EP2412870B1 - Composition et processus pour papier blanchi - Google Patents

Composition et processus pour papier blanchi Download PDF

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Publication number
EP2412870B1
EP2412870B1 EP10171451.7A EP10171451A EP2412870B1 EP 2412870 B1 EP2412870 B1 EP 2412870B1 EP 10171451 A EP10171451 A EP 10171451A EP 2412870 B1 EP2412870 B1 EP 2412870B1
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EP
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Prior art keywords
composition
paper
component
weight
starch
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Revoked
Application number
EP10171451.7A
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German (de)
English (en)
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EP2412870A1 (fr
Inventor
Bernhard Hunke
Andrei Tauber
Michael Kraemer
Günter Klug
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.)
Blankophor GmbH and Co KG
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Blankophor GmbH and Co KG
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Application filed by Blankophor GmbH and Co KG filed Critical Blankophor GmbH and Co KG
Priority to EP10171451.7A priority Critical patent/EP2412870B1/fr
Priority to BR112013002342A priority patent/BR112013002342A2/pt
Priority to US13/813,160 priority patent/US20130126117A1/en
Priority to PCT/EP2011/062081 priority patent/WO2012013513A1/fr
Priority to CA2802544A priority patent/CA2802544A1/fr
Publication of EP2412870A1 publication Critical patent/EP2412870A1/fr
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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
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/03—Non-macromolecular organic compounds
    • D21H17/05—Non-macromolecular organic compounds containing elements other than carbon and hydrogen only
    • D21H17/07—Nitrogen-containing compounds
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/03—Non-macromolecular organic compounds
    • D21H17/05—Non-macromolecular organic compounds containing elements other than carbon and hydrogen only
    • D21H17/09—Sulfur-containing compounds
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/33—Synthetic macromolecular compounds
    • D21H17/46—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/47—Condensation polymers of aldehydes or ketones
    • D21H17/49—Condensation polymers of aldehydes or ketones with compounds containing hydrogen bound to nitrogen
    • D21H17/51—Triazines, e.g. melamine

Definitions

  • the present invention relates to a composition suitable for surface treatment of paper, in particular a size press liquor, and a process for whitening paper using said composition.
  • a sizing step is usually carried out for achieving good writing and printing properties and strength.
  • Such a sizing step can take place, on the one hand, before the sheet formation in the paper pulp (internal sizing) and, on the other hand, after the sheet formation in the size press.
  • a combination of both processes is also possible.
  • whitening of the pulp or of the paper sheet is usually also carried out by means of a fluorescent whitening agent (FWA).
  • FWA fluorescent whitening agent
  • the size and fluorescent whitening agent are added separately to the paper pulp in the case of pulp application, whereas the fluorescent whitening agent is incorporated into the size press liquor and applied together with it to the paper sheet in the case of surface sizing.
  • EP 2 135 997 Al disclose aqueous compositions containing specific bis-triazinylamino-stilbene compounds containing alkylsulfonic acid groups, a salt of a bivalent cation, and a carrier.
  • the present invention relates to a composition suitable for surface treatment of paper, wherein the composition contains
  • the invention further relates to a process for whitening paper, wherein a cellulose sheet is brought into contact with the above defined composition, preferably in the size press.
  • a process for whitening paper wherein a cellulose sheet is brought into contact with the above defined composition, preferably in the size press.
  • Fig. 1 is a diagram showing the influence of calcium chloride on the performance of different fluorescent whitening agents according to Example 1.
  • the composition suitable for surface treatment of paper is a size press liquor
  • the process is a process for whitening paper in the size press, wherein a cellulose sheet is brought into contact with the size press liquor.
  • size press is understood as meaning a surface application unit, preferably of the paper machine, in which the cellulose sheet formed is brought into contact with a size press liquor, and in which the proportion of the liquor which is to be taken up by the sheet (liquor absorption) can preferably be adjusted by means of the roll pressure.
  • the composition contains at least one bis-triazinylamino-stilbene compound of the above defined formula (I), wherein n, m, R 1 to R 4 , and M are as defined above.
  • the alkyl group can be linear or branched, and the possible substituents of the alkyl group, which are alkoxy, hydroxyl and/or cyano groups, can be attached at any position of the alkyl chain.
  • C 2 -C 4 alkoxyalkyl means C 2 -C 4 alkyl substituted with C 2 -C 4 alkoxy.
  • n and m are integers from 1 to 2, most preferred 2.
  • R 1 , R 2 , R 3 and R 4 represent, independently of each other, hydrogen, C 1 - C 4 alkyl, C 2 -C 4 cyanoalkyl, or C 2 -C 4 hydroxyalkyl, in particular propyl, cyanoethyl, or hydroxypropyl.
  • the -SO 3 M groups at the terminal aromatic rings can be in o -, m-, or p -position. The preferred positions depend on the number of the -SO 3 M groups. If n or m is 1, p-position is preferred. If n or m is 2, the 2,5-position is preferred.
  • R 1 , R 2 , R 3 and R 4 is propyl, cyanoethyl or hydroxypropyl.
  • R 1 , R 2 , R 3 and R 4 are propyl or hydroxypropyl, in particular all are either propyl or hydroxypropyl, wherein preferably n and m are 2.
  • the hydroxypropyl group is a hydroxyisopropyl group.
  • n and m are 2, and the two - SO 3 M groups are in 2,5-position.
  • n and m are 2, R 1 , and R 3 are hydroxyisopropyl, and R 2 and R 4 are cyanoethyl.
  • At least one of R 1 , R 2 , R 3 and R 4 contains at least 3 carbon atoms.
  • at least one of R 1 and R 2 and at least one of R 3 and R 4 contain at least 3 carbon atoms.
  • at least one of R 1 , R 2 , R 3 and R 4 in particular at least one of R 1 and R 2 and at least one of R 3 and R 4 , represent(s) C 3 - C 4 alkyl, C 3 - C 4 alkoxyalkyl, C 3 -C 4 cyanoalkyl, or C 3 - C 4 hydroxyalkyl.
  • C 3 -C 4 alkoxyalkyl means C 3 or C 4 alkyl substituted with C 3 or C 4 alkoxy.
  • M are hydrogen, Na, K, Ca, Mg, in particular M is Na or K, most preferred is Na.
  • the fluorescent whitening agents of formula (I) can be produced by known procedures, and are used as free acids or as salts thereof, preferably alkali metal salts.
  • the compounds are prepared by reacting cyanuric chloride with 4,4'-diaminostilbene-2,2'-disulfonic acid or a salt thereof, and an appropriate aniline derivative containing a phenyl ring substituted with -SO 3 M group(s), and substituted aliphatic amines or heterocyclic compounds.
  • EP 0 860 437 Al describes the preparation of such compounds.
  • composition of the invention can contain more than one, preferably two or three, most preferred three, of the fluorescent whitening agents of formula (I).
  • Component (a) of the composition can contain, in addition to the at least one fluorescent whitening agent of formula (I), one or more known bis-triazinylamino-stilbene or distyryl-biphenyl based fluorescent whitening agents.
  • the salt of component (b) of the composition of the invention comprises bivalent cations, preferably cations of an earth alkaline metal, in particular calcium or magnesium.
  • the counterions of the bivalent cations are mono- or multivalent anions, in particular halide, sulphate, hydrosulphate, phosphate, hydro-phosphate, dihydrophosphate, carbonate, hydrocarbonate, nitrate, acetate, or a mixture thereof, preferably chloride or sulphate, most preferably chloride.
  • the salts disclosed in US 6,207,258 B1 are also suitable.
  • a preferred salt is calcium chloride, magnesium chloride, magnesium sulphate, or a mixture thereof; more preferred is calcium chloride, magnesium chloride, or a mixture thereof; most preferred is calcium chloride.
  • the carrier of component (c) is any compound known in the art to be suitable as a carrier, in particular carriers suitable for size press liquors.
  • Preferred carriers are carboxymethylcellulose (CMC), polyvinyl alcohol (PVA), starch or mixtures thereof, with starch being particularly preferred.
  • Suitable carrier substances are, for example, hydrophilic polymers having the ability to form hydrogen bridge bonds.
  • Preferred carrier substances are starch, polyvinyl alcohols, carboxymethyl-celluloses and polyethylene glycols having a number average molecular weight of from 200 to 8000 g/mol, as well as any desired mixtures of these substances, it being possible for these polymers optionally to be modified.
  • Preferred polyvinyl alcohols are those having a degree of hydrolysis >85%, preferred carboxymethyl-celluloses are those having a degree of substitution DS of >0.5.
  • Polyethylene glycols having a number average molecular weight Mn of from 200 to 8000 g/mol are particularly preferred.
  • Suitable starches are based e.g., but not exclusively, on potato starch, rice starch, wheat starch, maize starch or tapioca starch. In particular, starches whose molecular weights have already been reduced by partial degradation and/or which have been obtained by derivatization are preferably used instead of natural starches. Furthermore, starches for which both modification steps have been combined, i.e. which have been partially degraded and additionally derivatized, are suitable. Typical methods for starch degradation are, for example, enzymatic, oxidative, thermal or hydrolytic treatment. Examples of suitable starch derivatives are hydroxyethyl starch or cationic starch.
  • composition of the invention contains as component (d) water and, optionally, can contain sizing agents, such as alkenyl ketene dimer, alkyl ketene dimer (AKD), alkenyl succinic anhydride (ASA), rosin size, styrene maleic anhydride copolymers, styrene acrylate, styrene acrylic acid copolymers, polyurethane or ethylene acrylic acid copolymers, or other common paper chemicals, such as styryl-acrylate copolymers, latex, pigments, defoamers, or salts, such as NaClor NaHCO 3 , or mixtures of two or more thereof.
  • sizing agents such as alkenyl ketene dimer, alkyl ketene dimer (AKD), alkenyl succinic anhydride (ASA), rosin size, styrene maleic anhydride copolymers, styrene acrylate,
  • the composition of the invention contains preferably component (a) in an amount of 0.02 to 3, more preferably 0.05 to 2, most preferably 0.1 to 1, weight-% based on 100 weight-% of the composition. If fluorescent whitening agents other than those of formula (I) are used, their amount is 5 to 95 weight-% based on 100 weight-% of component (a).
  • Component (b) is preferably contained in an amount of 0.2 to 8, in particular 0.5 to 6, most preferably 1 to 5, weight-% based on 100 weight-% of the composition.
  • Component (c) is preferably contained in an amount of 3 to 20, in particular 5 to 15, most preferably 6 to 12, weight-% based on 100 weight-% of the composition.
  • the composition of the invention contains preferably water in an amount of 75 to 96.78, in particular 79 to 94.45, most preferably 82.5 to 92.9, weight-% based on 100 weight-% of the composition.
  • the composition contains a sizing agent, preferably in an amount of 0 to 5, in particular 0 to 4, most preferably 0 to 3, in each case weight-% based on 100 weight-% of the composition.
  • auxiliaries such as, for example, dispersants, thickeners, antifreezes, preservatives, complexing agents, etc., or organic byproducts from the fluorescent whitening agent synthesis which were not completely removed in the working-up, may be contained in the composition of the invention.
  • compositions are also described in US 6,207,258 B1 , wherein according to the invention as component (a) at least one fluorescent whitening agent of formula (I) is used.
  • the production of the composition is effected by known methods and preferably effected by combining an aqueous solution of the fluorescent whitening agent used as component (a), which preferably has a suitable pH value, with the other components, such as carrier substances, sizing agents, binders, pigments, salts or standardizing agents.
  • component (a) which preferably has a suitable pH value
  • component (c) an aqueous preparation of carrier component (c) is prepared, to which preparation an aqueous preparation of salt component (b) is added, followed by the addition of an aqueous preparation of the fluorescent whitening agent component (a), preferably adjusted in pH value, and the other components.
  • composition of the invention can be used for whitening paper, in particular for surface treatment of paper, e.g. in a size press.
  • the process of the invention for whitening paper is carried out according to known processes, preferably using a size press, and is subject to no restrictions.
  • the paper used is not critical and may be any cellulose sheet.
  • Paper obtained by the process of the invention exhibits, in addition to improved printing performance, improved whiteness, and is in particular suitable for inkjet printing applications.
  • the whiteness of the papers produced can be characterized by the CIE whiteness.
  • Different fluorescent whitening agents can be compared to each other with respect to the saturation behavior when determined according to CIE whiteness. In other words, if a larger amount of fluorescent whitening agent is used and no further increase in whiteness is found, there is a saturation behavior and there may even be adverse effects on the whiteness when using higher amounts.
  • the effect of saturation is also referred to as greening.
  • the greening limit i.e. the point at which increasing amounts of fluorescent whitening agent used results in virtually no further increase in whiteness, can be derived, for example, from the a*-b* diagram, where a* and b* are the color coordinates in the CIE-L*a*b system.
  • a 15% starch solution of neutral oxidatively degraded potato starch (Perfectamyl 4692) and a 50% calcium chloride solution were prepared.
  • the fluorescent whitening agent was weighed in a glass, and 13.33 g of 15% starch solution was added. Then, 50% calcium chloride solution was weighed in, and the solution was filled up with water to 20 g, so that the tests were carried out in a 10% starch solution. After stirring for a short time the solution was applied on one side of the basepaper by a semiautomatic lab coater with a Rakel (No. 2) which should simulate a film press application. 1.7 g/m2 of dry starch was applied on that basepaper. After the drawing the paper was directly dried on a drying cylinder at about 100°C. After climatization over night the prepared side of the papers were measured with a Datacolor spectrometer (IS02469) by determining CIE, L*, a* and b*, the light source used based on ISO2469 standard.
  • fluorescent whitening agent per 100g starch preparation were as indicated in Table 1 below.
  • the amount of calcium chloride was 2g for each fluorescent whitening agent.
  • the following fluorescent whitening agents were used:
  • the results of Table 1 are also shown in Fig. 1 .

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  • Chemical Kinetics & Catalysis (AREA)
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Claims (15)

  1. Composition convenant au traitement de surface du papier, la composition contenant
    (a) au moins un agent de blanchiment fluorescent de formule (I)
    Figure imgb0007
     dans laquelle n et m représentent chacun indépendamment de l'autre un entier valant 1, 2 ou 3 ;
    R1, R2, R3 et R4 représentent chacun indépendamment des autres un atome d'hydrogène, un groupe alkyle en C1-C4, alcoxyalkyle en C2-C4, cyanoalkyle en C2-C4 ou hydroxyalkyle en C2-C4 ; ou R1 et R2 ou R3 et R4, indépendamment les uns des autres, forment ensemble avec l'atome d'azote un noyau morpholine, pipéridine ou pyrrolidine ;
    où au moins l'un des radicaux R1, R2, R3 et R4 contient au moins 3 atomes de carbone ;
    M représente un atome d'hydrogène ou un équivalent d'un cation, en particulier Li, Na, K, Ca, Mg, ammonium, ou ammonium qui est mono-, di-, tri- ou tétra-substitué par un ou des substituants alkyle en C1-C4 ou hydroxyalkyle en C2-C4 ;
    (b) au moins un sel d'un cation bivalent ;
    (c) au moins un support ; et
    (d) de l'eau.
  2. Composition selon la revendication 1, dans laquelle n et m valent chacun 2, et les groupes -SO3M sont en position 2,5.
  3. Composition selon la revendication 1 ou 2, dans laquelle R1, R2, R3 et R4 représentent chacun indépendamment des autres un groupe propyle, cyanoéthyle ou hydroxypropyle.
  4. Composition selon l'une quelconque des revendications 1 à 3, dans laquelle n et m valent 2, et R1, R2, R3 et R4 sont des groupes propyle.
  5. Composition selon l'une quelconque des revendications 1 à 3, dans laquelle n et m valent 2, et R1, R2, R3 et R4 sont des groupes hydroxypropyle, en particulier hydroxyisopropyle.
  6. Composition selon l'une quelconque des revendications 1 à 3, dans laquelle n et m valent 2, R1 et R3 sont des groupes hydroxypropyle, en particulier hydroxyisopropyle, et R2 et R4 sont des groupes cyanoéthyle.
  7. Composition selon l'une quelconque des revendications précédentes, dans laquelle M est Na ou K.
  8. Composition selon l'une quelconque des revendications précédentes, dans laquelle le sel du composant (b) est le chlorure de calcium.
  9. Composition selon l'une quelconque des revendications précédentes, dans laquelle le support du composant (c) est choisi parmi la carboxyméthylcellulose, le poly(alcool vinylique), l'amidon et les mélanges de ceux-ci.
  10. Composition selon la revendication 9, dans laquelle le support est l'amidon.
  11. Composition selon l'une quelconque des revendications précédentes, la composition contenant le composant (a) en une quantité de 0,02 à 3 % en poids, le composant (b) en une quantité de 0,2 à 8 % en poids et le composant (c) en une quantité de 3 à 20 % en poids, chaque quantité étant rapportée à 100 % en poids de la composition.
  12. Composition selon l'une quelconque des revendications précédentes, la composition étant une liqueur de presse d'encollage qui en option contient un agent d'encollage.
  13. Procédé de blanchiment du papier, dans lequel une feuille de cellulose est mise en contact avec une composition telle que définie dans l'une quelconque des revendications précédentes.
  14. Procédé selon la revendication 13, dans lequel la mise en contact est effectuée dans une presse d'encollage.
  15. Papier pouvant être obtenu par le procédé selon la revendication 13 ou 14.
EP10171451.7A 2010-07-30 2010-07-30 Composition et processus pour papier blanchi Revoked EP2412870B1 (fr)

Priority Applications (5)

Application Number Priority Date Filing Date Title
EP10171451.7A EP2412870B1 (fr) 2010-07-30 2010-07-30 Composition et processus pour papier blanchi
BR112013002342A BR112013002342A2 (pt) 2010-07-30 2011-07-14 composição e processo para branqueamento de papel
US13/813,160 US20130126117A1 (en) 2010-07-30 2011-07-14 Composition and process for whitening paper
PCT/EP2011/062081 WO2012013513A1 (fr) 2010-07-30 2011-07-14 Composition et procédé de blanchiment de papier
CA2802544A CA2802544A1 (fr) 2010-07-30 2011-07-14 Composition et procede de blanchiment de papier

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP10171451.7A EP2412870B1 (fr) 2010-07-30 2010-07-30 Composition et processus pour papier blanchi

Publications (2)

Publication Number Publication Date
EP2412870A1 EP2412870A1 (fr) 2012-02-01
EP2412870B1 true EP2412870B1 (fr) 2013-04-17

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EP10171451.7A Revoked EP2412870B1 (fr) 2010-07-30 2010-07-30 Composition et processus pour papier blanchi

Country Status (5)

Country Link
US (1) US20130126117A1 (fr)
EP (1) EP2412870B1 (fr)
BR (1) BR112013002342A2 (fr)
CA (1) CA2802544A1 (fr)
WO (1) WO2012013513A1 (fr)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ES2566109T3 (es) * 2013-03-21 2016-04-11 Archroma Ip Gmbh Agentes abrillantadores ópticos para impresión por chorro de tinta de alta calidad
ES2583481T3 (es) * 2013-04-29 2016-09-21 Blankophor Gmbh & Co. Kg Uso de celulosa micronizada y agente de blanqueamiento fluorescente para el tratamiento de superficie de materiales celulósicos
CN104312197B (zh) * 2014-09-05 2016-09-21 旭泰（太仓）精细化工有限公司 一种六磺酸类液体荧光增白剂及其制备方法与应用

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GB8330404D0 (en) * 1983-11-15 1983-12-21 Dow Chemical Europ Activation of fluorescent whitening agents
DE3502038A1 (de) * 1985-01-23 1986-07-24 Sandoz-Patent-GmbH, 7850 Lörrach Waessrige aufhellerpraeparate und deren verwendung im papierstrich
DE19706238B4 (de) * 1997-02-18 2005-09-01 Bayer Chemicals Ag Verfahren zur Herstellung von substituierten 4,4'-Diaminostilben-2,2'-disulfonsäuren
MY125712A (en) 1997-07-31 2006-08-30 Hercules Inc Composition and method for improved ink jet printing performance
EP1054873B1 (fr) * 1998-02-20 2004-09-22 Ciba SC Holding AG Procede de preparation de composes de stilbene
US6165973A (en) * 1999-02-05 2000-12-26 Ciba Specialty Chemicals Corporation Fluorescent whitening agent, its preparation and use
DE10149313A1 (de) * 2001-10-05 2003-04-17 Bayer Ag Verwendung wässriger Aufhellerpräparationen zum Aufhellen von natürlichen und synthetischen Materialien
DE10217677A1 (de) * 2002-04-19 2003-11-06 Bayer Ag Verwendung von Aufhellern zur Herstellung von Streichmassen
US7270771B2 (en) * 2002-07-05 2007-09-18 Ciba Specialty Chemicals Corporation Triazinylaminostilbene disulphonic acid mixtures
DE602005016291D1 (de) * 2004-10-27 2009-10-08 Basf Se Zusammensetzungen optischer aufheller
US7682438B2 (en) * 2005-11-01 2010-03-23 International Paper Company Paper substrate having enhanced print density
EP2135997B1 (fr) 2008-06-11 2011-01-05 Kemira Germany GmbH Composition et processus pour papier blanchi
US20100129553A1 (en) * 2008-11-27 2010-05-27 International Paper Company Optical Brightening Compositions For High Quality Inkjet Printing

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Publication number Publication date
BR112013002342A2 (pt) 2016-05-24
CA2802544A1 (fr) 2012-02-02
US20130126117A1 (en) 2013-05-23
WO2012013513A1 (fr) 2012-02-02
EP2412870A1 (fr) 2012-02-01

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