Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
  • C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
  • C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
  • C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
  • C07D239/32—One oxygen, sulfur or nitrogen atom
  • C07D239/42—One nitrogen atom
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
  • C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
  • C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
  • C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
  • C07D239/46—Two or more oxygen, sulphur or nitrogen atoms
  • C07D239/47—One nitrogen atom and one oxygen or sulfur atom, e.g. cytosine
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
  • C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
  • C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
  • C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
  • C07D239/46—Two or more oxygen, sulphur or nitrogen atoms
  • C07D239/50—Three nitrogen atoms
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
  • C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
  • C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
  • C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
  • C07D239/46—Two or more oxygen, sulphur or nitrogen atoms
  • C07D239/52—Two oxygen atoms
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
  • C07D295/04—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms
  • C07D295/08—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly bound oxygen or sulfur atoms
  • C07D295/084—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly bound oxygen or sulfur atoms with the ring nitrogen atoms and the oxygen or sulfur atoms attached to the same carbon chain, which is not interrupted by carbocyclic rings
  • C07D295/088—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly bound oxygen or sulfur atoms with the ring nitrogen atoms and the oxygen or sulfur atoms attached to the same carbon chain, which is not interrupted by carbocyclic rings to an acyclic saturated chain
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
  • C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
  • C09B23/0066—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain being part of a carbocyclic ring,(e.g. benzene, naphtalene, cyclohexene, cyclobutenene-quadratic acid)
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
  • C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
  • C09B23/14—Styryl dyes
  • C09B23/148—Stilbene dyes containing the moiety -C6H5-CH=CH-C6H5
• • 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
  • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
  • G03C1/08—Sensitivity-increasing substances
  • G03C1/10—Organic substances
  • G03C1/12—Methine and polymethine dyes
• • 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
  • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
  • G03C1/08—Sensitivity-increasing substances
  • G03C1/28—Sensitivity-increasing substances together with supersensitising substances
• • 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
  • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
  • G03C1/34—Fog-inhibitors; Stabilisers; Agents inhibiting latent image regression
• • 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
  • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
  • G03C1/34—Fog-inhibitors; Stabilisers; Agents inhibiting latent image regression
  • G03C1/346—Organic derivatives of bivalent sulfur, selenium or tellurium

Definitions

• This invention relates to new and improved antifoggants and stabilizers for photographic elements and to photographic silver halide emulsions containing said antifoggants and stabilizers therein.
• the invention also relates to a process of developing photographic elements in the presence of new and improved antifoggants.
• n is either 1 or 2 and, when n is l, R and R may be alkyl (e.g. methyl, ethyl, octyl, etc.), cycloalkyl (e.g.
• a fogstabilizing amount of an N,N-disubstituted aminomethylthiocarboxylic acid is incorporated into the silver halide emulsion of a photographic element or in a layer contiguous to the silver halide emulsion.
• the N,N-disubstituted aminomethylthiocarboxylic acid stabilizes the emulsion against fog when the dried emulsion has been subjected to a prolonged high humidity and temperature incubation period without adversely affecting other sensitometric properties.
• a photographic element comprising a support coated with at least one silver halide emulsion layer is developed in the presence of an N,N-disubstituted aminomethylcarboxylic acid.
• this compound is present in the photographic element but it may be present elsewhere in the system--e.g., in the developer.
• Preferred groups of compounds of this invention which are particularly useful as antifoggants in photographic emulsions are those wherein the radical Y in the above general formula is one of the following groups: tCHfi wherein m is an integer from 1 to 5 and, preferably, is l or 2;
• n is an integer from 1 to 5 and, preferably, is l;
• p is an integer from 0 to 7 and, preferably is 0.
• novel compounds of this invention are prepared by reacting a thiocarboxylic acid with an N,N-disubstituted alkoxymethylamine in an appropriate solvent. Since the N,N-disubstituted aminomethylthiocarboxylic acids may exist as internal salts and the other products of the reaction are alcohols, it is preferable, for ease of isolation, that these compounds he prepared in a nonpolar reaction solvent in which the internal salts are insoluble or only sparingly soluble and in which the alcohols which are also formed during the reaction are miscible. Examples of such solvents are acetone, 2-butanone, benzene, diethyl ether, etc. The reaction usually proceeds without the need for external heating and is generally effected at or below room temperature.
• the N,N-disubstituted aminomethylcarboxylic acid may be incorporated into the silver halide emulsion of a photographic element or in a layer contiguous to the silver halide emulsion in any amount which will stabilize the silver halide emulsion against fog.
• a concentration of the N,N-disubstituted aminomethylcarboxylic acid in an amount of from about 0.01 to about 10, preferably about 0.015 to about 0.5 gram per mole of silver in the silver halide emulsion can be used with goOd results.
• the preparation of photographic silver halide emulsions such as are suitably stabilized with an N,N-disubstituted aminomethylcarboxylic acid typically involves three separate operations: (1) emulsification and digestion of silver halide, (2) the freeing of the emulsion of excess watersoluble salts, suitably by washing with water, and (3) the second digestion or after-ripening to obtain increased emulsion speed or sensitivity. (Mees, The Theory of the Photographic Process, 1954).
• the N,N-disubstituted aminomethylcarboxylic acid can be added to the emulsion before the final digestion or after-ripening or it can be added immediately prior to the coating. It may be added as a free acid or as its salts.
• the silver halide emulsion of a photographic element containing the antifoggants of this invention can contain conventional addenda such as gelatin plasticizers, coating aids, and hardeners such as aldehyde hardeners, e.g., formaldehyde, mucochloric acid, glutaraldehyde bissodiu'm bisulfite), maleic dialdehyde, aziridines, dioxane derivatives and oxypolysaccharides.
• Spectral sensitizers which can be used are the cyanines, merocyanines, complex (trinuclear) cyanines, complex (trinuclear) merocyanines, styryls, and hemicyanines.
• Sensitizing dyes useful in sensitizing such emulsions are described, for example in U.S. Patents 2,526,632 of Brooker and White issued Oct. 24, 1950, and 2,503,776 of Sprague issued Apr. 11, 1950.
• Developing agents can also be incorporated into the silver halide emulsion if desired or can be contained in a contiguous layer.
• Various silver salts can be used as the sensitive salt such as silver bromide, silver iodide, silver chloride, or mixed silver halides such as silver chlorobromide or silver bro-moiodide.
• the silver halides used can be those which form latent images pre dominantly on the surface of the silver halide grains or those which form latent images inside the silver halide crystals such as described in U.S. Patent 2,592,250 of Davey and Knott issued Apr. 8, 1952.
• the silver halide emulsion layer of a photographic element containing the antifoggants of the invention can contain any of the hydrophilic, water-permeable binding materials suitable for this purpose. Suitable materials include gelatin, colloidal albumin, polyvinyl compounds, cellulose derivatives, acrylamide polymers, etc. Mixtures of these binding agents can also be used.
• the binding agents for the emulsion layer of the photographic element can also contain dispersed polymerized vinyl compounds. Such compounds are disclosed, for example, in U.S. Patents 3,142,568 of Nottorf issued July 28, 1964; 3,193,386 of White issued July '6, 1965; 3,062,674 of Houck, Smith and Yudelson issued Nov.
• the silver halide emulsion of a photographic element containing the antifoggants of the invention can be coated on a wide variety of supports.
• Typical supports are cellulose nitrate film, cellulose ester film, polyvinyl acetal film, polystyrene film, poly(ethylene terephthalate) film and related films or resinous materials as well as glass, paper, metal and the like.
• Supports such as paper which are coated with a a-olefin poly'mers, particularly polymers or a-olefins containing two or more carbon atoms, as exemplified by polyethylene, polypropylene, ethylenebutene copolymers and the like can also be employed.
• the speed of the photographic emulsions containing the antifoggants of the invention can be further enhanced by including in the emulsions a variety of hydrophilic colloids such as carboxymethyl protein of the type described in U.S. Patent 3,011,890 of Gates, Jr., Miller and Koller issued Dec. 5, 1961, and polysaccharides of the type described in Canadian Patent 635,206 of Koller and Russell issued J an. 23, 1962.
• hydrophilic colloids such as carboxymethyl protein of the type described in U.S. Patent 3,011,890 of Gates, Jr., Miller and Koller issued Dec. 5, 1961, and polysaccharides of the type described in Canadian Patent 635,206 of Koller and Russell issued J an. 23, 1962.
• Photographic emulsions containing the antifoggants of the invention can also contain speed-increasing compounds such as quaternary ammonium compounds, polyethylene glycol or thioethers. Frequently, useful effects can be obtained by adding the afore-mentioned speedincreasing compounds to the photographic developer solutions instead of, or in addition to, the photographic emulsions.
• speed-increasing compounds such as quaternary ammonium compounds, polyethylene glycol or thioethers.
• Photographic elements containing the antifoggants of the instant invention can be used in various kinds of photographic systems. In addition to being useful in X-ray and other non-optically sensitized systems, they can also be used in orthochromatic, panchromatic and infrared sensitive systems.
• the sensitizing addenda can be added to photographic systems before or after any sensitizing dyes which are used.
• Silver halide emulsions containing the antifoggants of the invention can be used in color photography, for example, emulsions containing color forming couplers or emulsions to be developed by solutions containing couplers or other color-generating materials, emulsions of the mixed-packet type such as described in U.S. Patent 2,698,794 of Godowsky issued J an. 4, 1955; in silver dyebleach systems; and emulsions of the mixed-grain type such as described in U.S. Patent 2,592,243 of Carroll and Hanson issued Apr. 8, 1952.
• Silver halide emulsions containing the antifoggants of the invention can be sensitized using any of the wellknown techniques in emulsion making, for example, by digesting with naturally active gelatin or various sulfur, selenium, tellurium compounds and/or gold compounds.
• the emulsions can also be sensitized with salts of noble metals of Group VIII of the Periodic Table which have an atomic weight greater than 100.
• Silver halide emulsions containing the antifoggants of the invention can be used in diffusion transfer processes which utilize the undeveloped silver halide in non-image areas of the negative to form a positive by dissolving the undeveloped silver halide and precipitating it on a silver layer in close proximity to the original silver halide emulsion layer.
• diffusion transfer processes which utilize the undeveloped silver halide in non-image areas of the negative to form a positive by dissolving the undeveloped silver halide and precipitating it on a silver layer in close proximity to the original silver halide emulsion layer.
• the emulsions can also be used in diffusion transfer color processes which utilize a diffusion transfer of an imagewise distribution of developer, coupler or dye, from a light-sensitive layer to a second layer, while the two layers are in close proximity to one another.
• Silver halide emulsions containing the antifoggants of the invention can be processed in stabilization processes such as the ones described in U.S. Patent 2,614,927 of Broughton and Woodward issued Oct. 21, 1952, and as described in the article Stabilization Processing of Films and Papers by H. D. Russell, E. C. Yackel and J. S. Bruce in P.S.A. Journal, Photographic Science and Technique, Volume 16B, October 1950.
• Example 2 The process described in Example 1 is repeated except that amines having the formulae wherein the groups sa -a are defined in Table 1, are substituted for isobutoxy- Preparation of 2-(piperidinomethylthio)propionic acid
• EXAMPLES 8 TO 10 The process described in Example 7 is repeated except that amines having the formulae 7 1 III-CH2 )CH2-CHCH3 R] wherein the groups R l Ilq' R1 are defined in Table 2, are substituted for isobutoxymethylpiperidine.
• the products thus obtained have the formulae 1 1 1TIGH2S 01100 011 R1 CH: wherein the groups are defined in Table 2. The properties and yields of these products are given in Table 2.
• EXAMPLES 26 to 29 The process described in Example 25 is repeated except that an acid having the formula X-CH: (ll-O 0 OH wherein the groups X are defined in Table 6, are substituted for the 3-phenyl-2-mercaptoacrylic acid.
• the analyses of these products are given in Table 6. The melting points of the products are over a wide range above 7580 C. with decomposition.
• EXAMPLES 23 and 24 The process of Examples 7 and 11 are repeated except that the isobutoxymethylpiperidine in each example is replaced with di(isobutoxymethyl)piperazine.
• the resultant products have the formulae 6 HO O C-Y-S-GHz-N N-CHz-S-Y-C O OH wherein the groups Y are defined in Table 5.
• the yields Each of the compounds prepared in Examples 1 to 29 are added to separate portions of a high speed silver bromoiodide emulsion. Each emulsion sample is coated on a cellulose acetate film support at a coverage of 459 0 mg. of silver and 1040 mg. of gelatin per square foot.
• esters and salts such as hydrochloride salts, and other derivatives of the N,N-disubstituted aminomethylthiocarboxylic acids may be prepared by known techniques and used in the same manner as the acids.
• a composition comprising a photographic silver halide emulsion containing a fog-stabilizing amount of an N,N-disubstituted aminomethylthiocarboxylic acid.
• a composition comprising a photographic silver halide emulsion containing a fog-stabilizing amount of an N,N-disubstituted aminomethylthiocarboxylic acid having the general formula wherein n is either 1 or 2, and, when n is 1, R and R are members selected from the group consisting of alkyl, cycloalkyl, aryl and aralkyl and, when taken together with the nitrogen atom to which they are attached comprise a primary heterocyclic ring containing from 5 to 7 atoms in the ring, and, when n is 2, the group is the divalent piperazine radical and wherein Y is selected from the group consisting of alkylene groups and alkyl, aryl, carboxy or carboxyalkyl substituted alkylene groups.
• composition of claim 2 wherein said N,N- disubstituted aminomethylthiocarboxylic acid is present in an amount of from about 0.01 to about 10 grams per mole of silver in said silver halide emulsion.
• a photographic element comprising a support coated with a silver halide layer, said element containing a fogstabilizing amount of an N,N-disubstituted aminomethylthiocarboxylic acid.
• a photographic element comprising a support coated with a silver halide layer, said element containing a fogstabilizing amount of an N,N-disubstituted aminomethylthiocarboxylic acid having the general formula R1 wherein n is either 1 or 2, and, when n is 1, R and R are members selected from the group consisting of alkyl, cycloalkyl, aryl and aralkyl and, when taken together with the nitrogen atom to which they are attached comprise a primary heterocyclic ring containing from 5 to 7 atoms in the ring, and when n is 2, the group is the divalent piperazine radical and wherein Y is selected from the group consisting of alkylene groups and alkyl, aryl, carboxy or carboxyalkyl substituted alkylene groups.
• n is either 1 or 2
• R and R are members selected from the group consisting of alkyl, cycloalkyl, aryl and aralkyl and, when taken together with the nitrogen atom to which they are attached comprise a primary heterocyclic ring containing from 5 to 7 atoms in the ring, and, when n is 2, the group and wherein Y is selected from the group consisting of al'kylene groups and alkyl, aryl, carboxy or carboxyalkyl substituted alkylene groups.

Landscapes

• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Physics & Mathematics (AREA)
• Spectroscopy & Molecular Physics (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• General Physics & Mathematics (AREA)
• Silver Salt Photography Or Processing Solution Therefor (AREA)
• Hydrogenated Pyridines (AREA)

Applications Claiming Priority (2)

Publications (1)

Family

ID=26389075

Family Applications (2)

Family Applications After (1)

Country Status (5)

Cited By (1)

Families Citing this family (22)

Citations (2)

• 1967
  • 1967-06-20 US US647326A patent/US3547638A/en not_active Expired - Lifetime
• 1968
  • 1968-06-12 FR FR1572610D patent/FR1572610A/fr not_active Expired
  • 1968-06-13 BE BE716532D patent/BE716532A/xx unknown
  • 1968-06-20 GB GB29394/68A patent/GB1213056A/en not_active Expired
  • 1968-07-24 BE BE718498D patent/BE718498A/xx unknown
  • 1968-07-25 FR FR1573732D patent/FR1573732A/fr not_active Expired
  • 1968-07-25 DE DE19681772946 patent/DE1772946A1/de active Pending
  • 1968-07-26 US US747815A patent/US3615632A/en not_active Expired - Lifetime
  • 1968-07-29 GB GB36079/68A patent/GB1224257A/en not_active Expired

Patent Citations (2)

Also Published As

Similar Documents