EP1611284B1 - Dispersion - Google Patents

Dispersion Download PDF

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Publication number
EP1611284B1
EP1611284B1 EP04717341A EP04717341A EP1611284B1 EP 1611284 B1 EP1611284 B1 EP 1611284B1 EP 04717341 A EP04717341 A EP 04717341A EP 04717341 A EP04717341 A EP 04717341A EP 1611284 B1 EP1611284 B1 EP 1611284B1
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EP
European Patent Office
Prior art keywords
dispersion
paper
group
anionic
sizing
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EP04717341A
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English (en)
French (fr)
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EP1611284A1 (de
Inventor
Ralf KRÜCKEL
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Akzo Nobel NV
Nouryon Pulp and Performance Chemicals AB
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Akzo Nobel NV
Eka Chemicals AB
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Priority to EP04717341A priority Critical patent/EP1611284B1/de
Priority to SI200431799T priority patent/SI1611284T1/sl
Priority to PL04717341T priority patent/PL1611284T3/pl
Publication of EP1611284A1 publication Critical patent/EP1611284A1/de
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Publication of EP1611284B1 publication Critical patent/EP1611284B1/de
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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
    • 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
    • D21H21/16—Sizing or water-repelling 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
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/03—Non-macromolecular organic compounds
    • D21H17/05—Non-macromolecular organic compounds containing elements other than carbon and hydrogen only
    • D21H17/09—Sulfur-containing compounds
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/03—Non-macromolecular organic compounds
    • D21H17/05—Non-macromolecular organic compounds containing elements other than carbon and hydrogen only
    • D21H17/10—Phosphorus-containing compounds
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/33—Synthetic macromolecular compounds
    • D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/36—Polyalkenyalcohols; 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
    • D21H21/22—Agents rendering paper porous, absorbent or bulky
    • D21H21/24—Surfactants

Definitions

  • the present invention relates to an aqueous dispersion comprising a cellulose reactive sizing agent, a cellulose non-reactive sizing agent and an emulsifier, its preparation, and use thereof in paper making.
  • Cellulose reactive sizes such as those based on alkyl ketene dimer (AKD) and alkenyl succinic anhydride (ASA), are widely used for internal sizing in papermaking. They generally provide good internal sizing even in low dosages.
  • alkyl ketene dimer alkyl ketene dimer
  • ASA alkenyl succinic anhydride
  • Cellulose non-reactive sizes have so far mainly been used for surface sizing. Examples of such materials are starch and other polymeric sizes such as copolymers of styrene with vinyl monomers such as maleic anhydride, acrylic acid and its alkyl esters, acrylamide, etc. Cellulose non-reactive sizes generally exhibit improved toner adhesion, little or no effect on coefficient of friction, no effect, or an improved effect on high speed converting, and no size reversion when compared to reactive sizes. However, they are less efficient at sizing than the cellulose reactive sizes.
  • Cellulose reactive sizes are generally provided in the form of dispersions containing an aqueous phase and finely divided particles or droplets of the sizing agent dispersed therein.
  • the dispersions are usually prepared with the aid of a dispersant system consisting of an anionic compound, e.g. sodium lignosulfonate, in combination with a high molecular weight amphoteric or cationic polymer, e.g. cationic starch, polyamine, polyamide amine or a vinyl addition polymer.
  • an anionic compound e.g. sodium lignosulfonate
  • a high molecular weight amphoteric or cationic polymer e.g. cationic starch, polyamine, polyamide amine or a vinyl addition polymer.
  • the size dispersions will be cationic or anionic in nature.
  • US Patent 5969011 discloses an improved aqueous dispersion of a cellulose-reactive sizing agent dispersed in the aqueous phase by means of a dispersant system comprising a low molecular weight cationic organic compound and an anionic stabi!iser.
  • WO 02/090653 discloses a sizing composition comprising a sizing agent, a non-ionic surfactant, an anionic surfactant and a monohydric alcohol.
  • US Patent 4529447 discloses a sizing composition
  • a sizing composition comprising a carboxylic acid anhydride and a polyoxyalkylene non-ionic surfactant blocked with a lower alkyl, acyl or carbamoyl group and/or an alkaline earth metal salt of a sulfur-containing anionic surfactant.
  • EP-A1-151646 discloses a sizing agent composition based on alkyl-succinic anhydride.
  • US Patent 5498648 discloses a paper size mixture prepared by mixing a suspension of cationic starch with a polymer dispersion and emulsifying a alkyldiketene in this mixture.
  • formulations are predominantly cationic and have been found to interfere with anionic components used in paper making, particularly optical brightening agents.
  • US Patent 6162328 discloses a process for the production of paper in which cellulose reactive size that is not solid at 26°C and a cellulose non-reactive size that is a polymer of weight average molecular weight greater than about 1500 are applied to paper obtained by sheeting and drying an aqueous pulp suspension.
  • cellulose reactive size that is not solid at 26°C
  • a cellulose non-reactive size that is a polymer of weight average molecular weight greater than about 1500 are applied to paper obtained by sheeting and drying an aqueous pulp suspension.
  • dispersions of high stability comprising both a cellulose reactive size and a cellulose non-reactive size, particularly for anionic dispersions.
  • US 2002/0100567 discloses a process for sizing paper comprising separately adding a sizing dispersion and a sizing promoter comprising a cartionic organic polymer and an anionic polymer. It is an object of the invention to provide a dispersion of high stability comprising a cellulose reactive sizing agent.
  • the invention concerns an aqueous dispersion useful for internal sizing or surface sizing in the production of paper, comprising at least one cellulose reactive sizing agent selected from the group consisting of ketene dimers and multimers, at least one cellulose non-reactive sizing agent selected from the group consisting of copolymers of styrene or substituted styrene with at least one other kind of ethylenically unsaturated monomers and at least one emulsifier selected from the group consisting of oxyalkylene phosphate esters and salts thereof.
  • the weight ratio between the cellulose reactive sizing agent and the cellulose non-reactive sizing agent is preferably from about 1:99 to about 99:1, most preferably from about 1:9 to about 9:1.
  • the weight ratio preferably is from about 0,4:1 to about 99:1, most preferably from about 1:1 to about 9:1, while in a dispersion for surface sizing, suitable for being added to a paper web, the weight ratio preferably is from about 1:99 to about 1:1. most preferably from about 1.9 to about 1:1.5.
  • the dispersion also comprise at least one cationic organic compound having a weight average molecular weight less than about 10000 or at least one anionic stabiliser, or both, which is most preferred.
  • the dispersion thus comprises a cellulose reactive sizing agent selected from the group consisting of ketene dimers and multimers, a cellulose non-reactive sizing agent and a dispersing system comprising an emulsifier selected from the group consisting of oxyalkylene phosphate and salts thereof, a cationic organic compound having a weight average molecular weight less than about 10000 and an anionic stabiliser.
  • a cellulose reactive sizing agent selected from the group consisting of ketene dimers and multimers
  • a cellulose non-reactive sizing agent and a dispersing system comprising an emulsifier selected from the group consisting of oxyalkylene phosphate and salts thereof, a cationic organic compound having a weight average molecular weight less than about 10000 and an anionic stabiliser.
  • the amount of ketene dimers and multimers in the dispersion is preferably from about 0,1 to about 50 wt%, most preferably from about 0.5 to about 50 wt%.
  • at least one hydrophobic ketene dimer is present
  • Preferred ketene dimers have the general formula: where R 1 and R 2 represent the same or different saturated or unsaturated hydrocarbon groups such as alkyl, alkenyl, cycloalkyl, aryl or aralkyl.
  • the hydrocarbon groups preferably have from 6 to 36 carbon atoms, most preferably from 12 to 20 carbon atoms.
  • hydrocarbon groups examples include octyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, eicosyl, docosyl, tetracosyl, phenyl, benzyl, beta-naphthyl, cyclohexyl and hexadecyl groups.
  • Preferred hydrocarbon groups are straight or branched chain alkyl groups, such as hexadecyl and octadecyl groups.
  • Useful ketene dimers also include those prepared from organic adds such as montanic acid naphthenic acid, 9,10-decylenic acid, 9,10-dodecylenic acid, palmitoleic acid, oleic acid, ricinoleic acid, linoleic acid, eleostearic acid, naturally occurring mixtures of fatty acids found in coconut oil, babassu oil, palm kernel oil, palm oil, olive oil, peanut oil, rape oil, beef tallow, lard, whale blubber, and mixtures of any of the above named fatty acids with each other.
  • organic adds such as montanic acid naphthenic acid, 9,10-decylenic acid, 9,10-dodecylenic acid, palmitoleic acid, oleic acid, ricinoleic acid, linoleic acid, eleostearic acid, naturally occurring mixtures of fatty acids found in coconut oil, babassu oil, palm kernel oil,
  • the amount of emulsifier selected from oxyalkylene phosphate esters and salts thereof in the dispersion is preferably from about 0.01 to about 10 wt%, most preferably from about 0.1 to about 5 wt%.
  • Preferred phosphate esters fall under the formula: R a -A 1 -O-Q-R 4
  • the hydrocarbon groups may, for example, be alkyl, alkenyl, cycloalkyl, aryl or aralkyl, of which aliphatic groups and particularly alkyl groups are preferred.
  • the oxyalkylene chains preferably consist of oxyethylene units, oxypropylene units or a mixture thereof, of which pure oxyethylene chains are most preferred.
  • the most preferred emulsifiers belong to the group of aliphatic mono and di (polyoxyethylene alkyl) phosphate esters having one or two oxyethylene chains each comprising from 5 to 15 moles ethylene oxide and where the alkyl group(s) have from 10 to 15 carbon atoms. Examples of such polyoxyethylene alkyl phosphate esters include ethoxylated tridecyl phosphate esters. Most preferably a mixture of mono and di (polyoxyalkylene alkyl) esters of phosphate is used.
  • the emulsifier may also be one or more salt of compounds as described above, preferably ammonium or alkali metal salts, such as sodium or potassium salts, but also salts of other metals such as magnesium or calcium are possible.
  • a cationic organic compound having a weight average molecular weight less than about 10000 is present, the amount thereof in the dispersion is preferably from about 0.01 to about 5 wt%, most preferably from about 0.1 to about 2 wt%.
  • the cationic organic compound preferably contains one or more cationic groups of the same or different types and most preferably include cationic compounds having one cationic group and cationic compounds having two or more cationic groups, i.e. cationic polyelectrolytes.
  • Suitable cationic groups include sulfonium groups, phosphonium groups, acid addition salts of primary, secondary and tertiary amines or amino groups and quaternary ammonium groups, for example where the nitrogen has been quatemized with methyl chloride, dimethyl sulfate or benzyl chloride, preferably acid addition salts of amines/amino groups and quaternary ammonium groups,
  • Cationic polyelectrolytes can have a degree of substitution (DS c ) varying over a wide range, for example from about 0.01 to about 1.0, preferably from about 0.1 to about 0.8 and most preferably from about 0.2 to about 0.6.
  • Suitable cationic organic compounds for use in this invention include cationic compounds capable of functioning as a surfactant and/or dispersing agent and/or coupling agent between particles or droplets of a sizing agent and/or an anionic stabiliser.
  • the cationic organic compound is a surfactant.
  • Preferred cationic surfactants include compounds having the general formula R 4 N + X - , wherein each R group, independently of each other, is hydrogen or a hydrocarbon group having from 1 to 30 carbon atoms, preferably from 1 to 22 carbon atoms.
  • the hydrocarbon groups are suitably aliphatic and preferably alkyl groups, and may be interrupted by one or more heteroatoms, e.g.
  • R groups containing a heteroatom e.g. carbonyl and acyloxy groups.
  • At least one, suitably at least three and preferably all of said R groups contain carbon atoms.
  • at least one and preferably at least two of said R groups containing at least 7 carbon atoms, preferably at least 9 carbon atoms and most preferably at least 12 carbon atoms.
  • X- is an anion, suitably a halide like chloride, or an anionic group present in an anionic compound of the dispersion, e.g. where the surfactant is a protonated amine of the formula R 3 NH + where R is as defined above.
  • Suitable surfactants include dioctyldimethylammonium chloride, didecyldimethylammonium chloride, dicocodimethylammonium chloride, cocobenzyldimethylaminonium chloride, coco(fractionated)benzyldimethylammonium chloride, octadecyl trimethylammonium chloride, dioctadecyl dimethylammonium chloride, dihexadecyl dimethylammonium chloride, di(hydrogenated tallow)dimethylammonium chloride, di(hydrogenated tallow)-benzylmethylammonium chloride, (hydrogenated tallow)benzyldimethylammonium chloride, dioleyldimethylammonium chloride, and di(ethylene hexadecanecarboxylate)dimethylammonium chloride.
  • Particularly preferred cationic surfactants thus include those containing at least one hydrocarbon group with from 9 to 30 carbon atom
  • Useful cationic polyelectrolytes also include low molecular weight cationic organic polymers, optionally degraded, e.g. those derived from polysaccharides like starches and guar gums, cationic condensation products like cationic polyurethanes, polyamideamines, e.g. polyamideamine-epichlorohydrin copolymers, polyamines, e.g. dimethylamine-epichlorohydrin copolymers, dimethylamine-ethylenediamine-epichlorohydrin copolymers, ammonia-ethylenendichloride copolymers, vinyl addition polymers formed from monomers with cationic groups, e.g.
  • diallyldimethylammonium chloride dialkylaminoalkyl acrylates, methacrylates and acrylamides (e.g. dimethylaminoethyl acrylates and methacrylates) which usually are present as acid addition salts or quaternary ammonium salts, optionally copolymerized with non-ionic monomers including acrylamide, alkyl acrylates, styrene and acrylonitrile and derivatives of such monomers, vinyl esters, and the like.
  • non-ionic monomers including acrylamide, alkyl acrylates, styrene and acrylonitrile and derivatives of such monomers, vinyl esters, and the like.
  • the weight average molecular weight of the cationic organic compound generally can be up to about 10000, usually up to about 5000, suitably up to about 3000 and preferably up to about 800, and most preferably at least about 200.
  • Suitable cationic surfactants preferably have a weight average molecular weight up to about 3000, most preferably from about 200 to about 800.
  • an anionic stabiliser is present, the amount thereof in the dispersion is preferably from about 0.01 to about 5 wt%, most preferably from about 0.1 to about 3 wt%.
  • Suitable anionic stabilisers for use in this invention include anionic compounds functioning as stabilisers and/or being effective in combination with a cationic organic compound as described above to stabilise the sizing agent in an aqueous phase as well as anionic compounds known as useful as dispersants in the preparation of size dispersions.
  • the anionic compound is water-soluble or water-dispersable.
  • the anionic stabiliser can be can be selected from organic or inorganic compounds and can be derived from natural or synthetic sources.
  • the anionic stabiliser of the dispersant system contains one or more anionic groups of the same or different types and include anionic compounds having one anionic group and anionic compounds having two or more anionic groups, herein referred to as an anionic polyelectrolyte.
  • anionic polyelectrolyte is meant to include also anionic compounds acting as a polyelectrolyte, e.g. through chemical non-ionic interaction or attraction.
  • the anionic stabiliser is an anionic polyelectrolyte. Examples of suitable anionic groups, i.e.
  • anionic groups that are anionic or rendered anionic in water include phosphate, phosphonate, sulfate, sulfonate, sulphonic acid and carboxylic acid groups and salts thereof, usually ammonium or alkali metal (generally sodium) salts.
  • the anionic groups can be native or introduced by means of chemical modification in known manner.
  • the anionic stabiliser can have a degree of anionic substitution (DS A ) varying over a wide range; the DS A can be from 0.01 to 1.4, suitably from 0.1 to 1.2 and preferably from 0.2 to 1.0.
  • Anionic polyelectrolytes may contain one or more cationic groups as long as it has an overall anionic charge.
  • the anionic stabiliser is selected from organic compounds.
  • Suitable anionic stabilisers of this type include polymeric compounds such as those based on lignin or polysaccharides like starches, guar gums, celluloses, chitins, chitosans, glycans, galactans, glucans, xanthan gums, mannans, dextrins, etc., preferably phosphated, sulphonated and carboxylated lignin or polysaccharides, as well as synthethic organic polymers like condensation products, e.g. anionic polyurethanes and polymeric anionic compounds based on naphthalene, e.g.
  • condensated naphthalene sulfonates and further vinyl addition polymers formed from monomers with anionic groups, e.g. acrylic acid, methacylic acid, maleic acid, itaconic acid, crotonic acid, vinylsulfonic acid, sulfonated styrene and phosphates of hydroxyalkyl acrylates and methacrylates, optionally copolymerized with non-ionic monomers including acrylamide, alkyl acrylates, styrene and acrylonitrile as well as derivatives of such monomers, vinyl esters, and the like.
  • Particularly preferred organic anionic stabilisers include anionic polysaccharides, e.g. cellulose-derivatives like carboxymethyl celluloses, condensated naphthalene or lignin sulfonates, anionic acrylamide-based polymers and polymers based on acrylic acid and similar acid monomers.
  • the anionic stabiliser is hydrophobically-modified and contains one or more hydrophobic groups, suitably being a hydrophobically modified polysaccharide, preferably carboxymethyl cellulose.
  • suitable groups include hydrophobic substituents containing from 4 to about 30 carbon atoms, notably hydrophobic amide, ester and ether substituents comprising a saturated or unsaturated hydrocarbon chain of at least 4 and preferably from 8 to 30 carbon atoms, optionally being interrupted by one or more heteroatoms, e.g. oxygen or nitrogen, and/or groups containing a heteroatom, e.g. carbonyl or acyloxy.
  • the anionic stabiliser is an organic compound or polymer
  • its weight average molecular weight is preferably above about 200 most preferably above 500, but is preferably below 50000.
  • the anionic stabiliser is selected from inorganic anionic materials, preferably anionic inorganic polyelectrolytes such as, for example, compounds containing silicon atoms, e.g. various forms of condensated or polymerized silicic acid which have negative hydroxyl groups, e.g. oligomeric silicic acid, polysilicic acid, polysilicates and polyaluminiumsillicates.
  • inorganic anionic materials preferably anionic inorganic polyelectrolytes such as, for example, compounds containing silicon atoms, e.g. various forms of condensated or polymerized silicic acid which have negative hydroxyl groups, e.g. oligomeric silicic acid, polysilicic acid, polysilicates and polyaluminiumsillicates.
  • the anionic stabiliser can also be selected from microparticulate material where both organic and inorganic anionic materials are encompassed.
  • Suitable particulate materials of this type include highly cross-linked anionic vinyl addition polymers, e.g. acrylamide-based and acrylate-based polymers, anionic condensation polymers, e.g. melamine-sulfonic acid sols, inorganic silica-based materials, e.g. materials of the type present in aqueous silica-based sols like silica sols, aluminated silica sols, aluminiumsilicate sols, polysilicate microgels and polyaluminiumsilicate microgels, as well as silica gels and precipitated silica.
  • the microparticulate material preferably is colloidal, i.e. in the colloidal range of particle size.
  • the colloidal particles suitably have a particle size from about 1 nm to about 40 nm, preferably from 2 to 35 nm and most preferably from 2 to 10 nm.
  • a cellulose non-reactive sizing agent is preferably present in the dispersion in an amount from about 0.1 to about 50 wt%, most preferably from about 0.5 to about 50 wt%.
  • Suitable cellulose non-reactive sizing agents are polymeric materials preferably having a weight average molecular weight greater than 50000, most preferably from 50000 up to about 1000000.
  • the polymeric material is made from ethylenically unsaturated monomers.
  • Polymers include copolymers of styrene or substituted styrenes with at least one other kind of ethylenically unsaturated monomers, preferably comprising monomers containing one or more carboxyl groups.
  • monomers include maleic anhydride, acrylic acid, methacrylic acid and itaconic acid, as well as esters, amides and nitrile thereof, of which esters are particularly preferred.
  • esters are alkyl esters where the alkyl group preferably have from 1 to 12 carbon atoms, most preferably from 1 to 5 carbon atoms. Particularly preferred are esters of acrylic acid or methacrylic acid.
  • alkyl groups examples include methyl, ethyl, propyl, n-butyl, iso-butyl, tert-butyl and 2-butyl.
  • the monomers as described above may also be co-polymerised with other ethylenically unsaturated monomers.
  • the cellulose non-reactive sizing agent is a co-polymer obtained from ethylenically unsaturated monomers comprising from about 20 to about 80 wt%, preferably from about 30 to about 70 wt% of styrene or substituted styrene, from about 20 to about 80 wt%, preferably from about 30 to about 70 wt% of alkyl acrylate or methacrylate, and from 0 to about 15 wt%, preferably from 0 to about 10 wt% of other ethylenically unsaturated monomers.
  • the dispersion of the invention may also comprise other components, such as one or more of biocides, defoamers, inorganic compounds like aluminium or zirconium compounds, etc.
  • the dispersion of the invention is preferably predominantly anionic, which reduces the risk for interference with anionic components used in paper making.
  • the pH is preferably from about 2 to about 6, most preferably from about 3 to about 5, which improves the stability of e.g. ketene dimers.
  • the viscosity is preferably from about 1 to about 300 mPas, most preferably from about 5 to about 100 mPas.
  • the dry content is preferably from about 1 to about 50 wt%, most preferably from about 5 to about 40 wt%.
  • paper is meant to include not only ordinary paper but all types of cellulose-based products in sheet or web form, including, for example, board and paperboard.
  • the invention is particularly advantageous for preparation of graphic paper to be used in all kinds of printing processes, such as ink-jet printing, laser printing, copying, etc.
  • the invention also concerns a process for the preparation of a dispersion as described above.
  • the process comprises the steps of bringing together at least one cellulose reactive sizing agent selected from the group consisting of ketene dimers, and multimers, at least one cellulose non-reactive sizing agent, and at least one emulsifier selected from the group consisting of oxyalkylene phosphate and sulfate esters and salts thereof, in the presence of water to obtain a mixture, and homogenising the mixture to obtain an aqueous dispersion.
  • the temperature during the homogenisation is preferably sufficiently high for the cellulose reactive sizing agent to be liquid, and is in most case preferably from about 20 to about 100°C, most preferably from about 50 to about 95°C.
  • the cellulose non-reactive sizing agent is added in the form of an aqueous dispersion, for example a commercially available cellulose non-reactive size such as dispersions of poly (styrene/acrylate) marketed under the trademarks Jetsize ® AE 27, AE 35 and AE 76 (Eka Chemicals AB), Basoplast ® 400 DS (BASF), Perglutin ® A 281 (Giulini), or a dispersion as described in US Patent 6426381 .
  • a cationic organic compound having a weight average molecular weight less than about 10000 or an anionic stabiliser, or both, which is most preferred.
  • suitable and preferred variants of the components and amounts thereof the above description of the dispersion as such is referred to.
  • the invention further concerns use of a dispersion according to the invention as described above for surface sizing of paper and a process for the production of paper comprising the steps of forming a paper web from a stock containing cellulosic fibres and applying to the surface of the paper web an aqueous dispersion according to the invention as described above.
  • the dispersion may be applied to the paper web by all known methods in a size press or other suitable equipment and is preferably included in the size press liquor.
  • a dispersion of the invention is supplied to the paper in an amount from about 0.05 to about 20 wt%, preferably from about 0.1 to about 10 wt%, based on amount of paper produced.
  • optical brightening agents preferably in an amount from about 0 to about 2 wt% of amount of paper produced
  • pigments e.g. chalk, precipitated calcium carbonate, kaolin, titanium dioxide, barium sulphate or gypsum
  • starch preferably in an amount from about 0 to about 5 g/m 2 paper produce
  • crosslinkers such as zirconium compounds, insolubilisers, defoamers, etc.
  • the invention furthermore concerns use of a dispersion according to the invention as described above for internal sizing at production of paper and a process for the production of paper comprising the steps of adding a dispersion according to the invention as described above to a stock containing cellulosic fibres, and dewatering the stock on a wire to obtain paper and white water.
  • the dispersion may be added separately or be premixed with one or more other additive, such as a retention aid.
  • the stock preferably contains from about 50 to about 100 wt%, most preferably from about 70 to about 100 wt% of cellulosic fibres, based on dry stock.
  • the stock also contains one or more fillers, e.g. mineral fillers like kaolin, china clay, titanium dioxide, gypsum, talc, chalk, ground marble or precipitated calcium carbonate, and optionally other commonly used additives, such as retention aids, aluminium compounds, dyes, wet-strength resins, optical brightening agents, etc.
  • fillers e.g. mineral fillers like kaolin, china clay, titanium dioxide, gypsum, talc, chalk, ground marble or precipitated calcium carbonate
  • optionally other commonly used additives such as retention aids, aluminium compounds, dyes, wet-strength resins, optical brightening agents, etc.
  • aluminium compounds include alum, aluminates and polyaluminium compounds, e.g. polyaluminium chlorides and
  • retention aids include cationic polymers, anionic inorganic materials in combination with organic polymers, e.g. bentonite in combination with cationic polymers, silica-based sols in combination with cationic polymers or cationic and anionic polymers.
  • a dispersion of the invention is preferably added to the stock and/or the paper web in an amount so the total amount of cellulose reactive sizing agent added is from about 0.01 to about 10 wt%, most preferably from about 0.03 to about 5 wt% of the paper produced, while the total amount of cellulose non-reactive sizing agent added preferably is from about 0.01 to about 10 wt%, most preferably from about 0.03 to about 5 wt% of the paper produced.
  • the exact amounts depend on the quality of the pulp and the level of sizing desired.
  • the sizing effect compared to use of conventional sizes is improved at a corresponding doses of cellulose reactive sizing agent.
  • the possibility of using lower amounts of sizing agent to achieve a desired level of sizing reduces the risk of accumulation of non-adsorbed sizing agents in the white water recirculating in the process, thereby reducing the risk of aggregation and deposition of the sizing agents on the paper machine.
  • the invention is particularly advantageous in processes with high degree of white water closure, for example where from 0 to 30 tonnes, usually less than 20 tonnes, suitably less than 15 tonnes, preferably less than 10 tonnes and most preferably less than 5 tonnes of fresh water are used per ton of dry paper produced.
  • the invention gives a fast on-machine sizing and a very uniform sizing. Furthermore, the dispersion does not interfere significantly with strong anionic components present in the papermaking process, and does therefore not reduce the efficiency of, for example, optical brightening agents.
  • Example 1 An anionic aqueous sizing dispersion according to the invention was prepared from the following formulation for 1 kg dispersion:
  • the dispersion was used for internal sizing in a pilot plant paper machine producing paper from fine paper furnish with 15% ground calcium carbonate (HydrocarbTM 50BG GCC, Omya) and 0.6% optical brightening agent.
  • the retention system used was 0.5% cationic potato starch (Hi-CatTM 142, Roquette) and 0.3% anionic silica sol (EkaTM NP 442, Eka Chemicals).
  • paper was produced under the same conditions but sized with a standard AKD dispersion Keydime ® C (Eka Chemicals).
  • the papers were tested in respect of water absorption according to Cobb 60 (Tappi test method T 441 om-90) and ink resistance according to HST 80 (Tappi test method T 530 pm-89).
  • Example 2 A dispersion of the invention was prepared in the same way as in Example 1 from 30 g Keywax ® SF100, 200 g Jetsize ® AE 76, 4.8 g ArquadTM 2HT-75PG, 6.3 g RhodafacTM RS-710, 6.3 g OrotanTM SN and water to 1000 g.
  • the basis weight was 80 g/m 2 .
  • the retention system was 0.5% cationic potato starch (Hi-CatTM 142, Roquette) and 0.5% anionic silica sol (EkaTM NP 780, Eka Chemicals). Additionally 0.6% optical brightening agent was added to the stock.
  • the dispersion of the invention was added in the size press together with oxidised potato starch (PerfectamylTM P 255 SH, Avebe) at 5 % solids content.
  • oxidised potato starch PerfectamylTM P 255 SH, Avebe
  • the same kind of paper was surface sized under the same conditions with a standard surface size based on a styrene acrylate co-polymer dispersion (Jetsize ® AE 76, Eka Chemicals).
  • the papers were tested in respect of water absorption according to Cobb 60 and ink resistance according to HST 80.
  • Example 3 Dispersion were prepared in the same way as in Example 1 and the static storage stability was tested by storing the samples in bottles for five weeks and then measuring the dry content at the top and the bottom of the bottles.
  • the formulations (for 1 kg dispersion) and the results are shown in the table below:
  • Example 4 Dispersions were prepared in the same way as in Example 1 and the thermal stability was tested by shaking the samples 10 days at 250 rpm and 30°C and measuring the particle size distribution. The formulations (for 1 kg dispersion) and the results are shown in the table below.
  • the figures for particle size refer the particle size 50% and 90% by volume , respectively, of the particles in each sample are smaller than. Thus, in Formulation (1) after 10 days 50% of the particles were smaller than 0.59 ⁇ m and 90% smaller than 0.92 ⁇ m.

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Claims (15)

  1. Wässrige Dispersion, verwendbar zur Masseleimung oder Oberflächenleimung bei der Herstellung von Papier, umfassend mindestens ein mit Cellulose reaktives Leimungsmittel, ausgewählt aus der Gruppe bestehend aus Keten-Dimeren und -Multimeren, mindestens ein mit Cellulose nicht reaktives Leimungsmittel, ausgewählt aus der Gruppe bestehend aus Copolymeren von Styrol oder substituiertem Styrol mit mindestens einer anderen Art von ethylenisch ungesättigten Monomeren, und mindestens einen Emulgator, ausgewählt aus der Gruppe bestehend aus Oxyalkylenphosphatestern und Salzen davon.
  2. Dispersion wie in Anspruch 1 beansprucht, weiter umfassend mindestens eine kationische organische Verbindung mit einem Gewichtsmittel des Molekulargewichts von weniger als etwa 10.000.
  3. Dispersion wie in einem der Ansprüche 1-2 beansprucht, weiter umfassend mindestens einen anionischen Stabilisator.
  4. Dispersion wie in einem der Ansprüche 1-3 beansprucht, wobei die Oxyalkylenphosphatester die Formel:

            R3-A1-O-Q-R4

    aufweisen,
    wobei R4 -OH oder -O-A2-R5 ist;
    A1 und A2 unabhängig voneinander Oxyalkylenketten sind;
    Q PO(OH) ist; und
    R3 und R5 unabhängig voneinander Kohlenwasserstoffreste sind.
  5. Dispersion wie in einem der Ansprüche 1-4 beansprucht, wobei die mindestens eine andere Art von ethylenisch ungesättigten Monomeren aus der Gruppe bestehend aus Alkylestern von Acrylsäure oder Methacrylsäure ausgewählt ist.
  6. Dispersion wie in einem der Ansprüche 2-5 beansprucht, wobei die kationische organische Verbindung ein grenzflächenaktives Mittel, ausgewählt aus der Gruppe bestehend aus Verbindungen mit der allgemeinen Formel R4N+X-, ist, wobei jeder Rest R unabhängig voneinander Wasserstoff oder ein Kohlenwasserstoffrest mit 1 bis 30 Kohlenstoffatomen ist und X ein Anion ist.
  7. Dispersion wie in einem der Ansprüche 3-6 beansprucht, wobei der anionische Stabilisator aus der Gruppe bestehend aus kondensierten Naphthalin- und Ligninsulfonaten ausgewählt ist.
  8. Dispersion wie in einem der Ansprüche 1-7 beansprucht, wobei die Dispersion vorwiegend anionisch ist.
  9. Dispersion wie in einem der Ansprüche 1-8 beansprucht, wobei der pH-Wert etwa 2 bis etwa 6 beträgt.
  10. Ein Verfahren zur Herstellung einer Dispersion nach einem der Ansprüche 1-9, umfassend die Schritte des Vereinigens mindestens eines mit Cellulose reaktiven Leimungsmittels, ausgewählt aus der Gruppe bestehend aus Keten-Dimeren und -Multimeren, mindestens eines mit Cellulose nicht reaktiven Leimungsmittels, ausgewählt aus der Gruppe bestehend aus Copolymeren von Styrol oder substituiertem Styrol mit mindestens einer anderen Art von ethylenisch ungesättigten Monomeren, und mindestens eines Emulgators, ausgewählt aus der Gruppe bestehend aus Oxyalkylenphosphatestern und Salzen davon, in Gegenwart von Wasser, um ein Gemisch zu erhalten, und Homogenisieren des Gemischs, um eine wässrige Dispersion zu erhalten.
  11. Ein Verfahren wie in Anspruch 10 beansprucht, weiter umfassend die Schritte der Zugabe einer kationischen organischen Verbindung mit einem Gewichtsmittel des Molekulargewichts von weniger als etwa 10.000 und eines anionischen Stabilisators vor dem Homogenisieren des Gemischs.
  12. Verwendung einer Dispersion nach einem der Ansprüche 1-9 zur Oberflächenleimung von Papier.
  13. Verwendung einer Dispersion nach einem der Ansprüche 1-9 zur Masseleimung bei der Herstellung von Papier.
  14. Ein Verfahren zur Herstellung von Papier, umfassend die Schritte des Bildens einer Papierbahn aus einem Cellulosefasern enthaltenden Papierstoff und Aufbringen einer wässrigen Dispersion nach einem der Ansprüche 1-9 auf die Oberfläche der Papierbahn.
  15. Ein Verfahren zur Herstellung von Papier, umfassend die Schritte der Zugabe einer Dispersion nach einem der Ansprüche 1-9 zu einem Cellulosefasern enthaltenden Papierstoff und Entwässern des Papierstoffes auf einem Draht, um Papier und Rückwasser zu erhalten.
EP04717341A 2003-04-01 2004-03-04 Dispersion Expired - Lifetime EP1611284B1 (de)

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KR100983098B1 (ko) 2008-05-19 2010-09-17 주식회사 파피테크 해리성 무진 종이의 제조방법
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JP5754584B2 (ja) * 2010-05-27 2015-07-29 荒川化学工業株式会社 製紙用表面サイズ剤、表面サイズ塗工液および紙
CN102011341A (zh) * 2010-06-29 2011-04-13 上海东升新材料有限公司 用于可代替浆内施胶的复合型表面施胶剂及其应用
CN101942780B (zh) * 2010-09-15 2011-09-07 山东轻工业学院 一种akd乳液施胶剂的制备方法
RU2602061C2 (ru) * 2011-03-31 2016-11-10 Соленис Текнолоджиз Кейман,Л.П. Проклеивающие композиции
EP3008241B1 (de) * 2013-06-13 2021-03-10 Ecolab USA Inc. Wasserfreie oberflächenleimungszusammensetzung und verfahren zur behandlung eines papiersubstrats damit
CN103410040A (zh) * 2013-06-28 2013-11-27 池州浙源纸业有限公司 一种高抗水性瓦楞纸的制备方法
CN103410042A (zh) * 2013-06-28 2013-11-27 池州浙源纸业有限公司 一种高强度瓦楞纸的制备方法
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CN103866627B (zh) * 2014-02-28 2016-01-13 南通玖伍捌科技企业孵化器有限公司 一种聚氨酯施胶剂及其制备方法
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RU2691239C2 (ru) * 2014-10-23 2019-06-11 Басф Се Способ получения сборного строительного материала
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CN105696417B (zh) * 2016-04-26 2017-09-19 齐鲁工业大学 一种无表面活性剂的akd乳液的制备方法
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JP6867802B2 (ja) * 2016-12-26 2021-05-12 大王製紙株式会社 水系後糊圧着用紙及び水系後糊圧着用紙の製造方法
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JP7287148B2 (ja) * 2019-06-26 2023-06-06 荒川化学工業株式会社 製紙用表面サイズ剤、製紙用表面サイズ剤の製造方法及び塗工紙
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EP1611284A1 (de) 2006-01-04
ZA200506665B (en) 2006-12-27
CN100335720C (zh) 2007-09-05
BRPI0409152A (pt) 2006-03-28
NZ542293A (en) 2008-12-24
RU2005133635A (ru) 2006-03-10
JP4375625B2 (ja) 2009-12-02
WO2004088036A1 (en) 2004-10-14
TWI259224B (en) 2006-08-01
MY136991A (en) 2008-12-31
PL1611284T3 (pl) 2012-02-29
CA2520642A1 (en) 2004-10-14
ATE526456T1 (de) 2011-10-15
AU2004225562B2 (en) 2007-05-31
KR100771786B1 (ko) 2007-10-30
ES2373954T3 (es) 2012-02-10
RU2309213C2 (ru) 2007-10-27
CN1761789A (zh) 2006-04-19
TW200502462A (en) 2005-01-16
CA2520642C (en) 2010-03-02
AU2004225562A1 (en) 2004-10-14
JP2006522227A (ja) 2006-09-28
MXPA05009305A (es) 2005-11-04
KR20050118697A (ko) 2005-12-19
SI1611284T1 (sl) 2012-01-31

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