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
  • 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
  • G03C7/392—Additives
  • G03C7/39208—Organic compounds
  • G03C7/3924—Heterocyclic
  • G03C7/39276—Heterocyclic the nucleus containing nitrogen and sulfur
• • 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
  • G03C1/09—Noble metals or mercury; Salts or compounds thereof; Sulfur, selenium or tellurium, or compounds thereof, e.g. for chemical sensitising
• • 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
  • G03C7/407—Development processes or agents therefor
  • G03C7/413—Developers

Definitions

• multilayer photographic elements used for color photography there are usually three selectively sensitive emulsion layers coated on one side of a single support.
• the uppermost layer is generally blue sensitive
• the next layer is generally green sensitive
• the emulsion layer adjacent the support is generally red sensitive.
• a filter layer for absorbing blue radiation which may be intermitted through the blue sensitive layer.
• dye forming couplers which react with the oxidation products of the silver halide developer to form dyes.
• the multilayer coating can also have other interlayers for specialized purposes.
• Such multilayer materials have been previously described in the prior art, such as US. Patents 2,322,027, issued June 15, 1943, and 2,644,900, issued July 12, 1960. Other arrangements of the sensitive layers are also shown.
• Processing of multilayer photographic elements used for color photography is generally a time-consuming process so that it has been desirable to find a more rapid method of obtaining the processed film, particularly those containing incorporated dye forming couplers. Accordingly, since it is well known that increasing the temperature of a photographic developer will increase the rate at which it develops a silver halide emulsion, it has been proposed to process the multilayer photographic emulsions in a rapid, high temperature color process.
• a necessary step in preventing over-development of an emulsion when processed at a higher temperature is to shorten the time of development to an appropriate level.
• shortening the time of development of a color material will not, by itself, given balanced development in the separated layers of a normal color material. If the development time is adjusted for color development of the top, blue sensitive layer, then the lower green and red sensitive layers will be underdeveloped. It the time is adjusted so that the lower layers are correctly developed, then the top layer will be greatly overdeveloped. Moreover, adjustments in the speeds of emulsion will not balance the amount of development in a multilayer system. Therefore, the rate of development of each emulsion must be controlled so that all layers will arrive at optimum development at a given time.
• One object of this invention is to provide a multilayer photographic element having the rate of development controlled in the top emulsion layer so that it can he satisfactorily processed in a rapid, high temperature color process.
• a further object is to provide a prebath, such as a prehardener bath, in which a benzothiazolium salt is imbibed into the top layer of a multilayer photographic element to control its rate of development.
• the overdevelopment of the top emulsion layer in a multilayer color coating can be controlled by the addition of a benzothiazoliurn salt to the top emulsion layer.
• a benzothiazoliurn salt to the top emulsion layer.
• About 1-10 grams of the compound per silver mole are required for this purpose.
• These compounds may be incorporated in the emulsion, by incorporating the salt in a layer over the top light sensitive layer, or they may be added in a bath, such as a prehardener bath, prior to development. We prefer to use the following compounds. For example:
• R represents a hydrogen atom or a lower alkyl group, such as methyl, ethyl, etc. (e.g. an alkyl group containing from 1-2 carbon atoms)
• R represents a hydrogen atom, an aryl group (e.g. phenyl, o-, mor ptolyl, 0-, mor p-methoxyphenyl, etc.) or an arylenethiazolyl group (e.g. 2-benzothiazolyl, 3-benzothiazolyl, 2-(B-naphthothiazolyl) etc.)
• D represents the non-metallic atoms necessary to complete an aromatic nucleus (e.g.
• benzene, naphthalene, etc. as well as their substitution products, including such members substituted by methyl, ethyl, methoxyl, ethoxyl, etc.), it represents a positive integer of from 1-26 (provided that n represents a positive integer of only from about 1-3 when R represents an aryl group) and X represents an acid radical such as perchlorate, bromide, benzenesulfonate, toluenesulfonate, methyl sulfate, ethyl sulfate, etc.
• a particularly useful group of quaternary salts embraced by Formula A above includes the compounds represented by the following general formula:
• R, D and X each have the values given above, and m represents a positive integer of from about l-26.
• Typical quaternary salts embraced by Formula A above include, for example, the following:
• the his com pounds represented by Formula B can be prepared according to the methods described in Wilson US. (Patent 2,425,774, issued Aug. 19, 1947, as well as by the method described by Allen and Wilson US. Patent 2,694,716, issued Nov. 16, 1954. Such methods generally comprise the fusion of a heterocyclic base with an alkylene halide. Such techniques are well known to those skilled in the art. Alkyl esters of organic sulfonic acids can also be fused with thiazole bases to provide the salts of my invention.
• the cycloammonium salts useful in practicing my invention are employed in a prebath, they are used in the form of their aqueous solutions, and if desired, the prebath may contain known hardeners such as form-aldehyde, succinaldehyde, mucochloric acid, chrome alum, etc.
• the amount of qua-ternary salt used in the solutions can be varied, depending upon the particular emulsions employed, the concentration of silver halide in the emulsions, etc.
• the cycloammonium salts When incorporated in the emulsion or in an overcoat, the cycloammonium salts may be incorporated as aqueous solutions, alcohol-water solutions, or by any other manner known in the art.
• EXAMPLE 1 Four photographic films were made consisting of a cellulose acetate support coated with a blue sensitive silver bromoiodide gelatin emulsion containing a keto-methylene yellow color former such as coupler No. XIV of US. Patent 2,875,057. These coatings were alike except for the following changes.
• Coating Feature A Control, no further change. B Like control except compound I added at 6.0 g./Ag mole. C Like control except compound III added at 2.0 g./Ag mole. D Like control except compound IV added at 2.0 g./Ag mole.
• the transition to a multilayer color film can be shown by the following example.
• EXAMPLE 3 Two multilayer films were made consisting of a cellulose acetate support coated with a red sensitive silver bromoiodide gelatin emulsion containing a phenolic cyan color former over which was coated a gelatin interlayer. Next, a green sensitive silver bromoiodide emulsion layer was coated containing a pyrazolone magenta color former and over this a yellow filter layer. Over the entire film a blue sensitive silver bromoiodide emulsion was then coated containing a keto-methylene yellow color former and finally a gelatin overcoat.
• Each coating was given a sensitometric exposure and processed to a color positive in the reversal process of Example 1 at 75 F. and 160 F.
• the time of development in the negative developer of the high temperature process was adjusted so that the film with the controlled rate of development would approximate the speed of the lulose acetate support coated with a blue sensitive silver control film in the standard temperature process.
• Coating Feature E. Control, no further change. F Like control except compound II added at 3 g./Ag mole. G Like control except compound II added at 6 g./Ag mole.
• Example II Each coating was given in a sensitometric exposure and processed to a color positive in the process of Example I at 75 F. and at 160 F.
• the change in the rate of development is shown here by the Dmaxes, and the relative emulsion speeds at the extreme development temperatures.
• a negative multilayer coating I was prepared consisting of a celulose acetate support coated with a red sensitive layer silver bromoiodide gelatin emulsion containing a phenolic cyan color former and 0.05 g./Ag mole of com- 1 N 0t measurable.
• pound I over which was coated a gel interlayer.
• a green-sensitive silver bromoiodide emulsion layer was coated containing a pyrazolone magenta color former and 0.225 g./Ag mole of compound I and over this a yellow filter layer.
• a blue-sensitive silver bromoiodide emulsion was coated containing a ketomethylene yellow color former and 2.25 g./Ag mole of compound I.
• This coating J was compared with a product coating K of similar structure but containing no compound I.
• Each coating was given a sensitometric exposure and processed to a color negative in a negative process referred to below in the article by Hanson et al. The following results were obtained.
• the prehardener bath was prepared as follows: 800 ml. of water at 90 F. was used to dissolve 4.30 ml. of dimethoxytetrahydrofuran, 5.41 ml. of 18 Normal sulfuric acid and 0.5 gram of the sodium salt of para-toluenesulfinic acid. This solution was stirred for 10 minutes at 90 F. whereby the DMTF became hydrolyzed to succinaldehyde. 133 grams of sodium sulfate and 2 grams of sodium bromide were then added and the composition was mixed for 20 minutes. There was then added 20 grams of sodium acetate and 27 ml. of formalin, the volume was then brought to one liter with water and the pH was adjusted to 4.8 at 80 F.
• EXAMPLE 5 Twelve photographic films were made consisting of a cellulose acetate support coated with a blue-sensitive silver bromoiodide gelatin emulsion containing a ketomethylene yellow color former. These coatings were alike except for the features as listed.
• Example 1 Each coating was given a sensitometric exposure and processed to a color positive in the process of Example 1 either at 75 F. or at 160 F.
• the change in the rate of development of the emusions with each of the addenda present is shown by the dye D Feature 75 F. 160 F.
• Control 2 24 1. 18 Compound I at 0.1 g./Ag mole 0.99 Compound I at 0.5 gJAg mo1e 1. 09 Compound II at 0.1 g./Ag mo e. 1. 04 Compound II at 0.5 g./Ag mo 1. 24 Compound V 1 at 0.1 g./Ag mole 1. 29 Compound V 2 at 0.5 g./Ag mole 1. 52 Control 1. 40 Compound III at 0.1 gJAg mol 1. 08 Compound III at 0.5 g. 1. 31 Compound IV at 0.1 gJAg mole 1. 00 Compound IV at 0.5 gJAg mole 1.22
• Compound V is 1-phenyl-S-mercaptotetrazole.
• EXAMPLE 6 A multilayer film of Example 3, identified as H, was immersed in a prehardener bath containing 20 milligrams per liter of N-methyl benzothiazolium-p-toluene sulfonate for 2 /2 minutes. It was then passed through a neutralizer bath and processed as in Example 3 with similar results to those obtained with coating I, in which the compound was incorporated in the emulsion.
• the bath When used in a bath prior to development, from 1-200 milligrams per liter of the bath are employed.
• This may be a bath containing water and the benzothiazolium salt or the benzothiazolium salt may be used in a prehardener bath containing hardening agents which aid in conditioning the photographic element so that it can be processed at relatively high temperatures.
• the prehardener bath may be at any suitable temperature from 50 F. to 200 F., since the purpose of the bath is to imbibe the benzothiazolium salt into the top layer of the multilayer element.
• the developer is preferably above 100 F., but is useful range is from F. to 200 F.
• the amount of benzothiazolium salt depends upon the temperature at which the development is carried out within the ranges given above. This can be accomplished in the bath 'by increasing the concentration of the benzothiazolium salt or by leaving the photographic element in the bath for a longer period of time, or a combination of the two.
• the multilayer element is immersed in the bath for 2% minutes, the bath contains hardeners and the temperature is close to that of the developer solution.
• emul- SIOIIS may comprise various layer arrangements.
• the support may carry thereon a blue-sensitive layer containing a yellow coupler, an interlayer, a greensensitive layer containing cyan and magenta couplers and having thereon an overcoat. These couplers may occur in different layers and in different orders as a matter of choice.
• various supports known in the art may be used for the silver halide emulsion and that if a transparent support is used, that one or more light-sensitive layers may be coated on one side and one or more layers on the other side, provided the benzothiazolium salt is used on both sides of the support.
• Another useful photographic element may have a bleachable filter layer incorporated in the element between two light-sensitive layers or on the support when it is between the lightsensitive layers.
• the lightsensitive elements can have one or more strata of the type described in Millikan U.S. Ser. No. 159,057, filed Dec.
• amylbenzoylamino -5-pyrazolone 1-phenyl-3 -diarnylbenzoylamino-5-pyrazolone 1-phenyl-3-,8-naphthoylarnino-5 -pyrazolne
• phenyl-3 -palmitylamino-5 -pyrazol one
• the emulsions can be chemically sensitized by any of the accepted procedures.
• the emulsions can be digested 12 with naturally active gelatin, or sulfur compounds can be added such as those described in Sheppard U.S. Patent 1,574,944, issued Mar. 2, 1926; Sheppard et al. U.S. Patent 1,623,499, issued Apr. 5, 1927; and Sheppard et a1.
• the emulsions can also be chemically sensitized with reducing agents such as stannous salts (Carroll U.S. Patent 2,487,850, issued Nov. 15, 1949), polyarnines, such as diethyl triamine (Lowe and Jones U.S. Patent 2,518,- 698, issued Aug 15, 1950), polyamines, such as spermine (Lowe and Allen U.S. Patent 2,521,925, issued Sept. 12, 1950), or bis(fl aminoethyl)sulfide and its water-soluble salts (Lowe and Jones U.S. Patent 2,521,926, issued Sept. 12, 1950).
• reducing agents such as stannous salts (Carroll U.S. Patent 2,487,850, issued Nov. 15, 1949), polyarnines, such as diethyl triamine (Lowe and Jones U.S. Patent 2,518,- 698, issued Aug 15, 1950), polyamines, such as spermine (Lowe and Allen U.S. Patent 2,521,925, issued Sept. 12, 1950), or
• gelatin In preparation of the silver halide dispersions employed for preparing silver halide emulsions, there may be employed as the carrier for the silver halide in its preparation, gelatin or some other colloidal material such as colloidal albumin, a cellulose derivative, or a synthetic resin, for instance, a polyvinyl compound.
• colloidal albumin a cellulose derivative
• synthetic resin for instance, a polyvinyl compound.
• colloids which may be used are polyvinyl alcohol or a hydrolyzed polyvinyl acetate as described in Lowe U.S. Patent 2,286,- 215, issued June 16, 1942; a far hydrolyzed cellulose ester such as cellulose acetate hydrolyzed to an acetyl content of 1926% as described in U.S. Patent 2,326,808 of Lowe and Clark, issued Aug.
• cyano-acetyl groups such as the vinyl alcohol-vinyl cyanoacetate copolymer as described in Unruh, Smith and Priest U.S. Patent 2,808,331, issued Oct. 1, 1957; or a polymeric material which results from polymerizing a protein or a saturated acylated protein with a monomer having a vinyl group as described in U.S. Patent 2,852,382, of Illingsworth, Dann and Gates, issued Sept. 16, 1958.
• green sensitizers include acid merocyanines of Brooker et al. U.S. Patent 2,493,747, issued Jan. 10, 1950, such as 3 (p-carboxypheny1) -5( 3-methy1-2( 3 -benzoxazolylidene -rhodanine,
• a multilayer photographic element comprising a wherein R represents a member selected from the class consisting of a hydrogen atom and a lower alkyl group, R represents a member selected from the class consisting of a hydrogen atom, an aryl group and an arylenethiazolyl group, D represents the non-metallic atoms necessary to complete an aromatic nucleus, X represents an acid radical and n represents a positive integer of from 1 to 26 when R represents a member selected from the class consisting of a hydrogen atom and an arylenethiazolyl group, and n represents a positive integer of from 1 to 3 when R represents an aryl group.
• a prehardener bath for treating a photographic element having at least one gelatino-silver halide emulsion layer comprising:
• R represents a member selected from the class consisting of a hydrogen atom and a lower alkyl :group
• R represents a member selected from the class consisting of a hydrogen atom, an aryl group and an arylenethiazolyl group
• D represents the non-metallic atoms necessary to complete an aromatic nucleus
• X represents an acid radical
• n represents a positive integer of from 1 to 26 when R represents a member selected from the class consisting of a hydrogen atom and an arylenethiazolyl group
• n represents a positive integer of from 1 to 3 when R represents an aryl group.
• a hardening composition for use in an aqueous prehardener bath for treating a photographic element having at least one gelatino-silver halide emulsion layer comprising a gelatin hardening agent and a compound for preventing overdevelopment of the top emulsion layer and having the following general formula:
• R represents a member selected. from the class consisting of a hydrogen atom and a lower alkyl group
• R represents a member selected from the class consisting of a hydrogen atom, an aryl group and an arylenethiazolyl group
• D represents the non-metallic atoms necessary to complete an aromatic nucleus
• X represents an acid radical
• n represents a positive integer of from 1 to 26 when R represents a member selected from the class consisting of a hydrogen atom and an arylene'thiazolyl group
• n represents a positive integer of from 1 to 3 when R represents an aryl group.
• composition of claim 11 wherein said compound is N-methy-l-benzothiazolium-p-toluene sulfonate.
• composition of claim 11 wherein said compound is decamethylene-bis-benzothiazolium perchlorate.
• composition of claim 11 wherein said comound is propane-l,3-bis (3-methyl-2-benzothiaZolium-ptoluene sulfonate).
• composition of claim 11 wherein said compound is pentane-l,5-bis-(3-methyl-Z-benzothiazolium-ptoluene sulfonate).
• R represents a member selected from the class consisting of a hydrogen atom, an aryl group and an arylenethiazolyl group
• D represents the non-metallic atoms necessary to complete an aromatic nucleus
• X represents an acid radical
• n represents a positive integer of from 1 to 26 when R represents a member selected from the class consisting of a hydrogen atom and an arylenethiazolyl group
• n represents -a positive integer of from 1 to 3 when R represents an aryl group.
• R represents a member selected from the class consisting of a hydrogen atom and a lower alkyl group
• R represents a member selected from the class consisting of a hydrogen atom, an aryl group and an arylenethiazolyl group
• D represents the non-metallic atoms necessary to complete an aromatic nucleus
• X represents an acid radical
• n represents a positive integer of from 1 to 26 when R represents a member selected from the class consisting of a hydrogen atom and an arylenethiazolyl group
• n represents a positive integer of from 1 to 3 when R represents an aryl group.

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

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Citations (6)

• 0
  • DE DENDAT1303059D patent/DE1303059B/de active Pending
• 1964
  • 1964-03-11 US US351218A patent/US3342596A/en not_active Expired - Lifetime
• 1965
  • 1965-03-05 GB GB9395/65A patent/GB1106061A/en not_active Expired
  • 1965-03-05 FR FR8034A patent/FR1431975A/fr not_active Expired
  • 1965-03-08 BE BE660802A patent/BE660802A/xx unknown
  • 1965-03-10 CH CH342765A patent/CH442986A/fr unknown

Patent Citations (6)

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