Classifications

• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
  • G03C1/00—Photosensitive materials
  • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
  • G03C1/035—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein characterised by the crystal form or composition, e.g. mixed grain
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
  • G03C1/00—Photosensitive materials
  • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
  • G03C1/46—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein having more than one photosensitive layer
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
  • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
  • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
  • G03C7/3022—Materials with specific emulsion characteristics, e.g. thickness of the layers, silver content, shape of AgX grains
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
  • G03C1/00—Photosensitive materials
  • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
  • G03C1/035—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein characterised by the crystal form or composition, e.g. mixed grain
  • G03C2001/03564—Mixed grains or mixture of emulsions
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
  • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes

Definitions

• ABSTRACT least 30C by means of an aromatic primary amino colour developing agent in the presence of a colour forming coupling compound, wherein the said element comprises at least one layer of a silver halide emulsion obtained by mixing, prior to coating, with the silver halide emulsion capable of producing a visible image by the said radiation-wise exposure and subsequent development, a relatively low-speed silver chloridecontaining emulsion, the speed of which is insufficient to produce a visible image by the said exposure and development.
• the non-image forming silver chloride-containing emulsion to the image' forming silver halide emulsion colour images with satisfactory contrast are obtained upon processing at elevated temperature which is of particular importance for the production of radiographic colour images.
• the present invention relates to processes for producing photographic colour images by rapid processing at elevated temperature of exposed photographic lightsensitive silver halide colour materials.
• normal processing is modified e.g. in that one or more steps are combined or one or more steps are eliminated and other steps are included as is for instance the case in the so-called stabilisation processing
• speed of normal processing can be enhanced by such means as the use of higher concentrations of the processing ingredients, the use of higher temperatures, the recourse to more intense agitations and the use of development-activating substances.
• colour materials are of ever increasing interest. They are used in the most divergent areas of photography where it is often highly desirable to dispose of the recorded information in a minimum of time. For instance, colour materials are now used also in the field of radiography since the use of radiographic colour recording materials makes it possible to visually retrievemore information from the recorded image than from a corresponding black-andwhite image since the latter only provides differences in brightness while a colour image offers in addition thereto differences in hue and saturation.
• coloured radiographs reference may be made e.g.
• the gradation is not or much less reduced by rapid development at increased temperature and remains in a satisfactory range when to the image-forming silver halide emulsion a very low speed non-image-forming silver chloride-containing emulsion is added. This is illustrated in the examples below. Experiments wherein the low speed silver chloride containing emulsion was coated as a separate layer underneath the imageforming silver halide emulsion layer showed that this arrangement has less effect on the gradation when rapidly processing at increased temperature and therefore is less useful.
• a method of producing photographic colour images, which method comprises colour'developing in the presence of a colour coupler at a temperature of at least 30C, a photographic element comprising an exposed silver halide emulsion layer wherein the said silver halide emulsion layer is obtained by mixing prior to coating with the silver halide emulsion capable of producing a visible image by the said exposure and subsequent development, a relatively low-speed silver chloride containing emulsion, the speed of which is insufficient to produce a visible image by the said exposure and development.
• the colour couplers which upon colour develop ment couple with the oxidation products of the aromatic primary amino colour developing agent, are preferably incorporated into the photographic emulsion in a non-migratory form, but they may also be dissolved in the emulsion from the developing bath.
• the speed of the silver chloride-containing emulsion is not important as long as a visible image is not formed therein upon exposure and development of the imageforming silver halide emulsion.
• the blue light sensitivity of the image-forming silver halide emulsion is at least 100 times the blue-light-sensitivity of the silver chloride-containing emulsion. Since lightsensitivity of the silver chloride containing emulsion is not a factor the silver chloride-containing emulsion does not require a second digestion or after ripening.
• the low-speed silver chloride-containing emulsion, which is washed free of excess salts, is preferably a finegrain silver chloride-containing emulsion having a particle size in the range from 50 to 500 nm.
• the amount of low-speed silver chloride containing emulsion to be added to the image-forming silver halide emulsion may vary within very wide limits. Favourable results may be obtained even when the ratio of low speed silver chloride to image-forming silver halide, ex-
• pressed in parts by weight of silver nitrate is as low as 1:100.
• the amount to be added for obtaining optimal results is dependent on the particular effect desired, on the kind of image-forming silver halide emulsion, on the nature of the low speed silver chloride containing emulsion, etc., and can be easily determined by some simple tests known to those skilled in the art.
• the low'speed emulsion may be a pure silver chloride emulsion or an emulsion of mixed silver halides comprising silver chloride for example a silver chlorobromide emulsion.
• Low speed silver bromide or silver bromoiodide emulsions cannot be used. lt-would appear that the aimed effect is dependent on the silver chloride content in the said low speed emulsion, which means that the amount of low speed emulsion to be added for obtaining a certain effect is generally higher as the amount of silver chloride in the said emulsion is lower. Therefore, in order to minimize the amount of low speed emulsion to be added to the image-forming silver halide emulsion, the said low speed emulsion is preferably a silver chloride emulsion for the greater part.
• the image-forming silver halide emulsion is preferably a medium or high speed image-forming silver halide emulsion in which the silver halide is predominantly silver bromide for example pure silver bromide emulsions and silver bromoiodide emulsions, the iodide content of which is less than mole
• the image-forming silver halide emulsion may be chemically sensitized by any of the accepted procedures.
• the emulsions may be digested with naturally active gelatin or with small amounts of sulphur containing compounds such as allyl thiocyanate, allyl thiourea, sodium thiosulphate, etc.
• the image-forming emulsion may also be sensitized by means of reductors for instance tin compounds as described in the United Kingdom Patent Specification No. 789,823 filed Apr. 29, 1955 by Gevaert Photo-Producten N.V., polyamines e.g. diethyltriamine, and small amounts of noble metal compounds such as gold, platinum, palladium, iridium, ruthenium and rhodium as described by R. Koslowsky, Z. Wiss. Phot. 46, 67-72 1951).
• noble metal compounds are ammonium chloropalladate, potassium chloroplatinate, potassium chloroaurate and potassium aurithiocyanate.
• the reductors for instance tin compounds as described in the United Kingdom Patent Specification No. 789,823 filed Apr. 29, 1955 by Gevaert Photo-Producten N.V., polyamines e.g. diethyltriamine, and small amounts of noble metal compounds such as gold, platinum, palladium, irid
• emulsions may also be sensitized chemically by the combined use of these chemical sensitizers.
• Emulsion stabilizers and antifoggants may be added to the silver halide emulsion before or after admixture of the low-speed emulsion, for instance, the known sulphinic and selenic acids or salts thereof, aliphatic, aromatic or heterocyclic mercapto compounds or disulphides, preferably comprising sulpho groups or carboxyl groups, mercury compounds for example those described in Belgian Patents 524,121 filed Nov. 7, 1953 by Kodak S.A., 677,337 filed Mar. 4, 1966, 707,386 filed Dec. 1, 1967 and 709,195 filed Jan. 11, 1968 all three by Gevaert-Agfa NV. and tetraazaindenes as described by Birr in Z. Wiss. Phot. 47, 2-58 (1952) e.g. the hydroxy tetra-azaindenes of the following general formula:
• each of R and R represents a hydrogen atom, an alkyl, an aralkyl, or an aryl group
• R represents a hydrogen atom, an alkyl, a carboxy
• additives for example hardening agents, wetting agents, plasticizers, screening dyes and spectrally sensitizing dyes can be present in the radiationsensitive silver halide elements of the invention.
• development of the exposed photographic silver halide material occurs at temperatures of at least 30C, preferably between 35C and 45C.
• the development applied in carrying out the method of the present invention is preferably an energetic surface development.
• the high energy is required in order to allow the development to proceed quickly and may be obtained by properly alkalizing the developing liquid (pH 9-12), by using high-energy developing substances or a combination of developing substances, which as a consequence of their superadditive action is very energetic.
• Aromatic primary amino colour developing agents for example N,N-dialkyl-p-phenylene diamines and derivatives e.g. N,N-diethyl-p-phenylene diamine, N- butyl-N-sulphobutyl-p-phenylene diamine, 2-amino-5- diethylaminotoluene hydrochloride and 4-amino-N- ethyl-N(B-methane sulphonamidoe thyl)-m-toluidine sesquisulphate monohydrate and N-hydroxyethyl-N- ethyl-p-phenylene diamine can be used together with black-and-white developing agents for example l-phenyl-3-pyrazolidinone and p-monomethylaminophenol which are known to have a superadditive'effect on colour development (see L.F.A.
• development accelerators can be used either in the silver comprising in one or more silver halide emulsions colhalideemulsion or in the developing bath.
• development accelerators include alkylene oxide compounds ,of various types e.g. alkylene oxide condensation products or polymers as described in US. Pat. Nos. 1,970,578 of Conrad Schoeller and Max Wittwer, issued Aug. 21, 1934, 2,240,472 of Donald R. Swan, issued Apr.
• development accelerating compounds are onium and polyonium compounds preferably of the ammonium, phosphonium, and sulphonium type for example trialkyl sulphonium sa'ltssuch as dimethyl-n-nonyl sulphonium ptoluene sulphonate, tetra-alkyl ammonium salts such as dodecyl trimethyl ammonium p-toluene sulphonate, alkyl pyridinium and alkyl quinolinium salts such as l-m-nitrobenzyl quinolinium chloride and l-dodecyl pyridinium chloride, bisalkylene pyridinium salts such as N,N-trtramethylene bispyridinium chloride, quaternary ammonium and phosphonium polyoxyalky
• the developing solutions may also comprise any of the usual additional ingredients for example sodium sulphite and hydroxylamine or derivatives thereof, hardening agents, antifoggantsfor instance benzotriazole, S-nitro-benzimidazole, 5-nitro-indazole, halides such as potassium bromide, silver halide solvents, toning and intensifying compounds, solvents for instance dimethylformamide, dimethylacetamide and N-methylpyrrolidone for chemical ingredients that are difiicult to dissolve in the preparation of the developing solutions or that tend to precipitate upon standing, etc.
• additional ingredients for example sodium sulphite and hydroxylamine or derivatives thereof, hardening agents, antifoggantsfor instance benzotriazole, S-nitro-benzimidazole, 5-nitro-indazole, halides such as potassium bromide, silver halide solvents, toning and intensifying compounds, solvents for instance dimethylformamide, dimethylacetamide and N-methylpyrrolidone for chemical ingredients
• the invention is of particular importance for use in the production of coloured radiographs by rapid development at elevated temperature of radiographic colour our forming coupling compounds, which upon development enter into reaction with the oxidation products of the aromatic primaryamino colour developing agents to form dye images.
• radiographic colour elements are preferably of the type described in. United States Patent application Ser. No. 852,246 mentioned above, which corresponds to the published German Patent Application 1,946,652 mentioned above and therefore this application should be read in conjunction herewith.
• monochromic radiographic images are produced, optionally together with a silver image in radiographic elements, which preferably comprise a colourless support and at least one silver halide emulsion layer, each such layer containing at least one colour coupler producing by coupling with an oxidized aromatic primary amino developing agent a monochromic dye image mainly absorbing in the red and green spec tral regions.
• a low-speed-silver chloride-containing emulsion is mixed in the preparation of these radiographic elements, with the radiographic silver halide emulsions itis possible to obtain upon rapid development at elevated temperature improved speed and gradation characteristics and radiographic dye images can be obtained, which have as high a gradation as obtainable upon long time development at ambient temperature of the single radiographic colour emulsions.
• the monochromic radiographic dye image preferably has its main absorption in the red region (600-700 nm) of the visible spectrum and it absorbs in the green region (500-600 nm) of the visible spectrum for at least 30 percent in respect to the red region. in other words cyan dye images with a fairly large sideabsorption in the green region and blue dye images are favoured.
• phenol or a-naphthol type colour couplers that on colour development of the exposed silver halide with an aromatic primary amino developing agent form a quinoneimine dye mainly absorbing in the red and green and having an absorption maximum in the spectral wavelength range of 550 to 700 nm, are particularly suitable.
• Phenol couplers having such properties correspond, s. t thafqllsniasss tal.tq taula;
• R and R each represents a carboxylic acid acyl or sulphonic acid acyl group including said groups in substituted state, e.g. an aliphatic carboxylic acid acyl group, an aromatic carboxylic acid acyl group, an heterocyclic carboxylic acid acyl group, e.g. a 2-furoyl group or a 2-thienoyl group, an aliphatic sulphonic acid acyl group, an aromatic sulphonic acid acyl group, a sulphonyl thienyl group, an-
• aryloxy-substituted aliphatic carboxylic acid acyl group a phenyl carbamyl aliphatic carboxylic acid acyl group, or a tolyl carboxylic acid acyl group.
• the radiographic image-forming silver halide emulsions may comprise different types of silver halide e.g. silver chloride, silver bromide, silver chlorobromide, silver bromoiodide, and silver chlorobromoiodide.
• Bromide emulsions containing iodide, preferably containing less than mole of iodide, are especially useful for directly or indirectly recording penetrating radiation in the form of a monochromic image.
• the radiographic colour elements preferably comprise on both sides of a transparent support e.g. a transparent resin support, a silver halide emulsion layer comprising a colour coupler for producing a monochromic dye image and a protective hydrophilic colloid layer coated thereover.
• a transparent support e.g. a transparent resin support
• a silver halide emulsion layer comprising a colour coupler for producing a monochromic dye image and a protective hydrophilic colloid layer coated thereover.
• the formation of the silver halide emulsions and the protective colloid coatings all kinds of ingredients characteristic for the formation of radiographic elements used in the direct or indirect recording of penetrating radiation, may be employed.
• These ingredients include chemical and spectral sensitizers, antifoggants, stabilizers and development accelerators as described hereinbefore as well as hardening agents e.g. formaldehyde, dialdehydes, hydroxy aldehydes, mucochloric and mucobromic acid, acrolein, and glyoxal, lightscreening dyes, mordanting agents for anionic colour couplers or dyes formed therefrom, plasticizers and coating aids, e.g.
• dialkylsulphosuccinic acid salts such as sodium diisooctylsulphosuccinate, alkylaryl polyether sulphuric acids, alkylaryl polyether sulphonic acids, carboxyalkylated polyethylene glycol ethers or esters as described in French Patent Specification 1,537,417 filed September 18, 1967 by Agfa-Gevaert N.V.
• iSOC H17-'C6H4(OCH2CH2)EOCH- COONa fluorinated surfactants e.g. those described in Belgian Patent Specification 742,680 filed Decem her 5, 1969 by Gevaert-Agfa N.V.
• the exposed radiographic colour elements are processed in accordance with the present invention at elevated temperature, preferably in conventional automatic processing apparatus for X-ray films in which the photographic material may be guided automatically and at a constant speed from one processing unit to the other in such a way that the processing time in each processing unit does not last longer than 1 minute at 30C.
• the development step need not be followed by a bleaching step so that a processing as simple as that for producing black-and-white radiographs can be applied.
• EXAMPLE 1 5 samples were prepared by adding each time to 157 g of a high speed silver bromoiodide emulsion (9 mole of Agl), which comprises an amount of silver halide equivalent to 26.8 g of silver nitrate and 17.8 g of gelatin, the following:
• sample 1 14.5 g of gelatin for sample 2 14.2 g of gelatin and 4.6 g of a low speed silver chloride emulsion comprising an amount of silver chloride equivalent to 0.54 g of silver nitrate and 0.29 g of gelatin so as to obtain in the mixture the same total amount of gelatin as "in sample 1 and a ratio of silver bromoiodide to silver chloride corresponding to :2 in parts by weight of silver nitrate;
• the five samples thus contain the same amount of gelatin, the same amount of silver bromoiodide and increasing amounts of silver chloride.
• the low speed silver chloride emulsion was prepared by admixing an aqueous solution of silver nitrate to an aqueous gelatin-sodium chloride solution, precipitating the gelatin emulsion with ammonium sulphate, washing and peptizing. Gelatin was then added as well as 5- methyl-7-hydroxy-s triazolo[ l,5-a]pyrimidine so that no chemical ripening occurred.
• the mean grain-size of the silver chloride emulsion was 220 nm.
• Strips of the 5 film samples obtained were exposed to light through a wedge under identical circumstances and then colour-processed (A) at ambient temperature (C) and (B) at increased temperature (41C), as
• the coloured photographic wedge prints thus obtained were measured by means of a conventional colour densitometer provided with a red filter.
• the sensitometric results are listed in table 2.
• the log E values measured for the speed at density 0.25 above fog are given in the form of relative values, the value of 100 being given to the speed of filmsample 1 processed at ambient temperature.
• As gradation-values are given the slopes of the sensitometric curves between densities 0.25 above fog and 2.00 above fog.
• sample 1 15.2 g of gelatin for sample 2 9.4 g of gelatin and 91.2 g of the silver chloride emulsion of example 1 so as to obtain the same total amount of gelatin as in sample 1 and a ratio of silver bromoiodide to silver chloride corresponding to 100220 in parts by weight of silver nitrate;
• the addition of the silver chloride emulsion causes an increase of the speed both at 20C (from 100 to l 14) and 41C (from 95 to 141) the speed increase being, however, markedly higher at 41C.
• EXAMPLE 3 Five film samples were prepared in the same way as described in example 1 with the only'difference that the silver bromoiodide emulsion used now contained 5 mole of silver iodide instead of 9 mole Exposure and processing of the film samples occurred as described in example 1 with the difference that, owing to the greater developability of the high speed emulsion with lower silver iodide content, the development time was reduced to 3 min. 15 sec. at 20C (processing A) and to 18 sec. at 41C (processing B).
• EXAMPLE 4 Five emulsion samples were prepared in a similar way as described in example 1, with the difference that the low speed silver chloride emulsion was added to the high speed silver bromoiodide emulsion in the form of 'ide:
• sample 1 only silver bromoiodide sample 2 an amount of silver bromoiodide equivalent to 100 parts of silver'nitrate and an amount of silver chloride equivalent to 1.9 part of silver nitrate sample 3 an amount of silver bromoiodide equivalent to 100 parts of silver nitrate and an amount of silver chloride equivalent to 9.5 parts of silver nitrate.
• sample 4 an amount of silver bromoiodide equivalent to 100 parts of silver nitrate and an amount of silver chloride equivalent to 19 parts of silver nitrate.
• sample 5 an amount of silver bromoiodide equivalent to 100 parts of silver nitrate and an amount of silver chloride equivalent to 47.5 parts of silver nitrate.
• EXAMPLE 5 2 emulsion samples were prepared by adding each time to 202 g of a high speed silver bromoiodide emulsion (5 mole of Agl), which comprises an amount of silver halide equivalent to 25.9 g of silver nitrate and 25.9 gof gelatin, the following:
• sample 1 514.2 g of gelatin for sample 2: 7.2 g of gelatin and 117 g of a silve chloride emulsion as described in example 1 so as to obtain in the mixture the same total amount of gelatin as in sample 1 and a ratio of silver bromoiodide to silver chloride corresponding to 100250 in parts by weight of silver nitrate. Both samples were molten as described in example 1, and to each were added:
• a method for producing a color image with photographic color materials wherein a latent image in a radiographically exposed photographic element comprising at least one photographic silver halide emulsion layer is color developed at a temperature of at least 30C. by means of an aromatic primary amino colordeveloping agent in the presence of a color-forming coupling compound including the sequential steps of (a) mixing a silver halide emulsion which will produce a visible image upon radiographic exposure and subsequent development atsaid elevated temperature with a relatively lowspeed silver chloride-containing emulsion, the speed of which is insufficient to produce a visible image upon radiographic exposure and subsequent development at said elevated temperature; (b) using said mixed emulsion (a) to form a photographic element; (c) radiographically exposing said element (b); and (d) developing photographic element (c) at a temperature of at least 30C. with a color developer containing an aromatic primary amino color-developing agent and a color-forming coupler compound.
• said silver halide emulsion layer contains at least one color coupler which upon development by coupling with an oxidized aromatic primary amino color developing agent produces a monochromic dye image mainly absorbing in the red and green spectral regions.
• the said dye in said image has its main absorption in the red region (600-700 nm) of the visible spectrum and absorbs in the green region (500-600 nm) of the visible spectrum for at least 30 percent in respect of the red region.
• each of R, and R is a carboxylic or sulphonic acid a y p- 13.
• the said silverchloride-containing emulsion has a particle size between 50 and 500 nm.
• a radiographic element according to claim 14, wherein the image-forming silver halide emulsion is a medium or high speed silver bromide or silver bromoiodide emulsion.
• a radiographic element according to claim 14, wherein the said dye in said image has its main absorption in the red region (600-700 nm) of the visible spectrum and absorbs in the green region (500-600 nm) of the visible spectrum for at least 30 percent in respect of the red region.

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• 1971
  • 1971-01-05 GB GB47971*[A patent/GB1378171A/en not_active Expired
  • 1971-11-29 AU AU36238/71A patent/AU457982B2/en not_active Expired
  • 1971-12-17 ZA ZA718440A patent/ZA718440B/xx unknown
  • 1971-12-21 US US00210566A patent/US3820991A/en not_active Expired - Lifetime
  • 1971-12-24 JP JP414772A patent/JPS5440939B1/ja active Pending
  • 1971-12-27 CH CH1890571A patent/CH582895A5/xx not_active IP Right Cessation
  • 1971-12-27 FR FR7146924A patent/FR2120950A5/fr not_active Expired
  • 1971-12-29 CA CA131,301A patent/CA965290A/en not_active Expired
  • 1971-12-29 DE DE2165193A patent/DE2165193C2/de not_active Expired
  • 1971-12-30 BE BE777581A patent/BE777581A/nl not_active IP Right Cessation
• 1972
  • 1972-01-03 SU SU1732678A patent/SU507263A3/ru active
  • 1972-01-04 SE SE7200067A patent/SE381351B/xx unknown
  • 1972-01-04 IT IT86202/72A patent/IT949625B/it active
  • 1972-01-05 ES ES398642A patent/ES398642A1/es not_active Expired
  • 1972-01-05 NL NLAANVRAGE7200116,A patent/NL173101C/xx not_active IP Right Cessation

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