US3790384A - Light-sensitive color photographic elements with improved image quality - Google Patents
Light-sensitive color photographic elements with improved image quality Download PDFInfo
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- US3790384A US3790384A US00192355A US3790384DA US3790384A US 3790384 A US3790384 A US 3790384A US 00192355 A US00192355 A US 00192355A US 3790384D A US3790384D A US 3790384DA US 3790384 A US3790384 A US 3790384A
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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
- 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
- G03C7/3029—Materials characterised by a specific arrangement of layers, e.g. unit layers, or layers having a specific function
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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
- 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
- G03C7/32—Colour coupling substances
- G03C7/34—Couplers containing phenols
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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
- G03C2200/00—Details
- G03C2200/35—Intermediate layer
Definitions
- a multi-layer color photographic element comprising [21] APPL 2 355 a support having a plurality of silver halide emulsion layers, at least one layer being a red-sensitive silver Related Apphcat'on Dam halide emulsion layer, containing a cyan-forming cou- Continuation Of ly 1 1968.
- Green-sensitive 1 Foreign Appllcatlon Priority Data emulsion layers and blue-sensitive emulsion layers are 7 July18,T% Japan 46-217 generally used in combination with said red-sensitive layer.
- the order of application of said layers is of no [52] US. Cl 96/74, 96/22, 96/100 importance, as long as the red-sensitive emulsion layer [51] Int.
- the present invention relates to color photography and, more particularly, to a light-sensitive color photographic element having an intermediate layer which prevents interlayer migration of a development inhibiting substance.
- a cyan coupler carrying an iodine or a bromine atom at the coupling site is sometimes of a great value, because the coupler, on reaction with the oxidized developer, releases iodide or bromide ions which are, for the most part, captured by near-by silver halide grains and retard excessive reduction of these grains. This effect enables one to control photographic gradation and to improve sharpness and graininess without lowering sensitivity.
- the multi-layer color photographic element of the invention comprises a support having coated thereon a red-sensitive silver halide emulsion layer, a green-sensitive emulsion layer and a bluesensitive emulsion layer.
- the red-sensitive silver halide emulsion layer contains a cyan-forming coupler, such as phenol derivatives, a'Ipha-naphthol derivatives, each having an iodine or a bromine atom para to the hydroxyl group thereof, it is necessary that the red sensitive silver halide emulsion layer be separated from any greenor blue-sensitive emulsion layer by an intermediate silver halide layer of low photo-sensitivity which will prevent harmful migration.
- the cyan-forming coupler may be selected from compounds having the general formula:
- NHCOR2 wherein X is a member selected from the group consisting of an iodine atom and a bromine atom, R CO is an acyl group containing at least nine carbon atoms, and R and R are each a member selected from the group consisting of a hydrogen atom, a halogen atom and an alkyl group.
- the silver halide may generally be silver chloride, silver bromide, silver chlorobromide and silver iodobromide.
- An object of the present invention is to provide a multi-layer color photographic light-sensitive element having an emulsion layer containing a color-forming compound which carries an iodine atom or a bromine atom at the coupling position thereof, and releases iodide or bromide ions during its reaction with the oxidation product of an aromatic primary amino developing agent, said element being provided with an intermediate layer so that the inter-layervmigration of the iodide ion or bromide ion into other emulsion layers is effectively prevented.
- Another object of this invention is to provide a multilayer color photographic material having excellent definition and color reproduction.
- FIG. 1 is a plot of red color density versus both green and blue color density for Film E.
- FIG. 2 is a plot of red color density versus both green and blue color density for Film F.
- the present invention consists of a multi-layer color photographic element characterized by the presence of an intermediate layer containing a silver halide emulsion of low photosensitivity.
- This intermediate layer lies
- FIG. 3 is a plot of red color density versus both green between a silver halide emulsion layer containing a coupler and another silver halide emulsion containing another cyan-forming phenol or a-naphthol coupler that carries an iodine or a bromine atom at the coupling site.
- the composition of the silver halide to be employed in said intermediate layer depends on the substituent of the cyan-forming coupler which is employed.
- the substituent of the cyan-forming coupler is iodine
- silver iodobromide, silver bromide, silver chloro-bromide or silver chloride This silver halide is not ripened because no photosensitivity is required of it.
- the amount of the silver halide to be added depends upon the amount of liberated iodide or bromide ion. In normal multi-layer color photographic light-sensitive elements, l X mols to 1 X 10* mols per 100 sq. cm. of the color photographic element is sufficient.
- the silver halide grains of the intermediate layer be substantially transparent.
- smaller size silver halide grains are preferred, in particular, 0.5 microns or less in diameter are preferred.
- the low-sensitivity silver halide incorporated in the intermediate layer is not developed during the developing process, and it is removed by fixing.
- the cyan-forming coupler used in the color photographic light-sensitive element is a phenol or naphthol derivative having an iodine or a bromine atom para to the hydroxyl group, and usually it will have a ballasting group with more than eight carbon atoms ortho to the hydroxyl group to render the coupler fast to diffusion.
- Typical examples of the cyan-forming coupler used in this invention are illustrated below:
- Couplers 11, V, Vll and Vlll may also be prepared from the corresponding compounds by a similar procedure.
- Couplers IV, VI, 1X and X may be prepared similarly from the corresponding compounds by brominating in methylene chloride.
- couplers may be incorporated in the cyanforming emulsion layer either by themselves or as a mixture thereof, or in a mixture with conventional cyan-forming couplers having no halogen atom. Moreover, by adjusting the mixing ratio of these couplers, image definition can be controlled.
- EXAMPLE 1 The following three types of photographic films were prepared:
- this intermediate layer To the surface of this intermediate layer were successively applied a green-sensitive silver iodobromide emulsion containing, as a magentaforming coupler, l-(2', 6'-dichloro-4'-methoxy)-3- 3II[a (2I!I 4'-di-tert-amylphenoxy)-butyramido]phenylureido- S-pyrazolone, a dispersion of yellow colloidal silver, and a blue-sensitive emulsion containing as a yellow coupler a- 3-[a-(2, 4"-di-tert-amylphenoxy)- acetamido1-benzoyl -2-methoxyanilide.
- the final product was labeled Film A.
- Film B A multi-layer color photographic film having the same layer structure as Film A was prepared in the same manner as Film A, with the exception that the intermediate layer, the red-sensitive emulsion layer and the green-sensitive layer contained no silver bromide.
- Film A, Film B, and Film C were each exposed to blue light, green light and to red light separately, through an optical wedge. They were then subjected to a development process in order to provide the gradations shown in the following table, which correspond to the gradation of each light sensitive emulsion layer of the multi-layer color photographic film.
- Film D having the same layer structure as Film A was prepared using as the cyan-forming coupler l-hydroxy-4-chloro-N-ndodecyl-2-naphthamide, and the granularity of the cyan image was compared in both cases. The results showed that Film A of this invention was superior in granularity and definition to Film D.
- a blue-sensitive silver chloro-bromide emulsion containing as a yellow-forming coupler abenzoyllZ-methoxyanilide was applied to a film base.
- a superfine emulsion of silver chloride which had not been chemically ripened, at a dry thickness of 1 micron and at 2 X 10" mole-silver/l sq.cm., to provide an intermediate layer.
- Film F t A multi-layer color photographic film having the same layer structure as Film E was prepared. However, the two intermediate layers adjacent the red-sensitive emulsion layer contained no silver chloride.
- Film G A multi-layer color photographic film having the same layer structure as Film E was prepared, except that no intermediate layers were provided.
- Film H having the same layer construction as Film E was prepared using, as a cyanforming coupler, l-hydroxy-4-chloro-N-n-dodecyl-2- naphthamide. Film H and Film E were each closely contacted with a negative color image, and were processed to provide positive images, which, on projection, showed that Film E gave a finer and sharper cyan projection than Film H.
- EXAMPLE 3 The following three kinds of multi-layer color photographic films were prepared:
- the emulsion (25 g.) was added to l00 g. of a red-sensitive silver halide emulsion containing 5.0 g. of gelatin and 3.0 X 10' moles of silver iodo-bromide.
- the silver halide emulsion thus prepared was applied to a cellulose triacetate film at a dry thickness of 5 microns.
- On the surface of the silver halide emulsion layer thus formed there was applied an emulsion of fine silver chloride grains, which had not been chemically ripened, at a dry thickness of 1.5 microns so that 5 X 10" moles of silver chloride were contained per 100 sq.cm. of this intermediate layer.
- Film J A multi-layer color photographic film having the same layer construction as Film l was prepared, except that the intermediate layer between the red-sensitive emulsion layer and the green-sensitive emulsion layer was a gelatin layer of 1.5 microns thickness containing no i ri shlq d Film K A multi-layer color photographic film having the same layer structure as Film 1, except that no intermediate layer was provided between the red-sensitive emulsion layer and the green-sensitive emulsion layer, was prepared.
- the green-sensitive emulsion layer was not disturbed by the coupling in the red-sensitive emulsion layer and a correct color reproduction was obtained.
- Film L Another multi-layer color photographic film (Film L) having the same layer structure as Film I was prepared, using as the cyan-forming coupler'l-hydroxy-N- n-dedecyl-Z-naphthamide. After exposing and developing, the granularity of images was compared between Film l and Film L. Film I showed finer granularity and better definition than Film L.
- a multi-layer color photographic element com-' prising a support having coated thereon a red-sensitive silver halide e m ulsion layer ggntaining, a s a cyanforming coupler, a member selected from the group consisting of phenolic and a-naphtholic cyan-forming couplers, each having, at the para-position to the by droxyl group thereof, a member selected from the group consisting of an iodine and a bromine atom, a green-sensitive emulsion layer and a blue-sensitive emulsion layer, the improvement which comprises said red-sensitive silver halide emulsion layer being separated from said green-sensitive and said blue-sensitive silver halide emulsion layers which it is in contact with by an intermediate layer positioned on at least one side of said red-sensitive silver halide emulsion layer, said intermediate layer containing silver halide grains whose photosensitivity is sufficiently low such that no visible image is formed therein by exposure and
- a color photographic element as claimed in claim 1, wherein said cyan-forming coupler is selected from compounds having the general formula:
- R @jm R1 wherein X is a member selected from the group consisting of an iodine atom and a bromine atom, R is a member selected from the group consisting of a hydrogen atom, an alkyl group, an aryl group, and R, is a ballasting organic radical containing at least eight carbon atoms.
- a color photographic element as claimed in claim 1, wherein said cyan-forming coupler is selected from compounds having the general formula:
- X is a member selected from the group consisting of an iodine atom and a bromine atom
- R CO is an acyl group containing at least nine carbon atoms
- R and R are each a member selected from the group consisting of a hydrogen atom, a halogen atom and an alkyl group.
- a color photographic element as claimed in claim 1 wherein the amount of said silver halide in said intermediate layer varies from 1 X10 to l X 10" mole per cm of said photographic element.
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Abstract
A multi-layer color photographic element comprising a support having a plurality of silver halide emulsion layers, at least one layer being a red-sensitive silver halide emulsion layer, containing a cyan-forming coupler, such as phenol derivatives and Alpha -naphthol derivatives which have an iodine or a bromine atom at the ''''para'''' position to the hydroxyl group. Greensensitive emulsion layers and blue-sensitive emulsion layers are generally used in combination with said red-sensitive layer. The order of application of said layers is of no importance, as long as the red-sensitive emulsion layer is separated from different emulsion layers by an intermediate layer containing silver halide grains of reduced photo-sensitivity. Specific examples of the cyan-forming coupler and acceptable silver halide materials are defined in the disclosure.
Description
United States Patent Oishi et a1. Feb. 5, 1974 [54] LIGHT-SENSITIVE COLOR 3,364,022 1/1968 Barr 96/ 100 PHOTOGRAPH: ELEMENTS WITH 3,488,193 1/1970 Eynde et a1 96/74 IMPROVED IMAGE QUALITY 3,591,383 7/1971 Yoshlda et a1 96/22 [75] Inventors: Yashushi Oishi; Yoshinobu Yoshida; Primary Examiner-J, Travis Brown Kalllya of Karlagawa, Assistant Examiner-Richard L. Schilling Japan Attorney, Agent, or Firm-Sughrue, Rothwell, Mion, 73 Assignee: Fuji Photo Film 00., Ltd, Minami Macpeak Ashigara-shl, Kanagawa, Japan ABSTRACT [22] Flled: 1971 A multi-layer color photographic element comprising [21] APPL 2 355 a support having a plurality of silver halide emulsion layers, at least one layer being a red-sensitive silver Related Apphcat'on Dam halide emulsion layer, containing a cyan-forming cou- Continuation Of ly 1 1968. pler, such as phenol derivatives and a-naphthol derivabandonedatives which have an iodine or a bromine atom at the o para position to the hydroxyl group. Green-sensitive 1 Foreign Appllcatlon Priority Data emulsion layers and blue-sensitive emulsion layers are 7 July18,T% Japan 46-217 generally used in combination with said red-sensitive layer. The order of application of said layers is of no [52] US. Cl 96/74, 96/22, 96/100 importance, as long as the red-sensitive emulsion layer [51] Int. Cl G03c 1/76, G03c 3/00 is separated from different emulsion layers by an inter- [58] Field of Search 96/74, 100, 55,22 mediate layer containing silver halide grains of reduced photo-sensitivity. Specific examples of the cy- [56] References Cited an-forming coupler and acceptable silver halide mate- UNITED STATES PATENTS rials are defined in the disclosure.
3,152,907 10/1964 Godowsksy et a1 96/74 9 Claims, 3 Drawing Figures Film E Green Density 7 Blue Density Density Red Density memoir-1B w 3;790.3e4
v Film E -Green Density 5 t Blue Density v Density Red Density O 2:0
Film F f1 J? T 'Nreen Density NW Density LO Density Red Density ILIO 26 Film G 1 \Green Density l.O \lue Density INVENTORS' Red Density L O. 2:0 Yasush/ 0/s/7/ YOsh/hobu flash/bio Kazuya 5000 A RNEYS Density LIGHT-SENSITIVE COLOR PHOTOGRAPHIC ELEMENTS WITH IMPROVED IMAGE QUALITY This is a Continuation, of application Ser. No. 745,885, filed July 18, 1968, now abandoned.
BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to color photography and, more particularly, to a light-sensitive color photographic element having an intermediate layer which prevents interlayer migration of a development inhibiting substance.
Description of the Prior Art In the formation of color images in multilayer color photographic elements, a color reproduction process is usually employed in which couplers have been incorporated in differently sensitized silver halide emulsion layers. On development of the silver halide, the couplers form color images, in accordance with the silver image, by reaction with the oxidation product of aromatic primary amino developers, which are commonly used.
Among the couplers employed in such a multilayer system, a cyan coupler carrying an iodine or a bromine atom at the coupling site is sometimes of a great value, because the coupler, on reaction with the oxidized developer, releases iodide or bromide ions which are, for the most part, captured by near-by silver halide grains and retard excessive reduction of these grains. This effect enables one to control photographic gradation and to improve sharpness and graininess without lowering sensitivity.
However, when this kind of coupler is used in a multilayer material and is present in an emulsion layer which is adjacent a differently sensitized colonforming layer, a part of the iodide or bromide ion liberated during the coupling reaction migrates from its original layer and retard the development of the adjacent layer as well. This gives rise to an undesirable effect on the gradation of the latter layer, leading to deterioration of color reproducibility.
SUMMARY OF THE INVENTION It has now been found that deterioration in multilayer color emulsions due to migrating bromide or iodide ions can be prevented by inserting an intermediate layer between adjacent emulsion layers/Silver halide grains of low photosensitivity are incorporated in the intermediate layer which will capture the migrating bromide or iodide ions, thus insulating any other emulsion layers from the halide-releasing layer. The silver halide grains in the intermediate layer are not reduced during photographic development.
Generally, the multi-layer color photographic element of the invention comprises a support having coated thereon a red-sensitive silver halide emulsion layer, a green-sensitive emulsion layer and a bluesensitive emulsion layer. Since the red-sensitive silver halide emulsion layer contains a cyan-forming coupler, such as phenol derivatives, a'Ipha-naphthol derivatives, each having an iodine or a bromine atom para to the hydroxyl group thereof, it is necessary that the red sensitive silver halide emulsion layer be separated from any greenor blue-sensitive emulsion layer by an intermediate silver halide layer of low photo-sensitivity which will prevent harmful migration.
The cyan-forming coupler may be selected from compounds having the general formula:
CON
NHCOR2 wherein X is a member selected from the group consisting of an iodine atom and a bromine atom, R CO is an acyl group containing at least nine carbon atoms, and R and R are each a member selected from the group consisting of a hydrogen atom, a halogen atom and an alkyl group.
The silver halide may generally be silver chloride, silver bromide, silver chlorobromide and silver iodobromide.
An object of the present invention is to provide a multi-layer color photographic light-sensitive element having an emulsion layer containing a color-forming compound which carries an iodine atom or a bromine atom at the coupling position thereof, and releases iodide or bromide ions during its reaction with the oxidation product of an aromatic primary amino developing agent, said element being provided with an intermediate layer so that the inter-layervmigration of the iodide ion or bromide ion into other emulsion layers is effectively prevented.
Another object of this invention is to provide a multilayer color photographic material having excellent definition and color reproduction.
DESCRIPTION OF THE DRAWINGS FIG. 1 is a plot of red color density versus both green and blue color density for Film E.
FIG. 2 is a plot of red color density versus both green and blue color density for Film F.
and blue density for Film G.
DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention consists of a multi-layer color photographic element characterized by the presence of an intermediate layer containing a silver halide emulsion of low photosensitivity. This intermediate layer lies FIG. 3 is a plot of red color density versus both green between a silver halide emulsion layer containing a coupler and another silver halide emulsion containing another cyan-forming phenol or a-naphthol coupler that carries an iodine or a bromine atom at the coupling site.
The composition of the silver halide to be employed in said intermediate layer depends on the substituent of the cyan-forming coupler which is employed. For example, when the substituent of the cyan-forming coupler is iodine, there may be employed silver iodobromide, silver bromide, silver chloro-bromide or silver chloride. This silver halide is not ripened because no photosensitivity is required of it. The amount of the silver halide to be added depends upon the amount of liberated iodide or bromide ion. In normal multi-layer color photographic light-sensitive elements, l X mols to 1 X 10* mols per 100 sq. cm. of the color photographic element is sufficient.
In order to assure the sharpness of the images of the color photographic light sensitive element, it is desirable that the silver halide grains of the intermediate layer be substantially transparent. Thus, smaller size silver halide grains are preferred, in particular, 0.5 microns or less in diameter are preferred.
The low-sensitivity silver halide incorporated in the intermediate layer is not developed during the developing process, and it is removed by fixing.
The cyan-forming coupler used in the color photographic light-sensitive element is a phenol or naphthol derivative having an iodine or a bromine atom para to the hydroxyl group, and usually it will have a ballasting group with more than eight carbon atoms ortho to the hydroxyl group to render the coupler fast to diffusion. Typical examples of the cyan-forming coupler used in this invention are illustrated below:
OONHCizHzs n 0H M M h CONHCnH CONH(CH1)BOQCBHU(Q sHn(t) Ivy... OH W oonmcmmQcmm) V sHn) (v on 00Nncmonmcmcnmn00- IOCHIIH miii ss- C O NHCH CHgNHC 0 CH0 "H" T EDT h i i afiii OH N SOaH N vm). 0H
01- Imrcomno-Q-cnmo) CH1 11111) 01 NHCOOHO- 05m) $2116 CH: a iK X OH WW Cl NHCONHCuHn These cyan-forming couplers are conveniently obtained by introducing an iodine atom or a bromine atom into the 4-position of a corresponding 2- substituted naphthol or phenol by direct halogenation or by a Sandmeyer reaction. Examples of methods of preparation of these cyan-forming couplers are shown below.
1. Preparation of l#hydroxy-4-iodo-N-n-dodecyl-2- naphthamide:
CONHCuI-Iu To 500 ml. of glacial acetic acid were added g. of l-hydroxy-N-n-dodecyl-2-naphthamide, 28 g. of anhydrous sodium acetate, and 35 g. of anhydrous lead acetate. The mixture was heated to 70-80C. and there was added (dropwise) 50 g. of a saturated methanol solution of 50 g. of iodine over a 3 hour period while stirring and irradiating with sun light. After an additional hour, the product was filtered, the filtrate was cooled, and the crystals that deposited were collected. The crystals were then recrystallized from acetone and dried thoroughly. The yield of the product, melting at 93-94C., was 32 g.
Couplers 11, V, Vll and Vlll may also be prepared from the corresponding compounds by a similar procedure.
2. Preparation of 1-hydroxy-4-bromo-N-n-dodecyl-2- naththamide:
CONHCuHzs To 500 ml. of methylene chloride was added 70 g. of l-hydroxy-N-n-dodecyl-Z-naphthamide. While stirring the solution under cooling conditions, 100 ml. of a methylene chloride solution of 32 g. of bromine was added dropwise over a 2 hour period. The system was then stirred for an additional 30 minutes, whereupon the crystals of the coupler precipitated and were collected. The filtrate was concentrated to 150 ml. and cooled to separate a second crystal crop. The two crops were combined and recrystallized twice from methanol to provide 70 g. of pure product melting at 97C.
Couplers IV, VI, 1X and X may be prepared similarly from the corresponding compounds by brominating in methylene chloride.
These couplers may be incorporated in the cyanforming emulsion layer either by themselves or as a mixture thereof, or in a mixture with conventional cyan-forming couplers having no halogen atom. Moreover, by adjusting the mixing ratio of these couplers, image definition can be controlled.
The invention will be explained in more detail by the following examples, although the invention should not be limited thereby.
EXAMPLE 1 The following three types of photographic films were prepared:
Film A In a mixture of 10.0 ml. of tri-o-cresylphosphate and 7.0 ml. of ethyl acetate there was dissolved 5 g. of 1- hydroxy-4-iodo-N-n-dodecyl-naphthamide (Coupler l). The resulting solution was dispersed in 50 ml. of a percent aqueous gelatin solution containing 4 ml. of a 5 percent aqueous solution of sodium n-dodecylbenzenesulfonate. Twenty-one g. of the emulsion formed were added to 100 g. of a red sensitive silver halide emulsion containing 5.0 g. of gelatin and 3.0 X 10' moles of silver iodo-bromide, and the resultant emulsion was applied to a cellulose triacetate film at a dry thickness of 5 microns. To the surface of the thus formed emulsion layer was applied an emulsion of fine silver bromide particles, which had not been chemically ripened, at a dry thickness of 1.5 microns, so that 4 X10 moles of silver bromide were contained in 100 sq. cm. of the layer. To the surface of this intermediate layer were successively applied a green-sensitive silver iodobromide emulsion containing, as a magentaforming coupler, l-(2', 6'-dichloro-4'-methoxy)-3- 3II[a (2I!I 4'-di-tert-amylphenoxy)-butyramido]phenylureido- S-pyrazolone, a dispersion of yellow colloidal silver, and a blue-sensitive emulsion containing as a yellow coupler a- 3-[a-(2, 4"-di-tert-amylphenoxy)- acetamido1-benzoyl -2-methoxyanilide. The final product was labeled Film A.
Film B A multi-layer color photographic film having the same layer structure as Film A was prepared in the same manner as Film A, with the exception that the intermediate layer, the red-sensitive emulsion layer and the green-sensitive layer contained no silver bromide.
Film C A multi-layer color photographic film which otherwise was the same as Film A was prepared without an intermediate layer between the red-sensitive emulsion layer and the green-sensitive one.
These films, after exposure, were developed in a color developer (pl-l 10.8) containing as a developing agent N-ethyl-N-(fl-sulfoamidoethyl)-3-methyl-4- aminoaniline sulfate, for 14 minutes at 21C. These films were then subjected to conventional fixing, bleaching, fixing again and washing to provide colored films.
Film A, Film B, and Film C were each exposed to blue light, green light and to red light separately, through an optical wedge. They were then subjected to a development process in order to provide the gradations shown in the following table, which correspond to the gradation of each light sensitive emulsion layer of the multi-layer color photographic film.
Table 1 Gamma-Values (separate exposure) Density measured Coupling layer Film A B C Blue density Blue sensitive 1.25 1.20 1.22 Green density Green sensitive 1.30 1.35 1.30 Red density Red sensitive 1.45 1.40 1.40
Table 2 Gamma-values (white-light exposure) Density measured Coupling layer Film A B C Blue density Blue sensitive 1.20 1.20 1.15 Green density Green sensitive 1.20 0.90 0.85 Red density Red sensitive 1.22 1.20 1.25
The above results show that when the films were exposed separately (three-color exposure) followed by light, the gradations of the green-sensitive layer of Film B and C were greatly reduced, and that the gradations of the blue-sensitive layer and the red-sensitive layer were unbalanced, resulting in improper color reproduction. On the other hand, Film A, having the intermediate layer of this invention, showed the correct color reproduction and was free from any disturbance in the gradation of the green-sensitive layer due to the coupling in the red-sensitive layer.
Another film, Film D, having the same layer structure as Film A was prepared using as the cyan-forming coupler l-hydroxy-4-chloro-N-ndodecyl-2-naphthamide, and the granularity of the cyan image was compared in both cases. The results showed that Film A of this invention was superior in granularity and definition to Film D.
EXAMPLE 2 The following three kinds of films were prepared:
Film E A blue-sensitive silver chloro-bromide emulsion containing as a yellow-forming coupler abenzoyllZ-methoxyanilide was applied to a film base. To the surface of the emulsion layer formed there was applied a superfine emulsion of silver chloride, which had not been chemically ripened, at a dry thickness of 1 micron and at 2 X 10" mole-silver/l sq.cm., to provide an intermediate layer.
In a mixture of 10 ml. of di-n-butyl phthalate and ml. of ethyl acetate there was dissolved 5.0 g. of lhydroxy-4-bromo-N-n-dodecyl-2-naphthamide (Coupler ll), and the resulting solution was dispersed in 50 ml. of a percent aqueous solution containing 4 ml. of a 5 percent aqueous solution of sodium n-dodecyl sulfonate to provide a coupler emulsion. The coupler emulsion g.) was added to 100 g. ofa red-sensitive emulsion containing 5.0 g. of gelatin and 2.0 X 10 moles of silver chloro-bromide. The mixture was applied to the surface of the intermediate layer at a dry thickness of 5 microns. To the surface of the emulsion layer there was applied a second intermediate layer having the same composition as the first intermediate layer, and to the surface of the second intermediate layer, there was further applied a green-sensitive silver chloro-bromide emulsion containing as a magentaforming coupler l-(2,6-dichloro-4-methoxy)-3- {3'- [a- (2" 4"-di-tertamylphenoxy)-butylamido] plienylureido}-5-pyrazqlone.
Film F t A multi-layer color photographic film having the same layer structure as Film E was prepared. However, the two intermediate layers adjacent the red-sensitive emulsion layer contained no silver chloride.
Film G A multi-layer color photographic film having the same layer structure as Film E was prepared, except that no intermediate layers were provided.
After exposure, the films were developed in a color developer containing as a developing agent N,N-
were subjected to standard fixing, bleaching, fixing and washing utilized to provide color films.
Two samples were prepared from each of the films, i.e., two strips were cut from each of Films E, F and G. The filmswere initially exposed to red light under an optical wedge. Then, uniform blue and green irradiation of intermediate intensity was given to one strip and the other, respectively. The films were then developed and the blue, green and red density values thereof were measured. The relationship of these density values is shown in FIGS. 1, 2 and 3 of the accompanying drawings. The results show that while Film F and Film G had been uniformly exposed to green and blue light, respectively, these samples showed no uniformity in the green and blue sensitive layers due to the developmentinhibiting influence of the red-sensitive layer. On the other hand, Film E of this invention showed the correct green density and the correct blue density corresponding to the exposure.
Another film, Film H, having the same layer construction as Film E was prepared using, as a cyanforming coupler, l-hydroxy-4-chloro-N-n-dodecyl-2- naphthamide. Film H and Film E were each closely contacted with a negative color image, and were processed to provide positive images, which, on projection, showed that Film E gave a finer and sharper cyan projection than Film H.
EXAMPLE 3 The following three kinds of multi-layer color photographic films were prepared:
Film I In a mixture of 10.0 ml. of tri-o-cresyl phosphate and 7.0 ml. of ethyl acetate were dissolved 2.5 g. of lhydroxy-N-n-dodecyl-2-naphthamide and 2.5 g. of lhydroxy-4-iodo-N-n-dodecyl-2-naphthamide. The resulting solution was dispersed in 50 m1. of a 10 percent aqueous gelatin solution, containing 4 ml. of a 5 percent aqueous solution of sodium n-dodecyl-benzenesulfonate, to provide an emulsion. The emulsion (25 g.) was added to l00 g. of a red-sensitive silver halide emulsion containing 5.0 g. of gelatin and 3.0 X 10' moles of silver iodo-bromide. The silver halide emulsion thus prepared was applied to a cellulose triacetate film at a dry thickness of 5 microns. On the surface of the silver halide emulsion layer thus formed, there was applied an emulsion of fine silver chloride grains, which had not been chemically ripened, at a dry thickness of 1.5 microns so that 5 X 10" moles of silver chloride were contained per 100 sq.cm. of this intermediate layer. To this layer were applied, successively, a greensensitive silver iodo-bromide emulsion containing, as a magenta-forming coupler, l-(2', 6-dichloro-4- methoxy)-3-3"-[a-2", 4"-di-tert-amylphenoxy)-butyramido]phenylureido- 5-pyrazolone and then a blue-sensitive emulsion con- I taining, as a yellow-forming coupler, a-l3'-[a-(2", 4"-
10.7) for 14 minutes at 21C. Thereafter, the films I di-tert-amylphenoxy)-acetamido]-benzoyl} -2-r r ethoxyanilide, as in Example 1.
Film J A multi-layer color photographic film having the same layer construction as Film l was prepared, except that the intermediate layer between the red-sensitive emulsion layer and the green-sensitive emulsion layer was a gelatin layer of 1.5 microns thickness containing no i ri shlq d Film K A multi-layer color photographic film having the same layer structure as Film 1, except that no intermediate layer was provided between the red-sensitive emulsion layer and the green-sensitive emulsion layer, was prepared.
Each of Films 1, J and K thus prepared was exposed separately to blue light, green light and red light, under an optical wedge, and developed in a color developer containing, as a developing agent, N-ethyl-N-(B- methane-sulfoneamidoethyl)-3-methyl-4-aminoaniline sulfate (pl-l=l0.8) for 14 minutes at 21C., and subjected to fixing, bleaching, fixing and then washing to provide a film with the gradations shown in the Table E srad tiqa r nq ils KQBBQWEFILWQHHPE obtained by separate development of each silver halide layer in these multilayer photographic films.
Table 3 Gamma-values (separate exposure) Density measured Coupling Layer Film l J K Blue density Blue sensitive l.l2 l.l Green density Green sensitive 1.22 l.l9 Red density Red sensitive .29 1.28
ln another experiment, Films 1, J and K were exposed to white light under an optical wedge, and were developed as in Example 1 to provide the gradations which are shown in Table 4. A as.
Table 4 Gamma-values (white-light exposure) Density measured Coupling layer Film Blue density Blue sensitive .10 L07 1.06 Green density Green sensitive 1.18 1.01 1.00 Red density Red sensitive 1.20 L2] 1.19
the green-sensitive emulsion layer was not disturbed by the coupling in the red-sensitive emulsion layer and a correct color reproduction was obtained.
Another multi-layer color photographic film (Film L) having the same layer structure as Film I was prepared, using as the cyan-forming coupler'l-hydroxy-N- n-dedecyl-Z-naphthamide. After exposing and developing, the granularity of images was compared between Film l and Film L. Film I showed finer granularity and better definition than Film L.
What is claimed is:
1. In a multi-layer color photographic element com-' prising a support having coated thereon a red-sensitive silver halide e m ulsion layer ggntaining, a s a cyanforming coupler, a member selected from the group consisting of phenolic and a-naphtholic cyan-forming couplers, each having, at the para-position to the by droxyl group thereof, a member selected from the group consisting of an iodine and a bromine atom, a green-sensitive emulsion layer and a blue-sensitive emulsion layer, the improvement which comprises said red-sensitive silver halide emulsion layer being separated from said green-sensitive and said blue-sensitive silver halide emulsion layers which it is in contact with by an intermediate layer positioned on at least one side of said red-sensitive silver halide emulsion layer, said intermediate layer containing silver halide grains whose photosensitivity is sufficiently low such that no visible image is formed therein by exposure and development of the multi-layer color photographic element and wherein said silver halide grains of low photosensitivity are present only in said intermediate layer.
2. A color photographic element as claimed in claim 1, wherein said cyan-forming coupler is selected from compounds having the general formula:
R @jm R1 wherein X is a member selected from the group consisting of an iodine atom and a bromine atom, R is a member selected from the group consisting of a hydrogen atom, an alkyl group, an aryl group, and R, is a ballasting organic radical containing at least eight carbon atoms.
3. A color photographic element as claimed in claim 1, wherein said cyan-forming coupler is selected from compounds having the general formula:
NHOOR:
wherein X is a member selected from the group consisting of an iodine atom and a bromine atom, R CO is an acyl group containing at least nine carbon atoms, and R and R are each a member selected from the group consisting of a hydrogen atom, a halogen atom and an alkyl group.
4. A color photographic element as claimed in claim 1, wherein said silver halide which is incorporated in the intermediate layer is selected from the group consisting of silver chloride, silver bromide, silver chlorobromide, and silver iodobromide.
5. A color photographic element as claimed in claim 1 wherein the amount of said silver halide in said intermediate layer varies from 1 X10 to l X 10" mole per cm of said photographic element.
6. A color photographic element as claimed in claim 1 wherein said silver halide grains in said intermediate 9. A color photographic element a'sih'i'ifiea'in claim 2 wherein said cyan-forming coupler is selected from the group consisting of:
I Br
CONHC zHu s nQ) C O NIICHiCHINCIIzCIhNI-IC O- O C 11H CONHCHaCHiNHC 0 011cm K/ OaH on I H 01 NEC ocmoQcmm) CH; sHnU) Cl NHCONHCuHn
Claims (8)
- 2. A color photographic element as claimed in claim 1, wherein said cyan-forming coupler is selected from compounds having the general formula:
- 3. A color photographic element as claimed in claim 1, wherein said cyan-forming coupler is selected from compounds having the general formula:
- 4. A color photographic element as claimed in claim 1, wherein said silver halide which is incorporated in the intermediate layer is selected from the group consisting of silver chloride, silver bromide, silver chlorobromide, and silver iodobromide.
- 5. A color photographic element as claimed in claim 1 wherein the amount of said silver halide in said intermediate layer varies from 1 X 10 6 to 1 X 10 4 mole per 100 cm2 of said photographic element.
- 6. A color photographic element as claimed in claim 1 wherein said silver halide grains in said intermediate layer have a size of less than 0.5 micron.
- 7. A color photographic element as claimed in claim 1 comprising a support having coated thereon, successively, said red-sensitive emulsion layer, said intermediate layer, said green-sensitive emulsion layer and said blue-sensitive emulsion layer.
- 8. A color photographic element as claimed in claim 1 comprising a support having coated thereon, successively, said blue-sensitive emulsion layer, said intermediate layer, said red-sensitive emulsion layer, said intermediate layer and said green-sensitive emulsion layer.
- 9. A color photographic element as claimed in claim 2 wherein said cyan-forming coupler is selected from the group consisting of:
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2176767 | 1967-07-18 | ||
JP4621767 | 1967-07-18 |
Publications (1)
Publication Number | Publication Date |
---|---|
US3790384A true US3790384A (en) | 1974-02-05 |
Family
ID=26358862
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US00192355A Expired - Lifetime US3790384A (en) | 1967-07-18 | 1971-10-26 | Light-sensitive color photographic elements with improved image quality |
Country Status (4)
Country | Link |
---|---|
US (1) | US3790384A (en) |
BE (1) | BE718038A (en) |
FR (1) | FR1604052A (en) |
GB (1) | GB1201110A (en) |
Cited By (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3892572A (en) * | 1973-06-29 | 1975-07-01 | Fuji Photo Film Co Ltd | Multilayer color photographic material |
US3998642A (en) * | 1975-07-11 | 1976-12-21 | Eastman Kodak Company | Silver halide emulsions with incorporated 4,6-difluorophenolic couplers |
FR2379836A1 (en) * | 1977-02-05 | 1978-09-01 | Agfa Gevaert Ag | COLOR PHOTOGRAPHIC MATERIAL |
EP0112162A2 (en) | 1982-12-13 | 1984-06-27 | Konica Corporation | Light-sensitive silver halide photographic material |
EP0114306A2 (en) * | 1982-12-24 | 1984-08-01 | Minnesota Mining And Manufacturing Company | High sensitivity and developability multilayer color photographic material |
EP0124795A2 (en) | 1983-04-11 | 1984-11-14 | Fuji Photo Film Co., Ltd. | Silver halide photographic emulsion |
EP0147854A2 (en) | 1983-12-29 | 1985-07-10 | Fuji Photo Film Co., Ltd. | Silver halide photographic light-sensitive materials |
EP0209118A2 (en) | 1985-07-17 | 1987-01-21 | Konica Corporation | Silver halide photographic material |
US5550010A (en) * | 1992-03-16 | 1996-08-27 | Eastman Kodak Company | Method for processing photographic products comprising a fine-grain top layer |
US5552265A (en) * | 1990-07-04 | 1996-09-03 | Eastman Kodak Company | Reversal color photographic material with a fine grain sublayer |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6162595A (en) * | 1999-11-23 | 2000-12-19 | Eastman Kodak Company | Reversal photographic elements comprising an additional layer containing an imaging emulsion and a non-imaging emulsion |
US6737229B2 (en) | 2002-07-18 | 2004-05-18 | Eastman Kodak Company | Reversal photographic element comprising an imaging layer containing imaging and non-image forming emulsions |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3152907A (en) * | 1959-11-12 | 1964-10-13 | Eastman Kodak Co | Method for controlling speed and contrast of photographic emulsions |
US3364022A (en) * | 1963-04-01 | 1968-01-16 | Eastman Kodak Co | Direct positive photographic color reproduction process and element utilizing thio-substituted hydroquinones as development inhibitors |
US3488193A (en) * | 1965-07-28 | 1970-01-06 | Agfa Gevaert Nv | Silver halide emulsions containing naphthol color couplers |
US3591383A (en) * | 1967-10-13 | 1971-07-06 | Fuji Photo Film Co Ltd | Color photographic light sensitive material containing cyan coupler |
-
1968
- 1968-07-12 GB GB33491/68A patent/GB1201110A/en not_active Expired
- 1968-07-12 BE BE718038D patent/BE718038A/xx unknown
- 1968-07-16 FR FR1604052D patent/FR1604052A/fr not_active Expired
-
1971
- 1971-10-26 US US00192355A patent/US3790384A/en not_active Expired - Lifetime
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3152907A (en) * | 1959-11-12 | 1964-10-13 | Eastman Kodak Co | Method for controlling speed and contrast of photographic emulsions |
US3364022A (en) * | 1963-04-01 | 1968-01-16 | Eastman Kodak Co | Direct positive photographic color reproduction process and element utilizing thio-substituted hydroquinones as development inhibitors |
US3488193A (en) * | 1965-07-28 | 1970-01-06 | Agfa Gevaert Nv | Silver halide emulsions containing naphthol color couplers |
US3591383A (en) * | 1967-10-13 | 1971-07-06 | Fuji Photo Film Co Ltd | Color photographic light sensitive material containing cyan coupler |
Cited By (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3892572A (en) * | 1973-06-29 | 1975-07-01 | Fuji Photo Film Co Ltd | Multilayer color photographic material |
US3998642A (en) * | 1975-07-11 | 1976-12-21 | Eastman Kodak Company | Silver halide emulsions with incorporated 4,6-difluorophenolic couplers |
FR2379836A1 (en) * | 1977-02-05 | 1978-09-01 | Agfa Gevaert Ag | COLOR PHOTOGRAPHIC MATERIAL |
US4173479A (en) * | 1977-02-05 | 1979-11-06 | Agfa-Gevaert, A.G. | Color photographic recording material |
EP0112162A2 (en) | 1982-12-13 | 1984-06-27 | Konica Corporation | Light-sensitive silver halide photographic material |
EP0114306A2 (en) * | 1982-12-24 | 1984-08-01 | Minnesota Mining And Manufacturing Company | High sensitivity and developability multilayer color photographic material |
EP0114306A3 (en) * | 1982-12-24 | 1986-06-11 | Minnesota Mining And Manufacturing Company | High sensitivity and developability multilayer color photographic material |
EP0124795A2 (en) | 1983-04-11 | 1984-11-14 | Fuji Photo Film Co., Ltd. | Silver halide photographic emulsion |
EP0147854A2 (en) | 1983-12-29 | 1985-07-10 | Fuji Photo Film Co., Ltd. | Silver halide photographic light-sensitive materials |
EP0209118A2 (en) | 1985-07-17 | 1987-01-21 | Konica Corporation | Silver halide photographic material |
US5552265A (en) * | 1990-07-04 | 1996-09-03 | Eastman Kodak Company | Reversal color photographic material with a fine grain sublayer |
US5550010A (en) * | 1992-03-16 | 1996-08-27 | Eastman Kodak Company | Method for processing photographic products comprising a fine-grain top layer |
Also Published As
Publication number | Publication date |
---|---|
DE1772866B2 (en) | 1977-04-28 |
FR1604052A (en) | 1971-07-05 |
GB1201110A (en) | 1970-08-05 |
DE1772866A1 (en) | 1970-11-12 |
BE718038A (en) | 1968-12-16 |
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