EP2118214A2 - Mischungen von faserreaktiven azofarbstoffen - Google Patents
Mischungen von faserreaktiven azofarbstoffenInfo
- Publication number
- EP2118214A2 EP2118214A2 EP08708240A EP08708240A EP2118214A2 EP 2118214 A2 EP2118214 A2 EP 2118214A2 EP 08708240 A EP08708240 A EP 08708240A EP 08708240 A EP08708240 A EP 08708240A EP 2118214 A2 EP2118214 A2 EP 2118214A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- group
- hydrogen
- sulfo
- general formula
- independently
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
- C09B67/0033—Blends of pigments; Mixtured crystals; Solid solutions
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/30—Inkjet printing inks
- C09D11/32—Inkjet printing inks characterised by colouring agents
- C09D11/328—Inkjet printing inks characterised by colouring agents characterised by dyes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
- B41J2/00—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed
- B41J2/005—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed characterised by bringing liquid or particles selectively into contact with a printing material
- B41J2/01—Ink jet
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B62/00—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves
- C09B62/002—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the linkage of the reactive group being alternatively specified
- C09B62/006—Azodyes
- C09B62/01—Disazo or polyazo dyes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
- C09B67/0033—Blends of pigments; Mixtured crystals; Solid solutions
- C09B67/0046—Mixtures of two or more azo dyes
- C09B67/0047—Mixtures of two or more reactive azo dyes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
- C09B67/0033—Blends of pigments; Mixtured crystals; Solid solutions
- C09B67/0046—Mixtures of two or more azo dyes
- C09B67/0055—Mixtures of two or more disazo dyes
- C09B67/0057—Mixtures of two or more reactive disazo dyes
Definitions
- the invention is in the technical field of fiber-reactive azo dyes.
- Dye mixtures of fiber-reactive azo dyes and their use for dyeing hydroxy- and carbonamido-group-containing materials in golden yellow to orange shades are known, for example, from EP 1 000 982 A2 and from CN 1861695 A.
- these have certain application-related deficiencies, such as a not yet sufficient color structure at low dye concentrations, which ultimately affects the economics of the dyeing process.
- new reactive dyes or reactive dye mixtures having improved properties, such as steep color structure with good fastness properties.
- they must also have good dyeing yields and have a high reactivity, in particular dyeings with high degrees of fixation to be delivered.
- the new dye mixtures are characterized mainly by high Fixierausbeuten and easy leachability of not fixed to the fiber fractions.
- the dyeings have good fastness properties, such as high light fastness and very good wet fastness.
- the invention relates to dye mixtures which contain one or more dyes of the general formula (I) and one or more dyes of the general formulas (II)
- R 1 and R 2 independently of one another are hydrogen, (C 1 -CO-Al kVl, (C 1 -C 4 ) -alkoxy,
- X 1 is hydrogen, sulfo, a group of the formula -SO 2 -Z 2 , wherein
- Z 3 is hydroxy or an alkali cleavable group; or for a group of the formula (IV)
- D 1 , D 2 and D 3 independently of one another represent a group of the general formula (V) wherein
- R 3 and R 4 are independently hydrogen, (C r C 4 ) alkyl, (C r C 4 ) alkoxy, hydroxy, sulfo, carboxy, cyano, nitro, amido, ureido or halo; and X 2 has one of the meanings of X 1 ;
- D 1 , D 2 and D 3 are independently of one another a group of the general formula (VI)
- R 5 and R 6 independently of one another have one of the meanings of R 1 ;
- R 7 is hydrogen, (C r C 4 ) alkyl, unsubstituted or substituted by (C r C 4 ) alkyl, (C 1 -C 4 ) alkoxy, sulfo, halogen or carboxy-substituted phenyl; and
- Z 4 represents a group of the general formula (VII), (VIII) or (IX)
- V is fluorine or chlorine
- Mean U 1 and U 2 are independently fluorine, chlorine or hydrogen; and Q 1 and Q 2 are independently chlorine, fluorine, cyanamido, hydroxyl, (C 1 -C 6) - alkoxy, phenoxy, sulfophenoxy, mercapto, (CrCeJ-alkylmercapto , Pyridino,
- R 8 is hydrogen, (C r C 6 ) alkyl, sulfo (C r C 6 ) alkyl, phenyl or by (C r C 4 ) alkyl, (Ci-C 4 ) alkoxy, hydroxy, sulfo, halogen , Carboxy, acetamido, ureido substituted phenyl;
- R 9 and R 10 independently of one another have one of the meanings of R 8 or together represent a group of the formula - (CH 2 ) r or the formula - (CH 2 ) 2-E- (CH 2 ) 2-, where j is 4 or 5, E is oxygen, sulfur, sulfonyl or -NR 11 and R 11 is (C 1 -C 6 ) -alkyl; W is phenylene, by 1 or 2 substituents from the series (C r C4) alkyl, (C 1 -C 4) - alkoxy, carboxy, sulfo, chlorine and bromine-substituted phenylene, (C r C4) alkylene- phenylene, (C 2 -C 6) alkylene which is interrupted by oxygen, sulfur, sulfonyl, amino, carbonyl or carbonamido, (C 2 -C 6) -alkylene, phenylene-CONH-phenylene, (by 1 or 2 substituents from the
- D 1 , D 2 and D 3 independently of one another represent a group of the general formula (XII)
- R 12 is hydrogen, (C 1 -C 4 ) -alkyl, aryl or substituted aryl;
- R 13 and R 14 are independently hydrogen, (C 1 -C 4 ) -alkyl, (C 1 -C 4 ) -alkoxy, hydroxy, sulfo, carboxy, cyano, nitro, amido, ureido or halogen; and A for a group of the general formula (XIII)
- R 15 and R 16 independently of one another are hydrogen, (C 1 -C 4 ) -alkyl, (C 1 -C 4 ) -alkoxy, hydroxyl, sulfo, carboxyl, cyano, nitro, amido, ureido or halogen; or A is a group of the general formula (XIV)
- R 17 and R 18 independently of one another are hydrogen, (C 1 -C 4 ) -alkyl, (C 1 -C 4 ) -alkoxy, hydroxyl, sulfo, carboxyl, cyano, nitro, amido, ureido or halogen; or
- X 3 has one of the meanings of X 1 ;
- R A is hydrogen or a group of general formula (XVII) -CH 2 -SO 3 M (XVII);
- R B is acetamido, ureido, methyl, methoxy or a group of general formula (XVIII)
- Q 3 and Q 4 independently of one another are one of the meanings of Q 1 ;
- R c is hydrogen, methyl, methoxy or sulfo;
- Z 1 has one of the meanings of Z 4 ;
- M is hydrogen, an alkali metal or one equivalent of an alkaline earth metal; where the dyes of the general formulas (I) and (II) contain at least one fiber-reactive group of the formula -SO 2 Z 2 or Z 4 or of the formula (XVIII) or Z 1 , and where compounds of the formula (A)
- D 4 represents a group of the formula (B) or (C)
- d F_ B (0- 3) are the same or different and are 0 to 3 groups selected from hydrogen, -SO 3 M, -OH, -COOM, -F, -Cl, -Br, (dC 4) alkyl or
- Z A and Z B are a group of the formula (Da), (Db), (Dc) or (Dd),
- Y A is vinyl, ⁇ -chloroethyl, ⁇ -bromoethyl, ⁇ -acetylethyl, ⁇ -sulfatoethyl, ⁇ -phenoxyethyl, ⁇ -phosphatoethyl or a -CH 2 -CH 2 -U group; U is a group which can be split off under the action of alkali; and M is defined as above; at most in an amount of 1% by weight, based on the total colorant content.
- (C r C 4) alkyl groups may be straight or branched and is especially methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl and tert-butyl. Preferred are methyl and ethyl.
- (C 1 -C 4 ) -alkoxy groups which are therefore preferably methoxy and ethoxy.
- alkylene groups which stand in particular for etylene, propylene and butylene.
- Aryl is in particular phenyl or naphthyl, preferably phenyl.
- Substituted aryl preferably has one, two or three independent substituents selected from the group consisting of (C 1 -C 4 ) -alkyl, (C 1 -C 4 ) -alkoxy, hydroxyl, sulfo, carboxy, amido and halogen.
- Halogen is especially fluorine, chlorine and bromine, with fluorine and chlorine being preferred.
- lithium, sodium and potassium are those which stand for M; an equivalent of an alkaline earth metal for M is in particular the equivalent of calcium.
- M is preferably hydrogen or sodium.
- cleavable groups are for example halogen atoms, such as chlorine and bromine, ester groups of organic carboxylic and sulfonic acids, for example alkylcarboxylic acids, optionally substituted benzene and optionally substituted benzenesulfonic, especially alkanoyloxy of 2 to 5 carbon atoms such as acetyloxy, and benzoyloxy, Sulfobenzoyloxy, phenylsulfonyloxy and toluenesulfonyloxy, further acidic ester groups of inorganic acids, such as phosphoric acid, sulfuric acid and thiosulfuric acid (phosphato, sulfato and thiosulfato), as well dialkylamino groups with alkyl groups of 1 to 4 carbon atoms, such as dimethylamino and diethylamino.
- ester groups of organic carboxylic and sulfonic acids for example alkylcarboxylic acids, optionally
- Z 3 is preferably vinyl, ⁇ -chloroethyl and particularly preferably ⁇ -sulfatoethyl.
- the groups “sulfo”, “carboxy”, “thiosulfato”, “phosphato”, and “sulfato” include both their acid form and their salt form, accordingly corresponding to sulfo groups of the general formula -SO 3 M, thiosulfato groups of the general formula -S- SO 3 M, carboxy groups of the general formula -COOM, phosphato groups, groups of the general formula -OPO 3 M 2 and sulphato groups of the general formula -OSO 3 M, where M is in each case as defined above.
- the dyes of the general formulas (I) and (II) have fiber-reactive groups -SO 2 Z 2 or -SO 2 Z 5 , these may be present partly as vinylsulfonyl groups and partly as -CH 2 CH 2 Z 3 , preferably as ⁇ -sulfatoethylsulfonyl Groups, are present.
- the proportion of the particular dye with the vinylsulfonyl group is in particular up to about 30 mol%, based on the respective total amount of dye.
- the radicals R 1 and R 2 are preferably hydrogen, (C r C4) alkyl, (C r C4) -alkoxy, sulfo or carboxyl, and particularly preferably hydrogen, methyl, methoxy or sulfo.
- R 3 to R 6 and R 12 to R 20 are preferably hydrogen, R 3 to R 6 , R 17 and R 18 are also preferably sulfo.
- the radicals R 7 to R 10 are preferably hydrogen or methyl, R 7 and R 8 are also preferably phenyl and R 9 and R 10 also preferably 2-sulfoethyl, 2-, 3- or 4-sulfophenyl. In addition, R 9 and R 10 are preferably together - (CH 2 ) 2 -O- (CH 2 ) 2 -.
- the radicals R A and R c are preferably hydrogen, while the radical R B is preferably acetamido or ureido.
- preferred dye mixtures according to the invention are those in which
- R 1 and R 2 are hydrogen, methyl, methoxy or sulfo;
- R 3 to R 6 are hydrogen or sulfo;
- R 7 and R 8 are hydrogen or phenyl
- R 9 and R 10 are hydrogen, 2-sulfoethyl, 2-, 3- or 4-sulfophenyl or together -
- R 11 is hydrogen or methyl
- R 12 to R 16 , R 19 , R 20 , R A and R c are hydrogen
- R 17 and R 18 are hydrogen or sulfo
- R B means acetamido or ureido. If in the group of the general formula (IM) X 1 is -SO 2 Z 2 , this is preferably in the meta or para position to the diazo group.
- the bond which leads to the diazo group is preferably bonded to the naphthalene nucleus in the ⁇ -position.
- Preferred groups of the general formula (IM) and (V) are 4-sulfophenyl, 2,4-disulfophenyl, 2,5-disulfophenyl, 4,8-disulfo-naphth-2-yl, 6,8-disulfo-naphth-2 -yl, 1,5-disulfo-naphth-2-yl, 4,6,8-trisulfo-naphth-2-yl, 3,6,8-trisulfo-naphth-2-yl, 2- ( ⁇ -sulfatoethylsulfonyl) -phenyl , 2-sulfo-4- (4-sulfo-phenylazo) -phenyl, 3- ( ⁇ -sulfatoethylsulfony
- W preferably denotes 1, 3-phenylene, 1,4-phenylene, 2-sulfo-1, 4-phenylene, 2-methoxy-1, 5-phenylene, 2,5-dimethoxy 1, 4-phenylene, 2-methoxy-5-methyl-1, 4-phenylene, 1, 2-ethylene or 1, 3-propylene.
- Preferred examples of the groups Q 1 and Q 2 or Q 3 and Q 4 are independently fluorine, chlorine, hydroxyl, methoxy, ethoxy, phenoxy, 3-sulfophenoxy, 4-sulfophenoxy, methylmercapto, cyanamido, amino, methylamino, ethylamino, morpholino, piperidino, phenylamino, methylphenyl-amino, 2-sulfophenylamino, 3-sulfophenylamino, 4-sulfophenylamino, 2,4-disulfophenylamino, 2,5-disulfophenylamino, 2-sulfoethylamino, N-methyl-2-sulfoethylamino, pyridino, 3-carboxypyridino, 4-carboxypyridino, 3-carbamoylpyridino, 4-carbamoyl-pyridino, 2- (2-
- the groups Q 1 and Q 2 or Q 3 and Q 4 independently of one another are fluorine, chlorine, cyanamido, morpholino, 2-sulfophenylamino, 3
- Q 1 and Q 2 are fluorine or chlorine and Q 3 and Q 4 have one of the other meanings mentioned here.
- the groups Q 1 and Q 2 or Q 3 and Q 4 independently of one another are fluorine, chlorine, cyanamido, morpholino, 2-sulfophenylamino, 3-sulfophenylamino, 4-sulfophenylamino, 3- (2-sulfatoethylsulfonyl) -phenylamino, 4- (2-sulfatoethylsulfonyl) -phenylamino, 3- (vinylsulfonyl) -phenylamino, 4- (vinylsulfonyl) -phenylamino), N -methyl-N- (2- (2-sulfatoethylsulfonyl) -ethyl) -amino, N-phenyl-N- (2- (2-sulfatoethylsulfonyl) -ethyl) -amino or 2- [2- (2-chloro-eth
- the groups Z 1 and Z 4 preferably denote 2,4-difluoropyrimidin-6-yl, 4,6-difluoropyrimidin-2-yl, 5-chloro-2,4-difluoro-pyrimidin-6-yl, 5 Chloro-4,6-difluoro-pyrimidin-2-yl, 4,5-difluoro-pyrimidin-6-yl, 5-chloro-4-fluoro-pyrimidin-6-yl, 2,4,5-trichloro-pyrimidine -6-yl, 4,5-dichloro-pyrimidin-6-yl, 2,4-dichloro-pyrimidin-6-yl, 4-fluoro-pyrimidin-6-yl or 4-chloro-pytimidin-6-yl or the group of the general formula (VIII) having the preferred meanings given above for Q 1 and Q 2 .
- the groups Z 1 and Z 4 particularly preferably represent 2,4-difluoropyrimidin-6-yl, 4,6-difluoropyrimidin-2-yl, 5-chloro-2,4-difluoropyrimidin-6-yl or 5-chloro-4,6-difluoro-pyrimidin-2-yl or the group of the general formula (VIII) having the abovementioned particularly preferred meanings for Q 1 and Q 2 .
- the groups Z 1 and Z 2 are 2,4-difluoropyrimidin-6-yl or 5-chloro-2,4-difluoro-pyrimidin-6-yl or the group of the general formula (VIII) having the above very particular preferred meanings for Q 1 and Q 2 .
- the carbonamide group is preferably in para or meta position to the diazo group.
- the -SO 2 Z 2 group is preferably in the meta or para position to the nitrogen atom.
- the bond leading to the nitrogen atom is preferably bonded to the naphthalene nucleus in the ⁇ -position.
- Preferred examples of substituents standing for A are 1, 2-phenylene, 1, 3
- D 1 and D 2 preferably represent a group of the general formula (III) or (VI), the group of the general formula (III) being particularly preferred.
- D 1 and D 2 have the abovementioned preferred meanings.
- D 3 is preferably a group of the general formula (V), particularly preferably a group of the general formula (V) in which R 3 , R 4 and X 2 are hydrogen or sulfo.
- Z 1 preferably represents a group of the general formula (VIII) in which Q 1 and Q 2 have the abovementioned preferred meanings.
- Q 1 is fluorine or chlorine and C 2 H has one of the other preferred meanings.
- Z 1 particularly preferably represents a group of the general formula (VIII) in which Q 1 is fluorine or chlorine and Q 2 is cyanamido, morpholino, 2-sulfophenyl-amino, 3-sulfophenylamino, 4-sulfophenylamino, N-methyl-2 sulfoethylamino, 3
- R 1a , R 1b , R 2a and R 2b are each independently hydrogen, methyl, methoxy or sulfo;
- Z 2 and Z 5 independently of one another are vinyl or ⁇ -sulfatoethyl; and D 3 , R B , R c and M are as defined above.
- the dye mixtures according to the invention contain the dye or the dyes of the general formula (I) in an amount of 1 to 99 wt .-%, preferably 10 to 90 wt .-% and the dye or dyes of the general formula (II) in an amount of 1 to 99 wt .-%, preferably 10 to 90 wt .-%, each based on the total amount of dye.
- compounds of the formula (A) are present in an amount of 0.5% by weight, based on the total dye content, while particularly preferred inventive compounds contain no compounds of the formula (A).
- the dyes according to the invention can be present as a preparation in solid or in liquid (dissolved) form.
- solid form they generally contain the usual in water-soluble and especially fiber-reactive dyes
- Electrolyte salts such as sodium chloride, potassium chloride and sodium sulfate, and may further contain the usual in commercial dyes aids, such as
- Buffer substances capable of adjusting a pH between 3 and 7 in aqueous solution such as sodium acetate, sodium borate, sodium bicarbonate, sodium dihydrogen phosphate, sodium tricitrate and disodium hydrogen phosphate, small amounts of siccatives or, if they are in liquid, aqueous solution (including the Content of thickening agents, as are customary in printing pastes), substances which ensure the durability of these preparations, such as, for example, mildewproofing agents.
- the dye mixtures according to the invention are generally in the form of electrolytic salt-containing powders or granules (hereinafter generally referred to as preparation) with, if appropriate, one or more of the abovementioned auxiliaries.
- preparation electrolytic salt-containing powders or granules
- the dye mixture to 20 to 90 wt .-%, based on the preparation contained.
- the buffer substances are generally present in a total amount of up to 5% by weight, based on the preparation.
- the total dye content in these solutions is up to about 50 wt .-%, such as between 5 and 50 wt .-%, while the electrolyte salt content is preferably below 10 wt .-%, based on the aqueous solution is.
- the aqueous solutions or liquid preparations can also contain buffer substances, generally in an amount of up to 5% by weight, preferably in amounts of from 0.1 to 2% by weight.
- the dye mixtures according to the invention can be prepared by customary methods known to the person skilled in the art. For example, by mechanical mixing of the individual dyes, in the form of dye powders or granules or in the form of aqueous solutions, for example
- Synthesis solutions which may still contain conventional adjuvants may be present.
- Dye mixtures which, in addition to ⁇ -chloroethylsulfonyl or ⁇ -thiosulfatoethylsulfonyl or ⁇ -sulfatoethylsulfonyl groups, also have vinylsulfonyl groups as reactive radicals can be synthesized not only starting from correspondingly substituted vinylsulfonylanilines or naphthylamines, but also by reacting dye mixtures in which Z 3 is .beta.-chloroethyl, .beta.-thio-sulfatoethyl or .beta.-sulfatoethyl, with an amount of alkali required for the desired proportion and conversion of said .beta.-substituted ethylsulphonyl groups into vinylsulphonyl groups. This transfer takes place in a manner familiar to the person skilled in the art.
- dyes of the general formula (I) are known and described in EP 0 785 237 A1. Dyes of the general formula (II) are also known and numerous described in the literature. Both dyes of the general formula (I) and dyes of the general formula (II) are accessible via standard synthesis methods known to the person skilled in the art.
- the dye mixtures according to the invention have valuable performance properties and can be used for dyeing and printing materials containing carbonamide and / or hydroxyl groups.
- the materials mentioned can be present, for example, in the form of fabrics such as paper and leather, in the form of films, such as polyamide films or in the form of a composition, for example of polyamide or polyurethane.
- the dye mixtures according to the invention are used for dyeing and printing cellulosic fiber materials of all kinds. Prefers They are also suitable for dyeing or printing polyamide fibers or blended fabrics made of polyamide with cotton or polyester fibers. It is also possible to use the dye mixtures of the invention to print textiles, paper or other materials by the inkjet process.
- the present invention thus also relates to the use of the dye mixtures according to the invention for dyeing or printing carbonamide- and / or hydroxyl-containing materials or processes for dyeing or printing such materials in conventional procedures, in which one uses a dye mixture according to the invention as a colorant.
- the dye mixtures according to the invention provide on these materials, preferably fiber materials, orange to red colorations with very good fastness properties.
- the resulting in the production of solutions of the dye mixtures according to the invention optionally after addition of a buffer substance, optionally after concentration or dilution, can be supplied directly as a liquid preparation of the dyeing use.
- fiber materials or fibers is understood to mean, in particular, textile fibers which may be in the form of woven fabrics, yarns or in the form of strands or wound bodies.
- Carbonamidity perfume pieces are for example synthetic and natural polyamides and polyurethanes, especially in the form of fibers, such as wool and other animal hair, silk, leather, polyamide-6,6, polyamide-6, polyamide-11 and polyamide-4.
- Hydroxy-containing materials are those of natural or synthetic origin such as cellulosic fiber materials or their regenerated products and polyvinyl alcohols.
- Cellulose fiber materials are preferably cotton, but also other plant fibers, such as linen, hemp, jute and ramie fibers.
- Regenerated cellulose fibers are, for example, rayon and viscose rayon.
- the dye mixtures according to the invention can be applied and fixed on the abovementioned materials, in particular on the fiber materials mentioned, according to the application techniques known for water-soluble, in particular, those known for fiber-reactive dyes.
- cellulose fibers are obtained by the exhaust process both from short, as well as from long liquor using a variety of acid-binding agents and optionally neutral salts, such as sodium chloride or sodium sulfate, dyeings with very good, color yields.
- the extraction process at a pH of 3 to 7, in particular at a pH of 4 to 6 dyed.
- the liquor ratio can be chosen within a wide range and is for example between 1: 3 and 1: 100, preferably between 1: 5 and 1: 30. It is preferably dyed in an aqueous bath at temperatures between 40 and 105 0 C, optionally at a temperature up to 130 0 C under pressure, and optionally in the presence of conventional dyeing auxiliaries.
- To increase the wet fastness of the dyed material can be removed in a post-treatment unfixed dye. This aftertreatment is carried out in particular at a pH of 8 to 9 and at temperatures of 75 to 80 ° C.
- the neutral salts which accelerate the removal of the dyes can also be added to the bath only after the actual dyeing temperature has been reached.
- the single-phase - for example by printing with a sodium bicarbonate or other acid-binding agent containing printing paste and subsequent steaming at 100 to 103 0 C, - or two-phase - for example by printing with neutral or weakly acidic ink and subsequent fixing either by passing through a hot electrolyte-containing alkaline bath or by over-padding with an alkaline electrolyte-containing padding liquor and then lingering or steaming or treatment with dry heat of the alkaline padded material, - can be obtained strong prints with good contour and a clear white fund. The failure of the prints is only slightly dependent on changing fixing conditions.
- the acid-binding and the fixing of the dyes on the cellulose fibers causing agents are, for example, water-soluble basic salts of alkali metals and also alkaline earth metals of inorganic or organic acids or compounds which release alkali in the heat.
- the alkali metal hydroxides and alkali metal salts of weak to medium inorganic or organic acids may be mentioned, of the alkali metal compounds preferably the sodium and potassium compounds are meant.
- Such acid-binding agents are, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, sodium formate, sodium dihydrogen phosphate, disodium hydrogen phosphate, sodium trichloroacetate, water glass or trisodium phosphate.
- the dye mixtures according to the invention are characterized by cellulose fiber materials when used in the known dyeing and printing process by an excellent color strength and a steep course of the build-up curve. Furthermore, those with the dye mixtures according to the invention Available dyeings and prints on cellulose fiber materials good light fastness and especially good wet fastness, such as washing, Walk, water, seawater, dyeing and acid, and alkaline perspiration, furthermore a good pleating, ironing fastness and rubbing fastness.
- the dyeings and prints after the usual post-treatment by rinsing to remove unfixed dye fractions excellent wet fastness, especially since unfixed dye fractions can be easily washed out because of their good solubility in cold water.
- the dye mixtures according to the invention can also be used for the fiber-reactive dyeing of wool.
- Felt-free or low-felt wool (compare, for example, H. Rath, textbook of Textilchemie, Springer-Verlag, 3rd edition (1972), pp. 295-299, in particular the equipment according to the so-called Hercosett method (page 298); Soc. Dyers and Colorists 1972, 93-99, and 1975, 33-44) can be dyed with very good fastness properties.
- the process of dyeing wool is carried out here in the usual and well-known Därbeweise from an acidic environment.
- acetic acid and / or ammonium sulfate or acetic acid and ammonium acetate or sodium acetate may be added to the dyebath to obtain the desired pH.
- conventional leveling agents for example based on a reaction product of cyanuric chloride with three times the molar amount of an aminobenzenesulfonic acid and / or an aminonaphthalenesulfonic acid or on
- the dye mixture according to the invention is preferably first subjected to the exhaust process from acid dyebath having a pH of about 3.5 to 5.5 under the control of the pH and the pH then, towards the end of the dyeing time, in the neutral and optionally slightly alkaline range shifted to a pH of 8.5, especially in order to achieve high color depths full reactive binding between the dyes of the dye mixtures according to the invention and the fiber bring about. simultaneously the non-reactively bound dye fraction is removed.
- the procedure described here also applies to the production of dyeings on fiber materials from other natural polyamides or from synthetic polyamides and polyurethanes.
- dyeing these materials it is possible to use the customary dyeing and printing processes described in the literature and known to the person skilled in the art (see, for example, H. -K. Rouette, Handbuch der Textilveredlung, Deutscher fraverlag GmbH, Frankfurt am Main).
- the material to be dyed at a temperature of about 40 0 C introduced into the bath, there for some time moved therein, the dyebath then adjusted to the desired weakly acid, preferably weakly acetic acid, pH and the actual color in a Temperature between 60 and 98 ° C performed.
- the dyeings can also be carried out at boiling temperature or in closed dyeing apparatus at temperatures up to 106 0 C. Since the water solubility of the dye mixtures according to the invention is very good, they can also be used with advantage in conventional continuous dyeing processes. The color intensity of the dye mixtures according to the invention is very high.
- the present invention also relates to inks for digital textile printing by the ink-jet process, which are characterized in that they contain a Farbstoffmichung invention.
- the inks according to the invention comprise a dye mixture according to the invention, for example in amounts of from 0.1% by weight to 50% by weight, preferably in amounts of
- Dyes used in textile printing For the use of inks in the continuous flow process, a conductivity of 0.5 to 25 mS / m can be set by addition of electrolyte.
- Suitable electrolytes are, for example: lithium nitrate, potassium nitrate.
- the inks of the invention may contain organic solvents having a total content of 1-50%, preferably 5-30% by weight.
- Suitable organic solvents are, for example, alcohols, for. For example, methanol, ethanol, 1-propanol, isopropanol, 1-butanol, tert. Butanol, pentyl alcohol, polyhydric alcohols z. B, 1, 2-ethanediol, 1, 2,3-propanetriol, butanediol, 1, 3
- B. Polyethylene glycol monomethyl ether, polypropylene glycol glycerol ether, Polyethylenglykoltridecylether, Polyethylenglykolnonylphenylether, amines, such as.
- the inks of the invention may contain the usual additives, such as viscosity moderators to adjust viscosities in the range of 1, 5 to 40.0 mPas in a temperature range of 20 to 50 0 C.
- Preferred inks have a viscosity of 1.5 to 20 mPas and particularly preferred inks have a viscosity of 1.5 to 15 mPas.
- Suitable viscosity moderators are theological additives, for example: polyvinylcaprolactam, polyvinylpyrrolidone and their co-polymers polyetherpolyol, associative thickener, polyurea, polyurethane, sodium alginates, modified galactomannans, polyetherurea, polyurethane, nonionic cellulose ethers.
- the inks according to the invention can be surface-active
- Suitable surface-active substances are, for example: surfactants of all kinds, preferably nonionic surfactants, butyldiglycol and 1,2-hexanediol.
- the inks may still contain conventional additives such as fungicidal and bacterial growth inhibiting agents in amounts of from 0.01 to 1% by weight based on the total weight of the ink.
- the inks of the invention may be prepared in the usual manner by mixing the components in water.
- the inks according to the invention are suitable for use in ink-jet printing Process for printing a variety of prepared materials, such as silk, leather, wool, cellulose-containing fiber materials of all kinds and polyurethanes, and in particular polyamide fibers.
- the printing inks of the invention are also suitable for printing pretreated hydroxy-containing or amino-containing fibers contained in blend fabrics, z. As mixtures of cotton, silk, wool with polyester fibers or polyamide fibers.
- the auxiliaries In contrast to conventional textile printing, in which the printing ink already contains all fixing chemicals and thickeners for a reactive dye, in ink-jet printing the auxiliaries have to be applied to the textile substrate in a separate pretreatment step.
- the pretreatment of the textile substrate takes place before printing with an aqueous alkaline liquor.
- alkali such as sodium carbonate, sodium bicarbonate, sodium acetate,
- pre-preparation reagents are applied uniformly to the textile substrate in a defined amount using suitable application devices, for example a 2- or 3-roll padder, with non-contact spray technologies, by foam application or with appropriately adapted inkjet technologies, and then dried.
- suitable application devices for example a 2- or 3-roll padder, with non-contact spray technologies, by foam application or with appropriately adapted inkjet technologies, and then dried.
- the textile fiber material is dried at 120 to 150 0 C and then fixed.
- the fixation of the inkjet prints prepared with reactive dyes can be carried out at room temperature, or with saturated steam, with superheated steam, with hot air, with microwaves, with infrared radiation, with laser or electron beams or with other suitable types of energy transfer.
- this pretreatment can be omitted.
- alkali is needed, which is applied after the ink-jet printing before the fixing without intermediate drying.
- Other additives such as urea or thickener can be dispensed with.
- the prints made with the inks of the present invention, especially on polyamide, have high color strength and high fiber-dye bonding stability in both acidic and alkaline ranges, as well as good fastness to light and very good wet fastness properties such as washing, water, seawater -, over-dyeing and perspiration, as well as a good pleating, ironing and rubbing fastness.
- Sodium salts since they are generally prepared and isolated in the form of their salts, preferably sodium or potassium salts, and used in the form of their salts for dyeing.
- the starting compounds mentioned in the following examples, in particular table examples, can be used in the synthesis in the form of the free acid or else in the form of their salts, preferably alkali metal salts, such as sodium or potassium salts.
- the dye solution obtained can also be buffered by addition of a phosphate buffer at pH 5.5-6 and adjusted by further dilution or concentration as a liquid brand of certain strength.
- the dye solution obtained can also be buffered by addition of a phosphate buffer at pH 5.5-6 and adjusted by further dilution or concentration as a liquid brand of certain strength.
- the following examples describe further dye mixtures according to the invention in which the dyes of the general formulas (I) and (II) are each listed in the form of the sodium salts and which can be prepared by the processes described in Examples 1 to 3.
- the mixing ratios are given in percent by weight.
- the Dyestuff mixtures provide, according to the dyeing methods customary for reactive dyes, for example on cotton, yellow to orange-yellow dyeings.
- Example 24 4 parts of a dye mixture obtained according to Example 1 and 50 parts
- Example 23 Sodium chloride is dissolved in 998 parts of water and 5 parts of sodium carbonate, 2 parts of sodium hydroxide (in the form of a 32.5% aqueous solution) and optionally 1 part of a wetting agent added. In this dye bath is added 100 g of a cotton fabric. Further processing is carried out as indicated in Example 23. This gives a strong orange to red coloration with very good fastness properties.
- a textile fabric consisting of mercerized cotton is padded with a liquor containing 35 g / l of sodium carbonate, 100 g / l of urea and 150 g / l of a low-viscosity Na alginate solution (6%) and then dried.
- the fleet intake is 70%.
- An aqueous ink containing 2% of the dye mixture according to Example 1 20% sulfolane 0.01% Mergal K9N 77.99% water is printed onto the textile thus pretreated with a drop-on-demand (bubble jet) inkjet print head. The print is completely dried. The fixation takes place by means of saturated steam at 102 0 C for 8 minutes. Subsequently, the pressure is rinsed warm, subjected to hot water at 95 ° C a fastness wash, rinsed warm and then dried. This gives a bluish red print with excellent use fastness.
- Example 26 A textile fabric consisting of mercerized cotton is padded with a liquor containing 35 g / l of sodium carbonate, 50 g / l of urea and 150 g / l of a low-viscosity Na alginate solution (6%) and then dried. The fleet intake is 70%.
- On the thus pretreated textile is an aqueous ink containing 8% dye mixture according to Example 1 20% 1, 2-propanediol 0.01% Mergal K9N and 71, 99% water with a drop-on-demand (bubble jet) inkjet print head printed. The print is completely dried. The fixation takes place by means of saturated steam at 102 0 C for 8 minutes.
- a textile fabric consisting of mercerized cotton is padded with a liquor containing 35 g / l of sodium carbonate, 100 g / l of urea and 150 g / l of a low-viscosity Na alginate solution (6%) and then dried.
- the fleet intake is 70%.
- An aqueous ink containing 8% of dye mixture according to Example 1, 15% N-methylpyrrolidone 0.01 Mergal K9N and 77.99% water is printed on the textile thus pretreated with a drop-on-demand (bubble jet) inkjet print head , The print is completely dried. The fixation takes place by means of saturated steam at 102 0 C for 8 minutes. Then the pressure is rinsed warm, with hot Water at 95 ° C subjected to a fastness wash, rinsed warm and then dried. This gives a bluish red print with excellent use fastness.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Coloring (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
- Ink Jet (AREA)
- Ink Jet Recording Methods And Recording Media Thereof (AREA)
- Optical Filters (AREA)
- Nitrogen Condensed Heterocyclic Rings (AREA)
Abstract
Description
Claims
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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DE102007005795A DE102007005795A1 (de) | 2007-02-06 | 2007-02-06 | Mischungen von faserreaktiven Azofarbstoffen |
PCT/EP2008/050917 WO2008095802A2 (de) | 2007-02-06 | 2008-01-28 | Mischungen von faserreaktiven azofarbstoffen |
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EP2118214A2 true EP2118214A2 (de) | 2009-11-18 |
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Application Number | Title | Priority Date | Filing Date |
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EP08708240A Withdrawn EP2118214A2 (de) | 2007-02-06 | 2008-01-28 | Mischungen von faserreaktiven azofarbstoffen |
Country Status (12)
Country | Link |
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US (1) | US20090320217A1 (de) |
EP (1) | EP2118214A2 (de) |
JP (1) | JP2010520926A (de) |
KR (1) | KR20090122187A (de) |
CN (1) | CN101595186A (de) |
BR (1) | BRPI0807130A2 (de) |
CA (1) | CA2677474A1 (de) |
DE (1) | DE102007005795A1 (de) |
DO (1) | DOP2009000185A (de) |
MX (1) | MX2009008335A (de) |
TW (1) | TW200848474A (de) |
WO (1) | WO2008095802A2 (de) |
Families Citing this family (9)
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CN101307190B (zh) * | 2007-05-18 | 2011-05-25 | 明德国际仓储贸易(上海)有限公司 | 黄色反应性染料组成物 |
CN101544848B (zh) * | 2008-12-12 | 2013-01-16 | 天津德凯化工股份有限公司 | 活性染料组合物及其制备方法 |
CN102453348B (zh) * | 2010-10-28 | 2013-12-04 | 上海雅运纺织化工股份有限公司 | 黄色活性染料化合物及其应用 |
WO2013022044A1 (ja) * | 2011-08-09 | 2013-02-14 | 日本化薬株式会社 | インクジェット捺染用グレーインク組成物及びそれを用いた繊維の捺染方法 |
MX2014015538A (es) * | 2012-06-18 | 2015-06-05 | Dystar Colours Distrib Gmbh | Tinturas reactvas libres de metales, proceso para su produccion y su uso. |
EP2862902A1 (de) * | 2013-08-29 | 2015-04-22 | DyStar Colours Distribution GmbH | Farbstoffmischungen aus metallfreien Reaktivfarbstoffen, Herstellung und Verwendung |
CN106892874B (zh) * | 2015-12-17 | 2019-06-25 | 江苏安诺其化工有限公司 | 单偶氮类化合物的制备方法 |
CN107033628B (zh) * | 2016-12-31 | 2019-08-23 | 浙江龙盛化工研究有限公司 | 一种活性黄染料化合物及其制备方法和应用 |
WO2019151412A1 (ja) * | 2018-01-31 | 2019-08-08 | 富士フイルム株式会社 | インクセット及びインクジェット記録方法 |
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MY117759A (en) | 1996-01-19 | 2004-08-30 | Ciba Sc Holding Ag | Reactive dyes their preparation and use. |
DE19851497A1 (de) * | 1998-11-09 | 2000-05-18 | Dystar Textilfarben Gmbh & Co | Farbstoffmischungen von faserreaktiven Azofarbstoffen und ihre Verwendung |
BR0308754A (pt) * | 2002-03-22 | 2005-01-11 | Dystar Textilfarben Gmbh & Co | Misturas de corantes de corantes azo reativos para fibras, produção dos mesmos e uso dos mesmos |
DE10344127A1 (de) * | 2003-09-24 | 2005-04-21 | Dystar Textilfarben Gmbh & Co | Verfahren zum Mono, Di- oder Trichromie-Färben oder -Bedrucken von natürlichen oder synthetischen Polyamidfasermaterialien |
DE102004058151A1 (de) * | 2004-12-02 | 2006-06-08 | Dystar Textilfarben Gmbh & Co. Deutschland Kg | Mischungen von faserreaktiven Azofarbstoffen, Verfahren zu deren Herstellung und ihre Verwendung |
CN100412140C (zh) * | 2006-06-19 | 2008-08-20 | 湖北华丽染料工业有限公司 | 一种黄色偶氮染料混合物及其用途 |
-
2007
- 2007-02-06 DE DE102007005795A patent/DE102007005795A1/de not_active Withdrawn
-
2008
- 2008-01-28 WO PCT/EP2008/050917 patent/WO2008095802A2/de active Application Filing
- 2008-01-28 MX MX2009008335A patent/MX2009008335A/es unknown
- 2008-01-28 CA CA002677474A patent/CA2677474A1/en not_active Abandoned
- 2008-01-28 EP EP08708240A patent/EP2118214A2/de not_active Withdrawn
- 2008-01-28 JP JP2009548647A patent/JP2010520926A/ja not_active Withdrawn
- 2008-01-28 US US12/524,929 patent/US20090320217A1/en not_active Abandoned
- 2008-01-28 CN CNA2008800033900A patent/CN101595186A/zh active Pending
- 2008-01-28 BR BRPI0807130-6A2A patent/BRPI0807130A2/pt not_active IP Right Cessation
- 2008-01-28 KR KR1020097015436A patent/KR20090122187A/ko not_active Application Discontinuation
- 2008-02-04 TW TW097104338A patent/TW200848474A/zh unknown
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2009
- 2009-07-22 DO DO2009000185A patent/DOP2009000185A/es unknown
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Publication number | Publication date |
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BRPI0807130A2 (pt) | 2014-04-15 |
CA2677474A1 (en) | 2008-08-14 |
KR20090122187A (ko) | 2009-11-26 |
DE102007005795A1 (de) | 2008-08-07 |
WO2008095802A2 (de) | 2008-08-14 |
JP2010520926A (ja) | 2010-06-17 |
MX2009008335A (es) | 2009-12-14 |
WO2008095802A3 (de) | 2009-03-19 |
DOP2009000185A (es) | 2009-08-31 |
TW200848474A (en) | 2008-12-16 |
US20090320217A1 (en) | 2009-12-31 |
CN101595186A (zh) | 2009-12-02 |
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