CN1117191C - Aqueous dispersions of hydrophobic material - Google Patents
Aqueous dispersions of hydrophobic material Download PDFInfo
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- CN1117191C CN1117191C CN98802330A CN98802330A CN1117191C CN 1117191 C CN1117191 C CN 1117191C CN 98802330 A CN98802330 A CN 98802330A CN 98802330 A CN98802330 A CN 98802330A CN 1117191 C CN1117191 C CN 1117191C
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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
- D21H3/00—Paper or cardboard prepared by adding substances to the pulp or to the formed web on the paper-making machine and by applying substances to finished paper or cardboard (on the paper-making machine), also when the intention is to impregnate at least a part of the paper body
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
- D21H21/16—Sizing or water-repelling agents
-
- 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
- D21H17/03—Non-macromolecular organic compounds
- D21H17/05—Non-macromolecular organic compounds containing elements other than carbon and hydrogen only
- D21H17/14—Carboxylic acids; Derivatives thereof
- D21H17/15—Polycarboxylic acids, e.g. maleic acid
- D21H17/16—Addition products thereof with hydrocarbons
-
- 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
- D21H17/03—Non-macromolecular organic compounds
- D21H17/05—Non-macromolecular organic compounds containing elements other than carbon and hydrogen only
- D21H17/17—Ketenes, e.g. ketene dimers
-
- 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
- D21H17/23—Lignins
-
- 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
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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
- 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
- D21H17/42—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups anionic
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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
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
- D21H21/22—Agents rendering paper porous, absorbent or bulky
- D21H21/24—Surfactants
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- Paper (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Colloid Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Medicines Containing Plant Substances (AREA)
Abstract
The invention relates to an aqueous dispersion containing a dispersant and a disperse phase containing a hy-drophobic material, the dispersant comprising an anionic compound having a molecular weight less than 50000 and being selected from carbon-containing compounds and silicon-containing compounds, and a cati-onic organic compound having a molecular weight less than 50000. The invention further relates to the preparation and use of the dispersion in the production of paper. The invention also relates to a substantially water-free composition containing a hydrophobic material, an anionic compound having a molecular weight less than 50000 and being selected from carbon-containing compounds and silicon-containing compounds, and a cationic organic compound having a molecular weight less than 50000, as well as its use in the preparation of an aqueous dispersion.
Description
The present invention relates to the water-borne dispersions of lyophobic dust, more especially relate to dispersion, its preparation and purposes with dispersant system of forming by two kinds of compounds that have opposite charges.
The water-borne dispersions of lyophobic dust is known, is used for multiple use.Such as, in papermaking, the water-borne dispersions of lyophobic dust is as sizing material, to improve the ability that paper or cardboard opposing waterborne liquid soaks and permeates to a certain extent.The example that is widely used in the lyophobic dust of applying glue comprises the succinyl oxide of cellulolytic activity sizing material such as alkyl ketene dimer and replacement, and non-cellulose activated stock such as abietyl and resin-based sizing material.
The dispersion of lyophobic dust generally contains water and is dispersed in the particle or the drop of the lyophobic dust of superfine fragmentation wherein.The preparation of dispersion normally, in the presence of dispersant, under the condition of high shearing force and higher temperature, hydrophobicity, water-insoluble materials homogeneity at aqueous phase.Usually the dispersant that adopts comprises anion, both sexes or cation high molecular weight polymers, as lignosulfonates, starch, polyamine, polyamide-amide or alkene class addition polymer.Polymer can use separately, and is shared or be used to form dispersant system with other compound.Depend on the overall charge of each component of dispersant system, size dispersions can be cationic or anionic property on body.
Even under the quite low situation of solids content, the dispersion of lyophobic dust usually shows the stability of being on duty mutually and high viscosity, causes the difficulty of dispersion in handling significantly, such as when storing and use.Further shortcoming is that product can only further improve the cost of transportation of active hydrophobic material with the form supply of low concentration dispersion.
Therefore, an object of the present invention is to provide lyophobic dust water-borne dispersions with improved stability and viscosity characteristics.Another object of the present invention provides sizing material, preferably the modified water-borne dispersions of cellulolytic activity sizing material.Further purpose is seen below.
According to the present invention, discovery is by the water-borne dispersions of lyophobic dust, can realize improved stability and viscosity characteristics, the dispersant of lyophobic dust wherein by forming by two kinds of oppositely chargeds and the quite low compound of molecular weight, and be dispersed in aqueous phase.More particularly, the present invention relates to contain the water-borne dispersions of decentralized photo, wherein contain lyophobic dust and by molecular weight less than 50,000 and be selected from the dispersant that the anionic compound of organic compound and silicon-containing compound and molecular weight are formed less than 50,000 CATION organic compound.Therefore the present invention relates to water-borne dispersions, its preparation and purposes, and this point further specifies in the claims.
The dispersion that the present invention makes preparation have the lyophobic dust of improved bin stability, high solids content and/or low viscosity becomes possibility.In addition, when dispersion is used to relate to the purposes of very high dilution of the dense dispersion of initial height, find that decentralized photo is more stable, that is, dispersion shows improved dilution stability.The example that relates to high dilution factor purposes comprises the wet end environment of papermaking, and slurry or endosome applying glue, wherein relates to the dispersion of lyophobic dust is added in the aqueous suspension that contains the optional filler of cellulose fiber peacekeeping.In this article, improved dilution stability means that hydrophobicity sizing material particle or drop can assemble still less, so form the body and the low applying glue rate more with fixed attention of low content, hydrophobicity sizing material still less deposition on paper making equipment simultaneously, grid still less is infected with, and therefore reduces the needs that paper making equipment is safeguarded.The bigger benefit that this dispersion is brought comprises that there is improvement stability down in interfering material, as anion refuse from impure paper pulp and/reclaimed fibre, and lyophobic dust still less accumulation in paper technology recirculation plain boiled water.Therefore, dispersion of the present invention contains in the technology of refuse of significant quantity particularly useful in the recirculation of the plain boiled water degree of depth and cellulosic suspension.And dispersion of the present invention has also realized a kind of possibility, under same rubber material using quantity, reached than the improved applying glue of size dispersions commonly used, and under same degree of sizing, the consumption of sizing material is lower.Use the sizing material of low amount but to reach the degree of sizing of appointment, this possibility has reduced the risk of not adsorbing hydrophobic sizing material accumulation in the plain boiled water of technology recirculation, thereby has more reduced the aggegation of lyophobic dust on paper making equipment and the risk of precipitation.The present invention has big economy and technical benefits thus.
The lyophobic dust that exists in the dispersion is preferably water-fast substantially.The example of suitable lyophobic dust is included in the compound that can be used as sizing material in the papermaking, can be derived from natural and route of synthesis, as cellulolytic activity water-repelling agent and the agent of non-cellulose active hydrophobic.In a preferred embodiment, lyophobic dust has the fusing point that is less than about 100 ℃, is preferably lower than 75 ℃.
In an embodiment preferred of the present invention, lyophobic dust is the cellulolytic activity sizing material, can select from the known any cellulolytic activity sizing material of prior art.Suitable sizing material can be selected from hydrophobic ketene dimer, ketenes polymer, acid anhydrides, organic isocyanate, carbamyl chloride and their mixture, preferred ketene dimer and acid anhydrides, more preferably ketene dimer.Shown in the suitable following general formula of ketene dimer (I), R wherein
1And R
2Represent saturated or undersaturated alkyl, saturated hydrocarbyl normally, hydrocarbyl group is suitable to have 8～36 carbon atoms, normally has the alkyl of the straight or branched of 12～20 carbon atoms, as n-hexadecyl and n-octadecane base.Suitable acid anhydrides is feature, wherein R with following general formula (II)
3And R
4Can be identical or different, the suitable saturated or undersaturated alkyl that contains 8～30 carbon atoms of representative, perhaps R
3And R
4Same-C-O-C-part constitutes 5～6 yuan of rings together, and the optional alkyl that reaches 30 carbon atoms that further contained replaces.The example of Chang Yong acid anhydrides comprises alkyl and alkenyl succinic anhydrides on the market, especially different 18 alkenyl succinic anhydrides.
Suitable ketene dimer, acid anhydrides and organic isocyanate comprise United States Patent (USP) 4,522, disclosed compound in 686, herein therefore with regard to it with reference to quoting.The example of suitable carbamyl chloride comprises those at United States Patent (USP) 3,887, disclosed compound in 427, herein therefore with regard to it with reference to quoting.
In another embodiment preferred of the present invention, lyophobic dust is non-cellulolytic activity water-repelling agent, can select from the known any non-cellulose activated stock of prior art.Suitable non-cellulose activated stock can be selected from water-repelling agent such as the rosin of rosin, disproportionated rosin, Foral, newtrex, formaldehyde-treated rosin, esterified rosin, fortified rosin and these method mixed processing and the mixture that these methods were handled rosin based on rosin, aliphatic acid and derivative thereof such as fatty acid ester and acid amides such as bis-stearamides, resin and derivative thereof such as hydrogenated resin, resin acid, resinate and acid amides, wax such as rough and refined paraffin wax, synthetic wax, native paraffin etc.
Dispersion of the present invention contains dispersant, or dispersant system, comprises at least a anionic compound and at least a cationic compound, and the both has low molecular weight (after this claiming LMW).The LMW compound preferably is bonded together by electrostatic attraction, so present the state of boundling dispersant.When compound use, the LMW compound can play the effect of the dispersant of lyophobic dust effectively, though cationic compound and anionic compound when using separately not necessarily, be not suitable as dispersant usually.In a preferred embodiment, anion and cationic compound first polyelectrolyte at least.The meaning of " polyelectrolyte " this speech of herein using refers to the compound that has one or more charged groups (anion/CATION), and electrically charged (anion/CATION) compound that plays the polyelectrolyte effect such as nonionic effect or gravitation by chemistry.
The anionic compound of dispersant has the anionic group of one or more identical or different types, and comprise anionic compound that has an anionic group and the anionic compound that has two or more anionic groups, be referred to as anionic polyelectrolyte herein.Anionic polyelectrolyte can have one or more cation groups, as long as have anionic charge generally.The example of suitable anionic group comprises sulfate groups and carboxylic acid, sulfonic acid, phosphoric acid, phosphonyl group, can exist with the form of free acid or water soluble salt of ammonia or alkali metal salt (normally sodium salt), such as the carboxylate and the sulfonate of sodium.The substitution value that anionic polyelectrolyte has can change in wide scope: anion substitution value (DS
A) can be 0.01～1.4, suitable is 0.1～1.2, preferred 0.2～1.0.
The anionic compound of dispersant can be derived from natural or route of synthesis and preferably water-soluble or water dispersible.In a preferred embodiment, this anionic compound is an organic compound,, contains carbon atom that is.Suitable anionic compound comprises anion surfactant such as alkyl, aryl and alkaryl sulfate and ether sulfate, alkyl, aryl and alkaryl carboxylate, alkyl, aryl and alkylaryl sulfonate, alkyl, aryl and alkaryl phosphate and ether phosphate, and dialkyl group sulfosuccinate, wherein alkyl group contains 1～18 carbon atom, and aromatic yl group contains 6～12 carbon atoms, and alkylaryl group contains 7～30 carbon atoms.Suitable examples of anionic surfactants comprises lauryl sodium sulfate, dodecyl sodium sulfate and neopelex.The suitable more example of anionic compound comprises that anionic polyelectrolyte is such as the organic LMW polymer of anion, optional degraded, phosphatization, the polysaccharide of sulfonic acid salinization and carboxylic acid salinization is such as starch, guar gum, cellulose, the preferred cellulose derivative, carboxymethyl cellulose preferably, and condensation product such as anion polyurethane and condensation naphthalene sulfonate, more comprise from the monomer such as the acrylic acid that have anionic group, methacrylic acid, maleic acid, itaconic acid, crotonic acid, vinyl sulfonic acid, the thiazolinyl addition polymer of the phosphate of sulfonated phenylethylene and acrylic acid and hydroxyalkyl methacrylate preparation optionally comprises acrylamide with non-ionic monomer, alkyl acrylate, the derivative of styrene and acrylonitrile and these monomers, vinyl acetate and analog copolymerization thereof.Anionic compound also can be selected from siliceous LMW inorganic compound, such as, silicate and multi-form condensation or polymeric silicicacid such as oligomeric silicic acid, poly silicic acid, polysilicate, aluminium silicate polymer, polysilicate slightly soluble glue, aluminium silicate polymer slightly soluble glue and silica-based material Ludox form as band negativity hydroxyl.
The cationic compound of dispersant has the cation group of one or more identical or different types, and comprise cationic compound that has a cation group and the cationic compound that has two or more cation groups, be referred to as cationic polyelectrolyte herein.Cationic polyelectrolyte can have one or more anionic groups, as long as have cationic charge generally.The example of suitable cation group comprises sulfonium group phosphonium salt group, the primary, the acid-addition salts of the second month in a season and tertiary amine or amino and quaternary ammonium salt group, such as wherein nitrogen is quaternized by chloromethane, dimethyl suflfate or phenylchloride, the acid-addition salts of preferred amines/amino and quaternary ammonium salt group.The substitution value that cationic polyelectrolyte has can change in wide scope: CATION substitution value (DS
C) can be 0.01～1.0, suitable is 0.1～0.8, preferred 0.2～0.6.
The cationic compound of dispersant can be derived from natural or route of synthesis and preferably water-soluble or water dispersible.Cationic compound is organic compound preferably.The example of suitable cationic compound comprises cationic surfactant, suc as formula R
4N
+X
-The compound of type, wherein each R group is selected from following independently: (i) hydrogen; (ii) alkyl, suitable is contains 1～30, the aliphatic group of preferred 1～22 carbon atom, preferred alkyl; (iii) alkyl, suitable is contains nearly 30, the aliphatic group of preferred 4～22 carbon atoms, preferred alkyl, and be inserted with one or more hetero atoms such as oxygen and nitrogen, and/or contain heteroatom group such as carbonyl and acyloxy; Wherein at least one suits three at least, and preferred whole described R groups contain carbon atom; Suitable at least one, preferably at least two described R groups contain at least 7, preferably at least 9, at least 12 carbon atoms most preferably; And X wherein
-Be a kind of anion, the typical case is halogen ion such as chlorine, or the anionic group that exists in the dispersant anionic compound, is formula R such as surfactant wherein
3Protonated amines shown in the N, wherein R and N definition as above.The example of suitable surfactant comprises Quaternium 24, DDAC, two coconut oil base alkyl dimethyl ammonium chlorides, coconut oil base benzyl dimethyl ammonium chloride, coconut oil base (classification) benzyl dimethyl ammonium chloride, octadecyl trimethyl ammonium chloride, two (octadecyl) alkyl dimethyl ammonium chloride, two (cetyl) alkyl dimethyl ammonium chloride, two (hydrogenated-tallow group) alkyl dimethyl ammonium chloride, two (hydrogenated-tallow group) benzyl ammonio methacrylate, hydrogenated-tallow group benzyl dimethyl ammonium chloride, two oil base alkyl dimethyl ammonium chlorides and two (ethylidene hexadecane acid esters) alkyl dimethyl ammonium chloride.Particularly preferred cationic surfactant thereby comprise that those have the material of the hydrocarbyl group of 9～30 carbon atoms, preferably quaternary ammonium compound at least.More suitable cationic surfactant comprises season two and the many ammonium compoundss that has at least one hydrocarbyl group, suitable is 9～30, the aliphatic hydrocarbon of preferred 12～22 carbon atoms, preferred alkyl.The example of the surfactant that this type of is suitable comprises N-octadecyl-N-dimethyl-N '-trimethyl-propylidene-dichloride two ammoniums.The suitable further example of cationic compound comprises cationic polyelectrolyte such as the organic LMW polymer of CATION, optional degraded, as compound derived from polysaccharide such as starch and guar gum, CATION condensation product such as polyurethane, polyamide-amide such as daiamid-chloropropylene oxide, polyamines such as dimethylamine epichlorohydrin copolymer, dimethylamine-ethylenediamine-epichlorohydrin copolymer, ammonia-dichloroethylene, from the thiazolinyl addition polymer of the monomer preparation that has cation group such as the acrylate of diallyldimethylammonium chloride and dialkyl aminoalkyl, the homopolymerization or the copolymer of methacrylate and acrylamide thereof (as acrylic acid and dimethylaminoethyl acrylate methyl base ammonia ethyl ester), usually with acid-addition salts or quaternary ammonium salt, optionally comprise acrylamide with non-ionic monomer, alkyl acrylate, the derivative of styrene and acrylonitrile and these monomers, vinyl acetate and analog copolymerization thereof.
Be used for anion LMW compound of the present invention and CATION LMW compound and all have molecular weight (after this claiming MW) less than 50,000, suitable less than 30,000, preferably less than 20,000.As the MW of the anionic compound of dispersant and/or cationic compound even lower,,, can obtain further benefit preferably less than 10,000 o'clock such as less than 15,000.Anion and cationic compound generally have and are higher than 200 molecular weight, preferably are higher than 500.Anion and cationic surfactant have usually than anion and the lower molecular weight of cationic polyelectrolyte; It is 200～800 that preferred surfactant has MW.When a kind of compound in the dispersant was surfactant, the another kind of compound of dispersant is polyelectrolyte preferably, and its MW definition as above.
The preferred dispersion of the present invention contains dispersant, is selected from dispersant (i), and it is made up of cationic surfactant and anionic polyelectrolyte, and wherein dispersant has overall anionic charge; Dispersant (ii), it is made up of cationic polyelectrolyte and anionic polyelectrolyte, wherein dispersant has overall anionic charge; Dispersant (iii), it is made up of anion surfactant and cationic polyelectrolyte, wherein dispersant has overall cationic charge; Dispersant (iv), it is made up of anionic polyelectrolyte and cationic polyelectrolyte, wherein dispersant has overall cationic charge; On the definition of anion and cationic surfactant, anion and cationic polyelectrolyte and molecular weight thereof is seen.
The amount that the anion of dispersant and cationic compound can exist in dispersion changes in wide region, and the ion substitution value that especially depends on molecular weight, the compound of compound is the overall charge of dispersion of charge density, hope and the lyophobic dust of selecting for use.Based on lyophobic dust, the amount that anionic compound and cationic compound can exist all is maximum 100wt%, is suitably 0.1～20wt%, preferably 1～10wt%.
Find that dispersion of the present invention can be prepared into highly filled and still show extraordinary bin stability and low viscosity.Therefore the present invention has provided the dispersion with improved bin stability and/or highly filled lyophobic dust.The particularly preferred dispersion of this paper comprises the dispersion of cellulolytic activity sizing material, preferably contains the dispersion of the dispersant of overall anionic property electric charge.It is 0.1～50wt% that cellulolytic activity size dispersions of the present invention generally has sizing material content, the suitable 20wt% that is higher than.The dispersion that contains the ketene dimer sizing material of the present invention may have ketene dimer content in scope 5～50wt%, preferred 10～35wt%.Dispersion or the emulsion that contains the anhydrides sizing material of the present invention, may have anhydride content is 0.1～30wt%, common 1～20wt%.It is 5～50wt% that non-cellulose activated stock dispersion generally has sizing material content, preferred 10～35wt%.
The preparation of dispersion of the present invention is, preferably under the temperature that lyophobic dust is in a liquid state, water mixed with dispersant system and lyophobic dust, and the mixture that so obtains of homogeneity, suit under pressure.Cool off the water-based emulsion that obtains then, wherein contain the drop that common particle diameter is the water-repelling agent of 0.1～3.5 μ m.Except above-mentioned component, also can add other material in the size dispersions, such as additional dispersant and stabilizing agent such as non-ionic dispersing agent, extender such as urea and urea derivative and preservative agent.Recommend the plus or minus electric charge original position of compound dispersing agent to form, such as contacting with each other and/or compound is mixed and/or reduces the pH value of water with water by means of compound.Such as, acid groups loses hydrogen will form anionic charge, and basic amine or amino by protonated or absorb a hydrogen and will show cationic.Therefore, the preparation of dispersion can start from uncharged compound.Such as, can adopt the organic compound or the formula R that have alkali formula amino group
3The basic amine that N shows, wherein Dui Ying ammonium salt part R
4N
+X
-Generate in preparation process, wherein R, N and X definition is the same.
The component of further finding dispersion homogeneity at an easy rate in the presence of water particularly is less than about 100 ℃ at dispersant LMW compound, is preferably lower than under the condition that 75 ℃ lyophobic dust is used with fusing point.Technology with the common dispersion of preparation is compared, this technology generally need still less energy and lower shearing force, thereby simplified application apparatus.Therefore, preparation one of dispersion further method comprises that (i) lyophobic dust mixes with the anion and the cationic compound of dispersant, obtains midbody composite and (ii) homogeneity midbody composite in the presence of water, as above-mentioned.Preferred ingredient evenly mixed in the stage (i).The water-repelling agent that adopts in stage (i) can be solid-state, though preferred liquid to simplify even mixed process.If the words of wishing, midbody composite has just experienced after the mixing of stage (i) can discharging, optional cooling curing has just obtained containing the substantially anhydrous midbody composite of dispersant and lyophobic dust, has realized the simplification of transportation in attractive economically mode.In the institute place to use or other place, the intermediate hydrophobic composition can be in the presence of water with usually or the mode homogeneity of simplifying, at elevated temperatures optional, to keep the liquid condition of midbody composite.When the dispersion of preparation ketene dimer and acid anhydrides, this method is attractive especially, and the latter often is prepared in directly relating to its paper mill as the purposes of paper size.Coming across of the substantially anhydrous glueing composition of stable storage is that sizable economy and technical benefits can be provided.Therefore the present invention also relates to the substantially anhydrous concentrate composition of being made up of lyophobic dust, the anion LMW compound that is selected from carbon compound and silicon-containing compound and the organic LMW compound of CATION, wherein anion and cationic compound can play the effect of the dispersant system of aqueous phase lyophobic dust effectively when compound use, also relate to preparation of compositions and purposes, this point further specifies in the claims.
Each component that contains in the concentrate composition of the present invention, that is, lyophobic dust, zwitterion compound are preferably as above-mentioned definition.This composition is substantially anhydrous, and meaning promptly can contain a spot of water herein; The content of water can be 0～10wt%, and suitable is to be less than 5wt%, preferably is less than 2wt%.Most preferably not moisture.In quality be, composition preferably contains the lyophobic dust of the amount of occupying the majority, that is, 50wt% at least, composition is suitable to have water-repelling agent content in scope 80～99.9wt%, preferred 90～99.7wt%.With respect to its percetage by weight is the dispersion of base with the lyophobic dust, and the zwitterion compound can be present in the composition with above-mentioned amount.Based on lyophobic dust, the amount that anionic compound and cationic compound can contain in the composition all is maximum 100wt%, is suitably 0.1～20wt%, preferably 1～10wt%.
Dispersion of the present invention can with common mode in the paper of the cellulose fibre that adopts any kind is made as sizing material, can be used to top sizing, also can be endosome or slurry applying glue.The meaning of " paper " this speech of herein using not only comprises paper but also comprises sheet material and all types of cellulosicss of fabric shape, comprises, such as, sheet material and cardboard.Contain cellulose fibre in the slurry, optional the content of general cellulose fibre is 50wt% at least with the mineral filler cooperation, based on the slurry of doing.The example of the mineral filler of common type comprises kaolin, china clay, titanium dioxide, gypsum, talcum and natural and synthetic calcium carbonate such as chalk, heavy marble and precipitation method calcium carbonate.The amount of adding the hydrophobicity sizing material in the slurry to can be 0.01～5wt%, preferred 0.05～1.0wt%, based on the dry weight of the optional filler of cellulose fiber peacekeeping, wherein consumption is mainly by paper pulp or treat the degree of sizing decision that the quality of sized paper, the sizing material of selecting for use and hope reaches.
In a preferred embodiment, dispersion is used for the slurry applying glue of cellulose pulp, wherein slurry has high cationic demand degree and/or contains the significant quantity lipophilicity substance, has certain slurry that contains lignin and recovery paper pulp, for example wherein plain boiled water degree of depth recirculation certainly as preparation.Most preferred dispersion comprises the dispersion and the dispersion that contains overall anionic charge dispersant of cellulolytic activity sizing material in this class purposes.Usually the cationic demand degree is 50 at least, suits at least 100, preferably the female filtrate of at least 150 μ eq/l.The cationic demand degree can be measured with usual way, and such as by M ü tek particle charging detector, female filtrate of use is taken from through 1.6 μ m filters and filtered the thick slurries that form, and is titrant with poly-(diallyldimethylammonium chloride).The content of lipophile extract may be at least 10ppm, 20ppm at least usually, and suitable 30ppm at least and preferred 50ppm at least adopt known method to utilize DCM (carrene) to carry out extracting, and measurement result is represented with ppm DCM.This dispersion more preferably is used for plain boiled water by the paper technology of degree of depth recirculation, that is, and and the sealing of plain boiled water height, for example wherein make dried paper per ton and use 0～30 ton of fresh water, common paper low per ton is in 20, suitablely is less than 15, preferably is less than 10 and most preferably less than 5 tons of fresh waters/ton paper.The preferred enforcement of plain boiled water recirculation is in the technology, before or after size dispersions adds, preferably with the form of slurry or suspension plain boiled water is mixed with cellulose fibre, for example forms slurry to be drained off.Fresh water can be incorporated in the technology under any stage; Such as, it can mix to form slurry with cellulose fibre before or after slurry mixes with plain boiled water and before or after size dispersions adds, and also can mix with the slurry that contains cellulose fibre, dilutes it to form slurry to be drained off.
The chemical substance of adding in slurry usually in the papermaking is such as retention agent, aluminium compound, dyestuff, wet strengthening resin and glazing agent etc., certainly with the compound use of this size dispersions.The non-cellulose activated stock is used with aluminium compound usually, so that sizing material is fixed on the cellulose fibre.The example of aluminium compound comprises alum, aluminate and many aluminium compounds such as the many aluminium of chlorination and many aluminium of sulfuric acid salt.The example of suitable retention agent comprises cationic polymer, and organic polymer composite anion inorganic matter is as cationic polymer composite bentonite, cationic polymer or zwitterion polymer comprehensive silicon based sols.When dispersion of the present invention is equipped with the retention agent use that contains cationic polymer, can reach good especially slurry applying glue.Suitable cationic polymer comprises cationic starch, guar gum, acrylate and acrylamide-based polymers, poly-piperazine, dicyano diamides-formaldehyde, polyamines, polyamide-amide and poly-(diallyldimethylammonium chloride) and their mixture.Preferred cationic starch and cation acrylamide based polyalcohol, or use separately or be mixed with each other or mix with other material and use.In an embodiment preferred of the present invention, the application of dispersion is equipped with a kind of retention system, contains at least a cationic polymer and anion silicon basal granule.This dispersion can be before cationic polymer adds, middle, add afterwards or simultaneously.Also may be size dispersions with retention agent for example cationic polymer such as cationic starch or cation acrylamide based polyalcohol, or the silica-based material premixed of anion, then the mixture of preparation like this is added in the slurry.Therefore, this dispersion can contain cationic compound by handle to it before soon adding in the slurry, and the size dispersions of preferred cationic surfactant contacts with the silica-based material of aforesaid anion and prepares.
The present invention is further described in following embodiment, but the present invention is not limited to this.Umber and wt% represent parts by weight and percetage by weight respectively, except as otherwise noted.
Embodiment 1
The preparation of hydrophobic alkyl ketene dimer of the present invention (AKD) dispersion is, at 70 (C, with two (hydrogenated-tallow group) alkyl dimethyl ammonium chloride, MW is 340 cationic surfactant, and is on sale with trade name Querton 442, Akzo Nobel system, mix with the AKD of fusing, (calculate MW about 6,000 at a kind of condensation sodium naphthalene sulfonate, (SN is on sale, Luo Mu ﹠amp with trade name Orotan; Under the existence of aqueous solution Haars Co., Ltd's system), mixture cools off the dispersion that so obtains then via even matter device.Adding acid makes the pH value of dispersion adjust to about 5.This dispersion is expressed as the No.1 dispersion, has AKD content 30wt%, and contains the anionic compound of 6wt% and the cationic compound of 4wt%, all based on the quality of AKD.Dispersion contains cellulolytic activity water-repelling agent particle, and (this point is embodied in negative (on the electromotive force, measuring with ZetaMaster S Version PCS to its average grain diameter about 1 for m, band anionic charge.
Embodiment 2
The stable following mensuration of embodiment 1 dispersion: the dispersion dilute with water obtains containing the dispersion of 40ppmAKD.In some experiment,, added the stearic acid of 10ppm for estimating the stability under the existence of lipophile anion refuse.The dispersion of dilution is packed into and is equipped with in the wide-mouth bottle of cloud point test device, loop, circulation device and heating and cooling device.The dilute dispersion of certain volume circulates in loop, writes down turbidity simultaneously automatically, and makes dispersion stand to fix long heating in 45 minutes and freeze cycle.The temperature of dispersion rises to 62 ℃ from 20 ℃, is reduced to 20 ℃ then again.Turbidity is subjected to grain diameter influence, before the temperature cycles and the difference of dispersion turbidity afterwards be that the test dispersed particle withstands because of the grow up yardstick of ability of gathering, the yardstick of final dispersion stability.The following calculating of turbidity poor (Δ T): Δ T=(final turbidity/initial turbidity) * 100.Δ T is big more, and stability is high more.
For comparing purpose, two standard dispersions are also tested: reference example 1 is an anion AKD dispersion, contain the dispersant system of being made up of sodium lignin sulfonate and high molecular (HMW) cationic starch, wherein the anion lignosulfonates are excessive on number of ions; Reference example 2 is cation AKD dispersions, also contains sodium lignin sulfonate and HMW cationic starch, and wherein cationic starch is excessive on number of ions.Table 1 provide obtain the result.
Table 1 Dispersion number Stearic acid [ppm] Δ T1-72 1 10 55 reference example, 1-45 reference example, 1 10 32 reference examples, 2-35 reference examples 2 10 6
As shown in table 1, compare with those Δs T value of standard dispersion, the value of dispersion of the present invention is quite high, this thereby mean better dilution stability.
Embodiment 3
93 parts of AKD pills, the anionic compound of 3 parts of cationic surfactants and 4 parts of embodiment 1 employings is done and is mixed, to prepare anhydrous concentrate composition of the present invention.Then this mixture of doing is added in the hot water, and the aqueous mixture that will so obtain is heated to 80 ℃, cool to room temperature behind the high pressure shear pump is crossed in pumping.Final anionic dispersions, dispersion No.2 has AKD content 20wt%, the about 1 μ m of average grain diameter.
Applying glue efficient is passed judgment on,, contained 60: 40 the bleaching birch/pine sulfate of 80wt% and the chalk of 20wt% in the papermaking slurry of selecting for use, be added with the Na of 0.3g/l according to being applicable to that laboratory scale SCAN-C23X standard method prepares paper
2SO
410H
2O.The denseness of slurry is 0.5wt%, pH value 8.0.Dispersion is equipped with industrial retention and dewatering system, Compozil in use
TM, to form by cationic starch and anion al-modified silica sol, the two joins in the slurry respectively; The amount that cationic starch adds is the 12kg/ ton, and based on the dry pulp body, the amount that Ludox adds is the 0.8kg/ ton, with SiO
2For meter and based on the dry pulp body.
The Cobb value is measured according to T 441 OS-63 of TAPPI standard, and experimental result is listed in the table 2.The inventory of AKD is based on the dry pulp body.
Table 2 Dispersion number AKD inventory [kg/ ton] Cobb 60[g/m 2 ]2 0.30 58 2 0.40 30 reference examples, 1 0.30 84 reference examples, 1 0.40 65 reference examples, 2 0.30 66 reference examples 2 0.40 40
Table 2 shows, by size dispersions of the present invention, has reached the improvement of paper sizing.
Embodiment 4
Have the anion AKD dispersion of different AKD content by preparation, the difficulty of dispersion preparation of the present invention is passed judgment on.The preparation of dispersion of the present invention is, two (hydrogenated-tallow group) alkyl dimethyl ammonium chloride with 0.8wt%, the condensation sodium naphthalene sulfonate of 1.6wt%, the mixture of the water of 77.6wt% and the AKD of 20wt% is with one period regular time of Ultra Turrax blender homogeneity, revolution 15,000rpm, the dispersion that so obtains of cooling is 2 hours then.Prepare the different similar dispersion of AKD content in the same way, to obtain the dispersion of AKD content 10,20,30 and 40wt%.These dispersions are called example, follow with AKD content wt%.
For comparing purpose, in the same way, under identical condition, with the mixture homogeneity of 1.0wt% cationic starch, 0.25wt% sodium lignin sulfonate, 89wt% water and 10wt%AKD, preparation standard AKD dispersion.The different similar dispersion of preparation AKD content is to obtain the standard dispersion of AKD content 10,20,30 and 40wt%.These dispersions are called reference example 3, follow with AKD content wt%.
Measure particle diameter and viscosity with method commonly used.Table 3 provides the result who obtains.
Table 3 AKD dispersion number Particle diameter [μ m] Viscosity [cps]Example-10wt% 2.98 10 examples-20wt% 3.12 20 examples-30wt% 3.50 20 examples-40wt% 3.50 25 reference example 3-10wt% 4.31 15 reference example 3-20wt% 4.52 20 reference example 3-30wt% 5.20 25 reference example 3-40wt% 5.57 40
Table 3 shows that dispersion of the present invention is easier to make; Identical AKD content obtains lower viscosity, and the surperficial liberalization energy of same amount provides littler particle diameter.Compared with the standard dispersion, for preparing the dispersion that equates particle diameter, so the present invention need still less energy and lower shearing force.In addition, mixing speed rises to 25, and 000rpm reduces in scope 1～2 μ m particle diameter disease of dispersion of the present invention.
Claims (16)
1. by dispersant with contain the water-borne dispersions that the decentralized photo of hydrophobicity sizing material is formed, it is characterized in that dispersant contains (a) molecular weight less than 50,000 and be selected from the anionic compound of carbon compound and silicon-containing compound, and (b) molecular weight less than 50,000 CATION organic compound, wherein at least a in anion and the cationic compound is polyelectrolyte, and described sizing material is selected from hydrophobicity ketene dimer, acid anhydrides and its mixture.
2. the dispersion of claim 1 is characterized in that anionic compound and cationic compound have the molecular weight less than 20,000.
3. the dispersion of claim 1 is characterized in that anionic compound is an organic compound.
4. claim 1,2 or 3 dispersion is characterized in that dispersant is an anionic property, and are made up of cationic surfactant and anionic polyelectrolyte.
5. claim 1,2 or 3 dispersion is characterized in that dispersant is an anionic property, and are made up of cationic polyelectrolyte and anionic polyelectrolyte.
6. claim 1,2 or 3 dispersion is characterized in that dispersant is a cationic, and are made up of anion surfactant and cationic polyelectrolyte.
7. claim 1,2 or 3 dispersion is characterized in that dispersant is a cationic, and are made up of anionic polyelectrolyte and cationic polyelectrolyte.
8. claim 1,2 or 3 dispersion is characterized in that it has hydrophobicity sizing material content 0.1-50wt%.
9. claim 1,2 or 3 dispersion is characterized in that the hydrophobicity sizing material has and are lower than 75 ℃ fusing point.
10. the preparation method of water-borne dispersions, be by the hydrophobicity sizing material water and by molecular weight less than 50,000 and be selected from the anionic compound of carbon compound and silicon-containing compound, and molecular weight is less than 50, homogeneity under the existence of the dispersant that 000 CATION organic compound constitutes, wherein at least a in anion and the cationic compound is polyelectrolyte, and described sizing material is selected from hydrophobicity ketene dimer, acid anhydrides and its mixture.
11. the method for claim 10 is characterized in that anionic compound and cationic compound have the molecular weight less than 20,000.
12. the method for claim 10 or 11 is characterized in that anionic compound is an organic compound.
13. any one the purposes of water-borne dispersions of claim 1～9 is used in slurry applying glue or top sizing in the papermaking.
14. substantially anhydrous glueing composition, contain hydrophobicity sizing material, molecular weight less than 50,000 and be selected from the anionic compound of carbon compound and silicon-containing compound and molecular weight less than 50,000 CATION organic compound, wherein at least a in anion and the cationic compound is polyelectrolyte, and described sizing material is selected from hydrophobicity ketene dimer, acid anhydrides and its mixture.
15. the composition of claim 14 is characterized in that anionic compound is an organic compound.
16. the purposes of the composition of claim 14 or 15 is used to prepare any one water-borne dispersions of claim 1～9.
Applications Claiming Priority (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP97850016 | 1997-02-05 | ||
| EP97850016.3 | 1997-02-05 | ||
| EP97850017.1 | 1997-02-05 | ||
| EP97850017 | 1997-02-05 | ||
| SE97049324 | 1997-12-30 | ||
| SE9704932A SE9704932D0 (en) | 1997-02-05 | 1997-12-30 | Aqueous dispersions of hydrophobic material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1246900A CN1246900A (en) | 2000-03-08 |
| CN1117191C true CN1117191C (en) | 2003-08-06 |
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ID=27238797
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN98802330A Expired - Fee Related CN1117191C (en) | 1997-02-05 | 1998-02-03 | Aqueous dispersions of hydrophobic material |
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| Country | Link |
|---|---|
| EP (1) | EP0961855B1 (en) |
| JP (1) | JP3400803B2 (en) |
| KR (1) | KR100339883B1 (en) |
| CN (1) | CN1117191C (en) |
| AT (1) | ATE225435T1 (en) |
| AU (1) | AU729702B2 (en) |
| BR (1) | BR9807049B1 (en) |
| CA (1) | CA2280094C (en) |
| DE (1) | DE69808435T2 (en) |
| DK (1) | DK0961855T3 (en) |
| ES (1) | ES2183325T3 (en) |
| ID (1) | ID25962A (en) |
| NO (1) | NO328669B1 (en) |
| NZ (1) | NZ336786A (en) |
| PT (1) | PT961855E (en) |
| RU (1) | RU2168579C2 (en) |
| SE (1) | SE9704932D0 (en) |
| SK (1) | SK285268B6 (en) |
| WO (1) | WO1998033980A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101346513B (en) * | 2005-12-21 | 2012-05-23 | 阿克佐诺贝尔股份有限公司 | Sizing of paper |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU6333599A (en) * | 1998-10-16 | 2000-05-08 | Basf Aktiengesellschaft | Aqueous sizing agent dispersions adjusted to be anionic or cationic and designedfor paper sizing |
| US6245197B1 (en) * | 1999-10-20 | 2001-06-12 | Fort James Corporation | Tissue paper products prepared with an ion-paired softener |
| CN1262710C (en) * | 2000-04-12 | 2006-07-05 | 赫尔克里士公司 | Paper sizing composition |
| US6846384B2 (en) | 2000-08-07 | 2005-01-25 | Akzo Nobel N.V. | Process for sizing paper |
| US7740742B2 (en) | 2003-07-31 | 2010-06-22 | Kao Corporation | Powder composition for paper manufacturing |
| JP4406882B2 (en) | 2005-03-18 | 2010-02-03 | ハリマ化成株式会社 | Filler-attached paper and method for producing the same |
| US7754287B2 (en) * | 2006-05-31 | 2010-07-13 | E. I. Du Pont De Nemours And Company | Process for forming filled bearings from fluoropolymer dispersions stabilized with anionic polyelectrolyte dispersing agents |
| US20110009299A1 (en) * | 2009-07-10 | 2011-01-13 | Van Zanten Ryan | Emulsion stabilizing agents for drilling and completion fluids |
| RU2473725C1 (en) * | 2011-08-16 | 2013-01-27 | Общество с ограниченной ответственностью "Оптимальные химические технологии+консалтинг" | Method of production of cardboard with white cover layer |
| FI124556B (en) * | 2012-04-26 | 2014-10-15 | Stora Enso Oyj | Hydrophobic-bonded fiber web and process for manufacturing a bonded web layer |
| BR112015028705B1 (en) * | 2013-06-13 | 2022-03-15 | Ecolab Usa Inc | Water-free surface sizing composition, and method of treating a paper substrate |
| FI125311B (en) * | 2013-11-29 | 2015-08-31 | Kemira Oyj | Process for enzyme recovery in biofuel production |
| EP3237456B1 (en) * | 2014-12-22 | 2018-12-12 | Rohm and Haas Company | Suspensions comprising polyelectrolytes of opposite polarity |
| CN108342003A (en) * | 2018-02-10 | 2018-07-31 | 浙江鸿盛原汽车用品有限公司 | A kind of tasteless reclaimed rubber and its automatic foot-mat of preparation |
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- 1998-02-03 KR KR19997006869A patent/KR100339883B1/en not_active IP Right Cessation
- 1998-02-03 SK SK1025-99A patent/SK285268B6/en not_active IP Right Cessation
- 1998-02-03 JP JP53282498A patent/JP3400803B2/en not_active Expired - Fee Related
- 1998-02-03 PT PT98903334T patent/PT961855E/en unknown
- 1998-02-03 AU AU60101/98A patent/AU729702B2/en not_active Ceased
- 1998-02-03 DK DK98903334T patent/DK0961855T3/en active
- 1998-02-03 BR BRPI9807049-5A patent/BR9807049B1/en not_active IP Right Cessation
- 1998-02-03 EP EP98903334A patent/EP0961855B1/en not_active Expired - Lifetime
- 1998-02-03 ES ES98903334T patent/ES2183325T3/en not_active Expired - Lifetime
- 1998-02-03 WO PCT/SE1998/000193 patent/WO1998033980A1/en active IP Right Grant
- 1998-02-03 ID IDW990819A patent/ID25962A/en unknown
- 1998-02-03 CA CA002280094A patent/CA2280094C/en not_active Expired - Fee Related
- 1998-02-03 RU RU99119239/12A patent/RU2168579C2/en not_active IP Right Cessation
- 1998-02-03 DE DE69808435T patent/DE69808435T2/en not_active Expired - Lifetime
- 1998-02-03 AT AT98903334T patent/ATE225435T1/en active
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| EP0208667A1 (en) * | 1985-07-10 | 1987-01-14 | Eka Nobel Aktiebolag | Aqueous dispersions, a process for their preparation and the use of the dispersions as sizing agents |
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| EP0275851A1 (en) * | 1987-01-09 | 1988-07-27 | Eka Nobel Ab | Aqueous dispersions, a process for their preparation and their use as sizing agents |
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Also Published As
| Publication number | Publication date |
|---|---|
| AU729702B2 (en) | 2001-02-08 |
| CA2280094A1 (en) | 1998-08-06 |
| SK102599A3 (en) | 2000-08-14 |
| AU6010198A (en) | 1998-08-25 |
| DE69808435T2 (en) | 2003-07-10 |
| ID25962A (en) | 2000-11-16 |
| DE69808435D1 (en) | 2002-11-07 |
| WO1998033980A1 (en) | 1998-08-06 |
| EP0961855A1 (en) | 1999-12-08 |
| SE9704932D0 (en) | 1997-12-30 |
| ES2183325T3 (en) | 2003-03-16 |
| PT961855E (en) | 2003-01-31 |
| CA2280094C (en) | 2005-04-26 |
| RU2168579C2 (en) | 2001-06-10 |
| BR9807049A (en) | 2000-03-28 |
| NO993742L (en) | 1999-09-29 |
| CN1246900A (en) | 2000-03-08 |
| BR9807049B1 (en) | 2009-01-13 |
| KR20000070621A (en) | 2000-11-25 |
| NO993742D0 (en) | 1999-08-02 |
| JP2000509430A (en) | 2000-07-25 |
| JP3400803B2 (en) | 2003-04-28 |
| EP0961855B1 (en) | 2002-10-02 |
| SK285268B6 (en) | 2006-10-05 |
| KR100339883B1 (en) | 2002-06-10 |
| DK0961855T3 (en) | 2003-01-20 |
| NZ336786A (en) | 2001-02-23 |
| ATE225435T1 (en) | 2002-10-15 |
| NO328669B1 (en) | 2010-04-19 |
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