EP0016730B1 - Colour developer substance for producing a pressure sensitive recording material; sheet coated with this colour developer; pressure sensitive recording material and process for its preparation - Google Patents
Colour developer substance for producing a pressure sensitive recording material; sheet coated with this colour developer; pressure sensitive recording material and process for its preparation Download PDFInfo
- Publication number
- EP0016730B1 EP0016730B1 EP80810088A EP80810088A EP0016730B1 EP 0016730 B1 EP0016730 B1 EP 0016730B1 EP 80810088 A EP80810088 A EP 80810088A EP 80810088 A EP80810088 A EP 80810088A EP 0016730 B1 EP0016730 B1 EP 0016730B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- colour developer
- colour
- recording material
- sensitive recording
- developer composition
- 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
Links
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- 239000002184 metal Substances 0.000 claims description 27
- 150000003839 salts Chemical class 0.000 claims description 17
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- 229910002651 NO3 Inorganic materials 0.000 claims description 10
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- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 4
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- 229910052733 gallium Inorganic materials 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052621 halloysite Inorganic materials 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 125000001041 indolyl group Chemical group 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 1
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000002372 labelling Methods 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910001510 metal chloride Inorganic materials 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 229910001960 metal nitrate Inorganic materials 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 229940050176 methyl chloride Drugs 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- 239000004200 microcrystalline wax Substances 0.000 description 1
- 239000012184 mineral wax Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 235000019426 modified starch Nutrition 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- IPLJNQFXJUCRNH-UHFFFAOYSA-L nickel(2+);dibromide Chemical compound [Ni+2].[Br-].[Br-] IPLJNQFXJUCRNH-UHFFFAOYSA-L 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 150000002990 phenothiazines Chemical class 0.000 description 1
- 125000001644 phenoxazinyl group Chemical class C1(=CC=CC=2OC3=CC=CC=C3NC12)* 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 125000005506 phthalide group Chemical group 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- ODGAOXROABLFNM-UHFFFAOYSA-N polynoxylin Chemical compound O=C.NC(N)=O ODGAOXROABLFNM-UHFFFAOYSA-N 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 150000005599 propionic acid derivatives Chemical class 0.000 description 1
- 239000011814 protection agent Substances 0.000 description 1
- 235000018102 proteins Nutrition 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 235000010413 sodium alginate Nutrition 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- LTSUHJWLSNQKIP-UHFFFAOYSA-J tin(iv) bromide Chemical compound Br[Sn](Br)(Br)Br LTSUHJWLSNQKIP-UHFFFAOYSA-J 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229940117013 triethanolamine oleate Drugs 0.000 description 1
- 229960004418 trolamine Drugs 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 239000012178 vegetable wax Substances 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- 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
- B41M5/124—Duplicating or marking methods; Sheet materials for use therein using pressure to make a masked colour visible, e.g. to make a coloured support visible, to create an opaque or transparent pattern, or to form colour by uniting colour-forming components
- B41M5/132—Chemical colour-forming components; Additives or binders therefor
- B41M5/155—Colour-developing components, e.g. acidic compounds; Additives or binders therefor; Layers containing such colour-developing components, additives or binders
- B41M5/1555—Inorganic mineral developers, e.g. clays
Definitions
- the present invention relates to a color developer composition for the production of a pressure-sensitive recording material and to the pressure-sensitive recording material produced therewith which contains all the constituents necessary to produce a colored marking when exposed to pressure. Furthermore, the present invention relates to a color developing sheet for this pressure-sensitive recording material and a method for producing the pressure-sensitive recording material.
- Known coating compositions for pressure-sensitive copying systems generally contain a solution of color formers encapsulated in microcapsules and an acidic component which reacts with the color formers under pressure, such as active clay substances, for. B. attapulgite, bentonite, halloysite, zeolite, montmorillonite, kaolin, zinc oxide and phenolic compounds, phenolic resins or solid organic acids.
- This color developing or electron acceptor component can also be used in combination with an inorganic or organic metal salt.
- AT-A-268 331 or GB-A-1 071 724 proposes the addition of an inorganic metal salt to an attapulgite-containing coating composition in order to increase the reactivity, thereby protecting the active surface of the attapulgite from contamination and thus in contact with the color former a significant improvement in the resulting coloring is achieved.
- an inorganic metal salt in particular zinc chloride
- a reaction accelerator which is used in combination with an acidic clay, an organic acid or a phenolic compound.
- an inorganic metal salt in particular zinc chloride
- a reaction accelerator is known, which is used in combination with an acidic clay, an organic acid or a phenolic compound.
- the metal salt is described for example in DE-A-1 807 894, DE-A-2 303 405 and DE-A-2 163 905.
- a carbonless material has been developed, the acidic color-developing component of which consists of a chloride of a metal with an atomic mass of 50 to 66, preferably zinc chloride, consists.
- the metal chloride can also be used in combination with urea, thiourea or diphenylthiourea. The use of a solvent is dispensed with in such copying materials.
- the object of the invention is to provide a color developer composition for pressure-sensitive recording materials which, without the participation of microcapsules, produce strong and light-resistant color markings.
- This object is achieved according to the invention by incorporating a mixture of water-soluble inorganic metal salts into the color-developing acceptor mass, at least one metal salt being said to be a nitrate. Through a slow reaction, the nitrate strengthens and stabilizes the color formation of the faster reactant and thus improves the intensification and lightfastness of the dyeings obtained.
- the present invention accordingly relates to a color developer composition for producing a pressure-sensitive recording material which, as a color developer, contains at least two water-soluble metal salts, at least one of which is an inorganic nitrate.
- the color developer composition is characterized in that the color developer consists of the nitrate and at least one other inorganic water-soluble metal salt. If desired, the color developer can additionally contain maleic acid or its derivatives, which serve to improve the water resistance of the copies.
- the metal salt mixtures used according to the invention are advantageously derived from polyvalent metals with an atomic weight of 24 to 210, preferably 40 to 120 and in particular 50 to 120.
- metals are aluminum, barium, lead, cadmium, calcium, chromium, iron, gallium, cobalt, copper, magnesium, manganese, molybdenum, nickel, mercury, silver, strontium, tantalum, titanium, vanadium, tungsten, zinc, tin and Zirconium. Tin, zinc, manganese, iron, nickel and cobalt are preferred.
- Particularly preferred metal salt mixtures contain at least one halide and at least one a nitrate.
- the mixing ratio of metal halide and nitrate is preferably 1: 9 to 9: 1. Both the halide and the nitrate can be used individually or as mixtures.
- a fluoride, iodide, bromide or preferably a chloride can be considered as the halide.
- the metal halides advantageously have a molecular weight of 120 to 280, while the nitrates (in their anhydride form) preferably have molecular weights of 150 to 350.
- metal halides are nickel (II) chloride, cobalt (II) chloride, iron (II) chloride, copper chloride, zinc chloride, tin bromide, tin chloride, manganese (11) chloride, nickel (II) bromide, calcium fluoride, cadmium iodide or mixtures thereof.
- Zinc chloride and tin chloride are of particular interest.
- nitrates are iron nitrate, nickel nitrate, manganese nitrate and zinc nitrate or mixtures thereof.
- the color developer composition is expediently applied to the support in an amount of 1 to 6 g / m 2 .
- the proportion of inorganic metal salt mixture in this mass is advantageously 5 to 80% by weight, preferably 10 to 80% by weight.
- the proportion of the color former in the solids content of the coating compositions is 1 to 20, preferably 2 to 15 percent by weight.
- Both the color former and the color developer are preferably attached to the corresponding layer support by means of a suitable binder.
- this binder is mainly paper coating agents, such as gum arabic, polyvinyl alcohol, polyvinyl pyrrolidone, polyvinyl acetate, vinyl acetate copolymer, hydroxyethyl cellulose, casein, proteins, sodium alginates, methyl cellulose, carboxymethyl cellulose, dextrin, starch or modified starch types such as B. oxidized, hydrolyzed or hydroxyethylated starch or polymer latices.
- the latter are, for example, polystyrene, butadiene-styrene copolymers or acrylic homo- or copolymers, for. B.
- the proportion of the binder in the coating composition is generally 5 to 45, preferably 6 to 25 percent by weight, based on the dry content.
- the paper used is not only normal paper made from cellulose fibers, but also papers in which the cellulose fibers are (partially or completely) replaced by fibers made from synthetic polymers.
- the coating compositions containing color developers and color formers may also contain pigment solids or fillers.
- pigment solids or fillers include inorganic pigments such. B. talc, total dioxide, aluminum oxide, barium sulfate, calcium sulfate, satin white (calcium sulfoaluminate), zinc oxide, silicon dioxide, calcium carbonate, unreactive clays and / or kaolins, especially coating kaolin and organic pigments, for.
- B. urea-formaldehyde or melamine-formaldehyde condensation products can be used.
- the coating compositions may contain further auxiliaries, for example emulsifiers of the anionic, cationic or nonionic type, dispersants, plasticizers, UV protection agents, antifoams and fungicides.
- auxiliaries for example emulsifiers of the anionic, cationic or nonionic type, dispersants, plasticizers, UV protection agents, antifoams and fungicides.
- metal stearates which preferably have a melting point of 90 to 150 ° C., as well as nonylphenols, derivatives of triethanolamine or propionic acid and / or rosins improved particularly stable coating compositions with Properties.
- lead, calcium, cadmium, aluminum, barium, iron, magnesium, cobalt, tin and zinc stearate may be mentioned as metal stearates.
- Suitable derivatives of propionic acid and of triethanolamine are, in particular, octadecyl 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate and thearipropionic acid distearyl ester or triethanolamine oleate.
- Both the color former and the color developer can be applied to the carrier material using solvents or, preferably, in the form of a wax emulsion and / or melt.
- the application is usually carried out at a temperature of 20 to 180 ° C, preferably 60 to 160 ° C.
- solvents water or organic solvents such as aliphatic or aromatic, optionally chlorinated hydrocarbons, alcohols, esters, ketones or glycol ethers can be used.
- organic solvents which can be used include, for example, methanol, ethanol, isopropanol, butanol, acetone, ethyl acetate, butyl acetate, benzene, toluene, xylene, methyl chloride or mixtures thereof.
- the inorganic metal salts or the color formers are dissolved or dispersed in solvents, preferably water, whereupon a wax is emulsified in this solution or dispersion and the wax emulsions formed, advantageously at a temperature of 50 to 180 ° C., preferably 60 to 160 ° C is applied to the corresponding carrier.
- Both natural waxes e.g. B. vegetable, animal or mineral waxes and synthetic waxes can be used.
- Preferred waxes are chlorinated waxes, paraffins, oxide waxes and in particular polyethylene or polyethylene oxide waxes with a molecular weight of 400 to 12,000. Examples of waxes in question are carnauba wax, amide wax, hard wax, micro wax, polyethylene wax or ozokerite. These waxes can also be used as mixtures.
- the proportion of wax in the coating compositions, in particular in the color developer composition is generally 5 to 85% by weight, preferably 15 to 75% by weight, based on the dry content.
- the pressure-sensitive recording material according to the invention preferably consists of a carrier sheet with a layer containing a color former and a layer containing the color developer.
- the color former and the color developer can each be embedded together on a carrier.
- the recording material mainly contains solvents and can still contain up to 90% by weight of the solvent used for the application.
- a color image mass is produced as a test material consists. This coating slip is applied to a paper support (40 g / m 2 basis weight). The application density is 1 g / m 2.
- the color developer compositions contain, as color developers, the reagents specified in the second column of the table, acetone being used as the solvent for application.
- the color developer composition is brought into contact with the color image composition applied to the paper by means of a glass rod.
Landscapes
- Chemical & Material Sciences (AREA)
- Dispersion Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Color Printing (AREA)
- Heat Sensitive Colour Forming Recording (AREA)
Description
Die vorliegende Erfindung betrifft eine Farbentwicklermasse zur Herstellung eines druckempfindlichen Aufzeichnungsmaterials und das damit hergestellte drückempfindliche Aufzeichnungsmaterial, das alle erforderlichen Bestandteile enthält, um bei Einwirken von Druck eine farbige Markierung zu erzeugen. Weiterhin betrifft die vorliegende Erfindung ein Farbentwicklungsblatt für dieses druckempfindliche Aufzeichnungsmaterial und ein Verfahren zur Herstellung des druckempfindlichen Aufzeichnungsmaterials.The present invention relates to a color developer composition for the production of a pressure-sensitive recording material and to the pressure-sensitive recording material produced therewith which contains all the constituents necessary to produce a colored marking when exposed to pressure. Furthermore, the present invention relates to a color developing sheet for this pressure-sensitive recording material and a method for producing the pressure-sensitive recording material.
Bekannte Beschichtungsmassen für druckempfindliche Kopiersysteme enthalten in der Regel eine in Mikrokapseln eingekapselte Lösung von Farbbildnern und eine mit den Farbbildnern unter Druckanwendung reagierende saure Komponente, wie Aktivton-Substanzen, z. B. Attapulgit, Bentonit, Halloysit, Zeolith, Montmorillonit, Kaolin, Zinkoxyd sowie Phenolverbindungen, Phenolharze oder feste organische Säuren. Diese farbentwickelnde oder Elektronenakzeptorkomponente kann auch in Kombination mit einem anorganischen oder organischen Metallsalz verwendet werden. Durch Druckanwendung, z. B. beim Beschriften, werden die Mikrokapseln aufgebrochen, worauf sich durch Kontakt der Farbbildnerlösung mit der sauren Akzeptorkomponente die erwünschte Farbmarkierung entwickelt.Known coating compositions for pressure-sensitive copying systems generally contain a solution of color formers encapsulated in microcapsules and an acidic component which reacts with the color formers under pressure, such as active clay substances, for. B. attapulgite, bentonite, halloysite, zeolite, montmorillonite, kaolin, zinc oxide and phenolic compounds, phenolic resins or solid organic acids. This color developing or electron acceptor component can also be used in combination with an inorganic or organic metal salt. By applying pressure, e.g. B. when labeling, the microcapsules are broken open, whereupon the desired color marking develops by contact of the color former solution with the acidic acceptor component.
Aus der AT-A-284 880 oder GB-A-1 215 618 ist es bekannt, derartige-Beschichtungsmassen zu verwenden, in denen die Farbbildner in gelöster Form eingekapselt sind und die saure farbentwickelnde Komponente aus einer Mischung aus einem öllöslichen phenolischen Polymer, sauer reagierendem Kaolin und einem anorganischen Metallsalz, wie Zinkchlorid, besteht. Dabei liegen Farbbildner und Farbentwickler in zwei Schichten vor, die sich in unmittelbarem Kontakt miteinan der befinden. Beim Einwirken von Druck werden die Kapseln aufgerissen. Dadurch entsteht nach dem Kontakt des Farbbildners mit der sauer wirkenden Mischnung eine farbige Stelle.From AT-A-284 880 or GB-A-1 215 618 it is known to use such coating compositions in which the color formers are encapsulated in dissolved form and the acidic color-developing component is acidic from a mixture of an oil-soluble phenolic polymer reacting kaolin and an inorganic metal salt, such as zinc chloride. Color formers and color developers are in two layers that are in direct contact with each other. The capsules are torn open when pressure is applied. This creates a colored spot after the color former comes into contact with the acidic mixture.
In der AT-A-268 331 oder GB-A-1 071 724 wird der Zusatz eines anorganischen Metallsalzes zu einer Attapulgit-enthaltenden Beschichtungsmasse zur Steigerung der Reaktionsfähigkeit vorgeschlagen, wodurch die aktive Oberfläche des Attapulgits vor Verunreinigungen geschützt und somit in Berührung mit dem Farbbildner eine deutliche Verbesserung der daraus resultierenden Färbung erzielt wird.AT-A-268 331 or GB-A-1 071 724 proposes the addition of an inorganic metal salt to an attapulgite-containing coating composition in order to increase the reactivity, thereby protecting the active surface of the attapulgite from contamination and thus in contact with the color former a significant improvement in the resulting coloring is achieved.
Desweiteren ist die Verwendung eines anorganischen Metallsalzes, insbesondere Zinkchlorid, als Reaktionsbeschleuniger bekannt, welches in Kombination mit einem sauren Ton, einer organischen Säure oder einer phenolischen Verbindung eingesetzt wird. Eine derartige Verwendung des Metallsalzes ist beispielsweise in der DE-A-1 807 894, DE-A-2 303 405 und DE-A-2 163 905 beschrieben.Furthermore, the use of an inorganic metal salt, in particular zinc chloride, as a reaction accelerator is known, which is used in combination with an acidic clay, an organic acid or a phenolic compound. Such use of the metal salt is described for example in DE-A-1 807 894, DE-A-2 303 405 and DE-A-2 163 905.
Aus der DE-A-2 357 828 ist bekannt, dass man das Entwicklungsvermögen des Farbentwicklungsblattes und die Lichtechtheit des Farbbildes verbessern kann, wenn man als Farbentwickler ein Alkalimetallsalz eines Phenolharzes zusammen mit einem wasserlöslichen anorganischen Metallsalz wie Zinknitrat oder Zinkchlorid verwendet. Diese Farbentwicklerkombination aus einem organischen Metallsalz und einer anorganischen Metallverbindung wird jedoch lediglich in druckempfindliche Aufzeichnungsmaterialien eingesetzt, in denen der Farbbildner in Mikrokapseln vorliegt.From DE-A-2 357 828 it is known that the developability of the color development sheet and the light fastness of the color image can be improved if an alkali metal salt of a phenolic resin is used as a color developer together with a water-soluble inorganic metal salt such as zinc nitrate or zinc chloride. However, this color developer combination of an organic metal salt and an inorganic metal compound is only used in pressure-sensitive recording materials in which the color former is present in microcapsules.
Gemäss den österreichischen Patentschriften AT-A-329 595, AT-A-329 596 und AT-A-329 597 ist ein Durchschreibematerial entwickelt worden, dessen saure farbentwickelnde Komponente aus einem Chlorid eines Metalles mit der Atommasse von 50 bis 66, vorzugsweise Zinkchlorid, besteht. Dabei kann das Metallchlorid auch in Kombination mit Harnstoff, Thioharnstoff oder Diphenylthioharnstoff verwendet werden. Bei derartigen Durchschreibematerialien wird auf die Mitwirkung eines Lösungsmittels verzichtet.According to the Austrian patents AT-A-329 595, AT-A-329 596 and AT-A-329 597, a carbonless material has been developed, the acidic color-developing component of which consists of a chloride of a metal with an atomic mass of 50 to 66, preferably zinc chloride, consists. The metal chloride can also be used in combination with urea, thiourea or diphenylthiourea. The use of a solvent is dispensed with in such copying materials.
Aufgabe der Erfindung ist die Schaffung einer Farbentwicklermasse für druckempfindliche Aufzeichnungsmaterlalien, welche ohne Mitwirkung von Mikrokapseln starke und lichtbeständige Farbmarkierungen ergeben. Diese Aufgabe wird erfindungsgemäss gelöst, indem man ein Mischung von wasserlöslichen anorganischen Metallsalzen in die farbentwickelnde Akzeptormasse einverleibt, wobei mindestens ein Metallsalz ein Nitrat sein soll. Das Nitrat verstärkt und stabilisiert durch eine langsame Reaktion die Farbbildung des schnelleren Reaktionspartners und verbessert somit die Intensivierung und Lichtbeständigkeit der erhaltenen Färbungen.The object of the invention is to provide a color developer composition for pressure-sensitive recording materials which, without the participation of microcapsules, produce strong and light-resistant color markings. This object is achieved according to the invention by incorporating a mixture of water-soluble inorganic metal salts into the color-developing acceptor mass, at least one metal salt being said to be a nitrate. Through a slow reaction, the nitrate strengthens and stabilizes the color formation of the faster reactant and thus improves the intensification and lightfastness of the dyeings obtained.
Gegenstand vorliegender Erfindung ist demnach eine Farbentwicklermasse zur Herstellung eines druckempfindlichen Aufzeichnungsmaterials, die als Farbentwickler mindestens zwei wasserlösliche Metallsalze, von denen mindestens eines ein anorganisches Nitrat ist, enthält. Die Farbentwicklermasse ist dadurch gekennzeichnet, dass der Farbentwickler aus dem Nitrat und mindestens einem weiteren anorganischen wasserlöslichen Metallsalz besteht. Gewünschtenfalls kann der Farbentwickler zusätzlich Maleinsäure oder deren Derivate enthalten, welche zur Verbesserung der Wasserbeständigkeit der Kopien dienen.The present invention accordingly relates to a color developer composition for producing a pressure-sensitive recording material which, as a color developer, contains at least two water-soluble metal salts, at least one of which is an inorganic nitrate. The color developer composition is characterized in that the color developer consists of the nitrate and at least one other inorganic water-soluble metal salt. If desired, the color developer can additionally contain maleic acid or its derivatives, which serve to improve the water resistance of the copies.
Die erfindungsgemäss verwendeten Metallsalzmischungen leiten sich vorteilhafterweise von mehrwertigen Metallen mit einem Atomgewicht von 24 bis 210, vorzugsweise 40 bis 120 und insbesondere 50 bis 120 ab. Beispiele derartiger Metalle sind Aluminium, Barium, Blei, Cadmium, Calcium, Chrom, Eisen, Gallium, Kobalt, Kupfer, Magnesium, Mangan, Molybdän, Nickel, Quecksilber, Silber, Strontium, Tantal, Titan, Vanadium, Wolfran, Zink, Zinn und Zirkonium. Dabei sind Zinn, Zink, Mangan, Eisen, Nickel und Kobalt bevorzugt.The metal salt mixtures used according to the invention are advantageously derived from polyvalent metals with an atomic weight of 24 to 210, preferably 40 to 120 and in particular 50 to 120. Examples of such metals are aluminum, barium, lead, cadmium, calcium, chromium, iron, gallium, cobalt, copper, magnesium, manganese, molybdenum, nickel, mercury, silver, strontium, tantalum, titanium, vanadium, tungsten, zinc, tin and Zirconium. Tin, zinc, manganese, iron, nickel and cobalt are preferred.
Besonders bevorzugte Metallsalzmischungen enthalten mindestens ein Halogenid und mindestens ein Nitrat. Das Mischungsverhältnis von Metallhalogenid und Nitrat beträgt vorzugsweise 1 : 9 bis 9 : 1. Sowohl das Halogenid als auch das Nitrat können einzeln oder als Mischungen verwendet werden. Als Halogenid kann ein Fluorid, Jodid, Bromid oder vorzugsweise ein Chlorid in Betracht kommen.Particularly preferred metal salt mixtures contain at least one halide and at least one a nitrate. The mixing ratio of metal halide and nitrate is preferably 1: 9 to 9: 1. Both the halide and the nitrate can be used individually or as mixtures. A fluoride, iodide, bromide or preferably a chloride can be considered as the halide.
Die Metallhalogenide haben vorteilhafterweise ein Molekulargewicht von 120 bis 280, während die Nitrate (in ihrer Anhydridform) vorzugsweise Molekulargewichte von 150 bis 350 aufweisen.The metal halides advantageously have a molecular weight of 120 to 280, while the nitrates (in their anhydride form) preferably have molecular weights of 150 to 350.
Beispiele für Metallhalogenide sind Nickel(II)-chlorid, Kobalt(II)-chlorid, Eisen(II)-chlorid, Kupferchlorid, Zinkchlorid, Zinnbromid, Zinnchlorid, Mangan(11)-chlorid, Nickel(II)-bromid, Calciumfluorid, Kadmiumjodid oder Mischungen davon.Examples of metal halides are nickel (II) chloride, cobalt (II) chloride, iron (II) chloride, copper chloride, zinc chloride, tin bromide, tin chloride, manganese (11) chloride, nickel (II) bromide, calcium fluoride, cadmium iodide or mixtures thereof.
Von besonderem Interesse sind Zinkchlorid und Zinnchlorid.Zinc chloride and tin chloride are of particular interest.
Beispiele für Nitrate sind Eisennitrat, Nickelnitrat, Mangannitrat und Zinknitrat oder deren Gemische.Examples of nitrates are iron nitrate, nickel nitrate, manganese nitrate and zinc nitrate or mixtures thereof.
Ausgezeichnete Resultate werden insbesondere durch Zweierkombination oder Dreierkombination der Halogenide und Nitrate der Metalle Zinn, Zink, Mangan, Eisen, Nickel und Kobalt erreicht. Diese Kombinationen können vorteilhafterweise auch Maleinsäure enthalten.Excellent results are achieved in particular by a combination of two or three of the halides and nitrates of the metals tin, zinc, manganese, iron, nickel and cobalt. These combinations can advantageously also contain maleic acid.
Die Verwendung derartiger Kombinationen ergibt reaktionsintensivere und lichtbeständigere Aufzeichnungsmaterialien, welche dank dem Zusatz des langsam reagierenden Nitrates auch eine vollständige und stabile Farbbildung ermöglichen und zudem dauerhafte, wasserechte und lichtechte Farbmarkierungen ergeben.The use of such combinations results in more reaction-intensive and light-resistant recording materials, which, thanks to the addition of the slowly reacting nitrate, also enable complete and stable color formation and also give permanent, water-correct and lightfast color markings.
Zweckmässigerweise trägt man die Farbentwicklermasse auf den Träger in einer Menge von 1 bis 6 g/m2 auf. Der Anteil an anorganischer Metallsalzmischung in dieser Masse liegt vorteilhafterweise bei 5 bis 80 Gew.%, vorzugsweise 10 bis 80 Gew.%.The color developer composition is expediently applied to the support in an amount of 1 to 6 g / m 2 . The proportion of inorganic metal salt mixture in this mass is advantageously 5 to 80% by weight, preferably 10 to 80% by weight.
Die in der Farbbildnermasse in Betracht kommenden Farbbildner sind bekannte farblose oder schwach gefärbte Stoffe, die, sofern sie mit den Farbentwickler in Kontakt kommen, farbig werden oder die Farbe ändern. Farbbildner oder deren Mischungen können verwendet werden, die z. B. den Klassen der Phthalide, Fluorane, Spiropyrane, Azomethine, Triarylmethan-leukofarbstoffe, Leukoauramine, der substituierten Phenoxazine oder Phenothiazine, sowie der Chromeno- oder Chromanfarbbildner angehören. Als Beispiele solcher geeigneten Farbbildner seien genannt:
- Kristallviolettlakton, 3,3-(Bisaminophenyl)-phthalide,
- 3,3-(Bis-substituierte Indolyl)-phthalide,
- 3-(Aminophenyi)-3-indoiyi-phthaiide,
- 6-Dialkylamino-2-n-octylamino-fluorane,
- 6-Dialkylamino-2-arylamino-fluorane,
- 6-Dialkylamino-3-methyl-2-arylamino-fluorane,
- 6-Dialkylamino-2- oder 3-niederalkyl-fluorane,
- 6-Dialkylamino-2-dibenzylamino-fluorane,
- Bis-(aminophenyl)-furyl- oder -phenyl- oder -carbazolyl-methane oder Benzoylleukomethylenblau.
- Crystal violet lactone, 3,3- (bisaminophenyl) phthalide,
- 3,3- (bis-substituted indolyl) phthalides,
- 3- (aminophenyi) -3-indoiyi-phthaiide,
- 6-dialkylamino-2-n-octylamino-fluoranes,
- 6-dialkylamino-2-arylamino-fluoranes,
- 6-dialkylamino-3-methyl-2-arylamino-fluoranes,
- 6-dialkylamino-2- or 3-lower alkyl-fluoranes,
- 6-dialkylamino-2-dibenzylamino-fluoranes,
- Bis (aminophenyl) furyl or phenyl or carbazolyl methane or benzoyl leukomethylene blue.
Der Anteil des Farbbildners im Feststoffgehalt der Beschichtungsmassen beträgt 1 bis 20, vorzugsweise 2 bis 15 Gewichtsprozent.The proportion of the color former in the solids content of the coating compositions is 1 to 20, preferably 2 to 15 percent by weight.
Sowohl die Farbbildnermasse als auch die Farbentwicklermasse werden vorzugsweise mittels eines geeigneten Binders auf dem entsprechenden Schicht-Träger befestigt.Both the color former and the color developer are preferably attached to the corresponding layer support by means of a suitable binder.
Da Papier das bevorzugte Trägermaterial ist, handelt es sich bei diesem Binder hauptsächlich um Papierbeschichtungsmittel, wie Gummi arabicum, Polyvinylalkohol, Polyvinylpyrrolidon, Polyvinylacetat, Vinylacetat-copolymerisat, Hydroxyäthylcellulose, Casein, Proteine, Natriumalginate, Methylcellulose, Carboxymethylcellulose, Dextrin, Stärke oder modifizierte Stärkearten, wie z. B. oxydierte, hydrolysierte oder hydroxyäthylierte Stärke oder Polymerlatices. Letztere sind beispielsweise Polystyrol, Butadien-Styrolcopolymerisate oder Acrylhomo- oder -copolymere, z. B. der Acrylsäure oder Methacrylsäure oder deren Niederalkylester wie von Aethylacrylat, Butylacrylat oder Methylmethacrylat, sowie auch von Acrylamid. Der Anteil des Bindemittels in der Beschichtungsmasse beträgt in der Regel 5 bis 45, vorzugsweise 6 bis 25 Gewichtsprozent, bezogen auf den Trockengehalt.Since paper is the preferred carrier material, this binder is mainly paper coating agents, such as gum arabic, polyvinyl alcohol, polyvinyl pyrrolidone, polyvinyl acetate, vinyl acetate copolymer, hydroxyethyl cellulose, casein, proteins, sodium alginates, methyl cellulose, carboxymethyl cellulose, dextrin, starch or modified starch types such as B. oxidized, hydrolyzed or hydroxyethylated starch or polymer latices. The latter are, for example, polystyrene, butadiene-styrene copolymers or acrylic homo- or copolymers, for. B. acrylic acid or methacrylic acid or their lower alkyl esters such as ethyl acrylate, butyl acrylate or methyl methacrylate, and also of acrylamide. The proportion of the binder in the coating composition is generally 5 to 45, preferably 6 to 25 percent by weight, based on the dry content.
Als Papier werden nicht nur normale Papiere aus Cellulosefasern, sondern auch Papiere, in denen die Cellulosefasern (teilweise oder vollständig) durch Fasern aus synthetischen Polymerisaten ersetzt sind, verwendet.The paper used is not only normal paper made from cellulose fibers, but also papers in which the cellulose fibers are (partially or completely) replaced by fibers made from synthetic polymers.
Zur Erleichterung des Bedruckens können die Farbentwickler und Farbbildner enthaltenden Streichmassen noch Pigmentfeststoffe oder Füllstoffe enthalten. Als derartige Feststoffe können anorganische Pigmente wie z. B. Talkum, Totandioxyd, Aluminiumoxyd, Bariumsulfat, Calciumsulfat, Satinweiss (Calciumsulfoaluminat), Zinkoxyd, Siliciumdioxyd, Calciumcarbonat, unreaktive Tone und/oder Kaoline, insbesondere Streichkaolin sowie organische Pigmente, z. B. Harnstoff-Formaldehyd-oder Melamin-Formaldehyd-Kondensationsprodukte eingesetzt werden.In order to facilitate printing, the coating compositions containing color developers and color formers may also contain pigment solids or fillers. As such solids, inorganic pigments such. B. talc, total dioxide, aluminum oxide, barium sulfate, calcium sulfate, satin white (calcium sulfoaluminate), zinc oxide, silicon dioxide, calcium carbonate, unreactive clays and / or kaolins, especially coating kaolin and organic pigments, for. B. urea-formaldehyde or melamine-formaldehyde condensation products can be used.
Ausser den genannten Substanzen können die Ueberzugsmassen weitere Hilfsstoffe enthalten, z, B. Emulgatoren vom anionaktiven, kationaktiven oder nichtionogenen Typ, Dispergiermittel, Weichmacher, UV-Schutzmittel, Schaumverhütungsmittel und Fungizide.In addition to the substances mentioned, the coating compositions may contain further auxiliaries, for example emulsifiers of the anionic, cationic or nonionic type, dispersants, plasticizers, UV protection agents, antifoams and fungicides.
Es konnte auch festgestellt werden, dass der weitere Zusatz von Metallstearaten, die vorzugsweise einen Schmelzpunkt von 90 bis 150 °C aufweisen, sowie Nonylphenole, Derivate von Triäthanolamin oder Propionsäure und/oder Kolophoniumharze besonders stabile Beschichtungsmassen mit verbesserten Eigenschaften ergeben. Als Metallstearate seien im einzelnen Blei-, Calcium-, Cadmium-, Aluminium-, Barium-, Eisen-, Magnesium-, Kobalt-, Zinn- und Zinkstearat genannt. Geeignete Derivate der Propionsäure und des Triäthanolamins sind insbesondere Octadecyl-3-(3,5-di-tert. butyl-4-hydroxyphenyl)-propionat und Thiodipropionsäuredistearylester bzw. Triäthanolaminoleat.It was also found that the further addition of metal stearates, which preferably have a melting point of 90 to 150 ° C., as well as nonylphenols, derivatives of triethanolamine or propionic acid and / or rosins improved particularly stable coating compositions with Properties. In particular, lead, calcium, cadmium, aluminum, barium, iron, magnesium, cobalt, tin and zinc stearate may be mentioned as metal stearates. Suitable derivatives of propionic acid and of triethanolamine are, in particular, octadecyl 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate and thearipropionic acid distearyl ester or triethanolamine oleate.
Sowohl die Farbbildnermasse als auch die Farbentwicklermasse können auf das Trägermaterial mit Hilfe von Lösungsmitteln oder vorzugsweise in Form einer Wachsemulsion und/oder Schmelze aufgebracht werden. Die Auftragung erfolgt in der Regel bei einer Temperatur von 20 bis 180 °C, vorzugsweise 60 bis 160 °C.Both the color former and the color developer can be applied to the carrier material using solvents or, preferably, in the form of a wax emulsion and / or melt. The application is usually carried out at a temperature of 20 to 180 ° C, preferably 60 to 160 ° C.
Beim Lösungsmittelauftrag können Wasser oder organische Lösungsmittel wie aliphatische oder aromatische, gegebenenfalls chlorierte Kohlenwasserstoffe, Alkohole, Ester, Ketone oder Glykoläther verwendet werden. Zu den verwendbaren organischen Lösungsmitten gehören beispielsweise Methanol, Aethanol, lsopropanol, Butanol, Aceton, Aethylacetat, Butylacetat, Benzol, Toluol, Xylol, Methylchlorid oder Mischungen davon.When applying solvents, water or organic solvents such as aliphatic or aromatic, optionally chlorinated hydrocarbons, alcohols, esters, ketones or glycol ethers can be used. The organic solvents which can be used include, for example, methanol, ethanol, isopropanol, butanol, acetone, ethyl acetate, butyl acetate, benzene, toluene, xylene, methyl chloride or mixtures thereof.
Im Falle einer Schmelze werden die anorganischen Metallsalze oder die Farbbildner in Lösungsmitteln, vorzugsweise Wasser, gelöst oder dispergiert, worauf in dieser Lösung oder Dispersion ein Wachs emulgiert und die enstandene Wachsemultion, vorteilhafterweise bei einer Temperatur von 50 bis 180 °C, vorzugsweise 60 bis 160 °C auf den entsprechenden Träger aufgebracht wird.In the case of a melt, the inorganic metal salts or the color formers are dissolved or dispersed in solvents, preferably water, whereupon a wax is emulsified in this solution or dispersion and the wax emulsions formed, advantageously at a temperature of 50 to 180 ° C., preferably 60 to 160 ° C is applied to the corresponding carrier.
Als Wachse können sowohl Naturwachse, z. B. pflanzliche, tierische oder mineralische Wachse als auch synthetische Wachse verwendet werden. Bevorzugte Wachse sind chlorierte Wachse, Paraffine, Oxydwachs und insbesondere Polyäthylen- oder Polyäthylenoxydwachse mit einem Molekulargewicht von 400 bis 12000. Beispiele von in Frage kommenden Wachsen sind Carnaubawachs, Amidwachs, Hartwachs, Mikrowachs, Polyäthylenwachs oder Ozokerit. Diese Wachse können auch als Mischungen verwendet werden. Der Anteil des Wachses in den Beschichtungsmassen, insbesondere in der Farbentwicklermasse beträgt inder Regel 5 bis 85 Gew.%, vorzugsweise 15 bis 75 Gew.%, bezogen auf den Trockengehalt.Both natural waxes, e.g. B. vegetable, animal or mineral waxes and synthetic waxes can be used. Preferred waxes are chlorinated waxes, paraffins, oxide waxes and in particular polyethylene or polyethylene oxide waxes with a molecular weight of 400 to 12,000. Examples of waxes in question are carnauba wax, amide wax, hard wax, micro wax, polyethylene wax or ozokerite. These waxes can also be used as mixtures. The proportion of wax in the coating compositions, in particular in the color developer composition, is generally 5 to 85% by weight, preferably 15 to 75% by weight, based on the dry content.
Das erfindungsgemässe druckempfindliche Aufzeichnungsmaterial besteht vorzugsweise aus einem Trägerblatt mit einer einen Farbbildner enthaltenden Schicht und einer den Farbentwickler enthaltenden Schicht. Der Farbbildner und der Farbentwickler können jedoch jeweils eingebettet auch gemeinsam auf einem Träger vorhanden sein. Das Aufzeichnungsmaterial ist vorwiegend lösungsmittelhaltig und kann bis 90 Gew.% des für die Auftragung verwendeten Lösungsmittels noch enthalten. In der nachstehenden Tabelle sind die Ergebnisse der Vergleichsversuche zusammengefasst, aus denen der erfindungsgemäss erzielte Fortschritt ersichtlich ist.The pressure-sensitive recording material according to the invention preferably consists of a carrier sheet with a layer containing a color former and a layer containing the color developer. However, the color former and the color developer can each be embedded together on a carrier. The recording material mainly contains solvents and can still contain up to 90% by weight of the solvent used for the application. The table below summarizes the results of the comparative experiments, from which the progress achieved according to the invention can be seen.
Als Testmaterial wird eine Farbbildnermasse hergestellt, die aus
Die Farbentwicklermasse wird mittels eines Glasstabes mit der auf das Papier aufgetragene Farbbildnermasse in Berührung gebracht.The color developer composition is brought into contact with the color image composition applied to the paper by means of a glass rod.
Aus dieser Tabelle kann festgehalten werden, dass die Verwendung von Gemischen aus zwei oder mehreren anorganischen Metallsalzen, gegebenenfalls auch in Kombination mit Maleinsäure (Versuche 7 bis 11), in Vergleich mit den einzelnen Komponenten eine deutliche Verbesserung der allgemeinen Eigenschaften für Beschichtungsmassen und Aufzeichnungsmaterialien, nämlich Reaktionsintensität, Lichtechtheit und Wasserbeständigkeit mit sich bringt. Diese Ergebnisse können unter zusätzlicher Verwendung von Metallstearaten, Harzen, Nonylphenol, Harnstoffen, Propionsäurederivaten oder organischen Triäthanolaminsalzen in der Farbentwicklermasse noch verbessert werden.From this table it can be stated that the use of mixtures of two or more inorganic metal salts, optionally also in combination with maleic acid (experiments 7 to 11), compared to the individual components, a significant improvement in the general properties for coating compositions and recording materials, namely Reaction intensity, light fastness and water resistance. These results can be further improved by additionally using metal stearates, resins, nonylphenol, ureas, propionic acid derivatives or organic triethanolamine salts in the color developer composition.
In den folgenden Beispielen für erfindungsgemässe Beschichtungsmassen sind die Prozentsätze und Teile Gewichtsprozente und Gewichtsteile, wenn nichts anderes angegeben ist. Bei Beschichtungsmassen, die mit Hilfe eines Lösungsmittels auf das Trägermaterial aufgetragen werden, wird auch das betreffende Lösungsmittel genannt.
Claims (11)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AT0207379A AT372909B (en) | 1979-03-20 | 1979-03-20 | COLOR DEVELOPER MATERIALS FOR THE PRODUCTION OF A PRESSURE-SENSITIVE RECORDING MATERIAL WITH PARTICULARLY STRONG COLOR FORMATION AND LIGHT-RESISTANCE |
| AT2073/79 | 1979-03-20 |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| EP0016730A2 EP0016730A2 (en) | 1980-10-01 |
| EP0016730A3 EP0016730A3 (en) | 1980-10-15 |
| EP0016730B1 true EP0016730B1 (en) | 1983-02-16 |
Family
ID=3527197
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP80810088A Expired EP0016730B1 (en) | 1979-03-20 | 1980-03-14 | Colour developer substance for producing a pressure sensitive recording material; sheet coated with this colour developer; pressure sensitive recording material and process for its preparation |
Country Status (13)
| Country | Link |
|---|---|
| US (2) | US4348234A (en) |
| EP (1) | EP0016730B1 (en) |
| JP (1) | JPS55124695A (en) |
| AT (1) | AT372909B (en) |
| AU (1) | AU536968B2 (en) |
| BR (1) | BR8001638A (en) |
| DE (2) | DE3061967D1 (en) |
| ES (1) | ES490408A0 (en) |
| FI (1) | FI72079C (en) |
| MX (1) | MX154220A (en) |
| PT (1) | PT70971A (en) |
| YU (1) | YU43466B (en) |
| ZA (1) | ZA801587B (en) |
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| AT329596B (en) | 1973-07-27 | 1976-05-25 | Koreska Gmbh W | PRESSURE-SENSITIVE, SOLVENT-FREE RECORDING MATERIAL |
| AT329597B (en) | 1973-09-10 | 1976-05-25 | Koreska Gmbh W | PRESSURE-SENSITIVE TRANSPARENCY MATERIAL |
| FI61839C (en) * | 1973-07-27 | 1982-10-11 | Kores Holding Zug Ag | TRYCKKAENSLIGT KALKERINGSMATERIAL |
| AT335477B (en) * | 1975-02-25 | 1977-03-10 | Koreska Ges Mbh W | PRESSURE SENSITIVE RECORDING MATERIAL |
| AT340954B (en) * | 1975-06-06 | 1978-01-10 | Koreska Ges Mbh W | TRANSFER MATERIAL |
| US4183553A (en) * | 1977-02-04 | 1980-01-15 | Ciba-Geigy Corporation | Pressure- or heat-sensitive recording material and novel chromano compounds used therein |
| AT372909B (en) * | 1979-03-20 | 1983-11-25 | Manuel Ing Cespon | COLOR DEVELOPER MATERIALS FOR THE PRODUCTION OF A PRESSURE-SENSITIVE RECORDING MATERIAL WITH PARTICULARLY STRONG COLOR FORMATION AND LIGHT-RESISTANCE |
-
1979
- 1979-03-20 AT AT0207379A patent/AT372909B/en not_active IP Right Cessation
-
1980
- 1980-03-14 EP EP80810088A patent/EP0016730B1/en not_active Expired
- 1980-03-14 DE DE8080810088T patent/DE3061967D1/en not_active Expired
- 1980-03-14 US US06/130,304 patent/US4348234A/en not_active Expired - Lifetime
- 1980-03-17 DE DE19803010201 patent/DE3010201A1/en not_active Withdrawn
- 1980-03-17 FI FI800820A patent/FI72079C/en not_active IP Right Cessation
- 1980-03-18 YU YU739/80A patent/YU43466B/en unknown
- 1980-03-18 MX MX181625A patent/MX154220A/en unknown
- 1980-03-19 ZA ZA00801587A patent/ZA801587B/en unknown
- 1980-03-19 AU AU56586/80A patent/AU536968B2/en not_active Ceased
- 1980-03-19 PT PT70971A patent/PT70971A/en unknown
- 1980-03-19 BR BR8001638A patent/BR8001638A/en unknown
- 1980-03-19 JP JP3416680A patent/JPS55124695A/en active Granted
- 1980-03-20 ES ES490408A patent/ES490408A0/en active Granted
-
1982
- 1982-06-30 US US06/393,896 patent/US4422671A/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| ES8107093A1 (en) | 1981-10-01 |
| ES490408A0 (en) | 1981-10-01 |
| FI72079C (en) | 1987-04-13 |
| YU73980A (en) | 1983-01-21 |
| JPS6259679B2 (en) | 1987-12-11 |
| EP0016730A2 (en) | 1980-10-01 |
| PT70971A (en) | 1980-04-01 |
| ATA207379A (en) | 1983-04-15 |
| MX154220A (en) | 1987-06-19 |
| US4348234A (en) | 1982-09-07 |
| FI800820A (en) | 1980-09-21 |
| JPS55124695A (en) | 1980-09-25 |
| AT372909B (en) | 1983-11-25 |
| DE3010201A1 (en) | 1980-10-02 |
| AU5658680A (en) | 1980-11-27 |
| AU536968B2 (en) | 1984-05-31 |
| US4422671A (en) | 1983-12-27 |
| YU43466B (en) | 1989-08-31 |
| ZA801587B (en) | 1981-03-25 |
| DE3061967D1 (en) | 1983-03-24 |
| FI72079B (en) | 1986-12-31 |
| EP0016730A3 (en) | 1980-10-15 |
| BR8001638A (en) | 1980-11-18 |
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