US3016306A - Yellow filter layers for multi-layer photographic color elements - Google Patents

Yellow filter layers for multi-layer photographic color elements Download PDF

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US3016306A
US3016306A US698699A US69869957A US3016306A US 3016306 A US3016306 A US 3016306A US 698699 A US698699 A US 698699A US 69869957 A US69869957 A US 69869957A US 3016306 A US3016306 A US 3016306A
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layer
silver halide
blue
halide emulsion
dye
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Paul M Mader
Robert D Nelson
Thomas V Crevling
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Eastman Kodak Co
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Eastman Kodak Co
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    • 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
    • G03C1/835—Macromolecular substances therefor, e.g. mordants
    • 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
    • C09B23/10—The polymethine chain containing an even number of >CH- groups
    • C09B23/105—The polymethine chain containing an even number of >CH- groups two >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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
    • Y10S430/142—Dye mordant

Definitions

  • This invention relates to a process for preparing yellow filter layers for photographic multi-layer color elements, and to new photographic multi-layer color elements thereby obtained.
  • a multi-layer element comprising a support having coated thereon a plurality of light-sensitive layers which have been sensitized to particular regions of the spectrum.
  • a photographic element comprising a transparent, flexible support having coated thereon three light-sensitive photographic emulsion layers, one of these being sensitive to the red, one to the green and the third to blue. While the photographic element might contain additional layers,
  • the photographic element always contains at least two light-sensitive emulsion layers in the processes contemplated by the present invention.
  • a typical photographic element useful in our invention comprises a support having a red-sensitive emulsion coated thereon, a green-sensitive emulsion coated on top of the red-sensitive emulsion, a filter layer for absorbing blue light coated on top of the green-sensitive layer, and a blue-sensitive emulsion layer coated on top of the filter layer.
  • a red-sensitive emulsion coated thereon a green-sensitive emulsion coated on top of the red-sensitive emulsion
  • a filter layer for absorbing blue light coated on top of the green-sensitive layer and a blue-sensitive emulsion layer coated on top of the filter layer.
  • the yellow filter layer is an integral part of the photographic elements contemplated by the instant invention, inasmuch as this layer absorbs substantially all of the blue light which is transmitted by the blue-sensitive emulsion layer.
  • colloidal silver can be used as the light-absorbing ingredient in the yellow filter layers. However, it is recogm'zed that colloidal silver has certain serious drawbacks to its use in these filter layers.
  • colloidal silver has a ratio of green to blue density higher than desirable, and, in addition, the minute particles of colloidal silver (i.e., Carey-Lea silver) can act as centers for physical development, which may have an undesirable effect on the saturation and color balance of the resulting reproduction.
  • colloidal silver has been proposed in a number of technical articles and patents to replace the colloidal silver with various organic dyes. This alternative thus avoids certain of the undesirable effects of the colloidal silver, such as the physical development factor mentioned above, but other new difficulties are introduced at the same time. For example, it is difiicult to find dyes having the proper absorption characteristics, i.e., high density to blue light but little or no density to green and red light, and at the same time remain in the layer in which they are incorporated.
  • the dyes are likely to migrate from the filter layer into the blue-sensitive emulsion layer, where their presence might have serious efiects.
  • the dye be fixed in the filter layer by means of a mordant, which may be a high molecular weight polymer having an ionic charge opposite to that of the lightabsorbing dye.
  • a mordant which may be a high molecular weight polymer having an ionic charge opposite to that of the lightabsorbing dye.
  • the light-absorbing yellow dye might be an acid dye, in which case the organic mordant would be a cationic material.
  • mordanted filter layers In the preparation of mordanted filter layers, it is generally the practice to simply mix an aqueous solution containing the desired filter dye with the organic mordant, which might also contain a colloid, such as gelatin, albumen, etc., and coat the mixture onto an emulsion layer or an interlayer.
  • This method has the disadvantage in many instances of causing a precipitate of the mordant and dye to form. The precipitate then causes diffusion of the light transmitted by the blue-sensitive layer, so that pro or color balance is not rendered.
  • the process of our invention is concerned with organic mordants and yellow filter dyes and a means of preventing the formation of large precipitates or ag regates which might have a serious effect upon the proper rendition of the colors in the originals being reproduced.
  • the filter dye in a layer contiguous to the layer containing the mordant.
  • the filter dye migrates spontaneously from the layer in which it has been incorporated into the layer containing the mordant.
  • the dyes used in our invention are soluble in Water or dilute alkaline solutions and they have their maximum absorption between 400 and 500 millimicrons.
  • the filter dyes used in our invention have very sli ht absorption in the green and red regions of the spectrum.
  • the layer in which the filter dyes are incorporated can be conventional interlayers, such as gelatin,
  • polyvinyl alcohol, etc., interlayers, or these layers can be photographic emulsions which have been sensitized to a given spectral region.
  • the layer in which the filter dye is initially incorporated contains no material, such as a mordant, which would prevent migration of the dye to the layer containing the mordant.
  • the mordant is incorporated into a layer containing a hydrophilic colloid, such as gelatin, albumen, agar agar, etc.
  • the yellow filter dyes useful in practicing our invention are generally acid dyes.
  • the dyes contain one or more carboxylic acid or sulfonic acid groups, or a watersoluble salt of such groups (e.g., sodium, potassium, etc).
  • mordants useful in practicing our invention are basic in character and have a molecular Weight of at least 250. These mordants are readily dispersible in water, or
  • mordants comprise those having molecular weight of at least 250, at least one tertiary or quaternary nitrogen atom, and sutficient hydrophilic properties to enable these mordants to be dispersed readily in water.
  • most useful mordants in our invention comprise those derived from a linear polymer or interpolymer. Representative of such polymers are mordants obtained from a monoethylenically-unsaturated, polymerizable compound containing 21 dialkylamino group, or polymerized, monoethylenically-unsaturated compounds which have been modified to contain a dialkylamino group.
  • Typical mordants which can be used in our invention are piperidyl cellulose, chloromet-hylated polystyrene which has been solubilized by treatment with pyridine (see US. Patent 2,694,702), dialkylaminoalkyl esters or dialkylaminoalkylamino amides (e.g., such as those described in Carroll et al. US.
  • reaction products of carbonyl containing polymers and aminoguanidine or their salts e.g., those derived by reacting polyvinyl alkyl ketones or aldehydes, such as polyacrolein, polyvinyl methyl ketone, etc., with aminoguanidine, as described in the copending application of L. M. Minsk, Serial No. 554,114, filed December 19, .1955, now US. 2,882,156, granted April 14, 1959
  • polymers obtained by reacting a dialkylaminoalkyl amine with a polymer of maleic anhydride or a derivative of maleic anhydride e.g., as described in the copending application of L. M. Minsk and H.
  • Non-polymeric high molecular weight mordants which can be used in our invention comprise long-chain alkyl quaternary ammonium compounds, such as decamethylene-bis-trimethylammoniurn bromide, n-octyl tri- B-hydroxyethylammonium chloride, n-dodecyl diethyl-B- hydroxyethylammonium chloride, etc. (e.g., tetraalkylammonium halides containing an alkyl group having at least 8 carbon atoms).
  • mordants in our invention comprise those derived from maleic anhydride, or a derivative thereof as mentioned above. These mordants have been found to be particularly free of precipitation defects and can frequently be used in combination with acid yellow filter dyes by simply mixing the mordant with the filter dye.
  • Particularly useful interpolymers of maleic anhydride, or its substituted derivatives include those polymers representcd by the following general formula:
  • R, R and R each represents a hydrogen atom or a lower alkyl group, such as methyl, ethyl, etc.
  • R represents a hydrogen atom, an alkyl group (e.g., methyl, ethyl, etc), a monocyclic aryl group (e.g., phenyl, tolyl, etc.) or a carbalkoxyl group (e.g., car-bomethoxyl, carbethoxyl, etc.)
  • x represents a large whole number, such as a whole number greater than about 10.
  • Maleic anhydride interpolymers included by Formula I above have been previously described in numerous prior art references.
  • interpolymers are generally derived from monomers, such as ethylene, styrene, isobutylene, acrylic esters, etc.
  • maleic anhydride itself in the preparation of these interpolymers, it is possible to use maleic or fumaric acid esters to equal advantage, although the reaction times are generally lengthened in those cases where the ester derivatives are used in place of the anhydride.
  • the interpolymers can be obtained from maleic acid or fumaric acid.
  • R and R each represents a lower alkyl group (e.g., methyl, ethyl, n-propyl, n-butyl, etc.) or R and R together represent the atoms necessary to complete a piperidine or morpholine ring, and R represents an alkylene group (cg, ethylene, propylene, butylene, pentylene, etc., especially an alkylene group containing 2 to 3 carbon atoms).
  • R represents an alkylene group (cg, ethylene, propylene, butylene, pentylene, etc., especially an alkylene group containing 2 to 3 carbon atoms).
  • the reaction of the interpolymers of Formula I with the diamines of Formula II need not be on an equimolar basis, although generally it is advisable to use sufficient diamine to insure reaction of substantially all (i'.e., 100%), but at least about to of the anhydride units in the interpolymer. Where the interpolymer used contains acid groups or ester groups in place of the anhydride units illustrated in Formula I, it is generally preferable to use suflicient amine to react with all of these free acid groups or ester groups.
  • the first step in the reaction of the compounds of Formula I with those of Formula II leads to the formation of derived polymers containing carboxylic amide groups as a result of the reaction of the primary amino group of the compounds of Formula II with the anhydride groups of the polymers represented by Formula I.
  • Further heating either alone or in the presence of a dehydrating agent, such as acetic anhydride, propionic anhydride, etc. leads to the formation of the mordants of our invention which can be represented by the following general formula: (III) In R R,
  • R, R R R R R and R each have the values given above and 2 represents a large whole number, such as a whole number greater than about 10 (z may be the same as x, depending upon the molar quantity of the diamine used, which is used in an amount as indicated above to react with from about 75% to 80% of the anhydride units, as a minimum).
  • the product will contain combined acid.
  • This acid may be removed by treatment with a base. All, or a portion of all, of the residual anhydride units are hydrolyzed to carboxylic acid units under the above conditions.
  • the preparation of the mordants used in our invention can be carried out in the presence of an inert diluent, such as dioxane, benzene, acetone, etc.
  • the first step of the reaction resulting in the formation of carboxylic amide units in the interpolymer is generally carried out at about the temperature of the steam bath. After the addition of the dehydrating agent, the heating is continued for a period of time sufficient to cause reaction of most of the anhydride, acid or ester groups present in the interpolymer.
  • the preparation of imides has been previously illustrated in US. Patent 2,313,565.
  • the imides of Patent 2,313,565 generally contain ether groups attached to the linear polymer chain, and we have found that such groups generally cause color formation in the resulting imide polymers. In our process, such ether groups and undesirable free acid groups are avoided.
  • mordants of our invention as illustrated in Formula Hi above are in the form of their free bases, these mordants are customarily used in aqueous acid solutions so that at least a portion of the polymer units are in the following form:
  • X represents an acid radical (inorganic or organic), such as lactyloxy, glycolyl'oxy, acetoxy, propionoay, alkanesulfonoxy (e.g., methanesulfonoxy,
  • R R R and 1 each have the ethanesulfonoxy, n-butanesulfonoxy, etc., especially such radicals containing from 1 to 4 carbon atoms), chloride, etc. and y represents at least /22 but not more than 2.
  • a carboxylic anhydride used as the dehydrating agent as shown above, some of the free acid formed forms an acid-addition salt with the polymeric imide.
  • sufiicient acid in aqueous form
  • the amount of acid needed for this purpose will vary, depending on the particular acid and the intended use of the mordant. In general, sufiicient acid is present or used to give a pH below about 6.0.
  • maleic anhydride While maleic anhydride generally enters polymerizations in a 1:1 ratio with a comonomer, sometimes it interpolymerizes in smaller ratios, such as 1:2 (i.e., 33% maleic anhydride units).
  • Maleic anhydride derivatives such as maleic or itaconic esters, frequently interpolymerize at various ratios (US. Patent 2,298,039).
  • the useful interpolymers of Formula 1 above can contain between about 33 and 50 mol. percent maleic anhydride (or derivative) units.
  • Especially useful interpolymers are those containing a molar ratio of 1:1 of maleic anhydride units.
  • Particularly useful yellow dyes for the process of our invention comprise the following:
  • Dyes l, 2, 3 and 4 above are merocarbocyanine dyes. These dyes belong to a particularly useful group of dyes for our invention which can advantageously be represented by the following general formula:
  • R represents an alkyl group such as methyl, ethyl, n-propyl, n-butyl, isobutyl, fi-sulfoethyl, 3-sulfobutyl, 4-sulfobutyl, etc.
  • Z represents the non-metallic atoms necessary to complete a heterocyclic nucleus of the benzoxazole series (including benzoxazole and benzoxazole substituted by simple substituents, such as methyl, ethyl, phenyl, inethoxyl, ethoxyl, chlorine, bromine, etc.)
  • Q represents the non-metallic atoms necessary to complete a heterocyclic nucleus of the pyrazolinone series, provided that the nucleus defined by Q contains at least one acid substituent or radical in those cases where R represents a hydrocarbon group.
  • the most useful dyes of Formula IV comprise those dyes containing at least two hydrocarbon radicals or groups which have been further substituted by a carboxyl or sulfo group.
  • the yellow filter dyes of our invention are spontaneously removed during conventional color processing or they can be easily removed at any time simply by treatment with an aqueous alkaline solution. Certain of these dyes may actually be decolorized or bleached during processing, thus making complete removal thereof unnecessary, particularly in a negative process.
  • the resulting dispersion was then coated over the layer containing the mordant to a wet thickness of .006".
  • the coatings were then dried in the usual manner and cut into sections. Inspection of the sections under the microscope established that the tartrazine dye had completely difiused from the silver bromiodide layer into the mordant layer, leaving no visible trace of dye in the top layer containing the color coupler.
  • EXAMPLE 2 This example was prepared in exactly the manner shown in Example 1, except that 2.5 g. of the mordant in 3 ccs. of water were employed in place of the 5.5 g. of mordant used in Example 1, and 0.20 g. of dye 11 above were used in place of the tartrazine. As in the case of the coatings of Example 1, the dye completely diffused from the silver halide emulsion layer into the layer containing the mordant.
  • the filter dye can be incorporated in the lower silver halide emulsion layer, such as the red-sensitive or green-sensitive silver halide emulsion layer with which it is in contact.
  • the blue-sensitive silver halide emulsion layer is then coated over the filter layer in the customary manner.
  • the unsensitized silver halide emulsion layers employed in Examples 1 and 2 were bluesensitive and had little or no green and red sensitivity. The particular coupler employed was one for the formation of the yellow image.
  • the color coupler in the silver halide emulsion layer as shown in Examples 1 and 2, it is possible to have the color coupler present in one of the processing solutions, i.e., the filter layers of our invention are useful not only in photographic elements containing color couplers incorporated in the silver halide emulsion layer, which .may be used for producing a negative or positive image according to known reversal techniques, but they can also be used in photographic elements intended for reversal color processing wherein the .color couplers are present in one of the processing solutions, such as the color developer.
  • EXAMPLE 3 2.0 ccs. of a 10% aqueous solution of a -dimethylaminopropyl maleimide-styrene interpolymer, obtained as described in Example 1 of application Serial No. 663,810 were acled to a 10% aqueous acetic acid solution which was, in turn, added to 20 ccs. of a 10% aqueous gelatin solution. To this mixture were then added successively, 3 ccs. of a 2% aqueous solution of dye 3, 0.5 cc. of a 7.5% aqueous solution of saponin, 0.4 cc. of a 0.27% aqueous solution of mucochloric acid and enough Water to give 30 ccs.
  • the mixture was then stirred for 5 minutes at 40 C. and coated on an ordinary cellulose acetate film base at a gelatin coverage of about 0.466 g. per square foot and a concentration of the dye at 0.014 g. per square foot.
  • the coating was then washed under running water for 1 hour without any measurable loss of dye. Yet, immersion of the coating into a conventional photographic developer quickly removed the dye from the gelatin coating.
  • EXAMPLE 4 in exactly the manner illustrated in Example 3 above, dye 4 was incorporated in a morclant layer containing the maleimide interpolymer. Washing of the coating for 1 hour under running water did not remove any measurable amount of dye yet the coating was quickly bleached by immersion in ordinary photographic color developer.
  • the yellow acid dye need not be dispersed directly in the silver halide emulsions as illustrated in Examples 1 and 2 above, but the emulsions can be first coated and the photographic element immersed in an aqueous solution containing the dye, sufficient quantity of dye being absorbed under these conditions. Subsequent treatment of the coated silver halide emulsion layer with a mordanted, undyed layer as described above, causes migration of the dye into the desired mordanted layer. Alternatively, the silver halide emulsion layer and/or the mordanted, undyed layer can be surface-coated with an aqueous solution of the desired yellow dye so that the dye then migrates into the mordanted layer.
  • the dye need not be incorporated into the silver halide emulsion layer, but can be incorporated in one of the conventiona hydrophilic colloid layers used as interlayers, and the dyed layer placed in contact with the mordanted, but undyed, layer.
  • mordants are particularly useful in color photography where it is desired to fix a competing coupler compound, such as those described in Weller et al. U.S. Patent 2,689,793, dated September 21, 1954, in one of the layers of a multilayer element, such as in a particular light-sensitive silver halide emulsion layer.
  • a competing coupler compound such as those described in Weller et al. U.S. Patent 2,689,793, dated September 21, 1954
  • these mordants can be used to fix a competing coupler, such as citrazinic acid or H-acid, in a photographic silver halide emulsion which is sensitive to a particular region of the spectrum.
  • the silver halide emulsion layer contains one of the abovedescribed mordants which fixes the competing coupler during the coating procedures customarily employed in preparing photographic color elements, yet allows the competing coupler to react with oxidized developer for the purpose of controlling color balance. This tends to increase sharpness of the final color image by allowing less oxidized developer to wander away from its desired place. If desired, the unused competing coupler can be removed by washing the finished element in an aqueous alkaline solution.
  • FIG. 1 is a diagrammatic representation of the spectrophotometric curves of two of spectrophotometric of Carey Lea silver.
  • FIG. 2 is a diagrammatic representation of one of the multi-layer color elements which embody the mordanted filter layers of our invention.
  • curve A represents the spectrophotometric curve of colloidal silver (i.e., Carey Lea silver) which is customarily employed in color photography
  • curve B represents the spectrophotometric curve of the lter layer illustrated in Example 1 above (i.e., tartrazine dispersed in the mordanted layer)
  • curve C represents the spectrophotometric curve of the filter layer illustrated in Example 2 above (i.e., dye 11 in the mordanted layer).
  • FIG. 2 is depicted a multi-layer photographic ele ment utilizing a mordanted filter layer obtained according to our invention.
  • the multi-layer element comprises a support 10 having coated thereon a red-sensitive silver halide emulsion 11, a green-sensitive halide emulsion 12, a filter layer 14 containing -dimethylaminopropyl maleimide-styrene interpolymer and a yellow acid dye, such as dye 4 above, and finally a blue-sensitive silver halide emulsion layer 13.
  • the rnulti-layer element can also contain other interlayers (not shown) such as gelatin layers, etc.
  • the filter dye can be incorporated in either the redor green-sensitive emulsion layer which is in contact with the unsensitized colloid layer, such as layer 14 shown in FIGURE 2, instead of in the bluesensitive layer as illustrated in the above examples.
  • the following example will serve to illustrate the manner of incorporating the filter dye in the green-sensitive layer of a multi-color element of the type shown in FIGURE 2.
  • EXAMPLE A Control coating A photographic element was prepared in the usual manner using a cellulose acetate film support. On the support was coated an ordinary gelatino-silver-bromiodide emulsion which had been red-sensitized and contained a coupler for the cyan image. Typical of the couplers which can be used are those described in Fierke et al. US. Patent 2,801,171, issued July 30, 1957, and Salminen et al. US. Patent 2,423,730, issued July 8, 1947. Over the red-sensi tive emulsion was coated an ordinary gelatino-silverbromiodide emulsion which had been green-sensitized and contained a coupler for the magenta image.
  • Typical of the couplers which can be used are those shown in Loria et al. US. Patent 2,600,788, issued June 17, 1952. Over the green-sensitive coating, an ordinary colloidal silver layer was applied. Over the colloidal silver layer was coated an ordinary blue-sensitized gelatino-silver-bromiodide emulsion layer containing a coupler for the yellow image.
  • Typical of the couplers which can be used are those shown in the McCrossen et al. application Serial No. 575,099, US. Patent 2,875,057, granted February 24, 1959, referred to above. Some or all of the above silver bromiodide emulsion layers can be gold and/ or sulfur sensitized.
  • Filter dye coating A multi-layer element of the type described in A above was prepared, except that dye 1 was incorporated in the green-sensitive emulsion layer at a coverage of about 16 mg. per square foot, and the colloidal silver layer was replaced with a mixture of gelatin (151 mg. per square foot) and a copolymer of styrene and y-dimethylaminopropylacrylamide (60 mg. per square foot).
  • the filter dye (dye 1) was incorporated in the green-sensitive emulsion layer by dissolving it in methanol containing a small amount of triethanolamine, diluting the solution with water, and adding the aqueous solution directly to the green-sensitive layer.
  • the gelatin layer containing the acrylamide resin contained a small amount of hardener, such as mucochloric acid, and a spreading agent, such as saponin.
  • Example 5 instead of using the acrylamide resin shown in Example 5 above, equally eftective results were obtained using the same mordant described in Example 3 above.
  • the use of the filter dye as an addendum to the green-sensitive emulsion, rather than to the blue-sensitive emulsion layer has the advantage that no detectable amount of dye can find its way into the blue-sensitive layer, and thus adversely affect the blue speed.
  • the elements described in Ex ample 5 can be processed in the usual manner, such as by the Kodak Ektachrome E-2 process.
  • the filter dyes useful in practicing our invention can be prepared according to known techniques.
  • the dyes represented by Formula IV can be prepared according to the method described in Brooker et al. U.S. Patents 2,493,7478, issued January 10, 1950.
  • An improved method of preparing certain sulfoalkyl dyes of the type represented by Formula 1V above, is described in Brooker and Keyes US. application Serial No. 698,324, filed on even date herewith (now US 2,917,516, granted December 15, 1959).
  • dye 2 above was prepared according to the method described in the Brooker and Keyes application, and was obtained as a crystalline solid melting at 293-4" C.
  • Dye 3 was prepared as follows:
  • the filter dyes of our invention can be used either in the form of a free acid, or in the form of their water-soluble alkali metal salts. Accordingly, no differentiation between acids, or salts of the acids, is made in the following examples.
  • EXAMPLE B 1 p-sul f phenyl-3-carboxy-4-(4 -sztZfo-1 -naphthylaz0) S-pyrazolone disodium salt (dye 7)
  • the diazotization of the 4-amino-l-naphthalenesulfonic acid, 11.2 g. (.05 mole) was carried out in a mixture of acetic acid, 150 ml., and concentrated sulfuric acid, 10 ml., by the addition of 3.75 g. (.0545 mole) of sodium nitrite in 25 ,ml. of water at 0-8" C. with effective strring for one hour.
  • the above solution was treated with 1 .g. of sulfamic acid to destroy excess nitrite and added to 500 ml. of a water solution of 14.2 g (.05 mole) of l-(p-sulfophenyl- 3-carbethoxy-5-pyrazolone (prepared by condensing diethyl oxalacetate with p-sulfophenylhydrazine in ethyl alcohol, concentrated hydrochloric acid, 4 parts to 1 part, and crystallizing the product from water) at 5 to C. with effective stirring.
  • the orange-yellow dye formed on addition of sodium acetate to the mixed solutions and was filtered, washed with 100 ml. of ice water, and crystallized twice from 25% 3A-alcohol-75% water mixture.
  • the ester was hydrolyzed by heating on a steam bath for one hour in 125 ml. of aqueous 5% sodium hydroxide solution, neutralizing the cooled solution with acetic acid and crystallizing the product from 50% 3A-alcohol water mixture.
  • EXAMPLE C 1 (4-sulf0ph enyl -3-carboxy-4- 3-mcthy Isulfamy l-p/zenylaz0-5-pyraz0l0ne sodium salt (dye 8)
  • This compound was prepared by the same method employed for the preparation of 1-(psulfophenyl)-3-carboXy-4-(4-sulfo-l-naphthylazo)-5-pyrazolone, substituting m-methylsulfamylaniline in the place of 4-amino-1-naphthalenesulfonic acid.
  • the amine used here was prepared by condensing methylsulfonyl chloride with m-nitroaniline in acetic acid solutions using sodium acetate as the condensing agent and reducing the nitro compound to the amine catalytically.
  • the orange product was crystallized from 50% ethyl alcohol-water mixture.
  • EXAMPLE D 4-(2,5-disulfophenylazo)-5-lzydroxy-2-(B-rmp/ztlzy!- oxazole disodium salt (dye 9)
  • Ten g. (.04 mole) of Z-amino-p-benzenedisulfonic acid was suspended in 100 ml. of acetic acid and 10 ml. of concentrated sulfuric acid in a 125 ml. flask, 3 g. of sodium nitrite was added all at once. The flask was stoppered immediately, and shaken vigorously at -20 C. until complete solution took place, about minutes being required for this operation. On standing, the diazoniurn salt began to crystallize.
  • the flask was left in a refrigator overnight.
  • the diazo compound was filtered through a sintered glass funnel under water pump Vacuum.
  • the solid was suspended in 80 ml. or" acetone and 20 ml. of ice water was added, thus bringing about complete solution; 1 g. of sulfamic acid was added in two portions and the solution stirred for 30 minutes.
  • N-(fi-naphthoyhglycine prepared by condensing fl-naphthoyl chloride with glycine in dioxane, dimethylaniline being used as a condensing agent, and the product being crystallized from butyl alcohol
  • fi-naphthoyhglycine prepared by condensing fl-naphthoyl chloride with glycine in dioxane, dimethylaniline being used as a condensing agent, and the product being crystallized from butyl alcohol
  • carboxyl and sulfo as used in the following claims mean not only the free acid forms of these groups, but also salts of such groups, such as the sodium, potas sium, ammonium, organic ammonium, etc., salts.
  • a multilayer photographic element comprising (a) a support, (b) a redsensitive silver halide emulsion layer, (0) a green-sensitive silver halide emulsion layer, ((1) a blue-sensitive silver halide emulsion layer having substantially no sensitivity in the green and red regions of the spectrum, and (e) a blue-light absorbing colloid layer, said blue-sensitive silver halide emulsion layer (d) being outermost with respect to said silver halide emulsion layers (b) and (c), and said blue-light absorbing layer (e) being beneath said blue-sensitive silver halide emulsion layer (d) but outermost with respect to said silver halide emulsion layers (1)) and (c), the steps comprising (1) incorporating a blue-light absorbing dye (f) as a constituent of one of said silver halide emulsion layers contiguous to said colloid layer (e) and (2) diifusing substantially all of said blue-light absorbing dye (1)
  • said blue-light absorbing dye (7) being water-soluble and containing at least one radical selected from the class consisting of carboxyl and sulfo, said blue-light absorbing dye (f) having its maximum absorption between about 400 and 500 m with substantially no absorption beyond about 500 m and being adapted to he released from said element upon treatment with the alkaline solutions normally employed in color photography, and said colloid layer (e) containing a mordant comprising interpolymer units represented by the following general formula:
  • R, R and R each 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, a lower alkyl group, a monocyclic aryl group and a carbalkoxyl group
  • R and R each represents a member selected from the class consisting of (a) a lower alkyl group, (b) together represent the atoms necessary to complete a piperidine ring and (0) together represent the atoms necessary to com plete a morpholine ring
  • R represents an alkylene group containing from 2 to 5 carbon atoms
  • 2 represents a positive integer greater than about 10
  • X represents an acid anion selected from the'class consisting of lactyloxy, glycolyloxy, alkanesulfonoxy, chloride, and a saturated aliphatic acyloxy group
  • y represents a positive whole number
  • water 5 soluble dye is a dye represented by the following formula:

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  • Engineering & Computer Science (AREA)
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  • General Physics & Mathematics (AREA)
  • Organic Chemistry (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Developing Agents For Electrophotography (AREA)
  • Optical Filters (AREA)
US698699A 1957-11-25 1957-11-25 Yellow filter layers for multi-layer photographic color elements Expired - Lifetime US3016306A (en)

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BE573231D BE573231A (en(2012)) 1957-11-25
CA633929A CA633929A (en) 1957-11-25 Yellow filter layers for multi-layer photographic color elements
US698699A US3016306A (en) 1957-11-25 1957-11-25 Yellow filter layers for multi-layer photographic color elements
FR780014A FR1221619A (fr) 1957-11-25 1958-11-25 Procédé pour la préparation de produits photographiques à plusieurs couches d'émulsion contenant une couche filtre mordancée absorbant le bleu et nouveaux produitsphotographiques obtenus
GB38018/58A GB906083A (en) 1957-11-25 1958-11-25 Improvements in filters for photography

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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3282699A (en) * 1962-01-22 1966-11-01 Eastman Kodak Co Photographic elements containing bleachable mordanted dye layers
US3406069A (en) * 1965-06-03 1968-10-15 Du Pont Photographic element and process
US3408193A (en) * 1964-12-16 1968-10-29 Eastman Kodak Co Coating compositions for the coating out of anionic mordant-acid dye layers
US3425834A (en) * 1965-08-16 1969-02-04 Eastman Kodak Co Mordants for bleachable filter layers
US3425833A (en) * 1965-08-16 1969-02-04 Eastman Kodak Co Mordants for bleachable filter layers
US3658536A (en) * 1970-07-13 1972-04-25 Wilfred L Wolf Multilayered color film of increased sharpness
US4028112A (en) * 1974-05-10 1977-06-07 Fuji Photo Film Co., Ltd. Photographic sensitive materials having a dyed layer
US4110115A (en) * 1976-05-06 1978-08-29 Fuji Photo Film Co., Ltd. Photographic light-sensitive element having dyed layer
US4191571A (en) * 1974-04-26 1980-03-04 Hitachi, Ltd. Method of pattern forming in a photosensitive composition having a reciprocity law failing property

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3642482A (en) * 1967-07-25 1972-02-15 Eastman Kodak Co Photographic element and process
JPS511419B1 (en(2012)) * 1971-02-09 1976-01-17

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1954294A (en) * 1930-07-12 1934-04-10 Agfa Ansco Corp Superimposed colored photographic layers
GB551500A (en) * 1941-08-19 1943-02-25 Eastman Kodak Co Improvements in photographic materials containing dyes
US2548564A (en) * 1946-12-31 1951-04-10 Eastman Kodak Co Photographic silver halide element with mordanted dye layer
US2882156A (en) * 1955-12-19 1959-04-14 Eastman Kodak Co Basic mordants derived from the reaction of carbonyl containing polymers and aminoguanidine and their use

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1954294A (en) * 1930-07-12 1934-04-10 Agfa Ansco Corp Superimposed colored photographic layers
GB551500A (en) * 1941-08-19 1943-02-25 Eastman Kodak Co Improvements in photographic materials containing dyes
US2548564A (en) * 1946-12-31 1951-04-10 Eastman Kodak Co Photographic silver halide element with mordanted dye layer
US2882156A (en) * 1955-12-19 1959-04-14 Eastman Kodak Co Basic mordants derived from the reaction of carbonyl containing polymers and aminoguanidine and their use

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3282699A (en) * 1962-01-22 1966-11-01 Eastman Kodak Co Photographic elements containing bleachable mordanted dye layers
US3408193A (en) * 1964-12-16 1968-10-29 Eastman Kodak Co Coating compositions for the coating out of anionic mordant-acid dye layers
US3406069A (en) * 1965-06-03 1968-10-15 Du Pont Photographic element and process
US3425834A (en) * 1965-08-16 1969-02-04 Eastman Kodak Co Mordants for bleachable filter layers
US3425833A (en) * 1965-08-16 1969-02-04 Eastman Kodak Co Mordants for bleachable filter layers
US3438779A (en) * 1965-08-16 1969-04-15 Eastman Kodak Co Mordants for bleachable filter layers
US3455693A (en) * 1965-08-16 1969-07-15 Eastman Kodak Co Mordants for use in dyed filter layers
US3658536A (en) * 1970-07-13 1972-04-25 Wilfred L Wolf Multilayered color film of increased sharpness
US4191571A (en) * 1974-04-26 1980-03-04 Hitachi, Ltd. Method of pattern forming in a photosensitive composition having a reciprocity law failing property
US4028112A (en) * 1974-05-10 1977-06-07 Fuji Photo Film Co., Ltd. Photographic sensitive materials having a dyed layer
US4110115A (en) * 1976-05-06 1978-08-29 Fuji Photo Film Co., Ltd. Photographic light-sensitive element having dyed layer

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BE573231A (en(2012))
CA633929A (en) 1962-01-02
GB906083A (en) 1962-09-19

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