[go: up one dir, main page]

WO1997005330A1 - Polymeres cationiques synthetiques facilitant le collage de l'anhydride succinique d'alcenyle - Google Patents

Polymeres cationiques synthetiques facilitant le collage de l'anhydride succinique d'alcenyle Download PDF

Info

Publication number
WO1997005330A1
WO1997005330A1 PCT/US1996/012231 US9612231W WO9705330A1 WO 1997005330 A1 WO1997005330 A1 WO 1997005330A1 US 9612231 W US9612231 W US 9612231W WO 9705330 A1 WO9705330 A1 WO 9705330A1
Authority
WO
WIPO (PCT)
Prior art keywords
sizing
asa
examples
cationic
mole
Prior art date
Application number
PCT/US1996/012231
Other languages
English (en)
Inventor
Richard Barkman Wasser
Original Assignee
Cytec Technology Corp.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Cytec Technology Corp. filed Critical Cytec Technology Corp.
Priority to MX9800482A priority Critical patent/MX9800482A/es
Priority to EP96925482A priority patent/EP0840822A1/fr
Priority to BR9610142A priority patent/BR9610142A/pt
Priority to AU65979/96A priority patent/AU6597996A/en
Publication of WO1997005330A1 publication Critical patent/WO1997005330A1/fr
Priority to NO980330A priority patent/NO980330D0/no

Links

Classifications

    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • 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
    • D21H17/20—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
    • 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
    • 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

Definitions

  • This invention relates to emulsions using synthetic cationic polymers as promoters for alkenyl succinic anhydride sizing, and more specifically to an emulsion containing alkenyl succinic anhydride and a synthetic cationic polymer that enhances sizing efficiency and a method of using the same.
  • paper Sizing agents in the papermaking process are used to promote reduced water and ink abso ⁇ tion in the paper product as well as to resist aqueous acid and alkaline solutions.
  • paper is contemplated to include any sheet-like masses and molded products made from fibrous cellulosic materials which may be derived from both natural and synthetic sources.
  • Paper is often sized with various materials to increase resistance to water as well as to other types of aqueous solutions. These materials are referred to as sizes or sizing and they may be introduced during the actual papermaking process. Alternatively, the sizes or sizing may be applied to the surface of the finished web or sheet.
  • a sizing agent is alkenyl succinic anhydride ("ASA").
  • ASA alkenyl succinic anhydride
  • ASA alkenyl succinic anhydride
  • the use of ASA as a sizing agent is well known in the art, as described in Farley and Wasser, "Sizing with Alkenyl Succinic Anhydride” in The Sizing of Paper, W.F. Reynolds, Ed., TAPPI, 1989, Chapter 3. See also U.S. Patent No. 3,968,005, which is incorporated herein by reference.
  • ASA is water insoluble and hydrolytically unstable. Therefore, it must be emulsified at the paper mill prior to use. Specifically, the art requires that for retention the sizing agents be used in conjunction with a material that is cationic in nature, or is capable of producing one or more cations or other positively charged groups. Emulsification is normally achieved by passing the ASA and a protective colloid, starch and/or synthetic polymer, through a device such as a homogenizer, high shear turbine pump, etc.
  • Cationic starch plays several important roles in ASA sizing. First, it aids in the generation of small particle size ASA emulsions. Small particle size, in the micron range, is required for good sizing efficiency. Second, it imparts good physical stability to the emulsion. ASA emulsions must be stable in order to prevent deposits and press picking once they have been added to the paper furnish. Third, it retains the emulsion on the fiber surfaces and promotes sizing efficiency. Sizing levels for a given amount of ASA are found to increase several-fold as the amount of cationic starch in the pulp furnish increases. Normally, cationic starch is used at a ratio of 2 to 4 times that of the ASA to give optimum sizing efficiency.
  • starch cationic starch
  • the starch must be cooked at the mill, thus requiring large scale cooking equipment and storage tanks.
  • starch is susceptible to biological degradation, resulting in slime growth and the creation of deposits on paper mill equipment, causing runnability problems in the form of press picking, felt filling and poor cylinder vat consistency control.
  • ASA sizing system may be desirable, in some cases, to make the ASA sizing system function independently of cationic starch.
  • the variation in batch-to-batch starch viscosity and solids, and the need to cool the starch before emulsification can lead to unwanted variation in ASA emulsion particle size.
  • Some paper mills do not like to use starch because of the difficult cooking and handling requirements. Others, where fine paper grades are made and where much of the ASA sizes are currently being used, require cationic starch for dry strength, but the mills would prefer to use lower cost cationic com starches. Generally, more expensive cationic potato starch gives better results for ASA sizing.
  • the synthetic cationic polymers of the art as alternative to starch are not reactive with ASA.
  • U.S. Patent No. 4,657,946 teaches an improved emulsification of ASA sizing agent by using cationically charged water soluble vinyl addition polymers.
  • the '946 patent teaches a paper sizing method and emulsion using cationically charged, water soluble, vinyl addition polymers and condensation polymers that provide improved emulsification of alkenyl succinic anhydride sizing agents.
  • U.S. Patent No. 4,629,655 teaches a size composition as a solid product produced by mixing a cationic polymer suitable for functioning as a size retention aid and a size suitable for sizing a substrate.
  • the process for sizing a substrate in the '655 patent comprises dispersing the solid in an aqueous mixture, applying the resultant mixture to a substrate, and causing the size to be fixed to the substrate thereby.
  • the synthetic cationic polymers of the art have only been marginally successful as a suitable replacement for starch. None of these synthetic cationic polymers contain functional groups that are reactive with ASA.
  • the synthetic cationic polymers of the art which serve as additives and co-emulsifying agents for ASA sizing do not enhance sizing (or do not serve as good promoters).
  • U.S. Patent No. 4,217,214 teaches the use of high molecular weight poiyvinylamine hydrochloride for the flocculation of suspended solids in water purification or waste water clarification systems.
  • U.S. Patent No. 4,957,977 teaches a flocculating agent and paper strength increasing agent using a vinylamine copolymer and a process for producing the vinylamine polymer.
  • Patent Application GB 2,268,758A teaches a paper wet strength improvement by wet- or dry-end addition of an amine-functional poly(vinyl alcohol) and a cellulose reactive size which is a 4 or 5 membered cyclic ester or anhydride having one or more alkyl or alkenyl substituents of 4 or more carbon atoms and having a total of at least 8 carbon atoms in the substituents.
  • patents that are directed to synthetic cationic polymers in the art do not specifically relate to increasing the efficiency of paper sizing.
  • a hydrophobic, cellulose sizing material which comprises adding thereto a synthetic cationic polymer that is reactive with said sizing material.
  • Groups that are reactive with ASA include primary amine and hydroxyl.
  • the preferred sizing material is alkenyl succinic anhydride.
  • the preferred synthetic cationic polymer comprises a copolymer of primary amine.
  • a synthetic cationic polymer which contains one or more non-sizing reactive monomers, particularly, non-ASA reactive monomers, like acrylic acid.
  • non-sizing reactive monomer refers to a monomer that does not result in a significant reaction with a sizing material.
  • the synthetic cationic polymer may be a copolymer of vinyl alcohol and vinylamine.
  • the synthetic cationic polymer may also be a copolymer of acrylamide and vinylamine.
  • a method in papermaking for improving the sizing efficiency of a hydrophobic, cellulose sizing material which comprises adding to a cellulose sizing agent an effective amount of a synthetic cationic polymer containing hydroxyl and/or primary amine groups.
  • a synthetic cationic polymer containing hydroxyl and/or primary amine groups Preferably the polymer comprises about 50 to about 99 mole % vinylalcohol and about 50 to about 1 mole % vinylamine.
  • This invention discloses an alkaline sizing emulsion for improving the sizing efficiency in papermaking comprising a hydrophobic cellulose sizing material and a copolymer of cationic vinylamine that is reactive with said sizing material.
  • the sizing material is alkenyl succinic anhydride. It is preferable to have as a copolymer comprising a synthetic polymer of about 20 to about 90 mole % acrylamide and about 80 to about 10 mole % vinylamine. It is also preferable to have as a copolymer comprising a synthetic polymer of about 50 to about 99 mole % vinylalcohol and about 50 to about 1 mole % vinylamine.
  • an alkaline sizing emulsion comprising an alkenyl succinic anhydride sizing material and an effective amount of a synthetic cationic polymer reactive with the sizing material wherein the polymer contains hydroxyl and/or primary amine groups.
  • the term "effective amount” is defined as the quantity of material needed to increase the sizing efficiency of a sizing agent.
  • Various synthetic cationic polymers were evaluated as replacements for cationic starch that is normally used in the ASA paper sizing process.
  • Cationic starch has been shown to be a good sizing promoter for ASA.
  • promotion performance based on an increase in sizing efficiency using cationic starch were evaluated in comparison with a variety of different synthetic cationic polymers.
  • starch is distinct from the synthetic cationic polymers because starch is a natural substance, rather than synthetic.
  • Paper handsheets containing the size and promoter were prepared and used for sizing evaluation.
  • a handsheet is comprised of pulp, fillers, sizing agent (ASA) and promoter (a cationic starch or a synthetic cationic polymer).
  • Emulsification of ASA using cationic polyacrylamide For each handsheet evaluation, an ASA emulsion is prepared in deionized water.
  • the emulsification procedure proceeds as follows: 24.0 g of deionized water was weighed into a small (about 35 mL capacity) stainless steel blender jar. About 1 g of ASA (weighed by difference) is added and the blender is run at high speed for five minutes. Based on the calculated ASA concentration, the sample was immediately diluted to 0.25% with cold, pH 3 deionized water to minimize hydrolysis. The sample was kept on ice until used for the handsheet evaluation. Particle size was estimated to be in the 1.5 to 2 micron range.
  • a variety of synthetic cationic polymers containing copolymers of amide and amine groups, as well as alcohol and amine groups are within the scope of the invention.
  • Each of the polymers and copolymers was selected for evaluation because each contains functional groups (i.e., primary amine or hydroxyl) that can react with ASA.
  • Cationic polyvinylalcohol may contain 6 mole % vinylamine groups (PVOH/PVA) and have a molecular weight in the range of from 80 to 140 k daltons.
  • the copolymer was prepared by hydrolysis of a copolymer of vinylacetate and N-vinyl formamide.
  • Polyvinylamine (PVA) and polyvinylamine.HCI (PVA/HCI) are contemplated as useful in this invention.
  • the PVA is of a low molecular weight and is supplied as a 12.8% solution.
  • the PVA. HCI may be a medium molecular weight powder.
  • PAA Polyallylamine.HCI
  • PAA PDAA copolymer of allylamine and diallylamine.HCI
  • the PAA has an average molecular weight of about 100 k daltons and is supplied as a 40% aqueous solution.
  • the PAA/PDAA has a weight average molecular weight of 50 k daltons.
  • the Hofmann degradation of polyacrylamide using sodium hypochlorite introduces primary amine and carboxyl groups. Samples were prepared containing about 40 mole % primary amine using polyacrylamide samples of four different molecular weights ranging from 14 to 200 k daltons using the procedure from Tanaka (see, H. Tanaka, J. Polymer Science: Polymer Letters Edition 16, 87-89 (1978)).
  • Table I presents the Hofmann degradation products of polyacrylamide. In analyzing the amine and carboxyl contents of the Hofmann degradation products, it is shown that the variation in molecular weights does not significantly change the concentration of amine content, carboxyl content or isoelectric pH.
  • ASA-reactive synthetic cationic polymers various non ASA- reactive synthetic cationic polymers were considered as promoters, for example, acrylamide/methacryloxyethyltrimethyl ammonium chloride (acrylamide/Q6) copolymer, polyethylenimine (polymer with average molecular weight of 50 to 60 k daltons, containing mostly secondary amine groups), Mannich quaternary of polyacrylamide, and terpolymers of acrylamide, acryloxyethyltrimethyiammonium chloride (Q9) and alkyl methacrylate.
  • acrylamide/Q6 copolymer polyethylenimine (polymer with average molecular weight of 50 to 60 k daltons, containing mostly secondary amine groups)
  • Mannich quaternary of polyacrylamide and terpolymers of acrylamide, acryloxyethyltrimethyiammonium chloride (Q9) and alkyl methacrylate.
  • the ASA primarily used is ACCOSIZE® 18 (available from Cytec Industries Inc.).
  • the sizing level achievable with ASA significantly increases (is promoted) as the amount of cationic starch in the system increases.
  • the magnitude of the increase and that sizing continues to increase even with relatively large amount of cationic starch, up to 3:1 ratio of starch to ASA. Because of this effect, a high ratio of cationic starch to ASA is used in current commercial practice. It does not matter whether the cationic starch is part of the ASA emulsion or whether it is added separately to the furnish.
  • the sizing level of an ASA sizing agent may also be significantly increased by increasing the concentration of synthetic cationic polymers that are reactive with ASA. Handsheet evaluation of polymers as ASA promoters
  • the handsheet experiments are done using the following procedure.
  • the furnish is a 50/50 mixture of bleached hardwood and softwood kraft pulps beaten to a Canadian Standard Freeness of 500 to which 15% by weight of precipitated calcium carbonate is added and the pH adjusted to 7.5.
  • a batch of 0.6% consistency stock containing 10g of fiber is treated with the promoter, followed by a given dosage of ASA emulsion, then with 1.0 lb/ton of anionic polyacrylamide retention aid. Fifteen seconds of contact time is allowed between each addition.
  • Three-2.8 g handsheets 50 Ib/Tappi ream) are formed, pressed with 1-1/2 weights, and dried one minute on the rotary drum drier at 240°F.
  • Basis weight and sizing are measured on the sheets after conditioning for at least 24 hours at 23 °C and 50% R.H.
  • the handsheets are tested for ink penetration using a sizing test of the type described in Tappi Standard T-530 pm-83. It measures the elapsed time after contacting one side of the paper with ink for the reflectance of the opposite side to fall to 80% of its initial value.
  • the ink is the same as described in T-530 pm-83, but contains no formic acid and is buffered to pH 7.
  • the tests are normalized to 50 Ib/Tappi ream basis weight assuming sizing is proportional to the cube of the basis weight.
  • Example 5 of Table II shows the results of an evaluation of the ink penetration of an ASA emulsion made with a 90/10 mole ratio AMD/Q6 copolymer. This same emulsion was then post-diluted with either additional AMD/Q6 copolymer (a synthetic cationic polymer) or with cationic starch. The ASA dosage was 0.15% on fiber in all the examples. Post-dilution with additional AMD/Q6 copolymer (Examples 6 to 9) shows that the sizing efficiency does not increase appreciably, since the copolymer is not reactive with ASA. Examples 10 to 14 show that the AMD/Q6 copolymer post-diluted with cationic starch provided marked increase in sizing efficiency.
  • ink penetration is provided for in seconds. It is shown that the effect of the increase in sizing efficiency is attributed to the cationic starch (which is ASA-reactive) and not to the AMD/Q6 copolymer (which is not ASA-reactive). Table II
  • Table III presents results of an evaluation that is similar to that presented in Table II.
  • the 90/10 mole ratio AMD/Q6 copolymer of these examples is made by inverse emulsion techniques.
  • Example 15 shows the sizing obtained with ASA emulsion made using the AMD/Q6 copolymer.
  • the ASA dosage is 0.15% on fiber in all the examples.
  • This same emulsion is then post diluted with either additional AMD/Q6 copolymer (Examples 16 to 18) or with cationic starch (Examples 19 to 23).
  • These examples show that the addition of inverse emulsion AMD/Q6 copolymer does not increase sizing efficiency since the copolymer is not reactive with ASA.
  • Examples 19 to 23 show that the inverse AMD/Q6 copolymer diluted with cationic starch provided marked increase in sizing efficiency. It is shown that the effect of the increase in sizing efficiency is attributed to the cationic starch (which is ASA-reactive) and not to the AMD/Q6 copolymer (which is not ASA-reactive).
  • Table IV shows the results of an evaluation that is similar to those presented in Tables II and III.
  • the synthetic cationic copolymer is 99/1 mole ratio AMD/Q9.
  • An ASA emulsion is prepared using water only, Example 24. The ASA dosage was 0.125% on fiber in all of the examples.
  • This same emulsion is then post diluted with either AMD/Q9 copolymer (Examples 25 to 27) or with cationic starch (Examples 28 to 32).
  • These examples demonstrate that the addition of AMD/Q9 copolymer does not increase sizing efficiency since the copolymer is not reactive with ASA.
  • Post dilution with cationic starch provides a marked increase in sizing efficiency. It is shown that the effect of the increase in sizing efficiency is attributed to the cationic starch (which is ASA-reactive) and not to the AMD/Q9 copolymer (which is not ASA-reactive).
  • Table V shows that the results of an evaluation of sizing as a function of promoter dosage for various promoters.
  • Each of the examples in Table V is conducted using 0.2% on fiber of ASA.
  • Examples 33 to 35 use a 18/20/2 mole percent te ⁇ olymer of acrylamide/Q9/n-dodecylmethacrylate te ⁇ olymer. This is a non-ASA reactive polymer.
  • Examples 36 to 38 use cationic potato starch as the promoter.
  • Examples 39 to 41 use PVOH/PVA as the promoter. Ink penetration is provided for in seconds. These examples show that the promotion effect of PVOH/PVA, an ASA-reactive polymer, increases the sizing efficiency by increase in dosage. Table V
  • Table VI presents the results of an evaluation of the sizing as a function of promoter dosage for various promoters. Each of the examples in Table VI are conducted using 0.15% on fiber. Examples 42 to 45 use cationic potato starch as the promoter. Examples 46 to 49 use PVOH/PVA as the promoter. Other parameters of this analysis are similar to those of Table V (Examples 33 to 41). Table VI demonstrates that PVOH/PVA is a more effective promoter than cationic potato starch (over the range of 0.075 to 0.45 lb/ton). These examples show that the promoter efficiency is a function of promoter concentration. Here, the PVOH/PVA is a much more effective promoter than cationic potato starch when the cationic polymer (either the synthetic cationic polymer or the starch) concentration is less than about 0.45% on fiber.
  • Table Vll presents the results of an evaluation of sizing as a function of promoter dosage for various promoters, as in Table V (Examples 33 to 41).
  • the emulsions of Table Vll are prepared in the presence of either the PVOH/PVA or the cationic potato starch at 0.5/1 ratio to ASA. After emulsification, additional PVOH/PVA or cationic potato starch is added to the furnish to give dosages of 0.075, 0.15 or 0.3% on fiber.
  • Examples 50 to 52 use cationic potato starch as the promoter.
  • Examples 53 to 55 use PVOH/PVA, an ASA- reactive polymer, as the promoter.
  • Table VIII shows the results of an evaluation of sizing as a function of promoter dosage for various promoters, as in Table VI (Examples 42 to 49).
  • Examples 56 to 59 use polyethylenimine as the promoter.
  • Example 60 to 63 use a Hofmann degradation product as the promoter (Table I, Example 1).
  • Examples 64 to 66 use cationic potato starch as the promoter.
  • Examples 67 to 70 use PVOH/PVA as the promoter.
  • Table IX shows the results of an evaluation of sizing as a function of promoter dosage for various promoters, as in Table VI (Examples 42 to 49).
  • the dosage of ASA is 0.2% on dry fiber.
  • Examples 71 to 73 use a Mannich quatemary of polyacrylamide as the promoter.
  • Examples 74 to 76 use cationic potato starch as the promoter.
  • Examples 77 to 79 use PVOH/PVA as the promoter.
  • Examples 80 to 82 use a Hofmann degradation product as the promoter (Table I, Example 1). This experiment shows that the two ASA- reactive synthetic cationic polymers (PVOH/PVA and the Hofmann degradation product) provide promoting effect to sizing.
  • the Mannich quaternary of polyacrylamide which is not ASA-reactive, does not.
  • Table X shows the results of an evaluation of sizing as a function of promoter dosage for various promoters, as in Table VI (Examples 42 to 49). 0.15% ASA on fiber is used.
  • Examples 83 to 85 use PAA/PDAA of 50 k daltons molecular weight as the promoter.
  • Examples 86 to 88 use PAA of 100 k daltons molecular weight as the promoter.
  • Examples 89 to 91 use a Hofmann degradation product of 14 k daltons molecular weight (Table 1 , Example 4) as the promoter.
  • Examples 92 to 94 use a Hofmann degradation product of 47 k daltons molecular weight (Table 1 , Example 3) as the promoter.
  • Examples 95 to 97 use a Hofmann degradation product of 77 k daltons molecular weight (Table I, Example 2) as the promoter.
  • Examples 98 to 100 use a Hofmann degradation product of 200 k daltons molecular weight (Table I, Example 1 ) as the promoter.
  • Examples 101 to 103 use cationic potato starch as the promoter.
  • Examples 104 to 106 use PVOH/PVA as the promoter.
  • Table XI shows the comparative results of an evaluation of the ink penetration as a function of promoter dosage for various promoters, as in Table X (Examples 83 to 106).
  • Examples 107 to 109 use a Hofmann degradation product of 14 k daltons molecular weight
  • Examples 110 to 112 use a Hofmann degradation product of 47 k daltons molecular weight (Table I, Example 3) as the promoter.
  • Examples 113 to 115 use a Hofmann degradation product of 77 k daltons (Table I, Example 2) as the promoter.
  • Examples 116 to 118 use a Hofmann degradation product of 200 k daltons molecular weight (Table 1 , Example 1 ) as the promoter.
  • Examples 119 to 121 use PVA as the promoter.
  • Examples 122 to 124 use PVA.HCI as the promoter.
  • Examples 125 to 127 use PVOH/PVA as the promoter.
  • Examples 128 to 130 use cationic potato starch as the promoter.
  • These examples show that both PVA and PVA.HCI are effective promoters for ASA. Both are ASA-reactive. It again shows that PVOH/PVA is an effective promoter, and that the effectiveness of the Hofmann degradation products increase with increasing molecular weight.
  • Table XII presents a further comparative evaluation of PVOH/PVA polymer as a sizing promoter for ASA.
  • the performance of PVOH/PVA polymer as sizing promoter is compared to the use of cationic starch as the promoter.
  • the synthetic polymer is evaluated under varying mole percent of PVA in the PVA/PVOH polymer as well as under varying molecular weight and dosage of the PVA/PVOH polymer. Each evaluation is conducted using 0.15 mole % on fiber of ASA. It is shown that at higher PVA mole % content (i.e., at 6 or 18 mole %), the PVOH/PVA promoter is more efficient than cationic starch. At levels of 3 mole % of PVA or less, the copolymer is not effective as a promoter. It is also shown that better efficiency is obtained with higher molecular weight samples.
  • the paper that is used for the examples in Table XIII is made on a pilot paper machine.
  • the ASA is emulsified either with a copolymer of acrylamide/methyl chloride quaternary salt of dimethylaminoethyl methacrylate (AMD/Q6) or with cationic potato starch.
  • the emulsion is added to the pulp at the down leg of the stuff box.
  • ASA dosage is kept constant at 0.175%.
  • the furnish is 70/30 bleached hardwood/softwood with 25% (on dry fiber) added precipitated CaC0 3 .
  • the AMD/Q6 copolymer is provided in a final ratio to ASA of 0.13/1.
  • Example 156 the total AMD/Q6 copolymer is provided as in Example 155, but with additional polymer addition bringing the final ratio of AMD/Q6 to ASA as 1.0/1.
  • Example 157 the ASA emulsion is made using a 90/10 AMD/Q6 inverse emulsion copolymer, with a final polymer/ASA ratio of 0.13/1.
  • the result of these three examples show the average sizing for Examples 155, 156 and 157 as 20, 41 and 5 seconds, respectively. This demonstrates that the sizing was low, relative to the standard emulsions. Increasing the level of copolymer from 0.13:1 to 1 :1 resulted only in a small increase in sizing.
  • Examples 158 and 159 are ASA emulsions made using cationic starch in a ratio to ASA of 2.1/1. The much higher sizing values show the promoting effect of the ASA reactive cationic starch.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Paper (AREA)
  • Colloid Chemistry (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

Polymères cationiques synthétiques facilitant le collage de l'anhydride succinique d'alcényle. Il est démontré que l'addition de certains polymères cationiques synthétiques réagissant avec l'anhydride succinique d'alcényle améliore l'efficacité du collage de produits de collage cellulosiques hydrophobes lors de la fabrication de papier. Il est prévu que les polymères cationiques synthétiques remplacent l'amidon pour faciliter la fabrication de papier.
PCT/US1996/012231 1995-07-27 1996-07-25 Polymeres cationiques synthetiques facilitant le collage de l'anhydride succinique d'alcenyle WO1997005330A1 (fr)

Priority Applications (5)

Application Number Priority Date Filing Date Title
MX9800482A MX9800482A (es) 1995-07-27 1996-07-25 Polimeros cationicos sinteticos como promotores para el aprestamiento con anhidrido alquenil-succinico.
EP96925482A EP0840822A1 (fr) 1995-07-27 1996-07-25 Polymeres cationiques synthetiques facilitant le collage de l'anhydride succinique d'alcenyle
BR9610142A BR9610142A (pt) 1995-07-27 1996-07-25 Processo de fabricação de papel e emulsão de encolamento alcalina para aperfeiçoar a eficiência de encolamento na fabricação de papel
AU65979/96A AU6597996A (en) 1995-07-27 1996-07-25 Synthetic cationic polymers as promoters for ASA sizing
NO980330A NO980330D0 (no) 1995-07-27 1998-01-26 Syntetiske kationiske polymere som pådriver for ASA liming

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US50828695A 1995-07-27 1995-07-27
US08/508,286 1995-07-27

Publications (1)

Publication Number Publication Date
WO1997005330A1 true WO1997005330A1 (fr) 1997-02-13

Family

ID=24022111

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1996/012231 WO1997005330A1 (fr) 1995-07-27 1996-07-25 Polymeres cationiques synthetiques facilitant le collage de l'anhydride succinique d'alcenyle

Country Status (12)

Country Link
EP (1) EP0840822A1 (fr)
KR (1) KR19990035963A (fr)
CN (1) CN1192256A (fr)
AR (1) AR003054A1 (fr)
AU (1) AU6597996A (fr)
BR (1) BR9610142A (fr)
CA (1) CA2227605A1 (fr)
CO (1) CO4560502A1 (fr)
MX (1) MX9800482A (fr)
NO (1) NO980330D0 (fr)
WO (1) WO1997005330A1 (fr)
ZA (1) ZA966342B (fr)

Cited By (38)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998050630A1 (fr) * 1997-05-06 1998-11-12 Basf Aktiengesellschaft Procede de production de papier, de carton souple et de carton epais
WO2004059082A1 (fr) * 2002-12-17 2004-07-15 Lanxess Corporation Systeme de compositions d'anhydride alcenylsuccinique et son procede d'utilisation
WO2006096216A1 (fr) * 2005-03-03 2006-09-14 Kemira Oyj Agent d’encollage reactif a la cellulose a cisaillement reduit pour des applications en milieu humide
US7405198B2 (en) 2003-11-24 2008-07-29 Neose Technologies, Inc. Glycopegylated erythropoietin
WO2008141093A1 (fr) * 2007-05-09 2008-11-20 Buckman Laboratories International, Inc. Émulsions de collage à base d'asa pour le papier et le carton
US7473680B2 (en) 2001-11-28 2009-01-06 Neose Technologies, Inc. Remodeling and glycoconjugation of peptides
US7691603B2 (en) 2003-04-09 2010-04-06 Novo Nordisk A/S Intracellular formation of peptide conjugates
US7696163B2 (en) 2001-10-10 2010-04-13 Novo Nordisk A/S Erythropoietin: remodeling and glycoconjugation of erythropoietin
US7795210B2 (en) * 2001-10-10 2010-09-14 Novo Nordisk A/S Protein remodeling methods and proteins/peptides produced by the methods
US7803777B2 (en) 2003-03-14 2010-09-28 Biogenerix Ag Branched water-soluble polymers and their conjugates
US7943789B2 (en) 2002-12-17 2011-05-17 Kemira Oyj Alkenylsuccinic anhydride composition and method of using the same
US8063015B2 (en) 2003-04-09 2011-11-22 Novo Nordisk A/S Glycopegylation methods and proteins/peptides produced by the methods
US8268967B2 (en) 2004-09-10 2012-09-18 Novo Nordisk A/S Glycopegylated interferon α
US8361961B2 (en) 2004-01-08 2013-01-29 Biogenerix Ag O-linked glycosylation of peptides
US8716239B2 (en) 2001-10-10 2014-05-06 Novo Nordisk A/S Granulocyte colony stimulating factor: remodeling and glycoconjugation G-CSF
US8716240B2 (en) 2001-10-10 2014-05-06 Novo Nordisk A/S Erythropoietin: remodeling and glycoconjugation of erythropoietin
US8791066B2 (en) 2004-07-13 2014-07-29 Novo Nordisk A/S Branched PEG remodeling and glycosylation of glucagon-like peptide-1 [GLP-1]
US8841439B2 (en) 2005-11-03 2014-09-23 Novo Nordisk A/S Nucleotide sugar purification using membranes
US8911967B2 (en) 2005-08-19 2014-12-16 Novo Nordisk A/S One pot desialylation and glycopegylation of therapeutic peptides
US8916360B2 (en) 2003-11-24 2014-12-23 Novo Nordisk A/S Glycopegylated erythropoietin
US8969532B2 (en) 2006-10-03 2015-03-03 Novo Nordisk A/S Methods for the purification of polypeptide conjugates comprising polyalkylene oxide using hydrophobic interaction chromatography
US9005625B2 (en) 2003-07-25 2015-04-14 Novo Nordisk A/S Antibody toxin conjugates
US9029331B2 (en) 2005-01-10 2015-05-12 Novo Nordisk A/S Glycopegylated granulocyte colony stimulating factor
US9050304B2 (en) 2007-04-03 2015-06-09 Ratiopharm Gmbh Methods of treatment using glycopegylated G-CSF
US9150848B2 (en) 2008-02-27 2015-10-06 Novo Nordisk A/S Conjugated factor VIII molecules
US9187546B2 (en) 2005-04-08 2015-11-17 Novo Nordisk A/S Compositions and methods for the preparation of protease resistant human growth hormone glycosylation mutants
US9187532B2 (en) 2006-07-21 2015-11-17 Novo Nordisk A/S Glycosylation of peptides via O-linked glycosylation sequences
US9200049B2 (en) 2004-10-29 2015-12-01 Novo Nordisk A/S Remodeling and glycopegylation of fibroblast growth factor (FGF)
JP2016508551A (ja) * 2013-03-01 2016-03-22 ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ サイズ剤の水溶性エマルション
EP2920364A4 (fr) * 2012-11-15 2016-07-13 Ecolab Usa Inc Émulsification d'un anhydryde succinique alcényle avec un homopolymère ou un copolymère contenant de l'amine
US9493499B2 (en) 2007-06-12 2016-11-15 Novo Nordisk A/S Process for the production of purified cytidinemonophosphate-sialic acid-polyalkylene oxide (CMP-SA-PEG) as modified nucleotide sugars via anion exchange chromatography
US9702086B2 (en) 2014-10-06 2017-07-11 Ecolab Usa Inc. Method of increasing paper strength using an amine containing polymer composition
US9920482B2 (en) 2014-10-06 2018-03-20 Ecolab Usa Inc. Method of increasing paper strength
US9951475B2 (en) 2014-01-16 2018-04-24 Ecolab Usa Inc. Wet end chemicals for dry end strength in paper
US10145067B2 (en) 2007-09-12 2018-12-04 Ecolab Usa Inc. Method of improving dewatering efficiency, increasing sheet wet web strength, increasing sheet wet strength and enhancing filler retention in papermaking
EP3449057A4 (fr) * 2016-04-25 2019-09-18 Ecolab USA Inc. Procédés et compositions pour améliorer l'encollage dans un processus de fabrication de papier
US10648133B2 (en) 2016-05-13 2020-05-12 Ecolab Usa Inc. Tissue dust reduction
US10889939B2 (en) 2015-12-25 2021-01-12 Ecolab Usa Inc. Sizing method for making paper and paper prepared thereof

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19801064A1 (de) * 1998-01-14 1999-07-15 Bayerische Motoren Werke Ag Verfahren zum Betrieb eines Fahrzeugs und eine Vorrichtung zur Durchführung des Verfahrens
CN101693927B (zh) * 2009-10-21 2013-03-20 陕西科技大学 长链烷基醇改性asa防水加脂剂及其制备方法
CN110577672A (zh) * 2018-06-07 2019-12-17 国家纳米科学中心 可调控亲疏水性纳米纤维素薄膜、及其制备方法和应用

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0200504A1 (fr) * 1985-05-03 1986-11-05 Ciba Specialty Chemicals Water Treatments Limited Compositions pour l'encollage du papier
US4657946A (en) * 1984-06-25 1987-04-14 Nalco Chemical Company Paper sizing method and emulsion
GB2268758A (en) * 1992-07-15 1994-01-19 Air Prod & Chem Paper wet-strength improvement
US5281307A (en) * 1993-01-13 1994-01-25 Air Products And Chemicals, Inc. Crosslinked vinyl alcohol/vinylamine copolymers for dry end paper addition

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4657946A (en) * 1984-06-25 1987-04-14 Nalco Chemical Company Paper sizing method and emulsion
EP0200504A1 (fr) * 1985-05-03 1986-11-05 Ciba Specialty Chemicals Water Treatments Limited Compositions pour l'encollage du papier
GB2268758A (en) * 1992-07-15 1994-01-19 Air Prod & Chem Paper wet-strength improvement
US5281307A (en) * 1993-01-13 1994-01-25 Air Products And Chemicals, Inc. Crosslinked vinyl alcohol/vinylamine copolymers for dry end paper addition

Cited By (46)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6576086B1 (en) 1997-05-06 2003-06-10 Basf Aktiengesellschaft Method for producing paper, paperboard and cardboard using an uncrosslinked fixing agent during paper stock draining
WO1998050630A1 (fr) * 1997-05-06 1998-11-12 Basf Aktiengesellschaft Procede de production de papier, de carton souple et de carton epais
US8716239B2 (en) 2001-10-10 2014-05-06 Novo Nordisk A/S Granulocyte colony stimulating factor: remodeling and glycoconjugation G-CSF
US8716240B2 (en) 2001-10-10 2014-05-06 Novo Nordisk A/S Erythropoietin: remodeling and glycoconjugation of erythropoietin
US7795210B2 (en) * 2001-10-10 2010-09-14 Novo Nordisk A/S Protein remodeling methods and proteins/peptides produced by the methods
US7696163B2 (en) 2001-10-10 2010-04-13 Novo Nordisk A/S Erythropoietin: remodeling and glycoconjugation of erythropoietin
US7473680B2 (en) 2001-11-28 2009-01-06 Neose Technologies, Inc. Remodeling and glycoconjugation of peptides
US7943789B2 (en) 2002-12-17 2011-05-17 Kemira Oyj Alkenylsuccinic anhydride composition and method of using the same
WO2004059082A1 (fr) * 2002-12-17 2004-07-15 Lanxess Corporation Systeme de compositions d'anhydride alcenylsuccinique et son procede d'utilisation
US7803777B2 (en) 2003-03-14 2010-09-28 Biogenerix Ag Branched water-soluble polymers and their conjugates
US8247381B2 (en) 2003-03-14 2012-08-21 Biogenerix Ag Branched water-soluble polymers and their conjugates
US7691603B2 (en) 2003-04-09 2010-04-06 Novo Nordisk A/S Intracellular formation of peptide conjugates
US8853161B2 (en) 2003-04-09 2014-10-07 Novo Nordisk A/S Glycopegylation methods and proteins/peptides produced by the methods
US8063015B2 (en) 2003-04-09 2011-11-22 Novo Nordisk A/S Glycopegylation methods and proteins/peptides produced by the methods
US9005625B2 (en) 2003-07-25 2015-04-14 Novo Nordisk A/S Antibody toxin conjugates
US8916360B2 (en) 2003-11-24 2014-12-23 Novo Nordisk A/S Glycopegylated erythropoietin
US7405198B2 (en) 2003-11-24 2008-07-29 Neose Technologies, Inc. Glycopegylated erythropoietin
US8361961B2 (en) 2004-01-08 2013-01-29 Biogenerix Ag O-linked glycosylation of peptides
US8791066B2 (en) 2004-07-13 2014-07-29 Novo Nordisk A/S Branched PEG remodeling and glycosylation of glucagon-like peptide-1 [GLP-1]
US8268967B2 (en) 2004-09-10 2012-09-18 Novo Nordisk A/S Glycopegylated interferon α
US10874714B2 (en) 2004-10-29 2020-12-29 89Bio Ltd. Method of treating fibroblast growth factor 21 (FGF-21) deficiency
US9200049B2 (en) 2004-10-29 2015-12-01 Novo Nordisk A/S Remodeling and glycopegylation of fibroblast growth factor (FGF)
US9029331B2 (en) 2005-01-10 2015-05-12 Novo Nordisk A/S Glycopegylated granulocyte colony stimulating factor
WO2006096216A1 (fr) * 2005-03-03 2006-09-14 Kemira Oyj Agent d’encollage reactif a la cellulose a cisaillement reduit pour des applications en milieu humide
US9187546B2 (en) 2005-04-08 2015-11-17 Novo Nordisk A/S Compositions and methods for the preparation of protease resistant human growth hormone glycosylation mutants
US8911967B2 (en) 2005-08-19 2014-12-16 Novo Nordisk A/S One pot desialylation and glycopegylation of therapeutic peptides
US8841439B2 (en) 2005-11-03 2014-09-23 Novo Nordisk A/S Nucleotide sugar purification using membranes
US9187532B2 (en) 2006-07-21 2015-11-17 Novo Nordisk A/S Glycosylation of peptides via O-linked glycosylation sequences
US8969532B2 (en) 2006-10-03 2015-03-03 Novo Nordisk A/S Methods for the purification of polypeptide conjugates comprising polyalkylene oxide using hydrophobic interaction chromatography
US9050304B2 (en) 2007-04-03 2015-06-09 Ratiopharm Gmbh Methods of treatment using glycopegylated G-CSF
WO2008141093A1 (fr) * 2007-05-09 2008-11-20 Buckman Laboratories International, Inc. Émulsions de collage à base d'asa pour le papier et le carton
US9493499B2 (en) 2007-06-12 2016-11-15 Novo Nordisk A/S Process for the production of purified cytidinemonophosphate-sialic acid-polyalkylene oxide (CMP-SA-PEG) as modified nucleotide sugars via anion exchange chromatography
US10145067B2 (en) 2007-09-12 2018-12-04 Ecolab Usa Inc. Method of improving dewatering efficiency, increasing sheet wet web strength, increasing sheet wet strength and enhancing filler retention in papermaking
US9150848B2 (en) 2008-02-27 2015-10-06 Novo Nordisk A/S Conjugated factor VIII molecules
US10227731B2 (en) 2010-11-02 2019-03-12 Ecolab Usa Inc. Emulsification of alkenyl succinic anhydride with an amine-containing homopolymer of copolymer
US9624623B2 (en) 2010-11-02 2017-04-18 Ecolab Usa Inc. Emulsification of alkenyl succinic anhydride with an amine-containing homopolymer or copolymer
EP2920364A4 (fr) * 2012-11-15 2016-07-13 Ecolab Usa Inc Émulsification d'un anhydryde succinique alcényle avec un homopolymère ou un copolymère contenant de l'amine
US9708771B2 (en) 2013-03-01 2017-07-18 Basf Se Aqueous emulsion of a sizing agent
JP2016508551A (ja) * 2013-03-01 2016-03-22 ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ サイズ剤の水溶性エマルション
US9951475B2 (en) 2014-01-16 2018-04-24 Ecolab Usa Inc. Wet end chemicals for dry end strength in paper
US9702086B2 (en) 2014-10-06 2017-07-11 Ecolab Usa Inc. Method of increasing paper strength using an amine containing polymer composition
US9840810B2 (en) 2014-10-06 2017-12-12 Ecolab Usa Inc. Method of increasing paper bulk strength by using a diallylamine acrylamide copolymer in a size press formulation containing starch
US9920482B2 (en) 2014-10-06 2018-03-20 Ecolab Usa Inc. Method of increasing paper strength
US10889939B2 (en) 2015-12-25 2021-01-12 Ecolab Usa Inc. Sizing method for making paper and paper prepared thereof
EP3449057A4 (fr) * 2016-04-25 2019-09-18 Ecolab USA Inc. Procédés et compositions pour améliorer l'encollage dans un processus de fabrication de papier
US10648133B2 (en) 2016-05-13 2020-05-12 Ecolab Usa Inc. Tissue dust reduction

Also Published As

Publication number Publication date
NO980330L (no) 1998-01-26
NO980330D0 (no) 1998-01-26
AR003054A1 (es) 1998-05-27
AU6597996A (en) 1997-02-26
MX9800482A (es) 1998-04-30
BR9610142A (pt) 1999-02-02
CO4560502A1 (es) 1998-02-10
ZA966342B (en) 1997-02-11
CN1192256A (zh) 1998-09-02
CA2227605A1 (fr) 1997-02-13
EP0840822A1 (fr) 1998-05-13
KR19990035963A (ko) 1999-05-25

Similar Documents

Publication Publication Date Title
EP0840822A1 (fr) Polymeres cationiques synthetiques facilitant le collage de l'anhydride succinique d'alcenyle
MXPA98000482A (en) Synthetic cationic polymers as promoters for apresting with alkenil-succin anhydride
AU2010343125B2 (en) Process to enhancing dry strength of paper by treatment with vinylamine-containing polymers and acrylamide containing polymers
EP0462365B1 (fr) Microbilles chargées en polymères organiques pour la fabrication du papier
KR0159921B1 (ko) 양이온성 및 음이온성 중합체의 혼합물, 그 제법 및 종이용 건조강도 개선 첨가제로서의 용도
US5274055A (en) Charged organic polymer microbeads in paper-making process
US5338406A (en) Dry strength additive for paper
CA2405999C (fr) Procede de traitement d'une charge, charge modifiee au moyen d'un polymere hydrophobe et utilisation dudit polymere
JP2818677B2 (ja) 製紙用保持助剤及び排水助剤
AU2015310752A1 (en) Sizing composition, its use and a method for producing paper, board or the like
EP0151994B1 (fr) Méthode de préparation d'un agent d'encollage et méthode d'encollage de papier
RU2676070C2 (ru) Композиция агрегированного наполнителя и ее получение
KR920006423B1 (ko) 싸이즈 조성물 및 싸이징 방법
KR20010053378A (ko) 페이퍼 사이징용 표면 개질된 충진제
Wang et al. Aminated poly‐N‐vinylformamide as a modern retention aid of alkaline paper sizing with acid rosin sizes
JP2008502771A (ja) Ａｓａサイジングのための促進剤としてのメタクリル酸２−ヒドロキシエチルを含むカチオン性ポリマー
WO2023154840A1 (fr) Gpam à poids moléculaire élevé avec promoteur de polysaccharides anioniques
EP0628658A1 (fr) Composition cellulosique à base de lignine modifiée et d'un polymère cationique et procédé amélioré pour fabriquer du papier ou du carton
EP0414496A1 (fr) Méthode et pâte pour améliorer la rétention des poudres et des agents de remplissage du papier
JPS60246893A (ja) サイズ剤の調製方法
EP0000921A1 (fr) Méthode de préparation d'une matière composite de grande résistance et nappe fibreuse comprenant ladite matière composite séchée
CN118922600A (zh) 含阴离子多糖促进剂的高分子量gpam

Legal Events

Date Code Title Description
WWE Wipo information: entry into national phase

Ref document number: 96195835.9

Country of ref document: CN

AK Designated states

Kind code of ref document: A1

Designated state(s): AL AM AU BB BG BR BY CA CN CZ EE GE HU IS JP KG KP KR KZ LK LR LS LT LV MD MG MK MN MX NO NZ PL RO RU SD SG SI SK TJ TM TT UA UZ VN

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): KE LS MW SD SZ UG AT BE CH DE DK ES FI FR GB GR IE IT LU MC NL PT SE BF BJ CF CG CI CM GA GN ML MR NE SN TD TG

DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
121 Ep: the epo has been informed by wipo that ep was designated in this application
WWE Wipo information: entry into national phase

Ref document number: 1996925482

Country of ref document: EP

WWE Wipo information: entry into national phase

Ref document number: PA/a/1998/000482

Country of ref document: MX

ENP Entry into the national phase

Ref document number: 2227605

Country of ref document: CA

Ref document number: 2227605

Country of ref document: CA

Kind code of ref document: A

WWE Wipo information: entry into national phase

Ref document number: 1019980700624

Country of ref document: KR

WWP Wipo information: published in national office

Ref document number: 1996925482

Country of ref document: EP

WWW Wipo information: withdrawn in national office

Ref document number: 1996925482

Country of ref document: EP

WWP Wipo information: published in national office

Ref document number: 1019980700624

Country of ref document: KR

WWW Wipo information: withdrawn in national office

Ref document number: 1019980700624

Country of ref document: KR