EP0309908B1 - Process for colouring paper - Google Patents
Process for colouring paper Download PDFInfo
- Publication number
- EP0309908B1 EP0309908B1 EP88115563A EP88115563A EP0309908B1 EP 0309908 B1 EP0309908 B1 EP 0309908B1 EP 88115563 A EP88115563 A EP 88115563A EP 88115563 A EP88115563 A EP 88115563A EP 0309908 B1 EP0309908 B1 EP 0309908B1
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- EP
- European Patent Office
- Prior art keywords
- pigment
- copolymers
- paper
- colored
- acrylamide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
-
- D—TEXTILES; PAPER
- 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
-
- 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
- D21H17/37—Polymers of unsaturated acids or derivatives thereof, e.g. polyacrylates
- D21H17/375—Poly(meth)acrylamide
Definitions
- the present invention relates to a new process for coloring paper in bulk with pigments and fixing agents, pigment and fixing agent being added simultaneously to the paper pulp to be colored and a fixing agent being a cationic fixing agent in an amount of 0.01 to 3% by weight. , based on the dry paper pulp to be used.
- the coloring of paper is usually carried out with dyes (see e.g. Ullmanns Encyklopadie der Technische Chemie, 4th edition, volume 17, pages 613 and 614).
- the paper colored in this way usually has insufficient fastness properties, in particular light fastness that is too low.
- the object of the present application was to provide a new process for coloring paper in bulk, in which pigments are also used as colorants and the known disadvantages should no longer occur.
- Organic pigments which serve as colorants in the process according to the invention are, for example, those from the class of the monoazo pigments (for example products which are derived from acetoessigarylide derivatives or from ⁇ -naphthol derivatives), lacquered monoazo dyes (for example lacquered ⁇ -oxynaphthoic acid dyes), disazo pigments, condensed disazo pigments Isoindoline derivatives, derivatives of naphthalene or perylene tetracarboxylic acid, anthraquinone pigments, thioindigo derivatives, azomethine derivatives, quinacridones, dioxazines, pyrazoloquinazolones, phthalocyanine pigments or lacquered basic dyes (eg lacquered triarylmethane dyes).
- monoazo pigments for example products which are derived from acetoessigarylide derivatives or from ⁇ -naphthol derivative
- Examples include the inorganic pigments Pigment Yellow 42 (CI 77 492), Pigment White 6 (CI 77 891), Pigment Blue 27 (CI 77 510), Pigment Blue 29 (CI 77 007), or Pigment Black 7 (CI 77 266) and the organic pigments Pigment Yellow 1 (CI 11 680), Pigment Yellow 3 (CI 11 710), Pigment Yellow 42 (CI 77 492), Pigment Yellow 74 (CI 11 741), Pigment Yellow 83 (CI 21 108), pigment Yellow 106, Pigment Yellow 108 (CI 68 240), Pigment Yellow 117, Pigment Yellow 126, Pigment Yellow 139, Pigment Yellow 185, Pigment Orange 5 (CI 12 075), Pigment Orange 67, Pigment Red 3 (CI 12 120), Pigment Red 48: 1 (CI 15 865: 1), Pigment Red 48: 4 (15 865: 4), Pigment Red 101 (CI 77 491), Pigment Red 112 (CI 12 370), Pigment Red 123 (CI 71 145 ), Pigment Red 169
- Cationic fixatives of the above class (A) are known homopolymers of diallyldimethylammonium chloride and copolymers of diallyldimethylammonium chloride with acrylamide and / or methacrylamide.
- the copolymerization can be carried out in any monomer ratio.
- the K value of the homopolymers and copolymers of diallyldimethylammonium chloride is at least 30, preferably 95 to 180.
- Cationic fixatives of class (B) are described for example in EP-A-146,000.
- Cationic fixatives of class (C) are described for example in DE-A-3 613 651.
- Cationic fixatives of class (D) are described for example in EP-A-216 387.
- Cationic fixatives of the above class (E) are known copolymers of acrylamide and 90 to 10 wt .-%, preferably 70 to 30 wt .-% (C1-C4-dialkylamino) -C1-C4-alkyl acrylates and / or methacrylates .
- the cationic fixatives are used in an amount of 0.01 to 3% by weight, preferably 0.03 to 1% by weight and in particular 0.05 to 0.5% by weight, in each case based on the dry color to be colored Pulp, applied.
- the pigments are generally used in an amount of 0.01 to 5% by weight, preferably 0.05 to 2% by weight and in particular 0.1 to 2% by weight, in each case based on the dry paper pulp to be colored, applied.
- pigment and fixative it is preferred to add a previously prepared pigment / fixative mixture.
- a preparation can also contain other auxiliaries, e.g. Fungicides, water retention agents or surfactants, for example nonionic surfactants, such as addition products of alkylene oxides with fatty acids, alcohols, phenols, acid amides, mercaptans, amines or alkylphenols (cf. K. Lindner, Tenside-Textile Aid Detergent Raw Materials, Volume 1, pages 837 to 917, 1964).
- auxiliaries e.g. Fungicides, water retention agents or surfactants, for example nonionic surfactants, such as addition products of alkylene oxides with fatty acids, alcohols, phenols, acid amides, mercaptans, amines or alkylphenols (cf. K. Lindner, Tenside-Textile Aid Detergent Raw Materials, Volume 1, pages 837 to 917, 1964).
- the cationic fixatives are generally processed as an aqueous solution.
- the pigments used as colorants in the new process are expediently in the form of pigment preparations known per se, e.g. used as aqueous dispersions. Those aqueous pigment preparations which contain nonionic surfactants as dispersing agents are preferred. The above-mentioned components may be mentioned as nonionic surfactants, for example.
- Paper masses to be colored can e.g. unbleached or bleached cellulose, wood pulp or waste paper, optionally in each case together with fillers, such as kaolin, chalk or talc, or other auxiliaries, such as aluminum sulfate or resin glue.
- the pH of the stock suspension can be between 4 and 9. It is preferred to use papers that are manufactured in the neutral pH range, e.g. Tissue or graphic papers.
- homogeneous dyeings are obtained which have only a low two-sidedness. They also have high lightfastness and fastness to bleeding.
- Another advantage is that when using organic pigments from the class of monoazo pigments based on ⁇ -naphthol, for example Pigment Orange 5 (CI 12 075), the isoindoline derivatives, for example Pigment Yellow 139 or Pigment Yellow 185, or the lacquered basic dyes , e.g. Pigment Red 48: 1 (CI 15 865: 1, Pigment Red 48: 4 (CI 15 865: 4), Pigment Blue 1 (CI 42 595: 2) or Pigment Violet 27 (CI 42 535: 3)
- the usual bleaching agents known in the paper industry for example sodium hypochlorite or sodium dithionite, are used as bleaching agents.
- fixative The low consumption of fixative is also to be emphasized.
- An increase in the amount of fixative beyond the size according to the invention results in a marked deterioration in the coloration. Surprisingly, this is in contrast to paper coloring with dyes, where the quality of the coloring depends directly on the amount of fixing agent.
- a paper made from 80% by weight of bleached spruce sulfite pulp and 20% by weight of bleached beech sulfite pulp with a basis weight of 80 g / m 2 was produced on a test paper machine with a working width of 75 cm at a speed of 60 m / min.
- the pH of the stock suspension was 7.5, the mixed grinding degree 35 ° SR. Papers were produced from this stock suspension under the conditions specified below.
- the percentages given below are each% by weight.
- the percentages relating to pigment and fixative relate to the dry paper pulp.
Description
Die vorliegende Erfindung betrifft ein neues Verfahren zum Färben von Papier in der Masse mit Pigmenten und Fixiermitteln, wobei man Pigment und Fixiermittel gleichzeitig zu der zu färbenden Papiermasse gibt und als Fixiermittel ein kationisches Fixiermittel in einer Menge von 0,01 bis 3 Gew.-%, bezogen auf die zu färbende trockene Papiermasse, verwendet.The present invention relates to a new process for coloring paper in bulk with pigments and fixing agents, pigment and fixing agent being added simultaneously to the paper pulp to be colored and a fixing agent being a cationic fixing agent in an amount of 0.01 to 3% by weight. , based on the dry paper pulp to be used.
Die Färbung von Papier wird üblicherweise mit Farbstoffen durchgeführt (siehe z.B. Ullmanns Encyklopädie der technischen Chemie, 4. Auflage, Band 17, Seiten 613 und 614). Das so ausgefärbte Papier weist meist jedoch ungenügende Echtheitseigenschaften, insbesondere eine zu geringe Lichtechtheit auf.The coloring of paper is usually carried out with dyes (see e.g. Ullmanns Encyklopadie der Technische Chemie, 4th edition, volume 17, pages 613 and 614). However, the paper colored in this way usually has insufficient fastness properties, in particular light fastness that is too low.
Das Färben von Papier mit Pigmenten ist ebenfalls bekannt (Ullmann, loc.cit.), jedoch weisen die Pigmente im allgemeinen keine Affinität zu den Faserstoffen des Papiers auf und besitzen nur eine geringe Färbekraft. Bei der Massefärbung stellt sich zusätzlich das Problem der Zweiseitigkeit.The dyeing of paper with pigments is also known (Ullmann, loc.cit.), But the pigments generally have no affinity for the fibrous materials of the paper and have only a low coloring power. The problem of double-sidedness also arises with the mass coloring.
Im "Ratgeber für die Verwendung von BASF-Erzeugnissen in der Papierindustrie", 8/72, Seite 22, wird vorgeschlagen, Pigmente zusammen mit Fixiermitteln zu verwenden. Als Fixiermittel werden in diesem Zusammenhang, neben anderen, auch solche auf Basis von Polyiminen genannt. Dabei wird ausdrücklich darauf hingewiesen, daß es wichtig ist, zuerst das Fixiermittel und anschließend das Pigment dem Papierstoff zuzusetzen.In the "Guide for the Use of BASF Products in the Paper Industry", 8/72, page 22, it is proposed to use pigments together with fixing agents. In this context, among others, fixing agents based on polyimines are also mentioned. It is expressly pointed out that it is important to add the fixing agent first and then the pigment to the paper stock.
Aus "Bayer Farben Revue", Sonderheft 4/2, 1984, Seite 79 bis 82, ist bekannt, Laminatpapier mittels Pigmenten und kationischem Naßverfestigungsmittel zu färben. Auch hier ist die Reihenfolge der Zugabe der Komponenten sehr wichtig. So sollen zuerst ein Drittel der Menge an kationischem Naßverfestigungsmittel, daran anschließend Farbpigment und schließlich die restlichen zwei Drittel der Menge an kationischem Naßverfestigungsmittel der Zellstoffmasse zugegeben werden.From "Bayer Farben Revue", Special Issue 4/2, 1984, pages 79 to 82, it is known to dye laminate paper using pigments and cationic wet-strength agents. Here too, the order in which the components are added is very important. First, a third of the amount of cationic wet strength agent, then color pigment and finally the remaining two thirds of the amount of cationic wet strength agent should be added to the pulp.
Es hat sich jedoch gezeigt, daß bei der Färbung von Papier in der Masse nach den genannten Methoden, die obengenannten Mängel nicht behoben werden können.However, it has been shown that when coloring paper in bulk by the methods mentioned, the above-mentioned shortcomings cannot be remedied.
Aus der US-A-3 128 222 ist das Farben von Papier mittels Pigmenten u.a. in Gegenwart von speziellen kationischen Hilfsmitteln bekannt.The dyeing of paper by means of pigments is known from US-A-3 128 222, inter alia in the presence of special cationic auxiliaries.
Aufgabe der vorliegenden Anmeldung war es, ein neues Verfahren zur Färbung von Papier in der Masse bereitzustellen, bei dem ebenfalls Pigmente als Farbmittel zur Anwendung kommen und die bekannten Nachteile nicht mehr auftreten sollten.The object of the present application was to provide a new process for coloring paper in bulk, in which pigments are also used as colorants and the known disadvantages should no longer occur.
Es wurde nun überraschenderweise gefunden, daß das Färben von Papier in der Masse mit organischen Pigmenten und Fixiermitteln vorteilhaft gelingt, wenn man Pigment und Fixiermittel zusammen zu der zu färbenden Papiermasse gibt, und man als Fixiermittel ein kationisches Fixiermittel, ausgewählt aus der Gruppe, bestehend aus
- A) Homopolymerisaten von Diallyldimethylammoniumchlorid und Copolymerisaten von Diallyldimethylammoniumchlorid mit Acrylamid und (oder Methacrylamid, deren K-Wert mindestens 30 beträgt,
- B) Homopolymerisaten von Vinylimidazolen und Copolymerisaten von Vinylimidazolen mit Acrylamid und/oder Methacrylamid, die gegegebenenfalls mit Epichlorhydrin umgesetzt worden sind,
- C) Homopolymerisaten von Vinylimidazolin und Copolymerisaten von Vinylimidazolin mit Acrylamid und/oder Methacrylamid,
- D) Copolymerisaten, die Vinylamin-Einheiten einpolymerisiert enthalten, sowie
- E) Copolymerisaten von Acrylamid mit (C₁-C₄-Dialkylamino)-C₁-C₄-alkylacrylaten und/oder -methacrylaten,
- A) homopolymers of diallyldimethylammonium chloride and copolymers of diallyldimethylammonium chloride with acrylamide and (or methacrylamide, the K value of which is at least 30,
- B) homopolymers of vinylimidazoles and copolymers of vinylimidazoles with acrylamide and / or methacrylamide, which may have been reacted with epichlorohydrin,
- C) homopolymers of vinylimidazoline and copolymers of vinylimidazoline with acrylamide and / or methacrylamide,
- D) copolymers which contain copolymerized vinylamine units, and
- E) copolymers of acrylamide with (C₁-C₄-dialkylamino) -C₁-C₄-alkyl acrylates and / or methacrylates,
Organische Pigmente, die im erfindungsgemäßen Verfahren als Farbmittel dienen, sind beispielsweise solche aus der Klasse der Monoazopigmente (z.B. Produkte, die sich von Acetessigarylidderivaten oder von β-Naphtholderivaten ableiten), verlackten Monoazofarbstoffe (z.B. verlackte β-Oxynaphthoesäurefarbstoffe), Disazopigmente, kondensierten Disazopigmente, Isoindolinderivate, Derivate der Naphthalin- oder Perylentetracarbonsäure, Anthrachinonpigmente, Thioindigoderivate, Azomethinderivate, Chinacridone, Dioxazine, Pyrazolochinazolone, Phthalocyaninpigmente oder verlackte basischen Farbstoffe (z.B. verlackte Triarylmethanfarbstoffe) zu nennen.Organic pigments which serve as colorants in the process according to the invention are, for example, those from the class of the monoazo pigments (for example products which are derived from acetoessigarylide derivatives or from β-naphthol derivatives), lacquered monoazo dyes (for example lacquered β-oxynaphthoic acid dyes), disazo pigments, condensed disazo pigments Isoindoline derivatives, derivatives of naphthalene or perylene tetracarboxylic acid, anthraquinone pigments, thioindigo derivatives, azomethine derivatives, quinacridones, dioxazines, pyrazoloquinazolones, phthalocyanine pigments or lacquered basic dyes (eg lacquered triarylmethane dyes).
Beispielhaft seien die anorganischen Pigmente Pigment Yellow 42 (C.I. 77 492), Pigment White 6 (C.I. 77 891), Pigment Blue 27 (C.I. 77 510), Pigment Blue 29 (C.I. 77 007), oder Pigment Black 7 (C.I. 77 266) sowie die organischen Pigmente Pigment Yellow 1 (C.I. 11 680), Pigment Yellow 3 (C.I. 11 710), Pigment Yellow 42 (C.I. 77 492), Pigment Yellow 74 (C.I. 11 741), Pigment Yellow 83 (C.I. 21 108), Pigment Yellow 106, Pigment Yellow 108 (C.I. 68 240), Pigment Yellow 117, Pigment Yellow 126, Pigment Yellow 139, Pigment Yellow 185, Pigment Orange 5 (C.I. 12 075), Pigment Orange 67, Pigment Red 3 (C.I. 12 120), Pigment Red 48:1 (C.I. 15 865:1), Pigment Red 48:4 (15 865:4), Pigment Red 101 (C.I. 77 491), Pigment Red 112 (C.I. 12 370), Pigment Red 123 (C.I. 71 145), Pigment Red 169 (C.I. 45 160:2), Pigment Violet 23 (C.I. 51 319), Pigment Violet 27 (C.I. 42 555:3), Pigment Blue 1 (C.I. 42 595 : 2), Pigment Blue 15 : 1 (C.I. 74 160), Pigment Blue 15 : 3 (C.I. 74 160), Pigment Blue 61 (C.I. 42 765:1), Pigment Green 7 (C.I. 74 260) oder Pigment Green 36 (C.I. 74 265) genannt.Examples include the inorganic pigments Pigment Yellow 42 (CI 77 492), Pigment White 6 (CI 77 891), Pigment Blue 27 (CI 77 510), Pigment Blue 29 (CI 77 007), or Pigment Black 7 (CI 77 266) and the organic pigments Pigment Yellow 1 (CI 11 680), Pigment Yellow 3 (CI 11 710), Pigment Yellow 42 (CI 77 492), Pigment Yellow 74 (CI 11 741), Pigment Yellow 83 (CI 21 108), pigment Yellow 106, Pigment Yellow 108 (CI 68 240), Pigment Yellow 117, Pigment Yellow 126, Pigment Yellow 139, Pigment Yellow 185, Pigment Orange 5 (CI 12 075), Pigment Orange 67, Pigment Red 3 (CI 12 120), Pigment Red 48: 1 (CI 15 865: 1), Pigment Red 48: 4 (15 865: 4), Pigment Red 101 (CI 77 491), Pigment Red 112 (CI 12 370), Pigment Red 123 (CI 71 145 ), Pigment Red 169 (CI 45 160: 2), Pigment Violet 23 (CI 51 319), Pigment Violet 27 (CI 42 555: 3), Pigment Blue 1 (CI 42 595: 2), Pigment Blue 15: 1 ( CI 74 160), Pigment Blue 15: 3 (CI 74 160), Pigment Blue 61 (CI 42 765: 1), Pigment Green 7 (C.I. 74 260) or Pigment Green 36 (C.I. 74 265).
Kationische Fixiermittel der obengenannten Klasse (A) sind an sich bekannte Homopolymerisate von Diallyldimethylammoniumchlorid und Copolymerisate von Diallyldimethylammoniumchlorid mit Acrylamid und/oder Methacrylamid. Die Copolymerisation kann dabei in jedem beliebigen Monomerverhältnis vorgenommen werden. Der K-Wert der Homo- und Copolymerisate des Diallyldimethylammoniumchlorids beträgt mindestens 30, vorzugsweise 95 bis 180.Cationic fixatives of the above class (A) are known homopolymers of diallyldimethylammonium chloride and copolymers of diallyldimethylammonium chloride with acrylamide and / or methacrylamide. The copolymerization can be carried out in any monomer ratio. The K value of the homopolymers and copolymers of diallyldimethylammonium chloride is at least 30, preferably 95 to 180.
Kationische Fixiermittel der obengennanten Klasse (B) sind an sich bekannte Homopolymerisate des Vinylimidazols der Formel I
in der
R¹, R² und R³ gleich oder verschieden sind und unabhängig voneinander jeweils Wasserstoff oder Methyl und R¹ außerdem C₂-C₄-Alkyl bedeuten, und wasserlösliche Copolymerisate aus
- a) mindestens 10 Gew.-% eines Vinylimidazols der Formel I,
- b) bis zu 90 Gew.-% Acrylamid und/oder Methacrylamid sowie gegebenenfalls
- c) bis zu 30 Gew.-% Acrylnitril, Methacrylnitril, Vinylacetat, Vinylpyrrolidon, einer C₃-C₅-ethylenisch ungesättigten Carbonsäure oder deren Ester, wobei die Homo- und Copolymerisate gegebenenfalls mit
in the
R¹, R² and R³ are the same or different and are each independently hydrogen or methyl and R¹ is also C₂-C₄-alkyl, and water-soluble copolymers
- a) at least 10% by weight of a vinylimidazole of the formula I,
- b) up to 90% by weight of acrylamide and / or methacrylamide and optionally
- c) up to 30 wt .-% acrylonitrile, methacrylonitrile, vinyl acetate, vinyl pyrrolidone, a C₃-C₅-ethylenically unsaturated carboxylic acid or its ester, the homo- and copolymers optionally with
Kationische Fixiermittel der Klasse (B) sind beispielsweise in der EP-A-146 000 beschrieben.Cationic fixatives of class (B) are described for example in EP-A-146,000.
Kationische Fixiermittel der obengenannten Klasse (C) sind an sich bekannte Homopolymerisate des Vinylimidazolins der Formel II
in der
R⁴ Waserstoff, C₁-C₁₈-Alkyl, oder den Rest
wobei
R⁸, R⁹ gleich oder verschieden sind und unabhängig voneinander jeweils für Wasserstoff C₁-C₄-Alkyl oder Chlor stehen,
R⁵ Wasserstoff C₁-C₁₈-Alkyl, Benzyl, oder
R⁶ und R⁷ gleich oder verschiedens sind und unabhängig voneinander jeweils Wasserstoff oder C₁-C₄-Alkyl und
X⊖ ein Anion, vorzugsweise Chlorid, Bromid, Sulfat, Methosulfat, Ethosulfat oder ein Carboxylat, bedeuten, und wasserlösliche Copolymerisate, die
- a) mindestens 1 Gew.-% einer Verbindung der Formel II und
- b) Acrylamid und/oder Methacrylamid
in the
R⁴ hydrogen, C₁-C₁₈ alkyl, or the rest
in which
R⁸, R⁹ are the same or different and each independently represent hydrogen C₁-C₄-alkyl or chlorine,
R⁵ is hydrogen C₁-C₁₈ alkyl, benzyl, or
R⁶ and R⁷ are the same or different and are each independently hydrogen or C₁-C₄-alkyl and
X ⊖ is an anion, preferably chloride, bromide, sulfate, methosulfate, ethosulfate or a carboxylate, and water-soluble copolymers
- a) at least 1 wt .-% of a compound of formula II and
- b) acrylamide and / or methacrylamide
Kationische Fixiermittel der Klasse (C) sind beispielsweise in der DE-A-3 613 651 beschrieben.Cationic fixatives of class (C) are described for example in DE-A-3 613 651.
Kationische Fixiermittel der obengenannten Klasse (D) sind an sich bekannte Copolymerisate, die Vinylamin-Einheiten einpolymerisiert enthalten, die durch Copolymerisierung von
- a) 95 bis 10 Mol.-% N-Vinylformamid mit
- b) 5 bis 90 Mol.-% eines ethylenisch ungesättigten Monomeren aus der Gruppe Vinylacetat, Vinylpropionat, C₁-C₄-Alkylvinylether, N-Vinylpyrrolidon sowie Ester, Nitrile und Amide von Acrylsäure und Methacrylsäure
- a) 95 to 10 mol% of N-vinylformamide
- b) 5 to 90 mol .-% of an ethylenically unsaturated monomer from the group vinyl acetate, vinyl propionate, C₁-C₄-alkyl vinyl ether, N-vinyl pyrrolidone and esters, nitriles and amides of acrylic acid and methacrylic acid
Kationische Fixiermittel der Klasse (D) sind beispielsweise in der EP-A-216 387 beschrieben.Cationic fixatives of class (D) are described for example in EP-A-216 387.
Kationische Fixiermittel der obengenannten Klasse (E) sind an sich bekannte Copolymerisate aus Acrylamid und 90 bis 10 Gew.-%, vorzugsweise 70 bis 30 Gew.-% (C₁-C₄-Dialkylamino)-C₁-C₄-alkylacrylaten und/oder -methacrylaten.Cationic fixatives of the above class (E) are known copolymers of acrylamide and 90 to 10 wt .-%, preferably 70 to 30 wt .-% (C₁-C₄-dialkylamino) -C₁-C₄-alkyl acrylates and / or methacrylates .
Der obengenannte K-Wert der Polymerisate wurde jeweils nach H. Fikentscher, Cellulosechemie, 13, 58-64 und 71-74 (1932) bei einer Temperatur von 25°C in einer 5 gew.%igen wäßrigen Kochsalzlösung und einer Polymerkonzentration von 0,5 Gew.-% bestimmt; dabei bedeutet K = k.10³.The above-mentioned K value of the polymers was in each case according to H. Fikentscher, Cellulosechemie, 13, 58-64 and 71-74 (1932) at a temperature of 25 ° C. in a 5% strength by weight aqueous saline solution and a polymer concentration of 0. 5 wt .-% determined; where K = k.10³.
Erfindungsgemäß werden die kationischen Fixiermittel in einer Menge von 0,01 bis 3 Gew.-%, vorzugsweise 0,03 bis 1 Gew.-% und insbesondere 0,05 bis 0,5 Gew.-%, jeweils bezogen auf die zu färbende trockene Papiermasse, angewendet.According to the invention, the cationic fixatives are used in an amount of 0.01 to 3% by weight, preferably 0.03 to 1% by weight and in particular 0.05 to 0.5% by weight, in each case based on the dry color to be colored Pulp, applied.
Die Pigmente werden im allgemeinen in einer Menge von 0,01 bis 5 Gew.-%, vorzugsweise 0,05 bis 2 Gew.-% und insbesondere 0,1 bis 2 Gew.-%, jeweils bezogen auf die zu färbende trockene Papiermasse, angewendet.The pigments are generally used in an amount of 0.01 to 5% by weight, preferably 0.05 to 2% by weight and in particular 0.1 to 2% by weight, in each case based on the dry paper pulp to be colored, applied.
Das erfindungsgemäße Verfahren wird zweckmäßig so durchgeführt, daß man die zu färbende Papiermasse vorlegt und dann Pigment und kationisches Fixiermittel zugibt. Erfindungsgemäß werden dabei Pigment und kationisches Hilfsmittel zusammen zur Papiermasse gegeben. Dabei existieren mehrere Möglichkeiten der Zugabe:
- Zugabe von Pigment und Fixiermittel zusammen, wobei die Mischung der beiden Komponenten unmittelbar vor der Zugabe erfolgt (z.B. in der Förderapparatur) oder
- Zugabe einer vorher bereiteten Mischung (Präparation), die sowohl Pigment als auch kationisches Fixiermittel enthält.
- Addition of pigment and fixative together, the mixing of the two components taking place immediately before the addition (for example in the conveying apparatus) or
- Add a previously prepared mixture (preparation) that contains both pigment and cationic fixative.
Bevorzugt ist die Zugabe einer vorher bereiteten Pigment-Fixiermittel-Mischung. Eine solche Präparation kann neben Pigment und Fixiermittel noch weitere Hilfsmittel enthalten, z.B. Fungizide, Wasserrückhaltemittel oder Tenside, beispielsweise nichtionische Tenside, wie Anlagerungsprodukte von Alkylenoxiden an Fettsäuren, Alkohole, Phenole, Säureamide, Mercaptane, Amine oder Alkylphenole (vgl. dazu K. Lindner, Tenside-Textilhilfsmittel-Waschrohstoffe, Band 1, Seiten 837 bis 917, 1964).It is preferred to add a previously prepared pigment / fixative mixture. In addition to pigment and fixative, such a preparation can also contain other auxiliaries, e.g. Fungicides, water retention agents or surfactants, for example nonionic surfactants, such as addition products of alkylene oxides with fatty acids, alcohols, phenols, acid amides, mercaptans, amines or alkylphenols (cf. K. Lindner, Tenside-Textile Aid Detergent Raw Materials, Volume 1, pages 837 to 917, 1964).
Die kationischen Fixiermittel werden im allgemeinen als wäßrige Lösung verarbeitet.The cationic fixatives are generally processed as an aqueous solution.
Die im neuen Verfahren als Farbmittel eingesetzten Pigmente werden dabei zweckmäßig in Form von an sich bekannten Pigmentpräparationen, z.B. als wäßrige Dispersionen verwendet. Dabei sind solche wäßrige Pigmentpräparationen bevorzugt, die nichtionische Tenside als Dispergierhilfsmittel enthalten. Als nichtionische Tenside sind beispielsweise die obengenannten Komponenten zu nennen.The pigments used as colorants in the new process are expediently in the form of pigment preparations known per se, e.g. used as aqueous dispersions. Those aqueous pigment preparations which contain nonionic surfactants as dispersing agents are preferred. The above-mentioned components may be mentioned as nonionic surfactants, for example.
Als zu färbende Papiermassen können z.B. ungebleichte oder gebleichte Zellstoffe, Holzschliff oder Altpapier, gegebenenfalls jeweils zusammen mit Füllstoffen, wie Kaolin, Kreide oder Talkum, oder weiteren Hilfsmitteln, wie Aluminiumsulfat oder Harzleim verwendet werden. Der pH-Wert der Stoffsuspension kann dabei zwischen 4 und 9 liegen. Bevorzugt verwendet man Papiersorten, die im neutralen pH-Bereich hergestellt werden, z.B. Tissue oder graphische Papiere.Paper masses to be colored can e.g. unbleached or bleached cellulose, wood pulp or waste paper, optionally in each case together with fillers, such as kaolin, chalk or talc, or other auxiliaries, such as aluminum sulfate or resin glue. The pH of the stock suspension can be between 4 and 9. It is preferred to use papers that are manufactured in the neutral pH range, e.g. Tissue or graphic papers.
Mittels des erfindungsgemäßen Verfahrens gelangt man zu homogenen Färbungen, die nur eine geringe Zweiseitigkeit aufweisen. Sie besitzen außerdem hohe Lichtechtheit und Ausblutechtheit.By means of the method according to the invention, homogeneous dyeings are obtained which have only a low two-sidedness. They also have high lightfastness and fastness to bleeding.
Ein weiterer Vorteil ist, daß man bei der Verwendung von organischen Pigmenten aus der Klasse der Monoazopigmente auf β-Naphtholbasis, z.B. Pigment Orange 5 (C.I. 12 075), der Isoindolinderivate, z.B. Pigment Yellow 139 oder Pigment Yellow 185, oder der verlackten basischen Farbstoffe, z.B. Pigment Red 48 : 1 (C.I. 15 865 : 1, Pigment Red 48 : 4 (C.I. 15 865 : 4), Pigment Blue 1 (C.I. 42 595 : 2) oder Pigment Violet 27 (C.I. 42 535 : 3), zu bleichbaren Papieren gelangt. Als Bleichmittel dienen dabei die üblichen, in der Papierindustrie bekannten Bleichmittel, z.B. Natriumhypochlorit oder Natriumdithionit.Another advantage is that when using organic pigments from the class of monoazo pigments based on β-naphthol, for example Pigment Orange 5 (CI 12 075), the isoindoline derivatives, for example Pigment Yellow 139 or Pigment Yellow 185, or the lacquered basic dyes , e.g. Pigment Red 48: 1 (CI 15 865: 1, Pigment Red 48: 4 (CI 15 865: 4), Pigment Blue 1 (CI 42 595: 2) or Pigment Violet 27 (CI 42 535: 3) The usual bleaching agents known in the paper industry, for example sodium hypochlorite or sodium dithionite, are used as bleaching agents.
Weiterhin ist der geringe Verbrauch an Fixiermittel hervorzuheben. Eine Steigerung der Fixiermittelmenge über die erfindungsgemäße Größe hinaus hat nämlich eine deutliche Verschlechterung der Ausfärbung zur Folge. Dies steht überraschenderweise im Gegensatz zur Papierfärbung mit Farbstoffen, wo die Qualität der Färbung direkt von der Menge an Fixiermittel abhängt.The low consumption of fixative is also to be emphasized. An increase in the amount of fixative beyond the size according to the invention results in a marked deterioration in the coloration. Surprisingly, this is in contrast to paper coloring with dyes, where the quality of the coloring depends directly on the amount of fixing agent.
Bei der Durchführung des erfindungsgemäßen Verfahrens tritt außerdem keine Schaumbildung auf, und man benötigt nur eine relativ kurze Einwirkungszeit, d.h. die Pigmente ziehen schnell auf die Papiermasse auf.In addition, there is no foaming when the process according to the invention is carried out and only a relatively short exposure time is required, i.e. the pigments quickly absorb onto the paper pulp.
Schließlich ist darauf hinzuweisen, daß bei der Durchführung des neuen Verfahrens ein Abwasser anfällt, das praktisch überhaupt nicht oder allenfalls äußerst leicht angefärbt ist.Finally, it should be pointed out that when the new process is carried out, wastewater is obtained which is practically not colored at all or at most extremely lightly colored.
Die folgenden Beispiele sollen die Erfindung näher erläutern.The following examples are intended to explain the invention in more detail.
Auf einer Versuchspapiermaschine mit einer Arbeitsbreite von 75 cm wurde bei einer Geschwindigkeit von 60 m/min ein Papier aus 80 Gew.-% gebleichtem Fichtensulfitzellstoff und 20 Gew.-% gebleichtem Buchensulfitzellstoff mit einer Flächenmasse von 80 g/m² produziert. Der pH-Wert der Stoffsuspension betrug 7,5, der Mischmahlgrad 35° SR. Unter den unten angegebenen Bedingungen wurden aus dieser Stoffsuspension Papiere hergestellt.A paper made from 80% by weight of bleached spruce sulfite pulp and 20% by weight of bleached beech sulfite pulp with a basis weight of 80 g / m 2 was produced on a test paper machine with a working width of 75 cm at a speed of 60 m / min. The pH of the stock suspension was 7.5, the mixed grinding degree 35 ° SR. Papers were produced from this stock suspension under the conditions specified below.
-
Fixiermittel 1:
Homopolymerisat von Diallyldimethylammoniumchlorid mit einem K-Wert von 100 in Form einer 30 gew.-%igen wäßrigen Lösung (Viskosität 1000 mpa.s, 20°C).Fixing agent 1:
Homopolymer of diallyldimethylammonium chloride with a K value of 100 in the form of a 30% by weight aqueous solution (viscosity 1000 mpa.s, 20 ° C.). -
Fixiermittel 2:
Copolymerisat aus 20 Gew.-% Acrylamid und 80 Gew.-% 2-Diethylaminoethylacrylat in Form einer 10 gew.-%igen wäßrigen Lösung (Viskosität 5000 mpa.s, 20°C).Fixing agent 2:
Copolymer of 20 wt .-% acrylamide and 80 wt .-% 2-diethylaminoethyl acrylate in the form of a 10 wt .-% aqueous solution (viscosity 5000 mpa.s, 20 ° C). -
Fixiermittel 3:
Copolymerisat aus 80 Gew.-% Acrylamid und 20 Gew.-% Vinylimidazol, das mit Epichlorhydrin umgesetzt worden ist, in Form einer 10 gew.-%igen wäßrigen Lösung (Viskosität 1000 mpa.s, 20°C).Fixing agent 3:
Copolymer of 80 wt .-% acrylamide and 20 wt .-% vinylimidazole, which has been reacted with epichlorohydrin, in the form of a 10 wt .-% aqueous solution (viscosity 1000 mpa.s, 20 ° C.).
- Pigment 1: Pigment Yellow 185
- Pigment 2: Pigment Yellow 1 (C.I. 11 680)
- Pigment 3: Pigment Blue 15:1 (C.I. 74 160)
- Pigment 4: Pigment Orange 5 (C.I. 12 075)
- Pigment 5: Pigment Black 7 (C.I. 77 266)
Es wurden jeweils folgende Zugabevarianten durchgeführt:
- I (Vergleich)
Zusatz des unbehandelten Pigments zum Stoffdichteregler der Papiermaschine. - II (Vergleich)
Getrennter Zusatz des kationischen Fixiermittels zur Maschinenbütte und des unbehandelten Pigments zum Stoffdichteregler, d.h. zuerst Zugabe des Fixiermittels und anschließend Zugabe des Pigments. - III (erfindungsgemäß)
Herstellung einer wäßrigen Dispersion durch Zugabe des kationischen Fixiermittels zu einer wäßrigen Pigmentaufschlämmung und Zusatz dieser kationischen Dispersion zum Stoffdichteregler.
- Pigment 1: Pigment Yellow 185
- Pigment 2: Pigment Yellow 1 (CI 11 680)
- Pigment 3: Pigment Blue 15: 1 (CI 74 160)
- Pigment 4: Pigment Orange 5 (CI 12 075)
- Pigment 5: Pigment Black 7 (CI 77 266)
The following addition variants were carried out:
- I (comparison)
Add the untreated pigment to the stock density controller of the paper machine. - II (comparison)
Separate addition of the cationic fixing agent to the machine chest and the untreated pigment to the material density controller, ie first adding the fixing agent and then adding the pigment. - III (according to the invention)
Preparation of an aqueous dispersion by adding the cationic fixative to an aqueous pigment slurry and adding this cationic dispersion to the mass density controller.
Die im folgenden genannten Prozentangaben sind jeweils Gew.-%. Dabei beziehen sich die Prozentangaben, betreffend Pigment und Fixiermittel, jeweils auf die trockene Papiermasse.The percentages given below are each% by weight. The percentages relating to pigment and fixative relate to the dry paper pulp.
Claims (2)
- A process for the wet-end coloring of paper with organic pigments and fixers, wherein the pigment and fixer are added together to the paper pulp to be colored, and the fixer used is a cationic fixer selected from the group consisting ofA) homopolymers of diallyldimethylammonium chloride and copolymers of diallyldimethylammonium chloride with acrylamide and/or methacrylamide, whose K value is not less than 30,B) homopolymers of vinylimidazoles and copolymers of vinylimidazoles with acrylamide and/or methacrylamide, which may have been reacted with epichlorohydrin,C) homopolymers of vinylimidazoline and copolymers of vinylimidazoline with acrylamide and/or methacrylamide,D) copolymers which contain copolymerized vinylamine units, andE) copolymers of acrylamide with (C₁-C₄-dialkylamino)-C₁-C₄-alkyl acrylates and/or methacrylates,in an amount of from 0.01 to 3% by weight, based on the dry paper pulp to be colored.
- A process as claimed in claim 1, wherein a preparation containing pigment and cationic fixer is added.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3732981 | 1987-09-30 | ||
| DE19873732981 DE3732981A1 (en) | 1987-09-30 | 1987-09-30 | METHOD FOR DYING PAPER |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| EP0309908A2 EP0309908A2 (en) | 1989-04-05 |
| EP0309908A3 EP0309908A3 (en) | 1990-12-27 |
| EP0309908B1 true EP0309908B1 (en) | 1994-04-13 |
Family
ID=6337252
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP88115563A Expired - Lifetime EP0309908B1 (en) | 1987-09-30 | 1988-09-22 | Process for colouring paper |
Country Status (8)
| Country | Link |
|---|---|
| US (1) | US5131981A (en) |
| EP (1) | EP0309908B1 (en) |
| JP (1) | JPH01104898A (en) |
| AU (1) | AU605633B2 (en) |
| CA (1) | CA1302022C (en) |
| DE (2) | DE3732981A1 (en) |
| DK (1) | DK544388A (en) |
| FI (1) | FI95063C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7282263B2 (en) | 2001-05-18 | 2007-10-16 | Sun Chemical Corporation | Method for coloring cellulosic materials using cationic pigment dispersion |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2697996B2 (en) * | 1992-06-17 | 1998-01-19 | 日華化学株式会社 | Dye fixative |
| DE4233040A1 (en) * | 1992-10-01 | 1994-04-07 | Basf Ag | Process for dyeing paper |
| DE19646437A1 (en) * | 1996-11-11 | 1998-05-14 | Basf Ag | Use of quaternized vinylimidazole units containing polymers as a color-fixing and dye transfer-inhibiting additive to laundry after-treatment agents and to detergents |
| SE521265C3 (en) | 1997-10-09 | 2003-11-05 | Stora Kopparbergs Bergslags Ab | Ways to nuance paper and color mixture for nuance of paper |
| WO2000022232A1 (en) * | 1998-10-14 | 2000-04-20 | The Mead Corporation | Colorant application on the wet end of a paper machine |
| GB9907878D0 (en) * | 1999-04-08 | 1999-06-02 | Ciba Geigy Ag | Process of shading |
| TW587044B (en) | 2001-11-01 | 2004-05-11 | Ishigaki Mech Ind | Water jet propelling device of yacht |
| US6702922B2 (en) * | 2002-07-17 | 2004-03-09 | Mw Custom Papers, Llc | Papers for use in decorative laminates and methods of making the same |
| GB0308487D0 (en) * | 2003-04-14 | 2003-05-21 | Ciba Spec Chem Water Treat Ltd | Paper coating compositions |
| GB0308446D0 (en) * | 2003-04-14 | 2003-05-21 | Sentec Ltd | Low-power magnetic flow meter |
| US20040244929A1 (en) * | 2003-06-03 | 2004-12-09 | Henke Jason D. | Process for producing a fade-resistant paper |
| US8487022B2 (en) | 2006-01-26 | 2013-07-16 | Basf Se | Composition for surface colouration of paper |
| DE112009000401T5 (en) | 2008-02-19 | 2010-12-30 | Meadwestvaco Corp. | Colored paper with controlled color penetration |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3128222A (en) * | 1960-11-07 | 1964-04-07 | Crown Zellerbach Corp | Process of coloring cellulosic fibers |
Family Cites Families (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2730446A (en) * | 1952-03-15 | 1956-01-10 | American Cyanamid Co | Color improvement of unsized porous paper |
| US3016325A (en) * | 1955-11-01 | 1962-01-09 | Electro Chem Fiber Seal Corp | Process of combining water-insoluble additament with organic fibrous material |
| DE1073854B (en) * | 1956-04-10 | 1960-01-21 | Rohm &. Haas Company, Philadelphia, Pa. (V. St. A.) | Process for the production of filled papers and the like |
| NL231136A (en) * | 1957-09-05 | |||
| US3049468A (en) * | 1957-12-23 | 1962-08-14 | Ici Ltd | Manufacture of coloured paper |
| US3021257A (en) * | 1958-07-31 | 1962-02-13 | American Cyanamid Co | Paper containing pigment or filler |
| DE2060614C3 (en) * | 1970-12-09 | 1980-06-19 | Bayer Ag, 5090 Leverkusen | 9a-methyl-23,9,9a-tetrahydrooxazolo- [3,2, -a] indoles |
| DE2434816C3 (en) * | 1974-07-19 | 1981-01-22 | Basf Ag, 6700 Ludwigshafen | Process for the production of nitrogen-containing condensation products and their use as retention aids, flocculants and dewatering accelerators in paper manufacture |
| US4174998A (en) * | 1974-11-15 | 1979-11-20 | The Associated Portland Cement Manufacturers Limited | Preflocculated filler compositions for use in the manufacture of paper |
| US4348257A (en) * | 1977-06-03 | 1982-09-07 | Hercules Incorporated | Organic pigments |
| US4314001A (en) * | 1980-03-03 | 1982-02-02 | Sterling Drug Inc. | Novel polymeric compounds, processes and methods of use |
| US4370443A (en) * | 1980-03-03 | 1983-01-25 | Sterling Drug Inc. | Novel polymeric compounds, processes and methods of use |
| US4469555A (en) * | 1980-06-23 | 1984-09-04 | Hercules Incorporated | Organic pigments |
| DE3111713A1 (en) * | 1981-03-25 | 1982-10-07 | Basf Ag, 6700 Ludwigshafen | WATER-SOLUBLE BENZYLATED POLYAMIDOAMINE |
| DE3111712A1 (en) * | 1981-03-25 | 1982-10-07 | Basf Ag, 6700 Ludwigshafen | METHOD FOR DYING PAPER |
| GR79057B (en) * | 1982-09-24 | 1984-10-02 | Blue Circle Ind Plc | |
| DE3343105A1 (en) * | 1983-11-29 | 1985-06-05 | Basf Ag, 6700 Ludwigshafen | METHOD FOR PRODUCING PAPER, CARDBOARD AND CARDBOARD WITH HIGH DRY, WET AND LYE RESISTANCE |
-
1987
- 1987-09-30 DE DE19873732981 patent/DE3732981A1/en not_active Withdrawn
-
1988
- 1988-09-22 EP EP88115563A patent/EP0309908B1/en not_active Expired - Lifetime
- 1988-09-22 DE DE3889049T patent/DE3889049D1/en not_active Expired - Lifetime
- 1988-09-26 CA CA000578381A patent/CA1302022C/en not_active Expired - Lifetime
- 1988-09-27 JP JP63239875A patent/JPH01104898A/en active Pending
- 1988-09-27 FI FI884421A patent/FI95063C/en not_active IP Right Cessation
- 1988-09-29 DK DK544388A patent/DK544388A/en not_active Application Discontinuation
- 1988-09-29 AU AU22957/88A patent/AU605633B2/en not_active Ceased
-
1991
- 1991-06-06 US US07/711,378 patent/US5131981A/en not_active Expired - Lifetime
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3128222A (en) * | 1960-11-07 | 1964-04-07 | Crown Zellerbach Corp | Process of coloring cellulosic fibers |
Non-Patent Citations (1)
| Title |
|---|
| Ratgeber für die Verwendung von BASF-Erzeugnissen in der Papier- industrie, 8/72, Seite 22. * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7282263B2 (en) | 2001-05-18 | 2007-10-16 | Sun Chemical Corporation | Method for coloring cellulosic materials using cationic pigment dispersion |
Also Published As
| Publication number | Publication date |
|---|---|
| DK544388D0 (en) | 1988-09-29 |
| AU2295788A (en) | 1989-04-06 |
| EP0309908A2 (en) | 1989-04-05 |
| EP0309908A3 (en) | 1990-12-27 |
| DE3732981A1 (en) | 1989-04-13 |
| DE3889049D1 (en) | 1994-05-19 |
| FI884421A (en) | 1989-03-31 |
| JPH01104898A (en) | 1989-04-21 |
| DK544388A (en) | 1989-03-31 |
| US5131981A (en) | 1992-07-21 |
| AU605633B2 (en) | 1991-01-17 |
| CA1302022C (en) | 1992-06-02 |
| FI95063B (en) | 1995-08-31 |
| FI884421A0 (en) | 1988-09-27 |
| FI95063C (en) | 1995-12-11 |
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