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EP1268931A1 - Pates de couchage pour papier, contenant des liants a macromonomeres - Google Patents

Pates de couchage pour papier, contenant des liants a macromonomeres

Info

Publication number
EP1268931A1
EP1268931A1 EP01936144A EP01936144A EP1268931A1 EP 1268931 A1 EP1268931 A1 EP 1268931A1 EP 01936144 A EP01936144 A EP 01936144A EP 01936144 A EP01936144 A EP 01936144A EP 1268931 A1 EP1268931 A1 EP 1268931A1
Authority
EP
European Patent Office
Prior art keywords
ethylenically unsaturated
paper coating
weight
polymer
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.)
Granted
Application number
EP01936144A
Other languages
German (de)
English (en)
Other versions
EP1268931B1 (fr
Inventor
Volker Schädler
David Christie
Roland Ettl
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 EP1268931A1 publication Critical patent/EP1268931A1/fr
Application granted granted Critical
Publication of EP1268931B1 publication Critical patent/EP1268931B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime 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
    • 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
    • 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
    • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24802—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.]
    • 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
    • Y10T428/31899—Addition polymer of hydrocarbon[s] only
    • 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
    • Y10T428/31899—Addition polymer of hydrocarbon[s] only
    • Y10T428/31902—Monoethylenically unsaturated
    • 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
    • Y10T428/31906—Ester, halide or nitrile of addition polymer

Definitions

  • the invention relates to paper coating slips containing a copolymer as a binder, which is obtainable by radical polymerization of ethylenically unsaturated compounds, characterized in that at least one of the ethylenically unsaturated compounds is a polymer with at least one copolymerizable ethylenically unsaturated group, a number average molecular weight of 500 to 50,000 g / mol and at least one carboxylic acid group (hereinafter referred to as ethylenically unsaturated polymer).
  • Paper coating slips essentially consist of pigment and binder.
  • the binder is intended to fix the pigments on the paper and to ensure cohesion in the coating obtained.
  • pick resistance When printing e.g. in an offset printing machine, because of the high viscosity of the printing ink, strong tensile forces act on the coated paper (paper coating). The resistance that the paper coating provides to these forces is called pick resistance. A distinction is made between dry pick resistance and wet pick resistance. The wet pick resistance is particularly important in aqueous offset printing, since in the second printing unit you will find printing ink on water-moist paper and the paper coating must have sufficient binding power under these conditions.
  • the polymers generally contain acid groups. Such polymers are e.g. described in WO 97/00776.
  • Emulsion polymers which have ethylenically unsaturated polymers with several acid groups as structural components are the subject of WO 95/04767.
  • the object of the present invention was therefore paper coating slips with improved pick resistance. Accordingly, the paper coating slips defined at the outset were found.
  • the paper coating slip according to the invention contains the copolymer defined at the beginning as a binder.
  • the copolymer can be obtained by radical polymerization, preferably by emulsion polymerization of copolymerizable, ethylenically unsaturated compounds.
  • At least one of the ethylenically unsaturated compound is a polymer with at least one copolymerizable, ethylenically unsaturated group, a number average molecular weight of 500 to 50,000 g / mol and at least one carboxylic acid group (hereinafter referred to as ethylenically unsaturated polymer).
  • the content of ethylenically unsaturated groups and carboxylic acid groups relates to the content per polymer chain.
  • the ethylenically unsaturated polymer preferably contains one or two, particularly preferably an ethylenically unsaturated, group.
  • the or one (if more than one) ethylenically unsaturated group is particularly preferably in the terminal position in the respective polymer chain.
  • the ethylenically unsaturated group is an acrylic or methacrylic group, preferably a methacrylic group.
  • the ethylenically unsaturated polymer preferably contains more than 2, particularly preferably more than 4, very particularly preferably more than 8 carboxylic acid groups.
  • the ethylenically unsaturated polymer is preferably composed of compounds which can be polymerized by free radicals and is obtainable accordingly by free-radical polymerization of these compounds.
  • the ethylenically unsaturated polymer preferably consists of at least 50% by weight, particularly preferably 80% by weight, of -C-C 0 alkyl (meth) acrylates, (meth) acrylic acid and mixtures thereof.
  • the ethylenically unsaturated polymer very particularly preferably consists of at least 50% by weight, in particular at least 80% by weight, of acrylic acid or methacrylic acid. Methacrylic acid is preferred.
  • the average molecular weight Mn of the ethylenically unsaturated polymer is preferably 800 to 20,000, particularly preferably 1,000 to 10,000 g / mol. Mn is determined by gel permeation chromatography (polyacrylic acid standard and water as eluent).
  • the ethylenically unsaturated polymer is preferably produced by radical polymerization in the presence of a
  • Transition metal complex as a molecular weight regulator, e.g. of a cobalt chelate complex. This process is known as catalytic chain transfer polymerization (CCT) and is e.g. in WO 95/04767 and the documents cited in this document.
  • CCT catalytic chain transfer polymerization
  • the copolymer preferably consists of at least 0.1, particularly preferably at least 0.3, very particularly preferably at least 1% by weight, in particular also at least 2% by weight, of the ethylenically unsaturated polymer. A content of 30% by weight, in particular 20% by weight and particularly preferably 15% by weight, is generally not exceeded.
  • the copolymer is preferably composed entirely of
  • main monomers selected from Ci to C 2 o alkyl (eth) acrylates, vinyl esters of carboxylic acids containing up to 20 C atoms, vinyl aromatics with up to 20 C atoms, ethylenically unsaturated nitriles , Vinyl halides, vinyl ethers or allyl ethers from 1 to 10 C-
  • Alcohol-containing atoms aliphatic hydrocarbons with 2 to 8 carbon atoms and 1 or 2 double bonds or mixtures of these monomers
  • the copolymer is preferably composed entirely of
  • the copolymer is very particularly preferably composed of
  • the main monomers are z.
  • Vinyl esters of carboxylic acids with 1 to 20 carbon atoms are, for. B.
  • Vinyl laurate, stearate, vinyl propionate, vinyl versatic acid and vinyl acetate Vinyl laurate, stearate, vinyl propionate, vinyl versatic acid and vinyl acetate.
  • Suitable vinylaromatic compounds are vinyltoluene- and p-methylstyrene, ⁇ -butylstyrene, 4-n-butylstyrene, 4 -n-decylstyrene and preferably styrene.
  • Examples of nitriles are
  • the vinyl halides are chlorine, fluorine or bromine-substituted ethylenically unsaturated compounds, preferably vinyl chloride and
  • vinyl ethers examples include B. vinyl methyl ether or vinyl isobutyl ether. Vinyl ethers of alcohols containing 1 to 4 carbon atoms are preferred.
  • hydrocarbons with 2 to 8 carbon atoms and one or two olefinic double bonds butadiene, isoprene and chloroprene, ethylene and propylene may be mentioned.
  • the main monomers are the C 1 to C 10 alkyl acrylates and methacrylates, in particular C 1 to C 8 alkyl acrylates and methacrylates, the acrylates being particularly preferred in each case.
  • Methyl acrylate, methyl methacrylate, ethyl acrylate, n-butyl acrylate, n-hexyl acrylate, octyl acrylate and 2-ethylhexyl acrylate and mixtures of these monomers are very particularly preferred.
  • the copolymer is preferably an acrylate-based copolymer, ie the copolymer consists of at least 60% by weight of C .--C o alkyl (meth) acrylates or mixtures thereof with vinyl aromatics.
  • a copolymer based on butadiene is also preferred, ie the copolymer is composed of at least 60% by weight of butadiene or. their mixtures with vinyl aromatics.
  • the polymer may contain other ethylenically unsaturated compounds, e.g. B. monomers with carboxylic acid, sulfonic acid or phosphonic acid groups.
  • Carboxylic acid groups are preferred. May be mentioned for. As acrylic acid, methacrylic acid, itaconic acid, maleic acid or fumaric acid.
  • Monomers containing hydroxyl groups may also be mentioned, in particular C 1 -C 8 -hydroxyalkyl (meth) acrylates or (meth) acrylamide.
  • ethylenically unsaturated compounds are also phenyloxyethyl glycol mono- (meth) acrylate, glydidyl acrylate, glycidyl ethacrylate, amino (meth) acrylates such as 2-aminoethyl (meth) acrylate.
  • the glass transition temperature of the polymer is preferably below 50 ° C, in particular it is -40 to + 50 ° C, particularly preferably -20 to + 30 ° C and very particularly preferably -10 to + 25 ° C and in particular -5 to + 20 ° C.
  • the glass transition temperature of the polymer can be determined by conventional methods such as differential thermal analysis or differential scanning calorimetry (see e.g. ASTM 3418/82, so-called "midpoint te perature").
  • the copolymer is preferably prepared by emulsion polymerization, and is therefore an emulsion copolymer.
  • the manufacture can e.g. B. also by solution polymerization and subsequent dispersion in water.
  • ionic and / or nonionic emulsifiers and / or protective colloids or stabilizers are used as surface-active compounds.
  • Suitable protective colloids can be found in Houben-Weyl, Methods of Organic Chemistry, Volume XIV / 1, Macromolecular Substances, Georg-Thieme-Verlag, Stuttgart, 1961, pp. 411 to 420. Both anionic and cationic come as emulsifiers as well as nonionic emulsifiers. Preferably, only accompanying emulsifiers are used as accompanying surface-active substances, the molecular weight of which is The difference to the protective colloids is usually less than 2000 g / mol. Of course, if mixtures of surface-active substances are used, the individual components must be compatible with one another, which can be checked with a few preliminary tests if in doubt.
  • Anionic and nonionic emulsifiers are preferably used as surface-active substances.
  • Common accompanying emulsifiers are e.g. B. ethoxylated fatty alcohols (EO degree: 3 to 50, alkyl radical: Ca "to C 36 ), ethoxylated mono-, di- and tri-alkylphenols (EO degree: 3 to 50, alkyl radical: C 4 - to C 9 ) , Alkali metal salts of dialkyl esters of sulfosuccinic acid and alkali and ammonium salts of alkyl sulfates (alkyl radical: C 8 - to C ⁇ 2 ), of ethoxylated alkanols (EO degree: 4 to 30, alkyl radical: C ⁇ 2 - to Cia), of ethoxylated alkylphenols (EO grade: 3 to 50, alkyl radical: C - to C 9 ), of alkyl sulfonic acids (alkyl radical
  • Suitable emulsifiers are compounds of the general formula II
  • R 5 and R 6 are hydrogen or C - to C 14 alkyl and are not simultaneously hydrogen, and C and Y can be alkali metal ions and / or ammonium ions.
  • R 5 , R 6 are preferably linear or branched alkyl radicals having 6 to 18 carbon atoms or hydrogen and in particular having 6, 12 and 16 carbon atoms, where R 5 and R 6 are not both hydrogen at the same time.
  • X and Y are preferably sodium, potassium or ammonium ions, with sodium being particularly preferred.
  • Compounds II in which X and Y are sodium, R 5 is a branched alkyl radical having 12 C atoms and R 6 is hydrogen or R 5 are particularly advantageous.
  • Technical mixtures are frequently used which have a proportion of 50 to 90% by weight of the monoalkylated product, for example Dowfax® 2A1 (trademark of the Dow Chemical Company).
  • Suitable emulsifiers can also be found in Houben-Weyl, Methods of Organic Chemistry, Volume 14/1, Macromolecular Substances, Georg Thieme Verlag, Stuttgart, 1961, pages 192 to 208.
  • Trade names of emulsifiers are e.g. B. Dowfax®2 AI, Emulan® NP 50, Dextrol® OC 5 ' 0, Emulsifier 825, Emulsifier 825 S, Emulan® OG, Texapon®NSO, Nekanil® 904 S, Lumiten® I-RA, Lumiten E 3065, Dis - ponil FES 77, Lutensol AT 18, Steinapol VSL, Emulphor NPS 25.
  • the surface-active substance is usually used in amounts of 0.1 to 10% by weight, based on the monomers to be polymerized.
  • Water-soluble initiators for emulsion polymerization are e.g. B. ammonium and alkali metal salts of peroxidic sulfuric acid, e.g. As sodium peroxodisulfate, hydrogen peroxide or organic peroxides, e.g. B. tert-butyl hydroperoxide.
  • B. ammonium and alkali metal salts of peroxidic sulfuric acid e.g. As sodium peroxodisulfate, hydrogen peroxide or organic peroxides, e.g. B. tert-butyl hydroperoxide.
  • red-ox reduction-oxidation
  • the redox initiator systems consist of at least one mostly inorganic reducing agent and one inorganic or organic oxidizing agent.
  • the oxidation component is e.g. B. the initiators for emulsion polymerization mentioned above.
  • the reduction components are e.g. B. to alkali metal salts of sulfurous acid, such as. B. sodium sulfite, sodium bisulfite, alkali metal salts of disulfuric acid such as sodium disulfite, bisulfite addition compounds aliphatic aldehydes and ketones such as acetone bisulfite or reducing agents such as hydroxymethanesulfinic acid and its salts, or ascorbic acid.
  • the Red-Ox initiator systems can be used with the use of soluble metal compounds, the metallic component of which can occur in several valence levels.
  • Common Red Ox initiator systems are e.g. B. ascorbic acid / iron (II) sulfate / sodium peroxydisulfate, tert-butyl hydroperoxide / sodium disulfite, tert-butyl hydroperoxide / Na hydroxymethanesulfinic acid.
  • the individual components, e.g. B. the reduction component can also be mixtures e.g. a mixture of the sodium salt of hydroxymethanesulfinic acid and sodium disulfite.
  • the compounds mentioned are mostly used in the form of aqueous solutions, the lower concentration being determined by the amount of water acceptable in the dispersion and the upper concentration being determined by the solubility of the compound in question in water.
  • the concentration is generally 0.1 to 30% by weight, preferably 0.5 to 20% by weight, particularly preferably 1.0 to 10% by weight, based on the solution.
  • the amount of initiators is generally 0.1 to 10% by weight, preferably 0.5 to 5% by weight, based on the monomers to be polymerized. Several different initiators can also be used in emulsion polymerization.
  • Regulators can be used in the polymerization, e.g. B. 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. Are suitable for.
  • B. Compounds with a thiol group such as tert. -Butylmercaptan, thioglycolic acid ethyl acrylate, mercaptoethynol, mercaptopropyltrimethoxysilane or tert. -Dodecylmercapant.
  • the emulsion polymerization is usually carried out at 30 to 130, preferably 50 to 95 ° C.
  • the polymerization medium can consist only of water, as well as mixtures of water and thus miscible liquids such as methanol. Preferably only water is used.
  • the emulsion polymerization can be carried out either as a batch process or in the form of a feed process, including a step or gradient procedure.
  • the feed process is preferred, in which part of the polymerization batch is initially charged, heated to the polymerization temperature, polymerized and then the rest of the polymerization batch, usually via a plurality of spatially separate feeds, one or more of which contain the monomers in pure or in emulsified form , continuously, stepwise or by superimposing a concentration gradient while maintaining the polymerization of the polymerization zone.
  • a polymer seed In the polymerization z. B. to better adjust the particle size, 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 person skilled in the art. It can either be completely introduced into the polymerization vessel or used continuously or in stages in the course of the free radical aqueous emulsion polymerization, depending on its consumer. In detail, this depends on the chemical nature of the initiator system as well as on the polymerisation temperature. A portion is preferably introduced and the remainder is fed to the polymerization zone in accordance with the consumption. To remove the residual monomers, initiator is usually also added after the end of the actual emulsion polymerization, ie after a conversion of the monomers of at least 95%.
  • the individual components can be added to the reactor in the feed process from above, in the side or from below through the reactor floor.
  • aqueous dispersions of the polymer are generally obtained with solids contents of from 15 to 75% by weight, preferably from 40 to 75% by weight.
  • dispersions with the highest possible solids content are preferred.
  • solids contents of> 60% by weight one should set a bimodal or polymodal particle size, since otherwise the viscosity becomes too high and the dispersion can no longer be handled.
  • a new generation of particles can be generated, for example, by adding seeds (EP 81083), by adding excess amounts of emulsifier or by adding mini-emulsions.
  • Another advantage associated with the low viscosity at high solids content is the improved coating behavior at high solids contents.
  • a new / new generation of particles can be generated at any time. It depends on the particle size distribution desired for a low viscosity.
  • the copolymer is preferably used in the form of its aqueous dispersion.
  • the paper coating slips according to the invention contain the copolymer as a binder, preferably in amounts of 1 to 50, in particular 5 to 20 wt.
  • pigments are usually the main component of the paper coating slips.
  • pigments are, for example, barium sulfate, calcium carbonate, calcium sulfoaluminate, kaolin, talc, titanium dioxide, zinc oxide, chalk or coating clay or organic pigments, eg. B. Particulate plastics.
  • the paper coating slips can contain other additives.
  • the paper coating slips can contain, for example, dispersants. Suitable dispersants are polyanions, for example of polyphosphoric acids or of polyacrylic acids (polysalts), which are usually present in amounts of 0.1 to 3% by weight, based on the amount of pigment.
  • the paper coating slips can also contain so-called "co-binders".
  • cobinders examples include Starch, casein, gelatin, alginates and soy proteins, mentioned as modified natural products hydroxyethyl cellulose, methyl cellulose and carboxymethyl cellulose and cationically modified starch.
  • conventional synthetic cobinders e.g. based on vinyl acetate or acrylate.
  • These can e.g. in amounts of 0.1 to 10% by weight, based on the amount of pigment.
  • the constituents are mixed in a known manner, the polymer generally being used in the form of an aqueous dispersion, suspension or solution.
  • the water content in the paper coating slip is usually set to 25 to 75% by weight, based on the total paper coating slip (including water).
  • the paper coating slip can be applied to the papers to be coated by customary methods (cf. Ulimann's Encyclopedia of Technical Chemistry, 4th edition, vol. 17, pp. 603 ff).
  • the papers coated with the paper coating slips according to the invention have a high dry and wet pick resistance (adhesion of the paper coating slip). This makes them particularly suitable for offset printing, in which high tensile forces are exerted by the printing ink on the coated paper.
  • the papers coated with the paper coating slips according to the invention show good printability.
  • the papers are also particularly suitable for offset printing processes. Examples
  • the template was heated to 85 ° C. and polymerized for 15 minutes. Then the monomer emulsion was metered in over 2 hours and the initiator (1% by weight solution of 6.29 g of sodium peroxodisulfate in H0) was metered in over 2.5 hours. The mixture was then polymerized for a further 1 hour and cooled.
  • the preparation corresponded to Example 1, but only 12 g of acrylic acid and additionally 12 g of PMS were used.
  • the preparation corresponded to Example 1, but only 6 g of acrylic acid and an additional 18 g of PMS were used.
  • the preparation corresponded to Example 1, but no acrylic acid and instead 24 g of PMS were used.
  • composition of the copolymers in% by weight is given in Table 1.
  • a paper coating slip was prepared by stirring the following components.
  • CMC 7L2T carboxymethyl cellulose
  • the solids content was adjusted to 65% by weight with water.
  • a wood-free coating base paper with a basis weight of 70 g / m 2 was used as the base paper.
  • the paper coating slip was applied on one side at 10 g / m 2 on a laboratory coating machine. Drying was carried out using an IR radiator. Before the application tests, the papers passed four times through a laboratory calender (a pair of rollers, line pressure: 2000 N / cm).
  • Strips in the size of 33 x 3 cm were cut lengthwise from the papers to be tested and these strips were stored for 15 hours at 27 ° C. with a relative atmospheric humidity of 50 in the climatic room.
  • the strips were then printed in a printing unit (IGT printability tester AC2 / AIC2) with a standard color (printing ink 3808 from Lorilleux-Lefranc).
  • the test strips are performed with continuously increasing speed (maximum 'rate 200 cm / sec) through the printing unit. As a measure of the dry pick resistance, the speed is given in cm / sec, at which 10 tears from the paper coating slip (pick points) occurred after the start of printing.
  • test strips were produced and prepared as described above.
  • the printing unit (IGT printability tester AC2 / AIC2) was set up so that the test strips are moistened with water before the printing process.
  • Printing was carried out at a constant speed of 0.6 cm / s.
  • the papers to be tested are turned into samples with a size of
  • a corresponding amount of the printing ink is placed on the inking roller and run for 1 min. Then a pressure disc is inserted and colored for 30 s.
  • the printing speed is 1 m / s.
  • a paper strip is brought back to the starting position on a print sample carrier with the printed paper strip. After a specified period of time, the printing process is started again without replacing the printing disc. This process is repeated several times.
  • the picking on the printed side of the paper strip is checked visually. The number of passes is indicated until the first picking occurs. If the picking is very strong, the last pass is only started as half give (eg strong plucking after the 3rd pass is given as 2.5).

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Paper (AREA)
  • Control And Other Processes For Unpacking Of Materials (AREA)

Abstract

Pâtes de couchage pour papier, contenant en tant que liant un copolymère obtenu par polymérisation radicalaire de composés éthyléniquement insaturés. Selon la présente invention, au moins un des composés éthyléniquement insaturés est un polymère possédant au moins un groupe copolymérisable éthyléniquement insaturé, un poids moléculaire moyen en nombre de 500 à 50.000 g/mol et au moins un groupe acide carboxylique (désigné ultérieurement sous le terme de polymère éthyléniquement insaturé).
EP01936144A 2000-03-28 2001-03-27 Pates de couchage pour papier, contenant des liants a macromonomeres Expired - Lifetime EP1268931B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10015262A DE10015262A1 (de) 2000-03-28 2000-03-28 Papierstreichmassen, enthaltend Bindemittel mit Makromonomeren
DE10015262 2000-03-28
PCT/EP2001/003469 WO2001073199A1 (fr) 2000-03-28 2001-03-27 Pates de couchage pour papier, contenant des liants a macromonomeres

Publications (2)

Publication Number Publication Date
EP1268931A1 true EP1268931A1 (fr) 2003-01-02
EP1268931B1 EP1268931B1 (fr) 2003-11-19

Family

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Application Number Title Priority Date Filing Date
EP01936144A Expired - Lifetime EP1268931B1 (fr) 2000-03-28 2001-03-27 Pates de couchage pour papier, contenant des liants a macromonomeres

Country Status (7)

Country Link
US (1) US6852423B2 (fr)
EP (1) EP1268931B1 (fr)
CN (1) CN1234937C (fr)
AT (1) ATE254691T1 (fr)
AU (1) AU2001262138A1 (fr)
DE (2) DE10015262A1 (fr)
WO (1) WO2001073199A1 (fr)

Families Citing this family (42)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7666588B2 (en) 2001-03-02 2010-02-23 Ibis Biosciences, Inc. Methods for rapid forensic analysis of mitochondrial DNA and characterization of mitochondrial DNA heteroplasmy
US20040121311A1 (en) 2002-12-06 2004-06-24 Ecker David J. Methods for rapid detection and identification of bioagents in livestock
US20030027135A1 (en) 2001-03-02 2003-02-06 Ecker David J. Method for rapid detection and identification of bioagents
US7226739B2 (en) 2001-03-02 2007-06-05 Isis Pharmaceuticals, Inc Methods for rapid detection and identification of bioagents in epidemiological and forensic investigations
US8073627B2 (en) 2001-06-26 2011-12-06 Ibis Biosciences, Inc. System for indentification of pathogens
US7217510B2 (en) 2001-06-26 2007-05-15 Isis Pharmaceuticals, Inc. Methods for providing bacterial bioagent characterizing information
EP1578399A4 (fr) 2002-12-06 2007-11-28 Isis Pharmaceuticals Inc Procedes d'identification rapide de pathogenes chez l'homme et les betes
US8057993B2 (en) 2003-04-26 2011-11-15 Ibis Biosciences, Inc. Methods for identification of coronaviruses
US8158354B2 (en) 2003-05-13 2012-04-17 Ibis Biosciences, Inc. Methods for rapid purification of nucleic acids for subsequent analysis by mass spectrometry by solution capture
US7964343B2 (en) 2003-05-13 2011-06-21 Ibis Biosciences, Inc. Method for rapid purification of nucleic acids for subsequent analysis by mass spectrometry by solution capture
US8546082B2 (en) 2003-09-11 2013-10-01 Ibis Biosciences, Inc. Methods for identification of sepsis-causing bacteria
US8242254B2 (en) 2003-09-11 2012-08-14 Ibis Biosciences, Inc. Compositions for use in identification of bacteria
US8097416B2 (en) 2003-09-11 2012-01-17 Ibis Biosciences, Inc. Methods for identification of sepsis-causing bacteria
DE102004003262A1 (de) * 2004-01-21 2005-08-11 Basf Ag Thermisch polymerisierbare Mischungen aus multifunktionellen Makromonomeren und Polymerisationsinitiatoren und ihre Verwendung als Bindemittel für Substrate
US7666592B2 (en) 2004-02-18 2010-02-23 Ibis Biosciences, Inc. Methods for concurrent identification and quantification of an unknown bioagent
JP4810533B2 (ja) 2004-05-24 2011-11-09 アイビス バイオサイエンシズ インコーポレイティッド ディジタルスレショルド化による選択的イオン濾過作用を用いた質量分光測定法
US20050266411A1 (en) 2004-05-25 2005-12-01 Hofstadler Steven A Methods for rapid forensic analysis of mitochondrial DNA
US7811753B2 (en) 2004-07-14 2010-10-12 Ibis Biosciences, Inc. Methods for repairing degraded DNA
WO2006135400A2 (fr) 2004-08-24 2006-12-21 Isis Pharmaceuticals, Inc. Procedes pour l'identification rapide d'organismes recombinants
WO2006050873A1 (fr) * 2004-11-12 2006-05-18 Basf Aktiengesellschaft Pate a papier de couchage a base d'hybrides pigments-polymeres
US8084207B2 (en) 2005-03-03 2011-12-27 Ibis Bioscience, Inc. Compositions for use in identification of papillomavirus
US8182992B2 (en) 2005-03-03 2012-05-22 Ibis Biosciences, Inc. Compositions for use in identification of adventitious viruses
WO2007014045A2 (fr) 2005-07-21 2007-02-01 Isis Pharmaceuticals, Inc. Procede pour l'identification et la quantification rapide de variants d'acide nucleique
WO2007118222A2 (fr) 2006-04-06 2007-10-18 Ibis Biosciences, INC Compositions pour l'identification de champignons
WO2008143627A2 (fr) 2006-09-14 2008-11-27 Ibis Biosciences, Inc. Procédé d'amplification ciblée de génome entier pour l'identification d'agents pathogènes
JP5680304B2 (ja) 2007-02-23 2015-03-04 アイビス バイオサイエンシズ インコーポレイティッド 迅速な法医学的ｄｎａ分析法
WO2008151023A2 (fr) 2007-06-01 2008-12-11 Ibis Biosciences, Inc. Procédés et compositions pour l'amplification par déplacement multiple d'acides nucléiques
KR20100107010A (ko) * 2008-01-29 2010-10-04 가부시키가이샤 도쿠야마 연료전지용 격막 및 그 제조방법
EP2347254A2 (fr) 2008-09-16 2011-07-27 Ibis Biosciences, Inc. Unités de traitement d'échantillons, systèmes et procédés associés
EP2349549B1 (fr) 2008-09-16 2012-07-18 Ibis Biosciences, Inc. Cartouches de mélange, postes de mélange et kits, et système associé
WO2010033625A1 (fr) 2008-09-16 2010-03-25 Ibis Biosciences, Inc. Systèmes de manipulation de microplaques et produits-programmes informatiques et procédés connexes
WO2010093943A1 (fr) 2009-02-12 2010-08-19 Ibis Biosciences, Inc. Ensembles sonde d'ionisation
WO2010104798A1 (fr) 2009-03-08 2010-09-16 Ibis Biosciences, Inc. Procédés de détection d'un bioagent
WO2010114842A1 (fr) 2009-03-30 2010-10-07 Ibis Biosciences, Inc. Systèmes, dispositifs et procédés de détection d'agent biologique
WO2011008971A1 (fr) 2009-07-17 2011-01-20 Ibis Biosciences, Inc. Appareil de levage et de montage
WO2011008972A1 (fr) 2009-07-17 2011-01-20 Ibis Biosciences, Inc. Systèmes pour l'identification d'un bioagent
US9416409B2 (en) 2009-07-31 2016-08-16 Ibis Biosciences, Inc. Capture primers and capture sequence linked solid supports for molecular diagnostic tests
US9080209B2 (en) 2009-08-06 2015-07-14 Ibis Biosciences, Inc. Non-mass determined base compositions for nucleic acid detection
US9890408B2 (en) 2009-10-15 2018-02-13 Ibis Biosciences, Inc. Multiple displacement amplification
WO2011115840A2 (fr) 2010-03-14 2011-09-22 Ibis Biosciences, Inc. Recherche de parasites par le biais de la recherche d'endosymbiotes
CN104662056B (zh) 2012-09-28 2017-10-20 罗门哈斯公司 水性聚合物接枝乳胶
EP3075904B1 (fr) * 2015-03-31 2017-11-08 BillerudKorsnäs AB Substrat avec revêtement étirable

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3105779A1 (de) 1981-02-17 1982-09-02 Bayer Ag, 5090 Leverkusen Waessrige dispersionen, ihre herstellung und verwendung
FR2523984A1 (fr) 1982-03-24 1983-09-30 Rhone Poulenc Spec Chim Emulsions aqueuses d'interpolymere, procede pour les preparer et utilisations notamment comme liants pour le couchage du papier
DE3888644T3 (de) 1987-12-14 1998-11-05 New Oji Paper Co Wässrige härtbare Harzdispersionen, Verfahren zu deren Herstellung und deren Verwendung.
GB9316221D0 (en) 1993-08-05 1993-09-22 Zeneca Ltd Production of polymer emulsions
DE4442729A1 (de) 1994-12-01 1996-06-05 Basf Ag Alkenylnitril enthaltende Bindemittel für Papierstreichmassen
FR2729150A1 (fr) 1995-01-06 1996-07-12 Rhone Poulenc Chimie Poudres redispersables dans l'eau de polymeres filmogenes a structure "coeur/ecorce"
DE19522399A1 (de) 1995-06-21 1997-01-02 Basf Ag Verwendung von Papierstreichmassen mit hohem Butadiengehalt im Offsetdruck

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO0173199A1 *

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CN1419620A (zh) 2003-05-21
EP1268931B1 (fr) 2003-11-19
DE10015262A1 (de) 2001-10-04
WO2001073199A1 (fr) 2001-10-04
CN1234937C (zh) 2006-01-04
AU2001262138A1 (en) 2001-10-08
US20030068478A1 (en) 2003-04-10
ATE254691T1 (de) 2003-12-15
DE50101000D1 (de) 2003-12-24
US6852423B2 (en) 2005-02-08

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