EP1716288A1 - Modification de fibres de cellulose a l'aide d'un derive de cellulose amphotere - Google Patents
Modification de fibres de cellulose a l'aide d'un derive de cellulose amphotereInfo
- Publication number
- EP1716288A1 EP1716288A1 EP05704796A EP05704796A EP1716288A1 EP 1716288 A1 EP1716288 A1 EP 1716288A1 EP 05704796 A EP05704796 A EP 05704796A EP 05704796 A EP05704796 A EP 05704796A EP 1716288 A1 EP1716288 A1 EP 1716288A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- approximately
- cellulose
- cellulose fibers
- derivative
- electrolyte
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920002678 cellulose Polymers 0.000 title claims abstract description 31
- 239000001913 cellulose Substances 0.000 title claims abstract description 31
- 229920003043 Cellulose fiber Polymers 0.000 title claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 33
- 239000003792 electrolyte Substances 0.000 claims abstract description 25
- 238000011282 treatment Methods 0.000 claims abstract description 15
- 238000004519 manufacturing process Methods 0.000 claims abstract description 10
- 150000001768 cations Chemical class 0.000 claims abstract description 8
- 229920000297 Rayon Polymers 0.000 claims abstract description 4
- 239000002964 rayon Substances 0.000 claims abstract description 4
- 239000000835 fiber Substances 0.000 claims description 18
- 239000003795 chemical substances by application Substances 0.000 claims description 13
- 239000007864 aqueous solution Substances 0.000 claims description 9
- 239000007900 aqueous suspension Substances 0.000 claims description 6
- 238000006467 substitution reaction Methods 0.000 claims description 6
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 4
- 239000000243 solution Substances 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- 230000004048 modification Effects 0.000 abstract description 9
- 238000012986 modification Methods 0.000 abstract description 9
- 239000012978 lignocellulosic material Substances 0.000 abstract description 4
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 47
- 239000001768 carboxy methyl cellulose Substances 0.000 description 47
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 47
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 47
- 229940105329 carboxymethylcellulose Drugs 0.000 description 47
- 238000001179 sorption measurement Methods 0.000 description 22
- 239000000126 substance Substances 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 7
- 238000002474 experimental method Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000011122 softwood Substances 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 5
- 239000000654 additive Substances 0.000 description 5
- 238000010009 beating Methods 0.000 description 5
- 239000008186 active pharmaceutical agent Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229910021653 sulphate ion Inorganic materials 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 229920001131 Pulp (paper) Polymers 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 125000000129 anionic group Chemical group 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 125000002091 cationic group Chemical group 0.000 description 3
- 238000000402 conductometric titration Methods 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000002657 fibrous material Substances 0.000 description 2
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 2
- 230000008961 swelling Effects 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- MPNXSZJPSVBLHP-UHFFFAOYSA-N 2-chloro-n-phenylpyridine-3-carboxamide Chemical compound ClC1=NC=CC=C1C(=O)NC1=CC=CC=C1 MPNXSZJPSVBLHP-UHFFFAOYSA-N 0.000 description 1
- 244000025254 Cannabis sativa Species 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 229920002085 Dialdehyde starch Polymers 0.000 description 1
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- 240000000797 Hibiscus cannabinus Species 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- -1 Na2S04) Chemical class 0.000 description 1
- 229920002873 Polyethylenimine Polymers 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 159000000013 aluminium salts Chemical class 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 description 1
- 229920006317 cationic polymer Polymers 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- GQOKIYDTHHZSCJ-UHFFFAOYSA-M dimethyl-bis(prop-2-enyl)azanium;chloride Chemical compound [Cl-].C=CC[N+](C)(C)CC=C GQOKIYDTHHZSCJ-UHFFFAOYSA-M 0.000 description 1
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N dimethylmethane Natural products CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000005313 fatty acid group Chemical group 0.000 description 1
- 229940015043 glyoxal Drugs 0.000 description 1
- 239000011121 hardwood Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000004627 regenerated cellulose Substances 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
- D21C9/00—After-treatment of cellulose pulp, e.g. of wood pulp, or cotton linters ; Treatment of dilute or dewatered pulp or process improvement taking place after obtaining the raw cellulosic material and not provided for elsewhere
- D21C9/001—Modification of pulp properties
- D21C9/002—Modification of pulp properties by chemical means; preparation of dewatered pulp, e.g. in sheet or bulk form, containing special additives
- D21C9/005—Modification of pulp properties by chemical means; preparation of dewatered pulp, e.g. in sheet or bulk form, containing special additives organic compounds
-
- 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
- D21H17/26—Ethers thereof
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- 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
- D21H21/20—Wet strength agents
Definitions
- Modifying cellulose fibres by using amphoteric cellulose derivative This invention relates to a method for the modification of lignocellulosic materials. Further the invention relates to products obtainable by the above mentioned method and uses of said products.
- CMC carboxymethyl cellulose
- CMC is anionic and thus has a low affinity for lignocellulosic fibers, since these are anionically charged.
- Aluminium salts can be used to retain these additives, as has been described by, for example, L Laurell in"Svensk Papperstidning", 55th. annual edition, 1952, no. 10, page 366.
- a method for the modification of lignocellulosic fiber material is disclosed, which more specifically relates to a method whereby cellulose fibers are treated for at least 5 minutes with an aqueous electrolyte-containing solution (at acidic or basic conditions) of CMC (Carboxy methyl cellulose) or a derivative of CMC, whereby the temperature during the treatment is at least 100 °C (i.e. at relatively high temperatures) and at least one of the following conditions applies:
- condition C applies together with either condition A or condition B.
- Papwirtsch. 1 , 40 has some short- comings. It is e.g. difficult to adsorb more than approximately 25 mg/g CMC and then a loading of approximately 40 mg/g CMC must be used (see e.g. a comparative example which is to be found in the example part of the present description). In order to use the above method it would be an obvious advantage if the adsorption is quantitative. It would also be an advantage if a less amount of electrolyte could be used during the pulp treatment as it is desirable in closed mills to minimize leakage of added chemicals.
- the present invention solves one or more of the above problems and/or limitations by providing according to a first aspect a method for modifying cellulose fibers wherein the cellulose fibers are treated for at least 5 minutes with an aqueous electrolyte-containing solution of an amphoteric cellulose derivative whereby the temperature during the treatment is at least about 50 C C, and at least one of the following conditions apply:
- the pH of the aqueous solution during the treatment lies in the interval of approximately 1.5-4.5, preferably in the region 2-4;
- the pH of the aqueous solution during the treatment is higher than approximately 11 ;
- condition C the concentration of the electrolyte in the aqueous solution lies in the interval of approximately 0.0001-0.05 M, preferably approximately 0.001-0.04 M, if the electrolyte has monovalent cations (such as Na 2 S0 4 ) , or in the range of approximately 0.0002-0.1 M, preferably approximately 0.0005-0.02 M, if the electrolyte has divalent cations (such as CaCI 2 ). It is preferable if condition C applies together of either condition A or condition B.
- the present invention also provides according to a second aspect a modified lignocellulosic material obtainable by the method according to the first aspect.
- the present invention also provides according to a third aspect use of the lignocellulosic material of the second aspect.
- the cationization is preferably performed by the introduction of at least one ammonium function ; most preferred a secondary, tertiary or quaternary ammonium function (or a mixture thereof) into the derivative.
- the cellulose fibers that may be used with the present invention include all types of wood-based fibers, such as bleached, half-bleached and unbleached sulfite, sulfate and soda pulps, together with unbleached, half-bleached and bleached mechanical, thermo mechanical, chemo-mechanical and chemo-thermo mechanical pulps, and mixtures of these. Both new fibers and recycled fibers can be used with the present invention, as can mixtures of these.
- Pulps from both softwood and hardwood trees can be used, as can mixtures of such pulps. Pulps that are not based on wood, such as cotton linters, regenerated cellulose, kenaf and grass fibers can also be used with the present invention.
- the preferred concentration of amphoteric cellulose derivative is approximately 0.02
- CMC carboxymethyl cellulose
- the preferred molar degree of substitution is approximately 0.3 - 1.2 and the viscosity may be approximately 25 -8,000 mPa at a concentration of 4%.
- the preferred concentration of pulp is approximately 1 - 50%, a more preferred concentration interval is approximately 5 - 50%, and the most preferred concentration interval is approximately 10 - 30%.
- the cellulose fibers are treated for approximately 5 - 180 minutes, a more preferred adsorption period is approximately 10 - 120 min and the most preferred adsorption period is approximately 15 - 60 min.
- the temperature during the treatment is in excess of approximately 100 °C, preferably at least approximately 120 °C, and most preferred up to approximately 150 °C. The method according to the invention is thus carried out at a pressure in excess of atmospheric pressure. Suitable equipment and working conditions for this will be obvious for one skilled in the arts.
- the pulp can be washed or diluted directly after the treatment, or it can be dried in the normal manner.
- the present invention also provides according to a preferred embodiment of the first aspect of the present invention a method for manufacturing paper with a high wet strength, wherein -an aqueous suspension of cellulose fibers is produced; -the cellulose fibers are modified according to the first aspect of the present invention; and -wet-strength agent is added to the aqueous suspension of cellulose fibers.
- a debonding agent may also preferably be added to the aqueous suspension of cellulose fibers. Mixtures of compatible wet-strength agents and other chemicals used in paper production can be used within the scope of the present invention, as can what are known as " debonding agents" as set out earlier.
- wet-strength agent used as additive to the stock is up to approximately 2% w/w, calculated on the [weight of] dry fibers, a more preferred concentration is approximately 0.O2 - 1.5 % and the most preferred concentration is 0.05 - 0.8 %.
- Wet-strength agents that can be used include all cationic polymeric wet-strength resins. These include, for example, those wet-strength agents that give permanent wet strength: urea-formaldehyde resins, melamine-formaldehyde resins and polyamide-amine resins.
- wet-strength agents that give temporary wet strength are polyethylene imine, dialdehyde starch, polyvinyl amine and glyoxal polyacrylamide resins.
- the above method provided for making paper with a high wet strength but low dry strength, can be used, for example, for producing paper structures that are strong when wet and absorbent.
- debonding agents may be used in this embodiment, and preferred debonding agents are quaternary ammonium salts with fatty acid chains that can be retained by electrostatic attraction to the negatively charged groups on the surfaces of the fibers.
- the result is a paper with a wet strength/dry strength ratio that preferably exceeds 0.1, a more preferred value exceeds 0.2 and the most preferred value exceeds 0.3.
- the present invention also provides according to a preferred embodiment of the second aspect of the present invention a paper with a high wet strength obtainable by the preferred embodiment of the method according to the first aspect as set out above i.e. the method for manufacturing paper with a high wet strength.
- the present invention also provides according to a preferred embodiment of the third aspect of the present invention use of modified cellulose fibers according to the second aspect for the manufacture of rayon fibers.
- the modified cellulose fibers demonstrate a higher reactivity during subsequent chemical treatments, for example, when manufacturing rayon fibers
- Preferred features of each aspect of the invention are as for each of the other aspects mutatis mutandis.
- the prior art documents mentioned herein are incorporated to the fullest extent permitted by law.
- Fig 1 shows a comparison between the adsorption of an amphoteric cellulose derivative (CMC A) and pure carboxy methyl cellulose (CMC B) to a bleached, decrilied soft wood sulphate pulp.
- Figure 2 shows a comparison between adsorption (at different pH-values) of an amphoteric (CMC A) cellulose derivative and pure carboxy methyl cellulose (CMC B) to a bleached, decrilied soft wood sulphate pulp.
- Figure 3 shows a comparison between adsorption (at different temperatures) of an amphoteric (CMC A) cellulose derivative and pure carboxy methyl cellulose (CMC B) to a bleached, decrilied soft wood sulphate pulp.
- Figure 4 shows a comparison between adsorption (at different pH values) of an amphoteric (CMC A) cellulose derivative and pure carboxy methyl cellulose (CMC B) to a bleached, decrilied soft wood sulphate pulp.
- CMC A amphoteric
- CMC B pure carboxy methyl cellulose
- Example 1 This example shows how the chemical conditions (electrolyte concentration) influence the adsorbed amount of two types of CMC.
- CMC A The experimental cellulose preparation A (CMC A) hade been made through a method comprising the addition of 2,3-epoxi-trimethyl ammonium propane chloride to CMC at slightly elevated temperature and under basic conditions, pH 7-12. This method gives rise to a product which can be summarized as follows:
- an amphoteric CMC derivative is obtained by introducing into the CMC a quaternary ammonium function, through the hydroxyl groups of the CMC.
- a secondary such as di-methyl amine
- a tertiary amine or mixtures thereof which also may comprise substances comprising quaternary ammonium functions.
- the pulp was a bleached long-fibred never-dried soft wood pulp from M-Real/Husum mills.
- the fine material in the pulp was removed through screening the pulp on a Celleco- filter with the hole diameters of 100 ⁇ m.
- the adsorption experiments were performed at 2% pulp concentration.
- the totally adsorbed amount of cellulose derivative was determined either through the use of conductometric titration (FinnFix WRH) or through N-determination on the pulp (Antek 7000).
- the adsorption time was 120 min.
- FIG. 1 shows how an increased concentration of electrolyte increases the adsorption of the amphoteric cellulose derivative. The adsorption is quantitative at high concentrations of the electrolyte. If pure carboxy methyl cellulose is used then the adsorption becomes weaker to the pulp. It is difficult to adsorb more than 25 mg/g CMC/g fiber at an addition of 40 mg/g. The role of the electrolyte addition is to decrease the repulsion between the negatively charged cellulose and the negatively charged cellulose derivatives.
- Example 2 This example shows how the chemical conditions (pH) influence the adsorbed amount of two types of CMC.
- the same cellulose derivatives, pulp, pulp cone, and temperature as in example 1 were used. No addition of electrolyte concentration was done in this example but pH was varied between 2.5 and 4.2, the interval where the dissociation degree of the pulps and the cellulose derivatives carboxyl groups is varied.
- Figure 2 shows how a lower pH increases the adsorption of the amphoteric cellulose derivative. The adsorption is quantitative at lower pH-values than 3.3. If pure carboxy methyl cellulose is used then the adsorption becomes lower to the pulp. It is very difficult to adsorb more than 20 mg/g CMC/g fiber through varying pH at an addition of 40 mg/g of the pure CMC-derivative.
- Example 3 This example shows how the temperature influences the adsorbed amount of two types of CMC.
- the same cellulose derivatives, pulp, pulp cone, and adsorption time as in example 1 were used.
- Figure 3 shows how an increased temperature increases the adsorption.
- the adsorption becomes quantitative at the highest temperature, 120 °C.
- the adsorption of the pure CMC is lower than for the amphoteric preparation.
- Example 4 The method in the previously known WO 01/21890 is particularly characterized by that a great part of the adsorbed derivative was irreversibly adsorbed to the fibers. This is a distinguishing feature in the above method, which means that you are not only adsorbing a derivative to the fibers but also that you in fact has modified the fibers. The modification also becomes toposelective, depending on the molecular weight of the cellulose derivative. In the referred cases in the above application the toposelectivitity was over 70 %, i.e. more than 70 % of the adsorbed negative (and positive charges for the amphoteric derivative) charges is located on the fiber surface.
- the toposelectivitity is defined as surface charge determined with high molecular poly-DADMAC, Mw over 1.000.000/total charge determined by conductometric titration.
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Paper (AREA)
- Biochemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Wood Science & Technology (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
Abstract
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
SE0400396A SE0400396D0 (sv) | 2004-02-20 | 2004-02-20 | Method for modifying lignocellulosic material |
PCT/SE2005/000136 WO2005080678A1 (fr) | 2004-02-20 | 2005-02-03 | Modification de fibres de cellulose a l'aide d'un derive de cellulose amphotere |
Publications (2)
Publication Number | Publication Date |
---|---|
EP1716288A1 true EP1716288A1 (fr) | 2006-11-02 |
EP1716288B1 EP1716288B1 (fr) | 2014-09-17 |
Family
ID=31974269
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP05704796.1A Not-in-force EP1716288B1 (fr) | 2004-02-20 | 2005-02-03 | Modification de fibres de cellulose a l'aide d'un derive de cellulose amphotere |
Country Status (4)
Country | Link |
---|---|
EP (1) | EP1716288B1 (fr) |
ES (1) | ES2525524T3 (fr) |
SE (1) | SE0400396D0 (fr) |
WO (1) | WO2005080678A1 (fr) |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
SE0800807L (sv) * | 2008-04-10 | 2009-10-11 | Stfi Packforsk Ab | Nytt förfarande |
EP2451645A4 (fr) * | 2009-07-07 | 2012-12-26 | Tetra Laval Holdings & Finance | Couche barrière pour un stratifié d'emballage et stratifié d'emballage comprenant une telle couche barrière |
CN103145857B (zh) * | 2013-03-28 | 2016-08-17 | 东华大学 | 一种利用加拿大一枝黄花制备两性纤维素的方法 |
SE538863C2 (sv) * | 2015-05-22 | 2017-01-10 | Innventia Ab | Process for the production of paper or paperboard, paper or paperboard product obtained and uses thereof |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6228217B1 (en) * | 1995-01-13 | 2001-05-08 | Hercules Incorporated | Strength of paper made from pulp containing surface active, carboxyl compounds |
FI106273B (fi) * | 1998-04-30 | 2000-12-29 | Metsae Serla Oyj | Menetelmä kuitutuotteen valmistamiseksi |
SE9903418D0 (sv) | 1999-09-22 | 1999-09-22 | Skogsind Tekn Foskningsinst | Metod för att modifiera cellulosabaserade fibermaterial |
SE519032C2 (sv) * | 2002-03-25 | 2002-12-23 | Kvaerner Pulping Tech | Förfarande för modifiering av cellulosafibrer i samband med kokning |
SE0202652D0 (sv) * | 2002-09-09 | 2002-09-09 | Skogsind Tekn Foskningsinst | Method for sizing of paper or paperboard |
-
2004
- 2004-02-20 SE SE0400396A patent/SE0400396D0/xx unknown
-
2005
- 2005-02-03 WO PCT/SE2005/000136 patent/WO2005080678A1/fr not_active Application Discontinuation
- 2005-02-03 EP EP05704796.1A patent/EP1716288B1/fr not_active Not-in-force
- 2005-02-03 ES ES05704796.1T patent/ES2525524T3/es active Active
Non-Patent Citations (1)
Title |
---|
See references of WO2005080678A1 * |
Also Published As
Publication number | Publication date |
---|---|
EP1716288B1 (fr) | 2014-09-17 |
WO2005080678A1 (fr) | 2005-09-01 |
SE0400396D0 (sv) | 2004-02-20 |
ES2525524T3 (es) | 2014-12-26 |
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