EP0060468B1 - Process for the dyeing of paper and dyed paper - Google Patents
Process for the dyeing of paper and dyed paper Download PDFInfo
- Publication number
- EP0060468B1 EP0060468B1 EP82101762A EP82101762A EP0060468B1 EP 0060468 B1 EP0060468 B1 EP 0060468B1 EP 82101762 A EP82101762 A EP 82101762A EP 82101762 A EP82101762 A EP 82101762A EP 0060468 B1 EP0060468 B1 EP 0060468B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- alkyl
- optionally substituted
- methyl
- denotes
- hydrogen
- 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.)
- Expired
Links
Classifications
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
- D21H21/28—Colorants ; Pigments or opacifying agents
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S8/00—Bleaching and dyeing; fluid treatment and chemical modification of textiles and fibers
- Y10S8/916—Natural fiber dyeing
- Y10S8/919—Paper
Definitions
- Alkylene is in particular a radical having 1 to 3 carbon atoms.
- Acylamino is preferably understood to mean C 1 to C 3 alkylcarbonylamino, C 1 to C 3 alkylsulfonylamino, aminocarbonylamino or benzoylamino, optionally substituted by halogen or an ammonium group, but especially acetylamino, propionylamino or aminocarbonyl.
- Halogen is preferably chlorine or bromine.
- Anions An (-) are the colorless organic and inorganic anions customary for cationic dyes, for example chloride, bromide, iodide, hydroxide, hydrogen sulfate, sulfate, nitrate, dihydrogen phosphate, phosphate, carbonate, perchlorate, fluoroborate, chlorozincate, methosulfate, ethosulfate, acetate, Propionate, lactate, citrate, benzenesulfonate and toluenesulfonate.
- cationic dyes for example chloride, bromide, iodide, hydroxide, hydrogen sulfate, sulfate, nitrate, dihydrogen phosphate, phosphate, carbonate, perchlorate, fluoroborate, chlorozincate, methosulfate, ethosulfate, acetate, Propionate, lactate, citrate, benzenesulfonate and toluen
- the anion is generally given by the manufacturing process.
- the dyes are preferably present as chlorides, hydrogen sulfates, sulfates, methosulfates, phosphates, acetates, lactates, citrates.
- the anions can be exchanged for other anions in a known manner and can be present as mixtures.
- the dyes (I) are used for dyeing paper either as dye-powder preparations or preferably in the form of concentrated dye solutions.
- Powder preparations are made in the usual way with coupé agents such as sodium sulfate, phosphates, chloride, acetate or are marketed as spray drying brands.
- the concentrated dye solutions can be of an aqueous or aqueous / organic type, with customary environmentally friendly and readily degradable organic additives being preferred, such as organic acids such as acetic acid, formic acid, amides such as formamide, dimethylformamide, urea, alcohols such as glycol, diglycol, diglycol ether, especially the latter Methyl or ethyl ether.
- the concentrated dye solutions are prepared in a conventional manner, for example by dissolving the dye (as a paste or powder) in a suitable solvent or solvent mixture.
- the dye powders or solutions are generally used after dilution with water for the continuous or discontinuous dyeing of paper.
- the dyes are used for paper pulp dyeing or for paper surface dyeing. They are suitable for sized and unsized paper types based on bleached or unbleached pulp of different origins such as softwood or hardwood, sulfite and / or sulfate pulp.
- the dyeing is preferably carried out at pH values from 4 to 8, in particular pH 5 to 7.
- the dyeing temperature is generally 10 to 50, preferably about 20 ° C. (room temperature).
- auxiliaries and fillers customary in paper dyeing and production can also be used when using the dyes according to the invention.
- the dyes have excellent drawability when coloring paper.
- the paper dyeings obtained with the dyes according to the invention are notable for very good fastness to water (fastness to bleeding) and fastness to acids, alkali and alum.
- the dyes of the formula (I) are known, for example from US Pat. No. 602637, DE-PS No. 93499, DE-PS No. 95530 and DE-AS No. 1005486, and have hitherto been used for dyeing tannic cotton, half-wool and polyacrylonitrile used. It is therefore surprising that in the case of paper dyeing, even without auxiliaries, they produce almost colorless waste water with good wet fastness properties of the dyeings obtained.
- a desiccant consisting of 60% wood pulp and 40% unbleached sulfite pulp is beaten with water in the Dutch and ground to a degree of 40 ° SR so that the dryness is a little over 2.5%, and then with water to an exact 2.5% dryness of the thick matter adjusted.
Description
Gegenstand der Erfindung sind Verfahren zum Färben von Papier mit kationischen Azofarbstoffen der Formel
- X(+) eine gegebenenfalls substituierte Ammoniumgruppe,
- m 0 oder 1,
- R Wasserstoff, Halogen, C, - bis C4-Alkyl, C1- bis C4-Alkoxy, Hydroxy, Amino, Sulfon- und Carbonamido oder Acylamino,
- R1 Wasserstoff, C1- bis CQ4-Alkyl, Halogen oder C1- bis C4-Alkoxy,
- R2 und R3 unabhängig voneinander Wasserstoff, C1- bis C3-Alkyl, C1- bis C4-Alkoxy oder Acylamino, und
- An(-) ein Anion bedeuten,
worin an Ring a weitere carbocyclische oder heterocyclische Ringe ankondensiert sein können, die ihrerseits durch R substituiert sein können, sowie Mittel, die diese Farbstoffe enthalten.The invention relates to processes for dyeing paper with cationic azo dyes of the formula
- X (+) an optionally substituted ammonium group,
- m 0 or 1,
- R is hydrogen, halogen, C 1 -C 4 -alkyl, C 1 -C 4 alkoxy, hydroxy, amino, sulfone and carbonamido or acylamino,
- R 1 is hydrogen, C 1 to CQ 4 alkyl, halogen or C 1 to C 4 alkoxy,
- R 2 and R 3 independently of one another are hydrogen, C 1 to C 3 alkyl, C 1 to C 4 alkoxy or acylamino, and
- An (-) is an anion
in which further carbocyclic or heterocyclic rings may be fused to ring a, which in turn may be substituted by R, and agents which contain these dyes.
Alkylen steht insbesondere für einen Rest mit 1 bis 3 Kohlenstoffatomen. Unter Acylamino wird vorzugsweise gegebenenfalls durch Halogen oder eine Ammoniumgruppe substituiertes C1- bis C3-Alkylcarbonylamino, C1- bis C3-Alkylsulfonyl- amino, Aminocarbonylamino oder Benzoylamino, insbesondere aber Acetylamino, Propionylamino oder Aminocarbonyl verstanden.Alkylene is in particular a radical having 1 to 3 carbon atoms. Acylamino is preferably understood to mean C 1 to C 3 alkylcarbonylamino, C 1 to C 3 alkylsulfonylamino, aminocarbonylamino or benzoylamino, optionally substituted by halogen or an ammonium group, but especially acetylamino, propionylamino or aminocarbonyl.
Halogen steht vorzugsweise für Chlor oder Brom.Halogen is preferably chlorine or bromine.
Von den Farbstoffen der Formel (I) sind die Farbstoffe der Formel
- R, R1, R2, R3 und An(-) die in Formel (I) angegebene Bedeutung haben,
- n 0 bis 2,
- R4, Rs und Re unabhänging voneinander Wasserstoff, C1- bis C4-Alkyl, C3- oder C4-Alkenyl, Benzyl oder Phenylethyl, die durch Hydroxy, C1- bis C4-Alkoxy, Chlor oder Cyan und der Benzyl-und Phenylethylrest zusätzlich durch C, - bis C4-Alkyl substituiert sein können, bedeuten, oder
- R4 und R5 zusammen mit dem Stickstoffatom einen gegebenenfalls durch C1- bis C4-Alkyl substituierten Piperidin-, Morpholin-, Piperazin- oder Pyrrolinring, oder
- R4, R5 und Re zusammen mit dem Stickstoffatom, an das sie gebunden sind, einen gegebenenfalls durch C1- bis C4-Alkyl substituierten Pyridinring bilden.
- Besonders geeignet sind Farbstoffe der Formel (II), worin
- R für Wasserstoff, Methyl, Sulfon- oder Carbonamido, Aminocarbonylamino oder gegebenenfalls durch Halogen oder die Gruppe
- R1 für Wasserstoff, Methyl, Chlor oder Methoxy,
- R2 und Ra unabhängig voneinander für Wasserstoff, Methyl, Methoxy, Aminocarbonylamino oder gegebenenfalls durch Halogen oder die Gruppe
- R4, Rs und Re unabhängig voneinander für Methyl, Ethyl, Hydroxyethyl, Chlorethyl, Cyanethyl, Benzyl, Allyl oder zusammen mit dem Stickstoffatom für einen gegebenenfalls durch Methyl substituierten Pyridinring stehen.
- R, R 1 , R 2 , R 3 and An (-) have the meaning given in formula (I),
- n 0 to 2,
- R 4 , R s and R e independently of one another are hydrogen, C 1 - to C 4 -alkyl, C 3 - or C 4 -alkenyl, benzyl or phenylethyl, which are substituted by hydroxy, C 1 - to C 4 -alkoxy, chlorine or cyano and the benzyl and phenylethyl radical can additionally be substituted by C 1 -C 4 -alkyl, or
- R 4 and R 5 together with the nitrogen atom represent a piperidine, morpholine, piperazine or pyrroline ring which is optionally substituted by C 1 -C 4 -alkyl, or
- R 4 , R 5 and R e together with the nitrogen atom to which they are attached form a pyridine ring which is optionally substituted by C 1 -C 4 -alkyl.
- Dyes of the formula (II) in which
- R represents hydrogen, methyl, sulfone or carbonamido, aminocarbonylamino or optionally by halogen or the group
- R 1 represents hydrogen, methyl, chlorine or methoxy,
- R 2 and R a independently of one another for hydrogen, methyl, methoxy, aminocarbonylamino or optionally by halogen or the group
- R 4 , R s and R e independently of one another represent methyl, ethyl, hydroxyethyl, chloroethyl, cyanoethyl, benzyl, allyl or together with the nitrogen atom represent a pyridine ring which is optionally substituted by methyl.
Als Anionen An(-) kommen die für kationische Farbstoffe üblichen farblosen organischen und anorganischen Anionen beispielsweise Chlorid, Bromid, Jodid, Hydroxyd, Hydrogensulfat, Sulfat, Nitrat, Dihydrogenphosphat, Phosphat, Carbonat, Perchlorat, Fluoroborat, Chlorozinkat, Methosulfat, Ethosulfat, Acetat, Propionat, Lactat, Citrat, Benzolsulfonat und Toluolsulfonat in Betracht.Anions An (-) are the colorless organic and inorganic anions customary for cationic dyes, for example chloride, bromide, iodide, hydroxide, hydrogen sulfate, sulfate, nitrate, dihydrogen phosphate, phosphate, carbonate, perchlorate, fluoroborate, chlorozincate, methosulfate, ethosulfate, acetate, Propionate, lactate, citrate, benzenesulfonate and toluenesulfonate.
Das Anion ist im allgemeinen durch das Herstellungsverfahren gegeben. Vorzugsweise liegen die Farbstoffe als Chloride, Hydrogensulfate, Sulfate, Methosulfate, Phosphate, Acetate, Lactate, Citrate vor. Die Anionen können in bekannter Weise gegen andere Anionen ausgetauscht werden und als Mischungen vorliegen.The anion is generally given by the manufacturing process. The dyes are preferably present as chlorides, hydrogen sulfates, sulfates, methosulfates, phosphates, acetates, lactates, citrates. The anions can be exchanged for other anions in a known manner and can be present as mixtures.
Die Farbstoffe (I) werden zum Färben von Papier entweder als Farbstoff-Pulver-Präparationen verwendet oder bevorzugt in Form von konzentrierten Farbstofflösungen zum Einsatz gebracht. Pulverpräparationen werden in üblicher Weise mit Coupagemitteln wie Natriumsulfat, -phosphaten, -chlorid, -acetat eingestellt oder als Sprühtrocknungsmarken in den Handel gebracht. Die konzentrierten Farbstofflösungen können wässeriger oder wässerig/organischer Art sein, wobei übliche umweltfreundliche und möglichst gut abbaubare organische Zusätze bevorzugt werden, wie organische Säuren wie Essigsäure, Ameisensäure, Amide wie Formamid, Dimethylformamid, Harnstoff, Alkohole wie Glykol, Diglykol, Diglykolether, besonders dessen Methyl- oder Ethylether. Die Herstellung der konzentrierten Farbstofflösungen erfolgt in üblicher Weise beispielsweise durch Auflösen des Farbstoffs (als Paste oder Pulver) im geeigneten Lösungsmittel oder Lösungsmittelgemisch.The dyes (I) are used for dyeing paper either as dye-powder preparations or preferably in the form of concentrated dye solutions. Powder preparations are made in the usual way with coupé agents such as sodium sulfate, phosphates, chloride, acetate or are marketed as spray drying brands. The concentrated dye solutions can be of an aqueous or aqueous / organic type, with customary environmentally friendly and readily degradable organic additives being preferred, such as organic acids such as acetic acid, formic acid, amides such as formamide, dimethylformamide, urea, alcohols such as glycol, diglycol, diglycol ether, especially the latter Methyl or ethyl ether. The concentrated dye solutions are prepared in a conventional manner, for example by dissolving the dye (as a paste or powder) in a suitable solvent or solvent mixture.
Die Farbstoffpulver oder -lösungen werden im allgemeinen nach Verdünnen mit Wasser zum kontinuierlichen oder diskontinuierlichen Färben von Papier verwendet.The dye powders or solutions are generally used after dilution with water for the continuous or discontinuous dyeing of paper.
Eingesetzt werden die Farbstoffe zum Papiermassefärben oder zur Papieroberflächenfärbung. Sie sind geeignet für geleimte und für ungeleimte Papiersorten ausgehend von gebleichtem oder ungebleichtem Zellstoff verschiedener Provenienz wie Nadel- oder Laubholz-, Sulfit- und/oder - sulfatzellstoff.The dyes are used for paper pulp dyeing or for paper surface dyeing. They are suitable for sized and unsized paper types based on bleached or unbleached pulp of different origins such as softwood or hardwood, sulfite and / or sulfate pulp.
Das Färben erfolgtvorzugsweise bei pH-Werten von 4 bis 8, insbesondere pH 5 bis 7. Die Färbetemperatur beträgt im allgemeinen 10 bis 50, vorzugsweise etwa 20°C (Raumtemperatur).The dyeing is preferably carried out at pH values from 4 to 8, in particular pH 5 to 7. The dyeing temperature is generally 10 to 50, preferably about 20 ° C. (room temperature).
Die bei der Papierfärbung und -herstellung üblichen Hilfsmittel und Füllstoffe können beim Einsatz der erfindungsgemässen Farbstoffe mitverwendet werden.The auxiliaries and fillers customary in paper dyeing and production can also be used when using the dyes according to the invention.
Die Farbstoffe besitzen bei der Papierfärbung ein ausgezeichnetes Ziehvermögen.The dyes have excellent drawability when coloring paper.
Die mit den erfindungsgemässen Farbstoffen erhaltenen Papierfärbungen zeichnen sich durch sehr gute Wasserechtheit (Ausblutechtheit) sowie Säure-, Alkali- und Alaunechtheit aus.The paper dyeings obtained with the dyes according to the invention are notable for very good fastness to water (fastness to bleeding) and fastness to acids, alkali and alum.
Auch auf die Brillanz und Klarheit der Farbtöne ist hinzuweisen. Ferner ist das Kombinationsverhalten mit geeigneten Farbstoffen sehr gut.Attention should also be drawn to the brilliance and clarity of the color tones. The combination behavior with suitable dyes is also very good.
Die Farbstoffe der Formel (I) sind bekannt, beispielsweise aus US-PS Nr. 602637, DE-PS Nr. 93499, DE-PS Nr. 95530 und DE-AS Nr. 1005486 und wurden bisher zum Färben tannierter Baumwolle, Halbwolle und Polyacrylnitril eingesetzt. Daher ist es überraschend, dass sie bei Papierfärbungen auch ohne Hilfsmittel nahezu farblose Abwässer ergeben bei guten Nassechtheiten der erzielten Färbungen.The dyes of the formula (I) are known, for example from US Pat. No. 602637, DE-PS No. 93499, DE-PS No. 95530 and DE-AS No. 1005486, and have hitherto been used for dyeing tannic cotton, half-wool and polyacrylonitrile used. It is therefore surprising that in the case of paper dyeing, even without auxiliaries, they produce almost colorless waste water with good wet fastness properties of the dyeings obtained.
Die Verwendung kationischer Azofarbstoffe zum Färben von Papier ist z.B. aus der EP-A Nr. 0024321 bekannt. Die Farbstoffe der Formel (I) werden hergestellt, indem man in bekannter Weise Aminoazoverbindungen der Formel
- diazotiert und mit Verbindungen der Formel
- diazotized and with compounds of the formula
Ein aus 60% Holzschliff und 40% ungebleichtem Sulfitzellstoff bestehender Trockenstoff wird im Holländer mit Wasser angeschlagen und bis zum Mahlgrad 40° SR gemahlen, so dass der Trockengehalt etwas über 2,5% liegt, und anschliessend mit Wasser auf exakt 2,5% Trockengehalt des Dickstoffs eingestellt.A desiccant consisting of 60% wood pulp and 40% unbleached sulfite pulp is beaten with water in the Dutch and ground to a degree of 40 ° SR so that the dryness is a little over 2.5%, and then with water to an exact 2.5% dryness of the thick matter adjusted.
200 Teile des Dickstoffs werden mit 5 Teilen einer 0,5%igen wässerigen Lösung des Farbstoffs der Formel
Beim Färben ungeleimter Papiermasse unter sonst gleichen Färbebedingungen erhält man ebenfalls eine kräftige blaustichig rote Färbung mit praktisch farbstoffreien Abwasser.When dyeing unsized paper pulp under otherwise identical dyeing conditions, a strong bluish-red dyeing with practically dye-free waste water is also obtained.
Verwendet man gebleichten Sulfitzellstoff zur Herstellung des Dickstoffs und setzt diesen Dickstoff zur Färbung ein, so erhält man nach den oben angegebenen Verfahren blaustichig rote Papierfärbungen und praktisch farbstoffreies Abwasser.If bleached sulphite pulp is used to produce the thick material and this thick material is used for dyeing, the processes described above give blue-tinged red paper dyeings and practically dye-free waste water.
Verwendet man anstelle obigen Farbstoffs entsprechende Mengen der Farbstoffe bzw. Farbstoff-Lösungen, die in den nachfolgenden Beispielen beschrieben werden, so erhält man Papierfärbungen, deren Nuancen bei den einzelnen Farbstoff-Beispielen angegeben sind.
Claims (4)
wherein further carbocyclic or heterocyclic rings, which can in their turn be substituted by R, can be fused to ring a.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19813110223 DE3110223A1 (en) | 1981-03-17 | 1981-03-17 | METHOD FOR COLORING PAPER AND AGENTS CONTAINING AZO DYES |
DE3110223 | 1981-03-17 |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0060468A1 EP0060468A1 (en) | 1982-09-22 |
EP0060468B1 true EP0060468B1 (en) | 1984-10-03 |
Family
ID=6127491
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP82101762A Expired EP0060468B1 (en) | 1981-03-17 | 1982-03-06 | Process for the dyeing of paper and dyed paper |
Country Status (3)
Country | Link |
---|---|
US (1) | US4411669A (en) |
EP (1) | EP0060468B1 (en) |
DE (2) | DE3110223A1 (en) |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE24321C (en) * | B. HESS in Bayreuth | Process for the production of a substitute for scnmirgei1 dural races of serpentine, green stone, hornblende or talc | ||
GB630463A (en) | 1947-07-10 | 1949-10-13 | Victor Grayson Morgan | Improved process for the colouration of paper |
US3454552A (en) * | 1964-07-23 | 1969-07-08 | Mitsubishi Chem Ind | Disazo cationic dyestuffs containing a quaternary ammonium group |
US3759893A (en) * | 1970-07-27 | 1973-09-18 | Du Pont | Biscationic monoazo dyes for acid modified nylons |
DE2135152B2 (en) * | 1971-07-14 | 1979-11-15 | Bayer Ag, 5090 Leverkusen | Cationic monoazo dyes and their use for dyeing fiber materials made of polyacrylonitrile, copolymers of acrylonitrile, acid-modified aromatic polyesters and acid-modified polyamides |
DE2933030A1 (en) * | 1979-08-16 | 1981-03-26 | Bayer Ag, 51373 Leverkusen | CATIONIC AZO DYES, THEIR PRODUCTION, THEIR USE FOR COLORING PAPER AND THEIR CONTAINERS |
-
1981
- 1981-03-17 DE DE19813110223 patent/DE3110223A1/en not_active Withdrawn
-
1982
- 1982-02-26 US US06/352,722 patent/US4411669A/en not_active Expired - Lifetime
- 1982-03-06 EP EP82101762A patent/EP0060468B1/en not_active Expired
- 1982-03-06 DE DE8282101762T patent/DE3260864D1/en not_active Expired
Also Published As
Publication number | Publication date |
---|---|
DE3260864D1 (en) | 1984-11-08 |
US4411669A (en) | 1983-10-25 |
EP0060468A1 (en) | 1982-09-22 |
DE3110223A1 (en) | 1982-09-30 |
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