WO2010070205A1 - Coating colour composition and paper or paperboard coated with it - Google Patents

Coating colour composition and paper or paperboard coated with it Download PDF

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Publication number
WO2010070205A1
WO2010070205A1 PCT/FI2009/051012 FI2009051012W WO2010070205A1 WO 2010070205 A1 WO2010070205 A1 WO 2010070205A1 FI 2009051012 W FI2009051012 W FI 2009051012W WO 2010070205 A1 WO2010070205 A1 WO 2010070205A1
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WO
WIPO (PCT)
Prior art keywords
binder
parts
coating colour
coating
colour composition
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.)
Ceased
Application number
PCT/FI2009/051012
Other languages
French (fr)
Inventor
Jonni Ahlgren
Antti Matula
Tarja Turkki
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.)
Kemira Oyj
Original Assignee
Kemira Oyj
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
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First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=40240609&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=WO2010070205(A1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Priority to CN2009801512216A priority Critical patent/CN102257218A/en
Priority to RU2011129596/05A priority patent/RU2528639C2/en
Priority to KR1020117012297A priority patent/KR101488381B1/en
Priority to PL09796405T priority patent/PL2370631T3/en
Priority to ES09796405.0T priority patent/ES2655302T3/en
Application filed by Kemira Oyj filed Critical Kemira Oyj
Priority to EP09796405.0A priority patent/EP2370631B1/en
Priority to JP2011541527A priority patent/JP5677976B2/en
Priority to EP17200300.6A priority patent/EP3296459B1/en
Publication of WO2010070205A1 publication Critical patent/WO2010070205A1/en
Priority to ZA2011/03276A priority patent/ZA201103276B/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D125/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Coating compositions based on derivatives of such polymers
    • C09D125/02—Homopolymers or copolymers of hydrocarbons
    • C09D125/04—Homopolymers or copolymers of styrene
    • C09D125/08—Copolymers of styrene
    • C09D125/14—Copolymers of styrene with unsaturated esters
    • 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
    • D21H19/38—Coatings with pigments characterised by the pigments
    • D21H19/40—Coatings with pigments characterised by the pigments siliceous, e.g. clays
    • 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
    • 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
    • D21H19/54—Starch
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D103/00—Coating compositions based on starch, amylose or amylopectin or on their derivatives or degradation products
    • C09D103/02—Starch; Degradation products thereof, e.g. dextrin
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D109/00—Coating compositions based on homopolymers or copolymers of conjugated diene hydrocarbons
    • C09D109/06—Copolymers with styrene
    • C09D109/08—Latex
    • 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
    • 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
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31855—Of addition polymer from unsaturated monomers
    • Y10T428/3188—Next to cellulosic
    • Y10T428/31895—Paper or wood
    • Y10T428/31906—Ester, halide or nitrile of addition polymer

Definitions

  • the present invention relates to a coating colour composition and to the paper or paperboard according to the preambles of the enclosed claims.
  • the invention relates also to a use of styrene acrylate copolymer.
  • Paper and paperboard are coated with different coating colours in order to improve, among other things, their strength, phntability and appearance, e.g. smoothness and gloss.
  • Conventional coating compositions comprise mainly pigment and binder, and possible other additives, such as co-binders, preservatives, dispersing agents, defoaming agents, lubricants, hardeners and optical bhghteners.
  • binder in the coating composition is to bind the pigment particles to each other and to the base paper. Binder may also have an effect on the rheological properties of the coating composition.
  • Typical synthetic binders are polymers based on butadiene, styrene, vinyl acetate, butyl acrylate and acrylic acid monomers. Such polymer dispersions are conventionally called latex binders, and they have a particle size around 0.1 - 0.2 ⁇ m. As the latex binders are synthetic compounds their price may be relatively high. Therefore it would be advantageous to minimise the amount of binder in the coating composition without impairing the properties of the composition and the resulting coated paper.
  • Styrene/acrylate copolymers as surface sizing agents are known.
  • US 6,426,381 discloses styrene/(meth)acrylate copolymers that can be used for surface sizing.
  • JP 58/115196 discloses a water soluble paper strength increasing agent which is prepared by graft copolymerising styrene and acrylate in presence of starch. The agent is said to improve the strength and sizing degree of paper.
  • An object of this invention is to provide a coating colour composition with which the disadvantages in the prior art may be minimised or even eliminated.
  • An object is also to provide a coating colour composition which improves the strength properties of the coated paper or paperboard.
  • a further object of this invention is to provide a coating colour composition, where amount of the binder may be reduced without impairing the strength properties of the coated paper.
  • Typical coating colour composition for paper and/or paperboard according to the present invention comprises
  • binder substitute comprising styrene acrylate copolymer having mean particle size ⁇ I OO nm.
  • Typical paper or paperboard according to the present invention is coated with a coating colour composition according the present invention.
  • the binder substitute when used to replace a part of the conventional binder it has been found out that the amount of the total binder may easily be reduced by 20 - 30 % without impairment of the strength properties of the paper. Reduction of the amount of total binder naturally decreases the costs associated with it.
  • the styrene acrylate copolymer that is used as the binder substitute may be obtained by copolymerisation of ethylenically unsaturated monomers.
  • Suitable styrene monomers are styrene and substituted styrenes, such as ⁇ -methylstyrene or vinyltoluene or their mixtures, and suitable acrylate monomers are C1 -C4-alkyl acrylates, C1 -C4-alkyl methacrylates or their mixtures, e.g.
  • the mixtures of n-butyl acrylate and tert-butyl acrylate are used in polymerisation.
  • the mixing ratio may be 10:90 to 90:10.
  • the binder substitute is a styrene acrylate copolymer comprising starch.
  • the styrene acrylate copolymer may be obtained as described in US 6,426,381 , i.e. by free radical emulsion copolymerisation of ethylenically unsaturated monomers in the presence of starch.
  • Starch may be any suitable native starch, such as potato, rice, corn, waxy corn, wheat, barley or tapioca starch, potato starch being preferred. Starches having a amylopectin content > 80 %, preferably >95 %, are advantageous.
  • Starch may be also modified, for example, anionised, cationised or degraded.
  • Anionised starch comprises anionic groups, such as carboxylate or phosphate groups, whereas cationised starch comprises cationic groups, such as quaternized ammonium groups.
  • Degree of substitution (DS) indicating the number of anionic/cationic groups in the starch on average per glucose unit, is typically 0.01 -0.20.
  • Amphoteric starches, comprising both anionic and cationic groups, may also be used in the preparation of the styrene acrylate copolymer. Degraded starch is obtained by subjecting the starch to oxidative, thermal, acidic or enzymatic degradation, oxidative degradation being preferred. Hypochlorite, peroxodisulphate, hydrogen peroxide or their mixtures may be used as oxidising agents.
  • Degraded starch has typically an average molecular weight (Mn) 500 - 10 000, which can be determined by known gel chromatography methods.
  • the intrinsic viscosity is typically 0.05 to 0.12 dl/g, determined, for example, by known viscosimetric methods.
  • any other polysaccharide which contains a free hydroxyl group, such as amylose, amylopectine, carrageen, cellulose, chitosan, chitin, dexthnes, guar gum (guarane) and other galactomannans, arabic gum, hemicellulose components, and pullulan, for obtaining styrene acrylate copolymer used in the present invention.
  • Dextrin is more preferred of the polysaccharides listed, i.e. the styrene acrylate copolymer comprises dextrin.
  • the binder substitute may be used in form of aqueous polymer dispersion having a solids content of 10 - 50 %, preferably 20 - 50 %, more preferably 21 - 29 %, most preferably 35 - 40 %. High solids content is advantageous as the amount of water in the coating composition may be minimised.
  • the mean particle size of the binder substitute as an aqueous dispersion is at least 20 nm, preferably at least 25 nm, more preferably 30 nm, still more preferably 35 nm, most preferably at least 40 nm, and less than 90 nm, preferably less than 80 nm, more preferably less than 70 nm, still more preferably less than 60, most preferably less than 50 nm.
  • the mean particle size of the binder substitute is ⁇ 100 nm.
  • the mean particle size of the binder substitute as an aqueous dispersion is in the range 20 - 100, preferably 30 - 80 nm, more preferably 40 - 70 nm, most preferably 60 - 70.
  • the mean particle size of the binder substitute may be determined by photon correlation spectroscopy using for example a Malvern Zetamaster equipment.
  • the coating composition comprises, besides the binder substitute, also a latex binder.
  • Typical synthetic latex binders that may be used in the present invention are latices known in the art, such as styrene butadiene (SB) latex, styrene acrylate (SA) latex or polyvinyl acetate
  • Latex binder Preferably the latex binder is styrene butadiene (SB) latex. Latex binder may be considered as a main binder of the coating composition, amount of which is reduced by using the binder substitute according to the present invention.
  • the coating composition may also comprise in addition to the binder substitute and possible main binder also starch binder, which starch may be anionic or cationic.
  • Typical pigments that may be used in the present invention are calcium carbonate, kaolin, calcinated kaolin, talc, titanium dioxide, gypsum, chalk, satine white, barium sulphate, sodium aluminium silicate, aluminium hydroxide or any of their mixture.
  • Calcium carbonate may be ground calcium carbonate (GCC) or precipitated calcium carbonate (PCC) or their mixture.
  • GCC ground calcium carbonate
  • PCC precipitated calcium carbonate
  • the pigment is calcium carbonate.
  • Particle size D 50 of the pigments used in coating compositions is typically in the range of ⁇ 5 ⁇ m.
  • composition of the coating colour mixture is given, as conventional in the art, by giving the total amount of pigments value 100, and calculating the amounts of other components relative to the amount of the total pigment (pph). Proportions of all components are given as active substances.
  • the binder substitute may be used together with conventional co-binders, such as carboxy methyl cellulose (CMC), polyvinyl alcohol (PVOH), starch, casein or protein.
  • Amount of the co-binders in the coating composition is normally 0.05 - 3 parts. In case of starch, the amount of may be 0.05 - 12 parts, preferably 0.1 - 10 parts.
  • Possible additives are, for example, preservatives, dispersing agents, defoaming agents, lubricants, hardeners and optical bhghteners.
  • the amount of other additives are normally 0 - 3 parts.
  • binder preferably latex binder, - 1.5 - 9 parts of binder substitute
  • the coating colour composition comprises - 100 parts of pigment, - 4 - 12 parts of starch,
  • binder preferably latex binder
  • the coating colour comprises - 100 parts of pigment
  • binder substitute - 2 - 3 parts of binder substitute, and - 0 - 3 parts of known additives.
  • the coating colour according to the present invention may be prepared in conventional way, i.e. the pigment slurry is mixed with the binder substitute in dispersion form and possible other additives as added as customary. If conventional binder is used in addition to the binder substitute it is also added to the coating colour composition as customary. As existing equipment and procedures may be used when using the binder substitute according to the present invention, no extensive modification of the equipment is needed.
  • the coating colour according to the present invention has a solids content of 60 - 74 %, preferably 63 - 72 %, more preferably 65 - 71 % and viscosity ⁇ 2500, typically 1000 - 2000 mPas. Viscosities are measured by using Brookfield viscometer, type DV-II, with speed 100 rpm and using spindle 3 or 4.
  • the coating colour composition is applied on paper or paperboard surface in single or multiple coating layers.
  • Applied coating methods include for example blade, rod, film transfer or air brush coating.
  • Applied coat weights are typically in the range of 5 - 30 g/m 2 /side. In one applied coating layer the coat weight is generally 5 - 16 g/m 2 /side, more typically 6 - 14 g/m 2 /side, and most typically 8 - 12 g/m 2 /side.
  • Oxidatively degraded potato starch (Perfectamyl® A 4692) in amount of 67 g is dispersed in 536 g of demineralized water under constant stirring in a 2 I three- necked flask having a reflux condenser.
  • Starch is dissolved by heating to a temperature of 85 0 C, whereby 20.0 g of a 1 % aqueous solution of FeSO 4 x 7H2O (0.72 mmol) and 4.0 g of 35% hydrogen peroxide are added in succession. After 15 minutes, the starch degradation is complete.
  • the solution comprising monomers and the initiator solution are metered in simultaneously but separately in the course of 90 min at 85 0 C at constant feed rate.
  • the monomer solution comprises 86.6 g of styrene, 43.3 g of n-butyl acrylate and 43.3 g of tert-butyl acrylate.
  • the initiator solution comprises 4.3 g of hydrogen peroxide (35 %) and 127 g of water.
  • the polymerisation is performed in nitrogen atmosphere.
  • the mean particle size, measured by Malvern Zetamaster, is 61.3 nm.
  • Coating colours are prepared and diluted to 50% solids content in order to be used in laboratory coating. Paper samples are draw-down coated. Surface strength is measured with IGT-device (IGT Testing Systems). The results are summarized in table 2. Table 1. Coating colour composition used
  • Binder substitute 1 comprises styrene acrylate copolymer polymerised in presence of anionic starch and binder substitute 2 comprises styrene acrylate copolymer polymerised in presence of cationic starch.
  • Binder substitute 1 is prepared according to the general description above. Binder substitute 1 and binder substitute 2 have solids contents 24 and 25 %, respectively. Commercial styrene butadiene is used in the coating composition as main binder. Type of the binder substitute is the only variable in the coating colour compositions. Coating colour compositions are prepared using Diaf laboratory dissolver and diluted to 50% solids content. Coating colour compositions are shown in Table 1.
  • compositions are run without any problems with the coating apparatus. Blade pressures are on the same level with all compositions.
  • the reference composition has the lowest Brookfield viscosity.
  • Paper samples coated with the test compositions are calendered on Optiload Twinline. Calendering speed is 800 m/min and roll temperature 12O 0 C.
  • the coated paper samples are printed using 5-color (B, C, M, B, C) printing with constant density and speed 8000 sheets/h on Man Roland 300 printing press.
  • 5-color (B, C, M, B, C) printing with constant density and speed 8000 sheets/h on Man Roland 300 printing press.
  • Piling and picking of the paper samples were also analyzed and the results are shown in table 5.
  • IGT surface strength results on machine direction (MD) and cross direction (CD) are summarized in table 7.
  • IGT-surface strength (m/s): Comp. Comp. Comp. Comp. Comp. Ref. 3 4 5 6
  • binder substitutes Compatibility of the binder substitutes with starch is tested. Laboratory tests are carried out with binder substitutes 1 and 2, the binder substitute 1 comprising styrene acrylate copolymer polymerised in presence of cationic starch and binder substitute 2 comprising styrene acrylate copolymer polymerised in presence of anionic starch. Binder substitute 1 has solids content of 24 %, and binder substitute 2 has solids content of 25 %.
  • the used coating colour recipe is shown in table 8. Table 8. Starch containing coating colour composition
  • composition A comprised binder substitute 1 and composition B binder composition 2.
  • Table 9 Properties of the coating colour compositions comprising starch and binder substitute .
  • Binder substitute 1 gives similar viscosity to coating colour composition than the SB latex used as reference. Coating colour composition comprising binder substitute 2 has higher viscosity value than the reference. The reference colour has the lowest high shear viscosity. Binder substitute 1 gives lower viscosity to the coating colour composition than binder substitute 2. All viscosity values are good or acceptable for the tested coating compositions
  • Paper samples are draw-down coated with the tested coating compositions. The surface strength is determined, and the results are presented in table 10.
  • the tested coating colour compositions show similar surface strengths.

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  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
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Abstract

Invention relates to a coating colour composition for paper and/or paperboard comprising a pigment, optionally known additives used in coating compositions, and a binder substitute comprising styrene acrylate copolymer having mean particle size ≤100 nm. Invention relates also to paper or paperboard coated with a coating colour composition according to the invention.

Description

COATING COLOUR COMPOSITION AND PAPER OR PAPERBOARD COATED WITH IT
The present invention relates to a coating colour composition and to the paper or paperboard according to the preambles of the enclosed claims. The invention relates also to a use of styrene acrylate copolymer.
Paper and paperboard are coated with different coating colours in order to improve, among other things, their strength, phntability and appearance, e.g. smoothness and gloss. Conventional coating compositions comprise mainly pigment and binder, and possible other additives, such as co-binders, preservatives, dispersing agents, defoaming agents, lubricants, hardeners and optical bhghteners.
The role of binder in the coating composition is to bind the pigment particles to each other and to the base paper. Binder may also have an effect on the rheological properties of the coating composition. Typical synthetic binders are polymers based on butadiene, styrene, vinyl acetate, butyl acrylate and acrylic acid monomers. Such polymer dispersions are conventionally called latex binders, and they have a particle size around 0.1 - 0.2 μm. As the latex binders are synthetic compounds their price may be relatively high. Therefore it would be advantageous to minimise the amount of binder in the coating composition without impairing the properties of the composition and the resulting coated paper.
Styrene/acrylate copolymers as surface sizing agents are known. For example, US 6,426,381 discloses styrene/(meth)acrylate copolymers that can be used for surface sizing.
JP 58/115196 discloses a water soluble paper strength increasing agent which is prepared by graft copolymerising styrene and acrylate in presence of starch. The agent is said to improve the strength and sizing degree of paper. An object of this invention is to provide a coating colour composition with which the disadvantages in the prior art may be minimised or even eliminated.
An object is also to provide a coating colour composition which improves the strength properties of the coated paper or paperboard.
A further object of this invention is to provide a coating colour composition, where amount of the binder may be reduced without impairing the strength properties of the coated paper.
These objects are attained with a method and an arrangement having the characteristics presented below in the characterising parts of the independent claims.
Typical coating colour composition for paper and/or paperboard according to the present invention comprises
- a pigment,
- optionally known additives used in coating compositions, and
- a binder substitute comprising styrene acrylate copolymer having mean particle size ≤I OO nm.
Typical paper or paperboard according to the present invention is coated with a coating colour composition according the present invention.
Now it has been surprisingly found out that by using a binder substitute comprising copolymer of styrene and acrylate, which has a small well-defined particle-size, it is possible to replace all or a part of the conventional latex binder used in coating colour composition and, at the same time, to obtain coated paper with improved strength characteristics. It is also possible to reduce the amount of conventional binder without any significant impairment of the strength of the coated paper. When the binder substitute is used as main binder or sole binder in the coating composition, it is possible to obtain coated paper with clearly enhanced surface strength characteristics. On the other hand, when the binder substitute is used to replace a part of the conventional binder it has been found out that the amount of the total binder may easily be reduced by 20 - 30 % without impairment of the strength properties of the paper. Reduction of the amount of total binder naturally decreases the costs associated with it.
It is surprising that the small particle size of the styrene acrylate copolymer has such an effect on the strength properties of the resulting coated paper. It may be speculated, without being bound by the theory, that the increased surface area might be responsible for the effect.
The styrene acrylate copolymer that is used as the binder substitute may be obtained by copolymerisation of ethylenically unsaturated monomers. Suitable styrene monomers are styrene and substituted styrenes, such as α-methylstyrene or vinyltoluene or their mixtures, and suitable acrylate monomers are C1 -C4-alkyl acrylates, C1 -C4-alkyl methacrylates or their mixtures, e.g. n-butyl, iso-butyl, tert- butyl or 2-butyl acrylate and the corresponding butyl methacrylates; methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate or propyl methacrylate, mixture of at least two isomeric butyl acrylates being preferred, mixtures of n-butyl acrylate and methyl methacrylate being particularly preferred. According to one most preferred embodiment of the invention the mixtures of n-butyl acrylate and tert-butyl acrylate are used in polymerisation. For mixtures of two monomers the mixing ratio may be 10:90 to 90:10.
Preferably the binder substitute is a styrene acrylate copolymer comprising starch. The styrene acrylate copolymer may be obtained as described in US 6,426,381 , i.e. by free radical emulsion copolymerisation of ethylenically unsaturated monomers in the presence of starch. Starch may be any suitable native starch, such as potato, rice, corn, waxy corn, wheat, barley or tapioca starch, potato starch being preferred. Starches having a amylopectin content > 80 %, preferably >95 %, are advantageous. Starch may be also modified, for example, anionised, cationised or degraded. Anionised starch comprises anionic groups, such as carboxylate or phosphate groups, whereas cationised starch comprises cationic groups, such as quaternized ammonium groups. Degree of substitution (DS), indicating the number of anionic/cationic groups in the starch on average per glucose unit, is typically 0.01 -0.20. Amphoteric starches, comprising both anionic and cationic groups, may also be used in the preparation of the styrene acrylate copolymer. Degraded starch is obtained by subjecting the starch to oxidative, thermal, acidic or enzymatic degradation, oxidative degradation being preferred. Hypochlorite, peroxodisulphate, hydrogen peroxide or their mixtures may be used as oxidising agents. Degraded starch has typically an average molecular weight (Mn) 500 - 10 000, which can be determined by known gel chromatography methods. The intrinsic viscosity is typically 0.05 to 0.12 dl/g, determined, for example, by known viscosimetric methods.
According to one embodiment of the invention it is possible to use, instead of starch any other polysaccharide, which contains a free hydroxyl group, such as amylose, amylopectine, carrageen, cellulose, chitosan, chitin, dexthnes, guar gum (guarane) and other galactomannans, arabic gum, hemicellulose components, and pullulan, for obtaining styrene acrylate copolymer used in the present invention. Dextrin is more preferred of the polysaccharides listed, i.e. the styrene acrylate copolymer comprises dextrin.
The binder substitute may be used in form of aqueous polymer dispersion having a solids content of 10 - 50 %, preferably 20 - 50 %, more preferably 21 - 29 %, most preferably 35 - 40 %. High solids content is advantageous as the amount of water in the coating composition may be minimised.
According to one embodiment of the invention the mean particle size of the binder substitute as an aqueous dispersion is at least 20 nm, preferably at least 25 nm, more preferably 30 nm, still more preferably 35 nm, most preferably at least 40 nm, and less than 90 nm, preferably less than 80 nm, more preferably less than 70 nm, still more preferably less than 60, most preferably less than 50 nm. Usually the mean particle size of the binder substitute is < 100 nm. According to one embodiment of the invention the mean particle size of the binder substitute as an aqueous dispersion is in the range 20 - 100, preferably 30 - 80 nm, more preferably 40 - 70 nm, most preferably 60 - 70. The mean particle size of the binder substitute may be determined by photon correlation spectroscopy using for example a Malvern Zetamaster equipment.
According to one embodiment of the invention the coating composition comprises, besides the binder substitute, also a latex binder. Typical synthetic latex binders that may be used in the present invention are latices known in the art, such as styrene butadiene (SB) latex, styrene acrylate (SA) latex or polyvinyl acetate
(PVAc) latex. Preferably the latex binder is styrene butadiene (SB) latex. Latex binder may be considered as a main binder of the coating composition, amount of which is reduced by using the binder substitute according to the present invention.
According to one embodiment of the invention the coating composition may also comprise in addition to the binder substitute and possible main binder also starch binder, which starch may be anionic or cationic.
Typical pigments that may be used in the present invention are calcium carbonate, kaolin, calcinated kaolin, talc, titanium dioxide, gypsum, chalk, satine white, barium sulphate, sodium aluminium silicate, aluminium hydroxide or any of their mixture. Calcium carbonate may be ground calcium carbonate (GCC) or precipitated calcium carbonate (PCC) or their mixture. Preferably the pigment is calcium carbonate. Particle size D50 of the pigments used in coating compositions is typically in the range of < 5 μm.
In this application the composition of the coating colour mixture is given, as conventional in the art, by giving the total amount of pigments value 100, and calculating the amounts of other components relative to the amount of the total pigment (pph). Proportions of all components are given as active substances.
According to one embodiment of the invention the binder substitute may be used together with conventional co-binders, such as carboxy methyl cellulose (CMC), polyvinyl alcohol (PVOH), starch, casein or protein. Amount of the co-binders in the coating composition is normally 0.05 - 3 parts. In case of starch, the amount of may be 0.05 - 12 parts, preferably 0.1 - 10 parts. It is possible to add to the coating colour composition according to the present invention also small amount of conventional additives in order to improve the properties or handling of the composition or in order to provide it with desired functionality. Possible additives are, for example, preservatives, dispersing agents, defoaming agents, lubricants, hardeners and optical bhghteners. The amount of other additives are normally 0 - 3 parts.
According to one embodiment of the invention the coating colour composition comprises
- 100 parts of pigment,
- 0 - 12 parts of binder, preferably latex binder, - 1.5 - 9 parts of binder substitute, and
- 0 - 3 parts of known additives, provided that the total amount of binder and binder substitute is at least 5 parts.
According to another embodiment of the present invention the coating colour composition comprises - 100 parts of pigment, - 4 - 12 parts of starch,
- 3 - 6 parts of binder, preferably latex binder,
- 2 - 4 parts of binder substitute, and
- 0 - 3 parts of known additives.
According to still another embodiment of the invention the coating colour comprises - 100 parts of pigment,
- 4 - 5 parts of binder,
- 2 - 3 parts of binder substitute, and - 0 - 3 parts of known additives.
The coating colour according to the present invention may be prepared in conventional way, i.e. the pigment slurry is mixed with the binder substitute in dispersion form and possible other additives as added as customary. If conventional binder is used in addition to the binder substitute it is also added to the coating colour composition as customary. As existing equipment and procedures may be used when using the binder substitute according to the present invention, no extensive modification of the equipment is needed.
Typically the coating colour according to the present invention has a solids content of 60 - 74 %, preferably 63 - 72 %, more preferably 65 - 71 % and viscosity < 2500, typically 1000 - 2000 mPas. Viscosities are measured by using Brookfield viscometer, type DV-II, with speed 100 rpm and using spindle 3 or 4.
According to one embodiment of the invention the coating colour composition is applied on paper or paperboard surface in single or multiple coating layers. Applied coating methods include for example blade, rod, film transfer or air brush coating. Applied coat weights are typically in the range of 5 - 30 g/m2/side. In one applied coating layer the coat weight is generally 5 - 16 g/m2/side, more typically 6 - 14 g/m2/side, and most typically 8 - 12 g/m2/side.
EXAMPLES
The following non-limiting examples illustrate some embodiments of the present invention.
Preparation of the binder substitute comprising styrene acrylate copolymer in presence of anionic starch (General description)
Oxidatively degraded potato starch (Perfectamyl® A 4692) in amount of 67 g is dispersed in 536 g of demineralized water under constant stirring in a 2 I three- necked flask having a reflux condenser. Starch is dissolved by heating to a temperature of 85 0C, whereby 20.0 g of a 1 % aqueous solution of FeSO4 x 7H2O (0.72 mmol) and 4.0 g of 35% hydrogen peroxide are added in succession. After 15 minutes, the starch degradation is complete. The solution comprising monomers and the initiator solution are metered in simultaneously but separately in the course of 90 min at 85 0C at constant feed rate. The monomer solution comprises 86.6 g of styrene, 43.3 g of n-butyl acrylate and 43.3 g of tert-butyl acrylate. The initiator solution comprises 4.3 g of hydrogen peroxide (35 %) and 127 g of water. The polymerisation is performed in nitrogen atmosphere.
10 min after the end of the metering, a further 0.7 g of tert-butyl hydroperoxide are added for subsequent activation and stirring is carried out for a further 60 min. Thereafter, cooling is effected to room temperature, and filtration is performed through a 100 μm filter. The pH is adjusted to 6 with 20 % sodium hydroxide solution.
A polymer dispersion having a solids content of 24.9% and a turbidity value of A=O.380 (diluted 1 :10, 660 nm) is obtained. The mean particle size, measured by Malvern Zetamaster, is 61.3 nm.
COATING EXPERIMENTS
Comparative Experiment
Commercial styrene butadiene and styrene acrylate latices are tested using coating colour compositions in table 1. Coating colours are prepared and diluted to 50% solids content in order to be used in laboratory coating. Paper samples are draw-down coated. Surface strength is measured with IGT-device (IGT Testing Systems). The results are summarized in table 2. Table 1. Coating colour composition used
Figure imgf000010_0001
Table 2. Coating colour properties and surface strength results using normal viscosity oil.
Figure imgf000010_0002
The two commercial latices give similar surface strength results.
Experiment 1
Experiment is carried out in laboratory scale. Binder substitute 1 comprises styrene acrylate copolymer polymerised in presence of anionic starch and binder substitute 2 comprises styrene acrylate copolymer polymerised in presence of cationic starch. Binder substitute 1 is prepared according to the general description above. Binder substitute 1 and binder substitute 2 have solids contents 24 and 25 %, respectively. Commercial styrene butadiene is used in the coating composition as main binder. Type of the binder substitute is the only variable in the coating colour compositions. Coating colour compositions are prepared using Diaf laboratory dissolver and diluted to 50% solids content. Coating colour compositions are shown in Table 1.
Table 1. Coating colour composition used
Figure imgf000011_0001
Mixture of SB latex and a binder substitute (4.5 + 3 parts) is used. All tested coating colour compositions have solids content of 67% and Brookfield 100 viscosity ca. 2000 mPas or lower. Static water retention values are measured using AA-GWR instrument model 4 (manufacturer: DT-paper science) using 30 seconds time and 0.3 bar pressure. Static water retention values are similar with the reference.
Use of binder substitutes gives to the coating colour compositions high shear viscosity similar to the reference. Paper samples are draw-down coated. Surface strength of the coated paper samples is measured with IGT AIC2-5 device, according to standard procedure SCAN-P 63:90. The surface strength results are shown in table 2.
Table 2. Surface strength results
Figure imgf000012_0001
It can be seen from Table 2 by using 3 parts of binder substitute the SB-latex amount can be reduced by 50% and still the coated paper samples show the same surface strength properties.
Experiment 2
Experiment is carried out by using OptiBlade coater with binder substitute 1. Base paper is pre-coated, and the applied coat weight is 1 1 g/m2. The different binder compositions are shown in table 3. All coating colour compositions contain same amounts of normal coating colour additives not listed here.
Table 3. Test compositions with the binder substitute 1
Figure imgf000012_0002
All the compositions are run without any problems with the coating apparatus. Blade pressures are on the same level with all compositions. The reference composition has the lowest Brookfield viscosity.
Paper samples coated with the test compositions are calendered on Optiload Twinline. Calendering speed is 800 m/min and roll temperature 12O0C.
Then the coated paper samples are printed using 5-color (B, C, M, B, C) printing with constant density and speed 8000 sheets/h on Man Roland 300 printing press. In Table 4 is given results of a visual evaluation of the printed paper samples, with the following grading: 1 =very good, 2=good, 3=medium, 4=bad, 5=very bad.
Table 4. Visual evaluation of the printed samples
Figure imgf000013_0001
Piling and picking of the paper samples were also analyzed and the results are shown in table 5. The grading is following: 0 = good; 1 - 3 = comfortable; 4 = bad; 5 = very bad. All the coated paper samples had good piling resistance and comfortable picking properties. Runnability was also good with all samples. Table 5. Piling and picking results at 200C
Figure imgf000014_0001
The printed paper samples are analyzed and the average results from the pilot printing are summarized in table 6.
Table 6. Summary of the printing tests
Figure imgf000014_0002
The results show that in print and paper gloss, smoothness, rub-off and mottling on C50%, M50% and C100% the differences between the reference sample and samples comprising binder substitute 1 are not significant. The sample with the lowest total binder content comprising 4 parts SB latex and 2 parts binder substituent 1 is significantly faster than the reference sample in the set-off test.
IGT surface strength results on machine direction (MD) and cross direction (CD) are summarized in table 7.
Table 7. Surface strength results using IGT
Sample name
IGT-surface strength (m/s): Comp. Comp. Comp. Comp. Ref. 3 4 5 6
MD average 1 .73 1 .74 1.64 1 .57 1 .81
CD average 1 .13 1 .06 1.12 1 .03 1 .02
Average (MD + CD) 1 .43 1 .40 1.38 1 .30 1 .42
It can be seen from the results that the reducing of the total amount of the synthetic binder content down from 9 to 6 parts gave still acceptable printing results.
Experiment 3
Compatibility of the binder substitutes with starch is tested. Laboratory tests are carried out with binder substitutes 1 and 2, the binder substitute 1 comprising styrene acrylate copolymer polymerised in presence of cationic starch and binder substitute 2 comprising styrene acrylate copolymer polymerised in presence of anionic starch. Binder substitute 1 has solids content of 24 %, and binder substitute 2 has solids content of 25 %. The used coating colour recipe is shown in table 8. Table 8. Starch containing coating colour composition
Figure imgf000016_0001
The coating colour composition test results are summarized in Table 9. Composition A comprised binder substitute 1 and composition B binder composition 2.
Table 9. Properties of the coating colour compositions comprising starch and binder substitute .
Figure imgf000016_0002
Binder substitute 1 gives similar viscosity to coating colour composition than the SB latex used as reference. Coating colour composition comprising binder substitute 2 has higher viscosity value than the reference. The reference colour has the lowest high shear viscosity. Binder substitute 1 gives lower viscosity to the coating colour composition than binder substitute 2. All viscosity values are good or acceptable for the tested coating compositions
It can be also seen from table 9 that the static water retention (WR) values are better for the coating compositions according to the present invention than for the reference composition.
Paper samples are draw-down coated with the tested coating compositions. The surface strength is determined, and the results are presented in table 10.
Table 10. IGT-Surface strength of coating colour compositions comprising starch and binder substitute measured with medium viscosity oil
Figure imgf000017_0001
The tested coating colour compositions show similar surface strengths.
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

1. A coating colour composition for paper and/or paperboard comprising
- a pigment, - optionally known additives used in coating compositions, and
- a binder substitute comprising styrene acrylate copolymer having mean particle size <100 nm.
2. Coating colour composition according to claim 1 , characterised in that mean particle size of the binder substitute is 20 - 100 nm.
3. Coating colour composition according to claim 1 or 2, characterised in that it further comprises a latex binder.
4. Coating colour composition according to claim 3, characterised in that the latex binder is styrene butadiene latex styrene acrylate latex or polyvinyl acetate latex.
5. Coating colour composition according to claim 1 , characterised in that the binder substitute is a copolymer of a) styrene monomer or substituted styrene monomer, such as α-methylstyrene or vinyltoluene or their mixtures, and b) acrylate monomer selected from the group of C1 -C4-alkyl acrylates, C1-C4- alkyl methacrylates methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate or propyl methacrylate.
6. Coating colour composition according to claim 1 , characterised in that binder substitute is styrene acrylate copolymer comprising starch.
7. Coating colour composition according to claim 1 , characterised in that it comprises
- 100 parts of pigment,
- 0 - 12 parts of binder,
- 1.5 - 9 parts of binder substitute, and - 0 - 3 parts of known additives, provided that the total amount of binder and binder substitute is at least 5 parts.
8. Coating colour composition according to claim 1 , characterised in that it comprises
- 100 parts of pigment,
- 4 - 12 parts of starch,
- 3 - 6 parts of binder, preferably latex binder, - 2 - 4 parts of binder substitute, and - 0 - 3 parts of known additives.
9. Coating colour composition according to claim 1 , characterised in that it comprises
- 100 parts of pigment, - 4 - 5 parts of binder,
- 2 - 3 parts of binder substitute, and
- 0 - 3 parts of known additives.
10. Coating colour composition according to any of the preceding claims, characterised in that the pigment is calcium carbonate, kaolin, calcinated kaolin, talc, titanium dioxide, gypsum, chalk, satine white, barium sulphate, sodium aluminium silicate, aluminium hydroxide or any of their mixture.
11. Paper or paperboard coated with a coating colour composition according to any of the claims 1 - 10.
12. Paper or paperboard according to claim 11 , characterised in that coat weight of the coating applied on the paper is in the range of 5 - 30 g/m2/paper side.
13. Use of styrene acrylate copolymer having a mean particle size <100 nm as a binder substitute in coating compositions for paper or paperboard.
14. Use according to claim 13, characterised in that the copolymer is used in form of aqueous dispersion having a solids content of 10 - 50 %.
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JP2012512969A (en) 2012-06-07
US20100159263A1 (en) 2010-06-24
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RU2528639C2 (en) 2014-09-20
KR20110101140A (en) 2011-09-15
FI124806B (en) 2015-01-30
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CA2670397C (en) 2017-05-16
ZA201103276B (en) 2012-07-25
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EP3296459A1 (en) 2018-03-21
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PT2370631T (en) 2018-01-16

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