EP0391170A1 - Process for dyeing paper - Google Patents

Process for dyeing paper Download PDF

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Publication number
EP0391170A1
EP0391170A1 EP90105512A EP90105512A EP0391170A1 EP 0391170 A1 EP0391170 A1 EP 0391170A1 EP 90105512 A EP90105512 A EP 90105512A EP 90105512 A EP90105512 A EP 90105512A EP 0391170 A1 EP0391170 A1 EP 0391170A1
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EP
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Prior art keywords
dyes
alkyl
formula
paper
dyeing
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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.)
Granted
Application number
EP90105512A
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German (de)
French (fr)
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EP0391170B1 (en
Inventor
Klaus Dr. Kunde
Peter Dr. Wild
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Bayer AG
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Bayer AG
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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

  • substituents can in turn be substituted by substituents customary in dye chemistry, for example halogen, in particular Cl, OH, C1-C4alkoxy, acyloxy, for example acetoxy, C1-C4alkyl, SO3H, COOH.
  • substituents customary in dye chemistry for example halogen, in particular Cl, OH, C1-C4alkoxy, acyloxy, for example acetoxy, C1-C4alkyl, SO3H, COOH.
  • Alkyl preferably stands for optionally substituted C1-C Alkyl alkyl, aryl, preferably for optionally substituted phenyl and aralkyl preferably for optionally substituted benzyl.
  • the dyes are prepared in a known manner by coupling diazotized azo dyes of the formula with coupling components of the formula
  • the dyes are generally used in the form of their salts for dyeing, in particular the alkali salts (Li, Na, K), the ammonium salts, mono-, bis- or tris-C2-C4-alkyl-ammonium salts, in particular also the C2-C4- Alkanol-ammonium salts.
  • alkali salts Li, Na, K
  • ammonium salts mono-, bis- or tris-C2-C4-alkyl-ammonium salts, in particular also the C2-C4- Alkanol-ammonium salts.
  • Preferred ammonium salts are those with the cation wherein R5 H, C1-C4-alkyl, optionally substituted by OH or hydroxy-C1-C4-alkoxy, in particular CH3, C2H5, CH2-CH2-OH, CH2-CH2OCH3, CH2-CH2-OCH2-CH2OH, R6 C1-C4-hydroxyalkyl, C1-C4-hydroxyalkoxy-alkyl, in particular CH2-CH2-OH, CH2-CH2OCH3, CH2-CH2-OCH2-CH2-OH.
  • the radicals R5 can be the same or different.
  • the dyes can also be used as concentrated, aqueous solutions.
  • the blue paper dyeings obtained are notable for good light and wet fastness (bleeding fastness) as well as fastness to acid, alkali and alum. Attention should also be drawn to the brilliance and clarity of the color tones. Furthermore, the combination behavior with suitable dyes is very good.
  • a desiccant consisting of 60% wood pulp and 40% unbleached sulfite pulp is beaten in the Dutch and ground to a degree of grinding of 40 ° SR so that the dryness is slightly above 2.5%, and then adjusted to 2.5% dryness of the thick matter with water .
  • bleached sulfite pulp is used to produce the thick stock and this thick stock is used for dyeing, blue paper dyeings and practically dye-free waste water are obtained by the above-mentioned processes.

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  • Paper (AREA)
  • Coloring (AREA)

Abstract

Farbstoffe der Formel <IMAGE> mit den in der Beschreibung genannten Substituentenbedeutungen eignen sich hervorragend zum Färben von Papier. Sie liefern licht- und naßechte blaue Färbungen.Dyes of the formula <IMAGE> with the substituent meanings given in the description are outstandingly suitable for dyeing paper. They provide light and wet-fast blue dyeings.

Description

Gegenstand der vorliegenden Erfindung ist ein Verfahren zum Färben von Papier, das dadurch gekennzeichnet ist, daß man Farbstoffe der Formel

Figure imgb0001
verwendet, worin
X = H, OH, C₁-C₄-Alkoxy oder -NHR₃
R₁ = H, C₁-C₄-Alkyl
R₂, R₃ = H, Alkyl, Alkylcarbonyl, Alkylsulfonyl, Aryl, Arylcarbonyl, Arylsulfonyl Aral­kyl, Aralkylcarbonyl oder Aminocarbonyl.The present invention relates to a process for dyeing paper, which is characterized in that dyes of the formula
Figure imgb0001
 used where
X = H, OH, C₁-C₄ alkoxy or -NHR₃
R₁ = H, C₁-C₄ alkyl
R₂, R₃ = H, alkyl, alkylcarbonyl, alkylsulfonyl, aryl, arylcarbonyl, arylsulfonyl aralkyl, aralkylcarbonyl or aminocarbonyl.

Die genannten Substiuenten können ihrerseits durch in der Farbstoffchemie übliche Substituenten substituiert sein, beispielsweise Halogen, inbesondere Cl, OH, C₁-C₄-­Alkoxy, Acyloxy, beispielsweise Acetoxy, C₁-C₄-Alkyl, SO₃H, COOH.Said substituents can in turn be substituted by substituents customary in dye chemistry, for example halogen, in particular Cl, OH, C₁-C₄alkoxy, acyloxy, for example acetoxy, C₁-C₄alkyl, SO₃H, COOH.

Alkyl steht vorzugsweise für gegebenenfalls substitu­iertes C₁-C₄-Alkyl, Aryl, vorzugsweise für gegebenen­falls substituiertes Phenyl und Aralkyl vorzugsweise für gegebenenfalls substituiertes Benzyl.Alkyl preferably stands for optionally substituted C₁-C Alkyl alkyl, aryl, preferably for optionally substituted phenyl and aralkyl preferably for optionally substituted benzyl.

Bevorzugte Farbstoffe I sind ganz generell solche mit
R₁ = H, C₁-C₄-Alkyl
R₂, R₃ = H, C₁-C₄-Alkyl, C₁-C₄-Alkylcarbonyl, C₁-C₄-Alkylsulfonyl, Aminocarbonyl, Phenylcarbonyl, Phenyl, Phenylsulfonyl, Benzylcarbonyl,
wobei die Phenylringe auch durch SO₃H oder COOH sub­stituiert sein können,
X = H, C₁-C₂-Alkoxy, -NHR₃, OH
wobei die Farbstoffe mindestens 3 Sulfogruppen in den Naphthalinringen aufweisen.Preferred dyes I are generally those with
R₁ = H, C₁-C₄ alkyl
R₂, R₃ = H, C₁-C₄-alkyl, C₁-C₄-alkylcarbonyl, C₁-C₄-alkylsulfonyl, aminocarbonyl, phenylcarbonyl, phenyl, phenylsulfonyl, benzylcarbonyl,
the phenyl rings can also be substituted by SO₃H or COOH,
X = H, C₁-C₂ alkoxy, -NHR₃, OH
wherein the dyes have at least 3 sulfo groups in the naphthalene rings.

Bevorzugte Farbstoffe sind weiterhin solche der Formeln

Figure imgb0002
worin
R₁ - R₃ die in Formel I angegebene Bedeutung haben,
wobei
R₁ vorzugsweise = H oder CH₃
R₂, R₃ vorzugsweise = H, COCH₃, COC₆H₅, C₆H₅
und worin
R₄ = OH, OCH₃, OC₂H₅.Preferred dyes are also those of the formulas
Figure imgb0002
 wherein
R₁ - R₃ have the meaning given in formula I,
in which
R₁ preferably = H or CH₃
R₂, R₃ preferably = H, COCH₃, COC₆H₅, C₆H₅
and in what
R₄ = OH, OCH₃, OC₂H₅.

Die Herstellung der Farbstoffe erfolgt in bekannter Weise durch Kupplung diazotierter Azofarbstoffe der Formel

Figure imgb0003
mit Kupplungskomponenten der Formel
Figure imgb0004
 The dyes are prepared in a known manner by coupling diazotized azo dyes of the formula
Figure imgb0003
 with coupling components of the formula
Figure imgb0004

Für den Fall daß X = NH₂ verwendet man bei der Herstel­lung zweckmäßigerweise die entsprechenden Verbindungen V mit X = Acylamino, insbesondere -NHCOCH₃ und verseift nach erfolgter Kupplung.In the event that X = NH₂ used appropriately in the preparation of the corresponding compounds V with X = acylamino, in particular -NHCOCH₃ and saponified after coupling.

Die Farbstoffe werden im allgemeinen in Form ihrer Salze zum Färben eingesetzt, insbesondere der Alkalisalze (Li, Na, K), der Ammoniumsalze, Mono-, Bis- oder Tris-C₂-C₄-­alkyl-ammoniumsalze, insbesondere auch der C₂-C₄-Alka­nol-ammoniumsalze.The dyes are generally used in the form of their salts for dyeing, in particular the alkali salts (Li, Na, K), the ammonium salts, mono-, bis- or tris-C₂-C₄-alkyl-ammonium salts, in particular also the C₂-C₄- Alkanol-ammonium salts.

Bevorzugte Ammoniumsalze sind dabei solche mit dem Kation

Figure imgb0005
worin
R₅ H, C₁-C₄-Alkyl, gegebenenfalls substituiert durch OH oder Hydroxy-C₁-C₄-alkoxy, insbesondere CH₃, C₂H₅, CH₂-CH₂-OH, CH₂-CH₂OCH₃, CH₂-CH₂-OCH₂-CH₂OH,
R₆ C₁-C₄-Hydroxyalkyl, C₁-C₄-Hydroxyalkoxy-alkyl, ins­besondere CH₂-CH₂-OH, CH₂-CH₂OCH₃, CH₂-CH₂-OCH₂-CH₂-­OH.Preferred ammonium salts are those with the cation
Figure imgb0005
 wherein
R₅ H, C₁-C₄-alkyl, optionally substituted by OH or hydroxy-C₁-C₄-alkoxy, in particular CH₃, C₂H₅, CH₂-CH₂-OH, CH₂-CH₂OCH₃, CH₂-CH₂-OCH₂-CH₂OH,
R₆ C₁-C₄-hydroxyalkyl, C₁-C₄-hydroxyalkoxy-alkyl, in particular CH₂-CH₂-OH, CH₂-CH₂OCH₃, CH₂-CH₂-OCH₂-CH₂-OH.

Die Reste R₅ können dabei gleich oder verschieden sein.The radicals R₅ can be the same or different.

Die Farbstoffe können auch als konzentrierte, wäßrige Lösungen eingesetzt werden.The dyes can also be used as concentrated, aqueous solutions.

Sie können nach allen in der Papierindustrie für sub­stantive Farbstoffe gebräuchlichen Verfahren einge­setzt werden, insbesondere in der Masse- wie in der Oberflächenfärbung von Papier für geleimte und unge­leimte Sorten, ausgehend von gebleichten oder unge­bleichten Zellstoff verschiedender Provenienz wie Nadel- oder Laubholz-sulfit und/oder -Sulfat-Zellstoff.They can be used according to all processes used in the paper industry for substantive dyes, especially in the mass and surface coloring of paper for sized and unsized varieties, based on bleached or unbleached pulp of different provenances such as softwood or hardwood sulfite and / or -Sulfate pulp.

Die erhaltenen blauen Papierfärbungen zeichnen sich durch gute Licht- und Naßechtheit (Ausblutechtheit) sowie Säure-, Alkali- und Alaun-Echtheit aus. Auch auf die Brillanz und Klarheit der Farbtöne ist hinzuweisen. Ferner ist das Kombinationsverhalten mit geeigneten Farbstoffen sehr gut.The blue paper dyeings obtained are notable for good light and wet fastness (bleeding fastness) as well as fastness to acid, alkali and alum. Attention should also be drawn to the brilliance and clarity of the color tones. Furthermore, the combination behavior with suitable dyes is very good.

Beispiel AExample A

Ein aus 60 % Holzschliff und 40 % ungebleichtem Sulfit­zellstoff bestehender Trockenstoff wird im Holländer an­geschlagen und bis zum Mahlgrad 40° SR gemahlen, so daß der Trockengehalt etwas über 2,5 % liegt, und anschlie­ßend mit Wasser auf 2,5 % Trockengehalt des Dickstoffs eingestellt.A desiccant consisting of 60% wood pulp and 40% unbleached sulfite pulp is beaten in the Dutch and ground to a degree of grinding of 40 ° SR so that the dryness is slightly above 2.5%, and then adjusted to 2.5% dryness of the thick matter with water .

200 Teile dieses Dickstoffs werden mit 5 Teilen einer 0,5 %igen wässrigen Lösung des Farbstoffs der Formel

Figure imgb0006
versetzt, ca. 5 Minuten verrührt, 2 % Harzleim und 3 % Alaun (bezogen auf Trockenstoff) zugegeben und wiederum einige Minuten homogen verrührt. Man verdünnt dann die Masse mit ca. 500 Teilen Wasser und stellt hieraus in üblicher Weise durch Absaugen über einen Blattbildner Papierblätter her. Die Papierblätter weisen eine blaue Färbung auf. Das Abwasser ist praktisch farbstoffrei.200 parts of this thick matter are mixed with 5 parts of a 0.5% aqueous solution of the dye of the formula
Figure imgb0006
 added, stirred for about 5 minutes, 2% resin glue and 3% alum (based on dry matter) added and again stirred homogeneously for a few minutes. The mass is then diluted with about 500 parts of water and paper sheets are produced therefrom in a conventional manner by suctioning off through a sheet former. The paper sheets are colored blue. The wastewater is practically dye-free.

Beispiel BExample B

Beim Färben ungeleimter Papiermasse unter sonst gleichen Färbebedingungen erhält man ebenfalls eine kräftige blaue Färbung mit praktisch farbstoffreiem Abwasser.When dyeing unsized paper pulp under otherwise identical dyeing conditions, a strong blue dyeing with practically dye-free waste water is also obtained.

Beispiel CExample C

Verwendet man gebleichten Sulfitzellstoff zur Herstel­lung des Dickstoffs und setzt diesen Dickstoff zur Fär­bung ein, so erhält man nach den oben angegebenen Ver­fahren blaue Papierfärbungen und praktisch farbstoff­freies Abwasser.If bleached sulfite pulp is used to produce the thick stock and this thick stock is used for dyeing, blue paper dyeings and practically dye-free waste water are obtained by the above-mentioned processes.

Verwendet man an Stelle des in Beispiel A genannten Farbstoffs die folgenden Farbstoffe (2) bis (73), so erhält man ebenfalls blaue Papierfärbungen mit praktisch farbstoffreiem Abwasser.

Figure imgb0007
Figure imgb0008
Figure imgb0009
Figure imgb0010
Figure imgb0011
Figure imgb0012
Figure imgb0013
Figure imgb0014
Figure imgb0015
Figure imgb0016
Figure imgb0017
Figure imgb0018
Figure imgb0019
 If, instead of the dye mentioned in Example A, the following dyes (2) to (73) are used, blue paper dyeings with practically dye-free waste water are also obtained.
Figure imgb0007
Figure imgb0008
Figure imgb0009
Figure imgb0010
Figure imgb0011
Figure imgb0012
Figure imgb0013
Figure imgb0014
Figure imgb0015
Figure imgb0016
Figure imgb0017
Figure imgb0018
Figure imgb0019

Claims (4)

1. Verfahren zum Färben von Papier, dadurch gekenn­zeichnet, daß man Farbstoffe der Formel
Figure imgb0020
 verwendet, worin
X = H, OH, C₁-C₄-Alkoxy oder -NHR₃
R₁ = H, C₁-C₄-Alkyl
R₂, R₃ = H, Alkyl, Alkylcarbonyl, Alkylsulfo­nyl, Aryl, Arylcarbonyl, Arylsulfo­nyl, Aralkyl, Aralkylcarbonyl oder Aminocarbonyl.1. A method for dyeing paper, characterized in that dyes of the formula
Figure imgb0020
 used where
X = H, OH, C₁-C₄ alkoxy or -NHR₃
R₁ = H, C₁-C₄ alkyl
R₂, R₃ = H, alkyl, alkylcarbonyl, alkylsulfonyl, aryl, arylcarbonyl, arylsulfonyl, aralkyl, aralkylcarbonyl or aminocarbonyl. 2. Verfahren gemäß Anspruch 1, gekennzeichnet durch die Verwendung von Farbstof fen der Formel des An­spruchs 1 mit
R₁ = H, C₁-C₄-Alkyl
R₂, R₃ = H, C₁-C₄-Alkyl, C₁-C₄-Alkylcarbonyl, C₁-C₄-Alkylsulfonyl, Aminocarbonyl, Phenylcarbonyl, Phenyl, Phenylsulfo­nyl, Benzylcarbonyl,
wobei die Phenylringe durch SO₃H oder COOH substituiert sein können.
X = H, C₁-C₂-Alkoxy, -NHR₃,
wobei die Farbstoffe mindestens 3 Sulfogruppen in den Naphthalinringen aufweisen.2. The method according to claim 1, characterized by the use of dyes fen of the formula of claim 1 with
R₁ = H, C₁-C₄ alkyl
R₂, R₃ = H, C₁-C₄-alkyl, C₁-C₄-alkylcarbonyl, C₁-C₄-alkylsulfonyl, aminocarbonyl, phenylcarbonyl, phenyl, phenylsulfonyl, benzylcarbonyl,
the phenyl rings can be substituted by SO₃H or COOH.
X = H, C₁-C₂ alkoxy, -NHR₃,
wherein the dyes have at least 3 sulfo groups in the naphthalene rings. 3. Verfahren gemäß Ansprüchen 1 und 2, gekennzeichnet durch die Verwendung von Farbstoffen der Formel
Figure imgb0021
 mit R₄ = OH, OCH₃, OC₂H₅,
und
Figure imgb0022
 3. The method according to claims 1 and 2, characterized by the use of dyes of the formula
Figure imgb0021
 with R₄ = OH, OCH₃, OC₂H₅,
and
Figure imgb0022
 4. Nach dem Verfahren der Ansprüche 1-3 gefärbtes Papier.4. Paper colored by the process of claims 1-3.
EP90105512A 1989-04-05 1990-03-23 Process for dyeing paper Expired - Lifetime EP0391170B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3910923A DE3910923A1 (en) 1989-04-05 1989-04-05 METHOD FOR DYING PAPER
DE3910923 1989-04-05

Publications (2)

Publication Number Publication Date
EP0391170A1 true EP0391170A1 (en) 1990-10-10
EP0391170B1 EP0391170B1 (en) 1993-11-10

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EP90105512A Expired - Lifetime EP0391170B1 (en) 1989-04-05 1990-03-23 Process for dyeing paper

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US (1) US5034017A (en)
EP (1) EP0391170B1 (en)
JP (1) JPH02289198A (en)
DD (1) DD299326A5 (en)
DE (2) DE3910923A1 (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0831131A1 (en) * 1996-09-23 1998-03-25 Bayer Ag Process for dyeing cellulosic materials with disazo-dyestuffs
EP0992544A1 (en) * 1998-10-07 2000-04-12 Bayer Ag Disazo-dyestuffs

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE59208643D1 (en) * 1991-09-26 1997-07-31 Ciba Geigy Ag Process for dyeing paper with disazo dyes
US5198022A (en) * 1991-10-25 1993-03-30 Lexmark International, Inc. Waterfast dye and aqueous ink
JP5322463B2 (en) * 2008-03-11 2013-10-23 公立大学法人大阪府立大学 Azo dichroic dye

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR456232A (en) * 1912-06-12 1913-08-20 Societe Leopold Cassella & C G M B H Process for the preparation of trisazo dyes
DE3616128A1 (en) * 1985-05-14 1986-11-20 Canon Inc. DISAZO DYES AND RECORDING LIQUIDS CONTAINING THEM
EP0289458A2 (en) * 1987-04-27 1988-11-02 Ciba-Geigy Ag Anionic disazo dyes

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07119378B2 (en) * 1989-01-27 1995-12-20 キヤノン株式会社 Recording liquid and ink jet recording method using the same

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR456232A (en) * 1912-06-12 1913-08-20 Societe Leopold Cassella & C G M B H Process for the preparation of trisazo dyes
DE3616128A1 (en) * 1985-05-14 1986-11-20 Canon Inc. DISAZO DYES AND RECORDING LIQUIDS CONTAINING THEM
EP0289458A2 (en) * 1987-04-27 1988-11-02 Ciba-Geigy Ag Anionic disazo dyes

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0831131A1 (en) * 1996-09-23 1998-03-25 Bayer Ag Process for dyeing cellulosic materials with disazo-dyestuffs
US5883234A (en) * 1996-09-23 1999-03-16 Bayer Aktiengesellschaft Process for dyeing cellulosic materials with disazo dyestuffs
EP0992544A1 (en) * 1998-10-07 2000-04-12 Bayer Ag Disazo-dyestuffs

Also Published As

Publication number Publication date
DE3910923A1 (en) 1990-10-11
EP0391170B1 (en) 1993-11-10
US5034017A (en) 1991-07-23
DE59003396D1 (en) 1993-12-16
JPH02289198A (en) 1990-11-29
DD299326A5 (en) 1992-04-09

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