EP1392925A1 - Composition de blanchiment fluorescent du papier - Google Patents

Composition de blanchiment fluorescent du papier

Info

Publication number
EP1392925A1
EP1392925A1 EP02750970A EP02750970A EP1392925A1 EP 1392925 A1 EP1392925 A1 EP 1392925A1 EP 02750970 A EP02750970 A EP 02750970A EP 02750970 A EP02750970 A EP 02750970A EP 1392925 A1 EP1392925 A1 EP 1392925A1
Authority
EP
European Patent Office
Prior art keywords
weight
composition
paper
fluorescent whitening
composition according
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.)
Withdrawn
Application number
EP02750970A
Other languages
German (de)
English (en)
Inventor
Peter Rohringer
Marc Roger Grienenberger
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF Schweiz AG
Original Assignee
Ciba Spezialitaetenchemie Holding AG
Ciba SC Holding AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Ciba Spezialitaetenchemie Holding AG, Ciba SC Holding AG filed Critical Ciba Spezialitaetenchemie Holding AG
Priority to EP02750970A priority Critical patent/EP1392925A1/fr
Publication of EP1392925A1 publication Critical patent/EP1392925A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
    • D21H21/30—Luminescent or fluorescent substances, e.g. for optical bleaching
    • D—TEXTILES; PAPER
    • 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
    • D21H17/63—Inorganic compounds
    • D21H17/67—Water-insoluble compounds, e.g. fillers, pigments
    • D21H17/68—Water-insoluble compounds, e.g. fillers, pigments siliceous, e.g. clays
    • 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
    • D21H21/06—Paper forming aids
    • D21H21/10—Retention agents or drainage improvers

Definitions

  • the present invention relates to a composition useful for the fluorescent whitening of paper in the pulp mass, in coatings or in the size press or metering size press.
  • Aqueous slurries of fluorescent whitening agents have been found to be advantageous in their applications in the paper industry, both from a technical and from an ecological point of view, as opposed to solutions, which necessitate considerable quantities of solvating agents such as urea or solvents such as polyaikylene glycols.
  • solvating agents such as urea or solvents such as polyaikylene glycols.
  • aqueous slurries must be stable against sedimentation, serum formation and also to storage at elevated temperatures.
  • Such stabilization has previously been achieved by the addition of polymers, such as xanthogenates and synthetic water-soluble polymers, or dispersing agents.
  • bentonite is not suitable for the stabilization of aqueous slurries and, furthermore, it has been found that, for example, hectorite exerts a far more efficient increase in the retention of fillers than bentonite.
  • composition of the invention combines the advantages of these particular smectic, layered silicates with regard to their stabilizing influence of aqueous slurries with a vast improvement in filler retention, effects which are of high technical value for the paper- maker.
  • the subject of the present invention is, thus, a composition
  • a composition comprising a) 5 to 25%, preferably 10 to 20%, by weight of a fluorescent whitening agent of the formula
  • R and R independently represent C C 4 alkyl, C 2 -C hydroxyalkyl or together complete a morpholine ring and is an alkaline or alkaline earth metal, b) 0.5 to 5% by weight of a swellable layered silicate which is hectorite and/or vermiculite, c) water and, optionally, d) further adjuvants.
  • the composition comprises 0.5 to 3%, more preferably 0.5 to 1.5%, by weight of hectorite, whilst, in a further preferred aspect, the composition comprises 0.5 to 5%, more preferably 0.5 to 1.5%, by weight of vermiculite.
  • R ⁇ and/or R 2 represent CrC 4 alkyl
  • these may be methyl, ethyl, n- or isopropyl or n-, iso- or t-butyl
  • C 2 -C 4 hydroxyalkyl may be hydroxyethyl, hydroxypropyl or hydroxybutyl.
  • M is an alkaline metal
  • this may be lithium, potassium or sodium, whilst an alkaline earth metal may be calcium or magnesium.
  • Ri represents methyl, ethyl, hydroxyethyl or hydroxypropyl
  • R 2 represents hydroxyethyl or hydroxypropyl
  • f ⁇ and R 2 together complete a morpholine ring and M is lithium, potassium or sodium
  • a most preferable composition comprising a fluorescent whitening agent selected from the compounds of formulae
  • composition of the invention may comprise further adjuvants, for example, conserving agents such as 1 ,2-benzisothiazolin-2-one or aldehydes such as formaldehyde or acetaldehyde, anti-freeze agents or anti-foaming agents, whereby such adjuvants are normally employed in small quantities, for example, below 1 % by weight.
  • conserving agents such as 1 ,2-benzisothiazolin-2-one or aldehydes such as formaldehyde or acetaldehyde
  • anti-freeze agents or anti-foaming agents whereby such adjuvants are normally employed in small quantities, for example, below 1 % by weight.
  • composition of the invention may be obtained, for example, by intensive mixing of the FWA of formula (1), either in the form of a moist filter-cake or a dry powder, with water under high shear forces, subsequently, adding a pre-dispersion of hectorite and/or vermiculite in water and, finally stirring until a homogeneous mixture results, optionally, in the presence of appropriate adjuvants.
  • compositions are stable to storage over longer periods of time, for example, 6 months, even at temperatures ranging from 0°C to 40°C.
  • composition of the present invention it has been found that it is possible to increase the whiteness of a lignin-containing pulp by a process which comprises adding to an aqueous slurry comprising a lignin-containing pulp, during pulp manufacture, prior to the drying step or paper making step if the pulp is not isolated, an effective amount of an FWA.
  • the FWA composition can be added to the aqueous slurry comprising the lignin- containing pulp at any processing step, to minimize losses, it is advantageously added in the latter stages of pulp manufacture, prior to the final de-watering and drying steps. Preferably it is added after completion of the last bleaching step.
  • a lignin-containing pulp any pulp that still contains about 5% or more of lignin by weight on a dry basis.
  • lignin is that portion of the pulp which is insoluble in 72 weight percent sulfuric acid. Suitable test procedures for lignin content are given in TAPPI T 223 and ASTM D 1106.
  • the composition of this invention is useful to produce significant whitening of chemical pulps as well as pulps containing up to 100% of mechanical fibre.
  • the composition can be employed, e.g. in lignin-free pulps, such as certain bleached kraft pulps, up to and including higher lignin content pulps such as thermomechanical pulps, bleached chemi- thermomechanical pulps (CTMP), and even deinked bleached thermomechanical pulps.
  • the pulps contain at least 10% of lignin by weight on a dry weight basis; most preferably they contain at least 15%.
  • the range of brightness that can be obtained varies from about 50 to 90+ depending on starting pulp brightness and the type of pulp employed.
  • Addition of the composition of the invention to the pulp mass may be performed at any step of the paper-making process, but preferably is performed shortly before the head box.
  • chelating agents in processes to bleach pulps from mechanical pulping processes. See V. N. Gupta , Pulp Paper Mag. Can., 71 (18), T391-399 (1970).
  • a chelating agent to an aqueous pulp slurry controls the natural yellowing tendency of glucuronic acids, extractives and lignin present in the pulp by removing or minimizing iron and other heavy metals such as copper, zinc and manganese metals that catalyze color- forming side reactions.
  • the iron and other heavy metals are converted into the form of their highly soluble chelates and largely removed in the de-watering steps. This decreases the incorporation of the heavy metal ions into the pulp.
  • the chelating agent sequesters the salts of iron and other heavy metals which remain and which, in their own right would otherwise relax the excited state of FWA's and render them ineffective .
  • chelating agents are suitable in the present invention, i.e. those that offer thermodynamic or kinetic control of metal ions. However preference is given to chelating agents that offer thermodynamic control, that is, chelating agents that form a stable, isolable, complex with a heavy metal ion. Within this group it is particularly preferred to use aminocarboxylic acid chelates.
  • Well known and commercially available members of this class include ethylenediaminetetraacetic acid (EDTA), diethylenetriaminepentaacetic acid (DTPA), hydroxyethylethylenediaminetriacetic acid (HEDTA) and nitrilotriacetic acid (NTA).
  • thermodynamic and kinetic-controlling chelating agents e.g. citrates, keto acids, gluconates, heptagluconates, phosphates, and phosphonates
  • thermodynamic and kinetic-controlling chelating agents also work well in reducing the content of free heavy metal ions in the pulp to acceptable levels.
  • kinetic-controlling chelating agents are also commercially available.
  • Kinetic controlling chelating agents are those which do not form a stable, isolable, complex with a heavy metal ion.
  • compositions according to the present invention may also be applied to the paper substrate in the form of a paper coating composition or directly in the size press.
  • the present invention provides a method for the fluorescent whitening of a paper surface, comprising contacting the paper surface with a coating composition comprising a white pigment; a binder dispersion; optionally a water-soluble co-binder; and sufficient of a composition according to the present invention, to ensure that the treated paper contains 0.01 to 2 parts by weight, preferably 0.01 to 1 parts by weight, based on the white pigment, of the FWA (parts of the FWA per 100 parts of the pigment).
  • the white pigment component of the paper coating composition used according to the method of the present invention there are preferred inorganic pigments, e.g., aluminium or magnesium silicates, such as China clay and kaolin and, further, barium sulfate, satin white, titanium dioxide, calcium carbonate (chalk) or talcum; as well as white organic pigments.
  • inorganic pigments e.g., aluminium or magnesium silicates, such as China clay and kaolin and, further, barium sulfate, satin white, titanium dioxide, calcium carbonate (chalk) or talcum; as well as white organic pigments.
  • the paper coating compositions used according to the method of the present invention may contain, as binder, inter alia, plastics dispersions based on copolymers of butadiene/styrene, acrylonitrile/butadiene/styrene, acrylic acid esters, acrylic acid esters/styrene/acrylonitrile, ethylene/vinyl chloride and ethylene/vinyi acetate; or homopolymers, such as polyvinyl chloride, polyvinylidene chloride, polyethylene and polyvinyl acetate or polyurethanes.
  • plastics dispersions based on copolymers of butadiene/styrene, acrylonitrile/butadiene/styrene, acrylic acid esters, acrylic acid esters/styrene/acrylonitrile, ethylene/vinyl chloride and ethylene/vinyi acetate
  • homopolymers such as polyvinyl chloride, polyvinylidene chloride, poly
  • a preferred binder consists of styrene/butyl acrylate or styrene/butadiene/ acrylic acid copolymers or styrene/butadiene rubbers.
  • Other polymer latices are described, for example, in U.S.Patent Specifications 3,265,654, 3,657,174, 3,547,899 and 3,240,740.
  • the optional water-soluble protective colloid may be, e.g., soya protein, casein, carboxymethylcellulose, natural or modified starch, chitosan or a derivative thereof or, especially, polyvinyl alcohol.
  • the preferred polyvinyl alcohol protective colloid component may have a wide range of saponification levels and molecular weights; e.g. a saponification level ranging from 40 to 100; and an average molecular weight ranging from 10,000 to 100,000.
  • the paper coating compositions used according to the method of the present invention preferably contain 10 to 70% by weight of a white pigment.
  • the binder is preferably used in an amount which is sufficient to make the dry content of polymeric compound up to 1 to 30 parts by weight, preferably 5 to 25 parts by weight, of the white pigment.
  • the amount of FWA composition used according to the invention is calculated so that the FWA is preferably present in amounts of 0.01 to 1 part by weight, more preferably 0.05 to 1 part by weight, and especially 0.05 to 0.6 parts by weight, based on the white pigment.
  • the paper coating composition used in the method according to the invention can be prepared by mixing the components in any desired sequence at temperatures from 10 to 100°C, preferably 20 to 80°C.
  • the components here also include the customary auxiliaries which can be added to regulate the rheological properties, such as viscosity or water retention capacity, of the coating compositions.
  • auxiliaries are, for example, natural binders, such as starch, casein, protein or gelatin, cellulose ethers, such as carboxyalkylcellulose or hydroxyalkylcellulose, alginic acid, alginates, polyethylene oxide or polyethylene oxide alkyl ethers, copolymers of ethylene oxide and propylene oxide, polyvinyl alcohol, water-soluble condensation products of formaldehyde with urea or melamine, polyphosphates or polyacrylic acid salts.
  • natural binders such as starch, casein, protein or gelatin
  • cellulose ethers such as carboxyalkylcellulose or hydroxyalkylcellulose
  • alginic acid alginates
  • polyethylene oxide or polyethylene oxide alkyl ethers copolymers of ethylene oxide and propylene oxide
  • polyvinyl alcohol water-soluble condensation products of formaldehyde with urea or melamine
  • polyphosphates or polyacrylic acid salts such as sodium binders, sodium bicarbonate, sodium
  • the coating composition used according to the method of the present invention is preferably used to produce coated printed or writing paper, or special papers such as cardboard or photographic papers.
  • the coating composition used according to the method of the invention can be applied to the substrate by any conventional process, for example with an air blade, a coating blade, a roller, a doctor blade or a rod, in the size press or in the metering size press, after which the coatings are dried at paper surface temperatures in the range from 70 to 200°C, preferably 90 to 130°C, to a residual moisture content of 3-8%, for example with infra-red dryers and/or hot-air dryers. Comparably high degrees of whiteness are thus achieved even at low drying temperatures.
  • the coatings obtained are distinguished by optimum distribution of the FWA over the entire surface and by an increase in the level of whiteness thereby achieved, by a high fastness to light and to elevated temperature (e.g. stability for 24 hours at 60-100°C.) and excellent bleed-fastness to water.
  • the present invention provides a method for the fluorescent whitening of a paper surface comprising contacting the paper in the size press or metering press with an aqueous preparation containing a size, optionally an inorganic or organic pigment and 0.1 to 20g/l of an FWA.
  • the size is starch, a starch derivative or a synthetic sizing agent, especially a water-soluble copolymer.
  • a formulation containing 16% of the compound (2) and 1% hectorite is obtained, which, as opposed to the starting formulation, is stable to storage.
  • Example 1 such that, together with the FWA of formula (2), 0.04% of hectorite, based on the weight of fibre, is present.
  • Hand sheets are then prepared by means of the Rapid-Koethen System and the percentage retention of the filler is measured.

Landscapes

  • Paper (AREA)

Abstract

L'invention concerne une composition contenant a) 5 à 25 % en poids d'un agent de blanchiment fluorescent de formule (I) dans laquelle R1 et R2 sont indépendamment C1-C4alkyl, C2-C4hydroxyalkyl, ou forment ensemble un cycle morpholine, et M est un métal alcalin ou alcalino-terreux, b) 0,5 à 5 % en poids d'un silicate en couche expansible se présentant sous la forme d'hectorite et/ou de vermiculite, c) de l'eau, et d) éventuellement d'autres adjuvants. L'invention concerne également l'utilisation de ladite composition dans le blanchiment fluorescent de papier dans la pâte à papier, dans des revêtements ou dans la presse encolleuse ou la presse encolleuse de dosage.
EP02750970A 2001-05-29 2002-05-23 Composition de blanchiment fluorescent du papier Withdrawn EP1392925A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP02750970A EP1392925A1 (fr) 2001-05-29 2002-05-23 Composition de blanchiment fluorescent du papier

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
EP01810521 2001-05-29
EP01810521 2001-05-29
PCT/EP2002/005668 WO2002097193A1 (fr) 2001-05-29 2002-05-23 Composition de blanchiment fluorescent du papier
EP02750970A EP1392925A1 (fr) 2001-05-29 2002-05-23 Composition de blanchiment fluorescent du papier

Publications (1)

Publication Number Publication Date
EP1392925A1 true EP1392925A1 (fr) 2004-03-03

Family

ID=8183935

Family Applications (1)

Application Number Title Priority Date Filing Date
EP02750970A Withdrawn EP1392925A1 (fr) 2001-05-29 2002-05-23 Composition de blanchiment fluorescent du papier

Country Status (4)

Country Link
US (1) US20040149410A1 (fr)
EP (1) EP1392925A1 (fr)
AR (1) AR033770A1 (fr)
WO (1) WO2002097193A1 (fr)

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DE10217677A1 (de) 2002-04-19 2003-11-06 Bayer Ag Verwendung von Aufhellern zur Herstellung von Streichmassen
DE102004038578A1 (de) 2004-08-06 2006-03-16 Lanxess Deutschland Gmbh Alkanolammoniumhaltige Triazinylflavonataufheller
US8092649B2 (en) * 2005-12-14 2012-01-10 Nalco Company Method of decreasing the rate of photoyellowing with thiocyanic acid
KR100735711B1 (ko) 2006-01-09 2007-07-06 삼원산업주식회사 형광 증백제 및 이의 합성방법
CL2007002685A1 (es) * 2006-09-18 2008-01-25 Sca Hygiene Prod Ab Tela multicapas de material flexible que comprende un agente blanqueador fluorescente, la tela incluye primera y segunda capa interconectadas por una composicion adhesiva de polivinil alcohol y polimero cationico; producto; metodo para optimizar la rapidez de corrimiento del agente blanqueador.
US8613834B2 (en) 2008-04-03 2013-12-24 Basf Se Paper coating or binding formulations and methods of making and using same
CN104862120A (zh) * 2015-04-09 2015-08-26 广州立白企业集团有限公司 一种洗涤剂用荧光增白剂水溶液的制备方法

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Also Published As

Publication number Publication date
US20040149410A1 (en) 2004-08-05
WO2002097193A1 (fr) 2002-12-05
AR033770A1 (es) 2004-01-07

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