EP0522940B1 - Process for the preparation of paper and paper obtained therefrom - Google Patents
Process for the preparation of paper and paper obtained therefrom Download PDFInfo
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- EP0522940B1 EP0522940B1 EP92401913A EP92401913A EP0522940B1 EP 0522940 B1 EP0522940 B1 EP 0522940B1 EP 92401913 A EP92401913 A EP 92401913A EP 92401913 A EP92401913 A EP 92401913A EP 0522940 B1 EP0522940 B1 EP 0522940B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- process according
- paper
- comprised
- cationic starch
- weight
- 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
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- 238000000034 method Methods 0.000 title claims abstract description 23
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 40
- 229920002472 Starch Polymers 0.000 claims abstract description 22
- 239000000203 mixture Substances 0.000 claims abstract description 22
- 235000019698 starch Nutrition 0.000 claims abstract description 22
- 125000002091 cationic group Chemical group 0.000 claims abstract description 20
- 239000008107 starch Substances 0.000 claims abstract description 20
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 19
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 9
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000006467 substitution reaction Methods 0.000 claims abstract description 6
- 125000000129 anionic group Chemical group 0.000 claims abstract description 5
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 5
- 238000004519 manufacturing process Methods 0.000 claims abstract description 5
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 5
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 4
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 4
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 4
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 4
- 230000014759 maintenance of location Effects 0.000 claims description 17
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 14
- 239000003795 chemical substances by application Substances 0.000 claims description 11
- 239000012764 mineral filler Substances 0.000 claims description 11
- 238000004513 sizing Methods 0.000 claims description 8
- -1 aluminate ion Chemical class 0.000 claims description 7
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 7
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 7
- 150000001450 anions Chemical class 0.000 claims description 6
- 239000013065 commercial product Substances 0.000 claims description 6
- 229920005989 resin Polymers 0.000 claims description 6
- 239000011347 resin Substances 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- 238000009792 diffusion process Methods 0.000 claims description 4
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 2
- 229920002873 Polyethylenimine Polymers 0.000 claims description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 2
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 2
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 claims description 2
- 150000001735 carboxylic acids Chemical class 0.000 claims description 2
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 2
- 239000004927 clay Substances 0.000 claims description 2
- 229920001577 copolymer Polymers 0.000 claims description 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims description 2
- 150000003460 sulfonic acids Chemical class 0.000 claims description 2
- 239000000454 talc Substances 0.000 claims description 2
- 229910052623 talc Inorganic materials 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims 2
- 229960004279 formaldehyde Drugs 0.000 claims 2
- 229910052570 clay Inorganic materials 0.000 claims 1
- WOLATMHLPFJRGC-UHFFFAOYSA-N furan-2,5-dione;styrene Chemical compound O=C1OC(=O)C=C1.C=CC1=CC=CC=C1 WOLATMHLPFJRGC-UHFFFAOYSA-N 0.000 claims 1
- 239000004408 titanium dioxide Substances 0.000 claims 1
- 239000004411 aluminium Substances 0.000 abstract description 6
- 235000012239 silicon dioxide Nutrition 0.000 abstract description 2
- 239000002318 adhesion promoter Substances 0.000 abstract 1
- 239000011256 inorganic filler Substances 0.000 abstract 1
- 229910003475 inorganic filler Inorganic materials 0.000 abstract 1
- 239000000123 paper Substances 0.000 description 27
- 239000000047 product Substances 0.000 description 15
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 12
- 239000000725 suspension Substances 0.000 description 8
- 239000000654 additive Substances 0.000 description 5
- 239000000835 fiber Substances 0.000 description 5
- 229920001131 Pulp (paper) Polymers 0.000 description 4
- 239000002655 kraft paper Substances 0.000 description 4
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 3
- 229910004298 SiO 2 Inorganic materials 0.000 description 3
- 239000011149 active material Substances 0.000 description 3
- 229920006318 anionic polymer Polymers 0.000 description 3
- 239000007767 bonding agent Substances 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- 239000011121 hardwood Substances 0.000 description 3
- 229920002401 polyacrylamide Polymers 0.000 description 3
- 239000011122 softwood Substances 0.000 description 3
- 229920003043 Cellulose fiber Polymers 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 229920006317 cationic polymer Polymers 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 235000015927 pasta Nutrition 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- NGDLSKPZMOTRTR-OAPYJULQSA-N (4z)-4-heptadecylidene-3-hexadecyloxetan-2-one Chemical compound CCCCCCCCCCCCCCCC\C=C1/OC(=O)C1CCCCCCCCCCCCCCCC NGDLSKPZMOTRTR-OAPYJULQSA-N 0.000 description 1
- WECIKJKLCDCIMY-UHFFFAOYSA-N 2-chloro-n-(2-cyanoethyl)acetamide Chemical compound ClCC(=O)NCCC#N WECIKJKLCDCIMY-UHFFFAOYSA-N 0.000 description 1
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- 102100031260 Acyl-coenzyme A thioesterase THEM4 Human genes 0.000 description 1
- 235000014755 Eruca sativa Nutrition 0.000 description 1
- 244000024675 Eruca sativa Species 0.000 description 1
- 101000638510 Homo sapiens Acyl-coenzyme A thioesterase THEM4 Proteins 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- DZUHNVFSJJSSOM-UHFFFAOYSA-K aluminum chlorosulfate Chemical compound [Al+3].[O-]S(Cl)(=O)=O.[O-]S(Cl)(=O)=O.[O-]S(Cl)(=O)=O DZUHNVFSJJSSOM-UHFFFAOYSA-K 0.000 description 1
- 239000007900 aqueous suspension Substances 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 210000004534 cecum Anatomy 0.000 description 1
- XTHPWXDJESJLNJ-UHFFFAOYSA-M chlorosulfate Chemical compound [O-]S(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-M 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 1
- 230000005087 leaf formation Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000010813 municipal solid waste Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/63—Inorganic compounds
- D21H17/66—Salts, e.g. alums
-
- 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
-
- 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
- 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
- D21H17/68—Water-insoluble compounds, e.g. fillers, pigments siliceous, e.g. clays
Definitions
- the present invention relates to a process for manufacturing paper and also relates to the paper thus obtained.
- the raw paper pulp consisting essentially of cellulose fibers is put into the form of a dilute aqueous suspension which is brought into the headbox of the paper machine from where it is distributed on a filter cloth on which the sheet is formed. of paper. This sheet is then wrung and dried.
- the qualities and properties of the paper obtained are determined in particular by the operating conditions of the paper machine, the raw pulp, the various additives that are added to the suspension before the sheet is formed and also the products that are coated. on the sheet of paper downstream of the filter cloth.
- mineral fillers such as CaCO 3 , TiO 2 , etc.
- Sizing agents such as those of the dimeric alkyl ketene family, are added to make the sheet resistant to liquids, therefore allowing the glued sheet of paper to be used for writing and printing.
- the air or "leaf formation” is of great importance and is representative of the general quality of the paper.
- the epair represents the greater or lesser homogeneity of the distribution of the fibers in the plane and the thickness of the sheet.
- the quality of the air will therefore have a considerable impact on the general quality of printing in the case, for example, of print-writing papers, and on the mechanical properties in the case, for example, of packaging papers.
- more and more additives are added to the suspension entering the headbox.
- the object of the present invention is, among other things, while retaining the quality of the air and the other characteristics of the paper, to obtain high retention rates as well as to allow improved drainage.
- the present invention makes it possible to achieve a higher charge, in particular in products sensitive to acids, and leads to less polluting releases.
- the present invention has for A process for manufacturing paper according to claim 1.
- the suspension containing the cellulose fibers can be raw or bleached pulp, bleached chemical pulp of softwoods or hardwoods or annual plants, unbleached chemical pulp of softwoods or hardwoods, mechanical pulps (SGW, TMP, CTMP, %) unbleached or bleached, de-inked bleached or unbleached pasta, pasta already containing additives, and mixtures thereof.
- the cationic starch - mentioned as component c) 1) - used according to the present invention is a mixture of one or more products sold under the generic name of cationic starch.
- Starch has an average molecular weight of 2.10 4 to 2.10 5 , preferably 3.10 4 to 12.10 4 .
- Cationic starches have a degree of substitution (DS) of between 0.01 to 0.1.
- the cationic starches are, for example, those described in Kirk Othmer, 3rd edition, volume 21, page 503. They represent by weight from 0.2 to 1.7% of the weight of the fibrous suspension entering the headbox.
- the PAC is present in the fiber composition entering the headbox at a rate of 0.01 to 0.3% by weight, relative to the weight of said fibrous composition, said percentage being expressed relative to Al 2 O 3 .
- the PAC is from WAC.
- the WAC corresponds to formula IV.
- the silica is present in the fibrous composition in an amount of 0.01 to 0.3% by weight, relative to the weight of said fibrous composition, the percentage being expressed as a percentage of active material, that is to say in SiO 2 .
- the anionic silica used is that which is in the form of a silica sol, advantageously at 15% of SiO 2 .
- the mineral filler - component a) mentioned above - can be one or more of the following conventionally used fillers, given by way of illustration: clay, CaCO 3 , hydrated alumina, talc, TiO 2 , etc.
- the mineral filler represents 5 to 30% by weight, preferably 10 to 25% by weight, of the weight of said fibrous composition.
- the preferred mineral filler is formed from CaCO 3 .
- the sizing agent - component b) mentioned above - can be one or more of the following agents conventionally used in neutral medium: dimeric alkyl ketenes (AKD), fluorinated phosphates, carboxylic anhydrides, styrene / maleic anhydride copolymers, and their derivatives .
- the amount of sizing agent used is between 0.01 and 2% by weight of commercial product at 6% of active material, relative to the weight of said composition.
- the bonding agent preferably used is AKD.
- the fibrous suspension can also contain conventional additives, such as dyes, optical brighteners, mechanical reinforcing agents, defoamers, antislimes (anti-deposition agent), as well as products chosen from the group consisting of: polyacrylamides , polyethyleneimines, carboxymethylcellulose, urea-formaldehyde resins, melamine-formaldehyde resins, aminopolyamide-epichlorohydrin resins, polyamide-epichlorohydrin resins.
- additives such as dyes, optical brighteners, mechanical reinforcing agents, defoamers, antislimes (anti-deposition agent), as well as products chosen from the group consisting of: polyacrylamides , polyethyleneimines, carboxymethylcellulose, urea-formaldehyde resins, melamine-formaldehyde resins, aminopolyamide-epichlorohydrin resins, polyamide-epichlorohydrin resins.
- WAC is a product marketed by ATOCHEM and corresponds to a poly aluminum chloride of formula IV at 10% Al 2 O 3 .
- the silica is in the form of a silica sol and is commercially available under the name CECASOL from CECA.
- the cationic starch is that manufactured by ROQUETTE and marketed under the name HICAT 142.
- the AKD sizing agent is manufactured by HERCULES and marketed under the name AQUAPEL.
- test 1 there is a very significant improvement in the air caused by the use of WAC instead of silica, a result consistent with what one skilled in the art expects. .
- Test 3 shows the synergy that the association of small quantities of silica develops in the presence of WAC. At equivalent thickness, retention is increased by 10 points, ie an increase of 15 to 20%. This results in less pollution of the water in the circuits and greater ease of treatment of waste water at a lower cost.
Landscapes
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Paper (AREA)
- Detergent Compositions (AREA)
- Disintegrating Or Milling (AREA)
- Analysing Materials By The Use Of Radiation (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
- Diaphragms For Electromechanical Transducers (AREA)
Abstract
Description
La présente invention concerne un procédé de fabrication de papier et se rapporte également au papier ainsi obtenu.The present invention relates to a process for manufacturing paper and also relates to the paper thus obtained.
La pâte à papier brute constituée essentiellement de fibres de cellulose est mise sous forme d'une suspension aqueuse diluée qui est amenée dans la caisse de tête de la machine à papier d'où elle est distribuée sur une toile filtrante sur laquelle se forme la feuille de papier. Cette feuille est ensuite essorée puis séchée. Les qualités et les propriétés du papier obtenues sont déterminées notamment par les conditions de marche de la machine à papier, la pâte brute, les différents additifs qu'on ajoute dans la suspension avant la formation de la feuille et aussi les produits qu'on couche sur la feuille de papier en aval de la toile filtrante.The raw paper pulp consisting essentially of cellulose fibers is put into the form of a dilute aqueous suspension which is brought into the headbox of the paper machine from where it is distributed on a filter cloth on which the sheet is formed. of paper. This sheet is then wrung and dried. The qualities and properties of the paper obtained are determined in particular by the operating conditions of the paper machine, the raw pulp, the various additives that are added to the suspension before the sheet is formed and also the products that are coated. on the sheet of paper downstream of the filter cloth.
Parmi les produits ajoutés à la suspension de fibres entrant en caisse de tête, on peut citer les charges minérales, les agents de collage, les agents visant à améliorer les propriétés mécaniques du papier, les colorants, etc. Les charges minérales, telles que CaCO3, TiO2, etc, rendent la feuille de papier opaque, ce qui facilite l'écriture et l'impression. Les agents de collage, tels que ceux de la famille des alkylcétènes dimères, sont ajoutés pour rendre la feuille résistante aux liquides, par conséquent permettre à la feuille de papier collée d'être utilisée pour l'écriture et l'impression.Among the products added to the suspension of fibers entering the headbox, there may be mentioned mineral fillers, bonding agents, agents intended to improve the mechanical properties of the paper, dyes, etc. Mineral fillers, such as CaCO 3 , TiO 2 , etc., make the sheet of paper opaque, which facilitates writing and printing. Sizing agents, such as those of the dimeric alkyl ketene family, are added to make the sheet resistant to liquids, therefore allowing the glued sheet of paper to be used for writing and printing.
L'une des qualités des papiers, cartons et autres est la régularité des caractéristiques. Parmi celles-ci, "l'épair" ou "formation de la feuille" est d'une grande importance et est représentative de la qualité générale du papier. En effet, l'épair représente la plus ou moins grande homogénéité de la répartition des fibres dans le plan et l'épaisseur de la feuille. La qualité de l'épair aura donc une incidence considérable sur la qualité générale de l'impression dans le cas, par exemple, des papiers impression-écriture, et sur les propriétés mécaniques dans le cas, par exemple, des papiers d'emballage. Afin d'améliorer l'épair, de plus en plus d'additifs sont ajoutés à la suspension entrant en caisse de tête. Mais pour répondre aux exigences de plus en plus sévères des normes de pollution, les papeteries sont conduites à diminuer leur consommation en eau, ce qui provoque une augmentation de la charge polluante associée à ce type d'industrie (Matières en Suspension MES, Demande Biologique en Oxygène DBO, Demande Chimique en Oxygène DCO, Salinité, etc...) ainsi que d'autres problèmes, tels que des problèmes de poix et plus généralement ceux liés à la présence de déchets anioniques (dénommés en anglais "anionic trash"). Les caractéristiques du papier devant cependant rester identiques, et les problèmes de lutte pour l'environnement devant être résolus, l'une des méthodes proposées dans l'art antérieur consiste à augmenter la rétention des éléments au sein de la feuille en cours de formation sur la toile filtrante. Ce résultat est atteint, jusqu'à un certain point, par l'adjonction d'agents rétenteurs à la suspension de fibres entrant en caisse de tête. Malheureusement, cette méthode soit varie en efficacité, soit conduit à une détérioration importante de l'épair du papier selon les produits utilisés.One of the qualities of paper, cardboard and others is the regularity of the characteristics. Among these, "the air" or "leaf formation" is of great importance and is representative of the general quality of the paper. In fact, the epair represents the greater or lesser homogeneity of the distribution of the fibers in the plane and the thickness of the sheet. The quality of the air will therefore have a considerable impact on the general quality of printing in the case, for example, of print-writing papers, and on the mechanical properties in the case, for example, of packaging papers. To improve the look, more and more additives are added to the suspension entering the headbox. But to meet the increasingly stringent requirements of pollution standards, paper mills are led to reduce their water consumption, which causes an increase in the pollutant load associated with this type of industry (MES suspended matter, Biological Demand in Oxygen BOD, Chemical Demand in Oxygen COD, Salinity, etc ...) as well as other problems, such as pitch problems and more generally those related to the presence of anionic waste (called in English "anionic trash") . The characteristics of the paper having however to remain identical, and the problems of fight for the environment having to be solved, one of the methods proposed in the prior art consists in increasing the retention of the elements within the sheet being formed on the filter cloth. This result is achieved, to a certain extent, by the addition of retention agents to the suspension of fibers entering the headbox. Unfortunately, this method either varies in efficiency or leads to a significant deterioration in the appearance of the paper depending on the products used.
La présente invention a donc pour objet un nouveau procédé de fabrication de papiers et autres, dans lequel, en plus de la charge minérale et de l'agent de collage est mélangé à la suspension ou composition de fibres entrant en caisse de tête, un nouveau système rétenteur ternaire. L'état de la technique en la matière est essentiellement formé des documents suivants:
- EP-A-348 366 décrit un système ternaire comprenant de l'amidon cationique, du polychlorure d'aluminium, et un polymère d'acide silicique. L'acide polysilicique doit avoir une aire spécifique donnée (> 1 050 m2/g).
- WO-A- 88/6 659 décrit un système ternaire comprenant un polymère cationique, du polychlorure d'aluminium, et de la silice. Le polymère cationique est de préférence du polyacrylamide et l'amidon cationique n'est pas cité.
- EP-A-285 486 décrit un système rétenteur à base d'amidon cationique et de polychlorure d'aluminium. La charge minérale peut être par exemple de la silice. Néanmoins, cette demande ne décrit pas spécialement le système rétenteur ternaire selon la présence invention.
- US-A-4 643 801 décrit un système rétenteur à base d'amidon cationique, d'un polymère anionique à poids moléculaire élevé et de silice selon des rations en poids amidon/silice de 100/1 à 1/1 et polymère anionique/silice de 20/1 à 1/10. Un composé d'aluminium peut aussi être ajouté. Le présent système rétenteur ternaire seul n'est cependant pas décrit. WO-A-86/00100 décrit des additifs aux charges de caisses de tête, comprenant un composant type amidon cationique et un composant type silice à surface modifiée. Cette silice modifiée est obtenue par traitement de sa surface avec des ions aluminates, qui subissent un échange. Cette solution technique qui est exclue de l'objet de la revendication 1, est cependant complexe et d'un coût relativement élevé.
- EP-A-348 366 describes a ternary system comprising cationic starch, poly aluminum chloride, and a polymer of silicic acid. The polysilicic acid must have a given specific area (> 1050 m 2 / g).
- WO-A- 88/6659 describes a ternary system comprising a cationic polymer, poly aluminum chloride, and silica. The cationic polymer is preferably polyacrylamide and the cationic starch is not mentioned.
- EP-A-285 486 describes a retention system based on cationic starch and poly aluminum chloride. The mineral filler can for example be silica. However, this application does not specifically describe the ternary retention system according to the invention.
- US-A-4 643 801 describes a retention system based on cationic starch, a high molecular weight anionic polymer and silica according to starch / silica weight rations of 100/1 to 1/1 and anionic polymer / silica from 20/1 to 1/10. An aluminum compound can also be added. The present ternary retention system alone is however not described. WO-A-86/00100 describes additives to headbox fillers, comprising a cationic starch type component and a silica type component with modified surface. This modified silica is obtained by treating its surface with aluminate ions, which undergo an exchange. This technical solution, which is excluded from the subject of claim 1, is however complex and relatively expensive.
Dans "Polyaluminium hydroxychloride application in neutral pH rosin sizing of paper", B.H. Wortley et J.C. Steelhammer, est mentionné un système rétenteur comprenant de l'amidon cationique, de la bentonite et un polymère anionique, mais il n'est pas mentionné ni suggéré l'emploi de PAC dans ce système rétenteur particulier.In "Polyaluminium hydroxychloride application in neutral pH rosin sizing of paper", BH Wortley and JC Steelhammer, is mentioned a retentive system comprising cationic starch, bentonite and an anionic polymer, but it is not mentioned nor suggested l use of PAC in this particular retention system.
Aucune des publications ci-dessus seule ou en combinaison avec d'autres références ne décrit ni ne suggère l'emploi d'un système rétenteur du type de celui de la présente invention ni ne décrit ou suggère les effets surprenants et inattendus obtenus grâce à ce nouveau système rétenteur.None of the above publications alone or in combination with other references describes or suggests the use of a retention system of the type of that of the present invention or describes or suggests the surprising and unexpected effects obtained thanks to this. new retention system.
La présente invention a pour but, entre autres, tout en conservant la qualité de l'épair ainsi que les autres caractéristiques du papier, d'obtenir des taux de rétention élevés ainsi que de permettre un égouttage amélioré. La présente invention permet de réaliser une charge plus importante, notamment en produits sensibles aux acides, et conduit à des rejets moins polluants. Ainsi, la présente invention a pour objet un procédé de fabrication de papier, selon la revendication 1.The object of the present invention is, among other things, while retaining the quality of the air and the other characteristics of the paper, to obtain high retention rates as well as to allow improved drainage. The present invention makes it possible to achieve a higher charge, in particular in products sensitive to acids, and leads to less polluting releases. Thus, the present invention has for A process for manufacturing paper according to claim 1.
La suspension contenant les fibres de cellulose peut être de la pâte brute ou blanchie, des pâtes chimiques blanchies de résineux ou de feuillus ou de plantes annuelles, des pâtes chimiques écrues de résineux ou de feuillus, des pâtes mécaniques (SGW, TMP, CTMP, ...) écrues ou blanchies, des pâtes désencrées blanchies ou non-blanchies, des pâtes contenant déjà des additifs, et leurs mélanges.The suspension containing the cellulose fibers can be raw or bleached pulp, bleached chemical pulp of softwoods or hardwoods or annual plants, unbleached chemical pulp of softwoods or hardwoods, mechanical pulps (SGW, TMP, CTMP, ...) unbleached or bleached, de-inked bleached or unbleached pasta, pasta already containing additives, and mixtures thereof.
L'amidon cationique -mentionné à titre de composant c)1)- utilisé selon la présente invention est un mélange d'un ou plusieurs produits commercialisés sous le nom générique d'amidon cationique. L'amidon a un poids moléculaire moyen de 2.104 à 2.105, de préférence de 3.104 à 12.104. Les amidons cationiques ont un degré de substitution (D.S.) compris entre 0,01 à 0,1. Les amidons cationiques sont, par exemple, ceux décrits dans Kirk Othmer, 3ème édition, volume 21, page 503. Ils représentent en poids de 0,2 à 1,7% du poids de la suspension fibreuse entrant en caisse de tête.The cationic starch - mentioned as component c) 1) - used according to the present invention is a mixture of one or more products sold under the generic name of cationic starch. Starch has an average molecular weight of 2.10 4 to 2.10 5 , preferably 3.10 4 to 12.10 4 . Cationic starches have a degree of substitution (DS) of between 0.01 to 0.1. The cationic starches are, for example, those described in Kirk Othmer, 3rd edition, volume 21, page 503. They represent by weight from 0.2 to 1.7% of the weight of the fibrous suspension entering the headbox.
Le polychlorure d'aluminium ou "PAC" -mentionné à titre de composant c)2)- utilisé selon la présente invention désigne les produits qu'on appelle habituellement polychlorure d'aluminium, polychlorure basique d'aluminium, polychlorosulfate basique d'aluminium, et consiste de préférence en un ou plusieurs des produits suivants:
- 1. le sel de formule:
Aln(OH)mCl3n-m (I)
dans laquelle n est quelconque, 3n-m est positif, m et n sont des nombres entiers positifs;
- 2. le sel de formule:
Aln(OH)mCl3n-m-2k(SO4)k (II)
dans laquelle k, m et n sont des entiers positifs, et 3n > m + 2k, la basicité ou le rapport m/3n est compris entre 0,3 et 0,7 et k/n = 0,01 à 0,03;
- 3. le sel de formule:
[Aln(OH)3n-m-2pClm(SO4)p]z (III)
dans laquelle (3n-m-2p)/3n = 0,4 à 0,7; p = 0,04 à 0,25n; m/p = 8 à 35; k, m, n, et p sont des nombres entiers et z est au moins 1;
- 4. le chlorosulfate d'aluminium basique de formule:
AlnOHm(SO4)kCl3n-m-2k (IV)
dans laquelle la basicité ou le rapport molaire (m/3n)x100 est compris entre 40% environ et 65% environ
- MA = 7000-35000
- ØZ(Å) = 350-2500
- ØW(Å) = 200-1200;
- 1. the salt of formula:
Al n (OH) m Cl 3n-m (I)
where n is arbitrary, 3n-m is positive, m and n are positive integers;
- 2. the salt of formula:
Al n (OH) m Cl 3n-m-2k (SO 4 ) k (II)
in which k, m and n are positive integers, and 3n> m + 2k, the basicity or the ratio m / 3n is between 0.3 and 0.7 and k / n = 0.01 to 0.03;
- 3. the salt of formula:
[Al n (OH) 3n-m-2p Cl m (SO 4 ) p ] z (III)
in which (3n-m-2p) / 3n = 0.4 to 0.7; p = 0.04 to 0.25n; m / p = 8 to 35; k, m, n, and p are whole numbers and z is at least 1;
- 4. basic aluminum chlorosulfate of formula:
Al n OH m (SO 4 ) k Cl 3n-m-2k (IV)
in which the basicity or the molar ratio (m / 3n) x100 is between approximately 40% and approximately 65%
- MA = 7000-35000
- ØZ (Å) = 350-2500
- ØW (Å) = 200-1200;
Le PAC est présent dans la composition fibreuse entrant en caisse de tête à raison de 0,01 à 0,3% en poids, par rapport au poids de ladite composition fibreuse, ledit pourcentage étant exprimé par rapport à Al2O3. De préférence, le PAC est du WAC. Le WAC correspond à la formule IV.PAC is present in the fiber composition entering the headbox at a rate of 0.01 to 0.3% by weight, relative to the weight of said fibrous composition, said percentage being expressed relative to Al 2 O 3 . Preferably, the PAC is from WAC. The WAC corresponds to formula IV.
La silice est présente dans la composition fibreuse, à raison de 0,01 à 0,3% en poids, par rapport au poids de ladite composition fibreuse, le pourcentage étant exprimé en pourcentage de matière active, c'est-à-dire en SiO2. La silice à caractère anionique employée est celle qui est sous la forme d'un sol de silice, avantageusement à 15% de SiO2.The silica is present in the fibrous composition in an amount of 0.01 to 0.3% by weight, relative to the weight of said fibrous composition, the percentage being expressed as a percentage of active material, that is to say in SiO 2 . The anionic silica used is that which is in the form of a silica sol, advantageously at 15% of SiO 2 .
La charge minérale -le composant a) mentionné ci-dessus- peut être l'une ou plusieurs des charges classiquement utilisées suivantes, données à titre illustratif: argile, CaCO3, alumine hydratée, talc, TiO2, etc. La charge minérale représente 5 à 30 % en poids, de préférence de 10 à 25% en poids, du poids de ladite composition fibreuse. La charge minérale préférée est formée de CaCO3.The mineral filler - component a) mentioned above - can be one or more of the following conventionally used fillers, given by way of illustration: clay, CaCO 3 , hydrated alumina, talc, TiO 2 , etc. The mineral filler represents 5 to 30% by weight, preferably 10 to 25% by weight, of the weight of said fibrous composition. The preferred mineral filler is formed from CaCO 3 .
L'agent de collage -le composant b) mentionné ci-dessus- peut être un ou plusieurs des agents suivants classiquement utilisés en milieu neutre: alkylcétènes dimères (AKD), phosphates fluorés, anhydrides carboxyliques, copolymères styrène/anhydride maléique, et leurs dérivés. La quantité d'agent de collage employée est comprise entre 0,01 et 2% en poids de produit commercial à 6% de matière active, par rapport au poids de ladite composition. L'agent de collage employé de préférence est l'AKD.The sizing agent - component b) mentioned above - can be one or more of the following agents conventionally used in neutral medium: dimeric alkyl ketenes (AKD), fluorinated phosphates, carboxylic anhydrides, styrene / maleic anhydride copolymers, and their derivatives . The amount of sizing agent used is between 0.01 and 2% by weight of commercial product at 6% of active material, relative to the weight of said composition. The bonding agent preferably used is AKD.
Les composants a), b), c)1), c)2) et c)3) mentionnés ci-dessus peuvent être ajoutés séparément ou en mélange de deux ou plusieurs d'entre eux.The components a), b), c) 1), c) 2) and c) 3) mentioned above can be added separately or as a mixture of two or more of them.
La suspension fibreuse peut aussi contenir des additifs classiques, tels que des colorants, des azurants optiques, des agents de renforcement mécaniques, des antimousses, des antislimes (agent anti-dépôt), ainsi que des produits choisis dans le groupe consistant en: les polyacrylamides, les polyéthylèneimines, la carboxyméthylcellulose, les résines urée-formol, les résines mélamines- formol, les résines aminopolyamide-épichlorhydrine, les résines polyamide-épichlorhydrine.The fibrous suspension can also contain conventional additives, such as dyes, optical brighteners, mechanical reinforcing agents, defoamers, antislimes (anti-deposition agent), as well as products chosen from the group consisting of: polyacrylamides , polyethyleneimines, carboxymethylcellulose, urea-formaldehyde resins, melamine-formaldehyde resins, aminopolyamide-epichlorohydrin resins, polyamide-epichlorohydrin resins.
De préférence, les composants ajoutés sont :
- a) de 5 à 30% de CaCO3,
- b) de 0,01 à 1% d'AKD, et
- c) 1. de 0,2 à 1,7% d'amidon cationique de poids moléculaire 2.104 à 12.105 et de degré de substitution de 0,01 à 0,1; c)2. de 0,1 à 3% de WAC en produit commercial à 10% de Al2O3; et c)3. de 0,01 à 0,3% de sol de silice, exprimé en % de SiO2.
- a) from 5 to 30% of CaCO 3 ,
- b) from 0.01 to 1% of AKD, and
- c) 1. from 0.2 to 1.7% of cationic starch of molecular weight 2.10 4 to 12.10 5 and of degree of substitution from 0.01 to 0.1; c) 2. from 0.1 to 3% of WAC in commercial product to 10% of Al 2 O 3 ; and c) 3. from 0.01 to 0.3% silica sol, expressed as% of SiO 2 .
Les exemples suivants sont illustratifs de la présente invention et ne doivent en aucun cas être considérés comme limitatifs de celle-ci. Dans ces exemples, le WAC est un produit commercialisé par ATOCHEM et correspond à un polychlorure d'aluminium de formule IV à 10% de Al2O3. La silice est sous la forme de sol de silice et est disponible dans le commerce sous la dénomination CECASOL de CECA. L'amidon cationique est celui fabriqué par ROQUETTE et commercialisé sous la dénomination HICAT 142. L'agent de collage AKD est fabriqué par HERCULES et commercialisé sous la dénomination AQUAPEL.The following examples are illustrative of the present invention and should in no way be taken to limit it. In these examples, WAC is a product marketed by ATOCHEM and corresponds to a poly aluminum chloride of formula IV at 10% Al 2 O 3 . The silica is in the form of a silica sol and is commercially available under the name CECASOL from CECA. The cationic starch is that manufactured by ROQUETTE and marketed under the name HICAT 142. The AKD sizing agent is manufactured by HERCULES and marketed under the name AQUAPEL.
Le papier à fabriquer est du papier impression-écriture support pour autocopiant.
- . machine utilisée table plate équipée d'un former BEL BOND
- . vitesse 590 m/mn
- . laize 3 m
- . grammage 50 g/m2
- . machine used flat table equipped with a BEL BOND former
- . speed 590 m / min
- . width 3 m
- . grammage 50 g / m 2
- . Pâte kraft blanchie de résineux (KBR) 45%
- . Pâte kraft blanchie de feuillus (KBF) 55%
- . Charge CaCO3
- . Taux de charge du papier fini 14%
- . Collage (AKD) 0,15%
- . Amidon cationique 0,6%
- . Bleached softwood kraft pulp (KBR) 45%
- . Bleached hardwood kraft pulp (KBF) 55%
- . CaCO 3 charge
- . Load rate of finished paper 14%
- . Bonding (AKD) 0.15%
- . Cationic starch 0.6%
Entre l'essai 1 et l'essai 2, on note l'amélioration très importante de l'épair provoquée par l'utilisation du WAC à la place de la silice, résultat conforme à ce qu'attend l'homme de l'art.Between test 1 and test 2, there is a very significant improvement in the air caused by the use of WAC instead of silica, a result consistent with what one skilled in the art expects. .
L'essai 3 montre la synergie que développe l'association de faibles quantités de silice en présence du WAC. A épair équivalent la rétention est accrue de 10 points soit un accroissement de 15 à 20%. Il en résulte une moindre pollution de l'eau des circuits et une plus grande facilité de traitement des eaux de rejets pour un coût inférieur.Test 3 shows the synergy that the association of small quantities of silica develops in the presence of WAC. At equivalent thickness, retention is increased by 10 points, ie an increase of 15 to 20%. This results in less pollution of the water in the circuits and greater ease of treatment of waste water at a lower cost.
Le papier à fabriquer est du papier impression-écriture. La machine est identique à l'exemple 1.
- . Vitesse machine 540 m/mn
- . Grammage 60 g/m2
- . Machine speed 540 m / min
- . Weight 60 g / m 2
- . KBR 40%
- . KBR 60%
- . Charges CaCO3
- . Taux de charge 11%
- . Amidon cationique 0,5%
- . Collage: colle AKD 0,15% (en produit commercial)
- . KBR 40%
- . KBR 60%
- . CaCO 3 charges
- . Charge rate 11%
- . Cationic starch 0.5%
- . Bonding: 0.15% AKD glue (in commercial product)
La machine est la même que dans l'exemple 2
- . Vitesse 520 m/mn
- . Grammage 70 g/m2
- . Speed 520 m / min
- . Weight 70 g / m 2
- . KBR 35%
- . KBF 65%
- . Charge CaCO3
- . Taux de charge 14%
- . Amidon cationique 0,6%
- . Collage: colle AKD 0,15% (en produit commercial)
- . KBR 35%
- . KBF 65%
- . CaCO 3 charge
- . Charge rate 14%
- . Cationic starch 0.6%
- . Bonding: 0.15% AKD glue (in commercial product)
Claims (13)
- A process for manufacturing paper which comprises adding to the fibrous composition entering the head box:a) 5 to 30% of a mineral filler,b) 0.01 to 2% of a sizing agent, andc) a retention system characterised in that said retention system is comprised of:c)1) 0.2 to 1.7% of cationic starch having a molecular weight of 2.104 to 2.105 with a degree of substitution of 0.01 to 0.1;c)2) 0.01 to 0.3%, expressed as a percentage of Al2O3 of a polyaluminum chloride, andc)3) 0.01 to 0.3%, expressed as a percentage of SiO2, of a silica sol of anionic nature, excluding aluminate ion surface modified silica sol in an Si/Al surface group ratio of 9.5:0.5 to 7.5:2.5.
- The process for making paper according to claim 1, characterised in that the polyaluminum chloride is selected from the group comprising the salts of formulae I, II, III, and IV below and mixtures thereof:
Aln(OH)mCL3n-m-2k(SO4)k (II)
in which k, m and n are positive integers and 3n > m + 2k, the basicity m/3n is comprised between 0.3 and 0.7 and k/n = 0.01 to 0.03;
[Aln(HO)3n-m-2pClm(SO4)p]z (III)
in which (3n-m-2p)/3n = 0.4 to 0.7; p = 0.04 to 0.25n; m/p = 8 to 35, k, m, n and p are integers and z is at least 1;
AlnOHm(SO4)kCl3n-m-2k (IV)
in which the basicity (m/3n)100 is comprised between about 40% and about 65% and has an Al equivalent/Cl equivalent ratio comprised between 2.8 and 5, apparent molecular mass MA measured by conventional light diffusion and apparent hydrodynamic diameters ØZ and ØW measured by quasi-elastic light diffusion of the following values:MA = 7000-35000ØZ (Å) = 350-2500ØW (Å) = 200-1200 - The process according to claim 2, characterised in that the polyaluminum chloride is polychlorosulfate of aluminum of formula
AlnOHm(SO4)kCl3n-m-2k
- A process according to claim 3, characterised in that said polyaluminum chloride is WAC having 10% Al2O3.
- A process according to any one of claims 1 to 4, characterised in that the mineral filler is selected from clay, calcium carbonate, titanium dioxide, talc, hydrated alumina, and mixtures thereof.
- A process according to claim 5, characterised in that the mineral filler is CaCO3.
- A process according to any one of claims 1 to 6, characterised in that the mineral filler is present in an amount of from 10 to 25% by weight based on the weight of said composition.
- A process according to any one of claims 1 to 7, characterised in that the sizing agent is selected from the group comprising: alkyl ketene dimers (AKD), fluorinated phosphates, and carboxylic acid anhydrides, styrene/maleic anhydride, copolymers and derivatives and mixtures thereof.
- A process according to claim 8, characterised in that the sizing agent is AKD.
- A process according to any one of claims 1 to 9, characterised in that the cationic starch has a molecular weight of 3.104 to 12.104.
- A process according to any one of claims 1 to 10, characterised in that there is added to said fibrous composition an optional component selected from polyethylene imines, carboxymethyl cellulose, urea-formol resins, melamin-formol resins, aminopolyamide-epichlorhydrine resins, polyamide-epichlorhydrine resins and mixtures thereof.
- A process according to any one of claims 1 to 9, characterised in that the components added are:a) from 5 to 30% of CaCO3,b) from 0.01 to 1% of AKD, andc)1 from 0.2 to 1.7% of cationic starch of molecular weight 2.104 to 12.105 and a degree of substitution of from 0.01 to 0.1 ; c)2 from 0.1 to 3% of WAC as 10% Al2O3 commercial product; and c)3 from 0.01 to 0.3% of silica sol, expressed as % of SiO2.
- A paper obtained by the process according to any one of the above claims.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR9108819A FR2678961B1 (en) | 1991-07-12 | 1991-07-12 | NEW PROCESS FOR THE MANUFACTURE OF PAPER AND THE PAPER THUS OBTAINED. |
FR9108819 | 1991-07-12 |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0522940A1 EP0522940A1 (en) | 1993-01-13 |
EP0522940B1 true EP0522940B1 (en) | 1996-09-18 |
Family
ID=9415040
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP92401913A Revoked EP0522940B1 (en) | 1991-07-12 | 1992-07-03 | Process for the preparation of paper and paper obtained therefrom |
Country Status (13)
Country | Link |
---|---|
US (1) | US5501771A (en) |
EP (1) | EP0522940B1 (en) |
JP (1) | JPH05195486A (en) |
AT (1) | ATE143075T1 (en) |
CA (1) | CA2073610C (en) |
DE (1) | DE69213850T2 (en) |
DK (1) | DK0522940T3 (en) |
ES (1) | ES2092074T3 (en) |
FI (1) | FI923194A (en) |
FR (1) | FR2678961B1 (en) |
GR (1) | GR3021763T3 (en) |
IE (1) | IE922269A1 (en) |
NO (1) | NO179255B (en) |
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- 1991-07-12 FR FR9108819A patent/FR2678961B1/en not_active Expired - Fee Related
-
1992
- 1992-07-03 AT AT92401913T patent/ATE143075T1/en not_active IP Right Cessation
- 1992-07-03 ES ES92401913T patent/ES2092074T3/en not_active Expired - Lifetime
- 1992-07-03 DK DK92401913.6T patent/DK0522940T3/en active
- 1992-07-03 DE DE69213850T patent/DE69213850T2/en not_active Revoked
- 1992-07-03 EP EP92401913A patent/EP0522940B1/en not_active Revoked
- 1992-07-07 NO NO922672A patent/NO179255B/en unknown
- 1992-07-10 IE IE226992A patent/IE922269A1/en not_active Application Discontinuation
- 1992-07-10 FI FI923194A patent/FI923194A/en unknown
- 1992-07-10 CA CA002073610A patent/CA2073610C/en not_active Expired - Fee Related
- 1992-07-13 JP JP4208385A patent/JPH05195486A/en active Pending
-
1994
- 1994-04-28 US US08/234,632 patent/US5501771A/en not_active Expired - Fee Related
-
1996
- 1996-11-22 GR GR960403154T patent/GR3021763T3/en unknown
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1986000100A1 (en) * | 1984-06-07 | 1986-01-03 | Eka Ab | Papermaking process |
US4643801A (en) * | 1986-02-24 | 1987-02-17 | Nalco Chemical Company | Papermaking aid |
EP0348366A2 (en) * | 1988-05-25 | 1989-12-27 | Eka Nobel Aktiebolag | A process for the production of paper |
Cited By (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7955473B2 (en) | 2004-12-22 | 2011-06-07 | Akzo Nobel N.V. | Process for the production of paper |
US20110247773A1 (en) * | 2004-12-22 | 2011-10-13 | Akzo Nobel N.V. | Process for the production of paper |
US8308903B2 (en) * | 2004-12-22 | 2012-11-13 | Akzo Nobel N.V. | Process for the production of paper |
US8790493B2 (en) | 2004-12-22 | 2014-07-29 | Akzo Nobel N.V. | Process for the production of paper |
US9562327B2 (en) | 2004-12-22 | 2017-02-07 | Akzo Nobel N.V. | Process for the production of paper |
US9139958B2 (en) | 2005-05-16 | 2015-09-22 | Akzo Nobel N.V. | Process for the production of paper |
US8273216B2 (en) | 2005-12-30 | 2012-09-25 | Akzo Nobel N.V. | Process for the production of paper |
US8888957B2 (en) | 2005-12-30 | 2014-11-18 | Akzo Nobel N.V. | Process for the production of paper |
WO2016032831A1 (en) * | 2014-08-27 | 2016-03-03 | Ecolab Usa Inc. | Method of increasing paper surface strength by using polyaluminum chloride in a size press formulation containing starch |
US9365979B2 (en) | 2014-08-27 | 2016-06-14 | Ecolab Usa Inc. | Method of increasing paper surface strength by using polyaluminum chloride in a size press formulation containing starch |
Also Published As
Publication number | Publication date |
---|---|
ES2092074T3 (en) | 1996-11-16 |
FR2678961B1 (en) | 1993-10-15 |
IE922269A1 (en) | 1993-01-13 |
CA2073610A1 (en) | 1993-01-13 |
GR3021763T3 (en) | 1997-02-28 |
FR2678961A1 (en) | 1993-01-15 |
JPH05195486A (en) | 1993-08-03 |
DE69213850T2 (en) | 1997-02-20 |
NO922672L (en) | 1993-01-13 |
FI923194A0 (en) | 1992-07-10 |
FI923194A (en) | 1993-01-13 |
US5501771A (en) | 1996-03-26 |
NO179255B (en) | 1996-05-28 |
NO922672D0 (en) | 1992-07-07 |
DE69213850D1 (en) | 1996-10-24 |
ATE143075T1 (en) | 1996-10-15 |
DK0522940T3 (en) | 1996-11-11 |
CA2073610C (en) | 1996-09-17 |
EP0522940A1 (en) | 1993-01-13 |
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