EP2622131B1 - Method for improving papermaking or board making process, use of a polysaccharide and paper - Google Patents

Method for improving papermaking or board making process, use of a polysaccharide and paper Download PDF

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Publication number
EP2622131B1
EP2622131B1 EP11770475.9A EP11770475A EP2622131B1 EP 2622131 B1 EP2622131 B1 EP 2622131B1 EP 11770475 A EP11770475 A EP 11770475A EP 2622131 B1 EP2622131 B1 EP 2622131B1
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EP
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Prior art keywords
paper
polysaccharide
web
wet
applying
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EP11770475.9A
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German (de)
French (fr)
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EP2622131A1 (en
Inventor
Matti Hietaniemi
Kristian Salminen
Janne Kataja-Aho
Elias Retulainen
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Kemira Oyj
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Kemira Oyj
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    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21HPULP 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
    • D21H17/00Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20Macromolecular organic compounds
    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21HPULP 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
    • D21H17/00Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20Macromolecular organic compounds
    • D21H17/21Macromolecular organic compounds of natural origin; Derivatives thereof
    • D21H17/24Polysaccharides
    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21HPULP 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
    • D21H17/00Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20Macromolecular organic compounds
    • D21H17/33Synthetic macromolecular compounds
    • D21H17/34Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/41Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups
    • D21H17/42Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups anionic
    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21HPULP 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
    • D21H21/00Non-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
    • D21H21/14Non-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
    • D21H21/18Reinforcing agents
    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21HPULP 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
    • D21H17/00Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20Macromolecular organic compounds
    • D21H17/21Macromolecular organic compounds of natural origin; Derivatives thereof
    • D21H17/24Polysaccharides
    • D21H17/25Cellulose
    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21HPULP 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
    • D21H17/00Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20Macromolecular organic compounds
    • D21H17/21Macromolecular organic compounds of natural origin; Derivatives thereof
    • D21H17/24Polysaccharides
    • D21H17/31Gums
    • D21H17/32Guar or other polygalactomannan gum
    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21HPULP 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
    • D21H17/00Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20Macromolecular organic compounds
    • D21H17/33Synthetic macromolecular compounds
    • D21H17/34Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/41Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups
    • D21H17/44Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups cationic
    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21HPULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H23/00Processes or apparatus for adding material to the pulp or to the paper
    • D21H23/02Processes or apparatus for adding material to the pulp or to the paper characterised by the manner in which substances are added
    • D21H23/22Addition to the formed paper
    • D21H23/50Spraying or projecting

Definitions

  • the paper machine runnability is often evaluated by the number of web breaks in proportion to production speed. To attain good runnability, the paper must run well with a low number of web breaks in each sub-process along the entire paper machine line. For example, the fluttering of the paper web in the drying section should be minimised in order to avoid the possible web breaks. In order to avoid fluttering and web breaks, the paper web should preferably have a good tensile strength and good residual tension after strain.
  • Strength of wet paper web is one of the important factors in making of paper or board. Machines producing paper grades whose strength before drying is a critical factor may have high efficiency but their average production speed may be significantly lower than their nominal speed. The speed of these paper machines could be raised if the strength of the wet paper web could be increased.
  • An object of the present invention is to provide an effective and simple method for improving tensile strength of a paper web or the like.
  • An object of the present invention is to increase filler content of paper in order to reduce papermaking costs.
  • the tensile strength of the wet paper or board is clearly improved when a polysaccharide which is anionic carboxymethyl cellulose having 1,4- ⁇ -anomeric configuration in the linkages between saccharide units is brought into a contact with fibres in the stock or with fibres in a wet paper web.
  • the improved tensile strength of the wet web, as well as the improved dry tensile strength of the paper that may be achieved with the present invention enables an increase in the filler content of paper.
  • a high filler content in the base paper may be used, corresponding to ash content e.g.
  • the polysaccharide having 1,4- ⁇ -anomeric configuration in the linkages between saccharide units of the polysaccharide backbone or the main polysaccharide backbone is anionic carboxymethyl cellulose. It has been selected from the group comprising water soluble cellulose derivatives; galactomannans, such as guar gum or locust bean gum; galactoglucomannans; carboxymethyl cellulose; xylan and substituted glucans, such as xyloglucans; other suitable hydrocolloids, such as tamarind gum; chitosan; chitin; or their derivatives. According to the invention the polysaccharide having 1,4- ⁇ -anomeric configuration in the linkages between saccharide units is carboxymethyl cellulose.
  • the polysaccharide having 1,4- ⁇ -anomeric configuration in the linkages between saccharide units of the polysaccharide backbone or the main polysaccharide backbone is carboxymethyl cellulose, CMC.
  • Carboxymethyl cellulose is understood here as an anionic polymer, which is produced by introducing carboxylmethyl groups to the cellulose chain, the degree of substitution and the chain length of the cellulose backbone affecting the properties of CMC, such as water solubility. When the degree of substitution exceeds 0.3, carboxymethyl cellulose becomes water soluble.
  • the polysaccharide having 1,4- ⁇ -anomeric configuration in the linkages between saccharide units is applied as a solution to the wet fibre web in any suitable manner.
  • the solution is obtained by dissolving the polysaccharide in powder form into a solvent, typically water.
  • the polysaccharide solution is free from discrete polysaccharide particles.
  • the polysaccharide solution may comprise one polysaccharide or it may comprise a mixture of different polysaccharides, for example a mixture of two or three polysaccharides. Thus, a mixture of different polysaccharides may be applied to the fibre stock after machine chest or on the wet fibrous web.
  • the concentration of the polysaccharide(s) in the polysaccharide solution is ⁇ 60 weight-%, more typically 0.02 - 5 weight-%, preferably 0.05 - 3 weight-%, more preferably 0.05 - 2 weight-%.
  • Concentration of polysaccharides with high degree of polymerisation (DP) in the solution may be even ⁇ 1 weight-%, more typically 0.05 - 1 weight-%, even more typically 0.2 - 0.6 weight-%.
  • Polymeric retention agent dosage may be 50 - 1000 g/t, preferably 100 - 600 g/t, given as dry polymer, and the polysaccharide dosage may preferably be 200 - 4000 g/t, preferably 500 - 2500 g/t, given as dry polymer.
  • the polysaccharide is applied into the fibre stock together with an anionic, cationic or amphoteric dry strength agent.
  • the dry strength agent is selected from the group comprising polyacrylamides, glyoxylated polyacrylamides, polyvinylamines, polyamine epichlorohydrine co-polymers (PAAE), starch derivatives, and carboxymethyl cellulose.
  • the dry strength agent may be applied in amount of 0.1 - 4 kg/t paper, typically in amount 0.2 - 2 kg/t, given as active substance.
  • the polysaccharide is applied by spraying onto the wet paper web. It has been observed that the polysaccharide amount, which is applied, may be reduced when the application is done by spraying, and still the improved tensile strength characteristics of the paper web are obtained.
  • a polysaccharide solution suitable for use in the spraying may be obtained, for example, by dissolving a polysaccharide in powder form into water in order to form a 0.2 - 20 weight-%, preferably 0.3 - 3 weight-% solution.
  • the polysaccharide is applied in amount 0.3 - 3 kg/(ton paper).
  • the polysaccharide may be applied in amount ⁇ 2 g/m 2 , typically 0.05 - 1.5 g/m 2 , more typically ⁇ 1 g/m 2 , most typically 0.05 - 1 g/m 2 , preferably 0.05 - 0.5 g/m 2 , more preferably 0.05 - 0.3 g/m 2 on the wet paper web.
  • two or more polysaccharides may be applied on the wet fibre web after each other by spraying.
  • layers of different polysaccharides may easily be applied on top of each other in order to obtain desired properties.
  • an anionic or cationic polymer solution may be applied to the wet paper web before or after the addition of the polysaccharide.
  • the application of the anionic polymer is performed to the wet paper web before press section of a paper machine.
  • the application of the polysaccharide to the wet paper web may be preceded or followed by application of cationic or anionic polymer solution.
  • This kind of sequential application of polysaccharide and one or more polymers to the wet paper web, preferably through spraying may produce a marked improvement of dry and wet paper web strength.
  • Anionic and cationic polymer solutions may also be pre-mixed together before their application, preferably by spraying, to the wet paper web.
  • the paper web may comprise fibres originating from non-wood material, such as bamboo, sugar cane bagasse, hemp, wheat or rice straw.
  • the filler content of the paper or board is increased, whereby the ash content in the wet paper or board web is >25 % for wood-free uncoated paper, >25 % for wood-free coated paper base paper, >34 % for super calendered (SC) paper, >13 % for coated mechanical base paper, >15 % for newsprint paper, fluting board or testliner board, the ash content being measured by burning the stock sample completely in 525 °C.
  • SC super calendered
  • the backbone of the guar gum is a linear chain of ⁇ 1,4-linked mannose residues to which galactose residues are 1,6-linked at every second mannose, forming short side-branches.
  • Guar gum may be applied to the web in form of native guar gum, anionic guar gum or cationic guar gum.
  • native, cationic or anionic guar gum may be applied to the wet paper web, which is formed without using addition of a cationic polymer to the stock.
  • native or anionic guar gum may be applied to the wet paper web, which is formed from stock into which cationic polymer, such as cationic guar gum, is added.
  • the experimental unit comprised a vacuum box, moving sample sledge with wire, and spraying unit.
  • the amount of the chemical sprayed was adjusted by the speed of the moving sample sledge, while the spray remained constant and was immobilized.
  • the samples were wet pressed with 350 kPa and 50 kPa for 5+2 minutes after spraying. The higher pressure gives higher dryness for test sheet. Chemical consistency during spray tests was 0.5%.
  • Tensile strength was measured according to ISO 1924-2:2008. The dryness of the paper samples was determined by using a Mettler Toledo HR73 infra-red dryer.
  • Pulp containing 70% hardwood with SR-value 24 and 30 % softwood with SR-value 28 was acquired from a Finnish pulp mill. SR-value was measured according to ISO 5267-1. Precipitated calcium carbonate was used as filler. Filler was added to the pulp and target level for addition was 20 % filler content in the final web. Retention chemical was Fennopol K3400R (Kemira Oyj) with dosage 200 g/t and it was added to the headbox feed flow. Tests were made with a small fourdrinier type of wire section. Grammage of formed web was 70 g/m 2 . Chemicals were sprayed on the wet web at the wire. The samples were wet pressed with 350 kPa and 50 kPa for 5+2 minutes after spraying.
  • Tensile strength was measured according to ISO 1924-2:2008. The dryness of the paper samples was determined by using a Mettler Toledo HR73 infra-red dryer.
  • FIG 3 shows results for tensile strength in semipilot test (Example 2) for sprayed guar gum and Figure 4 shows tensile energy adsorption in semipilot test (Example 2) for sprayed guar gum.
  • the effect of guar gum wet web spraying dosage levels on wet web strength can be observed in the Figures. Spraying dosages were 0.1 g/m 2 (1.4 kg/t), 0.3 g/m 2 (4.2 kg/t) and 0.5 g/m 2 (7.1 kg/t). Dosages of 0.1 g/m 2 and 0.3 g/m 2 improved both wet web tensile and solids content after wet pressing.
  • 0.5 g/m 2 improves strength further, but solids content in wet pressing is reduced. Therefore optimum dosage may be between 0.1 g/m 2 and 0.5 g/m 2 , at least under these experimental conditions.
  • Tensile strength is needed for web to keep enough tension at paper machine dryer section to allow high operation speed. If the tension of the web is not high enough, the sheet does not follow dryer fabric and sheet fluttering may cause web break due to wind effect caused by high speed.
  • Tensile energy adsorption T.E.A. improvement helps to avoid web break, if web has fault such as a hole, slime spot, sticky particle or locally lower basis weight, because higher strength reduces risk that web tears apart beging from the fault position.
  • Test furnish was a mixture of softwood and hardwood kraft pulp for fine paper, containing 40 weigth-% scalenohedric precipitated calcium carbonate (PCC) filler. In some tests additional PCC was applied. Chemicals were added to furnish under stirring with magnetic stirrer before sheet preparation. Dosing time of cationic polyacrylamide (C-PAM) retention aid and guar gum was typical for paper machine retention system, see Table 1. Guar gum and C-PAM were premixed as powder in proportion 1:1, and then dissolved to 0.5 weight-% concentration with water, giving a final concentration of 0.25 weight-% guar gum and 0.25 weight-% C-PAM.
  • C-PAM cationic polyacrylamide
  • Chemicals used in the tests were: cationic potato starch (DS 0.035), guar gum (Sigma G4129) and cationic polyacrylamide, C-PAM, Fennopol K 3400 R (Kemira Oyj). All were dissolved to 0.5 weight-% solution except starch was cooked to 1 weight-% solution.
  • Handsheets were prepared with Rapid Kötchen semi-automatic sheet former to 80 g/m2 basis weight according to ISO 5269-2:2004. Ash content was measured according to ISO 1762:2001.
  • Dry tensile handsheets were vacuum dried according to Rapid-Kötchen method. Tensile indexes were measured according to ISO 1924-2:2008. The results can be seen in the Table 1. Table 1. The wet web tensile index and dry tensile index result for different handsheets.

Description

  • The present invention relates to a method for improving papermaking or board making process according to the preambles of the enclosed claims.
  • BACKGROUND OF THE INVENTION
  • Economical production of paper and board requires a good runnability of a paper machine. The paper machine runnability is often evaluated by the number of web breaks in proportion to production speed. To attain good runnability, the paper must run well with a low number of web breaks in each sub-process along the entire paper machine line. For example, the fluttering of the paper web in the drying section should be minimised in order to avoid the possible web breaks. In order to avoid fluttering and web breaks, the paper web should preferably have a good tensile strength and good residual tension after strain.
  • Strength of wet paper web is one of the important factors in making of paper or board. Machines producing paper grades whose strength before drying is a critical factor may have high efficiency but their average production speed may be significantly lower than their nominal speed. The speed of these paper machines could be raised if the strength of the wet paper web could be increased.
  • Common dry strength agents do not improve strength of the wet paper web. One example of such dry strength agents is starch, which has a 1,4-α-anomeric structure. Typical starches include amylose, which is a linear 1,4-α-glucan polymer and amylopectin, which has branched structure. The amylopectin backbone is 1,4-α-glucan polymer and the branches are linked to the backbone with 1,6-α-glycosidic bonds.
  • Fillers, such as clay, calcium carbonate, calcium sulphate or talc are used in paper and board making to reduce costs and to improve optical properties of paper or board. Fillers are added to the stock before the headbox of the paper machine. For coated paper grades coating pigments, which comprise the same minerals, may partly enter to the paper via the broke, which is recycled back to paper making process. The content of fillers and coating pigments is typically measured through ash content measurement by burning the stock or paper sample in 525 °C. The base paper for uncoated fine paper and for coated fine paper is made from softwood and hardwood and its ash content is typically 18 - 24 %. The base paper for 100 % softwood based uncoated fine paper and for coated fine paper has an ash content typically 10 - 17 %. An important limiting factor preventing the increase of filler content in fine papers is the reduced strength properties of the paper and reduced web runnability.
  • Known methods and compositions are disclosed in US 5,700,917 , EP 0738737 , US 6,346,554 , US 6,596,126 , WO 02/12388 and WO 02/12349 .
  • An object of this invention is to minimise or even eliminate the disadvantages existing in the prior art.
  • An object of the present invention is to provide an effective and simple method for improving tensile strength of a paper web or the like.
  • An object of the present invention is to increase filler content of paper in order to reduce papermaking costs.
  • These objects are attained with the present invention having the characteristics presented below in the characterising parts of the independent claims.
  • Typical method according to the present invention for improving papermaking or board making process is defined in claim 1. It comprises, inter alia,
    • forming a fibre stock,
    • leading the fibre stock to a headbox and feeding it to a wire to form a wet fibrous web, and
    • applying at least one polysaccharide which is anionic carboxymethyl cellulose having 1,4-β-anomeric configuration in linkages between saccharide units of the polysaccharide backbone or the main polysaccharide backbone to the fibre stock after machine chest or on the wet fibrous web.
  • Typical paper is produced by using the method according to the invention.
  • Now it has been surprisingly found out that the tensile strength of the wet paper or board is clearly improved when a polysaccharide which is anionic carboxymethyl cellulose having 1,4-β-anomeric configuration in the linkages between saccharide units is brought into a contact with fibres in the stock or with fibres in a wet paper web. The improved tensile strength of the wet web, as well as the improved dry tensile strength of the paper that may be achieved with the present invention enables an increase in the filler content of paper. When the residual tension after strain is improved by the use of the present invention, a high filler content in the base paper may be used, corresponding to ash content e.g. over 25 % both for uncoated fine paper and for coated fine paper base paper made from softwood and hardwood mixture. Correspondingly, a high filler content in the base paper may be used for 100 % softwood based uncoated fine paper and for coated fine paper base paper, the high filler content corresponding to an ash content over 18 %. An improvement in tensile strength may enable an ash content increase also for other paper and board grades, such as ash content increase to over 15 % for newsprint grades, or ash content increase over 12 % coated mechanical base paper, or ash content increase over 34 % for SC paper. Improvement in tensile strength also may be utilised by changing to a cheaper raw material mixture for the stock. For example, less old corrugated container (OCC) and more collected paper from households to make test liner or fluting board grade. The ash content of recycled fibre based fluting or test liner board may be increased over 15%.
  • Fillers, which are used in making or paper or board, and which are used in the present invention, and the content of which may be increased, are clay, calcium carbonate, calcium sulphate, titanium dioxide or talc, or their mixtures. Often the used filler has an anionic net charge.
  • According to the invention the polysaccharide having 1,4-β-anomeric configuration in the linkages between saccharide units of the polysaccharide backbone or the main polysaccharide backbone is anionic carboxymethyl cellulose. It has been selected from the group comprising water soluble cellulose derivatives; galactomannans, such as guar gum or locust bean gum; galactoglucomannans; carboxymethyl cellulose; xylan and substituted glucans, such as xyloglucans; other suitable hydrocolloids, such as tamarind gum; chitosan; chitin; or their derivatives. According to the invention the polysaccharide having 1,4-β-anomeric configuration in the linkages between saccharide units is carboxymethyl cellulose.
  • According to another embodiment which does not form part of the present invention the polysaccharide, which has 1,4-β-anomeric configuration in the linkages between saccharide units of the polysaccharide backbone or the main polysaccharide backbone, is guar gum. In this context guar gum is understood as a carbohydrate polymer containing galactose and mannose structural building blocks, especially containing one galactose unit for every two mannose units. The backbone is a linear chain of β 1,4-linked mannose residues to which galactose residues are 1,6-linked at every second mannose, forming short side-branches. Guar gum is typically obtained as an extract of guar bean. It may be used in native form or it may be used in cationised or anionised form.
  • According to one embodiment which does not form part of the present invention, anionised guar gum is applied to the fibre stock or on the wet fibre web after application of cationic strength agent to the fibre stock and/or on the wet fibre web. The cationic strength agent may be cationic or amphoteric polyacrylamide, polyvinylamide, polyamidoamine, epichlorohydrin, starch, cationic guar gum or derivative of these. For example, cationic wet strength agent may be applied on the wet fibre web by spraying, after which anionised guar gum is applied by spraying. More typically, cationic wet strength agent is applied into the fibre stock, after which anionised guar gum is applied by spraying on the wet fibre web. Anionised guar gum has typically a charge density < 2 meq/g.
  • According to the invention the polysaccharide having 1,4-β-anomeric configuration in the linkages between saccharide units of the polysaccharide backbone or the main polysaccharide backbone is carboxymethyl cellulose, CMC. Carboxymethyl cellulose is understood here as an anionic polymer, which is produced by introducing carboxylmethyl groups to the cellulose chain, the degree of substitution and the chain length of the cellulose backbone affecting the properties of CMC, such as water solubility. When the degree of substitution exceeds 0.3, carboxymethyl cellulose becomes water soluble.
  • According to the invention the polysaccharide having 1,4-β-anomeric configuration in the linkages between saccharide units of the polysaccharide backbone or the main polysaccharide backbone as defined in claim 1 is a polysaccharide with high degree of polymerisation (DP). This means polysaccharides which comprise > 500 anhydroglucose units. Size exclusion chromatography, SEC, may be used for determination of the polymerisation degree. It has been observed that the tensile strength of the wet paper or board is further improved when these polysaccharides are used.
  • Polysaccharide having 1,4-β-anomeric configuration in the linkages between saccharide units of the polysaccharide backbone or the main polysaccharide backbone and used in the present invention is water soluble. In case a derivative of the polysaccharide is used, the derivative is also water soluble. The viscosity (Brookfield) of the polysaccharide solution is < 5000 mPas, preferably < 2000 mPas. Solution may be diluted in order to achieve the desired concentration.
  • The polysaccharide having 1,4-β-anomeric configuration in the linkages between saccharide units is applied as a solution to the wet fibre web in any suitable manner. Preferably the solution is obtained by dissolving the polysaccharide in powder form into a solvent, typically water. Preferably the polysaccharide solution is free from discrete polysaccharide particles. The polysaccharide solution may comprise one polysaccharide or it may comprise a mixture of different polysaccharides, for example a mixture of two or three polysaccharides. Thus, a mixture of different polysaccharides may be applied to the fibre stock after machine chest or on the wet fibrous web. Typically the concentration of the polysaccharide(s) in the polysaccharide solution is < 60 weight-%, more typically 0.02 - 5 weight-%, preferably 0.05 - 3 weight-%, more preferably 0.05 - 2 weight-%. Concentration of polysaccharides with high degree of polymerisation (DP) in the solution may be even < 1 weight-%, more typically 0.05 - 1 weight-%, even more typically 0.2 - 0.6 weight-%.
  • According to one embodiment of the invention the polysaccharide is applied to the fibre stock between the last pump preceding the paper or board machine headbox and the outlet of the paper or board machine headbox. Preferably, the polysaccharide is added to the stock as near the headbox as possible, or the polysaccharide may be added directly to the headbox, if adequate mixing to the stock can be secured. Addition of the polysaccharide near the headbox improves the bonding of the fibres together with the polysaccharide, as the polysaccharide remains in outstretched form due to short residence time in the stock and the adsorption of the polysaccharide over the fibre surface is reduced. Also, when the polysaccharide is added to the stock after the last pump, the risk for breaking the flocks generated by the polysaccharide and fragmentation of the polysaccharide backbone due to shear forces is minimised. Thus, the activity of the polysaccharide remains in a high level, and it dosage may be reduced or better tensile strength values may be obtained by using the same dosage.
  • According to one embodiment of the invention the polysaccharide is applied into the fibre stock together with a retention or drainage agent. The polysaccharide and the retention agent are added to the fibre stock typically near the headbox, for example by dosing at the machine filter. The retention or drainage agent may be any suitable retention agent. The retention agent may be selected from a group comprising anionic or cationic polyacrylamide, polyvinylamine, polyethyleneimine, cationic starch, bentonite or silica. Especially the retention agent may be anionic or cationic polyacrylamide, polyvinylamine or polyethyleneimine. The retention agent and the polysaccharide may be added as separate solutions, or they may be added as single solution, comprising both the retention agent and the polysaccharide. Polymeric retention agent dosage may be 50 - 1000 g/t, preferably 100 - 600 g/t, given as dry polymer, and the polysaccharide dosage may preferably be 200 - 4000 g/t, preferably 500 - 2500 g/t, given as dry polymer.
  • According to another embodiment of the invention the polysaccharide is applied into the fibre stock together with an anionic, cationic or amphoteric dry strength agent. The dry strength agent is selected from the group comprising polyacrylamides, glyoxylated polyacrylamides, polyvinylamines, polyamine epichlorohydrine co-polymers (PAAE), starch derivatives, and carboxymethyl cellulose. The dry strength agent may be applied in amount of 0.1 - 4 kg/t paper, typically in amount 0.2 - 2 kg/t, given as active substance.
  • According to one preferred embodiment of the invention the polysaccharide is applied on the wet fibre web between the headbox and the last nip of a press section. According to one preferred embodiment of the invention the polysaccharide is applied on the wet fibre web by spraying, by coating, by film transfer or by foam layer application. It may be applied by using film transfer to a press belt, or by feeding of polysaccharide solution from a separate headbox. Preferably the application of the polysaccharide solution is performed by spraying. It has been found out that the spraying of the polysaccharide solution onto the fibre web provides many surprising advantages. Spraying of the polysaccharide solution does not influence the formation of the paper web, whereby there is no negative effects to be noticed in the final paper properties. On the other hand, it has also been noticed that the retention of the polysaccharide to the web is improved. This means that the used amount of the polysaccharide can be kept low, and chemical losses may be minimised. It has been observed that when the polysaccharide solution is added by spraying, the polysaccharide is evenly distributed through the whole web. No significant difference in amount of the polysaccharide can be observed between the surfaces and the core part of the web.
  • Preferably, the polysaccharide is applied by spraying onto the wet paper web. It has been observed that the polysaccharide amount, which is applied, may be reduced when the application is done by spraying, and still the improved tensile strength characteristics of the paper web are obtained. A polysaccharide solution suitable for use in the spraying may be obtained, for example, by dissolving a polysaccharide in powder form into water in order to form a 0.2 - 20 weight-%, preferably 0.3 - 3 weight-% solution.
  • According to still another embodiment, the polysaccharide is applied by foam layer application or foam coating. The polysaccharide may be applied by foam coating, whereby the polysaccharide is applied as a foam, which has an air content of 60 - 95 %, onto the wet paper web.
  • Irrespective of the method of application of the polysaccharide, the polysaccharide is applied in amount 0.3 - 3 kg/(ton paper). When the polysaccharide is applied by spraying, it may be applied in amount ≤ 2 g/m2, typically 0.05 - 1.5 g/m2, more typically ≤ 1 g/m2, most typically 0.05 - 1 g/m2, preferably 0.05 - 0.5 g/m2, more preferably 0.05 - 0.3 g/m2 on the wet paper web.
  • According to the invention the polysaccharide solution is applied on the wet paper web when the dryness of the web is < 50 %, typically < 40 %, more typically < 30 %, preferably 8 - 15 %. When the pulp suspension enters the headbox and thus the paper machine, its dryness level is typically more or equal to 0.3 % and less than 2 %. The first water removal from the web is driven by gravity when the web enters the wire section from the headbox. As paper travels further in the wire section, water removal is assisted by different vacuum units. After the wire section, the dryness of the paper is typically 14 - 22 %. The dryness of paper increases to 40 - 55 % during wet pressing. The applying of the polysaccharide solution is preferably conducted before the last vacuum zone of the wire section, preferably by spraying.
  • According to one embodiment of the invention two or more polysaccharides may be applied on the wet fibre web after each other by spraying. Thus layers of different polysaccharides may easily be applied on top of each other in order to obtain desired properties.
  • According to one embodiment an anionic or cationic polymer solution may be applied to the wet paper web before or after the addition of the polysaccharide. The application of the anionic polymer is performed to the wet paper web before press section of a paper machine. For example, the application of the polysaccharide to the wet paper web may be preceded or followed by application of cationic or anionic polymer solution. This kind of sequential application of polysaccharide and one or more polymers to the wet paper web, preferably through spraying, may produce a marked improvement of dry and wet paper web strength. Anionic and cationic polymer solutions may also be pre-mixed together before their application, preferably by spraying, to the wet paper web.
  • The present invention is advantageous for improving strength of the wet paper web when producing wood-free uncoated and coated paper grades. The present invention is also suitable for improving runnability of a wet paper or board web by improving strength of the wet paper web when producing paper grades including wood-free uncoated paper, wood-free coated paper, super calendered (SC) paper, ultralight weight coated (ULWC) paper, light weight coated (LWC) paper or newsprint paper, but not limited to these. Especially paper webs that are to be used for making recording substrates for the inkjet printing are suitable to be treated according to the method of the present invention. The paper web may comprise fibres from hardwood trees or softwood trees or a combination of both fibres. The fibres may be obtained by any suitable pulping or refining technique normally employed in paper making, such as thermomechanical pulping (TMP), chemimechanical (CMP), chemithermomechanical pulping (CTMP), groundwood pulping, alkaline sulphate (kraft) pulping, acid sulphite pulping, and semichemical pulping. The paper web may comprise only virgin fibres or recycled fibres or a combination of both. The weight of the final paper web is 30 - 800 g/m2, typically 30 - 600 g/m2, more typically 50 - 500 g/m2, preferably 60 - 300 g/m2, more preferably 60 - 120 g/m2, even more preferably 70 - 100 g/m2.
  • In some embodiments the paper web may comprise fibres originating from non-wood material, such as bamboo, sugar cane bagasse, hemp, wheat or rice straw. According to one embodiment of the invention the filler content of the paper or board is increased, whereby the ash content in the wet paper or board web is >25 % for wood-free uncoated paper, >25 % for wood-free coated paper base paper, >34 % for super calendered (SC) paper, >13 % for coated mechanical base paper, >15 % for newsprint paper, fluting board or testliner board, the ash content being measured by burning the stock sample completely in 525 °C.
  • One or more layers of chemical solutions may be applied to the wet paper web before the press section or drying section. The addition of a cationic polymer to the stock of fibres is not compulsory, but it may be performed. The chemical solutions are preferably applied to the wet paper web by spraying, as described in the application, but they may be applied by coating, film transfer, foam layer application or feeding from a separate headbox. The chemical solution that is applied to the web, e.g. by spraying, may be a solution of carboxymethyl cellulose (CMC), polyvinyl alcohol (PVA), chitosan or guar gum. Guar gum is here understood as a galactomannan. It is a polysaccharide comprising galactose and mannose. The backbone of the guar gum is a linear chain of β 1,4-linked mannose residues to which galactose residues are 1,6-linked at every second mannose, forming short side-branches. Guar gum may be applied to the web in form of native guar gum, anionic guar gum or cationic guar gum. For example, native, cationic or anionic guar gum may be applied to the wet paper web, which is formed without using addition of a cationic polymer to the stock. In another example, native or anionic guar gum may be applied to the wet paper web, which is formed from stock into which cationic polymer, such as cationic guar gum, is added.
  • EXPERIMENTAL Example 1
  • Elementary Chlorine Free-bleached pine pulp was obtained from a Finnish pulp mill. The pulp was refined and dewatered at the mill. The pulp was packed as never-dried into airtight polyethylene bags, and kept at -18°C until used for testing. The Schopper-Riegler (SR) value of the pulp after dewatering and freezing was 20, measured according to ISO 5267-1. Native dissolved guar gum (Sigma G4129), carboxymethyl cellulose (DS 0.7, DP 140) and chitosan (Mw 400,000 g/mol) was added to the thick stock pulp 30 - 90 min before sheet preparation as a 0.5 weight-% solution.
  • Wet and dry handsheets were prepared according to SCAN-C 26:76 standard. Grammage of handsheets was 60 g/m2. After wet pressing the handsheets were stored at cold storage room in airproof packages before measurements in order to maintain constant moisture in the sheets.
  • For the spraying of chemicals at laboratory, formed wet handsheets were placed onto the wire and attached using vacuum. Vacuum usage enhanced also the penetration of chemicals into the paper during spraying. The experimental unit comprised a vacuum box, moving sample sledge with wire, and spraying unit. The amount of the chemical sprayed was adjusted by the speed of the moving sample sledge, while the spray remained constant and was immobilized. The samples were wet pressed with 350 kPa and 50 kPa for 5+2 minutes after spraying. The higher pressure gives higher dryness for test sheet. Chemical consistency during spray tests was 0.5%.
  • Measurements
  • Tensile strength was measured according to ISO 1924-2:2008. The dryness of the paper samples was determined by using a Mettler Toledo HR73 infra-red dryer.
  • Results
    • Figure 1 shows results of laboratory tests (Example 1) for guar gum, which was added to thick stock pulp or sprayed on wet web. It can be seen that it is advantageous to add guar gum for wet web strength later at paper machine process rather than to thick stock pulp.
    • Figure 2 shows results for laboratory tests (Example 1) for CMC, chitosan and guar gum, each of which was sprayed on wet web. The effect of different polysaccharides on wet web strength can be seen. Guar gum is most effective. Chitosan and carboxymethyl cellulose (CMC) improved also wet web strength. As reference were used a spraying of water or handsheet without any spraying.
    Example 2 (not according to the present invention)
  • Pulp containing 70% hardwood with SR-value 24 and 30 % softwood with SR-value 28 was acquired from a Finnish pulp mill. SR-value was measured according to ISO 5267-1. Precipitated calcium carbonate was used as filler. Filler was added to the pulp and target level for addition was 20 % filler content in the final web. Retention chemical was Fennopol K3400R (Kemira Oyj) with dosage 200 g/t and it was added to the headbox feed flow. Tests were made with a small fourdrinier type of wire section. Grammage of formed web was 70 g/m2. Chemicals were sprayed on the wet web at the wire. The samples were wet pressed with 350 kPa and 50 kPa for 5+2 minutes after spraying.
  • Measurements
  • Tensile strength was measured according to ISO 1924-2:2008. The dryness of the paper samples was determined by using a Mettler Toledo HR73 infra-red dryer.
  • Results
  • Figure 3 shows results for tensile strength in semipilot test (Example 2) for sprayed guar gum and Figure 4 shows tensile energy adsorption in semipilot test (Example 2) for sprayed guar gum. The effect of guar gum wet web spraying dosage levels on wet web strength can be observed in the Figures. Spraying dosages were 0.1 g/m2 (1.4 kg/t), 0.3 g/m2 (4.2 kg/t) and 0.5 g/m2 (7.1 kg/t). Dosages of 0.1 g/m2 and 0.3 g/m2 improved both wet web tensile and solids content after wet pressing. Dosage of 0.5 g/m2 improves strength further, but solids content in wet pressing is reduced. Therefore optimum dosage may be between 0.1 g/m2 and 0.5 g/m2, at least under these experimental conditions. Tensile strength is needed for web to keep enough tension at paper machine dryer section to allow high operation speed. If the tension of the web is not high enough, the sheet does not follow dryer fabric and sheet fluttering may cause web break due to wind effect caused by high speed. Tensile energy adsorption T.E.A. improvement helps to avoid web break, if web has fault such as a hole, slime spot, sticky particle or locally lower basis weight, because higher strength reduces risk that web tears apart beging from the fault position.
  • Example 3 (not according to the present invention)
  • Test furnish was a mixture of softwood and hardwood kraft pulp for fine paper, containing 40 weigth-% scalenohedric precipitated calcium carbonate (PCC) filler. In some tests additional PCC was applied. Chemicals were added to furnish under stirring with magnetic stirrer before sheet preparation. Dosing time of cationic polyacrylamide (C-PAM) retention aid and guar gum was typical for paper machine retention system, see Table 1. Guar gum and C-PAM were premixed as powder in proportion 1:1, and then dissolved to 0.5 weight-% concentration with water, giving a final concentration of 0.25 weight-% guar gum and 0.25 weight-% C-PAM.
  • Chemicals used in the tests were: cationic potato starch (DS 0.035), guar gum (Sigma G4129) and cationic polyacrylamide, C-PAM, Fennopol K 3400 R (Kemira Oyj). All were dissolved to 0.5 weight-% solution except starch was cooked to 1 weight-% solution.
  • Handsheets were prepared with Rapid Kötchen semi-automatic sheet former to 80 g/m2 basis weight according to ISO 5269-2:2004. Ash content was measured according to ISO 1762:2001.
  • Wet web sheets were wet pressed according to ISO 5269-1:2005, but pressing time was 1 min at 2 bar pressure between 2 plotters on top and 2 plotters under. In tests D and E the wet pressing was 2 min at 4 bar pressure. Wet web tensile measurements were performed at the dry content after wet pressing.
  • Dry tensile handsheets were vacuum dried according to Rapid-Kötchen method. Tensile indexes were measured according to ISO 1924-2:2008. The results can be seen in the Table 1. Table 1. The wet web tensile index and dry tensile index result for different handsheets.
    Dose time -10min - 20 s -15 s -15 s
    Starch added PCC C-PAM Guar gum sheet ash, 525 °C wet web tensile index dry tensile index
    Test kg/t % g/t g/t % Nm/g Nm/g
    A
    0 0 0 0 11 0,46 40
    B 0 0 0 600 17 0,71 33
    C 0 0 150 150 32 0,46 21
    D 0 20 150 0 38 0,45 14
    E 6 20 150 0 38 0,37 15
  • From the results it can be seen that the wet web tensile index was improved in test B compared to test A; also ash content increased, which reduced the dry tensile index. In test C significantly higher ash content was achieved with guar gum and C-PAM blend with similar wet web tensile compared to test A. In test E cationic starch was used as strength agent in high filler containing pulp. Starch decreased wet web strength compared to test D.
  • Even if the invention was described with reference to what at present seems to be the most practical and preferred embodiments, it is appreciated that the invention shall not be limited to the embodiments described above, but the invention is intended to cover also different modifications and equivalent technical solutions within the scope of the enclosed claims.

Claims (12)

  1. Method for improving papermaking or board making process, comprising
    - forming a fibre stock,
    - using a filler in making of paper or board, which filler is selected from clay, calcium carbonate, calcium sulphate, titanium dioxide, talc, and their mixtures,
    - leading the fibre stock to a headbox and feeding it to a wire to form a wet fibrous web,
    characterised in
    applying to the fibre stock after machine chest or on the wet fibrous web when the dryness of the web is < 50 % at least one polysaccharide which is anionic carboxymethyl cellulose having 1,4-β-anomeric configuration in linkages between saccharide units of the polysaccharide backbone or the main polysaccharide backbone in amount of 0.3 - 3 kg/(ton paper), the polysaccharide comprising > 500 anhydroglucose units.
  2. Method according to claim 1, characterised in applying the polysaccharide as a solution, whereby the concentration of the polysaccharide in the polysaccharide solution is 0.02 - 5 weight-%, preferably 0.05 - 3 weight-%, more preferably 0.05 - 2 weight-%.
  3. Method according to any of preceding claims 1 - 2, characterised in applying a mixture of different polysaccharides to the fibre stock after machine chest or on the wet fibrous web.
  4. Method according to any of preceding claims 1 - 3, characterised in applying the polysaccharide to the fibre stock between the last pump preceding the paper machine headbox and the outlet of the paper machine headbox.
  5. Method according to claim 4, characterised in applying the polysaccharide into the fibre stock together with a retention agent, and selecting the retention agent from a group comprising anionic or cationic polyacrylamide, polyvinylamine, polyethyleneimine, cationic starch, bentonite or silica, especially from anionic or cationic polyacrylamide, polyvinylamine or polyethyleneimine.
  6. Method according to any of claims 1 - 3, characterised in applying the polysaccharide on the wet fibre web between the headbox and the last nip of the press section.
  7. Method according to claim 6, characterised in applying the polysaccharide on the fibre web by spraying, by coating, by film transfer or by foam layer application.
  8. Method according to claim 7, characterised in applying the polysaccharide by spraying as a solution with a concentration in the range of 0.2 - 20 weight-%, preferably 0.3 - 3 weight-%.
  9. Method according to claim 7, characterised in applying the polysaccharide by foam coating, whereby the polysaccharide is applied as a foam having an air content of 60 - 95 %.
  10. Method according to any of claims 7 - 9, characterised in applying the polysaccharide solution on the wet paper web when the dryness of the web is preferably 8 - 15 %.
  11. Method according to claim 1, characterised in producing wood-free uncoated paper, wood-free coated paper, super calendered (SC) paper, ultralight weight coated (ULWC) paper, light weight coated (LWC) paper or newsprint paper.
  12. Method according to claim 1, characterised in increasing filler content of the paper or board, whereby the ash content in the wet paper or board web is
    - >25 % for wood-free uncoated paper,
    - >25 % for wood-free coated paper base paper,
    - >34 % for super calendered (SC) paper,
    - >13 % for coated mechanical base paper,
    - >15 % for newsprint paper, fluting board or testliner board,
    the ash content being measured by burning the stock sample in 525 °C
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Families Citing this family (39)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FI125714B (en) 2012-11-12 2016-01-15 Kemira Oyj A process for treating fibrous pulp for making paper, cardboard or the like, and a product
US8999111B2 (en) * 2012-12-28 2015-04-07 Ecolab Usa Inc. Method of increasing paper surface strength by using acrylic acid/acrylamide copolymer in a size press formulation containing starch
SE539914C2 (en) 2014-04-29 2018-01-09 Stora Enso Oyj Process for making at least one layer of a paper or paperboard and a paper or paperboard made according to the process
CN104057769B (en) * 2014-06-07 2017-11-28 王志亮 A kind of Chinese Painting and Calligraphy wet-milling product method
US10407831B2 (en) 2014-09-04 2019-09-10 Kemira Oyj Sizing composition, its use and a method for producing paper, board or the like
CA2935497A1 (en) 2015-07-14 2017-01-14 Western Michigan University Research Foundation Chitosan as a biobased barrier coating for functional paperboard products
KR20180064535A (en) 2015-11-03 2018-06-14 킴벌리-클라크 월드와이드, 인크. Paper tissue with high bulk and low lint
ES2667544T3 (en) * 2016-05-20 2018-05-11 Kemira Oyj Method and treatment system for papermaking
ES2871534T3 (en) * 2016-09-26 2021-10-29 Kemira Oyj Composition of dry strength, its use, and method for the manufacture of paper, cardboard or similar
CN106638135A (en) * 2016-12-09 2017-05-10 苏州艾博迈尔新材料有限公司 Paper fiber dispersing agent and preparation method thereof
CN106638123A (en) * 2016-12-30 2017-05-10 芜湖市哈贝纸业有限公司 Composite filler paper and production process thereof
WO2019004950A1 (en) * 2017-06-30 2019-01-03 Scg Packaging Public Company Limited High-strength sheet material
CA3031639A1 (en) * 2017-09-19 2019-03-19 Kemira Oyj Paper strength improving polymer composition and additive system, use thereof, and manufacture of paper products
CN107869087A (en) * 2017-11-03 2018-04-03 广东松炀再生资源股份有限公司 A kind of method that reclaimed waste paper prepares highly intensified corrugated paper
US11255051B2 (en) 2017-11-29 2022-02-22 Kimberly-Clark Worldwide, Inc. Fibrous sheet with improved properties
CN108045034A (en) * 2017-12-11 2018-05-18 浙江希望包装有限公司 A kind of corrugated board
SE542093C2 (en) * 2018-02-27 2020-02-25 Stora Enso Oyj Method for production of a paper, board or non-woven product comprising a first ply
RU2020130387A (en) 2018-03-22 2022-04-22 Кемирa Ойй METHOD FOR MANUFACTURING MULTILAYER CARDBOARD, MULTILAYER CARDBOARD AND COMPOSITION USED IN MANUFACTURING MULTILAYER CARDBOARD
FI20185272A1 (en) 2018-03-22 2019-09-23 Kemira Oyj Dry strength composition, its use and method for making of paper, board or the like
US11214919B2 (en) 2018-05-31 2022-01-04 Ecolab Usa Inc. Wet web strength for fiberglass mats
GB2590316B (en) 2018-07-25 2022-06-01 Kimberly Clark Co Process for making three-dimensional foam-laid nonwovens
CN111525136A (en) * 2020-04-30 2020-08-11 青岛科技大学 Composite binder and application thereof in silicon cathode of lithium ion battery
WO2022117921A1 (en) * 2020-12-02 2022-06-09 Kemira Oyj A treatment system for manufacture of paper, board or the like
CN112602962A (en) * 2021-01-08 2021-04-06 中烟施伟策(云南)再造烟叶有限公司 Cigarette tipping base paper containing tobacco elements, preparation method thereof and cigarette made of same
CN112641125A (en) * 2021-01-08 2021-04-13 中烟施伟策(云南)再造烟叶有限公司 Paper filter tip rod of reconstituted tobacco and preparation method of filter tip rod
CN112617269A (en) * 2021-01-08 2021-04-09 中烟施伟策(云南)再造烟叶有限公司 Powder forming coating papermaking mixed pulping method
CN112853811A (en) * 2021-01-08 2021-05-28 中烟施伟策(云南)再造烟叶有限公司 Powder forming coating papermaking process
CN112779819A (en) * 2021-01-08 2021-05-11 中烟施伟策(云南)再造烟叶有限公司 Cigarette paper containing tobacco elements and preparation method of cigarette paper containing tobacco elements
CN112586796A (en) * 2021-01-08 2021-04-02 中烟施伟策(云南)再造烟叶有限公司 Center heating tobacco cigarette core material and preparation method of heating tobacco cigarette core material
CN112586795A (en) * 2021-01-08 2021-04-02 中烟施伟策(云南)再造烟叶有限公司 Plant scented chip for cigarette leaf group and preparation method thereof
CN112656025A (en) * 2021-01-08 2021-04-16 中烟施伟策(云南)再造烟叶有限公司 Cigar coating and preparation method thereof
CN112779818A (en) * 2021-01-08 2021-05-11 中烟施伟策(云南)再造烟叶有限公司 Heating tobacco cigarette paper and preparation method thereof
CN112716026A (en) * 2021-01-08 2021-04-30 中烟施伟策(云南)再造烟叶有限公司 Recombinant tobacco and preparation method thereof
CN112641126A (en) * 2021-01-08 2021-04-13 中烟施伟策(云南)再造烟叶有限公司 Circumferential heating tobacco cigarette core material and preparation method of heating tobacco cigarette core material
CN112741360A (en) * 2021-01-08 2021-05-04 中烟施伟策(云南)再造烟叶有限公司 High-quality center heating tobacco cigarette core material and preparation method thereof
FI4036305T3 (en) * 2021-02-02 2024-01-31 Billerud Ab Publ Papermaking method
WO2022167437A1 (en) * 2021-02-02 2022-08-11 Billerudkorsnäs Ab Papermaking method
CN113502689A (en) * 2021-07-06 2021-10-15 云南中烟工业有限责任公司 Microbial polysaccharide enhanced high-transparency filter stick forming paper and preparation method thereof
CN115093616B (en) * 2022-06-11 2023-06-16 云南杰商科技有限公司 Environment-friendly konjak mannan composite carton and preparation method thereof

Family Cites Families (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1163843A (en) * 1965-09-27 1969-09-10 Mead Corp Apparatus for Incorporating Additives in Paper and the like
US4362781A (en) * 1981-09-21 1982-12-07 Scott Paper Company Flushable premoistened wiper
ES2050802T5 (en) * 1988-06-14 1997-10-01 Procter & Gamble SOFT TISSUE PAPER CONTAINING A NON-CATIONAL SURFACE.
US4959125A (en) * 1988-12-05 1990-09-25 The Procter & Gamble Company Soft tissue paper containing noncationic surfactant
CA2108027C (en) * 1991-07-02 1997-05-27 Bruno Carre A process for the production of paper
US5318669A (en) * 1991-12-23 1994-06-07 Hercules Incorporated Enhancement of paper dry strength by anionic and cationic polymer combination
US5554745A (en) * 1992-05-14 1996-09-10 National Starch And Chemical Investment Holding Corporation Aldehyde cationic derivatives of galactose containing polysaccharides used as paper strength additives
DE19520092A1 (en) * 1995-06-01 1996-12-05 Bayer Ag Process for paper finishing using polyisocyanates with anionic groups
EP1011629B1 (en) * 1997-09-05 2012-03-21 The Procter & Gamble Company Cleansing and conditioning products for skin or hair with improved deposition of conditioning ingredients
AU3478799A (en) * 1998-04-06 1999-10-25 Calgon Corporation Asa size emulsification with a natural gum for paper products
EP0953680A1 (en) * 1998-04-27 1999-11-03 Akzo Nobel N.V. A process for the production of paper
US6241853B1 (en) * 1998-12-10 2001-06-05 Kimberly Clark Worldwide, Inc. High wet and dry strength paper product
US6596126B1 (en) * 1999-01-25 2003-07-22 Kimberly-Clark Worldwide, Inc. Modified polysaccharides containing aliphatic hydrocarbon moieties
BR8001232U (en) * 1999-06-24 2002-07-09 Edgardo Rene Peccorelli Stretcher for sanitizing prostrate patients
WO2002012388A2 (en) * 2000-08-03 2002-02-14 Hercules Incorporated Process for the production of chemically or enzymatically modified polysaccharides, and products made thereby
US20020076769A1 (en) * 2000-08-03 2002-06-20 Richard Brady Reduced molecular weight galactomannans oxidized by galactose oxidase
AU2003286432B2 (en) * 2002-10-17 2006-11-09 The Procter & Gamble Company Tissue paper softening compositions and tissue papers comprising the same
DE10308753A1 (en) 2003-02-28 2004-09-09 Bayer Ag Cationic starch graft copolymers and new process for the production of cationic starch graft copolymers
CA2543609A1 (en) * 2003-10-24 2005-05-12 National Gypsum Properties, Llc Process for making abrasion resistant paper and paper and paper products made by the process
GB0702249D0 (en) * 2007-02-05 2007-03-14 Ciba Sc Holding Ag Manufacture of paper or paperboard
EP2157237B1 (en) * 2007-03-30 2014-11-05 Nippon Paper Industries Co., Ltd. Methods for producing coating base papers and coated papers
CN102027170B (en) * 2008-05-15 2012-11-21 巴斯夫欧洲公司 Method for producing paper, paperboard and cardboard with a high dry strength

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
None *

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EP2622131A1 (en) 2013-08-07
FI20106021A0 (en) 2010-10-01
BR112013007876A2 (en) 2019-08-27
CA2813148C (en) 2018-02-06
BR112013007244A2 (en) 2016-06-14
CN103140626A (en) 2013-06-05
FI125713B (en) 2016-01-15
CA2813148A1 (en) 2012-04-05
FI20106021A (en) 2012-04-02
WO2012042116A1 (en) 2012-04-05
US20130299109A1 (en) 2013-11-14
CN103201426B (en) 2016-05-11
EP2622132A1 (en) 2013-08-07
BR112013007876B1 (en) 2020-12-29
EP2622132B1 (en) 2018-04-04
PT2622132T (en) 2018-07-03
FI20106021L (en) 2012-04-02
ES2674881T3 (en) 2018-07-04
CN103201426A (en) 2013-07-10
ES2791997T3 (en) 2020-11-06
WO2012042115A1 (en) 2012-04-05

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