EP1999314B1 - Procédé de fabrication de papier et de carton présentant une grande résistance à sec - Google Patents

Procédé de fabrication de papier et de carton présentant une grande résistance à sec Download PDF

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Publication number
EP1999314B1
EP1999314B1 EP07712497.2A EP07712497A EP1999314B1 EP 1999314 B1 EP1999314 B1 EP 1999314B1 EP 07712497 A EP07712497 A EP 07712497A EP 1999314 B1 EP1999314 B1 EP 1999314B1
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Prior art keywords
units
cationic polymer
process according
acid
paper
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EP07712497.2A
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German (de)
English (en)
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EP1999314A1 (fr
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Martin Rübenacker
Norbert Schall
Ellen KRÜGER
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BASF SE
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BASF SE
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Classifications

    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • 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
    • D21H17/23—Lignins
    • 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
    • D21H17/41—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups
    • D21H17/42—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups anionic
    • 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
    • D21H17/41—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups
    • D21H17/42—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups anionic
    • D21H17/43—Carboxyl groups or derivatives thereof

Definitions

  • the invention relates to a process for the production of paper, paperboard and cardboard with high dry strength by separately adding a polymer containing vinylamine units and a polymeric anionic compound to a pulp, dewatering the pulp and drying the paper products.
  • a method for the production of paper with high dry strength is known in which the paper stock is first a water-soluble cationic polymer, z. As polyethyleneimine, and then adding a water-soluble anionic polymer, eg. As a hydrolyzed polyacrylamide, added and dehydrated the pulp on the paper machine with sheet formation.
  • the anionic polymers contain up to 30 mol% of copolymerized acrylic acid.
  • From the DE-A 35 06 832 discloses a process for the production of paper with high dry strength, in which one adds to the stock first a water-soluble cationic polymer and then a water-soluble anionic polymer.
  • Suitable anionic polymers are, for example, homopolymers or copolymers of ethylenically unsaturated C 3 -C 5 -carboxylic acids.
  • the copolymers contain at least 35% by weight of an ethylenically unsaturated C 3 -C 5 -carboxylic acid (for example acrylic acid) in copolymerized form.
  • polyethyleneimine polyvinylamine, polydiallyldimethylammonium chloride and epichlorohydrin crosslinked condensation products of adipic acid and diethylenetriamine are described.
  • the use of partially hydrolyzed homo- and copolymers of N-vinylformamide has also been considered.
  • the degree of hydrolysis The N-vinylformamide polymer is at least 30 mol% and is preferably 50 to 100 mol%.
  • the JP-A 1999-140787 relates to a process for the production of corrugated board, wherein to improve the strength properties of a paper product to the pulp 0.05 to 0.5 wt .-%, based on dry pulp, of a polyvinylamine obtained by hydrolysis of polyvinylformamide having a degree of hydrolysis of 25 to 100 %, in combination with an anionic polyacrylamide, the pulp is then dewatered and dried.
  • WO 03/052206 discloses a paper product having improved strength properties obtainable by applying to the surface of a paper product a polyvinylamine and a polymeric anionic compound which can form a polyelectrolyte complex with polyvinylamine, or a polymeric compound having aldehyde functions such as aldehyde group-containing polysaccharides. Not only does the paper improve its dry and wet strength, it also observes a sizing effect of the treating agents.
  • the EP 672 212 discloses the sole use of hydrolyzed copolymers of N-vinylcarboxamides and monoethylenically unsaturated carboxylic acids as an additive to the paper stock.
  • EP 362 770 and EP 723,047 each disclose combinations of polyacrylamides and lignosulfonate, which are previously prepared as a polyelectrolyte complex and added as such to the stock.
  • both documents each disclose the addition of alum, which causes an increase in pH. It is known to the person skilled in the art that alum is used as fixing agent in order to fix the polyelectrolyte and lignosulphonate polyelectrolyte complex on the fiber.
  • EP-A 438 744 is the use of copolymers of, for example, N-vinylformamide and acrylic acid, methacrylic acid and / or maleic acid having a K value of 8 to 50 (determined according to H. Fikentscher in 1% aqueous solution at pH 7 and 25 ° C) and the from them by partial or complete removal of formyl groups from the copolymerized vinylformamide with the formation of vinylamine units polymers available as anti-scale agents in water-bearing systems such as boilers or pipes, known.
  • copolymers obtained by copolymerizing N-vinylcarboxamides, monoethylenically unsaturated carboxylic acids and optionally other ethylenically unsaturated monomers and subsequent hydrolysis of the vinylcarboxylic acid units contained in the copolymers to the corresponding Amine or ammonium units are available, can be used in papermaking as an additive to the paper stock to increase the rate of dewatering and retention and the dry and wet strength of the paper, see.
  • EP-B 672 212
  • the present invention has for its object to provide a further process for the production of paper with high dry strength and lowest possible wet strength available.
  • the dry strength in particular in packaging papers (for example, wave from waste paper, Fluting) should be further improved compared to the previously known methods.
  • a polymer comprising vinylamine units is added to the paper stock as the polymeric cationic component.
  • These compounds are preferably used as the sole cationic component. However, they may optionally be substituted by up to 50% by weight of other cationic polymers such as cationic poly (meth) acrylamides, polydiallyldimethylammonium chlorides, condensates of dimethylamine and epichlorohydrin or polydialkyl (meth) acrylamides.
  • Suitable cationic polymers containing vinylamine units are all polymers which are cited, for example, in the prior art WO 04/061235 , Page 12, line 28 to page 13, line 21 and in Figure 1 are indicated.
  • the molecular weight M w of the polymers containing vinylamine units is, for example, 1000 to 5 million, and is usually in the range of 5,000 to 500,000, preferably 40,000 D to 400,000 D.
  • the indication of vinylamine units comprises the sum of vinylamine and amidine units in the polymer.
  • a polymer containing at least 1 mol% of N-vinylformamide homopolymer is used as the polymer containing vinylamine units.
  • Polyvinylamine and / or at least 50 mol% of hydrolyzed homopolymers of N-vinylformamide are preferably used in the inventive method as a cationic component.
  • This group of polymers which are amphoteric and which have a total of more cationic than anionic groups contains, for example, up to a maximum of 35 mol%, preferably up to 10 mol%, of at least one acid group-containing monomer of group (b) in copolymerized form.
  • lignosulfonic acid and / or a lignosulfonate into consideration. Further details of these products can be found for example in the above reference Römpp, 9th edition, G. Thieme Verlag Stuttgart, 1990, page 2511 and in Ullmann's Encyclopedia of Industrial Chemistry, 5th Completely Revised Edition, Volume A15, pages 311-314 , Lignosulfonic acid is formed in cellulose production by sulphite digestion of wood, whereby lignin reacts with sulphurous acid. It is sulfonated here on the C 3 side chains of the phenylpropane units.
  • lignin sulphonic acid or lignin sulphonates are formed, for example, the sodium, potassium, ammonium, magnesium or calcium salts of lignosulphonic acid.
  • Lignosulfonic acid and the salts of lignosulfonic acid mentioned are soluble in water.
  • the molecular weight of the lignosulfonic acid is, for example 10,000 to 200,000 g / mol.
  • Lignosulfonates are z. B. obtained from the sulfite waste liquors (black liquor) of cellulose production.
  • Lignosulfonic acid and / or lignin sulfonate are used, for example, in an amount of from 0.1 to 10% by weight, preferably from 0.2 to 5% by weight and in particular from 0.5 to 2% by weight, based on dry paper stock.
  • Vinylamine units containing polymer and lignosulfonic acid and / or lignin sulfonate be used in the inventive method, for example in a weight ratio of 5: 1 to 1: 5, preferably in a weight ratio of 2: 1 to 1: 2.
  • Examples of monomers of group (a) are N-vinylformamide, N-vinyl-N-methylformamide, N-vinylacetamide, N-vinyl-N-methylacetamide, N-vinyl-N-ethylacetamide, N-vinyl-N-methylpropionamide and N -Vinylpropionamid.
  • the monomers of group (a) may be used alone or in admixture in the copolymerization with the monomers of the other groups.
  • Suitable monomers of group (b) are, in particular, monoethylenically unsaturated carboxylic acids having 3 to 8 carbon atoms and the water-soluble salts of these carboxylic acids.
  • This group of monomers includes, for example, acrylic acid, methacrylic acid, dimethacrylic acid, ethacrylic acid, maleic acid, fumaric acid, itaconic acid, mesaconic acid, citraconic acid, methylenemalonic acid, allylacetic acid, vinylacetic acid and crotonic acid.
  • monomers of group (b) are monomers containing sulfo groups, such as vinylsulfonic acid, acrylamido-2-methylpropanesulfonic acid and styrenesulfonic acid and also vinylphosphonic acid.
  • the monomers of this group can be used alone or in admixture with each other, in partially or completely neutralized form in the copolymerization.
  • neutralization for example, alkali metal or alkaline earth metal bases, ammonia, amines and / or alkanolamines are used.
  • the monomers of group (b) are preferably used in the copolymerization in partially neutralized form.
  • the copolymers may optionally contain monomers of group (c) in copolymerized form, for example esters of ethylenically unsaturated C 3 to C 5 carboxylic acids such as methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, isobutyl methacrylate, methyl methacrylate, ethyl methacrylate and vinyl esters such as vinyl acetate or Vinyl propionate, or other monomers such as N-vinylpyrrolidone, N-vinylimidazole, acrylamide and / or methacrylamide.
  • esters of ethylenically unsaturated C 3 to C 5 carboxylic acids such as methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, isobutyl methacrylate, methyl methacrylate, ethyl methacrylate and vinyl est
  • a further modification of the copolymers is possible by using in the copolymerization monomers (d) which contain at least two double bonds in the molecule, for.
  • monomers (d) which contain at least two double bonds in the molecule
  • methylenebisacrylamide glycol diacrylate, glycol dimethacrylate, Gylcerintriacrylat, triallylamine, Pentaerythrittriallylether, at least twice with acrylic acid and / or methacrylic acid esterified polyalkylene glycols or polyols such as pentaerythritol, soba or glucose.
  • the amounts used are up to 2 mol%, z. B. 0.001 to 1 mol%.
  • the copolymerization of the monomers is carried out in a known manner in the presence of free-radical polymerization initiators and optionally in the presence of polymerization regulators, cf. EP-B 672 212 , Page 4, lines 13 - 37 or EP-A 438 744 , Page 2, line 26 to page 8, line 18.
  • the average molecular weights M W of the anionic polymers (ii) are, for example, 30,000 D to 10 million D, preferably 100,000 D to 1 million D.
  • These polymers have, for example, K values (determined according to H. Fikentscher in 5% aqueous sodium chloride solution pH 7, a polymer concentration of 0.5% by weight and a temperature of 25 ° C) in the range of 20 to 250, preferably 50 to 150.
  • the invention further provides the use of a polymeric anionic compound according to the invention as an additive to the paper stock in the production of paper, paperboard and cardboard in the presence of at least one vinylamine units containing cationic polymers to increase the dry strength.
  • Wood pulp includes, for example, groundwood, thermomechanical pulp (TMP), chemo-thermo-mechanical pulp (CTMP), pressure groundwood, semi-pulp, high yield pulp, and refiner mechanical pulp (RMP).
  • TMP thermomechanical pulp
  • CMP chemo-thermo-mechanical pulp
  • RMP refiner mechanical pulp
  • pulp for example, sulphate, sulphite and soda pulps come into consideration.
  • unbleached pulp also referred to as unbleached kraft pulp, or a waste paper pulp.
  • Suitable annual plants for the production of pulps are, for example, rice, wheat, sugar cane and kenaf.
  • waste paper is usually used, which is used either alone or in admixture with other fibers or it is based on fiber blends of a primary material and recycled coated Committee, z. Bleached pine sulfate in admixture with recycled coated broke.
  • the dewatering of the stock usually takes place on the wire of a paper machine.
  • the method according to the invention has particular significance for the production of paper and board from waste paper, because it significantly increases the strength properties of the recycled fibers.
  • the pH of the stock suspension is, for example, in the range of 4.5 to 8, most 6 to 7.5.
  • an acid such as sulfuric acid or aluminum sulphate.
  • the vinylamine unit-containing polymer i. the cationic component of the polymer to be metered to the paper stock is added in the inventive method, for example to the thick material or preferably to a thin material.
  • the point of addition is preferably in front of the screens, but may also be between a shearing stage and a screen or afterwards.
  • the anionic component is preferably dosed to the thin.
  • first lignosulfonic acid or lignin sulfonate is metered in, thereafter as the sole cationic component a polymer containing vinylamine groups and subsequently an anionic polymer of vinylformamide.
  • the sole cationic component a polymer containing vinylamine groups and subsequently an anionic polymer of vinylformamide.
  • the cationic component (vinylamine units-containing polymer as the sole cationic component) to the paper stock and to meter the anionic component simultaneously but separately from the cationic component to the paper stock.
  • the vinylamine units-containing polymer is used, for example, in an amount of 0.05 to 2.0 wt .-%, preferably 0.1 to 1 wt .-%, based on dry pulp.
  • the ratio of cationic component (polymer containing vinylamine units) to polymeric anionic component (ligninsulfonic acid and / or ligninsulfonate or combination of ligninsulfonic acid and / or ligninsulfonate with at least one anionic polymer of vinylformamide) is for example 5: 1 to 1: 5 and is preferably in in the range of 2: 1 to 1: 2.
  • the process according to the invention gives paper products which, compared with the processes of the prior art, have a higher level of dry strength with simultaneously low wet strength.
  • these papers have a high CMT value compared with known paper products.
  • the parts given in the following examples are parts by weight, the percentages are based on the weight of the substances.
  • the K value of the polymers was after H. Fikentscher, Cellulose Chemistry, Vol. 13, 58-64 and 71-74 (1932 ) at a temperature of 20 ° C in 5 wt .-% aqueous saline solutions at a pH of 7 and a polymer concentration of 0.5%.
  • K k * 1000.
  • Example 1 in each case one sample of the above-described paper stock was first metered into the quantities of lignosulfonate indicated in Table 1, the sample was mixed, then the cationic polymer (PVAm 1) was added after a residence time of 20 seconds and the mixture was mixed In turn, after a 20 second residence time, the anionic polymer 1 was added, the mixed stock was mixed, and then dewatered on a Rapid-Kothen sheet former.
  • the values for the dry burst pressure, the SCT value and the CMT value converted to sheets having a basis weight of 120 g / m 2 are given in Table 1. Table 1 Comp.

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  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Claims (13)

  1. Procédé de fabrication de papier et de carton présentant une grande résistance à sec par ajout séparé d'un polymère cationique contenant des unités vinylamine et d'un composé anionique polymère à une pâte à papier, déshydratation de la pâte à papier et séchage des produits de papier, caractérisé en ce qu'on utilise en tant que composé anionique polymère
    (i) de l'acide ligninesulfonique et/ou un sulfonate de lignine et
    (ii) au moins un copolymère, qui peut être obtenu par copolymérisation de
    (a) au moins un amide d'acide N-vinylcarboxylique de formule
    Figure imgb0015
     dans laquelle R1, R2 = H ou alkyle en C1 à C6,
    (b) au moins un monomère monoéthyléniquement insaturé contenant des groupes acides et/ou ses sels de métaux alcalin, de métaux alcalino-terreux ou d'ammonium, et éventuellement
    (c) d'autres monomères monoéthyléniquement insaturés, et éventuellement
    (d) des composés qui comprennent au moins deux doubles liaisons éthyléniquement insaturées par molécule.
  2. Procédé selon la revendication 1, caractérisé en ce qu'on utilise en tant que polymère cationique contenant des unités vinylamine au moins un composé qui peut être obtenu par polymérisation d'au moins un monomère de formule
    Figure imgb0016
     dans laquelle R1, R2 = H ou alkyle en C1 à C6,
    puis clivage partiel ou total des groupes -CO-R1 des unités du monomère I polymérisées dans le polymère avec formation de groupes amino.
  3. Procédé selon la revendication 1 ou 2, caractérisé en ce qu'on utilise en tant que polymère cationique contenant des unités vinylamine un homopolymère de N-vinylformamide hydrolysé à hauteur d'au moins 1 % en moles.
  4. Procédé selon l'une quelconque des revendications 1 à 3, caractérisé en ce qu'on utilise en tant que polymère cationique contenant des unités vinylamine un copolymère qui peut être obtenu par copolymérisation de
    (a) au moins un amide d'acide N-vinylcarboxylique de formule
    Figure imgb0017
     dans laquelle R1, R2 = H ou alkyle en C1 à C6,
    (b) au moins un monomère monoéthyléniquement insaturé contenant des groupes acides et/ou ses sels de métaux alcalin, de métaux alcalino-terreux ou d'ammonium, et éventuellement
    (c) d'autres monomères monoéthyléniquement insaturés, et éventuellement
    (d) des composés qui comprennent au moins deux doubles liaisons éthyléniquement insaturées par molécule,
    puis clivage partiel ou total des groupes -CO-R1 des unités du monomère I polymérisées dans le polymère avec formation de groupes amino, la proportion des groupes amino dans le copolymère étant supérieure d'au moins 10 % en moles à la proportion des unités de monomères monoéthyléniquement insaturés contenant des groupes acides.
  5. Procédé selon l'une quelconque des revendications 1 à 4, caractérisé en ce qu'on utilise en tant que polymère cationique contenant des unités vinylamine de la polyvinylamine et/ou un homopolymère de N-vinylformamide hydrolysé à hauteur d'au moins 50 % en moles.
  6. Procédé selon l'une quelconque des revendications 1 à 5, caractérisé en ce qu'on utilise en tant que sulfonate de lignine les sels de sodium, de potassium, d'ammonium, de calcium, de magnésium solubles dans l'eau ou leurs mélanges.
  7. Procédé selon l'une quelconque des revendications 1 à 6, caractérisé en ce que le polymère cationique contenant des unités vinylamine est utilisé en une quantité de 0,05 à 2,0 % en poids, par rapport à la pâte à papier sèche.
  8. Procédé selon l'une quelconque des revendications 1 à 7, caractérisé en ce que le polymère cationique contenant des unités vinylamine et l'acide ligninesulfonique et/ou le sulfonate de lignine sont utilisés en un rapport en poids de 5:1 à 1:5.
  9. Procédé selon l'une quelconque des revendications 1 à 8, caractérisé en ce que le polymère cationique contenant des unités vinylamine et l'acide ligninesulfonique et/ou le sulfonate de lignine sont utilisés en un rapport en poids de 2:1 à 1:2.
  10. Procédé selon l'une quelconque des revendications 1 à 9, caractérisé en ce que l'acide ligninesulfonique et/ou le sulfonate de lignine sont tout d'abord ajoutés à la pâte à papier, puis le polymère cationique contenant des unités vinylamine est ajouté, et la pâte à papier est enfin déshydratée.
  11. Procédé selon l'une quelconque des revendications 1 à 9, caractérisé en ce que le polymère cationique contenant des unités vinylamine est tout d'abord ajouté à la pâte à papier, puis l'acide ligninesulfonique et/ou le sulfonate de lignine sont ajoutés, et la pâte à papier est enfin déshydratée.
  12. Procédé selon la revendication 10, caractérisé en ce qu'après l'ajout de l'acide ligninesulfonique et/ou du sulfonate de lignine et d'au moins un polymère cationique contenant des unités vinylamine à la pâte à papier, un copolymère anionique contenant des unités amide d'acide vinylcarboxylique est encore ajouté, qui peut être obtenu par copolymérisation de
    (a) au moins un amide d'acide N-vinylcarboxylique de formule
    Figure imgb0018
     dans laquelle R1, R2 = H ou alkyle en C1 à C6,
    (b) au moins un monomère monoéthyléniquement insaturé contenant des groupes acides et/ou ses sels de métaux alcalin, de métaux alcalino-terreux ou d'ammonium, et éventuellement
    (c) d'autres monomères monoéthyléniquement insaturés, et éventuellement
    (d) des composés qui comprennent au moins deux doubles liaisons éthyléniquement insaturées par molécule.
  13. Utilisation d'un composé anionique polymère selon la revendication 1 en tant qu'additif pour pâte à papier lors de la fabrication de papier et de carton en présence d'au moins un polymère cationique contenant des unités vinylamine pour augmenter la résistance à sec.
EP07712497.2A 2006-03-16 2007-03-09 Procédé de fabrication de papier et de carton présentant une grande résistance à sec Not-in-force EP1999314B1 (fr)

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EP07712497.2A EP1999314B1 (fr) 2006-03-16 2007-03-09 Procédé de fabrication de papier et de carton présentant une grande résistance à sec

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EP06111267 2006-03-16
PCT/EP2007/052238 WO2007104716A1 (fr) 2006-03-16 2007-03-09 Procédé de fabrication de papier et de carton présentant une grande résistance à sec
EP07712497.2A EP1999314B1 (fr) 2006-03-16 2007-03-09 Procédé de fabrication de papier et de carton présentant une grande résistance à sec

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EP1999314A1 EP1999314A1 (fr) 2008-12-10
EP1999314B1 true EP1999314B1 (fr) 2017-02-22

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US (1) US7922867B2 (fr)
EP (1) EP1999314B1 (fr)
JP (1) JP5156650B2 (fr)
CN (1) CN101405457B (fr)
CA (1) CA2644348C (fr)
ES (1) ES2625622T3 (fr)
PT (1) PT1999314T (fr)
WO (1) WO2007104716A1 (fr)

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US9816233B2 (en) 2012-09-28 2017-11-14 Kimberly-Clark Worldwide, Inc. Hybrid fiber compositions and uses in containerboard packaging
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WO2007104716A1 (fr) 2007-09-20
US20100108279A1 (en) 2010-05-06
CN101405457B (zh) 2011-08-17
JP5156650B2 (ja) 2013-03-06
CA2644348A1 (fr) 2007-09-20
PT1999314T (pt) 2017-05-26
JP2009530504A (ja) 2009-08-27
CA2644348C (fr) 2014-06-10
US7922867B2 (en) 2011-04-12
EP1999314A1 (fr) 2008-12-10
CN101405457A (zh) 2009-04-08
ES2625622T3 (es) 2017-07-20

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