, but in particular polyethylene terephthalate, these polyesters, e.g. B. with a view to easier dyeability, can also be modified, for example by cocondensation of other components, for. B. other dicarboxylic acids and / or other diols. However, the method according to the invention is also suitable for textile materials which predominantly contain hydrophobic fibers alongside other fibers, such as, for example, B. cell or cotton. In particular, those textile materials come into consideration that still provide a uniform appearance when dyeing or printing with disperse dyes. The textile material can e.g. B. in the form of random nonwovens, felts, 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. When using a dye liquor, the textile material is z. B. impregnated in a conventional manner, for. B. 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 block 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. This can e.g. B. by warm air with any previous infrared radiation, the temperature is about 60 to 80 ° C, maximum about 100 ° C with a corresponding reduction in time. 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 carried out between 160 and 230 ° C, superheated steam or hot air is preferably used as the heat transfer medium. When using steam for the heat treatment, a drying at 60 ° C to a maximum of 100 ° C, z. B. by warm air with possibly preceding infrared radiation. With some etchants, which only form a compound with a thiolate structure during the heat treatment, the presence of small amounts of water may be necessary during the heat treatment. In the case of such etching agents, the heat treatment is preferably carried out using superheated steam, in particular at 170 to 200 ° C. After the heat treatment, which results in the disperse dyes being fixed at the areas not overprinted with the etching reserve printing paste and the destruction of the dispersing dyes in the places printed with the etching reserve printing paste, the textile materials are aftertreated in the usual manner, hot and cold rinsed and dried.

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.

As already mentioned, 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. With this method, too, it is possible to add one or more disperse dyes which are resistant to etching agents to the color printing paste printed first, which may also contain several white-etchable disperse dyes of the type mentioned. In this case too, multi-colored designs are obtained. A further possibility for carrying out the process according to the invention is that 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.

Finally, it is also possible to first print an 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, ie "wet-on wet "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. In this case, multi-colored patterns are obtained if the etching reserve printing paste additionally contains one or more etching-resistant disperse dyes and / or the printing paste. for one or more white-etchable disperse dyes also contains one or more etch-resistant disperse 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 for the production of multi-colored designs, are e.g. B. anthraquinone, naphthalimide, nitro, quinophthalone or methine dyes or suitable caustic-resistant dyes are such. B. C.I. Disperse Yellow 54 and 58; C.I. Disperse Orange 146; C.I. Disperse Red 60, 91, 92 and 132; C.I. Vat Red 41; C.I. Disperse Violet 35; C.I. Disperse Blue 56 and 87.

In the production of white etching, it is also possible to add etching-resistant optical brighteners to the etching reserve printing pastes used according to the invention.

In the following examples, parts by weight to parts by volume behave like kilograms to liters.

example 1

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 squeezing 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. After thermosoling for 1 minute at 200 ° C, reductive post-treatment, soaps, then rinsing and drying, a white etch on a blue background with a sharp stand and very good color fastness is obtained.

Example 2

A polyester fabric is padded and dried as described in Example 1. Then, with an etching reserve printing paste which contains 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 glycerol and 80 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. 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.

Example 3

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.

Example 4

A polyester fabric is printed in film printing 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. The fabric is then "wet-on-wet" overprinted with an ink consisting of 20 parts by weight of C.I. 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. After drying, steaming is carried out for 7 minutes at 175 ° C., then reductively aftertreated, rinsed, soaped and dried with 2 parts by weight of hydrosulfite and 3 parts by volume of a 50% sodium hydroxide solution at 80 ° C. for 15 minutes. You get a white pattern on a blue background.

Example 5

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.

Example 6

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 6

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 (isopropoxythiocarbonyl) disulfide instead of the thioglycolic acid, is overprinted, fixed and aftertreated. In this way, one also obtains a white etching on a blue background with a sharp stand and very good coloristic fastness properties.

Claims (7)

1. Process for the production of discharge resist prints on textile materials which consist of hydrophobic fibres or contain hydrophobic fibres to a preponderant extent, wherein one or more disperse dyestuffs which are dischargeable to white and, if appropriate, one or more discharge-resistant disperse dyestuffs are applied, in the form of a dye liquor or printing paste, to the textile material and are then carefully incipiently dried or dried, and a discharge resist printing paste which can, if desired, contain in addition one or more discharge-resistant disperse dyestuffs is then printed on in the desired pattern, it being also possible to exchange the sequence of printing on the discharge resist printing paste and the printing paste and, if a printing paste is used, for the incipient drying or intermediate drying also to be omitted, and the material is subsequently subjected to heat treatment at 100 to 230°C, characterised in that a discharge resist printing paste containing, as the discharging agent, one or more salts of hydrogen sulphide or of the polysulphanes, and/or one or more compounds which have a thiolate structure or can form such a structure, is employed, if appropriate in combination with thiourea and/or salts of thiocyanic acid.

2. Process according to Claim 1, characterised in that a discharge resist printing paste containing, as the discharging agent, derivatives of dithiocarbonic acid and/or dithiophosphoric acid, if appropriate in the form of their salts, is employed.

3. Process according to Claim 1, characterised in that a discharge resist printing paste containing, as the discharging agent, a combination of derivatives of dithiocarbonic acid and/or dithiophosphoric acid or salts thereof together with thiourea and/or salts of thiocyanic acid, is employed.

4. Process according to Claim 1, characterised in that a discharge resist printing paste containing xanthates as the discharging agent is employed.

5. Process according to Claim 1, characterised in that a discharge resist printing paste containing, as the discharging agent, salts of thioglycollic acid and/or thioglycollic acid, in combination with inorganic or organic bases, is employed.

6. Process according to Claim 1, characterised in that a discharge resist printing paste containing, as the discharging agent, dithiocarbamates or dithiophosphoric acid esters, is employed.

7. Process according to Claim 1, characterised in that a discharge resist printing paste containing, as the discharging agent, one or more salts of hydrogen sulphide, is employed.