US3741765A - Process for developing silver halide color photographic light-sensitive materials at high temperature - Google Patents

Process for developing silver halide color photographic light-sensitive materials at high temperature Download PDF

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Publication number
US3741765A
US3741765A US00098880A US3741765DA US3741765A US 3741765 A US3741765 A US 3741765A US 00098880 A US00098880 A US 00098880A US 3741765D A US3741765D A US 3741765DA US 3741765 A US3741765 A US 3741765A
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United States
Prior art keywords
tetraazaindene
compound
thiol
development
color
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Expired - Lifetime
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US00098880A
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English (en)
Inventor
H Iwano
T Shishido
I Shimamura
R Ohi
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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
    • G03C7/407—Development processes or agents therefor
    • G03C7/413—Developers
    • 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
    • Y10S430/164—Rapid access processing

Definitions

  • a developing process which comprises subjecting a multi-layer silver halide color photographic material to high temperature processings in the presence of a compound represented by the following general formula I SH wherein R and R which may be the same or different, each represents a hydrogen atom, an alkyl group, an aralkyl group, an aryl group, or a haloaryl group, and R represents hydrogen atom, a halogen atom, or an alkyl group is disclosed.
  • the present invention relates to a process for developing color photographic materials. More particularly, the present invention relates to a rapid developing process for color photographic material at high temperatures.
  • a multiple layer color photographic material has at least three superposed silver halide emulsion layers having different spectral sensitivities on a support. For instance, in the case of a typical color photographic material, a red-sensitive emulsion layer, a green-sensitive emulsion layer, a yellow filter layer, and a blue-sensitive emulsion layer are coated on a support in this order.
  • One aspect of the progress in recent photographic processing engineering is the speeding up of processing by raising the temperature of development (higher than 30 C.). This is usually called high temperature rapid processing.
  • high temperature rapid processing One of the disadvantages occurring in the high temperature rapid processing of multi-layer color materials is that the uppermost layer is developed excessively before the bottom layers are completely developed.
  • An object of this invention is to provide a high temperaturerapid development process for multiple layer silver halide color photographic materials using an effective development inhibitor for the uppermost layer.
  • a pre-hardening bath that is, an aqueous solution containing an aldehyde for hardening the gelatin in a photographic emulsion layer, such as formaldehyde, glyoxal, succinaldehyde, glutaraldehyde, andthe like.
  • the aqueous solution further contains a salt such as sodium sulfate, a pH-controlling agent or a buffer agent, such as borax,,boric acid, acetic acid, sodium acetate, sodium hydroxide, sulfuric acid, and the like, and also an antifoggant for development, such as an alkali metal halide.
  • a salt such as sodium sulfate
  • a pH-controlling agent or a buffer agent such as borax,,boric acid, acetic acid, sodium acetate, sodium hydroxide, sulfuric acid, and the like
  • an antifoggant for development such as an alkali metal halide.
  • the development inhibitor of this invention can be added to such an aqueous pre-hardening solution.
  • the development inhibitor of this invention can be added to the neutralizing bath.
  • the neutralizing bath contains an aldehyde-scavenging agent, such as hydroxylamine and L-ascorbic acid,
  • the black & white developing solution for reversal color photographic films contain at least one of the developing agents such as hydroquinone, 1-phenyl-3- pyrazolidone and N-methyl-p-aminophenol.
  • the developing solution further contains a salt such as soduim sulfate, a pH-controlling agent or a buffer agent such as borax, boric acid, sodium hydroxide, sodium carbonate, and the like, and an alkalimetal halide.
  • the development inhibitor of this invention can also be added to the black and white developing solution.
  • alkaline aqueous derivative as a color developing agent, such as N,N-diethyl-p-phenylene-diamine sulfite, N,N-diethyl-3-methyl-p-phenylenediamine hydrochloride, 4-amino-3-methyl-N-ethyl-N-methanesulfoamidoethyl aniline sulfate, 4-amino-3-methyl-N-ethyl-N-hydroxyethyl aniline sulfate, N-ethyl-N-hydroxyethyl-p-phenylene-diamine sulfate,
  • alkaline aqueous derivative such as N,N-diethyl-p-phenylene-diamine sulfite, N,N-diethyl-3-methyl-p-phenylenediamine hydrochloride, 4-amino-3-methyl-N-ethyl-N-methanesulfoamidoe
  • the solution further contains a salt such as sodium sulfate, a pI-I-controlling agent or a bufler solution containing a p-phenylenediamine agent such as sodium hydroxide, sodium carbonate, sodium phosphate, and the like, and a conventional antifoggant such as an alkali metal halide.
  • a salt such as sodium sulfate, a pI-I-controlling agent or a bufler solution containing a p-phenylenediamine agent such as sodium hydroxide, sodium carbonate, sodium phosphate, and the like, and a conventional antifoggant such as an alkali metal halide.
  • the developing inhibitor of this invention can be added to the color de velopment solution.
  • a mercaptotetraazaindene compound represented by the following general formula wherein R and R which may be the same or different, each represents a hydrogen atom, an alkyl group, an aralkyl group, an aryl group or a haloaryl group and R represents a hydrogen atom, a halogen atom or an alkyl group, to any of the above-described processing solutions.
  • Each of the com- P ta lum br mide g 30.0 pounds represented by the general formula set forth above Water added to make 1 liter. can prevent the excessive development of the surface layer Fixing Solution. or the uppermost emulsion layer and development proc- Sodium thiosulfate 150 essing glvmg good color balance can be conducted. Sodium sulfite 10 gmpangttheseucompounds, however, compound 3 can give Wat?r added to make 1 men e es resu s.
  • the amount of the compound of this invention to be In the abVe'deSeT1bed e l development Ph employed can be varied according to the type of the comesslhgs, the eofhpouhd Of t IIIVBIIUOII a ed to the pound, the type of color photographic material to be used, black and Whlte developing f p h, and the nature of the composition of the processing soluthe e P h Was l e llslng a black and Whltfi tion.
  • the amount of compound used developlhg h h fohtalhlhg conventionally kIlOWIl can range f 1 to 1 g. liter f the processing antrfoggant, 6-n1tr1o-1so1ndazolelinstead of the compounds solution of this inventlon.
  • the optimum amount of the compound depends upon many factors, such as the compound to be employed, the Test No gg ggggg g gggg Amount additive composition of the processing solution, the activity of the developing solution, the processing temperature, and the 2 compoun d1 zoxwsmolemer properties of the multiple layer color photographic light- 3:" I Compound 3:" Do. sensitive material. 40 gfi'nitigisoindawle 5 365 mole/liter The invention will be explained below in greater detail by reference to the followmg examp The results obtained are shown in the following table, in
  • EXAMPLE 1 which the blue density (D and red density (D A multi-layer color reversal film composed of three of the e? P? of the test Strips (maximum deneity silver halide emulsion layers contain difierent couplers Part) Sensltlvltles for Ted and blue exposures are 11st and having dilferent spectral sensitivities was exposed ed to ate the photographic effect. using a sensitometer and then subjected to the following procedures Maximum density Sensitivity 1 Blue Red Test No density density Blue Red Te p 2.4 3.4 175 115 ature, 3.4 3.5 100 100 Process C.
  • Potassium iodide (0.1% aqueous solution cc 10.0 Water added to make 1 liter.
  • EXAMPLE 2 A multiple layer color photographic film prepared by coating a cellulosive triacetate film with a red-sensitive 'gelatino silver iodobromide emulsion layer, a green-sensitive gelatino silver iodobromide emulsion layer, a colloidal silver-containing gelatino yellow filter having blue absorption, and a blue-sensitive gelatino silver iodobromide emulsion layer successively was exposed using a sensitometer and then subjected to the following processmg.
  • Tempera- Process ture C. Time Pre-hardening 40 30 sec. Water washing 40 Do. First black and white developmen 40 76 sec. Water washing 40 30 sec. Reversal exposure (red light) from the back face of the film 200 cms. Cyan color development 40 180 sec Water washing 40 30 sec. Rev ersal exposure (blue light) from the front face of the film- 200 cms. Yellow color development 40 90 sec. Water washin 40 30 sec. Second black and white development 40 15 sec. Magenta color development 40 120 sec. Water washin 40 60 sec. Bleaching 40 Do. Fixing 40 Do. Water washing 40 Do.
  • compositions of the processing solutions used above were as set forth below.
  • N-methyl-p-aminophenol sulfate g 1.0 Sodium sulfite g 50.0 Hydroquinone g 1.0 Sodium carbonate (monohydrate) g 41.0 Potassium bromide g 2.5 Water added to make 1 liter.
  • the photographic properties obtained as a result of the development are shown in the following table.
  • the blue density (D and the red density (D of the unexposed part of the strips (maximum density part) are shown as the photographic properties.
  • the blue density is the density of the uppermost blue-sensitive emulsion layer of the film which gives the yellow color by color development and the red density is the density of the lower-most red-sensitive emulsion layer which gives the cyan. If the values are large and not so dilferent from each other it means a good color balance and an image having good color reproduction.
  • EXAMPLE 3 The photographic properties obtained as a result of the development are shown in the following table. The blue density and the red density photographic properties are shown below.
  • Blue Red density density As is clear from the table, by the addition of the compound of this invention the blue density is increased without reducing the red density.
  • EXAMPLE 4 A multiple layer type color photographic film consisting of three silver halide emulsion layers containing different couplers (cyan, yellow and magenta) and having different spectral sensitivities with each other was exposed by a sensitometer and then subjected to the following processings.
  • EXAMPLE 5 In the developing processings in Example 1, a preliardening step and a neutralizing step were conducted before the first black & White development. The prehardening processing was conducted for 2 minutes and 30 seconds at 37 C. and the neutralizing process was carried out for 30 seconds at 37 C. The compositions of the processing solutions were as shown below. Pre-hardening solution:
  • EXAMPLE 6 To any acetyl cellulose film were applied a red-sensitive gelatino silver iodobromide emulsion containing a phenolic cyan coupler and further an intermediate gelatin layer. Then, a green-sensitive gelatino silver bromide emulsion containing a pyrazolone magenta coupler was applied to the intermediate layer and' further a yellow filter layer was formed on the layer. Then, a blue-sensitive gelatino silver iodobromide emulsion containing a keto-methylene yellow coupler was applied to the filter layer, and finally a protective gelatin layer was formed on the blue-sensitive emulsion layer.
  • the blue density was sufliciently high even by the high temperature processings and an image having better color balance of the blue density and the red density was obtained.
  • a high temperature rapid processing developing process for color photographic material which comprises subjecting an exposed multi-layer silver halide color photographic material to development at a temperature higher than 30 C.
  • the improvement which comprises selectively inhibiting development of the uppermost photographic emulsion layer to improve the color balance and image quality of the developed photographic material by processing said color photographic material no later than development in the presence of an eifective development inhibitor for the uppermost photographic emulsion layer comprising a compound represented by general formula wherein R and R which may be the same or difi'erent, each is selected from the group consisting of a hydrogen atom, an alkyl group, an aralkyl group, an aryl group, and a haloaryl group, and wherein R is selected from the group consisting of a hydrogen atom, a halogen atom, and an alkyl group.
  • a high temperature rapid processing developing process for color photographic material comprising developing an exposed multi-layer silver halide color photographic material at a temperature higher than 30 C.
  • the improvement which comprises selectively inhibiting the development of the uppermost photographic emulsion layer of said multi-layer silver halide color photographic material to improve the color balance and image quality of the developed photographic material by treating said photographic material no later than development with a solution containing an effective development inhibitor for the uppermost photographic emulsion layer comprising a compound represented by the formula Rs-C I 1 G-R 4.
  • said solution is a pro-hardening solution.
  • said multi-layer silver halide color photographic material comprises a support having coated thereon, in succession, a red-sensitive photographic emulsion layer, a greensensitive photographic emulsion layer, a yellow filter layer and a blue-sensitive photographic emulsion layer.
  • said multi-layer silver halide color photographic material comprises a support having coated thereon, in succession, a red-sensitive photographic emulsion layer, a green-sensitive photographic emulsion layer, a yellow filter layer and a blue-sensitive photographic emulsion layer.
  • said compound is selected from the group consisting of 1,3,3a,7-tetraazaindene-4-thiol, 6-methyl-1,3,3a,7-tetraazaindene-4-thiol, 6-tertiary-butyl-1,3,3a,7-tetraazaindene-4-thiol, 6-pentyl-l,3,3a,7-tetraazaindene-4-thiol, 6-nonyl-1,3,3a,7-tetraazaindene-4-thiol,
  • a high temperature rapid processing developing process comprising developing an exposed multi-layer silver halide color photographic material at a temperature of greater than 30 C.
  • the improvement consisting of selectively inhibiting development of the uppermost photographic emulsion layer to improve the color balance and image quality of the developed color photographic material by processing said color photographic material no later than development in a photographic solution containing from 1 milligram to 1 gram per liter of solution of an effective development inhibitor for the uppermost photographic emulsion layer consisting essentially of a compound selected from the group consisting of 1,3,3a,7-tetraazaindene-4-thiol,

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
  • Nitrogen Condensed Heterocyclic Rings (AREA)
US00098880A 1969-12-16 1970-12-16 Process for developing silver halide color photographic light-sensitive materials at high temperature Expired - Lifetime US3741765A (en)

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JP44101117A JPS4834176B1 (https=) 1969-12-16 1969-12-16

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0601503A3 (en) * 1992-12-09 1994-07-06 Konica Corporation Composition for developing a black-and-white silver halide photographic light-sensitive material
US20190263574A1 (en) * 2015-01-12 2019-08-29 Thomas R. Lutz Systems and methods for de-oxygenation of a closed container

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0601503A3 (en) * 1992-12-09 1994-07-06 Konica Corporation Composition for developing a black-and-white silver halide photographic light-sensitive material
US5508153A (en) * 1992-12-09 1996-04-16 Konica Corporation Composition for developing a black-and-white silver halide photographic light-sensitive material
US20190263574A1 (en) * 2015-01-12 2019-08-29 Thomas R. Lutz Systems and methods for de-oxygenation of a closed container
US10829279B2 (en) * 2015-01-12 2020-11-10 Thomas R. Lutz Systems and methods for de-oxygenation of a closed container
US11565861B2 (en) 2015-01-12 2023-01-31 Thomas R. Lutz Systems and methods for de-oxygenation of a closed container

Also Published As

Publication number Publication date
DE2062031B2 (de) 1976-01-29
GB1317227A (en) 1973-05-16
DE2062031A1 (de) 1971-07-15
JPS4834176B1 (https=) 1973-10-19

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