EP1921207B1 - Method for application of nano-particles during a papermaking process - Google Patents

Method for application of nano-particles during a papermaking process Download PDF

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Publication number
EP1921207B1
EP1921207B1 EP20060025073 EP06025073A EP1921207B1 EP 1921207 B1 EP1921207 B1 EP 1921207B1 EP 20060025073 EP20060025073 EP 20060025073 EP 06025073 A EP06025073 A EP 06025073A EP 1921207 B1 EP1921207 B1 EP 1921207B1
Authority
EP
European Patent Office
Prior art keywords
nano
particles
paper
organic
styrene
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.)
Not-in-force
Application number
EP20060025073
Other languages
German (de)
French (fr)
Other versions
EP1921207A1 (en
Inventor
Gisela Goldhalm
Gerhard Drexler
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Mondi AG
Original Assignee
Mondi AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Mondi AG filed Critical Mondi AG
Priority to EP20060025073 priority Critical patent/EP1921207B1/en
Priority to PCT/EP2007/009621 priority patent/WO2008055661A1/en
Publication of EP1921207A1 publication Critical patent/EP1921207A1/en
Application granted granted Critical
Publication of EP1921207B1 publication Critical patent/EP1921207B1/en
Not-in-force legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • 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
    • D21H21/50—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 form
    • D21H21/52—Additives of definite length or shape
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/33—Synthetic macromolecular compounds
    • D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/35—Polyalkenes, e.g. polystyrene
    • 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
    • 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
    • D21H19/58—Polymers or oligomers of diolefins, aromatic vinyl monomers or unsaturated acids or derivatives thereof

Definitions

  • the invention deals with a method for inline application of nano-hybrid particles during a papermaking process.
  • EP-A 1 422 248 discloses an aqueous dispersion containing nano-particles which is used as a paper sizing composition to improve the surface characteristics of the paper or the like.
  • Object of the invention is therefore a method of making a paper with improved surface properties, characterized in that that nano-hybrid particles consisting of organic nano particles and inorganic particles, the organic nano-particles being adhered to the surface of the inorganic particles wherein the nanohybrid particles contain 1-99% organic nano particles of polystyrene or a styrene copolymer having a size of 2 - 100 nm and 99-1% inorganic particles having a size of 50 nm - 20 ⁇ m are applied in the wet end of the paper making process by addition to the fiber suspension or applied onto the wet or dried paper fiber web.
  • the nano-hybrid particles consist of an organic and an inorganic part.
  • the organic part is nano sized having a particle size of about 2-100 nm.
  • the organic part preferably is of spherical shape.
  • the organic nano-particles are adhered to the surface of the inorganic particles, thus when applied in an aqueous solution on the surface of a porous substrate the nano-particles cannot disappear in the pores but are kept close to the surface.
  • Organic part of the nano-hybrid particles may be a polymer or a copolymer preferably polystyrene or styrene copolymers. Especially preferred are styrene maleimid copolymers or other styrene containing copolymers e.g. with butadiene, acrylic acid and the like.
  • the styrene part may also have functional groups such as sulfonic acid groups, carboxylic groups or pyridine groups.
  • the nano-hybrid particles may be prepared for example by dissolving the polymer or a copolymer of maleic anhydride with a vinyl monomer in water, adding a RNH 2 compound, R being H, alkyl with 1 - 18 carbon atoms or aryl and heating the resultant mixture in the presence of larger particles to make the imides. The polymeric particles will settle down on the larger particles.
  • Inorganic part can be CaCO 3 (ground or precipitated), TiO 2 , clay, aluminium oxide, aluminium hydroxide, talkum, zincoxide, zeolithe and the like.
  • the hybrid particles contain 1-99 wt% organic and 99-1 wt% inorganic material. Preferably the hybrid particles contain 3-45% of organic material and 97-55 wt% of inorganic material.
  • the nano-hybrid particles are preferably applied dry or preferably in an aqueous suspension with a solid content of 1-99%, preferably 10 - 80wt%, more preferably 35 - 70 wt% .
  • the composition preferably contains 1- 20% of organic material and 99 - 80 wt% of inorganic material, for application on the dry or wet fiber web, the composition preferably contains 3 - 45 wt% of organic material and 97 - 55 wt% of inorganic material.
  • the nano-hybrid particles can be applied in the wet end by addition to the fiber suspension or applied onto the wet or dried fiber web.
  • the fiber content of the paper fiber suspension will be 0,6 to 1,5 wt%.
  • the nano-hybrid particles suspension may be applied pure or mixed with different types of binders, eg. starch and starch derivates, PVOH, branched polymers, styrene acrylate latex, styrene butadiene latex, casein and/or several additives for brightness, shading and adjustment of the dielectrical properties, as NaCl, KCI, CaCl 2 , and the like.
  • binders eg. starch and starch derivates, PVOH, branched polymers, styrene acrylate latex, styrene butadiene latex, casein and/or several additives for brightness, shading and adjustment of the dielectrical properties, as NaCl, KCI, CaCl 2 , and the like.
  • Starch and starch derivatives may be added in an amount up to 10 wt%, preferably 1 - 2 wt%, PVOH may be added up to 10 wt%, preferably 0- 5 wt%, branched polymers up to 20 wt%, preferably 2-10 wt%, styrene acrylate latex, and styrene butadiene latex up to 20 wt%, preferably 5- 12 wt%.
  • Additives for brightness may be present in an amount of 0 - 5 wt%, preferably 1- 2 wt%, shading additives may be present in an amount of 0 - 2 wt% preferably 0 - 1 wt%, additives for the adjustment of dielectric properties may be added 0 - 7 wt %, preferably 0 - 2 wt %.
  • the nano particles may be applied inline or offline on the fiberweb.
  • Inline application of the dry nano-hybrid particles or the suspension of the nano-hybrid particles may be carried out by conventional surface coating methods e.g. size press, film press, blade, roller bar, curtain coating, spray coating and the like.
  • Offline application may be carried out by conventional surface coating methods e.g. size press, film press, blade, roller bar, curtain coating, spray coating and the like or by conventional printing techniques such as intaglio or gravure printing or flexographic printing or the like.
  • conventional surface coating methods e.g. size press, film press, blade, roller bar, curtain coating, spray coating and the like or by conventional printing techniques such as intaglio or gravure printing or flexographic printing or the like.
  • the paper produced shows improved surface appearance, as well as improved printing quality, especially in laser and digital printing processes.
  • Product will be an uncoated, pigmented or coated office and communication paper. Depending on process parameters the resulting paper may be glossy ot have a matt glaze.

Landscapes

  • Paper (AREA)

Description

  • The invention deals with a method for inline application of nano-hybrid particles during a papermaking process.
  • EP-A 1 422 248 discloses an aqueous dispersion containing nano-particles which is used as a paper sizing composition to improve the surface characteristics of the paper or the like.
  • Application of this composition on porous substrates such as paper is not very effective, because the nano-particles tend to disappear in the pores of the substrate during application, especially when applied with a blade or roll.
  • It is desirable to further improve the surface characteristic of porous substrates such as paper, by using all beneficial properties of a coating solution and to simplify the method of producing said paper.
  • It is an object of the invention to provide a method for producing a paper especially a printing paper with improved surface properties, especially enhanced optical appearance and improved print quality.
  • Object of the invention is therefore a method of making a paper with improved surface properties, characterized in that that nano-hybrid particles consisting of organic nano particles and inorganic particles, the organic nano-particles being adhered to the surface of the inorganic particles wherein the nanohybrid particles contain 1-99% organic nano particles of polystyrene or a styrene copolymer having a size of 2 - 100 nm and 99-1% inorganic particles having a size of 50 nm - 20 µm are applied in the wet end of the paper making process by addition to the fiber suspension or applied onto the wet or dried paper fiber web.
  • The nano-hybrid particles consist of an organic and an inorganic part. Preferably the organic part is nano sized having a particle size of about 2-100 nm. The organic part preferably is of spherical shape.
  • The organic nano-particles are adhered to the surface of the inorganic particles, thus when applied in an aqueous solution on the surface of a porous substrate the nano-particles cannot disappear in the pores but are kept close to the surface.
  • Organic part of the nano-hybrid particles may be a polymer or a copolymer preferably polystyrene or styrene copolymers. Especially preferred are styrene maleimid copolymers or other styrene containing copolymers e.g. with butadiene, acrylic acid and the like. The styrene part may also have functional groups such as sulfonic acid groups, carboxylic groups or pyridine groups.
  • The nano-hybrid particles may be prepared for example by dissolving the polymer or a copolymer of maleic anhydride with a vinyl monomer in water, adding a RNH2 compound, R being H, alkyl with 1 - 18 carbon atoms or aryl and heating the resultant mixture in the presence of larger particles to make the imides. The polymeric particles will settle down on the larger particles.
  • Inorganic part can be CaCO3 (ground or precipitated), TiO2, clay, aluminium oxide, aluminium hydroxide, talkum, zincoxide, zeolithe and the like.
  • The hybrid particles contain 1-99 wt% organic and 99-1 wt% inorganic material. Preferably the hybrid particles contain 3-45% of organic material and 97-55 wt% of inorganic material.
  • The nano-hybrid particles are preferably applied dry or preferably in an aqueous suspension with a solid content of 1-99%, preferably 10 - 80wt%, more preferably 35 - 70 wt% .
  • For application at the wet end the composition preferably contains 1- 20% of organic material and 99 - 80 wt% of inorganic material, for application on the dry or wet fiber web, the composition preferably contains 3 - 45 wt% of organic material and 97 - 55 wt% of inorganic material.
  • The nano-hybrid particles can be applied in the wet end by addition to the fiber suspension or applied onto the wet or dried fiber web.
  • For application in the wet end of the paper making process up to 20 - 35 wt% of the nano hybrids may be added.
    Usually the fiber content of the paper fiber suspension will be 0,6 to 1,5 wt%.
  • In the second case (application to the dry or wet fiber web) the nano-hybrid particles suspension may be applied pure or mixed with different types of binders, eg. starch and starch derivates, PVOH, branched polymers, styrene acrylate latex, styrene butadiene latex, casein and/or several additives for brightness, shading and adjustment of the dielectrical properties, as NaCl, KCI, CaCl2, and the like.
  • Starch and starch derivatives may be added in an amount up to 10 wt%, preferably 1 - 2 wt%, PVOH may be added up to 10 wt%, preferably 0- 5 wt%, branched polymers up to 20 wt%, preferably 2-10 wt%, styrene acrylate latex, and styrene butadiene latex up to 20 wt%, preferably 5- 12 wt%. Additives for brightness may be present in an amount of 0 - 5 wt%, preferably 1- 2 wt%, shading additives may be present in an amount of 0 - 2 wt% preferably 0 - 1 wt%, additives for the adjustment of dielectric properties may be added 0 - 7 wt %, preferably 0 - 2 wt %.
  • The nano particles may be applied inline or offline on the fiberweb.
    Inline application of the dry nano-hybrid particles or the suspension of the nano-hybrid particles may be carried out by conventional surface coating methods e.g. size press, film press, blade, roller bar, curtain coating, spray coating and the like.
  • Offline application may be carried out by conventional surface coating methods e.g. size press, film press, blade, roller bar, curtain coating, spray coating and the like or by conventional printing techniques such as intaglio or gravure printing or flexographic printing or the like.
  • Further, if applied in the wet end of the paper making process addition of the aqueous solution of nano-hybrid particles results in improved process parameters, such as improved de-watering performance. Thus the process or method for preparing the paper becomes more economical and thus cheaper.
  • The paper produced shows improved surface appearance, as well as improved printing quality, especially in laser and digital printing processes.
  • Product will be an uncoated, pigmented or coated office and communication paper. Depending on process parameters the resulting paper may be glossy ot have a matt glaze.
    • Example1:
  • Production of a multipurpose grade:
    • Hybrid pigment:
    • 10 wt % organic nanoparticle
    • 90 wt% precipitated calcium carbonate (PCC)
    • pH=10
    • 50 % slurry
    • added to a 4 wt% fiber suspension in the mixing vat + additives (defoamers, starch, retention aids, optical brighteners, shading colors, sizing agent ...)
    Content of this suspension is
    • 50 wt% hybrid pigment
    • 46 wt% fibers
    • 4 wt % additives
    This suspension is diluted down to 0,8 % and processed on the paper machine as conventional or laser grade paper. Example2:
  • Production of a pigmented laser or digital printing grade paper Coating contents:
    100 parts Hybrid pigment
    Consisting of
    30 parts talcum
    30 parts clay
    40 parts Styrenemaleimid-Copolymer
    10 parts Styrene butadiene latex
    0,5parts Highly branched polymer (Hybrane)
    0,7 parts Rheology modifier (PVOH)
    1 part Optical brightener
    0,1 part Shading color
    0,1 part defoamer
    0,1 part biocide
    Solid content: 50 % +/- 2 %
    pH=7-10
    Application on film press with rod no.4 or different rod.
    Application of 15 g/m2 per side
    Machine calendering or offline calendering for enhanced smoothness
    • Product:
    • Laser and digital printing paper
    • 80 - 300 g/m2

Claims (9)

  1. Method of making a paper with improved surface properties, characterized in that that nano-hybrid particles consisting of organic nano particles and inorganic particles, the organic nano-particles being adhered to the surface of the inorganic particles wherein the nanohybrid particles contain 1-99% organic nano particles of polystyrene or a styrene copolymer having a size of 2 - 100 nm and 99-1% inorganic particles having a size of 50 nm - 20 µm are applied in the wet end of the paper making process by addition to the fiber suspension or applied onto the wet or dried paper fiber web.
  2. Method according to claim 1, characterized in that nano-hybrid particles contain 3-45% of organic material and 97-55 % of inorganic material, for application onto the wet or dried fiber web.
  3. Method according to claim 1, characterized in that nano-hybrid particles contain 1- 20% of organic material and 99 - 80% of inorganic material for application in the wet end of the paper making process.
  4. Method according to one of claims 1 to 3 characterized in that the inorganic particles are CaCO3 (ground or precipitated), TiO2, clay, aluminium oxide, aluminium hydroxide, talkum, zincoxide or zeolithe.
  5. Method according to one of claims 1 to 4 characterized in that, the organic paricles are formed from an copolymer of styrene with maleic imide or butadiene or acrylic acid.
  6. Method according to one of claims 1 to 5 characterized in that the solution applied contains binders, eg. starch and starch derivates, PVOH, branched polymers, styrene acrylate latex, styrene butadiene latex, casein and/or several additives for brightness, shading and adjustment of the dielectrical properties, as NaCl, KCl, CaCl2, and the like.
  7. Method according to claims 1 to 6, characterized in that the nano hybrid particles are applied inline by conventional surface coating methods e.g. size press, film press, blade, roller bar, curtain coating or spray coating.
  8. Method according to claims 1 to 6, characterized in that the nano hybrid particles are applied offline by conventional surface coating methods e.g. size press, film press, blade, roller bar, curtain coating, spray coating or by conventional printing techniques such as intaglio or gravure printing or flexographic printing.
  9. Use of the paper produced according to one of claims 1 to 9 as uncoated, pigmented or coated paper.
EP20060025073 2006-11-10 2006-11-10 Method for application of nano-particles during a papermaking process Not-in-force EP1921207B1 (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
EP20060025073 EP1921207B1 (en) 2006-11-10 2006-11-10 Method for application of nano-particles during a papermaking process
PCT/EP2007/009621 WO2008055661A1 (en) 2006-11-10 2007-11-07 Method for application of nano particles during a papermaking process

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP20060025073 EP1921207B1 (en) 2006-11-10 2006-11-10 Method for application of nano-particles during a papermaking process

Publications (2)

Publication Number Publication Date
EP1921207A1 EP1921207A1 (en) 2008-05-14
EP1921207B1 true EP1921207B1 (en) 2013-01-02

Family

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Family Applications (1)

Application Number Title Priority Date Filing Date
EP20060025073 Not-in-force EP1921207B1 (en) 2006-11-10 2006-11-10 Method for application of nano-particles during a papermaking process

Country Status (2)

Country Link
EP (1) EP1921207B1 (en)
WO (1) WO2008055661A1 (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010022410A2 (en) * 2008-08-18 2010-02-25 Air Revolution Technologies (Proprietary) Limited Air purifying means
CN105421142A (en) * 2015-11-03 2016-03-23 广东志造生物科技有限公司 Paper coating composition containing bio-based starch adhesive and coating method

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4567099A (en) * 1984-12-21 1986-01-28 The Dow Chemical Company High solids latexes for paper coatings
DE3924846A1 (en) * 1989-07-27 1991-02-14 Basf Ag Aq. paper-coating material with high solids content - contains pigment mixt. of coarse calcium carbonate and non-film-forming polymer dispersion, and synthetic polymer binder dispersion
US20010036990A1 (en) * 2000-03-30 2001-11-01 Bobsein Barrett Richard Waterborne paper or paperboard coating composition
US6579816B2 (en) * 2001-01-26 2003-06-17 The Procter & Gamble Company Multi-purpose absorbent and shred-resistant sheet material
WO2003031719A1 (en) * 2001-10-09 2003-04-17 Fletcher Building Holdings Limited Plasterboard liner
WO2004030917A1 (en) * 2002-10-01 2004-04-15 Sappi Netherlands Services B.V. Coated printing sheet and process for making same
EP1422248A1 (en) 2002-10-04 2004-05-26 Raisio Chemicals Ltd. A plastic pigment comprising an aqueous dispersion of styrene maleimine acid anhydride particles
US6942897B2 (en) * 2003-02-19 2005-09-13 The Board Of Trustees Of Western Michigan University Nanoparticle barrier-coated substrate and method for making the same

Also Published As

Publication number Publication date
WO2008055661A1 (en) 2008-05-15
EP1921207A1 (en) 2008-05-14

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