CN103966896B - Modified filler and preparation method thereof, applies its slurry and paper - Google Patents
Modified filler and preparation method thereof, applies its slurry and paper Download PDFInfo
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- CN103966896B CN103966896B CN201310047279.4A CN201310047279A CN103966896B CN 103966896 B CN103966896 B CN 103966896B CN 201310047279 A CN201310047279 A CN 201310047279A CN 103966896 B CN103966896 B CN 103966896B
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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
- D21H17/20—Macromolecular organic compounds
- D21H17/21—Macromolecular organic compounds of natural origin; Derivatives thereof
- D21H17/24—Polysaccharides
- D21H17/25—Cellulose
-
- 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
- D21H11/00—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only
- D21H11/16—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only modified by a particular after-treatment
- D21H11/18—Highly hydrated, swollen or fibrillatable fibres
-
- 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
- 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
- D21H17/68—Water-insoluble compounds, e.g. fillers, pigments siliceous, e.g. clays
Abstract
The invention provides a kind of modifying nanometer cellulose filler, it contains nanometer fibrillation cellulose and filler, the 0.1%-20% that wherein nanometer fibrillation cellulose over dry quality is packing quality; Nanometer fibrillation cellulose surface carboxyl-content is 0.05-1.5mmol/g; This filler is that surperficial Zeta potential is more than or equal to 0 papermaking filler. The present invention also provides a kind of preparation method of modifying nanometer cellulose filler, slurry and paper that the cellulose modified filler of applying nano makes. Modified filler of the present invention surface has more carboxyl functional group, can increase itself and interfibrous adhesion, improves binding site and the poor problem of adhesion between conventional filler and fiber.
Description
Technical field
The present invention relates to modifying nanometer cellulose filler and preparation thereof that a kind of field of papermaking is usedMethod, and apply slurry and the paper that this modifying nanometer cellulose filler makes.
Background technology
The trend of paper industry is in paper, to add more fillers to reduce making fiberWith, thereby reduce production costs. The intensity of paper depend primarily between fiber interweave withIn conjunction with intensity, the filler adding can be distributed in the contact point of fiber surface, fiber and fiberBetween. Most of filling surface is weak elecrtonegativity and surperficial without the official such as carboxyl, hydroxyl energyGroup, can not form effective combination by charge attraction or hydrogen bond action and fiber, therefore causesHimself keep rate variance, and can hinder adhesion between fiber and fiber.
Summary of the invention
In view of this, be necessary to provide a kind of nano-cellulose of effective raising filler retentionModified filler and preparation method thereof.
In addition, be also necessary to provide a kind of slurry of applying above-mentioned modifying nanometer cellulose filler.
In addition, be also necessary to provide a kind of paper that above-mentioned slurry makes of applying.
A kind of modifying nanometer cellulose filler, it contains nanometer fibrillation cellulose and filler,The 0.1%-20% that wherein nanometer fibrillation cellulose over dry quality is packing quality; Nanometer fentoCellulose surface carboxyl-content is 0.05-1.5mmol/g; This filler is surperficial Zeta potentialBe more than or equal to 0 papermaking filler.
A preparation method for modifying nanometer cellulose filler, it comprises the steps:
Nanometer fibrillation cellulose is provided, and this nanometer fibrillation cellulose surface carboxyl-content is0.05-1.5mmol/g；
Fillers dispersed liquid is provided, and this filler is that surperficial Zeta potential is more than or equal to 0 papermaking and fills outMaterial;
In the fillers dispersed liquid that nanometer fibrillation cellulose (NFC) is joined, stir allEven acquisition modifying nanometer cellulose filler.
A kind of slurry, it contains modifying nanometer cellulose filler and cationic polyelectrolyte, shouldModifying nanometer cellulose filler contains nanometer fibrillation cellulose and filler, wherein nanometer fentoThe 0.1%-20% that cellulose over dry quality is packing quality; Nanometer fibrillation cellulose surfaceCarboxyl-content is 0.05-1.5mmol/g; The surperficial Zeta potential of this filler is more than or equal to 0Papermaking filler.
A kind of above-mentioned slurry paper making of manufacturing paper with pulp of applying.
The nanometer fibrillation cellulose (NFC) that the present invention uses, has high-specific surface area, heightThe characteristic of intensity, high surface negative charge density and easy film forming, is used NFC modified filler, logicalCross this nano-cellulose to the coated of filler or suction-operated between the two, give fillerCarboxyl functional group and charge density that surface is certain. Then utilize cationic polyelectrolyte his-and-hers watchesFace presents the reservation of the interaction increase filler between stronger electronegative modified filler; WithThe carboxyl functional group that Shi Liyong modified filler surface is more, can increase itself and interfibrous knotMake a concerted effort, improve binding site and the poor problem of adhesion between conventional filler and fiber.
Detailed description of the invention
Nanometer fibrillation cellulose used in the present invention (NFC) adopts known TEMPOCatalytic oxidation preparation, is specially: fibrous raw material is through the oxidation taking TEMPO as catalystReaction, then carry out mechanical treatment acquisition. Fibrous raw material can be softwood, broadleaf and standing grain originallySlurry prepared by section plant, preferably sulfuric acid salt softwood pulp and sulfate hardwood pulp. WithTEMPO be the oxidation reaction of catalyst preferably use TEMPO-NaBr-NaClO system orTEMPO-NaClO-NaClO2System. Mechanical treatment can adopt high shear dispersion machine, ultrasonicOne or more processing modes in ripple processing, high pressure homogenizer, microfluidization device, preferably makeWith high pressure homogenizer and microfluidization device.
The composition of NFC prepared by TEMPO catalytic oxidation is single, and fibrillation is thorough, onlyContain water miscible nanofiber cellulosic material and derivative salt, be of a size of that (length is 100-numberThousand nanometers, width is 4-200 nanometer). Fibrillation fibrous material (MFC) also can adoptThe preparation of TEMPO catalytic oxidation, has water-soluble in the composition of MFC in the material composition containingFiber and the water-insoluble fiber of property, fibrillation is not thorough, is a kind of complicated ingredient. NFCMainly be with the difference of MFC, separate fibrillation degree difference, the MFC of complicated component is NFC" semi-finished product " in preparation process.
Carboxyl is contained on NFC surface prepared by TEMPO catalytic oxidation. Control fibrous raw materialUnder certain TEMPO and NaBr consumption, adjust NaClO consumption and can prepare differenceThe NFC of carboxyl-content.
A preparation method for slurry, it comprises the steps:
(1) preparation of modifying nanometer cellulose filler.
In the fillers dispersed liquid (mass percentage concentration is 10%-50%) that NFC is joined,Stir 5-15min and obtain modifying nanometer cellulose filler, wherein NFC over dry quality is fillerThe 0.1%-20% of over dry quality, is preferably the 0.1%-10% of filler over dry quality.
This NFC surface carboxyl-content is 0.05-1.5mmol/g, is preferably 0.1-1.0mmol/g.
The surperficial Zeta potential of this filler is more than or equal to 0, specifically can be winnofil(PCC), the papermaking filler such as grinding calcium carbonate (GCC), kaolin, talcum powder, preferablyPCC, kaolin, talcum powder.
This NFC be surface with strong elecrtonegativity, filler particles is that zeta current potential is greater than 0mv,Surface presents electropositive, and due to attracting each other of positive and negative charge, described water miscible NFC willPartly or entirely be coated on the surface of filler particles. In addition, NFC surface is with a large amount of carboxylsAnd hydroxyl, in the easy film forming in the surface of filler, thereby realize the absorption to filler or be coated.
(2) modifying nanometer cellulose filler is joined in slurry (slurry kind is not limit) to modificationThe over dry quality of filler is the 5%-100% of slurry over dry quality, and adds slurry over dry qualityThe cationic polyelectrolyte of 0.01%-1%, scattered slurry can handsheet for subsequent use. This cationElectrolyte can be the conventional cation of the papermaking such as cationic starch, PAMCPolyelectrolyte.
Modified filler is coated with NFC, is equivalent to modified filler surface with strong negative electrical charge,After adding in slurry, described strong electronegative modified filler cannot be weak electronegative with surfacePulp fiber directly combines, and therefore needs to use cationic polyelectrolyte, by sunThe instrumentality of ion polyelectrolyte, combines modified filler and pulp fiber, carriesThe retention of high modified filler.
A kind of modifying nanometer cellulose filler, its contain nanometer fibrillation cellulose (NFC) andFiller, the 0.1%-20% that wherein NFC over dry quality is packing quality, is preferably filler matterThe 0.1%-10% of amount. This NFC surface carboxyl-content is 0.05-1.5mmol/g, is preferably0.1-1.0mmol/g. The surperficial Zeta potential of this filler is more than or equal to 0, specifically can be precipitationThe papermaking fillers such as calcium carbonate (PCC), grinding calcium carbonate (GCC), kaolin, talcum powder,Preferably PCC, kaolin, talcum powder.
A slurry that contains above-mentioned modifying nanometer cellulose filler, also contains sun in this slurryIon polyelectrolyte.
The slurry that a kind of application the contains above-mentioned modifying nanometer cellulose filler paper making of manufacturing paper with pulp, this paper has higher filler retention, and its filler retention reaches and is greater than 85%.
The present invention uses TEMPO catalytic oxidation to prepare nanometer fibrillation cellulose (NFC),NFC has the characteristic of high-specific surface area, high strength, high surface negative charge density and easy film forming,Use NFC modified filler, by this nano-cellulose to the coated of filler or between the twoSuction-operated, give the certain carboxyl functional group of filling surface and charge density. Then profitPresent the mutual work between stronger electronegative modified filler with cationic polyelectrolyte effects on surfaceWith the reservation that increases filler; Utilize the more carboxyl functional group in modified filler surface simultaneously, canTo increase itself and interfibrous adhesion, improve binding site and combination between conventional filler and fiberThe problem that power is poor.
Below by specific embodiment, the present invention is described further.
Comparative example 1
Unmodified PCC is joined in leaf wood bleached kraft pulp (LBKP), addThe quality that enters PCC is 25% of LBKP over dry quality, adds LBKP over dry quality0.8% cationic starch. Handsheet after stirring, becoming the content of ashes of paper is 5.67%,Filler retention is 24.04%, and tensile strength is 52.9Nm/g.
Embodiment 1
Carboxyl-content is that the NFC of 1.5mmol/g carries out modification to PCC, and NFC consumption is0.1% of over dry PCC quality. PCC after modification joins in LBKP slurry, addsThe quality of PCC is 25% of LBKP slurry over dry quality, adds LBKP slurry over dry quality0.8% cationic starch. Handsheet after stirring, becoming the content of ashes of paper is 6.12%,Filler retention is 26.07%, and tensile strength is 52.5Nm/g.
Embodiment 2
Carboxyl-content is that the NFC of 1.5mmol/g carries out modification to PCC, and NFC consumption is1% of over dry PCC quality. PCC after modification joins in LBKP slurry, adds PCCQuality be 25% of LBKP slurry over dry quality, add 0.8% of LBKP slurry over dry qualityCationic starch. Handsheet after stirring, becoming the content of ashes of paper is 8.01%, fillerRetention rate is 34.83%, and tensile strength is 49.7Nm/g.
Embodiment 3
Carboxyl-content is that the NFC of 1.5mmol/g carries out modification to PCC, and NFC consumption is5% of over dry PCC quality. PCC after modification joins in LBKP slurry, adds PCCQuality be 25% of LBKP over dry quality, add the sun of LBKP slurry over dry quality 0.8%Ionic starch. Handsheet after stirring, becoming the content of ashes of paper is 12.30%, filler retainsRate is 56.10%, and tensile strength is 49.0Nm/g.
Embodiment 4
Carboxyl-content is that the NFC of 1.5mmol/g carries out modification to PCC, and NFC consumption is10% of over dry PCC quality. PCC after modification joins in LBKP slurry, addsThe quality of PCC is 25% of LBKP over dry quality, adds LBKP slurry over dry quality 0.8%Cationic starch. Handsheet after stirring, becoming the content of ashes of paper is 13.36%, fillerRetention rate is 61.68%, and tensile strength is 49.4Nm/g.
Embodiment 5
Carboxyl-content is that the NFC of 1.5mmol/g carries out modification to PCC, and NFC consumption is20% of over dry PCC quality. PCC after modification joins in LBKP slurry, addsThe quality of PCC is 25% of LBKP over dry quality, adds LBKP slurry over dry quality 0.8%Cationic starch. Handsheet after stirring, becoming the content of ashes of paper is 14.36%, fillerRetention rate is 67.07%, and tensile strength is 49.1Nm/g.
Embodiment 6
Carboxyl-content is that the NFC of 0.8mmol/g carries out modification to PCC, and NFC consumption is5% of over dry PCC quality. PCC after modification joins in LBKP slurry, adds PCCQuality be 5% of LBKP over dry quality, add the sun of LBKP slurry over dry quality 0.8%Ionic starch. Handsheet after stirring, becoming the content of ashes of paper is 1.16%, filler retainsRate is 23.47%, and tensile strength is 53.1Nm/g.
Embodiment 7
Carboxyl-content is that the NFC of 0.8mmol/g carries out modification to PCC, and NFC consumption is5% of over dry PCC quality. PCC after modification joins in LBKP slurry, adds PCCQuality be 25% of LBKP over dry quality, add the sun of LBKP slurry over dry quality 0.8%Ionic starch. Handsheet after stirring, becoming the content of ashes of paper is 11.52%, filler retainsRate is 52.08%, and tensile strength is 47.1Nm/g.
Embodiment 8
Carboxyl-content is that the NFC of 0.8mmol/g carries out modification to PCC, and NFC consumption is5% of over dry PCC quality. PCC after modification joins in LBKP slurry, adds PCCQuality be 75% of LBKP over dry quality, add the sun of LBKP slurry over dry quality 0.8%Ionic starch. Handsheet after stirring, becoming the content of ashes of paper is 24.53%, filler retainsRate is 43.34%, and tensile strength is 31.1Nm/g.
Embodiment 9
Carboxyl-content is that the NFC of 0.8mmol/g carries out modification to PCC, and NFC consumption is5% of over dry PCC quality. PCC after modification joins in LBKP slurry, adds PCCQuality be 100% of LBKP over dry quality, add LBKP slurry over dry quality 0.8%Cationic starch. Handsheet after stirring, becoming the content of ashes of paper is 28.16%, filler is protectedStaying rate is 39.20%, and tensile strength is 28.6Nm/g.
Embodiment 10
Carboxyl-content is that the NFC of 0.05mmol/g carries out modification to PCC, and NFC consumption is5% of over dry PCC quality. PCC after modification joins in LBKP slurry, adds PCCQuality be 25% of LBKP over dry quality, add the sun of LBKP slurry over dry quality 0.8%Ionic starch. Handsheet after stirring, becoming the content of ashes of paper is 7.16%, filler retainsRate is 30.85%, and tensile strength is 52.6Nm/g.
Embodiment 11
Carboxyl-content is that the NFC of 0.8mmol/g carries out modification to PCC, and NFC consumption is5% of over dry PCC quality. PCC after modification joins needlebush bleached sulphate(NBKP), in slurry, the quality that adds PCC is 25% of NBKP over dry quality, addsEnter the cationic starch of NBKP slurry over dry quality 0.8%. Handsheet after stirring, one-tenth paperContent of ashes is 7.76%, and filler retention is 33.65%, and tensile strength is 81.5Nm/g.
Embodiment 12
Carboxyl-content is that the NFC of 0.8mmol/g carries out modification to PCC, and NFC consumption is5% of over dry PCC quality. PCC after modification joins APMP(APMP), in slurry, the quality that adds PCC is 25% of APMP over dry quality, addsEnter the cationic starch of APMP slurry over dry quality 0.8%. Handsheet after stirring, one-tenth paperContent of ashes is 12.70%, and filler retention is 58.19%, and tensile strength is 22.7Nm/g.
Embodiment 1-12 and comparative example 1 the performance test results are as shown in following table one.
Table one
Known according to the test result of table one: comparative example 1 relatively, the filler of embodiment 1-12Retention rate all has obvious lifting.
In addition, those skilled in the art also can be in the claims in the present invention scope of disclosure and essenceIn god, make various amendments, interpolation and replacement in other form and details. Certainly, these are complied withThe variations such as various amendments, interpolation and the replacement of making according to spirit of the present invention, all should be included in thisWithin inventing scope required for protection.
Claims (14)
1. a modifying nanometer cellulose filler, is characterized in that: this modifying nanometer celluloseFiller mainly contains nanometer fibrillation cellulose and filler, and nanometer fibrillation cellulose is coatedIn the surface of filler particles, wherein nanometer fibrillation cellulose over dry quality is packing quality0.1%-20%; Nanometer fibrillation cellulose surface carboxyl-content is 0.05-1.5mmol/g; ShouldFiller is that surperficial Zeta potential is more than or equal to 0 papermaking filler.
2. modifying nanometer cellulose filler as claimed in claim 1, is characterized in that: receiveThe 0.1%-10% that rice fibrillation cellulose over dry quality is packing quality.
3. modifying nanometer cellulose filler as claimed in claim 1, is characterized in that: receiveRice fibrillation cellulose surface carboxyl-content is 0.1-1.0mmol/g.
4. modifying nanometer cellulose filler as claimed in claim 1, is characterized in that: shouldFiller is winnofil, grinding calcium carbonate, kaolin or talcum powder.
5. a modifying nanometer cellulose filler as described in any one in claim 1-4Preparation method, it comprises the steps:
Nanometer fibrillation cellulose is provided, and this nanometer fibrillation cellulose surface carboxyl-content is0.05-1.5mmol/g；
Fillers dispersed liquid is provided, and this filler is that surperficial Zeta potential is more than or equal to 0 papermaking and fills outMaterial;
In the fillers dispersed liquid that described nanometer fibrillation cellulose is joined, stir and obtainObtain modifying nanometer cellulose filler.
6. the preparation method of modifying nanometer cellulose filler as claimed in claim 5, its spyLevy and be: the mass percentage concentration of this fillers dispersed liquid is 10%-50%.
7. a slurry, is characterized in that: in this slurry, contain modifying nanometer cellulose fillerAnd cationic polyelectrolyte, this modifying nanometer cellulose filler contains nanometer fibrillation celluloseAnd filler, the 0.1%-20% that wherein nanometer fibrillation cellulose over dry quality is packing quality;Nanometer fibrillation cellulose surface carboxyl-content is 0.05-1.5mmol/g; The surface of this fillerZeta potential is more than or equal to 0 papermaking filler.
8. slurry as claimed in claim 7, is characterized in that: this modifying nanometer celluloseThe 0.1%-10% that in filler, nanometer fibrillation cellulose over dry quality is packing quality.
9. slurry as claimed in claim 7, is characterized in that: nanometer fibrillation celluloseSurface carboxyl-content is 0.1-1.0mmol/g.
10. slurry as claimed in claim 7, is characterized in that: this nano-cellulose changesFiller in property filler is winnofil, grinding calcium carbonate, kaolin or talcum powder.
11. slurries as claimed in claim 7, is characterized in that: this cationic polyelectrolyteFor cationic starch or PAMC.
12. slurries as claimed in claim 7, is characterized in that: this nano-cellulose changesThe over dry quality of property filler is the 5%-100% of slurry over dry quality.
13. 1 kinds of application rights require in 7-12 described in any one the slurry paper making of manufacturing paper with pulp.
14. paper as claimed in claim 13, is characterized in that: the filler of this paper is protectedStay rate to reach and be greater than 85%.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310047279.4A CN103966896B (en) | 2013-02-05 | 2013-02-05 | Modified filler and preparation method thereof, applies its slurry and paper |
| US14/161,813 US20140216673A1 (en) | 2013-02-05 | 2014-01-23 | Modified filler composition, method for making same, pulp and paper using same |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201310047279.4A CN103966896B (en) | 2013-02-05 | 2013-02-05 | Modified filler and preparation method thereof, applies its slurry and paper |
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| CN103966896A CN103966896A (en) | 2014-08-06 |
| CN103966896B true CN103966896B (en) | 2016-05-18 |
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| CN (1) | CN103966896B (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| NO3090099T3 (en) * | 2013-12-30 | 2018-07-21 | ||
| TWI654141B (en) * | 2014-03-31 | 2019-03-21 | 日商日本製紙股份有限公司 | Calcium carbonate microparticles and method of producing the same |
| CN104452425B (en) * | 2014-11-06 | 2017-04-26 | 陕西科技大学 | Microfiber cellulose enveloped and retained high filling papermaking process |
| CN104863008B (en) * | 2015-04-23 | 2018-04-17 | 中国制浆造纸研究院有限公司 | A kind of method that paper opacity is improved using the cellulose modified filler of fibrillation |
| JP6616764B2 (en) * | 2016-11-30 | 2019-12-04 | 大王製紙株式会社 | Wet wipe sheet |
| CN108277686A (en) * | 2018-03-09 | 2018-07-13 | 天津科技大学 | A method of pretreatment calcium carbonate and its raising paper retention |
| CN110080036B (en) * | 2019-04-09 | 2021-11-30 | 中国制浆造纸研究院有限公司 | Fiber composite material containing microfibrillated cellulose and preparation method thereof |
| CN114808524A (en) * | 2022-04-08 | 2022-07-29 | 金光纸业(中国)投资有限公司 | Paper and preparation method thereof |
| CN115821635B (en) * | 2022-12-08 | 2024-03-22 | 陕西科技大学 | Fibrous flexible filler high-filling paper and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009153225A1 (en) * | 2008-06-17 | 2009-12-23 | Akzo Nobel N.V. | Cellulosic product |
| WO2012168562A1 (en) * | 2011-06-09 | 2012-12-13 | Upm-Kymmene Corporation | Method for catalytic oxidation of cellulose and method for making a cellulose product |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1936032A1 (en) * | 2006-12-18 | 2008-06-25 | Akzo Nobel N.V. | Method of producing a paper product |
| FI124464B (en) * | 2009-04-29 | 2014-09-15 | Upm Kymmene Corp | Process for the preparation of pulp slurry, pulp slurry and paper |
| CA2810424C (en) * | 2010-10-01 | 2018-04-03 | Fpinnovations | Cellulose-reinforced high mineral content products and methods of making the same |
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2013
- 2013-02-05 CN CN201310047279.4A patent/CN103966896B/en active Active
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009153225A1 (en) * | 2008-06-17 | 2009-12-23 | Akzo Nobel N.V. | Cellulosic product |
| WO2012168562A1 (en) * | 2011-06-09 | 2012-12-13 | Upm-Kymmene Corporation | Method for catalytic oxidation of cellulose and method for making a cellulose product |
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| US20140216673A1 (en) | 2014-08-07 |
| CN103966896A (en) | 2014-08-06 |
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