CA2135555A1 - Water-soluble phthalocyanine dyes, preparation thereof and use thereof - Google Patents
Water-soluble phthalocyanine dyes, preparation thereof and use thereofInfo
- Publication number
- CA2135555A1 CA2135555A1 CA002135555A CA2135555A CA2135555A1 CA 2135555 A1 CA2135555 A1 CA 2135555A1 CA 002135555 A CA002135555 A CA 002135555A CA 2135555 A CA2135555 A CA 2135555A CA 2135555 A1 CA2135555 A1 CA 2135555A1
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- Prior art keywords
- carbon atoms
- formula
- zero
- alkyl
- phthalocyanine dye
- 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.)
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Classifications
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/38—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using reactive dyes
- D06P1/384—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using reactive dyes reactive group not directly attached to heterocyclic group
-
- 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
- C09B47/00—Porphines; Azaporphines
- C09B47/04—Phthalocyanines abbreviation: Pc
-
- 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
- C09B62/517—Porphines; Azaporphines
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
- D06P3/02—Material containing basic nitrogen
- D06P3/04—Material containing basic nitrogen containing amide groups
- D06P3/10—Material containing basic nitrogen containing amide groups using reactive dyes
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
- D06P3/58—Material containing hydroxyl groups
- D06P3/60—Natural or regenerated cellulose
- D06P3/66—Natural or regenerated cellulose using reactive dyes
- D06P3/666—Natural or regenerated cellulose using reactive dyes reactive group not directly attached to heterocyclic group
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- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Coloring (AREA)
- Nitrogen Condensed Heterocyclic Rings (AREA)
Abstract
Abstract Water-soluble phthalocyanine dyes, preparation thereof and use thereof Described are phthalocyanine dyes of the formula (1)
Description
213`~ ~ v ~
HOECHST AKTIENGESELLSCHAFT HOE 93/F 380 Dr.HU/do Description Water-soluble phthalocyanine dyes, preparation thereof and use thereof The invention relates to the field of fiber-reactive dyes.
The users of fiber-reactive dyes have ever increasing expectations of the quality of the dyeings and the ecological compatib~lity of the dyes and of the dyeing process. Consequently, there continues to be a demand, especially with regard to the ecological safeness of the use of the dyes, for novel, especially heavy metal-free, fiber-reactive dyes which also have good dyeing qualities and fastness properties. For example, U.S. Patents Nos.
4,237,050, 4,350,632 and 4,745,187 describe fiber-reactive heavy metal complex phthalocyanine dyes, in particular copper and nickel phthalocyanine dye~, which have good dyeing properties and which pos~e~s, linked through an N-arylsulfonamide or N-alkyl~ulfonamide radical, a fiber-reactive group of the vinyl ~ulfone series. As these heavy metal complex phthalocyanine dyes decompo~e, for example in the course of the dispo~al of dyehou~e waote water~ and in used textiles, their heavy metals are liberated into the environment, ~o that the heavy metals pas~ into the waste waters and sewage sludges. Since there is already extensive legi~lation limiting the levels of heavy metal ion~ in wa~te waters and sewage sludges, a way has to be sought to replace the prior art heavy metal phthalocyanine dye~ with other~
having no heavy metal ion content.
The pre~ent invention now provide~ novel, water-~oluble phthalocyanine dyes of the below-indicated formula (1), whose central metal atom is safe and which give high-quality dyeings in brilliant green ~hades having good . . . :: - , ,: , : : , . ~
HOECHST AKTIENGESELLSCHAFT HOE 93/F 380 Dr.HU/do Description Water-soluble phthalocyanine dyes, preparation thereof and use thereof The invention relates to the field of fiber-reactive dyes.
The users of fiber-reactive dyes have ever increasing expectations of the quality of the dyeings and the ecological compatib~lity of the dyes and of the dyeing process. Consequently, there continues to be a demand, especially with regard to the ecological safeness of the use of the dyes, for novel, especially heavy metal-free, fiber-reactive dyes which also have good dyeing qualities and fastness properties. For example, U.S. Patents Nos.
4,237,050, 4,350,632 and 4,745,187 describe fiber-reactive heavy metal complex phthalocyanine dyes, in particular copper and nickel phthalocyanine dye~, which have good dyeing properties and which pos~e~s, linked through an N-arylsulfonamide or N-alkyl~ulfonamide radical, a fiber-reactive group of the vinyl ~ulfone series. As these heavy metal complex phthalocyanine dyes decompo~e, for example in the course of the dispo~al of dyehou~e waote water~ and in used textiles, their heavy metals are liberated into the environment, ~o that the heavy metals pas~ into the waste waters and sewage sludges. Since there is already extensive legi~lation limiting the levels of heavy metal ion~ in wa~te waters and sewage sludges, a way has to be sought to replace the prior art heavy metal phthalocyanine dye~ with other~
having no heavy metal ion content.
The pre~ent invention now provide~ novel, water-~oluble phthalocyanine dyes of the below-indicated formula (1), whose central metal atom is safe and which give high-quality dyeings in brilliant green ~hades having good . . . :: - , ,: , : : , . ~
2 1 3 ~
- 2 - :
fastnes~ properties.
( S 03M )a ~t \R2 ~b ~S02-NH-B-s02-y]
,:
In this formula:
PC is the radical of the phthalocyanine of the formula (A) :
N ~N
N
~N M e N~[3 ( A ) ~
N ~ N ~:
where Me is the bivalent metal radical ~`
- Z n ~ T i ( I V ) O ,.
2 13 ~
-V( I V)- or -S 1-O R
where R is methyl, ethyl, hydroxyl or halogen, preferably chlorine;
M i~ hydrogen or an alkali metal, such as ~odium, potassium or lithium, or some other ~alt-forming metal;
R1 is hydrogen, alkyl o$ 1 to 6 carbon atomo, prefer-ably 1 to 4 carbon atoms, such as methyl and ethyl, or is alkyl of 2 to 6 carbon atoms, preferably of 2 to 4 carbon atoms, such as ethyl and n-propyl, which i~ substituted by alkoxy of 1 to 4 carbon atoms, such as methoxy and ethoxy, alkanoylamino of 2 to 5 carbon atoms, such a~ acetylamino and propionyl-amino, carboxyl, sulfo, phosphato, sulfato, hydroxyl or dialkylamino having an alkyl each of 1 to 4 carbon atoms, ~uch as dimethylamino and diethyl-amino, R2 i~ hydrogen, alkyl of 1 to 6 carbon atoms, pref~rably of 1 to 4 carbon atoms, such as methyl and ethyl, or iB alkyl of 2 to 6 carbon atom~, pre-ferably of 2 to 4 carbon atoms, such a~ ethyl and n-propyl, which i~ su~stituted by alkoxy of 1 to 4 carbon atoms, euch as methoxy and ethoxy, alkanoylamino of 2 to 5 carbon atoms, ~uch as acetylamino and propionylamino, carboxyl, sulfo, phosphato, sulfato, hydroxyl, phenyl, sulfophenyl, carboxyphenyl or dialkylamino having an alkyl each of 1 to 4 carbon atoms, suah as dimethylamino and diethylamino, or is phenyl which can be sulfo-eub-stituted, or 0 R1 and R2, together with the nitrogen atom and an alkylene of 3 to 8 carbon atoms, preferably 4 to 6 carbon atoms, or with a further hetero group, such as a - 2 1 3 ~
nitrogen atom or oxygen atom or an -NH- group, and two alkylenes of 1 to 5 carbon atoms, form the radical of a 4- to 8-membered heterocyclic ring, ~or example an N-piperidino, N-piperazino or N-morpholino radical, or the radical -NRlR~ i~ cyano-amino;
B is a radical of the formula (2a) or (2b) R ~ :
R ( S 03M )m ( S 03M ) n (2a) (2b) where R3 is hydrogen, alkyl of 1 to 4 carbon atoms, ~uch as ethyl and in particular methyl, or alkoxy of 1 to 4 carbon atoms, Quch as ethoxy and in par-ticular methoxy, R4 i~ hydrogen, halogen, ~uch as bromine and :
chlorine, alkyl of 1 to 4 carbon atomo, ~uch as :.
ethyl and in particular methyl, or alkoxy of 1 to 4 carbon atoms, such a~ ethoxy and in particular methoxy, -M i~ a~ defined above, :~
m is zero or 1 (if zero, this group being hydrogen), preferably zero, n is zero, 1 or 2, preferably 1 or 2, and :: :
in the formula (2a) the -SO2-Y group i~ preferably attached meta or para relative to the sulfonyl-amino group and in the Xormula (2b) the bond leading from the naphthalene radical to the ~ulfonylamino group i~ preferably di~po~ed in ~he ~-po~ition of the naphthalene radical;
Y is vinyl or i~ an ethyl group which, in the :~
~-po~ition, contains a substituent which is eliminable by alkali to leave a vinyl group, or i~
2 1 3 ~ ~ ` 5 ~ -sulfoethyl or ~-hydroxyethyl;
a i8 from zero to 3, b is from zero to 2, and C i8 from 1 to 4, the sum of (a+b+c) being from 1 to 4.
The individual symbols in the formula can be identical to or different from each other within the scope of their definition.
The phthalocyanine dyes of the invention are generally obtained in the form of mixtures of the individual compounds of the formula (1), which individual compounds differ from one another by the number of sulfo and sulfonamide groups on the phthalocyanine radical. The formulae of the phthalocyanine dye~ according to the invention therefore have generally fractional indices.
Alkali-eliminable substltuent~ in the ~-position of the ethyl group of Y include for example halogen atoms, such as bromine and chlorine, ester groups of organic carboxylic and sulfonic acid~, as of alkylcarboxylic acids, ~ubstituted or unsubstituted benzenecarboxylic acids and substituted or unsubstituted benzenesulfonic acidR, such as alkanoyloxy of 2 to 5 carbon atom~
2specially acetyloxy, benzoyloxy, sulfobenzoyloxy, phenylsulfonyloxy and toluylsul$onyloxy, also acid ester groups of inorganic acids, a~ of phosphoric acid, sulfuric acid and thio~ulfuric acid (phosphato, sulfato and thiosulfato groups), eimilarly dialkylamino group~
having alkyl groups of in each ca~e 1 to 4 carbon atoms, such as dimethylamino and diethylamino. Y is preferably ~-sulfatoethyl or vinyl, particularly preferably ~-8ul fatoethyl.
The groups "eulfo", "carboxyl", "thiosulfato", "pho~phato", and "sulfato~ include not only their acid form but also their salt form. Accordingly~ sulfo group~
are groups conforming to the formula -S03M, carboxyl groups are groups conforming to the formula -COOM, thio-sulfato groups are group~ confor~ing to the formula -S-SO3M, pho~phato groups are gxoups conforming to the formula -OPO3M2, and ~ulfato groups are groups conforming to the formula -OSO3M, in each of which M is as defined above.
Radical~ of the formula -B-S02-Y include for example:
2-(~-sulfatoethyleulfonyl)phenyl, 3-(~-sulfatoethylsul-fonyl)phenyl, 4-(~-sulfatoethylsulfonyl)phenyl, 2-carboxy-5-(~-~ulfatoethylsulfonyl)phenyl, 2-chloro-3-(~-sulfatoethylsulfonyl)phenyl, 2-chloro-4-(~-aulfato-ethylsulfonyl)phenyl, 2-bromo-4-(~-~ulfatoethylsulfonyl~-phenyl, 4-methoxy-3-(~-sulfatoethyl~ulfonyl)phenyl, 4-chloro-3-(~-sulfatoethylsulfonyl)phenyl,2-ethoxy-4-or lS -5-(~-sulfatoethylsulfonyl)phenyl, 2-methyl-4-(~-sulfato-ethylsulfonyl)phenyl, 2-methoxy-5- or -4-(~-sulfatoethyl-~ulfonyl)phenyl, 2,4-diethoxy-5-(~-sulfatoethyl~ulfonyl)-phenyl, 2,4-dimethoxy-5-(~-sulfatoethyl~ulfonyl)phenyl, 2,5-dimethoxy-4-(~-sulfatoethylsulfonyl)phenyl, 2-methoxy-5-methyl-4-(~-~ulfatoethylsulfonyl)phenyl, 2-or 3- or 4-(~-thiosulfatoethylsulfonyl)phenyl, 2-methoxy-5 - (~- t h io ~u l fa to e t hy l ~ u 1 f o n y l) p he n y l, 2-sulfo-4-(~-pho~phatoethylsulfonyl)phenyl, 2-sulfo-4-vinylsulfonylphenyl, 2-chloro-4- or -5-(~-chloro-ethylsulfonyl)phenyl, 3- or 4-(~-acetoxyethyl-sulfonyl)phenyl, 5-(~-sulfatoethylsulfonyl)naphth-2-yl, 6- or 7- or 8-(~-sulfatoethylsulfonyl)naphth-2-yl, 6-(~
sulfatoethylsulfonyl)-1-sulfonaphth-2-yl, 5-(~-sulfato-ethylsulfonyl)-1-sulfonaphth-2-yl and 8-(~-~ulfatoethyl-sulfonyl)-6-sulfonaphth-2-yl.
Preferably, in the phthalocyanine dyes of the formula (1), R3 i~ hydrogen, methyl or methoxy, and R~ is prefer-ably hydrogen or methoxy. Preference is further given to compounds of the formula (1) in which Rl and R2 are each independently of the other hydrogen, methyl or ethyl and b is 1 to 2, and al~o to those in which b i~ zero.
Preference i~ further given to phthalocyanine dye~ of the - ~ :-' ' .
: -2 ~
formula (1) in which a i~ from zero to 3, preferably from 1 to 2.5, b i8 from zero to 2, preferably zero, and c is from 1 to 4, preferably from 1 to 2.
Radicals of the formula -NRlR2 include for example amino, methylamino, ethylamino, butylamino, benzylamino, ~-hydroxyethylamino, dimethylamino, diethylamino, di-(isopropyl)amino, N-methylbenzylamino, N-piperidino, N-morpholino, di-(~-hydroxyethyl)amino, ~-eulfoethyl-amino, ~-carboxyethylamino, ~-(4-carboxyphenyl)ethyl-amino, phenylamino, N-methylphenylamino, 3-aulfophenyl-amino and 4-sulfophenylamino and cyanoamino.
The pre~ent invention further relates to a process for preparing the phthalocyanine compounds of the formula (1), which comprises reacting a phthalocyanine~ulfonyl chloride of the formula (3) ( S 0 3 M ) p ( 3 ~
~( S O 2 - C I )q : .
,' :'.:
where PC and M are each as defined above, p is from zero to 3, and q is from 1 to 4, the sum of (p+g) being from 1 to 4, or a mixture thereof, in an aqueous or non-aqueous medium with an amine of the formula (4) ;~
H2N--B--S2--Y (4) ~ ~
where B and Y are each a~ defined above and Y mayadditionally have the meaning of ~-hydroxyethyl, and optionally with a further amino-containing compound of the formula H-NRlR2 where Rl and R2 are each ae defined above, concurrently or in any de~ired order and with con-current or successive partial hydrolysi~ of the ~ulfonylchloride group~ to eulfo groups. At the end of the condensation reaction any sulfonyl chloride groups still . .
.: - : ~ - :. :-,, - . :
. .
.
- 213~5~5 pre~ent are hydrolyzed to ~ulfo groups. The reaction according to the invention will generally inevitably involve a partial hydroly~is of the sulfonyl chloride groups to ~ulfo groupa. In the ca~e of the u~e of an amine of the formula (4) where Y i~ ~-hydroxyethyl, the ~-hydroxyethyl6ulfonyl group $n the phthalocyanine compound obtained can be converted by generally known methodg into a group of the formula -S02-Y where Y i~ an ethyl group Rub~tituted in the ~-position by an e~ter group, for example into the ~-sulfatoethyl BUl fonyl group by mean~ of ~ulfuric acid or sulfur trioxide-containing ~ulfuric acid or chloro~ulfonic acid.
The condensation reactions according to the invention between the compound~ of the formula (3) and the amines of the formulae (4) and H-NRlR2 are carried out at a pH
between 3.5 and 8.5, preferably between 4 and 8, in particular between 5.5 and 6.5, and at a temperature between 0C and 100C, preferably between 20 and 60C, in particular between 45 and 55C. Generally they take place in the pre~ence of a catalyat, auch as pyridine, a pyridine~ulfonic acid, pyridinecarboxylic acid, pyridinesulfonamide or pyridinecarboxamide compound, preferably in the pre~ence of nicotinamide, analogously to the procedure~ known from the U.S. Patents cited at the beginning or from U.S. Patent 4,745,187.
The Rtarting phthalocyaninesulfonyl chloride co~pound~ of the formula (3) are prepared analogously to known pro~
cedures, a~ discernible for example from statements in -the above-cited U.S. Patenta and from German Patent No.
891,121. For example, a compound of the formula (3) i~
prepared by introducing phthalocyanine of the formula (A) into chloro~ulfonic acid and ~tirring the batch at a temperature of between 80 and 150C, preferably between 100 and 140C, for ~everal hour~, and then adding a chlorinating agent, preferably thionyl chloride, and further stirring the batch at 80 to 90C fox ~everal hours. The batch i~ then ~tirred into cru~hed ice and the ~, : ., :
' ~ ~ . ' -~ ~ 33~
precipitated phthalocyanineeulfonyl chloride i~ filtered off with euction.
Another way of preparing a compound of the formula (3) i8 to react the phthalocyanine of the formula (A) with ~ulfuric acid/eul~ur trioxide in eulfur trioxide-contain-ing ~ulfuric acid (oleum) having a eulfur trioxide content rom about 50 to 65% by weight at about 80C.
After thie reaction, the batch is stirred into an ice-cooled aqueoue solution of eodium chloride, and the metal-containing phthalocyanineeulfonic acid obtained ie converted in a conventional manner, or example by meane of thionyl chloride in dimethylformamide, into the phthalocyanine-eulfonyl chloride.
The metal phthalocyanine etarting compounde of the formula (A) are known or are preparable by known methode.
Relevant literature includee US Patent 2,202,632, British Patents 679,773 and 1,306,055, 3nd US Patent 2,155,038.
The eeparation from the eyntheeie batches of the phthalo-cyanine dyee of formula (1) prep~red according to the invention, hereinafter referred to ae "dyee (1)", ie effected by generally known methods either by precipitat-ing from the reaction medium by means of electrolyte ,for example sodium chloride or pota~eium chloride, or by evaporating the reaction ~olution, ~or example by epray drying, in which case thi~ reaction solution may have buffer eubstance added to it. The dyes (1) have fiber-reactive properties and very good dye propertiee. Theycan therefore be u~ed for dyeing and printing hydroxyl-and/or carboxa~lido-containing material, in particular fiber material, and leather. 5imilarly, the eelutione obtained in the eynthesie of the compounde according to the invention can be u~ed directly in dyeing ae liquid preparation with or without prior addition of buffer eubstance and with or without prior concentrating.
: - .. - :
: . :- : :. . ...
. . . - -. . . . .
" ' ~ ' ' . , ' ' 213~v~
The present invention therefore also provides for the use of the dyes (1) for dyeing (including printing) hydroxyl-and carboxamido-containing material~, i.e. processee for applying them to these sub~trates. The materials are preferably employed in the form of fiber materials, in particular in the form of textile fibers, such as yarns, packages and fabrics.
Hydroxyl-containing materials are natural or ~ynthetic hydroxyl-containing material~, for example cellulose fiber materials, even in the form of paper, or their regenerated products and polyvinyl alcohols. Cellulo~e fiber materials are preferably cotton but al~o other vegetable fibers, such ae linen, hemp, ~ute and ramie fibere; regenerated cellulose fibers include for example staple viscose and filament vi~cose.
, .
Carboxamido-containing materials lnclude 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-ll and nylon-4.
The dyes (1) can be applied to and fixed on the sub-strates mentioned, in particular on the fiber materiala mentioned, by the techniques customary for water-soluble dye~, in particular for fiber-reactive dyes. For instance, on cellulose fibers they produce from a long liquor by the exhaust method and by means of various acid-binding agents with or without neutral salts, such a~ sodium chloride or sodium sulfate, dyeings having very good color yields and also excellent color build-up. They are dyed at temperatures between 40 and 105C, if desired at temperatures up to 130C under superatmospheric pressure, and if desired in the presence in the agueou~
bath of customary dyeing as~istant~. One possible procedure is to introduce the material into the warm bath and to gradually heat the bath to the desired d~eing temperature and to complete the dyeing proces~ at that : .: .
' :. . : :: : . :
- :-: . : : . , ~ ~ 3 ~
temperature. The neutral salt~ which ~peed up the exhaustion of the dye can if desired not be added to the bath until after the actual dyeing temperature has been reached.
The padding processes likewi~e produce excellent color yields and a very good color build-up on cellulose fibers, on which fixing can be e$fected by batching at room temperature or elevated temperature, for example at up to about 60C, by steaming or with dry heat in a conventional manner.
Similarly, the cu~tomary printing processes for cellulose fiber~, which can be carried out either single-phase, for example by printing with a print paste containing sodium carbonate or some other acid-binding agent as well as the colorant and by subsequent ~teaming at 100 to 103C, or two-phase, for example by printing with a neutral or weakly acid print paste containing the colorant and subsequent fixation either by pas~ing the printed -~
material through a hot electrolyte-containing alkaline bath or by overpadding with an alkaline electrolyte-containing padding liquor with a ~ub~equent batching of -;~
this treated material or subsequent steaming or subse-quent treatment with dry heat, produce ~trong prints with well-defined contours and a bright white ground. The appearance of the print~ is not greatly affeoted by variations in the fixing conditions. Not only in dyeing but also in printing, the degrees of fixation obtained with the compounds of the invention are very high. ~;
When fixing by means of dry heat in accordance with the customary thermofix processes, hot air from 120 to 200C
is used. In addition to the cu~tomary steam at 101 to 103C it is al~o pos~ible to u~e superheated steam a~d high-pres~ure ~team at temperature~ of up to 160C.
The acid-binding agents which effect the fixation of the dyes on the cellulo~e fibers include for example ,: ~ . . ~ ........................................................ .
.. . .
~ . ~: . , .. . . - ~ v"
~13S~ 5 water-~oluble basic salts of the alkali metals and the alkaline earth metals of inorganic or organic acid~ a~
well as compounds which liberate alkali in the heat.
Especially ~uitable are the alkali metal hydroxide~ and alkali metal salts of weak to medium inorganic or organic acids, the preferred alkali metal compounds being the ~odium and potassium compounds. Such acid-binding agents include for example sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, sodium formate, sodium dihydrogen-phosphate and aisodium hydrogenphosphate.
By treating the dyes (1) with the acid-binding agents with or without heating, these compound~ are chemically bonded to the cellulose fibers; especially the cellulose dyeings have after the customary aftertreatment by rinsing to remove unfixed portions of the dyes excellent wetfastness propertie~, in particular since ~uch unfixed portions are easily wa~hed off on account of their good ~olubility in cold water.
The dyeings on polyurethane and polyamide fiber~ are customarily carried out from an acid medium. For instance, the dyebath may have added to it acetic acid and/or ammonium sulfate and/or acetic acid and ammonium acetate or sodium acetate in order to bring it to the desired pH. To achieve a usable levelneas of the dyeing, it i~ advi~able to add customary leveling aid~, for example ba~ed on a reaction product of cyanuric chlori~e with three times the molar amount of an aminobenzene-sulfonic acid or an aminonaphthalenesulfonic acid or based on a reaction product of for example stearylamine with ethylene oxide. Generally the material to be dyed is introduced at a temperature of about 40C into the bath, agitated therein for some time, the dyebath i8 then adjusted to the deeired weakly acid, preferably weakly acetic acid, pH, and the actual dyeing i8 carried out at a temperature between 60 and 98C. However, the dyeings can al~o be carried out at boiling point or at :' ''' - , :
.
21~3~v5 temperatures up to 120C (under superatmospheric pressure).
The dyeings and print~ prepared with the dyes (1) on cellulose fiber materials have a high color strength, in addition good lightfa~tne~ and good wetfastne~s proper-ties, such as wa~h, milling, water, seawater, cross dyeing and perspiration fa~tness properties, also good fastness to pleating, hot pressing and rubbing.
The examples which follow illustrate the invention. The compounds de~cribed in terms of a formula are indicated in the form of the free acid; generally they are prepared and isolated in the form of their alkali metal ~alt~ and used for dyeing in the form of their salt~. Similarly, the starting compounds mentioned in the form of the free acid in the following examples, in particular table examples, can be used in the synthesis as such or in the form of their salts, preferably alkali metal ~alt~, ~uch ~
a~ lithium, ~odium or pota~sium salts. ~-Part~ and percentages mentioned in the examples are by --~ -~
weight, unle~s otherwi~e ~tated. Part~ by weight relate to parts by volume as the kilogram relates to the liter.
The absorption maxima (~) in the visible region reported for the compounds of the invention were deter-mined in a~ueous solution using their alkali metal salts.
In the table examples the ~ values are given in paren-theses in the hue column; the wavelength un~t is nm.
Example A
25 parts of zinc(II) phthalocyanine are introduced into 120 parts of chlorosulfonic acid, and the temperature of the batch rises to 50 to 60C. Thereafter the batch i~
stirred at 135C for a further 3 to 4 hours and then cooled down to 80 to 90C, and 34 part~ by volume of thionyl chloride are gradually added with thorough stirring. After further stirring at 90C for about four hours, the batch is then ~tirred out onto ic~, and the : . , .' ~: , .: , - . , ~
.
.
2 ~
precipitated zinc(II) phthalocyaninesulfonyl chloride, which has an average degree of eubstitution in respect of the sulfonyl chloride groups of 2.5, is filtered off with suction and waehed with ice-water.
Example B
To a mixture of 60 parts of 2-cyanobenzamide, 610 parts of quinoline and 364 parts of 1,2-dichlGrobenzene are gradually added, over about 5 minutes, and at about 20C, 68 parts of ~ilicon tetrachloride, the reaction mixture i~ heated to 205C, and the reaction is continued for 10 minutee while stirring under reflux. Thereafter the batch iB cooled down to 180C and the re~idue is filtered off with ~uction at that temperature, suspended in 158 part~ of glacial acetic acid, filtered off again and subsequently washed with 150 parts of aqueou~ 2N acetic acid and 400 parts by volume of ethanol and dried.
:, ' 30 parts of this dichloroeilicon phthalocyanine compound are introduced into 440 parts of chlorosulfonic acid. The reaction i8 carried out during about four hours at 130C
with thorough stirring, the batch is then cooled down to 85C, and 180 parts of thionyl chloride are gradually added over about 30 minutes. The reaction is continued under reflux at about 85C for a further ~our hour~, and then stirred out onto 3000 parts of ice, and the result-ing dichloroeilicon phthalocyaninetetrasulfonyl chlorideof the formula - ~ 2~3~'3~
N =~3=N 1--( 5 2 - C I ) ~N S\ C l 2 N~
L ~ _ ,,'' is filtered off in the form of a moist filter cake.
Example C
To a mixture of 35 parts of dichlorosilicon phthalo-cyanine and 220 parts of tetrahydrofuran are added at 20C 29 part~ of methylmagne~ium bromide and the reaction is carried out under reflux (at about 67C) in the cour~e of about 14 hours. Then in~olubles are filtered off the cooled batch, and the filtrate i~ admixed with 100 part~
of aqueous 5% strength hydrochloric acid, the tetrahydro~
furan is distilled off, and the resulting dimethyl~ilicon phthalocyanine is isolated by evaporating the aqueou~
pha~e to dryness.
18 parts of the dimethylsilicon phthalocyanine are introduced into 520 parts of chloro~ulfonic actd. The reaction is carried out during about three hours at 140C
with thorough stirring, the batch i~ cooled down to 85C, and 100 parts of thionyl chloride are gradually added.
The reaction is completed under reflux at about 85C, the batch is then poured with thorough stirring onto 2000 part~ of ice, and the precipitated dimethylsilicon phthalocyaninetetrasulfonyl chloride of the formula ... .. .. . . .
213 ~3~
N=~ N ~-(52-C I )4 i8 filtered off in the form of a moi~t filtar cake.
Example 1 A pH 6.5 solution of 36 parta of 4-(~-sulfatoethyl-~ulfonyl)aniline in 100 part~ of water i~ admixed with the zinc(II) phthalocyanine~ulfonyl chloride moist filter residue of Example A and 4 part~ of nicotinamide by ~tirring. The batch i8 sub~equently ~tirrsd for a further two hours at 50C and thereafter at about 20C while the pH of 6.5 i5 maintained. After the conden~ation reaction ha~ ended, the batch i~ filtered and the phthalocyanine dye of the invention i~ i~olated by ~alting out with ~odium chloride or by evaporating the reaction solution to drynes~ under reduced pres~ure.
The phthalocyanine dye of the invention ha~, written in the form of the free acid, the formula N--~_ 11 , ~( S 0 ~¢N Z n N~3 N~ _ 502-NH~502-CH~-CH2~050~N
~A,l~a" = 670 nm). ~:
.
~ ~ .
- 2:L35~
It has very good $iber-reactive dye properties, ia very readily soluble in water and, applied by the application and fixing techniques customary for fiber-reactive dyes in industry, yields on the material~ mentioned in the description, in particular on cellulose fiber materials, ~uch as cotton, brilliant green dyeings and prints having good fastnees properties.
Example 2 Example 1 is repeated with the 4-(~-sulfatoethyl-sulfonyl)aniline replaced by the same amount of 3-(~-~ul-fatoethylsulfonyl)aniline. The resulting novel phthalocyanine dye of the formula (written in the form of the free acid) 11 ~ 11 SO~-~III ~ SO2-CH~-CH~-OSO~R ]
U~x = 670nm) ~ how0 good fiber-reactive application propertie~ and dyes for example cellulose fiber materials, such as cotton, by the dyeing and printing techniques cu~tomary in industry for fiber-reactive dyeR in strong, brilliant, green shades having good fastness properties.
Example 3 To a neutral solution of 30 part~ of 4-(~-sulfatoethyl-sulfonyl)aniline in 300 parts of water are added with thorough stirring at 35C and a pH between 5.8 and 6.2 the dichlorosilicon phthalocyaninetetrasulfonyl chloride obtained in Example B in the form of a moi~t filter cake and 3 parts of nicotinamide. The batch is stirred under the stated reaction conditions for about a further three hours and then the novel phthalocyanine dye of the formula (written in the form of the $ree acid) ~ ~ -: :
....
,,-.:
. . .
~ 2 1 ~ 5 --8=N , ~(SO~H)2.
~¢~1 SIIC12 1~3 ~
_ ~ _ --1SO2-UH ~ 3 SO~-CH2-CHI-OSOIII]
x = 677 nm) iB isolated by evaporating the aqueous synthesis solution to dryness under reduced pressure at about 60C.
The novel dye has very good $iber-reactive dye properties and applied to the fiber materials mentioned in the des-cription, for example cotton, by the printing and dyeingtechniques customary in industry for fiber-reactive dye~
produces ~trong, fast, green prints and dyeings.
Example 4 To a pH 6 solution of 16.3 part~ of 4-(~-~ulfatoethyl-sulfonyl)aniline in 200 parts of water are added at atemperature of 35C and while maintaining a pH between 5.8 and 6.2, 1.66 parts of nicotinamide and the dimethyl-silicon phthalocyaninetetrasulfonyl chloride obtained in Example C as a water-moist filter cake. The batch i8 further stirred under these reaction conditions for some time and then the resulting novel phthalocyanine dye, which written in the form of the free acid ha~ the ~ -formula ~
.:
~r ~ . . : : , ,: ' ' :, .
' . ' " ' ' ` ~' . ' ' ' ~' ~ : ' - 21~t~55 N~ /(SO~H),,, ~ .:
0~11 t~ CII~ N$~) _ ~ _ --{SO2-~ ~so2-cH~-cH~-osolH ]
U~x = 670nm) i~ isolated by evaporating the aqueou~ synthesi~ solution ~ :
to dryne~s under reduced pressure at about 60C. It has very good dye propertie~ and applied by the usual tech-niques customary in indu~try for fiber-reactive dye~ for example to cellulose fiber materials produces strong, fast dyeings and prints in dark green shades.
. ' :.
~, - : ~, , , ,::
. ~ ' ' ~ :
- 2 - :
fastnes~ properties.
( S 03M )a ~t \R2 ~b ~S02-NH-B-s02-y]
,:
In this formula:
PC is the radical of the phthalocyanine of the formula (A) :
N ~N
N
~N M e N~[3 ( A ) ~
N ~ N ~:
where Me is the bivalent metal radical ~`
- Z n ~ T i ( I V ) O ,.
2 13 ~
-V( I V)- or -S 1-O R
where R is methyl, ethyl, hydroxyl or halogen, preferably chlorine;
M i~ hydrogen or an alkali metal, such as ~odium, potassium or lithium, or some other ~alt-forming metal;
R1 is hydrogen, alkyl o$ 1 to 6 carbon atomo, prefer-ably 1 to 4 carbon atoms, such as methyl and ethyl, or is alkyl of 2 to 6 carbon atoms, preferably of 2 to 4 carbon atoms, such as ethyl and n-propyl, which i~ substituted by alkoxy of 1 to 4 carbon atoms, such as methoxy and ethoxy, alkanoylamino of 2 to 5 carbon atoms, such a~ acetylamino and propionyl-amino, carboxyl, sulfo, phosphato, sulfato, hydroxyl or dialkylamino having an alkyl each of 1 to 4 carbon atoms, ~uch as dimethylamino and diethyl-amino, R2 i~ hydrogen, alkyl of 1 to 6 carbon atoms, pref~rably of 1 to 4 carbon atoms, such as methyl and ethyl, or iB alkyl of 2 to 6 carbon atom~, pre-ferably of 2 to 4 carbon atoms, such a~ ethyl and n-propyl, which i~ su~stituted by alkoxy of 1 to 4 carbon atoms, euch as methoxy and ethoxy, alkanoylamino of 2 to 5 carbon atoms, ~uch as acetylamino and propionylamino, carboxyl, sulfo, phosphato, sulfato, hydroxyl, phenyl, sulfophenyl, carboxyphenyl or dialkylamino having an alkyl each of 1 to 4 carbon atoms, suah as dimethylamino and diethylamino, or is phenyl which can be sulfo-eub-stituted, or 0 R1 and R2, together with the nitrogen atom and an alkylene of 3 to 8 carbon atoms, preferably 4 to 6 carbon atoms, or with a further hetero group, such as a - 2 1 3 ~
nitrogen atom or oxygen atom or an -NH- group, and two alkylenes of 1 to 5 carbon atoms, form the radical of a 4- to 8-membered heterocyclic ring, ~or example an N-piperidino, N-piperazino or N-morpholino radical, or the radical -NRlR~ i~ cyano-amino;
B is a radical of the formula (2a) or (2b) R ~ :
R ( S 03M )m ( S 03M ) n (2a) (2b) where R3 is hydrogen, alkyl of 1 to 4 carbon atoms, ~uch as ethyl and in particular methyl, or alkoxy of 1 to 4 carbon atoms, Quch as ethoxy and in par-ticular methoxy, R4 i~ hydrogen, halogen, ~uch as bromine and :
chlorine, alkyl of 1 to 4 carbon atomo, ~uch as :.
ethyl and in particular methyl, or alkoxy of 1 to 4 carbon atoms, such a~ ethoxy and in particular methoxy, -M i~ a~ defined above, :~
m is zero or 1 (if zero, this group being hydrogen), preferably zero, n is zero, 1 or 2, preferably 1 or 2, and :: :
in the formula (2a) the -SO2-Y group i~ preferably attached meta or para relative to the sulfonyl-amino group and in the Xormula (2b) the bond leading from the naphthalene radical to the ~ulfonylamino group i~ preferably di~po~ed in ~he ~-po~ition of the naphthalene radical;
Y is vinyl or i~ an ethyl group which, in the :~
~-po~ition, contains a substituent which is eliminable by alkali to leave a vinyl group, or i~
2 1 3 ~ ~ ` 5 ~ -sulfoethyl or ~-hydroxyethyl;
a i8 from zero to 3, b is from zero to 2, and C i8 from 1 to 4, the sum of (a+b+c) being from 1 to 4.
The individual symbols in the formula can be identical to or different from each other within the scope of their definition.
The phthalocyanine dyes of the invention are generally obtained in the form of mixtures of the individual compounds of the formula (1), which individual compounds differ from one another by the number of sulfo and sulfonamide groups on the phthalocyanine radical. The formulae of the phthalocyanine dye~ according to the invention therefore have generally fractional indices.
Alkali-eliminable substltuent~ in the ~-position of the ethyl group of Y include for example halogen atoms, such as bromine and chlorine, ester groups of organic carboxylic and sulfonic acid~, as of alkylcarboxylic acids, ~ubstituted or unsubstituted benzenecarboxylic acids and substituted or unsubstituted benzenesulfonic acidR, such as alkanoyloxy of 2 to 5 carbon atom~
2specially acetyloxy, benzoyloxy, sulfobenzoyloxy, phenylsulfonyloxy and toluylsul$onyloxy, also acid ester groups of inorganic acids, a~ of phosphoric acid, sulfuric acid and thio~ulfuric acid (phosphato, sulfato and thiosulfato groups), eimilarly dialkylamino group~
having alkyl groups of in each ca~e 1 to 4 carbon atoms, such as dimethylamino and diethylamino. Y is preferably ~-sulfatoethyl or vinyl, particularly preferably ~-8ul fatoethyl.
The groups "eulfo", "carboxyl", "thiosulfato", "pho~phato", and "sulfato~ include not only their acid form but also their salt form. Accordingly~ sulfo group~
are groups conforming to the formula -S03M, carboxyl groups are groups conforming to the formula -COOM, thio-sulfato groups are group~ confor~ing to the formula -S-SO3M, pho~phato groups are gxoups conforming to the formula -OPO3M2, and ~ulfato groups are groups conforming to the formula -OSO3M, in each of which M is as defined above.
Radical~ of the formula -B-S02-Y include for example:
2-(~-sulfatoethyleulfonyl)phenyl, 3-(~-sulfatoethylsul-fonyl)phenyl, 4-(~-sulfatoethylsulfonyl)phenyl, 2-carboxy-5-(~-~ulfatoethylsulfonyl)phenyl, 2-chloro-3-(~-sulfatoethylsulfonyl)phenyl, 2-chloro-4-(~-aulfato-ethylsulfonyl)phenyl, 2-bromo-4-(~-~ulfatoethylsulfonyl~-phenyl, 4-methoxy-3-(~-sulfatoethyl~ulfonyl)phenyl, 4-chloro-3-(~-sulfatoethylsulfonyl)phenyl,2-ethoxy-4-or lS -5-(~-sulfatoethylsulfonyl)phenyl, 2-methyl-4-(~-sulfato-ethylsulfonyl)phenyl, 2-methoxy-5- or -4-(~-sulfatoethyl-~ulfonyl)phenyl, 2,4-diethoxy-5-(~-sulfatoethyl~ulfonyl)-phenyl, 2,4-dimethoxy-5-(~-sulfatoethyl~ulfonyl)phenyl, 2,5-dimethoxy-4-(~-sulfatoethylsulfonyl)phenyl, 2-methoxy-5-methyl-4-(~-~ulfatoethylsulfonyl)phenyl, 2-or 3- or 4-(~-thiosulfatoethylsulfonyl)phenyl, 2-methoxy-5 - (~- t h io ~u l fa to e t hy l ~ u 1 f o n y l) p he n y l, 2-sulfo-4-(~-pho~phatoethylsulfonyl)phenyl, 2-sulfo-4-vinylsulfonylphenyl, 2-chloro-4- or -5-(~-chloro-ethylsulfonyl)phenyl, 3- or 4-(~-acetoxyethyl-sulfonyl)phenyl, 5-(~-sulfatoethylsulfonyl)naphth-2-yl, 6- or 7- or 8-(~-sulfatoethylsulfonyl)naphth-2-yl, 6-(~
sulfatoethylsulfonyl)-1-sulfonaphth-2-yl, 5-(~-sulfato-ethylsulfonyl)-1-sulfonaphth-2-yl and 8-(~-~ulfatoethyl-sulfonyl)-6-sulfonaphth-2-yl.
Preferably, in the phthalocyanine dyes of the formula (1), R3 i~ hydrogen, methyl or methoxy, and R~ is prefer-ably hydrogen or methoxy. Preference is further given to compounds of the formula (1) in which Rl and R2 are each independently of the other hydrogen, methyl or ethyl and b is 1 to 2, and al~o to those in which b i~ zero.
Preference i~ further given to phthalocyanine dye~ of the - ~ :-' ' .
: -2 ~
formula (1) in which a i~ from zero to 3, preferably from 1 to 2.5, b i8 from zero to 2, preferably zero, and c is from 1 to 4, preferably from 1 to 2.
Radicals of the formula -NRlR2 include for example amino, methylamino, ethylamino, butylamino, benzylamino, ~-hydroxyethylamino, dimethylamino, diethylamino, di-(isopropyl)amino, N-methylbenzylamino, N-piperidino, N-morpholino, di-(~-hydroxyethyl)amino, ~-eulfoethyl-amino, ~-carboxyethylamino, ~-(4-carboxyphenyl)ethyl-amino, phenylamino, N-methylphenylamino, 3-aulfophenyl-amino and 4-sulfophenylamino and cyanoamino.
The pre~ent invention further relates to a process for preparing the phthalocyanine compounds of the formula (1), which comprises reacting a phthalocyanine~ulfonyl chloride of the formula (3) ( S 0 3 M ) p ( 3 ~
~( S O 2 - C I )q : .
,' :'.:
where PC and M are each as defined above, p is from zero to 3, and q is from 1 to 4, the sum of (p+g) being from 1 to 4, or a mixture thereof, in an aqueous or non-aqueous medium with an amine of the formula (4) ;~
H2N--B--S2--Y (4) ~ ~
where B and Y are each a~ defined above and Y mayadditionally have the meaning of ~-hydroxyethyl, and optionally with a further amino-containing compound of the formula H-NRlR2 where Rl and R2 are each ae defined above, concurrently or in any de~ired order and with con-current or successive partial hydrolysi~ of the ~ulfonylchloride group~ to eulfo groups. At the end of the condensation reaction any sulfonyl chloride groups still . .
.: - : ~ - :. :-,, - . :
. .
.
- 213~5~5 pre~ent are hydrolyzed to ~ulfo groups. The reaction according to the invention will generally inevitably involve a partial hydroly~is of the sulfonyl chloride groups to ~ulfo groupa. In the ca~e of the u~e of an amine of the formula (4) where Y i~ ~-hydroxyethyl, the ~-hydroxyethyl6ulfonyl group $n the phthalocyanine compound obtained can be converted by generally known methodg into a group of the formula -S02-Y where Y i~ an ethyl group Rub~tituted in the ~-position by an e~ter group, for example into the ~-sulfatoethyl BUl fonyl group by mean~ of ~ulfuric acid or sulfur trioxide-containing ~ulfuric acid or chloro~ulfonic acid.
The condensation reactions according to the invention between the compound~ of the formula (3) and the amines of the formulae (4) and H-NRlR2 are carried out at a pH
between 3.5 and 8.5, preferably between 4 and 8, in particular between 5.5 and 6.5, and at a temperature between 0C and 100C, preferably between 20 and 60C, in particular between 45 and 55C. Generally they take place in the pre~ence of a catalyat, auch as pyridine, a pyridine~ulfonic acid, pyridinecarboxylic acid, pyridinesulfonamide or pyridinecarboxamide compound, preferably in the pre~ence of nicotinamide, analogously to the procedure~ known from the U.S. Patents cited at the beginning or from U.S. Patent 4,745,187.
The Rtarting phthalocyaninesulfonyl chloride co~pound~ of the formula (3) are prepared analogously to known pro~
cedures, a~ discernible for example from statements in -the above-cited U.S. Patenta and from German Patent No.
891,121. For example, a compound of the formula (3) i~
prepared by introducing phthalocyanine of the formula (A) into chloro~ulfonic acid and ~tirring the batch at a temperature of between 80 and 150C, preferably between 100 and 140C, for ~everal hour~, and then adding a chlorinating agent, preferably thionyl chloride, and further stirring the batch at 80 to 90C fox ~everal hours. The batch i~ then ~tirred into cru~hed ice and the ~, : ., :
' ~ ~ . ' -~ ~ 33~
precipitated phthalocyanineeulfonyl chloride i~ filtered off with euction.
Another way of preparing a compound of the formula (3) i8 to react the phthalocyanine of the formula (A) with ~ulfuric acid/eul~ur trioxide in eulfur trioxide-contain-ing ~ulfuric acid (oleum) having a eulfur trioxide content rom about 50 to 65% by weight at about 80C.
After thie reaction, the batch is stirred into an ice-cooled aqueoue solution of eodium chloride, and the metal-containing phthalocyanineeulfonic acid obtained ie converted in a conventional manner, or example by meane of thionyl chloride in dimethylformamide, into the phthalocyanine-eulfonyl chloride.
The metal phthalocyanine etarting compounde of the formula (A) are known or are preparable by known methode.
Relevant literature includee US Patent 2,202,632, British Patents 679,773 and 1,306,055, 3nd US Patent 2,155,038.
The eeparation from the eyntheeie batches of the phthalo-cyanine dyee of formula (1) prep~red according to the invention, hereinafter referred to ae "dyee (1)", ie effected by generally known methods either by precipitat-ing from the reaction medium by means of electrolyte ,for example sodium chloride or pota~eium chloride, or by evaporating the reaction ~olution, ~or example by epray drying, in which case thi~ reaction solution may have buffer eubstance added to it. The dyes (1) have fiber-reactive properties and very good dye propertiee. Theycan therefore be u~ed for dyeing and printing hydroxyl-and/or carboxa~lido-containing material, in particular fiber material, and leather. 5imilarly, the eelutione obtained in the eynthesie of the compounde according to the invention can be u~ed directly in dyeing ae liquid preparation with or without prior addition of buffer eubstance and with or without prior concentrating.
: - .. - :
: . :- : :. . ...
. . . - -. . . . .
" ' ~ ' ' . , ' ' 213~v~
The present invention therefore also provides for the use of the dyes (1) for dyeing (including printing) hydroxyl-and carboxamido-containing material~, i.e. processee for applying them to these sub~trates. The materials are preferably employed in the form of fiber materials, in particular in the form of textile fibers, such as yarns, packages and fabrics.
Hydroxyl-containing materials are natural or ~ynthetic hydroxyl-containing material~, for example cellulose fiber materials, even in the form of paper, or their regenerated products and polyvinyl alcohols. Cellulo~e fiber materials are preferably cotton but al~o other vegetable fibers, such ae linen, hemp, ~ute and ramie fibere; regenerated cellulose fibers include for example staple viscose and filament vi~cose.
, .
Carboxamido-containing materials lnclude 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-ll and nylon-4.
The dyes (1) can be applied to and fixed on the sub-strates mentioned, in particular on the fiber materiala mentioned, by the techniques customary for water-soluble dye~, in particular for fiber-reactive dyes. For instance, on cellulose fibers they produce from a long liquor by the exhaust method and by means of various acid-binding agents with or without neutral salts, such a~ sodium chloride or sodium sulfate, dyeings having very good color yields and also excellent color build-up. They are dyed at temperatures between 40 and 105C, if desired at temperatures up to 130C under superatmospheric pressure, and if desired in the presence in the agueou~
bath of customary dyeing as~istant~. One possible procedure is to introduce the material into the warm bath and to gradually heat the bath to the desired d~eing temperature and to complete the dyeing proces~ at that : .: .
' :. . : :: : . :
- :-: . : : . , ~ ~ 3 ~
temperature. The neutral salt~ which ~peed up the exhaustion of the dye can if desired not be added to the bath until after the actual dyeing temperature has been reached.
The padding processes likewi~e produce excellent color yields and a very good color build-up on cellulose fibers, on which fixing can be e$fected by batching at room temperature or elevated temperature, for example at up to about 60C, by steaming or with dry heat in a conventional manner.
Similarly, the cu~tomary printing processes for cellulose fiber~, which can be carried out either single-phase, for example by printing with a print paste containing sodium carbonate or some other acid-binding agent as well as the colorant and by subsequent ~teaming at 100 to 103C, or two-phase, for example by printing with a neutral or weakly acid print paste containing the colorant and subsequent fixation either by pas~ing the printed -~
material through a hot electrolyte-containing alkaline bath or by overpadding with an alkaline electrolyte-containing padding liquor with a ~ub~equent batching of -;~
this treated material or subsequent steaming or subse-quent treatment with dry heat, produce ~trong prints with well-defined contours and a bright white ground. The appearance of the print~ is not greatly affeoted by variations in the fixing conditions. Not only in dyeing but also in printing, the degrees of fixation obtained with the compounds of the invention are very high. ~;
When fixing by means of dry heat in accordance with the customary thermofix processes, hot air from 120 to 200C
is used. In addition to the cu~tomary steam at 101 to 103C it is al~o pos~ible to u~e superheated steam a~d high-pres~ure ~team at temperature~ of up to 160C.
The acid-binding agents which effect the fixation of the dyes on the cellulo~e fibers include for example ,: ~ . . ~ ........................................................ .
.. . .
~ . ~: . , .. . . - ~ v"
~13S~ 5 water-~oluble basic salts of the alkali metals and the alkaline earth metals of inorganic or organic acid~ a~
well as compounds which liberate alkali in the heat.
Especially ~uitable are the alkali metal hydroxide~ and alkali metal salts of weak to medium inorganic or organic acids, the preferred alkali metal compounds being the ~odium and potassium compounds. Such acid-binding agents include for example sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, sodium formate, sodium dihydrogen-phosphate and aisodium hydrogenphosphate.
By treating the dyes (1) with the acid-binding agents with or without heating, these compound~ are chemically bonded to the cellulose fibers; especially the cellulose dyeings have after the customary aftertreatment by rinsing to remove unfixed portions of the dyes excellent wetfastness propertie~, in particular since ~uch unfixed portions are easily wa~hed off on account of their good ~olubility in cold water.
The dyeings on polyurethane and polyamide fiber~ are customarily carried out from an acid medium. For instance, the dyebath may have added to it acetic acid and/or ammonium sulfate and/or acetic acid and ammonium acetate or sodium acetate in order to bring it to the desired pH. To achieve a usable levelneas of the dyeing, it i~ advi~able to add customary leveling aid~, for example ba~ed on a reaction product of cyanuric chlori~e with three times the molar amount of an aminobenzene-sulfonic acid or an aminonaphthalenesulfonic acid or based on a reaction product of for example stearylamine with ethylene oxide. Generally the material to be dyed is introduced at a temperature of about 40C into the bath, agitated therein for some time, the dyebath i8 then adjusted to the deeired weakly acid, preferably weakly acetic acid, pH, and the actual dyeing i8 carried out at a temperature between 60 and 98C. However, the dyeings can al~o be carried out at boiling point or at :' ''' - , :
.
21~3~v5 temperatures up to 120C (under superatmospheric pressure).
The dyeings and print~ prepared with the dyes (1) on cellulose fiber materials have a high color strength, in addition good lightfa~tne~ and good wetfastne~s proper-ties, such as wa~h, milling, water, seawater, cross dyeing and perspiration fa~tness properties, also good fastness to pleating, hot pressing and rubbing.
The examples which follow illustrate the invention. The compounds de~cribed in terms of a formula are indicated in the form of the free acid; generally they are prepared and isolated in the form of their alkali metal ~alt~ and used for dyeing in the form of their salt~. Similarly, the starting compounds mentioned in the form of the free acid in the following examples, in particular table examples, can be used in the synthesis as such or in the form of their salts, preferably alkali metal ~alt~, ~uch ~
a~ lithium, ~odium or pota~sium salts. ~-Part~ and percentages mentioned in the examples are by --~ -~
weight, unle~s otherwi~e ~tated. Part~ by weight relate to parts by volume as the kilogram relates to the liter.
The absorption maxima (~) in the visible region reported for the compounds of the invention were deter-mined in a~ueous solution using their alkali metal salts.
In the table examples the ~ values are given in paren-theses in the hue column; the wavelength un~t is nm.
Example A
25 parts of zinc(II) phthalocyanine are introduced into 120 parts of chlorosulfonic acid, and the temperature of the batch rises to 50 to 60C. Thereafter the batch i~
stirred at 135C for a further 3 to 4 hours and then cooled down to 80 to 90C, and 34 part~ by volume of thionyl chloride are gradually added with thorough stirring. After further stirring at 90C for about four hours, the batch is then ~tirred out onto ic~, and the : . , .' ~: , .: , - . , ~
.
.
2 ~
precipitated zinc(II) phthalocyaninesulfonyl chloride, which has an average degree of eubstitution in respect of the sulfonyl chloride groups of 2.5, is filtered off with suction and waehed with ice-water.
Example B
To a mixture of 60 parts of 2-cyanobenzamide, 610 parts of quinoline and 364 parts of 1,2-dichlGrobenzene are gradually added, over about 5 minutes, and at about 20C, 68 parts of ~ilicon tetrachloride, the reaction mixture i~ heated to 205C, and the reaction is continued for 10 minutee while stirring under reflux. Thereafter the batch iB cooled down to 180C and the re~idue is filtered off with ~uction at that temperature, suspended in 158 part~ of glacial acetic acid, filtered off again and subsequently washed with 150 parts of aqueou~ 2N acetic acid and 400 parts by volume of ethanol and dried.
:, ' 30 parts of this dichloroeilicon phthalocyanine compound are introduced into 440 parts of chlorosulfonic acid. The reaction i8 carried out during about four hours at 130C
with thorough stirring, the batch is then cooled down to 85C, and 180 parts of thionyl chloride are gradually added over about 30 minutes. The reaction is continued under reflux at about 85C for a further ~our hour~, and then stirred out onto 3000 parts of ice, and the result-ing dichloroeilicon phthalocyaninetetrasulfonyl chlorideof the formula - ~ 2~3~'3~
N =~3=N 1--( 5 2 - C I ) ~N S\ C l 2 N~
L ~ _ ,,'' is filtered off in the form of a moist filter cake.
Example C
To a mixture of 35 parts of dichlorosilicon phthalo-cyanine and 220 parts of tetrahydrofuran are added at 20C 29 part~ of methylmagne~ium bromide and the reaction is carried out under reflux (at about 67C) in the cour~e of about 14 hours. Then in~olubles are filtered off the cooled batch, and the filtrate i~ admixed with 100 part~
of aqueous 5% strength hydrochloric acid, the tetrahydro~
furan is distilled off, and the resulting dimethyl~ilicon phthalocyanine is isolated by evaporating the aqueou~
pha~e to dryness.
18 parts of the dimethylsilicon phthalocyanine are introduced into 520 parts of chloro~ulfonic actd. The reaction is carried out during about three hours at 140C
with thorough stirring, the batch i~ cooled down to 85C, and 100 parts of thionyl chloride are gradually added.
The reaction is completed under reflux at about 85C, the batch is then poured with thorough stirring onto 2000 part~ of ice, and the precipitated dimethylsilicon phthalocyaninetetrasulfonyl chloride of the formula ... .. .. . . .
213 ~3~
N=~ N ~-(52-C I )4 i8 filtered off in the form of a moi~t filtar cake.
Example 1 A pH 6.5 solution of 36 parta of 4-(~-sulfatoethyl-~ulfonyl)aniline in 100 part~ of water i~ admixed with the zinc(II) phthalocyanine~ulfonyl chloride moist filter residue of Example A and 4 part~ of nicotinamide by ~tirring. The batch i8 sub~equently ~tirrsd for a further two hours at 50C and thereafter at about 20C while the pH of 6.5 i5 maintained. After the conden~ation reaction ha~ ended, the batch i~ filtered and the phthalocyanine dye of the invention i~ i~olated by ~alting out with ~odium chloride or by evaporating the reaction solution to drynes~ under reduced pres~ure.
The phthalocyanine dye of the invention ha~, written in the form of the free acid, the formula N--~_ 11 , ~( S 0 ~¢N Z n N~3 N~ _ 502-NH~502-CH~-CH2~050~N
~A,l~a" = 670 nm). ~:
.
~ ~ .
- 2:L35~
It has very good $iber-reactive dye properties, ia very readily soluble in water and, applied by the application and fixing techniques customary for fiber-reactive dyes in industry, yields on the material~ mentioned in the description, in particular on cellulose fiber materials, ~uch as cotton, brilliant green dyeings and prints having good fastnees properties.
Example 2 Example 1 is repeated with the 4-(~-sulfatoethyl-sulfonyl)aniline replaced by the same amount of 3-(~-~ul-fatoethylsulfonyl)aniline. The resulting novel phthalocyanine dye of the formula (written in the form of the free acid) 11 ~ 11 SO~-~III ~ SO2-CH~-CH~-OSO~R ]
U~x = 670nm) ~ how0 good fiber-reactive application propertie~ and dyes for example cellulose fiber materials, such as cotton, by the dyeing and printing techniques cu~tomary in industry for fiber-reactive dyeR in strong, brilliant, green shades having good fastness properties.
Example 3 To a neutral solution of 30 part~ of 4-(~-sulfatoethyl-sulfonyl)aniline in 300 parts of water are added with thorough stirring at 35C and a pH between 5.8 and 6.2 the dichlorosilicon phthalocyaninetetrasulfonyl chloride obtained in Example B in the form of a moi~t filter cake and 3 parts of nicotinamide. The batch is stirred under the stated reaction conditions for about a further three hours and then the novel phthalocyanine dye of the formula (written in the form of the $ree acid) ~ ~ -: :
....
,,-.:
. . .
~ 2 1 ~ 5 --8=N , ~(SO~H)2.
~¢~1 SIIC12 1~3 ~
_ ~ _ --1SO2-UH ~ 3 SO~-CH2-CHI-OSOIII]
x = 677 nm) iB isolated by evaporating the aqueous synthesis solution to dryness under reduced pressure at about 60C.
The novel dye has very good $iber-reactive dye properties and applied to the fiber materials mentioned in the des-cription, for example cotton, by the printing and dyeingtechniques customary in industry for fiber-reactive dye~
produces ~trong, fast, green prints and dyeings.
Example 4 To a pH 6 solution of 16.3 part~ of 4-(~-~ulfatoethyl-sulfonyl)aniline in 200 parts of water are added at atemperature of 35C and while maintaining a pH between 5.8 and 6.2, 1.66 parts of nicotinamide and the dimethyl-silicon phthalocyaninetetrasulfonyl chloride obtained in Example C as a water-moist filter cake. The batch i8 further stirred under these reaction conditions for some time and then the resulting novel phthalocyanine dye, which written in the form of the free acid ha~ the ~ -formula ~
.:
~r ~ . . : : , ,: ' ' :, .
' . ' " ' ' ` ~' . ' ' ' ~' ~ : ' - 21~t~55 N~ /(SO~H),,, ~ .:
0~11 t~ CII~ N$~) _ ~ _ --{SO2-~ ~so2-cH~-cH~-osolH ]
U~x = 670nm) i~ isolated by evaporating the aqueou~ synthesi~ solution ~ :
to dryne~s under reduced pressure at about 60C. It has very good dye propertie~ and applied by the usual tech-niques customary in indu~try for fiber-reactive dye~ for example to cellulose fiber materials produces strong, fast dyeings and prints in dark green shades.
. ' :.
~, - : ~, , , ,::
. ~ ' ' ~ :
Claims (9)
1. A phthalocyanine dye of the formula (1) (1) where PC is the radical of the phthalocyanine of the formula (A) (A) where Me is the bivalent metal radical - Z n ( I I ) - , - ? i ( I V ) - , or where R is methyl, ethyl, hydroxyl or halogen, preferably chlorine;
M is hydrogen or an alkali metal or some other salt-forming metal;
R1 is hydrogen, alkyl of 1 to 6 carbon atoms, or is alkyl of 2 to 6 carbon atoms, which is substi-tuted by alkoxy of 1 to 4 carbon atoms, cyano, alkanoylamino of 2 to 5 carbon atoms, carboxyl, sulfo, phosphato, sulfato, hydroxyl or dialkyl-amino having an alkyl each of 1 to 4 carbon atoms, R2 is hydrogen, alkyl of 1 to 6 carbon atoms, or is alkyl of 2 to 6 carbon atoms, which is substituted by alkoxy of 1 to 4 carbon atoms, cyano, alkanoylamino of 2 to 5 carbon atoms, carboxyl, sulfo, phosphato, sulfato, hydroxyl, phenyl, sulfophenyl, carboxyphenyl or dialkyl-amino having an alkyl each of 1 to 4 carbon atoms, or R1 and R2, together with the nitrogen atom and an alkylene of 3 to 8 carbon atoms, or with a further hetero group and two alkylenes of 1 to 5 carbon atoms, form the radical of a 4- to 8-membered heterocyclic ring, or the radical -NR1R2 is cyanoamino;
B is a radical of the formula (2a) or (2b) ( 2 a ) ( 2 b ) where R3 is hydrogen, alkyl of 1 to 4 carbon atoms, or alkoxy of 1 to 4 carbon atoms, R4 is hydrogen, halogen, alkyl of 1 to 4 carbon atoms, or alkoxy of 1 to 4 carbon atoms, M is as defined above, m is zero or 1, and n is zero, 1 or 2;
Y is vinyl or is an ethyl group which, in the .beta.-position, contains a substituent which is eliminable by alkali to leave a vinyl group, or Y is .beta.-sulfoethyl or .beta.-hydroxyethyl;
a is from zero to 3, b is from zero to 2, and c is from 1 to 4, the sum of (a+b+c) being from 1 to 4.
M is hydrogen or an alkali metal or some other salt-forming metal;
R1 is hydrogen, alkyl of 1 to 6 carbon atoms, or is alkyl of 2 to 6 carbon atoms, which is substi-tuted by alkoxy of 1 to 4 carbon atoms, cyano, alkanoylamino of 2 to 5 carbon atoms, carboxyl, sulfo, phosphato, sulfato, hydroxyl or dialkyl-amino having an alkyl each of 1 to 4 carbon atoms, R2 is hydrogen, alkyl of 1 to 6 carbon atoms, or is alkyl of 2 to 6 carbon atoms, which is substituted by alkoxy of 1 to 4 carbon atoms, cyano, alkanoylamino of 2 to 5 carbon atoms, carboxyl, sulfo, phosphato, sulfato, hydroxyl, phenyl, sulfophenyl, carboxyphenyl or dialkyl-amino having an alkyl each of 1 to 4 carbon atoms, or R1 and R2, together with the nitrogen atom and an alkylene of 3 to 8 carbon atoms, or with a further hetero group and two alkylenes of 1 to 5 carbon atoms, form the radical of a 4- to 8-membered heterocyclic ring, or the radical -NR1R2 is cyanoamino;
B is a radical of the formula (2a) or (2b) ( 2 a ) ( 2 b ) where R3 is hydrogen, alkyl of 1 to 4 carbon atoms, or alkoxy of 1 to 4 carbon atoms, R4 is hydrogen, halogen, alkyl of 1 to 4 carbon atoms, or alkoxy of 1 to 4 carbon atoms, M is as defined above, m is zero or 1, and n is zero, 1 or 2;
Y is vinyl or is an ethyl group which, in the .beta.-position, contains a substituent which is eliminable by alkali to leave a vinyl group, or Y is .beta.-sulfoethyl or .beta.-hydroxyethyl;
a is from zero to 3, b is from zero to 2, and c is from 1 to 4, the sum of (a+b+c) being from 1 to 4.
2. A phthalocyanine dye as claimed in claim 1, wherein B is a radical of the formula (2a) in which R3 is hydrogen, methyl or methoxy, R4 is hydrogen or methoxy, and m is zero.
3. A phthalocyanine dye as claimed in claim 1 or 2, wherein b is zero.
4. A phthalocyanine dye as claimed in claim 3, wherein a is from zero to 3 and c is from 1 to 2.
5. A phthalocyanine dye as claimed in at least one of claims 1 to 4, wherein Y is .beta.-sulfatoethyl or vinyl.
6. A phthalocyanine dye as claimed in at least one of claims 1 to 5, wherein Me is zinc(II).
7. A process for preparing a phthalocyanine dye of the formula (1) of claim 1, which comprises reacting a phthalocyaninesulfonyl chloride of the formula (3) ( 3 ) where PC and M are each as defined in claim 1, p is from zero to 3, and q is from 1 to 4, the sum of (p+q) being from 1 to 4, in an aqueous or non-aqueous medium with an amine of the formula (4) H2N - B - SO2 - Y (4) where B and Y are each as defined in claim 1, and optionally with a further amine of the formula H-NR1R2 where R1 and R2 are each as defined above, concurrently or in any desired order and with con-current or successive partial hydrolysis of the sulfonyl chloride groups to sulfo groups, and optionally in the case of Y being .beta.-hydroxyethyl converting the .beta.-hydroxyethylsulfonyl group into a group of the formula -SO2-Y where Y is an ethyl group substituted in the .beta.-position by an ester group.
8. The use of a phthalocyanine dye of at least one of claims 1 to 6 or of a phthalocyanine dye prepared a claimed in claim 7 for dyeing hydroxyl- and/or carboxamido-containing material, in particular fiber material.
9. A process for dyeing hydroxyl- and/or carboxamido-containing material, preferably fiber material, by applying a dye onto or into the material and fixing the dye on or in the material by means of heat or with the aid of an alkaline agent or by both measures, which comprises using a dye that is a phthalocyanine dye of at least one of claims 1 to 6 or a phthalocyanine dye prepared as claimed in claim 7.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4338853A DE4338853A1 (en) | 1993-11-13 | 1993-11-13 | Water-soluble heavy metal-free phthalocyanine dyes, preparation thereof and use thereof |
| DEP4338853.1 | 1993-11-13 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2135555A1 true CA2135555A1 (en) | 1995-05-13 |
Family
ID=6502563
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002135555A Abandoned CA2135555A1 (en) | 1993-11-13 | 1994-11-10 | Water-soluble phthalocyanine dyes, preparation thereof and use thereof |
Country Status (10)
| Country | Link |
|---|---|
| JP (1) | JPH07207177A (en) |
| KR (1) | KR950014230A (en) |
| CN (1) | CN1106846A (en) |
| BR (1) | BR9404422A (en) |
| CA (1) | CA2135555A1 (en) |
| CZ (1) | CZ278194A3 (en) |
| DE (1) | DE4338853A1 (en) |
| PL (1) | PL305794A1 (en) |
| TR (1) | TR28664A (en) |
| TW (1) | TW281688B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5856472A (en) * | 1996-06-16 | 1999-01-05 | Dystar Textilfarben Gmbh & Co. Deutschland Kg | Reactive aluminum phthalocyanine dyestuffs, processes for their preparation and their use |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19529853A1 (en) * | 1995-08-14 | 1997-02-20 | Bayer Ag | Aluminum phthalocyanine reactive dyes |
| CN100419030C (en) * | 2005-10-25 | 2008-09-17 | 上海汇友精密化学品有限公司 | Modified pathalocyanine dye |
| CN103205138A (en) * | 2013-03-14 | 2013-07-17 | 浙江理工大学 | Activity disperse dye photoactive under visible light irradiation and manufacturing method of activity disperse dye |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB931596A (en) * | 1960-12-30 | 1963-07-17 | Gen Aniline & Film Corp | Phthalocyanine dyestuffs |
| IN150949B (en) * | 1978-06-02 | 1983-01-29 | Hoechst Ag |
-
1993
- 1993-11-13 DE DE4338853A patent/DE4338853A1/en not_active Withdrawn
-
1994
- 1994-11-01 TW TW083110052A patent/TW281688B/zh active
- 1994-11-10 CA CA002135555A patent/CA2135555A1/en not_active Abandoned
- 1994-11-10 PL PL94305794A patent/PL305794A1/en unknown
- 1994-11-11 JP JP6277599A patent/JPH07207177A/en not_active Withdrawn
- 1994-11-11 TR TR01214/94A patent/TR28664A/en unknown
- 1994-11-11 CN CN94117928A patent/CN1106846A/en active Pending
- 1994-11-11 CZ CZ942781A patent/CZ278194A3/en unknown
- 1994-11-11 BR BR9404422A patent/BR9404422A/en not_active Application Discontinuation
- 1994-11-12 KR KR1019940029703A patent/KR950014230A/en not_active Application Discontinuation
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5856472A (en) * | 1996-06-16 | 1999-01-05 | Dystar Textilfarben Gmbh & Co. Deutschland Kg | Reactive aluminum phthalocyanine dyestuffs, processes for their preparation and their use |
Also Published As
| Publication number | Publication date |
|---|---|
| DE4338853A1 (en) | 1995-05-18 |
| CN1106846A (en) | 1995-08-16 |
| JPH07207177A (en) | 1995-08-08 |
| BR9404422A (en) | 1995-06-20 |
| TW281688B (en) | 1996-07-21 |
| PL305794A1 (en) | 1995-05-15 |
| CZ278194A3 (en) | 1995-07-12 |
| TR28664A (en) | 1996-12-25 |
| KR950014230A (en) | 1995-06-15 |
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