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
  • B41M5/136—Organic colour formers, e.g. leuco dyes
• • 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
  • B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
  • B41M5/30—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers
  • B41M5/323—Organic colour formers, e.g. leuco dyes

Definitions

• the present invention relates to chromogenic bis-quinazoline compounds, processes for their preparation and their use as color formers in pressure-sensitive or heat-sensitive recording materials.
• Ring B may be unsubstituted or substituted by cyano, halogen, lower alkyl, for example methyl or lower alkoxy such as methoxy
• ring D is a hydrogenated five- or six-membered nitrogen heterocycle, which optionally has a further heteroatom, for example oxygen, sulfur or nitrogen, and is unsubstituted or by Halogen, cyano, hydroxyl, lower alkyl, lower alkoxy, C 5 -C 6 cycloalkyl, benzyl or C 3 -C 6 alkylene is mono- or C-substituted, depending on the substituent.
• Lower alkyl and lower alkoxy in the definition of the residues of the bis-quinazoline compounds are groups or group components which have 1 to 5, preferably 1 to 3, carbon atoms, such as e.g. Methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl or amyl or methoxy, ethoxy, isopropoxy or tert-butoxy.
• Q represents the meaning of an aliphatic radical in particular an alkylene group which is optionally substituted by halogen atoms, especially chlorine.
• the alkylene group can contain 2 to 8 carbon atoms and can be straight-chain or branched.
• the alkylene group preferably has 2 to 5 carbon atoms. These are, for example, the -CH 2 CH 2 -, CH 2 CH 2 -, , , -CH 2 CH 2 CH 2 CH 2 -, -CH 2 - (CH 2 ) 3 -CH 2 -, -CH 2 - (CH 2 ) 4 -CH 2 - or -CH 2 (CH 2 ) 6 -CH 2 group.
• the aliphatic hydrocarbon radical can be interrupted by oxygen atoms and thus represent the remainder of a polyalkylene glycol, such as, for example, polyethylene glycol, polypropylene glycol or polybutylene glycol.
• Q advantageously means the rest of the formula wherein m are 1 to 9, particularly 1 to 3 and s 1 to 5, preferably 1 or 2.
• Q means, for example, the 1,2-cyclopentylene group, the 1,2-cyclohexylene group, the 1,3-cyclohexylene group, the 1,4-cyclohexylene group or
• cycloaliphatic radicals can have one or two methyl groups.
• Q can be used as an araliphatic radical, for example represent.
• Q is preferably the aliphatic or cycloaliphatic radical, in particular alkylene having 2 to 4 carbon atoms and especially ethylene.
• Ring A is preferably not further substituted. If it has substituents it is primarily halogen, lower alkyl or lower alkoxy e.g. further substituted by chlorine, methyl, isopropyl, tert-butyl or methoxy. There may advantageously be 1 or 2 substituents per benzene ring.
• substituents X 1 and X 2 are alkyl groups, they can be straight-chain or branched.
• alkyl radicals are methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, amyl, n-hexyl, 2-ethyl-hexyl, n-octyl, isooctyl or n-dodecyl.
• alkyl radicals in X 1 and X 2 are substituted, they are primarily cyanoalkyl, haloalkyl, hydroxyalkyl or alkoxyalkyl, the alkyl parts preferably having 2 to 4 carbon atoms, such as, for example, ⁇ -cyanoethyl, ⁇ -chloroethyl, ⁇ -hydroxyethyl, ⁇ -methoxyethyl or ⁇ -ethoxyethyl.
• cycloalkyl in the meaning of X 1 and X 2 are cyclopentyl or preferably cyclohexyl.
• the cycloalkyl radicals can contain one or more C 1 -C 4 -alkyl radicals, preferably methyl groups. They preferably have a total of 5 to 10 carbon atoms.
• Preferred substituents in the benzyl and phenyl group of X 1 and X 2 are, for example, halogens, cyano, methyl, methoxy or carbomethoxy.
• Examples of such araliphatic or aromatic radicals are methylbenzyl, chlorobenzyl, cyanophenyl, tolyl, xylyl, chlorophenyl, methoxyphenyl or carbomethoxyphenyl.
• X 1 and X 2 together with the common nitrogen atom represent a heterocyclic radical, this is, for example, pyrrolidino, piperidino, pipecolino, morpholino, thiomorpholino or piperazino, such as, for example, N-methylpiperazino.
• Preferred heterocyclic radicals for NX 1 X 2 are pyrrolidino, piperidino or morpholino.
• X 1 and X 2 are , independently of one another, preferably lower alkyl, benzyl, phenyl, lower alkylphenyl or lower alkoxyphenyl.
• X 3 preferably denotes hydrogen, chlorine, methyl, methoxy or ethoxy.
• Ring B is preferably unsubstituted. However, it can advantageously have a methyl group.
• the ring D is preferably six-membered and especially C-substituted by 1, 2 or 3 methyl groups.
• Z is preferably lower alkyl, benzyl or ⁇ -cyanoethyl.
• Y represents an aminophenyl radical of the formula (3a)
• X 4 and X 5 are lower alkyl or benzyl.
• X 6 is preferably hydrogen.
• Q 1 is preferably alkylene with 2 to 4 carbon atoms and in particular ethylene or propylene.
• Q 1 is preferably also CH 2 CH 2 -O-CH 2 CH 2 - or the cyclohexylene radical.
• the ring A 1 is preferably unsubstituted.
• the N-substituent Z is in particular benzyl, ⁇ -cyanoethyl or alkyl with 1 to 8 carbon atoms, for example n-octyl, n-butyl, isopropyl or especially methyl or ethyl.
• V 1 and V 2 ) or (V 3 and V 4 ) together mean alkylene, they advantageously have 4 or 5 carbon atoms and form a cyclopentane or cyclohexane ring with the carbon atom connecting them.
• bis-quinazoline compounds of the formula (5) in which Q 2 is C 2 -C 4 -alkylene, preferably propylene or especially ethylene or is also -CH 2 CH 2 -O-CH 2 -CH 2 - .
• X 7 and X 8 are preferably benzyl or especially lower alkyl.
• W and T 4 are preferably hydrogen.
• Halogen in compounds with the above substituents in formulas (1) to (5) means, for example, fluorine, bromine or preferably chlorine.
• the bis-quinazoline compounds of the formula (1) according to the invention are prepared by adding 1 mol of a diol compound of the formula (6) HO ⁇ Q ⁇ OH where Q has the meaning given, with 2 mol of a 4-haloquinazoline compound of the formula wherein A and Y have the meaning given and Hal means halogen, such as bromine, fluorine or preferably chlorine.
• the reaction of the compound of formula (6) with the compound of formula (7) is advantageously carried out in the presence of an acid-binding agent, such as, for example, an alkali metal hydroxide, alkali metal carbonate, a tertiary nitrogen base, such as, for example, pyridine or trialkylamines, and preferably also in the presence of a quaternary ammonium salt, such as tetrabutylammonium bromide, optionally in an organic solvent or in an aqueous-organic two-phase medium and at the reflux temperature.
• an acid-binding agent such as, for example, an alkali metal hydroxide, alkali metal carbonate, a tertiary nitrogen base, such as, for example, pyridine or trialkylamines, and preferably also in the presence of a quaternary ammonium salt, such as tetrabutylammonium bromide, optionally in an organic solvent or in an aqueous-organic two-phase medium and at
• solvents examples include cycloaliphatic or aromatic hydrocarbons, such as e.g. Cyclohexane, benzene, toluene or xylene; Chlorinated hydrocarbons, e.g. Chloroform, ethylene chloride or chlorobenzenes, especially dichlorobenzene; Ethers such as Diethyl ether or glycol dimethyl ether; cyclic ethers, e.g. Dioxane or tetrahydrofuran; as well as dimethylformamide, diethylformamide, dimethyl sulfoxide or acetonitrile.
• cycloaliphatic or aromatic hydrocarbons such as e.g. Cyclohexane, benzene, toluene or xylene
• Chlorinated hydrocarbons e.g. Chloroform, ethylene chloride or chlorobenzenes, especially dichlorobenzene
• Ethers such as Diethyl ether or
• the starting materials of the formula (7) can be prepared by, for example, a 2-amino-benzoic acid amide from Fermel with an aldehyde of the formula to a 1,2,3,4-tetrahydro-quinazolone (4) compound of the formula converts this into a compound of the formula oxidized, then the hydroxyl group on the heterocyclic ring of the quinazoline system by a halogen atom, for example by means of phosphorus oxi chloride in dichlorobenzene or thionyl chloride in dimethylformamide to form the starting material of the formula (7).
• the 4-haloquinazoline compound obtained can be used without being isolated.
• oxidizing agents are e.g. Chromates, bichromates, chlorates, chlorites, peroxides, e.g. Hydrogen peroxide, manganese dioxide, lead dioxide, molecular oxygen, air, perborates, permanganates, nitrites, chlorine, bromine and especially chloranil or bisulfites.
• 4-haloquinazoline compounds of formula (7) and 4-quinazolone compounds of formula (13) and their preparation are e.g. in European Patent Publication No. 33716.
• the bis-quinazolines of the formulas (1) to (5) are normally colorless or at most weakly colored. If these color formers are brought into contact with a preferably acidic developer, ie an electron acceptor, they result in intense yellow or orange hues which are outstandingly lightfast and above all sublimation-fast.
• color formers for example 3,3- (bis-aminophenyl) phthalides, 3-indolyl-3-aminophenyl-azaphthalides, 3,3- (bis-indolyl- ) phthalides, 3-aminofluoranes, 2,6-diaminofluoranes, leucoauramines, spiropyrans, Spirodipyrans, chromenoindoles, phenoxazines, phenothiazines, monoquinazolines, carbazolylmethanes or other triarylmethane leuco dyes to give blue, gray or black colors.
• 3- (bis-aminophenyl) phthalides 3-indolyl-3-aminophenyl-azaphthalides
• 3,3- (bis-indolyl- ) phthalides 3-aminofluoranes, 2,6-diaminofluoranes, leucoauramines, spiropyrans, Spi
• the bis-quinazolines of formulas (1) to (5) show excellent color intensity, sublimation and light fastness both on phenolic substrates and especially on activated clays. They are particularly suitable as rapidly developing color formers for use in a heat-sensitive or, in particular, pressure-sensitive recording material, which can be both copying and registration material.
• a pressure-sensitive material consists, for example, of at least one pair of sheets which contain at least one color former of the formulas (1) to (5) dissolved in an organic solvent and an electron acceptor as developer.
• Typical examples of such developers are active clay substances, such as attapulgus clay, acid clay, bentonite, montmorillonite, activated clay, such as, for example, acid-activated bentonite or montmorillonite, also zeolite, halloysite, silicon dioxide, aluminum oxide, aluminum sulfate, aluminum phosphate, zinc chloride, zinc nitrate, activated kaolin or any sound.
• active clay substances such as attapulgus clay, acid clay, bentonite, montmorillonite, activated clay, such as, for example, acid-activated bentonite or montmorillonite, also zeolite, halloysite, silicon dioxide, aluminum oxide, aluminum sulfate, aluminum phosphate, zinc chloride, zinc nitrate, activated kaolin or any sound.
• Other developers are acidic, organic compounds, such as optionally ring-substituted phenols, salicylic acid or salicylic acid esters and their metal salts, furthermore an acidic, polymeric material, such as a phenolic polymer, an alkylphenol acetylene resin, a maleic acid rosin resin, or a partial or Fully hydrolyzed polymer of maleic anhydride with styrene, ethylene or vinyl methyl ether, or carboxypolymethylene. It can mixtures of the polymeric compounds mentioned can also be used.
• Particularly preferred developers are acid clays, zinc salicylates or the condensation products of p-substituted phenols with formaldehyde. The latter can also contain zinc.
• the developers can also be mixed with other per se unreactive or less reactive pigments or other auxiliaries such as silica gel or UV adsorbers, such as 2- (2-hydroxyphenyl) benzotriazoles.
• pigments are: talc, titanium dioxide, zinc oxide, chalk, clays such as kaolin, and organic pigments, for example urea-formaldehyde condensates (BET surface area 2-75 m 2 / g) or melamine-formaldehyde condensation products.
• the color former provides a colored marking at the points where it comes into contact with the electron acceptor.
• these are usually separated from the electron acceptor. This can conveniently be achieved by incorporating the color formers into foam, sponge or honeycomb structures.
• the color formers are preferably enclosed in microcapsules which can usually be broken by pressure.
• the color former solution When the capsules are broken by pressure, for example using a pencil, the color former solution is transferred to an adjacent sheet coated with an electron acceptor, thereby producing a colored area. The color results from the dye formed, which absorbs in the visible range of the electromagnetic spectrum.
• the color formers are preferably encapsulated in the form of solutions in organic solvents.
• suitable solvents are preferably non-volatile solvents, for example polyhalogenated paraffin or diphenyl, such as chlorinated paraffin, monochlorodiphenyl or trichlorodiphenyl, furthermore tricresyl phosphate, di-n-butyl phthalate, di octyl phthalate, trichlorobenzene, trichloroethyl phosphate, aromatic ethers such as benzylphenyl ether, hydrocarbon oils such as paraffin or kerosene, for example derivatives of diphenyl, naphthalene or terphenyl alkylated with isopropyl, isobutyl, sec-butyl or tert-butyl, dibenzyltoluene, partially hydrogenated terphenol Xylenes, mono- to tetramethylated diphenylalkan
• Mixtures of various solvents in particular mixtures of paraffin oils or kerosene and diisopropylnaphthalene or partially hydrogenated terphenyl, are often used in order to achieve optimum solubility for color formation, rapid and intensive coloring and a viscosity which is favorable for microencapsulation.
• the capsule walls can be formed evenly around the droplets of the color former solution by coacervation forces, the encapsulation material e.g. may consist of gelatin and gum arabic, such as e.g. in U.S. Patent 2,800,457.
• the capsules can preferably also be formed from an aminoplast or modified aminoplast by polycondensation, as described in British Patents 989,264, 1 156 725, 301 052 and 1 355 124.
• Microcapsules formed by interfacial polymerization such as e.g. Capsules made of polyester, polycarbonate, polysulfonamide, polysulfonate, but especially made of polyamide or polyurethane.
• the color formers of the formulas (1) to (5) containing microcapsules can be used to produce pressure-sensitive copying materials of various known types.
• the different systems differ essentially from each other in the arrangement of the capsules, the color reactants and the carrier material.
• the encapsulated color former is in the form of a layer on the back of a transfer sheet and the electron acceptor is in the form of a layer on the front of a receiver sheet.
• microcapsules containing the color former and the developer are present in or on the same sheet in the form of one or more individual layers or in the paper pulp.
• the capsules are preferably attached to the carrier by means of a suitable binder.
• this binder is primarily paper coating agents, such as gum arabic, polyvinyl alcohol, hydroxymethyl cellulose, casein, methyl cellulose, dextrin, starch or starch derivatives or polymer latices.
• the latter are, for example, butadiene-styrene copolymers or acrylic homo- or copolymers.
• the paper used is not only normal papers made of cellulose fibers, but also papers in which the cellulose fibers are (partially or completely) replaced by fibers made of synthetic polymers.
• the compounds of formulas (1) to (5) can also be used as color formers in a thermoreactive recording material.
• This usually contains at least one layer support, a color former, an electron acceptor and optionally also a binder and / or wax.
• Thermoreactive recording systems include, for example, heat sensitive recording and copying materials and papers. These systems are used, for example, to record information, for example in electronic computers, remote printers, teletype machines or in recording devices and measuring instruments, such as, for example, electrocardiographs.
• the image generation (marking) can also be done manually done with a heated spring.
• Another device for producing markings by means of heat is laser beams.
• thermoreactive recording material can be constructed such that the color former is dissolved or dispersed in a binder layer and the developer is dissolved and dispersed in the binder in a second layer. Another possibility is that both the color former and the developer are dispersed in one layer.
• the binder becomes more specific. Districts softened by heat and at these points where heat is applied, the color former comes into contact with the electron acceptor and the desired color develops immediately.
• the same electron acceptors are suitable as developers.
• developers are the clay minerals already mentioned and especially phenolic resins, or also phenolic compounds, such as are described for example in DE-PS 12 51 348, e.g.
• 4-tert-butylphenol 4-phenylphenol, 4-hydroxydiphenyl ether, a-naphthol, ⁇ -naphthol, 4-hydroxy-diphenyl-sulfone, 4-hydroxybenzoic acid methyl ester or benzyl ester, 4-hydroxyacetophenone, 2,2'-dihydroxy -diphenyl, 4,4'-isopropylidenediphenol, 4,4'-isopropylidene-bis- (2-methylphenol), 2,2-methylene-bis- (4-phenylphenol), 4,4'-bis- (hydroxyphenyl) - valeric acid, hydroquinone, pyrogallol, phloroglucin, p-, m-, o-hydroxybenzoic acid, gallic acid, 1-hydroxy-2-naphthoic acid, as well as boric acid and organic, preferably aliphatic dicarboxylic acids, such as, for example Tartaric acid, oxalic acid,
• Fusible, film-forming binders are preferably used to produce the thermoreactive recording material. These binders are usually water-soluble, while the bis-quinazolines and developer are sparingly soluble or insoluble in water are. The binder should be able to disperse and fix the color former and developer at room temperature.
• Water-soluble or at least water-swellable binders are e.g. hydrophilic polymers, such as polyvinyl alcohol, polyacrylic acid, hydroxyethyl cellulose, methyl cellulose, CarSoxymethyl cellulose, polyacrylamide, polyvinyl pyrrolidone, gelatin, starch or esterified corn starch.
• hydrophilic polymers such as polyvinyl alcohol, polyacrylic acid, hydroxyethyl cellulose, methyl cellulose, CarSoxymethyl cellulose, polyacrylamide, polyvinyl pyrrolidone, gelatin, starch or esterified corn starch.
• water-insoluble binders i.e. binders soluble in non-polar or only weakly polar solvents, e.g. Natural rubber, synthetic rubber, chlorinated rubber, alkyd resins, polystyrene, styrene / butadiene copolymers, polymethylacrylates, ethyl cellulose, nitrocellulose and polyvinyl carbazole
• binders soluble in non-polar or only weakly polar solvents
• Natural rubber, synthetic rubber, chlorinated rubber, alkyd resins, polystyrene, styrene / butadiene copolymers, polymethylacrylates, ethyl cellulose, nitrocellulose and polyvinyl carbazole can be used.
• the preferred arrangement is one in which the color former and the developer are contained in one layer in a water-soluble binder.
• thermoreactive layers can contain further additives.
• these layers for example talc, titanium dioxide, zinc oxide, aluminum oxide, aluminum hydroxide, calcium carbonate (for example chalk), clays or even organic pigments, such as for example urea Formaldehyde polymers.
• substances such as urea, thiourea, diphenylthiourea, acetamide, acetanilide, stearic acid amide, phthalic anhydride, metal stearates, such as, for example, zinc stearate, phthalic acid nitrile, dimethyl terephthalate products or other corresponding, meltable products induce the simultaneous melting of the color former and the developer will.
• Thermographic recording materials preferably contain waxes, for example carnauba wax, montana wax, paraffin wax, polyethylene wax, condensates of higher fatty acid amides and formaldehyde or condensates of higher fatty acids and ethylenediamine.
• Example 1 29.3 g of the quinazolone compound of the formula 16 g of phosphorus oxychloride are added to 70 g of xylene (isomer mixture, bp. 138-142 ° C) at 90 ° C. The reaction mixture is stirred at this temperature for 1 hour and a dark red solution of the 4-chloro-2- (4'-diethylaninophenyl) -quinazoline compound of the formula is obtained
• the solution is added dropwise to a suspension of 3.1 g of ethylene glycol, 100 g of sodium hydroxide solution (50%) and 1 g of tetrabutylammonium bromide.
• the suspension is then stirred under reflux for one hour and then 150 ml of water are added at 90.degree.
• the xylene phase is separated and washed several times with hot water.
• the xylene phase is then allowed to cool with stirring and 100 g of methanol are added at 35.degree.
• the maximum reflectance of this bis-quinazoline compound on acid-coated paper is 464 nm.
• Example 15 17 g of the quinazolone compound of the formula are suspended in 90 g of toluene at 90 ° C. The mixture is chlorinated by metering in 8 g of phosphorus oxitrichloride at 90 ° C. for 30 minutes. The red reaction solution of the compound of the formula
• Recrystallization from toluene / isopropyl alcohol 7: 3 gives the pure product with a melting point of 228-229 ° C.
• This color former develops a yellow color with good light fastness on acid clay.
• the color former is also characterized by excellent sublimation fastness.
• a solution of 3 g of the bis-quinazoline compound of the formula (21) in 80 g of partially hydrogenated terphenyl and 17 g of kerosene is microencapsulated in a manner known per se with gelatin and gum arabic by coacervation, mixed with starch solution and spread on a sheet of paper.
• a second sheet of paper is coated on the front with acid-activated bentonite as a color developer.
• the first sheet and the paper coated with color developer are placed on top of each other with the coatings adjacent. Writing by hand or with the typewriter on the first sheet exerts pressure, and an intense yellow copy develops on the sheet coated with the developer, which is excellent in sublimation and lightfastness.
• Example 18 1 g of the bis-quinazoline compound of the formula (21) is dissolved in 17 g of toluene. 12 g of polyvinyl acetate, 8 g of calcium carbonate and 2 g of titanium dioxide are added to this solution with stirring. The suspension obtained is diluted in a weight ratio of 1: 1 with toluene and spread on a sheet of paper using a 10 ⁇ m doctor blade. A second sheet of paper is placed on this sheet of paper, the underside of which has been coated with a mixture consisting of 1 part of an amide wax, 1 part of a stearic wax and 1 part of zinc chloride at an application weight of 3 g / m 2 . By writing by hand or with a typewriter on the top sheet, pressure is exerted and an intense, sublimation and lightfast yellow color develops on the sheet coated with the color formers.
• Example119 Production of a heat sensitive recording material
• the two dispersions are combined and coated onto a paper with a dry application weight of 5.5 g / m 2 .
• a paper with a dry application weight of 5.5 g / m 2 By touching the paper with a heated ballpoint pen, an intense yellow color is obtained which has excellent sublimation and light fastness.
• Intense and lightfast yellow colors can also be obtained using any of the other color formers of formula (22) given in Preparation Examples 2-15.
• Example 20 2.7 g of the bis-quinazoline compound of the formula (21), 24 g of N-phenyl-N '- (1-hydroxy-2,2,2-trichloroethyl) urea, 16 g are placed in a ball mill Stearic acid amide, 59 g of an 88% hydrolyzed polyvinyl alcohol and 58 ml of water ground until the particle size is 2-5 ⁇ m. This suspension is spread on a sheet of paper at a dry application weight of 5.5 g / m 2 . By touching the paper with a heated ballpoint pen, an intense, sublimation and lightfast yellow color is obtained.

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• Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• General Chemical & Material Sciences (AREA)
• Physics & Mathematics (AREA)
• Optics & Photonics (AREA)
• Plural Heterocyclic Compounds (AREA)
• Color Printing (AREA)
• Heat Sensitive Colour Forming Recording (AREA)
• Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)

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• 1985
  • 1985-04-11 US US06/721,963 patent/US4668966A/en not_active Expired - Lifetime
  • 1985-04-12 EP EP85810163A patent/EP0159295B1/fr not_active Expired
  • 1985-04-12 DE DE8585810163T patent/DE3568733D1/de not_active Expired
  • 1985-04-15 FI FI851493A patent/FI87070C/fi not_active IP Right Cessation
  • 1985-04-16 YU YU00643/85A patent/YU64385A/xx unknown
  • 1985-04-17 ES ES542331A patent/ES542331A0/es active Granted
  • 1985-04-18 JP JP60081479A patent/JPS60233065A/ja active Granted

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