DE19930986A1 - Home ink-jet printing on textile fiber web, especially delicate or ink-permeable textile - Google Patents

Abstract

In ink-jet printing on textile fiber webs with aqueous inks containing dye, the back of the textile, away from the printing head, is covered closely with another web and the 2 webs are fed past to the printing head together.

Description

The present invention relates to a method for printing textiles Fiber materials after the inkjet printing process.

Inkjet printing processes have been used in the textile industry for a number of years applied. These methods make it possible to use the otherwise customary production of a To dispense with printing stencils, so that considerable cost and time savings are achieved can be. Especially in the production of templates, within It takes much less time to respond to changing needs.

Corresponding inkjet printing processes should in particular be optimal have application properties. Mention should be made in this one Related properties such as viscosity, stability, and surface tension Conductivity of the inks used. There are also increased demands on quality of the prints obtained, such as B. regarding color strength, fiber color fabric bond stability and wet fastness properties. Of the known methods are these requirements are not met in all properties, so there is still a need for there is a new process for textile inkjet printing.

The present invention is a method for printing flat, textile fiber materials according to the inkjet printing process with aqueous, dye-containing inks, which is characterized in that the fiber materials during printing on the side facing away from the print head be covered with a sheet-like medium lying closely against the fiber material and the fiber material and the medium are guided past the printhead.

The inks used for the process according to the invention preferably contain at least one acid dye, reactive dye, disperse dye or Pigment dye.

The reactive dyes are, for. B. to dyes from the group of Monoazo, disazo, polyazo, metal complex azo, anthraquinone, phthalocyanine, Formazan or dioxazine dyes which contain at least one reactive group. Preferably these dyes also contain at least one sulfo group.

Reactive groups are radicals which are reactive towards fibers and which are present in the Are able to with the hydroxyl groups of cellulose, the amino, carboxyl, and hydroxyl Mercapto groups of wool or silk or with the amino or optionally the Carboxyl groups of synthetic polyamides with the formation of chemical covalent bonds to react. The reactive groups are usually with the dye residue directly or via linked a bridge element. As reactive groups are z. B. those suitable that at least one of an aliphatic, aromatic or heterocyclic radical have removable substituents, or those in which these radicals have a reaction have suitable remainder with the fiber material, such as. B. a halotriazinyl, Halopyrimidinyl or vinyl radical.

As aliphatic reactive groups, for. B. Consider those of the following formulas:

-NH-CO-Y (1),

-SO ₂ -Z (1a),

wherein W is a group of the formula -SO ₂ -NR ₁ -, -CONR ₁ - or -NR ₁ CO-,
R _{1 is hydrogen, C 1} -C ₄ -alkyl which is unsubstituted or substituted by hydroxy, sulfo, sulfato, carboxy or cyano, or a radical of the formula

R is hydrogen, hydroxy, sulfo, sulfato, carboxy, cyano, halogen, C ₁ -C ₄ alkoxycarbonyl, C ₁ -C ₄ alkanoyloxy, carbamoyl or the group -SO ₂ -Z,
Z is vinyl or a radical -CH ₂ -CH ₂ -U ₁ and U _{1 is} a leaving group,
Y is a radical of the formula -CH (Hal) -CH ₂ -Hal or -C (Hal) = CH ₂ and Hal is halogen,
E is the radical -O- or -N (R ₂ ) -,
R _{2 is} hydrogen or C ₁ -C ₄ -alkyl, alkylene and alkylene 'independently of one another C ₁ -C ₆ -alkylene, and arylene is an unsubstituted or sulfo, carboxy, C ₁ -C ₄ -alkyl, C ₁ -C ₄ - Denotes alkoxy or halogen-substituted phenylene or naphthylene radical.

Aliphatic reactive groups are those of the formulas (1a) to (1d), in particular those of the formulas (1a) to (1c) and preferably those of the formula (1a) are preferred.

Preferred heterocyclic reactive radicals are 1,3,5-triazine radicals of the formula

considering where
R _{3 is hydrogen or C 1} -C ₄ -alkyl which is unsubstituted or substituted by carboxy, cyano, hydroxy, sulfo or sulfato,
X is a group which can be split off as an anion and
V is a residue of the formula

denotes in which R, R ₁ , R ₃ , E, W, Z, Y, alkylene, alkylene 'and arylene have the meanings given above and t is 0 or 1.

The leaving group U ₁ is z. B. -Cl, -Br, -F, -OSO ₃ H, -SSO ₃ H, -OCO-CH ₃ , -OPO ₃ H ₂ , -OCO-C ₆ H ₅ , -OSO ₂ -C ₁ -C _4- alkyl or -OSO ₂ -N (C ₁ -C ₄ -alkyl) ₂ . _{U 1} is preferably a group of the formula -Cl, -OSO ₃ H, -SSO ₃ H, -OCO-CH ₃ , -OCO-C ₆ H ₅ or -OPO ₃ H ₂ , in particular -Cl or -OSO ₃ H and particularly preferably -OSO ₃ H.

In alkylene and alkylene 'are, independently of one another, for. B. to a methylene, Ethylene, 1,3-propylene, 1,4-butylene, 1,5-pentylene or 1,6-hexylene radical or their branched isomers.

Alkylene and alkylene are preferably a C ₁ -C ₄ alkylene radical and particularly preferably an ethylene radical.

R preferably denotes hydrogen or the group -SO ₂ -Z, where the meanings and preferences given above apply to Z. R is particularly preferably hydrogen.

R ₁ is preferably hydrogen, C ₁ -C ₄ -alkyl or a group -alkylene-SO ₂ -Z, in which alkylene and Z each have the meanings given above. _{R 1} is particularly preferably hydrogen or C ₁ -C ₄ -alkyl, in particular hydrogen.

R ₃ is preferably hydrogen or a C ₁ -C ₄ -alkyl radical and particularly preferably hydrogen.

Arylene is preferably a 1,3- or 1,4-phenylene radical, which is unsubstituted or z. B. by Sulfo, methyl, methoxy or carboxy is substituted.

E preferably represents -NH- and particularly preferably represents -O-.

W preferably denotes a group of the formula -NHCO- or, in particular, -CONH-.

X stands z. B. for fluorine, chlorine, bromine, sulfo, C ₁ -C ₄ -alkylsulfonyl or phenylsulfonyl and preferably for chlorine or especially fluorine.

Hal preferably denotes chlorine or bromine, in particular bromine.

Further interesting reactive groups are those of the formula (2) in which V is an anion is a removable group or, in particular, denotes a non-reactive substituent.

If V is a group which can be split off as an anion, this is, for. B. fluorine, chlorine, bromine, sulfo, C ₁ -C ₄ -alkylsulfonyl or phenylsulfonyl and preferably chlorine or especially fluorine.

If V stands for a non-reactive substituent, this can e.g. B. a hydroxy, C ₁ -C ₄ alkoxy, C ₁ -C ₄ alkylthio, amino, NC ₁ -C ₄ alkylamino or N, N-di-C ₁ -C ₄ alkylamino, where the alkyl optionally z. B. is substituted by sulfo, sulfato, hydroxy, hydroxyethoxy, carboxy or phenyl, cyclohexylamino, morpholino, or NC ₁ -C ₄ -alkyl-N-phenylamino or phenylamino or naphthylamino, the phenyl or naphthyl optionally z. B. substituted by C ₁ -C ₄ -alkyl, C ₁ -C ₄ -alkoxy, carboxy, sulfo or halogen.

Examples of suitable non-reactive substituents V are amino, methylamino, ethylamino, β-Hydroxyäthylamino, N, N-Di-β-Hydroxyäthylamino, β-Sulfoäthylamino, Cyclohexylamino, Morpholino, o-, m- or p-chlorophenylamino, o-, m- or p-methylphenylamino, o-, m- or p-methoxyphenylamino, o-, m- or p-sulfophenylamino, disulfophenylamino, o-carboxyphenylamino, 1- or 2-naphthylamino, 1-sulfo-2-naphthylamino, 4,8-disulfo-2- naphthylamino, N-ethyl-N-phenylamino, N-methyl-N-phenylamino, methoxy, ethoxy, n- or iso-propoxy and hydroxy.

As a non-reactive substituent, V preferably has the meaning amino, NC ₁ -C ₄ -alkylamino which is unsubstituted in the alkyl part or substituted by hydroxy, hydroxyethoxy, sulfato or sulfo, morpholino, phenylamino or NC ₁ -C ₄ -alkyl-N- phenylamino, in which the phenyl is in each case unsubstituted or substituted by sulfo, carboxy, methyl or methoxy. Particularly preferred are the meanings as NC ₁ -C ₄ -alkylamino, which is unsubstituted in the alkyl moiety or substituted by hydroxy, hydroxyethoxy, sulfato or sulfo, and as phenylamino or NC ₁ -C ₄ -alkyl-N-phenylamino, in which the phenyl in each case is unsubstituted or substituted by sulfo, carboxy, methyl or methoxy.

The radicals of the formulas (3a) to (3f) here and below are those of the formulas (3a) to (3d), in particular those of the formulas (3b) and (3d) are preferred.

Preferred heterocyclic reactive radicals of the formula (2) are those in which X is fluorine or Is chlorine, especially fluorine, and V is a radical of the formulas (3a) to (3f).

Preference is also given to reactive radicals of the formula (2) in which X is fluorine or chlorine, in particular chlorine, and V is amino, NC ₁ -C ₄ -alkylamino substituted in the alkyl moiety by hydroxyethoxy, or optionally by C ₁ -C ₄ -alkyl, C ₁ -C ₄ -alkoxy, carboxy, halogen or, in particular, sulfo-substituted phenylamino or NC ₁ -C ₄ -alkyl-N-phenylamino. The phenyl radicals are preferably unsubstituted or substituted by sulfo. Of particular importance here are amino and phenylamino which is unsubstituted or substituted by sulfo in the phenyl radical or NC ₁ -C ₄ -alkyl-N-phenylamino.

Also of interest as heterocyclic reactive radicals are those of the formula

wherein one of the radicals X _{1 is} a group which can be split off as an anion and the other radical X _{1 has} the meanings and preferences given for V as a non-reactive substituent or is a radical of the formulas (3a) to (3f) or a group which can be split off as an anion ,
X _{2 is} a negative substituent and
R ₃ independently has the meaning given above.

The radical X ₁ which can be split off as an anion is preferably chlorine or, in particular, fluorine. Examples of suitable radicals X ₂ are nitro, cyano, C ₁ -C ₄ -alkylsulphonyl, carboxy, chlorine, hydroxy, C ₁ -C ₄ -alkoxysulphonyl, C ₁ -C ₄ -alkylsulphinyl, C ₁ -C ₄ -alkoxycarbonyl or C. ₂ -C ₄ -alkanoyl, where the meanings chlorine, cyano and methylsulfonyl, in particular chlorine, are preferred _{for X 2.} At least one of the radicals X _{1 is} particularly preferably fluorine or a radical of the formulas (3a) to (3f). One of the radicals X _{1 is} very particularly preferably fluorine and the other radical X _{1 is} fluorine or chlorine, where the meanings and preferences given above apply _{to X 2.}

Of particular interest are reactive groups of the formula (1a) or (2), where the given preferences apply.

The reactive dyes can, in addition to the reactive groups on their backbone, with Organic dyes contain common substituents bound.

Examples of such substituents on the reactive dyes are:
Alkyl groups having 1 to 4 carbon atoms, such as methyl, ethyl, propyl, isopropyl or butyl, the alkyl radicals, for. B. can be further substituted by hydroxyl, sulfo or sulfato; Alkoxy groups having 1 to 4 carbon atoms, such as methoxy, ethoxy, propoxy, isopropoxy or butoxy, the alkyl radicals, for. B. can be further substituted by hydroxyl, sulfo or sulfato; phenyl optionally substituted by C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, halogen, carboxy or sulfo; Acylamino groups having 1 to 8 carbon atoms, especially those alkanoylamino groups, such as. B. acetylamino or propionylamino; Benzoylamino optionally substituted in the phenyl ring by C ₁ -C ₄ -alkyl, C ₁ -C ₄ -alkoxy, halogen or sulfo; phenylamino optionally substituted in the phenyl ring by C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, halogen or sulfo; N, N-di-β-hydroxyethylamino; N, N-di-β-sulfatoethylamino; Sulfobenzylamino; N, N-disulfobenzylamino; Alkoxycarbonyl with 1 to 4 carbon atoms in the alkoxy radical, such as methoxycarbonyl or ethoxycarbonyl; Alkylsulfonyl with 1 to 4 carbon atoms, such as methylsulfonyl or ethylsulfonyl; Trifluoromethyl; Nitro; Amino; Cyano; Halogen, such as fluorine, chlorine or bromine; Carbamoyl; N-alkylcarbamoyl with 1 to 4 carbon atoms in the alkyl radical, such as N-methylcarbamoyl or N-ethylcarbamoyl; Sulfamoyl; N-mono- or N, N-dialkylsulfamoyl each having 1 to 4 carbon atoms, such as N-methylsulfamoyl, N-ethylsulfamoyl, N-propylsulfamoyl, N-isopropylsulfamoyl or N-butylsulfamoyl, the alkyl radicals e.g. B. can be further substituted by hydroxy or sulfo; N- (β-hydroxyethyl) sulfamoyl; N, N-di (β-hydroxyethyl) sulfamoyl; N-phenylsulfamoyl optionally substituted by C ₁ -C ₄ -alkyl, C ₁ -C ₄ -alkoxy, halogen, carboxy or sulfo; Ureido; Hydroxy; Carboxy; Sulfomethyl or sulfo. The reactive dyes preferably contain at least one sulfo or sulfato group, in particular 1 to 6 such groups and preferably 2 to 6 such groups.

As reactive dyes come z. B. those of the formula

A ₁ -U (5)

in which A _{1 is} the radical of a monoazo, disazo, polyazo, metal complex azo, anthraquinone, phthalocyanine, formazan or dioxazine dye and U is a reactive radical, here and below for the reactive radicals U, in particular those indicated above Meanings and preferences apply. The radical A ₁ can also contain one or more further reactive groups U, identical or different from one another. The total number of reactive groups in the dyes is preferably 1 to 3, preferably 1 or 2 and in particular 2. U is preferably a reactive radical of the above formula (1a) or (2).

As reactive dyes also come z. B. those of the formula

considering where
R ₄ , R ₅ , R ₆ and R ₇ independently of one another are hydrogen or optionally substituted C ₁ -C ₄ -alkyl,
X ₁ 'and X ₂ ' are halogen,
B _{1 is} an aromatic or aliphatic bridge member or the radical of the formula -N (R ₅ ) -B ₁ -N (R ₆ ) - is a piperazine radical, and
A ₂ and A ₃ independently of one another have the meanings given _{above for A 1.}

The radicals R ₄ , R ₅ , R ₆ and R ₇ are straight-chain or branched as alkyl radicals. The alkyl radicals can be further substituted, e.g. B. by hydroxy, sulfo, sulfato, cyano or carboxy. The following radicals may be mentioned as examples: methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl or tert-butyl, and the corresponding radicals substituted by hydroxy, sulfo, sulfato, cyano or carboxy. Hydroxy, sulfo or sulfato, in particular hydroxy or sulfato and preferably hydroxy, are preferred as substituents.

_{R 4} , R ₅ , R ₆ and R ₇ are preferably hydrogen or C ₁ -C ₄ -alkyl, in particular hydrogen.

X ₁ 'and X ₂ ' are preferably, independently of one another, chlorine or fluorine, in particular fluorine.

As an aliphatic bridge member, B _{1 is} z. B. a C ₂ -C ₁₂ alkylene radical, in particular a C ₂ -C ₆ alkylene radical, which can be interrupted by 1, 2 or 3 members from the group -NH-, -N (CH ₃ ) - or especially -O- can and is unsubstituted or substituted by hydroxy, sulfo, sulfato, cyano or carboxy. Hydroxy, sulfo or sulfato, in particular hydroxy, are preferred as substituents of the _{alkylene radicals mentioned for B 1.}

As aliphatic bridge members for B ₁ continue z. B. C ₅ -C ₉ cycloalkylene radicals, such as, in particular, cyclohexylene radicals, into consideration. The cycloalkylene radicals mentioned can optionally be _{substituted by C 1} -C ₄ -alkyl, C ₁ -C ₄ -alkoxy, C ₂ -C ₄ -alkanoylamino, sulfo, halogen or carboxy, in particular by C ₁ -C ₄ -alkyl. Also mentioned as aliphatic bridge members for B _{1 are} methylene-cyclohexylene-methylene radicals which are optionally substituted in the cyclohexylene ring by C ₁ -C _{4 -alkyl.}

For the remainder of the formula -N (R ₅ ) -B ₁ -N (R ₆ ) - comes as piperazine residue z. B. a residue of the formula

into consideration.

As an aromatic bridge member, B _{1 is} z. _{B. C 1} -C ₆ alkylenephenylene or phenylene which is optionally substituted by C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, C ₂ -C ₄ alkanoylamino, sulfo, halogen or carboxy or a radical of the formula

wherein the benzene rings I and II are optionally _{substituted by C 1} -C ₄ -alkyl, C ₁ -C ₄ -alkoxy, C ₂ -C ₄ -alkanoylamino, sulfo, halogen or carboxy and L is the direct bond or a C ₂ -C ₁₀ alkylene radical, which can be interrupted by 1, 2 or 3 oxygen atoms, or L is a bridge member of the formula -CH = CH-, -N = N-, -NH-, -CO-, -NH-CO-, - Is NH-CO-NH-, -O-, -S- or -SO ₂ -. As an aromatic bridge member, B _{1 is} preferably phenylene, which can be substituted as indicated above. The aromatic bridge members mentioned for B ₁ are preferably unsubstituted or substituted by sulfo.

_{B 1} is preferably a C ₂ -C ₁₂ alkylene radical, which can be interrupted by 1, 2 or 3 members from the group -NH-, -N (CH ₃ ) - or -O- and is unsubstituted or by hydroxy, sulfo, Sulfato, cyano or carboxy is substituted; or
_{a C 5} -C ₉ cycloalkylene radical, C ₁ -C ₆ alkylenephenylene radical or phenylene radical optionally substituted by C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, C ₂ -C ₄ alkanoylamino, sulfo, halogen or carboxy ;
or B ₁ is a radical of the formula (7) in which the benzene rings I and II are optionally _{substituted by C 1} -C ₄ -alkyl, C ₁ -C ₄ -alkoxy, C ₂ -C ₄ -alkanoylamino, sulfo, halogen or carboxy and L is the direct bond or a C ₂ -C ₁₀ alkylene radical, which can be interrupted by 1, 2 or 3 oxygen atoms, or L is a bridge member of the formula -CH = CH-, -N = N-, -NH- , -CO-, -NH-CO-, -NH-CO-NH-, -O-, -S- or -SO ₂ -;
or the radical of the formula -N (R ₅ ) -B ₁ -N (R ₆ ) - is a piperazine radical of the formula

_{B 1} is particularly preferably a C ₂ -C ₁₂ alkylene radical which can be interrupted by 1, 2 or 3 members -O- and is unsubstituted or substituted by hydroxy, sulfo, sulfato, cyano or carboxy, or
a phenylene radical which is optionally substituted by C ₁ -C _{4 -alkyl, C 1} -C ₄ -alkoxy, C ₂ -C ₄ -alkanoylamino, sulfo, halogen or carboxy.

_{B 1} is very particularly preferably a C ₂ -C ₁₂ alkylene radical, in particular a C ₂ -C ₆ alkylene radical, which can be interrupted by 1, 2 or 3 -O- members and is unsubstituted or substituted by hydroxyl.

_{C 2} -C ₆ -alkylene radicals, in particular 1,3-propylene and 1,2-ethylene, are of particular importance as radicals B _1.

Of particular interest as reactive dyes of the formula (6) are those in which X ₁ 'and X ₂ ' are fluorine.

The following are preferably suitable monoazo, polyazo or metal complex azo dye radicals for A ₁ , A ₂ and A ₃ :
Mono- or disazo dye residues of the formula

DN = N- (MN = N) _u -K- (8) or

-DN = N- (MN = N) _u -K (9),

where D the remainder of a diazo component of the benzene or naphthalene series, M the remainder of a middle component of the benzene or naphthalene series, K the remainder of a coupling component of the benzene, naphthalene, pyrazolone, 6-hydroxypyridone (2) or acetoacetic acid arylamide series and u is the number 0 or 1, where D, M and K are common substituents in azo dyes, e.g. _{B. C 1} -C ₄ -alkyl or C ₁ -C ₄ -alkoxy, halogen, carboxy, sulfo, nitro, cyano, trifluoromethyl, sulfamoyl, carbamoyl, amino, ureido, hydroxy, carboxy, optionally further substituted by hydroxy, sulfo or sulfato, Sulfomethyl, C ₂ -C ₄ -alkanoylamino, optionally in the phenyl ring by C ₁ -C ₄ -alkyl, C ₁ -C ₄ -alkoxy, halogen or sulfo-substituted benzoylamino, optionally by C ₁ -C ₄ -alkyl, C ₁ -C ₄ -alkoxy, halogen, carboxy or sulfo-substituted phenyl, as well as fiber-reactive radicals can carry. The metal complexes derived from the dyes of the formulas (8) and (9) are also suitable, in particular 1: 1 copper complex azo dyes of the benzene or naphthalene series, in which the copper atom is attached to a metallizable group, such as, for. B. a hydroxyl group, is bonded on both sides in the ortho position to the azo bridge. If the dye radicals of the formula (8) or (9) carry a reactive radical, the meanings and preferences given above apply to this.

The dye residues of the formulas (8) and (9) are preferably those of the formulas

wherein (R ₈ ) _0-3 for 0 to 3 identical or different substituents from the group C ₁ -C ₄ -alkyl, C ₁ -C ₄ -alkoxy, C ₂ -C ₄ -alkanoylamino, ureido, sulfamoyl, carbamoyl, sulfomethyl , Halogen, nitro, cyano, trifluoromethyl, amino, hydroxy, carboxy and sulfo, (R ₉ ) _0-2 for 0 to 2 identical or different substituents from the group hydroxy, amino, N-mono-C ₁ -C ₄ - alkylamino, N, N-di-C ₁ -C ₄ -alkylamino, C ₂ -C ₄ -alkanoylamino and benzoylamino and
(U) _{0-2 represents} 0 to 2 identical or different reactive groups;

in which (R ₉ ) _0-2 and (U) _{0-2 have} the meanings given above;

wherein (R ₁₀ ) _0-3 and (R ₁₁ ) _0-3 independently of one another for 0 to 3 identical or different substituents from the group C ₁ -C ₄ -alkyl, C ₁ -C ₄ -alkoxy, halogen, carboxy and sulfo and (U) _{0-2 has} the meanings given above;

wherein R ₁₂ and R _{14 are} independently hydrogen, C ₁ -C ₄ alkyl or phenyl, and R _{13 is} hydrogen, cyano, carbamoyl or sulfomethyl;

wherein (R ₁₆ ) _{0-3 represents} 0 to 3 identical or different substituents from the group C ₁ -C ₄ -alkyl, C ₁ -C ₄ -alkoxy, halogen, amino, carboxy and sulfo,
(R ₁₅ ) _0-3 and (R ₁₇ ) _0-3 independently of one another are the above for (R ₈ ) ₀ . _{3 have} given meanings, and
(U) _{0-2 has} the meanings given above;

wherein (R ₁₅ ) _0-3 , (R ₁₇ ) _0-3 and (U) _{0-2 have} the meanings given above and (R ₁₈ ) _0-2 for 0 to 2 identical or different substituents from the group C ₁ - C ₄ alkyl, C ₁ -C ₄ alkoxy, halogen, carboxy, sulfo, hydroxy, amino, N-mono-C ₁ -C ₄ alkylamino, N, N-di-C ₁ -C ₄ alkylamino, C ₂ -C ₄ alkanoylamino and benzoylamino.

As the remainder of a formazan dye for A ₁ , A ₂ and A _3, z. B. those of the formula

are considered, in which (U) _{0-2 has} the meanings given above and the benzene _{rings contain no further substituents or by C 1} -C ₄ -alkyl, C ₁ -C ₄ -alkoxy, C ₁ -C ₄ -alkylsulfonyl, halogen or Carboxy are further substituted.

The remainder of a phthalocyanine dye is used for A ₁ , A ₂ and A _3, for example. B. those of the formula

into consideration in which Pc is the radical of a metal phthalocyanine, in particular the radical of a copper or nickel phthalocyanine,
W '-OH and / or -NR ₂₀ R ₂₀ ',
R ₂₀ and R ₂₀ 'independently of one another are hydrogen or C ₁ -C ₄ -alkyl which is optionally substituted by hydroxy or sulfo,
R _{19 is} hydrogen or C ₁ -C ₄ -alkyl,
A is a _{phenylene radical optionally substituted by C 1} -C ₄ -alkyl, halogen, carboxy or sulfo or a C ₂ -C ₆ -alkylene radical and
k is 1 to 3.

The remainder of a dioxazine dye is used for A ₁ , A ₂ and A _3, for example. B. those of the formula

in which A 'is a _{phenylene radical optionally substituted by C 1} -C ₄ -alkyl, halogen, carboxy or sulfo or a C ₂ -C ₆ -alkylene radical,
r, s, v and v 'independently of one another each denote the number 0 or 1 and
Z has the meaning given above.

The remainder of an anthraquinone dye is used for A ₁ , A ₂ and A _3, for example. B. those of the formula

in which G denotes a phenylene radical which is unsubstituted or _{substituted by C 1} -C _{4 -alkyl, C 1} -C ₄ -alkoxy, halogen, carboxy or sulfo, or a cyclohexylene, phenylenemethylene or C ₂ -C ₆ -alkylene radical.

The above dye residues of the formulas (10a) to (10f) and (11) to (14) preferably contain in each case at least one sulfo group, in particular 1 to 4 sulfo groups and preferably 1 to 3 sulfo groups.

Particularly suitable reactive radicals U are the reactive radicals mentioned above, the above preferences apply.

Dye residues of the formulas (10a) to (10f), (12) and (14), in particular der, are preferred Formulas (10a) to (10f) and (14) and preferably those of the formulas (10a) to (10f).

Reactive dyes of the formula are of particular importance

wherein
Z and Z 'independently of one another are vinyl or a radical of the formula -CH ₂ -CH ₂ -OSO ₃ H, B ₁ and B _{2 are} a C ₂ -C ₆ alkylene radical, in particular 1,3-propylene or 1,2-ethylene mean, and CuPhC is a copper phthalocyanine residue. Preferred here are B ₁ 1,3-propylene and B ₂ 1,2-ethylene. Z is preferably vinyl and for Z 'the meaning as a radical of the formula -CH ₂ -CH ₂ -OSO ₃ H is preferred.

As disperse dyes are suitable for the inventive method, for. B. such Dyes, which are listed in the Color Index, 3rd edition (3rd revision 1987 including additions and Amendments to No. 85) are described under "Disperse Dyes". There are for example carboxylic acid and / or sulfonic acid group-free nitro, amino, aminoketone, ketoninim, Methine, polymethine, diphenylamine, quinoline, benzimidazole, xanthene, oxazine or Coumarin dyes and in particular anthraquinone and azo dyes, such as mono- or Disazo dyes.

A preferred group a) of the disperse dyes are dyes of the formula

wherein
R ₂₁ halogen, nitro or cyano,
R ₂₂ hydrogen, halogen, nitro or cyano,
R ₂₃ halogen or cyano,
R _{24 is} hydrogen, halogen, C ₁ -C ₄ -alkyl or C ₁ -C ₄ -alkoxy,
R _{25 is} hydrogen, halogen or acylamino, and
R ₂₆ and R ₂₇ independently of one another are C ₁ -C ₄ -alkyl which is unsubstituted or substituted by hydroxy, acetoxy or phenoxy, or dyes of the formula

wherein
R _{28 is} hydrogen, phenyl or phenylsulfoxy, the benzene ring in the phenyl and phenylsulfoxy optionally being substituted _{by C 1} -C ₄ -alkyl or C ₁ -C _{4 -alkylsulfo,}
R ₂₉ amino or hydroxy,
R _{30 is} hydrogen or C ₁ -C ₄ alkoxy,
R _{31 is} hydrogen or the radical -OC ₆ H ₅ -SO ₂ -NH- (CH ₂ ) ₃ -OC ₂ H ₅ ,
R _{32 is} hydrogen, hydroxy or nitro and
R _{33 denotes} hydrogen, hydroxy or nitro, or dyes of the formula

wherein
R ₃₄ C ₁ -C ₄ -alkyl which is unsubstituted or substituted by hydroxy,
R ₃₅ C ₁ -C ₄ -alkyl,
R ₃₆ cyano,
R _{37 is} the remainder of the formula - (CH ₂ ) ₃ -O- (CH ₂ ) ₂ -OC ₆ H ₅ ,
R ₃₈ halogen, nitro or cyano, and
R _{39 denotes} hydrogen, halogen, nitro or cyano, or dyes of the formula

wherein
R ₄₀ C ₁ -C ₄ -alkyl,
R _{41 is} C ₁ -C ₄ -alkyl which is unsubstituted or _{substituted by C 1} -C ₄ -alkoxy and
R _{42 is} the radical -COOCH ₂ CH ₂ OC ₆ H ₅ and R _{43 is} hydrogen or
R _{42 is} hydrogen and R _{43 is} -N = NC ₆ H ₅ , or dyes of the formula

where the rings A ″ and B ″ are unsubstituted or substituted one or more times by halogen, or dyes of the formula

wherein
R _{44 is} C ₁ -C ₄ -alkyl which is unsubstituted or substituted by hydroxy, C ₁ -C ₄ -alkoxy or C ₁ -C ₄ -alkoxy-C ₁ -C ₄ -alkoxy, or dyes of the formula

Particularly preferred dyes of group a) in the process according to the invention are the dyes of the formulas

used.

Another group b) of preferred disperse dyes are dyes of the formula

wherein
R _{45 is} hydrogen or phenyl which is optionally substituted _{by C 1} -C _{4 alkyl,}
R _{46 is} hydroxy or amino which is optionally substituted _{by C 1} -C _{4 -alkyl, and}
R _{47 is} hydrogen, C ₁ -C ₄ alkoxy or phenoxy, or dyes of the formula

wherein
R ₄₈ and R _{49 are} C ₁ -C ₄ alkyl,
R ₅₀ halogen, and
R _{51 is} hydrogen, nitro or halogen, or dyes of the formula

Interesting dyes of this group b) are the dyes of the formulas

Particularly suitable pigment dyes for the process according to the invention are orga niche pigments, preferably those of the phthalocyanine, anthraquinone, perinone, indigo id, thioindigoid, dioxazine, diketopyrrolopyrrole, isoindolinone, perylene, azo, quinacridone and metal complex series, for example metal complexes of azo-. Azomethine or methine dyes, as well as classic azo dyes of the β-oxynaphthoic acid and acetoacetarylidrei he or metal salts of azo dyes. Examples of such pigment dyes are im Color Index, 3rd edition (3rd revision 1987 including Additions and Amendments up to No. 85) listed under "Pigments". Pigment dyes are of particular interest Monoazo, disazo, phthalocyanine and anthraquinone series.

Particularly preferred pigment dyes are dyes of the formula

wherein
R _{52 is} hydrogen, halogen, C ₁ -C ₄ -alkyl, C ₁ -C ₄ -alkoxy, nitro or cyano,
R ₅₃ hydrogen, halogen, nitro or cyano,
R _{54 is} hydrogen, halogen or phenylaminocarbonyl,
R _{55 is} hydrogen or hydroxy, and
R _{56 is} hydrogen or a radical of the formula

is, where
R ₅₇ hydrogen, C ₁ -C ₄ -alkyl or C ₁ -C ₄ -alkoxy,
R _{58 is} hydrogen, C ₁ -C ₄ alkoxy or halogen, and
R _{59 is} hydrogen, C ₁ -C ₄ -alkyl, C ₁ -C ₄ -alkoxy or halogen, or dyes of the formula

wherein
R ₆₀ and R ₆₁ are independently C ₁ -C ₄ alkyl and R ₆₂ and R _{63 are} halogen, or dyes of the formula

where the rings A, B, D and E are unsubstituted or monosubstituted or polysubstituted by halogen, or dyes of the formula

wherein
R ₆₄ C ₁ -C ₄ -alkyl,
R _{65 is} hydrogen, halogen, C ₁ -C ₄ -alkyl, C ₁ -C ₄ -alkoxy, nitro or cyano,
R ₆₆ hydrogen, halogen, nitro or cyano,
R _{67 are} hydrogen, halogen, C ₁ -C ₄ -alkyl, C ₁ -C ₄ -alkoxy, nitro or cyano, or dyes of the formula

where the rings A 'and B' are unsubstituted or substituted one or more times by halogen are.

The dyes of the formulas are of particular interest as pigment dyes

As acid dyes are suitable for the inventive method, for. B. such Dyes, which are listed in the Color Index, 3rd edition (3rd revision 1987 including additions and Amendments to No. 85) are described under "Acid Dyes". The anionic ones that can be used Dyes can belong to a wide variety of dye classes and, if appropriate contain one or more sulfonic acid groups. It is z. B. to Triphenylmethane dyes with at least two sulfonic acid groups, free of heavy metals Monoazo and disazo dyes each with one or more sulfonic acid groups and Monoazo containing heavy metals, namely copper, chrome, nickel or cobalt, Disazo, azomethine and formazan dyes, especially metallized dyes, which at a metal atom, two molecules of azo dye or one molecule of azo dye and one molecule Azomethine dye, especially those that act as mono- and / or ligands Disazo dyes and / or azomethine dyes and a chromium or as the central atom Contain cobalt ion, as well as anthraquinone dyes, especially 1-amino-4- arylaminoanthraquinone-2-sulfonic acids or 1,4-diarylamino- or 1-cycloalkylamino-4- arylaminoanthraquinone sulfonic acids.

As anionic acid dyes, for. B. Consider:

• a) triphenylmethane dyes of the formula
  wherein R ₇₁ , R ₇₂ , R ₇₃ and R _{74 are} independently of one another C ₁ -C ₄ alkyl and R _{75 is} C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy or hydrogen;
• b) mono- and disazo dyes of the formulas
  wherein R _{76 is} benzoylamino, phenoxy, chlorophenoxy, dichlorophenoxy or methylphenoxy, R _{77 is} hydrogen, benzoyl, phenyl, C ₁ -C ₄ -alkyl, phenylsulfonyl, methylphenylsulfonyl, and the substituents R _{78 are} independently hydrogen or a phenylamino or N-phenyl-N -methylaminosulfonyl;
  wherein the phenyl ring B ₁₀ can be substituted by halogen, C ₁ -C ₄ -alkyl and sulfo and R _{79 is} α-bromoacryloylamino;
  wherein R _{76 has} the meanings given above;
  
• c) 1; 2-metal complex dyes, such as the 1: 2 chromium complex dyes of the azo and azomethine dyes of the formula
  wherein R _{80 is} hydrogen, sulfo or phenylazo and R _{81 is} hydrogen or nitro, and the phenyl ring B ₁₀ can be substituted by halogen, C ₁ -C ₄ -alkyl and sulfo;
• d) 1: 2 metal complex dyes, such as the symmetrical 1: 2 chromium complex dyes of the azo dyes of the formulas
  wherein the phenyl ring B ₁₀ can be substituted by halogen, C ₁ -C ₄ alkyl and sulfo and R ₈₂ and R ₈₃ independently of one another hydrogen, nitro, sulfo, halogen, C ₁ -C ₄ alkylsulfonyl, C ₁ -C ₄ - Alkylaminosulfonyl and -SO ₂ NH ₂ ;
  wherein R ₈₄ is hydrogen, C ₁ -C ₄ alkoxycarbonylamino, benzoylamino, C ₁ -C ₄ - alkylsulfonylamino, phenylsulfonylamino, methylphenylsulfonylamino or halogen, R ₈₅ is hydrogen or halogen and R ₈₆ is C ₁ -C ₄ alkylsulfonyl, C ₁ -C ₄ alkylaminosulfonyl, phenylazo, sulfo or -SO ₂ NH _2, where the hydroxyl group in the benzene ring D ₁₀ in the o-position to the azo group is bonded to the benzene ring D _10;
  the symmetrical 1: 2 cobalt complexes of the azo dyes of the formulas
  wherein R _{87 is} the -OH or -NH ₂ group, R _{88 is} hydrogen or C ₁ -C ₄ -alkylaminosulfonyl and R _{89 is} nitro or C ₁ -C ₄ -alkoxy-C ₁ -C ₄ -alkylenaminosulfonyl;
  the asymmetrical 1: 2 metal complex dyes, such as the 1: 2 chromium complex dyes of the azo dyes of the formulas
  wherein one R ₉₀ substituent is hydrogen and the other is sulfo;
  wherein R _{81 is} hydrogen or nitro, the phenyl rings B ₁₀ can be substituted by halogen, C ₁ -C ₄ -alkyl and sulfo and R _{85 is} hydrogen or halogen;
  wherein the phenyl ring B _{10 can in} each case be substituted by halogen, C ₁ -C ₄ -alkyl and sulfo, R _{81 is} hydrogen or nitro, R _{91 is} hydrogen, methoxycarbonylamino or acetylamino and R _{86 is} C ₁ -C ₄ -alkylsulfonyl, C ₁ -C ₄ -alkylaminosulfonyl, phenylazo, sulfo or -SO ₂ NH ₂ ;
  1: 2-chromium complex dyes of the azo dyes of the formulas (106) and (107);
  1: 2-chromium mixed complexes of the azo dyes of the formulas (106) and (107);
  the copper complex of the formula
  wherein the benz rings D ₂₀ are substituted by sulfo or sulfonamido;
• e) Anthraquinone dyes of the formulas
  wherein R _{79 is} α-bromoacryloylamino, R _{92 is} independently hydrogen or C ₁ -C ₄ alkyl and R _{93 is} hydrogen or sulfo;
  wherein the substituents R ₉₄ independently of one another are cyclohexyl and the diphenyl ether radical, which can be substituted _{by sulfo and the radical -CH 2} -NH-R _{79 , where R 79 has} the meaning given; and
  wherein R _{79 is} α-bromoacryloylamino, R _{92 has} the meanings given under formula (113) and R _{95 is} C ₄ -C ₈ -alkyl.
• f) and as metal-free anionic dyes anthraquinone dyes of the formulas (116) or (117)
  wherein (R ₉₆ ) _1-5 for 1 to 5 identical or different substituents selected from the group C ₁ -C ₄ -alkyl, which is optionally _{substituted by C 2} -C ₄ -alkanoylamino, which in turn can be substituted in the alkyl group by halogen , or benzoylamino is substituted; C ₁ -C ₄ alkoxy; C ₂ -C ₄ alkanoylamino or C ₂ -C ₄ hydroxyalkylsulfamoyl; R ₉₇ C ₁ -C ₄ alkyl, optionally substituted by C ₁ -C ₄ alkyl-substituted C ₅ -C ₇ -cycloalkyl or optionally substituted by phenoxy, C ₁ -C ₄ alkyl or sulfo-substituted phenyl, wherein the phenoxy group itself optionally substituted -C-C, is substituted in the phenyl ring by C ₁ -C ₄ alkyl, C _{1 4} alkoxy ₁ halogen or sulfo, in particular C ₁ -C ₄ alkyl or sulfo; R ₉₈ and R ₉₉ independently of one another are C ₁ -C ₄ -alkyl, which is optionally _{substituted by C 2} -C ₄ -alkanoylamino, which in turn may be substituted by halogen in the alkyl group, or optionally in the phenyl ring by C ₁ -C ₄ - Alkyl, C ₁ -C ₄ alkoxy, halogen or sulfo, in particular C ₁ -C ₄ alkyl or sulfo, are substituted phenoxy; or
• g) monoazo dyes of the formulas (118), (119), (120), (121), (122) or (123)
  wherein R _{100 is} halogen, trifluoromethyl or
  denotes where R _{103 is} cyclohexyl and R _{104 is} C ₁ -C ₄ alkyl, or the radicals R ₁₀₃ and R ₁₀₄ together with the nitrogen atom connecting them form an azepinyl ring; R _{101 denotes} hydrogen or halogen and R ₁₀₂ denotes hydrogen or phenoxy which is optionally substituted in the phenyl ring by halo;
  wherein R _{105 is} hydrogen, halogen or sulfo; R _{106 is} hydrogen, halogen, optionally phenoxy or phenoxysulfonyl substituted in the phenyl ring by C ₁ -C ₄ -alkyl, C ₁ -C ₄ -alkoxy or halogen, or a radical of the formula
  where R ₁₁₀ is phenyl optionally substituted by C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, halogen or sulfo, R _{111 is} hydrogen or C ₁ -C ₄ alkyl and X _{50 is} halogen; R _{107 is} hydroxy or amino; and R ₁₀₈ and R _{109 are} independently hydrogen or halogen;
  wherein R ₁₁₂ and R ₁₁₃ independently of one another are hydrogen, C ₁ -C ₄ -alkyl, C ₁ -C ₄ -alkoxy, halogen or C ₂ -C ₄ -alkanoylamino and preferably hydrogen or C ₁ -C ₄ -alkyl, R ₁₁₄ phenyl optionally substituted by C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, halogen or C ₂ -C ₄ alkanoylamino, preferably unsubstituted or substituted by C ₁ -C ₄ alkyl;
  wherein R _{115 is} hydrogen or C ₁ -C ₄ alkyl, R _{116 is} hydrogen or phenylsulfonyl optionally substituted in the phenyl ring by C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, halogen or C ₂ -C _{4 alkanoylamino,} preferably unsubstituted phenylsulfonyl;
  wherein R _{117 is} hydrogen, C ₁ -C ₄ -alkyl, C ₁ -C ₄ -alkoxy, halogen or optionally in the phenyl ring by C ₁ -C ₄ -alkyl, C ₁ -C ₄ -alkoxy, sulfo, halogen or C ₂ - C ₄ alkanoylamino substituted phenoxy, preferably unsubstituted phenoxy or phenoxy substituted by C ₁ -C ₄ alkyl or halogen, and
  R ₁₁₈ benzoyl optionally substituted in the phenyl ring by C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, sulfo or halogen, preferably unsubstituted benzoyl, or optionally C _{2 substituted in the alkyl group by hydroxy or C 1} -C _{4 alkoxy} -C ₄ alkanoyl and preferably unsubstituted C ₂ -C ₄ alkanoyl, such as. B. acetyl; or
  wherein R _{119 is} hydrogen, C ₁ -C ₄ -alkyl, C ₁ -C _{4 -alkoxy, halogen or C 2} -C ₄ -alkanoylamino which is optionally substituted in the alkyl group by hydroxy, C ₁ -C ₄ -alkoxy or halogen; R ₁₂₀ is phenyl optionally substituted by C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, sulfo or halogen, preferably unsubstituted phenyl, and R _{121 is} hydrogen or C ₁ -C ₄ alkyl;
  or a disazo dye of the formulas (124) or (125)
  wherein A ₂₀ and A _{21 are} radicals of the formula (124a)
  in which R ₁₀₇ , R ₁₀₈ and R ₁₀₉ independently of one another have the meanings given above; or
  

Suitable metal-free anionic acid dyes are, for example, CI Acid Yellow 79, 110 and 246; CI Acid Orange 67 and 94; CI Acid Red 127, 131, 252 and 361; CI Acid Green 40: 1 and CI Acid Blue 225, 239, 260, 277 and 324 and in particular the dyes of the formulas

In the acid dyes of the formulas (100) to (124), the radicals R ₇₁ to R _{121 have} the following meanings:
Alkyl groups having 1 to 4 carbon atoms, such as methyl, ethyl, propyl, isopropyl or butyl, the alkyl radicals, for. B. can be further substituted by hydroxyl, sulfo or sulfato; Alkoxy groups having 1 to 4 carbon atoms, such as methoxy, ethoxy, propoxy, isopropoxy or butoxy, the alkyl radicals, for. B. can be further substituted by hydroxyl, sulfo or sulfato; Halogen, such as fluorine, bromine or, in particular, chlorine; C ₁ -C ₄ -alkylsulfonyl, such as methylsulfonyl and ethylsulfonyl; C ₁ -C ₄ -alkylaminosulfonyl, such as methylaminosulfonyl and ethylaminosulfonyl; C ₁ -C ₄ alkoxycarbonylamino, such as methoxycarbonylamino and ethoxycarbonylamino; C ₁ -C ₄ -alkoxy-C ₁ -C ₄ -alkylenaminosulfonyl, such as methoxyethyleneaminosulfonyl; C ₂ -C ₄ alkanoylamino, such as propionylamino; C ₂ -C ₄ hydroxyalkylsulfamoyl, such as β-hydroxyethylsulfamoyl; C ₅ -C ₇ cycloalkyl, such as cyclopentyl and cyclohexyl.

Disperse dyes are preferably used in the process according to the invention or reactive dyes, in particular disperse dyes of groups a) and b), preferably those of group a).

The acid dyes, reactive dyes, disperse dyes and pigments mentioned dyes are known or can in analogy to known manufacturing processes, such as Diazotization, coupling, addition and condensation reactions can be obtained.

The acid dyes and reactive dyes used in the inks should be preferred be low in salt, d. H. a total salt content of less than 0.5% by weight, based on the weight of the dyes. Acid or reactive dyes, which, due to their Production and / or the subsequent addition of coupage agents with higher salt contents have, e.g. B. by membrane separation processes such as ultrafiltration, reverse osmosis or dialysis, desalinated.

The inks preferably contain a total content of dyes of 1 to 35% by weight, in particular 1 to 30% by weight and preferably 1 to 20% by weight, based on the Total weight of the ink. The lower limit here is a limit of 2.5% by weight, in particular 5% by weight and preferably 10% by weight, preferably.

Inks which have a viscosity are preferred for the method according to the invention from 1 to 40 mPa.s (millipascal second), in particular 1 to 20 mPa.s and preferably 1 to 10 mPa.s. Of particular importance are inks which have a viscosity of 2 to 5 mPa.s. Also of importance are inks which have a viscosity of 10 to 30 mPa.s.

The inks can include for the purpose of adjusting viscosity, natural or thickening agents of synthetic origin.

Examples of thickeners are commercially available alginate thickeners, starch ethers or locust bean gum ether, especially sodium alginate on its own or in the Mixture with modified cellulose, in particular with preferably 20 to 25 Percent by weight of carboxymethyl cellulose, called. As synthetic thickeners are further z. B. those based on poly (meth) acrylic acids or poly (meth) acrylamides called.

The inks contain such thickeners e.g. B. in an amount of 0.01 to 2 wt .-%, in particular 0.01 to 1 wt .-% and preferably 0.01 to 0.5 wt .-%, based on the Total weight of the ink.

Furthermore, the inks can contain buffer substances, such as. B. borax, borate or citrate. as Examples are borax, sodium borate, sodium tetraborate and sodium citrate. she are in particular in amounts of 0.1 to 3 wt .-%, especially 0.1 to 1 wt .-%, based on the total weight of the ink, used to maintain a pH of e.g. B. 4 to 10, preferably 5 to 8.

As further additives, the inks can be surfactants, redispersants or humectants contain.

The commercially available anionic or nonionic surfactants are used as surfactants costume. As a redispersant z. B. to mention betaine. Used as a humectant preferably a mixture of Na lactate (advantageously in the form of a 50 to 60% aqueous solution) and glycerine and / or propylene glycol in amounts of preferably 0.1 to 30% by weight, in particular 2 to 20% by weight, in the ink used used.

If desired, the inks can also contain acid donors such as butyrolactone or Sodium hydrogen phosphate, preservatives, fungal and / or bacterial growth inhibiting substances, foam suppressants, sequestering agents, emulsifiers, Contain water-insoluble solvents, oxidizing agents or deaerating agents.

Particularly suitable preservatives are formaldehyde-releasing agents, such as. B. paraformaldehyde and trioxane, especially aqueous, about 30 to 40 weight percent formaldehyde solutions, as a sequestering agent z. B. sodium nitrilotriacetic acid, ethylenediaminetetraacetic acid sodium, especially sodium polymethaphosphate, especially sodium hexamethaphosphate, as emulsifiers, especially adducts of an alkylene oxide and a fatty alcohol, especially an adduct of oleyl alcohol and ethylene oxide, as water-insoluble solvents, high-boiling, saturated hydrocarbons, especially Paraf fine with a boiling range of about 160 to 210 ° C (so-called mineral spirits), as Oxida tion agent z. B. an aromatic nitro compound, especially an aromatic mono- or dinitrocarboxylic acid or sulfonic acid, which is optionally present as an alkylene oxide adduct, in particular a nitrobenzenesulfonic acid and as a venting agent z. B. high-boiling solvents, especially turpentine oils, higher alcohols, preferably C ₈ - to C ₁₀ alcohols, Ter penalcohols or venting agents based on mineral and / or silicone oils, in particular re commercial formulations from about 15 to 25 percent by weight of a mineral and Silicone oil mixture and about 75 to 85 percent by weight of a C ₈ alcohol such as. B. 2-ethyl-n-hexanol. These are usually used in amounts of 0.01 to 5% by weight, in particular 0.01 to 5% by weight, based on the total weight of the ink.

Furthermore, the inks can be anionic copolymers, nonionic block polymers or Contain dispersants. This applies in particular to the at least one pigment dye or preferably inks containing at least one disperse dye.

Particularly suitable anionic copolymers for the inks are copolymers based on acrylic acid, methacrylic acid or maleic acid. Of these, preference is given to those which are obtained by polymerizing acrylic and / or methacrylic acid and one or more copolymerizable monomers selected from the group consisting of maleic acid, N-vinylformamide, N-vinyl acetamide, allylamine or diallylamine derivative, N-vinylpyrrolidone, N- Vinyl-N-methyl-formamide, N-vinyl-N-methyl-acetamide, N-vinyl-N-ethyl-acetamide, vinyl acetate, vinyl propionate, acrylonitrile, styrene, methacrylonitrile, acrylamide, methacrylamide and N-mono / NN-di- C ₁ -C ₁₀ alkyl (meth) acrylamide are available.

Particularly preferred are anionic copolymers which are obtained by copolymerization of Ac ryl or methacrylic acid and styrene are available.

Acrylic and methacrylic acid-styrene copolymers with a are very particularly preferred Molecular weight from 3,000 to 16,000, especially from 3,000 to 10,000.

Particularly suitable non-ionic block polymers for the inks are alkylene oxide Condensation products such as B. Ethylene oxide adducts with polypropylene oxide (so-called EO PO block polymers) and propylene oxide adducts with polyethylene oxide (so-called reverse EO-PO block polymers), and block polymers, which are formed by the addition of styrene to Polypropylene and / or polyethylene oxide are available. Ethylene propylene oxide are preferred Block polymers with molecular weights between 2,000 and 20,000, especially between 8,000 and 16,000, and an ethylene oxide content in the total molecule of 30 to 80%, in particular from 60 to 80%.

Particularly suitable dispersants are anionic dispersants from the group of

• (Ba) acidic esters or their salts of alkylene oxide adducts of the formula
  wherein
  X is the acid residue of an inorganic, oxygen-containing acid, such as. B. Schwefelsäu re or preferably phosphoric acid, or the remainder of an organic acid, and
  YC ₁ -C ₁₂ -alkyl, aryl or aralkyl, "alkylene" stands for the ethylene radical or propylene radical, and
  m is 1 to 4, and n is 4 to 50,
• (bb) polystyrene sulfonates,
• (bc) fatty acid taurides,
• (bd) alkylated diphenyl oxide mono- or disulfonates,
• (be) sulfonates of polycarboxylic acid esters,
• (bf) with an organic dicarboxylic acid, or an inorganic polybasic acid Adduct of 1 to 60, preferably 2 to 30, converted into an acidic ester Moles of ethylene oxide and / or propylene oxide on fatty amines, fatty amides, fatty acids or fatty alcohol get each with 8 to 22 carbon atoms or tri- to hexavalent alkanols with 3 to 6 Carbon atoms,
• (bg) lignosulfonates,
• (bh) naphthalene sulfonates, and
• (bi) formaldehyde condensation products.

Ligninsulfonates (bg) are primarily those ligninsulfonates or their alkali metal salts ze used, the content of sulfo groups does not exceed 25 wt .-%. Are preferred Lignosulfonates with a content of 5 to 15% by weight of sulfo groups.

As formaldehyde condensation products (bi) z. B. Condensation products of Lig ninsulfonaten and / or phenol and formaldehyde, condensation products of formaldehyde with aromatic sulfonic acids, such as B. Condensation products of ditolyl ether sulfonates and formaldehyde, condensation products of naphthalenesulfonic acid with formaldehyde and / or naphthol or naphthylaminosulfonic acids with formaldehyde, condensation products of phenolsulphonic acids and / or sulphonated dihydroxydiphenylsulphone and Phe nols or cresols with formaldehyde and / or urea and condensation products of Diphenyloxide-disulfonic acid derivatives with formaldehyde into consideration.

Preferred as (bi) are

• - Condensation products of ditolyl ether sulfonates and formaldehyde as z. Am US-A-4,386,037 are described,
• - Condensation products of phenol and formaldehyde with lignosulfonates, as they are, for. Am US-A-3,931,072 are described,
• - Condensation products of naphthol- (2) -sulfonic acid-6, cresol, sodium bisulfite and For maldehyde [cf. FIAT Report 1013 (1946)], and
• - Condensation products of diphenyl derivatives and formaldehyde, as they are, for. Am US-A-4,202,838.

The compound of the formula is particularly preferred as (bi)

wherein
X the direct bond or oxygen,
A is the remainder of an aromatic compound which is bonded to the methylene group by means of a ring carbon atom,
M is hydrogen or a salt-forming cation, e.g. B. an alkali metal, alkaline earth metal or ammonium and
n and p are, independently of one another, a number from 1 to 4.

The compound of the formula is very particularly preferred as (bi)

wherein (SO ₃ Na) _{1-3 means} an average degree of sulfonation of 1 to 3.

The above dispersants are known or can be used in analogy to known compounds genes are produced by well-known processes.

The total content of anionic copolymer, nonionic block polymer and disperser yeast in the inventive ink is z. B. 3 to 9 wt .-% based on the Ge total weight of the ink.

The ratio: anionic copolymer: nonionic block polymer: dispersant in the finished ink can vary widely, e.g. B. 1.5: 0.5: 1; 1: 0.5: 1.5; 1: 1: 1; 1: 0: 1; 1: 1: 0; 1: 0: 0; 0: 1: 1 or 0: 0: 1.

Preferred are inks which contain anionic copolymer and nonionic block polymer or anionic copolymer and dispersant or nonionic block polymer and Contain dispersants.

Particularly preferred are inks which contain anionic copolymer, nonionic block poly contain mer and dispersants.

The inks preferably contain N-methyl-2-pyrrolidone, diethylene glycol, glycerol or in particular 1,2-propylene glycol, usually in an amount of 2 to 30% by weight, in particular 5 to 30% by weight and preferably 5 to 25% by weight, based on the Total weight of the ink.

The inks containing acid dyes or reactive dyes can also be used Solubilizers, such as. B. ε-caprolactam included.

The inks can be used in the usual way by mixing the individual ingredients in the desired amount of water can be produced.

The inventive method for printing textile fiber materials can with per se known inkjet printers suitable for textile printing will.

In the case of the inkjet printing process, individual drops of the ink are controlled from sprayed onto a substrate using a nozzle. The continuous Ink-jet method as well as the drop on demand method are used. In the case of continuous Ink-jet method, the drops are generated continuously, not being for printing required drops are diverted into a collecting container and recycled. In case of Drop on demand method, on the other hand, creates and prints drops as required; d. H. drops are only created when this is necessary for printing. the Generation of the drops can, for. B. by means of a piezo inkjet head or by means of thermal Energy (bubble jet). Pressure is preferred for the process according to the invention by means of a piezo inkjet head. It is also preferred for the method according to the invention printing using the continuous ink-jet method.

After printing, the fiber material is advantageously dried, preferably at temperatures up to 150 ° C, in particular 80 to 120 ° C, and then a heat treatment process to complete the print, or the dye to fix.

The heat treatment can e.g. B. by a hot dwell process, a thermal insulation process or preferably carried out by a steaming process.

In the steaming process, the printed fiber material is z. B. a treatment in a steamer with possibly superheated steam, expediently a temperature of 95 to 180 ° C., advantageously in saturated steam. In the case of fixation of the fiber material by dry heat (thermosetting) this z. B. at a temperature of 150 to 230 ° C, especially 190 to 230 ° C.

The printed fiber material is then usually mixed with water in the usual way washed out to remove unfixed dye.

In particular, fiber materials containing hydroxyl groups are used as textile fiber materials into consideration. Cellulose-containing fiber materials are preferred, which are wholly or partially made of Cellulose. Examples are natural fiber materials such as cotton, or linen Hemp and regenerated fiber materials such as B. viscose and lyocell. Particularly viscose or preferably cotton are preferred here. This is preferably done Printing of these fiber materials with acid dyes or, in particular, reactive dyes containing inks.

Other fiber materials are such. B. wool, silk, polyvinyl, polyacrylonitrile, polyamide, Called aramid, polypropylene, polyester or polyurethane. Natural ones are preferred here or synthetic polyamide fiber materials, especially those containing polyester Fiber materials. Such materials are used as polyester-containing fiber materials Consider that consist entirely or partially of polyester. examples are Cellulose ester fibers, such as. B. Cellulose-2½-acetate fibers and triacetate fibers, and especially linear polyester fibers, which are optionally also acid-modified, which z. B. by condensation of terephthalic acid with ethylene glycol or of isophthalic acid or terephthalic acid with 1,4-bis (hydroxymethyl) cyclohexane can be obtained, as well as fibers from copolymers of terephthalic and isophthalic acid with ethylene glycol. Are suitable further polyester-containing mixed fiber materials, d. H. Blends of polyester and others Fibers. These fiber materials are preferably printed with disperse dyes containing inks, in particular the above-mentioned inks of group a) and b).

The fiber materials mentioned are preferably flat textile fabrics, knitted fabrics or lanes.

The fiber materials are preferably those which have a low Have inherent stability and / or are permeable to the ink during printing. These are z. B. highly stretchable and finely knitted or woven fiber materials that only a small thickness, such as. B. up to 0.5 cm, in particular 0.3 cm and preferably 0.1 cm exhibit. Examples are georgette and stretch. Also come as for the ink-permeable fiber materials still coarse-meshed fiber materials into consideration.

The two-dimensional medium lying close to the fiber material thus serves, on the one hand, for Stabilization of the fiber material and on the other hand should be prevented that only a small part of the ink remains on the fiber material. A stabilization of the Fiber material enables uniform and reproducible printing of the Fiber material, even when using the usual equipment for ink-jet printing. Especially in the case of coarse-meshed or highly stretchable fiber materials, fine knitted or woven fiber materials of only a small thickness only one remains less of the ink on the fiber material. This can be done by using a two-dimensional, closely adjacent to the fiber material medium can be prevented, so that almost all of the ink is used for printing.

As such a medium, it is preferable to use one which is substantially impermeable to the ink Medium used. An example of this is paper. This is advantageous Medium on the side with which it is brought into contact with the fiber material with a means by which the paper adheres to the fiber material. The paper is preferably on the side with which it is in contact with the fiber material is brought, self-adhesive. The paper can only be used in places or also be provided all over with an adhesive.

According to a preferred embodiment of the present invention takes place before Printing with inks containing reactive dyes is a pretreatment of the Fiber material, in which the fiber material to be printed is first treated with an aqueous Treated alkaline liquor and the treated fiber material optionally dries.

The aqueous alkaline liquor contains at least one of the usual bases, which in con conventional reactive printing processes are used to fix the reactive dyes. The base is z. B. in an amount of 10 to 100 g / l liquor, preferably 10 to 50 g / l Fleet. As a base, for example, sodium carbonate, sodium hydroxide, Disodium phosphate, trisodium phosphate, sodium acetate, sodium propionate, sodium hydrogen carbonate, aqueous ammonia or alkali donors, such as. B. sodium chloroacetate or sodium formate into consideration. Preferably sodium hydrogen carbonate is used, sodium carbonate or a mixture of water glass and sodium carbonate is used. The pH the alkaline liquor is usually 7.5 to 13.5, preferably 8.5 to 12.5. the Aqueous alkaline liquor can contain other additives in addition to the bases, e.g. B. Hydrotropic Agents or thickeners. As a hydrotropic z. B. urea, Dicyandiamide or ε-caprolactam into consideration. The hydrotropic agents are z. B. in a Amount of 20 to 300 g / l liquor, preferably 50 to 150 g / l liquor, are used. Preferred urea is used as a hydrotropic agent. As a thickener z. B. the mentioned above. The corresponding alginates are preferred here. the Thickeners are z. B. used in amounts of 2 to 40 g / l. Preferably the fiber material is dried after the above pretreatment.

However, the aqueous alkaline liquor can also be used simultaneously or before or after Printing can be applied with the ink containing the reactive dye.

Some preferred embodiments of the method according to the invention are to be explained with reference to FIGS . 1 and 2a to 2c of the accompanying drawings.

In Fig. 1 an arrangement is shown, wherein the fibrous material are to be printed 1 and at the same time by a carrier 4, the paper 2, which serves as a medium is unwound from a support 3. After passing the guide roller 5 , the fiber material, which is covered on the lower side by the paper, is printed by means of the print head 7. The printed material is then guided over a further guide roller 5. By means of a separator 6 , the fiber material 1 and the paper 2 are separated from one another and wound onto two different carriers 3 '(for the fiber material) and 4 ' (for the paper). This is an ongoing process. The paper and the fiber material to be printed expediently have the same width, so that the fiber material is completely covered by the paper on the lower side during printing.

In FIGS. 2a to 2c, arrangements are shown according to which a step-by-step procedure is to be explained.

In FIG. 2a, the fiber material 1 to be printed is unwound from a carrier 3 and, at the same time, the paper 2 , which serves as a medium, is unwound from a carrier 4. After passing the guide rollers 5 , the fiber material 9 , which is covered on the lower side by the paper, is wound onto a carrier 8.

In FIG. 2b, the fiber material 9 , which is covered on the lower side by the paper, is unwound from the carrier 8 , guided over a guide roller 5 , and printed on by means of the print head 7. The printed material 9 ′ is then guided over a further guide roller 5 and wound onto a carrier 10.

In FIG. 2c, the printed fiber material 9 ′, which is covered on the lower side by the paper, is unwound from the carrier 10. After passing the guide roller 5 , the printed fiber material 1 and the paper 2 are separated from one another by means of a separator 6 and wound onto two different carriers 12 (for the fiber material) and 11 (for the paper).

A particularly preferred embodiment is characterized in that the fiber material 1 to be printed is unwound from a carrier 3 and at the same time the flat medium from a carrier 4 and brought together in such a way that the fiber material on the side facing away from the print head is covered by the flat medium which Fiber material is printed and the fiber material 1 and the flat medium are separated from one another after printing and optionally wound onto two different carriers 3 'and 4 '.

Another particularly preferred embodiment is characterized in that the fiber material 9 to be printed, which is already covered on one side by the flat medium, is unwound from a carrier 8 , and the fiber material is printed and optionally wound onto a carrier 10 .

According to a variant of the inventive method is a on the back with a means, in particular Paper, covered fiber material with one of those commonly used in the home Ink-jet printer printed and then fixed. In particular, the Find corresponding commercially available color printers (e.g. those from the companies Hewlett-Packard, Canon, Epson, Encad or Mimaki). The fixation is preferably carried out by a Heat treatment, e.g. B. at a temperature of 120 to 180 ° C, for the duration of for example 0.5 to 5 minutes. The fixation can here for example by means of a Hot press. Alternatively, the fixation can also be done in a simple manner by means of a Iron. The fiber material to be printed here preferably only has smaller dimensions and in particular exceeds the dimensions of the DIN A3 format not. The paper to be used is preferably one which has one side is self-adhesive and preferably the same format as that has printing fiber material. Such a method is particularly preferred for the Printing with inks containing reactive dyes. As fiber materials are preferably silk or especially cellulosic fiber materials are used. Preferably, a fiber material is used which is previously specified as above was pretreated with an alkaline liquor. One such method of printing is also advantageously suitable for the imaging described below.

Particularly preferred is a process in which one uses an alkaline liquor treated and covered on the back with an agent, in particular paper Fiber material with one of the ink-jet printers commonly used in the home printed and then fixed the print, the fiber material to be printed from is only smaller and in particular the dimensions of the A3 format are not exceeds. Cellulosic fiber material is preferably used here Fiber material and preferably at least one reactive dye as the ink containing ink.

According to the method according to the invention, the fiber material to be printed and the two-dimensional medium, usually at the same time, moved past the print head. Here fiber material and medium are usually transported continuously. The printhead itself can usually only be perpendicular with respect to this transport direction move.

The inks containing a pigment are preferably applied to the fiber material together with a binder, it being possible for the ink to be applied simultaneously with the binder or before or after the binder. As a binder z. B. Acrylpoly merisate such. B. poly (meth) acrylic acid esters, poly (meth) acrylamide or the mixed polymers risate of (meth) acrylic acid esters or (meth) acrylamide with suitable comonomers, such as. B. maleic, fumaric, itaconic, mesaconic, citracon, vinylacetic, vinyloxyacetic, vinylpropion, croton, aconite, allyl vinegar, allyloxyacetic, allylmalon, 2-acrylamido-2-methylpropane sulfon , Glutaconic or allyl succinic acid or with esters of these acids, N-vinylpyrrolidone, N-vinylformamide, N-vinylacetamide, (meth) acrolein, N-vinyl-N-methylacetamide, vinylcaprolac tam, styrene derivatives or vinylphosphonic acid; Polyamide derivatives; Synthetic resin dispersions; Copolymers based on vinyl; Diamide-aldehyde precondensates; Copolymers containing N-vinyllactam or polymers based on butadiene, into consideration. Particularly suitable comonomers are the esters of the abovementioned acids with C ₁ -C ₆ alcohols, such as. B. methyl, ethyl, isopropyl or butyl alcohol.

Crosslinkers can also be used for printing with binders. These can be applied to the fiber material at the same time as the binders or before or after the binders. Suitable crosslinkers are, for. B. water-soluble melamine, formaldehyde-melamine and formaldehyde-urea resins or precondensates, such as trimethylolmelamine, hexamethylolmelamine or dimethylolurea, or water-soluble formaldehyde (pre) condensation products with formamide, thiourea, guanidine, cyanamide, dicyandiamide such as organic sulfonates and / or water-soluble. B. sodium salt of naphthalenesulfonic acid, or glyoxalurea derivatives, such as. B. the compound of formula

and especially N-methylol derivatives of nitrogen-containing compounds such. B. given if etherified melamine / formaldehyde condensation products or N-methylol urea Links.

Examples of the optionally etherified melamine / formaldehyde condensation products are the compounds of the formulas

The optionally etherified N-methylol urea compounds are, for. B. to possibly subsequently etherified reaction products of formaldehyde with urine substance or urea derivatives, with as urea derivatives, for example, cyclic ethylene or Propylene ureas, which in the alkylene group also have substituents such as hydroxyl groups may contain, urons or optionally substituted triazone resins are possible.

Examples of corresponding N-methylol urea compounds are optionally modified N-methylol-hydroxyethylene urea products, eg. B. the compounds of the formula

or methylolation pro products based on propylene urea or ethylene urea / melamine.

Preferred crosslinkers are optionally modified N-methylol-hydroxyethylene urea Compounds, methylolation products based on propylene urea or ethylene urea substance / melamine and in particular optionally etherified melamine / formaldehyde condensers station products. It can also be mixtures of two or more different what soluble crosslinkers can be used, e.g. B. one of an unsheathed and one only partially etherified melamine / formaldehyde condensation product existing Mi schung. If desired, crosslinking catalysts can also be used.

As crosslinking catalysts for the inventive method, for. B. all übli chormally used as a catalyst for the crease and crinkle-free finish in question, as they are from the textile auxiliaries catalog 1991, Konradin Verlag R. Kohlhammer, Lein felden-Echterdingen 1991, are known. Examples of suitable crosslinking catalysts are inorganic acids, e.g. B. phosphoric acid; Lewis acids, e.g. B. zinc chloride, zirconium oxychloride, NaBF ₄ , AlCl ₃ , MgCl ₂ ; Ammonium salts, e.g. B. ammonium sulfate, ammonium chloride; or hydrohalides, especially hydrochlorides of organic amines, e.g. B. CH ₃ -CH ₂ -CH ₂ -NH-CH ₃ . HCl. The use of ammonium salts or magnesium-containing Lewis acids and in particular of ammonium chloride or magnesium chloride is preferred.

When printing on the fiber material, the pigment, the binder and optionally other aids, such as. B. the crosslinker, on the fiber material upset. The application of the binder and the auxiliaries usually takes place in the form of aqueous preparations.

The fiber material is advantageously dried, preferably after printing at temperatures up to 150 ° C, in particular 80 to 120 ° C, and then a heat treatment process to complete the print, or the dye to fix.

The heat treatment can be carried out by a hot dwell process, a thermosoling process or preferably by a steaming process (HT fixation).

In the steaming process, the printed fiber material is treated in a steam fer with optionally superheated steam, expediently at a temperature of 95 to 210 ° C, advantageously 100 to 180 ° C.

The printed fiber material is preferably in the HT fixation for 2 to 5 minutes th treated at 150 to 170 ° C.

The completion of the prints by the so-called thermosoling process can be done after a or without intermediate drying, e.g. B. be carried out at a temperature of 100 to 210 ° C. Before Preferably, the thermal insulation takes place at a temperature of 120 to 210 ° C, in particular more 140 to 180 ° C. Depending on the temperature, the thermal insulation can last from 20 seconds to 5 Minutes, preferably 30 seconds to 4 minutes. Usually the Thermal insulation carried out for 1 to 2 minutes at 190 to 210 ° C.

Following the printing process, the printed fiber material can be used in the usual way washed to remove unfixed dye. To do this, one treats that Fiber material, for example, at 40 ° C to boiling temperature with water, which optionally a soap or a synthetic detergent can be added.

Both the ink-jet printing and the subsequent drying and fixing can be used can also be performed in a single step. This means in particular that these steps are carried out continuously. I.e. that devices for the ink-jet printing, the drying and the fixing are attached, through which the to printing fiber material is continuously moved through it. The apparatus for the Ink-jet printing, drying and fixing can also be done in a single machine be united. The fiber material is continuously transported through this machine and is then finished after leaving this machine. The drying can take place here, for. B. by means of thermal energy (such as specified above) or in particular by means of infrared radiation (IR). The fixation can be done here, for. B. by means of ultraviolet radiation (UV) or by means of thermal energy (such as specified above). Of course, the Ink-jet printing is done separately and drying and fixing are as stated above continuously, e.g. B. in a single machine executed.

With the above printing process it is possible to print the fiber materials in one single nuance as well as in different nuances. Does that happen Printing in one shade, the printing of the fiber material over the entire surface or can also be made with a pattern. Naturally, the use of a single one is sufficient for this Ink; however, the desired nuance can also be achieved by printing with several inks different nuances can be created. Should a print on the fiber material be created, which has several different nuances, so takes place the printing of the fiber material with several inks, which in each case the desired Nuance or printed to create that nuance (e.g. in that inks with different nuances on top of each other on the fiber material printed and thus result in the nuance to be achieved).

Another interesting embodiment relates to so-called imaging. Here is a template, d. H. an image which is to be adjusted with the pressure, digitized, z. B. by means of a video camera or a scanner. The digitized image is sent to a Computer, which then uses an ink-jet printer to transfer the image to the Fiber material prints. Of course, the digitized image can already be in the Computer stored so that digitization is not necessary. So can a to be printed Picture z. B. have been created on the computer with graphics software. With the one to be printed Image can be z. B. also about letters, numbers, words, any pattern or also act complex different colored images. Different colored images can e.g. B. by Use of multiple inks can be created with different nuances from each other.

The prints obtainable by the process according to the invention have good general properties authenticity on; they have z. B. a high fiber-dye bond stability both in the acid ren as well as in the alkaline range, good light fastness, good wet fastness, such as Fastness to water, washing, seawater, dyeing and perspiration, good fastness to chlorine, Rubbing fastness, ironing fastness and pleating fastness as well as sharp contours and a high Color strength. The printing inks used are characterized by good stability and good visco physical properties.

The following examples serve to illustrate the invention. Inside are the tempera Temperatures are given in degrees Celsius, parts are parts by weight and the percentages relate are based on percentages by weight, unless otherwise noted. Parts by weight are related to Volu parts in the ratio of kilograms to liters.

example 1

• a) A georgette fabric made of cotton is mixed with a liquor containing 40 g / l Sodium carbonate and 100 g / l urea, padded (liquor uptake 70%) and dried.
• b) The fabric pretreated in this way is wound onto a carrier 3. For printing, the fiber material 1 to be printed is unwound from a carrier 3 and at the same time the paper 2 , which serves as a medium and is self-adhesive on the side with which it comes into contact with the fiber material, is unwound from a carrier 4. After passing the guide roller 5 , the fiber material, which is covered on the lower side by the self-adhesive paper, is printed by means of the print head 7. Here, an ink containing 15% by weight of the reactive dye of the formula
  20% by weight 1,2-propylene glycol and 65% by weight water, printed on with a drop-on-demand piezo inkjet head.

The printed material is then guided over a further guide roller 5. By means of a separator 6 , the fiber material 1 and the paper 2 are separated from one another and wound onto two different carriers 3 '(for the fiber material) and 4 ' (for the paper).

The print is completely dried and fixed in saturated steam at 102 ° C. for 8 minutes, cold rinsed, washed at the boil, rinsed again and dried. A print is obtained with good general fastness properties.

Examples 2 to 19

If the procedure is as in Example 1, but used instead of 15 wt .-% of the reactive dye specified there an equal amount of one of the following The reactive dyes given in Table 1 also give prints of good quality General fastnesses.

Table 1

If the procedure is as indicated in Examples 1 to 19, but used instead of one Piezo inkjet head a bubble jet inkjet head so analog prints are obtained.

Example 20

• a) 5.0 parts by weight of the disperse dye of the formula
  be with
  0.3 parts by weight of a dispersant based on a sulfonated condensation product of chloromethyldiphenyl isomer mixture and naphthalene and
  3.0 parts by weight of an anionic copolymer of acrylic acid and styrene, mixed and then ground in a wet mill to an average particle size of 0.2 to 1.0 μm. Thereafter, by adding, with thorough stirring,
  1.0 part by weight of a commercially available surfactant,
  3.7 parts by weight of a commercially available redispersant,
  0.2 parts by weight of a commercially available preservative,
  20.0 parts by weight of a commercially available humectant and
  66.8 parts by weight of water
  the ink adjusted to a dye content of 5 percent by weight.
• b) A georgette fabric made of polyester is used as the fiber material to be printed. The fiber material 1 to be printed is unwound from a carrier 3 and at the same time from a carrier 4 the paper 2 , which serves as a medium and is self-adhesive on the side with which it comes into contact with the fiber material. After passing the guide rollers 5 , the fiber material 9 , which is covered on the lower side by the paper, is wound onto a carrier 8. </ 04196 00070 552 001000280000000200012000285910408500040 0002019930986 00004 04077LIS <The fiber material 9 , which is covered on the lower side by the paper, is unwound from the carrier 8 , guided over a guide roller 5 , and by means of a drop-on-demand piezo inkjet head 7 printed with the ink obtained as indicated under a). The printed material 9 'is then guided over a further guide roller 5 and wound onto a carrier 10. The printed fiber material 9 ', which is covered on the lower side by the paper, is unwound from the carrier 10. After passing the guide roller 5 , the printed fiber material 1 and the paper 2 are separated from one another by means of a separator 6 and wound onto two different carriers 12 (for the fiber material) and 11 (for the paper). The print is dried and imprinted for 8 minutes Fixed superheated steam at 180 ° C. A yellow print with good all-round fastness properties is obtained. A yellow print with good all-round fastness properties is also obtained if the dried print is fixed with hot air at 200 ° C. for 1 minute. EXAMPLES 21 to 32 If the procedure is as in Example 20, but instead of 5% by weight of the disperse dye indicated there under a), an equal amount of one of the disperse dyes indicated in Table 2 below is also obtained prints with good all-round fastness properties. Table 2 If the procedure is as indicated in Examples 20 to 32, but using a bubble jet inkjet head instead of a piezo inkjet head, analog prints are obtained. Example 33
  • a) A mercerized cotton satin fabric in DIN A3 format is padded with an aqueous liquor containing 40 g / l sodium carbonate, 200 g / l urea and 100 g / l of an aqueous sodium alginate thickener (6%) (liquor absorption 70%) and dried.
  • b) The fabric pretreated in this way is completely pasted on the back with a self-adhesive paper in DIN A3 format. Using an inkjet printer (Epson Stylus 3000), the fabric is printed in color with the inks A, B, C and D given below. The printed fabric and the paper are then separated from one another and the print is fixed by means of a hot press for about 1 minute at a temperature of 140.degree. Alternatively, the fixation can also be done by means of an iron.
  Ink A containing 10% by weight of the reactive dye of the formula
  20% by weight 1,2-propylene glycol and 70% by weight water. Ink B, containing 15% by weight of the reactive dye of the formula
  20% by weight 1,2-propylene glycol and 65% by weight water. Ink C, containing 10% by weight of the reactive dye of the formula
  20% by weight 1,2-propylene glycol and 70% by weight water. Ink D, containing 10% by weight of the reactive dye of the formula
  20% by weight 1,2-propylene glycol and 70% by weight water. If the procedure is as indicated in Example 33, but using an equal amount of sodium hydrogen carbonate instead of 40 g / l sodium carbonate in step a) of this example, a analog print received. If the procedure is as indicated in Example 33, but in step a) of this example, instead of 40 g / l sodium carbonate, an equal amount of sodium hydrogen carbonate and instead of 200 g / l urea an amount of 30 g / l dicyandiamide is used Received pressure.

Claims (15)

1. A method for printing flat, textile fiber materials according to the inkjet printing method with aqueous, dye-containing inks, which is characterized in that the fiber materials are covered during printing on the side facing away from the print head with a flat medium lying close to the fiber material and the fiber material and the medium are guided past the printhead. 2. The method according to claim 1, characterized in that one uses an ink used, which is a disperse dye, pigment dye, acid dye or Contains reactive dye. 3. The method according to any one of claims 1 and 2, characterized in that one an ink is used which contains a disperse dye or reactive dye. 4. The method according to any one of claims 1 to 3, characterized in that one an ink is used which has a total content of dyes of 1 to 35% by weight, in particular 2.5 to 30% by weight and preferably 5 to 20% by weight, based on the Total weight of ink. 5. The method according to any one of claims 1 to 4, characterized in that one an ink is used which has a viscosity of 2 to 5 mPa.s. 6. The method according to any one of claims 1 to 4, characterized in that one an ink is used which has a viscosity of 10 to 30 mPa.s. 7. The method according to any one of claims 1 to 6, characterized in that the flat medium on the side with which it is brought into contact with the fiber material is provided with a means by which it adheres to the fiber material. 8. The method according to any one of claims 1 to 7, characterized in that as flat medium paper used. 9. The method according to claim 8, characterized in that the paper on the side with which it is brought into contact with the fiber material, is self-adhesive. 10. The method according to any one of claims 1 to 9, characterized in that the fiber material 1 to be printed from a carrier 3 and at the same time the flat medium from a carrier 4 is unwound and brought together so that the fiber material on the side facing away from the print head of the sheet-like medium is covered, the fiber material is printed and the fiber material 1 and the sheet-like medium are separated from one another after printing and optionally wound onto two different carriers 3 'and 4 '. 11. The method according to any one of claims 1 to 9, characterized in that the fiber material 9 to be printed, which is already covered on one side by the flat medium, is unwound from a carrier 8 , and the fiber material is printed and optionally on a carrier 10 winds up. 12. The method according to any one of claims 1 to 11, characterized in that one as fiber materials those used which have a low inherent stability or are permeable to the ink during printing. 13. The method according to any one of claims 1 to 12, characterized in that one Georgette or stretch used as fiber materials. 14. The method according to any one of claims 1 to 9, 12 and 13, characterized in that that you have a treated with an alkaline liquor and on the back with a Means, especially paper, covered fiber material with one of the usually im Ink-jet printer used in the home and then fixed the print, whereby the fiber material to be printed is of only smaller dimensions and in particular does not exceed the dimensions of the A3 format. 15. The method according to claim 14, characterized in that the fiber material cellulosic fiber material and at least one reactive dye as the ink containing ink is used.