EP0588767B1 - Process for improving the brightness, the clearness and the colour of wooden fibrous material - Google Patents

Process for improving the brightness, the clearness and the colour of wooden fibrous material Download PDF

Info

Publication number
EP0588767B1
EP0588767B1 EP93810632A EP93810632A EP0588767B1 EP 0588767 B1 EP0588767 B1 EP 0588767B1 EP 93810632 A EP93810632 A EP 93810632A EP 93810632 A EP93810632 A EP 93810632A EP 0588767 B1 EP0588767 B1 EP 0588767B1
Authority
EP
European Patent Office
Prior art keywords
process according
paper making
making fibres
mixture
paper
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
EP93810632A
Other languages
German (de)
French (fr)
Other versions
EP0588767A1 (en
Inventor
Axel Dr. Von Raven
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 Schweiz AG
Original Assignee
Ciba Geigy AG
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Ciba Geigy AG filed Critical Ciba Geigy AG
Publication of EP0588767A1 publication Critical patent/EP0588767A1/en
Application granted granted Critical
Publication of EP0588767B1 publication Critical patent/EP0588767B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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
    • 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
    • D21H21/30—Luminescent or fluorescent substances, e.g. for optical bleaching
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06L—DRY-CLEANING, WASHING OR BLEACHING FIBRES, FILAMENTS, THREADS, YARNS, FABRICS, FEATHERS OR MADE-UP FIBROUS GOODS; BLEACHING LEATHER OR FURS
    • D06L4/00—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs
    • D06L4/60—Optical bleaching or brightening
    • D06L4/657—Optical bleaching or brightening combined with other treatments, e.g. finishing, bleaching, softening, dyeing or pigment printing
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06L—DRY-CLEANING, WASHING OR BLEACHING FIBRES, FILAMENTS, THREADS, YARNS, FABRICS, FEATHERS OR MADE-UP FIBROUS GOODS; BLEACHING LEATHER OR FURS
    • D06L4/00—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs
    • D06L4/60—Optical bleaching or brightening
    • D06L4/686—Fugitive optical brightening; Discharge of optical brighteners in discharge paste; Blueing; Differential optical brightening
    • D06L4/693—Blueing with mixtures of dyes; Blueing with mixtures of dyes and optical brighteners
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/22—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using vat dyestuffs including indigo
    • D06P1/26—Phthalocyanine dyes
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
    • D06P1/46—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing natural macromolecular substances or derivatives thereof
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
    • D21C9/00—After-treatment of cellulose pulp, e.g. of wood pulp, or cotton linters ; Treatment of dilute or dewatered pulp or process improvement taking place after obtaining the raw cellulosic material and not provided for elsewhere
    • D21C9/10—Bleaching ; Apparatus therefor
    • D21C9/1026—Other features in bleaching processes
    • D21C9/1036—Use of compounds accelerating or improving the efficiency of the processes

Definitions

  • the invention relates to the addition of water-soluble phthalocyanines as photosensitizing compounds to wood fiber materials and their mixtures to improve their whiteness, brightness and color location; as well as the resulting wood fiber materials and their use.
  • wood fiber materials e.g. Wood pulp and pulp understood.
  • the bleaching required to increase the degree of whiteness is an essential process step which determines the quality of the pulp and thus also of the finished product.
  • Lignins, lignin-like phenols and extract substances as well as their breakdown products are mainly responsible for the brownish-yellow color of the unbleached wood pulp. All of these compounds form chromophoric systems due to the presence of conjugated double bonds and auxochromic groups.
  • wood fiber materials also have a more or less strong yellowness index. If you want to reduce a yellow tinge of wood fiber to get to the required color locus, you have to add a blue dye, with a red tint a greenish-blue dye etc. By adding such dyes there is a certain decrease in the degree of whiteness, but above all a very sharp drop in brightness.
  • the invention now relates to a process for improving the whiteness, brightness and color locus of wood fiber materials or their mixtures by adding water-soluble phthalocyanines as photoactivators.
  • the photoactivator or a mixture of photoactivators is preferably used, optionally in the presence of further auxiliaries, such as surface-active auxiliaries, e.g. Dodecyl sulfate, complexing agents, e.g. Phosphates and fillers, e.g. Zeolites, as well as the fibrous materials or their mixtures, mixed intensively with water.
  • auxiliaries such as surface-active auxiliaries, e.g. Dodecyl sulfate, complexing agents, e.g. Phosphates and fillers, e.g. Zeolites, as well as the fibrous materials or their mixtures, mixed intensively with water.
  • Mixing is preferably carried out intensively at 10 to 90 ° C. and particularly preferably at 20 to 85 ° C. for more than half an hour, preferably for 1 to 4 hours, in order to obtain thorough mixing with the oxygen in the air.
  • the pH of the suspension is preferably from 7.0 to 11.
  • the mixing can be carried out
  • the proportion of photoactivator is generally 0.0001 to 0.1% and preferably 0.0005 to 0.03%, based on the amount of wood fiber used.
  • the suspension of the catalytically bleached wood fiber materials obtained in this way can then be dried, but, in this form, can also be processed immediately.
  • An additional advantage of the method according to the invention lies in the improved strength of the bleached fiber materials.
  • the catalytic sequence of the process is also advantageous, the photoactivator (catalyst), due to its remaining in the wood fiber materials, from yellowing again prevented. So it makes sense to combine the photoactivators with conventional bleaching processes.
  • the photoactivators can be added before, during or after the conventional bleaching process. For practical reasons, bleach and photoactivator are preferably used simultaneously.
  • the wood fiber materials bleached by the process according to the invention accordingly not only have an improvement in whiteness, brightness and color locus, but also a lower tendency to yellowing and an improved strength.
  • the water-soluble phthalocyanines such as e.g. the phthalocyanine metal complexes of aluminum, zinc, manganese, magnesium, calcium, iron, sodium or potassium are used. These compounds can be used individually or as mixtures.
  • the photoactivators used and their preparation are generally known and are used in part in the bleaching of textiles (GB-A-1 372 036, US-A-3 927 967, DE-A-2 613 936, DE-A-2 812 278) used. In contrast to those described there
  • the wood fiber materials that can be used in this process are e.g. Pulp, wood pulp, waste paper or their mixtures.
  • wood pulp are cut (GW), pressure cut (PGW), refiner (RMP), thermomechanical (TMP) and chemical thermomechanical (CTMP).
  • the invention further relates to the wood fiber materials and their mixtures treated with the method according to the invention, and to their use in the pulp industry and in particular in paper production.
  • the invention also relates to the papers produced from the wood fiber materials treated with the process according to the invention.
  • the wood fiber materials and their mixtures obtained in this way are used in the pulp and especially in the paper industry. You can do this with other components such as optical brighteners; Binders such as latex, acrylic acid or styrene polymers or their copolymers; Fillers and other auxiliaries such as polyethylene glycol or glycol ethers can be mixed.
  • otro refers to the dry weight of the fiber in grams.
  • a quantity of the fibrous material specified in Table 1 is weighed into a 1 liter polyethylene screw-top bottle, which corresponds to 3.0 otro (56.6 g A; 200 g B). After adding 500 ml of dist.
  • the other auxiliaries according to Table 1 are metered into water and, if necessary, the pH is adjusted with sodium hydroxide solution.
  • the screw-top bottles are closed and the mixtures (with the exception of the zero tests) are shaken vigorously for one hour on a shaker.
  • a pH of 6.0 is set, if indicated, with sulfuric acid.
  • Paper sheets are produced from the mixtures after dilution to 3l (experiments 1-8) or 7l (experiments 9-20) on the Rapid-Köthen sheet former and after drying (7 min. At 95 ° C) the whiteness, with a Device that meets the requirements of DIN 53145 Part 1.
  • the corresponding manganese compound can also be used.
  • Table 2 Experiment No. 1 day after production 4 weeks without light 5 days of sunlight 10 days of sunlight Difference 1 day - 10 days 1 66.80 66.20 64.80 63.25 3.55 2nd 67.90 67.70 66.35 65.75 2.15 4th 67.85 - 65.70 64.65 3.2 7 67.86 - 65.90 65.10 2.76 11 68.01 68.00 66.55 65.20 2.81 14 88.2 86.6 86.5 1.7 16 88.7 87.7 87.4 1.3 19th 88.9 87.6 87.4 1.5
  • Bag bleaching is carried out with 50 otro wood pulp (SGW) (consistency approx. 20%).
  • SGW otro wood pulp
  • the wood pulp is sprayed with the chemicals listed in Table 3 with constant mixing at 70 ° C from a spray bottle for 2 hours at pH 7.5.
  • the amount of the respective fiber material is weighed into a 1 liter polyethylene bottle, which corresponds to 6.0 otro (30.2 g A; 30.7 g B). After adding 800 ml of dist. The auxiliaries are metered into water in accordance with the amounts given in Table 4. The mixtures obtained are stirred vigorously at room temperature for about 4 hours (except for zero tests).
  • Paper sheets are formed from the mixtures on the Rapid-Köthen sheet former and, after drying (7 minutes at 95 ° C), the degree of whiteness is determined using a device that meets the requirements of DIN 53145 Part 1.
  • Table 4 Experiment No. Fiber Photoactivator [ml 0.1% solution] Rawesol® [% based on otro] Whiteness [%] (2) (3) 1 A - - - 60.4 2nd B - - - 60.8 3rd A 0.5 - - 60.8 4th A 1.0 - - 63.0 5 A 1.5 - - 63.4 6 A 1.0 - 0.2 63.4 7 A - 1.0 - 63.7 8th A - 2.0 - 63.5 9 B 0.5 - - 62.5 10th B 1.0 - - 62.0 11 B 1.0 - 0.2 62.3 12th B - 1.0 - 62.2
  • Fibrous A thermomechanical wood pulp with a dry matter content of 19.9%
  • Fibrous material B waste paper with a dry matter content of 19.5%
  • thermomechanical wood pulp (TMP) for coating base paper (consistency approx. 6%) is taken directly from industrial production and the photoactivator (2) according to table 5 is added. Each batch is made with 20 g otro thermomechanical wood pulp (TMP) at 3% consistency with constant stirring at 55 ° C.
  • Pulp samples or plates are soaked in a 0.001% solution of compound (2) for about 5 minutes and then dried at room temperature and daylight.
  • Bag bleaching is carried out with 50 otro wood pulp (TMP) each.
  • TMP otro wood pulp
  • the wood pulp is sprayed with the bleaching solution from a spray bottle with the chemicals specified in Table 3, with constant mixing.
  • the mixture is acidified to a pH of about 7 with sulfuric acid and 80 mg of compound (2) are added per kg of wood pulp.
  • the wood pulp is diluted to 3% at a pH of 8.5.
  • Paper sheets are formed from the mixtures on the Rapid-Köthen sheet former and after drying (7 min. At 95 ° C) the degree of whiteness is determined using a device that meets the requirements of DIN 53145 Part 1.
  • the strength test of the paper sheets is determined according to Brecht-Imset (tear propagation) DIN 53115, the tear length according to DIN 53112. Table 7: without (2) with (2) Whiteness 65.2 66.4 Light reference value 81.1 80.9 Tear length [m] 2523 3345 Tear-through work [mJ / m] 925 942

Landscapes

  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Paper (AREA)
  • Chemical And Physical Treatments For Wood And The Like (AREA)
  • Prostheses (AREA)
  • Endoscopes (AREA)
  • Optical Fibers, Optical Fiber Cores, And Optical Fiber Bundles (AREA)

Abstract

Addition of photosensitising compounds to wood fibre substances and mixtures thereof in order to improve their degree of whiteness, their brightness and their colour location, and the fibrous substances obtained thereby, and their use.

Description

Die Erfindung betrifft den Zusatz von wasserlöslichen Phthalocyaninen als photosensibilisierende Verbindungen zu Holzfaserstoffen und deren Gemischen zur Verbesserung von deren Weissgrad, Helligkeit und Farbort; sowie die damit erhaltenen Holzfaserstoffe und ihre Verwendung.The invention relates to the addition of water-soluble phthalocyanines as photosensitizing compounds to wood fiber materials and their mixtures to improve their whiteness, brightness and color location; as well as the resulting wood fiber materials and their use.

Unter Holzfaserstoffe werden z.B. Holzschliff und Zellstoff verstanden.Under wood fiber materials e.g. Wood pulp and pulp understood.

Die Diskussion über die Umweltbelastung der Zellstoffbleiche mit Aktivchlor hat dazu geführt, dass in der Zellstoffindustrie immer mehr alternative Bleichsysteme, wie Wasserstoffperoxid, Ozon und Sauerstoff, ihre Anwendung finden. Beim Einsatz von chlorfrei gebleichten Zellstoffen hat sich aber gezeigt, dass sich gewisse Festigkeitsverluste ergeben.The discussion about the environmental impact of pulp bleaching with active chlorine has led to an increasing number of alternative bleaching systems, such as hydrogen peroxide, ozone and oxygen, being used in the pulp industry. When using chlorine-free bleached cellulose, however, it has been shown that there are certain losses in strength.

Bei der Herstellung von Holzschliffen für graphische Papiere ist die zur Erhöhung des Weissgrades erforderliche Bleiche ein wesentlicher, die Qualität des Halbstoffes und damit auch des Fertigproduktes bestimmender Verfahrensschritt.In the manufacture of wood pulp for graphic papers, the bleaching required to increase the degree of whiteness is an essential process step which determines the quality of the pulp and thus also of the finished product.

Für die bräunlich-gelbe Farbe des ungebleichten Holzschliffes sind im wesentlichen Lignine, ligninähnliche Phenole und Extraktstoffe sowie deren Abbauprodukte verantwortlich. Alle diese Verbindungen bilden, infolge der Anwesenheit von konjugierten Doppelbindungen und auxochromen Gruppen, chromophore Systeme.Lignins, lignin-like phenols and extract substances as well as their breakdown products are mainly responsible for the brownish-yellow color of the unbleached wood pulp. All of these compounds form chromophoric systems due to the presence of conjugated double bonds and auxochromic groups.

Für die Bleichung von Holzschliff kommen, um die Stabilität nicht zu erniedrigen, nur kohlehydrat- und ligninerhaltende Bleichmittel in Betracht. Die Steigerung des Weissgrades erfordert eine spezifische Zerstörung der chromophoren Gruppen, möglichst ohne Stoffauflösung. Das chromophore System wird dabei chemisch verändert, ist jedoch noch vorhanden, so dass der Farbeffekt nach einer gewissen Zeit wieder auftreten kann. Dies ist der Grund für die hohe Vergilbungsneigung von holzstoffhaltigem Papier.In order to bleach wood pulp, only carbohydrate and lignin-containing bleaching agents come into consideration in order not to lower the stability. The increase in the degree of whiteness requires a specific destruction of the chromophoric groups, if possible without dissolving the substance. The chromophoric system is chemically changed, but is still there, so that the color effect can reappear after a certain time. This is the reason for the high yellowing tendency of paper containing wood pulp.

Vielfach wird beim Bleichen von Holzschliff, trotz hoher H2O2-Konzentrationen, der erforderliche Weissgrad nicht erreicht, so dass eine zusätzliche reduktive Bleichung z.B. mit Natriumdithionit durchgeführt werden muss. Dieser Zweistufenprozess erfordert nicht nur einen erhöhten Kostenaufwand, sondern zerstört auch das noch vorhandene H2O2, dessen biozide Wirkung dann bei der Papierherstellung nicht mehr vorhanden ist.In many cases, when bleaching wood pulp, despite high H 2 O 2 concentrations, the required whiteness has not been reached, so that additional reductive bleaching, for example with sodium dithionite, must be carried out. This two-step process not only requires increased costs, but also destroys the H 2 O 2 that is still present, the biocidal effect of which is then no longer present in paper production.

Trotz moderner Bleichverfahren weisen Holzfaserstoffe ausserdem einen mehr oder weniger starken Gelbwert auf. Will man einen Gelbstich von Holzfaserstoffen vermindern, um in den geforderten Farbortbereich zu gelangen, so muss man einen blauen Farbstoff zusetzen, bei einem Rotstich einen grünstichig-blauen Farbstoff usw. Durch die Zugabe von solchen Farbstoffen erfolgt ein gewisser Rückgang des Weissgrades, aber vor allem ein sehr starker Abfall in der Helligkeit.Despite modern bleaching processes, wood fiber materials also have a more or less strong yellowness index. If you want to reduce a yellow tinge of wood fiber to get to the required color locus, you have to add a blue dye, with a red tint a greenish-blue dye etc. By adding such dyes there is a certain decrease in the degree of whiteness, but above all a very sharp drop in brightness.

Gegenstand der Erfindung ist nun ein Verfahren zur Verbesserung von Weissgrad, Helligkeit und Farbort von Holzfaserstoffen oder deren Mischungen durch den Zusatz von wasserlöslichen Phthalocyaninen als Photoaktivatoren.The invention now relates to a process for improving the whiteness, brightness and color locus of wood fiber materials or their mixtures by adding water-soluble phthalocyanines as photoactivators.

Vorzugsweise wird zu diesem Zweck der Photoaktivator oder eine Mischung aus Photoaktivatoren, gegebenenfalls im Gegenwart von weiteren Hilfsmitteln, wie oberflächenaktiven Hilfsmitteln, z.B. Dodecylsulfat, Komplexbildnern, z.B. Phosphaten, und Füllmitteln, z.B. Zeolithen, sowie die Faserstoffe oder deren Mischungen, mit Wasser intensiv vermischt. Bevorzugt wird dabei bei 10 bis 90°C und besonders bevorzugt bei 20 bis 85°C, für mehr als eine halbe Stunde, bevorzugt während 1 bis 4 Stunden, intensiv gemischt, um eine gute Durchmischung mit dem Sauerstoff der Luft zu erhalten. Der pH-Wert der Suspension beträgt dabei bevorzugt 7,0 bis 11. Das Mischen kann dabei z.B. durch Rühren, Umpumpen oder Einblasen von Luft geschehen.For this purpose, the photoactivator or a mixture of photoactivators is preferably used, optionally in the presence of further auxiliaries, such as surface-active auxiliaries, e.g. Dodecyl sulfate, complexing agents, e.g. Phosphates and fillers, e.g. Zeolites, as well as the fibrous materials or their mixtures, mixed intensively with water. Mixing is preferably carried out intensively at 10 to 90 ° C. and particularly preferably at 20 to 85 ° C. for more than half an hour, preferably for 1 to 4 hours, in order to obtain thorough mixing with the oxygen in the air. The pH of the suspension is preferably from 7.0 to 11. The mixing can be carried out e.g. by stirring, pumping or blowing air.

Der Anteil an Photoaktivator liegt im allgemeinen bei 0,0001 bis 0,1 % und bevorzugt bei 0,0005 bis 0,03 %, in Bezug auf die Menge an eingesetztem Holzfaserstoff.The proportion of photoactivator is generally 0.0001 to 0.1% and preferably 0.0005 to 0.03%, based on the amount of wood fiber used.

Die Suspension der so erhaltenen katalytisch gebleichten Holzfaserstoffe kann danach getrocknet werden, kann aber auch, in dieser Form, sofort weiterverarbeitet werden. Ein zusätzlicher Vorteil des erfindungsgemässen Verfahrens liegt in der verbesserten Festigkeit der so gebleichten Fasermaterialien.The suspension of the catalytically bleached wood fiber materials obtained in this way can then be dried, but, in this form, can also be processed immediately. An additional advantage of the method according to the invention lies in the improved strength of the bleached fiber materials.

Vorteilhaft ist weiterhin der katalytische Ablauf des Verfahrens, wobei der Photoaktivator (Katalysator), durch sein Verbleiben bei den Holzfaserstoffen ein erneutes Vergilben verhindert. So ist es auch sinnvoll, die Photoaktivatoren mit konventionellen Bleichverfahren zu kombinieren. Die Photoaktivatoren können dabei vor, während oder nach dem konventionellen Bleichvorgang zugesetzt werden. Aus praktischen Überlegungen werden Bleichmittel und Photoaktivator bevorzugt gleichzeitig angewendet.The catalytic sequence of the process is also advantageous, the photoactivator (catalyst), due to its remaining in the wood fiber materials, from yellowing again prevented. So it makes sense to combine the photoactivators with conventional bleaching processes. The photoactivators can be added before, during or after the conventional bleaching process. For practical reasons, bleach and photoactivator are preferably used simultaneously.

Die nach dem erfindungsgemässen Verfahren gebleichten Holzfaserstoffe weisen demnach nicht nur eine Verbesserung von Weissgrad, Helligkeit und Farbort, sondern auch eine geringere Vergilbungsneigung sowie eine verbesserte Festigkeit auf.The wood fiber materials bleached by the process according to the invention accordingly not only have an improvement in whiteness, brightness and color locus, but also a lower tendency to yellowing and an improved strength.

Als Photoaktivatoren werden die wasserlöslichen Phthalocyanine wie z.B. die Phthalocyanin-Metallkomplexe des Aluminiums, zinks, Mangans, Magnesiums, Calciums, Eisens, Natriums oder Kaliums verwendet. Diese Verbindungen können dabei einzeln oder als Gemische eingesetzt werden.The water-soluble phthalocyanines such as e.g. the phthalocyanine metal complexes of aluminum, zinc, manganese, magnesium, calcium, iron, sodium or potassium are used. These compounds can be used individually or as mixtures.

Besonders bevorzugt sind Verbindungen der Formel (1)

Figure imgb0001
   sowie deren Mischungen, worin

MePC
das Zink-, Mangan oder Aluminiumphthalocyaninringsystem,
Y
Wasserstoff, ein Alkalimetall oder Ammonium, bevorzugt Wasserstoff, Kalium oder Natrium,
v
eine beliebige Zahl von 1 bis 4, bevorzugt eine Zahl von 2 bis 4,
R
Fluor, Chlor, Brom oder Iod, bevorzugt Chlor oder Brom,
x
eine beliebige Zahl von 0 bis 8, bevorzugt ( wenn MePC das Zink- oder Aluminiumphthalocyaninringsystem ist) eine beliebige Zahl von 0,8 bis 2 bedeutet.
Compounds of the formula (1) are particularly preferred
Figure imgb0001
 and mixtures thereof, in which
MePC
the zinc, manganese or aluminum phthalocyanine ring system,
Y
Hydrogen, an alkali metal or ammonium, preferably hydrogen, potassium or sodium,
v
any number from 1 to 4, preferably a number from 2 to 4,
R
Fluorine, chlorine, bromine or iodine, preferably chlorine or bromine,
x
any number from 0 to 8, preferably (if MePC is the zinc or aluminum phthalocyanine ring system) means any number from 0.8 to 2.

Die verwendeten Photoaktivatoren und ihre Herstellung sind allgemein bekannt und werden zum Teil beim Bleichen von Textilien (GB-A-1 372 036, US-A-3 927 967, DE-A-2 613 936, DE-A-2 812 278) eingesetzt. Im Unterschied zu den dort beschriebenenThe photoactivators used and their preparation are generally known and are used in part in the bleaching of textiles (GB-A-1 372 036, US-A-3 927 967, DE-A-2 613 936, DE-A-2 812 278) used. In contrast to those described there

Bedingungen ist bei der erfindungsgemässen Behandlung (Bleichen) der genannten Holzfaserstoffe überraschenderweise eine Bestrahlung mit Licht und ein Zusatz von Gerüststoffen sowie Detergentien nicht erforderlich.Conditions in the treatment (bleaching) of the wood fiber materials mentioned, surprisingly, do not require irradiation with light and the addition of builders and detergents.

Die in diesem Verfahren einsetzbaren Holzfaserstoffe sind z.B. Zellstoff, Holzstoff, Altpapier oder deren Gemische. Beispiele für Holzstoffe sind Schliff (GW), Druckschliff (PGW), Refinerstoff (RMP), thermomechanischer (TMP) und chemisch-thermomechanischer (CTMP) Stoff.The wood fiber materials that can be used in this process are e.g. Pulp, wood pulp, waste paper or their mixtures. Examples of wood pulp are cut (GW), pressure cut (PGW), refiner (RMP), thermomechanical (TMP) and chemical thermomechanical (CTMP).

Ein weiterer Gegenstand der Erfindung sind die mit dem erfindungsgemässen Verfahren behandelten Holzfaserstoffe und deren Gemische, sowie deren Verwendung in der Zellstoffindustrie und insbesondere bei der Papierherstellung.The invention further relates to the wood fiber materials and their mixtures treated with the method according to the invention, and to their use in the pulp industry and in particular in paper production.

Ein Gegenstand der Erfindung sind ausserdem die aus den mit dem erfindungsgemässen Verfahren behandelten Holzfaserstoffen hergestellten Papiere.The invention also relates to the papers produced from the wood fiber materials treated with the process according to the invention.

Die so erhaltenen Holzfaserstoffe und deren Gemische finden in der Zellstoff- und vor allem in der Papierindustrie Verwendung. Dazu können sie mit weiteren Bestandteilen wie optischen Aufhellern; Bindemitteln wie Latex, Acrylsäure- oder Styrolpolymere oder deren Copolymere; Füllstoffen und anderen Hilfsmitteln wie Polyethylenglykol oder Glykolethern, vermischt werden.The wood fiber materials and their mixtures obtained in this way are used in the pulp and especially in the paper industry. You can do this with other components such as optical brighteners; Binders such as latex, acrylic acid or styrene polymers or their copolymers; Fillers and other auxiliaries such as polyethylene glycol or glycol ethers can be mixed.

Besonders vorteilhafte synergistische Effekte findet man auch bei der Kombination der Photoaktivatoren mit optischen Aufhellern wie z.B. Diphenylbistyrylaufhellern.Particularly advantageous synergistic effects can also be found in the combination of photoactivators with optical brighteners, e.g. Diphenylbistyrylighteners.

Die folgenden Beispiele erläutern die Erfindung ohne sie darauf zu beschränken. Die %-Angaben beziehen sich dabei, soweit nicht anders angegeben, auf das Gewicht. Die Bezeichnung otro (ofen-trocken) bezieht sich auf das Trockengewicht des Faserstoffes in Gramm.The following examples illustrate the invention without restricting it thereto. Unless otherwise stated, the% figures relate to the weight. The term otro (oven-dry) refers to the dry weight of the fiber in grams.

Beispiel 1:Example 1:

Es wird eine Menge des in Tabelle 1 angegebenen Faserstoffes in eine 1 l Polyethylen-Schraubflasche eingewogen, die 3,0 otro entspricht (56,6 g A; 200 g B). Nach dem Zusetzen von 500 ml dest. Wasser werden die weiteren Hilfsstoffe gemäss Tabelle 1 zudosiert und gegebenenfalls der pH-Wert mit Natronlauge eingestellt. Die Schraubflaschen werden verschlossen und die Gemische (mit Ausnahme der Nullversuche) für eine Stunde kräftig auf einer Schüttelmaschine geschüttelt. Nach Beendigung der Reaktionszeit wird, sofern angegeben, mit Schwefelsäure ein pH-Wert von 6,0 eingestellt.A quantity of the fibrous material specified in Table 1 is weighed into a 1 liter polyethylene screw-top bottle, which corresponds to 3.0 otro (56.6 g A; 200 g B). After adding 500 ml of dist. The other auxiliaries according to Table 1 are metered into water and, if necessary, the pH is adjusted with sodium hydroxide solution. The screw-top bottles are closed and the mixtures (with the exception of the zero tests) are shaken vigorously for one hour on a shaker. When the reaction time has ended, a pH of 6.0 is set, if indicated, with sulfuric acid.

Aus den Gemischen werden nach dem Verdünnen auf 3l (Versuche 1-8) bzw. 7l (Versuche 9-20) am Rapid-Köthen-Blattbildner Papierblätter hergestellt und nach der Trocknung (7 min. bei 95°C) der Weissgrad, mit einem Gerät das die Anforderungen von DIN 53145 Teil 1 erfüllt, bestimmt.Paper sheets are produced from the mixtures after dilution to 3l (experiments 1-8) or 7l (experiments 9-20) on the Rapid-Köthen sheet former and after drying (7 min. At 95 ° C) the whiteness, with a Device that meets the requirements of DIN 53145 Part 1.

Die Photoaktivatoren der Formeln (2) und (3) werden als 0,1 %ige Lösungen eingesetzt.

Figure imgb0002
Figure imgb0003
 Tabelle 1: Versuchs Nr. Faserstoff Photoaktivator [ml] Dodecylsulfat [%] Phosphat [%] Rawesol® [%] pH Weissgrad 2 3 1 A - - - - - a 66,80 2 A 0,5 - - - - a 67,91 3 A 1,0 - - - - a 67,58 4 A 2,5 - - - - a 67,85 5 A - 0,5 - - - a 67,40 6 A - 1,0 - - - a 67,47 7 A - 2,5 - - - a 67,86 8 A 1,0 - 0,05 0,2 - a 67,29 9 A - 1,0 0,05 0,2 - a 67,26 10 A 1,0 - 0,05 - 0,2 a 67,51 11 A - 1,0 0,05 - 0,2 a 68,01 12 A 1,0 - 0,05 - 0,2 7,5 67,26 13 A 1,0 - 0,05 - 0,2 9/6 67,05 14 B - - - - - a 88,15 15 B 1,0 - 0,05 0,2 - 9,0 88,29 16 B 1,0 - 0,05 - 0,2 9,0 88,75 17 B - 1,0 0,05 0,2 - 9,0 88,30 18 B - 1,0 0,05 - 0,2 9,0 88,63 19 B - 1,0 0,05 - 0,2 9/6 88,88 Faserstoff A = Holzschliff feucht, Trockengehalt 5,3 %
Faserstoff B = Gebleichter Kurzfaserzellstoff (Laubholz-Sulfitzellstoff), Trockengehalt 1,5 %
a) = pH wurde nicht eingestellt
9/6 = pH zunächst auf 9,0 und nach der Reaktion auf 6,0 eingestellt
Rawesol = Spezial-Zeolith The photoactivators of the formulas (2) and (3) are used as 0.1% solutions.
Figure imgb0002
Figure imgb0003
 Table 1: Experiment No. Fiber Photoactivator [ml] Dodecyl sulfate [%] Phosphate [%] Rawesol® [%] pH Whiteness 2nd 3rd 1 A - - - - - a 66.80 2nd A 0.5 - - - - a 67.91 3rd A 1.0 - - - - a 67.58 4th A 2.5 - - - - a 67.85 5 A - 0.5 - - - a 67.40 6 A - 1.0 - - - a 67.47 7 A - 2.5 - - - a 67.86 8th A 1.0 - 0.05 0.2 - a 67.29 9 A - 1.0 0.05 0.2 - a 67.26 10th A 1.0 - 0.05 - 0.2 a 67.51 11 A - 1.0 0.05 - 0.2 a 68.01 12th A 1.0 - 0.05 - 0.2 7.5 67.26 13 A 1.0 - 0.05 - 0.2 9/6 67.05 14 B - - - - - a 88.15 15 B 1.0 - 0.05 0.2 - 9.0 88.29 16 B 1.0 - 0.05 - 0.2 9.0 88.75 17th B - 1.0 0.05 0.2 - 9.0 88.30 18th B - 1.0 0.05 - 0.2 9.0 88.63 19th B - 1.0 0.05 - 0.2 9/6 88.88 Fibrous material A = wood pulp moist, dry matter content 5.3%
Pulp B = bleached short-pulp (hardwood sulfite pulp), dry matter content 1.5%
a) = pH was not adjusted
9/6 = pH initially adjusted to 9.0 and after the reaction to 6.0
Rawesol = special zeolite

Aus den Ergebnissen von Tabelle 1 zeigt sich eine Zunahme des Weissgrades bei den mit Photoaktivatoren gebleichten Versuchen gegenüber den ungebleichten Kontrollen (Nrn. 1 und 14).The results of Table 1 show an increase in the degree of whiteness in the tests bleached with photoactivators compared to the unbleached controls (Nos. 1 and 14).

Anstelle der Photoaktivatoren der Formeln (2) oder (3) kann man auch die entsprechende Manganverbindung verwenden.Instead of the photoactivators of the formulas (2) or (3), the corresponding manganese compound can also be used.

Beispiel 2:Example 2:

Die aus Beispiel 1 erhaltenen Proben werden für die in Tabelle 2 angegebene Zeit gelagert und danach der Weissgrad bestimmt. Die in Tabelle 2 angegebenen Versuchsnummern beziehen sich dabei auf Tabelle 1. Tabelle 2: Versuchs- Nr. 1 Tag nach Herstellung 4 Wochen ohne Licht 5 Tage Sonnenlicht 10 Tage Sonnenlicht Differenz 1 Tag - 10 Tage 1 66,80 66,20 64,80 63,25 3,55 2 67,90 67,70 66,35 65,75 2,15 4 67,85 - 65,70 64,65 3,2 7 67,86 - 65,90 65,10 2,76 11 68,01 68,00 66,55 65,20 2,81 14 88,2 86,6 86,5 1,7 16 88,7 87,7 87,4 1,3 19 88,9 87,6 87,4 1,5 The samples obtained from Example 1 are stored for the time indicated in Table 2 and the whiteness is then determined. The test numbers given in Table 2 refer to Table 1. Table 2: Experiment No. 1 day after production 4 weeks without light 5 days of sunlight 10 days of sunlight Difference 1 day - 10 days 1 66.80 66.20 64.80 63.25 3.55 2nd 67.90 67.70 66.35 65.75 2.15 4th 67.85 - 65.70 64.65 3.2 7 67.86 - 65.90 65.10 2.76 11 68.01 68.00 66.55 65.20 2.81 14 88.2 86.6 86.5 1.7 16 88.7 87.7 87.4 1.3 19th 88.9 87.6 87.4 1.5

Aus den Ergebnissen von Tabelle 2 geht hervor, dass die Tendenz zur Vergilbung bei den unbehandelten Papieren (Versuch 1 und 14) deutlich grösser ist als bei den mit Photoaktivator behandelten.The results in Table 2 show that the tendency to yellowing is clearly greater in the untreated papers (tests 1 and 14) than in those treated with photoactivator.

Beispiel 3:Example 3:

Mit jeweils 50 otro Holzschliff (SGW) wird eine Beutelbleiche durchgeführt (Stoffdichte ca. 20 %). Dazu wird der Holzschliff mit den in Tabelle 3 angegebenen Chemikalien unter ständiger Durchmischung bei 70°C aus einer Sprühflasche für 2 Stunden bei pH 7,5 besprüht.

Figure imgb0004
Bag bleaching is carried out with 50 otro wood pulp (SGW) (consistency approx. 20%). For this, the wood pulp is sprayed with the chemicals listed in Table 3 with constant mixing at 70 ° C from a spray bottle for 2 hours at pH 7.5.
Figure imgb0004

Die Ergebnisse aus Tabelle 3 zeigen, das auch bei Anwendung einer Peroxidbleiche eine weitere Steigerung des Weissgrades, sowie eine Verschiebung des Farbortes ohne wesentlichen Helligkeitsverlust, durch den Zusatz der Photoaktivatoren erreicht werden kann.The results from Table 3 show that even with the use of peroxide bleaching, a further increase in the degree of whiteness and a shift in the color locus without a significant loss in brightness can be achieved by adding the photoactivators.

Beispiel 4:Example 4:

Es werden die Menge des jeweiligen Faserstoffes in eine 1 l Polyethylenflasche eingewogen, die 6,0 otro entsprechen (30,2 g A; 30,7 g B). Nach Zusatz von 800 ml dest. Wasser werden die Hilfsstoffe gemäss den in Tabelle 4 angegebenen Mengen zudosiert. Die erhaltenen Gemische werden ca. 4 Stunden bei Raumtemperatur stark gerührt (ausgenommen Nullversuche).The amount of the respective fiber material is weighed into a 1 liter polyethylene bottle, which corresponds to 6.0 otro (30.2 g A; 30.7 g B). After adding 800 ml of dist. The auxiliaries are metered into water in accordance with the amounts given in Table 4. The mixtures obtained are stirred vigorously at room temperature for about 4 hours (except for zero tests).

Aus den Gemischen werden am Rapid-Köthen-Blattbildner Papierblätter gebildet und nach der Trocknung (7 min. bei 95°C) der Weissgrad mit einem Gerät, das die Anforderungen von DIN 53145 Teil 1 erfüllt, bestimmt. Tabelle 4: Versuchs Nr. Faserstoff Photoaktivator [ml 0,1% Lsg.] Rawesol® [% bezogen auf otro] Weissgrad [%] (2) (3) 1 A - - - 60,4 2 B - - - 60,8 3 A 0,5 - - 60,8 4 A 1,0 - - 63,0 5 A 1,5 - - 63,4 6 A 1,0 - 0,2 63,4 7 A - 1,0 - 63,7 8 A - 2,0 - 63,5 9 B 0,5 - - 62,5 10 B 1,0 - - 62,0 11 B 1,0 - 0,2 62,3 12 B - 1,0 - 62,2 Faserstoff A = thermomechanischer Holzstoff mit 19,9 % Trockengehalt
Faserstoff B = Altpapier mit 19,5 % Trockengehalt Paper sheets are formed from the mixtures on the Rapid-Köthen sheet former and, after drying (7 minutes at 95 ° C), the degree of whiteness is determined using a device that meets the requirements of DIN 53145 Part 1. Table 4: Experiment No. Fiber Photoactivator [ml 0.1% solution] Rawesol® [% based on otro] Whiteness [%] (2) (3) 1 A - - - 60.4 2nd B - - - 60.8 3rd A 0.5 - - 60.8 4th A 1.0 - - 63.0 5 A 1.5 - - 63.4 6 A 1.0 - 0.2 63.4 7 A - 1.0 - 63.7 8th A - 2.0 - 63.5 9 B 0.5 - - 62.5 10th B 1.0 - - 62.0 11 B 1.0 - 0.2 62.3 12th B - 1.0 - 62.2 Fibrous A = thermomechanical wood pulp with a dry matter content of 19.9%
Fibrous material B = waste paper with a dry matter content of 19.5%

Beispiel 5:Example 5:

Ein thermomechanischer Holzstoff (TMP) für Streichrohpapier (Stoffdichte ca. 6 %) wird direkt aus der industriellen Fertigung entnommen und der Photoaktivator (2) gemäss Tabelle 5 zugesetzt. Jeder Ansatz erfolgt mit 20 g otro thermomechanischen Holzstoff (TMP) bei 3 % Stoffdichte unter ständigem Rühren bei 55°C.

Figure imgb0005
A thermomechanical wood pulp (TMP) for coating base paper (consistency approx. 6%) is taken directly from industrial production and the photoactivator (2) according to table 5 is added. Each batch is made with 20 g otro thermomechanical wood pulp (TMP) at 3% consistency with constant stirring at 55 ° C.
Figure imgb0005

Beispiel 6:Example 6:

Zellstoffproben bzw. Platten werden für ca. 5 Minuten in einer 0,001 %igen Lösung der Verbindung (2) getränkt und anschliessend bei Zimmertemperatur und Tageslicht getrocknet.Pulp samples or plates are soaked in a 0.001% solution of compound (2) for about 5 minutes and then dried at room temperature and daylight.

Beim Messen des Weissgrades ergeben sich, für eine ungebleichte und eine wie oben beschreiben gebleichte Probe, die in Tabelle 6 angegebenen Werte. Tabelle 6: ohne (2) mit (2) Weissgrad 79,93 83,05 Hellbezugswert y [%] 87,35 87,70 Normfarbwertanteil K x 0,3249 0,3190 Normfarbwertanteil K y 0,4342 0,3387 When measuring the degree of whiteness, the values given in Table 6 result for an unbleached and a bleached sample as described above. Table 6: without (2) with (2) Whiteness 79.93 83.05 Light reference value y [%] 87.35 87.70 Standard color value component K x 0.3249 0.3190 Standard color value component K y 0.4342 0.3387

Beispiel 7:Example 7:

Mit jeweils 50 otro Holzstoff (TMP) wird eine Beutelbleiche durchgeführt. Dazu wird der Holzstoff mit den in Tabelle 3 angegebenen Chemikalien unter ständiger Durchmischung aus einer Sprühflasche mit der Bleichlösung besprüht.Bag bleaching is carried out with 50 otro wood pulp (TMP) each. For this purpose, the wood pulp is sprayed with the bleaching solution from a spray bottle with the chemicals specified in Table 3, with constant mixing.

Bleichbedingungen :Bleaching conditions:

Stoffdichte ca.Fabric density approx. 20 %20% WasserglasWater glass 2,8 %2.8% NaOHNaOH 2,7 %2.7% H2O2 H 2 O 2 2,5 %2.5% Temperaturtemperature 70°C70 ° C BleichdauerBleaching time 2,5 Stunden2.5 hours

Nach dem Bleichen wird mit Schwefelsäure auf einen pH-Wert von ca. 7 abgesäuert und 80 mg der Verbindung (2) pro kg Holzschliff zugegeben.After bleaching, the mixture is acidified to a pH of about 7 with sulfuric acid and 80 mg of compound (2) are added per kg of wood pulp.

Zur Dosierung der chemischen Hilfsmittel wird der Holzschliff auf 3 %, bei einem pH-Wert von 8,5, verdünnt.To meter the chemical additives, the wood pulp is diluted to 3% at a pH of 8.5.

Aus den Gemischen werden am Rapid-Köthen-Blattbildner Papierblätter gebildet und nach der Trocknung (7 min. bei 95°C) der Weissgrad mit einem Gerät, das die Anforderungen von DIN 53145 Teil 1 erfüllt, bestimmt.Paper sheets are formed from the mixtures on the Rapid-Köthen sheet former and after drying (7 min. At 95 ° C) the degree of whiteness is determined using a device that meets the requirements of DIN 53145 Part 1.

Die Festigkeitsprüfung der Papierblätter wird nach Brecht-Imset (Weiterreissarbeit) DIN 53115, die Reisslänge nach DIN 53112 bestimmt. Tabelle 7: ohne (2) mit (2) Weissgrad 65,2 66,4 Hellbezugswert 81,1 80,9 Reisslänge [m] 2523 3345 Weiterreissarbeit [mJ/m] 925 942 The strength test of the paper sheets is determined according to Brecht-Imset (tear propagation) DIN 53115, the tear length according to DIN 53112. Table 7: without (2) with (2) Whiteness 65.2 66.4 Light reference value 81.1 80.9 Tear length [m] 2523 3345 Tear-through work [mJ / m] 925 942

Claims (22)

  1. A process for enhancing the whiteness, brightness and chromaticity of paper making fibres or a mixture thereof by the addition of water-soluble phthalocyanines as photoactivator.
  2. A process according to claim 1, which comprises mixing the photoactivator or a mixture of photoactivators, the paper making fibres or a mixture thereof as well as further optional components with water to form an aqueous suspension.
  3. A process according to claim 2, wherein the pH of the suspension is in the range from 7.0 to 11.
  4. A process according to claim 2, wherein the components are stirred for longer than half an hour.
  5. A process according to claim 4, wherein the components are stirred thoroughly for 1 to 4 hours.
  6. A process according to any one of claims 2 to 5, wherein the components are stirred thoroughly in the temperature range from 10 to 90°C.
  7. A process according to any one of claims 2 to 5, wherein the components are stirred thoroughly in the temperature range from 20 to 85°C.
  8. A process according to claim 1, wherein the amount of photoactivator is from 0.0001 to 0.1 %, based on the amount of paper making fibres.
  9. A process according to claim 8, wherein the mount of photoactivator is from 0.0005 to 0.03 %, based on the amount of paper making fibres.
  10. A process according to claim 1, which comprises using a phthalocyanine metal complex of aluminium, zinc, manganese, magnesium, calcium, iron, sodium or potassium.
  11. A process according to claim 1, which comprises using a phthalocyanine metal complex of manganese.
  12. A process according to claim 10, which comprises using one or more than one compound of formula (1)
    Figure imgb0008
     wherein
    MePC   is the zinc or aluminium phthalocyanine ring system,
    Y   is hydrogen, an alkali metal or ammonium,
    v   is any number from 1 to 4,
    R   is fluoro, chloro, bromo or iodo, and
    x   is any number from 0 to 8.
  13. A process according to claim 11, which comprises using one or more than one compound of formula (1)
    Figure imgb0009
     wherein
    MePC   is the manganese phthalocyanine ring system,
    Y   is hydrogen, an alkali metal or ammonium,
    v   is any number from 1 to 4,
    R   is fluoro, chloro, bromo or iodo, and
    x   is any number from 0 to 8.
  14. A process according to either claim 12 or claim 13, which comprises using one or more than one compound of formula (1), wherein
    Y   is hydrogen, potassium or sodium,
    v   is a number from 2 to 4,
    R   is chloro or bromo,
    x   is any number from 0 to 2.
  15. A process according to claim 14, which comprises the use of one or more than one compound of formula (1), wherein MePC is the zinc or aluminium phthalocyanine ring system and x is any number from 0.8 to 2.
  16. A process according to claim 1, wherein pulp, groundwood pulp, waste paper and mixtures thereof are used as paper making fibres .
  17. Paper making fibres prepared by a process as claimed in any one of claims 1 to 16, or a mixture thereof.
  18. Use of paper making fibres as claimed in claim 17, or a mixture thereof, in the pulp industry.
  19. Use of paper making fibres as claimed in claim 17, or a mixture thereof, in paper manufacture.
  20. Mechanical woodpulp paper prepared from paper making fibres by a process as claimed in any one of claims 1 to 16.
  21. A process as claimed in any one of claims 1 to 16, which comprises adding the photoactivators before, during or after a conventional bleaching process.
  22. A process as claimed in any one of claims 1 to 16, whioh comprises adding a fluorescent whitening agent before, during or after the addition of the photoactivators.
EP93810632A 1992-09-14 1993-09-06 Process for improving the brightness, the clearness and the colour of wooden fibrous material Expired - Lifetime EP0588767B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE4230655 1992-09-14
DE4230655A DE4230655A1 (en) 1992-09-14 1992-09-14 Process for improving the whiteness, brightness and color location of fibrous materials

Publications (2)

Publication Number Publication Date
EP0588767A1 EP0588767A1 (en) 1994-03-23
EP0588767B1 true EP0588767B1 (en) 1996-06-12

Family

ID=6467877

Family Applications (1)

Application Number Title Priority Date Filing Date
EP93810632A Expired - Lifetime EP0588767B1 (en) 1992-09-14 1993-09-06 Process for improving the brightness, the clearness and the colour of wooden fibrous material

Country Status (11)

Country Link
US (1) US5482514A (en)
EP (1) EP0588767B1 (en)
JP (1) JPH06207391A (en)
AT (1) ATE139280T1 (en)
AU (1) AU661195B2 (en)
BR (1) BR9303764A (en)
CA (1) CA2105922A1 (en)
DE (2) DE4230655A1 (en)
ES (1) ES2089777T3 (en)
FI (1) FI933991A (en)
MX (1) MX9305598A (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19916078A1 (en) * 1999-04-09 2000-10-12 Jorax Labor Fuer Chemische Und Enhancement of whiteness, lightness and color of fibrous materials, inorganic fillers, pigments and binders for paper manufacture and finishing uses water-soluble copper phthalocyanine complex as photoactivator
DE102007036376A1 (en) * 2007-07-31 2009-02-05 Voith Patent Gmbh Bleached pulp

Families Citing this family (26)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0960184B1 (en) * 1997-01-24 2003-04-16 Case Western Reserve University Photobleaching compositions comprising mixed metallocyanines
US6232281B1 (en) * 1997-01-24 2001-05-15 Procter & Gamble Co. Singlet oxygen generators having enhanced heavy atom effect
BR9917226A (en) * 1999-03-05 2002-02-26 Procter & Gamble Composition comprising a photo-oxidation agent and uses of the agent
US6030443A (en) * 1999-04-29 2000-02-29 Hercules Incorporated Paper coating composition with improved optical brightener carriers
FR2804446B1 (en) * 2000-02-02 2003-01-17 Atofina PROCESS FOR BLEACHING DE-INK AND / OR RECYCLED PASTA
US6893473B2 (en) * 2002-05-07 2005-05-17 Weyerhaeuser.Company Whitened fluff pulp
FR2842200B1 (en) * 2002-07-12 2005-12-16 Centre Nat Rech Scient PROCESS FOR OBTAINING MODIFIED POLYSACCHARIDES
KR101136843B1 (en) * 2002-09-04 2012-05-25 시바 홀딩 인코포레이티드 Formulations comprising water-soluble granulates
FI122175B (en) * 2003-12-23 2011-09-30 Teknologian Tutkimuskeskus Vtt Process for making a fiber product
FI117439B (en) * 2003-12-23 2006-10-13 Valtion Teknillinen A process for preparing a fiber composition
FI121892B (en) * 2003-12-23 2011-05-31 Teknologian Tutkimuskeskus Vtt A process for making composite fiber products
US20050217809A1 (en) * 2004-03-31 2005-10-06 Weyerhaeuser Company Bleached crosslinked cellulosic fibers having high color and related methods
US20050217811A1 (en) * 2004-03-31 2005-10-06 Weyerhaeuser Company Whitened crosslinked cellulosic fibers and related methods
CN101128630A (en) * 2005-02-19 2008-02-20 国际纸业公司 Fixation of optical brightening agents onto papermaking fiber
US7638016B2 (en) * 2005-02-19 2009-12-29 International Paper Company Method for treating kraft pulp with optical brighteners after chlorine bleaching to increase brightness
US7682438B2 (en) 2005-11-01 2010-03-23 International Paper Company Paper substrate having enhanced print density
JP2009524747A (en) * 2006-01-26 2009-07-02 クラリアント インターナショナル リミティド Method for producing fluorescent white paper
US7622022B2 (en) * 2006-06-01 2009-11-24 Benny J Skaggs Surface treatment of substrate or paper/paperboard products using optical brightening agent
US7967948B2 (en) * 2006-06-02 2011-06-28 International Paper Company Process for non-chlorine oxidative bleaching of mechanical pulp in the presence of optical brightening agents
US20070284425A1 (en) * 2006-06-13 2007-12-13 John Raymond Garvey Blank and gable top carton thereof
JP5364088B2 (en) * 2007-04-05 2013-12-11 アクゾ ノーベル ナムローゼ フェンノートシャップ Methods for improving the optical properties of paper
WO2008144074A1 (en) * 2007-05-21 2008-11-27 International Paper Company Recording sheet with improved image waterfastness, surface strength, and runnability
WO2009085308A2 (en) 2007-12-26 2009-07-09 International Paper Company A paper substrate containing a wetting agent and having improved print mottle
WO2010039996A1 (en) * 2008-10-01 2010-04-08 International Paper Company A paper substrate containing a wetting agent and having improved printability
US20130189457A1 (en) 2012-01-23 2013-07-25 International Paper Company SEPARATED TREATMENT OF PAPER SUBSTRATE WITH MULTIVALENT METAL SALTS AND OBAs
CN108138447A (en) 2015-08-14 2018-06-08 巴斯夫欧洲公司 For paper and the aqueous surface treating composition of cardboard

Family Cites Families (40)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AT32159B (en) * 1906-03-17 1908-03-10 Hoechst Ag Process for coloring paper pulp in the Hollander.
DE658703C (en) * 1933-10-04 1938-04-09 Uddeholms Ab Process for treating fibrous materials
CH466507A (en) * 1965-12-31 1968-12-15 Ciba Geigy Dentifrices containing optical brighteners
US3479349A (en) * 1967-08-03 1969-11-18 Geigy Chem Corp Polysulfonated bis-s-triazinylamino-stilbene-2,2'-disulfonic acids
CH554848A (en) * 1967-10-03 1974-10-15 Ciba Geigy Ag PROCESS FOR PRODUCING NEW STILBENE DERIVATIVES.
ES366464A1 (en) * 1968-04-26 1971-03-16 Geigy Ag J R Asymmetrically substituted bistriazinylamino stilbene compounds
CH533670A (en) * 1968-12-05 1973-02-15 Ciba Geigy Ag Inorganic white pigments containing optical brighteners
DE2151727A1 (en) * 1970-10-20 1972-04-27 Nasa Process for stabilizing pigments against degradation by irradiation
CH564529A5 (en) * 1970-11-12 1975-07-31 Ciba Geigy Ag
GB1408144A (en) * 1972-06-02 1975-10-01 Procter & Gamble Ltd Bleaching process
US3960589A (en) * 1971-10-13 1976-06-01 Stanford Research Institute Stabilized pigment and method for producing the same
JPS5119042B2 (en) * 1971-11-15 1976-06-15
GB1372036A (en) * 1972-05-26 1974-10-30 Procter & Gamble Ltd Washing machine
JPS5138992B2 (en) * 1972-05-31 1976-10-25
GB1394910A (en) * 1972-10-23 1975-05-21 Pluss Stauffer Ag Process for the optical brightening of minerals
US3883331A (en) * 1973-01-08 1975-05-13 Dover Corp Filter, particularly for smoke solids filtration
US3948828A (en) * 1973-04-13 1976-04-06 Ciba-Geigy Corporation Liquid to pasty dyestuff preparations
DE2434468A1 (en) * 1974-07-18 1976-01-29 Bayer Ag Impregnating and dyeing textiles - with a foamed treatment bath foamed with a combustible fuel gas and burning off gases
GB1537512A (en) * 1976-04-07 1978-12-29 Ass Portland Cement Method for the production of ultrafine chalk
DE2816306C3 (en) * 1977-04-18 1980-11-13 Ciba-Geigy Ag, Basel (Schweiz) Granules of water-soluble dyes or optical brighteners, their production and use
IN153407B (en) * 1979-09-28 1984-07-14 Ciba Geigy Ag
DE2943652C2 (en) * 1979-10-29 1985-12-12 Plüss-Staufer AG, Oftringen, Aargau Mineral filler in the form of natural calcium carbonate
GR71714B (en) * 1979-11-09 1983-06-21 Colgate Palmolive Co
US4294654A (en) * 1980-03-21 1981-10-13 International Paper Company Delignification and bleaching of lignocellulosic pulp via photo-oxygenation
GB2082195A (en) * 1980-07-22 1982-03-03 Showa Kagaku Kogyo Kk Colour Salts and Optically Brightening Compositions Containing the Same
SU958454A1 (en) * 1981-02-02 1982-09-15 Предприятие П/Я А-7850 Composition of loundry blue
SU1232719A1 (en) * 1982-02-26 1986-05-23 Ленинградская Ордена Ленина Лесотехническая Академия Им.С.М.Кирова Light-stabilizing agent for paper pulp
SU1079717A1 (en) * 1982-07-19 1984-03-15 Ленинградская лесотехническая академия им.С.М.Кирова Light fastness stabilizer for wood pulp and cellulose
DE3400161A1 (en) * 1983-01-13 1984-07-19 Sandoz-Patent-GmbH, 7850 Lörrach Phthalocyanine compounds, their preparation and use
FR2539424B1 (en) * 1983-01-13 1986-11-07 Sandoz Sa NOVEL PHTHALOCYANINS, THEIR PREPARATION AND THEIR USE AS DYES
SU1097717A1 (en) * 1983-02-16 1984-06-15 Вильнюсский Ордена Трудового Красного Знамени И Ордена Дружбы Народов Государственный Университет Им.В.Капсукаса Electrolyte for deposition of silver-copper alloy
CH654121A5 (en) * 1983-03-25 1986-01-31 Ciba Geigy Ag METHOD FOR PRODUCING SOLID PHOTOACTIVATOR PREPARATIONS.
IT1180236B (en) * 1983-09-30 1987-09-23 Melamine Chemicals Inc IMPROVED PROCEDURE TO PRODUCE WOOD PASTE USING AN ADDITIVE OF S-TRIAZINE AND A WOOD PASTE AND AN IMPROVED PAPER CONTAINING AN S-TRIAZINE
CS249337B1 (en) * 1984-12-03 1987-03-12 Karel Vesely Power filler for plastics
SU1305227A1 (en) * 1985-12-03 1987-04-23 Сибирский научно-исследовательский институт целлюлозы и картона Method of bleaching pulp
DE3626777A1 (en) * 1986-08-07 1988-02-11 Basf Ag REINFORCED THERMOPLASTIC MOLDS WITH LIGHT COLORING
DE3875142T2 (en) * 1987-03-17 1993-03-04 Procter & Gamble Bleach.
GB8806016D0 (en) * 1988-03-14 1988-04-13 Danochemo As Encapsulated photoactivator dyes for detergent use
US5232535A (en) * 1989-02-23 1993-08-03 Anthony Industries, Inc. Process for preparing embossed, coated paper
JPH0617217B2 (en) * 1989-02-28 1994-03-09 水澤化学工業株式会社 Amorphous silica / alumina spherical particles and method for producing the same

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19916078A1 (en) * 1999-04-09 2000-10-12 Jorax Labor Fuer Chemische Und Enhancement of whiteness, lightness and color of fibrous materials, inorganic fillers, pigments and binders for paper manufacture and finishing uses water-soluble copper phthalocyanine complex as photoactivator
DE102007036376A1 (en) * 2007-07-31 2009-02-05 Voith Patent Gmbh Bleached pulp

Also Published As

Publication number Publication date
MX9305598A (en) 1994-03-31
BR9303764A (en) 1994-04-26
DE59302896D1 (en) 1996-07-18
FI933991A0 (en) 1993-09-10
ES2089777T3 (en) 1996-10-01
US5482514A (en) 1996-01-09
ATE139280T1 (en) 1996-06-15
FI933991A (en) 1994-03-15
AU661195B2 (en) 1995-07-13
EP0588767A1 (en) 1994-03-23
DE4230655A1 (en) 1994-03-17
JPH06207391A (en) 1994-07-26
AU4731293A (en) 1994-03-24
CA2105922A1 (en) 1994-03-15

Similar Documents

Publication Publication Date Title
EP0588767B1 (en) Process for improving the brightness, the clearness and the colour of wooden fibrous material
EP0588768B1 (en) Process for improving the degree of whiteness, the brightness and the colour location of fillers and pigments
DE2640027C2 (en)
DE2219504A1 (en) MULTI-STAGE BLEACHING OF PULP WITH SIGNIFICANTLY REDUCED CHLORINE USE
DE3302580C2 (en)
EP0226114B1 (en) Process for bleaching and delignification of cellulosic products
EP0171575A1 (en) Process for the delignification and bleaching of cellulose pulps
EP0087553B1 (en) Process for producing half-bleached cellulose pulps
DE602004002934T2 (en) Bleaching and brightness stabilization of lignocellulosic materials with water-soluble phosphine or phosphonium compounds
DE60114005T2 (en) FLUORESCENT LIGHTING PIGMENT COMPOSITIONS
DE19916078A1 (en) Enhancement of whiteness, lightness and color of fibrous materials, inorganic fillers, pigments and binders for paper manufacture and finishing uses water-soluble copper phthalocyanine complex as photoactivator
DE69917692T2 (en) Process for bleaching pigments
DE3009473B2 (en) Sodium hydrosulfite composition
DE2124325C3 (en) Process for bleaching chemical wood pulp
DE931690C (en) Process for bleaching wood pulp and other mechanically produced fiber material
DE602004011911T9 (en) Activator for pulp bleaching
DE2754949C3 (en) Process for the treatment of material containing lignocellulose
DE69810663T2 (en) COMPOSITION FOR BLEACHING MECHANICAL POWDER
DE818344C (en) Process for the preparation of acyl derivatives of 4,4'-diaminostilbene-2, 2'-disulfonic acid
DE3616816A1 (en) METHOD FOR REMOVING BULK COLORED PAPER AND SELF-COPYING PAPER
DE654991C (en) Process for bleaching cellulose obtained by alkaline digestion
EP0379858A2 (en) Process for bleaching fibre stock for making paper
DE3037718C2 (en)
DE2826821A1 (en) PROCESS FOR REDUCING WOOD PULP OR CLAY
EP0771902A1 (en) Process for the production of pulp and paper

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE CH DE ES FR GB IT LI NL SE

17P Request for examination filed

Effective date: 19940819

17Q First examination report despatched

Effective date: 19950719

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE CH DE ES FR GB IT LI NL SE

REF Corresponds to:

Ref document number: 139280

Country of ref document: AT

Date of ref document: 19960615

Kind code of ref document: T

ET Fr: translation filed
REG Reference to a national code

Ref country code: ES

Ref legal event code: BA2A

Ref document number: 2089777

Country of ref document: ES

Kind code of ref document: T3

REF Corresponds to:

Ref document number: 59302896

Country of ref document: DE

Date of ref document: 19960718

ITF It: translation for a ep patent filed

Owner name: SOCIETA' ITALIANA BREVETTI S.P.A.

GBT Gb: translation of ep patent filed (gb section 77(6)(a)/1977)

Effective date: 19960828

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2089777

Country of ref document: ES

Kind code of ref document: T3

REG Reference to a national code

Ref country code: CH

Ref legal event code: PUE

Owner name: CIBA-GEIGY AG TRANSFER- CIBA SC HOLDING AG

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2089777

Country of ref document: ES

Kind code of ref document: T3

BECN Be: change of holder's name

Effective date: 19961129

NLS Nl: assignments of ep-patents

Owner name: CIBA SC HOLDING AG

REG Reference to a national code

Ref country code: FR

Ref legal event code: TP

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

REG Reference to a national code

Ref country code: CH

Ref legal event code: PFA

Free format text: CIBA SC HOLDING AG TRANSFER- CIBA SPECIALTY CHEMICALS HOLDING INC.

REG Reference to a national code

Ref country code: GB

Ref legal event code: 732E

NLT1 Nl: modifications of names registered in virtue of documents presented to the patent office pursuant to art. 16 a, paragraph 1

Owner name: CIBA SPECIALTY CHEMICALS HOLDING INC.

26N No opposition filed
REG Reference to a national code

Ref country code: CH

Ref legal event code: PUE

Owner name: CIBA SPECIALTY CHEMICALS HOLDING INC. TRANSFER- JO

REG Reference to a national code

Ref country code: FR

Ref legal event code: CD

REG Reference to a national code

Ref country code: ES

Ref legal event code: PC2A

REG Reference to a national code

Ref country code: CH

Ref legal event code: PFA

Free format text: JORAX GMBH TRANSFER- JORAX LABOR FUER CHEMISCHE UND PHYSIKALISCHE PAPIERUNTERSUCHUNGEN GMBH

Ref country code: CH

Ref legal event code: NV

Representative=s name: KELLER & PARTNER PATENTANWAELTE AG

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 19990616

Year of fee payment: 7

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: SE

Payment date: 19990705

Year of fee payment: 7

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 19990903

Year of fee payment: 7

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: ES

Payment date: 19990910

Year of fee payment: 7

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: CH

Payment date: 19990924

Year of fee payment: 7

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 19990930

Year of fee payment: 7

Ref country code: AT

Payment date: 19990930

Year of fee payment: 7

REG Reference to a national code

Ref country code: GB

Ref legal event code: 732E

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BE

Payment date: 19991119

Year of fee payment: 7

REG Reference to a national code

Ref country code: FR

Ref legal event code: TP

REG Reference to a national code

Ref country code: ES

Ref legal event code: PC2A

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20000906

Ref country code: AT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20000906

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20000907

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Free format text: THE PATENT HAS BEEN ANNULLED BY A DECISION OF A NATIONAL AUTHORITY

Effective date: 20000929

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20000930

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20000930

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20000930

BERE Be: lapsed

Owner name: JORAX LABOR FUER CHEMISCHE UND PHYSIKALISCHE PAPIE

Effective date: 20000930

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20010401

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20000906

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

EUG Se: european patent has lapsed

Ref document number: 93810632.5

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20010531

NLV4 Nl: lapsed or anulled due to non-payment of the annual fee

Effective date: 20010401

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20010717

Year of fee payment: 9

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20030401

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20011011

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED.

Effective date: 20050906