WO2010057830A1 - Colorants réactifs fluorés à noyau - Google Patents

Colorants réactifs fluorés à noyau Download PDF

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Publication number
WO2010057830A1
WO2010057830A1 PCT/EP2009/065084 EP2009065084W WO2010057830A1 WO 2010057830 A1 WO2010057830 A1 WO 2010057830A1 EP 2009065084 W EP2009065084 W EP 2009065084W WO 2010057830 A1 WO2010057830 A1 WO 2010057830A1
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Prior art keywords
group
formula
alkyl
alkoxy
hydrogen
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PCT/EP2009/065084
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English (en)
Inventor
Stefan Ehrenberg
Warren Ebenezer
Michael Hutchings
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Dystar Colours Deutschland Gmbh
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Priority to CN2009801550203A priority Critical patent/CN102292399A/zh
Publication of WO2010057830A1 publication Critical patent/WO2010057830A1/fr

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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
    • C09B62/00—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves
    • C09B62/44—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group not directly attached to a heterocyclic ring
    • C09B62/4401—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group not directly attached to a heterocyclic ring with two or more reactive groups at least one of them being directly attached to a heterocyclic system and at least one of them being directly attached to a non-heterocyclic system
    • C09B62/4403—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group not directly attached to a heterocyclic ring with two or more reactive groups at least one of them being directly attached to a heterocyclic system and at least one of them being directly attached to a non-heterocyclic system the heterocyclic system being a triazine ring
    • C09B62/4411—Azo dyes
    • C09B62/4413—Non-metallized monoazo 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
    • C09B62/00—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves
    • C09B62/02—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group directly attached to a heterocyclic ring
    • C09B62/04—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group directly attached to a heterocyclic ring to a triazine ring
    • C09B62/043—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group directly attached to a heterocyclic ring to a triazine ring containing two or more triazine rings linked together by a non-chromophoric link
    • 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
    • C09B62/02—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group directly attached to a heterocyclic ring
    • C09B62/04—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group directly attached to a heterocyclic ring to a triazine ring
    • C09B62/08—Azo dyes
    • C09B62/085—Monoazo 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
    • C09B62/00—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves
    • C09B62/02—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group directly attached to a heterocyclic ring
    • C09B62/20—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group directly attached to a heterocyclic ring to a pyrimidine ring
    • C09B62/24—Azo dyes
    • C09B62/25—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
    • C09B62/00—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves
    • C09B62/44—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group not directly attached to a heterocyclic ring
    • C09B62/503—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group not directly attached to a heterocyclic ring the reactive group being an esterified or non-esterified hydroxyalkyl sulfonyl or mercaptoalkyl sulfonyl group, a quaternised or non-quaternised aminoalkyl sulfonyl group, a heterylmercapto alkyl sulfonyl group, a vinyl sulfonyl or a substituted vinyl sulfonyl group, or a thiophene-dioxide group
    • C09B62/507—Azo dyes
    • C09B62/51—Monoazo 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
    • C09B62/00—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves
    • C09B62/44—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group not directly attached to a heterocyclic ring
    • C09B62/503—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group not directly attached to a heterocyclic ring the reactive group being an esterified or non-esterified hydroxyalkyl sulfonyl or mercaptoalkyl sulfonyl group, a quaternised or non-quaternised aminoalkyl sulfonyl group, a heterylmercapto alkyl sulfonyl group, a vinyl sulfonyl or a substituted vinyl sulfonyl group, or a thiophene-dioxide group
    • C09B62/507—Azo dyes
    • C09B62/513—Disazo or polyazo dyes

Definitions

  • This invention relates to the technical field of fibre-reactive azo dyes.
  • Dyestuffs and colorants, respectively, containing fluorine atoms in form of a trifluoromethyl group are known and described in literature.
  • GB732121 discloses monozo acid dyestuffs comprising a trifluoromethyl-benzenesulfonic acid.
  • Monoazoanilide pigments which are ring fluorinated are described in Dyes and Pigments 42 (1999) 159-172, whereas azo dyes comprising fluorinated diazo components are disclosed in GB 882,001.
  • Fibre-reactive azo dyes comprising fluorinated diazo components are described in EP 0 043 560A1. Further, fibre-reactive thphendioxazine dyes carrying a fluorine atom at the triphendioxazine chromophor are described in WO 2007/077129 A2. Azo dyes comprising a diazo component which carry a fluorine atom besides two sulfo groups are known from EP 0 167 785 A1
  • fibre-reactive dyestuffs as described below obtained from ring fluorinated anilinesulfonic acids as diazo components show particularly advantageous fastness profiles when reactively applied to cotton especially in relation to fastness to light, chlorine and perspiration light fastness and additionally exhibit very good levels of build up. Also, the dyestuffs give level shades with good contact fastness after wash off.
  • the present invention provides dyestuffs of the formula (I)
  • a is 1 or 2;
  • X 1 is an aromatic or heteroaromatic divalent group;
  • RG is a reactive group capable of forming a covalent bond to carboxamido- and/or hydroxyl-containing material under dyeing conditions or a group comprising a reactive group capable of forming a covalent bond to cellulose under dyeing conditions or is hydrogen;
  • R 1 is hydrogen, (Ci-C 4 )-alkyl, (CrC 4 )-alkoxy, hydroxy, chlorine or a group of the formula (II)
  • X 2 is an aromatic or heteroaromatic group
  • R 3 is hydrogen or -SO 3 M
  • R 4 is hydrogen, (Ci-C 4 )-alkyl, (Ci-C 4 )-alkoxy, hydroxy, fluorine, chlorine,
  • Z is -OSO 3 M, -OAc, -OPO 3 H 2 or chlorine; b is 1 or 2; c is 1 , 2 or 3;
  • R 2 is hydrogen, (CrC 4 )-alkyl, (Ci-C 4 )-alkoxy, sulfo, hydroxy or chlorine;
  • M is hydrogen, an alkali metal or an equivalent of an alkaline earth metal
  • B is hydrogen or phenyl and M is defined as given above, are excluded.
  • Preferred aromatic or heteroaromatic divalent groups standing for X 1 correspond to one of the formulae (Ilia) to (MIj)
  • Ar is phenylen or phenylen which is substituted by 1 , 2 or 3 substituents selected from the group comprising (Ci-C 4 )-alkyl, (Ci-C 4 )-alkoxy, halogen and -SO 3 M;
  • E 1 has one of the meanings of Ar , is naphthyl or naphthyl which is substituted by 1 , 2 or 3 substituents selected from the group comprising (Ci-C 4 )-alkyl, (CrC 4 )-alkoxy, - SO3M, amino, acetylamino or hydroxy; or is a 5- or 6-membered heterocyclic residue comprising one or two heteroatoms, selected from the group comprising nitrogen, oxygen and sulphur, or is a 5- or 6-membered heterocyclic residue comprising one or two heteroatoms, selected from the group comprising nitrogen, oxygen and sulphur, which is substituted by 1 , 2 or 3 substituents selected from the group comprising (Ci-C 4 )-alkyl and (Ci-C 4 )-alkoxy;
  • E 2 is phenylene or naphthylene which are unsubstituted or substituted by 1 , 2 or 3 substituents selected from the group comprising (CrC 4 )-alkyl, (Ci-C 4 )-alkoxy -SO3M, amino, acetylamino or hydroxy; or is a divalent 5- or 6-membered heterocyclic residue comprising one or two heteroatoms, selected from the group comprising nitrogen, oxygen and sulphur, or is a divalent 5- or 6-membered heterocyclic residue comprising one or two heteroatoms, selected from the group comprising nitrogen, oxygen and sulphur, which is substituted by 1 , 2 or 3 substituents selected from the group comprising (Ci-C 4 )-alkyl and (Ci-C 4 )-alkoxy; or is a group of the formula (IV)
  • R 7 is (Ci-C 4 )-alkyl, (Ci-C 4 )-alkoxy -SO 3 M or hydroxy;
  • R 8 and R 8 ' independently are hydrogen, (Ci-C 6 )-alkyl, sulfo-(Ci-C 6 )-alkyl, phenyl or phenyl substituted by (CrC 4 )-alkyl, (Ci-C 4 )-alkoxy, hydroxyl, -SO3M, halogen, -
  • R 8a is hydrogen or acetamido
  • R 5 is (Ci-C 4 )-alkyl or -COOM
  • R 6 is hydrogen, CN or -CONH 2 ;
  • L is 1 ,2-phenylene, 1 ,3-phenylene or 1 ,4 phenylene, which are unsubstituted or substituted by -SO 3 M, -COOM or R 8 , or is (C 2 -C 6 )-alkylene or (Ci-C 4 )-alkylene- phenylene which are unsubstituted or substituted by R 8 ;
  • Examples of 5- or 6-membered heterocyclic residues comprising one or two heteroatoms standing for E 1 are pyridones, pyrazolones and diaminopyhdines.
  • examples of divalent 5- or 6-membered heterocyclic residues comprising oonnee oorr ttwwoo hheetteerrooaattoommss ssttanding for E 2 are divalent pyhdone, pyrazolone and diaminopyhdine residues.
  • Especially preferred aromatic or heteroaromatic divalent groups standing for X 1 correspond to the formulae (Him) to (MIu)
  • Z 1 is an alkali-eliminatable group
  • R 8 is defined as given above
  • A is a group of the formula (Va), (Vb) or (Vc)
  • V is fluorine or chlorine; U 1 and U 2 are independently fluorine, chlorine or hydrogen; and Q 1 and Q 2 are independently chlorine, fluorine, cyanamido, hydroxyl, (CrC ⁇ J-alkoxy, phenoxy, sulfophenoxy, mercapto, (Ci-CeJ-alkylnnercapto, pyridine carboxypyhdino, carbamoyl pyridino or a group of the formula (Vl) or (VII)
  • R 9 has one of the meanings of R 1 or is phenyl
  • R 10 and R 11 independently have one of the meanings of R 1 , are phenyl, hydroxy-(Ci-
  • C 6 )-alkyl a group of the formula -(CH 2 )2-S-(CH 2 )2-OH or combine to form a group of the formula -(CH 2 ) r or of the formula -(CH 2 )2-B 1 -(CH 2 )2-, where j is 4 or 5, B 1 is oxygen, sulfur, sulfonyl or -NR 9 - and R 9 is (Ci-C ⁇ J-alkyl;
  • Especially preferred reactive groups capable of forming a covalent bond to cellulose under dyeing conditions standing for RG are the groups of the formulae (Vd) to (Vi)
  • alkyl groups may be straight chain or branched and are in particular methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec- butyl and tert-butyl.
  • Ci-C ⁇ J-alkyl groups may in addition be n-pentyl or n-hexyl. Methyl and ethyl are preferred.
  • alkoxy groups which accordingly are preferably methoxy and ethoxy and to alkylene groups, which are in particular ethylene, propylene and butylene.
  • Halogen is preferably bromine, chlorine and fluorine.
  • Alkali M is in particular lithium, sodium or potassium; an alkaline earth metal equivalent M is in particular the equivalent of calcium. M is preferably hydrogen or sodium.
  • Alkali-eliminatable groups standing for Z 1 are for example halogen, such as chlorine and bromine; ester groups of organic carboxylic and sulfonic acids, for example alkylcarboxylic acids, substituted or unsubstituted benzenecarboxylic acids and substituted or unsubstituted benzenesulfonic acids, in particular alkanoyloxy of 2 to 5 carbon atoms such as acetyloxy, benzoyloxy, sulfobenzoyloxy, phenylsulfonyloxy and toluylsulfonyloxy; also acidic ester groups of inorganic acids, as of phosphoric acid, sulfuric acid and thiosulfuric acid (phosphato, sulfato and thiosulfato groups) and dialkylamin
  • R 1 is preferably hydrogen, methyl or a group of the formula (II).
  • R 2 is hydrogen, whereas in another preferred embodiment of the present invention R 2 is sulfo.
  • Preferred aromatic or heteroaromatic groups standing for X 2 correspond to formula (MIv)
  • Especially preferred groups of the formula (Ma) are the groups to the formulae (Ma1 ) to (Ma4)
  • M is preferably hydrogen, sodium or potassium.
  • Preferred dyestuffs of the formula (I) correspond to the formulae (Ia) to (In) (Id) (Ie) (If)
  • dyestuffs of the formula (I) are for example the dyestuffs of the formulae (lo) to (It)
  • a 1 is a group of the formula (Vf), (Vg), (Vh) or (Vi);
  • a 2 is a group of the formula (Vd) or (Ve);
  • a 2 is a group of the formula (Vd) or (Ve);
  • R 12 is methyl, methoxy or -SO3M;
  • R 12 is methyl, methoxy or -SO 3 M; and M is defined as given above.
  • the dyestuffs of the formula (I) can be prepared by synthesis steps which are known to a skilled person.
  • the compounds of formula (VII) are known and can be prepared by known methods.
  • the compounds of formula (Vl) are partly known and can be prepared by known methods.
  • 4-amino-2-fluorobenzenesulphonic acid can be prepared according to the method described in US 5,106,960, 4-amino-3-fluorobenzene- sulphonic acid according to the method described in HeIv. Chim. Acta 1982, (65), p546-550 and 2-amino-5-fluorobenzenesulphonic acid according to the method described in HeIv. Chim. Acta 1983, (66), p68-75.
  • Additional compounds of the formula (Vl) are disclosed in Arzneistoffforschung/Drug Research, Vol. 18. No. (9), 1968, pages 1220-1221 and J.Chem.So ⁇ , Dalton Trans., Vol. 1990, 1990, pages 3773-3779.
  • R 1a is (Ci-C 4 )-alkyl, (CrC 4 )-alkoxy, hydroxy, fluorine, chlorine or a group of the formula (II)
  • X 2 is an aromatic or heteroaromatic group
  • R 3 is hydrogen or -SO 3 M
  • M is hydrogen, an alkali metal or an equivalent of an alkaline earth metal; with the proviso that the compounds of the formulae C and D
  • R 1a is fluorine, methyl, methoxy or a group of the formula (II).
  • Examples of preferred compounds of the formula (Via) are the compounds of formulae (VIaI ) to (Vla9)
  • the compounds of the formula (Via) can be prepared by treating compounds of the formula (VIII)
  • R 1a is defined as given above, with a sulphonating agent.
  • Preferred sulfonating agents are chlorosulphoic acid, sulphuric acid and oleum.
  • the compounds of the formula (VIII) are known and can be prepared by using known methods.
  • the present invention's dyes of the formula (I) have useful application properties and can be used for dyeing and printing carboxamido- and/or hydroxyl-containing materials.
  • the materials mentioned can be present for example in the form of sheetlike constructions such as paper and leather, in the form of films, as for example polyamide films, or in the form of a bulk composition, for example composed of polyamide or polyurethane. In particular, however, they are present in the form of fibres of the materials mentioned.
  • the present invention's dyes of the formula (I) are used for dyeing and printing cellulosic fibrous materials of any kind. They are preferably also useful for dyeing or printing polyamide fibres or of blend fabrics of polyamide with cotton or with polyester fibres. It is also possible to use the present invention's dyes of the formula (I) to print textiles or paper by the ink jet process.
  • the present invention thus also provides for the use of the present invention's dyes of the formula (I) for dyeing or printing carboxamido- and/or hydroxyl-containing materials, or as the case may be for processes for dyeing or printing such materials in a conventional manner wherein one or more dyes of the formula (I) according to the present invention are utilized as a colorant.
  • the as-synthesized solutions of the present invention's dyes of the formula (I), if appropriate after addition of a buffer substance, and if appropriate also after concentrating or diluting, can be directly used for dyeing as a liquid preparation.
  • Fibrous materials or fibres herein refer in particular to textile fibers which can be present as wovens, yarns or in the form of hanks or wound packages.
  • Carboxamido-containing materials are for example synthetic and natural polyamides and polyurethanes, in particular in the form of fibers, for example wool and other animal hairs, silk, leather, nylon-6,6, nylon-6, nylon-11 and nylon-4.
  • Hydroxyl-containing materials are those of natural or synthetic origin, for example cellulosic fibre materials or their regenerated products and polyvinyl alcohols.
  • Cellulosic fibre materials are preferably cotton, but also other vegetable fibres, such as linen, hemp, jute and ramie fibers.
  • Regenerated fibres of cellulose are for example staple viscose and filament viscose.
  • the present invention's dyes of the formula (I) can be applied to and fixed on the materials mentioned, in particular on the fibrous materials mentioned, by the application techniques known for water-soluble dyes, in particular known for fibre- reactive dyes.
  • Wool which has been given a nonfelting or low-felting finish (cf. for example H. Rath, Lehrbuch der Textilchemie, Springer-Verlag, 3rd edition (1972), pp. 295-299, in particular the finish by the so-called Hercosett process (p. 298); J. Soc. Dyers and Colouhsts 1972, 93-99, and 1975, 33-44) can be dyed with very good fastness properties.
  • the process of dyeing on wool is here carried out in a conventional manner from an acidic medium. For instance, 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.
  • a customary leveling agent for example on the basis of a reaction product of cyanuhc chloride with 3 times the molar amount of an aminobenzenesulfonic acid and/or of an aminonaphthalenesulfonic acid or on the basis of a reaction product of for example stearylamine with ethylene oxide.
  • the dyes of the present invention are preferably subjected to the exhaust process initially from an acidic dyebath having a pH of about 3.5 to 5.5 under pH control and the pH is then, toward the end of the dyeing time, shifted into the neutral and optionally weakly alkaline range up to a pH of 8.5 to bring about, especially for very deep shades, the full reactive bond between the dyes of the present invention and the fibre. At the same time, the dye portion not reactively bound is removed.
  • the dyeing liquors and print pastes, as well as the dyes of the formula (I) may contain further additions.
  • Additions are for example wetting agents, antifoam agents, leveling agents and agents which influence the properties of the textile material, such as softeners, additions for a flameproof finish and soil-, water- and oil-rejecting or water-softening agents.
  • Print pastes in particular may also contain natural or synthetic thickeners, such as for example alginates and cellulose ethers.
  • the dye quantities in the dyebaths and print pastes can vary within wide limits according to the desired depth of shade.
  • the dyes of the formula (I) are present in amounts of 0.01 % to 15% by weight and in particular in amounts of 0.1 % to 10% by weight based respectively on the material to be dyed and on the print paste.
  • cellulose fibres they produce by the exhaust method from a long liquor using a wide variety of acid-binding agents and if appropriate neutral salts, such as sodium chloride or sodium sulfate, dyeings having very good color yields.
  • Application of the dye is preferably at a pH of 3 to 7, and in particular at a pH of 4 to 6 for the exhausts method.
  • the liquor ratio can be chosen within a wide range and is for example between 3:1 and 50:1 , preferably between 5:1 and 30:1.
  • Dyeing is preferably carried out in an aqueous bath at temperatures between 40 and 105 0 C, if appropriate at a temperature of up to 130 0 C under pressure, and if appropriate in the presence of customary dyeing auxiliaries.
  • unfixed dye can be removed in an aftertreatment. This aftertreatment is carried out in particular at a pH of 8 to 9 and temperatures of 75 to 80°C.
  • One possible procedure here is to introduce the material into the warm bath and to gradually heat the bath to the desired temperature and complete the dyeing process at that temperature.
  • the neutral salts which accelerate the exhaustion of the dyes may also if desired only be added to the bath after the actual dyeing temperature has been reached.
  • Padding processes likewise provide excellent color yields and a very good color buildup on cellulose fibres, the dyes being fixable in a conventional manner by batching at room temperature or elevated temperature, for example at up to about 60 0 C, by steaming or using dry heat.
  • customary printing processes for cellulose fibers which can be carried out in one step, for example by printing with a print paste containing sodium bicarbonate or some other acid-binding agent and by subsequent steaming at 100 to 103°C, or in two steps, for example by printing with a neutral or weakly acidic print color and then fixing either by passing the printed material through a hot electrolyte- containing alkaline bath or by overpadding with an alkaline electrolyte-containing padding liquor and subsequent batching or steaming or dry heat treatment of the alkali-overpadded material, produce strong color prints with well-defined contours and a clear white ground. The outcome of the prints is affected by variations in the fixing conditions.
  • thermofix processes When fixing by means of dry heat in accordance with the customary thermofix processes, hot air at 120 to 200°C is used. In addition to the customary steam at 101 to 103°C, it is also possible to use superheated steam and high-pressure steam at temperatures of up to 160 0 C.
  • the acid-binding agents which effect the fixation of the dyes on the cellulose fibers are for example water-soluble basic salts of alkali metals and likewise alkaline earth metals of inorganic or organic acids or compounds which liberate alkali in the heat.
  • the alkali metal hydroxides and alkali metal salts of weak to medium inorganic or organic acids are the preferred alkali metal compounds being the sodium and potassium compounds.
  • Such acid-binding agents are for example sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, sodium formate, sodium dihydrogenphosphate, disodium hydrogenphosphate, sodium trichloroacetate, waterglass or trisodium phosphate.
  • the present invention's dyes of the formula (I) are notable for high reactivity, good fixing ability, very good build-up ability and also high light and perspiration light fastness. They can therefore be applied by the exhaust dyeing process at low dyeing temperatures and require only short steam times in the pad-steam process.
  • the degrees of fixation are high and unfixed portions are readily washed off with the difference between the degree of exhaustion and the degree of fixation being remarkably small, i.e., the loss on soaping is very low.
  • They are also particularly useful for printing, particularly on cotton, but also for printing nitrogenous fibers, for example wool or silk or blend fabrics containing wool or silk.
  • the present invention's dyes of the formula (I) are notable for unfixed portions of dye being readily washed off the fibrous material after the dyeing operation without whites included in the washing operation being stained or tainted by the dye which comes off. This results in advantages for the dyeing operation, in which washing cycles and hence costs are saved.
  • the dyeings and prints produced using the present invention's dyes of the formula (I) possess a high color strength and a high fibre-dye bond stability not only in the acidic region but also in the alkaline region, and also good light fastness and very good wet fastness properties, such as wash, water, seawater, cross-dyeing and perspiration fastnesses and also good fastness to pleating, hotpressing and crocking.
  • the present invention also provides inks for digital textile printing by the ink jet process, the inks comprising a present invention's dye of the formula (I).
  • the present invention's inks contain one or more of the present invention's dyes of the formula (I), for example in amounts from 0.1 % by weight to 50% by weight, preferably in amounts from 1 % by weight to 30% by weight and more preferably in amounts from 1 % by weight to 15% by weight, based on the total weight of the ink.
  • a conductivity of 0.5 to 25 mS/m can be set by adding an electrolyte.
  • Useful electrolytes include for example lithium nitrate and potassium nitrate.
  • the inks of the present invention may include organic solvents at a total level of 1 -50% and preferably 5-30% by weight.
  • Suitable organic solvents are for example alcohols, for example methanol, ethanol, 1 - propanol, isopropanol, 1 -butanol, tert-butanol, pentyl alcohol, polyhydhc alcohols for example: 1 ,2-ethanediol, 1 ,2,3-propanetriol, butanediol, 1 ,3-butanediol, 1 ,4- butanediol, 1 ,2-propanediol, 2,3-propanediol, pentanediol, 1 ,4-pentanediol, 1 ,5- pentanediol, hexanediol, D,L-1 ,2-hexanediol, 1 ,6-hexanediol, 1 ,2,6-hexanetriol, 1 ,2- octanediol, poly
  • the inks of the invention may further include customary additives, for example viscosity moderators to set viscosities in the range from 1.5 to 40.0 mPas in a temperature range from 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.
  • Useful viscosity moderators include rheological additives, for example polyvinylcaprolactam, polyvinylpyrrolidone and their copolymers polyetherpolyol, associative thickeners, polyurea, polyurethane, sodium alginates, modified galactomannans, polyetherurea, polyurethane and nonionic cellulose ethers.
  • rheological additives for example polyvinylcaprolactam, polyvinylpyrrolidone and their copolymers polyetherpolyol, associative thickeners, polyurea, polyurethane, sodium alginates, modified galactomannans, polyetherurea, polyurethane and nonionic cellulose ethers.
  • the inks of the invention may include surface-active substances to set surface tensions of 20 to 65 mN/m, which are adapted if necessary as a function of the process used (thermal or piezo technology).
  • Useful surface-active substances include for example all surfactants, preferably nonionic surfactants, butyldiglycol and 1 ,2-hexanediol.
  • the inks may further include customary additives, for example substances to inhibit fungal and bacterial growth in amounts from 0.01 to 1 % by weight based on the total weight of the ink.
  • customary additives for example substances to inhibit fungal and bacterial growth in amounts from 0.01 to 1 % by weight based on the total weight of the ink.
  • the inks of the invention may be prepared in a conventional manner by mixing the components in water.
  • the inks of the invention are particularly useful in inkjet printing processes for printing a wide variety of pretreated materials, such as silk, leather, wool, cellulosic fibre materials of any kind, polyurethanes and polyamide fibres.
  • the printing inks of the invention are also suitable for printing pretreated hydroxyl-containing and/or amino- containing fibers present in blends, examples being blends of cotton, silk, wool with polyester fibres or polyamide fibres.
  • auxiliaries In contrast to conventional textile printing, where the printing ink already contains all the fixing chemicals and thickeners for a reactive dye, in inkjet printing the auxiliaries have to be applied to the textile substrate in a separate pretreatment step.
  • the pretreatment of the textile substrate is effected with an aqueous alkaline liquor prior to printing.
  • alkali for example sodium carbonate, sodium bicarbonate, sodium acetate, thsodium phosphate, sodium silicate, sodium hydroxide
  • alkali donors such as, for example, sodium chloroacetate, sodium formate
  • hydrotropic substances such as, for example, urea
  • reduction inhibitors for example sodium nitrobenzenesulfonates
  • thickeners to prevent flowing of the motives when the printing ink is applied, for example sodium alginates, modified polyacrylates or highly ethehfied galactomannans.
  • pretreatment reagents are uniformly applied to the textile substrate in a defined amount using suitable applicators, for example using a 2- or 3-roll pad, contactless spraying technologies, by means of foam application or using appropriately adapted inkjet technologies, and subsequently dried.
  • the textile fiber material is dried at 120 to 150 0 C and subsequently fixed.
  • the fixing of the inkjet prints prepared with reactive dyes may be effected 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 energy transfer techniques.
  • the prints produced with the inks of the present invention possess high color strength and a high fiber-dye bond stability not only in the acidic but also in the alkaline region, also good lightfastness and very good wet fastness properties such as fastness to washing, water, seawater, crossdyeing and perspiration, and also good fastness to pleating, hotpressing and crocking.
  • 2-amino-4-fluorobenzenesulphonic acid (1.74g, 0.0082mol) was added to water (5OmIs) with stirring and the pH adjusted to 6.5 with 10% sodium bicarbonate solution to effect solution.
  • Sodium nitrite (0.57g, 0.0082mol) was added to the solution and after I Omins stirring the solution was added dropwise to a stirred mixure of ice (5Og) and cone.
  • HCI (1 OmIs) ensuring the temperature remained ⁇ 5°C by the use of external cooling. After a further 30mins the diazotization was complete and the excess nitrite was destroyed by the addition of sulphamic acid.
  • Example 3 a) The monoazo red obtained according to Example 2b above was isolated before determining its strength by combustion analysis. b) A mixture of compounds of the formulae
  • the reaction mixture was drowned out onto stirred crushed ice (ca. 40Og) cooled in an external ice bath such that T ⁇ 30°C to give a pink slurry of precipitated solid.
  • the solid was filtered off and the solid washed on the nutsch with saturated brine (3X80mls) before pulling down.
  • the solid was then slurried in acetone filtered and pulled dry before drying in the fan oven at 40 0 C.
  • the pale pink solid was ground to a powder (39.72g) and showed a single peak by HPLC. Analytical data was consistent with the proposed structure.
  • Sulfuric acid mono-[2-(4-amino-benzenesulfonyl)-ethyl] ester (28.85g, 0.1 mol) was suspended in water (40OmIs) with stirring and adjusted to pH7 with 10% sodium carbonate to effect solution. To this solution was added 5M sodium nitrite solution (22ml; 0.11 mol). This solution was then added over 1 hr to a stirred mixture of ice (15Og) and cone, hydrochloric acid (70ml) and then stirred for a further 1 hr. The excess nitrous acid was destroyed by the addition of sulphamic acid.
  • 2-amino-5- fluorobenzenesulphonic acid (19.Og, 0.09mol) was added in one portion to the diazo with stirring, after the addition the reaction mixture adjusted to pH4, initially with solid sodium bicarbonate and then maintained at this pH with 10% sodium carbonate before stirring overnight at room temperature, pH4.
  • To the reaction mixture was added cone, hydrochloric acid (20ml) and 1 ,3,6-naphthalenetrisulphonic acid (1Og) before heating at 45 0 C for 5 Hrs. Salt 10% w/v was added and the resulting solid collected by filtration before drying at 4O 0 C in a fan oven to give a brown solid (31.5g) and analytical data were consistent with the proposed structure.
  • the Solid was dissolved in water (100 ml) at pH 7 with 2N NaOH and extracted with dichloromethane (3x 50 ml). The solution was acidified to pH 1 with cone HCI producing a light gray precipitate. The solid was filtered off and washed with acetone before drying in a fan oven at 40 0 C to yield the product (7.09g) which exhibited analytical data consistent with the expected structure
  • the solution was acidified to pH 1 with cone HCI producing a light gray precipitate.
  • the solid was filtered off and washed with acetone before drying in a fan oven at 40 0 C to yield the product (14.94g) which exhibited analytical data consistent with the expected structure
  • the reaction mixture was drowned out onto stirred crushed ice (21 Og) which resulted in the formation of a precipitate.
  • the precipitate was screened off and pulled down.
  • the solid was slurried in water (7OmIs) warmed to 60 0 C and basified with sodium carbonate to pH 10 to give a clear solution.
  • the solution was then acidified with cHCI and allowed to cool to ambient temperature.
  • the resulting solid was filtered off and pulled down before drying in the fan oven at 40°C to yield an off white solid (10.087g) which exhibited analytical data consistent with the expected structure.
  • a textile fabric consisting of mercerized cotton is padded with a liquor containing 35 g/l of anhydrous sodium carbonate, 100 g/l of urea and 150 g/l of a low viscosity sodium alginate solution (6%) and then dried.
  • the wet pick-up is 70%.
  • the textile thus pretreated is printed with an aqueous ink containing 2% of the dye obtained according to Example 1 , 20% of sulfolane, 0.01 % of Mergal K9N and 77.99% of water using a drop-on-demand (bubble jet) ink jet print head.
  • the print is fully dried. Fixation is effected by means of saturated steam at 102 0 C for 8 minutes.
  • the print is subsequently rinsed warm, subjected to a fastness wash with hot water at 95°C, rinsed warm and then dried to obtain a print having excellent service fastnesses.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Coloring (AREA)

Abstract

La présente invention concerne des colorants de la formule (I) dans laquelle a vaut 1 ou 2; X1, X2, RG, R1, R2, R3, R4, a, b, c et M sont tels que définis dans la revendication 1, ainsi qu'un procédé pour leur préparation et leur utilisation.
PCT/EP2009/065084 2008-11-20 2009-11-13 Colorants réactifs fluorés à noyau WO2010057830A1 (fr)

Priority Applications (1)

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EP08105834.9 2008-11-20
EP08105834 2008-11-20
EP09152545 2009-02-11
EP09152545.1 2009-02-11

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013189817A1 (fr) * 2012-06-18 2013-12-27 Dystar Colours Distribution Gmbh Colorants réactifs exempts de métaux, leur procédé de production et leur utilisation
CN105176139A (zh) * 2015-05-26 2015-12-23 浙江龙盛集团股份有限公司 一种多偶氮棕色活性染料化合物及其制备方法和应用
WO2015193104A1 (fr) * 2014-06-18 2015-12-23 Huntsman Advanced Materials (Switzerland) Gmbh Mélanges de colorants réactifs
EP3020770A1 (fr) * 2014-11-17 2016-05-18 DFI Chem GmbH Colorants noirs tris-azo, leur préparation et utilisation
CN113906009A (zh) * 2019-06-06 2022-01-07 朗盛德国有限责任公司 用于喷墨打印的三偶氮化合物

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102876079A (zh) * 2012-09-20 2013-01-16 天津德凯化工股份有限公司 一种活性黑染料及其制备方法
EP2862902A1 (fr) * 2013-08-29 2015-04-22 DyStar Colours Distribution GmbH Mélanges de colorants réactifs dépourvus de métaux, production et utilisation
CN105603776A (zh) * 2015-10-30 2016-05-25 无锡市长安曙光手套厂 一种活性染料的配方

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US4937326A (en) * 1980-11-26 1990-06-26 Sumitomo Chemical Company, Limited Reactive scarlet dyes having both monochlorotriazinyl and vinylsulfone type reactive groups linked via N-alkylated amino
EP0748850A1 (fr) * 1995-06-14 1996-12-18 Ciba-Geigy Ag Des colorants, leur procédé de préparation et leur utilisation

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GB882001A (en) * 1959-09-16 1961-11-08 Ici Ltd New colouration process for cellulose textile materials
FR1321960A (fr) * 1962-05-14 1963-03-22 Acna Colorants réactifs
US4492654A (en) * 1980-07-05 1985-01-08 Hoechst Aktiengesellschaft Water-soluble azo compounds, a process for their preparation and their use as dyes
EP0051808A2 (fr) * 1980-11-06 1982-05-19 Hoechst Aktiengesellschaft Composés monoazoiques solubles dans l'eau, procédé pour leur préparation et leur utilisation comme colorants
US4430259A (en) * 1980-11-06 1984-02-07 Hoechst Aktiengesellschaft Water-soluble disazo compounds suitable as fiber-reactive dyestuffs
US4937326A (en) * 1980-11-26 1990-06-26 Sumitomo Chemical Company, Limited Reactive scarlet dyes having both monochlorotriazinyl and vinylsulfone type reactive groups linked via N-alkylated amino
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EP0748850A1 (fr) * 1995-06-14 1996-12-18 Ciba-Geigy Ag Des colorants, leur procédé de préparation et leur utilisation

Cited By (10)

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WO2013189817A1 (fr) * 2012-06-18 2013-12-27 Dystar Colours Distribution Gmbh Colorants réactifs exempts de métaux, leur procédé de production et leur utilisation
JP2015527420A (ja) * 2012-06-18 2015-09-17 ダイスター・カラーズ・ディストリビューション・ゲゼルシャフト・ミト・ベシュレンクテル・ハフツング 金属原子を含まない反応性染料、それらを製造するための方法、及びそれらの使用
WO2015193104A1 (fr) * 2014-06-18 2015-12-23 Huntsman Advanced Materials (Switzerland) Gmbh Mélanges de colorants réactifs
EP3020770A1 (fr) * 2014-11-17 2016-05-18 DFI Chem GmbH Colorants noirs tris-azo, leur préparation et utilisation
WO2016078988A1 (fr) * 2014-11-17 2016-05-26 Dfi Chem Gmbh Colorants réactifs, leur préparation et leur utilisation
US10259942B2 (en) 2014-11-17 2019-04-16 Dfi Chem Gmbh Black trisazo dyes, their preparation and their use
CN105176139A (zh) * 2015-05-26 2015-12-23 浙江龙盛集团股份有限公司 一种多偶氮棕色活性染料化合物及其制备方法和应用
CN105176139B (zh) * 2015-05-26 2020-09-29 浙江龙盛集团股份有限公司 一种多偶氮棕色活性染料化合物及其制备方法和应用
CN113906009A (zh) * 2019-06-06 2022-01-07 朗盛德国有限责任公司 用于喷墨打印的三偶氮化合物
CN113906009B (zh) * 2019-06-06 2024-01-30 朗盛德国有限责任公司 用于喷墨打印的三偶氮化合物

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