WO2012168398A1 - Composition pulvérulente et utilisation de ladite composition pour la production de papier - Google Patents

Composition pulvérulente et utilisation de ladite composition pour la production de papier Download PDF

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Publication number
WO2012168398A1
WO2012168398A1 PCT/EP2012/060847 EP2012060847W WO2012168398A1 WO 2012168398 A1 WO2012168398 A1 WO 2012168398A1 EP 2012060847 W EP2012060847 W EP 2012060847W WO 2012168398 A1 WO2012168398 A1 WO 2012168398A1
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WO
WIPO (PCT)
Prior art keywords
powder composition
polymer
paper
filler
composition according
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PCT/EP2012/060847
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German (de)
English (en)
Inventor
Rainer Blum
Gabriel Skupin
Original Assignee
Basf Se
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Basf Se filed Critical Basf Se
Priority to CN201280028539.7A priority Critical patent/CN103620117A/zh
Priority to EP12728434.7A priority patent/EP2718497A1/fr
Publication of WO2012168398A1 publication Critical patent/WO2012168398A1/fr

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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
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/63—Inorganic compounds
    • D21H17/67—Water-insoluble compounds, e.g. fillers, pigments
    • D21H17/69—Water-insoluble compounds, e.g. fillers, pigments modified, e.g. by association with other compositions prior to incorporation in the pulp or paper
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/02—Compounds of alkaline earth metals or magnesium
    • C09C1/021—Calcium carbonates
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/10—Treatment with macromolecular organic compounds
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/63—Inorganic compounds
    • D21H17/67—Water-insoluble compounds, e.g. fillers, pigments
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/63—Inorganic compounds
    • D21H17/67—Water-insoluble compounds, e.g. fillers, pigments
    • D21H17/675—Oxides, hydroxides or carbonates
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/63—Inorganic compounds
    • D21H17/67—Water-insoluble compounds, e.g. fillers, pigments
    • D21H17/68—Water-insoluble compounds, e.g. fillers, pigments siliceous, e.g. clays

Definitions

  • the present invention relates to powder compositions whose particles comprise at least one inorganic pigment having on its surface at least one biodegradable polyester polymer and / or polyalkylene carbonate polymer, a process for the preparation of these powder compositions and their use as additives in the production of paper, board and board ,
  • WO 92/14881 discloses the treatment of an aqueous filler dispersion with a combination of water-soluble cationic and anionic hardeners for paper, such as polyethyleneimine, polymers of N-vinylformamide and copolymers of acrylamide and acrylic acid.
  • aqueous suspensions of inorganic particles which have a positive zeta potential are mixed with an anionic latex of a resin, the amounts used being such that the coated particles obtained have a zeta potential of essentially of 0.
  • aqueous filler suspensions are known which are obtained by treating aqueous filler suspensions with at least one binder for paper coating by stirring or by the action of shear forces.
  • WO 2006/128814 and US 2007/0266898 teach polymer-pigment hybrids for papermaking which are obtained by grinding an aqueous slurry of inorganic pigment in the presence of a binder, preferably a styrene-acrylate dispersion.
  • EP 792309 teaches biodegradable polymers and EP 792309 teaches crosslinked biodegradable polymers.
  • Paper products which are monolayer-coated with biodegradable polymer (mixtures) are known from WO 2010/034712.
  • PCT / EP 2010/066079 teaches a process for sizing paper in which biodegradable polymers are used as polymeric sizing agent. These are useful both as a bulk and as a surface sizing agent.
  • the present invention was based on a process for the production of paper, paperboard and paperboard with a high filler content, which, despite the filler content, results in paper products having improved strength and / or printability with the same or improved efficiency of the paper machine.
  • a powder composition has been found, the particles of which comprise at least one inorganic pigment, wherein at least one biodegradable polyester polymer and / or polyalkylene carbonate polymer is disposed on the pigment surface. Further, there has been found a process for producing this powder composition and its use as an additive in the production of paper, paperboard and paperboard, and a process for producing paper, paperboard and paperboard using these powder compositions.
  • biodegradable in the context of the present invention is then fulfilled for a substance or a substance mixture if this substance or the substance mixture according to DIN EN 13432, Chapter A.2 a percentage degree of biodegradation of at least 90% of a suitable reference substance (eg, microcrystalline cellulose).
  • a suitable reference substance eg, microcrystalline cellulose
  • biodegradability results in the polymers and polymer blends (hereinafter abbreviated to polymer (blends)) decomposing in a reasonable and detectable period of time.
  • Degradation can be effected enzymatically, hydrolytically, oxidatively and / or by the action of electromagnetic radiation, for example UV radiation, and mostly for the most part be effected by the action of microorganisms such as bacteria, yeasts, fungi and algae.
  • the biodegradability can be quantified, for example, by mixing polymer (mixtures) with compost and storing them for a specific time.
  • biodegradability is determined by the ratio of the net CO 2 release of the sample (after deduction of CO 2 release by the compost without sample) to the maximum CO 2 release of the sample (calculated from the carbon content of the sample) as a percentage of biodegradation Are defined.
  • Biodegradable polymers mixtures usually show after a few days of composting significant signs of degradation such as fungal growth, crack and hole formation.
  • Biodegradable polymers are already known to the person skilled in the art and are disclosed, inter alia, in Ullmann 's Encyclopedia of Industrial Chemistry (online version 2009), Polymers, Biodegradable, Wiley-VCH Verlag GmbH & Co. KG, Weinheim, 2009, pages 131.
  • biodegradable polyester polymer in the context of the present invention includes biodegradable, aliphatic-aromatic polyesters as described in WO 2010/034712.
  • Biodegradable polyester polymers are preferably understood as meaning aliphatic polyesters or aliphatic-aromatic (partially aromatic) polyesters based on aliphatic and aromatic dicarboxylic acids and aliphatic dihydroxy compounds.
  • the pigment / polymer assembly includes both polymer-clad pigments and pigmentary polymer-grade pigment particles.
  • agglomerates of less than 1000 pigment particles with a proportionate or complete polymer coating are included.
  • the ratio of the polymer mass to the pigment mass can vary in the range from 0.001 and less to 10 and more. Preferably, the range is from 0.01 to 1.
  • At least one polymer is selected, selected from polyalkylene carbonates and aliphatic or aliphatic-aromatic (partially aromatic) polyesters based on aliphatic and aromatic dicarboxylic acids and aliphatic dihydroxy compounds. These polymers can be present individually or in their mixtures.
  • the biodegradable polyester polymer and / or polyalkylene carbonate polymer is water-insoluble.
  • polyesters based on aliphatic and aromatic dicarboxylic acids and aliphatic dihydroxy compound so-called partially aromatic polyesters or aliphatic polyesters of aliphatic dicarboxylic acids and aliphatic diols or of aliphatic hydroxycarboxylic acids are suitable for the preparation of the biodegradable polyester mixtures.
  • partially aromatic polyesters or aliphatic polyesters of aliphatic dicarboxylic acids and aliphatic diols or of aliphatic hydroxycarboxylic acids are suitable for the preparation of the biodegradable polyester mixtures.
  • common to these polyesters is that they are biodegradable according to DIN EN 13432. Of course, mixtures of several such polyesters are suitable.
  • At least one aliphatic-aromatic polyester polymer is used.
  • Aliphatic-aromatic polyesters are polyesters based on aliphatic and aromatic dicarboxylic acids and aliphatic dihydroxy compound, known as partially aromatic polyesters.
  • polyester derivatives are also to be understood here as polyether esters, polyester amides or polyetheresteramides and polyester urethanes (see EP patent no.
  • Suitable partially aromatic polyesters include linear non-chain extended polyesters (WO 92/09654). Preferred are chain-extended and / or branched partially aromatic polyesters. The latter are known from WO 96/15173 to 15176, 21689 to 21692, 25446, 25448 or WO 98/12242, to which reference is expressly made. Mixtures of different partially aromatic polyesters are also possible. Interesting recent developments are based on renewable raw materials (see WO-A
  • Suitable aliphatic dicarboxylic acids and their ester-forming derivatives (a1) are generally those having 2 to 18 carbon atoms, preferably 4 to 10 carbon atoms. They can be both linear and branched. In principle, however, it is also possible to use dicarboxylic acids having a larger number of carbon atoms, for example having up to 30 carbon atoms.
  • Examples which may be mentioned are: oxalic acid, malonic acid, succinic acid, 2-methylsuccinic acid, glutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, .alpha.-ketoglutaric acid, adipic acid, pimelic acid, azelaic acid, sebacic acid, brassylic acid, fumaric acid, 2,2-dimethylglutaric acid, suberic acid (Suberic acid), diglycolic acid, oxaloacetic acid, glutamic acid, aspartic acid, itaconic acid and maleic acid.
  • the dicarboxylic acids or their ester-forming derivatives may be used singly or as a mixture of two or more thereof.
  • Succinic acid, adipic acid, azelaic acid, sebacic acid, brassylic acid or their respective ester-forming derivatives or mixtures thereof are preferably used.
  • Succinic acid, adipic acid or sebacic acid or their respective ester-forming derivatives or mixtures thereof are particularly preferably used.
  • Succinic acid, azelaic acid, sebacic acid and brassylic acid also have the advantage that they are accessible from renewable raw materials.
  • PBAzeT polybutylene azalate-co-butylene terephthalate
  • PBBrasT polybutylene-brassylate-co-butylene terephthalate
  • PBAT polybutylene adipate terephthalate
  • PBSeT polybutylene sebacate terephthalate
  • PBST polybutylene succinate terephthalate
  • the aromatic dicarboxylic acids or their ester-forming derivatives (a2) may be used singly or as a mixture of two or more thereof. Particularly preferred is terephthalic acid or its ester-forming derivatives such as dimethyl terephthalate used.
  • the diols (B) are selected from branched or linear alkanediols of 2 to 12 carbon atoms, preferably 4 to 6 carbon atoms, or cycloalkanediols of 5 to 10 carbon atoms.
  • alkanediols examples include ethylene glycol, 1, 2-propanediol, 1, 3-propanediol, 1, 2-butanediol, 1, 4-butanediol, 1, 5-pentanediol, 2,4-dimethyl-2-ethylhexane-1, 3 diol, 2,2-dimethyl-1,3-propanediol, 2-ethyl-2-butyl-1,3-propanediol, 2-ethyl-2-isobutyl-1,3-propanediol, 2,2,4-trimethyl- 1, 6-hexanediol, in particular ethylene glycol, 1, 3-propanediol, 1, 4-butanediol and 2,2-dimethyl-1, 3-propanediol (neopentyl glycol); Cyclopentanediol, 1,4-cyclohexanediol, 1,2-cyclohexan
  • 1,4-butanediol in particular in combination with adipic acid as component a1) and 1,3-propanediol, in particular in combination with sebacic acid as component a1).
  • 1, 3 propandiol also has the advantage that it is available as a renewable resource. It is also possible to use mixtures of different alkanediols.
  • the preferred partially aromatic polyesters are characterized by a molecular weight (Mn) in the range from 1000 to 100,000, in particular in the range from 9,000 to 75,000 g / mol. Preferably in the range of 10,000 to 50,000 g / mol and a melting point in the range of 60 to 170 ° C, preferably in the range of 80 to 150 ° C.
  • Mn molecular weight
  • Polyesters of aliphatic dicarboxylic acids and aliphatic diols are understood as meaning polyesters of aliphatic diols and aliphatic dicarboxylic acids such as polybutylene succinate (PBS), polybutylene adipate (PBA), polybutylene succinate adipate (PBSA), polybutylene succinate sebacate (PBSSe), polybutylene sebacate (PBSe).
  • PBS polybutylene succinate
  • PBA polybutylene adipate
  • PBSA polybutylene succinate adipate
  • PBSSe polybutylene succinate sebacate
  • PBSe polybutylene sebacate
  • the aliphatic polyesters are marketed, for example, by the companies Showa Highpolymers under the name Bionolle and by Mitsubishi under the name GSPIa. More recent developments are described in WO 2010/03471 1.
  • the biodegradable polyesters may contain, in addition to or in place of the aforementioned aliphatic and aliphatic / aromatic polyesters, other polyesters such as polylactic acid, polybutylene succinates, polybutylene succinate-co-adipates, polyhydroxyalkanoates, polyesteramides, polyalkylene carbonate, polycaprolactone. Polyesters based on aliphatic hydroxycarboxylic acids, in particular polylactic acid and polycaprolactone and polyhydroxyalkanoates are mentioned.
  • Preferred components in the polymer mixtures or as pure components are polylactic acid (PLA), polybutylene succinates, polybutylene succinate-co-adipates and polyhydroxyalkanoates, and in particular polyhydroxybutyrate (PHB) and polyhydroxybutyrate co-hydroxyvalerate (PHBV) and polyhydroxybutyrate-co-hydroxyhexanoates (PHBH )
  • Polylactic acid having the following property profile is preferably used:
  • melt volume rate (MVR at 190 ° C and 2.16 kg according to ISO 1 133 of 0.5 - preferably 2 to 30 especially 9 ml / 10 minutes
  • Tg glass transition point
  • Preferred polylactic acids are, for example, NatureWorks® 6201 D, 6202 D, 6251 D, 3051 D and in particular 3251 D, 4032 D, 4043 D or 4044 D (polylactic acid from NatureWorks).
  • Polyhydroxyalkanoates are understood as meaning primarily poly-4-hydroxybutyrates and poly-3-hydroxybutyrates, and also include copolyesters of the abovementioned hydroxybutyrates with 3-hydroxyvalerates (P (3HB) -co-P (3HV)) or 3-hydroxyhexanoate.
  • Poly-3-hydroxybutyrate-co-4-hydroxybutyrate (P (3HB) -co-P (4HB)) are known in particular from the company Metabolix. They are sold under the trade name Mirel®.
  • Poly-3-hydroxybutyrate-co-3-hydroxyhexanoates (P (3HB) -co-P (3HH)) are available from the company P & G or Kane- ka known.
  • Poly-3-hydroxybutyrates are sold, for example, by PHB Industrial under the brand name Biocycle® and by Tianan under the name Enmat®.
  • the polyhydroxyalkanoates generally have a molecular weight M w of from 100,000 to 1,000,000, and preferably from 300,000 to 600,000.
  • Polycaprolactone is marketed for example by the company. Daicel under the product names Placcel ®. Preferred polyester mixtures of partially aromatic polyesters and polylactic acid or polyhydroxyalkanoates are described in EP 1656 423, EP 1838784, WO 2005/063886, WO
  • Polyalkylene carbonates are understood to be primarily polyethylene carbonate (see EP-A 1264860) obtainable by copolymerization of ethylene oxide and carbon dioxide and in particular polypropylenecarbonate (see, for example, WO 2007/125039), obtainable by copolymerization of propylene oxide and carbon dioxide.
  • the polyalkylene carbonate chain may contain both ether and carbonate groups.
  • the proportion of carbonate groups in the polymer is dependent on the reaction conditions, in particular the catalyst used. In the preferred polyalkylene carbonates, more than 85 and preferably more than 90% of all linkages are cabonate groups. Suitable zinc and cobalt catalysts are described in US 4789727 and US 7304172.
  • Polypropylene carbonate can also be prepared analogously to Soga et al., Polymer Journal, 1981, 13, 407-10. The polymer is also commercially available and is marketed, for example, by Empower Materials Inc. or Aldrich.
  • the reaction mixture is usually diluted to 2 to 10 times the volume with a polar aprotic solvent such as, for example, a carboxylic acid ester (in particular ethyl acetate), a ketone (in particular acetone), an ether (in particular tetrahydrofuran).
  • a polar aprotic solvent such as, for example, a carboxylic acid ester (in particular ethyl acetate), a ketone (in particular acetone), an ether (in particular tetrahydrofuran).
  • a polar aprotic solvent such as, for example, a carboxylic acid ester (in particular ethyl acetate), a ketone (in particular acetone), an ether (in particular tetrahydrofuran).
  • an acid such as acetic acid and / or an acid anhydride such as acetic anhydride
  • stirred for several hours at a slightly elevated temperature.
  • the organic phase is washe
  • the molecular weight Mn of the polypropylene carbonates produced by the abovementioned processes is generally from 70,000 to 90,000 Da.
  • the molecular weight Mw is usually 250,000 to 400,000 Da.
  • the ratio of the ether to carbonate groups in the polymer is 5: 100 to 90: 100.
  • Polypropylencar- Bonates having a molecular weight Mn of from 30,000 to 5,000,000, preferably from 35,000 to 250,000 and more preferably from 40,000 to 150,000 Da can be prepared in this way.
  • Polypropylene carbonates with a Mn of less than 25,000 Da have a low glass transition temperature of less than 25 ° C. They are therefore only of limited suitability for surface applications (eg coating) with the pigments mentioned.
  • the polydispersity ratio of weight average (Mw) to number average (Mn)
  • Mw weight average
  • Mn number average
  • the polypropylene carbonates used may contain up to 1% carbacate and urea groups.
  • Particularly suitable chain extenders for the polyalkylene carbonates are MSA, acetic anhydride, di- or polyisocyanates, di- or polyoxazolines or -oxazines or di- or polyepoxides.
  • isocyanates are toluylene-2,4-diisocyanate, toluylene-2,6-diisocyanate, 2,2'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, naphthylene-1,5-diisocyanate or xylylene diisocyanate and in particular 1,6-hexamethylene diisocyanate, isophorone diisocyanate or methylene bis (4-isocyanatocyclohexane).
  • Particularly preferred aliphatic diisocyanates are isophorone diisocyanate and in particular 1,6-hexamethylene diisocyanate.
  • bisoxazolines are 2,2'-bis (2-oxazoline), bis (2-oxazolinyl) methane, 1, 2-bis (2-oxazolinyl) ethane, 1, 3-bis (2-oxazolinyl) propane or 1, 4 Bis (2-oxazolinyl) butane, especially 1, 4-bis (2-oxazolinyl) benzene, 1, 2-bis (2-oxazolinyl) benzene or 1, 3-bis (2-oxazolinyl) benzene.
  • the chain extenders are preferably used in amounts of 0.01 to 5, preferably 0.05 to 2, particularly preferably 0.08 to 1 wt .-%, based on the amount of polymer.
  • additives include the typical plasticizers such as polybutylene terephthalate (PBT) in copolyesters of PBT (e.g., PBAT, PBSeT, PBST), polybutylene succinate in polylactic acid; Lubricants and release agents such as stearates (especially zinc, tin, and calcium stearate); Plasticizers such as citric acid esters (especially tributyl citrate and acetyl tributyl citrate), glyceric acid esters such as triacetylglycerol or ethylene glycol derivatives; Surfactants such as polysorbates, palmitates or laurates; Waxes such as carauba wax, candelilla wax, beeswax or beeswax esters, Jofana oil, Japan wax, spermaceti, wool wax; UV absorbers (for example, PBT) in copolyesters of PBT (e.g., PBAT, PBSeT, PBST
  • the additives are used in concentrations of from 0 to 5% by weight, in particular from 0.1 to 2% by weight, based on the biodegradable polyester polymer, and / or polyalkylene carbonate polymer.
  • Plasticizers may be included in 0.1 to 30 weight percent (preferably 0.1 to 10 weight percent) based on the biodegradable polyester polymer, and / or polyalkylene carbonate polymer.
  • Inorganic pigments are all pigments customarily used in the paper industry on the basis of metal oxides, silicates and / or carbonates, in particular of pigments from the group consisting of calcium carbonate, in the form of ground (GCC) lime, chalk, marble or precipitated calcium carbonate (PCC).
  • GCC ground
  • PCC precipitated calcium carbonate
  • GCC ground
  • kaolin kaolin
  • bentonite satin white
  • calcium sulfate barium sulfate
  • titanium dioxide titanium dioxide in question. It is also possible to use mixtures of two or more pigments.
  • inorganic pigments having an average particle size (Z average) ⁇ 10 ⁇ m, preferably from 0.1 to 5 ⁇ m, in particular from 0.1 to 4 ⁇ m, are used.
  • the determination of the mean particle size (Z-average) of the inorganic pigments and of the particles of the powder composition generally takes place in the context of this document by the method of quasi-elastic light scattering (DIN-ISO 13320-1), for example with a Mastersizer 2000 from Malvern Instruments Ltd ..
  • biodegradable polyester polymers and / or polyalkylene carbonate polymers are disposed on the surface of the inorganic pigments.
  • the particles may be individual particles as well as interconnected individual particles, so-called agglomerates, which are presumably bound together by the biodegradable polymer.
  • the proportion of the biodegradable polymer is 0.1 to 100 wt .-% based on the inorganic pigment.
  • the proportion of polymer is preferably from 0.25 to 7% by weight, in particular from 0.5 to 5% by weight, based on the weight of the inorganic pigments.
  • the biodegradable polyester polymer and / or polyalkylene carbonate polymer is applied to the surface of the inorganic pigment.
  • Solvents for the biodegradable polyester polymer and / or polyalkylene carbonate polymer are diluents which are capable of dissolving at least 1 g of the polymer per 100 g of solvent.
  • Preferred solvents are for polyester polymers: chlorinated hydrocarbons, hexafluoroisopropanol at room temperature (23 ° C) and a mixture of toluene and tetrahydrofuran at about 60 ° C.
  • polyesteramides and polyalkylenecarbonates can be dissolved in toluene or tetrahydrofuran, or in ethanol or isopropanol, or in alkyl acetates, such as ethyl acetate, or in halogenated hydrocarbons.
  • the biodegradable polymer is used to 0.5 to 10 wt .-%, preferably from 1 to 5 wt .-% based on the pigment content (filler content).
  • the preparation of the powder composition according to the invention is preferably carried out by a) treating inorganic pigment with a solution of a polyester polymer
  • the spraying of the mixture obtained according to a) takes place in the hot air stream by means of single-substance nozzles.
  • the droplet size at exit is chosen so that a pigment powder is formed in which the powder particles have an average particle size (Z-average) in the range of 1 to 200 ⁇ m.
  • Z-average average particle size
  • the person skilled in the art will choose the diameter of the nozzle and the admission pressure of the material stream. The higher the form, the smaller the droplets are produced.
  • the pigment dispersion obtained according to a) is fed in the range of about 3 bar.
  • a single-fluid nozzle with swirl generator is used. By selecting the swirl generator, droplet size and spray angle can be additionally influenced.
  • a pigment dispersion (mixture) obtained according to a) containing from 0.1 to 10% by weight, preferably from 0.5 to 5% by weight, of polyester polymer and / or polyalkylene carbonate polymer based on the inorganic pigment.
  • An advantageous solids concentration of the pigment dispersion obtained according to a) is 10 to 40% by weight.
  • the solids concentration preferably used is 25-35 wt .-%.
  • the procedure is such that the inlet temperature of the hot air flow in the range of 100 to 200 ° C, preferably 120 to 180 ° C, and the outlet temperature of the hot air flow in the range of 30 to 1 10 ° C, preferably 50 to 90 ° C.
  • the temperature difference between inlet and outlet temperature is preferably at least 25 ° C, and more preferably at least 30 ° C.
  • the separation of the fines from the gas stream is normally carried out using cyclones or filter separators. The fines are preferably redispersed and recycled into the stream.
  • the sprayed pigment dispersion obtained according to a) and the hot air stream are preferably conducted in parallel.
  • the powder properties can also be influenced by the temperature of the aftertreatment with which the powder is discharged from the spray tower. Typically, one sets temperature ranges of 20-30 ° C, rarely higher than 40 ° C.
  • spraying aids are added for spray drying in order to facilitate spray drying or to adjust certain powder properties, eg low dust, flowability or improved redispersibility.
  • a variety of spraying aids are familiar to the person skilled in the art. Examples thereof can be found in DE-A 19629525, DE-A 19629526, DE-A 2214410, DE-A 2445813, EP-A 407889 or EP-A 784449.
  • Advantageous spray aids are, for example, water-soluble polymers of the polyvinyl alcohol or partially hydrolyzed polyvinyl acetates, cellulose lulose derivatives such as hydroxyethylcellulose, carboxymethylcellulose, methylcellulose, methylhydroxyethylcellulose and methylhydroxypropylcellulose, polyvinylpyrrolidone, copolymers of vinylpyrrolidone, gelatin, preferably polyvinyl alcohol and partially hydrolyzed polyvinyl acetates and methylhydroxypropylcellulose.
  • the powder compositions obtained by spray-drying have a particle size of from 0.3 to 300 ⁇ m, preferably from 0.3 to 30 ⁇ m, in particular from 0.3 to 10 ⁇ m.
  • the powder compositions of the invention are advantageously suitable as fillers for the production of paper, cardboard and paperboard. Therefore, the present application also relates to the use of the powder composition of the invention as a filler in the production of filler-containing papers, cardboard and paperboard.
  • the powder composition according to the invention is preferably used in the form of an aqueous suspension, also referred to as a slurry, which is obtainable by suspending the powder composition according to the invention in water.
  • the aqueous suspension of the powder composition is obtainable by the following process steps:
  • the aqueous suspensions of the powder compositions according to the invention preferably contain from 1 to 60% by weight, preferably from 10 to 50% by weight, of powder composition according to the invention.
  • the powder compositions of the invention are processed, for example, by incorporation in water to form an aqueous suspension.
  • an anionic dispersant for example polyacrylic acids having an average molecular weight M w of, for example, 1000 to 40,000 daltons. If an anionic dispersant is used, so For example, from 0.01 to 0.5% by weight, preferably from 0.2 to 0.3% by weight, is used to prepare aqueous suspensions.
  • the powder compositions of the invention dispersed in water in the presence of anionic dispersants are anionic.
  • the aqueous suspensions of the powder composition according to the invention can be used for the production of all filler-containing paper grades, for example newsprint, SC paper (supercalendered paper), wood-free or wood-containing writing and printing papers.
  • the main raw material components used are groundwood, thermomechanical (TMP), chemo-thermomechanical (CTMP), pressure ground (PGW) and sulphite and sulphate pulp.
  • the aqueous suspensions of the powder compositions according to the invention are added to the pulp in papermaking so as to form the total paper stock.
  • the overall fabric may contain other conventional paper additives.
  • Conventional paper additives are, for example, sizing agents, wet strength agents, cationic or anionic retention aids based on synthetic polymers and dual systems, dewatering agents, other dry strength agents, pigments not coated according to the invention, fillers, optical brighteners, defoamers, biocides and paper dyes. These conventional paper additives can be used in the usual amounts.
  • the sizing agents to be mentioned are alkylketene dimers (AKD), alkenylsuccinic anhydrides (ASA) and rosin size.
  • Suitable retention agents are, for example, anionic microparticles (colloidal silicic acid, bentonite), anionic polyacrylamides, cationic polyacrylamides, cationic starch, cationic polyethyleneimine or cationic polyvinylamine.
  • anionic microparticles colloidal silicic acid, bentonite
  • anionic polyacrylamides cationic polyacrylamides
  • cationic starch cationic polyethyleneimine or cationic polyvinylamine
  • any combination thereof is conceivable, for example, dual systems consisting of a cationic polymer with an anionic microparticle or an anionic polymer with a cationic microparticle.
  • retention aids of this kind which can be added to the thick material, for example, but also to the thin material.
  • Dry strength agents are to be understood as meaning synthetic dry strength agents such as polyvinylamine or natural dry strength agents such as starch.
  • the powder composition according to the invention make it possible to produce paper with a high filler content.
  • the invention in a process for the production of paper and paper products used powder compositions make it possible to produce paper with higher filler content.
  • the loss of strength due to the higher filler content is significantly lower in comparison to known processes of the prior art.
  • the powder compositions according to the invention lead to good strengths as a filler in paper and paper products. As a result, a good printability (improved linting and dusting) is possible with the same or improved efficiency of the paper machine.
  • the invention further relates to the use of the powder composition according to the invention as a filler in the surface coating of papers and paper products.
  • the powder composition according to the invention is used in the form of an aqueous suspension.
  • An object of the invention is also a paper coating slip containing
  • paper coating slips In addition to water, paper coating slips generally contain pigments, binders and auxiliaries for adjusting the required rheological properties, eg. B. thickener.
  • the pigments are usually dispersed in water.
  • the paper coating composition contains pigments in an amount of preferably at least 80% by weight, e.g. 80 to 95 wt .-% or 80 to 90 wt .-%, based on the total solids content.
  • the pigment only the powder composition of the present invention can be used. However, it is also possible to replace part of the total pigment amount with conventional pigment.
  • the proportion of the powder composition according to the invention should be at least 30% by weight, based on the total amount of pigment.
  • Suitable pigments are, for example, metal salt pigments, such as e.g. Calcium sulfate, calcium aluminate sulfate, barium sulfate, magnesium carbonate and calcium carbonate, of which carbonate pigments, especially calcium carbonate, are preferred.
  • the calcium carbonate may be ground calcium carbonate (GCC), precipitated calcium carbonate (PCC), lime or chalk.
  • Suitable calcium carbonate pigments are e.g. available as Covercarb® 60, Hydrocarb® 60 or Hydrocarb® 90 ME.
  • Other suitable pigments are e.g. Silicas, aluminum oxides, aluminum hydrate, silicates, titanium dioxide, zinc oxide, kaolin, clay, talc or silica.
  • Suitable further pigments are e.g. available as Capim® MP 50 (Clay), Hydragloss® 90 (Clay) or Talcum C10.
  • the paper coating contains at least one binder.
  • the most important tasks of binders in paper coating slips are to bond the pigments to the paper and the pigments and to partially fill voids between pigment particles.
  • Suitable binders are firstly a natural-based binder, in particular a starch-based binder, and also synthetic binders, in particular emulsion polymers which can be prepared by emulsion polymerization.
  • starch-based binders in this context any native, modified or degraded starch.
  • Native starches may consist of amylose, amylopectin or mixtures thereof.
  • Modified starches may be oxidized starch, starch esters or starch ethers. Hydrolysis can reduce the molecular weight of the starch (degraded starch). The degradation products are oligosaccharides or dextrins into consideration.
  • Preferred starches are corn, corn and potato starch. Particularly preferred are corn and corn starch, most preferably cereal starch.
  • Suitable synthetic binders are polymers obtainable by radical polymerization of ethylenically unsaturated compounds.
  • Suitable synthetic binders are, for example, polymers comprising at least 40% by weight of so-called main monomers selected from C 1 - to C 20 -alkyl (meth) acrylates, vinyl esters of carboxylic acids containing up to 20 carbon atoms, vinylaromatics having up to 20 C atoms, ethylenically unsaturated nitriles, vinyl halides, vinyl ethers of alcohols containing 1 to 10 carbon atoms, aliphatic hydrocarbons having 2 to 8 carbon atoms and one or two double bonds or mixtures of these monomers is constructed.
  • Paper coating slips according to the invention may additionally comprise further additives and auxiliaries, for example fillers, co-binders and thickeners for further optimization of viscosity and water retention, optical brighteners, dispersants, surfactants, lubricants (for example calcium stearate and waxes), neutralizing agents (eg NaOH or ammonium hydroxide ) for pH adjustment, defoamers, deaerating agents, preservatives (eg biocides), leveling agents, dyes (in particular soluble dyes), etc.
  • Suitable thickeners are, in addition to synthetic polymers (eg crosslinked polyacrylate), in particular celluloses, preferably carboxymethylcellulose.
  • Optical brighteners are, for example, fluorescent or phosphorescent dyes, in particular stilbenes. It is preferably an aqueous paper coating slip; it contains water in particular already by the preparation form of the ingredients (aqueous polymer dispersions, aqueous pigment slurries); the desired viscosity can be adjusted by adding more water. Typical solids contents of the paper coating slips are in the range of 30 to 70 wt .-%.
  • the pH of the paper coating slip is preferably adjusted to values of 6 to 10, in particular 7 to 9.5.
  • the invention also relates to paper, board and cardboard coated with a paper coating slip according to the invention and to a method for painting paper, cardboard and paperboard, wherein
  • a powder composition according to the invention is prepared or made available.
  • a paper coating slip is prepared; and the paper coating is applied to at least one surface of paper, cardboard and paperboard.
  • the paper coating slip is preferably applied to uncoated base papers or uncoated cardboard or uncoated cardboard.
  • the amount is generally from 1 to 50 g, preferably from 5 to 30 g (solid, that is to say without water or other solvents which are liquid at 21 ° C., 1 bar) per square meter.
  • the coating can be done by conventional application methods, e.g. using a size press, film press, blade coater, air brush, squeegee, curtain coating or spray coater.
  • the aqueous dispersions of the water-soluble copolymers can be used in paper coating slips for the base coat and / or for the top coat.
  • the paper coating slips of the invention show good performance properties. In particular, they improve the strength of the papers.
  • the molecular weights M n and M w of the partially aromatic polyesters were determined as follows: 15 mg of the partially aromatic polyesters were dissolved in 10 ml of hexafluoroisopropanol (HFIP).
  • the determination of the viscosity numbers was carried out according to DIN 53728 Part 3, January 3, 1985, capillary viscosimetry. A micro Ubbelohde type M-II was used.
  • the solvent used was the mixture: phenol / dichlorobenzene in a weight ratio of 50/50.
  • the determination of the melt volume flow rate (MVR) was carried out according to EN ISO 1 133. The test conditions were 190 ° C, 2.16 kg. The melting time was 4 minutes.
  • the MVR indicates the rate of extrusion of a molten plastic molded article through an extrusion tool of fixed length and fixed diameter under the conditions described above: temperature, load and position of the piston.
  • the volume extruded in a specified time in the cylinder of an extrusion plastometer is determined.
  • Ecovio FS Paper C1500 containing compound) polybutylene sebacate terephthalate (PBSeT), and polylactic acid (PLA) with MVR (190 ° C, 2.16 kg) according to EN ISO 1 133 of 20 ml / 10 min.
  • Polypropylene carbonate having an average molecular weight Mn of 52,000 g / mol and a molecular weight Mw of 910000 g / mol, which is determined by gel permeation chromatography.
  • Cationic polyacrylamide Percol 540, retention agent based on polyacrylamide, manufacturer BASF SE
  • Example 1 Spray-drying a suspension of calcium carbonate with polypropylene carbonate
  • the suspension thus obtained was conveyed with a peristaltic pump into the spray tower.
  • the suspension to be dried was atomized with nitrogen gas (4 m 3 / h, 3 bar) in a two-fluid nozzle with 1, 2 mm diameter.
  • nitrogen gas heated to 80 ° C. was introduced, which dried the dispersed suspension particles to give solid particles of about 5 to 20 ⁇ m.
  • the drying gas was fed tangentially in the inlet area of the spray dryer.
  • the dry were separated in a cyclone and the exhaust gas was removed via the construction exhaust.
  • the cyclone was heated to about 53 ° C.
  • Bleached pulp (100% eucalyptus pulp) and drinking water were pitched free of specks at a solids concentration of 4% in the laboratory pulper and then ground to a freeness of 30-35 SR.
  • the pH of the substance was in the range between 7 and 8.
  • the ground substance was then diluted with drinking water to a solids concentration of 0.5% (5 g / l pulp concentration).
  • Example D1 To the above paper stock suspension, the 20 wt .-% dispersion of Example D1 was metered, wherein on 75 parts by weight of paper pulp (solid) 25 parts by weight of powder composition (solid) were used. Subsequently, 0.01 wt .-% (solid) based on pulp (solid) of a cationic polyacrylamide (Percol 540) used. From this, a sheet was formed, which has a basis weight of 80 g / m 2 (filler content 25 wt .-%).
  • Percol 540 a cationic polyacrylamide
  • the paper sheets were each produced on a Rapid-Köthen sheet former according to ISO 5269/2 with a sheet weight of 80 g / m 2 and then dried for 7 minutes at 90 ° C and then calendered with a line pressure of 300 N / cm.
  • Example D2 To the above paper stock suspension, the 20 wt .-% dispersion of Example D2 was metered, wherein on 80 parts by weight of paper pulp (solid) 20 parts by weight of powder composition (solid) were used. Subsequently, 0.01% by weight (solid) based on paper stock (solid) of a cationic polyacrylamide (Percol 540) was used. From this, a sheet was formed which has a basis weight of 80 g / m 2 (filler content 20% by weight). The paper sheets were each produced on a Rapid-Köthen sheet former according to ISO 5269/2 with a sheet weight of 80 g / m 2 and then dried for 7 minutes at 90 ° C and then calendered with a line pressure of 300 N / cm.
  • a Rapid-Köthen sheet former according to ISO 5269/2 with a sheet weight of 80 g / m 2 and then dried for 7 minutes at 90 ° C and then calendered with a line pressure of 300 N / cm.
  • Example D3 To the above paper stock suspension, the 20 wt .-% dispersion of Example D3 was metered, wherein on 80 parts by weight of paper pulp (solid) 20 parts by weight of powder composition (solid) were used. Subsequently, 0.01% by weight (solid) based on pulp (solid) of a cationic polyacrylamide (Percol 540) was added. From this, a sheet was formed which has a basis weight of 80 g / m 2 (filler content 20% by weight). The paper sheets were each produced on a Rapid-Köthen sheet former according to ISO 5269/2 and then dried for 7 minutes at 90 ° C and then calendered with a line pressure of 300 N / cm.
  • a Rapid-Köthen sheet former according to ISO 5269/2
  • Example P1 Analogously to Example P1, a 20% strength by weight calcium carbonate dispersion (Hydrocarb OG) was metered into the above paper stock suspension, 25 parts by weight powder composition (solid) being used per 75 parts by weight of paper stock (solid). Subsequently, 0.01% by weight (solid) based on pulp (solid) of a cationic polyacrylamide (Percol 540) was added. It was prepared as in Example 1, a paper sheet with a sheet weight of 80g / m2, then dried for 7 minutes at 90 ° C and then calendered with a line pressure of 300 N / cm.
  • Example P5 (not according to the invention)
  • a paper sheet was produced as in Example P4, with the difference that 20 parts by weight of calcium carbonate (solid) in the form of a 20% by weight dispersion were used per 80 parts by weight of paper stock (solid). Examination of the paper sheets

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Abstract

L'invention concerne des compositions pulvérulentes dont les particules contiennent au moins un pigment anorganique. Lesdites compositions pulvérulentes sont caractérisées en ce qu'au moins un polymère de polyester et/ou un polymère de carbonate de polyalkylène biodégradable est disposé sur la surface du pigment. L'invention concerne également un procédé de fabrication desdites compositions pulvérulentes et l'utilisation de ces dernières en tant qu'additif dans la production de papier et de carton.
PCT/EP2012/060847 2011-06-10 2012-06-08 Composition pulvérulente et utilisation de ladite composition pour la production de papier WO2012168398A1 (fr)

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CN103790068A (zh) * 2014-02-18 2014-05-14 福建农林大学 淀粉喷雾干燥制备胶囊型造纸填料的方法
US8753481B2 (en) 2011-06-10 2014-06-17 Basf Se Powder composition and use thereof for paper production
US8940135B2 (en) 2011-12-01 2015-01-27 Basf Se Production of filled paper using biodegradable polyester fibers and/or polyalkylene carbonate fibers
EP3231939A1 (fr) 2016-04-11 2017-10-18 Fuhrmann, Uwe Mouchoir en papier multicouche destine a reduire la transmission d'agents infectieux
CN113396039A (zh) * 2019-01-30 2021-09-14 巴斯夫欧洲公司 制备淀粉共混物的方法

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FR3025532A1 (fr) * 2014-09-05 2016-03-11 Oberthur Fiduciaire Sas Support papier, son procede de fabrication et document de securite fabrique avec celui-ci

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US8753481B2 (en) 2011-06-10 2014-06-17 Basf Se Powder composition and use thereof for paper production
US8940135B2 (en) 2011-12-01 2015-01-27 Basf Se Production of filled paper using biodegradable polyester fibers and/or polyalkylene carbonate fibers
CN103790068A (zh) * 2014-02-18 2014-05-14 福建农林大学 淀粉喷雾干燥制备胶囊型造纸填料的方法
EP3231939A1 (fr) 2016-04-11 2017-10-18 Fuhrmann, Uwe Mouchoir en papier multicouche destine a reduire la transmission d'agents infectieux
CN113396039A (zh) * 2019-01-30 2021-09-14 巴斯夫欧洲公司 制备淀粉共混物的方法

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