WO2014207100A1 - Procédé de couchage du papier à la cellulose à l'aide d'une solution contenant de la cellulose - Google Patents

Procédé de couchage du papier à la cellulose à l'aide d'une solution contenant de la cellulose Download PDF

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WO2014207100A1
WO2014207100A1 PCT/EP2014/063508 EP2014063508W WO2014207100A1 WO 2014207100 A1 WO2014207100 A1 WO 2014207100A1 EP 2014063508 W EP2014063508 W EP 2014063508W WO 2014207100 A1 WO2014207100 A1 WO 2014207100A1
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process according
alkyl
radicals
hydrogen
group
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Michael Siemer
Klemens Massonne
Hubertus KRÖNER
Hermann Seyffer
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BASF SE
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BASF SE
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    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00—Coated paper; Coating material
    • D21H19/10—Coatings without pigments
    • D21H19/14—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12
    • D21H19/34—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12 comprising cellulose 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
    • D21H19/44—Coatings with pigments characterised by the other ingredients, e.g. the binder or dispersing agent
    • D21H19/52—Cellulose; 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
    • D21H27/00—Special paper not otherwise provided for, e.g. made by multi-step processes
    • D21H27/10—Packing paper

Definitions

  • a process for coating paper with cellulose using a solution containing cellulose relates to a process for coating paper with cellulose.
  • the process comprises the step of contacting paper with a solution containing cellulose which is preferably obtained by dissolving cellulose in a solvent including one or more ionic liquids.
  • the present invention also relates to the cellulose coated paper obtained by said process.
  • paper based materials are required that are water resistant, grease and oil resistant and preferably also permeable to water vapor.
  • a hamburger wrapping paper is required to hold off greasy and aqueous components of the burger.
  • the wrapping paper is preferably also able to release the water vapor emanating from the hot burger, since otherwise the water formed by condensation within the wrapper would impair the quality of the burger.
  • paper based packaging materials for such applications were commonly obtained by coating paper substrates with perfluoronated compounds which are widely used for imparting resistance to oil, grease and water without severely blocking the passage of water vapor. Examples for these
  • perfluorinated compounds are commercially available under the trade names Lodyne® (Ciba), Zonyl® (Dupont) and Scotchban® (3M).
  • Lodyne® Ciba
  • Zonyl® Dupont
  • Scotchban® 3M
  • a suitable replacement for said perfluorinated compounds may be cellophane which is well known in the marketplace as food packaging material possessing the
  • Cellophane basically consists of regenerated cellulose in the form of transparent sheets that are prepared by a rather expensive process.
  • cellophane sheets have to be attached to the paper by gluing. This is not only a comparatively complicated coating procedure but also involves adding glue as another compound which may pose a health or environmental risk.
  • Other suitable methods for coating paper with a layer of cellulose are based on nanocelluslose.
  • the present invention provides a process for coating paper with a cellulose product, comprising the steps of
  • step (b) optionally contacting the paper product obtained in step (a) with a coagulant
  • the present invention also provides coated paper obtained by the aforementioned process.
  • paper as used herein includes both paper as well as paperboard and refers to sheet-like, usually porous structures containing a web of cellulosic pulp fibers such as fibers derived from hardwood trees, softwood trees, or a combination of hardwood and softwood trees.
  • the fibers may be prepared for use in papermaking and possibly furnished by any known suitable digestion, refining, and bleaching operations.
  • the paper may contain recycled fibers and/or virgin fibers.
  • at least a portion of the fibers may be synthetic fibers and/or may be provided from non-woody herbaceous plants, e.g. hemp, jute, flax or sisal.
  • the paper may include conventional additives such as, for example, starch, mineral fillers, sizing agents, retention aids, and strengthening polymers.
  • fillers that may be used are organic and inorganic pigments, such as, for example, polymeric particles, such as polystyrene latexes and polymethylmethacrylate, and minerals, such as calcium carbonate, kaolin, and talc.
  • cellulosic fibers included in the web may be physically and/or chemically modified according to methods known in the art.
  • the surface of the paper may optionally be completely or partly coated with one or more layers, such as primer layers, further barrier layers, or colored or black-and-white layers of printing inks.
  • cellulose refers to a linear long-chain polysaccharide of the general formula (C6Hio05) n comprising (1 -4)-linked ⁇ -glucose moieties as repeating units (C6H10O5), with the variable n being the average number of repeating units.
  • Cellulose is usually a natural product found in plant cell walls accompanied mainly by lignin and hemicellulose.
  • the cellulose included in the cellulose product used in the process of the present invention may include other hexose moieties besides ⁇ -glucose moieties as repeating units, such as ⁇ -galactose moieties or a-glucose moieties.
  • the cellulose of the cellulose product consist of at least 95 %, more preferably of at least 98 % and in particular of at least 99 % of ⁇ -glucose moieties, based on the total average number n of repeating units included in the cellulose.
  • some or all of the repeating units of the cellulose may be derivatized for example by partial or complete etherifica- tion or esterification of its hydroxyl groups.
  • the cellulose product used in the inventive process includes cellulose that is not derivatized.
  • the cellulose of the cellulose product usually has an average number of repeating units n in the range of 50 to 20,000, preferably in the range from 100 to 12,000, more preferably in the range from 150 to 6,000 and in particular in the range of 200 to 2,000.
  • the cellulose product used in the inventive process is preferably obtained from renewable resources, such as wood or cotton and may contain byproducts such as hemicel- lulose.
  • the cellulose product comprises cellulose in an amount of at least 80 % by weight, preferably at least 90 % by weight and in particular at least 95 % by weight, e.g. in an amount within the range of 80 to 100% by weight, preferably 90 to 99.5 % by weight and in particular 95 to 99 % by weight, based in each case on the total amount of the cellulose product.
  • the solvent used for preparing the solution of dissolved cellulose product according to the process of the present invention (herein also called solvent A) is selected from ionic liquids, DMSO, N-methylmorpholine-N-oxide and mixtures thereof, and preferably from ionic liquids, DMSO and mixtures thereof.
  • solvent A includes one or more ionic liquids.
  • solvent A comprises one or more ionic liquids in an total amount of at least 20 % by weight, preferably at least 60 % by weight, more preferably at least 90 % by weight and in particular at least 99 % by weight, based on the total weight of the sol- vent.
  • the proportion of ionic liquid in solvent A therefore is generally in the range of 20 to 100 % by weight, preferably in the range of 60 to 100 % by weight and in particular in the range of 90 % to 100 %by weight, based on the total weight of the solvent.
  • the solvent A comprises DMSO as co- solvent in an amount of 0.05 to 80 % by weight, preferably of 0.1 to 50 % by weight, in particular of 0.5 to 20 % by weight and specifically of 0.8 to 10 % by weight, based on the total weight of solvent A.
  • solvent A consists of one or more ionic liquids and DMSO with the ratio of ionic liquid to DMSO in the range from 20/80 to 99.95/0.05, preferably from 60/40 to 99.9/0.1 and in particular from 90/10 to 99.5/0.5, based in each case on the weights of ionic liquid and DMSO.
  • solvent A consists of one or more ionic liquids.
  • the ionic liquids used in the process of the present invention are organic salts which are liquid at temperatures below 180°C.
  • the melting points of the ionic liq- uids are in the range from -50°C to 180°C, preferably in the range from -20°C to 150°C, in particular in the range from -10°C to 120°C and especially in the range from 0°C to 100°C.
  • Cations and anions are present in the ionic liquids.
  • a proton or an alkyl radical can be transferred from the cation to the anion in an ionic liquid, resulting in two uncharged molecules.
  • An equilibrium of anions, cations and uncharged molecules formed therefrom can thus be present in the ionic liquids used according to the invention.
  • alkyl as used herein comprises straight-chain or branched alkyl.
  • the alkyl group is preferably straight-chain or branched Ci-C3o-alkyl, in particular Ci-Cis-alkyl and very particularly preferably Ci-Ci2-alkyl.
  • alkyl groups are, in particular, methyl, ethyl, n-propyl, isopropyl, n-butyl, Isobutyl, sec-butyl, tert-butyl, n-pentyl, iso- pentyl, 1 -methylbutyl, tert-pentyl, neopentyl, n-hexyl, 3-hexyl, 2-methyl-1 -pentyl, 3- methyl-1 -pentyl, 4-methyl-1 -pentyl, 2-methyl-2-pentyl, 3-methyl-2-pentyl, 4-methyl-2- pentyl, 2-methyl-3-pentyl, 3-methyl-3-pentyl, 2,2-dimethyl-1 -butyl, 2,3-dimethyl-1 -butyl, 3,3-dimethyl-1 -butyl, 2-ethyl-1 -butyl, 2,3-dimethyl-2-butyl, 3,3
  • R a is preferably hydrogen, alkyi, cycloalkyl, heterocycloalkyl, aryl or hetaryl.
  • R aa is preferably hydrogen, alkyi, cycloalkyl, heterocycloalkyl or aryl.
  • alkyi radicals whose carbon chains are interrupted by one or two nonadjacent heteroatoms -O- are the following: methoxymethyl, diethoxymethyl, 2- methoxyethyl, 2-ethoxyethyl, 2-propoxyethyl, diethoxyethyl, 2-butoxyethyl, 2- octyloxyethyl, 2-methoxypropyl, 3-methoxypropyl, 3-ethoxypropyl, 3-propoxypropyl, 2- isopropoxyethyl, 2-butoxypropyl, 3-butoxypropyl, 4-methoxybutyl, 4-ethoxybutyl, 4- propoxybutyl, 6-methoxyhexyl, 3,6-dioxaheptyl (5-methoxy-3-oxapentyl), 3,6-dioxaoctyl (7-methoxy-4-oxaheptyl), 4,8-dioxanonyl (7-methoxy
  • alkyi radicals whose carbon chains are interrupted by three or more than three nonadjacent heteroatoms -O- are also oligooxyalkylenes and polyoxyalkylenes, i.e. compounds having repeating units which are preferably selected from among
  • x1 , x2 and x3 are each, independently of one another, an integer from 3 to 100, preferably from 3 to 80.
  • the sum of x1 , x2 and x3 is an integer from 3 to 300, in particular from 3 to 100.
  • the order is immaterial, i.e. the repeating units can be arranged randomly, alternately or in blocks.
  • Examples are 3,6,9-trioxadecyl, 3,6,9-trioxaundecyl, 3,6,9-trioxadodecyl, 4,8,12-trioxatridecyl (1 1 - methoxy-4,8-dioxaundecyl), 4,8,12-trioxatetradecyl, 14-methoxy-5,10-dioxatetradecyl, 5,10,15-trioxaheptadecyl, 3,6,9,12-tetraoxatridecyl, 3,6,9, 12-tetraoxatetradecyl, 4,8,12,16-tetraoxaheptadecyl (15-methoxy-4,8,12-trioxa-pentadecyl), 4,8,12,16- tetraoxaoctadecyl and the like.
  • alkyi radicals whose carbon chains are interrupted by one or more, e.g. 1 , 2, 3, 4 or more than 4, nonadjacent heteroatoms -S- are the following: butylthiomethyl,
  • alkyi radicals whose carbon chains are interrupted by one or two nonadja- cent heteroatom-comprising groups -NR a - are the following: 2-monomethyl- and 2- monoethylaminoethyl, 2-dimethylaminoethyl, 3-methylaminopropyl, 2- and
  • 3-dimethylaminopropyl 3-monoisopropylaminopropyl, 2- and 4-monopropylaminobutyl, 2- and 4-dimethylaminobutyl, 6-methylaminohexyl, 6-dimethylaminohexyl, 6-methyl- 3,6-diazaheptyl, 3,6-dimethyl-3,6-diazaheptyl, 3,6-diazaoctyl and 3,6-dimethyl-3,6- diazaoctyl.
  • alkyi radicals whose carbon chains are interrupted by three or more than three nonadjacent heteroatom-comprising groups -NR a - are also oligoalkyleneimines and polyalkyleneimines.
  • polyoxyalkylenes applies analogously to polyalkyleneimines, with the oxygen atom being in each case replaced by an NR a group in which R a is preferably hydrogen or Ci-C4-alkyl.
  • Examples are 9-methyl-3,6,9-triazadecyl, 3,6,9-trimethyl-3,6,9-triazadecyl, 3,6,9-triazaundecyl, 3,6,9-trimethyl-3,6,9-triazaundecyl, 12-methyl-3,6,9,12-tetraazatridecyl,
  • alkyi radicals whose carbon chains are interrupted by one or more, e.g. 1 or 2, nonadjacent groups -SO2- are 2-methylsulfonylethyl, 2-ethylsulfonylethyl, 2-propylsulfonylethyl, 2-isopropylsulfonylethyl, 2-butylsulfonylethyl,
  • alkyi also comprises substituted alkyi radicals.
  • Cycloalkyl, cycloalkyloxy, polycycloalkyl, polycycloalkyloxy, heterocycloalkyl, aryl and hetaryl substituents of the alkyi groups may in turn be unsubstituted or substituted; suitable substituents are those mentioned below for these groups.
  • alkyi also applies in principle to the alkyi parts of alkoxy, alkylamino, dialkylamino, alkylthio (alkylsulfanyl), alkylsulfinyl, alkylsulfonyl, etc.
  • Suitable substituted alkyi radicals are the following:
  • alkyi which is substituted by carboxy, e.g. carboxymethyl, 2-carboxyethyl,
  • alkyi which is substituted by SO3R, where R is H, a cation equivalent or an alkyi radical.
  • SOsR-substituted alkyi are sulfomethyl, 2-sulfoethyl, 3-sulfopropyl,
  • a cation equivalent is, for the purposes of the invention, a monovalent cation or the part of a polyvalent cation corresponding to a single positive charge.
  • the cation M+ serves merely as counter ion to neutralize the sulfonate group and can in principle be selected freely. Preference is therefore given to using alkali metal ions, in particular Na+, K+-, Li+ ions, or onium ions such as ammonium, monoalkylammonium, dialkylammonium, trialkylammonium, tetraalkylammonium, phosphonium, tetraalkylphosphonium or tetraarylphosphonium ions;
  • alkyi which is substituted by carboxylate, for example alkoxycarbonylalkyl, e.g. meth- oxycarbonylmethyl, ethoxycarbonylmethyl, n-butoxycarbonylmethyl,
  • aminocarbonylalkyl e.g. aminocarbonylmethyl, ami- nocarbonylethyl, aminocarbonylpropyl and the like, alkylaminocarbonylalkyl such as methylaminocarbonylmethyl, methylaminocarbonylethyl, ethylcarbonylmethyl, ethylcar- bonylethyl and the like or dialkylaminocarbonylalkyl such as dimethylaminocarbonyl- methyl, dimethylaminocarbonylethyl, dimethylcarbonylpropyl, diethylaminocarbonylme- thyl, diethylaminocarbonylethyl, diethylcarbonylpropyl and the like;
  • alkyi which is substituted by hydroxyl, e.g. 2-hydroxyethyl, 2-hydroxypropyl,
  • alkyi which is substituted by amino, e.g. 2-aminoethyl, 2-aminopropyl, 3-aminopropyl,
  • alkyi which is substituted by cyano, e.g. 2-cyanoethyl, 3-cyanopropyl, 3-cyanobutyl and 4-cyanobutyl;
  • Ci-Ci8-fluoroalkyl e.g. trifluoromethyl, difluoromethyl, fluoromethyl, pentafluoroethyl, heptafluoropropyl, heptafluoroisopropyl, nonafluorobutyl, nonafluoroisobutyl, un- decylfluoropentyl, undecylfluoroisopentyl and the like
  • Ci-Ci8-chloroalkyl e.g. chloro- methyl, dichloromethyl, trichloromethyl, 2-chloroethyl, 2- and 3-chloropropyl
  • alkyl which is substituted by nitro, e.g. 2-nitroethyl, 2- and 3-nitropropyl and 2-, 3- and 4-nitrobutyl and the like;
  • alkyl which is substituted by amino, e.g. 2-aminoethyl, 2-aminopropyl, 3-aminopropyl, 4-aminobutyl, 6-aminohexyl and the like;
  • alkyl which is substituted by cycloalkyl, e.g. cyclopentyl methyl, 2-cyclopentylethyl,
  • alkyl which is substituted by 0 (oxo group), e.g. 2-oxopropyl, 2-oxobutyl, 3-oxobutyl, 1 -methyl-2-oxopropyl, 2-oxopentyl, 3-oxopentyl, 1 -methyl-2-oxobutyl, 1 -methyl-3- oxobutyl, 2-oxohexyl, 3-oxohexyl, 4-oxohexyl, 2-oxoheptyl, 3-oxoheptyl, 4-oxoheptyl,
  • alkyl which is substituted by S (thioxo group), e.g. 2-thioxopropyl, 2-thioxobutyl, 3-thioxobutyl, 1 -methyl-2-thioxopropyl, 2-thioxopentyl, 3-thioxopentyl, 1 -methyl-2- thioxobutyl, 1 -methyl-3-thioxobutyl, 2-thioxohexyl, 3-thioxohexyl, 4-thioxohexyl, 2- thioxoheptyl, 3-thioxoheptyl, 4-thioxoheptyl, 4-thioxoheptyl and the like;
  • S thioxo group
  • alkyl which is substituted by NR a -, preferably one in which R a is hydrogen or C1-C4- alkyl, e.g. 2-iminopropyl, 2-iminobutyl, 3-iminobutyl, 1 -methyl-2-iminopropyl,
  • Alkoxy is an alkyl group bound via an oxygen atom.
  • alkoxy examples are: methoxy, ethoxy, n-propoxy, 1 -methylethoxy, butoxy, 1 -methylpropoxy, 2-methylpropoxy, 1 ,1 -dimethylethoxy, n-pentoxy, 1 -methylbutoxy, 2-methylbutoxy, 3-methylbutoxy, 1 ,1 -dimethylpropoxy, 1 ,2-dimethylpropoxy, 2,2-dimethylpropoxy, 1 -ethyl propoxy, hexoxy, 1 -methylpentoxy, 2-methylpentoxy, 3-methylpentoxy, 4-methylpentoxy, 1 ,1 -dimethylbutoxy, 1 ,2-dimethylbutoxy, 1 ,3-dimethylbutoxy, 2,2-dimethylbutoxy, 2,3-dimethylbutoxy, 3,3-dimethylbutoxy, 1 -ethylbutoxy, 2-ethylbutoxy,
  • R A 0-(CH2CH2CH2CH20)n-CH2CH2CH2CH 2 0- where R A is hydrogen or Ci-C4-alkyl, preferably hydrogen, methyl or ethyl and n is from 0 to 10, preferably from 0 to 3.
  • Alkylthio (alkylsulfanyl) is an alkyl group bound via a sulfur atom. Examples of alkylthio are methylthio, ethylthio, propylthio, butylthio, pentylthio and hexylthio.
  • Aryl-substituted alkyl radicals (“arylalkyl”) have at least one unsubstituted or substituted aryl group as defined below. Suitable substituents on the aryl group are those men- tioned below.
  • the alkyl group in "arylalkyl” can bear at least one further substitu- ent as defined above and/or be interrupted by one or more nonadjacent heteroatoms or heteroatom-comprising groups selected from among -0-, -S-, -NR a - and/or -SO2-.
  • Arylalkyl is preferably phenyl-Ci-Cio-alkyl, particularly preferably phenyl-Ci-C4-alkyl, e.g.
  • benzyl 1 -phenethyl, 2-phenethyl, 1 -phenprop-1 -yl, 2-phenprop-1 -yl, 3-phenprop-1 -yl, 1 -phenbut-1 -yl, 2-phenbut-1 -yl, 3-phenbut-1 -yl, 4-phenbut-1 -yl, 1 -phenbut-2-yl, 2-phenbut-2-yl, 3-phenbut-2-yl, 4-phenbut-2-yl, 1 -(phenmeth)eth-1 -yl,
  • alkenyl as used herein comprises straight-chain and branched alkenyl groups which, depending on the chain length, can bear one or more double bonds (e.g. 1 , 2, 3, 4 or more than 4). Preference is given to C2-C18-, particularly preferably
  • alkenyl also comprises alkenyl radicals whose carbon chain can be interrupted by one or more nonadjacent heteroatoms or heteroatom-comprising groups which are preferably selected from among -0-, -S-, -NR a - and -SO2-.
  • Alkenyl is then, for example, ethenyl (vinyl), 1 -propenyl, 2-propenyl, 1 -methylethenyl, 1 - butenyl, 2-butenyl, 3-butenyl, 1 -pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1 -hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, penta-1 ,3-dien-1 -yl, hexa-1 ,4-dien-1 -yl, hexa-1 ,4-dien-3-yl, hexa-1 ,4-dien-6-yl, hexa-1 ,5-dien-1 -yl, hexa-1 ,5-dien-3-yl, hexa- 1 ,5-dien-4-yl, hepta-1 ,4-dien
  • cycloalkyl as used herein comprises both unsubstituted and substituted monocyclic saturated hydrocarbon groups which generally have from 3 to 12 ring carbons, preferably C3-Ci2-cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl or cyclodo- decyl, in particular C5-Ci2-cycloalkyl.
  • C3-Ci2-cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl or cyclodo- decyl, in particular C5-C
  • Suitable substituents are generally selected from among alkyl, the substituents mentioned above for the alkyl groups, alkoxy and al- kylthio.
  • Substituted cycloalkyl groups can have one or more (e.g. 1 , 2, 3, 4, 5 or more than 5) substituents, in the case of halogen the cycloalkyl radical being partially or completely substituted by halogen.
  • cycloalkyl groups are cyclopentyl, 2- and 3-methylcyclopentyl, 2- and 3-ethylcyclopentyl, chloropentyl, dichloropentyl, dimethylcyclopentyl, cyclohexyl, 2-, 3- and 4-methylcyclohexyl, 2-, 3- and 4-ethylcyclohexyl, 3- and 4-propylcyclohexyl, 3- and 4-isopropylcyclohexyl, 3- and 4-butylcyclohexyl, 3- and 4-sec-butylcyclohexyl, 3- and 4- tert-butylcyclohexyl, chlorohexyl, dimethylcyclohexyl, diethylcyclohexyl, methoxy- cyclohexyl, dimethoxycyclohexyl, diethoxycyclohexyl, butoxycyclohexyl, methylthiocy- clohexyl, chloro
  • cycloalkenyl as used herein comprises unsubstituted and substituted, mon- ounsaturated or doubly unsaturated hydrocarbon groups having from 3 to 5, from 3 to 8, from 3 to 12, preferably from 5 to 12, ring carbons, e.g. cyclopent-1 -en-1 -yl, cyclopent-2-en-1 -yl, cyclopent-3-en-1 -yl, cyclohex-1 -en-1 -yl, cyclohex-2-en-1 -yl, cyclohex-3-en-1 -yl, cyclohexa-2,5-dien-1 -yl and the like. Suitable substituents are those mentioned above for cycloalkyl.
  • Cycloalkenyloxy is a cycloalkenyl group as defined above bound via oxygen.
  • polycyclyl as used herein comprises in the widest sense compounds which comprise at least two rings, regardless of how these rings are linked.
  • the rings can be carbocyclic and/or heterocyclic rings.
  • the rings can be saturated or unsaturated.
  • the rings can be linked via a single or double bond ("multiring systems"), be joined by fusion (“fused ring systems") or be bridged ("bridged ring systems", “cage compounds”).
  • Preferred polycyclic compounds are bridged ring systems and fused ring systems.
  • Fused ring systems can be aromatic, hydroaromatic and cyclic compounds joined by fusion (fused compounds).
  • Fused ring systems comprise two, three or more than three rings.
  • bicyclo, tricyclo, tetracyclo compounds, etc. which comprise two, three, four, etc. rings.
  • the expression "bicycloalkyl” comprises bicyclic hydrocarbon radicals which preferably have from 5 to 10 carbon atoms, e.g.
  • a further example is the expression "bicycloalkenyl" which comprises monounsaturated, bicyclic hydrocarbon radicals which preferably have from 5 to 10 carbon atoms, e.g. bicyclo[2.2.1 ]hept-2-en-1 -yl.
  • aryl as used herein comprises aromatic hydrocarbon radicals which have one or more rings and can be unsubstituted or substituted.
  • Aryl generally refers to hy- drocarbon radicals having from 6 to 10, up to 14, up to 18, preferably from 6 to 10, ring carbons.
  • Aryl is preferably unsubstituted or substituted phenyl, naphthyl, anthracenyl, phenanthrenyl, naphthacenyl, chrysenyl, pyrenyl, etc., and particularly preferably phenyl or naphthyl.
  • Substituted aryls can, depending on the number and size of their ring systems, have one or more (e.g.
  • substituents 1 , 2, 3, 4, 5 or more than 5) substituents. These are preferably selected independently from among alkyl, alkoxy, cycloalkyl, cycloalkyloxy, heterocycloalkyl, aryl, aryloxy, arylthio, hetaryl, halogen, hydroxy, SH, alkylthio, alkyl- sulfinyl, alkylsulfonyl, COOH, carboxylate, SO3H, sulfonate, NE 5 E 6 , nitro and cyano, where E 5 and E 6 are each, independently of one another, hydrogen, alkyl, cycloalkyl, cycloalkyloxy, polycyclyl, polycyclyloxy, heterocycloalkyl, aryl, aryloxy or hetaryl. Particular preference is given to aryl being phenyl which, if it is substituted, can generally bear 1 , 2, 3, 4 or 5, preferably 1 , 2
  • Aryl which bears one or more radicals is, for example, 2-, 3- and 4-methylphenyl, 2,4-, 2,5-, 3,5- and 2,6-dimethylphenyl, 2,4,6-trimethylphenyl, 2-, 3- and 4-ethylphenyl, 2,4-, 2,5-, 3,5- and 2,6-diethylphenyl, 2,4,6-triethylphenyl, 2-, 3- and 4-propylphenyl, 2,4-, 2,5-, 3,5- and 2,6-dipropylphenyl, 2,4,6-tripropylphenyl, 2-, 3- and 4-isopropylphenyl,
  • 4-dimethylaminophenyl 4-acetylphenyl; methoxyethylphenyl, ethoxymethylphenyl; me- thylthiophenyl, isopropylthiophenyl or tert-butylthiophenyl; methylnaphthyl; iso- propylnaphthyl or ethoxynaphthyl.
  • substituted aryl in which two substituents which are bound to adjacent carbon atoms of the aryl ring form a fused-on ring or fused ring system are indenyl and fluoroenyl.
  • aryloxy refers to aryl bound via an oxygen atom.
  • arylthio refers to aryl bound via a sulfur atom.
  • heterocycloalkyl comprises nonaromatic, unsaturated or fully saturated, cycloaliphatic groups which generally have from 5 to 8 ring atoms, preferably 5 or 6 ring atoms, and in which 1 , 2 or 3 of the ring carbons have been replaced by heteroatoms selected from among oxygen, nitrogen, sulfur and an -NR a - group and which is unsubstituted or substituted by one or more, for example, 1 , 2, 3, 4, 5 or 6, Ci- C6-alkyl groups.
  • heterocycloaliphatic groups examples include pyrrolidinyl, piperi- dinyl, 2,2,6,6-tetramethylpiperidinyl, imidazolidinyl, pyrazolidinyl, oxazolidinyl, morphol- idinyl, thiazolidinyl, isothiazolidinyl, isoxazolidinyl, piperazinyl, tetrahydrothienyl, dihy- drothienyl, tetrahydrofuranyl, dihydrofuranyl, tetrahydropyranyl, 1 ,2-oxazolin-5-yl, 1 ,3- oxazolin-2-yl and dioxanyl.
  • Nitrogen-comprising heterocycloalkyl can in principle be bound either via a carbon atom or via a nitrogen atom.
  • heteroaryl as used herein comprises unsubstituted or substituted, heteroaromatic groups which have one or more rings and generally have from 5 to 14 ring atoms, preferably 5 or 6 ring atoms, and in which 1 , 2 or 3 of the ring carbons have been replaced by one, two, three or four heteroatoms selected from among O, N, -NR a - and S, for example furyl, thienyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, benzo- furanyl, benzthiazolyl, benzimidazolyl, pyridyl, quinolinyl, acridinyl, pyridazinyl, pyrim- idinyl, pyrazinyl, pyrrolyl, imidazolyl, pyrazolyl, indolyl, purinyl, indazolyl, benzotri
  • 5- to 7-membered nitrogen-comprising heterocycloalkyl or heteroaryl radicals are, for example, pyrrolyl, pyrazolyl, im- idazolyl, triazolyl, pyrrolidinyl, pyrazolinyl, pyrazolidinyl, imidazolinyl, imidazolidinyl, pyridinyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl, piperidinyl, piperazinyl, oxazolyl, isooxazolyl, thiazolyl, isothiazolyl, indolyl, quinolinyl, isoquinolinyl or quinaldinyl, which can be unsubstituted or substituted as mentioned above.
  • Halogen is fluorine, chlorine, bromine or iodine.
  • carboxylate and sulfonate preferably denote derivatives of a carboxylic acid function or a sulfonic acid function, in particular a metal carboxylate or sulfonate, a carboxylic acid ester or sulfonic ester func- tion or a carboxamide or sulfonamide function.
  • esters with Ci-C4-alkanols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, sec- butanol and tert-butanol.
  • acyl refers to alkanoyl, hetaroyl or aroyl groups which gen- erally have from 1 to 1 1 , preferably from 2 to 8, carbon atoms, for example formyl, ace- tyl, propanoyl, butanoyl, pentanoyl, hexanoyl, heptanoyl, 2-ethylhexanoyl, 2- propylheptanoyl, benzoyl or naphthoyl group.
  • the radicals E 1 , E 2 , E 3 and E 4 are selected independently from among hydrogen, alkyl, cycloalkyi, heterocycloalkyi, aryl and hetaryl.
  • the groups NE 1 E 2 and NE 3 E 4 are preferably ⁇ , ⁇ -dimethylamino, N,N-diethylamino, ⁇ , ⁇ -dipropylamino, N,N-diisopropylamino, N,N-di-n-butylamino, N,N-di-tert-butylamino, ⁇ , ⁇ -dicyclohexylamino or N,N- diphenylamino.
  • the solvent A usually comprises up to 3 different ionic liquids and preferably up to 2 different ionic liquid. According to a preferred embodiment of the invention solvent A comprises only one ionic liquid.
  • the one or more ionic liquids comprised in solvent A are preferably selected from among
  • [Y] n - is a monovalent, divalent, trivalent or tetravalent anion or a mixture of these anions; mixed salts of the general formulae (II)
  • [A] m+ is preferably a quaternary ammonium cation, an oxonium cation, a sulfonium cation or a phosphonium cation. It goes without saying that m is then 1 .
  • the metal cations [M 1 ] + , [M 2 ] + , [M 3 ] + , [M 4 ] 2+ and [M 5 ] 3+ mentioned in the formulae (111. a) to (lll.j) are generally metal cations of groups 1 , 2, 3, 4, 5, 6, 7, 8, 9, 10, 1 1 , 12, 13 and 14 of the Periodic Table.
  • Suitable metal cations are, for example, Li + , Na + , K + , Cs + , Mg 2+ , Ca 2+ , Ba 2+ , Sc 3+ , Ti 4+ , Zr* + , V 5+ , Cr 3+ , Fe 2+ , Fe 3+ , Co 2+ , Ni 2+ , Cu 2+ , Ag + , Zn 2+ and Al 3+ .
  • Compounds which are suitable for forming the cations [A] + of ionic liquids are described, for example, in DE 102 02 838 A1. These compounds preferably comprise at least one heteroatom, e.g. from 1 to 10 heteroatoms, which are preferably selected from among nitrogen, oxygen, phosphorus and sulfur atoms.
  • the last-mentioned nitrogen compounds may comprise further heteroatoms such as oxygen, sulfur or phosphorus atoms.
  • the positive charge of a cation of the ionic liquids can be localized on one atom in the molecule of the cation or, according to a further possibility, be partially or completely delocalized over the molecule of the cation.
  • a nitrogen atom is a suitable carrier of the positive charge in the cation of the ionic liquids.
  • a cation can firstly be produced by quaternization of the nitrogen atom of, for instance, an amine or a nitrogen heterocycle in the synthesis of the ionic liquids. The quaternization can be ef- fected by protonation of the nitrogen atom.
  • salts having different anions are obtained.
  • it can be formed in a further synthetic step.
  • the halide can be reacted with a Lewis acid, forming a complex anion of halide and Lewis acid.
  • a halide ion can be replaced by the desired anion. This can be achieved by addition of a metal salt with precipitation of the metal halide formed, by means of an ion exchanger or by displacement of the halide ion by a strong acid (with liberation of the hydrohalic acid). Suitable processes are described, for example, in Angew. Chem. 2000, 1 12, pp.
  • Particularly preferred compounds are those which have a molar mass of less than 1500 g/mol, very particularly preferably less than 1000 g/mol and in particular less than 800 g/mol.
  • the one or more ionic liquids comprised in solvent A preferably have at least one cation selected from among the compounds of the formulae (IV.a) to (IV. z),
  • R is hydrogen, alkyl, alkenyl, cycloalkyi, cycloalkenyl, polycyclyl, heterocycloalkyi, aryl or heteroaryl; radicals R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 and R 9 which are bound to a ring carbon are each, independently of one another, hydrogen, a sulfo group, COOH, carbox- ylate, sulfonate, acyl, alkoxycarbonyl, CO(NE 1 E 2 ), cyano, halogen, hydroxyl, SH, nitro, NE 3 E 4 , alkyl, alkoxy, alkylthio, alkylsulfinyl, alkylsulfonyl, alkenyl, cycloalkyi, cycloalkyloxy, cycloalkenyl, cycloalkenyloxy, polycyclyl, polycyclyloxy, hetero
  • R 1 and R 3 or R 3 and R 5 in the compounds of the formula (IV.x.1 ) may together also represent the second bond of a double bond between the ring atoms bearing these radicals or, as an alternative, the radicals R, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 and R 9 can be alkanediyl, cycloalkanediyl, alkenediyl or cycloalkenediyl which links a cation of one of the formulae (IV. a) to (IV.z) to a further cation of one of the formulae (IV.
  • radicals additionally function, via their second point of bonding, as radical R, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 or R 9 of said further cation; and the radicals alkanediyl, cycloalkanediyl, alkenediyl and cycloalkenediyl mentioned can, corresponding to the above definitions of alkyl and alkenyl, be branched, substituted and/or interrupted by at least one heteroatom or heteroatom-comprising group; in the compounds of the formulae (IV.x.1 ) and (IV.x.2) together with the C-N group to which it is bound forms a 4- to 12-membered, preferably 4- to 8- membered, saturated or unsaturated or aromatic ring which may optionally be substituted and/or may optionally have further heteroatoms or heteroatom- comprising groups and/or can comprise the further fused-on saturated,
  • radicals carboxylate, sul- fonate, acyl, alkoxycarbonyl, halogen, NE 1 E 2 , alkyl, alkoxy, alkylthio, alkylsulfinyl, alkyl- sulfonyl, alkenyl, cycloalkyl, cycloalkyloxy, cycloalkenyl, cycloalkenyloxy, polycyclyl, polycyclyloxy, heterocycloalkyi, aryl, aryloxy or heteroaryl, what has been said above is fully incorporated by reference at this point.
  • Radicals R 1 to R 9 which are bound to a carbon atom in the abovementioned formulae (IV) and have a heteroatom or heteroa- torn-comprising group can also be bound directly via a heteroatom to the carbon atom.
  • radicals R 1 to R 9 together with the ring atoms to which they are bound form at least one fused-on, saturated, unsaturated or aromatic ring or a ring system having from 1 to 30 carbon atoms, where the ring or the ring system can have from 1 to 5 nonadjacent heteroatoms or heteroatom-comprising groups and the ring or the ring system may be unsubstituted or substituted
  • these radicals can together preferably be, as fused-on building blocks, 1 ,3-propylene, 1 ,4-butylene, 1 ,5-pentylene, 2-oxa-1 ,3- propylene, 1 -oxa-1 ,3-propylene, 2-oxa-1 ,3-propylene, 1 -oxa-1 ,3-propenylene, 3-oxa- 1 ,5-pentylene, 1 -aza-1 ,3-propenylene, 1 -Ci-C4-alkyl-1
  • Ci-Cis-alkyl such as methyl, ethyl, 1 -propyl, 2-propyl, 1 -butyl, 2-butyl, 2-methyl-1 -propyl (isobutyl), 2-methyl-2-propyl (tert-butyl), 1 -pentyl,
  • Ci-Cis-alkyl substituted by one or more hydroxy, halogen, phenyl, cyano, C1-C6- alkoxycarbonyl and/or SO3H groups, especially hydroxy-Ci-Ci8-alkyl such as 2- hydroxyethyl or 6-hydroxyhexyl; phenyl-Ci-Cis-alkyl such as benzyl,
  • cyano-Ci-Cis-alkyl such as 2-cyanoethyl
  • Ci-C6-alkoxy- Ci-Cis-alkyl such as 2-(methoxycarbonyl)ethyl, 2-(ethoxycarbonyl)ethyl or
  • Ci-Ci8-fluoroalkyl such as trifluoromethyl, difluorome- thyl, fluoromethyl, pentafluoroethyl, heptafluoropropyl, heptafluoroisopropyl, non- afluorobutyl, nonafluoroisobutyl, undecylfluoropentyl, undecylfluoroisopentyl;
  • sul- fo-Ci-Ci8-alkyl such as 3-sulfopropyl;
  • oligoalkylene and polyalkylene glycols such as polyethylene glycols and polypropylene glycols and oligomers thereof having from 2 to 100 units and a hydrogen or a Ci-Cs-alkyl as end group, for example R A 0-(CHR B -CH 2 -0) n -CHR B -CH 2 - where R A and R B are preferably hydrogen, methyl or ethyl and n is preferably from 0 to 3, in particular 3-oxabutyl, 3-oxa-pentyl, 3,6-dioxaheptyl, 3,6-dioxaoctyl, 3,6,9-trioxadecyl, 3,6,9-trioxaundecyl, 3,6,9,12- tetraoxatridecyl and 3,6,9,12-tetraoxatetradecyl; and
  • C2-C6-alkenyl such as vinyl or propenyl.
  • the radical R is particularly preferably linear Ci-Cis-alkyl, for example methyl, ethyl, 1 -propyl, 1 -butyl, 1 -pentyl, 1 -hexyl, 1 -heptyl, 1 -octyl, 1 -decyl, 1 -dodecyl, 1 -tetradecyl, 1 -hexadecyl, 1 -octadecyl, very particularly preferably methyl, ethyl, 1 -butyl or 1 -octyl, or CH 3 0-(CH2CH20)n-CH 2 CH2- and CH 3 CH20-(CH2CH20) m -CH 2 CH2- where m is from 0 to 3.
  • the radicals R 1 to R 9 each being, independently of one another, hydrogen;
  • Ci-Ci8-alkyl which may be unsubstituted or substituted as defined above and/or be interrupted by at least one heteroatom or heteroatom-comprising group as defined above;
  • C2-Ci8-alkenyl which may be unsubstituted or substituted as defined above and/or interrupted by at least one heteroatom as defined above;
  • C5-Ci2-cycloalkyl which may be unsubstituted or substituted as defined above; polycyclyl which may be unsubstituted or substituted as defined above;
  • C5-Ci2-cycloalkenyl which may be unsubstituted or substituted as defined above;
  • - heterocycloalkyl having 5 or 6 ring atoms, where the ring has, in addition to ring carbons, 1 , 2 or 3 heteroatoms or heteroatom-comprising groups selected from among oxygen, nitrogen, sulfur and NR a and is unsubstituted or substituted as defined above;
  • heteroaryl having from 5 to 10 ring atoms, where the ring has, in addition to ring carbons, 1 , 2 or 3 heteroatoms or heteroatom-comprising groups selected from oxygen, nitrogen, sulfur and NR a and is unsubstituted or substituted as defined above.
  • R 1 to R 9 are alkoxy, R 1 to R 9 are preferably methoxy or ethoxy or
  • R A 0-(CH2CH2CH2CH20)n-CH2CH2CH2CH 2 0- where R A is preferably hydrogen, methyl or ethyl and n is preferably from 0 to 3.
  • R 1 to R 9 are acyl, R 1 to R 9 are preferably formyl or Ci-C4-alkylcarbonyl, in particular formyl or acetyl.
  • R 1 to R 9 are Ci-Ci 8 -alkyl
  • R 1 to R 9 are preferably unsubstituted Ci-Ci 8 -alkyl such as methyl, ethyl, 1 -propyl, 2-propyl, 1 -butyl, 2-butyl, 2-methyl-1 -propyl (isobutyl), 2-methyl-2-propyl (tert-butyl), 1 -pentyl, 2-pentyl, 3-pentyl, 2-methyl-9-butyl, 3-methyl-1 - butyl, 2-methyl-2-butyl, 3-methyl-2-butyl, 2,2-dimethyl-1 -propyl, 1 -hexyl, 2-hexyl, 3-hexyl, 2-methyl-1 -pentyl, 3-methyl-1 -pentyl, 4-methyl-1 -pentyl, 2-methyl-2-pentyl, 3-methyl-2-pentyl, 4-methyl-2-pentyl, 2-methyl-3-p
  • Ci-Cis-haloalkyl especially Ci-Cis-fluoroalkyl, for example trifluoromethyl, difluorome- thyl, fluoromethyl, pentafluoroethyl, heptafluoropropyl, heptafluoroisopropyl, no- nafluorobutyl, nonafluoroisobutyl, undecylfluoropentyl, undecylisopentyl, C6F13, C&Fn, C10F21 , C12F25, especially Ci-Ci8-chloroalkyl such as chloromethyl, 2-chloroethyl, tri- chloromethyl, 1 ,1 -dimethyl-2-chloroethyl;
  • amino-Ci-Ci8-alkyl such as 2-aminoethyl, 2-aminopropyl, 3-aminopropyl, 4-aminobutyl, 6-aminohexyl,
  • Ci-C6-alkylamino-Ci-Ci8-alkyl such as 2-methylaminoethyl, 2-methylaminopropyl, 3-methylaminopropyl, 4-methylaminobutyl, 6-methylaminohexyl;
  • di(Ci-C6-alkyl)-Ci-Ci8-alkyl such as 2-dimethylaminoethyl, 2-dimethylaminopropyl,
  • cyano-Ci-Cis-alkyl such as 2-cyanoethyl, 2-cyanopropyl,
  • Ci-Cio-alkoxy-Ci-Ci8-alkyl such as methoxymethyl, 2-methoxyethyl, 2-methoxypropyl, 3-methoxypropyl, 2-methoxyisopropyl, 4-methoxybutyl, 6-methoxyhexyl, 2-ethoxyethyl,
  • Ci-C6-alkoxycarbonyl-Ci-Ci8-alkyl such as 2-(methoxycarbonyl)ethyl
  • di(Ci-C6-alkoxycarbonyl)-Ci-Ci8-alkyl such as 1 ,2-di(methoxycarbonyl)ethyl, hydroxy-Ci-Ci8-alkyl such as 2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl,
  • Ci-Ci2-alkylsulfanyl-Ci-Ci8-alkyl such as butylthiomethyl, 2-dodecylthioethyl,
  • C5-Ci2-cycloalkyl-Ci-Ci8-alkyl such as cyclopentylmethyl, 2-cyclopentylethyl,
  • phenoxy-Ci-Ci8-alkyl such as 2-phenoxyethyl, 2-phenoxypropyl, 3-phenoxypropyl, 4-phenoxybutyl, 6-phenoxyhexyl;
  • phenylthio-Ci-Ci8-alkyl such as 2-phenylthioethyl.
  • R 1 to R 9 are C2-Cis-alkenyl
  • R 1 to R 9 are preferably C2-C6-alkenyl such as vinyl
  • R 1 to R 9 are C6-Cio-aryl
  • R 1 to R 9 are preferably phenyl or naphthyl, where phenyl or naphthyl may be unsubstituted or substituted by one, two, three or four substituents selected independently from among halogen, Ci-Cis-alkyl, Ci-C6-alkoxy, C1-C6- alkylsulfanyl, Ci-C6-alkoxy-Ci-C6-alkyl, Ci-C6-alkylcarbonyl, amino, Ci-C6-alkylamino, di(Ci-C6-alkyl)amino and nitro, e.g.
  • phenyl methylphenyl (tolyl), dimethylphenyl (xylyl) such as 2,6-dimethylphenyl, trimethylphenyl such as 2,4,6-trimethylphenyl, ethylphenyl, diethylphenyl, isopropylphenyl, tert-butylphenyl, dodecylphenyl, chlorophenyl, di- chlorophenyl, trichlorophenyl, fluorophenyl, difluorophenyl, trifluorophenyl, tetrafluoro- phenyl, pentafluorophenyl, 2,6-dichlorophenyl, 4-bromophenyl, methoxyphenyl, di- methoxyphenyl, ethoxyphenyl, hexyloxyphenyl, 2,6-dimethoxyphenyl, 2-nitrophenyl, 4-nitrophenyl, 2,4-dinitrophenyl
  • R 1 to R 9 are C5-Ci2-cycloalkyl
  • R 1 to R 9 are preferably unsubstituted cycloalkyl such as cyclopentyl or cyclohexyl
  • C5-Ci2-cycloalkyl which may bear one or two substituents selected independently from among Ci-C6-alkyl, Ci-C6-alkoxy, Ci-C6-alkylsulfanyl and chlorine, e.g. butylcyclohexyl, methoxycyclohexyl, dimethoxycyclohexyl, diethoxycyclohexyl, butylthiocydohexyl, chlo- rocyclohexyl, dichlorocyclohexyl, dichlorocyclopentyl;
  • R 1 to R 9 are preferably C5-Ci2-bicycloalkyl such as nor- bornyl or C5-Ci2-bicycloalkenyl such as norbornenyl.
  • R 1 to R 9 are C5-Ci2-cycloalkenyl, R 1 to R 9 are preferably unsubstituted cycloal- kenyl such as cyclopent-2-en-1 -yl, cyclopent-3-en-1 -yl, cyclohex-2-en-1 -yl, cyclohex-1 - en-1 -yl, cyclohexa-2,5-dien-1 -yl or partially fluorinated or perfluorinated cycloalkenyl.
  • R 1 to R 9 are heterocycloalkyl having 5 or 6 ring atoms
  • R 1 to R 9 are preferably 1 ,3-dioxolan-2-yl, 1 ,3-dioxan-2-yl, 2-methyl-1 ,3-dioxolan-2-yl, 4-methyl-1 ,3-dioxolan-2-yl.
  • R 1 to R 9 are heteroaryl
  • R 1 to R 9 are preferably furyl, thienyl, pyrryl, pyridyl, indol- yl, benzoxazolyl, benzimidazolyl, benzthiazolyl.
  • hetaryl bears 1 , 2 or 3 substituents which are selected independently from among Ci-C6-alkyl, Ci-C6-alkoxy and halogen, for example dimethylpyridyl, methylquinolyl, dimethylpyrryl, methoxyfuryl,dimethoxypyridyl or difluoropyridyl.
  • radicals R 1 to R 9 each being, independently of one another,
  • Ci-Cis-alkyl which may be unsubstituted or substituted by one or more hydroxy, halogen, phenyl, cyano, Ci-C6-alkoxycarbonyl and/or sulfo groups, for example methyl, ethyl, 1 -propyl, 2-propyl, 1 -butyl, 2-butyl, 2-methyl-1 -propyl (isobutyl), 2-methyl-2-propyl (tert-butyl), 1 -pentyl, 2-pentyl,
  • hydroxyethyloxyalkyl radicals of oligoalkylene and polyalkylene glycols such as polyethylene glycols and polypropylene glycols and oligomers thereof having from 2 to 100 units and a hydrogen or a Ci-Cs-alkyl as end group, for example R A 0-(CH R B -CH 2 -0) n -CH R B -CH 2 - or RAO-CCHzCHzCHzCHzO CHzCHzCHzCHzO- where R A and R B are preferably hydrogen, methyl or ethyl and n is preferably from 0 to 3, in particular 3-oxabutyl, 3-oxapentyl, 3,6-dioxaheptyl, 3,6-dioxaoctyl, 3,6,9-trioxadecyl, 3,6,9-trioxaundecyl, 3,6,9, 12-tetraoxatridecyl and 3,6,9,12-
  • N,N-di-Ci-C6-alkylamino such as ⁇ , ⁇ -dimethylamino and N,N-diethylamino.
  • radicals R 1 to R 9 each being, independently of one another, hydrogen; Ci-Cis-alkyl such as methyl, ethyl, 1 -butyl, 1 -pentyl, 1 -hexyl,
  • N,N-(Ci-C4-dialkyl)amino such as ⁇ , ⁇ -dimethylamino or ⁇ , ⁇ -diethylamino; chlorine or radicals of oligoalkylene glycol, e.g. CH30-(CH2CH20)n-CH2CH2- or
  • one of the radicals R 1 to R 5 is methyl, ethyl or chlorine and the remaining radicals R 1 to R 5 are each hydrogen;
  • R 3 is dimethylamino and the remaining radicals R 1 , R 2 , R 4 and R 5 are each hydrogen;
  • R 2 is carboxy or carboxamide and the remaining radicals R 1 , R 2 , R 4 and R 5 are each hydrogen; or
  • R 1 and R 2 or R 2 and R 3 together are 1 ,4-buta-1 ,3-dienylene and the remaining radicals R 1 , R 2 , R 4 and R 5 are each hydrogen;
  • R 1 to R 5 are each hydrogen;
  • one of the radicals R 1 to R 5 is methyl or ethyl and the remaining radicals R 1 to R 5 are each hydrogen.
  • radicals R 1 to R 4 are each hydrogen or
  • one of the radicals R 1 to R 4 is methyl or ethyl and the remaining radicals R 1 to R 4 are each hydrogen.
  • R 1 is hydrogen, methyl or ethyl and R 2 to R 4 are each, independently of one another, hydrogen or methyl or
  • R 1 is hydrogen, methyl or ethyl and R 2 and R 4 are each methyl and R 3 is hydrogen.
  • R 1 is hydrogen, methyl or ethyl and R 2 to R 4 are each, independently of one another, hydrogen or methyl or
  • R 1 is hydrogen, methyl or ethyl and R 2 and R 4 are each methyl and R 3 is hydrogen or R 1 to R 4 are each methyl or
  • R 1 to R 4 are each hydrogen.
  • R 1 is hydrogen, methyl, ethyl, 1 -propyl, 1 -butyl, 1 -pentyl, 1 -hexyl, 1 -octyl,
  • 2-hydroxyethyl or 2-cyanoethyl and R 2 to R 4 are each, independently of one another, hydrogen, methyl or ethyl.
  • imidazolium ions are 1 -methylimidazolium, 1 -ethylimidazolium, 1 -(1 -propyl)imidazolium, 1 -(1 -allyl)imidazolium, 1 -(1 -butyl)imidazolium, 1 -(1 -octyl)- imidazolium, 1 -(1 -dodecyl)imidazolium, 1 -(1 -tetradecyl)imidazolium, 1 -(1 -hexadecyl)- imidazolium, 1 ,3-dimethylimidazolium, 1 ,3-diethylimidazolium, 1 ,3-di-(1 - propyl)imidazolium, 1 -ethyl-3-methylimidazolium, 1 -(1 -butyl)-3-methylimidazolium,
  • Particularly preferred pyrazolium ions (IVf), (IVg) and (IVg') are those in which R 1 is hydrogen, methyl or ethyl and R 2 to R 4 are each, independently of one another, hydrogen or methyl.
  • R 1 to R 4 are each, independently of one another, hydrogen or methyl.
  • pyrazolium ions particular preference is given to 1 ,4-dimethylpyrazolium and 1 ,2,4-trimethylpyrazolium.
  • 1 -Pyrazolinium ions (IVi) used in the process of the invention are particularly preferably those in which R 1 to R 6 are each, independently of one another, hydrogen or methyl.
  • Particularly preferred 2-pyrazolinium ions (IVj) and (IVj') are those in which R 1 is hydrogen, methyl, ethyl or phenyl and R 2 to R 6 are each, independently of one another, hydrogen or methyl.
  • Particularly preferred 3-pyrazolinium ions (IVk) and (IVk') are those in which R 1 and R 2 are each, independently of one another, hydrogen, methyl, ethyl or phenyl and R 3 to R 6 are each, independently of one another, hydrogen or methyl.
  • Particularly preferred imidazolinium ions (IV I) are those in which R 1 and R 2 are each, independently of one another, hydrogen, methyl, ethyl, 1 -propyl, 1 -butyl, 1 -hexyl or phenyl and R 3 and R 4 are each, independently of one another, hydrogen, methyl or ethyl and R 5 and R 6 are each, independently of one another, hydrogen or methyl.
  • Particularly preferred imidazolinium ions (IVm) and (IVrrT) are those in which R 1 and R 2 are each, independently of one another, hydrogen, methyl, ethyl, 1 -propyl, 1 -butyl or 1 - hexyl and R 3 to R 6 are each, independently of one another, hydrogen or methyl.
  • Particularly preferred imidazolinium ions (IVn) and (IVn') are those in which R 1 to R 3 are each, independently of one another, hydrogen, methyl or ethyl and R 4 to R 6 are each, independently of one another, hydrogen or methyl.
  • Particularly preferred thiazolium ions (IVo) and (IVo') and oxazolium ions (IVp) are those in which R 1 is hydrogen, methyl, ethyl or phenyl and R 2 and R 3 are each, independently of one another, hydrogen or methyl.
  • Particularly preferred 1 ,2,4-triazolium ions are those in which R 1 and R 2 are each, independently of one another, hydrogen, methyl, ethyl or phenyl and R 3 is hydrogen, methyl or phenyl.
  • Particularly preferred 1 ,2,3-triazolium ions are those in which R 1 is hydrogen, methyl or ethyl, R 2 and R 3 are each, independently of one another, hydrogen or methyl or R 2 and R 3 together are 1 ,4-buta-1 ,3-dienylene.
  • Particularly preferred pyrrolidinium ions are those in which R 1 is hydrogen, methyl, ethyl or phenyl and R 2 to R 9 are each, independently of one another, hydrogen or me- thyl.
  • Particularly preferred imidazolidinium ions are those in which R 1 and R 4 are each, independently of one another, hydrogen, methyl, ethyl, 1 -propyl, 1 -butyl, 1 -hexyl or phenyl and R 2 , R 3 and R 5 to R 8 are each, independently of one another, hydrogen or methyl.
  • ammonium ions (IVu) are those in which
  • R 1 to R 3 are each, independently of one another, Ci-Cis-alkyl or
  • R 1 and R 2 together are 1 ,5-pentylene or 3-oxa-1 ,5-pentylene and R 3 is selected from among Ci-Cis-alkyl, 2-hydroxyethyl and 2-cyanoethyl.
  • tertiary amines from which the quaternary ammonium ions of the general formula (IVu) can be derived by quaternization with the abovementioned radical R are diethyl-n-butylamine, diethyl-tert-butylamine, diethyl-n-pentylamine, diethylhexylamine, diethyloctylamine, diethyl(2-ethylhexyl)amine, di-n-propylbutylamine, di-n-propyl-n- pentylamine, di-n-propylhexylamine, di-n-propyloctylamine, di-n-propyl(2-ethylhexyl)- amine, diisopropylethylamine, diisopropyl-n-propylamine, diisopropylbutylamine, diisop- ropylpentylamine, diisopropyl
  • N,N-di-n-butylcyclohexylamine N-n-propylpiperidine, N-isopropylpiperidine,
  • Preferred tertiary amines (IVu) are diisopropylethylamine, diethyl-tert-butylamine, diiso- propylbutylamine, di-n-butyl-n-pentylamine, N,N-di-n-butylcyclohexylamine and also tertiary amines derived from pentyl isomers.
  • tertiary amines are di-n-butyl-n-pentylamine and tertiary amines derived from pentyl isomers.
  • a further preferred tertiary amine which has three identical radicals is triallylamine.
  • R 1 to R 5 are each methyl.
  • a very particularly preferred guanidinium ion (IVv) is
  • Particularly preferred cholinium ions (IVw) are those in which
  • R 1 and R 2 are each independently of one another, methyl, ethyl, 1 -butyl or 1 -octyl and R 3 is hydrogen, methyl, ethyl, acetyl, -SO2OH or -PO(OH) 2 or
  • R 1 is methyl, ethyl, 1 -butyl or 1 -octyl
  • R 2 is a -CH2-CH2-OR 4 group and R 3 and R 4 are each, independently of one another, hydrogen, methyl, ethyl, acetyl, -SO2OH or -PO(OH) 2 or
  • R 1 is a -CH2-CH2-OR 4 group
  • R 2 is a -CH2-CH2-OR 5 group
  • R 3 to R 5 are each, independently of one another, hydrogen, methyl, ethyl, acetyl, -SO2OH or -PO(OH)2.
  • cholinium ions IVw
  • R 3 is selected from among hydrogen, methyl, ethyl, acetyl, 5-methoxy-3-oxapentyl
  • the cations (IV.x.1 ) are particularly preferably selected from among cations of
  • DBN 1 ,5-diazabicyclo[4.3.0]non-5-ene
  • DBU 1 ,8-diazabicyclo[5.4.0]-undec-7-ene
  • Particularly preferred phosphonium ions (IVy) are those in which
  • R 1 to R 3 are each, independently of one another, Ci-Cis-alkyl, in particular butyl, isobu- tyl, 1 -hexyl or 1 -octyl, or phenyl which may be unsubstituted or substituted by 1 , 2, 3, 4 or 5 substituents selected independently from among Ci-Cis-alkyl, carboxylate, sulfonate, COOH and S0 3 H.
  • Particularly preferred sulfonium ions (IVz) are those in which
  • R 1 and R 2 are each, independently of one another, Ci-Cis-alkyl, in particular butyl, iso- butyl, 1 -hexyl or 1 -octyl.
  • heterocyclic cations preference is given to the imidazoli- um ions, imidazolinium ions, pyridinium ions, pyrazolinium ions and pyrazolium ions. Particular preference is given to the imidazolium ions and also cations of DBU and DBN.
  • the cations of the one or more ionic liquids are selected from among pyridinium ions of the formula (IV. a), imidazolium ions of the formu- la (IV.e), pyrazolium ions of the formulae (IV.f), (IV. g), (IV. g') and (IV. h) and also ammonium ions of the formulae (IV. u) and (IV.w).
  • the cations of the one or more ionic liquids are selected from among pyridinium ions of the formula (IV.a), imidazolium ions of the formula (IV.e), pyrazolium ions of the formula (IV.f) and ammonium ions of the formula (IV. u), where the radicals R, R 1 , R 2 , R 3 , R 4 and R 5 are each, independently of one another, preferably hydrogen, alkyl, cycloalkyl or aryl.
  • the cations of the one or more ionic liquids are selected from among imidazolium ions of the formula (IV.e) and ammonium ions of the formula (IV. u), where the radicals R, R 1 , R 2 and R 3 which are bound to a nitrogen atom are each, independently of one another, Ci-C6-alkyl and the radicals R 2 , R 3 and R 4 which are bound to a carbon atom are each hydrogen.
  • the anions [Y] n_ of the one or more ionic liquids are, for example, selected from:
  • Ci-C3o-alkyl preferably Ci-C3o-alkyl, particularly preferably Ci-Cis-alkyl, which may un- substituted or substituted as defined above and/or be interrupted by at least one heteroatom or heteroatom-comprising group as defined above;
  • aryl preferably C6-Ci4-aryl, particularly preferably C6-Cio-aryl which may be un- substituted or substituted as defined above;
  • - cycloalkyl preferably C5-Ci2-cycloalkyl which may be unsubstituted or substituted as defined above;
  • heterocycloalkyl preferably heterocycloalkyl having 5 or 6 ring atoms, where the ring has, apart from ring carbons, 1 , 2 or 3 heteroatoms or heteroatom- comprising groups, which may be unsubstituted or substituted as defined above;
  • - heteroaryl preferably heteroaryl having from 5 to 10 ring atoms, where the ring has, apart from ring carbons, 1 , 2 or 3 heteroatoms or heteroatom-comprising groups selected from among oxygen, nitrogen, sulfur and NR a , which may be unsubstituted or substituted as defined above;
  • two of these radicals together with the part of the anion to which they are bound can also form at least one saturated, unsaturated or aromatic ring or a ring system having from 1 to 12 carbon atoms, where the ring or the ring system can have from 1 to 5 nonadja- cent heteroatoms or heteroatom-comprising groups which are preferably selected from among oxygen, nitrogen, sulfur and NR a , and the ring or the ring system may be unsubstituted or substituted.
  • Ci-C3o-alkyls in particular Ci-Cis-alkyls, C6-Ci4-aryls, in particular C6-Cio-aryls, C5-Ci2-cycloalkyls, heterocycloalkyls having 5 or 6 ring atoms and heteroaryls having 5 or 6 ring atoms, what has been said above is incorporated by reference at the present point.
  • Ci-C3o-alkyl especially Ci-Cis-alkyl, C6-Ci2-aryl, C5-Ci2-cycloalkyl, heterocycloalkyl having 5 or 6 ring atoms and heteroaryl having 5 or 6 ring atoms, what has been said above in respect of substituents is likewise incorporated by reference at the present point.
  • Ci-Cis-alkyl When at least one of the radicals R c to R f is optionally substituted Ci-Cis-alkyl, it is preferably methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, 2,4,4-trimethylpentyl, decyl, dodecyl, tetradecyl, hetadecyl, octadecyl, 1 ,1 -dimethylpropyl, 1 ,1 -dimethylbutyl, 1 ,1 ,3,3-tetramethylbutyl, benzyl, 1 -phenylethyl, ⁇ , ⁇ -dimethylbenzyl, benzhydryl, p-tolylmethyl, 1 -(p-
  • 3- dimethylaminopropyl 4-dimethylaminobutyl, 6-dimethylaminohexyl, 2-hydroxy- 2,2-dimethylethyl, 2-phenoxyethyl, 2-phenoxypropyl, 3-phenoxypropyl, 4-phenoxybutyl, 6-phenoxyhexyl, 2-methoxyethyl, 2-methoxypropyl, 3-methoxypropyl, 4-methoxybutyl, 6-methoxyhexyl, 2-ethoxyethyl, 2-ethoxypropyl, 3-ethoxypropyl, 4-ethoxybutyl or 6-ethoxyhexyl.
  • the radicals R c to R f is Ci-Cis-alkyl interrupted by one or more nonadjacent heteroatoms or heteroatom-comprising groups, it is preferably 5-hydroxy- 3-oxapentyl, 8-hydroxy-3,6-dioxaoctyl, 1 1 -hydroxy-3,6,9-trioxaundecyl, 7-hydroxy-4- oxaheptyl, 1 1 -hydroxy-4,8-dioxaundecyl, 15-hydroxy-4,8,12-trioxapentadecyl,
  • radicals R c to R f form a ring
  • these radicals can together be, for example, a fused-on 1 ,3-propylene, 1 ,4-butylene, 2-oxa-1 ,3-propylene, 1 -oxa-1 ,3-propylene, 2- oxa-1 ,3-propenylene, 1 -aza-1 ,3-propenylene, 1 -Ci-C4-alkyl-1 -aza-1 ,3-propenylene, 1 ,4-buta-1 ,3-dienylene, 1 -aza-1 ,4-buta-1 ,3-dienylene or 2-aza-1 ,4-buta-1 ,3-dienylene building block.
  • the number of nonadjacent heteroatoms or heteroatom-comprising groups in the radicals R c to R f is in principle not critical and is generally restricted only by the size of the respective radical or ring building block. In general, there will be no more than 5 in the respective radical, particularly preferably no more than 4 and very particularly preferably no more than 3. Furthermore, there will generally be at least one carbon atom, preferably at least two carbon atoms, between each two heteroatoms.
  • Substituted and unsubstituted imino groups can be, for example, imino, methylimino, isopropylimino, n-butylimino or tert-butylimino.
  • radicals R c to R f are carboxy, carboxamide, hydroxy, di(Ci-C4-alkyl)amino, Ci-C4-alkyloxycarbonyl, cyano or Ci-C4-alkoxy.
  • radicals R c to R f which are not alkyl can be substituted by one or more Ci-C4-alkyl groups, preferably methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl or tert-butyl.
  • radicals R c to R f When at least one of the radicals R c to R f is optionally substituted C6-Cio-aryl, it is pre- ferably phenyl, methylphenyl (tolyl), xylyl, a-naphthyl, ⁇ -naphthyl, chlorophenyl, dichlo- rophenyl, trichlorophenyl, difluorophenyl, dimethylphenyl, trimethylphenyl, ethylphenyl, diethylphenyl, isopropylphenyl, tert-butylphenyl, dodecylphenyl, methoxyphenyl, dime- thoxyphenyl, ethoxyphenyl, hexyloxyphenyl, methylnaphthyl, isopropylnaphthyl, chloro- naphthyl, ethoxynap
  • radicals R c to R f are optionally substituted C5-Ci2-cycloalkyl, it is preferably cyclopentyl, cyclohexyl, cyclooctyl, cyclododecyl, methylcyclopentyl, dime- thylcyclopentyl, methylcyclohexyl, dimethylcyclohexyl, diethylcyclohexyl, butylcyclohex- yl, methoxycyclohexyl, dimethoxycyclohexyl, diethoxycyclohexyl, butylthiocyclohexyl, chlorocyclohexyl, dichlorocyclohexyl, dichlorocyclopentyl or a saturated or unsaturated bicyclic system such as norbornyl or norbornenyl.
  • radicals R c to R f are an optionally substituted five- or six- membered heterocycle, it is preferably furyl, thienyl, pyrryl, pyridyl, indolyl, benzoxazol- yl, dioxolyl, dioxyl, benzimidazolyl, benzthiazolyl, dimethylpyridyl, methylquinolyl, dime- thylpyryl, methoxyfuryl, dimethoxypyridyl, difluoropyridyl, methylthiophenyl, iso- propylthiophenyl or tert-butylthiophenyl.
  • the substituents are preferably selected independently from among alkyl, alkoxy, alkylsulfanyl, cycloalkyl, cycloalkoxy, polycyclyl, heterocycloalkyl, aryl, aryloxy, arylthio and heteroaryl.
  • the anions of the on or more ionic liquids are preferably selected from among:
  • the anions of the one or more ionic liquids are selected from among:
  • the anions of the one or more ionic liquids are selected from among: CI-, Br, R c OS0 3 -, R c S0 3 -, R c R d P0 4 " and R c COO-;
  • R c and R d are selected independently from hydrogen, Ci-Cn-alkyl or C 3 -C7- cycloalkyl.
  • the anions of the one or more ionic liquids are selected from among:
  • R c and R d are selected independently from hydrogen and Ci-Cn-alkyl.
  • the anions of the one or more ionic liquids are selected from the ranges of anions given above, in particular from those mentioned as preferred, and the cations of said one or more ionic liquids are compounds of the formula (IV. e), where R and R 1 are each, independently of one another, Ci-Ce-alkyl and the radicals R 2 , R 3 and R 4 are each hydrogen.
  • the one or more ionic liquids are selected from 1- ethyl-3-methylimidazolium acetate, 1 ,3-diethylimidazolium acetate, 1 ,3-di-(1- propyl)imidazolium acetate, 1 ,3-diethylimidazolium octanoate and 1 -ethyl-3- methylimidazolium octanoate.
  • Cations and anions are present in the ionic liquid.
  • a proton or an alkyl radical is transferred from the cation to the anion. This results in two uncharged molecules. An equilibrium in which anions, cations and the two uncharged molecules formed therefrom is thus present.
  • the viscosity of the solvent A at temperatures of from 20 to 100°C is in the range from 10 to 5000 mPa-s, preferably in the range from 100 to 2000 mPa-s and particularly preferably in the range from 300 to 1500 mPa-s.
  • the solution of the cellulose product in solvent A used in the inventive process can be prepared according to established methods usually involves mixing the cellulose prod- uct and solvent A, optionally with agitation, at temperatures in range of 15 to 180°C and preferably in the range of 50 to 150°C.
  • solvent A comprises or consists of one or more ionic liquids the cellulose product is dissolved in solvent A according to the methods described in WO 03/029329 such as by heating to about 80 to 150° or by heating to about 50 to 120°C in an ultrasonic bath.
  • the cellulose product is dissolved in solvent A by heating a mixture of the two components with a microwave heater to a temperature of about 100 to 150°C.
  • the solution of the cellulose product in solvent A contains the cellulose product typically in an amount of 1 to 40 % by weight, preferably in an amount of 2 to 30 % by weight, in particular in an amount of 3 to 15 % by weight and specifically in an amount of 3 to 10 % by weight, based on the total weight of the solution.
  • step (a) of the process of the invention for coating a paper with a cellulose product the paper is contacted with a solution of the cellulose product, usually in order to form a layer of the solution on the paper.
  • step (a) therefore comprises forming a layer of the solution on at least one side of the paper.
  • the layer of the solution is applied to the areas of the paper that are desired to be coated with the cellulose product.
  • the solution is evenly applied to the paper in such a way that one side or both sides of the paper are completely or almost completely covered by a layer of uniform thickness.
  • the solution is applied to only these sections.
  • the solution is applied to the paper so that one side of the paper is completely or almost completely covered by a layer of uniform or approximately uniform thickness.
  • the layer of the solution containing the dissolved cellulose product that is formed on at least one side of the paper typically has a thickness in the range of 5 to 2000 ⁇ , preferably of 10 to 1000 ⁇ , more preferably of 20 to 500 ⁇ , in particular of 30 to 250 ⁇ and specifically of 35 to 200 ⁇ .
  • the solution of the cellulose product can be applied using any suitable method known in the art. Suitable methods are especially those that allow applying thin layers of liquids having viscosities of more than 100 mPa-s, in particular more than 500 mPa-s, to solid substrates.
  • the solution of the cellulose product is applied to the paper by using suitable coating machinery that may include e.g. a one-roll or a two-roll system.
  • the solution may be applied, for example, from a trough by way of an applicator roll and leveled, if required, for example with the aid of an air knife.
  • Other successful methods of applying the solution of the cellulose product use, e.g.
  • at least one side of the paper is provided with a coating, i.e. single- or double-sided coating of the paper is possible.
  • Preferred application processes are roll coating, curtain coating, airbrush coating, bar coating, and doctor blade coating.
  • the application of the solution of the cellulose product to the paper can be carried out during the manufacture of the paper, such as at the wet end of a paper machine during papermaking. Preferably, however, the solution is applied only after the formation of the paper is completed. An example of this is the application of the solution at the dry end of the paper machine, or at any time after formation of the paper.
  • step (b) of the process of the invention the paper product obtained in step (a) is contacted with a coagulant which preferably comprises a protic solvent.
  • a protic solvent here are those known in the art and that are described e.g. in WO 03/029329, WO2007/076979, WO 2009/027250 and WO 201 1/154890 for the purpose of regenerating cellulose.
  • the protic solvent included in the coagulant is selected from water, Ci-C4-alkanol, such as methanol, ethanol, propanol or
  • the protic solvent is water.
  • the coagulant comprises protic solvent in an amount of at least 30 % by weight, preferably at least 60% by weight, more preferably at least 80% by weight, in particular at least 90% by weight and specifically at least 95% by weight, based on the weight of the coagulant.
  • the coagulant is water.
  • contacting the paper product with the coagulant causes the cellulose product to precipitate from the solution, which has been applied to the paper, onto the surface of the paper. This results in a layer of cellulose that is already tightly attached to the paper, as during the precipitation process cellulose molecules enter the pores on the surface of the paper.
  • some or typically at least a major portion of the solvent used to dissolve the cellulose product can be readily removed together with coagulant, as the solvent is usually, at least partly, miscible with the coagulant.
  • the resulting contaminated coagulant includes the solvent, or a portion of it, in dissolved or dispersed form.
  • the contaminated coagulant mainly consists of a mixture of these two components.
  • the ionic liquid can be recovered from these mixtures for example by using methods described in WO2007/076979, WO 2009/027250 and WO 201 1/154890.
  • the paper product can be contacted with the coagulant according to any method known in the art for such purposes.
  • the paper is contacted with the coagulant in such a way that at least the areas of the paper to which the solution of the cellulose product have be applied in step (a) are wetted with the coagulant.
  • the paper product can be contacted with the coagulant by submerging it in the coagulant, by letting it float on the surface of the coagulant, by overlaying or rinsing it with the coagulant, or by a combination of these measures.
  • step (b) of the process of the invention is an optional step the inventive process may or may not include step (b). In case step (b) is omitted the paper product obtained in step (a) of the inventive process is directly subjected to the procedure of step (c).
  • step (b) is included in the inventive process.
  • step (c) of the process of the invention the paper product obtained in step (a) or step (b) is dried.
  • drying means the removal either of the solvent used for dissolving the cellulose product, in case step (b) has been omitted, or of the residual coagulant which may be contaminated with said solvent, in case step (b) has been carried out.
  • the inventive process for coating paper with cellulose comprises as step (c) the drying of the paper product obtained in step (b) of the process.
  • the drying of the paper product obtained in step (a) or step (b) can be effected by any method known in the art. Suitable methods usually remove volatile components, in particular those included in the coagulant, by vaporizing them. Examples for such methods include contact drying, which typically involve passing the paper product sheets over a hot surface, e.g. a heated drying cylinder, and non-contact drying, which typically involve treating the paper product with infrared light or hot air.
  • the paper product obtained in step (b) is dried in step (c) by contact drying or non-contact drying, and in particular by contact drying.
  • the coated paper obtained after the drying in step (c) includes a coating film that has a thickness on average of at least 0.3 ⁇ , often at least 0.4 ⁇ , preferably at least 0.5 ⁇ , more preferably at least 0.7 ⁇ , and in particular at least 1 ⁇ , e.g. in the range from 0.3 to 50 ⁇ , preferably from 0.4 to 35 ⁇ , more preferably from 0.5 to 20 ⁇ , in particular from 1.0 to 15 ⁇ and specifically from 2.0 to 10 ⁇ .
  • the coating film typically contains cellulose in an amount of at least 80 % by weight, preferably of at least 90 % by weight, in particular of at least 95 % by weight and specifically of at least 98 % by weight, based in each case on the total weight of the film.
  • the coated paper is usually cooled to ambient temperature, for instance by passing it over a cooling roll, and may finally be reeled.
  • Another preferred embodiment of the present invention provides a process for coating paper with cellulose in the manner described above, where the resulting coated paper has good resistance to grease, oil and water as well as good permeability to water vapor.
  • the invention provides a process of this type in which the paper is intended as packaging material for food or drink.
  • these materials are sales packaging, such as cartons or paper products, and also consumer packaging, for example disposable tableware, e.g. plates, cups or beakers made of paperboard.
  • the coating obtained by the process of the invention is found on at least one of the paper surfaces, such as the surfaces of standard writing paper, wrapping paper, paperboard or cardboard. It can also form at least one, e.g. one or two, and in particular one, of a plurality of layers of a multilayer coating of the paper.
  • the coating of the invention can have been arranged directly on a so far uncoated paper surface. However, between the paper and the coating of the invention there can also be other layers, e.g. primer layers, further barrier layers, or colored or black-and-white layers of printing inks.
  • the coating is found on the inner side of the packaging: the side facing toward the contents of the package.
  • the present invention also relates to coated paper that is obtainable by the herein described process of the invention. It features excellent resistances to grease, oil and water, good barrier properties against the permeation of gases and aromas, as well as good permeability to water vapor.
  • the coated paper of the invention has improved tear strength, is non-hazardous and also fully biodegradable and repulpable.
  • the mechanical properties of coated papers were measured in accordance with the industry standards. More particularly, the tensile breaking strength and the breaking length were measured in accordance with TAPPI standard T 494, the Z-direction tensile strength was measured in accordance with TAPPI standard T 541 , the burst strength was measured in accordance with TAPPI standard T 541 , the water vapor transmission rate according to TAPPI standard T 448 with the exception that a relative humidity of 85 % was used.
  • the "Oil Penetration Test” was used to study the oil barrier properties of the uncoated papers and of the papers coated with cellulose. To this end a 10 cm by 10 cm sheet of the coated paper was placed, with the coated side facing upwards, on a graph paper lying on a glass plate. On top of the coated paper sheet was placed a filter paper to which 2 ml of oleic acid stained with 2 % by weight of Sudan® Blue 670 (BASF SE, 1 ,4-bis(butylamino) anthraquinone) were applied. A second glass plate was put on the filter paper and the whole assembly was then stored for 1 hour or for 18 hours at 60°C. The back side of the coated paper was then assessed visually at various junctures to determine the extent of staining. 100% means complete penetration, and 0% means no penetration.
  • a solution of 5 % by weight of cellulose in 1 -ethyl-3-methylimidazolium acetate (EMIM) was prepared by mixing corresponding amounts of sulfite pulp from eucalyptus wood (sai lyo, Sappi Saiccor SA) and EMIM at 100°C. After cooling down to ambient temperature the solution was applied to a sheet of unsized paper (birch/pine (70:30)) using a doctor roller on spacers to give a layer of the solution on the paper with a thickness of 150 ⁇ . Afterwards coagulation was effected by transferring the treated paper sheet to a water bath and keeping it in the bath for about 15 minutes. Finally, the sheet is dried by passing it over a drying cylinder. Assessment of the obtained coated paper using the aforementioned testing methods gave the data listed in Table 1 . An identical untreated paper sheet was examined in parallel for comparison purposes.
  • the thickness of the cellulose coat was calculated by dividing the weight increase resulting from coating (1 1 .2 g/m 2 ) by the density of cellulose (1 .5 g/cm 3 );
  • Example 2 The paper coating procedure described in Example 1 was repeated using cellulose solutions with concentrations of 1 , 3 and 5 % by weight and applying the cellulose solutions to thicknesses of 45, 90 and 150 ⁇ , as summarized in Table 2.
  • Table 2 The data obtained for the resulting coated papers regarding oil penetration after 1 hour and after 18 hours at 60°C are also listed in Table 2.
  • Example 2 full resistance to oil penetration over 18 hour at 60°C can already be achieved by applying a 90 ⁇ layer of a solution containing cellulose in a concentration of 5 % by weight (Example 2).
  • the coated paper finally obtained by the procedure of Example 2 has a cellulose coating with a calculated thickness of 4.5 ⁇ .

Landscapes

  • Paints Or Removers (AREA)

Abstract

Cette invention concerne un procédé de couchage du papier à la cellulose et le papier à couchage cellulose obtenu par ledit procédé, le procédé comprenant l'étape de mise en contact du papier avec une solution contenant de la cellulose qui est de préférence obtenue par dissolution de la cellulose dans un solvant comprenant un ou plusieurs liquides ioniques.
PCT/EP2014/063508 2013-06-27 2014-06-26 Procédé de couchage du papier à la cellulose à l'aide d'une solution contenant de la cellulose Ceased WO2014207100A1 (fr)

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US10106528B2 (en) 2016-03-24 2018-10-23 Bristol-Myers Squibb Company 6-hydroxy-4-oxo-1,4-dihydropyrimidine-5-carboxamides as APJ agonists
US10392347B2 (en) 2015-10-14 2019-08-27 Bristol-Myers Squibb Company 2,4-dihydroxy-nicotinamides as APJ agonists
US10669261B2 (en) 2015-12-16 2020-06-02 Bristl-Myers Squibb Company Heteroarylhydroxypyrimidinones as agonists of the APJ receptor
US11168068B2 (en) 2016-07-18 2021-11-09 Janssen Pharmaceutica Nv Tau PET imaging ligands
WO2023222955A1 (fr) * 2022-05-20 2023-11-23 Teknologian Tutkimuskeskus Vtt Oy Couche de revêtement pour papier et carton utilisant de la cellulose dissoute
US11878958B2 (en) 2022-05-25 2024-01-23 Ikena Oncology, Inc. MEK inhibitors and uses thereof
EP4389970A1 (fr) * 2022-12-23 2024-06-26 Ahlstrom Oyj Substrat recyclable à base de cellulose comprenant des fibres cellulosiques et une matière cellulosique non fibreuse
CN119121696A (zh) * 2024-10-09 2024-12-13 广东冠豪新材料研发有限公司 一种高阻隔抗菌性天然纤维素基包装材料的制备方法
FI131348B1 (en) * 2019-12-23 2025-03-05 Metsae Fibre Oy Dispersion of cellulose fibers and method of producing the same

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US10669261B2 (en) 2015-12-16 2020-06-02 Bristl-Myers Squibb Company Heteroarylhydroxypyrimidinones as agonists of the APJ receptor
CN105568768A (zh) * 2015-12-17 2016-05-11 华南理工大学 一种透明纸以及多次表面涂布法快速制备透明纸的方法
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