EP1240389A1 - Method for modifying cellulose-based fiber material - Google Patents
Method for modifying cellulose-based fiber materialInfo
- Publication number
- EP1240389A1 EP1240389A1 EP00966646A EP00966646A EP1240389A1 EP 1240389 A1 EP1240389 A1 EP 1240389A1 EP 00966646 A EP00966646 A EP 00966646A EP 00966646 A EP00966646 A EP 00966646A EP 1240389 A1 EP1240389 A1 EP 1240389A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- approximately
- electrolyte
- cellulose fibers
- cmc
- aqueous solution
- 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
- 238000000034 method Methods 0.000 title claims abstract description 32
- 229920002678 cellulose Polymers 0.000 title description 4
- 239000001913 cellulose Substances 0.000 title description 4
- 239000002657 fibrous material Substances 0.000 title description 3
- 239000003792 electrolyte Substances 0.000 claims abstract description 29
- 229920003043 Cellulose fiber Polymers 0.000 claims abstract description 28
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 23
- 238000011282 treatment Methods 0.000 claims abstract description 21
- 239000000835 fiber Substances 0.000 claims abstract description 20
- 239000007864 aqueous solution Substances 0.000 claims abstract description 15
- 150000001768 cations Chemical class 0.000 claims abstract description 14
- 238000004519 manufacturing process Methods 0.000 claims abstract description 10
- 239000007900 aqueous suspension Substances 0.000 claims abstract description 7
- 229920000297 Rayon Polymers 0.000 claims abstract description 3
- 239000002964 rayon Substances 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 3
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 44
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 44
- 238000001179 sorption measurement Methods 0.000 description 22
- 239000000654 additive Substances 0.000 description 11
- 239000000126 substance Substances 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 5
- 239000011122 softwood Substances 0.000 description 5
- 125000000129 anionic group Chemical group 0.000 description 4
- 125000002091 cationic group Chemical group 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000006467 substitution reaction Methods 0.000 description 4
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 3
- -1 Na2S04 Chemical class 0.000 description 3
- 239000008186 active pharmaceutical agent Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 159000000013 aluminium salts Chemical class 0.000 description 3
- 239000001110 calcium chloride Substances 0.000 description 3
- 229910001628 calcium chloride Inorganic materials 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 230000000717 retained effect Effects 0.000 description 3
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 description 2
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 239000010813 municipal solid waste Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- 244000025254 Cannabis sativa Species 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 229920002085 Dialdehyde starch Polymers 0.000 description 1
- 240000000797 Hibiscus cannabinus Species 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229920001131 Pulp (paper) 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
- 229920006318 anionic polymer Polymers 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 125000005313 fatty acid group Chemical group 0.000 description 1
- IVJISJACKSSFGE-UHFFFAOYSA-N formaldehyde;1,3,5-triazine-2,4,6-triamine Chemical compound O=C.NC1=NC(N)=NC(N)=N1 IVJISJACKSSFGE-UHFFFAOYSA-N 0.000 description 1
- 229940015043 glyoxal Drugs 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000011121 hardwood Substances 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920000867 polyelectrolyte Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- ODGAOXROABLFNM-UHFFFAOYSA-N polynoxylin Chemical compound O=C.NC(N)=O ODGAOXROABLFNM-UHFFFAOYSA-N 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000004627 regenerated cellulose Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
- 238000004448 titration Methods 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
- 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
- This invention concerns the technical field of paper manufacture, in particular chemical additives during paper manufacture.
- CMC carboxymethyl cellulose
- the present invention concerns a method whereby cellulose fibers are treated for at least 5 minutes with an aqueous electrolyte-containing solution of CMC or a derivative of CMC, whereby the temperature during the treatment is at least 100 °C and at least one of the following conditions applies: A) the pH of the aqueous solution du ⁇ ng the treatment lies in the interval of approximately 1.5 - 4 5, or B) the pH of the aqueous solution du ⁇ ng the treatment is higher than approximately 11; or
- the concentration of the electrolyte in the aqueous solution lies in the interval of approximately 0.001 - 0.5 M if the electrolyte has monovalent cations, or in the range approximately 0.0002 - 0.25 M if the electrolyte has divalent cations
- condition C applies together with either condition A or condition B.
- a method for modifying cellulose fibers with a cellulose de ⁇ vative such as CMC is desc ⁇ bed in the published international patent application WO 99/57370. This method is performed at a pH of 6 - 13 and a temperature of up to 100 °C, preferably m the approximate range of 20 - 80 °C. It is specified (on page 7, lines 29-30) that the temperature does not constitute a c ⁇ tical factor. There is nothing specified or even implied that a temperature over 100 °C would involve significant advantages for the adsorption.
- the cellulose fibers that are 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, thermomechanical, chemo-mechanical and chemo-thermomechamcal 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 hnters, regenerated cellulose, kenaf and grass fibers can also be used with the present invention.
- the preferred concentration of CMC is approximately 0.02 - 4 % w/w, calculated on the dry weight of the fiber material. A more preferred concentration is approximately 0 04 - 2 % w/w, and the most preferred concentration of additive is approximately 0.08 - 1% w/w.
- the concept "CMC" is used here to include, in addition to carboxymethyl cellulose, vanous derivatives thereof.
- the preferred molar degree of substitution is approximately 0.3 - 1.2 and the preferred viscosity is approximately 25 - 8,000 mPa at a concentration of 4%. A higher viscosity is preferred, since it has become clear that the irreversibility of the adsorption is higher for higher molecular weights.
- a high concentration of pulp is particularly desirable if the adsorption is not quantitative, since the loss of CMC can thus be reduced and CMC solution can easily be reintroduced into the reaction vessel.
- Treatment of pulp preferably takes place as a separate treatment step at high pulp concentration, but it can naturally also be earned out at the same time as, for example, digesting, or du ⁇ ng a bleaching step. As high a concentration of pulp as possible is thus desired, but this is naturally limited by practical conditions du ⁇ ng the conduct of the method.
- the preferred concentration of pulp is approximately 3 - 50%, a more preferred concentration interval is approximately 5 - 50%, and the most preferred concentration interval is approximately 10 - 30%.
- Such high concentration mixes are known to one skilled in the arts withm the relevant technical field, and are suitable for use m association with the present invention.
- a preferred range of pH is approximately 2 - 4, in particular approximately 2.5 - 3.5.
- the preferred concentration interval for salts with monovalent cations is approximately 0.002 - 0.25 M, in particular within the range approximately 0.005 - 0.1 M
- the preferred concentration interval for salts with divalent cations, such as CaCl 2 is between approximately 0.0005 - 0.1 M, m particular approximately 0.02 - 0.05 M.
- the preferred adsorption pe ⁇ od is approximately 5 - 180 mm, a more preferred adsorption pe ⁇ od is approximately 10 - 120 mm and the most preferred adsorption pe ⁇ od is approximately 15 - 60 min.
- the preferred temperature is m excess of approximately 100 °C, a more preferred temperature is in excess of approximately 120 °C and the most preferred adsorption temperature is up to approximately 150 °C.
- the method according to the invention is thus earned out at a pressure m excess of atmosphe ⁇ c 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 dned m the normal manner.
- the present invention also concerns a method for production of paper with a high wet strength, whereby
- the cellulose fibers are modified by treatment for at least 5 minutes with an aqueous solution of CMC or a CMC derivative containing electrolyte, whereby
- the temperature du ⁇ ng the treatment is at least approximately 100 °C and at least one of the following conditions apply:
- the concentration of the electrolyte in the aqueous solution lies in the interval of approximately 0.001 - 0.5 M if the electrolyte has monovalent cations, or m the range of approximately 0.0002 - 0.25 M if the electrolyte has divalent cations;
- cellulose fibers treated according to the present invention when treated with wet-strength agent, provide a much higher wet strength than the strength that can be explained by the higher adsorption of wet-strength agent to the fibers.
- a paper can be defined as wet-strengthened m this context when the geometric mean value of the wet strength divided by the dry strength exceeds 0.15.
- 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 0.02 - 1.5 % and the most preferred concentration is 0.05 - 0.8 %.
- wet-strength agents that can be used include all cationic polymenc resms. These include, for example, those wet-strength agents that give permanent wet strength: urea-formaldehyde resms, melamine-formaldehyde resms and polyamide-amme resms. Examples of wet-strength agents that give temporary wet strength are polyethylene lmme, dialdehyde starch, polyvmyl amme and glyoxal polyacrylamide resins.
- a method for making paper with a high wet strength but low dry strength, a method that can be used, for example, for producing paper structures that are strong when wet and absorbent.
- debonding agents are 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.
- Example 1 This example according to known technology demonstrates how the conditions in the chemical environment affect the amounts of different types of CMC that are irreversibly adsorbed.
- the CMC preparations that were used were commercially available preparations from Metsa-Serla:
- the pulp was a bleached, long-fibered, und ⁇ ed softwood sulfate pulp from Metsa-Serla/Husum's facto ⁇ es. The adsorption t ⁇ als were conducted at a pulp concentration of 2%. The pulp was washed with 0.01 M HC1 after the treatment and then transferred to its Na-form in de-iomsed water. The pulp was washed after 2 hours with de-ionised water. The amount of CMC adsorbed was determined by conductomet ⁇ c titration.
- the amount of CMC that was added was 40 mg/g. "DS" is used to denote the degree of molar substitution for the CMC used.
- Table 1 shows that the presence of electrolyte is necessary to obtain adsorption. It is also clear that the adsorption is higher at higher temperatures. Higher alkalinity is also advantageous for the adsorption.
- the degree of molar substitution or the molecular weight of CMC is not c ⁇ tical, but the adsorption increases when the degree of substitution decreases.
- Example 2 This example shows that a very high relative amount of CMC can be irreversibly bound to a bleached und ⁇ ed softwood sulfate pulp (Metsa-Serla/Husum factones) by the selection of a high temperature and a high electrolyte concentration.
- the expe ⁇ ment was performed by treating the pulp at 120 °C or at 150 °C for 2 hours m 0.05 M CaCl 2 buffered with 0001 M NaHCOj.
- the amounts of CMC adsorbed were measured both after washing the pulp with de-ionised water (Ca-form) and after washing the pulp with 0 01 M HC1, de-ionised water, adjusting its pH value using NaOH to a pH of 8 and equilibrating it with an 0 001 M NaHC0 3 buffer for 2 hours (Na-form)
- WRV is an abbreviation for "Water Retention Value” and is a measure of the ability of the pulp to retain water (here the Na-form was measured at 3,000 g and 15 minutes in de-ionised water)
- Example 3 CMC (Fmnfix WRH) was adsorbed onto a bleached undned softwood sulfate pulp (Metsa-Serla/Husum facto ⁇ es) at different pH values in de-ionised water at 120 °C. The pulp had been transferred to its Na-form before the pH was adjusted. The amount of CMC added was 20 mg/g. The results in Table 3 show that a certain amount is adsorbed at 120 °C, but better adsorption is achieved if electrolyte is present during the treatment (compare with Table 2).
- Example 4 This example shows that the adsorbed amount of CMC is adsorbed to the cellulose fibers so strongly that it remains on the fibers even after a prolonged pe ⁇ od of leachmg.
- the bleached sulfate pulp from Example 2 was treated with 40 mg/g Fmnfix WRH for 2 hours at 120 °C in 0.1 M NaCl. The amount adsorbed after this treatment was 7.7 mg/g. After leachmg the pulp in de- lomsed water for 19 hours, the adsorbed amount was 7.4 mg/g.
- Example 5 This example shows that selecting a high temperature and a high concentration of electrolyte at the adsorption step gives a pulp that has a lower water retention ability than that obtained if the CMC is adsorbed onto the pulp at a lower temperature.
- the expe ⁇ ment was performed by treating an undned softwood sulfate pulp (Metsa- Serla/Husum factories) at 23 °C, 80 °C and 120 °C for 12 hours m 0.05 M CaCl 2 buffered by 0.001 M NaHC0 3 .
- the amount of adsorbed CMC (Fmnfix WRH, 20 mg/g) was measured after washing the pulp with 0.01 M HCl, de-iomsed water, adjusting its pH with NaOH to a pH of 8 and equilibrating it with 0.001 M NaHC0 3 buffer for 2 hours (Na-form).
- WRV is an abbreviation for "Water Retention Value" according to the definition given earlier.
- Table 10 shows that the increase in WRV per mg/g of adsorbed CMC is considerably lower if the CMC has been adsorbed at a higher temperature (120 °C) than if it has been adsorbed at a lower temperature This is particularly advantageous if it is to be easy to de-water the pulp on the paper machine. The ability of the pulp to retain water, however, does not reflect the strength of the paper that is manufactured from the pulp under consideration.
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Wood Science & Technology (AREA)
- Biochemistry (AREA)
- Paper (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
Abstract
Description
Claims
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
SE9903418 | 1999-09-22 | ||
SE9903418A SE9903418D0 (en) | 1999-09-22 | 1999-09-22 | Method for modifying cellulose-based fiber materials |
PCT/SE2000/001823 WO2001021890A1 (en) | 1999-09-22 | 2000-09-20 | Method for modifying cellulose-based fiber material |
Publications (2)
Publication Number | Publication Date |
---|---|
EP1240389A1 true EP1240389A1 (en) | 2002-09-18 |
EP1240389B1 EP1240389B1 (en) | 2010-06-02 |
Family
ID=20417102
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP00966646A Expired - Lifetime EP1240389B1 (en) | 1999-09-22 | 2000-09-20 | Method for modifying cellulose-based fiber material |
Country Status (7)
Country | Link |
---|---|
EP (1) | EP1240389B1 (en) |
AT (1) | ATE470011T1 (en) |
AU (1) | AU7696000A (en) |
DE (1) | DE60044504D1 (en) |
ES (1) | ES2346634T3 (en) |
SE (1) | SE9903418D0 (en) |
WO (1) | WO2001021890A1 (en) |
Families Citing this family (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
SE519032C2 (en) * | 2002-03-25 | 2002-12-23 | Kvaerner Pulping Tech | Method for modifying cellulose fibers in connection with cooking |
SE0202652D0 (en) * | 2002-09-09 | 2002-09-09 | Skogsind Tekn Foskningsinst | Method for sizing paper or paperboard |
SE0400396D0 (en) | 2004-02-20 | 2004-02-20 | Skogsind Tekn Foskningsinst | Method of modifying lignocellulosic material |
SE0401600D0 (en) * | 2004-06-18 | 2004-06-18 | Stfi Packforsk Ab | Method of manufacturing paper or similar |
RU2341603C1 (en) * | 2004-11-05 | 2008-12-20 | Акцо Нобель Н.В. | Method for processing of cellulose fiber |
US8007636B2 (en) | 2004-11-05 | 2011-08-30 | Akzo Nobel N.V. | Method of treating cellulose fibres with chlorine dioxide and an alkyl cellulose derivative |
SE0800807L (en) * | 2008-04-10 | 2009-10-11 | Stfi Packforsk Ab | New procedure |
FI124724B (en) | 2009-02-13 | 2014-12-31 | Upm Kymmene Oyj | A process for preparing modified cellulose |
FI125829B (en) | 2011-03-07 | 2016-02-29 | Aalto Korkeakoulusã Ã Tiã | Double click technology |
SE538863C2 (en) * | 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 (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3468696A (en) * | 1965-04-05 | 1969-09-23 | C H Dexter & Sons Inc | Method of producing a fibrous web material having retained wet strength at high humidity and the fibrous material produced thereby |
US4199367A (en) * | 1975-11-07 | 1980-04-22 | Avtex Fibers Inc. | Alloy rayon |
EP0337310A1 (en) * | 1988-04-15 | 1989-10-18 | Air Products And Chemicals, Inc. | Poly(vinyl alcohol-vinylamine)copolymers for improved moist compressive strength of paper products |
US5354424A (en) * | 1989-02-10 | 1994-10-11 | Rha Chokyun | Paper composition and methods therefor |
US5318669A (en) * | 1991-12-23 | 1994-06-07 | Hercules Incorporated | Enhancement of paper dry strength by anionic and cationic polymer combination |
US6228217B1 (en) * | 1995-01-13 | 2001-05-08 | Hercules Incorporated | Strength of paper made from pulp containing surface active, carboxyl compounds |
EP0802282A1 (en) * | 1995-11-02 | 1997-10-22 | Uni-Charm Company Limited | Process for preparing hydrolyzable sheet |
JP3296989B2 (en) * | 1997-03-31 | 2002-07-02 | ユニ・チャーム株式会社 | Water disintegrable sheet and method for producing the same |
FI106273B (en) * | 1998-04-30 | 2000-12-29 | Metsae Serla Oyj | Process for the manufacture of a fiber product |
-
1999
- 1999-09-22 SE SE9903418A patent/SE9903418D0/en unknown
-
2000
- 2000-09-20 ES ES00966646T patent/ES2346634T3/en not_active Expired - Lifetime
- 2000-09-20 AU AU76960/00A patent/AU7696000A/en not_active Abandoned
- 2000-09-20 EP EP00966646A patent/EP1240389B1/en not_active Expired - Lifetime
- 2000-09-20 WO PCT/SE2000/001823 patent/WO2001021890A1/en active Application Filing
- 2000-09-20 AT AT00966646T patent/ATE470011T1/en active
- 2000-09-20 DE DE60044504T patent/DE60044504D1/en not_active Expired - Lifetime
Non-Patent Citations (1)
Title |
---|
See references of WO0121890A1 * |
Also Published As
Publication number | Publication date |
---|---|
ATE470011T1 (en) | 2010-06-15 |
ES2346634T3 (en) | 2010-10-19 |
AU7696000A (en) | 2001-04-24 |
WO2001021890A1 (en) | 2001-03-29 |
SE9903418D0 (en) | 1999-09-22 |
DE60044504D1 (en) | 2010-07-15 |
EP1240389B1 (en) | 2010-06-02 |
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