EP1817456A1 - Pate a papier de couchage a base d'hybrides pigments-polymeres - Google Patents

Pate a papier de couchage a base d'hybrides pigments-polymeres

Info

Publication number
EP1817456A1
EP1817456A1 EP05801743A EP05801743A EP1817456A1 EP 1817456 A1 EP1817456 A1 EP 1817456A1 EP 05801743 A EP05801743 A EP 05801743A EP 05801743 A EP05801743 A EP 05801743A EP 1817456 A1 EP1817456 A1 EP 1817456A1
Authority
EP
European Patent Office
Prior art keywords
paper coating
weight
parts
coating slip
pigment
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.)
Granted
Application number
EP05801743A
Other languages
German (de)
English (en)
Other versions
EP1817456B1 (fr
Inventor
Jürgen Schmidt-Thümmes
Hubertus KRÖNER
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
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 BASF SE filed Critical BASF SE
Publication of EP1817456A1 publication Critical patent/EP1817456A1/fr
Application granted granted Critical
Publication of EP1817456B1 publication Critical patent/EP1817456B1/fr
Not-in-force legal-status Critical Current
Anticipated expiration legal-status Critical

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
    • 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
    • D21H19/58—Polymers or oligomers of diolefins, aromatic vinyl monomers or unsaturated acids or derivatives thereof
    • 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
    • D21H19/38—Coatings with pigments characterised by the pigments
    • D21H19/42—Coatings with pigments characterised by the pigments at least partly organic
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31855—Of addition polymer from unsaturated monomers
    • Y10T428/3188—Next to cellulosic
    • Y10T428/31895—Paper or wood

Definitions

  • the invention relates to a paper coating slip containing
  • At least one inorganic pigment and, based on 100 parts by weight of the inorganic pigments, less than 40 parts by weight of organic polymers and less than 25 parts by weight of water or other solvents having a boiling point below 150 0 C at 1 bar.
  • the invention also relates to above paper coating compositions in which binder is bound to the inorganic pigment (hereinafter referred to as pigment polymer hybrid).
  • Paper coating slips usually contain pigments, organic binders and water.
  • Water or other solvents are required only for the coating process itself. They allow a uniform distribution of pigment and polymer on the paper to be coated.
  • Anhydrous paper coating slips have the advantage of weight savings. Transportation costs can be reduced.
  • anhydrous paper coating slips which contain organic polymers as pigments (in short organic pigments).
  • WO 93/12183 discloses a process for the preparation of polymer-pigment composite particles.
  • the polymer adheres to the pigment surface.
  • Pigment polymer hybrids and processes for their preparation are known from patent application FR 04 07 806 by Omya (filing date 13.07.2004).
  • Object of the present invention was paper coating slips with the lowest possible content of water or solvents.
  • the paper coating slips should have good performance properties, in particular, they should adhere well to paper or cardboard.
  • the coated papers or cartons should be easy to print. Accordingly, the initially defined paper coating slip was found. Also found were paper coating slips which contain pigment-polymer hybrids.
  • the paper coating slip according to the invention contains inorganic pigments as an essential constituent.
  • it is white pigments.
  • white pigments To name a few are z.
  • titanium dioxide or calcium carbonate is particularly preferred.
  • organic pigments in addition to inorganic pigments and organic pigments, as z. As described in WO 01/00712 and WO 01/00713, be used. However, such organic pigments are no longer absolutely necessary in the context of the present invention.
  • the proportion of organic pigments is preferably less than 20 parts by weight, in particular less than 10 parts by weight, more preferably less than 5 parts by weight, based on 100 parts by weight of inorganic pigment.
  • binders are natural and synthetic polymers. As a natural polymer, for. B. strength into consideration.
  • Suitable synthetic polymers are, in particular, polymers which are obtainable by radical polymerization of ethylenically unsaturated compounds (monomers).
  • the binder is preferably a polymer which consists of at least 40% by weight, preferably at least 60% by weight, particularly preferably at least 80% by weight, of so-called main monomers.
  • the main monomers are selected from C 1 -C 2 o-alkyl (meth) acrylates, vinyl esters of carboxylic acids containing up to 20 carbon atoms, vinyl aromatics having up to 20 carbon atoms, ethylenically unsaturated nitriles, vinyl halides, vinyl ethers of 1 to 10 C. -Atome-containing alcohols, aliphatic hydrocarbons having 2 to 8 carbon atoms and one or two double bonds or mixtures of these monomers. To name a few are z.
  • (meth) acrylic acid alkyl ester having a Ci-Ci O -alkyl radical such as methyl methacrylate, methyl acrylate, n-butyl acrylate, ethyl acrylate and 2-ethylhexyl acrylate.
  • mixtures of (meth) acrylic acid alkyl esters are also suitable.
  • Vinyl esters of carboxylic acids having 1 to 20 carbon atoms are, for. As vinyl laurate, stearate, vinyl propionate, vinyl versatate and vinyl acetate.
  • Suitable vinylaromatic compounds are vinyltoluene, ⁇ - and p-methylstyrene, ⁇ -butylstyrene, 4-n-butylstyrene, 4-n-decylstyrene and preferably styrene.
  • nitriles are acrylonitrile and methacrylonitrile.
  • the vinyl halides are ethylenically unsaturated compounds substituted with chlorine, fluorine or bromine, preferably vinyl chloride and vinylidene chloride.
  • vinyl ethers are, for. As vinyl methyl ether or vinyl isobutyl ether. Vinyl ether is preferably from 1 to 4 C-containing alcohols.
  • hydrocarbons having 2 to 8 carbon atoms and one or two olefinic Doppel ⁇ compounds ethylene, propylene, butadiene, isoprene and chloroprene may be mentioned.
  • Preferred principal monomers are Ci-Ci o alkyl (meth) acrylates and mixtures of the Al alkyl (meth) acrylates with vinyl aromatics, in particular styrene, (polymers with these main monomers are collectively referred to briefly polyacrylates) or, alterna ⁇ tively, hydrocarbons having 2 double bonds , in particular butadiene, or mixtures of such hydrocarbons with vinylaromatics, in particular styrene (polymers with these main monomers are collectively referred to briefly as polybutadienes).
  • the ratio z. B between 10:90 to 90:10, in particular 20:80 to 80:20.
  • the polymer may contain monomers having at least one acid group (short acid monomer), eg. As monomers with carboxylic acid, sulfonic acid or phosphonic acid groups. Preferred are carboxylic acid groups. Called z. As acrylic acid, methacrylic acid, itaconic acid, maleic acid or fumaric acid.
  • Both the polybutadienes and the polyacrylates preferably contain acid monomers as comonomers, preferably in an amount of 1 to 5 wt.%.
  • the maximum amount of the above aliphatic hydrocarbons in the polybuadienes and the alkyl (meth) acrylates in the polyacrylates is reduced accordingly by the minimum amount of the acid monomers.
  • the polymers are prepared in a preferred embodiment by emulsion polymerization, it is therefore an emulsion polymer.
  • the production can z. B. also be carried out by solution polymerization and anschlie ⁇ tungsde dispersion in water.
  • ionic and / or nonionic emulsifiers and / or protective colloids or stabilizers are used as surface-active compounds.
  • the surfactant is usually used in amounts of from 0.1 to 10% by weight, based on the monomers to be polymerized.
  • Water-soluble initiators for the emulsion polymerization are z.
  • ammonium and alkali metal salts of peroxodisulfuric z.
  • sodium peroxodisulfate, hydrogen peroxide or organic peroxides eg. B. tert-butyl hydroperoxide.
  • the amount of initiators is generally 0.1 to 10 wt.%, Preferably 0.5 to 5 wt.%, Based on the monomers to be polymerized. It is also possible to use several different initiators in the emulsion polymerization.
  • regulators may be used, e.g. in amounts of 0 to 0.8 parts by weight, based on 100 parts by weight of the monomers to be polymerized, by which the molecular weight is reduced.
  • Suitable are e.g. Compounds with a thiol group such as tert-butylmercaptan, Thioglycolklareethylacrylester, mercaptoethynol, mercaptopropyltrimethoxysilane or tert-dodecylmercaptan.
  • the emulsion polymerization is generally carried out at 30 to 130, preferably 50 to 9O 0 C.
  • the polymerization medium may consist of both water, as well as Mi ⁇ mixtures of water and thus miscible liquids such as methanol. Preferably, only water is used.
  • the emulsion polymerization can be carried out both as a batch process and in the form of a feed process, including a stepwise or gradient procedure.
  • the feed process in which one submits a portion of the polymerization, heated to the Polymerisationstempera ⁇ tur, polymerized and then the remainder of the polymerization, usually over several spatially separate feeds, one or more of the monomers in pure or in emulsified form , continuously, utilizatnwei ⁇ se or under superposition of a concentration gradient while maintaining the polymerization of the polymerization zone supplies.
  • the polymerization can also z. B. be presented for better adjustment of the particle size of a polymer seed.
  • the manner in which the initiator is added to the polymerization vessel in the course of the free radical aqueous emulsion polymerization is known to the average person skilled in the art. It can be introduced both completely into the polymerization vessel, or used continuously or in stages according to its consumption in the course of the free radical aqueous emulsion polymerization. In detail, this depends on the chemical nature of the initiator system as well as on the polymerisation temperature. Preferably, a part is initially charged and the remainder supplied according to the consumption of the polymerization.
  • To remove the residual monomers is usually also after the end of ei ⁇ tual emulsion polymerization, d. H. after a conversion of the monomers of at least 95%, initiator added.
  • aqueous dispersions of the polymer are generally obtained with solids contents of 15 to 75 wt .-%, preferably from 40 to 75 wt .-%.
  • Suitable binders are, in particular, mixtures of various binders, eg. As well as mixtures of synthetic and natural polymers.
  • the paper coating slip according to the invention contains in total less than 40 parts by weight, preferably less than 20 parts by weight, more preferably less than 15 parts by weight of organic polymers per 100 parts by weight of inorganic pigments.
  • the content of organic polymers is preferably at least 1 part by weight, more preferably at least 3 parts by weight, and most preferably at least 5 parts by weight, per 100 parts by weight of inorganic pigments.
  • the organic polymers are, in particular, the above binders or mixtures of binders, optionally additionally used organic pigments (see above) or other polymer additives, eg. As dispersing aids or synthetic or natural waxes.
  • At least 60% by weight of the total amount of the organic polymers are binders, more preferably at least 80% by weight, very particularly preferably at least 90% by weight of the organic Polymers to binders.
  • the paper coating slip may optionally contain other non-volatile compounds (boiling point above 150 ° C. at 1 bar) or other polymeric compounds as additives.
  • other non-volatile compounds oiling point above 150 ° C. at 1 bar
  • release agents such as silica, talc or inorganic salts.
  • the paper coating slip according to the invention contains less than 25 parts by weight of water or other solvents having a boiling point below 150 ° C. (1 bar), based on 100 parts by weight of inorganic pigments. In particular, it contains less than 20 parts by weight, more preferably less than 15 parts by weight, most preferably less than 5 parts by weight or less than 2 parts by weight of water or such solvents per 100 parts by weight of inorganic pigments.
  • the paper coating slip according to the invention contains less than 1 part by weight and in a particular embodiment less than 0.2 part by weight of water or such solvents per 100 parts by weight of inorganic pigments. In particular, it contains no water or other solvents with a boiling point below 15O 0 C (1 bar).
  • the inorganic pigment is preferably used in admixture with organic polymers, in particular binders.
  • the inorganic pigments and organic polymers, in particular the binder are first mixed by customary methods and then water or solvent are removed up to the above residual content or completely.
  • the latter can z. B. also be done by spray drying.
  • the inorganic pigment can be ground in the presence of the binder.
  • Water or solvent can be removed before, during or preferably after the milling process.
  • the inorganic pigment is particularly preferably used in the form of pigment-polymer hybrids.
  • the organic polymer or binder is chemically or physically bound to the inorganic pigment.
  • the binder is adsorbed to the pigment surface.
  • the pigment-polymer hybrids are an independent particle of uniform density.
  • the measuring method of the static density gradient is z. In W. Mächtle, MD Lechner, Progr. Colloid Polym. Sci (2002) 119, 1.
  • polymer about 1 g / cm.sup.3
  • calcium carbonate 2.6 to 2.95 g / cm.sup.3, depending on the modification
  • polymer / carbonate hybrid differ significantly from one another in the densities of the particles Measurements of the hybrids in suitable static density gradients the detection of free polymer or the exclusion of free polymer carried out.
  • a pigment-polymer hybrid is obtainable by the above-described mixing and drying or grinding of the pigment in the presence of the binder.
  • the pigment-polymer hybrids have self-binding properties, as described in FR 04 07 806.
  • the content of the organic polymers and binders in the pigment-polymer hybrids is in particular less than 40 parts by weight, preferably less than 20 parts by weight, more preferably less than 15 parts by weight of organic polymers per 100 parts by weight of the Hybrid existing pigments.
  • the content of organic polymers and binders in the pigment-polymer hybrids is preferably at least 1 part by weight, more preferably at least 3 parts by weight and most preferably at least 5 parts by weight, per 100 parts by weight of the pigments present in the hybrids.
  • organic polymers in particular special binders and inorganic pigments are particularly preferably used in the form of the pigment-polymer hybrids.
  • organic binders and inorganic pigments which are not present in the form of the pigment-polymer hybrids.
  • the paper coating slip according to the invention preferably comprises at least 50% by weight, in particular at least 80% by weight, very particularly preferably at least 90% by weight, of pigment-polymer hybrids;
  • the paper coating composition can consist of at least 95% by weight or 98% by weight or 100% by weight of the pigment-polymer hybrids.
  • At least 60 wt .-%, in particular at least 80 wt .-% and very particularly preferably at least 95 wt .-% and in particular 100 wt .-% are the total existing in the paper coating inorganic pigment in the form of pigment-polymer hybrids before.
  • the paper coating is suitable for coating paper or cardboard.
  • the paper coating slip can be applied by suitable methods, in particular dry coating methods, for. As by knife coating or electrostatic charging of the particles to be coated and subsequent coating, in particular special spraying.
  • the paper coating slip is preferably sprayed on. After coating, a filming of the organic polymers, or binders, at elevated temperatures, preferably from 100 to 25O 0 C, take place.
  • a drying preferably spray-drying of the resulting mixture to remove the water or other solvents with a boiling point below 150 0 C at 1 bar except one, are ground in the presence of a binder and optionally water or solvent and optionally further auxiliaries Parts less than 20 parts by weight, preferably less than 5 parts by weight to 100 parts by weight of inorganic pigment er ⁇ follows and then optionally further auxiliaries are added, and then the paper coating slip is applied to papers or cartons.
  • the paper coating slips have good performance properties, eg. As a good adhesion to the paper and good printability in conventional printing processes.
  • the polymer hybrids H1 and H2 and the polymer Acronal S 728 used were measured by the method described above in the static density gradient of the ultracentrifuge. By using four different density gradients, a density range of 0.95 g / cm3 to 1.30 g / cm3 was covered. When measuring the polymer used, a sharp peak is observed at a density of 1.050 g / cm 3. When measuring the two polymer hybrids H1 and H2, no peaks are observed in the entire accessible density range, in particular at the density of the pure polymer. The polymer / pigment hybrids thus contain no unbound polymer.
  • the starting material used was a 25% slurry which was stirred on an Ultraturrax at 2000 rpm.
  • Powder H1 has a monomodal particle size distribution, determined by Fraunho ⁇ fer diffraction in air, with an average particle size of 7 microns.
  • H2 corresponding to 6 ⁇ m
  • the powders were applied with a doctor blade to an untreated 80 g / m 2 wood-free base paper from Stora Enso, OuIu plant, a hot 155 ° C steel plate was placed on the coating and pressed manually for about 10 seconds. A uniformly coated paper having a smooth surface was obtained. The thickness of the obtained coating was 10 ⁇ m. The whiteness of the coating was measured with a Datacolor Elrepho 2000 laboratory instrument and was 90.01 (at R 457). The white (R 457) of conventional papers coated with paper coating slips is between 85 and 95.

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

Abstract

L'invention concerne une pâte à papier de couchage contenant au moins un pigment inorganique et, par rapport à 10 parties en poids des pigments inorganiques, 40 parties en poids maximum de polymères organiques et 25 parties en poids maximum d'eau ou autre solvant ayant un point d'ébulliion inférieur à 150 °C pour 1 bar.
EP20050801743 2004-11-12 2005-11-05 Pate a papier de couchage a base d'hybrides pigments-polymeres Not-in-force EP1817456B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102004054913 2004-11-12
PCT/EP2005/011851 WO2006050873A1 (fr) 2004-11-12 2005-11-05 Pate a papier de couchage a base d'hybrides pigments-polymeres

Publications (2)

Publication Number Publication Date
EP1817456A1 true EP1817456A1 (fr) 2007-08-15
EP1817456B1 EP1817456B1 (fr) 2015-01-07

Family

ID=35583487

Family Applications (1)

Application Number Title Priority Date Filing Date
EP20050801743 Not-in-force EP1817456B1 (fr) 2004-11-12 2005-11-05 Pate a papier de couchage a base d'hybrides pigments-polymeres

Country Status (5)

Country Link
US (1) US7858154B2 (fr)
EP (1) EP1817456B1 (fr)
CN (1) CN101057036B (fr)
CA (1) CA2584919C (fr)
WO (1) WO2006050873A1 (fr)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102005025374A1 (de) * 2005-05-31 2006-12-07 Basf Ag Polymer-Pigment-Hybride für die Papierherstellung
FI20086122A (fi) * 2008-11-24 2010-05-25 Kemira Oyj Polymeerikoostumus
FI121937B (fi) * 2008-11-24 2011-06-15 Kemira Oyj Menetelmä päällystyskoostumuksen valmistamiseksi paperille tai kartongille sekä kuivapäällystyskoostumus
PT2565237E (pt) * 2011-08-31 2015-07-02 Omya Int Ag Processo para preparar suspensões de partículas de pigmentos autoligantes

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0407059B1 (fr) * 1989-06-30 1994-11-09 Japan Synthetic Rubber Co., Ltd. Procédé de préparation d'un latex d'un copolymer et composition pour revêtement de papier, composition pour sous-couche de tapis de composition adhésive contenant ledit latex
EP0615534B1 (fr) 1991-12-03 1997-04-16 Rohm And Haas Company Dispersion aqueuse de particules composites comprenant du latex polymere
US6080802A (en) * 1991-12-03 2000-06-27 Rohm And Haas Company Process for preparing an aqueous dispersion of composite particles including polymeric latex adsorbed to titanium dioxide
DE19636490A1 (de) 1996-09-09 1998-03-12 Basf Ag Verfahren zur Herstellung wäßriger Polymerisatdispersionen
FI991438A (fi) * 1999-06-24 2000-12-25 Neste Chemicals Oy Orgaaninen pigmenttigranulaatti paperin päällystystä varten
FI19991742A (fi) * 1999-06-24 2000-12-24 Neste Chemicals Oy Kuivana applikoituva polymeeripigmentti
DE10008276A1 (de) 2000-02-23 2001-08-30 Basf Ag Papierstreichmassen auf Basis von gering vernetzten Bindemitteln
DE10015262A1 (de) * 2000-03-28 2001-10-04 Basf Ag Papierstreichmassen, enthaltend Bindemittel mit Makromonomeren
DE10135380A1 (de) 2001-07-25 2003-02-06 Basf Ag Papierstreichmassen für das Gussstrichverfahren
DE10318066A1 (de) 2003-04-17 2004-11-11 Basf Ag Verfahren zur Behandlung von Papieroberflächen
FR2873127B1 (fr) 2004-07-13 2008-08-29 Omya Development Ag Procede de fabrication de particules pigmentaires autoliantes, seches ou en suspension ou dispersion aqueuses, contenant des matieres inorganiques et des liants

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2006050873A1 *

Also Published As

Publication number Publication date
EP1817456B1 (fr) 2015-01-07
US7858154B2 (en) 2010-12-28
CN101057036B (zh) 2012-03-28
CA2584919C (fr) 2015-06-02
WO2006050873A1 (fr) 2006-05-18
US20090075108A1 (en) 2009-03-19
CA2584919A1 (fr) 2007-04-20
CN101057036A (zh) 2007-10-17

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