[go: up one dir, main page]

WO2011146367A1 - Procédé de fabrication du papier - Google Patents

Procédé de fabrication du papier Download PDF

Info

Publication number
WO2011146367A1
WO2011146367A1 PCT/US2011/036603 US2011036603W WO2011146367A1 WO 2011146367 A1 WO2011146367 A1 WO 2011146367A1 US 2011036603 W US2011036603 W US 2011036603W WO 2011146367 A1 WO2011146367 A1 WO 2011146367A1
Authority
WO
WIPO (PCT)
Prior art keywords
copolymer
derived compound
polymer latex
carbohydrate derived
latex binder
Prior art date
Application number
PCT/US2011/036603
Other languages
English (en)
Inventor
Ron Levin
Craig Leavitt
Dwight Pakan
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
Priority to CA2799783A priority Critical patent/CA2799783A1/fr
Priority to US13/698,438 priority patent/US20130062029A1/en
Priority to BR112012029267A priority patent/BR112012029267A2/pt
Priority to CN2011800296857A priority patent/CN102947506A/zh
Priority to EP11721682A priority patent/EP2572040A1/fr
Publication of WO2011146367A1 publication Critical patent/WO2011146367A1/fr

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
    • D21H21/18—Reinforcing agents
    • 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
    • D21H17/20—Macromolecular organic compounds
    • D21H17/21—Macromolecular organic compounds of natural origin; Derivatives thereof
    • D21H17/24—Polysaccharides
    • D21H17/28—Starch
    • 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
    • D21H17/20—Macromolecular organic compounds
    • D21H17/33—Synthetic macromolecular compounds
    • D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/35—Polyalkenes, e.g. polystyrene
    • 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
    • D21H17/20—Macromolecular organic compounds
    • D21H17/33—Synthetic macromolecular compounds
    • D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/36—Polyalkenyalcohols; Polyalkenylethers; Polyalkenylesters
    • 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
    • D21H17/20—Macromolecular organic compounds
    • D21H17/33—Synthetic macromolecular compounds
    • D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/37—Polymers of unsaturated acids or derivatives thereof, e.g. polyacrylates
    • 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
    • D21H23/00—Processes or apparatus for adding material to the pulp or to the paper
    • D21H23/02—Processes or apparatus for adding material to the pulp or to the paper characterised by the manner in which substances are added
    • D21H23/04—Addition to the pulp; After-treatment of added substances in the pulp

Definitions

  • This disclosure relates to papermaking and more particularly to a method of making paper that includes adding a polymer latex binder derived from a carbohydrate derived compound to an aqueous slurry to form paper.
  • Papermaking is a process of introducing an aqueous slurry of pulp or wood cellulosic fibers onto a screen or similar device so that the water can be removed, thereby forming a sheet of consolidated fibers, which upon pressing and drying can be processed into dry roll or sheet form.
  • the feed or inlet to the paper machine is an aqueous slurry or water suspension of pulp fibers, which can be provided from a wet end system.
  • the pulp along with other additives can be mixed in an aqueous slurry and subjected to mechanical and other operations such as beating and refining to improve interfiber bonding and other physical properties of the finished sheet.
  • Additives commonly introduced along with the pulp fibers may include pigments such as titanium dioxide, mineral fillers such as clay and calcium carbonate, and other materials introduced into paper to achieve properties such as improved brightness, opacity, smoothness, ink receptivity, fire retardancy, water resistance, and increased bulk.
  • a polymer latex binder that has a copolymer of one or more unsaturated monomers and a carbohydrate derived compound having a dextrose equivalent (DE) of 10 to 35 such as a dextrin or maltodextrin.
  • DE dextrose equivalent
  • the polymer latex binder can be used in a wet end application of a papermaking process. Paper sheets made with the polymer latex binder can have enhanced dry paper strength, even in the presence of relatively high filler contents.
  • a method of making paper can include mixing a polymer latex binder with an aqueous suspension that has pulp fibers.
  • the polymer latex binder can include a copolymer that is obtained by polymerizing one or more unsaturated monomers and a carbohydrate derived compound that has a dextrose equivalent (DE) of 10 to 35.
  • the method can also include removing water from the mixture of the aqueous suspension and the polymer latex binder and forming the paper.
  • the mixture of the aqueous suspension and the polymer latex binder can be dried to form paper.
  • the polymer latex binder can be prepared by copolymerizing in an aqueous medium a mixture of the one or more unsaturated monomers and the carbohydrate derived compound.
  • the one or more unsaturated monomers can be present in an amount of greater than 60 wt% based on total monomer weight.
  • the carbohydrate derived compound can be present in an amount of less than 50 wt% based on total monomer weight (e.g. 5 to 45 wt%).
  • the copolymer can be present in an amount of 2 to 12 wt% of the solids content based on the total solids content of the mixture of the aqueous slurry and the polymer latex binder.
  • the copolymer can include a pure acrylic copolymer, a styrene acrylic copolymer, a styrene butadiene copolymer, or a vinyl acrylic copolymer.
  • the one or more unsaturated monomers can include an ethylenically unsaturated monomer.
  • the carbohydrate derived compound can be selected from the group consisting of dextrins, maltodextrins, and mixtures thereof.
  • the carbohydrate derived compound can have a weight average molecular weight of 3000 to 20,000.
  • the carbohydrate derived compound can be soluble in water at room temperature in an amount of greater than 40% by weight.
  • a solution of the carbohydrate derived compound in an amount of 50% by weight in water at room temperature can have a viscosity of 100 to 1000 cps.
  • the carbohydrate derived compound can have a non-uniformity of 6 to 12.
  • the carbohydrate derived compound can be chemically modified by etherification or esterification.
  • One or more additional binders can be added to the mixture of the aqueous suspension and the polymer latex binder.
  • One or more cationic retention aids can also be added to the mixture.
  • the aqueous suspension can have less than 2 wt% solids when the polymer latex binder is added.
  • the polymer latex binder can be added at a temperature of 40°C to 80°C.
  • a paper sheet can include a matrix of pulp fibers that has a copolymer uniformly dispersed throughout.
  • the copolymer can be derived from one or more unsaturated monomers and a carbohydrate derived compound that has a dextrose equivalent (DE) of 10 to 35.
  • DE dextrose equivalent
  • FIGS. 1-5 show tensile strength for various papers prepared according to working and comparative examples.
  • paper as used herein describes cellulosic materials such as newsprint, SC paper (super-calendered paper), wood-free or wood-containing writing and printing paper, paperboard, cardboard, linerboard, corrugating medium, tissue, toweling, and the like.
  • a method of making paper includes adding to an aqueous suspension containing pulp fibers a polymer latex binder comprising a copolymer obtained by polymerization of one or more unsaturated monomers and a carbohydrate derived compound having a dextrose equivalent (DE) of 10 to 35 to form a mixture thereof.
  • the method also includes removing water from the mixture of the aqueous suspension and the polymer latex binder and forming paper.
  • the paper can be formed (e.g. into a sheet) and the aqueous pulp suspension can be dried.
  • the resultant paper can have increased paper properties such as enhanced dry paper strength.
  • the copolymer can be a pure acrylic copolymer, a styrene acrylic copolymer, a styrene butadiene copolymer, or a vinyl acrylic copolymer.
  • Suitable unsaturated monomers for use in forming the copolymer are generally ethylenically unsaturated monomers and include vinylaromatic compounds (e.g. styrene, a-methylstyrene, o- chlorostyrene, and vinyltoluenes); 1,2-butadiene (i.e. butadiene); conjugated dienes (e.g.
  • ⁇ , ⁇ -monoethylenically unsaturated mono and dicarboxylic acids or anhydrides thereof e.g. acrylic acid, methacrylic acid, crotonic acid, dimethacrylic acid, ethylacrylic acid, allylacetic acid, vinylacetic acid maleic acid, fumaric acid, itaconic acid, mesaconic acid, methylmalonic acid, citraconic acid, maleic anhydride, itaconic anhydride, and methylmalonic anhydride
  • esters of ⁇ , ⁇ - monoethylenically unsaturated mono and dicarboxylic acids having 3 to 6 carbon atoms with alkanols having 1 to 12 carbon atoms e.g.
  • (meth)acrylonitrile vinyl and vinylidene halides (e.g. vinyl chloride and vinylidene chloride); vinyl esters of CI -CI 8 mono or dicarboxylic acids (e.g. vinyl acetate, vinyl propionate, vinyl n-butyrate, vinyl laurate and vinyl stearate); C1-C4 hydro xyalkyl esters of C3-C6 mono or dicarboxylic acids, especially of acrylic acid, methacrylic acid or maleic acid, or their derivatives alkoxylated with from 2 to 50 moles of ethylene oxide, propylene oxide, butylene oxide or mixtures thereof, or esters of these acids with CI -CI 8 alcohols alkoxylated with from 2 to 50 moles of ethylene oxide, propylene oxide, butylene oxide or mixtures thereof (e.g.
  • hydroxyethyl (meth)acrylate hydroxypropyl (meth)acrylate, and methylpolyglycol acrylate
  • monomers containing glycidyl groups e.g. glycidyl methacrylate.
  • Additional monomers that can be used include linear 1 -olefins, branched-chain 1- olefins or cyclic olefins (e.g., ethene, propene, butene, isobutene, pentene, cyclopentene, hexene, and cyclohexene); vinyl and allyl alkyl ethers having 1 to 40 carbon atoms in the alkyl radical, wherein the alkyl radical can possibly carry further substituents such as a hydroxyl group, an amino or dialkylamino group, or one or more alkoxylated groups (e.g.
  • allylsulfonic acid methallylsulfonic acid, styrenesulfonate, vinylsulfonic acid, allyloxybenzenesulfonic acid, 2-acrylamido-2- methylpropanesulfonic acid, and their corresponding alkali metal or ammonium salts, sulfopropyl acrylate and sulfopropyl methacrylate); vinylphosphonic acid, dimethyl vinylphosphonate, and other phosphorus monomers; alky lamino alky 1 (meth)acrylates or alkylaminoalkyl(meth)acrylamides or quaternization products thereof (e.g.
  • acetoacetoxyethyl(meth)acrylate or diacetonacrylamide monomers containing urea groups (e.g. ureidoethyl (meth)acrylate, acrylamidoglycolic acid, and
  • methacrylamidoglycolate methyl ether methacrylamidoglycolate methyl ether
  • monomers containing silyl groups e.g. trimethoxysilylpropyl methacrylate
  • the monomers can also include one or more crosslinkers such as N-alkylolamides of ⁇ , ⁇ -monoethylenically unsaturated carboxylic acids having 3 to 10 carbon atoms and esters thereof with alcohols having 1 to 4 carbon atoms (e.g. N-methylolacrylamide and N-methylolmethacrylamide); glyoxal based crosslinkers; monomers containing two vinyl groups; monomers containing two vinylidene groups; and monomers containing two alkenyl groups.
  • exemplary crosslinking monomers include diesters of dihydric alcohols with ⁇ , ⁇ -monoethylenically unsaturated monocarboxylic acids, of which in turn acrylic acid and methacrylic acid can be employed.
  • alkylene glycol diacrylates and dimethacrylates such as ethylene glycol diacrylate, 1,3-butylene glycol diacrylate, 1,4-butylene glycol diacrylate and propylene glycol diacrylate, divinylbenzene, vinyl methacrylate, vinyl acrylate, allyl methacrylate, allyl acrylate, diallyl maleate, diallyl fumarate and methylenebisacrylamide.
  • the crosslinking monomers include alkylene glycol diacrylates and dimethacrylates, and/or
  • crosslinking monomers when used in the copolymer can be present in an amount of from 0.2% to 5% by weight based on the weight of the total monomer and are considered part of the total amount of monomers used in the copolymer.
  • molecular weight regulators such as tert- dodecyl mercaptan
  • Such substances are preferably added to the polymerization zone in a mixture with the monomers to be polymerized and are considered part of the total amount of unsaturated monomers used in the copolymer.
  • the unsaturated monomers can include styrene, a- methylstyrene, (meth)acrylic acid (i.e., acrylic acid and/or methacrylic acid), itaconic acid, maleic acid, fumaric acid, crotonic acid, methyl (meth)acrylate, ethyl
  • (meth)acrylic acid i.e., acrylic acid and/or methacrylic acid
  • itaconic acid i.e., maleic acid, fumaric acid, crotonic acid
  • maleic acid fumaric acid
  • crotonic acid methyl (meth)acrylate
  • the copolymer can be a styrene acrylic copolymer derived from unsaturated monomers including styrene, (meth)acrylic acid, (meth)acrylic acid esters, (meth)acrylamide, (meth)acrylonitrile, and mixtures thereof.
  • the styrene acrylic copolymer can include styrene and at least one of (meth)acrylic acid, itaconic acid, methyl (meth)acrylate, ethyl (meth) acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate,
  • the unsaturated monomers of the styrene acrylic copolymer can include from 39 to 69% by weight of (meth)acrylates, from 30 to 60% by weight of styrene, 0 to 3% by weight of (meth)acrylamide, and 0 to 10% by weight of (meth)acrylonitrile.
  • the unsaturated monomers of the styrene acrylic copolymer can also include from 0 to 5% by weight of one or more crosslinking monomers as described above such as alkylene glycol diacrylates and dimethacrylates.
  • the copolymer can be pure acrylic copolymer derived from one or more unsaturated monomers including (meth)acrylic acid, (meth)acrylic acid esters, (meth)acrylamide, (meth)acrylonitrile, and mixtures thereof.
  • the pure acrylic copolymer can include at least one of (meth)acrylic acid, itaconic acid, methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl
  • the unsaturated monomers of the pure acrylic copolymer can include from 76 to 100% of at least one (meth)acrylic acid ester (e.g. 90 to 99%); 0 to 6% of itaconic acid and/or meth(acrylic) acid; 0 to 3% of at least one (meth)acrylamide, and 0 to 10% of at least one (meth)acrylonitrile.
  • the styrene acrylic copolymer can also include from 0 to 5% by weight of one or more crosslinking monomers as described above such as alkylene glycol diacrylates and dimethacrylates.
  • the copolymer can be a styrene butadiene copolymer derived from unsaturated monomers including styrene, butadiene, (meth)acrylamide, (meth)acrylonitrile, itaconic acid and (meth)acrylic acid.
  • the unsaturated monomers of the styrene butadiene copolymer can include from 40 to 75% by weight of styrene, from 25 to 60% by weight of butadiene, 1 to 10% of itaconic and/or (meth)acrylic acid, 0 to 3% by weight of (meth)acrylamide, and 0 to 20% by weight (meth)acrylonitrile.
  • the styrene butadiene copolymer can also include from 0 to 5% by weight of one or more crosslinking monomers as described above such as divinylbenzene.
  • the copolymer is derived from the unsaturated monomers in an amount of from greater than 50 to less than 100 wt%, 55 to 95 wt%, 60 to 92 wt%, or 65 to 85 wt%, based on the total monomer weight (or dry polymer weight in the paper).
  • the copolymer is formed from a carbohydrate derived compound.
  • the carbohydrate derived compound can have a dextrose equivalent (DE) of 10 to 35, 12.5 to 25, or 15 to 20.
  • the DE value can be determined in accordance with the Lane and Eynon test method (International Standard ISO 5377: 1981).
  • the weight average molecular weight (M w ) of the carbohydrate derived compound can be 3000 to 20,000, 5000 to 17,000, or 8000 to 14,000.
  • the weight average molecular weight data can be determined using gel permeation chromatography (GPC).
  • the carbohydrate derived compound can be soluble in water at room temperature (e.g., 25 degree C) in an amount of greater than 40%, greater than 50%, or greater than 60% by weight, or can even be completely soluble in water at room temperature.
  • Solutions of the carbohydrate derived compound in an amount of 50% by weight in water at room temperature can have a viscosity of 100 to 1000 cps, or 200 to 500 cps.
  • the carbohydrate derived compound can include dextrins, maltodextrins, or mixtures thereof.
  • the dextrins, malto dextrins, or mixtures thereof can have the DE's, molecular weights, water solubilities, and viscosities described above.
  • the dextrins and maltodextrins are generally degraded starches whose degradation is effected by heating with or without addition of chemicals, it being possible to recombine degradation fragments under the degradation conditions to form new bonds which were not present in this form in the original starch.
  • Roast dextrins such as white and yellow dextrins that are prepared by heating moist-dry starch, usually in the presence of small amounts of acid, are less preferred.
  • the carbohydrate derived compound can be prepared as described in Guinther Tegge, Starke und Starkederivate, Behr's Verlag, Hamburg 1984, p. 173 and p. 220 and in EP 441 197.
  • the carbohydrate derived compound can be prepared from any native starches, such as cereal starches (e.g. corn, wheat, rice or barley), tuber and root starches (e.g. potatoes, tapioca roots or arrowroot) or sago starches.
  • the carbohydrate derived compound can also have a bimodal molecular weight distribution and can have a weight average molecular weight as described above.
  • the carbohydrate derived compound can have a nonuniformity U (defined as the ratio between the weight average weight M w and the number average molecular weight M n ) that characterizes the molecular weight distribution in the range from 6 to 12, from 7 to 1 1 or from 8 to 10.
  • the proportion by weight of carbohydrate derived compound having a molecular weight of below 1000 can be from 10% to 70% by weight, or 20 to 40% by weight.
  • the carbohydrate derived compound in a 40% strength by weight aqueous solution can have a dynamic viscosity ⁇ 40 [Pa-s], determined in accordance with DIN 53 019 at 25°C and a shear gradient of 75 s "1 , of from 0.01 to 0.06, 0.015 to 0.04, or 0.02 to 0.035.
  • the carbohydrate derived compound can be chemically modified such as by etherification or esterification.
  • the chemical modification can be carried out in advance on a starting starch before its degradation. Esterification is possible using both inorganic and organic acids, or anhydrides or chlorides thereof.
  • Phosphated and acetylated degraded starches can also be used.
  • the most common method of etherification is treatment with organohalogen compounds, epoxides or sulfates in aqueous alkaline solution.
  • the ethers can be alkyl ethers, hydroxyalkyl ethers, carboxyalkyl ethers and allylethers.
  • the copolymer can be derived from greater than 0 to less than 50 wt%, 5 to 45 wt%, 8 to 40 wt%, or 15 to 35 wt%, of the carbohydrate derived compound based on the total monomer weight (or dry polymer weight in the paper).
  • the papermaking method described herein can include providing the polymer latex binder by polymerizing in an aqueous medium a mixture of the unsaturated monomer(s) and the carbohydrate derived compound to produce the copolymer.
  • the polymer latex binder can be prepared by polymerizing the unsaturated monomers using free-radical aqueous emulsion polymerization in the presence of the carbohydrate derived compound. Suitable methods are described in U.S. Patent No. 6,080,813, which is hereby incorporated by reference in its entirety.
  • the emulsion polymerization temperature is generally from 30 to 95°C or from 75 to 90°C.
  • the polymerization medium can include water alone or a mixture of water and water-miscible liquids, such as methanol. In some embodiments, water is used alone.
  • 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. In some embodiments, a feed process is used in which part of the polymerization batch is heated to the polymerization
  • the initially introduced mixture and/or the monomer feed stream can contain small amounts of emulsifiers, generally less than 0.5% by weight, based on the total amount of monomers to be polymerized.
  • the monomers can be frequently fed to the polymerization zone after pre-emulsification with these assistant emulsifiers.
  • the feed process can be designed by initially introducing the entire carbohydrate derived compound to be used in dissolved form in an aqueous mixture.
  • the aqueous solution produced on partial hydrolysis of the starting starch can, after the hydrolysis has been terminated to form the carbohydrate derived compound, for example by neutralization of the catalytic acid and cooling, be further used directly for the aqueous emulsion polymerization.
  • Prior isolation of the carbohydrate derived compound, for example by spray drying, is unnecessary but can also be used.
  • the free-radical emulsion polymerization can be carried out in the presence of a free-radical polymerization initiator.
  • the free-radical polymerization initiators that can be used in the process are all those which are capable of initiating a free-radical aqueous emulsion polymerization including alkali metal peroxydisulfates and H2O2, or azo compounds.
  • Combined systems can also be used comprising at least one organic reducing agent and at least one peroxide and/or hydroperoxide, e.g., tert-butyl hydroperoxide and the sodium metal salt of hydroxymethanesulfinic acid or hydrogen peroxide and ascorbic acid.
  • Combined systems can also be used additionally containing a small amount of a metal compound which is soluble in the polymerization medium and whose metallic component can exist in more than one oxidation state, e.g., ascorbic acid/iron(II) sulfate/hydrogen peroxide, where ascorbic acid can be replaced by the sodium metal salt of hydroxymethanesulfinic acid, sodium sulfite, sodium hydrogen sulfite or sodium metal bisulfite and hydrogen peroxide can be replaced by tert-butyl hydroperoxide or alkali metal peroxydisulfates and/or ammonium peroxydisulfates.
  • the carbohydrate derived compound can also be used as the reducing component.
  • the amount of free-radical initiator systems employed is from 0.1 to 2% by weight, based on the total amount of the monomers to be polymerized.
  • the initiators are ammonium and/or alkali metal peroxydisulfates (e.g. sodium peroxydisulfates), alone or as a constituent of combined systems.
  • polymerization reactor during the free-radical aqueous emulsion polymerization is not critical. It can either all be introduced into the polymerization reactor at the beginning, or added continuously or stepwise as it is consumed during the free-radical aqueous emulsion polymerization. In detail, this depends in a manner known to an average person skilled in the art both from the chemical nature of the initiator system and on the polymerization temperature. In some embodiments, some is introduced at the beginning and the remainder is added to the polymerization zone as it is consumed. It is also possible to carry out the free-radical aqueous emulsion polymerization under
  • the polymer latex binder can be prepared with a solid content of from 10 to 75% by weight, 15 to 65% by weight, or 20 to 60% by weight.
  • the copolymer can be present in an amount of 2 to 12 wt%, 4 to 10 wt%, or 6 to 9 wt% of the solid content of the solids content of the mixture of the aqueous suspension and the polymer latex binder.
  • the polymer latex binder can then be concentrated if desired to provide a total solid content of 40-75% by weight.
  • the polymer latex binder can be converted, in a manner known per se, to redispersible polymer powders (e.g., spray drying, roll drying or suction-filter drying). If the polymer latex binder is to be dried, drying aids can be used.
  • the copolymers have a long shelf life and can be redispersed in water for use in the paper coating or binding formulation.
  • the polymer latex binder contains no or substantially no polyvinyl alcohol, carboxylmethylcellulose, polyvinylpyrrolidone and water-insoluble starches.
  • the method can include the addition of one or more polymer binders that have not been derived from the carbohydrate derived compound.
  • the polymer binder can be a pure acrylic copolymer, styrene acrylic copolymer, styrene butadiene copolymer, vinyl acrylic copolymer, or a mixture thereof.
  • a styrene acrylic copolymer or a styrene butadiene copolymer could be included.
  • the method can include the addition of fillers.
  • Fillers can be added to impart certain properties to the paper such as smoothness, whiteness, increased density or weight, decreased porosity, increased opacity, flatness, glossiness, and the like.
  • Suitable fillers include calcium carbonate (precipitated or ground), kaolin, bentonite, or other clays; talc; diatomaceous earth; mica; barium sulfate; magnesium carbonate; vermiculite; graphite; carbon black; alumina; silicas (fumed or precipitated in powders or dispersions); colloidal silica; silica gel; titanium oxide; aluminum hydroxide; aluminum trihydrate; satine white; magnesium oxide; plastic pigments; white urea resin pigments; and rubber powder.
  • the paper can have a filler content of 4 to 60% by weight based on dried paper stock. In some embodiments, the paper can have a filler content of 5 to 40 wt%.
  • the method can include the addition of one or more cationic retention aids to increase the retention of fillers in paper.
  • Suitable cationic retention aids include polyethylene amides or modified polyamides, poly-diallyl-dimethyl ammonium chloride (poly-DADMAC), dimethylamine/epichlorohydrin resins, epichlorohydrin/polyamidoamine resins, polyethyleneimines, aluminum sulphonate (Alum) or poly-aluminum chloride.
  • poly-DADMAC poly-diallyl-dimethyl ammonium chloride
  • Alum aluminum sulphonate
  • a polyethyleneimine commercially available under the POLYMIN trademark from BASF Corporation can be used as a cationic retention aid.
  • the retention aids can be added to the paper stock in the aqueous slurry along with the polymer latex binder and any other wet end additives.
  • the cationic retention aid can be added in an amount of from 0.01% to 2%, from 0.05 to 1%, or from 0.1 to 0.5% (e.g. 0.3%), based on the total pulp content present in the aqueous suspension.
  • the method can include the addition of dyes and/or pigments to produce colored or patterned paper.
  • dyes include basic dyes, acid dyes, anionic direct dyes, cationic direct dyes, anionic pigment dispersions, and cationic pigment dispersions.
  • organic pigments and inorganic pigments can be used as coloring agents including non-toxic anticorrosive pigments.
  • pigments examples include phosphate -type anticorrosive pigments such as zinc phosphate, calcium phosphate, aluminum phosphate, titanium phosphate, silicon phosphate, and ortho and fused phosphates of these; molybdate-type anticorrosive pigments such as zinc molybdate, calcium molybdate, calcium zinc molybdate, potassium zinc molybdate, potassium zinc phosphomolybdate and potassium calcium phosphomolybdate; and borate-type anticorrosive pigments such as calcium borate, zinc borate, barium borate, barium meta-borate and calcium meta-borate.
  • phosphate -type anticorrosive pigments such as zinc phosphate, calcium phosphate, aluminum phosphate, titanium phosphate, silicon phosphate, and ortho and fused phosphates of these
  • molybdate-type anticorrosive pigments such as zinc molybdate, calcium molybdate, calcium zinc molybdate, potassium zinc molybdate, potassium zinc phosphomolybdate
  • the method can include the addition of a thickener.
  • Suitable thickeners include (meth)acrylic acid/alkyl (meth)acrylate copolymers (e.g. SterocoU® FD thickener and SterocoU® FS thickener, both of which are commercially available from BASF Corporation), hydroxyethyl cellulose, guar gum, jaguar, carrageenan, xanthan, acetan, konjac mannan, xyloglucan, urethanes and mixtures thereof.
  • the thickener can be added to the formulation as an aqueous dispersion or emulsion, or as a solid powder.
  • the method can include the addition of other additives.
  • the additives can be any additives that can be generally included in a papermaking process. Further additives include surfactants, wetting agents, protective colloids, biocides, dispersing agents, thixotropic agents, freeze store stability additives, pH adjusting agents, corrosion inhibitors, ultraviolet light stabilizers, crosslinkers, crosslinking promoters, and lubricants.
  • the polymer latex binder is added in a wet end application where in the aqueous suspension include less than 2 wt% solids (i.e., pulp fibers and optionally fillers and other additives) and greater than 98 wt% water (e.g. 1 wt% solids and 99% water).
  • Suitable pulp fibers can include bleached and unbleached Kraft pulps, bleached and unbleached sulfite and sulfate pulps, thermomechanical,
  • the polymer latex binder can be added in an amount of from 0.1% to 10%, from 0.5 to 7.5%), from 1 to 6%, or from 3 to 5%, based on the total pulp content present in the aqueous suspension.
  • the polymer latex binder can be added to the aqueous suspension at any suitable temperatures.
  • the polymer latex binder can be added at a temperature of from room temperature to less than 100°C, from 40°C to 80°C, or from 45°C to 70°C.
  • the papermaking method described herein can advantageously use relatively high filler contents without substantially impairing the dry strength of the resulting paper.
  • the papermaking method described herein can include typical filler contents and can be used to increase the dry strength of the paper.
  • the paper sheet can include a matrix of pulp fibers having a copolymer uniformly dispersed throughout.
  • the copolymer is derived from one or more unsaturated monomers and a carbohydrate derived compound having a dextrose equivalent (DE) of 10 to 35. Suitable unsaturated monomers and carbohydrate derived compounds are discussed herein.
  • the dry strength of the paper sheet can be increased by 5-300% or more over compositions that do not include the polymer latex binder described herein.
  • An aqueous suspension having 50 parts of Kraft pulp and 50 parts of groundwood pulp was prepared at 1% solids. 16 parts of precipitated calcium carbonate (PCC) were added to the aqueous suspension for paper glossiness. 3 parts dry polymer based on the amount of dry cellulosic material of Acronal® NX 8777 (a styrene/butyl acrylate copolymer dispersion that is derived from 23% maltodextrin and commercially available from BASF Corporation) were added to the aqueous suspension as a polymer latex binder in Working Examples 1-3.
  • PCC precipitated calcium carbonate
  • Comparative Examples 3-4 No polymer latex binder was used in Comparative Example 5.
  • the polymer latex binders were added at 50°C.
  • the polymer latex binders were added at room temperature.
  • 0.3 parts based on the amount of copolymer dispersion added of Polymin® SNA (a polyethyleneimine cationic retention aid commercially available from BASF Corporation) were used in Working Examples 1 -2 and Comparative Examples 1-4.
  • No retention aid was used in Working Example 3 and Comparative Example 5.
  • the tensile strength of the papers made in these examples was measured according to TAPPI test method T404 and results of these measurements are shown in FIG. 1.
  • FIG. 1 also demonstrates that the use of a cationic retention aid and an elevated temperature (50°C) increased the tensile strength of the resulting papers.
  • An aqueous suspension having 50 parts of Kraft pulp and 50 parts of groundwood pulp was prepared.
  • 16 parts of hydrous kaolin or ground calcium carbonate (GCC) were used for paper glossiness: 16 parts of kaolin were added in Working Examples 5 and 7-8, and 16 parts of GCC were added in Working Examples 4, 6 and 9.
  • 3 parts dry polymer based on the amount of dry cellulosic material of Acronal® NX 8777 were used in all the examples as a polymer latex binder.
  • the Acronal® NX 8777 was added at 50°C
  • Examples 4-5 the Acronal® NX 8777 was added at room temperature.
  • An aqueous suspension having 30 parts of Kraft pulp and 70 parts of groundwood pulp was prepared. 16 parts of GCC were added for paper glossiness. 5 parts dry polymer based on the amount of dry cellulosic material of Acronal® NX 8777 were used in Working Example 10 as a polymer latex binder. 5 parts dry polymer based on the amount of dry cellulosic material of Acronal® S728 NA were used in Comparative Example 6 as a polymer latex binder. 5 parts dry polymer based on the amount of dry cellulosic material of Acronal® S504 NA were used in Comparative Example 7 as a polymer latex binder. No polymer latex binder was used in Comparative Example 8.
  • the polymer latex binders were added at room temperature in all of the examples. 0.5 parts based on the amount of copolymer dispersion added of Polymin® SNA were used as a retention aid in Working Example 10 and Comparative Examples 6-7. No retention aid was used in Comparative Example 8. The tensile strength of the papers made in these examples was measured and shown in FIG. 3.
  • the papers prepared using 5 parts of Acronal® NX 8777 which was prepared using maltodextrin, possessed greater tensile strength than the papers using 5 parts of Acronal® S728 NA or Acronal® S504 NA, and was not dependent on the presence of the cationic retention aid or the temperature at which the polymer latex binder was added.
  • Aqueous suspensions having 50, 60, 70 or 80 parts of groundwood pulp and 50, 40, 30 or 20 parts of Kraft pulp were prepared.
  • Comparative Example 9 used the aqueous suspension having 50 parts of groundwood pulp and 50 parts of Kraft pulp;
  • Working Examples 16-19 used the aqueous suspension having 60 parts of groundwood pulp and 40 parts of Kraft pulp;
  • Working Examples 20-22 and Comparative Example 10 used the aqueous suspension having 70 parts of groundwood pulp and 30 parts of Kraft pulp;
  • Working Examples 23-27 used the aqueous suspension having 80 parts of groundwood pulp and 20 parts of Kraft pulp. 16 parts of GCC were added for paper glossiness.
  • the Acronal® NX 8777 was added at 50°C, and for the other examples, the Acronal® NX 8777 was added at room temperature.
  • 0.1 parts based on the amount of copolymer dispersion added of Polymin® SNA were used as a retention aid in Working Examples 11, 16, 20 and 23;
  • 0.3 parts based on the amount of copolymer dispersion added of Polymin® SNA were used in Working Examples 12, 14, 17, 19, 21 , 24, and 26-27; and 0.5 parts based on the amount of copolymer dispersion added of Polymin® SNA were used in Working Examples 13, 18, 22 and 25.
  • No retention aid was used in Working Example 15 and Comparative Examples 9-10.
  • the tensile strength of the papers made in these examples was measured and shown in FIG. 4 and FIG. 5 (adjusted for basis weight).

Landscapes

  • Paper (AREA)

Abstract

La présente invention concerne un procédé de fabrication du papier comprenant l'étape consistant à ajouter un liant de type latex de polymère à une bouillie aqueuse contenant des fibres de pâte à papier, le liant de type latex de polymère comprenant un copolymère obtenu en polymérisant un ou plusieurs monomères insaturés et un composé dérivé d'un glucide ayant un équivalent en dextrose (DE) de 10 à 35. Dans certains modes de réalisation, le composé dérivé d'un glucide peut comprendre des dextrines, des maltodextrines, ou des mélanges de celles-ci.
PCT/US2011/036603 2010-05-17 2011-05-16 Procédé de fabrication du papier WO2011146367A1 (fr)

Priority Applications (5)

Application Number Priority Date Filing Date Title
CA2799783A CA2799783A1 (fr) 2010-05-17 2011-05-16 Procede de fabrication du papier
US13/698,438 US20130062029A1 (en) 2010-05-17 2011-05-16 Method of making paper
BR112012029267A BR112012029267A2 (pt) 2010-05-17 2011-05-16 método para fabricação de papel, e, folha de papel
CN2011800296857A CN102947506A (zh) 2010-05-17 2011-05-16 造纸方法
EP11721682A EP2572040A1 (fr) 2010-05-17 2011-05-16 Procédé de fabrication du papier

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US34534310P 2010-05-17 2010-05-17
US61/345,343 2010-05-17

Publications (1)

Publication Number Publication Date
WO2011146367A1 true WO2011146367A1 (fr) 2011-11-24

Family

ID=44486075

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2011/036603 WO2011146367A1 (fr) 2010-05-17 2011-05-16 Procédé de fabrication du papier

Country Status (6)

Country Link
US (1) US20130062029A1 (fr)
EP (1) EP2572040A1 (fr)
CN (1) CN102947506A (fr)
BR (1) BR112012029267A2 (fr)
CA (1) CA2799783A1 (fr)
WO (1) WO2011146367A1 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014202116A1 (fr) * 2013-06-17 2014-12-24 Synthomer Deutschland Gmbh Latex de polymère à faible odeur et composition de revêtement le comprenant
WO2015040242A1 (fr) * 2013-09-23 2015-03-26 Basf Se Formulations adhésives pour papier et procédés de fabrication et leur utilisation
WO2016093689A1 (fr) 2014-12-12 2016-06-16 Synthomer Sdn. Bhd. Composition de latex polymère pour des applications de revêtement au trempé
WO2017158302A1 (fr) 2016-03-16 2017-09-21 Arjo Wiggins Fine Papers Limited Procédé de fabrication de papier imprégné par un fluide à pression supercritique - papier imprégné, notamment coloré

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BR112017021342B1 (pt) 2015-04-30 2022-01-11 Kimberly-Clark Worldwide, Inc Produtos de papel tissue com excipientes com alto teor de carboidratos
US11028538B2 (en) * 2019-02-28 2021-06-08 Solenis Technologies, L.P. Composition and method for increasing wet and dry paper strength
EP4148174A1 (fr) 2021-09-09 2023-03-15 ecobrain AG Procédé de fabrication de matériaux composites semblables à du tissu non-tissé revêtu à partir de produits de papier revêtu de polymères déchiquetés et de marc de café

Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0441197A2 (fr) 1990-02-03 1991-08-14 BASF Aktiengesellschaft Copolymère greffé à base de monosaccharides, oligosaccharides, polysaccharides et de polysaccharides modifiées, procédé de fabrication de celle-ci et son utilisation
US5578678A (en) * 1991-08-22 1996-11-26 Basf Aktiengesellschaft Graft polymers of natural substances containing saccharide structures or derivatives thereof and ethylenically unsaturated compounds and their use
EP0806522A1 (fr) * 1996-05-09 1997-11-12 Röhm Gmbh Dispersions pour l'imprégnation du papier comprenant l'eau à verre et/ou dextrine
DE19701524A1 (de) * 1997-01-17 1998-07-23 Basf Ag Polymermodifizierte Stärke, Verfahren zu ihrer Herstellung und ihre Verwendung
US6080813A (en) 1991-10-07 2000-06-27 Basf Aktiengesellschaft Aqueous polymer dispersions
US20050215153A1 (en) * 2004-03-23 2005-09-29 Cossement Marc R Dextrin binder composition for heat resistant non-wovens
EP1743976A1 (fr) * 2005-07-13 2007-01-17 SAPPI Netherlands Services B.V. Papiers enduits pour l'impression offset
US20080289786A1 (en) * 2007-05-21 2008-11-27 Koenig Michael F Recording sheet with improved image waterfastness, surface, strength, and runnability
DE102007030102A1 (de) * 2007-06-28 2009-01-02 Technocell Dekor Gmbh & Co. Kg Vorimprägnat
DE102007030406A1 (de) * 2007-06-29 2009-01-08 Henkel Ag & Co. Kgaa Verminderung der Adhäsion von biologischem Material durch Algenextrakte
WO2010089334A1 (fr) * 2009-02-05 2010-08-12 Basf Se Procédé de fabrication de papier, de carton-pâte et de carton présentant une grande résistance à sec

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5705563A (en) * 1991-10-07 1998-01-06 Basf Aktiengesellschaft Aqueous polymer dispersions
DE4221381C1 (de) * 1992-07-02 1994-02-10 Stockhausen Chem Fab Gmbh Pfropf-Copolymerisate von ungesättigten Monomeren und Zuckern, Verfahren zu ihrer Herstellung und ihre Verwendung
US7829611B2 (en) * 2006-08-24 2010-11-09 Rohm And Haas Company Curable composition
US8613834B2 (en) * 2008-04-03 2013-12-24 Basf Se Paper coating or binding formulations and methods of making and using same

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0441197A2 (fr) 1990-02-03 1991-08-14 BASF Aktiengesellschaft Copolymère greffé à base de monosaccharides, oligosaccharides, polysaccharides et de polysaccharides modifiées, procédé de fabrication de celle-ci et son utilisation
US5578678A (en) * 1991-08-22 1996-11-26 Basf Aktiengesellschaft Graft polymers of natural substances containing saccharide structures or derivatives thereof and ethylenically unsaturated compounds and their use
US6080813A (en) 1991-10-07 2000-06-27 Basf Aktiengesellschaft Aqueous polymer dispersions
EP0806522A1 (fr) * 1996-05-09 1997-11-12 Röhm Gmbh Dispersions pour l'imprégnation du papier comprenant l'eau à verre et/ou dextrine
DE19701524A1 (de) * 1997-01-17 1998-07-23 Basf Ag Polymermodifizierte Stärke, Verfahren zu ihrer Herstellung und ihre Verwendung
US20050215153A1 (en) * 2004-03-23 2005-09-29 Cossement Marc R Dextrin binder composition for heat resistant non-wovens
EP1743976A1 (fr) * 2005-07-13 2007-01-17 SAPPI Netherlands Services B.V. Papiers enduits pour l'impression offset
US20080289786A1 (en) * 2007-05-21 2008-11-27 Koenig Michael F Recording sheet with improved image waterfastness, surface, strength, and runnability
DE102007030102A1 (de) * 2007-06-28 2009-01-02 Technocell Dekor Gmbh & Co. Kg Vorimprägnat
DE102007030406A1 (de) * 2007-06-29 2009-01-08 Henkel Ag & Co. Kgaa Verminderung der Adhäsion von biologischem Material durch Algenextrakte
WO2010089334A1 (fr) * 2009-02-05 2010-08-12 Basf Se Procédé de fabrication de papier, de carton-pâte et de carton présentant une grande résistance à sec

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
GUINTHER TEGGE: "Starke und Starkederivate", 1984, BEHR'S VERLAG, pages: 173,220

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014202116A1 (fr) * 2013-06-17 2014-12-24 Synthomer Deutschland Gmbh Latex de polymère à faible odeur et composition de revêtement le comprenant
US9957404B2 (en) 2013-06-17 2018-05-01 Synthomer Deutschland Gmbh Low odor polymer latex and coating composition comprising the same
RU2659396C2 (ru) * 2013-06-17 2018-07-02 Зюнтомер Дойчланд Гмбх Слабопахнущий полимерный латекс и композиция покрытия, содержащая его
WO2015040242A1 (fr) * 2013-09-23 2015-03-26 Basf Se Formulations adhésives pour papier et procédés de fabrication et leur utilisation
WO2016093689A1 (fr) 2014-12-12 2016-06-16 Synthomer Sdn. Bhd. Composition de latex polymère pour des applications de revêtement au trempé
US10377882B2 (en) 2014-12-12 2019-08-13 Synthomer Sdn. Bhd. Polymer latex composition for dip-molding applications
WO2017158302A1 (fr) 2016-03-16 2017-09-21 Arjo Wiggins Fine Papers Limited Procédé de fabrication de papier imprégné par un fluide à pression supercritique - papier imprégné, notamment coloré
US11091878B2 (en) 2016-03-16 2021-08-17 Arjo Wiggins Fine Papers Limited Method for producing paper impregnated by a supercritical-pressure fluid, and impregnated, particularly coloured paper

Also Published As

Publication number Publication date
BR112012029267A2 (pt) 2016-07-26
CA2799783A1 (fr) 2011-11-24
EP2572040A1 (fr) 2013-03-27
CN102947506A (zh) 2013-02-27
US20130062029A1 (en) 2013-03-14

Similar Documents

Publication Publication Date Title
RU2311507C2 (ru) Составы набухшего крахмала-латекса, применяемые при изготовлении бумаги
US20130062029A1 (en) Method of making paper
US9074322B2 (en) Paper coating or binding formulations and methods of making and using same
CA2777115C (fr) Procede de production de papier, carton et carton blanchi de grande resistance a la traction a l'etat sec
CA2692301C (fr) Procede pour preparer des suspensions de charges en fines particules et leur utilisation pour produire des papiers a teneur en charges et a resistance a sec elevees
US20150197892A1 (en) Filler suspension and its use in the manufacture of paper
KR20170052564A (ko) 사이징 조성물, 그의 용도 및 종이 또는 보드 등의 제조 방법
EP2393982B1 (fr) Procédé de fabrication de papier, de carton-pâte et de carton présentant une grande résistance à sec
EP2262949B1 (fr) Formulations de revêtement ou de liaison de papier et procédés de fabrication et d'utilisation de celles-ci
EP2199463A1 (fr) Agent de traitement de surface pour papier
JP2017040021A (ja) ロジン系エマルジョンサイズ剤及び紙
CN107923127B (zh) 制备纸的方法
CN111433407A (zh) 纸强度改进聚合物组合物和添加剂体系、其用途以及纸制品的制造
US20150197890A1 (en) Filler suspension and its use in the manufacture of paper
CN103620115B (zh) 制备纸、纸板和卡板的方法
EP2904145A1 (fr) Suspension de charge et son utilisation dans la fabrication de papier
AU2010279029A1 (en) Novel glossing system for paper and paperboard coatings
JP7456556B2 (ja) 製紙用サイズ剤の製造方法
KR20240144403A (ko) 고분자량 gpam과 음이온성 다당류 촉진제
JP5883326B2 (ja) 印刷用非塗工紙およびその製造方法
CA2336660A1 (fr) Utilisation d'amidons modifies en tant qu'agents de retention dans la fabrication de papier

Legal Events

Date Code Title Description
WWE Wipo information: entry into national phase

Ref document number: 201180029685.7

Country of ref document: CN

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 11721682

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2799783

Country of ref document: CA

WWE Wipo information: entry into national phase

Ref document number: 13698438

Country of ref document: US

NENP Non-entry into the national phase

Ref country code: DE

REEP Request for entry into the european phase

Ref document number: 2011721682

Country of ref document: EP

WWE Wipo information: entry into national phase

Ref document number: 2011721682

Country of ref document: EP

REG Reference to national code

Ref country code: BR

Ref legal event code: B01A

Ref document number: 112012029267

Country of ref document: BR

ENP Entry into the national phase

Ref document number: 112012029267

Country of ref document: BR

Kind code of ref document: A2

Effective date: 20121116