FI124832B - Paperituote sekä menetelmä ja järjestelmä paperituotteen valmistamiseksi - Google Patents
Paperituote sekä menetelmä ja järjestelmä paperituotteen valmistamiseksi Download PDFInfo
- Publication number
- FI124832B FI124832B FI20116132A FI20116132A FI124832B FI 124832 B FI124832 B FI 124832B FI 20116132 A FI20116132 A FI 20116132A FI 20116132 A FI20116132 A FI 20116132A FI 124832 B FI124832 B FI 124832B
- Authority
- FI
- Finland
- Prior art keywords
- cellulose
- paper
- pulp
- nanofibrillary
- nanofibrillar
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims description 25
- 238000004519 manufacturing process Methods 0.000 title claims description 13
- 229920002678 cellulose Polymers 0.000 claims description 156
- 239000001913 cellulose Substances 0.000 claims description 156
- 239000000463 material Substances 0.000 claims description 64
- 229920003043 Cellulose fiber Polymers 0.000 claims description 29
- 239000002994 raw material Substances 0.000 claims description 18
- 239000003795 chemical substances by application Substances 0.000 claims description 13
- 239000010410 layer Substances 0.000 claims description 13
- 229920001131 Pulp (paper) Polymers 0.000 claims description 10
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 7
- 230000003647 oxidation Effects 0.000 claims description 7
- 238000007254 oxidation reaction Methods 0.000 claims description 7
- 230000035699 permeability Effects 0.000 claims description 7
- 238000006467 substitution reaction Methods 0.000 claims description 6
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 claims description 5
- -1 heterocyclic nitroxyl compound Chemical class 0.000 claims description 5
- TWNIBLMWSKIRAT-VFUOTHLCSA-N levoglucosan Chemical group O[C@@H]1[C@@H](O)[C@H](O)[C@H]2CO[C@@H]1O2 TWNIBLMWSKIRAT-VFUOTHLCSA-N 0.000 claims description 5
- 125000000129 anionic group Chemical group 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 3
- 229920006321 anionic cellulose Polymers 0.000 claims 1
- 239000004447 silicone coating Substances 0.000 claims 1
- 239000000123 paper Substances 0.000 description 87
- 239000000126 substance Substances 0.000 description 20
- 239000000835 fiber Substances 0.000 description 9
- 125000002091 cationic group Chemical group 0.000 description 8
- 238000012360 testing method Methods 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 229920000867 polyelectrolyte Polymers 0.000 description 6
- 238000012512 characterization method Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 229920002472 Starch Polymers 0.000 description 4
- 238000010009 beating Methods 0.000 description 4
- 238000003490 calendering Methods 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- 239000008107 starch Substances 0.000 description 4
- 235000019698 starch Nutrition 0.000 description 4
- 241000196324 Embryophyta Species 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 239000011086 glassine Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methyl-cyclopentane Natural products CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 description 3
- 210000001724 microfibril Anatomy 0.000 description 3
- 238000002203 pretreatment Methods 0.000 description 3
- 238000004537 pulping Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000001212 derivatisation Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000011121 hardwood Substances 0.000 description 2
- 230000001404 mediated effect Effects 0.000 description 2
- 239000002121 nanofiber Substances 0.000 description 2
- ODUCDPQEXGNKDN-UHFFFAOYSA-N nitroxyl Chemical compound O=N ODUCDPQEXGNKDN-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000011122 softwood Substances 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- ATACSYDDCNWCLV-UHFFFAOYSA-N 2-chloroacetic acid;sodium Chemical compound [Na].OC(=O)CCl ATACSYDDCNWCLV-UHFFFAOYSA-N 0.000 description 1
- 244000283070 Abies balsamea Species 0.000 description 1
- 235000007173 Abies balsamea Nutrition 0.000 description 1
- 244000198134 Agave sisalana Species 0.000 description 1
- 235000011624 Agave sisalana Nutrition 0.000 description 1
- 241000609240 Ambelania acida Species 0.000 description 1
- 235000017166 Bambusa arundinacea Nutrition 0.000 description 1
- 235000017491 Bambusa tulda Nutrition 0.000 description 1
- 235000018185 Betula X alpestris Nutrition 0.000 description 1
- 235000018212 Betula X uliginosa Nutrition 0.000 description 1
- 241000219495 Betulaceae Species 0.000 description 1
- 240000008564 Boehmeria nivea Species 0.000 description 1
- 244000025254 Cannabis sativa Species 0.000 description 1
- 235000012766 Cannabis sativa ssp. sativa var. sativa Nutrition 0.000 description 1
- 235000012765 Cannabis sativa ssp. sativa var. spontanea Nutrition 0.000 description 1
- 241000283707 Capra Species 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 240000000491 Corchorus aestuans Species 0.000 description 1
- 235000011777 Corchorus aestuans Nutrition 0.000 description 1
- 235000010862 Corchorus capsularis Nutrition 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 125000002353 D-glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 description 1
- 235000014466 Douglas bleu Nutrition 0.000 description 1
- 244000004281 Eucalyptus maculata Species 0.000 description 1
- 241000219146 Gossypium Species 0.000 description 1
- 240000000797 Hibiscus cannabinus Species 0.000 description 1
- 240000005979 Hordeum vulgare Species 0.000 description 1
- 235000007340 Hordeum vulgare Nutrition 0.000 description 1
- 241000218652 Larix Species 0.000 description 1
- 235000005590 Larix decidua Nutrition 0.000 description 1
- 235000004431 Linum usitatissimum Nutrition 0.000 description 1
- 240000006240 Linum usitatissimum Species 0.000 description 1
- 240000000907 Musa textilis Species 0.000 description 1
- 229920001046 Nanocellulose Polymers 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 235000014676 Phragmites communis Nutrition 0.000 description 1
- 244000082204 Phyllostachys viridis Species 0.000 description 1
- 235000015334 Phyllostachys viridis Nutrition 0.000 description 1
- 241000218657 Picea Species 0.000 description 1
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 1
- 241000018646 Pinus brutia Species 0.000 description 1
- 235000011613 Pinus brutia Nutrition 0.000 description 1
- 241000209504 Poaceae Species 0.000 description 1
- 241000219000 Populus Species 0.000 description 1
- 241000183024 Populus tremula Species 0.000 description 1
- 240000001416 Pseudotsuga menziesii Species 0.000 description 1
- 235000005386 Pseudotsuga menziesii var menziesii Nutrition 0.000 description 1
- 241000209056 Secale Species 0.000 description 1
- 235000007238 Secale cereale Nutrition 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 235000021307 Triticum Nutrition 0.000 description 1
- 244000098338 Triticum aestivum Species 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- 238000004378 air conditioning Methods 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 230000003113 alkalizing effect Effects 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000010905 bagasse Substances 0.000 description 1
- 239000011425 bamboo Substances 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical group OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- 235000009120 camo Nutrition 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 235000005607 chanvre indien Nutrition 0.000 description 1
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000000402 conductometric titration Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 125000002791 glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 239000011487 hemp Substances 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000013081 microcrystal Substances 0.000 description 1
- 108700005457 microfibrillar Proteins 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 239000002073 nanorod Substances 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 238000011020 pilot scale process Methods 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 239000010902 straw Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 239000011345 viscous material Substances 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
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
- D21H11/00—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only
- D21H11/16—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only modified by a particular after-treatment
- D21H11/18—Highly hydrated, swollen or fibrillatable fibres
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
- C08L1/02—Cellulose; Modified cellulose
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21D—TREATMENT OF THE MATERIALS BEFORE PASSING TO THE PAPER-MAKING MACHINE
- D21D1/00—Methods of beating or refining; Beaters of the Hollander type
- D21D1/20—Methods of refining
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21F—PAPER-MAKING MACHINES; METHODS OF PRODUCING PAPER THEREON
- D21F11/00—Processes for making continuous lengths of paper, or of cardboard, or of wet web for fibre board production, on paper-making machines
-
- 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
- D21H11/00—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only
- D21H11/16—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only modified by a particular after-treatment
- D21H11/20—Chemically or biochemically modified fibres
-
- 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
- D21H17/25—Cellulose
-
- 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
-
- 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
- D21H23/06—Controlling the addition
- D21H23/14—Controlling the addition by selecting point of addition or time of contact between components
- D21H23/16—Addition before or during pulp beating or refining
-
- 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
- D21H27/00—Special paper not otherwise provided for, e.g. made by multi-step processes
- D21H27/001—Release paper
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Paper (AREA)
Description
A PAPER PRODUCT AND A METHOD AND A SYSTEM FOR MANUFACTURING A PAPER PRODUCT
Field of the Invention
This invention relates to a method and a system for manufacturing paper product comprising nanofibrillar cellulose material. In addition, this invention relates to a paper product.
Background of the Invention
Cellulose, which is an abundant natural raw material, is a polysaccharide consisting of a linear chain of several hundreds to ten thousand linked D-glu-cose units. Cellulose is typically used as a raw material for paper products. Papers may also comprise, for example, fillers and chemicals. Typically the produced paper should have, among other things, good strength properties. In addition, the produced paper should typically be manufactured with good production efficiency.
It is an object of the present invention to present a novel solution for manufacturing paper.
Summary of the Invention
The present invention discloses a method and a system for manufacturing paper comprising nanofibrillar cellulose. In addition, the invention discloses a paper product comprising nanofibrillar cellulose.
The invention is based on a usage of nanofibrillar cellulose in paper furnish and in papers. Cellulose fibers, preferably chemically pre-treated and/or mechanically pre-treated cellulose fibers, can be reduced to nanofibrillar cellulose material that can be used as a strengthening agent in paper. Nanofibrillar cellulose as such may provide a paper product with new functional properties.
It has been found that if release paper had lower grammage it would be possible to have a longer amount of paper in customer rolls. However, in order to lower the grammage of the paper, the initial wet strength of the paper should be improved to maintain the runnability of the paper and, moreover, to maintain the tensile strength of the paper without sacrificing tear strength of the paper. Nanofibrillar cellulose, when used as a paper additive, has surprisingly shown to achieve these needed properties.
The present invention is based on a usage of nanofibrillar cellulose in paper furnish.
Advantageously in the method according to the present invention, wherein the manufactured paper comprises nanofibrillar cellulose material, the method comprises: introducing raw materials to a system, which raw materials include cellulose pulp and nanofibrillar cellulose material, and conveying the raw materials to a paper machine in order to produce paper having nanofibrillar cellulose content between 0.1 and 5 % of dry weight of furnish.
Advantageously, in the system according to the present invention, wherein the manufactured paper comprises nanofibrillar cellulose material, the method comprises: means for introducing cellulose pulp and nanofibrillar cellulose material to the system, at least one conveyer to convey the introduced raw materials to the paper machine in order to produce paper having nanofibrillar cellulose content between 0.1 and 5 % of dry weight.
The nanofibrillar cellulose used in this invention may be produced with mechanical treatment from anionized cellulose fibers and/or from cellulose fibers that are not anionized. The anionization of the cellulose fibers may be implemented, for example, by a reaction wherein the primary hydroxyl groups of cellulose are oxidized catalytically by a heterocyclic nitroxyl compound, or by a reaction wherein cellulose fibers are reacted with the carboxymethylating agents to form lightly carboxymethylated cellulose.
Therefore, in an embodiment of the invention, cellulose fibers are oxidized by nitroxyl-mediated oxidation of hydroxyl groups of the cellulose in order to achieve anionized cellulose fibers, after which the cellulose fibers are refined into nanofibrillar cellulose material, which is added to the paper.
In another embodiment of the invention, cellulose fibers are reacted with car-boxymethylating agents in order to achieve anionized cellulose fibers, after which the cellulose fibers are refined into nanofibrillar cellulose material, which is added to the paper. In this embodiment, cellulose fibers are reacted with the agents to form lightly carboxymethylated cellulose having such a degree of substitution that it is not soluble in water, i.e. cellulose fibers have a degree of substitution preferably between 0.05 and 0.35 carboxymethyl group per anhydroglucose unit, more preferably between 0.10 and 0.30 carboxymethyl group per anhydroglucose unit.
In another embodiment of the invention, cellulose fibers are refined into nanofibrillar cellulose material without anionization stage, which refined nanofibrillar cellulose material is added to the paper.
Thanks to the present invention, it may be possible to achieve at least some of the below mentioned advantages: - improved initial wet web strength of the product, - improved dry paper strength properties, especially internal bond strength, - low air permeability and absorption properties of the product, and - decreased coating usage in case of a coated paper, for example decreased silicon usage in the case of a release liner.
In addition, by using nanofibrillar cellulose in the paper furnish it may be possible to significantly decrease the basis weight of the paper, especially glassine type paper, without sacrificing the properties of the paper. Therefore, thanks to the present invention, it is possible to maintain strength level of the product and, in addition, to form a denser paper structure if compared to heavier reference papers.
Aspects of the invention are characterized by what is stated in the independent claims. Various embodiments of the invention are disclosed in the dependent claims.
Description of the Drawings
In the following, the invention will be illustrated by drawings in which
Figs 1a-1e show schematically some example embodiments of the invention, and
Figs 2-3 show results from experimental tests.
Detailed Description of the Invention
In the following disclosure, all percentages are by weight, if not indicated otherwise.
Figures 1 to 3 show some advantageous embodiments of the invention. The following reference numbers are used in this application: 1 paper, 2 cellulose pulp, 2a chemical pulp, 3 anionized cellulose material, 4 nanofibrillar cellulose material, 5 chemical pre-treatment, 8 refiner, 10 refined cellulose pulp, and 20 paper machine.
Cellulose is a renewable natural polymer that can be converted to many chemical derivatives. The derivatization takes place mostly by chemical reactions of the hydroxyl groups in the β-D-glucopyranose units of the polymer. By chemical derivatization the properties of the cellulose can be altered in comparison to the original chemical form while retaining the polymeric structure.
The term "cellulose raw material" refers to any cellulose raw material source that can be used in the production of chemically and/or mechanically treated cellulose fibers. The raw material can be based on any plant material that contains cellulose. The plant material may be wood. The wood can be from softwood trees such as spruce, pine, fir, larch, douglas fir or hemlock, or from hardwood trees such as birch, aspen, poplar, alder, eucalyptus or acasia, or from a mixture of softwood and hardwood. Nonwood material can be from agricultural residues, grasses or other plant substances such as straw, leaves, bark, seeds, hulls, flowers, vegetables or fruits from cotton, corn, wheat, oat, rye, barley, rice, flax, hemp, manila hemp, sisal hemp, jute, ramie, kenaf, bagasse, bamboo or reed.
The term "chemical (cellulose) pulp" 2a refers to cellulose fibers, which are isolated from any cellulose raw material(s) by a chemical pulping process. Therefore, lignin is at least for the most part removed from the cellulose raw material. Chemical cellulose pulp is preferably sulfate wood pulp. The used chemical cellulose pulp may be unbleached or bleached. Typically, the diameter of the fibers varies from 15 to 25 pm and the length exceeds 500 pm, but the present invention is not intended to be limited to these parameters. The term "mechanical (cellulose) pulp" refers to cellulose fibers, which are isolated from any cellulose raw material by a mechanical pulping process. The mechanical pulping process could be preceded by a chemical pretreatment, producing chemimechanical pulp. The cellulose fibers used in this invention preferably comprises mechanically and/or chemically and/or chemi-mechanically treated cellulose fibers. Herein they are also referred as "raw material pulp".
The term "SEC" refers to specific energy consumption.
The term "SR" refers to so-called Schopper-Riegler freeness of pulp.
The term "WRV" refers to water retention value.
It is possible to use nanofibrillar cellulose 4 in mechanical pulp containing papers, such as printing paper. The method according to the present invention may be used, for example, in Light Weight Coated (LWC) or Super Calendered (SC) papers. Advantageously the method according to the present invention is used in paper grades having high chemical pulp share, i.e. in papers comprising more chemical pulp 2a than mechanical pulp. In an embodiment, at least 80 % of dry weight, more preferably at least 90 % of dry weight and most preferably at least 95 % of dry weight of the cellulose fibers used in this invention is from chemical pulp 2a.
The term "nanofibrillar cellulose" 4 refers to a collection of isolated cellulose microfibrils or microfibril bundles derived from cellulose raw material. There are several widely used synonyms for nanofibrillar cellulose. For example: nanofibrillated cellulose (NFC), nanocellulose, microfibrillar cellulose, cellulose nanofiber, nano-scale fibrillated cellulose, m icrof i bri 11 ated cellulose (MFC), or cellulose microfibrils. Nanofibrillar cellulose described in this application is not the same material as the so called cellulose whiskers, which are also known as: cellulose nanowhiskers, cellulose nanocrystals, cellulose nanorods, rod-like cellulose microcrystals or cellulose nanowires. In some cases, similar terminology is used for both materials, for example by Kuth-carlapati et al. (Metals Materials and Processes 20(3):307-314, 2008) where the studied material was called "cellulose nanofiber" although they clearly referred to cellulose nanowhiskers. Typically these materials do not have amorphous segments along the fibrillar structure as nanofibrillar cellulose does, which leads to a more rigid structure. Cellulose whiskers are also shorter than nanofibrillar cellulose.
Characterizations for the nanofibrillar cellulose (advantageous examples) are presented in Tables 1 to 2.
Viscosity of the nanofibrillar cellulose: There are several commercial Brookfield viscosimeters available for measuring apparent viscosity, which are all based on the same principle. The vane spindle is preferable because of its vane geometry, which is particularly suitable for testing heterogeneous viscous materials. A low rotation speed (10 rpm) is preferable, because higher rotational speed may give falsely high viscosity values. The viscosity of anionized nanofibrillar cellulose is measured at 0.8% concentration. Attention should also be paid to obtaining dilutions of nanofibrillar cellulose having constant standard concentration to be able to compare the results correctly. Further, it is preferably that flocking is avoided. Yield Stress of the nanofibrillar cellulose can be calculated from the viscosity measurement.
Turbidity of the nanofibrillar cellulose: Typically nanofibrillar cellulose is substantially transparent in an aqueous medium. More fibrillated cellulose materials have lower turbidity values when compared to less fibrillated ones. The units of turbidity from a calibrated nephelometer are called Nephelometric Turbidity Units (NTU). The measurement is carried out at 0,1% concentration. Suitably a nanofibrillar cellulose sample is diluted with water.
Charge of the nanofibrillar cellulose: Charge can be determined by conductometric titration.
Yield Stress of the nanofibrillar cellulose: Yield stress can be measured at 0.5% concentration.
Characterization for the nanofibrillar cellulose manufactured using catalytic oxidation of fibers is presented in Table 1.
Table 1: Characterization for the nanofibrillar cellulose manufactured using a TEMPO pre-treatment of the cellulose material.
Characterization for the nanofibrillar cellulose manufactured using carboxy-methylating reaction is presented in Table 2.
Table 2: Characterization for the nanofibrillar cellulose manufactured using carboxymethylation of the cellulose material.
Advantageously, the present invention is used as a solution for manufacturing low basis weight paper comprising nanofibrillar cellulose. Preferably the manufactured paper is so-called glassine type paper. The most advantageously the manufactured paper is so called release paper of a label laminate.
The label laminate comprises two layers which are laminated together, i.e. a release liner and a face layer, wherein an adhesive layer is provided between the release liner and the face layer. The term "face layer" refers to "the top layer" of the label laminate, also called the face stock. The face layer comprises at least one layer that is attached to another surface with an adhesive layer, when the label laminate is used.
The term "release liner" refers to a structure comprising at least one backing material layer as base material and at least one release coating layer on the backing material layer. In other words, the backing material layer is usually coated with a thin layer of release agent, such as silicone. Therefore, the release liner can be easily removed from the face layer when the label is adhered to a substrate
Low basis weight of release paper may be needed to maximize the number of labels in a reel of manufactured label laminate. Nanofibrillar cellulose used as an additive for the paper offers a good combination of properties difficult to obtain otherwise in a cost-efficient way. Therefore, due to the present invention, it may be possible to improve the competitiveness of fibre based release papers.
Advantageously the basis weight range of the manufactured paper is between 30 and 90 g/m2, more preferably between 40 and 50 g/m2
The amount of nanofibrillar cellulose in the manufactured paper is preferably between 0.1 and 5.0 w-% of the paper (dry weight), more preferably between 0.5 and 2.5 w-% (dry weight), and most preferably between 1 and 2 w-% of the manufactured paper (dry weight).
The produced paper may be, among other things, coated, surface sized and/or calendered. Advantageously the produced paper is coated with at least one silicon coating layer in order to produce a release liner for a label laminate.
The pulp from which the handsheet is made is preferably collected from the pulp flow that is going to a headbox of a paper machine. In other words, the pulp preferably comprises every compounds of the base paper to be manufactured, such as fillers, chemicals, pulps etc., but the process parameters of the paper machine cannot have any effect on the results. Typically, nanofibrillar cellulose added in small amount in paper has one, two, three or four of the following effects on handsheet, if the handsheet is manufactured from the pulp produced according to the present invention: - Clearly lower air permeance if compared to a reference handsheets. - Improved initial wet strength if compared to a reference handsheets. - Improved tensile strength if compared to a reference handsheets. - Improved Scott Bond if compared to a reference handsheets . - Higher SR or WRV without adjusting beating if compared to a reference handsheets.
Nanofibrillar cellulose 4 can be added to the system as already manufactured nanofibrillar cellulose material as shown in Figures 1a, 1c and 1 e, or it can be added to the system as material to be refined into nanofibrillar cellulose material as shown in Figures 1b and 1d.
The nanofibrillar cellulose material 4 may be dosed to the short circulation of a paper machine 20. In order to guarantee a proper mixing to basic furnish, the nanofibrillar cellulose material 4 is preferably dosed to a place where shear forces are present, such as a refiner 8, a pump, a mixer or a screen. In an embodiment of the invention, nanofibrillar cellulose material 4 is dosed to a thick stock and/or to a diluted stock.
Cationic polyelectrolyte, such as starch, is preferably dosed to the cellulose pulp 2 before the dosage of nanofibrillar cellulose material 4. Cationic polyelectrolyte should be added before the dosage of nanofibrillar cellulose material in case of nanofibrillar cellulose addition to short circulation.
Cationic polyelectrolyte can be any retention or strength polymer used in paper manufacturing, e.g. cationic starch, cationic polyacrylamide (CPAM) or polydimethyldiallyl ammonium chloride (PDADMAC). Also, combinations of the different polyelectrolytes can be used. Preferably, the cationic polyelectrolyte is cationic starch (CS). The cationic polyelectrolyte is added in an amount of 0.01 to 5% of dry weight of fibres in the furnish, preferably approximately 0.15 to 1.50% of dry weight.
The solution may comprise a chemical pre-treatment stage 5 (shown in Figure 1b), wherein at least a part of the cellulose pulp 2 is anionized before it is, at least partly, refined into nanofibrillar cellulose to be added to the paper 1.
The terms "anionized material 3" and "anionized cellulose fibers 3" refer to a material comprising at least 90 w-% (dry weight) cellulose material, in which - cellulose is oxidized by nitroxyl-mediated (such as "TEMPO"-medi-ated) oxidation of hydroxyl groups of the cellulose, and/or - cellulose is reacted with a carboxymethylating agent in order to form lightly carboxymethylated cellulose having such a degree of substitution that it is not soluble in water, i.e. the cellulose fibers have a degree of substitution preferably between 0.05 and 0.35 carboxymethyl group per anhydroglucose unit, more preferably between 0.10 and 0.30 carboxymethyl group per anhydroglucose unit.
If the anionized cellulose fibers comprise the lightly carboxymethylated cellulose, the manufacturing of said lightly carboxymethylated cellulose advan tageously comprises a step in which a first chemical, i.e. an alkalizing agent, is dosed and absorbed into the cellulose raw material before or during dosing of a second chemical, i.e. an anionic agent. The first chemical added to the system, i.e. an alkalization agent, may be an alkali metal hydroxide and it is used for activating the pulp. In other words, alkalization agent activates the fibers and contributes to the penetration of the second chemical into the fibers. The alkalization agent can be added to the reaction mixture, for example, in an aqueous solution and/or in a dry state. The most preferably said first chemical (i.e. the alkalization agent) is sodium hydroxide NaOH. The second chemical, i.e. the main chemical added to the system is preferably monochloroacetic acid or a salt thereof, and most preferably sodium mono-chloroacetic acid. The second chemical can be added to the system in a dry state and/or in an aqueous alkaline solution and/or in a gas form in order to produce cellulosic material. According to this embodiment of the invention, a third chemical, for example H2O2 may be added to the system in order to control (i.e. to decrease) the degree of substitution of the cellulose material.
The anionized cellulose fibers may comprise cellulose material, wherein primary hydroxyl groups of cellulose are oxidized catalytically by a heterocyclic nitroxyl compound, for example 2,2,6,6-tetramethylpiperidinyl-1-oxy free radical, ''TEMPO", after which the material is refined at least partly into nano-fibrillar cellulose. Other heterocyclic nitroxyl compounds known to have selectivity in the oxidation of the hydroxyl groups of C-6 carbon of the glucose units of the cellulose can also be used. The term "oxidation of cellulose" refers to the oxidation of the hydroxyl groups (of cellulose) to aldehydes and/or carboxyl groups. It is preferred that the hydroxyl groups are oxidized to carboxyl groups, i.e. the oxidation is complete, before the refining step in at least one refiner is implemented.
In an advantageous embodiment of the present invention, anionized cellulose material 3 is added to the system as material to be refined into nanofibrillar cellulose material 4. In this embodiment shown in Figures 1b and 1 d, an addition of the anionized cellulose material 3 is preferably implemented before at least one refiner stage of the cellulose pulp 2a. Most preferably the addition of said anionized cellulose material 3 is done to the unbeaten chemical pulp to be conveyed to at least one refiner 8. The cellulose pulp 2 to be conveyed to at least one refiner 8 may, in addition or instead of, comprise fibers that are pre-refined by at least one refiner. The refiner 8 is preferably a conical refiner, a disc refiner or cylindrical refiner. If the cellulose pulp 2 and the anionized cellulose material 3 are combined with each other before at least one refiner step, anionized cellulose material 3 is fed together with cellulose pulp 2 through beating process in paper machine approach system. In this case, fibrillating of nanofibrillar cellulose takes advantageously place at least partly during pulp beating, i.e. fibres get fibrillated due to energy consumed during the beating process. Therefore, advantageously, a separate fibrillating stage to produce nanofibrillar cellulose is not needed in order to refine nanofibrillar cellulose material from the anionized cellulose material 3. The anionized cellulose material 3 has preferably a high anionic charge and, thus, it is relatively easily fibrillated under shear forces. Thanks to this embodiment of the present invention, it is possible to mix pulp 2 and nanofibrillar cellulose efficiently with each other without any separate mixing and fibrillating aggregates.
Due to the present invention it is possible to manufacture a paper product comprising at least some of the following properties: - high wet strength, - increased dry tensile strength, - greatly improved internal bonding, - lower air permeability, and - higher transparency.
The invention may cause an effective dispersing of nanofibrillar cellulose and a proper mixing with base furnish. In addition, thanks to the present invention, paper properties may be improved without loss of drainage speed.
Experimental tests
In the experimental tests, different kind of pulps for paper products were manufactured. Paper sheets were made from the produced pulps and tested afterwards.
Example 1
Raw materials and a trial plan
The trial comprised: - a fourdrinier type former, - a press section with two nips, - running speed at 15 m/min, - bar coating, - calendering surface temperature ~100°C, pressure setting 140 kN/m, 2 nips
Coating and calendering were done in laboratory and paper was made with a pilot machine.
Trial plan was adjusted to 1% and 3% nanofibrillar cellulose addition. Starch amount was varied from 1 % to 2 %. The trial plan is shown in Table 3.
Table 3. Trial plan for example 1.
The paper sample size used was A4. Coated sheets were moisturized over night at RH 80%, +23°C. Air conditioning before measurements was 50 %RH, +23°C.
Test Results
Results based on laboratory sheets. Air permeability results are shown in Figure 2a, and tensile strength results are shown in Figure 2b.
It was shown during the experimental tests that basis weight of the produced paper could be decreased 10 g/m2 with constant or improved dry paper strength properties if only a small amount of nanofibrillar cellulose (between 1 and 1,5 %) was added to the pulp. Simultaneously original wet web strength of paper was increased. Air permeability was greatly reduced even in case of lower basis weight paper compared to reference paper. In addition, converting tests have shown a reduction in silicon consumption. Release values of nanofibrillar cellulose trial points were comparable to reference samples with lower silicon weight.
Especially good results were shown with an amount of approximately 3% of nanofibrillar cellulose. An addition of 2% of CS together with the addition of nanofibrillar cellulose showed some good properties.
Example 2
Raw materials and a trial plan
The trial was implemented with realistic running conditions: - glassine type furnish, - running speed at 600 m/min, - a head box, - a hybrid former, and - a shoe press.
Two kind of anionized cellulose fibers were fibrillated: 1) Tempo-treated nanofibrillar cellulose (nanofibrillar cellulose type 1 in Figures 3a-3b), and 2) lightly carboxymethylated nanofibrillar cellulose (nanofibrillar cellulose type 2 in Figures 3a-3b).
During the trial the two anionized cellulose material were compared with each other. In addition, basis weight and amount of nanofibrillar cellulose were studied.
Results
The trial showed very promising results. Thanks to the nanofibrillar cellulose used in the paper: - porosity level decreased by 20%, - 10 g/m2 basis weight reduction potential was shown at constant tensile level, - 1 %-unit lower brightness but up to 4%-units lower opacity, - oil absorption decreased by 20%, - significant increase in wet web strength, - both tested anionized pulps seemed to give good results, and - no major difference between 1% and 2% nanofibrillar cellulose dosing.
Drainage is an issue with nanofibrillar cellulose. However, in pilot scale trials the decrease of dry matter after wire section was only 1 %-unit. Dry matter after wet pressing seems to depend on the press construction. In addition, the reduction of grammage may improve drainage.
In Figure 3a is shown an effect of nanofibrillar cellulose on tensile strength of the produced paper. As can be seen, a small amount of nanofibrillar cellulose has a strong effect on tensile strength. In Figure 3b is shown an effect of nanofibrillar cellulose on air permeability of the produced paper. As can be seen, the addition of nanofibrillar cellulose clearly decreased the air permeability properties of the produced paper. A paper produced from the pulp manufactured according to the present invention may have many advantages. For example, a grammage of the manufactured paper may be decreased. In addition, the amount of a coating may be decreased due to the new properties of the paper. Thus, the competitiveness of renewable fibre based release products against plastic may be improved due to the present invention
One skilled in the art readily understands that the different embodiments of the invention may have applications in environments where optimization of a paper product comprising nanofibrillar cellulose is desired. Therefore, it is obvious that the present invention is not limited solely to the above-presented embodiments, but it can be modified within the scope of the appended claims.
Claims (11)
1. Menetelmä nanofibrilliselluloosamateriaalia käsittävän paperituotteen val¬mistamiseksi, jossa menetelmässä johdetaan järjestelmään raaka-aineita, jotka raaka-aineet käsittävätselluloosamassaa (2) ja nanofibrilliselluloosamateriaalia (4), johdetaan raaka-aineet paperikoneeseen (20) nanofibrilliselluloosa-materiaalia (4) käsittävän irrokepaperituotteen valmistamiseksi, jonka valmis¬tetun irrokepaperin nanofibrilliselluloosapitoisuus on 0,1-5% kuivapainosta,edullisemmin 0,5-2,5 p-% ja sopivimmin 1-2 p-%, ja valmistetun irroke¬paperin neliöpaino on 40-50 g/m2, ja paperilla on parantunut rainan märkä-lujuus ja kuivavetolujuus verrattuna paperiin, jolla on sama neliöpaino ilmannanofibrilliselluloosaa.
2. Patenttivaatimuksen 1 mukainen menetelmä, tunnettu siitä, että valmis¬tettu paperi lisäksi päällystetään ainakin yhdellä siIikonipäällystekerrokse11a.
3. Patenttivaatimuksen 1 tai 2 mukainen menetelmä, tunnettu siitä, ettäainakin osa nanofibrilliselluloosamateriaalista lisätään ennen ainakin yhtäjauhinta (8).
4. Jonkin edellisen patenttivaatimuksen mukainen menetelmä, tunnettusiitä, että nanofibrilliselluloosamateriaali (4) käsittää materiaalia, joka on val¬mistettu anionoidusta selluloosamateriaalista (3).
5. Patenttivaatimuksen 4 mukainen menetelmä, tunnettu siitä, että ainakinosa nanofibrilliselluloosamateriaalista on jauhettu anionoidusta massastananofibrilliselluloosamateriaaliksi ainakin yhdessä jauhimessa (8).
6. Patenttivaatimuksen 4 tai 5 mukainen menetelmä, tunnettu siitä, että sel¬luloosan primääriset hydroksyyliryhmät hapetetaan katalyyttisesti heterosykli-sen nitroksyyliyhdisteeen välittämässä hapetuksessa ennen kuin materiaalivalmistetaan nanofibrilliselluloosamateriaaliksi (4).
7. Patenttivaatimuksen 4 tai 5 mukainen menetelmä, tunnettu siitä, että sel-luloosakuidut saatetaan reagoimaan karboksimetyloivien aineiden kanssa, jotta saadaan anionoituja selluloosakuituja, joiden substituutioaste on0,05-0,35 karboksimetyyliryhmää anhydroglukoosiyksikköä kohti, minkäjälkeen selluloosakuidut valmistetaan nanofibrilliselluloosamateriaaliksi.
8. Jonkin edellisen patenttivaatimuksen 4-7 mukainen menetelmä, tunnettusiitä, että anionoitu selluloosamassa johdetaan ainakin yhteen jauhimeen (8)yhdessä anionoimattoman kemiallisen massan kanssa, ja että anionoitu sel¬luloosamassa jauhetaan ainakin osittain nanofibrilliselluloosamateriaaliksimainitussa ainakin yhdessä jauhimessa (8).
9. Jonkin edellisen patenttivaatimuksen mukainen menetelmä, tunnettusiitä, että ainakin osa nanofibrilliselluloosasta (4) lisätään paperikoneen lyhy¬een kiertoon valmiina nanofibrilliselluloosana.
10. Irrokepaperi, joka käsittää nanofibrilliselluloosamateriaalia ja selluloosa-massaa, jossa - valmistetun paperin sisältämän nanofibrilliselluloosan määrä, joka onsekoitettu paperin seossuhteeseen, on 0,1-5 %, edullisemmin 0,5-2,5 p% jasopivimmin 1-2 % kuivapainosta, - valmistetun paperin neliöpaino on 40-50 g/m2, - valmistetulla paperilla on: parantuneet sidoslujuusominaisuudet,parantunut rainan märkävetoindeksi, ja pienentyneet ilmanläpäisevyysominaisuudet, kaikki verrattuna pape¬riin, jolla on sama neliöpaino ilman nanofibrilliselluloosaa.
11. Nanofibrilliselluloosan käyttö lujiteaineena paperin seossuhteessa irroke-paperin valmistukseen, jossa valmistetun irrokepaperin nanofibrilliselluloosa-pitoisuus on 0,1-5 % kuivapainosta ja paperin neliöpaino on 40-50 g/m2, japaperilla on parantunut rainan märkälujuus ja kuivavetolujuus verrattunapaperiin, jolla on sama neliöpaino ilman nanofibrilliselluloosaa.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FI20116132A FI124832B (fi) | 2011-11-15 | 2011-11-15 | Paperituote sekä menetelmä ja järjestelmä paperituotteen valmistamiseksi |
| PCT/FI2012/000045 WO2013072550A2 (en) | 2011-11-15 | 2012-11-15 | A paper product and a method and a system for manufacturing a paper product |
| EP12849476.2A EP2780506A4 (en) | 2011-11-15 | 2012-11-15 | PAPER PRODUCT AND METHOD AND SYSTEM FOR PRODUCING A PAPER PRODUCT |
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| FI20116132A FI124832B (fi) | 2011-11-15 | 2011-11-15 | Paperituote sekä menetelmä ja järjestelmä paperituotteen valmistamiseksi |
| FI20116132 | 2011-11-15 |
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| FI20116132L FI20116132L (fi) | 2013-05-16 |
| FI124832B true FI124832B (fi) | 2015-02-13 |
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| FI20116132A FI124832B (fi) | 2011-11-15 | 2011-11-15 | Paperituote sekä menetelmä ja järjestelmä paperituotteen valmistamiseksi |
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| EP (1) | EP2780506A4 (fi) |
| FI (1) | FI124832B (fi) |
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| FI126733B (fi) | 2013-09-27 | 2017-04-28 | Upm Kymmene Corp | Menetelmä massalietteen valmistamiseksi sekä paperituote |
| FI127348B (fi) | 2014-08-18 | 2018-04-13 | Kemira Oyj | Lujuusaine, sen käyttö ja menetelmä paperin lujuusominaisuuksien lisäämiseksi |
| BR112018007308B1 (pt) | 2015-10-12 | 2023-03-07 | Solenis Technologies, L.P. | Método para aumentar o desempenho de drenagem de uma pasta de polpa e produto de papel |
| WO2019189615A1 (ja) * | 2018-03-30 | 2019-10-03 | 日本製紙株式会社 | 紙または板紙の製造方法 |
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| JP2887911B2 (ja) * | 1991-01-25 | 1999-05-10 | 王子製紙株式会社 | 剥離紙 |
| JP2962147B2 (ja) * | 1994-06-23 | 1999-10-12 | 特種製紙株式会社 | 透き入れ紙の製造方法 |
| US6602994B1 (en) * | 1999-02-10 | 2003-08-05 | Hercules Incorporated | Derivatized microfibrillar polysaccharide |
| JP5528760B2 (ja) * | 2009-09-30 | 2014-06-25 | 日本製紙株式会社 | セルロースナノファイバーを添加して抄紙した紙およびその製造方法 |
| FI121999B (fi) * | 2009-10-06 | 2011-07-15 | Upm Kymmene Corp | Menetelmä rainan valmistamiseksi ja raina |
| EP2319984B2 (en) * | 2009-11-04 | 2025-04-02 | Kemira Oyj | Process for production of paper |
| SE535014C2 (sv) * | 2009-12-03 | 2012-03-13 | Stora Enso Oyj | En pappers eller kartongprodukt och en process för tillverkning av en pappers eller kartongprodukt |
| FI126513B (fi) * | 2011-01-20 | 2017-01-13 | Upm Kymmene Corp | Menetelmä lujuuden ja retention parantamiseksi ja paperituote |
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Also Published As
| Publication number | Publication date |
|---|---|
| EP2780506A4 (en) | 2015-07-15 |
| WO2013072550A3 (en) | 2013-07-18 |
| FI20116132L (fi) | 2013-05-16 |
| EP2780506A2 (en) | 2014-09-24 |
| WO2013072550A2 (en) | 2013-05-23 |
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