EP0282761B1 - Procédé de fabrication de papier et de carton ayant une résistance élevée à l'état sec - Google Patents

Procédé de fabrication de papier et de carton ayant une résistance élevée à l'état sec Download PDF

Info

Publication number
EP0282761B1
EP0282761B1 EP88102520A EP88102520A EP0282761B1 EP 0282761 B1 EP0282761 B1 EP 0282761B1 EP 88102520 A EP88102520 A EP 88102520A EP 88102520 A EP88102520 A EP 88102520A EP 0282761 B1 EP0282761 B1 EP 0282761B1
Authority
EP
European Patent Office
Prior art keywords
potato starch
dry strength
paper
polymer
weight
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP88102520A
Other languages
German (de)
English (en)
Other versions
EP0282761A1 (fr
Inventor
Hans-Juergen Dr. Degen
Sigberg Dr. Pfohl
Volkmar Dr. Weberndoerfer
Gerd Dr. Rehmer
Michael Dr. Kroener
Andreas Dr. Stange
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
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 BASF SE filed Critical BASF SE
Priority to AT88102520T priority Critical patent/ATE76135T1/de
Publication of EP0282761A1 publication Critical patent/EP0282761A1/fr
Application granted granted Critical
Publication of EP0282761B1 publication Critical patent/EP0282761B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/21—Macromolecular organic compounds of natural origin; Derivatives thereof
    • D21H17/24—Polysaccharides
    • D21H17/28—Starch
    • D21H17/29—Starch cationic
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/33—Synthetic macromolecular compounds
    • D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/41—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups
    • D21H17/44—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups cationic
    • D21H17/45—Nitrogen-containing groups
    • D21H17/455—Nitrogen-containing groups comprising tertiary amine or being at least partially quaternised
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/21—Macromolecular organic compounds of natural origin; Derivatives thereof
    • D21H17/24—Polysaccharides
    • D21H17/28—Starch
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H5/00—Special paper or cardboard not otherwise provided for
    • D21H5/26—Special paper or cardboard manufactured by dry method; Apparatus or processes for forming webs by dry method from mainly short-fibre or particle material, e.g. paper pulp
    • D21H5/265—Treatment of the formed web
    • D21H5/2657—Consolidation
    • D21H5/2664—Addition of a binder, e.g. synthetic resins or water
    • 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
    • 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
    • D21H21/18—Reinforcing agents

Definitions

  • graft copolymers which are obtained by grafting dextran, a naturally occurring polymer with a molecular weight of 20,000 to 50 million, with cationic monomers, e.g. Diallyldimethylammonium chloride, mixtures of diallyldimethylammonium chloride and acrylmid or mixtures of acrylamide and basic methacrylates, such as dimethylaminoethyl methacrylate.
  • cationic monomers e.g. Diallyldimethylammonium chloride, mixtures of diallyldimethylammonium chloride and acrylmid or mixtures of acrylamide and basic methacrylates, such as dimethylaminoethyl methacrylate.
  • the graft polymerization is preferably carried out in the presence of a redox catalyst.
  • a process for cationizing starch is known from US Pat. No. 4,097,427, in which the starch is boiled in an alkaline medium in the presence of water-soluble quaternary ammonium polymers and an oxidizing agent.
  • Quaternary ammonium polymers include quaternized diallyldialkylamine polymers or quaternized polyethyleneimines.
  • the oxidizing agent used is, for example, ammonium persulfate, hydrogen peroxide, sodium hypochlorite, ozone or tert-butyl hydroperoxide.
  • the modified cationic starches which can be prepared in this way are added to the paper stock as dry strength agents in the production of paper. However, the wastewater is polluted by a very high COD value.
  • a process for the production of cationic starch which is used for surface sizing and coating of paper and paper products.
  • an aqueous slurry of oxidized starch is digested together with a cationic polymer in a continuous cooker.
  • Suitable cationic polymers are condensates of epichlorohydrin and dimethylamine, polymers of diallyldimethylammonium chloride, quaternized reaction products of ethylene chloride and ammonia, quaternized polyethyleneimine and quaternized polyepichlorohydrin.
  • the invention has for its object to achieve an improvement in the dry strength of paper when using starch compared to the known methods.
  • the substantivity of the starch is increased when it is drawn onto the fibers in the paper stock, thereby reducing the COD load in the wastewater.
  • the mixtures to be used as dry strength agents according to the invention have good retention towards paper fibers in the paper stock.
  • the COD value in the white water is significantly reduced with the mixtures according to the invention compared to the native starch.
  • the interfering substances contained in the water circuits of paper machines affect the effectiveness of the dry strength agents to be used according to the invention only slightly.
  • the pH of the paper stock suspension can be in the range from 4 to 9, preferably 6 to 8.5.
  • the modified starch to be used according to the invention is produced in the absence of oxidizing agents, polymerization initiators and also in the absence of alkali.
  • the modification of the native potato starch is preferably achieved by heating it in aqueous slurry with the cationic polymers in question to a temperature above the gelatinization temperature of the native potato starch.
  • the gelatinization temperature of the starch is the temperature at which the birefringence of the starch grains is lost, cf. Ullman's Encyclopedia of Technical Chemistry, Urban and Schwarzenberg, Kunststoff-Berlin, 1965, 16th volume, page 322.
  • the modification of the native potato starch can generally be done in various ways.
  • An already digested native potato starch which is in the form of an aqueous solution, can be reacted with the cationic polymers in question to temperatures in the range from 15 to 70 ° C. Longer contact times are required at even lower temperatures. If the reaction is carried out at even higher temperatures, e.g. up to 110 ° C, shorter contact times are required, e.g. 0.1 to 15 min.
  • the simplest way of modifying the native potato starch is to heat an aqueous slurry of the starch in the presence of the cationic polymers in question to a temperature above the gelatinization temperature of the native potato starch.
  • the starch for modification is heated to temperatures in the range from 70 to 110 ° C., the reaction being carried out in pressure-tight apparatus at temperatures above 110 ° C.
  • the starch is always solubilized in the absence of oxidizing agents, initiators and alkali in about 3 minutes to 5 hours, preferably 5 to 30 minutes. Higher temperatures here require a shorter dwell time.
  • aqueous phase of the reaction mixture increases.
  • a 3.5% by weight aqueous solution of the mixture to be used as dry strength agent has viscosities in the range from 50 to 10,000 mPas (measured according to Brookfield at 20 rpm and 20 ° C.).
  • (A) Polymers of diallyldimethylammonium chloride are suitable for the preparation of the dry strength agents to be used according to the invention. Polymers of this type are known. Under Polymers of diallyldimethylammonium chloride should primarily be understood to mean the homopolymers and the copolymers with acrylamide and / or methacrylamide. The copolymerization can be carried out in any monomer ratio.
  • the K value of the homopolymers and copolymers of diallyldimethylammonium chloride is at least 30, preferably 95 to 180.
  • the substituent X ⁇ in the formulas I and II can in principle be any acid residue of an inorganic and an organic acid.
  • the monomers of formula I are obtained by using the free base, i.e. 1-vinyl-2-imidazoline, neutralized with the equivalent amount of an acid.
  • the vinylimidazolines can also be neutralized, for example, with trichloroacetic acid, benzenesulfonic acid or toluenesulfonic acid.
  • quaternized 1-vinyl-2-imidazolines can also be used.
  • quaternizing agents are, for example, C1 to C18 alkyl chlorides or bromides, benzyl chloride, benzyl bromide, epichlorohydrin, dimethyl sulfate and diethyl sulfate. Epichlorohydrin, benzyl chloride, dimethyl sulfate and methyl chloride are preferably used as quaternizing agents.
  • the compounds of the formula I or II are preferably polymerized in an aqueous medium.
  • the copolymers are obtained by using the monomers of the compound of the formulas I and II with acrylamide and / or methacrylamide polymerized.
  • the monomer mixture used in the polymerization contains at least 1% by weight of a monomer of the formula I or II, preferably 10 to 40% by weight.
  • Copolymers of 60 to 85% by weight of acrylamide and / or methacrylamide and 15 to 50% by weight of N-vinylimidazoline or N-vinyl-2-methylimidazoline are particularly suitable for modifying native potato starch.
  • the copolymers can also by copolymerizing other monomers, such as styrene, vinyl acetate, vinyl propionate, N-vinylformamide, C1- to C4-alkyl vinyl ether, N-vinylpyridine, N-vinylpyrrolidone, N-vinylimidazole, acrylic acid esters, methacrylic acid esters, ethylenically unsaturated C3- to C5 -Carboxylic acids, sodium vinyl sulfonate, acrylonitrile, methacrylonitrile, vinyl chloride and vinylidene chloride can be modified in amounts up to 25% by weight.
  • other monomers such as styrene, vinyl acetate, vinyl propionate, N-vinylformamide, C1- to C4-alkyl vinyl ether, N-vinylpyridine, N-vinylpyrrolidone, N-vinylimidazole, acrylic acid esters, methacrylic acid esters
  • polymerization in aqueous solution it is possible, for example, to prepare the homopolymers and copolymers in a water-in-oil emulsion.
  • the monomers can also be polymerized by the reverse suspension polymerization method, in which bead-like polymers are obtained.
  • the polymerization is initiated with the aid of conventional polymerization initiators or by the action of high-energy radiation.
  • Suitable polymerization initiators are, for example, hydrogen peroxide, inorganic and organic peroxides, and hydroperoxides and azo compounds. Mixtures of polymerization initiators can be used as well as so-called redox polymerization initiators, e.g.
  • the polymerization is carried out at temperatures in the range from 0 to 100 ° C., preferably 15 to 80 ° C. It is of course also possible to polymerize at temperatures above 100 ° C., but it is then necessary to carry out the polymerization under pressure. For example, temperatures up to 150 ° C are possible.
  • the reaction time depends on the temperature. The higher the temperature during the polymerization, the shorter the time required for the polymerization.
  • copolymers of compounds of the formula I with acrylamide or methacrylamide are preferably used as cationic polymers of group (c) for economic reasons. These copolymers then contain the compounds of the formula I only in effective amounts, ie in an amount of 1 to 40% by weight.
  • the dry strength agents to be used according to the invention can be used in the production of all known paper, cardboard and cardboard qualities, for example writing paper, printing paper and packaging paper.
  • the papers can be made from a variety of different types of fiber materials, for example from sulfite or sulfate pulp in the bleached or unbleached state, wood pulp, waste paper, thermomechanical material (TMP) and chemothermomechanical material (CTMP).
  • TMP thermomechanical material
  • CTMP chemothermomechanical material
  • the pH of the stock suspension is between 4.0 and 10, preferably between 6.0 and 8.5.
  • the dry strength agents can be used both in the production of base paper for papers with low basis weight (LWC papers) and for cardboard.
  • the basis weight of the papers is between 30 and 200, preferably 35 and 150 g / m2, while it can be up to 600 g / m2 for cardboard.
  • the paper products produced according to the invention have a noticeably improved strength compared to such papers which were produced in the presence of an equal amount of native potato starch, which strength can be quantified, for example, on the basis of the tear length, the burst pressure, the CMT value and the tear resistance.
  • the parts given in the examples are parts by weight, the percentages relate to the weight.
  • the viscosities of the solidifiers were determined in an aqueous solution at a solids concentration of 3.5% by weight and a temperature of 20 ° C. in a Brookfield viscometer at 20 rpm.
  • the sheets were made in a Rapid-Köthen laboratory sheet former.
  • the dry tear length was determined according to DIN 53 112, sheet 1, the dry burst pressure according to Mullen, DIN 53 141, the CMT value according to DIN 53 143 and the tear propagation resistance according to Brecht-Inset according to DIN 53 115.
  • the leaves were tested after 24-hour air conditioning at a temperature of 23 ° C and a relative humidity of 50%.
  • a 3% slurry of native potato starch (gelatinization temperature 90 ° C.) in water is mixed with such an amount of polymer 1 that the resulting mixture contains 10% polymer 1, based on the native potato starch used.
  • the mixture is then heated with stirring to a temperature in the range from 90 to 95 ° C. for 15 minutes and, after cooling to a temperature in the range from 10 to 40 ° C. according to the invention, is used as a dry strength agent for paper by placing it in a stock suspension before Sheet formation admits (viscosity: 656 mPa ⁇ s).
  • a dry strength agent for paper is prepared by reacting a 3% aqueous slurry of native potato starch with polymer 2 instead of polymer 1 used there (viscosity: 870 mPa ⁇ s).
  • a dry strength agent for paper is produced by using polymer 3 instead of polymer 1 described there (viscosity: 950 mPa ⁇ s).
  • a dry hardening agent is prepared by using polymer 4 instead of the polymer used there (viscosity: 398 mPa ⁇ s).
  • a 3% aqueous slurry of native potato starch (gelatinization temperature 90 ° C) is heated with stirring for 15 minutes to a temperature in the range from 90 to 95 ° C, the starch dissolving. After the starch solution has cooled to a temperature of 70 ° C., a 5% aqueous solution of polymer 2 is added, so that the amount of the polymer, based on the native potato starch, is 10%. The mixture is then stirred for a further 10 minutes at a temperature of 70 ° C. and then cooled to room temperature. A dry strength agent for paper is obtained (viscosity: 784 mPa ⁇ s).
  • a dry hardening agent is produced by using polymer 5 instead of the polymer used there (viscosity: 250 mPa ⁇ s).
  • a dry hardening agent is produced by using polymer 6 instead of the polymer used there (viscosity: 150 mPa ⁇ s).
  • a dry hardening agent is produced by using polymer 7 instead of the polymer used there (viscosity: 206 mPa ⁇ s).
  • a dry hardening agent is produced by using polymer 8 instead of the polymer used there (viscosity: 86 mPa ⁇ s).
  • a dry strength agent for paper is produced according to the specification given under hardener 1, but polymer 9 is used instead of the polymer used there (viscosity: 766 mPa ⁇ s).
  • a dry strength agent for paper is made according to the method described in US Pat. No. 4,097,427 in Example 7 using Polymer 3 in an amount of 6.6% based on starch, 5% sodium hydroxide based on starch and ammonium persulfate produced as an oxidizing agent (viscosity: 30 mPa ⁇ s).
  • a dry strength agent for paper is prepared by using polymer 3 instead of polymer 1 described there, in such an amount that the resulting mixture is now only 6.6% polymer instead of 10% 3, based on starch, contains (viscosity: 985 mPa ⁇ s).
  • a dry hardening agent is produced by using native corn starch instead of the native potato starch used there (viscosity: 290 mPa ⁇ s).
  • a dry hardening agent is produced by using native wheat starch instead of the native potato starch used there (viscosity: 220 mPa ⁇ s).
  • Sheets with a weight of 120 g / m2 are produced in a Rapid Köthen sheet former.
  • the paper stock consists of 80% mixed waste paper and 20% bleached beech sulfite pulp, which is ground to 50 ° SR (Schopper-Riegler) and to which the solidifier 1 described above is added in an amount such that the solids content of solidifier 1, based on dry Paper stock, 2.2%.
  • the pH of the stock suspension is adjusted to 7.6.
  • the leaves made from this fabric model are air-conditioned and then the CMT value, the dry burst pressure and the dry tear length are measured using the methods specified above. The results are shown in Table 1.
  • Example 1 is repeated in each case with the exception that the hardeners given in Table 1 are used instead of the hardeners 1 used in Example 1. The results thus obtained are shown in Table 1.
  • Example 1 is repeated without adding a dry strength agent, ie a fabric made from 80% mixed waste paper and 20% bleached beech sulfite pulp, which is ground to 50 ° SR is dewatered in a Rapid-Köthen sheet former, whereby sheets with a basis weight of 120 g / m2 are obtained.
  • a dry strength agent ie a fabric made from 80% mixed waste paper and 20% bleached beech sulfite pulp, which is ground to 50 ° SR is dewatered in a Rapid-Köthen sheet former, whereby sheets with a basis weight of 120 g / m2 are obtained.
  • a dry strength agent ie a fabric made from 80% mixed waste paper and 20% bleached beech sulfite pulp, which is ground to 50 ° SR is dewatered in a Rapid-Köthen sheet former, whereby sheets with a basis weight of 120 g / m2 are obtained.
  • Comparative example 1 is repeated with the exception that 2% native potato starch, based on dry fiber material, is added to the paper stock.
  • the strength values of the paper sheets thus obtained are given in Table 1.
  • Example 1 is repeated with the exception that the strengthening agent described therein is replaced by the same amount of strengthening agent 10.
  • the strength values of sheets thus obtained are given in Table 1.
  • Example 1 is repeated with the exception that the dry strength agent indicated therein is replaced by the same amount of the strength agent 11.
  • the strength values of paper sheets produced in this way are given in Table 2.
  • Example 1 is repeated with the exception that the strengthening agent described therein is replaced by the same amount of strengthening agent 12.
  • the strength values of sheets thus obtained are given in Table 2.
  • Example 1 is repeated with the exceptions that the strengthening agent described therein is replaced by the same amount of strengthening agent 12 and that instead of the paper stock consisting of 80% mixed waste paper and 20% bleached beech sulfite pulp, a paper stock made of 100% unbleached coniferous wood sulfate is used for sheet formation , which is ground to 30 ° SR (Schopper-Riegler), and the sheets formed from it have a basis weight of 100 g / m2.
  • the strength values of these sheets are given in Table 3.
  • Example 1 is repeated with the exceptions that the strengthening agent described therein is replaced by the same amount of strengthening agent 11 and that instead of the paper stock consisting of 80% mixed waste paper and 20% bleached beech sulfite pulp, a paper stock made of 100% unbleached coniferous wood sulfate is used , which is ground to 30 ° SR (Schopper-Riegler), and the sheets formed from it have a basis weight of 100 g / m2.
  • the strength values of these sheets are given in Table 3.
  • Comparative example 1 is repeated with the exception that instead of the paper stock consisting of 80% mixed waste paper and 20% bleached beech sulfite pulp, a paper stock made of 100% unbleached coniferous wood sulfate, which is ground to 30 ° SR (Schopper-Riegler), is used for sheet formation and forms sheets with a basis weight of 100 g / m2.
  • SR Schopper-Riegler
  • Paper with a basis weight of 120 g / m 2 and a width of 68 cm is produced on a test paper machine at a speed of the paper machine of 50 m / min.
  • 80% mixed waste paper and 20% bleached sulfite pulp with a freeness of 50 ° SR are used as paper stock.
  • hardener 1 is added in an amount of 2.2%, based on dry paper stock.
  • the white water has a pH of 7.6.
  • the strength values of the paper thus produced are given in Table 4.
  • Example 12 is repeated with the exception that the same amount of hardener 3 is used.
  • the strength values of the paper so produced are given in Table 4.
  • Example 12 is repeated with the exception that instead of the dry strength agent used there, the hardener 4 is used.
  • the strength values of the paper thus obtained are given in Table 4.
  • Example 12 is repeated with the exception that the solidifying agent 6 is used instead of the dry hardening agent used there.
  • the strength values of the paper thus obtained are given in Table 4.
  • paper with a basis weight of 120 g / m 2 is produced from a paper stock which consists of 80% mixed waste paper and 20% bleached beech sulfite pulp with a freeness of 50 ° SR.
  • the speed of the paper machine is set to 50 m / min, the pH value of the white water is 7.6.
  • the difference to example 12 is that no dry strength agent is used.
  • the strength values of the paper thus obtained are given in Table 4.
  • Comparative Example 7 is repeated with the exception that 2% native potato starch, based on dry fiber, is additionally added to the paper stock described there before dewatering.
  • the strength values of the paper thus obtained are given in Table 4.
  • Comparative example 7 is repeated with the exception that 2% native corn starch, based on dry fiber, is additionally added to the paper stock described there before dewatering.
  • the strength values of the paper thus obtained are given in Table 4.
  • Comparative Example 7 is repeated with the exception that 2% native wheat starch, based on dry fiber, is additionally added to the paper stock described there before dewatering.
  • the strength values of the paper thus obtained are given in Table 4.
  • Example 12 is repeated with the exception that the same amount of hardener 13 is used instead of hardener 1.
  • the strength values of the paper thus obtained are given in Table 4.
  • Example 12 is repeated with the exception that the same amount of hardener 14 is used instead of hardener 1.
  • the strength values of the paper thus obtained are given in Table 4.
  • Table 4 example Solidified No. used CMT value [N] Dry burst pressure [kPa] Dry tear length [m] COD value in white water [mg / l] 12 1 139 163 3381 139 13 3rd 177 151 3151 130 14 4th 130 147 3278 146 15 6 202 161 3488 134 7 - 109 129 2425 129 8th native potato starch 110 118 2823 320 9 native cornstarch 112 105 2672 287 10th native wheat starch 119 117 2652 256 11 13 122 115 2732 185 12 14 117 121 2767 172
  • an LWC paper is produced from the following fabric model: 40% bleached wood pulp, 30% bleached softwood sulfite pulp and 30% bleached birch sulfate pulp with a grinding degree of 35 ° SR. Based on dry fibrous material, 20% china clay and 0.3% of a commercially available cationic polyacrylamide with a K value of 120 are added in the form of a 7% aqueous solution. In addition, 0.5% alum is added so that the water running off the sieve has a pH of 6. Before the dewatering on the paper machine sieve, hardener 1 is added in an amount of 2.2%, based on dry pulp. At a production speed of the paper machine of 60 m / min, paper with a basis weight of 50 g / m 2 is obtained, the strength values of which are given in Table 5.
  • Example 16 is repeated with the exception that the same amount of hardener 2 is used instead of the hardener used there.
  • the dry strength values of the paper thus obtained are given in Table 5.
  • Example 16 is repeated with the exception that instead of the hardener stated there, hardener 4 is now used.
  • An LWC paper is obtained, the dry strength values of which are given in Table 5.
  • Example 16 is repeated, except that LWC paper is made in the absence of a dry strength agent.
  • the strength values of the paper thus obtained are given in Table 5.
  • Example 16 is repeated with the exception that instead of the hardening agent 1 used there, 2% native potato starch, based on dry fiber material, is now used.
  • the strength values of the LWC paper thus obtained are given in Table 5.

Claims (7)

  1. Procédé de fabrication de papier, carte et carton à haute résistance ou solidité à l'état sec, par l'addition d'un agent de renforcement de la résistance ou solidité à l'état sec, constitué d'un mélange de polymères cationiques et d'amidon, à la pâte à papier et égouttage de la pâte à papier sous formation de la feuille, caractérisé en ce que l'on met en oeuvre, à titre d'agent de renforcement de la résistance ou solidité à l'état sec, un mélange de polymères cationiques, qui contiennent, incorporés par polymérisation et à titre d'unités monomériques caractéristiques,
    a) du chlorure de diallyldiméthylammonium,
    b) de la N-vinylamine, ou
    c) des N-vinylimideazolines de la formule
    Figure imgb0017
    dans laquelle
    R¹ = H,alkyle en C₁-C₁₈,
    Figure imgb0018
    R⁵, R⁶ = H, alkyle en C₁-C₁₈, Cl,
    R² = H,alkyle en C₁-C₁₈
    Figure imgb0019
    R³, R⁴ = H, alkyle en C₁-C₄, et
    X⁻ désigne un reste d'acide
    et qui possèdent un valeur K d'au moins 30, ainsi que de la fécule de pomme de terre naturelle qui est convertie en une forme soluble dans l'eau par chauffage dans un milieu aqueux à des températures supérieures à la température de gélification de la fécule de pomme de terre naturelle, en l'absence d'agents d'oxydation, d'amorceurs de polymérisation et d'alcalis, où on chauffe la fécule de pomme de terre naturelle en présence des polymères cationiques, ou bien on la fait réagir avec les polymères cationiques à des températures de 15 à 70°C sous forme de fécule de pomme de terre déjà dégradée.
  2. Procédé suivant la revendication 1, caractérisé en ce que l'on utilise, pour 100 parties en poids de fécule de pomme de terre naturelle, 1 à 20 parties en poids d'un polymère cationique ou d'un mélange de polymères cationiques.
  3. Procédé suivant les revendications 1 et 2, caractérisé en ce qu'à titre d'agent de renforcement de la résistance ou solidité à l'état sec, on utilise un mélange que l'on peut obtenir par le chauffage de la fécule de pomme de terre naturelle en présence d'homopolymères du chlorure de diallyldiméthylamonium, d'une valeur K de 60 à 180.
  4. Procédé suivant les revendications 1 et 2, caractérisé en ce qu'à titre d'agent de renforcement de la résistance ou solidité à l'état sec, on met en oeuvre un mélange que l'on peut obtenir par le chauffage de la fécule de pomme de terre naturelle en présence d'homopolymères du N-vinylformamide hydrolysés, où les radicaux formyle des polymères sont scindés à raison de 70 à 100% molaires , sous formation d'unités N-vinylamine et les polymères hydrolysés possèdent une valeur K de 75 à 170.
  5. Procédé suivant les revendications 1 et 2, caractérisé en ce qu'à titre d'agent de renforcement de la résistance ou solidité à l'état sec, on met en oeuvre un mélange que l'on peut obtenir par le chauffage de la fécule de pomme de terre naturelle en présence de copolymères hydrolysés, constitués de
    a) 95 à 10% molaires de N-vinylformamide et
    b) 5 à 90% molaires d'acétate de vinyle ou de propionate de vinyle,
       où les radicaux formyle du polymère sont scindés à raison de 70 à 100% molaires, sous formation d'unités N-vinylamine et les radicaux acétyle et propionyle sont scindés à raison de 70 à 100% molaires, sous formation d'unités alcool vinylique et les polymères hydrolysés possèdent une valeur K de 70 à 170.
  6. Procédé suivant les revendications 1 et 2, caractérisé en ce qu'à titre d'agent de renforcement de la résistance ou solidité à l'état sec, on met en oeuvre un mélange que l'on peut obtenir par le chauffage de la fécule de pomme de terre naturelle en présence d'homopolymères d'une N-vinylimidazoline éventuellement substitutée, ou d'un copolymère de cette N-vinylimidazoline avec l'acrylamide et/ou le méthacrylamide d'un valeur K de 80 à 220.
  7. Procédé suivant les revendications 1 et 2, caractérisé en ce qu'à titre d'agent de renforcement de la solidité ou résistance à l'état sec, on met en oeuvre un mélange que l'on peut obtenir par le chauffage de la fécule de pomme de terre naturelle en présence de copolymères qui contiennent, incorporés par polymérisation,
    a) 70 à 96,5% en poids d'acrylamide et/ou de méthacrylamide,
    b) 2 à 20% en poids de N-vinylimidazoline ou de N-vinyl-2-méthylimidazoline et
    c) 1,5 à 10% en poids de N-vinylimidazole,
    et qui possèdent un valeur K de 80 à 220.
EP88102520A 1987-02-28 1988-02-20 Procédé de fabrication de papier et de carton ayant une résistance élevée à l'état sec Expired - Lifetime EP0282761B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT88102520T ATE76135T1 (de) 1987-02-28 1988-02-20 Verfahren zur herstellung von papier, pappe und karton mit hoher trockenfestigkeit.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19873706525 DE3706525A1 (de) 1987-02-28 1987-02-28 Verfahren zur herstellung von papier, pappe und karton mit hoher trockenfestigkeit
DE3706525 1987-02-28

Publications (2)

Publication Number Publication Date
EP0282761A1 EP0282761A1 (fr) 1988-09-21
EP0282761B1 true EP0282761B1 (fr) 1992-05-13

Family

ID=6322010

Family Applications (1)

Application Number Title Priority Date Filing Date
EP88102520A Expired - Lifetime EP0282761B1 (fr) 1987-02-28 1988-02-20 Procédé de fabrication de papier et de carton ayant une résistance élevée à l'état sec

Country Status (13)

Country Link
US (1) US4818341A (fr)
EP (1) EP0282761B1 (fr)
JP (1) JP2642384B2 (fr)
KR (1) KR960003188B1 (fr)
AT (1) ATE76135T1 (fr)
AU (1) AU591380B2 (fr)
CA (1) CA1290508C (fr)
DE (2) DE3706525A1 (fr)
DK (1) DK168640B1 (fr)
ES (1) ES2030776T3 (fr)
FI (1) FI89730C (fr)
NO (1) NO171173C (fr)
NZ (1) NZ223534A (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5851300A (en) * 1994-10-29 1998-12-22 Basf Aktiengesellschaft Cationic modification of starch and use of the cationically modified starch
US6746542B1 (en) 1999-04-01 2004-06-08 Basf Aktiengesellschaft Modifying starch with cationic polymers and use of the modified starches as dry-strength agent

Families Citing this family (31)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3724646A1 (de) * 1987-07-25 1989-02-02 Basf Ag Verfahren zur herstellung von papier, pappe und karton mit hoher trockenfestigkeit
DE3909004A1 (de) * 1989-03-18 1990-09-27 Basf Ag Verwendung von nicht hydrolysierten n-vinylformamid-einheiten enthaltenden copolymerisaten bei der papierherstellung
US5349089A (en) * 1989-07-07 1994-09-20 National Starch And Chemical Investment Holding Corporation Reagent for preparing polycationic polysaccharides
US5227481A (en) * 1989-07-07 1993-07-13 National Starch And Chemical Investment Holding Corporation Cationic polysaccharides and reagents for their preparation
DE4007312C2 (de) * 1990-03-08 2000-04-27 Basf Ag Verfahren zur Herstellung von feinteiligen, wasserlöslichen, Vinylamin-Einheiten enthaltenden Polymerisaten
US5122231A (en) * 1990-06-08 1992-06-16 Cargill, Incorporated Cationic cross-linked starch for wet-end use in papermaking
DE4127733A1 (de) * 1991-08-22 1993-02-25 Basf Ag Pfropfpolymerisate aus saccharidstrukturen enthaltenden naturstoffen oder deren derivaten und ethylenisch ungesaettigten verbindungen und ihre verwendung
EP0560265B1 (fr) * 1992-03-09 1998-01-21 Canon Kabushiki Kaisha Papier recyclé pour électrophotographie, et méthode de formation d'image l'utilisant
JP2697996B2 (ja) * 1992-06-17 1998-01-19 日華化学株式会社 染料固着剤
US5382324A (en) * 1993-05-27 1995-01-17 Henkel Corporation Method for enhancing paper strength
IT1271003B (it) * 1994-09-08 1997-05-26 Ausimont Spa Processo per la produzione di carta e cartone ad elevata resistenza meccanica
US5572825A (en) * 1995-01-24 1996-11-12 Woodstream Corporation Glue trap
US20030192664A1 (en) * 1995-01-30 2003-10-16 Kulick Russell J. Use of vinylamine polymers with ionic, organic, cross-linked polymeric microbeads in paper-making
US5591799A (en) * 1995-03-03 1997-01-07 Air Products And Chemicals, Inc. Aqueous emulsion materials containing copolymerized vinyl amide monomers and hydrolysis products thereof
DE19701524A1 (de) * 1997-01-17 1998-07-23 Basf Ag Polymermodifizierte Stärke, Verfahren zu ihrer Herstellung und ihre Verwendung
DE19701523A1 (de) * 1997-01-17 1998-07-23 Basf Ag Polymermodifizierte anionische Stärke, Verfahren zu ihrer Herstellung und ihre Verwendung
DE19713755A1 (de) * 1997-04-04 1998-10-08 Basf Ag Verfahren zur Herstellung von Papier, Pappe und Karton mit hoher Trockenfestigkeit
US6165322A (en) 1997-07-29 2000-12-26 Hercules Incorporated Polyamidoamine/epichlorohydrin resins bearing polyol sidechains as dry strength agents
US20040226675A1 (en) * 2000-01-11 2004-11-18 Raisio Chemicals Ltd. Method for improving printability and coatability of paper and board
US6485609B1 (en) 2001-03-08 2002-11-26 Celanese International Corporation Ink jet printing paper incorporating amine functional poly(vinyl alcohol)
US7214633B2 (en) * 2001-12-18 2007-05-08 Kimberly-Clark Worldwide, Inc. Polyvinylamine treatments to improve dyeing of cellulosic materials
US6824650B2 (en) * 2001-12-18 2004-11-30 Kimberly-Clark Worldwide, Inc. Fibrous materials treated with a polyvinylamine polymer
DE10233524B4 (de) * 2002-07-23 2006-02-09 Mühle Rüningen GmbH & Co. KG Mittel zur Erhöhung der Aufnahmefähigkeit von Papiermasse für Stärke, Verfahren zur Herstellung, Verwendung sowie Verfahren zur Herstellung von Papier
US7090745B2 (en) * 2002-09-13 2006-08-15 University Of Pittsburgh Method for increasing the strength of a cellulosic product
US7494566B2 (en) * 2002-09-13 2009-02-24 University Of Pittsburgh - Of The Commonwealth System Of Higher Education Composition for increasing cellulosic product strength and method of increasing cellulosic product strength
US20050109476A1 (en) * 2003-07-21 2005-05-26 Muhle Runingen Gmbh & Co. Kg Medium for increasing the absorption capacity of paper pulp for starch
WO2005085361A2 (fr) * 2004-02-27 2005-09-15 University Of Pittsburgh Gels polymeres en reseau et leur utilisation pour recuperer des hydrocarbures
US20060016569A1 (en) * 2004-07-20 2006-01-26 Sonoco Development, Inc. High strength paperboard and method of making same
CA2813996C (fr) * 2010-11-05 2015-01-27 Hercules Incorporated Application en surface de polymeres pour ameliorer la resistance du papier
WO2013026578A1 (fr) 2011-08-25 2013-02-28 Ashland Licensing And Intellectual Property Llc Procédé permettant d'accroître les avantages apportés par des adjuvants d'augmentation de la résistance dans la production de papier et de carton
US11846074B2 (en) 2019-05-03 2023-12-19 First Quality Tissue, Llc Absorbent structures with high strength and low MD stretch

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1347071A (en) * 1971-07-01 1974-02-13 Starch Products Ltd Paper fillers
US4097427A (en) * 1977-02-14 1978-06-27 Nalco Chemical Company Cationization of starch utilizing alkali metal hydroxide, cationic water-soluble polymer and oxidant for improved wet end strength
US4146515A (en) * 1977-09-12 1979-03-27 Nalco Chemical Company Making a lightly oxidized starch additive by adding a cationic polymer to starch slurry prior to heating the slurry
DE2821830A1 (de) * 1978-05-19 1979-11-22 Basf Ag Verfahren zur oberflaechenleimung von papier

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5851300A (en) * 1994-10-29 1998-12-22 Basf Aktiengesellschaft Cationic modification of starch and use of the cationically modified starch
EP0788516B2 (fr) † 1994-10-29 2002-10-30 Basf Aktiengesellschaft Procede de modification cationique d'amidon et utilisation d'amidon cationiquement modifie
US6746542B1 (en) 1999-04-01 2004-06-08 Basf Aktiengesellschaft Modifying starch with cationic polymers and use of the modified starches as dry-strength agent

Also Published As

Publication number Publication date
NZ223534A (en) 1989-10-27
US4818341A (en) 1989-04-04
KR880010192A (ko) 1988-10-07
ATE76135T1 (de) 1992-05-15
JPS63227895A (ja) 1988-09-22
JP2642384B2 (ja) 1997-08-20
DE3870941D1 (de) 1992-06-17
AU591380B2 (en) 1989-11-30
ES2030776T3 (es) 1992-11-16
FI880836A (fi) 1988-08-29
NO880856D0 (no) 1988-02-26
AU1234388A (en) 1988-09-01
NO171173C (no) 1993-02-03
DK101788A (da) 1988-08-29
CA1290508C (fr) 1991-10-15
DK168640B1 (da) 1994-05-09
KR960003188B1 (ko) 1996-03-06
NO171173B (no) 1992-10-26
NO880856L (no) 1988-08-29
EP0282761A1 (fr) 1988-09-21
DK101788D0 (da) 1988-02-26
FI89730C (fi) 1993-11-10
FI89730B (fi) 1993-07-30
DE3706525A1 (de) 1988-09-08
FI880836A0 (fi) 1988-02-23

Similar Documents

Publication Publication Date Title
EP0282761B1 (fr) Procédé de fabrication de papier et de carton ayant une résistance élevée à l'état sec
EP0301372B1 (fr) Procédé de fabrication de papier et de carton ayant une résistance élevée à l'état sec
EP0972110B1 (fr) Procede pour produire du papier, du carton-pate et du carton a haute resistance a la traction a l'etat sec
EP2443284B1 (fr) Procédé de fabrication pour augmenter la résistance à sec de papier et de carton présentant
EP0416427B1 (fr) Produit d'encollage neutre pour masses de papier brut utilisant des dispersions polymères cationiques
EP1819877B1 (fr) Procede pour produire du papier, du carton, du carton blanchi presentant une resistance elevee a sec
EP0952988B1 (fr) Amidon anionique modifie avec un polymere, son procede de production et son utilisation
EP0788516B1 (fr) Procede de modification cationique d'amidon et utilisation d'amidon cationiquement modifie
DE60016186T2 (de) Polymerdispersion und verfahren zu deren herstellung
EP0418343B1 (fr) Procede de fabrication de papier, de carton-pate et de carton en presence de copolymeres contenant des unites de n-vinylformamide
DE3730887A1 (de) Verfahren zur verbesserung der bedruckbarkeit von papier
DE2263089C3 (de) Papier mit einem Gehalt an einem Copolymeren mit Acrylamid- und N-(DialkylaminomethyOacrylamideinheiten sowie Verfahren zu seiner Herstellung
EP2393982A1 (fr) Procédé de fabrication de papier, de carton-pâte et de carton présentant une grande résistance à sec
EP2443282A1 (fr) Procédé de réduction de dépôts dans la partie sèche lors de la fabrication de papier et carton
EP0951505B1 (fr) Amidon modifie avec un polymere, son procede de production et son utilisation
DE2335330A1 (de) Polymerisate, die n-(alkylamino)- und/ oder n-(alkylammonium)-acrylamide als retentionshilfen und entwaesserungshilfsmittel bei der papierherstellung enthalten
EP0146000B1 (fr) Procédé de fabrication de papier et carton à résistance élevée à l'état sec ou humide et vis-à-vis des lessives
DE1264942B (fr)
DE3719480A1 (de) Verfahren zur herstellung von papier, pappe und karton mit hoher trockenfestigkeit
DE1617204C (de) Harzleimmassen und Verfahren zu deren Herstellung
WO2006136556A2 (fr) Procede de fabrication de papier et de carton
CH496079A (de) Harzleimmasse, Verfahren zu deren Herstellung und deren Verwendung
DE3613651A1 (de) Verfahren zur herstellung von papier mit hoher trockenfestigkeit
DE1546245A1 (de) Zellulosefaserprodukt und Verfahren zu dessen Herstellung
DE2548393A1 (de) Leimungsmittel fuer papier

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE CH DE ES FR GB IT LI NL SE

17P Request for examination filed

Effective date: 19880802

17Q First examination report despatched

Effective date: 19910207

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE CH DE ES FR GB IT LI NL SE

REF Corresponds to:

Ref document number: 76135

Country of ref document: AT

Date of ref document: 19920515

Kind code of ref document: T

ITF It: translation for a ep patent filed

Owner name: ING. C. GREGORJ S.P.A.

REF Corresponds to:

Ref document number: 3870941

Country of ref document: DE

Date of ref document: 19920617

GBT Gb: translation of ep patent filed (gb section 77(6)(a)/1977)
ET Fr: translation filed
REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2030776

Country of ref document: ES

Kind code of ref document: T3

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed
EAL Se: european patent in force in sweden

Ref document number: 88102520.9

REG Reference to a national code

Ref country code: GB

Ref legal event code: IF02

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 20060205

Year of fee payment: 19

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: SE

Payment date: 20060207

Year of fee payment: 19

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: AT

Payment date: 20060213

Year of fee payment: 19

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20060215

Year of fee payment: 19

Ref country code: CH

Payment date: 20060215

Year of fee payment: 19

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20060216

Year of fee payment: 19

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20060220

Year of fee payment: 19

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: IT

Payment date: 20060228

Year of fee payment: 19

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: ES

Payment date: 20060317

Year of fee payment: 19

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BE

Payment date: 20060410

Year of fee payment: 19

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20070221

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20070228

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20070228

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

EUG Se: european patent has lapsed
GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20070220

NLV4 Nl: lapsed or anulled due to non-payment of the annual fee

Effective date: 20070901

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20070220

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

Effective date: 20071030

BERE Be: lapsed

Owner name: *BASF A.G.

Effective date: 20070228

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20070228

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20070901

Ref country code: NL

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20070901

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20070220

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20070228

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20070221

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20070221

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20070220