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
  • G03C8/00—Diffusion transfer processes or agents therefor; Photosensitive materials for such processes
  • G03C8/42—Structural details
  • G03C8/44—Integral units, i.e. the image-forming section not being separated from the image-receiving section
  • G03C8/48—Integral units, i.e. the image-forming section not being separated from the image-receiving section characterised by substances used for masking the image-forming section
• • 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
  • G03C1/22—Methine and polymethine dyes with an even number of CH groups
• • 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
  • G03C1/76—Photosensitive materials characterised by the base or auxiliary layers
  • G03C1/825—Photosensitive materials characterised by the base or auxiliary layers characterised by antireflection means or visible-light filtering means, e.g. antihalation
  • G03C1/83—Organic dyestuffs therefor
  • G03C1/832—Methine or 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
  • G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
  • G03C5/26—Processes using silver-salt-containing photosensitive materials or agents therefor
  • G03C5/40—Chemically transforming developed images
  • G03C5/48—Mordanting

Definitions

• This invention relates to novel and improved photographic materials, and more particularly to light-sensitive photographic silver halide emulsions containing certain merocyanine dyes derived from cyanomethyl sulfones as filter and sensitizing dyes therein, to novel merocyanine dyes of the above kind, and to the preparation of these materials and dyes.
• light-screening substances are often required (a) in backing layers on either side of the support to reduce halation, (b) in overcotas on photographic elements to protect the light-sensitive emulsion or emulsions from the efiects of ultraviolet light, particularly in the case of color photographic elements, and (c) in interlayers between differentially color-sensitized emulsions to protect an underlying emulsion layer or layers from unwanted action of certain wavelengths of light.
• merocyanine dyes derived from cyanomethyl sulfones are especially useful as filter dyes and sensitizers in light-sensitive photographic silver halide emulsions. These dyes not only have desirably sharp absorption maxima and high extinction coefllcients, but also show very high resistance to diffusion and remain firmly fixed in the applied positions in the photographic element. They are further characterized by providing photographic filter layers which absorb to appreciably shorter wavelengths in the ultraviolet region of the spectrum as compared with similar layers prepared with any of the previously known related dimethine type of dyes. This is of particular advantage in certain photographic applications. The dyes are further useful for the preparation of non-light sensitive photographic elements such as diffusion transfer sheets (color and black-and-white), etc.
• an object of this invention to provide novel and improved photographic materials, and more particularly light-sensitive photographic silver halide emulsions containing at least one of the merocyanine dyes of the invention.
• Another object of this invention is to provide novel and "ice improved light-sensitive photographic elements comprising a support material having thereon at least one layer of the above novel emulsions of the invention.
• Another object of this invention is to provide novel and improved light-sensitive photographic elements comprising a support material having thereon at least one light sensitive silver halide emulsion layer and at least one light-absorbing filter layer comprising a merocyanine dye of the invention.
• Another object of this invention is to provide novel merocyanine dyes derived from cyanomethyl sulfones which absorb in the ultraviolet region of the spectrum, which have sharp absorption maxima and high extinction coeflicients, and which have low difiusibility in the photographic layers of the invention.
• novel merocyanine dyes which are suitable for accomplishing the above objects of my invention include those represented by the following general formula:
• R represents a hydrogen atom, an alkyl group (including substituted alkyl) and preferably containing about from 1 to 8 carbon atoms, e.g., methyl, ethyl, propyl, isopropyl, butyl, hexyl, octyl, etc., an aryl group, e.g., phenyl, chlorophenyl, tolyl, etc., or an aralkyl group, e.g., benzyl, phenylethyl, etc.;
• R represents an alcohol radical, e.g., an alkyl substituent (including substituted alkyl) and preferably containing from 1 to 12 carbon atoms, e.g., methyl, sulfoethyl, carboxyethyl, hydroxypropyl, sulfobutyl, carboxybutyl, hexyl,
• thionaphtheno-7',6', 4,5-thiazole nucleus e.g., 4' methoxythianaphtheno 7',6,4,5 thiazole, etc.
• an oxazole nucleus e.g., 4-methyloxazole, S-methyloxazole, 4-pheny1oxazole, 4,5-diphenyloxazole, 4-ethyloxazole, 4,5- dimethyloxazole, S-phenyloxazole, etc.
• a benzoxazole nucleus e.g., benzoxazole, 5-chlorobenzoxazole, S-methylbenzoxazole, 5 phenylbenzoxazole, 6 methylbenzoxazole, 5,6-dimethylbenzoxazole, 4,6-dimethylbenzoxazole, S-methoxybenzoxazole, S-ethoxybenzoxazole, 5-ch1orobenzoxazole, 6-me
• merocyanine dyes of the invention can conveniently be prepared, for example, by condensing a cyanomethyl sulfone corresponding to the formula R SO CH CN, wherein R is as previously defined, (prepared, for example, by the general method of Dijkstra and Backer, Rec. Trav. Chim., 73, 569 (1954)) with (1) derivatives of heterocyclic bases such as those represented by the general formula:
• R represents an acyl group, e.g., acetyl, propionyl, benzoyl, etc.
• R represents an aryl group, e.g., phenyl or tolyl
• X represents an acid anion, e.g., chloride, bromide, iodide, p-toluenesulfonate, sulfamate, methyl sulfate, ethyl sulfate, perchlorate, etc., or (2) compounds represented by the general formula:
• n, R, R X and Z are as previously defined, and R represents methyl or ethyl, in an inert solvent medium e.g., alkanol such as methanol, butanol, etc., acetone, 1,4- dioxane, pyridine, dimethylformamide, dimethylacetamide, quinoline, and the like, at elevated temperatures and preferably at refluxing temperatures of the reaction mixture, in the presence of a basic condensing agent such as a trialkylamine, e.g., triethylamine, tri-n-propylamine, trin-butylamine, etc., N-methylpiperidine, N-ethylpiperidine, N,N-dimethylaniline, etc.
• alkanol such as methanol, butanol, etc.
• acetone 1,4- dioxane
• pyridine dimethylformamide
• dimethylacetamide dimethylacetamide
• quinoline quinoline
• the dye compounds are then separated from the reaction mixtures by chilling and dilution with nonsolvents such as water, alkanols such as methanol, ethanol, etc. and purified by one or more recrystallizations from suitable solvents such as above and mixtures of solvents, for example, pyridine and methanol.
• nonsolvents such as water, alkanols such as methanol, ethanol, etc.
• suitable solvents such as above and mixtures of solvents, for example, pyridine and methanol.
• EXAMPLE 2 2 (3 cyano 3-dodecylsulfonylallylidene)-3-ethylbenzoxazotline A mixture of 2 B acetanilidovinyl 3 ethyl'benzoxazolium iodide (4.34 g., 10 mmole), dodecylsulfonylacetonitrile (2.73 g., 10 rnmole), acetic anhydride (0.9 ml.), pyridine (15 ml.) and triethylamine (2.8 mg., 20 rnmole) was boiled under reflux for 5 minutes, cooled and diluted with water.
• EXAMPLE 3 (3 cyano 3-dodecylsulfonylallylidene)-3-ethylthiazolidine
• EXAMPLE 4 2 (3 cyano 2-rnethyl-3-methylsu1fonylallylidene)- 3-ethylbenzothiazoline 3 ethyl 2 thioacetonylidenebenzothiazoline (3.52 g.,
• EXAMPLE 5 2 (3 cyano Z-methyl-3-methylsulfonylallylidene)- 3-ethyl-naphtho 1,2-d] thiazoline
• This dye was prepared from 1-ethyl-2-thioacetonylidenenaphtho 1,2-d] thiazoline and methylsulfonylacetonitrile by the method of Example 4.
• EXAMPLE 8 2-(3-cyano3-dodecylsulfonylallylidene)-1-ethylnaptho 1,2-d1thiazoline This dye was prepared from 2-ani1inovinyl-l-ethylnaphthol[1,2-d]thiazolium iodide and dodecylsulfonylacetoni trile by the method of Example 7. The pure dye, M.P. -156 C. from methanol, was obtained in 69% yield.
• the crude dye was dissolved in ethanol and treated with an ethanolic solution of potassium acetate (1.07 g., 11 mmole) to precipitate the potassium salt of the dye.
• the resulting suspension was heated to boiling, treated with ethanol until solution was almost complete, and chilled.
• the crude product (3.48 g., 64%) was then collected on a filter and recrystallized twice from ethanol containing 15-20% water to obtain the pure dye salt, M.P. 218-220 C., in 39% yield.
• EXAMPLE 1O 2-(3-cyano-3-dodecylsulfonylallylidine)-3-(3-sulfopropyl)benzoxazoline, sodium salt employed in Example 9.
• EXAMPLE 12 2- (3 -o-carboxyphenylsulfonyl-3-cyano-2-methylallylidene)-1-ethylnaphthol[ 1,2-d] thiazoline 3-ethyl 2 thioacetonylidenebenzothiazoline (7.13 g., 25 mmol.) and methyl p-toluenesulfonate (5.12 g., 27.5 mmol.) were heated with dimethylacetamide (15 ml.) on the steam bath until the mixture solidified.
• the dye of above Example 9 is particularly efiicacious and is preferred.
• the dyes of this invention have light-absorbing characteristics that make them valuable for use in lightabsorbing filter layers in photographic elements. These characteristics are illustrated in the following Table 1 and in Example 13.
• filter layers for photographic elements such as that illustrated in above Example 13; filter layers between ditferentially sensitized emulsion layers; filter layers on diffusion transfer receiving sheets such as those described in Land US. Patent 2,543,181, issued Feb. 27, 1951; filter layers in or upon color print materials such as those described in Van Campen US. Patent 2,956,- 879, issued Oct. 18, 1960; filter layers in or upon color transfer materials such as those described in British Patent 890,861, dated Mar. 7, 1962, Belgian Patent 636,371, and Rogers US. Patents 3,087,817, issued Apr.
• the dyes of this invention are preferably incorporated in colloid layers which are permeable to aqueous processing solutions, said dyes being employed in concentrations which may vary considerably depending upon the particular product concerned and the effect desired. Methods for selecting the particular colloid to be employed, and for determining the amount of dye to be included, are well known in the art and need not be enumerated here.
• colloids which may be employed include natural materials such as gelatin, protein derivatives, albumin, agar-agar, gum arabic, alginic acid and the like; and synthetic resins such as polyvinyl alcohol, polyvinyl pyrrolidone, polyacrylamide, cellulose ethers and carboxylated derivatives of cellulose ethers, partially hydrolyzed cellulose esters, copoymers of acrylic and methacrylic acids, polymeric latexes or hydrosols, mixtures of these, and the like.
• Gelatin is the preferred colloid.
• the new dyes of this invention are advantageously incorporated in the washed, finished, silver halide emulsion and should be uniformly distributed throughout the emulsion.
• Methods of incorporating dyes in emulsions are relatively simple and well known to those familiar with the art of emulsion making.
• the dyes may be added from solutions in appropriate solvents which are free from deleterious effects on the ultimate lightsensitive materials. Methanol, isopropanol, and pyridine, alone or in admixture, have proven satisfactory as solvents for incorporating the majority of the dyes of this invention into emulsions.
• the types of silver halide emulsions that can be sensitized with the new dyes of this invention include any of the conventional emulsions prepared with light-sensitive silver salts including silver chloride, silver bromide, silver iodide, silver chlorobromide, silver bromoiodide, silver chlorobromo-iodide, etc.
• concentration of the new dyes in the emulsion can vary widely, e.g., from about to about 100 mg. per liter of flowable emulsion.
• the specific concentration will vary according to the type of light-sensitive material in the emulsion and the effects desired.
• the suitable and most economical concentration for a given emulsion will be apparent to those skilled in the art upon making the tests and observations customarily used in the art of emulsion making.
• the following example illustrates photographic elements prepared with the novel silver halide emulsions of the invention.
• the dyes dissolved in suitable solvents were added to separate portions of either a silver chloride emulsion or a silver chlorobromide (60:40) emulsion as indicated in Table 2 below, and at the indicated concentrations.
• the emulsions in each case were coated at a coverage of 432 mg. of silver per square foot and 1190 mg. of gelatin per square foot on a cellulose acetate film support.
• a sample of each coating was exposed on an Eastman 1B sensitometer and to a wedge spectrograph, processed in a developer of the composition:
• Photographic silver halide emulsions containing the sensitizing dyes of this invention can also contain other addenda such as chemical sensitizers, e.g., sulfur sensitizers (e.g., allyl thiocarbamide, thiourea, allylisothiocyanate, cystine, etc.), selenium and tellurium sensitizers, various gold compounds (e.g., potassium chloroaurate, auric trichloride, etc.) (see U.S.
• chemical sensitizers e.g., sulfur sensitizers (e.g., allyl thiocarbamide, thiourea, allylisothiocyanate, cystine, etc.)
• gold compounds e.g., potassium chloroaurate, auric trichloride, etc.
• Photographic silver halide emulsion layers and other layers present in the photographic elements made according to the invention may contain developing agents such as hydroquinones, catchols, 1,3-pyrazolidones, aminophenols, etc.; and the layers can be hardened with any suitable hardeners such as aldehyde hardeners, aziridine hardeners, hardeners which are derivatives of dioxane, oxy polysaccharides such as oxy starch and oxy plant gums, mixtures of these, and the like.
• the layers present in photographic elements made according to the invention may also contain color couplers such as those described in I. F. Salminen et a1.
• Dispersing agents for color couplers such as those set forth in U.S. Patents to E. E. Jelley et al. U.S. Patent No. 2,322,027, issued June 15, 1943, and L. D. Mannes et a1.
• U.S. Patent No. 2,304,940, issued Dec. 15, 1942; and non-ionic, anionic and amphoteric coating aids; can also be employed in the above described emulsions and colloid layers.
• the photographic emulsions can also contain additional additives, particularly those known to be beneficial in photographic emulsion, including, for example, stabilizers, particularly the water soluble inorganic acid salts of cadmium, cobalt, manganese, and zinc, such as disclosed in Jones U.S. Patent No. 2,839,405, issued June 17, 1958, and the substituted triazaindolizines such as disclosed in Heimbach et al. US. Patent No. 2,444,- 605, issued July 6, 1948 and in Heimbach, U.S. Patent No.
• spectral sensitizers such as the cyanine, merocyanine, styryl, and hemicyanine dyes
• speed increasing materials such as polyalkylene glycols, onium salts, thioethers, etc.
• plasticizers such as polyalkylene glycols, onium salts, thioethers, etc.
• absorbing dyes such as mixtures of these additives; and the like.
• the photographic silver halide emulsions may be coated advantageously on any of the support materials commonly used in photographic elements, including glass, metals, paper, baryta coated paper, cellulose acetate, cellulose acetate butyrate, cellulose nitrates, etc., and synthetic film forming resinous materials such as polystyrenes, polyolefins, e.g., polyethylene, polypropylene, etc.; such as polyethlene terephthalate, polyamides, e.g., nylon, etc., polycarbonates, polyvinyl acetals, etc.
• support materials including glass, metals, paper, baryta coated paper, cellulose acetate, cellulose acetate butyrate, cellulose nitrates, etc.
• synthetic film forming resinous materials such as polystyrenes, polyolefins, e.g., polyethylene, polypropylene, etc.; such as polyethlene terephthalate, polyamides,
• Supports such as papers Which are partially acetylated or coated with an a-olefin polymer, particularly a polymer derived from an a-olefin containing 2-10 carbon atoms as exemplified by polyethylene and polypropylene, ethylene-butene copolymers, and the like, also give good results.
• an a-olefin polymer particularly a polymer derived from an a-olefin containing 2-10 carbon atoms as exemplified by polyethylene and polypropylene, ethylene-butene copolymers, and the like, also give good results.
• R m Boa- 2 wherein n and In each represents a positive integer of from 1 to 2, R represents a member selected from the group consisting of a hydrogen atom, an alkyl group, a monocyclic aryl group and an aralkyl group, R represents a member selected from the group consisting of an alcohol radical and an aryl group, R represents a member selected from the group consisting of an alkyl group, an aryl group, an aralkyl group, an oxazolyl group, a benzoxazolyl group, a pyridyl group, a quinolyl group, an imidazolyl group and a benzimidazolyl group, and Z represents the nonmetallic atoms required to complete a 5- to 6-membered heterocyclic nucleus selected from the class consisting of a thiazole nucleus, a benzothiazole nucleus, a napththothiazole nucleus, a thianaphtheno
• a photographic element comprising a support having thereon at least one silver halide emulsion layer, and wherein at least one of said layers contains a dye compound having the formula set forth in claim 1.
• a photographic element comprising a support having thereon at least one silver halide emulsion layer, and wherein at least one of said layers contains a dye corn pound having the formula set forth in claim 2.
• a photographic element comprising a support having thereon at least one silver halide emulsion layer, and wherein at least one of said layers contains a dye compound defined in claim 6.
• a photographic element comprising a support having thereon at least one silver halide emulsion layer, and wherein at least one of said layers contains the dye compound defined in claim 7.
• a photographic element comprising a support, having thereon at least one nonsensitive layer containing a dye compound having the formula set forth in claim 1.
• a photographic element comprising a support having thereon at least on nonsensitive layer containing a dye compound having the formula set forth in claim 2.
• a photographic element comprising a support having thereon at least one nonsensitive layer containing a dye compound defined in claim 6.
• a photographic element comprising a support having thereon at least one nonsensitive layer containing the dye compound defined in claim 7.
• a photographic element comprising a support having thereon at least one silver halide emulsion layer, and wherein at least one of said layers contains a dye compound having the general formula set forth in claim 1 wherein R represents an aryl group.
• a photographic element comprising a support having thereon at least one nonsensitive layer containing a dye compound having the formula set forth in claim 1 and having at least one silver halide emulsion layer.

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• 1966
  • 1966-07-22 US US567070A patent/US3486897A/en not_active Expired - Lifetime
• 1967
  • 1967-06-28 GB GB29713/67A patent/GB1128113A/en not_active Expired
  • 1967-07-20 BE BE701697D patent/BE701697A/xx unknown
• 1969
  • 1969-06-11 US US832415A patent/US3629274A/en not_active Expired - Lifetime

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