EP3339508B1 - Procede pour le traitement de materiaux contenant des fibres - Google Patents

Procede pour le traitement de materiaux contenant des fibres Download PDF

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Publication number
EP3339508B1
EP3339508B1 EP17207499.9A EP17207499A EP3339508B1 EP 3339508 B1 EP3339508 B1 EP 3339508B1 EP 17207499 A EP17207499 A EP 17207499A EP 3339508 B1 EP3339508 B1 EP 3339508B1
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European Patent Office
Prior art keywords
paper
mixture
polymer
cellulose
process according
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EP17207499.9A
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German (de)
English (en)
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EP3339508A1 (fr
Inventor
Michael Ramin
Klaus Langerbeins
Christian Maier
Karlheinz SÜNKEL
Alexis Krupp
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AMSilk GmbH
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AMSilk GmbH
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Priority claimed from LU93386A external-priority patent/LU93386B1/de
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Classifications

    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H25/00—After-treatment of paper not provided for in groups D21H17/00 - D21H23/00
    • D21H25/02—Chemical or biochemical treatment
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/21—Macromolecular organic compounds of natural origin; Derivatives thereof
    • D21H17/24—Polysaccharides
    • D21H17/25—Cellulose
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/21—Macromolecular organic compounds of natural origin; Derivatives thereof
    • D21H17/24—Polysaccharides
    • D21H17/30—Alginic acid or alginates
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/33—Synthetic macromolecular compounds
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
    • D21H21/36—Biocidal agents, e.g. fungicidal, bactericidal, insecticidal agents
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H25/00—After-treatment of paper not provided for in groups D21H17/00 - D21H23/00
    • D21H25/18—After-treatment of paper not provided for in groups D21H17/00 - D21H23/00 of old paper as in books, documents, e.g. restoring

Definitions

  • the invention relates to a method for processing materials containing fibers and to materials and systems obtainable with this method.
  • the invention also relates to the use of a mixture containing a polymer for processing a material containing fibers, the use of dimethyl sulfoxide as an antioxidant in the processing of paper and the use of ionic liquids as an antimicrobial agent for the processing of paper.
  • Organic materials containing fibers experience mechanical destabilization in that the macromolecules forming the fiber, such as cellulose macromolecules, are broken down over time. Especially in the case of paper, this can lead to the paper being so destabilized that the books made from this paper can no longer be used.
  • the problems of destabilization do not only exist with paper and cellulose-containing materials in general, such as wood, but also generally represent a problem for materials containing fibers. To counteract this problem, appropriate processing methods are used for the material containing fibers needed. Paper, in particular printed paper in books, as a material containing fibers, places the highest demands on the processing method, which is why the further discussion should take place using the example of paper, in particular printed paper.
  • the processing method should not only allow single sheet processing. Rather, the process should be able to process multiple sheets at once. The pages should not stick together. In addition, if possible, the method should not damage the cover of a book and / or the binding or spine gluing of the sheets. In this way, the method can be carried out more economically, since several sheets can be processed at the same time or entire books can be processed at once and there is no need to separate the sheets from books. Furthermore, the process should not attack the paper in any other way, in particular the paper should not swell irreversibly. The process should also not wash out the ink and / or printing inks on the paper to be processed. At the same time, however, it is desirable that the processing of the paper does not only take place superficially, but ideally begins throughout the paper.
  • a process for strengthening paper is also known in which the paper is impregnated with acrylic acid derivatives which are polymerized by exposure to gamma rays. Irradiation with gamma rays, however, leads to further damage to the paper, as a result of the impregnation with acrylic acid, paints and inks on the paper at least partially bleed, and residual monomers remaining in the paper lead to an odor nuisance.
  • this process can only be combined with other conventional means of paper restoration with difficulty.
  • the processing of paper by lamination is also known, a thin polymer film or a thin stabilizing paper being applied to one or both sides of the paper.
  • a thin polymer film or a thin stabilizing paper being applied to one or both sides of the paper.
  • a well-known method for processing paper is the so-called Wiener method, which is in the EP 0 273 9602 A2 is described.
  • Wiener method which is in the EP 0 273 9602 A2 is described.
  • the material to be processed is soaked in an aqueous solution that contains methyl cellulose to strengthen the paper.
  • the processing solution is then pumped out, residues of the processing solution are allowed to drip off the processed paper, and the paper is then shock-frozen and freeze-dried.
  • the main disadvantage of this method is that book covers are damaged, which is why the pages of the book have to be removed before processing.
  • a derivatized polymer must be used with methyl cellulose.
  • the DE 100 57 554 A1 describes a process in which the paper to be processed is processed with a silylated polymer derivative such as silylated cellulose, which is dissolved in a non-polar solvent. The silyl groups are then split off by the action of moisture or water.
  • the disadvantage of this process is the compulsory use of derivatized polymers.
  • the EP 3 072 933 A1 describes alkaline nanoparticles containing at least one hydroxide or carbonate or an organic compound of an alkaline earth metal and optionally a hydrophilic cellulose derivative and a stabilizing outer layer made of hydrophobic polymers for deacidifying and strengthening cellulose-based artifacts.
  • the nanoparticles must first be synthesized.
  • the EP 0 285 227 A1 describes a process for the preservation of paper sheets or paper webs, in which the solution of a deacidifying agent and a polymeric reinforcing agent for the paper in an organic solvent or in a mixture of organic solvents is sprayed onto one surface of the paper, and one is sprayed onto the other surface of the paper exerts strong suction to pull the solution through the paper and also to at least partially dry the treated paper.
  • the WO 2014/201544 A1 describes antimicrobial polymers which impart prolonged antimicrobial activity to a surface or in a solution, the polymers comprising as repeating monomers a polymerizable cyclic unit which forms part of the polymer backbone and an antimicrobial unit such as a quaternary ammonium unit in the side chain.
  • the object of the invention is therefore to provide a method for processing, in particular for strengthening, material containing fibers, in particular paper, which at least partially overcomes one or more disadvantages of the methods known from the prior art.
  • the paper to be processed should not be damaged any further.
  • the paper to be processed should be strengthened. Any inks and printing inks on the paper to be processed should not bleed.
  • the bindings and / or the paper backing should not be damaged by the process.
  • substances that are easy to obtain, such as polymers, which in particular are not derivatized, can be used in the process.
  • a particular advantage of the method according to the invention is that, by using a polar aprotic solvent, non-derivatized polymers such as cellulose can also be used as the at least one polymer in the method according to the invention. Furthermore, by using a polar aprotic solvent, mixtures, in particular solutions, with a low viscosity can be produced which are particularly suitable for processing books or similar substrates.
  • the method according to the invention can be combined with other methods, in particular deacidification methods.
  • a solution of the substance in the solvent can be produced which is at least 0.5 Weight%, in particular at least 1 weight%, 2 weight%, 3 weight%, 4 weight%, 5 weight%, 6 weight%, 7 weight%, 8 weight%, 9 weight% or at least 10% by weight, and at most 25% by weight, in particular at most 20% by weight, 15% by weight, 14% by weight, 13% by weight or at most 12% by weight, each based on the total weight of the solution, of the substance.
  • the term "accumulation”, in particular the accumulation of a substance on another substrate, can mean in particular the precipitation, crystallization, deposition, growth and / or settling, in particular on the other substrate .
  • the polymer can be completely or partially attached to the material containing fibers, in particular to the fibers of the material containing fibers. If the polymer only partially attaches to the fibers of the material containing fibers, a residual amount of polymer remains in the mixture.
  • the fibers of the material containing fibers are preferably completely or partially sheathed by attachment. This can strengthen the fiber.
  • “Derivatized polymers” can in particular be those polymers which have been obtained by chemical modification of another polymer.
  • the derivatization can also be reversible, so that the original polymer can be recovered.
  • derivatized polymers are made from naturally occurring polymers such as cellulose or starch.
  • the derivatized polymer methylcellulose can be obtained from nonderivatized cellulose by chemical modification.
  • Further examples of non-derivatized polymers are starch, chitosan, chitin, lignin, viscose, cellulose, silk and alginate.
  • Various chemical modifications can be used for the derivatization.
  • the derivatization can for example by partial or complete alkylation, partial or complete acylation, partial or complete silylation or partial or complete sulfonylation can be achieved.
  • Fiber-containing fibers is also referred to below as “fiber-containing material” or “fiber-containing material”.
  • Steps a. to c. of the method according to the invention are advantageously carried out in the order given.
  • the fiber-containing material can contain a polymer with at least one polar group, in particular in a proportion of 50 wt.%, 60 wt.%, 70 wt.%, 80 wt.%, 90 wt.%, 95 wt.%, 99 wt .%, or consist of it.
  • the at least one polar group can be contained in the polymer backbone and / or be linked to the polymer backbone as a side chain. If several polar groups are contained, these can be the same or different. Polar groups are known to the person skilled in the art.
  • polar groups include the hydroxyl group, acid groups such as the carboxyl group and the sulfonic acid group, the amide group, the amine group, the thiol group, the ether group, in particular the C1-C4- Alkyl ether group, the ester group and the urethane group.
  • the fiber-containing material contains cellulose, microcrystalline cellulose, pulp, hemicellulose, viscose, chitin, chitosan, alginate, starch, lignin, polyvinyl alcohol, proteins or mixtures thereof. Further components of the fiber-containing material can be further polymers, in particular further polymers with at least one polar group, but also, for example, fillers such as calcium carbonate or pigments such as titanium dioxide.
  • the fiber-containing material can be a cellulose-containing material, in particular paper, cardboard, cardboard, textiles or wood.
  • the fiber-containing material is paper, in particular paper sheets. Examples of paper are typewriter paper, printer paper, magazine paper, newsprint, and book paper.
  • a mixture containing a polymer is provided.
  • Various polymers can be used as the polymer.
  • the polymer can be a copolymer or a homopolymer.
  • the polymer can in particular have a mass average molecular weight Mw of 1000 to 10000000 g / mol, in particular from 3000 to 1000000 g / mol, from 5000 to 500000 g / mol or from 10,000 to 100,000 g / mol, exhibit.
  • the polymer can also contain at least one polar group.
  • the at least one polar group can be contained in the polymer backbone and / or be linked to the polymer backbone as a side chain. If several polar groups are contained, these can be the same or different.
  • Polar groups are known to the person skilled in the art. Examples of polar groups include the hydroxyl group, acid groups such as the carboxyl group and the sulfonic acid group, the amide group, the amine group, the thiol group, the ether group, in particular the C1-C4- Alkyl ether group, the ester group and the urethane group.
  • the polymer can have at least one hydroxyl group, at least one amine group, at least one acid group, in particular a carboxyl group, at least one amide group, at least one thiol group, at least one ether group, in particular a C1- C4-alkyl ether group, at least one ester group and / or at least one urethane group, in particular at least one hydroxyl group.
  • the polymer is selected from the group consisting of cellulose, alpha-cellulose, microcrystalline cellulose, cellulose, hemicellulose, viscose, chitin, lignin, chitosan, alginate, starch, silk, natural silk, silk biopolymers, polyvinyl alcohol, polyvinyl acetate, polyurethanes, polyamides, proteins , Polymers or copolymers based on acrylic acid and / or its ester and / or amide derivatives, methacrylic acid and / or its ester and / or amide derivatives, vinyl acetate, itaconic acid, maleic acid, fumaric acid, acryloxypropionic acid, methacryloxypropionic acid, styrene sulfonic acid, ethyl methacrylate -2-sulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, phosphoethyl methacrylate, cellulose ethers and mixtures thereof.
  • the polymer can be selected from the group consisting of cellulose, alpha cellulose, microcrystalline cellulose, cellulose, hemicellulose, viscose, chitin, lignin, chitosan, alginate, starch, silk, silk biopolymers, polyvinyl alcohol and mixtures thereof.
  • the polymer is preferably selected from the group consisting of cellulose, alpha-cellulose, microcrystalline cellulose, cellulose, silk, silk biopolymers, viscose and mixtures thereof.
  • the polymer is advantageously selected from the group consisting of cellulose, alpha-cellulose, microcrystalline cellulose, cellulose, viscose and mixtures thereof.
  • the polymer is alpha-cellulose.
  • the polymer is viscose, in particular essentially non-derivatized viscose. It has been shown that fiber-containing materials can be processed particularly well with the aforementioned polymers. In particular, processing with the above polymers made good Strengthening, especially of cellulosic materials such as paper, cardboard, cardboard and wood can be achieved.
  • the polymer can in particular be used in the form of fibers.
  • Viscose is made up of regenerated cellulose in particular. Viscose can in particular be in the form of fibers. Viscose can in particular be a regenerated cellulose fiber, as it is in FIG EP 2 546 396 (see in particular paragraphs [0026], [0028], [0029], [0030], [0031], [0032], [0033], [0034], [0035], [0036], [0037] and / or [0038]) is described. Accordingly, the viscose can be in the form of fibers which have several legs and in which at least one leg differs from the other legs in terms of its length. In particular, it can be asymmetrical cellulose fibers.
  • the titer of the asymmetrical cellulose fibers can be from 1.3 dtex to 10 dtex, in particular 3.3 dtex.
  • the titer indicates the fineness, with 1 dtex corresponding in particular to a weight of one gram per 10,000 meters of cellulose fibers.
  • Silk biopolymers can, in particular, be silk biopolymers, as described in FIG WO 2014/037453 or in the WO 2011/113446 are described.
  • the silk biopolymers can in particular consist of polypeptides which are essentially built up from one or more repeating polypeptide units and one or more non-repeating polypeptide units.
  • the repeating polypeptide units can in particular contain oligoalanine units.
  • the repeating polypeptide units may comprise or consist thereof, wherein the sequences given in brackets represent amino acids in one-letter code, as it is, for example, in the book " Enzymes - A Practical Introduction to Structure, Mechanism, and Data Analysis ", 2nd Edition by Robert A.
  • Non-repeating polypeptide units can be selected from the WO 2014/037453 , in particular on page 16, described "non-repetitive (NR)" units NR3, NR4, NR5, NR6 or in the WO 2014/037453 be selected variants thereof described.
  • the polymer in step a. of the method according to the invention can be the same as or different from the polymer with at least one polar group, which can be contained in the fiber-containing material.
  • a cellulose-containing material can be brought into contact as a fiber-containing material with a mixture which also contains cellulose as a polymer.
  • a cellulose-containing material can also be brought into contact as a fiber-containing material, for example with a mixture which contains polyvinyl alcohol as a polymer.
  • the polymer contained in the mixture contains a polar group
  • the polar group of the polymer with at least one polar group which can be contained in the fiber-containing material and the polar group of the at least one polymer contained in the mixture can be the same or different.
  • the fiber-containing material can be a cellulosic material and the polar polymer can be a polyurethane.
  • polar aprotic solvents can be used as polar aprotic solvents in the process according to the invention.
  • the molecules can have a dipole moment and / or the polar aprotic solvent can be composed of ions.
  • polar aprotic solvents can be free of groups, in particular polar groups, from which protons can be split off. Examples of such groups are the OH group, acid groups such as the carboxyl group, the sulfonic acid group and hydrogen halide groups, the thiol group, and primary and secondary amines.
  • Particularly suitable polar aprotic solvents are ketones, lactones, lactams, in particular N-alkylated lactams, nitriles, tertiary carboxamides, urea derivatives, in particular alkylated urea derivatives, sulfoxides, sulfones, carbonic acid esters, ionic liquids and / or mixtures thereof.
  • ketones are acetone, methyl ethyl ketone, 2-pentanone, 3-pentanone, 2-hexanone, 3-hexanone, cyclohexanone and their C1 to C4 alkylated derivatives.
  • lactones examples include propriolactone, gammabutyrolactone, deltavalerolactone, epsiloncaprolactone and their C1- to C4-alkylated derivatives.
  • lactams are propiolactam, gammabutyrolactam and their C1- to C4-alkylated derivatives.
  • alkylated lactams are N-methyl-propiolactam, N-methyl-2-pyrrolidone and their C1- to C4-alkylated derivatives.
  • nitriles examples include acetonitrile, propionitrile, butyronitrile, valeronitrile and their C1 to C4 alkylated derivatives.
  • tertiary carboxamides such as dimethylformamide, dimethylacetamide, dimethylpropionamide and their C1- to C4-alkylated derivatives.
  • urea derivatives in particular alkylated urea derivatives, are dimethylpropylene urea, tetramethylurea and their C1 to C4 alkylated derivatives.
  • sulfoxides are dimethyl sulfoxide, ethyl methyl sulfoxide, diethyl sulfoxide and their C1 to C4 alkylated derivatives.
  • sulfones are sulfolane, ethylmethyl sulfone and their C1 to C4 alkylated derivatives.
  • carbonic acid esters are dimethyl carbonate, ethylene carbonate, propylene carbonate, 1,2-butylene carbonate, 1,3-butylene carbonate and their C1 to C4 alkylated derivatives.
  • the polar aprotic solvent is preferably selected from the group consisting of acetonitrile, dimethylformamide, dimethylacetamide, tetrahydrofuran, dimethyl sulfoxide, acetone, gammabutyrolactone, N-methyl-2-pyrrolidone, tetramethylurea, dimethylpropyleneurea, sulfolane, dimethyl carbonate ionic liquids and mixtures thereof
  • the polar aprotic solvent is selected from the group consisting of dimethylacetamide, dimethyl sulfoxide, acetonitrile, ionic liquids and mixtures thereof.
  • Polar aprotic solvents that are a mixture of an ionic liquid and at least one of acetonitrile, dimethylformamide, dimethylacetamide, tetrahydrofuran, dimethyl sulfoxide, acetone, gammabutyrolactone, N-methyl-2-pyrrolidone, tetramethylurea, dimethylpropyleneurea, sulfolane, dimethyl carbonate and contain ethylene ionic liquid.
  • the polar aprotic solvent can contain one or more ionic compounds, for example salts, inorganic salts and / or ionic liquids, or in particular consist of one or more ionic liquids.
  • Inorganic salts are, for example, lithium fluoride, lithium chloride, lithium bromide, lithium iodide, sodium fluoride, sodium chloride, sodium bromide, sodium iodide, potassium fluoride, potassium chloride, potassium bromide or potassium iodide, in particular lithium chloride or lithium bromide and mixtures thereof.
  • Inorganic salts can be present in an amount of 1 to 10% by weight, 3 to 8% by weight or 4 to 6% by weight, based in each case on the total amount of polar aprotic solvent and inorganic salt or inorganic salts.
  • a polar aprotic solvent can be, for example, dimethylacetamide containing 5% by weight of lithium chloride.
  • the polar aprotic solvent contains an ionic liquid. Suitable ionic liquids are described in detail below.
  • the polar aprotic solvent is preferably a mixture of an ionic liquid and at least one of dimethylacetamide, dimethyl sulfoxide and acetonitrile.
  • the polar aprotic solvent is a mixture of an ionic liquid and dimethylacetamide or dimethyl sulfoxide.
  • the polar aprotic solvent is a mixture of an ionic liquid and dimethylacetamide.
  • the polar aprotic solvent is a mixture of an ionic liquid and dimethyl sulfoxide.
  • polar aprotic solvents can be used to produce mixtures, in particular solutions, with the most varied of polymers.
  • many poorly soluble polymers in particular polymers containing at least one polar group, can dissolve well in these polar aprotic solvents.
  • the polar aprotic solvent contains one or more ionic compounds, polymers containing at least one polar group, in particular cellulose, can be better dissolved in them.
  • mixtures, in particular solutions with a content of, for example, 0.5 wt.%, 1 wt.%, 2 wt.%, 3 wt.%, 4 wt.%, 5 wt.%, 6 wt.
  • the polar aprotic solvent can contain or consist of one or more ionic liquids.
  • Particularly suitable ionic liquids are organic salts, the ions of which hinder the formation of a stable crystal lattice through charge delocalization and steric effects.
  • Ionic liquids have the particular advantage that many poorly soluble polymers such as cellulose dissolve well in them. Furthermore, ionic liquids can be modified well and thus adapted to different requirements.
  • the polar aprotic solvent contains an ionic liquid
  • the ionic liquid contains in particular a cation selected from a 1,3-dialkylimidazolium cation, an alkylpyridinium cation, a tetraalkylammonium cation and a phosphonium cation, and an anion selected from fluoride, chloride, bromide, iodide, formate, Acetate, propionate, butyrate, hydrogen sulfate, tosylate, trifluoromethanesulfonate, bis (trifluoromethanesulfonyl) imide, hexafluorophosphate, tetrafluoroborate, benzoate, glycolate, thioglycolate, lactate and glycinate, or it consists of them.
  • the ionic liquid preferably contains a dialkylimidazolium cation and an anion selected from chloride, bromide and acetate, or it consists of these.
  • the alkyl groups of the dialkylimidazolium cation can in particular be identical or different.
  • the alkyl groups of the dialkylimidazolium cation can in particular be C1 to C10, in particular C1 to C5 alkyl groups.
  • the alkyl groups of the dialkylimidazolium cation independently of one another, can preferably be selected from the group consisting of methyl, ethyl, propyl and butyl.
  • the ionic liquid contains 1-butyl-3-methylimidazolium chloride and / or 1-butyl-3-methylimidazolium acetate or consists thereof.
  • the cations and anions listed above have the particular advantage that many polymers, in particular also sparingly soluble polymers such as cellulose, are readily soluble in ionic liquids that contain or consist of these cations and anions.
  • the acetate anion in particular has the advantage that the pH value of fiber-containing materials with an acidic pH value is brought into contact with a mixture in which the polar aprotic solvent contains an ionic liquid containing acetate anions can be raised. This is particularly important when processing paper, since by increasing the pH value in the paper, the degradation of the cellulose fibers can be slowed down or even prevented.
  • the mixture containing at least one polymer and a polar aprotic solvent is preferably a homogeneous mixture, in particular a solution.
  • the polymer in the mixture can be partially dissolved or swollen by the polar aprotic solvent.
  • Providing a mixture containing a polar aprotic solvent has the advantage, inter alia, that mixtures, in particular solutions, with a low viscosity can be obtained.
  • Such mixtures, in particular solutions are particularly suitable for processing fiber-containing materials, in particular cellulose-containing materials such as paper.
  • the mixture, in particular the solution with which the fiber-containing material to be processed is brought into contact can in particular have a viscosity of 0.01 to 100 mPas, preferably 0.1 to 70 mPas, preferably 0.5 to 50 mPas, more preferably 1 to 30 mPas, even more preferably 1 to 15 mPas.
  • Mixtures, in particular solutions, with such viscosities are particularly suitable for processing fiber-containing materials, especially cellulose-containing materials such as paper, since they can penetrate deep into the fiber-containing material and thus not only allow superficial deposition of the polymer.
  • Methods for determining the viscosity of mixtures, in particular of solutions are known to the person skilled in the art.
  • the viscosity can be determined at 25 ° C. using a "Gemini" rotary viscometer from Bohlin.
  • the fiber-containing material in particular paper
  • the fiber-containing material can be sprayed or coated with the mixture, or the fiber-containing material, in particular paper, can be soaked in the mixture.
  • the fiber-containing material is advantageously soaked in the mixture. If the fiber-containing material is soaked in the mixture, this can be for a period of 0.1 to 10 minutes, in particular 0.2 to 8 minutes, 0.2 to 7 minutes, 0.4 to 6 minutes, 0.5 to 5 minutes Minutes, 0.5 to 4 minutes, 0.5 to 3 minutes, or 0.5 to 2 minutes.
  • the at least one polymer can penetrate well into the fiber-containing material, so that it can easily attach itself to the fibers of the material.
  • the soaked fiber-containing material can then be rinsed off with a polar aprotic solvent, in particular with dimethylacetamide and / or dimethyl sulfoxide, in particular for a period of 10 to 60 seconds, 20 to 50 seconds or 25 to 40 seconds. Rinsing can remove excess polymer.
  • the method according to the invention comprises the step of treating the mixture of the fiber-containing material and the mixture containing at least one polymer and a polar aprotic solvent, so that at least part of the polymer is deposited on the fibers of the material.
  • the mixture can be treated in different ways.
  • the treatment of the mixture in step c. is selected from bringing the mixture into contact with a non-polar solvent.
  • ionic compounds are salts or polymers with at least one ionic side group.
  • Salts consist in particular of at least one cation and at least one anion, it being possible for the cation to be selected from cations which are selected from metals from the group consisting of Li, Na, K, Rb, Cs, Be, Mg, Ca, Sr, Ba , Sc, Y, La, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Re, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag , Au, Zn, Cd, Hg, Al, Ga, In, Tl, Ge, Sn, Pb, and wherein the anion can be selected from anions which are derived from elements of the group consisting of F, Cl, Br, I , O, S, Se, Te.
  • cations are ammonium ions.
  • anions are hydride, hydroxide, phosphates, phosphites, sulfates, sulfites, sulfides and carboxylates such as formate, acetate, propionate, salicylate and benzoate.
  • the salt can in particular contain ammonium sulfate or potassium sulfate or a mixture thereof.
  • polymers with ionic side groups are polymers with at least one deprotonated acid group, in particular a deprotonated carboxyl group such as deprotonated polyacrylate, deprotonated polymethacrylate, polymers with at least one quaternary ammonium compound such as quaternized polydimethylaminoethyl methacrylate.
  • the mixture can be brought into contact with the ionic compound by adding the salt directly or in the form of a solution, in particular an aqueous solution.
  • non-ionic compounds are water, alcohols such as methanol, ethanol, propanol, butanol, octane, nonane, isocyanate-containing compounds, hydrocarbons with 1 to 20, in particular 5 to 18, carbon atoms, polymers such as polyethers, polyesters, polyamides, polyurethanes. This can be done directly with the in step b. obtained mixture are brought into contact, for example by adding the respective nonionic compound.
  • acids are hydrochloric acid, sulfuric acid, nitric acid, carboxylic acids having 1 to 20, in particular 1 to 10, carbon atoms, in particular formic acid, acetic acid, propionic acid and benzoic acid, and mixtures thereof.
  • the acid be selected from hydrochloric acid and carboxylic acids having 1 to 10 carbon atoms. This can be done directly with the in step b. obtained mixture are brought into contact, for example by adding the respective acid, or by dipping the mixture in acid. The acid can be concentrated or diluted, for example as a dilute aqueous solution.
  • bases examples include hydroxide bases such as sodium hydroxide, potassium hydroxide, calcium hydroxide, amine bases such as primary amines, secondary amines, tertiary amines, in particular triethylamine, pyridine and dimethylaminopyridine and mixtures thereof.
  • hydroxide bases such as sodium hydroxide, potassium hydroxide, calcium hydroxide
  • amine bases such as primary amines, secondary amines, tertiary amines, in particular triethylamine, pyridine and dimethylaminopyridine and mixtures thereof.
  • the respective base can also be used as a solution, in particular as an aqueous solution, with the in step b. obtained mixture are brought into contact, for example by adding a solution, or by immersing the mixture in the solution.
  • polar solvents are water and alcohols such as methanol, ethanol, propanol and butanol, primary and secondary amines, carboxylic acids and mixtures thereof.
  • the polar solvent can be water, an alcohol or a mixture thereof. This can be done directly with the in step b. obtained mixture are brought into contact, for example by adding the polar solvent, or by immersing the mixture in the polar solvent.
  • non-polar solvents are hydrocarbons with 5 to 16 carbon atoms, benzene, toluene, pentane, hexane, heptane, cyclohexane, carbon tetrachloride, tetrachloroethene, trichloroethene, carbon disulfide, tetramethylsilane and hexamethyldisiloxane.
  • the non-polar solvent can in particular be hexamethyldisiloxane. This can be done directly with the in step b. obtained mixture are brought into contact, for example by adding the polar solvent, or by dipping the mixture into the non-polar solvent.
  • Solvent mixtures include, in particular, mixtures of the aforementioned polar and non-polar solvents, in particular mixtures of hexamethyldisiloxane with other solvents such as ethanol, methanol, propanol and butanol. This can be done directly with the in step b. obtained mixture are brought into contact, for example by adding the solvent mixture, or by the mixture is immersed in the solvent mixture. In the case of freeze-drying, the mixture from step b. are first quick-frozen and then dried at temperatures equal to or less than 0 ° C by applying a vacuum.
  • the temperature can in particular be lowered to below the temperature at which the polymer is poorly or no longer soluble in the polar aprotic solvent.
  • the temperature decrease can include a decrease to temperatures from -5 ° C to 15 ° C, in particular 0 ° C to 10 ° C.
  • the temperature can be increased so that the polar aprotic solvent evaporates completely and leaves the polymer on the fibers of the material.
  • the evaporation can be carried out at temperatures from 50 ° C to 250 ° C, in particular from 70 ° C to 200 ° C.
  • the temperature can be increased to temperatures from 50 ° C. to 200 ° C., in particular from 70 ° C. to 150 ° C.
  • the temperature increase can take place gradually or suddenly.
  • the pressure reduction can take place at pressures from 0.1 mbar to 900 mbar, in particular from 1 mbar to 800 mbar, 10 mbar to 700 mbar or 50 mbar to 500 mbar.
  • the reduction in pressure can in particular be combined with the increase in temperature and the decrease in temperature.
  • the lowering of the temperature can also, in particular, involve bringing into contact with an ionic compound, bringing into contact with a non-ionic compound, bringing into contact with an acid, bringing into contact with a base, bringing into contact with a polar solvent , bringing into contact with a non-polar solvent and bringing into contact with a solvent mixture.
  • the treatment of the mixture in step c preferably comprises. bringing into contact with a non-polar solvent, in particular immersion in a non-polar solvent, in particular hexamethyldisiloxane, or consists of it.
  • a non-polar solvent in particular immersion in a non-polar solvent, in particular hexamethyldisiloxane, or consists of it.
  • Optimal results have been achieved when the mixture of the fiber-containing material and the mixture containing at least one polymer and a polar aprotic solvent was brought into contact with hexamethyldisiloxane, in particular immersed in hexamethyldisiloxane.
  • the aforementioned treatment options allow the polymer to accumulate on the fibers of the material containing fibers. Better results were achieved if the deposition took place as slowly as possible.
  • This can be achieved in particular by treating the mixture of the fiber-containing material and the mixture containing at least one polymer and a polar aprotic solvent for at least 15 seconds, in particular 30 seconds, 1 minute, 5 minutes, 15 minutes, 30 minutes Minutes, 45 minutes, 1 hour, 5 hours, 10 hours, 15 hours or 24 hours and at most for a period of 150 hours, in particular 144 hours, 120 hours, 100 hours, 96 hours, 90 hours or 85 hours.
  • Optimal results have been obtained when the treatment in step c. takes place over a period of 24 to 85 hours, in particular 50 to 80 hours or 65 to 75 hours or 72 hours. This results in a slow accumulation of the polymer on the fibers of the material containing fibers.
  • the mixture of the fiber-containing material and the mixture containing at least one polymer and a polar aprotic solvent is advantageously treated by bringing it into contact with a non-polar solvent, in particular immersion in a non-polar solvent, in particular hexamethyldisiloxane, over a period of 65 to 75 hours , especially 72 hours.
  • the method according to the invention can preferably also be used after the treatment in step c. the additional step of drying the in step c. obtained fibrous material comprise.
  • the fiber-containing material obtained in the process according to the invention is preferably carried out at 20 ° C to 100 ° C, in particular 30 ° C to 90 ° C, 40 ° C to 80 ° C, or 45 ° C to 65 ° C. This is done in step c.
  • fiber-containing material obtained by the process according to the invention is preferably dried for 1 to 25 hours, in particular for 5 to 20 hours, 8 to 16 hours, 9 to 15 hours, 10 to 14 hours or 11 to 13 hours.
  • the method according to the invention can also be carried out prior to step a. comprise the further step that the material containing fibers, in particular paper, is predried at a temperature of 40 to 80 ° C., in particular 45 to 70 ° C. or 45 to 65 ° C.
  • the predrying can take place for a period of 1 minute to 60 hours, in particular 1 hour to 50 hours or 12 to 48 hours.
  • the mixture containing at least one polymer and a polar aprotic solvent can be produced in different ways.
  • the mixture can be prepared at room temperature or at a lower or higher temperature, for example at 10 ° C to 150 ° C.
  • the mixture can also be prepared in several steps.
  • the polar aprotic solvent contains an ionic liquid or the polar aprotic solvent is a mixture of an ionic liquid and at least one of acetonitrile, dimethylformamide, dimethylacetamide, tetrahydrofuran, dimethyl sulfoxide, acetone, gammabutyrolactone, N-methyl-2-pyrrolidone, tetramethylurea, dimethylpropylene urea , Sulfolane, dimethyl carbonate and ethylene carbonate, in particular at least one of dimethylacetamide, dimethyl sulfoxide and acetonitrile
  • the mixture containing at least one polymer and a polar aprotic solvent can be prepared in particular by first dissolving the polymer in the ionic liquid and then dissolving the resulting solution with at least one of acetonitrile, dimethylformamide, dimethylacetamide, tetrahydrofuran, dimethyl sulfoxide, acetone, gamm
  • the ionic liquid can first be mixed with at least one of acetonitrile, dimethylformamide, dimethylacetamide, tetrahydrofuran, dimethyl sulfoxide, acetone, gammabutyrolactone, N-methyl-2-pyrrolidone, tetramethylurea, dimethylpropyleneurea, sulfolane, dimethyl carbonate and ethylene carbonate and then mixed with the, especially dimethyl sulfoxide desired amount of the polymer can be added.
  • the mixture containing at least one polymer and a polar aprotic solvent can in particular 1 to 30% by weight, in particular 3 to 30% by weight, 5 to 30% by weight, 10 to 30% by weight, 12 to 25% by weight or 15% by weight Up to 20% by weight or 17 to 19% by weight of ionic liquid, based in each case on the total weight of the mixture. Mixtures with the abovementioned contents of ionic liquids can be easily produced; in particular, solutions can be obtained in this way that allow the fiber-containing material to be processed effectively.
  • the mixing, in particular the swelling, dissolving or dissolving, of the polymer and / or the subsequent dilution can take place at temperatures from 10 ° C. to 150 ° C., in particular from 20 ° C. to 140 ° C., 30 ° C. to 130 ° C., 40 ° C. ° C to 120 ° C, 50 ° C to 110 ° C or 60 ° C to 100 ° C be performed.
  • a mixture in particular a solution, with a concentration of the polymer of 5 to 20% by weight, in particular 7 to 15% by weight, 8 to 13% by weight or 9 to 11% by weight, can be obtained in each case based on the total weight of the polymer and the ionic liquid in which the ionic liquid is produced.
  • This solution can then in particular with at least one of acetonitrile, dimethylformamide, dimethylacetamide, tetrahydrofuran, dimethyl sulfoxide, acetone, gammabutyrolactone, N-methyl-2-pyrrolidone, tetramethylurea, dimethylpropyleneurea, sulfolane, dimethyl carbonate and ethylene carbonate, in particular at least one of dimetonethylsulfamide, dimetonethyl sulfoxide, and in particular at least one of dimetonethylsulfamide , can be diluted to the desired concentration.
  • the ionic liquid can also be mixed with at least one of acetonitrile, dimethylformamide, dimethylacetamide, tetrahydrofuran, dimethyl sulfoxide, acetone, gammabutyrolactone, N-methyl-2-pyrrolidone, tetramethylurea, dimethylpropyleneurea, sulfolane, dimethyl carbonate, especially dimethyl carbonate, with a concentration of the ionic liquid of 1 to 30% by weight, in particular 3 to 30% by weight or 5 to 30% by weight or 10 to 30% by weight or 12 to 25% by weight or 15 to 20% by weight or 17 to 19% by weight, based in each case on the total weight of the mixture, in particular the ionic liquid and dimethyl sulfoxide, are mixed.
  • the polymer can then be added to this solution in the desired amount.
  • the mixture containing at least one polymer and a polar aprotic solvent can be produced in a simple manner. Furthermore, the concentration of the polymer in the mixture can be adjusted well in this way.
  • the mixture containing at least one polymer and a polar aprotic solvent advantageously contains 0.1 to 10% by weight, in particular 0.5 to 8% by weight or 1 to 5% by weight, based in each case on the total weight of the mixture, of polymer. Solutions with these concentrations have in particular a suitable viscosity for the method according to the invention.
  • a material containing fibers, in particular paper, can be obtained by the process according to the invention.
  • a system comprising at least two materials containing fibers can be obtained by the method according to the invention, in particular a book.
  • the materials of the system can be the same or different.
  • the materials containing fibers can have been processed simultaneously or at different times by the method according to the invention.
  • the system can furthermore also comprise materials, in particular materials containing fibers, which have not been processed with the method according to the invention.
  • the system can in particular be a book, a booklet, a magazine or a newspaper.
  • the material containing fibers can in particular be paper.
  • a book in particular can contain further material containing fibers, in particular cardboard, cardboard, textiles or wood.
  • the system contains materials containing different fibers, these can be processed separately or together using the method according to the invention.
  • the paper can be processed separately from the rest of the book, in particular separately from the cover.
  • the book can, however, also be edited without first separating any components, especially with its cover. Whether the components are processed separately can be decided in particular on the basis of the way in which the materials containing fibers are held together in the system, in particular in the book. Examples of ways in which the fiber-containing materials in the system can be held together include thread stitching and adhesive binding.
  • the invention also relates to the use of a mixture containing at least one polymer and a polar aprotic solvent for processing material containing fibers, in particular paper, in the process according to the invention.
  • the invention also relates to the use of dimethyl sulfoxide as an antioxidant for processing paper in the process according to the invention.
  • the invention also relates to the use of an ionic liquid containing a quaternary ammonium cation, in particular an ionic liquid containing a dialkylimidazolium cation, in particular 1-butyl-3-methylimidazolium chloride or 1-butyl-3-methylimidazolium acetate, as an antimicrobial agent for processing paper, in the process according to the invention.
  • an ionic liquid containing a quaternary ammonium cation in particular an ionic liquid containing a dialkylimidazolium cation, in particular 1-butyl-3-methylimidazolium chloride or 1-butyl-3-methylimidazolium acetate, as an antimicrobial agent for processing paper, in the process according to the invention.
  • BMIM-Cl 1-butyl-3-methylimidazolium chloride
  • BMIM-OAc 1-butyl-3-methylimidazolium acetate
  • Viscose danufil, 3.3 dtex / 0.3 mm, hereinafter: "Danufil”
  • DMAc Dimethylacetamide
  • DMSO Dimethyl sulfoxide
  • HMDO Hexamethyldisiloxane
  • MCC microcrystalline cellulose
  • ENO PINE ECF Pulp
  • Stora Enso Oyj alpha-cellulose, Sigma-Aldrich.
  • Example 1 processing of paper with viscose in a mixture of DMAc and BMIM-OAc
  • a solution containing 10% by weight of Danufil in BMIM-OAc was produced, which was then diluted to a viscose content of 2% by weight, based on the total weight of the solution, by adding DMAc, the solution of BMIM-OAc and DMAc 18% by weight BMIM-OAc and 82% by weight DMAc, each based on the weight of BMIM-OAc and DMAc.
  • the viscosity of the solution was 10 mPa ⁇ s.
  • the paper to be processed was soaked in the prepared solution for one minute and then rinsed with DMAc for 30 seconds.
  • Table 2 shows that the breaking force, the elongation at break and the pH value when using mixtures containing viscose and mixtures of BMIM-OAc and DMAc can be significantly increased by the processing according to the invention compared to unprocessed paper.
  • the processed paper was visually and haptically equivalent to unprocessed paper. In particular, no bleeding of the ink or the printing inks was observed.
  • Example 2 processing of paper with viscose in a mixture of DMAc and BMIM-Cl
  • a solution containing 10% by weight of Danufil in BMIM-CI was prepared, which was then diluted by adding DMAc to a viscose content of 2% by weight, based on the total weight of the solution, the solution being made up of BMIM-CI and DMAc 18% by weight BMIM-CI and 82% by weight DMAc, each based on the weight of BMIM-CI and DMAc.
  • the viscosity of the solution was 10 mPa ⁇ s.
  • the paper to be processed was then soaked in the prepared solution for one minute and then rinsed with DMAc for 30 seconds.
  • Table 3 shows that the breaking force and elongation at break when using mixtures containing viscose and mixtures of BMIM-CI and DMAc can be significantly increased by the processing according to the invention compared to unprocessed paper.
  • the processed paper was visually and haptically equivalent to unprocessed paper. In particular, no bleeding of the ink or the printing inks was observed. Furthermore, the pH of the processed paper increased.
  • a solution containing 2% by weight of microcrystalline cellulose in DMAc (containing 5% by weight of LiCl, based on the total weight of LiCl and DMAc), based on the total weight of the solution, was prepared.
  • the viscosity of the solution was 13 mPa ⁇ s.
  • the paper to be processed was then soaked in the prepared solution for five minutes.
  • the paper obtained in this way was then immersed in HMDO (500 g) for 72 hours, as a result of which the viscose attached to the paper fibers. After treatment in HMDO, the paper was heated at 55 ° C for 12 hours.
  • Table 4 shows that the breaking force and elongation at break when using mixtures containing MCC and DMAc (containing 5% by weight LiCl) are significantly higher due to the processing according to the invention compared to paper that has not come into contact with a polymer such as MCC .
  • the processed paper was visually and haptically equivalent to unprocessed paper. In particular, no bleeding of the ink or the printing inks was observed.
  • Test papers were soaked with a solution according to Example 1, MCC being used instead of viscose. After soaking in the solution, the papers were rinsed with DMAc as in Example 1 and immersed in the solvents listed in Table 5 for the specified duration.
  • Table 5 Treatments sample Solvent (duration of impregnation) Test paper 4 HMDO (72 h) Test paper 5 5 wt.% EtOH / 95 wt.% HMDO (24 h) Test paper 6 EtOH ( ⁇ 1 min)
  • test papers 4 to 6 After being immersed in the solvents listed in Table 5, the test papers 4 to 6 were heated at 55 ° C. for 12 hours. While test paper 4 had a matt appearance, was flexible and was still stable even after being folded several times, test papers 5 and 6 partly showed a gloss. This suggests that in test paper 4 the MCC accumulated on the paper fibers as above, while in test papers 5 and 6 an inhomogeneous, rather superficial accumulation of the MCC took place.
  • the duration of the treatment and the accumulation of the polymer can thus be influenced by the choice of treatment, in particular by the choice of the solvent in which the dipping is carried out.
  • Test papers were first soaked in the solution for five minutes. The test papers obtained in each case were then immersed in HMDO (500 g) for 72 hours, as a result of which the polymers indicated in Table 6 were attached to the paper fibers. After the treatment in HMDO, the test papers were heated at 55 ° C. for 12 hours. The breaking force and elongation at break of the processed papers were then determined.
  • the reference sample in Table 6 was soaked in a mixture of BMIM-CI and DMAc without the polymer for five minutes and then immersed in HMDO for 72 hours and then heated at 55 ° C. for 12 hours. It is noticeable from Table 6 that the breaking force as a result of the processing according to the invention has increased significantly compared to the reference paper, while the elongation at break has decreased somewhat.
  • the abovementioned polymers are therefore suitable for strengthening paper in the process according to the invention.
  • Example 6 (can be combined with deacidification process)
  • Example 7 application of different polymers to deacidified and non-deacidified substrate
  • Tables 8 and 9 show that processing according to the method according to the invention enables, in particular, a higher breaking force to be achieved for deacidified and non-deacidified papers.
  • a higher breaking force for starch, in the case of paper that has not been deacidified, an increase in elongation at break can also be observed (see Table 8).
  • chitin in the case of deacidified paper (see Table 9).
  • Tables 8 and 9 thus show that the mechanical properties of the papers can be improved by the process according to the invention.
  • a solution was prepared according to Example 2. This solution was applied to one side of a wooden board with a brush, rinsed with water and dried for 16 hours at 25 ° C. The surface of the wood shows a clear smoothing of the surface in the processed areas. Varnishes can also be easily applied to the processed areas.
  • Fluorescence-marked cellulose is made of, for example W. Helbert et al. Biomacromolecules 2003, 4, 481-471 , known.
  • the fluorescent marker used was a DTAF marker which is excited at 488 nm, the emission being measured at 515 nm.
  • Two test papers were soaked in this solution for one minute and then rinsed off with DMSO for 30 seconds. The first of these papers (test paper 7) was then immersed for 72 hours in HMDO containing 1% by volume of ethanol (500 g in total).
  • test paper 8 The second of these papers (test paper 8) was immersed in HMDO (500 g) for 72 hours. After the treatment in HDMO or in HMDO / ethanol, the papers were heated at 55 ° C. for 12 hours. A blank sample was also created by first soaking a third test paper (test paper 9) in a mixture of DMSO containing 13% by weight BMIM-OAc but without polymer, then immersing it in HMDO (500 g) for 72 hours and then at 55 ° C was heated for 12 hours. A fourth test paper (test paper 10) that was not processed was used as a reference.
  • Fig. 1 shows a picture of layer 3 of test paper 7. It can be clearly seen that the fibers of the paper stand out against the background with a very high contrast.
  • Fig. 2 shows a photograph of layer 3 of test paper 8. It can be clearly seen that the fibers of the paper stand out against the background with a very high contrast.
  • Fig. 3 shows a photograph of layer 3 of the reference. The cellulose fibers can be distinguished from the background, but do not stand out from the background as well as in Fig. 1 and Fig. 2 .
  • Fig. 4 shows a photograph of layer 3 of the blank sample. Here, too, the cellulose fibers can be distinguished from the background, but do not stand out from the background in such a high contrast as in Fig. 1 and Fig. 2 .
  • the figures are consistent with an accumulation of the fluorescence-labeled cellulose from the mixture on the fibers of the paper.
  • the paper fibers were thus coated with fluorescence-marked cellulose, which strengthened the paper fibers and thus the paper.
  • a solution containing 1% by weight of alpha-cellulose in a mixture of DMSO and BMIM-OAc, the DMSO containing 6.5% by weight of BMIM-OAc, and a solution containing 2% by weight of alpha-cellulose in a mixture were produced from DMSO and BMIM-OAc, the DMSO containing 11.3% by weight of BMIM-OAc.
  • the middle part of the book was then placed in a vessel, fanned out, after which the vessel was filled with the above-described solution containing 1% by weight of alpha-cellulose and closed.
  • the middle part of the book would be soaked in the solution for 1 minute.
  • the middle part of the book was fanned out in a second vessel and rinsed with DMSO for 30 seconds.
  • the middle part of the book was fanned out and placed in a third vessel, after which the vessel was filled with HMDO and sealed.
  • the middle part of the book was removed, 6 hours at 55 ° C and dried over orange gel in a desiccator for a week.
  • the upper part of the book was processed like the middle part of the book with the difference that instead of the solution containing 1% by weight of alpha-cellulose, the solution containing 2% by weight of alpha-cellulose was used.
  • the lower part of the book was not edited and served as a reference.
  • the cover sheet which is the sheet that forms the first and last pages
  • a center sheet which in this case is the sheet that forms the 4th page from the front and the 4th page from the back
  • the inner leaf which is the arch that forms the two innermost pages. None of the constituent parts of the parts of the edited book were impaired by the editing according to the invention. The color impression was almost unchanged.
  • the mechanical properties of the various components of the edited book as well as the reference are listed in Tables 10 (1% by weight alpha-cellulose) and 11 (2% by weight alpha-cellulose).
  • Tables 10 and 11 show for all components of the processed parts of the book more than a doubling of both the breaking force and the breaking elongation compared to the non-processed reference. Books can thus be processed as a whole using the method according to the invention.
  • a solution containing 1% by weight of Danufil in a mixture of DMSO and BMIM-Cl, the DMSO containing 9.9% by weight of BMIM-CI (hereinafter: “DMSO solution”), and a solution containing 1% by weight were obtained.
  • DMSO solution a solution containing 1% by weight of Danufil in a mixture of DMAc and BMIM-Cl, the DMAc containing 9.9% by weight of BMIM-CI
  • Test paper 11 was soaked in the DMSO solution for one minute, then rinsed with DMSO for 30 seconds, immersed in HMDO (500 g) for 72 hours and then heated at 55 ° C. for 12 hours.
  • Test paper 12 (blind test without Danufil) was soaked for one minute in DMSO containing 9.9% by weight BMIM-CI, then rinsed with DMSO for 30 seconds, immersed in HMDO (500 g) for 72 hours and then at 55 ° C for Heated for 12 hours.
  • Test paper 13 was soaked in DMSO for 1.5 minutes, then immersed in HMDO (500 g) for 72 hours and then heated at 55 ° C. for 12 hours.
  • Test paper 14 was soaked in the DMAc solution for one minute, then rinsed with DMAc for 30 seconds, immersed in HMDO (500 g) for 72 hours and then heated at 55 ° C. for 12 hours.
  • Test paper 15 (blank test without Danufil) was soaked for one minute in DMAc containing 9.9% by weight of BMIM-CI, then rinsed with DMAc for 30 seconds, immersed in HMDO (500 g) for 72 hours and then at 55 ° C. for Heated for 12 hours.
  • Test paper 16 was soaked in DMAc for 1.5 minutes, then immersed in HMDO (500 g) for 72 hours and then heated at 55 ° C. for 12 hours.
  • test papers 11 to 16 and of the reference were determined and are listed in Table 12 below.
  • Table 12 Mechanical properties of test papers 11 to 13 and the reference Substrate Breaking force [N] Elongation at break [%] Test paper 11 8.1 ⁇ 0.9 0.55 ⁇ 0.10 Test paper 12 5.0 ⁇ 1.6 0.65 ⁇ 0.36 Test paper 13 5.9 ⁇ 1.1 0.55 ⁇ 0.19 Test paper 14 7.1 ⁇ 1.2 0.52 ⁇ 0.11 Test paper 15 5.8 ⁇ 1.0 0.60 ⁇ 0.12 Test paper 16 6.1 ⁇ 1.5 0.59 ⁇ 0.20 reference 3.5 ⁇ 0.64 0.16 ⁇ 0.03
  • Table 12 shows that the test papers 11 and 14 that were brought into contact with a solution containing Danufil had a higher breaking strength than the test papers 12, 13, 15 and 16 and the reference that was not with a solution containing Danufil in Were brought into contact.
  • the elongation at break values of the test papers 11 to 16 differed only slightly.
  • the test papers 11 to 16 had both a significantly increased breaking force and a significantly increased elongation at break, the increase in breaking force in the test papers 11 and 14, in which the test paper was each brought into contact with a solution containing Danufil, turned out to be the highest.
  • This example also shows that the mechanical properties can be improved by machining with the method according to the invention.
  • BMIM-Cl and Danufil to be somewhat more suitable than DMAc in the method according to the invention, especially in combination with BMIM-Cl and Danufil. In terms of elongation at break, no clear difference could be seen between test papers 11 and 14.
  • the above exemplary embodiments show that the mechanical properties of substrates such as paper can be improved by the method according to the invention. Furthermore, the pH of paper can be increased.
  • the method according to the invention is therefore suitable, for example, for the preservation of books.
  • other substrates such as wood can also be subjected to the method according to the invention. In this way, among other things, smoothing of surface unevenness can be achieved, especially with massive material application.
  • various polymers can be used in the process according to the invention.
  • the process according to the invention can be combined with paper deacidification processes such as the papersave process.
  • the method is also suitable for processing books as a whole.

Claims (19)

  1. Procédé de traitement d'un matériau contenant des fibres, le matériau contenant de la cellulose, de la cellulose microcristalline, de la pâte de cellulose, de l'hémicellulose, de la viscose, de la chitine, du chitosane, de l'alginate, de l'amidon, de la lignine, de l'alcool polyvinylique, des protéines ou leurs mélanges, comprenant les étapes suivantes consistant à :
    a. mettre à disposition un mélange contenant
    (i) au moins un polymère choisi dans le groupe constitué par la cellulose, l'alpha-cellulose, la cellulose microcristalline, la pâte de cellulose, l'hémicellulose, la viscose, la chitine, la lignine, le chitosane, l'alginate, l'amidon, la soie, la soie naturelle, les biopolymères de la soie, l'alcool polyvinylique, l'acétate de polyvinyle, les polyuréthanes, les polyamides, les protéines, les polymères ou copolymères à base d'acide acrylique et/ou de ses dérivés esters et/ou amides, l'acide méthacrylique et/ou ses dérivés esters et/ou amides, l'acétate de vinyle, l'acide itaconique, l'acide maléique, l'acide fumarique, l'acide acryloxypropionique, l'acide méthacryloxypropionique, l'acide styrènesulfonique, l'acide éthylméthacrylate-2-sulfonique, l'acide 2-acrylamido-2-méthylpropane sulfonique, le méthacrylate de phosphoéthyle, les éthers de cellulose et leurs mélanges, et
    (ii) un solvant aprotique polaire,
    b. mettre en contact le matériau à traiter avec le mélange mis à disposition à l'étape a. pour obtenir un mélange du matériau et du mélange mis à disposition à l'étape a,
    c. traiter le mélange obtenu à l'étape b. de manière à ce qu'au moins une partie du polymère se fixe sur les fibres du matériau,
    caractérisé en ce que le traitement du mélange à l'étape c. comprend ou consiste à mettre le mélange en contact avec un solvant non polaire.
  2. Procédé selon la revendication 1, caractérisé en ce que le matériau est un matériau contenant de la cellulose, en particulier du papier, du carton, des textiles ou du bois, en particulier du papier.
  3. Procédé selon l'une des revendications précédentes, caractérisé en ce que le polymère est choisi dans le groupe constitué par la cellulose, l'alpha-cellulose, la cellulose microcristalline, la pâte de cellulose, la viscose et leurs mélanges.
  4. Procédé selon l'une des revendications précédentes, caractérisé en ce que le polymère est de la viscose, en particulier de la viscose sensiblement non dérivatisée.
  5. Procédé selon l'une des revendications précédentes, caractérisé en ce que le solvant aprotique polaire est choisi dans le groupe constitué par l'acétonitrile, le diméthylformamide, le diméthylacétamide, le tétrahydrofuranne, le diméthylsulfoxyde, l'acétone, la gamma-butyrolactone, la N-méthyl-2-pyrrolidone, la tétraméthylurée, la diméthylpropylène-urée, le sulfolane, le carbonate de diméthyle, le carbonate d'éthylène, les liquides ioniques et leurs mélanges.
  6. Procédé selon l'une des revendications précédentes, caractérisé en ce que le solvant aprotique polaire est choisi dans le groupe constitué par le diméthylacétamide, le diméthylsulfoxyde, l'acétonitrile, les liquides ioniques et leurs mélanges.
  7. Procédé selon l'une des revendications précédentes, caractérisé en ce que le solvant aprotique polaire contient un liquide ionique.
  8. Procédé selon l'une des revendications précédentes, caractérisé en ce que le solvant aprotique polaire est un mélange d'un liquide ionique et d'au moins un composé parmi le diméthylacétamide, le diméthylsulfoxyde et l'acétonitrile.
  9. Procédé selon l'une des revendications 5 à 8, caractérisé en ce que le liquide ionique contient ou est constitué d'un cation choisi parmi un cation 1,3-dialkylimidazolium, un cation alkylpyridinium, un cation tétraalkylammonium et un cation phosphonium, et d'un anion choisi parmi le fluorure, le chlorure, le bromure, l'iodure, le formiate, l'acétate, le propionate, le butyrate, le sulfate d'hydrogène, le tosylate, le trifluorométhanesulfonate, le bis(trifluorométhanesulfonyl)imide, l'hexafluorophosphate, le tétrafluoroborate, le benzoate, le glycolate, le thioglycolate, le lactate et le glycinate.
  10. Procédé selon l'une des revendications 5 à 9, caractérisé en ce que le liquide ionique contient ou est constitué d'un cation dialkylimidazolium et d'un anion choisi parmi le chlorure, le bromure et l'acétate.
  11. Procédé selon l'une des revendications précédentes, caractérisé en ce que la mise en contact avec un solvant non polaire comprend ou consiste en une immersion dans le solvant non polaire, en particulier l'hexaméthyldisiloxane.
  12. Procédé selon l'une des revendications précédentes, caractérisé en ce que le procédé comprend, après le traitement à l'étape c., l'étape supplémentaire consistant à sécher le matériau contenant des fibres obtenu à l'étape c.
  13. Procédé selon l'une des revendications 7 à 12, caractérisé en ce que le mélange contenant (i) au moins un polymère et (ii) un solvant aprotique polaire est préparé en dissolvant d'abord le polymère dans le liquide ionique, puis en diluant la solution ainsi obtenue avec au moins un composé parmi le diméthylacétamide, le diméthylsulfoxyde et l'acétonitrile, en particulier le diméthylacétamide.
  14. Procédé selon l'une des revendications 7 à 13, caractérisé en ce que le mélange contenant (i) au moins un polymère et (ii) un solvant aprotique polaire contient de 1 à 30 % en poids, en particulier de 3 à 30 % en poids ou de 5 à 30 % en poids ou de 10 à 30 % en poids ou de 12 à 25 % en poids ou de 15 à 20 % en poids ou de 17 à 19 % en poids de liquide ionique, dans chaque cas par rapport au poids total du mélange.
  15. Procédé selon l'une des revendications précédentes, caractérisé en ce que le mélange contenant (i) au moins un polymère et (ii) un solvant aprotique polaire contient de 0,1 à 10 % en poids, en particulier de 0,5 à 8 % en poids ou de 1 à 5 % en poids de polymère, dans chaque cas par rapport au poids total du mélange.
  16. Utilisation d'un mélange contenant (i) au moins un polymère et (ii) un solvant aprotique polaire pour le traitement de matériaux contenant des fibres, en particulier du papier, dans un procédé selon l'une des revendications 1 à 15.
  17. Utilisation selon la revendication 16, caractérisée en ce que le solvant aprotique polaire est caractérisé par au moins une caractéristique des revendications 5 à 10 et/ou le polymère est caractérisé par au moins une caractéristique des revendications 3 à 4.
  18. Utilisation de diméthylsulfoxyde comme antioxydant pour le traitement du papier dans un procédé selon l'une des revendications 1 à 15.
  19. Utilisation d'un liquide ionique contenant un cation ammonium quaternaire, en particulier d'un liquide ionique contenant un cation dialkylimidazolium, en particulier le chlorure de 1-butyl-3-méthylimidazolium ou l'acétate de 1-butyl-3-méthylimidazolium, comme agent antimicrobien pour le traitement du papier dans un procédé selon l'une des revendications 1 à 15.
EP17207499.9A 2016-12-20 2017-12-14 Procede pour le traitement de materiaux contenant des fibres Active EP3339508B1 (fr)

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LU93386A LU93386B1 (de) 2016-12-20 2016-12-20 Verfahren zur Bearbeitung von Materialien enthaltend Fasern
EP16205513 2016-12-20

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CN109957993A (zh) * 2019-02-20 2019-07-02 常州苏达欧包装材料有限公司 一种防水抗拉伸砂纸原纸
CN114113361A (zh) * 2021-10-15 2022-03-01 中科院广州化学有限公司 一种萃取纸及其制备方法以及在检测酸性药物中的应用

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US3529925A (en) * 1967-09-25 1970-09-22 Itt Rayonier Inc Process for interfiber bonding of cellulosic fibrous webs
NL8700766A (nl) * 1987-04-01 1988-11-01 Guillaume Petrus Gerardus Mari Werkwijze voor het conserveren van vel- of baanvormig papier alsmede vloeistof ten gebruike daarbij en inrichting voor het uitvoeren daarvan.
US10993437B2 (en) * 2013-06-18 2021-05-04 Chemgreen Innovation Inc. Anti-microbial polymer incorporating a quaternary ammonium group

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