EP2432934A1 - Improving the strength of paper and board products - Google Patents
Improving the strength of paper and board productsInfo
- Publication number
- EP2432934A1 EP2432934A1 EP10722156A EP10722156A EP2432934A1 EP 2432934 A1 EP2432934 A1 EP 2432934A1 EP 10722156 A EP10722156 A EP 10722156A EP 10722156 A EP10722156 A EP 10722156A EP 2432934 A1 EP2432934 A1 EP 2432934A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- product
- paper
- fibres
- polyvinyl alcohol
- 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.)
- Granted
Links
Classifications
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/63—Inorganic compounds
- D21H17/67—Water-insoluble compounds, e.g. fillers, pigments
- D21H17/675—Oxides, hydroxides or carbonates
-
- 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
- D21H13/00—Pulp or paper, comprising synthetic cellulose or non-cellulose fibres or web-forming material
- D21H13/10—Organic non-cellulose fibres
- D21H13/12—Organic non-cellulose fibres from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
-
- 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
- D21H13/00—Pulp or paper, comprising synthetic cellulose or non-cellulose fibres or web-forming material
- D21H13/10—Organic non-cellulose fibres
- D21H13/12—Organic non-cellulose fibres from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D21H13/16—Polyalkenylalcohols; Polyalkenylethers; Polyalkenylesters
-
- 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
- D21H17/63—Inorganic compounds
-
- 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
- D21H17/63—Inorganic compounds
- D21H17/67—Water-insoluble compounds, e.g. fillers, pigments
-
- 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
- D21H17/63—Inorganic compounds
- D21H17/70—Inorganic compounds forming new compounds in situ, e.g. within the pulp or paper, by chemical reaction with other substances added separately
-
- 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
- D21H19/00—Coated paper; Coating material
- D21H19/10—Coatings without pigments
-
- 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
- D21H19/00—Coated paper; Coating material
- D21H19/10—Coatings without pigments
- D21H19/12—Coatings without pigments applied as a solution using water as the only solvent, e.g. in the presence of acid or alkaline compounds
-
- 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
- D21H19/00—Coated paper; Coating material
- D21H19/36—Coatings with pigments
- D21H19/44—Coatings with pigments characterised by the other ingredients, e.g. the binder or dispersing agent
- D21H19/56—Macromolecular organic compounds or oligomers thereof obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D21H19/60—Polyalkenylalcohols; Polyalkenylethers; Polyalkenylesters
-
- 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
- D21H19/00—Coated paper; Coating material
- D21H19/80—Paper comprising more than one coating
-
- 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
- D21H23/00—Processes or apparatus for adding material to the pulp or to the paper
- D21H23/02—Processes or apparatus for adding material to the pulp or to the paper characterised by the manner in which substances are added
- D21H23/22—Addition to the formed paper
- D21H23/66—Treating discontinuous paper, e.g. sheets, blanks, rolls
-
- 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
- D21H23/00—Processes or apparatus for adding material to the pulp or to the paper
- D21H23/02—Processes or apparatus for adding material to the pulp or to the paper characterised by the manner in which substances are added
- D21H23/22—Addition to the formed paper
- D21H23/70—Multistep processes; Apparatus for adding one or several substances in portions or in various ways to the paper, not covered by another single group of this main group
-
- 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
- D21H23/00—Processes or apparatus for adding material to the pulp or to the paper
- D21H23/76—Processes or apparatus for adding material to the pulp or to the paper characterised by choice of auxiliary compounds which are added separately from at least one other compound, e.g. to improve the incorporation of the latter or to obtain an enhanced combined effect
-
- 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
- D21H27/00—Special paper not otherwise provided for, e.g. made by multi-step processes
- D21H27/30—Multi-ply
Definitions
- the present invention concerns a paper or board product comprising cellulose fibres, a zirconium carbonate compound and fibres of water- insoluble polyvinyl alcohol, and a process for manufacturing a paper or board product.
- the mechanical strength of paper and board is related to the bonding degree of the fibre network.
- improvements of the strength properties of paper and board products are generally attempted through increasing said bonding degree. This may be done, for example, by adding to the paper or board pulp an additive that binds the cellulosic fibres to each other.
- Zirconium compounds have been used to some extent in improving the strength of paper and board, particularly the wet tensile strength of the paper coatings. This use is based on said zirconium compounds having the ability to react with the OH groups of the cellulose fibres and with the starch, soluble polyvinyl alcohol and other polymers used as binders, thus forming a strong network.
- PVA Water-soluble polyvinyl alcohol
- Water- insoluble PVA has been widely used in the construction industry for improving the strength and toughness of cement-based constructs, sprayable masses and building boards.
- Typical examples are the use of the fibres in the cast concrete of earthquake-resistant buildings, in bridges, in sprayable masses of tunnels, as well as in building boards to replace the asbestos fibre now forbidden for health reasons.
- the function of the insoluble PVA is based on its significantly high tensile strength and its capability to form a very strong bond with the concrete on curing, using the OH bonds on the surface of the PVA fibre.
- the present invention concerns a paper or board product comprising cellulose fibres, as well as a process for manufacturing a cellulose-containing paper or board product.
- paper or board product of the present invention is characterized by what is stated in the characterizing part of Claim 1.
- the process of the present invention is characterized by what is stated in the characterizing part of Claim 7.
- the present invention provides a paper or board product having improved tensile strength compared to similar known products.
- a paper or board product can be obtained, which has a tensile strength that is up to 3 - 5 times higher than the strength obtained using, for example, polypropylene fibre.
- Figure 1 is a drawing of the network structure formed between the cellulose fibres, the fibres of water-insoluble polyvinyl alcohol and the zirconium carbonate compound according to the present invention, the fibres being shown as lines and dotted lines, and the zirconium carbonate(s) being shown in the form of their molecular structure.
- Figure 2 is a microscopic image of the end of a single fibre torn from a paper strip manufactured according to the method of the present invention.
- the present invention concerns a paper or board product comprising cellulose fibres, one or more zirconium carbonate compound(s) and water-insoluble polyvinyl alcohol fibres, as well as a process for manufacturing a paper or board product.
- paper or board product includes all fibrous cellulose-containing preformed products, such as paper, board and preformed papermaking pulp.
- the product contains one or more further conventional paper chemicals, selected from coatings, binders, fillers, sizing agents, retention agents or other paper chemicals.
- the further binder(s) can be, for example, soluble polyvinyl alcohol or starch, which can be any modified or unmodified starch, preferably cationic starch, most preferably starch derived from rice, wheat, potato, corn or cassava.
- the coating(s) can be any conventionally used coating, such as a polymeric coating.
- the filler(s) may be a mineral filler, preferably calcium carbonate (e.g. precipitated), kaolin, talc, aluminium oxide, titanium dioxide, a mineral sulphate or a silicate.
- the retention agent(s) may be any resin or further ionic or polymeric retention agent.
- the water-insoluble polyvinyl alcohol (PVA) fibres used in the invention have a fibre length of 2-1 Omm, preferably 4-8mm, most preferably about 5mm. They function by forming hydrogen bonds with the cellulose fibres through their reactive functional groups, such as their OH groups, thus forming a cross-linked network of cellulose and polyvinyl alcohol fibres. This network is further strengthened by the addition of a zirconium carbonate compound.
- Polyvinyl alcohol may occur in various forms, such as in various stereoisomeric forms. This provides, among others, differences in the solubility properties.
- soluble PVA water is the most commonly used solvent.
- This form of PVA is, among others, used in water-soluble films.
- water- insoluble polyvinyl alcohol is used here to describe a form of PVA having a significantly poorer solubility than the commonly used soluble PVA.
- the zirconium carbonate compound(s) is/are preferably present in the final paper or board product as an aqueous solution of a zirconium carbonate compound impregnated into the product.
- the zirconium carbonate compound may be ammonium zirconium carbonate (AZC) or potassium zirconium carbonate (KZC). These are anionic inorganic hydroxylated zirconium polymers commonly available in water based solutions and used in paper coatings, paint and ink formulations, metal surface treatments, adhesives and catalysts.
- Traditional cross-linkers used in the manufacture of paper or board products are generally organic compounds containing at least two functional groups within their structures that react with the hydroxylic groups of the cellulose molecules.
- the formed cross-links stabilize the fibrous product, giving the product an increased tendency to return to its original shape after being, e.g., bent or deformed in other ways.
- Paper or board products manufactured from cross-linked fibre generally have an increased thickness, brightness, light scattering efficiency and opacity, as well as a good strength.
- the water retention properties of a paper or board product are also improved through cross-linking.
- cross-linkers can be used in addition to the zirconium carbonate compound(s).
- These may be, e.g., compounds containing carboxylic groups, such as succinic acid, maleic acid or citric acid.
- the present invention also concerns a process for manufacturing a paper or board product, such as the product of the present invention, which process comprises the steps of forming a combined aqueous suspension of cellulose fibres and water-insoluble polyvinyl alcohol fibres, and pressing it into a paper or board product in a conventional way, or pressing layers of polyvinyl alcohol fibres and cellulose fibres into a product having a sandwich-structure, treating the product before drying with an aqueous solution of a zirconium carbonate compound by impregnating one or more of the surfaces of the product or the complete product with the solution, and drying the treated product.
- the combined aqueous suspension of cellulose fibres and fibres of water-insoluble polyvinyl alcohol can either be formed directly by mixing these fibres into water, or by first forming both an aqueous suspension of the cellulose fibres and an aqueous suspension of the water-insoluble polyvinyl alcohol fibres, and then combining these suspensions and forming them into the combined suspension.
- an essentially homogeneous suspension is formed of the cellulose fibres and the fibres of water-insoluble polyvinyl alcohol through powerful mixing, e.g. using a high-speed rotating blade agitator, and it is pressed into a paper or board product with an essentially uniform thickness, whereafter the fibres are allowed to cross-link.
- the optionally used separately prepared aqueous suspension of cellulose fibres preferably has a fibre content of 5-20 g/1, most preferably 10-14 g/1, whereas the optionally used separately prepared aqueous suspension of water-insoluble polyvinyl alcohol fibres preferably has a fibre content of 3-10 g/1, most preferably 5-7 g/1.
- the zirconium carbonate molecules used in the present invention are in a stable form. Since they are complex compounds, their concentrations are generally presented as the concentration of zirconium oxide, ZrO 2 . In the present invention this concentration is preferably 1-25 weight-%, more preferably 3-15 weight-%, most preferably 3-10 weight- % OfZrO 2 .
- the solution of zirconium carbonate compound is spread onto both surfaces of the pressed paper or board product in an amount sufficient to impregnate the outermost layer of the surfaces, the solution thus being absorbed into 1-95% of the fibrous material of the product, preferably into 25-90% of the material, most preferably into 50-80% of the material.
- This is sufficient to cause a substantial increase in the tensile strength of the product, whereas more caution is necessary when thoroughly impregnating the complete product in order to limit the amount of used solution to an amount not weakening the existing fibre-to-fibre bonds of the cellulose fibres and the fibres of water-insoluble polyvinyl alcohol.
- the sandwich- structure contains 2-10 alternating layers of polyvinyl alcohol fibres and cellulose fibres, preferably 3-8 alternating layers, most preferably 4-5 alternating layers.
- the sandwich-structure contains 3 layers, whereby the paper or board product contains, as fibre, only cellulose fibres in its centre layer, with both surface layers being formed using a mixture of cellulose fibre and polyvinyl alcohol fibres.
- the paper product is preferably dried, either before the treatment using the zirconium carbonate compound or after the treatment or at both of these stages, at an elevated temperature, which temperature may be in the range of 30-120 0 C, preferably 50-100 0 C, most preferably 70-100 0 C.
- Example 1 Carrying out the reaction between the fibres and potassium zirconium carbonate
- the cellulose fibre was obtained by tearing apart coarse, acid free paper (250g/m 2 ) using a high-speed rotating blade agitator in warm water (50 0 C).
- the ratio of fibre/water was 6g/500ml.
- the water-insoluble polyvinyl alcohol fibre (King's PVA-fibre PF-120 / fibre length 5mm / 12.0 ⁇ 0.2 cN/dtex) was mixed into water using the same agitator. The ratio of fibre/water was 2g/300ml. The fibre suspensions were combined (800ml) and mixed into a homogeneous mixture. The obtained suspension (cellulose and insoluble PVA) was filtered through a metal mesh (mesh 120), and the residual water was partially removed using vacuum suction, leaving a moist fibre mass, containing only a small amount of starch used as glue in the paper.
- the moist fibre mass was pressed into uniform thickness in a conventional manner, and dried at 90-100 0 C.
- Test strips were cut from the dried material and some strips were impregnated completely using diluted (30% or 35%) potassium zirconium carbonate solution, KZC (Raisacoat KZ 20: ZrO 2 concentration 20%), the diluted carbonate solution having a final ZrO 2 concentration of 6% or 7%. Excess KZC solution was removed by pressing the strips between the steel plates, and the test strips were dried at 90-100 0 C.
- the tensile strength can be regulated by adjusting the added amount of water-insoluble
- PVA fibre and the concentration/amount of ammonium or potassium zirconium carbonate.
- Example 2 Manufacturing laboratory paper sheets using ammonium zirconium carbonate
- oriented laboratory sheets were produced in a dynamic sheet former (Formette Dynamic) in accordance with the method of the present invention, i.e. by forming an aqueous suspension of the cellulose fibres and water-insoluble polyvinyl alcohol fibres, and pressing it into the used laboratory paper sheets, by treating the sheets with an aqueous solution of ammonium zirconium carbonate by impregnating the surfaces of the sheets with the solution, and by drying the treated sheets.
- the sheets were surface sized, and the produced papers were tested for Tensile, Tear and Internal Bonding Strength (see Table 2).
- the sample papers were coated (surface sized) with a paint brush, dried in frames in an oven with air recirculation at 80-90 0 C for 30 min, and conditioned at 50 % relative humidity and 23 0 C for 1 week.
- Test conditions 50 % RH, 23 oC
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Paper (AREA)
Abstract
Description
Claims
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FI20095547A FI121478B (en) | 2009-05-18 | 2009-05-18 | Improving the strength of paper and board products |
PCT/FI2010/050397 WO2010133762A1 (en) | 2009-05-18 | 2010-05-17 | Improving the strength of paper and board products |
Publications (2)
Publication Number | Publication Date |
---|---|
EP2432934A1 true EP2432934A1 (en) | 2012-03-28 |
EP2432934B1 EP2432934B1 (en) | 2013-09-04 |
Family
ID=40680729
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP10722156.6A Not-in-force EP2432934B1 (en) | 2009-05-18 | 2010-05-17 | Improving the strength of paper and board products |
Country Status (10)
Country | Link |
---|---|
US (1) | US20120055642A1 (en) |
EP (1) | EP2432934B1 (en) |
JP (1) | JP2012527544A (en) |
KR (1) | KR20120036315A (en) |
CN (1) | CN102482850B (en) |
BR (1) | BRPI1010992A2 (en) |
CA (1) | CA2762024A1 (en) |
FI (1) | FI121478B (en) |
WO (1) | WO2010133762A1 (en) |
ZA (1) | ZA201108255B (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2016001016A1 (en) | 2014-07-03 | 2016-01-07 | Basf Se | Aqueous surface-coating agent for paper and paperboard |
Families Citing this family (9)
Publication number | Priority date | Publication date | Assignee | Title |
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FI121478B (en) * | 2009-05-18 | 2010-11-30 | Sinoco Chemicals | Improving the strength of paper and board products |
CN102615859A (en) * | 2011-01-31 | 2012-08-01 | 康士达生物科技股份有限公司 | Manufacturing method of paper container |
US9777129B2 (en) | 2014-04-11 | 2017-10-03 | Georgia-Pacific Consumer Products Lp | Fibers with filler |
US9777143B2 (en) | 2014-04-11 | 2017-10-03 | Georgia-Pacific Consumer Products Lp | Polyvinyl alcohol fibers and films with mineral fillers and small cellulose particles |
CN105525534A (en) * | 2015-12-31 | 2016-04-27 | 上海全宇生物科技遂平有限公司 | High-strength special paper and preparation method thereof |
CN113661290A (en) | 2019-04-02 | 2021-11-16 | 凯米拉公司 | Paper strength enhancement using metal chelates and synthetic cationic polymers |
WO2020205905A1 (en) | 2019-04-02 | 2020-10-08 | Kemira Oyj | Use of metal chelates as a surface application for abrasion and/or taber stiffness, improvement in paper and paperboard |
WO2020201862A1 (en) | 2019-04-04 | 2020-10-08 | Dipped Products Plc | Latex dipped article with a modified polyvinyl alcohol layer which resist to water, solvents and diluted solvents |
JP7478388B2 (en) | 2020-02-27 | 2024-05-07 | ユニマテック株式会社 | Fluorine-containing cellulose zirconium composite |
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2010
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- 2010-05-17 JP JP2012511314A patent/JP2012527544A/en active Pending
- 2010-05-17 KR KR1020117030376A patent/KR20120036315A/en not_active Application Discontinuation
- 2010-05-17 BR BRPI1010992A patent/BRPI1010992A2/en not_active IP Right Cessation
- 2010-05-17 CA CA2762024A patent/CA2762024A1/en not_active Abandoned
- 2010-05-17 WO PCT/FI2010/050397 patent/WO2010133762A1/en active Application Filing
- 2010-05-17 EP EP10722156.6A patent/EP2432934B1/en not_active Not-in-force
- 2010-05-17 CN CN201080022102.3A patent/CN102482850B/en not_active Expired - Fee Related
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2011
- 2011-11-10 ZA ZA2011/08255A patent/ZA201108255B/en unknown
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Cited By (1)
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WO2016001016A1 (en) | 2014-07-03 | 2016-01-07 | Basf Se | Aqueous surface-coating agent for paper and paperboard |
Also Published As
Publication number | Publication date |
---|---|
CN102482850B (en) | 2015-11-25 |
WO2010133762A1 (en) | 2010-11-25 |
JP2012527544A (en) | 2012-11-08 |
KR20120036315A (en) | 2012-04-17 |
CN102482850A (en) | 2012-05-30 |
BRPI1010992A2 (en) | 2019-04-09 |
CA2762024A1 (en) | 2010-11-25 |
ZA201108255B (en) | 2012-08-29 |
FI121478B (en) | 2010-11-30 |
FI20095547A0 (en) | 2009-05-18 |
US20120055642A1 (en) | 2012-03-08 |
EP2432934B1 (en) | 2013-09-04 |
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