EP0588767A1 - 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

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Publication number
EP0588767A1
EP0588767A1 EP93810632A EP93810632A EP0588767A1 EP 0588767 A1 EP0588767 A1 EP 0588767A1 EP 93810632 A EP93810632 A EP 93810632A EP 93810632 A EP93810632 A EP 93810632A EP 0588767 A1 EP0588767 A1 EP 0588767A1
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EP
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Prior art keywords
mixtures
fibrous materials
photoactivator
photoactivators
compounds
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EP93810632A
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German (de)
French (fr)
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EP0588767B1 (en
Inventor
Axel Dr. Von Raven
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BASF Schweiz AG
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Ciba Geigy AG
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Classifications

    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
    • D21H21/30—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 photosensitizing compounds to fibrous materials and their mixtures to improve their whiteness, brightness and color location; as well as the resulting fiber materials and their use.
  • fibrous materials should essentially be understood as meaning wood fibrous materials, such as wood pulp and cellulose.
  • 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.
  • fiber materials also have a more or less strong yellowness index. If you want to reduce a yellow tinge of fibers in order to reach 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 method for improving the degree of whiteness, brightness and color locus of fiber materials or their mixtures by adding 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. It is preferred to mix 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.
  • the proportion of photoactivator is generally from 0.0001 to 0.1% and preferably from 0.0005 to 0.03%, based on the amount of fiber used.
  • the suspension of the catalytically bleached fibers 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 fibrous materials, 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 fibrous materials bleached by the process according to the invention accordingly not only have an improvement in whiteness, brightness and color location, but also a lower tendency to yellowing and an improved strength.
  • All dyes which have a photodynamic effect such as eosin, rose bengal, fluorescein, chlorophyll, porphyrin compounds, methylene blue or mixtures thereof, can be used as photoactivators suitable for the process.
  • the water-soluble phthalocyanines such as e.g. the phthalocyanine metal complexes of aluminum, zinc, manganese, magnesium, calcium, iron, sodium or potassium. 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.
  • irradiation with light and the addition of builders and detergents is not necessary.
  • the 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 application also relates to the fibrous materials and their mixtures treated with the process according to the invention, and to their use in the pulp industry and in particular in papermaking.
  • the application also relates to the papers produced from the fibrous materials treated with the process according to the invention.
  • the fibrous materials and their mixtures thus obtained 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 fiber 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 photoactivators of the formulas (2) and (3) are used as 0.1% solutions.
  • 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 min. At 95 ° C) the degree of whiteness is determined using a device that meets the requirements of DIN 53145 Part 1.
  • 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

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  • 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 photosensibilisierenden Verbindungen zu Faserstoffen und deren Gemischen zur Verbesserung von deren Weissgrad, Helligkeit und Farbort; sowie die damit erhaltenen Faserstoffe und ihre Verwendung.The invention relates to the addition of photosensitizing compounds to fibrous materials and their mixtures to improve their whiteness, brightness and color location; as well as the resulting fiber materials and their use.

Unter Faserstoffen sollen nachfolgend im wesentlichen Holzfaserstoffe, wie Holzschliff und Zellstoff, verstanden werden.In the following, fibrous materials should essentially be understood as meaning wood fibrous materials, such as wood pulp and cellulose.

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.Often when bleaching wood pulp, despite high H₂O₂ concentrations, the required whiteness has not been reached, so that additional reductive bleaching, for example with sodium dithionite, must be carried out. This two-stage process not only requires increased costs, but also destroys the H₂O₂ that is still present, the biocidal effect of which is then no longer present in paper production.

Trotz moderner Bleichverfahren weisen Faserstoffe ausserdem einen mehr oder weniger starken Gelbwert auf. Will man einen Gelbstich von Faserstoffen 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, fiber materials also have a more or less strong yellowness index. If you want to reduce a yellow tinge of fibers in order to reach 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 Faserstoffen oder deren Mischungen durch den Zusatz von Photoaktivatoren.The invention now relates to a method for improving the degree of whiteness, brightness and color locus of fiber materials or their mixtures by adding 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. It is preferred to mix 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 Faserstoff.The proportion of photoactivator is generally from 0.0001 to 0.1% and preferably from 0.0005 to 0.03%, based on the amount of fiber used.

Die Suspension der so erhaltenen katalytisch gebleichten Faserstoffe 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 fibers 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 Faserstoffen, 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 fibrous materials, 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 Faserstoffe weisen demnach nicht nur eine Verbesserung von Weissgrad, Helligkeit und Farbort, sondern auch eine geringere Vergilbungsneigung sowie eine verbesserte Festigkeit auf.The fibrous materials bleached by the process according to the invention accordingly not only have an improvement in whiteness, brightness and color location, but also a lower tendency to yellowing and an improved strength.

Als für das Verfahren geeignete Photoaktivatoren können alle Farbstoffe die einen photodynamischen Effekt aufweisen, wie Eosin, Bengalrosa, Fluorescein, Chlorophyll, Porphyrin-Verbindungen, Methylenblau oder deren Mischungen, verwendet werden. Bevorzugt sind dabei die wasserlöslichen Phthalocyanine wie z.B. die Phthalocyanin-Metallkomplexe des Aluminiums, Zinks, Mangans, Magnesiums, Calciums, Eisens, Natriums oder Kaliums. Diese Verbindungen können dabei einzeln oder als Gemische eingesetzt werden.All dyes which have a photodynamic effect, such as eosin, rose bengal, fluorescein, chlorophyll, porphyrin compounds, methylene blue or mixtures thereof, can be used as photoactivators suitable for the process. The water-soluble phthalocyanines such as e.g. the phthalocyanine metal complexes of aluminum, zinc, manganese, magnesium, calcium, iron, sodium or potassium. 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) any number from 0.8 to 2

means.

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 beschriebenen Bedingungen ist bei der erfindungsgemässen Behandlung (Bleichen) der genannten Faserstoffen überraschenderweise eine Bestrahlung mit Licht und ein Zusatz von Gerüststoffen sowie Detergentien nicht erforderlich.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 the conditions described there, surprisingly, in the treatment (bleaching) of the fibrous materials according to the invention, irradiation with light and the addition of builders and detergents is not necessary.

Die in diesem Verfahren einsetzbaren Faserstoffe 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 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 Anmeldung sind die mit dem erfindungsgemässen Verfahren behandelten Faserstoffe und deren Gemische, sowie deren Verwendung in der Zellstoffindustrie und insbesondere bei der Papierherstellung.The application also relates to the fibrous materials and their mixtures treated with the process according to the invention, and to their use in the pulp industry and in particular in papermaking.

Ein Gegenstand der Anmeldung sind ausserdem die aus den mit dem erfindungsgemässen Verfahren behandelten Faserstoffen hergestellten Papiere.The application also relates to the papers produced from the fibrous materials treated with the process according to the invention.

Die so erhaltenen Faserstoffe 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 fibrous materials and their mixtures thus obtained 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 1l Polethylen-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 fiber 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
Figure imgb0004
 The photoactivators of the formulas (2) and (3) are used as 0.1% solutions.
Figure imgb0002
Figure imgb0003
Figure imgb0004

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 imgb0005
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 imgb0005

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 1l 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.

Figure imgb0006
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.
Figure imgb0006

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 imgb0007
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 imgb0007

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% H₂O₂H₂O₂ 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 (25)

Verfahren zur Verbesserung von Weissgrad, Helligkeit und Farbort von Faserstoffen oder deren Mischungen durch den Zusatz von Photoaktivatoren.Process for improving the whiteness, brightness and color location of fibrous materials or their mixtures by adding photoactivators. Verfahren gemäss Anspruch 1, dadurch gekennzeichnet, dass der Photoaktivator oder eine Mischung aus Photoaktivatoren, die Faserstoffe oder deren Mischungen sowie gegebenenfalls weitere Komponente mit Wasser zu einer wässrigen Suspension vermischt werden.A method according to claim 1, characterized in that the photoactivator or a mixture of photoactivators, the fibrous materials or their mixtures and optionally other components are mixed with water to form an aqueous suspension. Verfahren gemäss Anspruch 2, dadurch gekennzeichnet, dass der pH-Wert der Suspension bei 7,0 bis 11 liegt.A method according to claim 2, characterized in that the pH of the suspension is 7.0 to 11. Verfahren gemäss Anspruch 2, dadurch gekennzeichnet, dass man länger als eine halbe Stunde intensiv mischt.A method according to claim 2, characterized in that intensive mixing is carried out for more than half an hour. Verfahren gemäss Anspruch 4, dadurch gekennzeichnet, dass man während 1 bis 4 Stunden intensiv mischt.A method according to claim 4, characterized in that intensive mixing is carried out for 1 to 4 hours. Verfahren gemäss einem der Ansprüche 2 bis 5, dadurch gekennzeichnet, dass bei 10 bis 90°C intensiv gemischt wird.Method according to one of claims 2 to 5, characterized in that intensive mixing is carried out at 10 to 90 ° C. Verfahren gemäss Anspruch 6, dadurch gekennzeichnet, dass bei 20 bis 85°C intensiv gemischt wird.A method according to claim 6, characterized in that intensive mixing is carried out at 20 to 85 ° C. Verfahren gemäss Anspruch 1, dadurch gekennzeichnet, dass der Anteil an Photoaktivator bei 0,0001 bis 0,1 %, bezogen auf die Menge an eingesetztem Faserstoff, liegt.A method according to claim 1, characterized in that the proportion of photoactivator is 0.0001 to 0.1%, based on the amount of fiber used. Verfahren gemäss Anspruch 8, dadurch gekennzeichnet, dass der Anteil an Photoaktivator bei 0,0005 bis 0,03 %, bezogen auf die Menge an eingesetztem Faserstoff, liegt.A method according to claim 8, characterized in that the proportion of photoactivator is 0.0005 to 0.03%, based on the amount of fiber used. Verfahren gemäss Anspruch 1, dadurch gekennzeichnet, dass als Photoaktivator Farbstoffe, die einen photodynamischen Effekt aufweisen, verwendet werden.A method according to claim 1, characterized in that dyes which have a photodynamic effect are used as the photoactivator. Verfahren gemäss Anspruch 10, dadurch gekennzeichnet, dass als Photoaktivator Eosin, Bengalrosa, Fluorescein, Chlorophyll, Porphyrin-Verbindungen, Methylenblau oder deren Mischungen, verwendet werden.A method according to claim 10, characterized in that eosin, rose bengal, fluorescein, chlorophyll, porphyrin compounds, methylene blue or mixtures thereof are used as the photoactivator. Verfahren gemäss Anspruch 1, dadurch gekennzeichnet, dass als Photoaktivator wasserlösliche Phthalocyanine verwendet werden.A method according to claim 1, characterized in that water-soluble phthalocyanines are used as the photoactivator. Verfahren gemäss Anspruch 12, dadurch gekennzeichnet, dass Phthalocyanin-Metallkomplexe des Aluminiums, Zinks, Magnesiums, Calciums, Eisens, Natriums oder Kaliums verwendet werden.A method according to claim 12, characterized in that phthalocyanine metal complexes of aluminum, zinc, magnesium, calcium, iron, sodium or potassium are used. Verfahren gemäss Anspruch 12, dadurch gekennzeichnet, dass Phthalocyanin-Metallkomplexe des Mangans verwendet werden.A method according to claim 12, characterized in that phthalocyanine metal complexes of manganese are used. Verfahren gemäss Anspruch 13, dadurch gekennzeichnet, dass eine oder mehrere Verbindungen der Formel (1) verwendet werden,
Figure imgb0008
 worin
MePC das Zink- oder Aluminiumphthalocyaninringsystem, Y   Wasserstoff, ein Alkalimetall oder Ammonium, v   eine beliebige Zahl von 1 bis 4, R   Fluor, Chlor, Brom oder Iod, x   eine beliebige Zahl von 0 bis 8 bedeutet.A method according to claim 13, characterized in that one or more compounds of formula (1) are used,
Figure imgb0008
 wherein
MePC the zinc or aluminum phthalocyanine ring system, Y is hydrogen, an alkali metal or ammonium, v any number from 1 to 4, R fluorine, chlorine, bromine or iodine, x any number from 0 to 8 means. Verfahren gemäss Anspruch 14, dadurch gekennzeichnet, dass eine oder mehrere Verbindungen der Formel (1) verwendet werden,
Figure imgb0009
 worin
MePC das Manganphthalocyaninringsystem, Y   Wasserstoff, ein Alkalimetall oder Ammonium, v   eine beliebige Zahl von 1 bis 4, R   Fluor, Chlor, Brom oder Iod, x   eine beliebige Zahl von 0 bis 8 bedeutet.A method according to claim 14, characterized in that one or more compounds of formula (1) are used,
Figure imgb0009
 wherein
MePC the manganese phthalocyanine ring system, Y is hydrogen, an alkali metal or ammonium, v any number from 1 to 4, R fluorine, chlorine, bromine or iodine, x any number from 0 to 8 means. Verfahren gemäss Anspruch 15 oder 16, dadurch gekennzeichnet, dass eine oder mehrere Verbindungen der Formel (1) verwendet werden, worin Y   Wasserstoff, Kalium oder Natrium, v   eine Zahl von 2 bis 4, R   Chlor oder Brom, x   eine beliebige Zahl von 0 bis 2 bedeuten.A method according to claim 15 or 16, characterized in that one or more compounds of formula (1) are used, wherein Y is hydrogen, potassium or sodium, v is a number from 2 to 4, R chlorine or bromine, x any number from 0 to 2 mean. Verfahren gemäss Anspruch 17, dadurch gekennzeichnet, dass eine oder mehrere Verbindungen der Formel (1) verwendet werden, worin MePC das Zink- oder Aluminiumphthalocyaninringsystem und x eine beliebige Zahl von 0,8 bis 2 bedeuten.A method according to claim 17, characterized in that one or more compounds of formula (1) are used, in which MePC is the zinc or aluminum phthalocyanine ring system and x is any number from 0.8 to 2. Verfahren gemäss Anspruch 1, dadurch gekennzeichnet, das als Faserstoffe Zellstoff, Holzstoff, Altpapier oder deren Gemische verwendet werden.A method according to claim 1, characterized in that cellulose, wood pulp, waste paper or mixtures thereof are used as fibrous materials. Die gemäss einem der Ansprüche 1 bis 19 hergestellten Faserstoffe, sowie deren Mischungen.The fibrous materials produced according to one of claims 1 to 19, and mixtures thereof. Verwendung der Faserstoffe gemäss Anspruch 20 sowie deren Gemische in der Zellstoffindustrie.Use of the fibrous materials according to claim 20 and their mixtures in the pulp industry. Verwendung der Faserstoffe gemäss Anspruch 20 sowie deren Gemische bei der Papierherstellung.Use of the fibrous materials according to claim 20 and their mixtures in papermaking. Die aus den Faserstoffen gemäss dem Verfahren der Ansprüche 1 bis 19 hergestellten holzhaltigen Papiere.The wood-containing papers produced from the fibrous materials according to the process of claims 1 to 19. Verfahren gemäss einem der Ansprüche 1 bis 19, dadurch gekennzeichnet, dass man die Photoaktivatoren vor, während oder nach einem konventionellen Bleichvorgang zusetzt.Process according to one of claims 1 to 19, characterized in that the photoactivators are added before, during or after a conventional bleaching process. Verfahren gemäss einem der Ansprüche 1 bis 19, dadurch gekennzeichnet, dass man vor, während oder nach der Zugabe der Photoaktivatoren einen optischen Aufheller zusetzt.Process according to one of claims 1 to 19, characterized in that an optical brightener is added before, during or after the addition of the photoactivators adds.
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2804446A1 (en) * 2000-02-02 2001-08-03 Atofina PROCESS FOR WHITENING PASTE AND / OR RECYCLED PULP
WO2004007560A1 (en) * 2002-07-12 2004-01-22 Centre National De La Recherche Scientifique Method for obtaining modified polysaccharides by oxidation of hydroxyl groups

Families Citing this family (26)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6413924B2 (en) * 1997-01-24 2002-07-02 Case Western Reserve University Photobleaching compositions comprising mixed metallocyanines
ZA98527B (en) * 1997-01-24 1998-07-23 Procter & Gamble 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
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
US6030443A (en) * 1999-04-29 2000-02-29 Hercules Incorporated Paper coating composition with improved optical brightener carriers
US6893473B2 (en) * 2002-05-07 2005-05-17 Weyerhaeuser.Company Whitened fluff pulp
US8080511B2 (en) * 2002-09-04 2011-12-20 Basf Se Formulations comprising water-soluble granulates
FI121892B (en) * 2003-12-23 2011-05-31 Teknologian Tutkimuskeskus Vtt A process for making composite fiber products
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
US20050217811A1 (en) * 2004-03-31 2005-10-06 Weyerhaeuser Company Whitened crosslinked cellulosic fibers and related methods
US20050217809A1 (en) * 2004-03-31 2005-10-06 Weyerhaeuser Company Bleached crosslinked cellulosic fibers having high color and related methods
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
NZ561652A (en) * 2005-02-19 2010-10-29 Int Paper Co Pulp and paper having increased brightness
US7682438B2 (en) 2005-11-01 2010-03-23 International Paper Company Paper substrate having enhanced print density
KR20080095862A (en) * 2006-01-26 2008-10-29 클라리언트 파이넌스 (비브이아이)리미티드 Process for producing optically brightened 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
EP2132381A1 (en) * 2007-04-05 2009-12-16 Akzo Nobel N.V. Process for improving 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
DE102007036376A1 (en) * 2007-07-31 2009-02-05 Voith Patent Gmbh Bleached pulp
CA2710804C (en) 2007-12-26 2013-07-02 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
WO2013112511A2 (en) 2012-01-23 2013-08-01 International Paper Company Separated treatment of paper substrate with multivalent metal salts and obas
EP3334862A2 (en) 2015-08-14 2018-06-20 Basf Se Aqueous surface treatment composition for paper and board

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3927967A (en) * 1972-06-02 1975-12-23 Procter & Gamble Photoactivated bleaching process and composition
DE3041682A1 (en) * 1979-11-09 1981-05-21 Colgate-Palmolive Co., 10022 New York, N.Y. DYE MIXTURE FOR LIGHTENING AND WHITENING CELLULOSE MATERIAL AND THEIR USE FOR PRODUCING SUCTIONABLE DISPOSABLE ARTICLES WITH IMPROVED COLOR
SU1305227A1 (en) * 1985-12-03 1987-04-23 Сибирский научно-исследовательский институт целлюлозы и картона Method of bleaching pulp

Family Cites Families (37)

* 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.
GB1211812A (en) * 1968-04-26 1970-11-11 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
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
US4227880A (en) * 1977-04-18 1980-10-14 Ciba-Geigy Corporation Process for the production of dustfree granules of dyes and optical brighteners
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
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
FR2539424B1 (en) * 1983-01-13 1986-11-07 Sandoz Sa NOVEL PHTHALOCYANINS, THEIR PREPARATION AND THEIR USE AS DYES
DE3400161A1 (en) * 1983-01-13 1984-07-19 Sandoz-Patent-GmbH, 7850 Lörrach Phthalocyanine compounds, their preparation and use
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.
SE464031B (en) * 1983-09-30 1991-02-25 Melamine Chemicals Inc PREPARED PROCEDURES FOR PREPARING PASS OF WHEN USING AN S-TRIAZIN ADDITIONAL
CS249337B1 (en) * 1984-12-03 1987-03-12 Karel Vesely Power filler for plastics
DE3626777A1 (en) * 1986-08-07 1988-02-11 Basf Ag REINFORCED THERMOPLASTIC MOLDS WITH LIGHT COLORING
FI881255A (en) * 1987-03-17 1988-09-18 Procter & Gamble BLEKNINGSKOMPOSITIONER.
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

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3927967A (en) * 1972-06-02 1975-12-23 Procter & Gamble Photoactivated bleaching process and composition
DE3041682A1 (en) * 1979-11-09 1981-05-21 Colgate-Palmolive Co., 10022 New York, N.Y. DYE MIXTURE FOR LIGHTENING AND WHITENING CELLULOSE MATERIAL AND THEIR USE FOR PRODUCING SUCTIONABLE DISPOSABLE ARTICLES WITH IMPROVED COLOR
SU1305227A1 (en) * 1985-12-03 1987-04-23 Сибирский научно-исследовательский институт целлюлозы и картона Method of bleaching pulp

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Section Ch Derwent World Patents Index; Class A97, AN 71-66977S *
DATABASE WPI Section Ch Derwent World Patents Index; Class E24, AN 72-63413T *
DATABASE WPI Section Ch Week 8749, Derwent World Patents Index; Class E13, AN 87-346688 *
DATABASE WPI Section Ch Week 8951, Derwent World Patents Index; Class D16, AN 89-376261 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2804446A1 (en) * 2000-02-02 2001-08-03 Atofina PROCESS FOR WHITENING PASTE AND / OR RECYCLED PULP
WO2001057309A2 (en) * 2000-02-02 2001-08-09 Atofina Method for bleaching de-inked and/or recycled pulps
WO2001057309A3 (en) * 2000-02-02 2001-12-20 Atofina Method for bleaching de-inked and/or recycled pulps
WO2004007560A1 (en) * 2002-07-12 2004-01-22 Centre National De La Recherche Scientifique Method for obtaining modified polysaccharides by oxidation of hydroxyl groups

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ES2089777T3 (en) 1996-10-01
CA2105922A1 (en) 1994-03-15
EP0588767B1 (en) 1996-06-12
AU4731293A (en) 1994-03-24
BR9303764A (en) 1994-04-26
DE59302896D1 (en) 1996-07-18
MX9305598A (en) 1994-03-31
ATE139280T1 (en) 1996-06-15
FI933991A0 (en) 1993-09-10
JPH06207391A (en) 1994-07-26
FI933991A (en) 1994-03-15
AU661195B2 (en) 1995-07-13
US5482514A (en) 1996-01-09

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