EP0960236B1 - Remplissage de lumiere de fibres cellulosiques par une charge minerale en vue de la fabrication de papier - Google Patents
Remplissage de lumiere de fibres cellulosiques par une charge minerale en vue de la fabrication de papier Download PDFInfo
- Publication number
- EP0960236B1 EP0960236B1 EP98905092A EP98905092A EP0960236B1 EP 0960236 B1 EP0960236 B1 EP 0960236B1 EP 98905092 A EP98905092 A EP 98905092A EP 98905092 A EP98905092 A EP 98905092A EP 0960236 B1 EP0960236 B1 EP 0960236B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- filler
- lumens
- pulp
- calcium carbonate
- paper
- 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.)
- Revoked
Links
- 239000012764 mineral filler Substances 0.000 title claims abstract description 24
- 238000011068 loading method Methods 0.000 title abstract description 24
- 229920003043 Cellulose fiber Polymers 0.000 title description 3
- 239000000945 filler Substances 0.000 claims abstract description 87
- 239000000835 fiber Substances 0.000 claims abstract description 76
- 238000000034 method Methods 0.000 claims abstract description 51
- 230000008569 process Effects 0.000 claims abstract description 41
- 229920001131 Pulp (paper) Polymers 0.000 claims abstract description 16
- 239000002245 particle Substances 0.000 claims abstract description 14
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical group [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 80
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 27
- 239000002002 slurry Substances 0.000 claims description 25
- 229940088417 precipitated calcium carbonate Drugs 0.000 claims description 23
- 239000000203 mixture Substances 0.000 claims description 19
- 229920002472 Starch Polymers 0.000 claims description 18
- 235000019698 starch Nutrition 0.000 claims description 18
- 239000007787 solid Substances 0.000 claims description 17
- 239000008107 starch Substances 0.000 claims description 12
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 11
- 239000011707 mineral Substances 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 10
- 125000002091 cationic group Chemical group 0.000 claims description 5
- 229920002261 Corn starch Polymers 0.000 claims description 4
- 238000013019 agitation Methods 0.000 claims description 4
- 239000008120 corn starch Substances 0.000 claims description 4
- 125000000129 anionic group Chemical group 0.000 claims description 3
- 239000000126 substance Substances 0.000 abstract description 17
- 239000008394 flocculating agent Substances 0.000 abstract description 6
- 239000013055 pulp slurry Substances 0.000 abstract 1
- 235000010216 calcium carbonate Nutrition 0.000 description 23
- 239000011121 hardwood Substances 0.000 description 18
- 239000011122 softwood Substances 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 238000004519 manufacturing process Methods 0.000 description 8
- 235000010755 mineral Nutrition 0.000 description 8
- 230000008901 benefit Effects 0.000 description 7
- 230000003993 interaction Effects 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
- 238000010998 test method Methods 0.000 description 6
- 230000003287 optical effect Effects 0.000 description 5
- 239000002023 wood Substances 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 238000009792 diffusion process Methods 0.000 description 4
- 230000003311 flocculating effect Effects 0.000 description 4
- 238000004513 sizing Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000005995 Aluminium silicate Substances 0.000 description 3
- 241000196324 Embryophyta Species 0.000 description 3
- 235000012211 aluminium silicate Nutrition 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229920002678 cellulose Polymers 0.000 description 3
- 239000001913 cellulose Substances 0.000 description 3
- 239000013043 chemical agent Substances 0.000 description 3
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 3
- 238000004537 pulping Methods 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 239000000454 talc Substances 0.000 description 3
- 229910052623 talc Inorganic materials 0.000 description 3
- 239000004408 titanium dioxide Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 240000003183 Manihot esculenta Species 0.000 description 2
- 235000016735 Manihot esculenta subsp esculenta Nutrition 0.000 description 2
- 244000061456 Solanum tuberosum Species 0.000 description 2
- 235000002595 Solanum tuberosum Nutrition 0.000 description 2
- 241000209140 Triticum Species 0.000 description 2
- 235000021307 Triticum Nutrition 0.000 description 2
- 240000008042 Zea mays Species 0.000 description 2
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 2
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 239000007767 bonding agent Substances 0.000 description 2
- 238000007707 calorimetry Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 235000005822 corn Nutrition 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
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- 230000035515 penetration Effects 0.000 description 2
- 229920002401 polyacrylamide Polymers 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000012216 screening Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 230000008961 swelling Effects 0.000 description 2
- QNRATNLHPGXHMA-XZHTYLCXSA-N (r)-(6-ethoxyquinolin-4-yl)-[(2s,4s,5r)-5-ethyl-1-azabicyclo[2.2.2]octan-2-yl]methanol;hydrochloride Chemical compound Cl.C([C@H]([C@H](C1)CC)C2)CN1[C@@H]2[C@H](O)C1=CC=NC2=CC=C(OCC)C=C21 QNRATNLHPGXHMA-XZHTYLCXSA-N 0.000 description 1
- GHCVXTFBVDVFGE-UHFFFAOYSA-N 4-amino-6-chloro-1,3,5-triazin-2-ol Chemical compound NC1=NC(O)=NC(Cl)=N1 GHCVXTFBVDVFGE-UHFFFAOYSA-N 0.000 description 1
- 244000198134 Agave sisalana Species 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
- 240000008564 Boehmeria nivea Species 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 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
- 240000008886 Ceratonia siliqua Species 0.000 description 1
- 235000013912 Ceratonia siliqua Nutrition 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
- 244000303965 Cyamopsis psoralioides Species 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 244000299507 Gossypium hirsutum Species 0.000 description 1
- 240000006240 Linum usitatissimum Species 0.000 description 1
- 235000004431 Linum usitatissimum Nutrition 0.000 description 1
- 229920000168 Microcrystalline cellulose Polymers 0.000 description 1
- 244000082204 Phyllostachys viridis Species 0.000 description 1
- 235000015334 Phyllostachys viridis Nutrition 0.000 description 1
- 229920002522 Wood fibre Polymers 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- -1 alkyl ketene dimer Chemical compound 0.000 description 1
- 239000010905 bagasse Substances 0.000 description 1
- 239000011425 bamboo Substances 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 235000009120 camo Nutrition 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 210000002421 cell wall Anatomy 0.000 description 1
- 235000010980 cellulose Nutrition 0.000 description 1
- 235000005607 chanvre indien Nutrition 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 230000001143 conditioned effect Effects 0.000 description 1
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- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000003657 drainage water Substances 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 239000011487 hemp Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 235000019813 microcrystalline cellulose Nutrition 0.000 description 1
- 239000008108 microcrystalline cellulose Substances 0.000 description 1
- 229940016286 microcrystalline cellulose Drugs 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001592 potato starch Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
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- 230000000153 supplemental effect Effects 0.000 description 1
- 229920001059 synthetic polymer Polymers 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
- 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
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/63—Inorganic compounds
- D21H17/67—Water-insoluble compounds, e.g. fillers, pigments
-
- 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
- D21C9/004—Modification of pulp properties by chemical means; preparation of dewatered pulp, e.g. in sheet or bulk form, containing special additives inorganic compounds
-
- 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
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/63—Inorganic compounds
- D21H17/67—Water-insoluble compounds, e.g. fillers, pigments
- D21H17/675—Oxides, hydroxides or carbonates
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/21—Macromolecular organic compounds of natural origin; Derivatives thereof
- D21H17/24—Polysaccharides
- D21H17/28—Starch
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/21—Macromolecular organic compounds of natural origin; Derivatives thereof
- D21H17/24—Polysaccharides
- D21H17/28—Starch
- D21H17/29—Starch cationic
-
- 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
- D21H21/06—Paper forming aids
- D21H21/10—Retention agents or drainage improvers
Definitions
- the present invention relates to a process for the preparation of mineral filled paper wherein the filler is dispersed within the lumens of the pulp fiber and wherein a chemical flocculant is added to the furnish, in order to bind the filler inside the lumens as well as to the use of certain flocculants.
- a chemical flocculant is added to the furnish, in order to bind the filler inside the lumens as well as to the use of certain flocculants.
- Any fibrous raw material such as wood, straw, bamboo, hemp, bagasse, sisal. flax, cotton, jute and ramie, can be used in the manufacture of paper. Separation of the fibers of such materials is called pulping. The separated fibers which are used to make paper, are called pulp. Due to the fact that wood is plentiful and readily available, paper consists primarily of wood pulp fiber and insoluble particulate mineral fillers. Most fillers are considerably less expensive than the fibers, and as such, are added during papermaking to reduce the overall cost of producing the paper. Fillers are also added to the pulp fiber to impart certain mechanical properties such as bulk and stiffness, and optical properties such as brightness and opacity to the paper. Kaolin clays. chalk, talc, titanium dioxide, calcium carbonates including precipitated calcium carbonate (PCC) and ground calcium carbonate (GCC) are commonly used as mineral fillers in paper production.
- PCC precipitated calcium carbonate
- GCC ground calcium carbonate
- PCC Precipitated calcium carbonate
- PCC has been widely used as a preferred paper filling mineral over the last decade.
- the versatility of PCC has been one of the major catalysts for its success.
- PCC can be prepared in a variety of particle sizes and crystal shapes or morphologies.
- PCC generally exhibits high brightness, resulting in high sheet brightness.
- Some PCC morphologies are particularly effective at increasing sheet opacity, which is desirable when both sides of the sheet are printed.
- Other PCC morphologies are effective in controlling the thickness (caliper) of the sheet, which is related to sheet stiffness.
- PCC can also affect sheet porosity, which can influence the ability of certain pneumatic devices to physically handle the sheet during papermaking. There are also other advantages in using PCC in paper production.
- the material costs of producing paper generally decrease in direct proportion with increasing amounts of mineral filler in the filled paper. Therefore, maximizing the mineral content of paper is a major objective of the paper maker.
- Optical properties of the filled paper such as brightness and opacity, also tend to improve by increasing the filler content. These benefits are offset however, by a reduction in mechanical strength that generally occurs as the level of mineral filler in the sheet is increased.
- Paper derives its mechanical strength from bonding between adjacent pulp fibers. Fillers that are dispersed throughout the pulp fibers will disrupt the intimate contact that allows bonding between adjacent pulp fibers, to occur. The greater the amount of filler in the paper, the greater will be the tendency toward disruption of fiber to fiber bonds, resulting in lower sheet strength.
- Supplemental bonding agents are also well known as a means of improving the strength of filler loaded papers.
- These bonding agents can be natural or synthetic polymeric substances that are added at the wet-end of a paper machine to improve the mechanical strength of the dried paper.
- These materials are typically starches derived from various plants such as corn, tapioca, potato and wheat, or gums derived from locust bean or guar seeds. Such gums and starches arc "cooked” or otherwise prehydrated to promote swelling before they are used. Gums and starches also are commonly used in papermaking as surface coatings to improve the sizing (i.e., resistance to penetration by water) of paper.
- Lumen loading Another means of improving the strength of filled papers is through a technique called lumen loading. This involves placing the fillers directly inside the hollow spaces (i.e. lumens) of the pulp fibers. Fillers that reside inside the lumens of pulp fibers do not interfere with inter-fiber bonding. and therefore have less negative impact on the mechanical strength of filled papers. Lumen loading can be accomplished through simple mechanical mixing. However, just as fillers will migrate into these lumens, they can also diffuse out. Using known techniques, loading of the lumens and diffusion of the filler loaded lumens during the papermaking process, continues to be a problem for papermakers. What has been found to be novel and unanticipated by the prior art is a product and process for lumen loading pulp fibers wherein a substantial level of a mineral filler can be loaded into the lumens, while paper strength reduction, is minimized.
- U.S. Pat. No. 5223090 discloses a method of loading cellulose fibers with calcium carbonate filler by reacting calcium hydroxide with carbon dioxide in the presence of cellulosic fibrous material.
- U.S. Pat. No. 5,096,539 discloses a process for preparing a filled paper wherein the filler comprises an insoluble precipitate that is precipitated in situ within the cell wall of the fibers.
- U.S. Pat. No. 4,510,020 discloses a process for preparing a filled paper wherein substantially all of the filler present is within the lumens of the cellulosic fibers.
- the present invention provides a process for adding a mineral filler to wood pulp fiber in a papermaking process wherein a chemical additive is used to flocculate the filler particles inside of the lumens of the fibers as defined in claim 1.
- the filler is maintained inside the lumens of the fibers during the dilute, high shear conditions of papermaking.
- the present invention further provides a use as defined in claim 12.
- the present invention provides a process for producing filled paper by loading the lumens of the pulp fiber with a mineral filler.
- the filler is added to the papermaking process at a point where the concentration of the pulp is from 1.0 to 5.0 weight percent.
- a chemical flocculant down-stream of the filler addition point the filler is fixed and remains within the lumens during papermaking.
- additional filler may be added to the papermaking process at a second addition point, in order to achieve fine control of the filler content of the final paper.
- the filler is loaded into the pulp fiber lumens by mixing or agitating the pulp fiber, the filler, and a flocculant at a point in the papermaking process when the pulp concentration is from about 1.0 to about 5.0 weight percent. Dilution of the filler/pulp fiber mixture may be necessary to obtain the desired furnish consistency of usually from about 0.3 to about 1.0 percent, preferably about 0.5 percent, prior to delivery to the paper machine.
- An integral aspect of the process of the present invention is the structure of the papermaking fiber.
- the strength of paper is highly dependent upon the fibers of the pulp, used to make paper, becoming bonded extensively to one another during papermaking.
- the most widely used fibers are those derived from wood and, as liberated by pulping, the majority appear under the microscope as long hollow tubes. uniform in size for most of the length but tapered at each end.
- the fiber wall is perforated by small apertures(pits) which connect the central cavity(lumen) to the fiber exterior.
- the process for placing mineral fillers within the lumens is called lumen loading and is applicable to a wide range of papermaking fibers.
- the present process can be carried out on fibers derived from many species of wood, by any of the common pulping and bleaching procedures.
- the fiber may be hardwood fiber, softwood fiber or a mixture of both hard and soft wood fibers.
- the pulp fiber should enter the process of the present invention in "never-dried" form. Drying the pulp fiber irreversibly collapses a large portion of the lumens and renders them inaccessible to the mineral filler. Reslurrying of dried pulp fiber is less susceptible to the full benefit of the novel process for lumen loading of the present invention, but having full knowledge of this limitation, may be used.
- the concentration or consistency of the pulp fiber slurry is preferably in the range of from about one percent to about five percent, based on the total weight of the slurry. In a preferred embodiment of the invention, the consistency of the pulp fiber slurry is preferably in the range of from about two percent to about four percent, based on the total weight of the slurry.
- Kaolin clays chalk, talc, titanium dioxide, alumina, silica, precipitated calcium carbonate (PCC) and ground calcium carbonate (GCC) are commonly used as mineral fillers in paper production.
- a filler consists of fine particles of an insoluble solid, usually of a mineral origin.
- fillers confer improved optical properties such as opacity and brightness to the paper. Enhancement of the optical properties of the mineral filled paper is a principal objective in adding fillers to the paper furnish, although other advantages, such as improved smoothness, improved printability and improved durability, can be imparted to the paper.
- the preferred filler is precipitated calcium carbonate (PCC).
- the PCC has an average particle size in the range from about 0.5 to about 2.0 microns( ⁇ m). In a preferred embodiment of the present invention, the average size of the PCC is in the range of from about 0.7 ⁇ m to about 1.4 ⁇ m.
- the PCC morphology may be orthorhombic. rhombic or scalenohedral.
- Other fillers, such as ultrafine ground limestone (UFGL) also may be used in the process of the present invention.
- an aqueous slurry of mineral filler is mixed, by any known mechanical means, into an aqueous slurry of wood pulp fiber.
- the pulp is in a never-dried state, in order to obtain the maximum loading benefit.
- the filler is added to the pulp as an aqueous slurry, so that the filler solids, after mixing with the pulp fiber, represent from about 5 weight percent to about 80 weight percent based on the total solids.
- the filler solids represents from about 20 weight percent to about 40 weight percent based on the total solids.
- the filler and fiber components are mixed under agitation for a period of time to allow maximum loading of the lumens. It has been found that a minimum of five minutes of agitation is necessary to obtain maximum loading. Shorter mixing times do not provide maximum lumen loading benefits.
- the period of mixing or agitation can range from about 10 minutes to about 30 minutes. There is no known upper limit on the time of mixing, outside of that imposed by practicality and economics. During the time that the fiber and filler components are mixed together, some of the filler becomes dispersed within the fiber lumens. This occurs by mechanical diffusion.
- One such factor is the average particle size of the mineral filler. Fillers having smaller average particle sizes will more easily diffuse into the lumens than larger particle size fillers.
- the relative concentrations of fiber and filler that are present when the two components are mixed will also determine the extent to which lumen loading occurs. Finally, the period of time the filler and fiber components are mixed, influence how much lumen loading will occur in the paper furnish.
- the amount of filler that diffuses into the lumens is from about 0.5 percent to about 10 percent of the combined weight of fiber and filler. In a preferred embodiment of the invention from about 3 percent to about 6 percent of the total weight of fiber and filler is lumen loaded filler.
- Another integral aspect of the process of lumen loading of the present invention requires that a flocculating chemical be added to the pulp fiber-filler mixture, after the pulp fiber-filler components have been sufficiently mixed.
- a flocculant causes any filler that resides within the fiber lumens to form agglomerates of sufficient size to prevent diffusion outside the lumens during paper production. This also causes filler outside the lumens to also form agglomerates.
- the formation of agglomerates reduces the tendency of filler particles to interfere with inter-fiber bonding, fixes and holds the filler inside and outside the lumens, thus preventing dislodgement of the filler during papermaking.
- the flocculating chemical is selected from that group of materials that are polymers of glucose derived from plants, called starches. Plants from which starches are principally obtained are corn, tapioca, potato and wheat. Before it is used as a chemical flocculant in the present produces, the starch is "cooked", in a manner consistent with the manufacturer's recommendation, to promote dissolution and swelling. This is an important aspect of the present invention since the formation of agglomerates both inside the lumens and outside of the lumens result in maximum lumen loading.
- the starches to be used according to the invention are chemically modified to render the starch cationic, anionic or amphoteric. According to the process of the present invention.
- the starch is preferably an amphoteric waxy corn starch.
- the flocculating agent is selected from those materials that exhibit a stronger chemical affinity for PCC than for wood pulp fiber.
- the chemical affinity is measured using the technique of batch calorimetry. When a chemical agent is brought into contact with the mineral surface, adsorption of the chemical agent will occur at the mineral surface only if sufficient affinity exists between the two materials. Adsorption is an exothermic process that liberates heat. Adsorption also can occur for a chemical agent that is brought into contact with wood pulp fibers.
- the magnitude of the interaction between a flocculating agent and the mineral filler is measured to determine which provides maximum benefit. A separate measurement is made to determine the magnitude of the interaction between the flocculating agent and a microcrystalline cellulose that is chemically similar to wood pulp.
- the magnitude of the flocculant-mineral interaction is at least equal to the magnitude of the flocculant-cellulose interaction for equal proportions of materials. More preferably, the magnitude of the flocculant-mineral interaction is at least 50 percent greater than the interaction between flocculant and cellulose. Most preferably, the magnitude of the flocculant-cellulose interaction is zero (0).
- the current invention is advantageous over other lumen loading techniques in that it offers a means of preventing diffusion of filler particles outside the fiber lumens without the need for a drying step. This results in a reduction in energy cost and an increase margin of profit for the papermaker.
- Figure I demonstrates an aspect of how the process of the present invention could be used in a typical papermaking process.
- the filler addition is split such that filler may be added to the furnish at the blend chest and again at the head box. Between these two addition points, but after the first addition point, a chemical flocculant is added to the pre-mixed fiber-filler components in order to fix or hold the filler where it resides inside and outside of the fiber lumens.
- one or more processes involve addition of a mineral filler to a high-consistency slurry of wood pulp fiber.
- a flocculating chemical is added so that filler particles that have diffused into the fiber lumens are agglomerated and prevented from diffusing outside the lumens.
- the flocculating agent is selected from those chemicals that exhibit greater chemical affinity for the filler than for cellulose fiber. Chemical affinity is quantified using the technique of batch calorimetry.
- the mineral filler and flocculating chemical are mixed and then added to a high consistency slurry of wood pulp fiber slurry. The resulting mixture is formed into paper exhibiting good mechanical strength at high filler loading levels.
- amphoteric waxy corn starch (CATO 225 from National Starch Corporation) which was cooked at 93.3°C (200°F) for 30 minutes at 1 weight percent solids was added to the calcium carbonate/pulp aqueous slurry.
- the quantity of starch corresponds to a 4.0 weight percent on a dry calcium carbonate basis.
- the calcium carbonate/pulp/starch aqueous slurry was stirred for 30 minutes.
- the mixture was made into a paper sheet on a stainless steel wire using a Formax unit.
- the basis weight of the sheet approximates 170 grams per meter square (g/m 2 ).
- the sheet was pressed between felts at 1.7 ⁇ 10 5 pascal (25 psi) and dried on a drum drier at 265°C.
- These dried sheets represent the commercial hardwood dry lap containing calcium carbonate, which was combined with softwood dry lap in the desired proportions.
- the percent calcium carbonate of the hardwood dry lap is measured so as to definitively determine the amount of dry hardwood present.
- the hardwood containing sheets were refined by combining 360 grams hardwood (from the hardwood dry lap) and 24 liters of water and stirring the mixture in a Valley Beater to 360 Canadian Standard Freeness (CSF).
- CSF Canadian Standard Freeness
- a mixture was prepared by combining 360 grams of untreated softwood pulp and 24 liters of water.
- the mixture was refined by mixing in a Valley Beater to 400 CSF.
- the refined hardwood and the refined softwood were combined such that a 60 percent hardwood/40 percent softwood mixture results. Water was added to the mixture to adjust the solids to 0.3 weight percent on a dry pulp basis.
- Handsheets were prepared (60 g/m 2 ) using a Formax Sheet Former (Noble and Wood type, from Adirondack Machine Corp) from a furnish of 60 percent hardwood (containing calcium carbonate in the lumen) and 40 percent bleached softwood pulps beaten to 400 CFS at pH 7 in distilled water. The pulp consistency was 0.3 percent.
- a retention aid high molecular weight cationic polyacrylamide
- Percol® from Allied Colloids was added to the pulp furnish in an amount equal to 0.05 percent (0.5 kg/ton ⁇ 1lb./ton of paper).
- Synthetic sizing agent alkyl ketene dimer was added to the pulp furnish at a level of 0.25 percent (2.5 kg/ton ⁇ 5lbs./ton of paper).
- the mixture was made into a paper sheet on a stainless steel wire using a Formax unit.
- the sheet was pressed between felts at 1.7 ⁇ 10 5 pascal (25p.s.i) and dried on a drum dryer at 265°C.
- the sheets were conditioned at 50 percent relative humidity and 23°C. prior to testing.
- the paper strength was determined by testing the breaking length (TAPPI test method T-494 OM-88) and the Scott Bond (TAPPI test method UM 403).
- the paper brightness was measured according to TAPPI test method T452-OM92 and the paper opacity was measured according to TAPPI test method T425-OM-91 (corrected to 60.5 grams/m 2 basis weight).
- the strength of the paper, using as filler the lumen containing calcium carbonate in accordance with the present invention, is greater than that of the control paper (not lumen loaded. but having an equivalent amount of filler added in the conventional manner).
- the pulp fine water was set aside for later use.
- the 3.8 percent consistency was used to simulate the solids of pulp in an integrated mill.
- An integrated paper mill is one that prepares its own pulp as opposed to acquiring pulp from the open market.
- the quantity of starch corresponds to 4.0 weight percent on a dry calcium carbonate basis.
- the calcium carbonatc/pulp/starch aqueous slurry was then stirred for 10 minutes.
- the mixture was then diluted with 1622 ml of the pulp fine water so as to re-introduce all fines that were removed during the screening process.
- the mixture was further diluted with 9500 ml water to adjust the final consistency to approximately 0.3 percent.
- Paper handsheets were then prepared from the above-described hardwood/softwood pulp containing the calcium carbonate and hardwood/softwood pulp containing no calcium carbonate loaded in the lumen.
- the handsheets were prepared and tested as described in Example 1 .
- Hercules Size Test (HST) was used to measure the penetration of liquid through the handsheets. The test was performed on a Hercules Sizing Tester Model KA or KC and the test method employed is TAPPI Test Method T-530 PM-89 (Revised 1989).
- the paper strength, i.e. Breaking Length and Scott Bond of the paper. which contains the calcium carbonate loaded lumen in accordance with the present invention is greater than that of the control paper (not lumen loaded).
- the paper which contains the calcium carbonate loaded lumen also exhibits improved sizing.
Landscapes
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Wood Science & Technology (AREA)
- Paper (AREA)
- Artificial Filaments (AREA)
Claims (17)
- Procédé pour la production d'un papier renfermant une charge minérale, qui comprend les étapes consistant à ajouter une suspension aqueuse de particules d'une charge minérale à une suspension aqueuse de fibres de pâte de bois n'ayant jamais été déshydratée, la concentration des fibres de pâte de bois étant comprise dans l'intervalle de 1,0% en poids à 5,0% en poids sur la base du poids de la suspension de fibres de pâte de bois n'ayant jamais été déshydratée, les matières solides de charge, après le mélange aux fibres de pâte, étant présentes en une quantité de 5 à 80% en poids sur la base des matières solides totales, à mélanger la charge et les fibres sous agitation pendant au moins 5 minutes, à ajouter un agent floculant du type amidon amphotère, anionique ou cationique pour fixer la charge minérale à l'intérieur des lumens et pour produire du papier dans lequel une quantité de 0,5 à 10% en poids de charge, sur la base de la somme des poids de la charge et des fibres, est située à l'intérieur des lumens.
- Procédé suivant la revendication 1, dans lequel une quantité de 3 à 6% en poids du poids total des fibres et de la charge est incorporée aux lumens.
- Procédé suivant la revendication 1 ou la revendication 2, dans lequel le mélange de charge et de pâte est dilué à une concentration en pâte de 0,3% en poids à 1,0% en poids avant d'être amené à la machine à papier.
- Procédé suivant l'une quelconque des revendications précédentes, dans lequel la charge minérale consiste en carbonate de calcium.
- Procédé suivant la revendication 4, dans lequel le carbonate de calcium consiste en carbonate de calcium précipité.
- Procédé suivant la revendication 5, dans lequel le carbonate de calcium précipité a un diamètre moyen de particule de 0,5 micromètre à 2,0 micromètres.
- Procédé suivant la revendication 6, dans lequel le diamètre moyen de particule est compris dans l'intervalle de 0,7 micromètre à 1,4 micromètre.
- Procédé suivant l'une quelconque des revendications 4 à 7, dans lequel le carbonate de calcium est présent en une quantité de 20% en poids à 40% en poids de matières solides totales du mélange de charge et de pâte.
- Procédé suivant l'une quelconque des revendications précédentes, dans lequel la concentration des fibres de pâte de bois est comprise dans l'intervalle de 2,0% en poids à 4,0% en poids, sur la base du poids total de la suspension.
- Procédé suivant l'une quelconque des revendications précédentes, dans lequel la suspension aqueuse de charge minérale et la suspension aqueuse de fibres sont mélangées pendant un temps de 10 à 30 minutes.
- Procédé suivant l'une quelconque des revendications précédentes, dans lequel l'amidon consiste en amidon amphotère de maïs cireux.
- Utilisation d'un agent floculant du type amidon amphotère anionique ou cationique dans une composition de fabrication de papier constituée de fibres de pâte de bois n'ayant jamais été déshydratée et d'une charge minérale pour fixer la charge minérale à l'intérieur des lumens de la pâte de bois.
- Utilisation suivant la revendication 12, pour fixer 0,5 à 10% de charge, sur la base de la somme des poids de la charge et des fibres à l'intérieur des lumens.
- Utilisation suivant la revendication 12 ou 13, dans laquelle la charge minérale consiste en carbonate de calcium.
- Utilisation suivant l'une quelconque des revendications 12 à 14, dans laquelle le carbonate de calcium consiste en carbonate de calcium précipité.
- Utilisation suivant l'une quelconque des revendications 12 à 15, dans un système dans lequel la concentration de fibres de pâte de bois est comprise dans l'intervalle de 1,0% en poids à 5,0% en poids, sur la base du poids total de la suspension.
- Utilisation suivant l'une quelconque des revendications 12 à 16, dans laquelle l'amidon consiste en amidon amphotère de maïs cireux.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US79721997A | 1997-02-11 | 1997-02-11 | |
| US797219 | 1997-02-11 | ||
| PCT/US1998/002925 WO1998035095A1 (fr) | 1997-02-11 | 1998-02-10 | Remplissage de lumiere de fibres cellulosiques par une charge minerale en vue de la fabrication de papier |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0960236A1 EP0960236A1 (fr) | 1999-12-01 |
| EP0960236B1 true EP0960236B1 (fr) | 2003-09-10 |
Family
ID=25170245
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP98905092A Revoked EP0960236B1 (fr) | 1997-02-11 | 1998-02-10 | Remplissage de lumiere de fibres cellulosiques par une charge minerale en vue de la fabrication de papier |
Country Status (14)
| Country | Link |
|---|---|
| EP (1) | EP0960236B1 (fr) |
| JP (1) | JP2001511853A (fr) |
| KR (1) | KR20000070779A (fr) |
| CN (1) | CN1213200C (fr) |
| AT (1) | ATE249549T1 (fr) |
| AU (1) | AU6279498A (fr) |
| BR (1) | BR9807212A (fr) |
| CA (1) | CA2280043A1 (fr) |
| DE (1) | DE69818012T2 (fr) |
| NO (1) | NO993772D0 (fr) |
| PL (1) | PL334939A1 (fr) |
| PT (1) | PT960236E (fr) |
| SK (1) | SK82499A3 (fr) |
| WO (1) | WO1998035095A1 (fr) |
Families Citing this family (29)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6423183B1 (en) * | 1997-12-24 | 2002-07-23 | Kimberly-Clark Worldwide, Inc. | Paper products and a method for applying a dye to cellulosic fibers |
| AU2708799A (en) | 1998-03-23 | 1999-10-18 | Pulp And Paper Research Institute Of Canada | Method for producing pulp and paper with calcium carbonate filler |
| CA2282211C (fr) * | 1998-10-16 | 2007-01-09 | Grain Processing Corporation | Methode de fabrication d'une bande continue de papier |
| US6749721B2 (en) | 2000-12-22 | 2004-06-15 | Kimberly-Clark Worldwide, Inc. | Process for incorporating poorly substantive paper modifying agents into a paper sheet via wet end addition |
| US6582560B2 (en) | 2001-03-07 | 2003-06-24 | Kimberly-Clark Worldwide, Inc. | Method for using water insoluble chemical additives with pulp and products made by said method |
| US7749356B2 (en) | 2001-03-07 | 2010-07-06 | Kimberly-Clark Worldwide, Inc. | Method for using water insoluble chemical additives with pulp and products made by said method |
| DE10113998A1 (de) * | 2001-03-22 | 2002-09-26 | Voith Paper Patent Gmbh | Verfahren zum Beladen von in einer Faserstoffsuspension enthaltenen Fasern mit einem Hilfsstoff |
| DE10120526A1 (de) * | 2001-04-26 | 2002-10-31 | Voith Paper Patent Gmbh | Verfahren zur Herstellung von Zellstoff |
| US6916402B2 (en) | 2002-12-23 | 2005-07-12 | Kimberly-Clark Worldwide, Inc. | Process for bonding chemical additives on to substrates containing cellulosic materials and products thereof |
| WO2005033403A1 (fr) * | 2003-10-01 | 2005-04-14 | Imerys Pigments, Inc. | Preparation d'une composition comprenant un oxyde de metal alcalino-terreux et un substrat et possedant une teneur reduite en grains |
| US7670459B2 (en) | 2004-12-29 | 2010-03-02 | Kimberly-Clark Worldwide, Inc. | Soft and durable tissue products containing a softening agent |
| JP2007092203A (ja) * | 2005-09-28 | 2007-04-12 | Nippon Paper Industries Co Ltd | オフセット印刷用中性新聞用紙 |
| DE102007059736A1 (de) | 2007-12-12 | 2009-06-18 | Omya Development Ag | Oberflächenmineralisierte organische Fasern |
| ES2526757T3 (es) * | 2008-09-09 | 2015-01-15 | Omya International Ag | Composiciones de carbonatos cálcicos/pigmentos para formulaciones de papel, que muestran reducción del traspaso de impresión |
| CN103290722B (zh) * | 2012-02-28 | 2015-04-22 | 金东纸业(江苏)股份有限公司 | 浆料的制备方法,浆料及由其制得的纸张 |
| WO2014158104A2 (fr) * | 2013-03-29 | 2014-10-02 | Siam Kraft Industry Co., Ltd. | Feuilles contenant une charge organique |
| CN103653233B (zh) * | 2013-12-06 | 2016-01-06 | 武汉淡雅香科技发展股份有限公司 | 一种提高造纸法再造烟叶灰分的方法 |
| CN104179069B (zh) * | 2014-08-18 | 2016-09-14 | 武汉地质资源环境工业技术研究院有限公司 | 一种抑制植物纤维衰变的造纸方法 |
| JP2019518848A (ja) | 2016-06-10 | 2019-07-04 | エコラブ ユーエスエイ インク | 製紙用乾燥強化剤としての使用のための低分子量乾燥粉末ポリマー |
| US10487452B1 (en) * | 2017-01-26 | 2019-11-26 | Kimberly-Clark Worldwide, Inc. | Treated fibers and fibrous structures comprising the same |
| WO2019027994A1 (fr) | 2017-07-31 | 2019-02-07 | Ecolab Usa Inc. | Procédé d'application de polymère sec |
| JP7657050B2 (ja) | 2017-07-31 | 2025-04-04 | エコラブ ユーエスエイ インク | 低分子量アクリラミド系ポリマーを含む粉末の高速溶解のためのプロセス |
| US11708481B2 (en) | 2017-12-13 | 2023-07-25 | Ecolab Usa Inc. | Solution comprising an associative polymer and a cyclodextrin polymer |
| CA3099233A1 (fr) | 2018-05-31 | 2019-12-05 | Argaman Technologies Ltd. | Procede et systeme d'application de composes chimiques a des fibres naturelles et fibres traitees obtenues par lesdits procede et systeme |
| CN110700009B (zh) * | 2019-10-10 | 2020-08-18 | 建滔(佛冈)绝缘材料有限公司 | 一种压制覆铜板作垫层用的热压垫板纸的生产工艺及其用途 |
| CN111472196A (zh) * | 2020-04-10 | 2020-07-31 | 浙江科技学院 | 一种填充微纳米钙的耐久性手工书画纸及其制备方法 |
| US20230228036A1 (en) * | 2020-06-12 | 2023-07-20 | Specialty Minerals (Michigan) Inc. | Surface mineralized organic fibers and methods of making the same |
| CN114293399B (zh) * | 2022-01-14 | 2022-10-21 | 九洲生物技术(苏州)有限公司 | 一种化学改性造纸填料及其制备方法 |
| CN116145470A (zh) * | 2023-02-21 | 2023-05-23 | 衢州东大复合材料科技有限公司 | 一种伸缩性小的热升华转印原纸 |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4510020A (en) * | 1980-06-12 | 1985-04-09 | Pulp And Paper Research Institute Of Canada | Lumen-loaded paper pulp, its production and use |
| US5096539A (en) * | 1989-07-24 | 1992-03-17 | The Board Of Regents Of The University Of Washington | Cell wall loading of never-dried pulp fibers |
-
1998
- 1998-02-10 AT AT98905092T patent/ATE249549T1/de not_active IP Right Cessation
- 1998-02-10 CA CA002280043A patent/CA2280043A1/fr not_active Abandoned
- 1998-02-10 CN CNB988019752A patent/CN1213200C/zh not_active Expired - Fee Related
- 1998-02-10 PT PT98905092T patent/PT960236E/pt unknown
- 1998-02-10 DE DE69818012T patent/DE69818012T2/de not_active Revoked
- 1998-02-10 BR BR9807212-9A patent/BR9807212A/pt not_active IP Right Cessation
- 1998-02-10 WO PCT/US1998/002925 patent/WO1998035095A1/fr not_active Ceased
- 1998-02-10 EP EP98905092A patent/EP0960236B1/fr not_active Revoked
- 1998-02-10 PL PL98334939A patent/PL334939A1/xx unknown
- 1998-02-10 AU AU62794/98A patent/AU6279498A/en not_active Abandoned
- 1998-02-10 KR KR1019997007040A patent/KR20000070779A/ko not_active Withdrawn
- 1998-02-10 SK SK824-99A patent/SK82499A3/sk unknown
- 1998-02-10 JP JP53508698A patent/JP2001511853A/ja active Pending
-
1999
- 1999-08-04 NO NO993772A patent/NO993772D0/no unknown
Non-Patent Citations (1)
| Title |
|---|
| "Pulp and Paper Manufacture, Vol. 6 "Stock Preparation" 3rd. ed 1983, The Joint Textbook Committee of the Paper Industry, TAPPI Atlanta USA * |
Also Published As
| Publication number | Publication date |
|---|---|
| PT960236E (pt) | 2004-02-27 |
| EP0960236A1 (fr) | 1999-12-01 |
| WO1998035095A1 (fr) | 1998-08-13 |
| JP2001511853A (ja) | 2001-08-14 |
| AU6279498A (en) | 1998-08-26 |
| SK82499A3 (en) | 2000-02-14 |
| KR20000070779A (ko) | 2000-11-25 |
| NO993772L (no) | 1999-08-04 |
| CN1244227A (zh) | 2000-02-09 |
| CA2280043A1 (fr) | 1998-08-13 |
| BR9807212A (pt) | 2002-05-21 |
| ATE249549T1 (de) | 2003-09-15 |
| DE69818012D1 (de) | 2003-10-16 |
| CN1213200C (zh) | 2005-08-03 |
| PL334939A1 (en) | 2000-03-27 |
| NO993772D0 (no) | 1999-08-04 |
| DE69818012T2 (de) | 2004-04-01 |
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