EP0663031B1 - Procedes pour colorer du papier - Google Patents

Procedes pour colorer du papier 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
Authority
EP
European Patent Office
Prior art keywords
mol
paper
vinylformamide
cationic polymers
copolymerized
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP93920806A
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German (de)
English (en)
Other versions
EP0663031A1 (fr
Inventor
Claudia Nilz
Norbert Sendhoff
Walter Breitschaft
Manfred Zillig
Primoz Lorencak
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
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Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Publication of EP0663031A1 publication Critical patent/EP0663031A1/fr
Application granted granted Critical
Publication of EP0663031B1 publication Critical patent/EP0663031B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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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
    • 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).

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Paper (AREA)
  • Coloring (AREA)
  • Developing Agents For Electrophotography (AREA)
  • Polarising Elements (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Claims (5)

  1. Procédé de teinture du papier au cours de la fabrication du papier par l'addition de colorants anioniques solubles dans l'eau et de polymères cationiques à titre d'agents de fixation à la pâte à papier et l'égouttage de la pâte à papier sous formation de papier teint, caractérisé en ce que, à titre de polymères cationiques, on utilise des homopolymères hydrolysés du N-vinylformamide, qui contiennent
    a)   0,1 à 100% molaires d'unités vinylamine sous forme de sel et
    b)   99,9 à 0% molaires d'unités vinylformamide.
  2. Procédé de teinture du papier au cours de la fabrication du papier par l'addition de colorants anioniques solubles dans l'eau et de polymères cationiques à titre d'agents de fixation à la pâte à papier et égouttage de la pâte à papier sous formation de papier teint, caractérisé en ce que l'on utilise, à titre de polymères cationiques, des copolymères hydrolysés de N-vinylcarboxamides, que l'on peut obtenir par la copolymérisation de
    (1)   1 à 99% molaires de N-vinylcarboxamides et
    (2)   99 à 1% molaires de monomères monoéthyléniquement insaturés dépourvus de radicaux acide
    et l'hydrolyse subséquente de 0,1 à 100% molaires des N-vinylcarboxamides polymérisés sous formation d'unités vinylamine sous forme de sel.
  3. Procédé suivant la revendication 2, caractérisé en ce que l'on utilise, à titre de polymères cationiques, des copolymères hydrolysés du N-vinylformamide, que l'on peut obtenir par la copolymérisation de
    (1)   1 à 99% molaires de N-vinylformamide et
    (2)   99 à 1% molaires d'au moins un monomère appartenant au groupe formé par l'acétate de vinyle, le propionate de vinyle, la vinylurée, des éthers alkyl(C₁-C₄)vinyliques, la N-vinylpyrrolidone, les esters, nitriles et amides de l'acide acrylique ou de l'acide méthacrylique
    et l'hydrolyse subséquente de 0,1 à 100% molaires du N-vinylformamide incorporé par polymérisation.
  4. Procédé suivant la revendication 2, caractérisé en ce que l'on utilise, à titre de polymères cationiques, des copolymères du N-vinylformamide, que l'on peut obtenir par la copolymérisation de
    (1)   1 à 99% molaires de N-vinylformamide et
    (2)   99 à 1% molaires d'acétate de vinyle et/ou de propionate de vinyle
    et l'hydrolyse subséquente de 40 à 100% molaires du N-vinylformamide incorporé par polymérisation et la séparation de 50 à 100% molaires des radicaux acétyle ou propionyle des monomères (2) incorporés par polymérisation.
  5. Procédé suivant la revendication 2, caractérisé en ce que, à titre de polymères cationiques, on utilise des copolymères qui contiennent, incorporées par polymérisation,
    - 40 à 80% molaires d'unités vinylamine sous forme de sel et
    - 60 à 20% molaires d'unités alcool vinylique, acrylonitrile et/ou vinylurée.
EP93920806A 1992-10-01 1993-09-23 Procedes pour colorer du papier Expired - Lifetime EP0663031B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE4233040A DE4233040A1 (de) 1992-10-01 1992-10-01 Verfahren zum Färben von Papier
DE4233040 1992-10-01
PCT/EP1993/002580 WO1994008092A1 (fr) 1992-10-01 1993-09-23 Procede pour colorer du papier

Publications (2)

Publication Number Publication Date
EP0663031A1 EP0663031A1 (fr) 1995-07-19
EP0663031B1 true EP0663031B1 (fr) 1996-03-13

Family

ID=6469404

Family Applications (1)

Application Number Title Priority Date Filing Date
EP93920806A Expired - Lifetime EP0663031B1 (fr) 1992-10-01 1993-09-23 Procedes pour colorer du papier

Country Status (9)

Country Link
US (1) US5554261A (fr)
EP (1) EP0663031B1 (fr)
JP (1) JP3188465B2 (fr)
AT (1) ATE135431T1 (fr)
CA (1) CA2143747C (fr)
DE (2) DE4233040A1 (fr)
ES (1) ES2084513T3 (fr)
FI (1) FI951516A (fr)
WO (1) WO1994008092A1 (fr)

Families Citing this family (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5519093A (en) * 1994-05-11 1996-05-21 Air Products And Chemicals, Inc. Synthesis of amine functional co-and terpolymers
DE19651243A1 (de) 1996-12-10 1998-06-18 Basf Ag Amphiphile Pfropfpolymerisate auf Basis von N-Vinylcarbonsäureamid-Einheiten enthaltenden Pfropfgrundlagen, Verfahren zu ihrer Herstellung und ihre Verwendung
DE19719059A1 (de) * 1997-05-06 1998-11-12 Basf Ag Verfahren zur Herstellung von Papier, Pappe und Karton
US5948125A (en) * 1997-05-20 1999-09-07 Ciba Specialty Chemicals Corporation Method of treating dyed, natural or synthetic polyamide fibre materials
EP1632535B1 (fr) * 2004-09-02 2010-12-29 Basf Se Formulations liquides des colorants directs
ATE493477T1 (de) 2004-09-02 2011-01-15 Basf Se Flüssigformulierungen von direktfarbstoffen
EP1994222A1 (fr) * 2006-02-20 2008-11-26 Clariant International Ltd. Procede ameliore de fabrication de papier et de carton
AU2007247781B2 (en) * 2006-05-09 2011-03-10 Visy R & D Pty Ltd Improved paper dyeing process
JP2008248459A (ja) * 2007-03-30 2008-10-16 Nippon Paper Industries Co Ltd 紙の製造方法
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

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA686202A (en) * 1964-05-12 E. Eddy Roderick Process for improving the dye retention characteristics of cellulosic materials
DE3111712A1 (de) * 1981-03-25 1982-10-07 Basf Ag, 6700 Ludwigshafen Verfahren zum faerben von papier
DE3128478A1 (de) * 1981-07-18 1983-02-03 Basf Ag, 6700 Ludwigshafen Verfahren zur herstellung von linearen, basischen polymerisaten
DE3534273A1 (de) * 1985-09-26 1987-04-02 Basf Ag Verfahren zur herstellung von vinylamin-einheiten enthaltenden wasserloeslichen copolymerisaten und deren verwendung als nass- und trockenverfestigungsmittel fuer papier
DE3732981A1 (de) * 1987-09-30 1989-04-13 Basf Ag Verfahren zum faerben von papier
DE4001045A1 (de) * 1990-01-16 1991-07-18 Basf Ag Verfahren zur herstellung von papier, pappe und karton
DE4007312C2 (de) * 1990-03-08 2000-04-27 Basf Ag Verfahren zur Herstellung von feinteiligen, wasserlöslichen, Vinylamin-Einheiten enthaltenden Polymerisaten

Also Published As

Publication number Publication date
ATE135431T1 (de) 1996-03-15
FI951516A0 (fi) 1995-03-30
US5554261A (en) 1996-09-10
ES2084513T3 (es) 1996-05-01
WO1994008092A1 (fr) 1994-04-14
DE59301914D1 (de) 1996-04-18
EP0663031A1 (fr) 1995-07-19
JP3188465B2 (ja) 2001-07-16
JPH08501835A (ja) 1996-02-27
FI951516A (fi) 1995-03-30
CA2143747A1 (fr) 1994-04-14
DE4233040A1 (de) 1994-04-07
CA2143747C (fr) 2005-03-22

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