EP0470871B1 - Papierhilfsmittel und seine Verwendung - Google Patents

Papierhilfsmittel und seine Verwendung Download PDF

Info

Publication number
EP0470871B1
EP0470871B1 EP91307417A EP91307417A EP0470871B1 EP 0470871 B1 EP0470871 B1 EP 0470871B1 EP 91307417 A EP91307417 A EP 91307417A EP 91307417 A EP91307417 A EP 91307417A EP 0470871 B1 EP0470871 B1 EP 0470871B1
Authority
EP
European Patent Office
Prior art keywords
paper
mixture
oligomers
molecular weight
water
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
EP91307417A
Other languages
English (en)
French (fr)
Other versions
EP0470871A1 (de
Inventor
Chokyun Rha
Maritta Timonen
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.)
Alko Oy AB
Original Assignee
Alko Oy AB
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 Alko Oy AB filed Critical Alko Oy AB
Publication of EP0470871A1 publication Critical patent/EP0470871A1/de
Application granted granted Critical
Publication of EP0470871B1 publication Critical patent/EP0470871B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

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
    • D21H5/00—Special paper or cardboard not otherwise provided for
    • D21H5/12—Special paper or cardboard not otherwise provided for characterised by the use of special fibrous materials
    • D21H5/14—Special paper or cardboard not otherwise provided for characterised by the use of special fibrous materials of cellulose fibres only
    • D21H5/141—Special paper or cardboard not otherwise provided for characterised by the use of special fibrous materials of cellulose fibres only of fibrous cellulose derivatives
    • 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
    • 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
    • D21H17/005—Microorganisms or enzymes
    • 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

Definitions

  • This invention pertains to the field of paper pulp making and their chemistry.
  • the kraft or sulfate process is probably the most extensively employed method to produce strong cellulose fibers.
  • the active ingredients in pulping wood to its fibrous state are sodium hydroxide and sodium sulfide, in a strong alkaline solution.
  • the process generates objectionable smells from the sodium sulfide produced during the process.
  • Kraft pulps are dark in color, difficult to bleach and very strong.
  • cellulose fibers obtained from the pulping process are generally unsuited for paper making and must first be refined. With given pulps, final paper properties are largely controlled by the type and extent of refining action employed.
  • a variety of additive materials can be introduced to the paper-making pulps, commonly called “furnish", during stock preparation. Fillers such as clays, or calcium carbonate are used for the control of sheet opacity and for other reasons. Dyes are used extensively for color control and other additives such as wet-strength agents, and defoamers are used as needed.
  • off-machine converting operations designed to increase the strength and/or other physical properties of paper take place subsequent to the paper making operation and are called "off-machine converting".
  • These converting operations are highly complex and include embossing, coating, waxing, laminating, impregnating, saturating, corrugating, and printing.
  • food packaging has led to extensive paper utilization with the paper often being coated, waxed, resin-impregnated, or combined with other foils and films.
  • a relatively simple and inexpensive method of improving the paper making process and increasing the stiffness and ultimate strength of paper is needed.
  • EP-A-0301372 describes the use of enzymatically degraded starch having a viscosity of 20 to 2000 mPa.s (as a 7.5% aqueous solution at 45°C) with a cationic polymer of specified type in paper making to improve dry strength.
  • DE-A-2636951 describes the use of amylases to break down starch and starch derivatives to be used in paper making.
  • the present invention provides a method of stengthening paper which comprises incorporating into said paper during or after its manufacture a mixture of water-soluble or water dispersible oligomers derived by enzymatic degradation of a cellulose derivative, a majority of said oligomers having a degree of polymerization and molecular weight such that the oligomer conforms to a rod-like configuration and an average degree of polymerization in the range of about 5 to about 100.
  • the invention also provides a method of enhancing the dewatering properties of paper pulp by treating the pulp with a mixture of water-soluble or water-dispersible oligomers as aforesaid.
  • the water soluble or water dispersable oligomers used in the invention have an average degree of polymerization in the range of about 5 to about 100, preferably 5 to 50.
  • the cellulose derivative is degraded by enzymatic mechanisms, typically using a polysaccharide degrading enzyme.
  • a polymer or an initially degraded polysaccharide derivative mixture may be further separated into fractions of polymers of differing average chain lengths, e.g. using chromatographic techniques.
  • the viscosity of the various fractions will vary with the degree of average chain length of the polymers contained within a fraction.
  • one or more fractions are selected from an initial polymeric mixture having a viscosity (average chain length) which is most appropriate for the particular application.
  • the method of strengthening paper of the invention comprises treating the paper with a water soluble or water dispersable mixture of relatively low molecular weight polymers obtained by enzymatically degrading a cellulose derivative.
  • the method of enhancing the dewatering properties of paper pulp of the invention comprises treating the pulp with a water soluble or water dispersable mixture of relatively low molecular weight polymers obtained by enzymatically degrading a cellulose derivative.
  • Figure 1 is a force-distance curve of Whatman No. 1 filter paper treated with carboxymethyl cellulose hydrolyzate.
  • Figure 2 is a force-distance curve of Whatman No. 1 filter paper dipped in distilled water.
  • Figure 3 is a force-distance curve of untreated Whatman No. 1 filter paper.
  • Figure 4 shows results of drainage tests on furnish treated with carboxymethyl cellulose (CMC) hydrolyzate ( ⁇ ), carboxymethyl cellulose ( ⁇ ), carboxymethyl starch (CM starch) hydrolyzate ( ⁇ ), carboxymethyl starch (CM starch) ( ⁇ ), and untreated furnish ( ⁇ ).
  • CMC carboxymethyl cellulose
  • Figure 5 shows results of drainage tests on furnish/calcium carbonate mixtures treated with carboxymethyl cellulose (CMC) hydrolyzate ( ⁇ ), carboxymethyl cellulose ( ⁇ ), carboxymethyl starch (CM starch) hydrolyzate ( ⁇ ), and carboxymethyl starch (CM starch) ( ⁇ ).
  • CMC carboxymethyl cellulose
  • CM starch carboxymethyl starch
  • CM starch carboxymethyl starch
  • This invention describes paper materials treated with the degradation product of a cellulose derivative and methods therefor.
  • Cellulose is made up of glucose monomers and is the major structural component of plants.
  • the term "derivative” is meant to define cellulose that is substituted.
  • the cellulose starting material has a degree of derivatization or substitution of between about 0.1 and about 3.0.
  • “Degree of substitution” refers to the number of derivative groups (e.g. carboxymethyl, hydroxypropyl) per monomer unit in the cellulose backbone.
  • a degree of substitution of 0.2 means, for example that there is about one derivative substitutent for every five monomer units in the cellulose backbone.
  • a degree of substitution of three would mean there are three derivative substituents per every monomer unit in a cellulose chain.
  • Typical substituents comprise one or more of sulfate, carboxylic acid, carboxylic ester, pyruvic acid, carboxymethyl, hydroxpropyl, methyl, methylethyl, hydroxyethyl, hydroxethylmethyl and the like.
  • Cellulose derivatives are commercially available. Such exemplary products as methylcellulose (MC, Methocel MC, 64630, Fluka Chemie AG, CH-9470 Buchs, Switzerland), hydroxypropylmethylcellulose (HPMC, H-9262, Sigma Chem. Co., St Louis, MO) and carboxymethyl cellulose (CMC 7MFD, Blanose, Hercules Chem. Co., 92507 Rueil-Malmaison Ceder, France) all have a degree of substitution between 0.1 and 3. Hydroxpropyl celluloses are also commercially available and suitable for use.
  • MC Methocel MC, 64630, Fluka Chemie AG, CH-9470 Buchs, Switzerland
  • HPMC hydroxypropylmethylcellulose
  • HPMC hydroxypropylmethylcellulose
  • CMC 7MFD carboxymethyl cellulose
  • Hydroxpropyl celluloses are also commercially available and suitable for use.
  • such cellulose derivatives may be degraded to polymeric mixtures of average degree of polymerization (DP) between about 5 and about 100 by enzymatic means.
  • the polymeric mixtures are generally referred to as a "hydrolyzate".
  • the term "degraded” refers to the procedure whereby cellulose derivatives are broken down into smaller polymeric units.
  • Exemplary enzymes for use in degrading certain of the above described cellulose derivatives are various cellulases. They can be produced from a multitude of different microorganisums such as strains of Trichoderma , Aspergillus , Penicillium , etc. A selected microorganism strain is grown by conventional means in a suitable medium such that the cellulases are produced, the microorganism is separated from the medium, the medium is collected and typically concentrated and dried.
  • Cellulase preparations suitable for use herein are, e.g. the commercially available cellulase preparations designated as the Econase series as produced by Alko Ltd. Helsinki, Finland.
  • the method comprises preparing a polymeric mixture of substituted cellulose having an average degree of polymerization (DP) in the range of 5-100. Next, the mixture is then contacted with paper for a period of time sufficient to treat the paper with the polymer mixture.
  • DP average degree of polymerization
  • This invention relates more specifically to a paper or paper product treated with water soluble or dispersable mixture of polymers derived from a cellulose derivative.
  • the polymeric mixtures are characterized by having an average degree of polymerization (DP) in the range of about 5 to 100.
  • paper and pulp products are intended to include a variety of products made from cellulose, synthetic or other fibers, such products being recognised by those skilled in the art as paper, boards, construction paper.
  • these terms refer to articles prepared from cellulose, synthetic, or other fibers or filamentous materials such as those used in the textile industry. Specific examples include felted or matted sheets of cellulose fibers, formed on a fine wire screen from a dilute water suspension, and bonded together as the water is removed and the sheet is dried. These terms may also include sheet materials produced from other types of fibers, particularly mineral or synthetic fibers, formed and bonded by other means.
  • pulped fibers commonly called “furnish”
  • various materials such as fillers (clays, calcium carbonate), dyes, wet-strength agents and the like during the typical paper-making process.
  • Methods of paper manufacture include the basic steps of pulping fibers, refining the pulp by addition of various materials, as described below, forming the paper on mesh screens, and drying the matted fibers.
  • the polymer mixtures can be applied after the paper is made, in the so-called "off-machine converting" procedures.
  • the mixtures can be applied using methods well known in the art such as dipping, spraying, and rolling.
  • the cellulose derivative mixture thus prepared coats the surface of the paper and becomes fixed thereon by attraction between the cellulose derivative mixture and the polysaccharide components of the paper including by physical forces such as hydrogen bonding, Van der Waals forces and the like.
  • the low molecular weight polymers of the invention are aligned along the cellulose, or other fibers. As a result, the intermolecular attraction per unit length increases, facilitating the quality of the final product and improving the processability of the paper or pulp product.
  • the polymeric mixtures can also be incorporated into the paper furnish during pulp defining procedures.
  • the mixture of degraded cellulose derivatives can be incorporated into the pulp furnish along with other dyes, colorants, wet-strength agents (agents capable of increasing the strength of wet or suspended materials), defoamers, and the like. In this procedure, the cellulose derivatives will become impregnated into the matrix of the paper fibers.
  • treated or “treatment” are intended to include means or methods for contacting paper products with the polymeric mixtures so that at least one effect of such contact is to strengthen the paper, coat or impregnate the paper, improve the paper or pulp handling properties during manufacture, and/or increase the dewatering capacity of the paper pulp.
  • methods of treatment include the two methods of introducing the cellulose derivatives of the invention to the paper or paper products described above.
  • Paper produced according to the method of this invention may be stronger than non-treated paper. Moreover, treated paper may less water spreading than untreated paper. Furnish treated with the polymers of the invention show an increased rate of dewatering during the early stages of draining.
  • Cellulose derivative hydrolyzates may be prepared from soluble cellulose derivatives as discussed above by an enzymatic hydrolysis utilizing a cellulase preparation having endo -1, 4- beta -glucanase as the sole active hydrolytic agent.
  • the average degree of polymerization (DP) of the polymers formed by such a hydrolysis is less than about 100, and thus the viscosity of solutions of the hydrolyzate is reduced significantly compared to the viscosity of solutions of the unhydrolysed cellulose derivatives.
  • the specific conditions suitable for and the specific time sufficient to secure the desired hydrolysis may be readily determined for each selected cellulose derivative and each selected enzyme preparation.
  • methylcellulose (MC, Methocel MC, 64630, Fluka Chemie AG, CH-9470 Buchs, Switzerland) was mixed in 3 l of water and the pH of the solution was adjusted to 5.5 with 15% phosphoric acid and the temperature was raised to 40°C.
  • the hydrolyzate product contained less than 0.5% by weight of glucose and cellobiose.
  • hydroxypropylmethylcellulose (HPMC, H-9262, Sigma Chemical Company, St. Louis, MO, U.S.A.) was mixed in 1 l of water and the pH of the solution was adjusted to 5.5 with 15% phosphoric acid and the temperature was raised to 40° C. 0.24 ml of the enzyme preparation having a total endo-1, 4 beta-glucanase activity of 1340 nkat from which the beta-glucosidase activity was removed chromatographically (as described above) was added to the solution. After two hours another 20g of hydroxypropylmethylcellulose was added to the solution. After the hydrolysis of 22 hours the enzyme was inactivated by heating (90°C, 15 min.). Finally the hydrolyzate solution was cooled and freeze-dried.
  • the product contained less than 0.05% by weight of glucose and cellobiose.
  • CMC 7MFD-type a cellulose gum, also designated by the tradename Blanose and available from Hercules Chemical Company, 92507, Rueil-Malmaison Cede, France; 7MFD designates a medium viscosity, food grade carboxymethylcellulose having 7 out of 10 glucose units substituted with carboxymethyl
  • 7MFD designates a medium viscosity, food grade carboxymethylcellulose having 7 out of 10 glucose units substituted with carboxymethyl
  • the product contained less than 2% by weight of glucose and cellobiose.
  • the amount of produced glucose and cellobiose was above 5% by weight.
  • the enzyme preparations selected were commercially available Cellulase AP 3 (Amano Pharmaceutical Co., Ltd., Nagoya, Japan) produced using an Aspergillus strain and Cellulase CP (Sturge Enzymes, North Yorkshire, England) produced using a Penicillium strain.
  • Carboxymethylcellulose hydrolyzates were prepared as described in Example c(i), except that 30g of CMC-7MFD was used in 1 l of water, and the amounts of enzymes added were 0.028 g of Cellulase AP 3 (having a total endo -1, 4 beta -glucanase activity of 1350 nkat) and 0.048 g of Cellulase CP (having a total endo -1, 4 beta -glucanase activity of 1350 nkat).
  • the viscosities and molecular weight distributions of the hydrolyzates produced by either cellulase were similar to the hydrolyzate produced with enzymes derived from Trichoderma reesei .
  • the hydrolyzate of n cellulose derivative has a substantially lower viscosity than an equal amount by weight in aqueous solution of the cellulose derivative itself.
  • CMC hydrolyzates used in present invention have the average degree of polymerization in the range of 5 to 100, based on the viscosity average molecular weight.
  • the viscosity average molecular weights of the CMC hydrolyzates were calculated using the Mark-Houwink equation: where [ ⁇ ] is intrinsic viscosity, Mv is the viscosity average molecular weight of the polymer and K and a are hydrodynamic constants characteristic of the particular polymer-solvent system.
  • the CMC hydrolysates have the viscosity value in the range of from 5 to 100 mPa.s, when measured in 20% (by weight) solution at 25°C with shear rate 584 ⁇ 1 using a Haake Viscotester, VI 500 with sensor system NV (Karlsruhe, Federal Republic of Germany).
  • the Mark-Houwink exponent, a is indicative of the conformation of the polymer chain in solution.
  • the conformation of the polymer chain in solution may be classified as an 1) impermeable dense sphere, 2) random coil, e.g. semi-permeable or free draining, and 3) rodlet or rod-like.
  • Mark-Houwink exponents of 0.002 to about 0.5 correspond to dense spheres
  • exponents of about 0.5 to about 0.8 correspond to semi-permeable random coils
  • exponents of 0.8 to about 1.2 correspond to free draining random coils
  • exponents of about 1.2 to about 2 correspond to rodlets or rod-like oligomers or polymers.
  • the degradation product of the polysaccharide derivative comprises a mixture of oligomers of the polysaccharide having a Mark-Houwink exponent of at least 1.5 at an NaCl concentration of about 0.005N to about 0.5N.
  • This NaCL concentration range is typically used when measuring Mark-Houwink exponents.
  • the salt content of foodstuffs may also typically fall into this range.
  • CMC raw material (Mw>15,000 Daltons) has Mark-Houwink exponents of 0.83-0.97, indicating a free draining random coil conformation.
  • polymer coils are confined by the intra-chain interactions; therefore less change is seen in the Mark-Houwink exponent within the same range of ionic strength.
  • the weight average molecular weight is less than 15,000 Daltons, the CMC chain is not sufficiently long to form a winding coil, the polymer chain is no longer subjected to the constraint of intra-chain interactions, and a chain of free strip or rod-like configuration may form.
  • the electrostatic repulsion force becomes dominant due to the negative charge of the carboxymethyl groups, and the polymer assumes its most stiff rod-like conformation with the highest value of the Mark-Houwink exponents.
  • the negative charge of carboxymethyl groups is shielded, the repulsion forces between the neighbouring groups are reduced, and the polymer chains relax, yielding a lower Mark-Houwink exponent.
  • the experimentally determined data show that the molecular weight and chain conformational characteristics of the most preferred cellulose derivative oligomeric mixtures used in the invention, i.e. mixtures comprising a significant or substantial portion of oligomers of rod-like conformation, are distinctly different from those of undegraded cellulose derivatives.
  • M w weight average molecular weights
  • the most preferred oligomeric mixtures according to the invention have a relatively narrow range of molecular weights, i.e. relatively monodispersed, having a polydispersity index (M w /M n , weight average molecular weight divided by number average molecular weight) of less than about 2.0 and typically less than about 1.8.
  • M w /M n polydispersity index
  • the weight average molecular weights and number average molecular weights of a variety of CMC hydrolysate samples of different degree of hydrolysis were measured and the polydispersity index of all such hydrolysates was calculated as ranging between about 1.1 and about 1.9.
  • the oligomers in a most preferred mixture of oligomers extend over a relatively narrow range of M w and, even as to mixtures having an average molecular weight at or near the upper limit of M W where the oligomers may begin to assume a random coil configuration, are comprised of a significant portion, preferably a majority, of oligomers having a rod-like configuration.
  • CMC solutions were prepared in 0.2N NaCl solution at pH of 7.
  • the solutions were passed through an HPLC column, and the light intensity was detected by multiangle laser light scattering using a Wyatt Technology, multiangle laser light scattering instrument, model DAWN-F.
  • the flow rate was 0.2 ml/min.
  • the concentrations of the solutions were detected by refractometer, and the sensitivity of the refractometer was 64.
  • the weight average molecular weights, M w were determined using appropriate computer software.
  • Example 3 Treatment of Paper with Polymers derived from Carboxymethyl cellulose (CMC)
  • FIGS. 1, 2, 3 for hydrolyzate-treated water-treated, and untreated papers, respectively.
  • the resultant values of the maximum tensile strength before rupturing of treated paper showed a 2 to 3 fold increase over untreated or water treated papers when the paper was treated with the hydrolyzate.
  • the strain limit and modulus increased by dipping paper in hydrolyzate (Table 3). Dipping paper in water alone decreased the mechanical strength and increased the strain limit (Table 3).
  • Polysaccharide derivatives or their hydrolyzates were prepared and dissolved in water. After stirring for 10 minutes, the solution was added to furnish. The final mixture contained furnish (0.106% w/v solid) and 0.0053% (w/v) polysaccharide derivatives or their hydrolyzates. The mixture was mixed for 10 minutes and poured on basement paper which serves as a screen. The amount of water drained was recorded for the determination of dewatering rate and final water content was measured. The furnish was dried in the oven and used in the tensile strength test.
  • this experiment shows that cellulose derivatives and their hydrolyzate increase the rate of dewatering in the early stage of drainage.
  • the cellulose derivative hydrolyzates of the invention significantly improve the mechanical properties of the pulp product.
  • Polysaccharides or their hydrolyzates were prepared and dissolved in a warm water (80°C, CM starch and its hydrolyzate) or room temperature water (CMC and its hydrolyzate). After stirring for 10 minutes, the solution was mixed with Ca(CO3)2 solution. After stirring for 10 minutes, the mixture was added to furnish. The mixture contained furnish with 0.106% (w/v) solid, 0.106% (w/v) Ca(CO3)2, and 0.00575% (w/v) polysaccharides or their hydrolyzates. The test for dewatering was repeated. The draining rates were faster in those mixtures containing hydrolyzate than those of high molecular weight polysaccharides (Figure 5).

Landscapes

  • Life Sciences & Earth Sciences (AREA)
  • Microbiology (AREA)
  • Paper (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
  • Pens And Brushes (AREA)
  • Polysaccharides And Polysaccharide Derivatives (AREA)

Claims (13)

  1. Verfahren des Verstärkens von Papier mit:
    Einbringen in das Papier während oder nach seiner Herstellung einer Mischung von wasserlöslichen oder wasserdispergierbaren Oligomeren, die durch enzymatischen Abbau eines Cellulosederivates erhalten werden,
    wobei eine Mehrheit der Oligomere einen Polymerisationsgrad und ein Molekulargewicht derart aufweisen, daß das Oligomer einer stäbchenartigen Konfiguration und einem mittleren Polymerisationsgrad in dem Bereich von ungefähr 5 bis ungefähr 100 entspricht.
  2. Verfahren nach Anspruch 1, bei dem die Mischung von Oligomeren einen mittleren Polymerisationsgrad in dem Bereich von ungefähr 5 bis 50 aufweist.
  3. Verfahren nach Anspruch 1, bei dem die Mischung von Oligomeren ein mittleres Molekulargewicht von weniger als ungefähr 15000 Dalton aufweist.
  4. Verfahren nach einem der Ansprüche 1 bis 3, bei dem die Mischung von Oligomeren eine Molekulargewichtsverteilung derart aufweist, daß sein Polydispersieindex geringer als 2 ist und die Mischung weniger als 25 Gewichtsprozent von Mono- und Disacchariden enthält.
  5. Verfahren nach einem der Ansprüche 1 bis 4, bei dem das Cellulosederivat durch Carboxymethyl, Methyl, Hydroxypropyl, Methylethyl, Hydroxyethyl, Hydroxymethylethyl, Hydroxypropylmethyl, Sulfat, Carbonsäure, Carbonsäureester oder Pyruvat substituiert ist.
  6. Verfahren nach einem der Ansprüche 1 bis 5, bei dem ein oder mehr Farbstoff, Färbemittel, Naßverstärkungsmittel und Entschäumer ebenfalls in das Papier eingebracht werden.
  7. Verfahren nach einem der Ansprüche 1 bis 6, bei dem die Mischung von Oligomeren durch Beschichten des Papieres durch Eintauchen, Sprühen oder Rollen oder durch Einschließen der Mischung in den Eintrag eingebracht wird.
  8. Verfahren des Vergrößerns der Entwässerungseigenschaften von Papierzellstoff, mit Behandeln des Zellstoffes mit einer Mischung aus wasserlöslichen oder wasserdispergierbaren Oligomeren, die durch enzymatischen Abbau eines Cellulosederivates erhalten werden, wobei eine Mehrheit der Oligomere einen Polymerisationsgrad und ein Molekulargewicht derart aufweisen, daß die Oligomere einer stäbchenartigen Konfiguration und einem mittleren Polymerisationsgrad in dem Bereich von ungefähr 5 bis ungefähr 100 entspricht.
  9. Verfahren nach Anspruch 8, bei dem die Mischung von Oligomeren einen mittleren Polymerisationsgrad in dem Bereich von ungefähr 5 bis 50 aufweist.
  10. Verfahren nach Anspruch 8, bei dem die Mischung von Oligomeren ein mittleres Molekulargewicht von weniger als ungefähr 15000 Dalton aufweist.
  11. Verfahren nach einem der Ansprüche 8 bis 10, bei dem die Mischung von Oligomeren eine Molekulargewichtsverteilung derart aufweist, daß ihr Polydispersieindex weniger als 2 ist und die Mischung weniger als 25 Gewichtsprozent Mono- und Disaccharide enthält.
  12. Verfahren nach einem der Ansprüche 8 bis 11, bei dem der Zellstoff Cellulosefasern oder synthetische oder mineralische Fasern enthält.
  13. Verfahren nach einem der Ansprüche 8 bis 12, bei dem das Cellulosederivat durch Carboxymethyl, Methyl, Hydroxypropyl, Methylethyl, Hydroxyethyl, Hydroxymethylethyl, Hydroxypropylmethyl, Sulfat, Carbonsäure, Carbonsäureester oder Pyruvat substituiert ist.
EP91307417A 1990-08-10 1991-08-12 Papierhilfsmittel und seine Verwendung Expired - Lifetime EP0470871B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US56601390A 1990-08-10 1990-08-10
US566013 1990-08-10

Publications (2)

Publication Number Publication Date
EP0470871A1 EP0470871A1 (de) 1992-02-12
EP0470871B1 true EP0470871B1 (de) 1995-11-02

Family

ID=24261084

Family Applications (1)

Application Number Title Priority Date Filing Date
EP91307417A Expired - Lifetime EP0470871B1 (de) 1990-08-10 1991-08-12 Papierhilfsmittel und seine Verwendung

Country Status (10)

Country Link
EP (1) EP0470871B1 (de)
JP (1) JPH04245997A (de)
KR (1) KR920004666A (de)
AT (1) ATE129764T1 (de)
AU (1) AU648094B2 (de)
CA (1) CA2042560C (de)
DE (1) DE69114208T2 (de)
DK (1) DK0470871T3 (de)
ES (1) ES2081439T3 (de)
NZ (1) NZ239350A (de)

Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4994112A (en) * 1989-10-30 1991-02-19 Aqualon Company Hydrophobically modified cellulosic thickeners for paper coating
KR100337995B1 (ko) * 2000-03-15 2002-05-24 정삼열 재활용이 가능한 레자질감을 갖는 특수지의 제조방법
GB0219281D0 (en) * 2002-08-19 2002-09-25 Unilever Plc Fabric care composition
EP2370511B1 (de) 2008-12-03 2016-08-24 Beardow and Adams (Adhesives) Limited Benutzung einer polysaccharidzusammensetzung zur bildung eines schutzfilms auf oberflächen aus beton, metall, stein, glas, holz, stoff, gewebe und papier
US8652610B2 (en) 2008-12-19 2014-02-18 Kimberly-Clark Worldwide, Inc. Water-dispersible creping materials
US8506978B2 (en) 2010-12-28 2013-08-13 Kimberly-Clark Worldwide, Inc. Bacteriostatic tissue product
BR112013023849A2 (pt) * 2011-03-29 2019-09-24 Basf Se E Wintershall Holding Gmbh método para revestir um material contendo celulose tipo lâmina, composição, material contendo celulose tipo lâmina revestido, e, uso de uma glucana
RU2623472C2 (ru) 2011-11-18 2017-06-26 Рокетт Фрер Частично растворимые высокомолекулярные декстрины
EP3334862A2 (de) 2015-08-14 2018-06-20 Basf Se Wässrige oberflächenbehandlungszusammensetzung für papier und pappe
CN113502689A (zh) * 2021-07-06 2021-10-15 云南中烟工业有限责任公司 一种微生物多糖增强的高透滤棒成型纸及其制备方法
CN116005489B (zh) * 2022-12-13 2024-04-26 大家智合(北京)网络科技股份有限公司 一种茶渣模塑包装纸及其制备方法

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2636951A1 (de) * 1976-08-17 1978-02-23 Pelikan Werke Wagner Guenther Staerkeabbau in der leimung von papieren mittels amylasen
CA1254316A (en) * 1983-02-16 1989-05-16 Donald N. Van Eenam Functionalized polyacrylamide grafted starch polymer wet strength additives
DE3724646A1 (de) * 1987-07-25 1989-02-02 Basf Ag Verfahren zur herstellung von papier, pappe und karton mit hoher trockenfestigkeit
FI103583B1 (fi) * 1989-02-10 1999-07-30 Alko Yhtioet Oy Vesiliukoisesta karboksimetyyliselluloosasta entsymaattisesti valmistettu hydrolysaatti
FI895708A7 (fi) * 1989-02-10 1990-08-11 Alko Ab Oy Vesiliukoinen hajoamistuote

Also Published As

Publication number Publication date
AU8174391A (en) 1992-02-13
CA2042560A1 (en) 1992-02-11
EP0470871A1 (de) 1992-02-12
DE69114208D1 (de) 1995-12-07
ES2081439T3 (es) 1996-03-16
AU648094B2 (en) 1994-04-14
NZ239350A (en) 1994-01-26
ATE129764T1 (de) 1995-11-15
KR920004666A (ko) 1992-03-27
CA2042560C (en) 2006-07-11
DE69114208T2 (de) 1996-04-25
DK0470871T3 (da) 1995-12-04
JPH04245997A (ja) 1992-09-02

Similar Documents

Publication Publication Date Title
US5354424A (en) Paper composition and methods therefor
EP0362770B1 (de) Trockenfestigkeitszusatz für Papier
Hannuksela et al. Sorption of dissolved galactoglucomannans and galactomannans to bleached kraft pulp
US5338406A (en) Dry strength additive for paper
FI127284B (en) A process for making paper, cardboard or the like
KR101444396B1 (ko) 인쇄지 코팅용 조성물
EP2396470B1 (de) Verfahren zur herstellung von modifizierter zellulose
Okita et al. TEMPO-mediated oxidation of softwood thermomechanical pulp.
EP0470871B1 (de) Papierhilfsmittel und seine Verwendung
EP2622132B1 (de) Verfahren zur verbesserten verdruckbarkeit einer nassen papierbahn, verwendung einer lösung und papier
Janne Laine et al. Characterization of unbleached kraft pulps by enzymatic treatment, potentiometric titration and polyelectrolyte adsorption
CN114599714A (zh) 表面涂覆的纤维素膜
US4102738A (en) Use of chitosan in corrugating medium
EP1105571B1 (de) Hilfsmittelzusammensetzung zur papierherstellung
US4865691A (en) Process for internally strengthening paper and board products and products resulting therefrom
JP2023503197A (ja) 化学修飾セルロース繊維を含むシートを製造する方法
CN115491927A (zh) 一种高强度拷贝纸及其生产方法
Gigac et al. Improvement of paper strength via surface application of sugar beet pectin
EP0737777A1 (de) Verfahren zur Oberflächenleimung vom Papier, und hergestelltes Papier
WO2025238307A1 (en) Composition for dewatering, its use and method for dewatering
EP4093911A1 (de) Produkt mit einem anionischen cellulosederivat und seine verwendung in der papierindustrie
Ren et al. Sorption of two kinds of hemicellulosic derivatives onto spruce bleached kraft pulp fibres and masson pine thermo-mechanical pulp

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 DK ES FR GB GR IT LI LU NL SE

17P Request for examination filed

Effective date: 19920327

17Q First examination report despatched

Effective date: 19930928

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: ALKO GROUP LTD.

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 DK ES FR GB GR IT LI LU NL SE

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

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 19951102

REF Corresponds to:

Ref document number: 129764

Country of ref document: AT

Date of ref document: 19951115

Kind code of ref document: T

REG Reference to a national code

Ref country code: DK

Ref legal event code: T3

REF Corresponds to:

Ref document number: 69114208

Country of ref document: DE

Date of ref document: 19951207

ITF It: translation for a ep patent filed
REG Reference to a national code

Ref country code: CH

Ref legal event code: NV

Representative=s name: SCHAAD, BALASS & PARTNER AG

ET Fr: translation filed
REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2081439

Country of ref document: ES

Kind code of ref document: T3

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

Ref country code: GB

Effective date: 19960812

Ref country code: AT

Effective date: 19960812

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: 19960813

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

Ref country code: LU

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

Effective date: 19960831

Ref country code: LI

Effective date: 19960831

Ref country code: CH

Effective date: 19960831

Ref country code: BE

Effective date: 19960831

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
BERE Be: lapsed

Owner name: ALKO GROUP LTD

Effective date: 19960831

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 19960812

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

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

Ref country code: FR

Payment date: 19970811

Year of fee payment: 7

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

Ref country code: DK

Payment date: 19970815

Year of fee payment: 7

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

Ref country code: SE

Payment date: 19970818

Year of fee payment: 7

Ref country code: DE

Payment date: 19970818

Year of fee payment: 7

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

Ref country code: NL

Payment date: 19970826

Year of fee payment: 7

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

Ref country code: DK

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

Effective date: 19980812

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: 19980813

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

Ref country code: NL

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

Effective date: 19990301

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

Ref country code: FR

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

Effective date: 19990430

EUG Se: european patent has lapsed

Ref document number: 91307417.5

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

Effective date: 19990301

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: 19990601

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

REG Reference to a national code

Ref country code: DK

Ref legal event code: EBP

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 19970912

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;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED.

Effective date: 20050812