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.e. 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 normally used in a paper machine and, since it is immiscible with the solvent of the gravure printing ink, causes a kind of rejection of the printing ink.
• the present invention aims at an improvement of the H oldouts organic solvent systems, such as printing inks, paints and coating compositions, in other ways.
• the problem of holdouts is particularly pronounced in gravure printing processes, since gravure inks have to have a much lower viscosity compared to other 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 fabrics made of fibers to be printed according to the invention are primarily those made of paper, although nonwovens or textiles (for example silk, cotton and linen fabrics) can also be printed using the present invention.
• the line of the coated varieties In order to have a good level of gravure ink on the paper surface, the line of the coated varieties must have a minimum thickness of about 6.5 to 7 g / m 2 and page; with double-sided coated low
• Printing paper with a total weight of 50 g / m 2 results in a base paper of approximately 36 g / m2. 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 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 (the so-called print opacity) is a particular problem with these papers when the basis weight 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 into the Paper strikes.
• the invention therefore primarily relates to a method for improving the holdout of printing inks, lacquers and coating compositions, containing organic solvents, on fabrics 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 organophilic complex with the organic solvent gives a more or less strong swelling reaction.
• This swelling reaction is surprisingly so strong and so fast that the capillary forces of the fibrous sheet or even a line, especially a sheet of natural paper, do not take effect. That possibly also an adsorption of the colors or their binders on the particles of the organophilic complex takes place, is of minor importance, since the holdout behavior of the treated surface for the pure solvent is practically as great as 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 60%.
• 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. 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 phyllosilicates can often still be colloidal solutions.
• the converted part reacts with the organic solvents of the printing ink, the lacquer or the coating compound.
• 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, especially gravure printing inks, is particularly 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 is preferably used in gravure printing inks, Xylene or petrol, possibly 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 coating 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 important for application, e.g. is cheap in a gravure 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 also acts as a dryer for the organophilic complex, so energy is saved.
• 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 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.
• 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 can be used to situate the organophilic complex in situ generate the surface of the fabric by making the inorganic layered silicate in the form of an aqueous colloidal dispersion which optionally contains binders, surfactants and / or coating pigments, introduces them into the surface and then reacts with the organic compound. This is possible, for example, 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.
• 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 method variant is characterized in DAB, if appropriate, with a binder and / or an inert coating pigment, for example an opacity enhancing pigment rganischen in a D solvent as a pre-preparation by means of a solvent coating machine or a printing press in D of the reactive organophilic complex brings the surface of the fabric, after which the printing ink (s), the lacquer or the coating composition are applied after an intermediate drying.
• a binder and / or an inert coating pigment for example an opacity enhancing pigment rganischen in a D solvent as a pre-preparation by means of a solvent coating machine or a printing press in D of the reactive organophilic complex brings the surface of the fabric, after which the printing ink (s), the lacquer or the coating composition are applied after an intermediate drying.
• 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 costs for gravure printing are limited if, as 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.
• the invention further relates to a mass for carrying out the method variants described above, which 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 fabrics 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 flat structures according to the invention, it is preferably present in a finely divided amount in an amount of 0.1 to 3, preferably 0.2 to 0.8 g / m 2 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 be used, for example, for the production of zinc oxide papers. With these papers, a toluene varnish, which is filled with photoconductive zinc oxide and non-conductive binders, is spread onto the surface of a conductive base paper. The conductivity of the base paper is obtained by adding a conductive polymer (coneuctie 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. Until now, it was only possible to achieve a holdout for toluene that is hole-free, only with great effort, partly double size press coating, partly pre-coating with the conductive polymer and the colloidal binder. By adding the reactive organophilic layered silicate in the size press preparation and / or in the primer, it is possible to achieve a spot-free toluene density for the subsequent coating.
• 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 coated 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 made 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 not 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, in such cases, expensive glue press preparations such as Casein, or polyvinyl alcohol, tries to improve 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% solids 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 thing will take about 10 min. well mixed.
• a 4% strength aqueous solution of dimethyl-benzyl-alkyl- (C12-C22) ammonium chloride is then mixed in in an amount equimolar to the complete ion exchange.
• a commercially available organophilic bentonite coated with quaternary ammonium ions (Tixogel VZ ( R ) from F a. Süd-Chemie AG) is mixed in a high-speed mixer with high shear forces as a dispersion with a solids content of 20% by weight in the presence of a nonylphenol ethoxylate type 15 min. 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 is produced which, after satinizing, has a Bekk smoothness of 1500 to 1600 seconds and a toluene holdout of 65 seconds.
• a comparable coated rotogravure paper has a toluene holdout of 40 seconds.
• 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 commercially available bentonite, the exchangeable cations of which are 40% Na and 60% Ca is applied in the first and third coating unit.
• the order is about 1.5 g / m 2 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, even if it adheres poorly, the use of colloidal and / or disperse binders is not necessary.
• a wood-containing, highly filled paper which, according to EU-PS 0 017 793, was produced with a film-forming colloidal bentonite, the sodium-magnesium atomic ratio of which was 60:40, and, based on the paper, contains 2.5% by weight of the film-forming bentonite , is treated at the end of the dryer section of a paper machine using a conventional size press with the dilute 3% 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 enters into 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 (Tixogel VP ( R ) from Süd-Chemie AG) coated with quaternary ammonium ions 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 10 min. dispersed in a high shear high-speed mixer. This dispersion is applied to both sides of the paper by means of a reverse roll coater, so that 0.5 g / m 2 of application (air-dry calculated) result on each side.
• the paper pretreated in this way has a toluene holdout of 60 seconds.
• Printing with a black gravure ink shows almost no show through on the back and an increased print gloss.
• a colorless pre-printing ink is pre-printed with a 3% by weight colloidal dispersion in toluene, produced analogously to Example 6, using a screen roller with a 70 screen and an engraving depth of 65 ⁇ m over the entire surface and regardless of registration.
• this form applies an application of 0.3 g / m 2 to the paper to be printed. While sec at a lightly filled wood-containing N aturpapier the absorption time for dyed toluene solution is about 6., It yields at the "preprinted" paper at a coating of 0.3 g / m 2 has a value of 70 sec.
• a further increase of the order of reactive organophilic complex from the toluene solution, for example 0.6 g / m 2 does not give a higher value nor a sharper level of the colored toluene drop, since with a coating of only 0.3 g / m 2 the printing paper was already fully sealed against toluene is.
• 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 2 was printed with a dispersion according to Example 6 by gravure printing, the dried application being only 0.2 g / m 2 .
• 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 a dispersing fiber is impregnated with a plastic dispersion of polyacrylic acid ester after it has been produced in an aqueous suspension on a steep sieve machine.
• 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 3.5% by weight suspension of the organophilic complex according to Example 6 which is blended with a further 5% by weight of a fine calcium carbonate and contains a 2% by weight polyvinyl acetate additive, spread out. It is advisable to choose the knife 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 15 seconds for an untreated nonwoven, the holdout is improved by the line to about 40 seconds.
• 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 a 10th, based on the pulp wt .-% share is reached.
• a 3% by weight solution of the quaternary ammonium compound according to Example 1 is prepared in a separate dissolving vessel.
• the wood-free paper thus produced using standard methods has a Bekk smoothness of 1100 sec. At 80 g / m 2 , a density of 1.35 g / cm 2 and a toluene holdout by the drop method (toluene colored with Ceres red) of 15 sec compared to 3 seconds for untreated paper.

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

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• 1985
  • 1985-02-22 DE DE19853506278 patent/DE3506278A1/de not_active Withdrawn
• 1986
  • 1986-01-27 GR GR860225A patent/GR860225B/el unknown
  • 1986-02-19 AT AT86102140T patent/ATE41684T1/de not_active IP Right Cessation
  • 1986-02-19 DE DE8686102140T patent/DE3662539D1/de not_active Expired
  • 1986-02-19 EP EP86102140A patent/EP0192252B1/fr not_active Expired
  • 1986-02-20 ES ES552236A patent/ES8708153A1/es not_active Expired
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  • 1986-02-21 JP JP61035374A patent/JPH0718119B2/ja not_active Expired - Lifetime
  • 1986-02-21 ZA ZA861316A patent/ZA861316B/xx unknown
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  • 1986-02-21 DK DK082986A patent/DK167939B1/da not_active IP Right Cessation
• 1988
  • 1988-01-28 US US07/149,633 patent/US4867844A/en not_active Expired - Lifetime

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