EP1242682B1 - Matieres a retention d'eau elevee pour enduire le papier - Google Patents

Matieres a retention d'eau elevee pour enduire le papier Download PDF

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Publication number
EP1242682B1
EP1242682B1 EP00990658A EP00990658A EP1242682B1 EP 1242682 B1 EP1242682 B1 EP 1242682B1 EP 00990658 A EP00990658 A EP 00990658A EP 00990658 A EP00990658 A EP 00990658A EP 1242682 B1 EP1242682 B1 EP 1242682B1
Authority
EP
European Patent Office
Prior art keywords
weight
paper coating
pva
polyvinyl alcohol
coating slip
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.)
Expired - Lifetime
Application number
EP00990658A
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German (de)
English (en)
Other versions
EP1242682A2 (fr
Inventor
Reinhold J. Leyrer
Harutyun Hanciogullari
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 SE
Original Assignee
BASF SE
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Publication date
Application filed by BASF SE filed Critical BASF SE
Publication of EP1242682A2 publication Critical patent/EP1242682A2/fr
Application granted granted Critical
Publication of EP1242682B1 publication Critical patent/EP1242682B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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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
    • D21H19/00—Coated paper; Coating material
    • D21H19/36—Coatings with pigments
    • D21H19/44—Coatings with pigments characterised by the other ingredients, e.g. the binder or dispersing agent
    • D21H19/56—Macromolecular organic compounds or oligomers thereof obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H19/60—Polyalkenylalcohols; Polyalkenylethers; Polyalkenylesters

Definitions

  • Aqueous coating compositions are often used to coat water-absorbing (absorbent) substrates used.
  • Textilstreichmnassen e.g. applied to base paper or cardboard and dried the coating obtained. Too fast Water absorption through the substrate is generally disadvantageous for the manufacturing process. It makes an even distribution difficult the coating mass on the substrate and the formation a homogeneous coating.
  • the ability of a coating mass to quickly absorb the Preventing water from absorbent substrates becomes water retention called.
  • a high water retention of the paper coating slip desired is a high water retention of the paper coating slip desired.
  • EP-A-627450 polymers are already known, which in Presence of polyvinyl alcohol as a protective colloid and used as a thickener. With polyvinyl alcohol Stabilized polymers are also described in EP-A-863163. The use of polyvinyl alcohol as an additive to aqueous Paper coating slips and dyes for textiles are in EP-A-624687 and EP-A-44995.
  • the object of the present invention was the water retention of Improve paper coating slips. Accordingly, the beginning defined paper coating slip found.
  • the paper coating slip according to the invention contains a with polyvinyl alcohol (PVA) as a protective colloid dispersed polymer (short Called PVA-dispersed polymer).
  • PVA polyvinyl alcohol
  • PVA is understood to mean a polymer which comprises at least 10% by weight, in particular at least 20% by weight, based on the polymer, from groups of the formula which is derived from vinyl alcohol.
  • Polyvinyl alcohols are usually obtained by saponification of polyvinyl esters, in particular polyvinyl acetate.
  • the PVA can therefore also contain non-saponified structural units derived from vinyl esters.
  • the polyvinyl alcohol preferably has a viscosity of 0.1 to 100, in particular from 0.1 to 30, particularly preferably from 0.5 to 8 mPas, measured on a 4% by weight solution of the polyvinyl alcohol in water at 20 ° C (according to DIN 53015).
  • the PVA-dispersed polymers can be prepared by Polymerization of radically polymerizable starting compounds (Monomers) in the aqueous phase in the presence of PVA respectively.
  • the polymerization is preferably carried out in the presence at least by 0.5 part by weight, particularly preferably at least 2 parts by weight, very particularly preferably of at least 26 parts by weight PVA, in particular at least 40 parts by weight of PVA, based on 100 Parts by weight of monomers.
  • 0.5 part by weight particularly preferably at least 2 parts by weight, very particularly preferably of at least 26 parts by weight PVA, in particular at least 40 parts by weight of PVA, based on 100 Parts by weight of monomers.
  • no more than 250 parts by weight preferably 150 parts by weight of PVA, particularly preferably not more than 100 parts by weight, based on 100 parts by weight of monomers.
  • the PVA is usually initially introduced in the aqueous phase.
  • PVA protective colloids or emulsifiers can also be used.
  • the polymerization can be carried out according to the generally known The emulsion polymerization method is used.
  • the monomers can be used as usual in emulsion polymerization in the presence of a water-soluble initiator, the PVA and optionally further protective colloids and emulsifiers at preferably 30 to 140 ° C are polymerized.
  • Suitable initiators are, for example, sodium, potassium and ammonium persulfate, tert-butyl hydroperoxides, water-soluble azo compounds or redox initiators, such as H 2 O 2 / ascorbic acid.
  • Additional protective colloids and emulsifiers are e.g. alkali metal salts of longer-chain fatty acids, alkyl sulfates, alkyl sulfonates, alkylated Aryl sulfonates, alkylated biphenyl ether sulfonates, longer chain fatty alcohols and the corresponding alkoxylated Products of the sulfates, sulfonates and alcohols mentioned.
  • the PVA-dispersed polymer is preferably from the following Monomers built up.
  • the weight specifications refer in each case on the total amount of the monomers from which the PVA-dispersed Polymer is built up.
  • Main monomers are selected from C 1 to C 16 alkyl (meth) acrylates, vinyl aromatics with up to 20 C atoms, vinyl esters of carboxylic acids with 1 to 20 C atoms, vinyl halides, ethylenically unsaturated nitriles, non-aromatic hydrocarbons with one or two conjugated double bonds or mixtures of these monomers.
  • Examples include (meth) acrylic acid alkyl esters with a C 1 -C 10 alkyl radical, such as methyl methacrylate, methyl acrylate, n-butyl acrylate, ethyl acrylate and 2-ethylhexyl acrylate.
  • mixtures of the (meth) acrylic acid alkyl esters suitable.
  • the vinyl esters of carboxylic acids with 1 to 20 carbon atoms are, for example Vinyl laurate, stearate, vinyl propionate and vinyl acetate.
  • Vinyl toluene ⁇ -butylstyrene, 4-n-butylstyrene, 4-n-decylstyrene and preferably styrene.
  • ethylenically unsaturated Nitriles are acrylonitrile and methacrylonitrile.
  • Vinyl halides are substituted with chlorine, fluorine or bromine ethylenically unsaturated compounds, preferably vinyl chloride and Vinylidene chloride.
  • non-aromatic hydrocarbons with one or two conjugated olefinic double bonds are butadiene and isoprene and called chloroprene and ethylene.
  • the PVA can stabilize the polymer other monomers, e.g. Monomers containing hydroxyl groups, such as hydroxyalkyl acrylates or monomers with alkoxy groups as they by alkoxylation of monomers containing hydroxyl groups Alkoxides, especially ethylene oxide or propylene oxide, are available are monomers with acid or anhydride groups or their salts, e.g. Contain (meth) acrylic acid, maleic acid, vinyl sulfonic acid.
  • the polymer dispersed in PVA is used as a thickener.
  • the PVA preferably contains dispersed polymer in the Use as a thickener at least 5 wt .-%, particularly preferred at least 15% by weight, particularly preferably at least 30% by weight Monomers with at least one acid group (acid monomers for short).
  • the PVA-dispersed polymer does not contain more than 80% by weight, especially not more than 60% by weight, especially preferably not more than 50% by weight of the acid monomers.
  • the PVA-dispersed polymer can in particular also the main monomers described above and others Contain monomers.
  • the acid groups of the PVA-dispersed polymer are preferably at least partially before later use neutralized. Preferably at least 30 mol%, especially preferably 50 to 100% of the acid groups neutralized. Volatile bases such as Ammonia or non-volatile bases such as alkali hydroxides.
  • the PVA-dispersed polymer obtained after the polymerization can be easily spray dried if desired.
  • the paper coating slip can be in addition to the PVA-dispersed polymer contain a fluorescent or phosphorescent dye.
  • Fluorescent dyes in particular so-called optical dyes, are preferred Brighteners.
  • Brighteners are fluorescent dyes, which the degree of brightness, e.g. with white coated papers the whiteness, increase.
  • Stilbene derivatives in particular are known as optical brighteners.
  • optical brighteners are water-soluble of at least 1 g, in particular at least 5 g per liter Water (at 20 ° C) preferred.
  • the Paper coating slip in addition to the PVA present as a protective colloid also PVA, which is dissolved in the aqueous phase.
  • This additional PVA can e.g. the aqueous phase after production of the PVA-dispersed polymer can be added at any time.
  • PVA is preferably 5 to 100% by weight, particularly preferably 20 to 100% by weight, very particularly preferably 30 to 100 wt .-% around PVA as a protective colloid dispersed in the PVA Polymer and at 0 to 95 wt .-%, particularly preferred 0 to 80% by weight and very particularly preferably 0 to 70% by weight additionally PVA dissolved in water.
  • PVA a protective colloid dispersed in the PVA Polymer
  • PVA dissolved in water particularly preferred 0 to 80% by weight and very particularly preferably 0 to 70% by weight additionally PVA dissolved in water.
  • more than 50% by weight of the total amount of PVA or the total amount of PVA as Protective colloid is present.
  • aqueous coating or impregnation compound especially used as a paper coating slip.
  • the binder a) is preferably a free-radically polymerized polymer which in total preferably consists of at least 30% by weight, particularly preferably at least 50% by weight, of the main monomers listed above.
  • Paper coating slips are generally C 1 -C 16 alkyl (meth) acrylates or their mixtures with vinyl aromatics, in particular styrene, or alternatively non-aromatic hydrocarbons with two conjugated double bonds, in particular butadiene, or their mixtures with vinyl aromatics, in particular styrene.
  • thickeners b) include usual organic and inorganic thickeners such as Hydroxymethyl cellulose or concrete.
  • the pigment or filler d) is generally around white pigments, e.g. Barium sulfate, calcium carbonate, calcium sulfoaluminate, Kaolin, talc, titanium dioxide, zinc oxide, chalk or Coating clay.
  • white pigments e.g. Barium sulfate, calcium carbonate, calcium sulfoaluminate, Kaolin, talc, titanium dioxide, zinc oxide, chalk or Coating clay.
  • the paper coating slip preferably has the following weight composition.
  • the total amount of PVA contained in the paper coating slip is preferably 0.05 to 50% by weight, particularly preferably 0.1 to 5 parts by weight of PVA based on 100 parts by weight of the total amount of Components a) to d).
  • the preferred distribution on PVA as Protective colloid and additionally dissolved PVA is as stated above.
  • the amount of the submitted in the emulsion polymerization PVA depends on whether the resulting PVA dispersed polymer later used as a binder or thickener.
  • the binder it can be used in the later paper coating slip desired amount of PVA with very small amounts of PVA protective colloid can be achieved because the amount of binder is much larger is than usual amounts of thickener.
  • the paper coating slips can contain further constituents.
  • the paper slip masses are aqueous paper coating slips.
  • the water content can vary depending on the desired viscosity or gradient properties can be set.
  • the paper coating slip To produce the paper coating slip, the components in be mixed in a known manner.
  • the paper coating slips are suitable for coating e.g. of paper or cardboard.
  • the paper coating slip can then be applied to the surfaces to be coated using customary methods Papers or cardboard can be applied.
  • coated papers or cardboard boxes can be made in customary processes, e.g. Offset, high or gravure printing processes can be printed.
  • a wood-free coating base paper from Scheufelen GmbH + Co.KG, D-73250 Lenningen, with a basis weight of 70 g / m 2 was used as the base paper.
  • the paper coating slip was applied on one side with a dry layer thickness of 12 g / m 2 on a laboratory coating machine with a blade.
  • the applied wet layer was dried with IR radiators.
  • the water retention was measured in the pressure filtration device AA-GWR from Abo Akademi-Gravimetric Water Retention by OY Gradek AB, Mariantie 9, SF-02700 Kauniainen, Finland.
  • AA-GWR Abo Akademi-Gravimetric Water Retention by OY Gradek AB, Mariantie 9, SF-02700 Kauniainen, Finland.
  • Served as a filter a polycarbonate membrane, 5.0 ⁇ m pore size, 47 mm Diameter, 100 / pk from Osmonics Inc., manufactured by Infiltec GmbH, Alte Rheinhaeuser Strasse 8, D-67346 Speyer / Rhine.
  • the device was connected to a compressed air line and a pressure of 4 bar was set.
  • Five stapled and weighed filters were placed on the rubber plate, taking care that after the measurement the 5th filter is still dry. If not, increase to 8 or 10.
  • the plug was closed with the lever.
  • a pressure of 0.5 bar was set by pulling out the pressure setting button. Approx. 5 ml. Paper coating slip was placed in the metal cylinder. 0.5 bar pressure was applied for 60 seconds.
  • the wet filter papers were weighed again. The moisture absorption was multiplied by 1250. The result is the amount of water released in g / m 2 .
  • optical brightening was done with the spectrophotometer Elrepho 2000 by Datacolor GmbH (D-45769 Marl).
  • the papers to be checked were stacked at least four times. 5 measurements were carried out per paper sample.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Paper (AREA)
  • Paints Or Removers (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Claims (10)

  1. Matière d'enduction de papier, contenant
    a) un ou plusieurs liants,
    b) un épaississant,
    c) éventuellement un colorant fluorescent ou phosphorescent, et
    d) des pigments ou des matières de remplissage,
       caractérisée en ce qu'au moins un polymère dispersé dans l'eau avec de l'alcool polyvinylique comme colloïde de protection (polymère dispersé PVA) est contenu comme épaississant b) dans la composition.
  2. Matière d'enduction de papier suivant la revendication 1, caractérisée en ce que l'alcool polyvinylique est constitué d'au moins 10% en poids de groupes -H2C-CH(OH)-.
  3. Matière d'enduction de papier suivant l'une des revendications 1 et 2, caractérisée en ce que l'alcool polyvinylique présente une viscosité de 1 à 100 mPa.s mesurée selon la norme DIN 53015, sur une solution aqueuse à 4% en poids de l'alcool polyvinylique à 20°C.
  4. Matière d'enduction de papier suivant l'une des revendications 1 à 3, caractérisée en ce que la préparation du polymère dispersé PVA a lieu par polymérisation des composés de départ polymérisables par voie radicalaire (monomères) en phase aqueuse en présence de 0,5 à 250 parties en poids d'alcool polyvinylique comme colloïde de protection, par rapport à 100 parties en poids des monomères à polymériser.
  5. Matière d'enduction de papier suivant l'une des revendications 1 à 4, caractérisée en ce que le polymère dispersé PVA est constitué pour au moins 5% en poids de monomères ayant un groupe acide.
  6. Matière d'enduction de papier suivant l'une des revendications 1 à 5, caractérisée en ce que la matière d'enduction de papier contient un colorant fluorescent ou phosphorescent.
  7. Matière d'enduction de papier suivant la revendication 1, caractérisée en ce qu'elle contient 0,05 à 50 parties en poids d'alcool polyvinylique par rapport à 100 parties en poids de la quantité globale des composants a), b), c) et d).
  8. Matière d'enduction de papier suivant l'une des revendications 1 à 7, caractérisée en ce qu'elle contient 5 à 100% en poids d'alcool polyvinylique présent comme colloïde de protection,
       et
       0 à 95% en poids d'alcool polyvinylique en solution dans l'eau, par rapport à la quantité globale d'alcool polyvinylique.
  9. Utilisation de matières d'enduction de papier suivant l'une des revendications 1 à 8, pour enduire des papiers et du carton.
  10. Papier ou carton enduit par une matière d'enduction de papier suivant l'une des revendications 1 à 8.
EP00990658A 1999-12-17 2000-12-06 Matieres a retention d'eau elevee pour enduire le papier Expired - Lifetime EP1242682B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19960862 1999-12-17
DE19960862A DE19960862A1 (de) 1999-12-17 1999-12-17 Papierstreichmassen mit erhöhter Wasserretention
PCT/EP2000/012274 WO2001044574A2 (fr) 1999-12-17 2000-12-06 Matieres a retention d'eau elevee pour enduire le papier

Publications (2)

Publication Number Publication Date
EP1242682A2 EP1242682A2 (fr) 2002-09-25
EP1242682B1 true EP1242682B1 (fr) 2004-03-17

Family

ID=7932998

Family Applications (1)

Application Number Title Priority Date Filing Date
EP00990658A Expired - Lifetime EP1242682B1 (fr) 1999-12-17 2000-12-06 Matieres a retention d'eau elevee pour enduire le papier

Country Status (6)

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US (2) US20030166766A1 (fr)
EP (1) EP1242682B1 (fr)
AT (1) ATE262081T1 (fr)
CA (1) CA2394114C (fr)
DE (2) DE19960862A1 (fr)
WO (1) WO2001044574A2 (fr)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ATE321079T1 (de) 1999-12-21 2006-04-15 Omnova Solutions Inc Polyvinylalkoholcopolymerzusammensetzung
ITRM20040129A1 (it) * 2004-03-11 2004-06-11 Wittsun Sa Additivo per patina e relativo processo di produzione.
EP1712677A1 (fr) * 2005-04-08 2006-10-18 Clariant International Ltd. Solutions aqueuses d'azurants optiques
JP2010500429A (ja) * 2006-08-08 2010-01-07 クラリアント ファイナンス （ビーブイアイ） リミティド 光増白剤の水溶液
US20100167063A1 (en) * 2006-08-14 2010-07-01 Basf Se Paper coating compounds containing silicasols
CN102016173A (zh) * 2008-05-01 2011-04-13 阿克佐诺贝尔股份有限公司 纸涂料组合物
CN110878494B (zh) * 2019-12-03 2022-09-13 佛山市长盛兴隆装饰材料有限公司 一种金属粉水性乳液及制备方法和三聚氰胺木纹纸

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US2851423A (en) * 1951-08-17 1958-09-09 Switzer Brothers Inc Fluorescent compositions
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JPS5943069B2 (ja) * 1980-09-26 1984-10-19 日本合成化学工業株式会社 木材用接着剤
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Also Published As

Publication number Publication date
US20030166766A1 (en) 2003-09-04
WO2001044574A3 (fr) 2001-12-20
CA2394114C (fr) 2009-05-12
EP1242682A2 (fr) 2002-09-25
ATE262081T1 (de) 2004-04-15
WO2001044574A2 (fr) 2001-06-21
US6964993B2 (en) 2005-11-15
DE50005740D1 (de) 2004-04-22
US20040214941A1 (en) 2004-10-28
CA2394114A1 (fr) 2001-06-21
DE19960862A1 (de) 2001-06-28

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