EP0192252B1 - Procédé d'amélioration du "holdout" des couleurs d'impression, laques et masses de revêtement sur des produits en feuille constitués de fibres et de désencrage des fibres ainsi que masse pour la mise en oeuvre du procédé et produits en feuille obtenus - Google Patents

Procédé d'amélioration du "holdout" des couleurs d'impression, laques et masses de revêtement sur des produits en feuille constitués de fibres et de désencrage des fibres ainsi que masse pour la mise en oeuvre du procédé et produits en feuille obtenus Download PDF

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Publication number
EP0192252B1
EP0192252B1 EP86102140A EP86102140A EP0192252B1 EP 0192252 B1 EP0192252 B1 EP 0192252B1 EP 86102140 A EP86102140 A EP 86102140A EP 86102140 A EP86102140 A EP 86102140A EP 0192252 B1 EP0192252 B1 EP 0192252B1
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EP
European Patent Office
Prior art keywords
organophilic complex
complex
paper
organic
coating
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
EP86102140A
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German (de)
English (en)
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EP0192252A1 (fr
Inventor
Guido Prof. Dr. Dessauer
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Institut fuer Papier Zellstoff und Fasertechnik
Original Assignee
INSTITUT fur PAPIER- ZELLSTOFF-UND FASERTECHNIK DER TECHNISCHEN UNIVERSITAT GRAZ
Institut fuer Papier Zellstoff und Fasertechnik
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Priority to AT86102140T priority Critical patent/ATE41684T1/de
Publication of EP0192252A1 publication Critical patent/EP0192252A1/fr
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Publication of EP0192252B1 publication Critical patent/EP0192252B1/fr
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Classifications

    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • 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
    • D21H19/46—Non-macromolecular organic compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
    • B41M5/52—Macromolecular coatings
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/63—Inorganic compounds
    • D21H17/67—Water-insoluble compounds, e.g. fillers, pigments
    • D21H17/69—Water-insoluble compounds, e.g. fillers, pigments modified, e.g. by association with other compositions prior to incorporation in the pulp or paper
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00—Coated paper; Coating material
    • D21H19/36—Coatings with pigments
    • D21H19/38—Coatings with pigments characterised by the pigments
    • D21H19/40—Coatings with pigments characterised by the pigments siliceous, e.g. clays
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
    • B41M5/52—Macromolecular coatings
    • B41M5/5218—Macromolecular coatings characterised by inorganic additives, e.g. pigments, clays
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
    • B41M5/52—Macromolecular coatings
    • B41M5/5227—Macromolecular coatings characterised by organic non-macromolecular additives, e.g. UV-absorbers, plasticisers, surfactants

Definitions

  • the invention relates to a method for improving the holdout of printing inks, lacquers and coating compositions, on fabrics made of fibers, in particular on paper, and for improving the de-inking of the fibers.
  • the printing ink strikes the paper and diffuses, i. H. it spreads out in the paper, which leads to a non-uniform and fuzzy and mostly matt print image.
  • the main reason for the improved color level is seen in the fact that the hydratable, film-forming, colloidal clays contain a considerable proportion of bound water. This water cannot escape at the drying temperatures that are usually used in a paper machine and, because it is immiscible with the solvent of the gravure printing ink, to a certain extent repels the printing ink.
  • the polyglycols like the water, are deposited between the colloidal clays, i.e. they do not form any reaction products, and because of their waxy nature, they improve the satinability after drying. There is no reaction with the organic solvent in which the ink is dissolved or dispersed.
  • the present invention aims to improve the holdout of organic solvent systems such as printing inks, lacquers and coating compositions in other ways.
  • the problem of holdouts is particularly pronounced in gravure printing processes, since gravure printing processes have to have a significantly lower viscosity compared to other printing inks (for high pressure or offset printing).
  • the invention is therefore primarily applicable in the field of gravure printing, which is why the explanations below relate primarily to this field.
  • the sheet-like structures made of fibers to be printed according to the invention are primarily those made of paper, although nonwovens or textiles (e.g. silk, cotton and linen fabrics) can also be printed using the present invention.
  • Gravure is one of the most common types of printing for all types of mass printing.
  • the line of the coated types In order to have a good level of gravure ink on the paper surface, the line of the coated types must have a minimum thickness of about 6.5 to 7 gm 'and page; in the case of gravure paper coated on both sides, this results in a base paper of approximately 36 g m 2 with a total weight of 50 gm '. From today's perspective, this is a lower limit, since it is only the fibers of the coating base paper that contribute to the physical strength values of the printing paper.
  • the uncoated natural rotogravure papers are not equivalent to the coated rotogravure papers neither in the whiteness nor in the gloss of the print products that can be produced.
  • the consumption of gravure printing ink is about two and a half to three times that of the coated paper, because the porosity and thus the absorbency of the gravure printing paper is much greater.
  • the shining through of the print on the back is a particular problem with these papers when the grammage is further reduced.
  • the invention has for its object to treat the surface of fabrics made of fibers, in particular paper, so that the coating composition or printing ink or the lacquer, in particular a low-viscosity gravure printing ink dispersed or dissolved in an organic solvent, as little as possible in the Paper strikes. The less they penetrate, the lower the consumption and the more the gloss of the treated surface (print gloss) is more beautiful.
  • the invention thus primarily relates to a method for improving the holdout of printing inks, lacquers and coating compositions, containing organic solvents, on flat structures made of fibers, in particular on paper, and for improving the de-inking of the fibers by introducing water-insoluble substances into the fiber mass or in the surface of the fiber structure.
  • the organic residue which generally has a molecular weight of less than 1000, is bound to the inorganic layered silicate in an ion formation.
  • the property of the inorganic layered silicate to form a gel in the aqueous phase is obviously important so that the organophilic complex also reacts with the organic solvent and swells to form a gel. Since the organic residue is to be bound to the inorganic layered silicate via ion formation, the inorganic layered silicate expediently has a high ion exchange capacity.
  • the organophilic complex with the organic solvent gives a more or less strong swelling reaction.
  • This swelling reaction is surprisingly strong and also so fast that the capillary forces of the fibrous sheet or a line, in particular a sheet of natural paper, are not effective.
  • the fact that the colors or their binders may possibly also be adsorbed on the particles of the organophilic complex should be of secondary importance, since the holdout behavior of the treated surface for the pure solvent is practically the same as that for the solution or dispersion of the printing ink of the Paint or the coating composition.
  • the organophilic complex for example, a fully hydrated, cation-exchangeable, colloidal film-forming smectic layered silicate with an ion exchange capacity of 50 to 130, preferably 70 to 100 meq / 100 g is used.
  • an exchange of the cations in the vicinity of 100% is preferred.
  • the degree of exchange is preferably about 20 to 6000.
  • Montmorillonite, hectorite, saponite, sauconite, beidellite and or nontronite are preferably used as smectitic layered silicate to produce the organophilic complex.
  • Bentonite which is available as a mineral substance with different exchangeable cations (Na, Ca, Mg) and whose main constituent is montmorillonite, is generally used as a smectitic layered silicate for practical purposes.
  • the organophilic complexes are preferably reaction products of the inorganic sheet silicate with an organic ammonium compound, preferably a quaternary ammonium compound; instead of the quaternary ammonium compound, other organic compounds with a quaternary onium ion, e.g. B. quaternary phosphonium compounds can be used. Further usable organophilic complexes are also the partially reacted complexes of the layered inorganic silicates with quaternary onium compounds.
  • organophilic complexes with partially converted inorganic layered silicates, especially in aqueous dispersions can often still be colloidal solutions.
  • the suitable organophilic complex will become an integral part of the gravure printing ink or the coating composition or the lacquer after drying. This is important for the so-called de-inking, since the organophilic complex separates from the fiber together with the color, the lacquer or the coating material.
  • the wettability of the printing inks is favorably influenced by the oleophilic character of the organic residues of the organophilic complex which face outwards.
  • organic solvents used for dissolving or dispersing printing inks, lacquers, coating compositions or adhesives are suitable as organic solvents.
  • an organic solvent from the group of toluene, xylene or gasoline is preferably used, optionally in a mixture with higher-boiling components.
  • Such components are common in printing technology and serve to influence the evaporation behavior when the printing ink dries.
  • the usual paint solvents such as esters, acetone, alcohols etc. are used for coating compositions.
  • the invention can also be used to improve the holdout of pressure-sensitive adhesive coating compositions.
  • These coating compositions contain sticky resins such as polyacrylates and polyisobutylene, some of which are mixed with plasticizers.
  • Preferred solvents for such coating compositions are those based on hydrocarbons, such as gasoline.
  • the reactive organophilic complex is preferably in the form of a 1.5 to 10% dispersion.
  • the dispersions of the reactive organophilic complexes according to the invention in organic solvents are strongly thixotropic, which is favorable for application, for example in an intaglio printing unit, with an anilox roller.
  • the organophilic complex can either be introduced into the fiber mass or into the surface of the fiber structure.
  • the process according to the invention can be used, in particular for the production of satined papers, in such a way that the reactive organophilic complex is introduced into the suspended fiber mass in aqueous dispersion before the sheet is produced, with or without the fillers.
  • a variant of the process according to the invention is characterized in that the organophilic complex is generated in situ in the fiber mass by reacting the inorganic layered silicate with the organic compound before the fabric is produced.
  • the filler suspension can also be provided instead of the fiber mass (pulp), or fibers and filler are already present as a total.
  • the advantage of generating in situ, e.g. B. in the paper mill, is particularly the fact that the paper machine acts as a dryer for the organophilic complex, so energy is saved. If the two above-mentioned process variants are carried out in the paper mill, the usual fillers can be partially replaced by the organophilic complex. The usual retention aids and other additives, such as paints, can also be used.
  • a process variant which is particularly suitable for the production of coated, highly satinized papers is characterized in that the reactive organophilic complex, optionally with a binder, a surfactant and, or an inert coating pigment, in aqueous suspension in or on the surface of the fabric brings.
  • the usual white pigments which improve the opacity can be used as inert coating pigments, for example.
  • a line or a surface preparation is not expected to contribute to the opacity of a sheet of paper, but if only the print opacity is in the foreground and thus the ink consumption and gloss of the print, then a variant of this process allows the organophilic complex to be in situ in situ generate the surface of the fabric by introducing the inorganic layered silicate into the surface in the form of an aqueous colloidal dispersion which may contain binders, surfactants and / or coating pigments and then reacting it with the organic compound.
  • This is e.g. possible in all those coating machines that have two coating devices on each side, which is common today. Machines with two size presses are also particularly suitable. For example, a film-forming hydrated, highly swellable bentonite is applied in the first size press. A separate binder is not necessary. The dilute solution of a quaternary ammonium compound is then applied in the second size press.
  • the inorganic layered silicate is introduced into the fiber mass in the form of an aqueous colloidal dispersion, which optionally contains binders, surfactants and / or pigments, and then only in the surface reacted with the organic compound to obtain the organophilic complex.
  • aqueous colloidal dispersion which optionally contains binders, surfactants and / or pigments, and then only in the surface reacted with the organic compound to obtain the organophilic complex.
  • aqueous colloidal dispersion which optionally contains binders, surfactants and / or pigments
  • the organophilic complex in situ in the surface can also be produced by reacting the inorganic sheet silicate with the organic compound in the presence of binders, surfactants and / or coating pigments and bringing the reaction product as a coating composition into or onto the surface of the fiber material.
  • a further process variant is characterized in that the reactive organophilic complex, optionally with a binder and / or an inert coating pigment, for.
  • the reactive organophilic complex according to the invention can in principle be applied from the organic solution or dispersion to a so-called solvent coater at high speeds and in the widths of modern paper machines (about 7 to 8 meters).
  • the method according to the invention can advantageously also be carried out in the printing house.
  • a printing unit e.g. a simple screen gravure printing unit, can therefore be used in the process variant described above to produce an invisible form of the organophilic complex, which is dried as usual before the actual gravure begins.
  • the cost of gravure printing is modest if, as is usual, 92 to 96% of the solvent is recovered. Since, according to the invention, the organic dispersant for the organophilic complex is the same as for the solvent for the subsequent printing inks, the joint recovery makes no problems.
  • the pre-stretching unit i.e. the first printing unit used here, can retain its function as such, because the form with the reactive organophilic complex can be printed over the entire surface and without registering.
  • the same or similar organic solvents can be used as dispersants for the reactive organophilic complex and the printing ink (s) or the lacquer or the coating composition.
  • a mass for carrying out the process variants described above is applied to the surface of the fiber structure.
  • This mass is characterized in that it is in the form of a dispersion of a reactive organophilic complex in an aqueous or organic medium.
  • the reactive organophilic complex is preferably in the form of a 1.5 to 10% dispersion, in particular in an organic solvent, such as toluene or xylene. In an aqueous medium, the reactive organophilic complex is preferably in a 2 to 20% dispersion.
  • the invention further relates to flat structures made of fibers, in particular paper, which are characterized in that they contain in the surface and or in the fiber mass a reactive organophilic complex which can be obtained by the process according to the invention.
  • the organophilic complex is in the surface of the sheetlike structures according to the invention, it is preferably finely divided in an amount of 0.1 to 3, preferably 0.2 to 0.8 g / m 'and side. If it is in the fiber mass, it is preferably present in an amount of about 1.5 to 12% by weight.
  • the invention can also e.g. be used for the production of zinc oxide papers.
  • a toluene varnish which is filled with photoconductive zinc oxide and non-conductive binders, is spread on the surface of a conductive base paper.
  • the conductivity of the base paper is obtained by adding a conductive polymer to the size press preparation from starch ethers or starches or from polyvinyl alcohol.
  • the toluene coating behaves analogously to a printing ink. Because of the barrier effect of the reactive organophilic complex in the fiber mass or in the surface of the fiber structure, the toluene lacquer filled with zinc oxide is prevented from penetrating into the fiber mass.
  • the conductive base paper has a flaw, i.e. If toluene is absorbed, a defect in the image reproduction occurs in the surface of the zinc oxide paper.
  • the present invention can also be used to prevent the penetration of lacquers such as nitro lacquer, zapon lacquer, plastic lacquer, spirit lacquer etc. into fiber structures.
  • lacquers such as nitro lacquer, zapon lacquer, plastic lacquer, spirit lacquer etc.
  • label papers are overlaid with a so-called protective label varnish after printing so that the labels on the bottles are scrub-resistant and not unsightly due to the absorption of moisture.
  • a label paper In order for a label paper to be paintable, it usually has to be coated on one side. So-called natural label papers cannot be varnished because the varnish does not remain on the surface but penetrates into the fiber material.
  • the reactive barrier layer of the organophilic complex according to the invention prevents the label lacquer from penetrating into the fiber material.
  • the precoating of a paper surface or another sheet-like fiber structure with the spontaneously reacting organophilic complex materials can make it printable, in particular paintable and coatable from organic solution, for which this was previously no longer possible.
  • this includes the simple wood-containing and wood-free natural papers, including those that are not or hardly filled and that have not been satined.
  • the invention is particularly important for cardboard, where, whether coated or not, every satin finish and smoothing in a smoothing unit leads to an undesirable loss of volume and thus a loss of rigidity.
  • the invention is also suitable for the production of adhesive labels.
  • PSA coatings are made from an organic solution of the adhesives.
  • the impact behavior of the adhesive coating masses in the paper plays an important role. This is because they should hit the paper as little as possible. So far, one has in such cases with expensive size press preparations, such as. As casein or polyvinyl alcohol, tries to improve the holdout.
  • coating with the reactive organophilic complex not only leads to a reduction in the application of pressure-sensitive adhesive, but also enables the use of previously little or unsuitable fabrics, such as nonwovens or textiles. According to the invention, these materials can also be made printable.
  • quaternary ammonium compounds are contained in the organophilic complexes, they influence the electrical properties of the fabrics according to the invention, e.g. the surface or volume resistance. These values play a role in printability.
  • the modification according to the invention reduces the surface and volume resistances and thereby eliminates interference caused by electrostatic charges.
  • a semi-bleached needle sulfate pulp is pulped in a pulper at a consistency of 5% and at a pH of 7 to 7.8 and then brought to a degree of grinding of 26 ° SR (Schopper-Riegler) in a refiner.
  • This pulp is mixed in a ratio 25:75 in a pulping center with a splinter-free wood pulp with a freeness of 78 ° SR.
  • a separately produced kaolin slurry of 40% at a pH of 7 to 7.8 is mixed into the fiber mixture in a ratio of 70 parts of fibers to 30 parts of kaolin (all air dry).
  • a slurry of 3.5 ° o solid of a pre-swollen sodium bentonite with an ion exchange capacity of 90 mVal 100 g is mixed into this total substance until, based on fibers and filler, 4% by weight of the bentonite has been introduced. The whole is mixed well for about 10 minutes.
  • a 4% strength aqueous solution of dimethyl-benzyl-alkyl- (C 12 -C 22 ) -ammonium chloride is then mixed in in an amount equimolar to the complete ion exchange.
  • paper with a basis weight of 40 g / m ' is produced from this substance after dilution to 0.6% on a paper machine and dried to a residual moisture content of 8.5% by weight. Then the paper is satined on a super calender. It has a Bekk smoothness of 900s with a density of 1.10 g / cm 3 . It contains about 5% by weight, based on the total input, of reactive organophilic bentonite. It has a toluene holdout (measured by the spotting method with 0.05 ml of toluene stained with Ceres red) of 65 s compared to 36 for an otherwise identical paper without the organophilic bentonite. The organophilic bentonite adheres well to the fibers and fillers.
  • the small amount of NaCI does not interfere in the wastewater.
  • a commercially available organophilic bentonite coated with quaternary ammonium ions (Tixogel VZ (R) from Süd-Chemie AG) is dispersed for 15 minutes in a high-shear mixer with high shear forces as a dispersion with a solids content of 20% by weight in the presence of a nonylphenol ethoxylate surfactant sheared.
  • This dispersion is admixed to the fibers produced as in Example 1 and then the kaolin slurry is added in an amount such that, based on the total, 6% by weight of the reactive organophilic clay are in the total.
  • a coated rotogravure paper After the line of 7 g m 'and each side, a coated rotogravure paper is produced which has a Bekk smoothness from 1500 to 1600 and a toluene holdout of 65s after the satin finish.
  • a comparable coated rotogravure paper has a toluene holdout of 40 s.
  • Example 1 a wood-containing, kaolin-filled, satined, gravure printing paper without bentonite or quaternary ammonium compound is produced in bulk.
  • a 5% slurry of a commercial bentonite is applied in the first and third coating unit, the exchangeable cations of which consist of 40% Na and 60% Ca cations.
  • the order is about 1.5 gm and side.
  • a 4% solution of the quaternary ammonium compound from Example 1 is applied in the coating units 2 and 4 in the relation given there.
  • This solution reacts by ion exchange in the surface with the bentonite to form the reactive organophilic complex. Since both the hydrated bentonite is film-forming and the reactive organophilic complex forms a film, albeit a weak adhesive, the use of colloidal and / or disperse binders is not necessary.
  • a wood-containing, highly filled paper which has been produced according to EU-PS 0017793 with a film-forming colloidal bentonite, the sodium-magnesium atomic ratio of which was 60:40, and which contains 2.5% by weight of the film-forming bentonite, based on the paper at the end of the drying section of a paper machine, using a conventional size press, treated with the dilute 3% strength aqueous solution of the quaternary ammonium compound from Example 1. Since the fibers and fillers of this paper in any case carry a film of bentonite, albeit a thin one, this occurs in ion exchange with the quaternary ammonium compound and results in the reactive organophilic complex according to the invention being present especially in the surface after renewed drying. The resulting sodium and magnesium chloride does not interfere.
  • So-called solvent coaters are found in many factories that deal with the finishing of paper. These are coating machines that use various organic solvents as solvents or dispersants instead of water and usually recover them from the exhaust air.
  • a wood-containing gravure printing paper with a basis weight of 40 g / m 2 has a filler content of 18% by weight. Its opacity and print opacity are unsatisfactory.
  • a commercial bentonite coated with quaternary ammonium ions (Tixogel VP (R) from Süd-Chemie AG) is in the form of a dispersion with a solids content of 3.5% by weight in a solvent mixture of 99 parts by weight of toluene and 1 Part by weight of ethanol dispersed in a high-shear high-speed mixer for 10 min.
  • This dispersion is applied to both sides of the paper by means of a reverse roll coater, so that 0.5 g / m 'of application (air-dry calculated) results on each side.
  • the pretreated paper has a toluene holdout of 60 s.
  • the print with a black gravure ink shows almost no show through on the back and an increased print gloss.
  • this first printing unit using a screen roller with a 70 screen and an engraving depth of 65 ⁇ m, a colorless pre-printing ink is pre-printed over the entire surface and regardless of registration with a 3% by weight colloidal dispersion in toluene, produced analogously to Example 6.
  • this form applies an order of 0.3 g ' m' to the paper to be printed.
  • the time to strike for colored toluene solutions is about 6 s, it results on the «pre-printed» paper with a coating of 0.3 g.'m 'a value of 70s.
  • a wood-free label paper is made from 60 parts by weight of highly bleached needle sulfate pulp with a freeness of 30 ° SR and 40 parts by weight of bleached birch sulfate pulp with a freeness of 45 ° SR.
  • 10 parts by weight of kaolin, 5 parts by weight of TiO 2 and 5 parts by weight of aluminum hydroxide are added.
  • the paper is taken out with 2.5 parts by weight of resin glue with the addition of a melamine-formaldehyde resin to improve the wet strength at a pH of 4.6 as smooth paper on one side and heated to 136 ° C. at the end of the drying section in order to crosslink the melamine. Ensure formaldehyde resin.
  • This label paper should be coated with a scouring varnish after printing.
  • the label printing is carried out in gravure printing, a dispersion of the reactive organophilic complex according to Example 6 in toluene being pre-printed in the first gravure printing unit.
  • the protective label varnish is applied as a nitro varnish. It does not penetrate the natural printing paper treated according to the invention, although it has not been deleted.
  • a non-coated chromo replacement cardboard with a basis weight of 300 g / m ' was printed with a dispersion according to Example 6 by gravure printing, the dried application being only 0.2 g m'.
  • a nitro lacquer, which would otherwise be knocked off, remains shiny on the pre-treated cardboard.
  • a nonwoven fabric made of 80% polyester fiber and 20% bleached needle sulfate pulp as the dispersing fiber is impregnated with a plastic dispersion of polyacrylic acid ester after it has been placed on a
  • This nonwoven is to be prepared for textile screen printing. Similar to gravure inks, screen printing inks are low-viscosity and contain toluene as a solvent.
  • a conventional coating slip for organic solvents is a 3.5 wt .-% suspension of the organophilic complex according to Example 6, which is blended with a further 5 wt .-% of a fine calcium carbonate and contains a polyvinyl acetate additive of 2 wt .-% , spread. It is advisable to choose the doctor blade coating process so that the large pores of the nonwoven material close.
  • a toluene-containing screen printing ink has a toluene holdout of 10 to about 15s for an untreated nonwoven, the holdout is improved to about 40s by the line.
  • the print gloss that can be achieved is increased and the consumption of screen printing ink is reduced.
  • a swollen Na-Mg-bentonite slurry with 5% by weight solids is mixed into a suspension of bleached needle sulfate pulp of 4.5% by weight consistency and a freeness of 23 ° SR until, based on the pulp, a 10% by weight. -% share is reached.
  • a 3% by weight solution of the quaternary ammonium compound according to Example 1 is prepared in a separate solution vessel.
  • the wood-free paper thus produced according to standard methods has a Bekk smoothness of 1100s, a density of 1.35 g cm 'and a toluene holdout according to the drop method (toluene colored with Ceres red) of 15s compared to 3s for untreated paper at 80g / m 2 .

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Paper (AREA)
  • Coloring (AREA)
  • Medicines Containing Antibodies Or Antigens For Use As Internal Diagnostic Agents (AREA)
  • Medicines That Contain Protein Lipid Enzymes And Other Medicines (AREA)
  • Paints Or Removers (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Artificial Filaments (AREA)

Claims (17)

1. Procédé pour améliorer le pouvoir de non- pénétration d'encres d'imprimerie, de peintures et vernis et de compositions de revêtement, contenant des solvants organiques, dans des structures bidimensionnelles constituées de fibres, en particulier dans du papier, de même que pour améliorer le désencrage des fibres, par introduction de substances insolubles dans l'eau dans la masse fibreuse ou dans la surface de la structure fibreuse, caractérisé en ce qu'on introduit dans la masse fibreuse ou dans la surface de la structure fibreuse un complexe organophile constitué
a) d'un silicate à structure en feuillets, de type smectite, filmogène, pouvant échanger des cations, hydratable, insoluble dans l'eau, présentant un pouvoir d'échange d'ions d'au moins 50 mVal 100g, et
b) d'un radical organique, fixé à ce dernier, et dérivant d'un composé onium,
le complexe organophile formant une couche barrière par réaction avec le solvant organique.
2. Procédé selon la revendication 1, caractérisé en ce qu'on utilise un silicate anionique à structure en feuillets, ayant un pouvoir d'échange d'ions de 50 à 130 mVal/100g, et que, pour produire le complexe organophile, on remplace au moins 20% des cations échangeables par des radicaux organiques.
3. Procédé selon la revendication 1 ou 2, caractérisé en ce qu'on utilise, pour préparer le complexe organophile, de la montmorillonite, de l'hectorite, de la saponite, de la sauconite, de la beidellite etou de la nontronite.
4. Procédé selon l'une des revendications 1 à 3, caractérisé en ce qu'on fait réagir le silicate inorganique à structure en feuillets sur un composé organique de l'ammonium, de préférence un composé de l'ammonium quaternaire.
5. Procédé selon l'une des revendications 1 à 4, caractérisé en ce qu'on utilise un solvant organique appartenant au groupe des solvants pour vernis ou encore au groupe des solvants pour encres d'imprimerie.
6. Procédé selon l'une des revendications 1 à 4, caractérisé en ce qu'on introduit le complexe organophile réactif dans la masse fibreuse en suspension, avant réalisation de la structure bidimensionnelle, en dispersion aqueuse.
7. Procédé selon l'une des revendications 1 à 4, caractérisé en ce qu'on produit le complexe organophile réactif avant de réaliser la structure bidimensionnelle, in situ dans la masse fibreuse, par réaction du silicate inorganique à structure en feuillets sur le composé organique.
8. Procédé selon l'une des revendications 1 à 4, caractérisé en ce qu'on applique dans ou sur la surface de la structure bidimensionnelle, en suspension aqueuse, le complexe organophile réactif, éventuellement avec und liant, un surfactif et ou un pigment de couchage inerte.
9. Procédé selon l'une des revendications 1 à 4, caracterisé en ce qu-on produit le complexe organophile réactif in situ dans la surface de la structure bidimensionnelle, en appliquant dans ou sur la surface le silicate inorganique à structure en feuillets, sous la forme d'une dispersion colloïdale aqueuse contenant éventuellement de liants, des surfactifs et ou des pigments de couchage, puis qu'on le fait réagir sur le composé organique.
10. Procédé selon l'une des revendications 1 à 4, caractérisé en ce qu'on produit le complexe organophile in situ dans la surface de la structure bidimensionnelle en introduisant dans la masse fibreuse le silicate inorganique à structure en feuillets, sous la forme d'une dispersion colloïdale aqueuse contenant éventuellement des liants, des surfactifs etou des pigments, puis qu'on le fait réagir dans la surface, sur le composé organique.
11. Procédé selon l'une des revendications 1 à 4, caractérisé en ce qu'on produit le complexe organophile réactif par la réaction du silicate inorganique à structure en feuillets sur le composé organique en présence de liants, de surfactifs et ou de pigments de couchage, et qu'on applique le produit de réaction, sous la forme d'une composition de couchage, dans ou sur la surface du matériau fibreux.
12. Procédé selon l'une des revendications 1 à 4, caractérisé en ce qu'on applique dans ou sur la surface de la structure bidimensionnelle, dans un solvant organique, en tant que préparation préalable, et à l'aide d'une coucheuse aux solvants, le complexe organophile réactif, éventuellement avec un liant et/ou un pigment de couchage inerte, ce après quoi on applique, après un séchage intermédiaire, la ou les encres d'imprimerie, le vernis ou la composition de revêtement.
13. Procédé selon la revendication 12, caractérisé en ce qu'on utilise comme dispersant du complexe organophile réactif et de la ou les encres d'imprimerie ou du vernis, ou de la composition de revêtement, des solvants organiques identiques ou équivalents.
14. Procédé selon la revendication 12 ou 13, caractérisé en ce qu'on n'applique que partiellement le complexe organophile réactif sur ou dans la surface de la structure bidimensionnelle.
15. Structure bidimensionnelle constituée de fibres, en particulier papier, caractérisé en ce qu'il contient dans sa surface et ou dans la masse fibreuse un complexe organophile réactif pouvant être obtenu selon l'une des revendications 1 à 14.
16. Structure bidimensionnelle selon la revendication 15, caractérisée en ce que le complexe organophile réactif est présent dans la surface en une quantité de 0,1 à 3g;m', de préférence de 0,2 à 0,8 g/ml par face.
17. Structure bidimensionnelle selon la revendication 15, caractérisée en ce que le complexe organophile réactif est présent dans la masse fibreuse en une quantité de 1,5 à 12% en poids.
EP86102140A 1985-02-22 1986-02-19 Procédé d'amélioration du "holdout" des couleurs d'impression, laques et masses de revêtement sur des produits en feuille constitués de fibres et de désencrage des fibres ainsi que masse pour la mise en oeuvre du procédé et produits en feuille obtenus Expired EP0192252B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT86102140T ATE41684T1 (de) 1985-02-22 1986-02-19 Verfahren zur verbesserung des holdouts von druckfarben, lacken und beschichtungsmassen auf flaechengebilden aus fasern sowie zur verbesserung des de-inkings der fasern sowie masse zur durchfuehrung des verfahrens und damit erzeugte flaechengebilde.

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DE3506278 1985-02-22
DE19853506278 DE3506278A1 (de) 1985-02-22 1985-02-22 Verfahren zur verbesserung des holdouts von druckfarben, lacken und beschichtungsmassen auf flaechengebilden aus fasern sowie masse zur durchfuehrung des verfahrens und damit erzeugte flaechengebilde

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EP0192252A1 EP0192252A1 (fr) 1986-08-27
EP0192252B1 true EP0192252B1 (fr) 1989-03-22

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US (1) US4867844A (fr)
EP (1) EP0192252B1 (fr)
JP (1) JPH0718119B2 (fr)
AT (1) ATE41684T1 (fr)
BR (1) BR8600732A (fr)
CA (1) CA1273759A (fr)
DE (2) DE3506278A1 (fr)
DK (1) DK167939B1 (fr)
ES (1) ES8708153A1 (fr)
FI (1) FI84382C (fr)
GR (1) GR860225B (fr)
NO (1) NO171121C (fr)
YU (1) YU26586A (fr)
ZA (1) ZA861316B (fr)

Families Citing this family (32)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3703957A1 (de) * 1987-02-10 1988-08-18 Inst Zellstoff & Papier Verfahren zur herstellung eines fuer die papier- und kartonindustrie geeigneten, die bedruckbarkeit von papier und karton verbessernden mittels auf pigmentbasis, das mittel und seine verwendung
GB8706634D0 (en) * 1987-03-20 1987-04-23 Ecc Int Ltd Paper coating
DE3710849A1 (de) * 1987-04-01 1988-10-20 Henkel Kgaa Verwendung von mit quartaeren ammoniumverbindungen beladenen schichtsilikaten als seifhilfsmittel in seifprozessen zum fixieren von farbstoffen
GB8808552D0 (en) * 1988-04-12 1988-05-11 Ecc Int Ltd Paper coating
JP2504819B2 (ja) * 1988-12-22 1996-06-05 日本製紙株式会社 新聞印刷用紙
US5298064A (en) * 1990-12-06 1994-03-29 Hoechst Aktiengesellschaft Water-containing organophilic phylloisilicates
US5336372A (en) * 1991-05-09 1994-08-09 Rheox, Inc. Process for deinking wastepaper utilizing organoclays formed in situ
DE4137091C2 (de) * 1991-11-12 1995-06-01 Hoechst Ag Wäßrige Feindispersion eines organophilen Schichtsilikates
DE4217779A1 (de) * 1992-05-29 1993-12-02 Sued Chemie Ag Streichpigment
US5389200A (en) * 1993-04-26 1995-02-14 Rheox, Inc. Process for removing inorganic components that form ash on ignition and oily waste from paper during recycling
DE4321376A1 (de) * 1993-06-26 1995-01-05 Hoechst Ag Wäßrige Feindispersion eines organophilen Schichtsilikates
DE4419201A1 (de) * 1994-06-01 1996-01-11 Hoechst Ag Verfahren zur Herstellung einer wäßrigen Feindispersion eines organophilen Schichtsilikates
DE4438306A1 (de) * 1994-10-26 1996-05-02 Sued Chemie Ag Pigmente für Druckträger nach dem Tintenstrahl-Druckverfahren
US5989696A (en) * 1996-02-13 1999-11-23 Fort James Corporation Antistatic coated substrates and method of making same
US5858076A (en) * 1996-06-07 1999-01-12 Albion Kaolin Company Coating composition for paper and paper boards containing starch and smectite clay
GB9703725D0 (en) * 1997-02-22 1997-04-09 Ecc Int Ltd Particulate materials and their uses
DE19753271A1 (de) * 1997-12-01 1999-06-02 Sued Chemie Ag Farbentwicklerpigment für Selbstdurchschreibepapiere
US20050150625A1 (en) * 2000-09-25 2005-07-14 Takashi Ochi Gravure paper
JP2002173895A (ja) * 2000-09-25 2002-06-21 Nippon Paper Industries Co Ltd グラビア印刷用紙
JP2002173892A (ja) * 2000-09-27 2002-06-21 Nippon Paper Industries Co Ltd グラビア印刷用塗工紙
JP4911876B2 (ja) * 2001-12-26 2012-04-04 日本製紙株式会社 印刷用ダル調塗工紙
US6966972B2 (en) * 2002-11-25 2005-11-22 Wausau Paper Corp. Coating composition, paper product having flexible coating and method for manufacturing a paper product
US20070166512A1 (en) * 2004-08-25 2007-07-19 Jesch Norman L Absorbent Release Sheet
US7416767B2 (en) * 2004-09-30 2008-08-26 Graphic Packaging International, Inc. Anti-blocking coatings for PVdc-coated substrates
US7404999B2 (en) * 2004-09-30 2008-07-29 Graphic Packaging International, Inc. Anti-blocking barrier composite
US20070292569A1 (en) * 2005-06-29 2007-12-20 Bohme Reinhard D Packaging material for food items containing permeating oils
US20070000568A1 (en) * 2005-06-29 2007-01-04 Bohme Reinhard D Packaging material for food items containing permeating oils
US8753012B2 (en) 2006-06-29 2014-06-17 Graphic Flexible Packaging, Llc High strength packages and packaging materials
US8826959B2 (en) 2006-06-29 2014-09-09 Graphic Packaging International, Inc. Heat sealing systems and methods, and related articles and materials
FR2954361B1 (fr) 2009-12-23 2012-06-15 Arjo Wiggins Fine Papers Ltd Feuille imprimable ultra lisse et recyclable et son procede de fabrication
KR102145822B1 (ko) 2012-01-13 2020-08-28 아르조 위긴스 파인 페이퍼즈 리미티드 시트의 제조방법
EP3156540A1 (fr) * 2015-10-12 2017-04-19 Omya International AG Procédé de désencrage de papier ou carton revêtu

Family Cites Families (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE492240A (fr) * 1948-11-18
US2795545A (en) * 1953-04-14 1957-06-11 Monsanto Chemicals Organic materials
BE542642A (fr) * 1954-11-09
US3276359A (en) * 1959-08-28 1966-10-04 Warren S D Co Printing master with base of ketene dimer sized paper
US3293115A (en) * 1964-03-20 1966-12-20 Riegel Paper Corp Process for impregnating paper while partially dry with a quaternized resin polyelectrolyte and a clay coating
GB1379254A (en) * 1971-09-28 1975-01-02 Laporte Industries Ltd Clays
US3855147A (en) * 1972-05-26 1974-12-17 Nl Industries Inc Synthetic smectite compositions, their preparation, and their use as thickeners in aqueous systems
US4097437A (en) * 1977-05-27 1978-06-27 M & T Chemicals Inc. Thixotropic aqueous coating composition of solubilized polymer with dispersion of quaternary ammonium clay in aliphatic hydrocarbon
DE2911679B2 (de) * 1979-03-24 1981-07-30 Feldmühle AG, 4000 Düsseldorf Verfahren zum Herstellen von gestrichenem Papier und Karton und Streichmasse zur Durchführung des Verfahrens
EP0017353B2 (fr) * 1979-03-28 1992-04-29 Ciba Specialty Chemicals Water Treatments Limited Production de papier et de carton
DE2913941B1 (de) * 1979-04-06 1980-05-14 Feldmuehle Ag Verwendung einer nichtgestrichenen Papierbahn im Rotationstiefdruckverfahren
US4412018A (en) * 1980-11-17 1983-10-25 Nl Industries, Inc. Organophilic clay complexes, their preparation and compositions comprising said complexes
US4450095A (en) * 1980-11-17 1984-05-22 Nl Industries, Inc. Organophilic clay gellant having enhanced dispersibility
US4387132A (en) * 1980-12-29 1983-06-07 Champion International Corporation Heat transfer paper
US4517112A (en) * 1982-02-18 1985-05-14 Nl Industries, Inc. Modified organophilic clay complexes, their preparation and non-aqueous systems containing them
DE3215890A1 (de) * 1982-04-29 1983-11-03 Bassermann + Co, 6800 Mannheim Verfahren zum behandeln von mineralischen fuellstoffen und verwendung der behandelten fuellstoffe

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JPH0718119B2 (ja) 1995-03-01
FI860769A (fi) 1986-08-23
CA1273759A (fr) 1990-09-11
DK167939B1 (da) 1994-01-03
JPS6440695A (en) 1989-02-10
DK82986A (da) 1986-08-23
ATE41684T1 (de) 1989-04-15
FI84382B (fi) 1991-08-15
DE3662539D1 (en) 1989-04-27
GR860225B (en) 1986-05-28
NO171121B (no) 1992-10-19
US4867844A (en) 1989-09-19
ES8708153A1 (es) 1987-09-16
NO860662L (no) 1986-08-25
YU26586A (en) 1987-12-31
ZA861316B (en) 1986-10-29
DE3506278A1 (de) 1986-08-28
EP0192252A1 (fr) 1986-08-27
NO171121C (no) 1993-01-27
DK82986D0 (da) 1986-02-21
ES552236A0 (es) 1987-09-16
BR8600732A (pt) 1986-11-04
FI860769A0 (fi) 1986-02-21
FI84382C (fi) 1991-11-25

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