US3790384A - Light-sensitive color photographic elements with improved image quality - Google Patents

Light-sensitive color photographic elements with improved image quality Download PDF

Info

Publication number
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
Authority
US
United States
Prior art keywords
layer
sensitive
film
color photographic
red
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US00192355A
Other languages
English (en)
Inventor
Y Oishi
Y Yoshida
K Sano
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Fujifilm Holdings Corp
Original Assignee
Fuji Photo Film Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Fuji Photo Film Co Ltd filed Critical Fuji Photo Film Co Ltd
Application granted granted Critical
Publication of US3790384A publication Critical patent/US3790384A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

Classifications

    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
    • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
    • G03C7/3029—Materials characterised by a specific arrangement of layers, e.g. unit layers, or layers having a specific function
    • 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
    • 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.

Landscapes

  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
US00192355A 1967-07-18 1971-10-26 Light-sensitive color photographic elements with improved image quality Expired - Lifetime US3790384A (en)

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 (enrdf_load_stackoverflow)
BE (1) BE718038A (enrdf_load_stackoverflow)
FR (1) FR1604052A (enrdf_load_stackoverflow)
GB (1) GB1201110A (enrdf_load_stackoverflow)

Cited By (10)

* Cited by examiner, † Cited by third party
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 (fr) * 1977-02-05 1978-09-01 Agfa Gevaert Ag Materiau photographique couleur
EP0112162A2 (en) 1982-12-13 1984-06-27 Konica Corporation Light-sensitive silver halide 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
EP0114306A3 (en) * 1982-12-24 1986-06-11 Minnesota Mining And Manufacturing Company High sensitivity and developability multilayer color photographic material
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)

* Cited by examiner, † Cited by third party
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)

* Cited by examiner, † Cited by third party
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

Patent Citations (4)

* Cited by examiner, † Cited by third party
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 (11)

* Cited by examiner, † Cited by third party
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 (fr) * 1977-02-05 1978-09-01 Agfa Gevaert Ag Materiau photographique couleur
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
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
FR1604052A (enrdf_load_stackoverflow) 1971-07-05
BE718038A (enrdf_load_stackoverflow) 1968-12-16
DE1772866A1 (de) 1970-11-12
DE1772866B2 (de) 1977-04-28
GB1201110A (en) 1970-08-05

Similar Documents

Publication Publication Date Title
US4388401A (en) Multilayer color reversal light-sensitive material
US3620747A (en) Photographic element including superimposed silver halide layers of different speeds
DE2439424C2 (de) Mehrschichtiges lichtempfindliches farbphotographisches Aufzeichnungsmaterial
US3620746A (en) Color photographic material comprising nondiffusing coupler and dir hydroquinone
US3790384A (en) Light-sensitive color photographic elements with improved image quality
JPH0690463B2 (ja) カラ−写真感光材料
US2527583A (en) Merocyanine filter and backing dyes
US2403721A (en) Preventing color fog in photographic material
US3620745A (en) Color photographic silver halide emulsions of different developing speed one layer having a dir coupler
JPH0242208B2 (enrdf_load_stackoverflow)
US2689180A (en) Process of obtaining three-color separation records from a bipack color film
US2742832A (en) Controlling grain and contrast in color photography
JP2571074B2 (ja) ハロゲン化銀カラー写真感光材料
US3642485A (en) Color-photographic silver halide materials containing colored and uncolored couplers
US2266441A (en) Photographic filter and colored image
US3342592A (en) Photographic color films and processes
US2689793A (en) Controlling grain and contrast in color photography
US3737312A (en) Multicolor photographic film elements comprising a minimum sensitivity sound track recording silver halide emulsion layer and processes for their use
US2947628A (en) Multilayer print film having incorporated coloring material
US3667953A (en) Color photographic positive materials
GB447092A (en) Improvements in and relating to colour photography
US2719088A (en) Photographic element containing silver salt-forming bleachable filter dyes
US4200464A (en) Silver halide color photographic materials containing a UV filter compound
US2319369A (en) Process of color photography
US3819372A (en) Film element and method for production of spatially distinct dye and silver photographic images