EP0391170B1 - Process for dyeing paper - Google Patents

Process for dyeing paper Download PDF

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Publication number
EP0391170B1
EP0391170B1 EP90105512A EP90105512A EP0391170B1 EP 0391170 B1 EP0391170 B1 EP 0391170B1 EP 90105512 A EP90105512 A EP 90105512A EP 90105512 A EP90105512 A EP 90105512A EP 0391170 B1 EP0391170 B1 EP 0391170B1
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EP
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Prior art keywords
alkyl
paper
dyes
formula
dyestuffs
Prior art date
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Application number
EP90105512A
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German (de)
French (fr)
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EP0391170A1 (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

  • the present invention relates to a process for dyeing paper in blue tones with certain disazo dyes.
  • Dyes which are suitable for dyeing paper in blue tones have long been known from the prior art (cf. e.g. C.I. Direct Blue, 23 850; C.I. Direct Blue, 24400).
  • anionic disazo dyes which include can be used for dyeing and printing paper in red shades.
  • FR-A-456 232 discloses certain disazo dyes which can be converted into trisazo dyes by reaction with a diazo component.
  • 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
  • X NH2
  • 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.
  • 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 acid, alkali and alum fastness. 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)

Description

Die vorliegende Erfindung betrifft ein Verfahren zum Färben von Papier in blauen Tönen mit bestimmten Disazofarbstoffen.The present invention relates to a process for dyeing paper in blue tones with certain disazo dyes.

Aus dem Stand der Technik sind bereits seit langem Farbstoffe bekannt, die zum Färben von Papier in blauen Tönen geeignet sind (vgl. z.B. C.I. Direct Blue, 23 850; C.I. Direct Blue, 24400).Dyes which are suitable for dyeing paper in blue tones have long been known from the prior art (cf. e.g. C.I. Direct Blue, 23 850; C.I. Direct Blue, 24400).

Aus EP-A-0 289 458 sind bestimmte anionische Disazofarbstoffe bekannt, die u.a. zum Färben und Bedrucken von Papier in roten Farbtönen verwendet werden können.From EP-A-0 289 458 certain anionic disazo dyes are known which include can be used for dyeing and printing paper in red shades.

Aus FR-A-456 232 sind bestimmte Disazofarbstoffe bekannt, die durch Umsetzung mit einer Diazokomponente in Trisazofarbstoffe überführt werden können.FR-A-456 232 discloses certain disazo dyes which can be converted into trisazo dyes by reaction with a diazo component.

Gegenstand der vorliegenden Erfindung ist ein Verfahren zum Farben von Papier in blauen Tönen, 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 in blue tones, 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 Substituenten 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
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.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
In the event that X = NH₂, the appropriate compounds V with X = acylamino, in particular -NHCOCH₃, and saponified after coupling have been used in the preparation.

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 Oberflachenfärbung 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 in 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 acid, alkali and alum fastness. 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 suction 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 the following dyes (2) to (73) are used instead of the dye mentioned in Example A, blue paper dyeings with practically dye-free waste water are likewise 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. Process for the colouring of paper in blue hues, characterized in that dyestuffs of the formula
    Figure imgb0023
     are used in which
    X   is H, OH, C₁-C₄-alkoxy or -NHR₃
    R₁   is H, C₁-C₄-alkyl
    R₂, R₃   are H, alkyl, alkylcarbonyl, alkylsulphonyl, aryl, arylcarbonyl, arylsulphonyl, aralkyl, aralkylcarbonyl or aminocarbonyl.
  2. Process according to Claim 1, characterized by the use of dyestuffs of the formula of Claim 1 in which
    R₁   is H, C₁-C₄-alkyl,
    R₂, R₃   are H, C₁-C₄-alkyl, C₁-C₄-alkylcarbonyl, C₁-C₄-alkylsulphonyl, aminocarbonyl, phenylcarbonyl, phenyl, phenylsulphonyl, benzylcarbonyl,
    it being possible for the phenyl rings to be substituted by SO₃H or COOH,
    X   is H, C₁-C₂-alkoxy, -NHR₃,
    the dyestuffs having at least 3 sulpho groups in the naphthalene rings.
  3. Process according to Claims 1 and 2, characterized by the use of dyestuffs of the formula
    Figure imgb0024
     in which R₄ is OH, OCH₃, OC₂H₅,
    and
    Figure imgb0025
  4. Paper coloured 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 EP0391170A1 (en) 1990-10-10
EP0391170B1 true EP0391170B1 (en) 1993-11-10

Family

ID=6377860

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

Country Status (5)

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

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0534903B1 (en) * 1991-09-26 1997-06-25 Ciba SC Holding AG Process for dyeing of paper with diazo dyes
US5198022A (en) * 1991-10-25 1993-03-30 Lexmark International, Inc. Waterfast dye and aqueous ink
DE19638891A1 (en) * 1996-09-23 1998-03-26 Bayer Ag Process for dyeing cellulosic materials with disazo dyes
DE19846098A1 (en) * 1998-10-07 2000-04-13 Bayer Ag Disazo dyes
JP5322463B2 (en) * 2008-03-11 2013-10-23 公立大学法人大阪府立大学 Azo dichroic dye

Family Cites Families (4)

* 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
US4724001A (en) * 1985-05-14 1988-02-09 Canon Kabushiki Kaisha Disazoic dye and recording liquid containing the same
EP0289458B1 (en) * 1987-04-27 1994-02-02 Ciba-Geigy Ag Anionic disazo dyes
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

Also Published As

Publication number Publication date
JPH02289198A (en) 1990-11-29
DD299326A5 (en) 1992-04-09
US5034017A (en) 1991-07-23
DE59003396D1 (en) 1993-12-16
EP0391170A1 (en) 1990-10-10
DE3910923A1 (en) 1990-10-11

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