US3767411A - Color photographic light-sensitive material forming novel cyan images - Google Patents

Color photographic light-sensitive material forming novel cyan images Download PDF

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Publication number
US3767411A
US3767411A US00190866A US3767411DA US3767411A US 3767411 A US3767411 A US 3767411A US 00190866 A US00190866 A US 00190866A US 3767411D A US3767411D A US 3767411DA US 3767411 A US3767411 A US 3767411A
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United States
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group
coupler
color
sensitive material
photographic light
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Expired - Lifetime
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US00190866A
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English (en)
Inventor
H Iwano
A Arai
K Kishimoto
I Shimamura
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Fujifilm Holdings Corp
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Fuji Photo Film Co Ltd
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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
    • G03C7/344—Naphtholic couplers

Definitions

  • a color photographic light-sensitive material having at least one silver halide emulsion layer containing a cyan coupler of the formula:
  • X represents a member selected from the group consisting of a hydrogen atom and a halogen atom
  • Y represents a member selected from the group consisting of RCONH-, RNHCO-, or RNHCONH-; the substituted position of said Y being limited to the mposition and the p-position
  • R represents an alkyl group having more than 10 carbon atoms
  • n is an integer of one to two
  • Y may be the same or different if n is an integer of two, but in this case, if the p-position has been substituted with Y, the other Y has been substituted, at the m-position
  • Z represents a member selected from the group consisting of a hydrogen atom, a halogen atom, a methyl group, a methoxy group and an ethoxy group
  • m is an integer one to two; said Z may be the same or different, if n is an integer two.
  • This invention relates to a color photographic lightsensitive material having an improved novel cyan color forming layer containing a napththolic cyan coupler with a long chain alkyl group, in a silver halide emulsion layer, the said cyan coupler forming the dye exhibiting an absorption maximum at a wavelength region of 635 to 700 nm, when the silver halide emulsion layer containing the cyan coupler is developed with an ordinary color developer containing a p-phenylene diamine as a color developing agent.
  • V NBC 0 C Has(n) I s (V) as well as the coupler (II), gives a colored dye image having an absorption maximum at too short a wavelength side for color reproduction and is thus undesirable, as well.
  • the cyan color image of the color photographic lightsensitive material of this invention has an absorption maximum in the region of wavelength from 635 to '[00 nm, preferably from 640 to 670 nm and is quite preferable in color reproduction.
  • This invention provides a color photographic lightsensitive material, composed of a red-sensitive silver halide emulsion layer containing a naphtholic cyan coupler with a long chain alkyl as a ballasting group, said cyan coupler giving the color image, having an absorption maximum wavelength at a region of from 635 to 670 nm, preferably from 640 to 670 nm, when the silver halide emulsionlayer having the cyan coupler is developed with a color developer with a p-phenylene diamine color developing agent.
  • the coupler having RN HCO- as a ballasting group is more preferable than the coupler having RCONH-.
  • R represents a long chain alkyl group.
  • the cyan coupler in this invention is used as a solution thereof such as in an ordinary solvent for couplers as dibutyl phthalate, tricresyl phosphate, etc.
  • the solvent may also be used together with an auxiliary solvent, such as ethyl acetate, propyl acetate, etc.
  • the coupler solution is dispersed into a gelatin-containing silver halide emulsion at the state of emulsification by a known way and the photographic emulsion is coated on a support and dried.
  • the binding agent for the gelatin-containing silver halide emulsion may be gelatin alone, or gelatin containing a water-soluble polymer.
  • gelatin as the binding agent may contain a water-soluble polymer; such as polyvinyl pyrrolidone or a copolymer of maleic acid and acrylamide, but it is preferable that at least 50 wt percent of the total binder be gelatin.
  • the support used in this invention may be a transparent film base, such as triacetyl cellulose, polyethylene terephthalate, polystyrene, and the like or an opaque support, such as baryta-coated paper, polyolefin-coated paper, synthetic paper, or an opaque or translucent plastic base.
  • the light-sensitive material of this invention is colordeveloped by a color developer containing a p-phenylene-diamine color developing agent and then subjected to the subsequent processings.
  • the p-phenylenediamine type color developing agent used in this invention is preferably a compound represented by the following general formula (XV), although it is not limited to such compound of the general formula (XV):
  • R represents a hydrogen atom or a methyl group and R
  • R represent a lower alkyl group or a substituted lower alkyl group, such as a methyl group, a B-hydroxyethyl group, a B-methylsulfoaminoethyl group, a 4-sulfobutyl group and a butyl group, etc.
  • the crystals formed were collected by filtration.
  • the filtrate was concentrated under a reduced pressure and was cooled to form crystals, which were collected by filtration.
  • the combined crystals were washed with water, dissolved in a mixture of a 10 percent aqueous sodium hydroxide solution and ethanol (1:1) and acidified with concentrated hydrochloric acid to form crystals.
  • the crystals obtained were recrystallized from ethanol to provide 6.1 g of the coupler (V) having a melting point of l57.5l58.0'C.
  • a mixture of 40 g of m-aminobenzoyl cetylamide and 29.5 g of l-hydroxy-Z-naphthoic acid phenyl ester was heated for 3 hours at l70l80 C in an oil bath under reduced pressure and then the reaction product was recrystallized from ethanol to provide 43 g of the objective material having a melting point of l4l-l41.5 C.
  • the coupler (VIII) could be readily produced with a good yield.
  • 45 g of the colorless crystals of the coupler (VIII) having a melting point of 162 C was obtained.
  • Example 1 3.9 g of l-hydroxy-2-[N-(3-n-hexadecylcarbamoyl)- phenyl]-naphthamide (VII) was dissolved in a mixture of 5 ml of tricresyl phosphate and 5 ml of ethyl acetate as an auxiliary solvent and the solution thus obtained as dispersed by emulsification in 50 g of 10 percent aqueous gelatin solution in the presence of an alkyl-benzensulfonate type surface active agent. 23 g of the prepared emulsion was added to g of a silver iodo-bromide emulsion that had been post-ripened.
  • the smulsi on was coated on a film base by an ordinary manner and dried.
  • the light-sensitive film was light-exposed and developed for 5 minutes in a developing solution having the following composition: 2-methyl-4-[(N-B-hydroxyethyl-N-ethyl)I- aminoaniline sulfate (XVI) 2.5 g
  • Sodium carbonate (monohydrate) 82.0 g
  • Potassium ferricyanide Potassium bromide Water was added up to 1,000 ml.
  • the film was washed with water for 10 minutes and fixed in a bath having the following composition:
  • EXAMPLE 3 A photographic light-sensitive film was prepared by the same process as in Example 1 using the coupler (IX) instead of the coupler (VII) used in Example 1. After light exposure, the photographic film was developed in a color developing bath having the same composition as that of Example 1, except that the color developing agent (XXI) was used instead of the color developing agent (XVI) and then subjected to the subsequent processings as in Example 1 to provide a sharp blue-green image having a spectral absorption maximum at 650 nm.
  • EXAMPLE 4 A photographic light-sensitive film was prepared by the same procedure as in Example 2 using the cyan coupler (X). After light exposure, the photographic film was developed in a color developing solution having the same composition as that of Example 2, except that the color developing agent (XVII) was used in place of the color developing agent (XIX) and then subjected to the subsequent processings as in Example 1 to provide a sharp cyan color image having a spectral absorption maximum at 692 nm.
  • the color developing agent (XVII) was used in place of the color developing agent (XIX) and then subjected to the subsequent processings as in Example 1 to provide a sharp cyan color image having a spectral absorption maximum at 692 nm.
  • EXAMPLE 5 The same film as used in Example 4 was developed in the developing bath having the same composition as that in Example 4, except that the color developing agent (XVIII) was used in place of the colordeveloping agent (XVII) and then subjected to the subsequent processings as in Example 1 to provide a sharp cyan color image having the spectral absorption maximum at 696 EXAMPLE 6
  • a photographic light-sensitive film was prepared by the same manner as in Example 1, except that the coupler (XIV) was used in place of the coupler (VII).
  • Example 2 After light exposure, the film was developed in a developing bath having the same composition as in Example 1, except that the color developing agent (XX) was used in place of the color developing agent (XVI) and then subjected the subsequent processings as in Example l to provide a cyan dye image having the spectral absorption maximum at a longer wavelength region of 684 nm.
  • the color developing agent (XX) was used in place of the color developing agent (XVI) and then subjected the subsequent processings as in Example l to provide a cyan dye image having the spectral absorption maximum at a longer wavelength region of 684 nm.
  • the example of the cyan color image produced by the photographic light-sensitive image of this invention is shown as the curve (1) in the FIGURE and the absorption maximum of the cyan color image was at 655 nm. This value isparticularly suitable for color positive films, color reversal films and color papers, but it is clear that the spectral absorption curves of the cyan color images forming from the comparison examples, shown by the curve (2) and the curve (3) in theFIG- URE are not preferable for the purposes of color positive films and the like.
  • the spectral absorption curve of a color image obtained from the coupler II having the long chain alkyl group as the ballasting group illustrates clearly that the absorption maximum is in the shorter wavelength side, to make it difficult to obtain correct color reproduction. Also, it has been confirmed that a desirable absorption pattern cannot be obtained throughout the whole region, even if the ratio of the color and the silver halide and the kind of the color developing agent are varied.
  • the color photographic light-sensitive material of this invention is characterized by using l-hydroxy-Z- naphthanilide type cyan coupler having a long chain alkyl group as a ballasting group and provides a color image having an absorption maximum at the wavelength regions of 635-700 nm, and a sharp curve of spectral absorption for cyan color, which is not expected by an ordinary technique.
  • the absorption maximum of a color image formed by using a lhydroxy-2-naphthanilide type cyan coupler having an oil solubilizing group is at a wavelength region longer than 700 nm as shown by the curve (3) in the FIGURE.
  • a color image in a case of using a l-hydroxy-2-naphthanilide type cyan coupler having a long chain alkyl group as the ballasting group has an absorption maximum or excess absorption in a shorter wavelength region than 630 nm or shows absorption in a region of longer than 700 nm, a wide absorption curve near the range of absorption maximum wavelength, or much undesirable absorptions, which make the use of such a cyan coupler undesirable.
  • These examples are shown as the curve (2) in the FIGURE mentioned above and reported by Hans I-I. Credner in the text described before.
  • the spectral absorption character of the cyan dye image by the photographic lightsensitive material of this invention is suitable for the cyan coupler, using a red-light sensitive silver halide emulsion layer, of color positive film, color reversal film, and color paper.
  • the cyan coupler used in this invention can be easily produced with a low cost.
  • a color photographic light-sensitive material having at least one silver halide emulsion layer containing a cyan coupler represented by the following general formula, said cyan coupler giving a cyan color image having the absorption maximum wavelength at 640-670 nm when the emulsion layer is colordeveloped by a color developer containing a pphenylene diamine type color developing agent:
  • Z represents a member selected from the group consisting of a hydrogen atom, a halogen atom, a methyl group, a methoxy group and an ethoxy group; and m is an integer of one or two; said Z may be the same or different if n is an integer two.
  • R represents a member selected from the group consisting of a hydrogen atom and a methyl group
  • R and R represent a member selected from the group consisting of an alkyl group having one to four carbon atoms, a B-hydroxyethyl group, a B-methylsulfoaminoethyl group and a 4-sulfobutyl group.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
US00190866A 1970-10-20 1971-10-20 Color photographic light-sensitive material forming novel cyan images Expired - Lifetime US3767411A (en)

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JP45091824A JPS5014523B1 (enrdf_load_stackoverflow) 1970-10-20 1970-10-20

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JP (1) JPS5014523B1 (enrdf_load_stackoverflow)
DE (1) DE2152336A1 (enrdf_load_stackoverflow)
GB (1) GB1334299A (enrdf_load_stackoverflow)

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4250251A (en) * 1978-07-27 1981-02-10 Eastman Kodak Company Phenylsulfamoyl couplers, coupler compositions and photographic elements suited to forming integral sound tracks
US4282312A (en) * 1978-12-20 1981-08-04 Fuji Photo Film Co., Ltd. Color image forming process
US4288532A (en) * 1979-02-13 1981-09-08 Fuji Photo Film Co., Ltd. Color photographic materials containing cyan color-forming couplers
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
EP0202616A2 (en) 1985-05-16 1986-11-26 Konica Corporation Method for color-developing a silver halide photographic light-sensitive material
EP0204530A2 (en) 1985-05-31 1986-12-10 Konica Corporation Method for forming direct positive color image
EP0228914A2 (en) 1985-12-28 1987-07-15 Konica Corporation Method of processing lightsensitive silver halide color photographic material
US4690889A (en) * 1984-05-10 1987-09-01 Fuji Photo Film Co., Ltd. Silver halide color photographic light-sensitive material containing novel cyan dye forming coupler
US4920041A (en) * 1986-08-07 1990-04-24 Fuji Photo Film Co., Ltd. Method for processing a silver halide color photographic material using a developer substantially free of benzyl alcohol and sulfite
US5258270A (en) * 1990-10-04 1993-11-02 Fuji Photo Film Co., Ltd. Silver halide color photographic material
US5354646A (en) * 1986-03-26 1994-10-11 Konishiroku Photo Industry Co., Ltd. Method capable of rapidly processing a silver halide color photographic light-sensitive material
US5380638A (en) * 1991-10-08 1995-01-10 Fuji Photo Film Co., Ltd. Cyan dye-forming coupler and a silver halide color photographic material containing the same

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3488193A (en) * 1965-07-28 1970-01-06 Agfa Gevaert Nv Silver halide emulsions containing naphthol color couplers
US3615604A (en) * 1968-03-02 1971-10-26 Agfa Gevaert Ag Silver halide color photographic material containing cyan-forming color coupler

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3488193A (en) * 1965-07-28 1970-01-06 Agfa Gevaert Nv Silver halide emulsions containing naphthol color couplers
US3615604A (en) * 1968-03-02 1971-10-26 Agfa Gevaert Ag Silver halide color photographic material containing cyan-forming color coupler

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4250251A (en) * 1978-07-27 1981-02-10 Eastman Kodak Company Phenylsulfamoyl couplers, coupler compositions and photographic elements suited to forming integral sound tracks
US4282312A (en) * 1978-12-20 1981-08-04 Fuji Photo Film Co., Ltd. Color image forming process
US4288532A (en) * 1979-02-13 1981-09-08 Fuji Photo Film Co., Ltd. Color photographic materials containing cyan color-forming couplers
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
US4690889A (en) * 1984-05-10 1987-09-01 Fuji Photo Film Co., Ltd. Silver halide color photographic light-sensitive material containing novel cyan dye forming coupler
EP0202616A2 (en) 1985-05-16 1986-11-26 Konica Corporation Method for color-developing a silver halide photographic light-sensitive material
EP0204530A2 (en) 1985-05-31 1986-12-10 Konica Corporation Method for forming direct positive color image
EP0228914A2 (en) 1985-12-28 1987-07-15 Konica Corporation Method of processing lightsensitive silver halide color photographic material
US5354646A (en) * 1986-03-26 1994-10-11 Konishiroku Photo Industry Co., Ltd. Method capable of rapidly processing a silver halide color photographic light-sensitive material
US4920041A (en) * 1986-08-07 1990-04-24 Fuji Photo Film Co., Ltd. Method for processing a silver halide color photographic material using a developer substantially free of benzyl alcohol and sulfite
US5258270A (en) * 1990-10-04 1993-11-02 Fuji Photo Film Co., Ltd. Silver halide color photographic material
US5380638A (en) * 1991-10-08 1995-01-10 Fuji Photo Film Co., Ltd. Cyan dye-forming coupler and a silver halide color photographic material containing the same

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DE2152336A1 (de) 1972-05-25
JPS5014523B1 (enrdf_load_stackoverflow) 1975-05-28
GB1334299A (en) 1973-10-17

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JPS5930262B2 (ja) ハロゲン化銀写真感光材料