EP1355004B1 - Utilisation d'agents de blanchiment optiques pour la fabrication des melanges d'enduisage - Google Patents

Utilisation d'agents de blanchiment optiques pour la fabrication des melanges d'enduisage Download PDF

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Publication number
EP1355004B1
EP1355004B1 EP03008210A EP03008210A EP1355004B1 EP 1355004 B1 EP1355004 B1 EP 1355004B1 EP 03008210 A EP03008210 A EP 03008210A EP 03008210 A EP03008210 A EP 03008210A EP 1355004 B1 EP1355004 B1 EP 1355004B1
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EP
European Patent Office
Prior art keywords
alkyl
brightener
formula
coating
cobinder
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Revoked
Application number
EP03008210A
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German (de)
English (en)
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EP1355004A1 (fr
Inventor
Karl-Heinz Drenker
Heinz Dr. Giesecke
Bernhard Hunke
Bernd Dr. Hauschel
Reiner Gottschalk
Claudia Dr. Hundertmark
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Blankophor GmbH and Co KG
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Lanxess Deutschland GmbH
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Application filed by Lanxess Deutschland GmbH filed Critical Lanxess Deutschland GmbH
Priority to EP06015669A priority Critical patent/EP1754829A1/fr
Publication of EP1355004A1 publication Critical patent/EP1355004A1/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

Definitions

  • the invention relates to the use of special brighteners for the production of coating slips, coating slips per se and their use for producing brightened papers.
  • Optical brighteners are mainly used for whitening paper, textiles or as an additive to detergents.
  • the whitening of uncoated papers or base paper can be done by mass application and / or surface application of optical brighteners, which are usually present in dissolved form.
  • optical brighteners In the production of coated papers, the addition of optical brightener to the coating color is common, so that the optical brightener in the finished coated paper is also in the pigment layer applied to the paper.
  • Coated papers are particularly suitable for making high quality prints. In addition to good printability properties, their quality is therefore assessed mainly for optical properties such as gloss and whiteness. There is a continuing trend towards coated papers with high whiteness and therefore the desire for most effective optical brighteners as coating components.
  • the other hexasulfoflavonate brightener shown in formula (I) is particularly suitable for producing coated, off-white papers.
  • the exact amounts at which the greening occurs in the case of tetra- or hexasulfoflavone brighteners depend on the composition of the respective coating color, inter alia on its carrier content.
  • the coated paper When recycling coated papers, e.g. in the reuse of coated broke in the paper mill, the coated paper is re-opened, with the non-fiber-fixed brightener from the line first dissolving and partially drawing on paper fibers.
  • the increased solubility of the hexasulfoflavone brightener is disadvantageous because non-fiber-fixed brightener in the recirculating water of the papermaking machine acts as an anionic impurity and the effect of cationic paper chemicals such as e.g. Retention or engine sizing agents reduced, so that an excess consumption of these paper chemicals results.
  • the main focus is on the whitening of coating colors based on synthetic cobinders.
  • Natural cobinders in particular starch, are poorly suited for topcoats or single strokes due to their swelling behavior on contact with aqueous liquids. The swelling reduces the quality of the printed image when printing the coated paper.
  • Starch is therefore preferably used as a co-primer in precursors for multi-coated papers.
  • synthetic co-weighters are preferred for single-coated papers or toppings.
  • Whiteness is generally higher for single-stroke or top-coat than for primer.
  • EP-A 192 600 describes that certain polyethylene glycol-containing brightener formulations are particularly suitable as coating color additives. However, only latex binders are used explicitly in combination with natural coasters for coating compounds.
  • the synthetic cobinder is not a latex binder.
  • GB-A 896 533 describes the preparation of this brightener and the use in mass and size press use for whitening paper.
  • the brighteners used according to the invention can be used as an aqueous solution which contains substantially dissolved brightener salts, water and optionally adjusters. Furthermore, they can be used as aqueous carrier-containing formulations containing substantially dissolved brightener salts, water and carrier substances.
  • the brightener according to the invention in solid form, for example as a powder or granules. It is advantageous if the brighteners go into solution before applying the coating color. The dissolving process of the brightener can be combined with the application of the coating color when using powder or granules.
  • the preparation of the brighteners used in the invention is carried out by known methods, such as e.g. in GB-A 896 533 or in EP-A 860 437 are described, for example, from about 2 moles of cyanuric chloride, about 1 mole of 4,4'-diaminostilbene-2,2'-disulfonic acid or a corresponding salt, approx 2 mol of aniline, sulphanilic acid or a corresponding salt and about 2 to 2.5 mol of the amines corresponding to the substituent Y.
  • the crude solution of the corresponding brightener may be e.g. desalted and concentrated by suitable membrane separation techniques, e.g. in EP-A-992,547.
  • Preferred membrane separation processes are ultrafiltration, diffusion dialysis and electrodialysis.
  • the resulting solid may then be e.g. isolated on a filter press and optionally further purified by washing.
  • the brightener can also be prepared from solution, e.g. be isolated by spray drying in the form of a powder, wherein optionally before drying further additives such as dispersants, dedusting agents, etc. are added.
  • Aqueous preparations can be prepared from crude solutions, on concentrated and desalted solutions, or from aqueous presscakes. For particularly good whiteness build-up, it is advantageous to incorporate so-called carrier substances into the aqueous whitener preparations.
  • Usual adjusting means are e.g. Urea, diethylene glycol, triethylene glycol, propanediol, glycerol, ⁇ -caprolactam, ethanolamine, diethanolamine and triethanolamine. Preference is given to each adjusting agent-free preparations.
  • Suitable carrier substances are generally hydrophilic polymers capable of forming hydrogen bonds.
  • Preferred carrier substances are polyvinyl alcohols, carboxymethylcelluloses 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, these polymers optionally being able to be modified.
  • Preferred polyvinyl alcohols are those with a degree of hydrolysis> 85%
  • preferred carboxymethylcelluloses are those with a degree of substitution DS of> 0.5.
  • Particularly preferred are polyethylene glycols having a number average molecular weight Mn of 200 to 8000 g / mol.
  • formulations of this kind can generally be used to achieve more favorable whiteness build-up curves than with carrier-free brightener preparations.
  • carrier-less as well as carrier-containing preparations in smaller amounts, usually in amounts below 5 wt .-%, other adjuvants such. Dispersants, thickeners, antifreeze, preservatives, complexing agents, etc., or organic by-products from the brightener synthesis, which were not completely removed in the work-up, be included.
  • carrier-containing preparations can also be added adjusting agents to increase the solubility and storage stability.
  • the preparation of the carrier-free aqueous brightener preparations takes place i.A. by setting a brightener solution (crude or membrane-filtered) with a base to a neutral to slightly alkaline pH, optionally adding and dissolving one or more adjusting agents and optionally diluting with water to the desired final concentration. If the brightener is used in the form of a water-moist press cake, a certain amount of press cake is completely dissolved in water with addition of base, stirring and optionally elevated temperatures and optionally adjusted to the desired concentration by adding further water.
  • Preferred bases for this are alkali hydroxides, for dilution demineralized water is preferred.
  • the adjusted pH is in the range of 7 to 11, preferably from 8 to 10.
  • For dissolving temperatures of 25 to 80 ° C are common.
  • the preparation of the carrier-containing preparations is generally carried out in an analogous manner, wherein additionally the carrier substance is added at any point in the production process. If the carrier substance is added in solid form, it is generally completely dissolved with stirring and optionally elevated temperatures. so that a homogeneous liquid preparation is formed.
  • the usual dissolution temperature is in the range of 25 to 100 ° C.
  • Concentrated, aqueous brightener preparations are usually characterized by the so-called E1 / 1 value.
  • E1 / 1 value the extinction of a highly diluted solution of the preparation is determined by the usual and known to the expert methods of UV / Vis spectroscopy in a 1 cm cuvette at a certain wavelength. This wavelength corresponds to the long-wavelength absorption maximum of the respective brightener molecule. For flavonate brighteners it is about 350 nm.
  • the E1 / 1 value then corresponds to the fictitious extinction value extrapolated to a 1% solution.
  • the E1 / 1 values of the brightener preparations used according to the invention are preferably between 50 and 180, more preferably between 70 and 140.
  • the coating compositions to be brightened according to the invention comprise, for example, latices based on styrene-butadiene, styrene-acrylate or vinyl acetate as latex binder. These polymers may optionally be modified by further monomers such as acrylonitrile, acrylamide, ⁇ , ⁇ -unsaturated carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid or maleic acid, acrylates, vinyl esters, ethylene, vinyl chloride, vinylidene chloride, etc. In general, however, all cyanogenic latex binders which are used for the production of paper coating slips come into question.
  • Preferred latex binders are those based on styrene-butadiene.
  • Preferred synthetic co-binders are polyvinyl alcohols having a degree of hydrolysis of> 85%, and in particular a Brookfield viscosity of 2-80 mPas (measured on a 4% aqueous solution at 20 ° C.), carboxymethylcelluloses, with a degree of substitution of> 0.5, and in particular a Brookfield viscosity of 5-5000 mPas (measured on a 2% aqueous solution at 25 ° C) and mixtures of these two substances.
  • the coating compositions to be lightened according to the invention preferably also contain white pigments.
  • white pigments usually calcium carbonate in natural or precipitated form, kaolin, talc, titanium dioxide, satin white, aluminum hydroxide and barium sulfate are used, often in the form of mixtures.
  • dispersing agents are to be mentioned.
  • polyacrylates polyphosphates or Na citrate.
  • polyaspartic acid is also suitable.
  • Other possible additives are crosslinkers. Examples of these are urea-formaldehyde resins, melamine-formaldehyde resins, glyoxal or ammonium zirconium carbonate.
  • wet strength agents based on polyamidoamine-epichlorohydrin resins, glyoxalated polyacrylamides or hydrophilicized polyisocyanates, such as, for example, are also suitable.
  • EP-A-825 181 as crosslinkers in question.
  • the coating compositions to be brightened according to the invention preferably contain the latex binder in an amount of from 3 to 20% by weight and the synthetic cobinder in an amount of 0.1 to 3 wt .-%, each based on the white pigment of the coating.
  • the amount of latex binder (calculated as dry substance) is preferably 3 to 20% by weight, in particular 5 to 15% by weight, regardless of the amount of cobinder 0.1 to 3% by weight, in particular 0.5 to 1.5 wt .-% and also independently of the amount of brightener of the formula (II) 0.025 to 1 wt .-%, each based on the amount of white pigment.
  • the coating composition preferably additionally contains at least one dispersing agent, in particular in an amount of from 0.05 to 1% by weight, based on the white pigment in the coating composition.
  • a dispersant is preferably polyacrylic acid or corresponding salts in question.
  • the water content of the coating composition is preferably from 30 to 50% by weight, based on the total amount of coating composition.
  • the invention further relates to the use of the coating compositions according to the invention for the production of coated papers.
  • the coating compositions can preferably be applied to the paper simply or multiply by means of all suitable application methods, such as, for example In various embodiments, air knife, blade, roll coater, film press, cast coating, etc.
  • the immobilization and drying of the coating color usually takes place first by contactless hot air and / or IR drying, which is usually followed by a contact drying by heated rollers , Thereafter, a calendering is usually carried out for densification, smoothing or gloss influence of the coated paper, for example with a calender.
  • uncoated base papers or base papers cardboard and cardboard are in principle made of bleached or unbleached, wood-containing or wood-free, waste paper-containing and deinked fibers produced papers, cardboard and cardboard. These may also contain mineral fillers such as natural or precipitated chalk, kaolin, talc or annaline.
  • the uncoated papers, boards and cardboards may be sized in the mass and / or surface which, among other things, affect the penetration and adhesion of the coating color.
  • Conventional engine sizing agents are alkyl ketene dimerene (AKD), alkenylsuccinic anhydride (ASA) or a combination of rosin size and alum, customary surface sizing agents the above-mentioned polymer solutions based on styrene-acrylic acid, styrene-maleic anhydride or oligourethanes, and polymer dispersions based on acrylonitrile acrylate or Styrene acrylate.
  • the base papers may be lightened in bulk and / or surface using, for example, flavonate brighteners.
  • a membrane-filtered aqueous concentrate having an E1 / 1 value of 161 and a pH of 8.5, which contains the brightener of the formula (IIa) as sodium salt are stirred at room temperature with 31 g of polyethylene glycol 1550 (average molecular weight Mn 1550 g / mol).
  • polyethylene glycol 1550 waxy at room temperature is heated to about 60 ° C. before the addition, while being melted, and added as hot liquid at about 60 ° C. It continues to use 3.5 g of demineralized water and the pH is adjusted to 9.0 with about 10% sodium hydroxide solution. The preparation is then heated with stirring to 50 ° C and stirred for 30 min at this temperature.
  • a carrier-containing whitener preparation having an E1 / 1 value of 105 in the form of a yellow-brownish, fluorescent, homogeneous liquid is obtained. This corresponds to a content of (IIa) of about 19 wt .-%.
  • the brightener preparation has an E 1/1 value of 125. This corresponds to a content of the brightener of about 21 wt .-%.
  • the used CMC Finnfix 10 has an active content of 98%.
  • the Brookfield viscosity of a 4% solution measured at 25 ° C is 50-200 mPas.
  • the amount of water and soda lye is chosen so that a solids content of 57%. and a pH of 9.0 results.
  • the coating composition is divided into 10 parts and one part each with 0.4%, 0.8%, 1.2%, 1.6% and 1.8% of the brightener preparation from Example 1 and then stirred for 10 min. The added amounts are based on the solids content of the coating. For comparison, each part of the coating composition is mixed in the same manner with equal amounts of the brightener preparation from Example 4.
  • the resulting, lightened coating slips are applied to wood-free base papers having a basis weight of about 80 g / m 2 using a laboratory doctor blade (Erichsen, K-Control Coater, model K 202).
  • the coated papers are dried for 1 min at 95 ° C on a drying cylinder and then stored for 3 h at 23 ° C and 50% relative humidity.
  • the measurement of the parameters L *, a *, b * and the determination of the CIE whiteness is then carried out with a whiteness measuring device (Datacolor Elrepho 2000).
  • the procedure is as in Application Example 1, but uses a polyvinyl alcohol-containing coating composition of other composition and uses the carrier-containing Brightener preparations from Examples 2 and 3 with respective aggregate amounts of 0.8%, 1.6%, 2.4% and 3.2%, based on the solids content of the coating.
  • Polyviol LL 603 (Wacker chemistry) was used. It is a 20% aqueous solution of a polyvinyl alcohol with degree of hydrolysis 88%, which has a Brookfield viscosity of about 900 mPas at 20 ° C.
  • the coating is divided into 8 parts and one part each with the above amounts of brightener preparations from Examples 2 and 3 added.
  • the whitener preparation according to the invention from Example 2 in the polyvinyl alcohol-containing coating color shows a significantly improved build-up behavior with respect to the CIE whiteness, compared to the preparation of Example 3 which is not according to the invention.
  • the procedure is as in Application Example 1, but uses a polyvinyl alcohol-containing coating composition of other composition and uses the brightener preparations of Example 1 in concentrations of 1%, 4.5% and 8%, based on the pigment content in the coating.
  • Polyvinyl alcohol used was Polyviol® LL 603 (Wacker Chemie).
  • composition of the coating :
  • the water content is chosen so that a solids content of 50% results.
  • the coating composition is mixed in 3 parts and one part each with the above amounts of brightener preparation of Example 1.
  • the coating had the following composition: 100 Parts kaolin 24 Parts Acronal® S 320 (BASF AG) 8th Parts of starch, calculated as dry substance 0.3 Parts Polysalt® S (BASF AG) 0.1 Part of NaOH water
  • the water content is chosen so that a solids content of 50% results.

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Claims (9)

  1. Utilisation d'agents de blanchiment optiques de formule (II)
    Figure imgb0023
     dans laquelle
    Y est un radical de formule
    Figure imgb0024
     ou
    Figure imgb0025
     et
    R1 désigne un groupe alkyle en C1 à C6 et
    R2 est un atome d'hydrogène ou
    R1 est un atome d'hydrogène et
    R2 est un groupe alkyle en C1 à C6, et indépendamment de ceux-ci,
    R3 est un atome d'hydrogène, un groupe méthyle, éthyle, CH2CH2OH ou CH2CH2OCH3,
    R1' est un groupe alkyle en C1 à C6 et
    R2' est un atome d'hydrogène, ou
    R1' est un atome d'hydrogène et
    R2' est un groupe alkyle en C1 à C6 et indépendamment de ceux-ci,
    R3' un atome d'hydrogène, un groupe méthyle, éthyle, CH2CH2OH ou CH2CH2OCH3, et
    R4 est un groupe alkyle en C1 à C4,
    Z désigne un groupe SO3M, les groupes sulfo pouvant être en position o-, m- ou p-, et
    M est un atome d'hydrogène ou un équivalent d'un cation, choisi dans le groupe comprenant Li, Na, K, Ca, Mg, ammonium ou ammonium mono-, di-, tri- ou tétra-substitué par le radical alkyle en C1 à C4 ou hydroxyalkyle en C2 à C4,
    pour blanchir des compositions d'enduction aqueuses contenant au moins un liant à base de latex et au moins un co-liant parmi divers liants synthétiques, choisi dans le groupe comprenant les alcools de polyvinyle, les carboxyméthyl-celluloses ainsi que des mélanges de ces substances individuelles.
  2. Utilisation selon la revendication 1, caractérisée en ce que l'agent de blanchiment correspond à la formule (IIA),
    Figure imgb0026
     dans laquelle
    M a la signification indiquée à la revendication 1.
  3. Utilisation selon la revendication 1, caractérisée en ce que le liant à base de latex utilise au moins un latex à base de styrène-butadiène, de styrène-acrylate ou d'acétate de vinyle.
  4. Utilisation selon la revendication 1, caractérisée en ce que le liant à base de latex utilise un latex à base de styrène-butadiène et comme co-liant, au moins une carboxyméthyl-cellulose et/ou un alcool de polyvinyle.
  5. Utilisation selon la revendication 1, caractérisée en ce que la composition d'enduction contient au moins un pigment blanc.
  6. Utilisation selon la revendication 1, caractérisée en ce que la composition d'enduction contient le liant à base de latex en une quantité de 3 à 20 % en poids, en particulier de 5 à 15 % en poids et le co-liant en une quantité de 0,1 à 3 % en poids, en particulier, de 0,5 à 1,5 % en poids, respectivement, par rapport à la quantité de pigment blanc.
  7. Composition d'enduction comprenant
    - au moins un pigment blanc
    - au moins un liant à base de latex
    - au moins un co-liant synthétique différent de celui-ci et choisi dans le groupe comprenant les alcools de polyvinyle, les carboxyméthyl-celluloses ainsi que des mélanges de ces substances individuelles
    - au moins un agent de blanchiment de formule (II),
    Figure imgb0027
     dans laquelle
    Y est un radical de formule
    Figure imgb0028
     ou
    Figure imgb0029
     et
    R1 désigne un groupe alkyle en C1 à C6 et
    R2 est un atome d'hydrogène ou
    R1 est un atome d'hydrogène et
    R2 est un groupe alkyle en C1 à C6, et indépendamment de ceux-ci,
    R3 est un atome d'hydrogène, un groupe méthyle, éthyle, CH2CH2OH ou CH2CH2OCH3,
    R1' est un groupe alkyle en C1 à C6 et
    R2' est un atome d'hydrogène, ou
    R1' est un atome d'hydrogène et
    R2' est un groupe alkyle en C1 à C6 et indépendamment de ceux-ci,
    R3' un atome d'hydrogène, un groupe méthyle, éthyle, CH2CH2OH ou CH2CH2OCH3, et
    R4 est un groupe alkyle en C1 à C4,
    Z désigne un groupe SO3M, les groupes sulfo pouvant être en position o-, m- ou p-, et
    M est un atome d'hydrogène ou un équivalent d'un cation, choisi dans le groupe comprenant Li, Na, K, Ca, Mg, ammonium ou ammonium mono-, di-, tri- ou tétra-substitué par le radical alkyle en C1 à C4 ou hydroxyalkyle en C2 à C4.
  8. Composition d'enduction selon la revendication 7, contenant
    3 à 20 % en poids, en particulier, 5 à 15 % en poids d'un liant à base de latex,
    0,1 à 3 % en poids, en particulier 0,5 à 1,5 % en poids d'un co-liant
    0,025 à 1 % en poids d'un agent de blanchiment de formule (II)
    par rapport respectivement à la quantité de pigment blanc.
  9. Utilisation de la composition d'enduction selon la revendication 7 pour produire des papiers enduits.
EP03008210A 2002-04-19 2003-04-09 Utilisation d'agents de blanchiment optiques pour la fabrication des melanges d'enduisage Revoked EP1355004B1 (fr)

Priority Applications (1)

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EP06015669A EP1754829A1 (fr) 2002-04-19 2003-04-09 Utilisation d'agents de blanchiment optiques pour la fabrication des melange d'enduisage

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE10217677A DE10217677A1 (de) 2002-04-19 2002-04-19 Verwendung von Aufhellern zur Herstellung von Streichmassen
DE10217677 2002-04-19

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EP1355004B1 true EP1355004B1 (fr) 2006-09-06

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EP03008210A Revoked EP1355004B1 (fr) 2002-04-19 2003-04-09 Utilisation d'agents de blanchiment optiques pour la fabrication des melanges d'enduisage

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EP (2) EP1754829A1 (fr)
JP (1) JP4571784B2 (fr)
DE (2) DE10217677A1 (fr)

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US8652593B2 (en) 2009-12-17 2014-02-18 International Paper Company Printable substrates with improved brightness from OBAs in presence of multivalent metal salts
US8652594B2 (en) 2008-03-31 2014-02-18 International Paper Company Recording sheet with enhanced print quality at low additive levels
US8795796B2 (en) 2010-07-23 2014-08-05 International Paper Company Coated printable substrates providing higher print quality and resolution at lower ink usage

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AU2005298779B2 (en) * 2004-10-27 2010-06-17 Basf Se Compositions of fluorescent whitening agents
JP4873520B2 (ja) * 2005-03-30 2012-02-08 特種東海製紙株式会社 塗工印刷用紙
EP1712677A1 (fr) * 2005-04-08 2006-10-18 Clariant International Ltd. Solutions aqueuses d'azurants optiques
US8758886B2 (en) 2005-10-14 2014-06-24 International Paper Company Recording sheet with improved image dry time
US7682438B2 (en) * 2005-11-01 2010-03-23 International Paper Company Paper substrate having enhanced print density
SE530020C2 (sv) * 2006-06-15 2008-02-12 Holmen Ab Förfarande för stabilisering av vitheten hos i ytbehandlingslim/smet för papper ingående fluroescerande vitmedel (FWA) och hos av detta/dessa formade ytbehandlingsskikt
EP1881108A1 (fr) * 2006-07-18 2008-01-23 CIBA SPECIALTY CHEMICALS HOLDING INC. Patent Departement Composition de blanchiment fluorescent
RU2445327C2 (ru) * 2006-08-08 2012-03-20 Клариант Файненс (Бви) Лимитед Водные растворы оптических осветлителей
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US8613834B2 (en) 2008-04-03 2013-12-24 Basf Se Paper coating or binding formulations and methods of making and using same
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JP4571784B2 (ja) 2010-10-27
US20030236326A1 (en) 2003-12-25
JP2004036071A (ja) 2004-02-05
DE10217677A1 (de) 2003-11-06
EP1355004A1 (fr) 2003-10-22
EP1754829A1 (fr) 2007-02-21
DE50304916D1 (de) 2006-10-19
US7258815B2 (en) 2007-08-21

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