EP0663031A1 - Method of dyeing paper. - Google Patents
Method of dyeing paper.Info
- Publication number
- EP0663031A1 EP0663031A1 EP93920806A EP93920806A EP0663031A1 EP 0663031 A1 EP0663031 A1 EP 0663031A1 EP 93920806 A EP93920806 A EP 93920806A EP 93920806 A EP93920806 A EP 93920806A EP 0663031 A1 EP0663031 A1 EP 0663031A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- mol
- vinyl
- paper
- vinylformamide
- cationic polymers
- 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.)
- Granted
Links
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 fixatives 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. In practice, therefore, mainly condensates of dicyandiamide and formaldehyde or condensates of urea and formaldehyde are used as
- 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 different classes of cationic mixtures being used as fixing agents
- Polymers used 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 Partly hydrolyzed homopolymers of N-vinylformamide are known from US Pat. No. 4,421,602, which contain N-vinylformamide and vinylamine units. They are used as retention aids, drainage aids and flocculants in the manufacture of paper.
- 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 deteriorated.
- 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), 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,
- the dyes are based on dry fiber e.g. in amounts of 0.01 to 10, preferably 0.1 to 5,% by weight.
- R 1 , R 2 H or Ci to C ß- alkyl, into consideration.
- copolymerized and hydrolyzed the copolymers so obtainable that 0.1 to 100 mol% of the copolymerized N-vinylform ⁇ amide are hydrolyzed.
- the monomers of group (2) incorporated into the copolymer remain practically unchanged.
- 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
- Such copolymers may also contain vinylformamide units or vinyl acetate and / or vinyl propionate units.
- 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 ci- to Cs-carboxylic acids and aliphatic or aromatic sulfonic acids, are preferably used.
- the acidic hydrolysis pH is
- Per formyl group equivalent which is to be split off from the copolymerized vinyl carboxamide units 0.05 to 2, preferably 1 to 1.5 mol equivalent of an acid is required.
- 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, in particular of alkali metal and alkaline earth metal hydroxides.
- bases e.g. of metal hydroxides, in particular 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 neutralized with bases, preferably sodium hydroxide solution, if necessary. If the hydrolysis was carried out with bases, the reaction mixture can optionally 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 saline 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.
- pulp includes wood pulp, thermomechanical material (TMP), chemo-thermomechanical material (CTMP), pressure grinding, 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 agents 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.
- Dose fixer and then add the water-soluble anionic dye or a dye mixture.
- 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 sodium chloride 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:
- 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)
Abstract
Description
Claims
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE4233040A DE4233040A1 (en) | 1992-10-01 | 1992-10-01 | Process for dyeing paper |
DE4233040 | 1992-10-01 | ||
PCT/EP1993/002580 WO1994008092A1 (en) | 1992-10-01 | 1993-09-23 | Method of dyeing paper |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0663031A1 true EP0663031A1 (en) | 1995-07-19 |
EP0663031B1 EP0663031B1 (en) | 1996-03-13 |
Family
ID=6469404
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP93920806A Expired - Lifetime EP0663031B1 (en) | 1992-10-01 | 1993-09-23 | Methods of dyeing paper |
Country Status (9)
Country | Link |
---|---|
US (1) | US5554261A (en) |
EP (1) | EP0663031B1 (en) |
JP (1) | JP3188465B2 (en) |
AT (1) | ATE135431T1 (en) |
CA (1) | CA2143747C (en) |
DE (2) | DE4233040A1 (en) |
ES (1) | ES2084513T3 (en) |
FI (1) | FI951516A (en) |
WO (1) | WO1994008092A1 (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1632535A1 (en) * | 2004-09-02 | 2006-03-08 | Basf Aktiengesellschaft | Liquid formulations of direct dyes |
US7160336B2 (en) | 2004-09-02 | 2007-01-09 | Basf Aktiengesellschaft | Liquid formulations of direct dyes |
Families Citing this family (10)
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 (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 |
WO2007096242A1 (en) * | 2006-02-20 | 2007-08-30 | Clariant International Ltd | Improved process for the manufacture of paper and board |
NZ560597A (en) * | 2006-05-09 | 2010-08-27 | 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 |
ES2663483T3 (en) * | 2013-03-19 | 2018-04-12 | Mitsubishi Rayon Co., Ltd. | Use of a cationizing agent, method for firmly fixing water insoluble particles and method for producing dyed material |
Family Cites Families (7)
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 (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 |
DE4007312C2 (en) * | 1990-03-08 | 2000-04-27 | Basf Ag | Process for the preparation of finely divided, water-soluble polymers containing vinylamine units |
-
1992
- 1992-10-01 DE DE4233040A patent/DE4233040A1/en not_active Withdrawn
-
1993
- 1993-09-23 ES ES93920806T patent/ES2084513T3/en not_active Expired - Lifetime
- 1993-09-23 DE DE59301914T patent/DE59301914D1/en not_active Expired - Fee Related
- 1993-09-23 EP EP93920806A patent/EP0663031B1/en not_active Expired - Lifetime
- 1993-09-23 JP JP50866394A patent/JP3188465B2/en not_active Expired - Fee Related
- 1993-09-23 CA CA002143747A patent/CA2143747C/en not_active Expired - Fee Related
- 1993-09-23 US US08/397,060 patent/US5554261A/en not_active Expired - Lifetime
- 1993-09-23 AT AT93920806T patent/ATE135431T1/en not_active IP Right Cessation
- 1993-09-23 WO PCT/EP1993/002580 patent/WO1994008092A1/en active IP Right Grant
-
1995
- 1995-03-30 FI FI951516A patent/FI951516A/en unknown
Non-Patent Citations (1)
Title |
---|
See references of WO9408092A1 * |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1632535A1 (en) * | 2004-09-02 | 2006-03-08 | Basf Aktiengesellschaft | Liquid formulations of direct dyes |
US7160336B2 (en) | 2004-09-02 | 2007-01-09 | Basf Aktiengesellschaft | Liquid formulations of direct dyes |
Also Published As
Publication number | Publication date |
---|---|
ES2084513T3 (en) | 1996-05-01 |
JP3188465B2 (en) | 2001-07-16 |
US5554261A (en) | 1996-09-10 |
CA2143747A1 (en) | 1994-04-14 |
DE4233040A1 (en) | 1994-04-07 |
ATE135431T1 (en) | 1996-03-15 |
EP0663031B1 (en) | 1996-03-13 |
JPH08501835A (en) | 1996-02-27 |
FI951516A0 (en) | 1995-03-30 |
CA2143747C (en) | 2005-03-22 |
DE59301914D1 (en) | 1996-04-18 |
WO1994008092A1 (en) | 1994-04-14 |
FI951516A (en) | 1995-03-30 |
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