WO2012013513A1 - Composition et procédé de blanchiment de papier - Google Patents

Composition et procédé de blanchiment de papier Download PDF

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Publication number
WO2012013513A1
WO2012013513A1 PCT/EP2011/062081 EP2011062081W WO2012013513A1 WO 2012013513 A1 WO2012013513 A1 WO 2012013513A1 EP 2011062081 W EP2011062081 W EP 2011062081W WO 2012013513 A1 WO2012013513 A1 WO 2012013513A1
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WO
WIPO (PCT)
Prior art keywords
composition
paper
component
weight
starch
Prior art date
Application number
PCT/EP2011/062081
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English (en)
Inventor
Bernhard Hunke
Andrei Tauber
Michael Kraemer
Günter Klug
Original Assignee
Blankophor Gmbh & Co. Kg
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
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First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=43446405&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=WO2012013513(A1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Blankophor Gmbh & Co. Kg filed Critical Blankophor Gmbh & Co. Kg
Priority to CA2802544A priority Critical patent/CA2802544A1/fr
Priority to BR112013002342A priority patent/BR112013002342A2/pt
Priority to US13/813,160 priority patent/US20130126117A1/en
Publication of WO2012013513A1 publication Critical patent/WO2012013513A1/fr

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
    • 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

  • composition and process for whitening paper 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.
  • Ri, R- 2 , R-3, and R4 represent, independently of each other, hydrogen, C 1 -C 4 alkyl, C 2 -C 4 alkoxyalkyl, C 2 -C 4 cyanoalkyl, or C 2 -C 4 hydroxyalkyl; or Ri and R 2 or R 3 and R4 independently of each other together with N atom form morpholine, piperidine or pyrrolidine ring; wherein at least one of Ri, R 2 , R 3 and R4 contains at least 3 carbon atoms; M represents hydrogen, or one equivalent of a cation, in particular Li, Na, K, Ca, Mg, ammonium, or ammonium which is mono-, di-, tri- or tetra- substituted by Ci - C 4 alkyl or C 2 - C 4 hydroxyalkyl;
  • 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, Ri to R4, 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 -C4 alkoxyalkyl means C 2 -C4 alkyl substituted with C 2 -C4 alkoxy.
  • n and m are integers from 1 to 2, most preferred 2.
  • Ri, R 2 , R 3 and R4 represent, independently of each other, hydrogen, Ci - C 4 alkyl, C 2 -C4 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 0-, m-, or ⁇ -position. The preferred positions depend on the number of the -SO 3 M groups.
  • Ri, R 2 , R 3 and R 4 are propyl, cyanoethyl or hydroxypropyl.
  • Ri, 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.
  • Ri and R 3 are hydroxyisopropyl
  • R 2 and R 4 are cyanoethyl.
  • At least one of Ri, R 2 , R 3 and R 4 contains at least 3 carbon atoms.
  • at least one of Ri and R 2 and at least one of R 3 and R 4 contain at least 3 carbon atoms.
  • at least one of Ri, R 2 , R 3 and R 4 in particular at least one of Ri 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.
  • C3-C4 alkoxyalkyl means C3 or C 4 alkyl substituted with C3 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.
  • the 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 mul- tivalent 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 Bl 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.
  • 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.
  • 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.
  • 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 (A D), 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 NaCl or NaHCC , or mixtures of two or more thereof.
  • sizing agents such as alkenyl ketene dimer, alkyl ketene dimer (A D), 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 prefera- bly 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 Bl, wherein according to the invention as component (a) at least one fluorescent whitening agent of for- mula (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 (Perfec- tamyl 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/m 2 of dry starch was applied on that basepaper. After the drawing the paper was directly dried on a drying cylinder at about 100°C.
  • fluorescent whitening agent used an improvement in whiteness in the presence of calcium chloride compared to the comparative FWA which does not contain that specific combination of groups.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Paper (AREA)

Abstract

L'invention porte sur une composition appropriée pour le traitement de surface de papier, la composition contenant un agent de blanchiment fluorescent spécifié avec une combinaison de groupes terminaux spécifiques, un sel d'un cation bivalent, et un excipient. La composition est utilisée pour le blanchiment de papier, en particulier dans la presse encolleuse.
PCT/EP2011/062081 2010-07-30 2011-07-14 Composition et procédé de blanchiment de papier WO2012013513A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
CA2802544A CA2802544A1 (fr) 2010-07-30 2011-07-14 Composition et procede de blanchiment de papier
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

Applications Claiming Priority (2)

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

Publications (1)

Publication Number Publication Date
WO2012013513A1 true WO2012013513A1 (fr) 2012-02-02

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ID=43446405

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2011/062081 WO2012013513A1 (fr) 2010-07-30 2011-07-14 Composition et procédé de blanchiment de papier

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)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2781648A1 (fr) 2013-03-21 2014-09-24 Clariant International Ltd. Agents de blanchiment optique pour impression à jet d'encre de haute qualité
JP2016522862A (ja) * 2013-04-29 2016-08-04 ブランコファー ゲーエムベーハー ウント コー．カーゲー セルロース系材料の表面処理用の微粉化セルロース及び蛍光増白剤の使用

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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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EP0860437A1 (fr) 1997-02-18 1998-08-26 Bayer Ag Procédé de préparation des acides 4,4'-diaministilbènes-2,2'-disulfoniques substitués
US6207258B1 (en) 1997-07-31 2001-03-27 Hercules Incorporated Composition and method for improved ink jet printing performance
WO2004005617A1 (fr) * 2002-07-05 2004-01-15 Ciba Specialty Chemicals Holding Inc. Melanges d'acides disulphoniques triazinylaminostilbene
WO2009150180A1 (fr) 2008-06-11 2009-12-17 Kemira Germany Gmbh Composition et processus de blanchiment de papier

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Publication number Priority date Publication date Assignee Title
EP0860437A1 (fr) 1997-02-18 1998-08-26 Bayer Ag Procédé de préparation des acides 4,4'-diaministilbènes-2,2'-disulfoniques substitués
US6207258B1 (en) 1997-07-31 2001-03-27 Hercules Incorporated Composition and method for improved ink jet printing performance
WO2004005617A1 (fr) * 2002-07-05 2004-01-15 Ciba Specialty Chemicals Holding Inc. Melanges d'acides disulphoniques triazinylaminostilbene
WO2009150180A1 (fr) 2008-06-11 2009-12-17 Kemira Germany Gmbh Composition et processus de blanchiment de papier
EP2135997A1 (fr) 2008-06-11 2009-12-23 Kemira Germany GmbH Composition et processus pour papier blanchi

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2781648A1 (fr) 2013-03-21 2014-09-24 Clariant International Ltd. Agents de blanchiment optique pour impression à jet d'encre de haute qualité
WO2014146798A1 (fr) 2013-03-21 2014-09-25 Archroma Ip Gmbh Agents azurants optiques pour l'impression par jet d'encre de haute qualité
CN105102712A (zh) * 2013-03-21 2015-11-25 昂高知识产权有限公司 用于高质量喷墨印刷的光学增白剂
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US9868858B2 (en) 2013-03-21 2018-01-16 Archroma Ip Gmbh Optical brightening agents for high quality ink-jet printing
JP2016522862A (ja) * 2013-04-29 2016-08-04 ブランコファー ゲーエムベーハー ウント コー．カーゲー セルロース系材料の表面処理用の微粉化セルロース及び蛍光増白剤の使用

Also Published As

Publication number Publication date
BR112013002342A2 (pt) 2016-05-24
EP2412870B1 (fr) 2013-04-17
US20130126117A1 (en) 2013-05-23
CA2802544A1 (fr) 2012-02-02
EP2412870A1 (fr) 2012-02-01

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