EP0663031B1 - Methods of dyeing paper - Google Patents

Methods of dyeing paper Download PDF

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Publication number
EP0663031B1
EP0663031B1 EP93920806A EP93920806A EP0663031B1 EP 0663031 B1 EP0663031 B1 EP 0663031B1 EP 93920806 A EP93920806 A EP 93920806A EP 93920806 A EP93920806 A EP 93920806A EP 0663031 B1 EP0663031 B1 EP 0663031B1
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mol
paper
vinylformamide
cationic polymers
copolymerized
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German (de)
French (fr)
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EP0663031A1 (en
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Claudia Nilz
Norbert Sendhoff
Walter Breitschaft
Manfred Zillig
Primoz Lorencak
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BASF SE
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BASF SE
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    • 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
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/33—Synthetic macromolecular compounds
    • D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • 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

Definitions

  • the invention relates to a process for dyeing paper in papermaking by adding water-soluble anionic dyes and cationic polymers as fixing agents for the pulp and dewatering the pulp to form colored paper.
  • EP-A-0 061 173 discloses a process for dyeing paper with water-soluble acid dyes and / or direct dyes in an aqueous medium in the presence of cationic auxiliaries.
  • the dyeing of the paper is preferably carried out in bulk, i.e. during the manufacture of the paper.
  • the cationic auxiliaries used are water-soluble reaction products which can be obtained by reacting alkylating agents which have an aromatic substituent with cationic polyelectrolytes.
  • Suitable auxiliaries of this type are, for example, benzylated polyethyleneimines.
  • the known strongly cationic polymers have the disadvantage that they greatly tarnish the brilliance of the colored papers.
  • condensates of dicyandiamide and formaldehyde or condensates of urea and formaldehyde are used as fixatives for water-soluble anionic dyes in the dyeing of paper.
  • the condensates have the disadvantage that they contain a certain amount of free formaldehyde.
  • EP-A-0 309 908 discloses a process for coloring paper in bulk with pigments and fixing agents, pigments and fixing agents being added to the paper pulp to be colored at the same time and various classes of cationic polymers being used as fixing agents, e.g. Polymers of diallyl-dimethylammonium chlorides, polymers of N-vinylimidazoles, polymers of N-vinylimidazolines, copolymers containing vinylamine units and copolymers of acrylamide with dialkylaminoalkyl acrylates and / or methacrylates.
  • cationic polymers e.g. Polymers of diallyl-dimethylammonium chlorides, polymers of N-vinylimidazoles, polymers of N-vinylimidazolines, copolymers containing vinylamine units and copolymers of acrylamide with dialkylaminoalkyl acrylates and / or methacrylates.
  • N-vinylformamide contains N-vinylformamide and vinylamine units. They are used as retention, drainage and flocculants in the manufacture of paper.
  • EP-A-0 216 387 also discloses that copolymers of 95-10 mol% N-vinylformamide and 5-90 mol% of an ethylenically unsaturated monomer from the group vinyl acetate, vinyl propionate, the C1- to C4- Alkyl vinyl ether, N-vinyl pyrrolidone, the esters, nitriles and amides of acrylic acid and methacrylic acid in at least partially hydrolyzed form, in which up to 100 mol% of the formyl groups have been split off from the copolymer, in amounts of 0.1-5% by weight, based on dry fibers, Adds the paper stock before sheet formation as a wet and dry strength agent for paper.
  • the present invention has for its object to provide methods for dyeing paper, in which one carries out the dyeing in the mass during the paper manufacturing process with water-soluble anionic dyes and cationic formaldehyde-free polymers as fixatives, whereby colored papers with high lightfastness and less Tarnishes the brilliance.
  • the object is achieved according to the invention by processes for dyeing paper in paper production by adding water-soluble anionic dyes and cationic polymers as fixatives for the paper stock and dewatering the paper stock to form colored paper if, as cationic polymers, either hydrolyzed homopolymers of N-vinylformamide are used which contain 0.1 to 100 mol% of vinylamine units in salt form and 99.9 to 0 mol% of vinylformamide units or hydrolyzed copolymers of N-vinylcarboxamides which can be obtained by copolymerizing 1 to 99 mol% of N-vinylcarboxamides and 99 to 1 mol% of acid-group-free monoethylenically unsaturated monomers and subsequent hydrolysis of 0.1 to 100 mol% of the polymerized N-vinylcarboxamides to form vinylamine units in salt form
  • the paper is colored during papermaking.
  • water-soluble anionic dyes and specially selected cationic polymers are added to the paper stock.
  • colored papers are obtained by the process according to the invention which have high light fastness and in which the brilliance is only slightly tarnished.
  • Suitable water-soluble anionic dyes for dyeing paper in bulk are known and commercially available. These dyes are, for example, mono- or polyazo dyes, each having at least one sulfonic acid group, triarylmethane dyes carrying sulfonic acid groups, copper phthalocyanine sulfonic acids, quinoline dyes containing sulfonic acid groups or stilbene dyes.
  • Examples include Direct Yellow 4 (CI 24890), Direct Yellow 5 (CI 47035), Direct Yellow 11 (CI 40,000), Direct Yellow 50 (CI 29025), Direct Yellow 127, Direct Yellow 132, Direct Yellow 147, Direct Yellow 153, Acid Orange 7 (CI 15510), Acid Orange 8 (CI 15575), Direct Orange 15 (CI 40003), 5 Direct Orange 34 (CI 40215), Direct Orange 102 (CI 29156), Direct Red 81 (CI 28160), Direct Red 239, Direct Red 252-255, Direct Violet 9 ( CI 27855), Direct Violet 51 (CI 27905), Acid Blue 9 (CI 42090), Direct Blue 86 (CI 74180), Direct Blue 199 (CI 74190), Direct Blue 218 (CI 24401), Direct Blue 267, Direct Blue 273, Direct Blue 279, Direct Blue 281, Acid Black 194, Acid Black 208, Acid Black 210, Acid Black 221, Direct Black 19 (CI 35255), Direct Black 161, Direct Black 170 or Direct Black 171.
  • the dyes are based on dry fiber e.g. in amounts of 0.01 to 10, preferably 0.1 to 5,% by weight.
  • Suitable monomers are, for example, N-vinylformamide, N-vinyl-N-methylformamide, N-vinyl acetamide, N-vinyl-N-methylacetamide, N-vinyl-N-ethylacetamide, N-vinyl-N-methylpropionamide and N-vinyl-propionamide.
  • the monomers mentioned can be used either alone or as a mixture with one another to prepare the copolymers. From this group of monomers, preference is given to using N-vinylformamide.
  • the copolymers contain the monomers of group (1) in amounts of 1 to 99, preferably 10 to 40 mol% in copolymerized form.
  • the hydrolysis of the formyl groups contained in the polymers can also be carried out with the aid of bases, e.g. of metal hydroxides, especially of alkali metal and alkaline earth metal hydroxides.
  • bases e.g. of metal hydroxides, especially of alkali metal and alkaline earth metal hydroxides.
  • Sodium hydroxide or potassium hydroxide is preferably used.
  • the hydrolysis is preferably carried out in aqueous solution or suspension at reaction temperatures of 20 to 100 ° C.
  • the reaction mixture is optionally neutralized with bases, preferably sodium hydroxide solution. If the hydrolysis was carried out with bases, the reaction mixture can, if appropriate, be neutralized by adding acids, preferably hydrochloric acid.
  • the vinylamine units a) are then in salt form.
  • the K value of the hydrolyzed copolymers is 30 to 200, preferably 30 to 80 (determined according to H. Fikentscher in 1% aqueous sodium chloride solution at 25 ° C., a polymer concentration of 1% by weight and pH 7).
  • the cationic polymers described above are used as fixatives for water-soluble anionic dyes and, for example, in amounts of 0.1 to 5, preferably 0.1 to 0.5 wt .-%, based on the dry solids in the pulp, added to the paper stock.
  • wood pulp includes wood pulp, thermomechanical material (TMP), chemo-thermomechanical material (CTMP), pressure sanding, semi-pulp, high-yield pulp and refiner mechanical pulp (RMP).
  • TMP thermomechanical material
  • CMP chemo-thermomechanical material
  • RMP refiner mechanical pulp
  • suitable pulps are sulfate, sulfite and sodium pulps.
  • Suitable annual plants for the production of paper materials are, for example, rice, wheat, sugar cane and kenaf. Waste paper is also used to produce the pulps, either alone or in a mixture with other fibrous materials.
  • inorganic fillers such as kaolin, chalk, titanium dioxide or talc and, if appropriate, auxiliaries customary in paper production, such as aluminum sulfate, retention aid or sizing agents, can also be added to the paper pulps to be colored.
  • the pH of the stock suspension can be between 4 and 9.
  • the K values of the copolymers were determined according to H. Fikentscher, Cellulose Chemie, Vol. 13, 48-64 and 71-74 (1932) in 5% aqueous saline solution at 25 ° C. and a polymer concentration of 1% by weight and pH 7 certainly.
  • the percentages in the examples are% by weight, unless stated otherwise.
  • Paper was produced on a paper machine from a wood-free, glued material with chalk as filler in the neutral pH range.
  • the fabric composition was: 65% bleached beech sulfite pulp 35% bleached pine sulfate pulp 20% Industrial chalk DX 1 1.1% promoter-free fatty alkyl diketene sizing agents 0.02% cationic polyacrylamide as a retention agent
  • Direct Yellow 11 (C.I. 40,000), Acid Orange 7 (C.I. 15510) and Direct Blue 86 (C.I. 74180).

Abstract

PCT No. PCT/EP93/02580 Sec. 371 Date Mar. 15, 1995 Sec. 102(e) Date Mar. 15, 1995 PCT Filed Sep. 23, 1993 PCT Pub. No. WO94/08092 PCT Pub. Date Apr. 14, 1994A process for dyeing paper in connection with paper manufacture by adding water-soluble anionic dyes and cationic polymers which contain vinylamine units to the paper pulp as fixing agents and removing water from the paper pulp with the formation of dyed paper is described.

Description

Die Erfindung betrifft ein Verfahren zum Färben von Papier bei der Papierherstellung durch Zusatz von wasserlöslichen anionischen Farbstoffen und kationischen Polymerisaten als Fixiermittel zum Papierstoff und Entwassern des Papierstoffs unter Bildung von 0 gefärbtem Papier.The invention relates to a process for dyeing paper in papermaking by adding water-soluble anionic dyes and cationic polymers as fixing agents for the pulp and dewatering the pulp to form colored paper.

Aus der EP-A-0 061 173 ist ein Verfahren zum Färben von Papier mit wasserlöslichen sauren Farbstoffen und/oder Direktfarbstoffen in wäßrigem Medium in Gegenwart von kationischen Hilfsmitteln bekannt. Das Färben des Papiers erfolgt bei diesem Verfahren vorzugsweise in der Masse, d.h. während der Herstellung des Papiers. Als kationische Hilfsmittel verwendet man dabei wasserlösliche Umsetzungsprodukte, die durch Reaktion von Alkylierungsmitteln, die einen aromatischen Substituenten aufweisen, mit kationischen Polyelektrolyten erhältlich sind. Geeignete Hilfsmittel dieser Art sind beispielsweise benzylierte Polyethylenimine. Die bekannten stark kationischen Polymeren haben den Nachteil, daß sie Brillanz der gefärbten Papiere sehr stark abtrüben. In der Praxis werden deshalb hauptsächlich Kondensate aus Dicyandiamid und Formaldehyd oder Kondensate aus Harnstoff und Formaldehyd als Fixiermittel für wasserlösliche anionische Farbstoffe beim Färben von Papier verwendet. Die Kondensate haben den Nachteil, daß sie eine bestimmte Menge an freiem formaldehyd enthalten.EP-A-0 061 173 discloses a process for dyeing paper with water-soluble acid dyes and / or direct dyes in an aqueous medium in the presence of cationic auxiliaries. In this process, the dyeing of the paper is preferably carried out in bulk, i.e. during the manufacture of the paper. The cationic auxiliaries used are water-soluble reaction products which can be obtained by reacting alkylating agents which have an aromatic substituent with cationic polyelectrolytes. Suitable auxiliaries of this type are, for example, benzylated polyethyleneimines. The known strongly cationic polymers have the disadvantage that they greatly tarnish the brilliance of the colored papers. In practice, therefore, mainly condensates of dicyandiamide and formaldehyde or condensates of urea and formaldehyde are used as fixatives for water-soluble anionic dyes in the dyeing of paper. The condensates have the disadvantage that they contain a certain amount of free formaldehyde.

Aus der EP-A-0 309 908 ist ein Verfahren zum Färben von Papier in der Masse mit Pigmenten und Fixiermitteln bekannt, wobei man Pigmente und Fixiermittel gleichzeitig zu der zu färbenden Papiermasse gibt und als Fixiermittel verschiedene Klassen von kationischen Polymerisaten verwendet, z.B. Polymerisate von Diallyl-dimethylammoniumchloriden, Polymerisate von N-Vinylimidazolen, Polymerisate von N-Vinylimidazolinen, Vinylamineinheiten enthaltende Copolymerisate und Copolymerisate von Acrylamid mit Dialkylaminoalkylacrylaten und/oder -methacrylaten.EP-A-0 309 908 discloses a process for coloring paper in bulk with pigments and fixing agents, pigments and fixing agents being added to the paper pulp to be colored at the same time and various classes of cationic polymers being used as fixing agents, e.g. Polymers of diallyl-dimethylammonium chlorides, polymers of N-vinylimidazoles, polymers of N-vinylimidazolines, copolymers containing vinylamine units and copolymers of acrylamide with dialkylaminoalkyl acrylates and / or methacrylates.

Aus der US-A-4 421 602 sind partiell hydrolysierte Homopolymerisate des N-Vinylformamids bekannt, die N-Vinylformamid und Vinylamineinheiten enthalten. Sie werden als Retentions-, Entwässerungs- und Flockungsmittel bei der Herstellung von Papier verwendet. Aus der EP-A-0 216 387 ist außerdem bekannt, daß man Copolymerisate aus 95 - 10 Mol-% N-Vinylformamid und 5 - 90 Mol-% eines ethylenisch ungesättigten Monomeren aus der Gruppe Vinylacetat, Vinylpropionat, der C₁- bis C₄-Alkylvinylether, N-Vinylpyrrolidon, der Ester, Nitrile und Amide von Acrylsäure und Methacrylsäure in zumindest partiell hydrolysierter Form, bei der bis zu 100 Mol-% der Formylgruppen aus dem Copolymerisat abgespalten sind, in Mengen von 0,1 - 5 Gew.-%, bezogen auf trockene Fasern, dem Papierstoff vor der Blattbildung als Naß- und Trockenverfestigungsmittel für Papier zusetzt.From US-A-4 421 602 partially hydrolyzed homopolymers of N-vinylformamide are known which contain N-vinylformamide and vinylamine units. They are used as retention, drainage and flocculants in the manufacture of paper. EP-A-0 216 387 also discloses that copolymers of 95-10 mol% N-vinylformamide and 5-90 mol% of an ethylenically unsaturated monomer from the group vinyl acetate, vinyl propionate, the C₁- to C₄- Alkyl vinyl ether, N-vinyl pyrrolidone, the esters, nitriles and amides of acrylic acid and methacrylic acid in at least partially hydrolyzed form, in which up to 100 mol% of the formyl groups have been split off from the copolymer, in amounts of 0.1-5% by weight, based on dry fibers, Adds the paper stock before sheet formation as a wet and dry strength agent for paper.

Außerdem ist die Verwendung von hydrolysierten Homo- und/oder Copolymerisaten des N-Vinylformamids mit einem Hydrolysegrad von mindestens 60 % der einpolymerisierten N-Vinylformamid-Einheiten als Fixiermittel in Kombination mit einem kationischen Retentionsmittel bei der Herstellung von Papier, Pappe und Karton durch Entwassern eines Störstoffe enthaltenden Papierstoffs aus der EP-A-0 438 707 bekannt.In addition, the use of hydrolyzed homo- and / or copolymers of N-vinylformamide with a degree of hydrolysis of at least 60% of the polymerized N-vinylformamide units as fixative in combination with a cationic retention aid in the manufacture of paper, cardboard and cardboard by dewatering one Paper containing impurities is known from EP-A-0 438 707.

Der vorliegenden Erfindung liegt die Aufgabe zugrunde, Verfahren zum Färben von Papier zur Verfügung zu stellen, bei denen man das Färben in der Masse während des Papierherstellungsprozesses mit wasserlöslichen anionischen Farbstoffen und kationischen formaldehydfreien Polymerisaten als Fixiermittel vornimmt, wobei man gefärbte Papiere mit hoher Lichtechtheit und geringer Abtrübung der Brillanz erhält.The present invention has for its object to provide methods for dyeing paper, in which one carries out the dyeing in the mass during the paper manufacturing process with water-soluble anionic dyes and cationic formaldehyde-free polymers as fixatives, whereby colored papers with high lightfastness and less Tarnishes the brilliance.

Die Aufgabe wird erfindungsgemäß gelöst mit Verfahren zum Färben von Papier bei der Papierherstellung durch Zusatz von wasserlöslichen anionischen Farbstoffen und kationischen Polymerisaten als Fixiermittel zum Papierstoff und Entwässern des Papierstoffs unter Bildung von gefärbtem Papier, wenn man als kationische Polymerisate entweder hydrolysierte Homopolymerisate von N-Vinylformamid einsetzt, die 0,1 bis 100 Mol-% Vinylamineinheiten in Salzform und 99,9 bis 0 Mol-% Vinylformamideinheiten enthalten oder hydrolysierte Copolymerisate von N-Vinylcarbonsäureamiden, die erhältlich sind durch Copolymerisieren von 1 bis 99 Mol-% N-Vinylcarbonsäureamiden und 99 bis 1 Mol-% säuregruppenfreien monoethylenisch ungesättigten Monomeren und anschließende Hydrolyse von 0,1 bis 100 Mol-% der einpolymerisierten N-Vinylcarbonsäureamide unter Bildung von Vinylamineinheiten in SalzformThe object is achieved according to the invention by processes for dyeing paper in paper production by adding water-soluble anionic dyes and cationic polymers as fixatives for the paper stock and dewatering the paper stock to form colored paper if, as cationic polymers, either hydrolyzed homopolymers of N-vinylformamide are used which contain 0.1 to 100 mol% of vinylamine units in salt form and 99.9 to 0 mol% of vinylformamide units or hydrolyzed copolymers of N-vinylcarboxamides which can be obtained by copolymerizing 1 to 99 mol% of N-vinylcarboxamides and 99 to 1 mol% of acid-group-free monoethylenically unsaturated monomers and subsequent hydrolysis of 0.1 to 100 mol% of the polymerized N-vinylcarboxamides to form vinylamine units in salt form

Nach den erfindungsgemäßen Verfahren wird das Papier während der Papierherstellung gefärbt. Hierzu fügt man zum Papierstoff wasserlösliche anionische Farbstoffe und speziell ausgewählte kationische Polymerisate. Verglichen mit anderen bekannten Fixiermitteln erhält man nach den erfindungsgemäßen Verfahren gefärbte Papiere, die eine hohe Lichtechtheit aufweisen und bei denen die Brillanz nur geringfügig abgetrübt ist.According to the method according to the invention, the paper is colored during papermaking. For this purpose, water-soluble anionic dyes and specially selected cationic polymers are added to the paper stock. Compared with other known fixing agents, colored papers are obtained by the process according to the invention which have high light fastness and in which the brilliance is only slightly tarnished.

Geeignete wasserlösliche anionische Farbstoffe zum Färben von Papier in der Masse sind bekannt und im Handel erhältlich. Bei diesen Farbstoffen handelt es sich beispielsweise um Mono- oder Polyazofarbstoffe, die jeweils mindestens eine Sulfonsäuregruppe aufweisen, um Sulfonsauregruppen tragende Triarylmethanfarbstoffe, um Kupferphthalocyaninsulfonsäuren, um sulfonsäuregruppenhaltige Chinolinfarbstoffe oder Stilbenfarbstoffe. Beispielhaft seien Direct Yellow 4 (C.I. 24890), Direct Yellow 5 (C.I. 47035), Direct Yellow 11 (C.I. 40.000), Direct Yellow 50 (C.I. 29025), Direct Yellow 127, Direct Yellow 132, Direct Yellow 147, Direct Yellow 153, Acid Orange 7 (C.I. 15510), Acid Orange 8 (C.I. 15575), Direct Orange 15 (C.I. 40003), 5 Direct Orange 34 (C.I. 40215), Direct Orange 102 (C.I. 29156), Direct Red 81 (C.I. 28160), Direct Red 239, Direct Red 252-255, Direct Violet 9 (C.I. 27855), Direct Violet 51 (C.I. 27905), Acid Blue 9 (C.I. 42090), Direct Blue 86 (C.I. 74180), Direct Blue 199 (C.I. 74190), Direct Blue 218 (C.I. 24401), Direct Blue 267, Direct Blue 273, Direct Blue 279, Direct Blue 281, Acid Black 194, Acid Black 208, Acid Black 210, Acid Black 221, Direct Black 19 (C.I. 35255), Direct Black 161, Direct Black 170 oder Direct Black 171 erwähnt.Suitable water-soluble anionic dyes for dyeing paper in bulk are known and commercially available. These dyes are, for example, mono- or polyazo dyes, each having at least one sulfonic acid group, triarylmethane dyes carrying sulfonic acid groups, copper phthalocyanine sulfonic acids, quinoline dyes containing sulfonic acid groups or stilbene dyes. Examples include Direct Yellow 4 (CI 24890), Direct Yellow 5 (CI 47035), Direct Yellow 11 (CI 40,000), Direct Yellow 50 (CI 29025), Direct Yellow 127, Direct Yellow 132, Direct Yellow 147, Direct Yellow 153, Acid Orange 7 (CI 15510), Acid Orange 8 (CI 15575), Direct Orange 15 (CI 40003), 5 Direct Orange 34 (CI 40215), Direct Orange 102 (CI 29156), Direct Red 81 (CI 28160), Direct Red 239, Direct Red 252-255, Direct Violet 9 ( CI 27855), Direct Violet 51 (CI 27905), Acid Blue 9 (CI 42090), Direct Blue 86 (CI 74180), Direct Blue 199 (CI 74190), Direct Blue 218 (CI 24401), Direct Blue 267, Direct Blue 273, Direct Blue 279, Direct Blue 281, Acid Black 194, Acid Black 208, Acid Black 210, Acid Black 221, Direct Black 19 (CI 35255), Direct Black 161, Direct Black 170 or Direct Black 171.

Die Farbstoffe werden, bezogen auf trockenen Faserstoff, z.B. in Mengen von 0,01 bis 10, vorzugsweise 0,1 bis 5, Gew.-% eingesetzt.The dyes are based on dry fiber e.g. in amounts of 0.01 to 10, preferably 0.1 to 5,% by weight.

Erfindungsgemäß werden als Fixiermittel hydrolysierte Homopolymerisate von N-Vinylformamid eingesetzt, die

  • a) 0,1 bis 100 Mol-% Vinylamineinheiten in Salzform und
  • b) 99,9 bis 0 Mol-% Vinylformamideinheiten
enthalten oder hydrolysierte Copolymerisate von N-Vinylcarbonsäureamiden, die erhältlich sind durch Copolymerisieren von
(1)
1 bis 99 Mol-% N-Vinylcarbonsäureamiden und
(2)
99 bis 1 Mol-% säuregruppenfreien monoethylenisch ungesättigten Monomeren
und anschließende Hydrolyse von 0,1 bis 100 Mol-% der einpolymerisierten N-Vinylcarbonsäureamide unter Bildung von Vinylamineinheiten in Salzform.According to the invention, hydrolyzed homopolymers of N-vinylformamide are used as fixatives, which
  • a) 0.1 to 100 mol% of vinylamine units in salt form and
  • b) 99.9 to 0 mole% vinyl formamide units
contain or hydrolyzed copolymers of N-vinylcarboxamides, which are obtainable by copolymerizing
(1)
1 to 99 mol% of N-vinylcarboxamides and
(2)
99 to 1 mol% of acid group-free monoethylenically unsaturated monomers
and subsequent hydrolysis of 0.1 to 100 mol% of the polymerized N-vinylcarboxamides to form vinylamine units in salt form.

Als Monomere der Gruppe (1) kommen N-Vinylcarbonsäureamide der Formel

Figure imgb0001
in der R¹, R = H oder C₁ bis C6-Alkyl bedeuten, in Betracht. Geeignete Monomere sind beispielsweise N-Vinylformamid, N-Vinyl-N-Methylformamid, N-Vinylacetamid, N-Vinyl-N-methylacetamid, N-Vinyl-N-ethylacetamid, N-Vinyl-N-methylpropionamid und N-Vinyl-propionamid. Zur Herstellung der Copolymeren können die genannten Monomeren entweder allein oder in Mischung untereinander eingesetzt werden. Vorzugsweise verwendet man aus dieser Gruppe von Monomeren N-Vinylformamid. Die Copolymerisate enthalten die Monomeren der Gruppe (1) in Mengen von 1 bis 99, vorzugsweise 10 bis 40 Mol-% in einpolymerisierter Form.The monomers of group (1) are N-vinylcarboxamides of the formula
Figure imgb0001
 in which R¹, R = H or C₁ to C6-alkyl, into consideration. Suitable monomers are, for example, N-vinylformamide, N-vinyl-N-methylformamide, N-vinyl acetamide, N-vinyl-N-methylacetamide, N-vinyl-N-ethylacetamide, N-vinyl-N-methylpropionamide and N-vinyl-propionamide. The monomers mentioned can be used either alone or as a mixture with one another to prepare the copolymers. From this group of monomers, preference is given to using N-vinylformamide. The copolymers contain the monomers of group (1) in amounts of 1 to 99, preferably 10 to 40 mol% in copolymerized form.

Bevorzugt ist die Verwendung von hydrolysierten Copolymerisaten des N-Vinylformamids, die dadurch erhältlich sind, daß man

(1)
1 bis 99 Mol-% N-Vinylformamid und
(2)
99 bis 1 Mol-% mindestens eines Monomeren aus der Gruppe bestehend aus Vinylacetat, Vinylpropionat, Vinylharnstoff, C₁- bis C₄-Alkylvinylether, N-Vinylpyrrolidon, der Ester, Nitrile und Amide von Acrylsäure- oder Methacrylsäure
copolymerisiert und die so erhältlichen Copolymerisate hydrolysiert, daß 0,1 bis 100 Mol-% des einpolymerisierten N-Vinylformamids hydrolysiert sind. Bei dieser Hydrolyse bleiben die in das Copolymerisat eingebauten Monomeren der Gruppe (2) praktisch unverändert. Die Hydrolyse der Vinylformamid einpolymerisiert enthaltenen Copolymerisate kann jedoch auch in der Weise ausgeführt werden, daß die in das Copolymerisat einpolymerisierten Comonomeren hydrolysieren. Solche hydrolysierten Copolymerisate sind beispielsweise erhältlich durch Copolymerisieren von
(1)
1 bis 99 Mol-% N-Vinylformamid und
(2)
99 bis 1 Mol-% Vinylacetat und/oder Vinylpropionat
und anschließende Hydrolyse von 40 bis 100 Mol-% des einpolymerisierten N-Vinylformamids und Hydrolyse von 50 bis 100 Mol-% der Acetyl- bzw. Propionylgruppen der einpolymerisierten Monomeren (2). Bevorzugt werden Copolymerisate verwendet, die
  • 40 bis 80 Mol-% Vinylamin-Einheiten und
  • 60 bis 20 Mol-% Vinylalkohol-, Acrylnitril- und/oder Vinylharnstoffeinheiten
einpolymerisiert enthalten. Solche Copolymerisate können gegebenenfalls noch Vinylformamideinheiten bzw. Vinylacetat- und/oder Vinylpropionateinheiten enthalten. Die Herstellung solcher Polymerisate ist beispielsweise aus der EP-A-0 216 387 bekannt. Als Hydrolysemittel eignen sich vor allem Mineralsäuren, wie Halogenwasserstoffe, die gasförmig oder in wäßriger Lösung eingesetzt werden können. Vorzugsweise verwendet man Salzsäure, Schwefelsäure, Salpetersaure und Phosphorsäure sowie organische Säuren, wie C₁- bis C₅-Carbonsäuren und aliphatische oder aromatische Sulfonsauren. Der pH-Wert bei der sauren Hydrolyse beträgt -1 bis 5, vorzugsweise 0 bis 2. Pro Formylgruppenäquivalent, das aus den einpolymerisierten Vinylcarbonsäureamideinheiten abgespalten werden soll, benötigt man 0,05 bis 2, vorzugsweise 1 bis 1,5 Moläquivalent einer Säure.Preferred is the use of hydrolyzed copolymers of N-vinylformamide, which are obtainable by
(1)
1 to 99 mol% of N-vinylformamide and
(2)
99 to 1 mol% of at least one monomer from the group consisting of vinyl acetate, vinyl propionate, vinyl urea, C₁ to C₄ alkyl vinyl ether, N-vinylpyrrolidone, the esters, nitriles and amides of acrylic or methacrylic acid
copolymerized and hydrolyzed the copolymers so obtainable that 0.1 to 100 mol% of the copolymerized N-vinylformamide are hydrolyzed. During this hydrolysis, the monomers of group (2) incorporated into the copolymer remain practically unchanged. However, the hydrolysis of the copolymers containing copolymerized vinylformamide can also be carried out in such a way that the comonomers copolymerized into the copolymer hydrolyze. Such hydrolyzed copolymers can be obtained, for example, by copolymerizing
(1)
1 to 99 mol% of N-vinylformamide and
(2)
99 to 1 mole% vinyl acetate and / or vinyl propionate
and subsequent hydrolysis of 40 to 100 mol% of the polymerized N-vinylformamide and hydrolysis of 50 to 100 mol% of the acetyl or propionyl groups of the polymerized monomers (2). Copolymers are preferably used which
  • 40 to 80 mol% of vinylamine units and
  • 60 to 20 mol% of vinyl alcohol, acrylonitrile and / or vinyl urea units
polymerized included. Such copolymers may optionally also contain vinylformamide units or vinyl acetate and / or vinyl propionate units. The preparation of such polymers is known, for example, from EP-A-0 216 387. Particularly suitable hydrolysis agents are mineral acids, such as hydrogen halides, which can be used in gaseous form or in aqueous solution. Hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid and organic acids such as C₁ to C- carboxylic acids and aliphatic or aromatic sulfonic acids are preferably used. The pH in the acidic hydrolysis is -1 to 5, preferably 0 to 2. Per formyl group equivalent which is to be split off from the copolymerized vinylcarboxamide units, 0.05 to 2, preferably 1 to 1.5 molar equivalent of an acid is required.

Die Hydrolyse der in den Polymerisaten enthaltenen Formylgruppen kann auch mit Hilfe von Basen vorgenommen werden, z.B. von Metallhydroxyden, insbesondere von Alkalimetall- und Erdalkalimetallhydroxyden. Vorzugsweise verwendet man Natriumhydroxid oder Kaliumhydroxid.The hydrolysis of the formyl groups contained in the polymers can also be carried out with the aid of bases, e.g. of metal hydroxides, especially of alkali metal and alkaline earth metal hydroxides. Sodium hydroxide or potassium hydroxide is preferably used.

Die Hydrolyse wird vorzugsweise in wäßriger Lösung oder Suspension bei Reaktionstemperaturen von 20 bis 100°C durchgeführt. Im Anschluß an eine sauer durchgeführte Hydrolyse wird das Reaktionsgemisch gegebenenfalls mit Basen, vorzugsweise Natronlauge, neutralisiert. Falls die Hydrolyse mit Basen durchgeführt wurde, kann das Reaktionsgemisch gegebenenfalls durch Zusatz von Säuren, vorzugsweise von Salzsäure, neutralisiert werden. Die Vinylamin-einheiten a) liegen dann in Salzform vor. Der K-Wert der hydrolysierten Copolymerisate beträgt 30 bis 200, vorzugsweise 30 bis 80 (bestimmt nach H. Fikentscher in 1 %iger wäßriger Kochsalzlösung bei 25°C, einer Polymerkonzentration von 1 Gew.-% und pH 7).The hydrolysis is preferably carried out in aqueous solution or suspension at reaction temperatures of 20 to 100 ° C. Following an acidic hydrolysis, the reaction mixture is optionally neutralized with bases, preferably sodium hydroxide solution. If the hydrolysis was carried out with bases, the reaction mixture can, if appropriate, be neutralized by adding acids, preferably hydrochloric acid. The vinylamine units a) are then in salt form. The K value of the hydrolyzed copolymers is 30 to 200, preferably 30 to 80 (determined according to H. Fikentscher in 1% aqueous sodium chloride solution at 25 ° C., a polymer concentration of 1% by weight and pH 7).

Die oben beschriebenen kationischen Polymerisate werden als Fixiermittel für wasserlösliche anionische Farbstoffe verwendet und z.B. in Mengen von 0,1 bis 5, vorzugsweise 0,1 bis 0,5 Gew.-%, bezogen auf die trockenen Feststoffe in der Pulpe, dem Papierstoff zugesetzt.The cationic polymers described above are used as fixatives for water-soluble anionic dyes and, for example, in amounts of 0.1 to 5, preferably 0.1 to 0.5 wt .-%, based on the dry solids in the pulp, added to the paper stock.

Als Faserstoffe zur Herstellung der Pulpen kommen sämtliche dafür gebräuchlichen Qualitäten in Betracht, z.B. Holzstoff, gebleichter und ungebleichter Zellstoff sowie Papierstoffe aus allen Einjahrespflanzen. Zu Holzstoff gehören beispielsweise Holzschliff, thermomechanischer Stoff (TMP), chemo-thermomechanischer Stoff (CTMP), Druckschliff, Halbzellstoff, Hochausbeute-Zellstoff und Refiner Mechanical Pulp (RMP). Als Zellstoffe kommen beispielsweise Sulfat-, Sulfit- und Natronzellstoffe in Betracht. Geeignete Einjahrespflanzen zur Herstellung von Papierstoffen sind beispielsweise Reis, Weizen, Zuckerrohr und Kenaf. Zur Herstellung der Pulpen wird auch Altpapier verwendet, entweder allein oder in Mischung mit anderen Faserstoffen. Des weiteren können den zu färbenden Papiermassen im Bedarfsfall auch anorganische Füllstoffe wie Kaolin, Kreide, Titandioxid oder Talkum und gegebenenfalls in der Papierherstellung übliche Hilfsmittel wie Aluminiumsulfat, Retentionsmittel oder Leimungsmittel zugefügt werden. Der pH-Wert der Stoffsuspension kann zwischen 4 und 9 liegen.As fiber materials for the production of the pulps, all the qualities commonly used for this purpose come into consideration, e.g. Wood pulp, bleached and unbleached pulp and paper pulp from all annual plants. For example, wood pulp includes wood pulp, thermomechanical material (TMP), chemo-thermomechanical material (CTMP), pressure sanding, semi-pulp, high-yield pulp and refiner mechanical pulp (RMP). Examples of suitable pulps are sulfate, sulfite and sodium pulps. Suitable annual plants for the production of paper materials are, for example, rice, wheat, sugar cane and kenaf. Waste paper is also used to produce the pulps, either alone or in a mixture with other fibrous materials. In addition, if necessary, inorganic fillers such as kaolin, chalk, titanium dioxide or talc and, if appropriate, auxiliaries customary in paper production, such as aluminum sulfate, retention aid or sizing agents, can also be added to the paper pulps to be colored. The pH of the stock suspension can be between 4 and 9.

Um brillante Färbungen mit hoher Lichtechtheit zu erhalten, kann man zunächst den Farbstoff zum Papierstoff geben und nach dem Homogenisieren das Fixiermittel zusetzen oder zunächst das Fixiermittel dosieren und danach den wasserlöslichen anionischen Farbstoff oder eine Farbstoffmischung zusetzen.In order to obtain brilliant dyeings with high light fastness, one can first add the dye to the paper stock and after the homogenization add the fixative or first meter the fixative and then add the water-soluble anionic dye or a dye mixture.

Die K-Werte der Copolymerisate wurden nach H. Fikentscher, Cellulose Chemie, Band 13, 48 - 64 und 71 - 74 (1932) in 5 %iger wäßriger Kochsalzlösung bei 25°C und einer Polymerkonzentration von 1 Gew.-% und pH 7 bestimmt. Die Prozentangaben in den Beispielen sind Gew.-%, sofern nichts anderes angegeben ist.The K values of the copolymers were determined according to H. Fikentscher, Cellulose Chemie, Vol. 13, 48-64 and 71-74 (1932) in 5% aqueous saline solution at 25 ° C. and a polymer concentration of 1% by weight and pH 7 certainly. The percentages in the examples are% by weight, unless stated otherwise.

BeispieleExamples

Folgende kationische Polymere wurden als Fixiermittel getestet:The following cationic polymers were tested as fixatives:

Polymer 1:Polymer 1:

ein handelsübliches Kondensat aus Dicyandiamid, Harnstoff und Formaldehyd (Vergleich).a commercially available condensate of dicyandiamide, urea and formaldehyde (comparison).

Polymer 2:Polymer 2:

ein handelsübliches Kondensat aus Dicyandiamid und Formaldehyd (Vergleich).a commercially available condensate of dicyandiamide and formaldehyde (comparison).

Polymer 3:Polymer 3:

Copolymerisat aus 70 Mol-% Vinylamin und 30 Mol-% Vinylalkohol, K-Wert 60.Copolymer of 70 mol% vinylamine and 30 mol% vinyl alcohol, K value 60.

Polymer 4:Polymer 4:

Copolymerisat aus 60 Mol-% Vinylamin und 40 Mol-% Acrylnitril, K-Wert 60.Copolymer of 60 mol% vinylamine and 40 mol% acrylonitrile, K value 60.

Polymer 5:Polymer 5:

ein Copolymerisat aus 80 Mol-% Vinylamin und 20 Mol-% Vinylharnstoff, K-Wert 30.a copolymer of 80 mol% vinylamine and 20 mol% vinyl urea, K value 30.

Polymer 6:Polymer 6:

ein Copolymerisat aus 50 Mol-% Vinylamin und 50 Mol-% Vinylharnstoff, K-Wert 30.a copolymer of 50 mol% vinylamine and 50 mol% vinyl urea, K value 30.

Beispiel 1example 1

Als Stoffmodell diente eine Mischung aus 70 % gebleichtem Kiefernsulfatzellstoff und 30 % gebleichtem Birkensulfatzellstoff. Der Stoff wurde 4 %ig aufgeschlagen und bis zu einem Mahlgrad von 30°SR (SR = Schopper-Riegler) gemahlen. Daraus wurden Aliquote, die 5 g trockenem Stoff entsprachen, entnommen, Fixiermittel und entweder 2 % (bezogen auf trockenen Stoff) einer Flüssigformulierung von C.I. Direct Red 254 oder 10 % einer Flüssigformulierung von Acid Orange 7 (C.I. 15510) zugegeben. Nach der Blattbildung auf einem Rapid-Köthen-Blattbildner wurden die Farbstärken der Papierblätter mittels eines Elrepho 2000 farbmetrisch ermittelt.A mixture of 70% bleached pine sulfate pulp and 30% bleached birch sulfate pulp served as the fabric model. The material was whipped to 4% and ground to a freeness of 30 ° SR (SR = Schopper-Riegler). From this, aliquots corresponding to 5 g of dry matter were removed, fixative and either 2% (based on dry matter) of a liquid formulation of C.I. Direct Red 254 or 10% of a liquid formulation of Acid Orange 7 (C.I. 15510) was added. After the sheet was formed on a Rapid-Köthen sheet former, the color strengths of the paper sheets were determined colorimetrically using an Elrepho 2000.

Folgende Ergebnisse wurden erhalten:

Figure imgb0002
The following results were obtained:
Figure imgb0002

Beispiel 2Example 2

Auf einer Papiermaschine wurde Papier aus einem holzfreien, geleimten Stoff mit Kreide als Füllstoff im neutralen pH-Bereich hergestellt. Die Stoffzusammensetzung war: 65 % gebleichter Buchensulfit Zellstoff 35 % gebleichter Kiefernsulfat Zellstoff 20 % Industriekreide DX 1 1,1 % promoterfreie Fettalkyldiketen-Leimungsmittel 0,02 % kationisches Polyacrylamid als Retentionsmittel Paper was produced on a paper machine from a wood-free, glued material with chalk as filler in the neutral pH range. The fabric composition was: 65% bleached beech sulfite pulp 35% bleached pine sulfate pulp 20% Industrial chalk DX 1 1.1% promoter-free fatty alkyl diketene sizing agents 0.02% cationic polyacrylamide as a retention agent

Zu diesem Papierstoff wurden jeweils die in den folgenden Tabellen angegebenen Mengen an Fixiermittel, bezogen auf trockenen Papierstoff, und 2 % Flüssigformulierungen von Farbstoffen zugegeben.The amounts of fixing agent, based on dry paper stock, and 2% liquid formulations of dyes given in the following tables were added to this paper stock.

Es wurden folgende Farbstoffe ausgewählt:The following dyes were selected:

Direct Yellow 11 (C.I. 40.000), Acid Orange 7 (C.I. 15510) und Direct Blue 86 (C.I. 74180).Direct Yellow 11 (C.I. 40,000), Acid Orange 7 (C.I. 15510) and Direct Blue 86 (C.I. 74180).

Die Ergebnisse sind in den nachfolgenden Tabellen zusammengefaßt.

Figure imgb0003
Figure imgb0004
 The results are summarized in the tables below.
Figure imgb0003
Figure imgb0004

Claims (5)

  1. A process for dyeing paper during paper manufacture by adding water-soluble anionic dyes and cationic polymers to the paper pulp as fixing agents and removing water from the paper pulp with the formation of dyed paper, which comprises employing, as cationic polymers, hydrolyzed homopolymers of N-vinylformamide which contain
    a)   0.1 - 100 mol % of vinylamine units in salt form and
    b)   99.9 - 0 mol % of vinylformamide units.
  2. A process for dyeing paper during paper manufacture by adding water-soluble anionic dyes and cationic polymers to the paper pulp as fixing agents and removing water from the paper pulp with the formation of dyed paper, wherein the cationic polymers employed are hydrolyzed copolymers of N-vinylcarboxamides which are obtainable by copolymerizing
    (1)   1 - 99 mol % of N-vinylcarboxamides and
    (2)   99 - 1 mol % of acid-free monoethylenically unsaturated monomers
    and subsequently hydrolyzing 0.1 - 100 mol % of the copolymerized N-vinylcarboxamides with the formation of vinylamine units in salt form.
  3. A process as claimed in claim 2, wherein the cationic polymers employed are hydrolyzed copolymers of N-vinylformamide which are obtainable by copolymerizing
    (1)   1 - 99 mol % of N-vinylformamide and
    (2)   99 - 1 mol % of at least one monomer from the group consisting of vinyl acetate, vinyl propionate, vinylurea, C₁- to C₄-alkyl vinyl ether, N-vinylpyrrolidone, and the esters, nitriles and amides of acrylic acid or methacrylic acid
    and subsequently hydrolyzing 0.1 - 100 mol % of the copolymerized N-vinylformamide.
  4. A process as claimed in claim 2, wherein the cationic polymers employed are copolymers of N-vinylformamide which are obtainable by copolymerizing
    (1)   1 - 99 mol % of N-vinylformamide and
    (2)   99 - 1 mol % of vinyl acetate and/or vinyl propionate
    and subsequently hydrolyzing 40 - 100 mol % of the copolymerized N-vinylformamide and removing 50 - 100 mol % of the acetyl or propionyl groups from the copolymerized monomers (2) .
  5. A process as claimed in claim 2, wherein the cationic polymers employed are copolymers which contain
    - 40 - 80 mol % of vinylamine units in salt form and
    - 60 - 20 mol % of vinyl alcohol, acrylonitrile and/or vinylurea units
    in copolymerized form.
EP93920806A 1992-10-01 1993-09-23 Methods of dyeing paper Expired - Lifetime EP0663031B1 (en)

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DE4233040 1992-10-01
DE4233040A DE4233040A1 (en) 1992-10-01 1992-10-01 Process for dyeing paper
PCT/EP1993/002580 WO1994008092A1 (en) 1992-10-01 1993-09-23 Method of dyeing paper

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US5519093A (en) * 1994-05-11 1996-05-21 Air Products And Chemicals, Inc. Synthesis of amine functional co-and terpolymers
DE19651243A1 (en) * 1996-12-10 1998-06-18 Basf Ag Amphiphilic graft polymers based on graft bases containing N-vinylcarboxamide units, process for their preparation and their use
DE19719059A1 (en) * 1997-05-06 1998-11-12 Basf Ag Process for the production of paper, cardboard and cardboard
US5948125A (en) * 1997-05-20 1999-09-07 Ciba Specialty Chemicals Corporation Method of treating dyed, natural or synthetic polyamide fibre materials
DE502005010744D1 (en) 2004-09-02 2011-02-10 Basf Se Liquid formulations of direct dyes
EP1632535B1 (en) * 2004-09-02 2010-12-29 Basf Se Liquid formulations of direct dyes
EP1994222A1 (en) * 2006-02-20 2008-11-26 Clariant International Ltd. Improved process for the manufacture of paper and board
WO2007128077A1 (en) * 2006-05-09 2007-11-15 Visy R & D Pty Ltd Improved paper dyeing process
JP2008248459A (en) * 2007-03-30 2008-10-16 Nippon Paper Industries Co Ltd Method for producing paper
US7833335B2 (en) * 2007-04-12 2010-11-16 Hewlett-Packard Development Company, L.P. Ink-jet ink sets
GB0813574D0 (en) * 2008-07-24 2008-09-03 Barnwell Andrew D A hanger
US9803315B2 (en) 2013-03-19 2017-10-31 Mitsubishi Chemical Corporation Cationizing agent, method for firmly fixing water-insoluble particles, and method for producing dyed material

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CA686202A (en) * 1964-05-12 E. Eddy Roderick Process for improving the dye retention characteristics of cellulosic materials
DE3111712A1 (en) * 1981-03-25 1982-10-07 Basf Ag, 6700 Ludwigshafen METHOD FOR DYING PAPER
DE3128478A1 (en) * 1981-07-18 1983-02-03 Basf Ag, 6700 Ludwigshafen METHOD FOR PRODUCING LINEAR, BASIC POLYMERISATS
DE3534273A1 (en) * 1985-09-26 1987-04-02 Basf Ag METHOD FOR PRODUCING VINYLAMINE UNITS CONTAINING WATER-SOLUBLE COPOLYMERISATS AND THE USE THEREOF AS WET AND DRY-FASTENING AGENTS FOR PAPER
DE3732981A1 (en) * 1987-09-30 1989-04-13 Basf Ag METHOD FOR DYING PAPER
DE4001045A1 (en) * 1990-01-16 1991-07-18 Basf Ag Paper, paste-board and cardboard prodn. - by draining pulp contg. retention agent and as fixing agent, min. 60 per cent-hydrolysed homo- or copolymer of N-vinyl-formamide
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