CA2180404C - Process for the production of paper - Google Patents
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- CA2180404C CA2180404C CA002180404A CA2180404A CA2180404C CA 2180404 C CA2180404 C CA 2180404C CA 002180404 A CA002180404 A CA 002180404A CA 2180404 A CA2180404 A CA 2180404A CA 2180404 C CA2180404 C CA 2180404C
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/24—Homopolymers or copolymers of amides or imides
- C08L33/26—Homopolymers or copolymers of acrylamide or methacrylamide
-
- 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
- D21H17/20—Macromolecular organic compounds
- D21H17/33—Synthetic macromolecular compounds
- D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D21H17/37—Polymers of unsaturated acids or derivatives thereof, e.g. polyacrylates
- D21H17/375—Poly(meth)acrylamide
-
- 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
- D21H17/33—Synthetic macromolecular compounds
- D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D21H17/41—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups
- D21H17/44—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups cationic
- D21H17/45—Nitrogen-containing groups
- D21H17/455—Nitrogen-containing groups comprising tertiary amine or being at least partially quaternised
-
- 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
- D21H17/33—Synthetic macromolecular compounds
- D21H17/46—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D21H17/54—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen
- D21H17/55—Polyamides; Polyaminoamides; Polyester-amides
-
- 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
- D21H17/33—Synthetic macromolecular compounds
- D21H17/46—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D21H17/54—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen
- D21H17/56—Polyamines; Polyimines; Polyester-imides
-
- 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
-
- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/50—Aqueous dispersion, e.g. containing polymers with a glass transition temperature (Tg) above 20°C
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L3/00—Compositions of starch, amylose or amylopectin or of their derivatives or degradation products
- C08L3/04—Starch derivatives, e.g. crosslinked derivatives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/02—Polyamines
Abstract
The invention relates to a process for the production of paper from a suspension of cellulose containing fibers, and optional fillers, wherein a low molecular weight cationic organic polymer, a high molecular weight cationic or ampho-teric polymer and anionic inorganic particles are added to the suspension and the suspension is formed and drained on a wire, wherein the low molecular weight polymer has a molecular weight below 700,000, the high molecular weight polymer has a molecular weight above 1,000,000 and said polymers are simul-taneously added to the suspension. The invention further relates to a polymer mixture in the form of an aqueous dispersion comprising at least one high molecular weight cationic and/or amphoteric acrylamide-based polymer having a molecular weight above 1,000,000, at least one low molecular weight cationic organic polymer having a molecular weight below 700,000 and at least one water-soluble inorganic salt, wherein the weight ratio of said high molecular weight polymer to said low molecular weight polymer is within the range of from 9:1 to 1:2.
Description
; 1 2 1 80404 A process for the production of paPer The present invention relates to a process for the production of paper and, more particularly, to a process in which a low molecular weight cationic polymer, a high molecu-lar weight charged polymer and anionic inorganic particles areadded to a papermaking stock. The process provides improved drainage and retention.
It is known in the art to use systems of drainage and retention aids comprising high molecular weight (hereafter HMW) charged polymers and anionic inorganic particles, e.g.
bentonite and silica based particles. These additives are introduced into the stock in order to facilitate drainage and increase adsorption of fine particles onto the cellulose fibres so that they are retained with the fibres. However, the efficiency of drainage and retention aids usually is deterio-rated in stocks which have a high cationic demand due to the presence of interfering anionic substances. In the art, such substances are commonly referred to as anionic trash. The level of anionic trash usually is high in stocks based on recycled fibres and mechanically derived pulps. To counter the deteriorated performance of additives observed in such stocks, it is known to use low molecular weight (hereafter LMW) cationic polymers as anionic trash catchers which are initi-ally added to the stock in order to neutralize the anionic trash and reduce the cationic demand, thereby enhancing the efficiency of drainage and retention aids subsequently added.
European Patent Application No. 0335575 discloses a process for the production of paper which comprises a prelimi-nary polymer inclusion stage in which a LMW cationic polymer is added to a cellulosic suspension followed by addition of a main polymer selected from cationic starch or HMW cationic polymer and then an inorganic material selected from bentonite or colloidal silica. European Patent Application No. 0308752 relates to a method for making paper which comprises the steps of adding to paper furnish a LMW cationic organic polymer and then colloidal silica and a HMW charged acrylamide copolymer having a molecular weight of at least 500,000.
According to the present invention it has been found that very good drainage and/or retention can be obtained with additives comprising LMW cationic polymer, HMW cationic and/or amphoteric polymer and anionic inorganic particles when the LMW cationic polymer and HMW cationic and/or amphoteric polymer are simultaneously added to the stock, in particular when using the LMW polymer and HMW polymer in the form of a mixture. This discovery is contrary to prior art techniques which emphasize the initial addition of LMW cationic polymers for obtaining adequate performance with subsequently added drainage and retention aids comprising HMW charged polymers and anionic inorganic particles. More specifically, the present invention relates to a process for the production of paper from a suspension of cellulose containing fibres, and optional fillers, which comprises adding to the suspension a low molecular weight cationic organic polymer, a high molecular weight cationic and/or amphoteric polymer and anionic inorganic particles, forming and draining the suspension on a wire, wherein the low molecular weight polymer has a molecular weight below 700,000; the high molecular weight polymer has a molecular weight above 1,000,000; and said polymers are simultaneously added to the suspension.
The process according to the present invention results in improved drainage and/or retention compared to processes in which HMW cationic or amphoteric polymers are used as a sole polymer additive in conjunction with anionic inorganic particles. Furthermore, the present process results in improved drainage and/or retention compared to processes comprising pre-dosing LMW cationic polymer prior to adding HMW
cationic and/or amphoteric polymers and anionic inorganic particles. Hereby the present invention makes it possible to increase the speed of the paper machine and to use lower dosages of additives to give the same drainage and/or retention effect, which lead to an improved papermaking process and economic benefits.
The polymers simultaneously added to the stock according to the invention comprise at least one high molecular weight charged polymer that functions as a drainage and/or retention aid. The HMW polymer can be selected from cationic polymers, amphoteric polymers or mixtures thereof. The use of such polymers as drainage and/or retention aids is known in the art. Preferred HMW polymers are water-soluble. Suitably at least one HMW cationic organic polymer is used. Generally, the S cationicity of the HMW polymers can be within the range of from 1 to 100 mole~, suitably from 1 to 80 mole~ and preferably from 1 to 60 mole~. The term "cationicity", as used herein, refers to the amount of cationic mer units present in the polymer. The charge density of the HMW polymer can be from 200 to 7,000 ~eq/g of dry polymer. The HMW polymer can be derived from natural or synthetic sources, and it can be linear or branched. Examples of suitable polymers include cationic and amphoteric starches, guar gums, acrylamide-based and N-vinylamide-based polymers, polymers based on diallyldi-methylammonium chloride, polyethylene imines, polyamines andpolyamideamines. Cationic starches and cationic acrylamide-based polymers are preferred HMW polymers. The molecular weight of the HMW polymer suitably is above 1,000,000 and preferably above 2,000,000. The upper limit is not critical;
it can be about 50,000,000, usually 30,000,000 and suitably 25,000,000. However, the molecular weight of polymers derived from natural sources may be higher.
The polymers simultaneously added to the stock according to the invention further comprises at least one low molecular weight cationic organic polymer. Preferred polymers include water-soluble, highly charged LMW polymers which can have a cationicity of from 10 to 100 mole~, suitably from 20 to 100 mole~ and preferably from 50 to 100 mole~. The charge density of the LMW polymer can be above 1,000 ~eq/g and is suitably above 2,000 ~eq/g and preferably within the range of from 3,000 to 15,000 ~eq/g of dry polymer. It is preferred that the LMW polymer has a higher cationicity and/or higher cationic charge density than the HMW polymer. Examples of suitable LMW
cationic polymers include modified starches, e.g. degraded starch, polyamines, polyethylene imine, polyamideamine/-epichlorohydrin, dialkylamine/epichlorohydrin, homo- and copolymers based on monomers selected from diallyldimethyl-ammonium chloride, vinyl amines, (meth)acrylamides and (meth)acrylates. Preferred LMW cationic polymers include _ 4 polyamines, polyethylene imines, epichlorohydrin-based polymers and diallyldimethylammonium chloride-based polymers.
The cationic monomers can be acid addition salts and/or quaternary ammonium salts. Examples of suitable (meth)acryl-amides and (meth)acrylates include dialkylaminoalkyl(meth)acrylamides and dialkylaminoalkyl (meth)acrylates, preferably their quaternary ammonium salts. The moleclar weight of the LMW cationic polymer may depend on the type of polymer and its charge density. Suitably the molecular weight is below 700,000 and preferably below 500,000. The lower limit is usually 2,000 and preferably about 5,000.
The weight ratio of HMW polymer to LMW polymer added to the stock according to the invention can be varied over a broad range and it can be within the range from 30:1 to 1:20, usually from 20:1 to 1:20, suitably from 9:1 to 1:3, prefer-ably from 7:1 to 1:2 and most preferably from 5:1 to 1:1.
The simultaneous addition to the stock of the HMW and LMW polymers according to the invention can be conducted at any position in the paper machine or stock preparation depart-ment. Hereby is meant that the polymers are added to the stockwith substantially no time difference and essentially at the same position in the stock preparation department or paper machine prior to draining the stock on the wire. This means that the polymers can be added in the form of a mixture as well as separately, e.g. by adding one polymer during the addition of the other.
According to a preferred embodiment of the invention, the LMW cationic polymer in admixture with the HMW cationic and/or amphoteric polymer are added to the stock. The use of a polymer mixture and anionic inorganic particles according to the invention provides considerable improvements over prior art processes, in particular improved retention performance in stocks having a high cationic demand. The addition of a polymer mixture containing both LMW polymer and HMW polymer is further advantageous from an operational viewpoint since the number of polymer additions required can be reduced. Hereby it is possible to dispense with storage tanks, dosing equipment, control devices, etc., otherwise needed for polymer dosage, leading to a simplified papermaking process.
The polymer mixture of this embodiment can be prepared at any time prior to incorporating it into the stock, for example by mixing the polymers which may be in any state of aggregation, e.g. solids, solutions, emulsions, dispersions and mixtures thereof. When being added to the stock, the poly-mer mixture suitably is in a liquid form, e.g. in the form of an aqueous solution or dispersion.
In a preferred embodiment, use is made of a freshly prepared mixture of HMW polymer and LMW polymer, as defined above. S~ch a pre-mix can be formed by bringing an aqueous stream of HMW polymer into contact with an aqueous stream of LMW polymer and then introducing the resulting stream into the suspension. If desired, the streams can be mixed by means of any mixing device having at least two inlets into which separate streams of the polymers to be mixed are supplied and having at least one outlet through which the resulting mixture is passed and subsequently introduced into the stock.
The present invention further relates to a mixture of water-soluble polymers in the form of an aqueous dispersion containing at least one HMW polymer, at least one LMW cationic organic polymer and at least one water soluble inorganic salt. The invention also relates to a method for its preparation. The polymer mixture provides improved drainage and/or retention when used in combination with anionic inorganic particles. Suitably the HMW polymer is a cationic and/or amphoteric acrylamide-based polymer, preferably cationic. The LMW cationic polymer preferably is a homo- or copolymer based on monomers selected from diallyl-dimethylammonium chloride, vinylamines, (meth)acrylamides, e.g. dialkylaminoalkyl (meth)acrylamides, (meth)acrylates, e.g. dialkylaminoalkyl (meth)acrylates, or mixtures thereof.
The cationic monomers can be acid addition salts and/or quaternary ammonium salts, preferably quaternary ammonium salts. The HMW polymer and LMW polymer can have cationicities, charge densities and molecular weights as defined above. The weight ratio of HMW polymer to LMW polymer can be within the range of from 9:1, suitably from 7:1 and preferably from 5:1, to 1:2, suitably to 1:1 and preferably to 2:1. The aqueous dispersion of polymers can have a high dry polymer content, e.g. ranging from 5 to 75~ by weight and suitably from 10 to 60~ by weight. It is preferred that the inorganic salt is an inorganic salt producing an aqueous phase in which the HMW
polymer is insoluble. Examples of suitable salts include sodium sulfate, ammonium sulfate, magnesium sulfate, aluminium sulfate, sodium chloride, sodium dihydrogenphosphate, diammonium hydrogenphosphate and dipotassium hydrogen-phosphate. Generally, polyvalent anion salts are preferred, e.g. the sulfates. The amount of water-soluble salt present in the polymer dispersions can be at least 2~ by weight, based on the dispersion, and suitably the amount is within the range of from about 5% up to the limit of solubility of the salt, e.g.
up to 50~.
The subject polymer mixture can be obtained by polymeri-zation of water-soluble monomers intended for formation of the HMW polymer in an aqueous phase containing the LMW cationic polymer and the inorganic salt. Examples of suitable monomers include (meth)acrylamide, (meth)acrylamide-based monomers, e.g. dialkylaminoalkyl (meth)acrylamides, acid addition salts and quaternary ammonium salts thereof, (meth)acrylate-based monomers, e.g. dialkylaminoalkyl (meth)acrylates, acid addition salts and quaternary ammonium salts thereof, diallyl-dialkylammonium halides, e.g. diallyldimethylammonium chloride, and the like. The HMW polymer formed is precipitated in the aqueous phase due to the presence of the inorganic salt and the fine particles of HMW polymer so obtained are disper-sed and stabilized in the aqueous phase by means of the LMW
polymer. Generally, the polymerization of monomers in the presence of salt and polymeric dispersing agents is known in the art, for example from EP 0183466 and EP 0525751, and the present polymer mixture can be prepared according to the methods disclosed therein except that other polymers and/or weight ratios are used to produce the polymer mixture of the present invention.
The amount of polymers added to the stock according to the process of the present invention can be varied over a broad range depending on, among other things, the type of polymers used and if the polymers are utilized for further purposes. In addition to providing drainage and/or retention, the polymers may impart wet-strength and dry-strength to the cellulosic web or sheet produced. Examples of wet-strength improving polymer combinations include HMW cationic starch and cationic acrylamide-based polymer in combination with poly-amideamine/epichlorohydrin. Usually, the total amount ofpolymers added is within the range of from 0.01 to 30 kg/ton, calculated as dry polymers on dry fibres and optional fillers.
When using synthetic HMW polymers, e.g. cationic polyacryl-amides, the total amount of polymers usually is at least 0.01 kg/ton, suitably from 0.02 to 15 kg/ton and preferably from 0.05 to 8 kg/ton. When using HMW polymers derived from natural sources such as those based on carbohydrates, e.g. cationic starch and cationic guar gum, the total amount of polymers usually is at least 0.05 kg/ton, calculated as dry polymers on dry fibres and optional fillers, suitably from 0.1 to 30 kg/ton and preferably from 1 to 20 kg/ton.
Anionic inorganic particles that can be used according to the invention include silica based particles, clays of the smectite type and titanyl sulphate sols. It is preferred that the particles are colloidal, i.e. in the colloidal range of particle size. It is preferred to use silica based particles, i.e. particles based on SiO2, including colloidal silica, colloidal aluminium-modified silica or aluminium silicate, different types of polysilicic acid and mixtures thereof, either alone or in combination with other types of anionic inorganic particles. Suitable silica based particles include those disclosed in US 4,388,150, US 4,954,220, US 4,961,825, US 4,980,025, US 5,127,994, US 5,176,891, US 5,368,833, US
5,447,604, EP 0656872, and WO 95/23021 The silica based particles suitably have a particle size below about 50 nm, preferably below about 20 nm and more preferably in the range of from about 1 to about 10 nm. The silica based particles suitably have a specific surface area above 50 m2/g, preferably above 100 m2/g, and suitably up to about 1700 m2/g. The specific surface area can be measured by means of titration with NaOH according to the method described by Sears in Analytical Chemistry 28(1956):12, 1981-1983.
According to a preferred embodiment of the invention, 2t 80404 ~_ 8 the silica based particles have a specific surface area within the range of from 50 to 1000 m2/g and suitablty from 100 to 950 m2/g. In a particularly preferred embodiment, use is made of a silica sol having an S-value within the range of from 8 to 45%, preferably from 10 to 30%, containing silica particles having a specific surface area within the range of from 750 to 1000 m2/g, preferably from 8C0 to 950 m2/g, which are surface-modified with aluminium to a degree of from 2 to 25%
substitution of silicon atoms, as disclosed in US 5,368,833.
The S-value can be measured and calculated as described by Iler & Dalton in J. Phys. Chem. 60(1956), 955-957. The S-value indicates the degree of aggregate or microgel formation and a lower S-value is indicative of a higher degree of aggregation.
According to another preferred embodiment of the invention, use is made of a polysilicic acid having a high specific surface area, suitably above about 1000 m2/g. In the art, polysilicic acid is also referred to as polymeric silicic acid, polysilicic acid microgel and polysilicate microgel, which are all encompassed by the term polysilicic acid.
Suitably, the polysilicic acid has a specific surface area within the range of from 1000 to 1700 m2/g, preferably from 1050 to 1600 m2/g. Polysilicic acids that can be used according to the present invention include those disclosed in US 4,388,150, US 4,954,220, US 5,127,994 and US 5,279,807.
According to another preferred embodiment of the invention, use is made of colloidal aluminium-modified silica or aluminium silicate having a high specific surface area, suitably above about 1000 m2/g. In the art, compounds of this type are also referred to as polyaluminosilicates and poly-aluminosilicate microgels, which are both encompassed by the terms colloidal aluminium-modified silica and aluminium silicate used herein. Suitably, the specific surface area is within the range of from 1000 to 1700 m2/g, preferably from 1050 to 1600 m2/g. Examples of suitable high surface area silica based particles of this type include those disclosed in US 4,961,825, US 4,980,025, US 4,927,498, US 5,176,891 and US
5,470,435.
Clays of the smectite type that can be used in the present process are known in the art and include naturally g occurring, synthetic and chemically treated materials.
Examples of suitable smectite clays include montmorillonite/-bentonite, hectorite, beidelite, nontronite and saponite, preferably bentonite and especially such which after swelling preferably has a surface area of from 400 to 800 m2/g.
Suitable bentonites and hectorites are disclosed in EP 0235893 and EP 0446205, respectively, which are both incorporated herein by reference. Suitable mixtures of silica based particles and smectite clays, preferably natural sodium bentonite, are disclosed in WO 94/05595, wherein the weight ratio of silica based particles to clay particles can be in the range of from 20:1 to 1:10, preferably from 6:1 to 1:3. Useful titanyl sulphate sols are, for example, disclosed in EP 0148647.
The amount of anionic inorganic particles added to the suspension may vary within wide limits depending on, among other things, the type of particles used. The amount usually is at least 0.01 kg/ton and often at least 0.05 kg/ton, calculated as dry particles on dry fibres and optional fillers. The upper limit can be 10 kg/ton and suitably is 5 kg/ton. When using silica based particles, the amount suitably is within the range of from 0.05 to 5 kg/ton, calculated as SiO2 on dry stock system, and preferably from 0.1 to 2 kg/ton.
In the present process it is preferred to add the polymers to the stock before the anionic inorganic particles, even if the opposite order of addition may be used. It is further preferred to add the first component, e.g. the poly-mers, before a shear stage which can be selected for example from pumping, mixing, cleaning, etc., and to add the second component, e.g. the anionic inorganic particles, after that shear stage. The present process further encompasses split additions, e.g. at least two positions for simultaneously adding the polymers, either separately or in admixture, and/or at least two positions for adding anionic inorganic particles, preferably with a shear stage between each addition. The high dewatering and retention effects observed with the additives of the invention can be obtained over a broad stock pH range.
The pH can be in the range from about 3 to about 10, suitably above 3.5 and preferably within the range of from 4 to 9.
Additives which are conventional in papermaking such as, for example, stock sizes based on rosin, ketene dimers or alkenyl succinic anhydrides, dry strength agents, wet strength agents, aluminium compounds, etc., can of course be co-used in the process of the invention. The improved performance observed in the process of the present invention means that further benefits can be obtained, such as for example improved retention of such additives which can lead to improved sizing and strength of the paper. Aluminium compounds can be used to further improve drainage and/or retention in the present process. Examples of suitable aluminium compounds that can be used include alum, aluminates, aluminium chloride, aluminium nitrate and polyaluminium compounds, such as polyaluminium chlorides, polyaluminium sulphates, polyaluminium compounds containing both chloride and sulphate ions and polyaluminium silicate-sulphates. The suspension or stock can also contain mineral fillers of conventional types such as, for example, kaolin, china clay, titanium dioxide, gypsum, talc and natural and synthetic calcium carbonates such as chalk, grinded marble and precipitated calcium carbonate.
The process according to the invention can be used for producing cellulose fibre containing products in sheet or web form such as for example pulp sheets and paper. It is prefer-red that the present process is used for the production of paper. The term "paper", as used herein, of course include not only paper and the production thereof, but also other sheet or web-like products, such as for example board and paperboard, and the production thereof.
The process according to the invention can be used in the production of sheet or web-like products from different types of aqueous suspensions containing cellulosic fibres, or stocks, and the suspensions suitably contain at least 25% by weight and preferably at least 50% by weight of such fibres, based on dry substance. The suspensions can be based on fibres from chemical pulp such as sulphate and sulphite pulp, mechanical pulp such as thermomechanical pulp, chemo-thermomechanical pulp, refiner pulp and groundwood pulp, from both hardwood and softwood, and can also be based on recycled fibres from de-inked pulps, and mixtures thereof. It is 2 1 ~0404 ```, 11 preferred that at least 10~ by weight and preferably at least 20~ by weight of the pulp is derived from recycled fibre, de-inked pulp, coated broke or mechanical pulp or any mixture thereof. Such stocks, normally, have a high cationic demand and contains high levels of anionic trash which may be pulping residues, bleaching residues, de-inking residues, binders, inks, fillers, fines, sizes, dispersing agents and deposit control chemicals.
The invention is further illustrated in the following Examples which, however, are not intended to limit same. Parts and ~ relate to parts by weight and ~ by weight, respectively, unless otherwise stated.
Exam~le 1 In the following tests, drainage performance was evaluated by means of a Dynamic Drainage Analyser (DDA), available from Akribi, Sweden, which measures the time for draining a set volume of stock through a wire when removing a plug and applying a vacuum to that side of the wire opposite to the side on which the stock is present.
The furnish contained 54~ of pulp based on a 60:40 mixture of bleached birch:pine sulphate refined to 200O CSF, 23~ of grinded marble and 23~ of coated broke (magazine paper) having an ash content of 30~. Stock volume was 800 ml, consistency 0.3~ and pH about 7. The stock was stirred in a baffled jar at a speed of 1500 rpm throughout the test and chemical additions to the stock were conducted as follows:
i) adding either HMW polymer used for comparison purposes or polymers according to the invention followed by stirring for 30 seconds, ii) adding anionic inorganic particles followed by stirring for 15 seconds, iii) draining the stock while automatically recording the drainage time.
A polymer mixture, herein designated M1, in the form of an aqueous dispersion of a HMW cationic polyacrylamide and a LMW cationic polyacrylate was used in the process of the invention. The polymer mixture was prepared by polymerization of acrylamide (90 mole~) and methacryloyloxyethyldimethyl-benzylammonium chloride (10 mole~) to an average molecular weight of about 8 million in the presence of a homopolymer of acryloyloxyethyltrimethylammonium chloride having a molecular ~`~ 12 ~l 804~4 weight of about 10,000; deionized water; ammonium sulphate and a polymerization initiator. The resulting polymer mixture had a weight ratio HMW polymer to LMW polymer of 2.7:1, and a dry polymer content of about 18.5~. The polymer mixture was diluted to a dry polymer content of 0.1% prior to use.
Polymers used for comparison purposes were: P1) a HMW
cationic polyacrylamide having a molecular weight of about 8 million; and P2) a HMW cationic polyacrylamide having a molecular weight of about 16 million. The polymers P1 and P2 were dissolved in water and used as 0.1~ aqueous solutions.
The anionic inorganic material used was a silica based sol of the type disclosed in US 5,368,833. The sol had an S-value of about 25~ and contained silica particles with a specific surface area of about 900 m2/g which were surface-modified with aluminium to a degree of 5~. This sol isdesignated Sol 1. Sol 1 was added in an amount of 0.8 kg/ton, calculated as dry particles on dry stock system.
Table 1 shows the drainage time at varying dosages of P1, P2 and M1, calculated as dry polymer on dry stock system.
Table 1 Polymer Drainage time [seconds] at polymer dosage of used 0.5 kq/ton 0.8 kq/ton 1.2 kg/ton 2.0 kq/ton P1 15.7 15.4 11.4 6.3 P2 15.7 14.0 11.8 6.6 M1 14.9 13.0 7.5 4.8 As can be seen from Table 1, the process using the mixture of LMW and HMW cationic polymers according to the invention resulted in improved drainage.
Example 2 In this test series, retention was evaluated by means of the DDA used in Example 1 in combination with a nephelometer.
First pass retention was evaluated by measuring the turbidity of the filtrate, the white water, obtained by draining the stock. The polymers and anionic inorganic particles according to Example 1 were similarly used in this test series.
Table 2 shows the retention effect measured as turbidity of white water obtained at varying dosages of P1, P2 and M1, calculated as dry polymer on dry stock system.
Table 2 Polymer Turbidity [NTU] at polymer dosage of used 0. 5 kq/ton 0.8 kq/ton 1. 2 kq/ton 2.0 kq/ton Pl 236 149 87 42 Ml 161 90 53 29 As can be seen from the Table 2, the process using a mixture of HMW and LMW cationic polymers according to the invention resulted in markedly improved first pass retention.
Example 3 Retention was evaluated as in Example 2, except that different polymers were used. The order of addition according to Example 1 was applied, unless otherwise indicated.
A polymer mixture designated M2 was prepared by dissolving the HMW cationic polyacrylamide P2 according to Example 1 in an aqueous solution of a LMW cationic polyamine having a molecular weight of 50,000, which is designated P3.
M2 had a weight ratio P2 to P3 of 2.7:1.
Another embodiment of the invention was tested in which use was made of a freshly prepared mixture of P2 and P3. An aqueous solution of P2 was brought into contact with an aqueous solution of P3 by means of a mixing device, where the separate solutions were intimately mixed for about 2-3 seconds prior to introducing the resulting solution into the stock.
The polymers were added in a weight ratio P2 to P3 of 2.7:1.
This mixture is designated M3.
A further embodiment of the invention, designated Sl, was tested in which P2 and P3 were separately but simultane-ously added to the stock in a weight ratio P2 to P3 of 2.7:1.
P2 and P3 were also used for comparison purposes, where P3 was added to the stock followed by stirring for 120 seconds before adding P2. The polymers were used in an amount corre-sponding to a weight ratio P2 to P3 of 2.7:1. In Table 3, this test is designated P3+P2. In one test, P2 was also used as a single cationic polymer additive.
Table 3 shows the retention effect observed when adding 1.2 kg of total polymer and 0.8 kg of silica based particles per ton of dry stock system. As can be seen from Table 3, considerably improved retention was obtained with the 21 8~404 processes according to the present invention.
Table 3 Total polymer addition, 1.2 kg/ton P3+P2 P2 M2 M3 S1 Turbidity [NTU] 96 101 62 71 83 Example 4 First pass retention was evaluated as in Example 3, except that other additives were used. The furnish was based on 80~ of a 80:20 mixture of peroxide bleached thermomechan-ical pulp:stoneground wood pulp and 20~ of the pulp accordingto Example 1. To the stock obtained were added 30~ of china clay, based on dry substance, 4 g/l of sodium acetate tri-hydrate and 10 mg/l of extractives. Stock volume was 800 ml, consistency 0.15~ and pH 5.5.
Polymer mixtures designated M4 and M5 were prepared by dissolving HMW cationic polyacrylamide P1 according to Example 1 in aqueous solutions of LMW polymers. The LMW polymer used in M4 was a cationic polyacrylamide having a molecular weight of about 100,000 and a cationic charge density of 2.9 meq/g, which is designated P4. M4 had a weight ratio P4 to P1 of 1:1.
The LMW polymer used in M5 was a cationic starch having a molecular weight of about 400,000 and a cationic charge density of 2. 5 meq/g, which is designated P5. M5 had a weight ratio P5 to P1 of 1:1.
The polymer mixtures were compared to prior art pro-cesses in which the polymers P1, P4 and P5 were separately added wherein the LMW polymers were added to the stock followed by stirring for 30 seconds before adding P1. The weight ratios of P4:P1 and P5:P1 were both 1:1. These comparison tests are designated P4+P1 and P5+P1.
The anionic inorganic particulate materials used were Sol 1 according to Example 1 and a silica sol of the type disclosed in US 4,388,150 which contained silica particles with a specific surface area of 500 m2/g, which is designated Sol 2. The amount of Sol 1 and Sol 2 added was 3.0 and 6.0 kg/ton, respectively, calculated as dry particles on dry stock system.
Table 4 shows the retention effect, measured as turbi-dity, when using varying amounts of polymer, calculated as dry 2 ~ 80404 polymer on dry stock system, in combination with the sols.
Table 4 Polymer Sol Turbidity [NTU] at polymer dosage [kg/ton]
used used 1.0 2.03.0 4.06.0 8.0 10.0 P4+P1 Sol 1 100 7250 44 - 16 M4 Sol 1 80 5945 40 - 8 P4+P1 Sol 2 - - - - 37 30 32 M4 Sol 2 - - - - 27 17 13 P5+P1 Sol 1 - 62 - 42 - 13 13 M5 Sol 1 - 61 - 38 - 9 4 ExamPle 5 The procedure of Example 4 was followed except that different polymers were used. Cationic potato starch desig-nated P6 was used as the HMW polymer and the polyamine P3 according to Example 3 was used as the LMW polymer. A polymer mixture designated M6 was obtained by mixing the polymers in the form of aqueous solutions in a weight ratio P6 to P3 of 5:1.
Table 4 shows the retention effect obtained with varying amounts of P3+P6 and M6, calculated as dry polymer on dry stock system, when the polymers were used in combination with Sol 1 added in an amount of 3.0 kg/ton.
Table 5 PolymerTurbidity [NTU] at polymer dosage of 25 used 18 kq/ton 24 kq/ton P3+P6 28 27 Example 6 Further cationic polymers and anionic inorganic particles were evaluated for retention performance by means of a Britt Dynamic Drainage Jar at a stirring speed of 1000 rpm, which is conventional in the art. The stock and polymers used in Example 4 were similarly used in this test series. The anionic inorganic particles used were a suspension of the type disclosed in WO 94/05595 containing silica based particles according to Example 1 and natural sodium bentonite in a weight ratio of 2:1, designated Susp 1, and a suspension of natural sodium bentonite, designated Susp 2. The amount of Susp 1 and Susp 2 added was 4.0 and 6.0 kg/ton, respectively, ~ 16 calculated as dry on dry stock system.
Table 6 set forth the first pass retention of fines and filler at varying polymer dosages, calculated as dry polymers on dry stock system.
Table 6 Polymer Suspension Retention [~] at polymer dosage [kg/ton~
used used 1 2 4 5 P4+Pl Susp 1 26.1 32.2 56.7 70.5 M4 Susp l 29.4 43.0 61.9 75.1 P4+Pl Susp 2 - 43.5 43.5 M4 Susp 2 - 46.5 61.6
It is known in the art to use systems of drainage and retention aids comprising high molecular weight (hereafter HMW) charged polymers and anionic inorganic particles, e.g.
bentonite and silica based particles. These additives are introduced into the stock in order to facilitate drainage and increase adsorption of fine particles onto the cellulose fibres so that they are retained with the fibres. However, the efficiency of drainage and retention aids usually is deterio-rated in stocks which have a high cationic demand due to the presence of interfering anionic substances. In the art, such substances are commonly referred to as anionic trash. The level of anionic trash usually is high in stocks based on recycled fibres and mechanically derived pulps. To counter the deteriorated performance of additives observed in such stocks, it is known to use low molecular weight (hereafter LMW) cationic polymers as anionic trash catchers which are initi-ally added to the stock in order to neutralize the anionic trash and reduce the cationic demand, thereby enhancing the efficiency of drainage and retention aids subsequently added.
European Patent Application No. 0335575 discloses a process for the production of paper which comprises a prelimi-nary polymer inclusion stage in which a LMW cationic polymer is added to a cellulosic suspension followed by addition of a main polymer selected from cationic starch or HMW cationic polymer and then an inorganic material selected from bentonite or colloidal silica. European Patent Application No. 0308752 relates to a method for making paper which comprises the steps of adding to paper furnish a LMW cationic organic polymer and then colloidal silica and a HMW charged acrylamide copolymer having a molecular weight of at least 500,000.
According to the present invention it has been found that very good drainage and/or retention can be obtained with additives comprising LMW cationic polymer, HMW cationic and/or amphoteric polymer and anionic inorganic particles when the LMW cationic polymer and HMW cationic and/or amphoteric polymer are simultaneously added to the stock, in particular when using the LMW polymer and HMW polymer in the form of a mixture. This discovery is contrary to prior art techniques which emphasize the initial addition of LMW cationic polymers for obtaining adequate performance with subsequently added drainage and retention aids comprising HMW charged polymers and anionic inorganic particles. More specifically, the present invention relates to a process for the production of paper from a suspension of cellulose containing fibres, and optional fillers, which comprises adding to the suspension a low molecular weight cationic organic polymer, a high molecular weight cationic and/or amphoteric polymer and anionic inorganic particles, forming and draining the suspension on a wire, wherein the low molecular weight polymer has a molecular weight below 700,000; the high molecular weight polymer has a molecular weight above 1,000,000; and said polymers are simultaneously added to the suspension.
The process according to the present invention results in improved drainage and/or retention compared to processes in which HMW cationic or amphoteric polymers are used as a sole polymer additive in conjunction with anionic inorganic particles. Furthermore, the present process results in improved drainage and/or retention compared to processes comprising pre-dosing LMW cationic polymer prior to adding HMW
cationic and/or amphoteric polymers and anionic inorganic particles. Hereby the present invention makes it possible to increase the speed of the paper machine and to use lower dosages of additives to give the same drainage and/or retention effect, which lead to an improved papermaking process and economic benefits.
The polymers simultaneously added to the stock according to the invention comprise at least one high molecular weight charged polymer that functions as a drainage and/or retention aid. The HMW polymer can be selected from cationic polymers, amphoteric polymers or mixtures thereof. The use of such polymers as drainage and/or retention aids is known in the art. Preferred HMW polymers are water-soluble. Suitably at least one HMW cationic organic polymer is used. Generally, the S cationicity of the HMW polymers can be within the range of from 1 to 100 mole~, suitably from 1 to 80 mole~ and preferably from 1 to 60 mole~. The term "cationicity", as used herein, refers to the amount of cationic mer units present in the polymer. The charge density of the HMW polymer can be from 200 to 7,000 ~eq/g of dry polymer. The HMW polymer can be derived from natural or synthetic sources, and it can be linear or branched. Examples of suitable polymers include cationic and amphoteric starches, guar gums, acrylamide-based and N-vinylamide-based polymers, polymers based on diallyldi-methylammonium chloride, polyethylene imines, polyamines andpolyamideamines. Cationic starches and cationic acrylamide-based polymers are preferred HMW polymers. The molecular weight of the HMW polymer suitably is above 1,000,000 and preferably above 2,000,000. The upper limit is not critical;
it can be about 50,000,000, usually 30,000,000 and suitably 25,000,000. However, the molecular weight of polymers derived from natural sources may be higher.
The polymers simultaneously added to the stock according to the invention further comprises at least one low molecular weight cationic organic polymer. Preferred polymers include water-soluble, highly charged LMW polymers which can have a cationicity of from 10 to 100 mole~, suitably from 20 to 100 mole~ and preferably from 50 to 100 mole~. The charge density of the LMW polymer can be above 1,000 ~eq/g and is suitably above 2,000 ~eq/g and preferably within the range of from 3,000 to 15,000 ~eq/g of dry polymer. It is preferred that the LMW polymer has a higher cationicity and/or higher cationic charge density than the HMW polymer. Examples of suitable LMW
cationic polymers include modified starches, e.g. degraded starch, polyamines, polyethylene imine, polyamideamine/-epichlorohydrin, dialkylamine/epichlorohydrin, homo- and copolymers based on monomers selected from diallyldimethyl-ammonium chloride, vinyl amines, (meth)acrylamides and (meth)acrylates. Preferred LMW cationic polymers include _ 4 polyamines, polyethylene imines, epichlorohydrin-based polymers and diallyldimethylammonium chloride-based polymers.
The cationic monomers can be acid addition salts and/or quaternary ammonium salts. Examples of suitable (meth)acryl-amides and (meth)acrylates include dialkylaminoalkyl(meth)acrylamides and dialkylaminoalkyl (meth)acrylates, preferably their quaternary ammonium salts. The moleclar weight of the LMW cationic polymer may depend on the type of polymer and its charge density. Suitably the molecular weight is below 700,000 and preferably below 500,000. The lower limit is usually 2,000 and preferably about 5,000.
The weight ratio of HMW polymer to LMW polymer added to the stock according to the invention can be varied over a broad range and it can be within the range from 30:1 to 1:20, usually from 20:1 to 1:20, suitably from 9:1 to 1:3, prefer-ably from 7:1 to 1:2 and most preferably from 5:1 to 1:1.
The simultaneous addition to the stock of the HMW and LMW polymers according to the invention can be conducted at any position in the paper machine or stock preparation depart-ment. Hereby is meant that the polymers are added to the stockwith substantially no time difference and essentially at the same position in the stock preparation department or paper machine prior to draining the stock on the wire. This means that the polymers can be added in the form of a mixture as well as separately, e.g. by adding one polymer during the addition of the other.
According to a preferred embodiment of the invention, the LMW cationic polymer in admixture with the HMW cationic and/or amphoteric polymer are added to the stock. The use of a polymer mixture and anionic inorganic particles according to the invention provides considerable improvements over prior art processes, in particular improved retention performance in stocks having a high cationic demand. The addition of a polymer mixture containing both LMW polymer and HMW polymer is further advantageous from an operational viewpoint since the number of polymer additions required can be reduced. Hereby it is possible to dispense with storage tanks, dosing equipment, control devices, etc., otherwise needed for polymer dosage, leading to a simplified papermaking process.
The polymer mixture of this embodiment can be prepared at any time prior to incorporating it into the stock, for example by mixing the polymers which may be in any state of aggregation, e.g. solids, solutions, emulsions, dispersions and mixtures thereof. When being added to the stock, the poly-mer mixture suitably is in a liquid form, e.g. in the form of an aqueous solution or dispersion.
In a preferred embodiment, use is made of a freshly prepared mixture of HMW polymer and LMW polymer, as defined above. S~ch a pre-mix can be formed by bringing an aqueous stream of HMW polymer into contact with an aqueous stream of LMW polymer and then introducing the resulting stream into the suspension. If desired, the streams can be mixed by means of any mixing device having at least two inlets into which separate streams of the polymers to be mixed are supplied and having at least one outlet through which the resulting mixture is passed and subsequently introduced into the stock.
The present invention further relates to a mixture of water-soluble polymers in the form of an aqueous dispersion containing at least one HMW polymer, at least one LMW cationic organic polymer and at least one water soluble inorganic salt. The invention also relates to a method for its preparation. The polymer mixture provides improved drainage and/or retention when used in combination with anionic inorganic particles. Suitably the HMW polymer is a cationic and/or amphoteric acrylamide-based polymer, preferably cationic. The LMW cationic polymer preferably is a homo- or copolymer based on monomers selected from diallyl-dimethylammonium chloride, vinylamines, (meth)acrylamides, e.g. dialkylaminoalkyl (meth)acrylamides, (meth)acrylates, e.g. dialkylaminoalkyl (meth)acrylates, or mixtures thereof.
The cationic monomers can be acid addition salts and/or quaternary ammonium salts, preferably quaternary ammonium salts. The HMW polymer and LMW polymer can have cationicities, charge densities and molecular weights as defined above. The weight ratio of HMW polymer to LMW polymer can be within the range of from 9:1, suitably from 7:1 and preferably from 5:1, to 1:2, suitably to 1:1 and preferably to 2:1. The aqueous dispersion of polymers can have a high dry polymer content, e.g. ranging from 5 to 75~ by weight and suitably from 10 to 60~ by weight. It is preferred that the inorganic salt is an inorganic salt producing an aqueous phase in which the HMW
polymer is insoluble. Examples of suitable salts include sodium sulfate, ammonium sulfate, magnesium sulfate, aluminium sulfate, sodium chloride, sodium dihydrogenphosphate, diammonium hydrogenphosphate and dipotassium hydrogen-phosphate. Generally, polyvalent anion salts are preferred, e.g. the sulfates. The amount of water-soluble salt present in the polymer dispersions can be at least 2~ by weight, based on the dispersion, and suitably the amount is within the range of from about 5% up to the limit of solubility of the salt, e.g.
up to 50~.
The subject polymer mixture can be obtained by polymeri-zation of water-soluble monomers intended for formation of the HMW polymer in an aqueous phase containing the LMW cationic polymer and the inorganic salt. Examples of suitable monomers include (meth)acrylamide, (meth)acrylamide-based monomers, e.g. dialkylaminoalkyl (meth)acrylamides, acid addition salts and quaternary ammonium salts thereof, (meth)acrylate-based monomers, e.g. dialkylaminoalkyl (meth)acrylates, acid addition salts and quaternary ammonium salts thereof, diallyl-dialkylammonium halides, e.g. diallyldimethylammonium chloride, and the like. The HMW polymer formed is precipitated in the aqueous phase due to the presence of the inorganic salt and the fine particles of HMW polymer so obtained are disper-sed and stabilized in the aqueous phase by means of the LMW
polymer. Generally, the polymerization of monomers in the presence of salt and polymeric dispersing agents is known in the art, for example from EP 0183466 and EP 0525751, and the present polymer mixture can be prepared according to the methods disclosed therein except that other polymers and/or weight ratios are used to produce the polymer mixture of the present invention.
The amount of polymers added to the stock according to the process of the present invention can be varied over a broad range depending on, among other things, the type of polymers used and if the polymers are utilized for further purposes. In addition to providing drainage and/or retention, the polymers may impart wet-strength and dry-strength to the cellulosic web or sheet produced. Examples of wet-strength improving polymer combinations include HMW cationic starch and cationic acrylamide-based polymer in combination with poly-amideamine/epichlorohydrin. Usually, the total amount ofpolymers added is within the range of from 0.01 to 30 kg/ton, calculated as dry polymers on dry fibres and optional fillers.
When using synthetic HMW polymers, e.g. cationic polyacryl-amides, the total amount of polymers usually is at least 0.01 kg/ton, suitably from 0.02 to 15 kg/ton and preferably from 0.05 to 8 kg/ton. When using HMW polymers derived from natural sources such as those based on carbohydrates, e.g. cationic starch and cationic guar gum, the total amount of polymers usually is at least 0.05 kg/ton, calculated as dry polymers on dry fibres and optional fillers, suitably from 0.1 to 30 kg/ton and preferably from 1 to 20 kg/ton.
Anionic inorganic particles that can be used according to the invention include silica based particles, clays of the smectite type and titanyl sulphate sols. It is preferred that the particles are colloidal, i.e. in the colloidal range of particle size. It is preferred to use silica based particles, i.e. particles based on SiO2, including colloidal silica, colloidal aluminium-modified silica or aluminium silicate, different types of polysilicic acid and mixtures thereof, either alone or in combination with other types of anionic inorganic particles. Suitable silica based particles include those disclosed in US 4,388,150, US 4,954,220, US 4,961,825, US 4,980,025, US 5,127,994, US 5,176,891, US 5,368,833, US
5,447,604, EP 0656872, and WO 95/23021 The silica based particles suitably have a particle size below about 50 nm, preferably below about 20 nm and more preferably in the range of from about 1 to about 10 nm. The silica based particles suitably have a specific surface area above 50 m2/g, preferably above 100 m2/g, and suitably up to about 1700 m2/g. The specific surface area can be measured by means of titration with NaOH according to the method described by Sears in Analytical Chemistry 28(1956):12, 1981-1983.
According to a preferred embodiment of the invention, 2t 80404 ~_ 8 the silica based particles have a specific surface area within the range of from 50 to 1000 m2/g and suitablty from 100 to 950 m2/g. In a particularly preferred embodiment, use is made of a silica sol having an S-value within the range of from 8 to 45%, preferably from 10 to 30%, containing silica particles having a specific surface area within the range of from 750 to 1000 m2/g, preferably from 8C0 to 950 m2/g, which are surface-modified with aluminium to a degree of from 2 to 25%
substitution of silicon atoms, as disclosed in US 5,368,833.
The S-value can be measured and calculated as described by Iler & Dalton in J. Phys. Chem. 60(1956), 955-957. The S-value indicates the degree of aggregate or microgel formation and a lower S-value is indicative of a higher degree of aggregation.
According to another preferred embodiment of the invention, use is made of a polysilicic acid having a high specific surface area, suitably above about 1000 m2/g. In the art, polysilicic acid is also referred to as polymeric silicic acid, polysilicic acid microgel and polysilicate microgel, which are all encompassed by the term polysilicic acid.
Suitably, the polysilicic acid has a specific surface area within the range of from 1000 to 1700 m2/g, preferably from 1050 to 1600 m2/g. Polysilicic acids that can be used according to the present invention include those disclosed in US 4,388,150, US 4,954,220, US 5,127,994 and US 5,279,807.
According to another preferred embodiment of the invention, use is made of colloidal aluminium-modified silica or aluminium silicate having a high specific surface area, suitably above about 1000 m2/g. In the art, compounds of this type are also referred to as polyaluminosilicates and poly-aluminosilicate microgels, which are both encompassed by the terms colloidal aluminium-modified silica and aluminium silicate used herein. Suitably, the specific surface area is within the range of from 1000 to 1700 m2/g, preferably from 1050 to 1600 m2/g. Examples of suitable high surface area silica based particles of this type include those disclosed in US 4,961,825, US 4,980,025, US 4,927,498, US 5,176,891 and US
5,470,435.
Clays of the smectite type that can be used in the present process are known in the art and include naturally g occurring, synthetic and chemically treated materials.
Examples of suitable smectite clays include montmorillonite/-bentonite, hectorite, beidelite, nontronite and saponite, preferably bentonite and especially such which after swelling preferably has a surface area of from 400 to 800 m2/g.
Suitable bentonites and hectorites are disclosed in EP 0235893 and EP 0446205, respectively, which are both incorporated herein by reference. Suitable mixtures of silica based particles and smectite clays, preferably natural sodium bentonite, are disclosed in WO 94/05595, wherein the weight ratio of silica based particles to clay particles can be in the range of from 20:1 to 1:10, preferably from 6:1 to 1:3. Useful titanyl sulphate sols are, for example, disclosed in EP 0148647.
The amount of anionic inorganic particles added to the suspension may vary within wide limits depending on, among other things, the type of particles used. The amount usually is at least 0.01 kg/ton and often at least 0.05 kg/ton, calculated as dry particles on dry fibres and optional fillers. The upper limit can be 10 kg/ton and suitably is 5 kg/ton. When using silica based particles, the amount suitably is within the range of from 0.05 to 5 kg/ton, calculated as SiO2 on dry stock system, and preferably from 0.1 to 2 kg/ton.
In the present process it is preferred to add the polymers to the stock before the anionic inorganic particles, even if the opposite order of addition may be used. It is further preferred to add the first component, e.g. the poly-mers, before a shear stage which can be selected for example from pumping, mixing, cleaning, etc., and to add the second component, e.g. the anionic inorganic particles, after that shear stage. The present process further encompasses split additions, e.g. at least two positions for simultaneously adding the polymers, either separately or in admixture, and/or at least two positions for adding anionic inorganic particles, preferably with a shear stage between each addition. The high dewatering and retention effects observed with the additives of the invention can be obtained over a broad stock pH range.
The pH can be in the range from about 3 to about 10, suitably above 3.5 and preferably within the range of from 4 to 9.
Additives which are conventional in papermaking such as, for example, stock sizes based on rosin, ketene dimers or alkenyl succinic anhydrides, dry strength agents, wet strength agents, aluminium compounds, etc., can of course be co-used in the process of the invention. The improved performance observed in the process of the present invention means that further benefits can be obtained, such as for example improved retention of such additives which can lead to improved sizing and strength of the paper. Aluminium compounds can be used to further improve drainage and/or retention in the present process. Examples of suitable aluminium compounds that can be used include alum, aluminates, aluminium chloride, aluminium nitrate and polyaluminium compounds, such as polyaluminium chlorides, polyaluminium sulphates, polyaluminium compounds containing both chloride and sulphate ions and polyaluminium silicate-sulphates. The suspension or stock can also contain mineral fillers of conventional types such as, for example, kaolin, china clay, titanium dioxide, gypsum, talc and natural and synthetic calcium carbonates such as chalk, grinded marble and precipitated calcium carbonate.
The process according to the invention can be used for producing cellulose fibre containing products in sheet or web form such as for example pulp sheets and paper. It is prefer-red that the present process is used for the production of paper. The term "paper", as used herein, of course include not only paper and the production thereof, but also other sheet or web-like products, such as for example board and paperboard, and the production thereof.
The process according to the invention can be used in the production of sheet or web-like products from different types of aqueous suspensions containing cellulosic fibres, or stocks, and the suspensions suitably contain at least 25% by weight and preferably at least 50% by weight of such fibres, based on dry substance. The suspensions can be based on fibres from chemical pulp such as sulphate and sulphite pulp, mechanical pulp such as thermomechanical pulp, chemo-thermomechanical pulp, refiner pulp and groundwood pulp, from both hardwood and softwood, and can also be based on recycled fibres from de-inked pulps, and mixtures thereof. It is 2 1 ~0404 ```, 11 preferred that at least 10~ by weight and preferably at least 20~ by weight of the pulp is derived from recycled fibre, de-inked pulp, coated broke or mechanical pulp or any mixture thereof. Such stocks, normally, have a high cationic demand and contains high levels of anionic trash which may be pulping residues, bleaching residues, de-inking residues, binders, inks, fillers, fines, sizes, dispersing agents and deposit control chemicals.
The invention is further illustrated in the following Examples which, however, are not intended to limit same. Parts and ~ relate to parts by weight and ~ by weight, respectively, unless otherwise stated.
Exam~le 1 In the following tests, drainage performance was evaluated by means of a Dynamic Drainage Analyser (DDA), available from Akribi, Sweden, which measures the time for draining a set volume of stock through a wire when removing a plug and applying a vacuum to that side of the wire opposite to the side on which the stock is present.
The furnish contained 54~ of pulp based on a 60:40 mixture of bleached birch:pine sulphate refined to 200O CSF, 23~ of grinded marble and 23~ of coated broke (magazine paper) having an ash content of 30~. Stock volume was 800 ml, consistency 0.3~ and pH about 7. The stock was stirred in a baffled jar at a speed of 1500 rpm throughout the test and chemical additions to the stock were conducted as follows:
i) adding either HMW polymer used for comparison purposes or polymers according to the invention followed by stirring for 30 seconds, ii) adding anionic inorganic particles followed by stirring for 15 seconds, iii) draining the stock while automatically recording the drainage time.
A polymer mixture, herein designated M1, in the form of an aqueous dispersion of a HMW cationic polyacrylamide and a LMW cationic polyacrylate was used in the process of the invention. The polymer mixture was prepared by polymerization of acrylamide (90 mole~) and methacryloyloxyethyldimethyl-benzylammonium chloride (10 mole~) to an average molecular weight of about 8 million in the presence of a homopolymer of acryloyloxyethyltrimethylammonium chloride having a molecular ~`~ 12 ~l 804~4 weight of about 10,000; deionized water; ammonium sulphate and a polymerization initiator. The resulting polymer mixture had a weight ratio HMW polymer to LMW polymer of 2.7:1, and a dry polymer content of about 18.5~. The polymer mixture was diluted to a dry polymer content of 0.1% prior to use.
Polymers used for comparison purposes were: P1) a HMW
cationic polyacrylamide having a molecular weight of about 8 million; and P2) a HMW cationic polyacrylamide having a molecular weight of about 16 million. The polymers P1 and P2 were dissolved in water and used as 0.1~ aqueous solutions.
The anionic inorganic material used was a silica based sol of the type disclosed in US 5,368,833. The sol had an S-value of about 25~ and contained silica particles with a specific surface area of about 900 m2/g which were surface-modified with aluminium to a degree of 5~. This sol isdesignated Sol 1. Sol 1 was added in an amount of 0.8 kg/ton, calculated as dry particles on dry stock system.
Table 1 shows the drainage time at varying dosages of P1, P2 and M1, calculated as dry polymer on dry stock system.
Table 1 Polymer Drainage time [seconds] at polymer dosage of used 0.5 kq/ton 0.8 kq/ton 1.2 kg/ton 2.0 kq/ton P1 15.7 15.4 11.4 6.3 P2 15.7 14.0 11.8 6.6 M1 14.9 13.0 7.5 4.8 As can be seen from Table 1, the process using the mixture of LMW and HMW cationic polymers according to the invention resulted in improved drainage.
Example 2 In this test series, retention was evaluated by means of the DDA used in Example 1 in combination with a nephelometer.
First pass retention was evaluated by measuring the turbidity of the filtrate, the white water, obtained by draining the stock. The polymers and anionic inorganic particles according to Example 1 were similarly used in this test series.
Table 2 shows the retention effect measured as turbidity of white water obtained at varying dosages of P1, P2 and M1, calculated as dry polymer on dry stock system.
Table 2 Polymer Turbidity [NTU] at polymer dosage of used 0. 5 kq/ton 0.8 kq/ton 1. 2 kq/ton 2.0 kq/ton Pl 236 149 87 42 Ml 161 90 53 29 As can be seen from the Table 2, the process using a mixture of HMW and LMW cationic polymers according to the invention resulted in markedly improved first pass retention.
Example 3 Retention was evaluated as in Example 2, except that different polymers were used. The order of addition according to Example 1 was applied, unless otherwise indicated.
A polymer mixture designated M2 was prepared by dissolving the HMW cationic polyacrylamide P2 according to Example 1 in an aqueous solution of a LMW cationic polyamine having a molecular weight of 50,000, which is designated P3.
M2 had a weight ratio P2 to P3 of 2.7:1.
Another embodiment of the invention was tested in which use was made of a freshly prepared mixture of P2 and P3. An aqueous solution of P2 was brought into contact with an aqueous solution of P3 by means of a mixing device, where the separate solutions were intimately mixed for about 2-3 seconds prior to introducing the resulting solution into the stock.
The polymers were added in a weight ratio P2 to P3 of 2.7:1.
This mixture is designated M3.
A further embodiment of the invention, designated Sl, was tested in which P2 and P3 were separately but simultane-ously added to the stock in a weight ratio P2 to P3 of 2.7:1.
P2 and P3 were also used for comparison purposes, where P3 was added to the stock followed by stirring for 120 seconds before adding P2. The polymers were used in an amount corre-sponding to a weight ratio P2 to P3 of 2.7:1. In Table 3, this test is designated P3+P2. In one test, P2 was also used as a single cationic polymer additive.
Table 3 shows the retention effect observed when adding 1.2 kg of total polymer and 0.8 kg of silica based particles per ton of dry stock system. As can be seen from Table 3, considerably improved retention was obtained with the 21 8~404 processes according to the present invention.
Table 3 Total polymer addition, 1.2 kg/ton P3+P2 P2 M2 M3 S1 Turbidity [NTU] 96 101 62 71 83 Example 4 First pass retention was evaluated as in Example 3, except that other additives were used. The furnish was based on 80~ of a 80:20 mixture of peroxide bleached thermomechan-ical pulp:stoneground wood pulp and 20~ of the pulp accordingto Example 1. To the stock obtained were added 30~ of china clay, based on dry substance, 4 g/l of sodium acetate tri-hydrate and 10 mg/l of extractives. Stock volume was 800 ml, consistency 0.15~ and pH 5.5.
Polymer mixtures designated M4 and M5 were prepared by dissolving HMW cationic polyacrylamide P1 according to Example 1 in aqueous solutions of LMW polymers. The LMW polymer used in M4 was a cationic polyacrylamide having a molecular weight of about 100,000 and a cationic charge density of 2.9 meq/g, which is designated P4. M4 had a weight ratio P4 to P1 of 1:1.
The LMW polymer used in M5 was a cationic starch having a molecular weight of about 400,000 and a cationic charge density of 2. 5 meq/g, which is designated P5. M5 had a weight ratio P5 to P1 of 1:1.
The polymer mixtures were compared to prior art pro-cesses in which the polymers P1, P4 and P5 were separately added wherein the LMW polymers were added to the stock followed by stirring for 30 seconds before adding P1. The weight ratios of P4:P1 and P5:P1 were both 1:1. These comparison tests are designated P4+P1 and P5+P1.
The anionic inorganic particulate materials used were Sol 1 according to Example 1 and a silica sol of the type disclosed in US 4,388,150 which contained silica particles with a specific surface area of 500 m2/g, which is designated Sol 2. The amount of Sol 1 and Sol 2 added was 3.0 and 6.0 kg/ton, respectively, calculated as dry particles on dry stock system.
Table 4 shows the retention effect, measured as turbi-dity, when using varying amounts of polymer, calculated as dry 2 ~ 80404 polymer on dry stock system, in combination with the sols.
Table 4 Polymer Sol Turbidity [NTU] at polymer dosage [kg/ton]
used used 1.0 2.03.0 4.06.0 8.0 10.0 P4+P1 Sol 1 100 7250 44 - 16 M4 Sol 1 80 5945 40 - 8 P4+P1 Sol 2 - - - - 37 30 32 M4 Sol 2 - - - - 27 17 13 P5+P1 Sol 1 - 62 - 42 - 13 13 M5 Sol 1 - 61 - 38 - 9 4 ExamPle 5 The procedure of Example 4 was followed except that different polymers were used. Cationic potato starch desig-nated P6 was used as the HMW polymer and the polyamine P3 according to Example 3 was used as the LMW polymer. A polymer mixture designated M6 was obtained by mixing the polymers in the form of aqueous solutions in a weight ratio P6 to P3 of 5:1.
Table 4 shows the retention effect obtained with varying amounts of P3+P6 and M6, calculated as dry polymer on dry stock system, when the polymers were used in combination with Sol 1 added in an amount of 3.0 kg/ton.
Table 5 PolymerTurbidity [NTU] at polymer dosage of 25 used 18 kq/ton 24 kq/ton P3+P6 28 27 Example 6 Further cationic polymers and anionic inorganic particles were evaluated for retention performance by means of a Britt Dynamic Drainage Jar at a stirring speed of 1000 rpm, which is conventional in the art. The stock and polymers used in Example 4 were similarly used in this test series. The anionic inorganic particles used were a suspension of the type disclosed in WO 94/05595 containing silica based particles according to Example 1 and natural sodium bentonite in a weight ratio of 2:1, designated Susp 1, and a suspension of natural sodium bentonite, designated Susp 2. The amount of Susp 1 and Susp 2 added was 4.0 and 6.0 kg/ton, respectively, ~ 16 calculated as dry on dry stock system.
Table 6 set forth the first pass retention of fines and filler at varying polymer dosages, calculated as dry polymers on dry stock system.
Table 6 Polymer Suspension Retention [~] at polymer dosage [kg/ton~
used used 1 2 4 5 P4+Pl Susp 1 26.1 32.2 56.7 70.5 M4 Susp l 29.4 43.0 61.9 75.1 P4+Pl Susp 2 - 43.5 43.5 M4 Susp 2 - 46.5 61.6
Claims (20)
1. A process for the production of paper from a suspension of cellulose containing fibers comprising:
adding a low molecular weight cationic organic polymer, a high molecular weight cationic or amphoteric polymer and anionic inorganic particles to the suspension, and forming and draining the suspension on a wire;
said low molecular weight polymer having a molecular weight below 700,000, said high molecular weight polymer having a molecular weight above 1,000,000 and said polymers being added simultaneously to the suspension, with substantially no time difference and essentially at the same position.
adding a low molecular weight cationic organic polymer, a high molecular weight cationic or amphoteric polymer and anionic inorganic particles to the suspension, and forming and draining the suspension on a wire;
said low molecular weight polymer having a molecular weight below 700,000, said high molecular weight polymer having a molecular weight above 1,000,000 and said polymers being added simultaneously to the suspension, with substantially no time difference and essentially at the same position.
2. A process according to claim 1, wherein the low molecular weight polymer and the high molecular weight polymer are added to the suspension in the form of a mixture.
3. A process according to claim 1, wherein the low molecular weight polymer and the high molecular weight polymer are added simultaneously but separately to the suspension.
4. A process according to claim 1, 2 or 3, wherein the high molecular weight polymer is cationic starch, cationic guar gum or cationic acrylamide-based polymer.
5. A process according to claim 1, 2, 3 or 4, wherein the low molecular weight cationic polymer is modified starch, polyamine, polyethylene imine, polyamideamine/epichlorohydrin, dimethylamine/epichloro-hydrin or a homo- or copolymer based on monomers selected from diallyldimethyl ammonium chloride, vinylamines, (meth)acrylamides, (meth)acrylates or mixtures thereof.
6. A process according to claim 1, 2, 3, 4 or 5, wherein the weight ratio of high molecular weight polymer to low molecular weight polymer is within the range of from 9:1 to 1:3.
7. A process according to claim 1, 2, 3, 4, 5 or 6, wherein the anionic inorganic particles are silica based particles.
8. A process according to claim 7, wherein the silica based particles are colloidal silica, colloidal aluminium modified silica, colloidal aluminium silicate or polysilicic acid.
9. A process according to claim 1, 2, 3, 4, 5, or 6, wherein the anionic inorganic particles are bentonite.
10. A process according to any one of claims 1 to 9, wherein said suspension further contains fillers.
11. A process according to any one of claims 1 to 10, further including adding at least one water-soluble inorganic salt to said suspension.
12. A process according to claim 2, wherein said mixture further includes at least one water-soluble inorganic salt.
13. A process according to any one of claims 1 to 12, wherein the low molecular weight polymer has at least one of a higher cationicity and a higher cationic charge density than the high molecular weight polymer.
14. A polymer mixture in the form of an aqueous dispersion comprising at least one high molecular weight cationic or amphoteric acrylamide-based polymer having a molecular weight above 1,000,000, at least one low molecular weight cationic organic polymer having a molecular weight below 700,000 and at least one water-soluble inorganic salt, wherein the weight ratio of said high molecular weight polymer to said low molecular weight polymer is within the range of from 9:1 to 1:3.
15. A polymer mixture according to claim 14, wherein the high molecular weight acrylamide-based polymer is cationic and the low molecular weight cationic polymer is a homo- or copolymer based on monomers selected from diallyldimethyl ammonium chloride, (meth)acrylamides, (meth)acrylates, or mixtures thereof.
16. A polymer mixture according to claim 14 or 15, wherein the inorganic salt is sodium sulfate, ammonium sulfate, magnesium sulfate or aluminium sulfate and the inorganic salt is present in an amount of at least 5% by weight, based on the dispersion.
17. A polymer mixture according to claim 14, 15 or 16, wherein said ratio is 7:1 to 1:2.
18. A polymer mixture according to claim 14, 15, 1 or 17, wherein the high molecular weight polymer is a cationic acrylamide-based polymer; and the low molecular weight cationic polymer is modified starch, polyamine, polyethylene imine, polyamideamine/epichlorohydrin, dimethylamine/epichlorohydrin or a homo- or copolymer based on monomers selected from diallyldimethyl ammonium chloride, vinylamines, (meth)acrylamides, (meth)acrylates or mixtures thereof.
19. A polymer mixture according to any one of claims l4 to 18, having a dry polymer content ranging from 10 to 60%, by weight.
20. A polymer mixture according to any one of claims 14 to 19, wherein the dispersion comprises particles of the high molecular weight acrylamide-based polymer.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| SE9502522-7 | 1995-07-07 | ||
| SE9502522A SE9502522D0 (en) | 1995-07-07 | 1995-07-07 | A process for the production of paper |
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| CA2180404C true CA2180404C (en) | 2002-09-17 |
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| EP (1) | EP0752496B1 (en) |
| JP (1) | JP4053620B2 (en) |
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| CN (1) | CN1087370C (en) |
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-
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- 1995-07-07 SE SE9502522A patent/SE9502522D0/en unknown
-
1996
- 1996-06-14 DE DE69616439T patent/DE69616439T2/en not_active Expired - Lifetime
- 1996-06-14 AT AT96201662T patent/ATE207989T1/en active
- 1996-06-14 ES ES96201662T patent/ES2166424T3/en not_active Expired - Lifetime
- 1996-06-14 PT PT96201662T patent/PT752496E/en unknown
- 1996-06-14 EP EP96201662A patent/EP0752496B1/en not_active Expired - Lifetime
- 1996-06-14 DK DK96201662T patent/DK0752496T3/en active
- 1996-07-01 TW TW085107933A patent/TW308618B/zh not_active IP Right Cessation
- 1996-07-01 KR KR1019960026619A patent/KR100194229B1/en not_active IP Right Cessation
- 1996-07-01 BR BR9602943A patent/BR9602943A/en not_active IP Right Cessation
- 1996-07-02 NZ NZ286923A patent/NZ286923A/en not_active IP Right Cessation
- 1996-07-02 ZA ZA965610A patent/ZA965610B/en unknown
- 1996-07-03 CA CA002180404A patent/CA2180404C/en not_active Expired - Fee Related
- 1996-07-03 AU AU58300/96A patent/AU691428B2/en not_active Ceased
- 1996-07-04 CN CN96108626A patent/CN1087370C/en not_active Expired - Fee Related
- 1996-07-04 CZ CZ19962011A patent/CZ293559B6/en not_active IP Right Cessation
- 1996-07-05 JP JP19406796A patent/JP4053620B2/en not_active Expired - Fee Related
- 1996-07-05 RU RU96115352A patent/RU2121538C1/en not_active IP Right Cessation
- 1996-07-05 NO NO19962845A patent/NO323050B1/en not_active IP Right Cessation
- 1996-07-05 PL PL315106A patent/PL190930B1/en not_active IP Right Cessation
- 1996-07-08 US US08/676,763 patent/US5858174A/en not_active Expired - Lifetime
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1998
- 1998-10-02 US US09/165,431 patent/US6100322A/en not_active Expired - Lifetime
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| EP0752496B1 (en) | 2001-10-31 |
| PL315106A1 (en) | 1997-01-20 |
| PL190930B1 (en) | 2006-02-28 |
| EP0752496A3 (en) | 1997-01-22 |
| NO323050B1 (en) | 2006-12-27 |
| DE69616439D1 (en) | 2001-12-06 |
| DE69616439T2 (en) | 2002-07-11 |
| KR100194229B1 (en) | 1999-06-15 |
| BR9602943A (en) | 1998-04-28 |
| CN1087370C (en) | 2002-07-10 |
| NO962845D0 (en) | 1996-07-05 |
| US6100322A (en) | 2000-08-08 |
| DK0752496T3 (en) | 2002-01-21 |
| CA2180404A1 (en) | 1997-01-08 |
| CZ9602011A3 (en) | 2001-01-17 |
| JPH0931885A (en) | 1997-02-04 |
| JP4053620B2 (en) | 2008-02-27 |
| ES2166424T3 (en) | 2002-04-16 |
| SE9502522D0 (en) | 1995-07-07 |
| US5858174A (en) | 1999-01-12 |
| NO962845L (en) | 1997-01-08 |
| ZA965610B (en) | 1997-01-27 |
| EP0752496A2 (en) | 1997-01-08 |
| ATE207989T1 (en) | 2001-11-15 |
| KR970006668A (en) | 1997-02-21 |
| PT752496E (en) | 2002-02-28 |
| NZ286923A (en) | 1997-09-22 |
| AU691428B2 (en) | 1998-05-14 |
| AU5830096A (en) | 1997-01-23 |
| CZ293559B6 (en) | 2004-06-16 |
| RU2121538C1 (en) | 1998-11-10 |
| TW308618B (en) | 1997-06-21 |
| CN1145967A (en) | 1997-03-26 |
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