US3753719A - Light-sensitive color photographic material - Google Patents

Light-sensitive color photographic material Download PDF

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Publication number
US3753719A
US3753719A US00126360A US3753719DA US3753719A US 3753719 A US3753719 A US 3753719A US 00126360 A US00126360 A US 00126360A US 3753719D A US3753719D A US 3753719DA US 3753719 A US3753719 A US 3753719A
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United States
Prior art keywords
photographic material
compound
light
color photographic
coupler
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
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US00126360A
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English (en)
Inventor
K Sakamoto
I Fushiki
E Sakamoto
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Konica Minolta Inc
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Konica Minolta Inc
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D257/00—Heterocyclic compounds containing rings having four nitrogen atoms as the only ring hetero atoms
    • C07D257/02—Heterocyclic compounds containing rings having four nitrogen atoms as the only ring hetero atoms not condensed with other rings
    • C07D257/04—Five-membered rings
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • G03C1/34—Fog-inhibitors; Stabilisers; Agents inhibiting latent image regression
    • G03C1/346—Organic derivatives of bivalent sulfur, selenium or tellurium
    • 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
    • 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
    • G03C7/392—Additives
    • G03C7/39296—Combination of additives

Definitions

  • ABSTRACT A new combination of a merocyanine type compound of the formula (1) wherein R is a lower alkyl group; R, is a lower alkyl, lower alkenyl or aryl group; Z, represents a nonmetallic atom group necessary to complete a 5- or 6- memberd heterocyclic ring nucleus; Z, represents a non-metallic atom group necessary to complete a 5- membered ring; and n is 0 or 1, in combination with at least one compound of the formula N N N (II) wherein R R and R are individually a hydrogen atom, or an alkyl, alkenyl, aryl or aralkyl group, and R and R may be the same or different, is found to be useful in a light-sensitive
  • This invention relates to a light-sensitive color photographic material which, when subjected to color development, can give a dye image high in graininess.
  • the object of the present invention is to provide a light-sensitive color photographic material capable of giving a color image excellent in graininess by incorporating into the layer of a light-sensitive silver halide emulsion, which has or has not been spectrally sensitized, a merocyanine type compound of the formula wherein R is a lower alkyl group; R, is a lower alkyl, lower alkenyl or aryl group, Z represents a nonmetallic atom group necessary to complete a 5- or 6- membered heterocyclic ring nucleus; Z represents a non-metallic atom group necessary to complete a 5- membered ring; and n is
  • the compounds of formula (I) and the compounds of formula (ll) may individually be used in combination of two or more. Further, the compounds of formula (I) and the compounds of formula (II) may be incorporated together into one layer or may be incorporated separately into layers adjacent to each other. These compounds may be incorporated not only into emulsion layers but also into such auxiliary layers as sub layers, inter layers or protetive layers. The compounds may be added to silver halides at any stage of the preparation thereof, but are preferably added during second ripening or before coating.
  • both the compounds of formula (I) and the compounds of formula (ll) are preferably added in proportions of to 10 mole per mole of AgX.
  • those which'are lipophilic may be added in the form of dispersions in a high boiling organic solvent such as dibutyl phthalate or in a low boiling organic solvent such as chloroform, acetone or dimethylformamide, while those which are water-soluble may be added in the form of solutions in a water-miscible organic solvent or in an aqueous alkali solution.
  • Photographic emulsions used in the present invention may contain AgCl, AgBr, AgClBr, AgBrl, etc.
  • Spectral sensitizing dyes used in the present invention may have been optically sensitized with cyanine dyes or other merocyanine type compounds than those used in the present invention, or may have been subjected to chemical sensitization using sulfur-containing compounds, noble metal salts or polyalkylene oxide derivatives.
  • hardeners there may be used formalin and the like, and as coating aids, there may be used synthetic surface active agents or natural surface active compounds, e.g. saponin.
  • Couplers used in a light-sensitive silver halide color photographic material of the present invention are those which form a color image by treatment with p-phenylenediamine type color developing agents, andinclude, for example, yellow couplers having benzoylacetanilide groups, magenta couplers having a pyrazolone or indazolone nucleus, and cyan couplers having a phenol or naphthol nucleus. These couplers may be those which contain in the active methylene or methine positions such substituents as halogens, arylazo groups or aryloxy groups which split ofi upon color development reaction.
  • these couplers may contain in the molecules long chain alkyl groups, alkylphenoxy groups or the like non-diffusible groups, either alone or in combination with sulfonic groups, carboxyl groups or the like water-solubilizing groups.
  • those which are lipophilic may be used in the form of dispersions in a high boiling organic solvent such as dibutyl phthalate or in a low boiling organic solvent such as chloroform, acetone or dimethylformamide, while those which are watersoluble are dissolved in an alkali, and may be added to silver halide emulsions or may be incorporated into color developing solutions.
  • the light-sensitive layer of the color photographic material may be composed, for example, either of protective layer, blue sensitive layer, yellow filter layer, green sensitive layer, inter layer, red sensitive layer, anti-halation layer and support, or in this order from the uppermost layer. Sometimes, the green or red sensitive layer may be the uppermost layer. Further, the color development layer may be composed of one or two layers.
  • the support used in the present invention is ordinarily a paper or a natural or synthetic film of the cellulose acetate or polyester type.
  • Development of the color photographic material is carried out either in such a manner that a dye image is formed by the primary development, as in the treatment of color negative, or in such a manner that the primary development is effected by using Metol or bydroquinone and then a dye image is formed with a color developer, as in the treatment of reversal color photographic film.
  • Typical examples of color developing agents used for development of the light-sensitive color photographic material are sulfates, hydrochlorides and sulfites of N,- N-diethyl-p-phenylenediamine, N-ethyl-N-hydroxyethyl-p-phenylenediamine, N-ethyl-N-hydroxy-ethyl-2- methyl-p-phenylenediamine and N-ethyl-N-B- methanesulfonamidbethyl-3-methyl-4-aminoaniline.
  • Coupler 180 g. 2,5-Di-(t)-octyl hydroquinone 3 g. Dibutyl phthalate I20 g. Ethyl acetate 300 g. 5% Alkanol B (trade name of 5 a product of Du Pont) 285 ml. 3% Gelatin 2,000 ml.
  • the coupler dispersion After mixing the coupler dispersion with the emulsion, 200 ml. of 1 percent formalin and 300 ml. of 5 percent saponin were added to the emulsion. Subsequently, the emulsion was coated on a cellulose triacetate film base to a dry thickness of 5 p. and then dried to prepare a sample. Thereafter, the sample was exposed to a definite amount of light through an optical wedge and then subjected to the following development treatments:
  • the composition of the fixing solution was the same as in the first fixing. 8. Water-washing; 10 minutes.
  • EXAMPLE 2 A high speed silver iodobromide emulsion (containing 4.0 mole percent of Agl, and 160 g. of gelatin per mole of AgX) was subjected to second ripening, and then charged with 1.4 g. (per mole of AgX) of 5- methyl-7-hydroxy-l ,3,4-triazaindolizine and 0.2 g. (per mole of AgX) of a spectral sensitizing dye of the structure shown below to obtain a green-sensitive emulsion.
  • Spectral sensitizing dye Spectral sensitizing dye:
  • the thus obtained emulsion was divided into two emulsions.
  • the compound (l)37 was added in the amount as shown in Table 2 Thereafter, a coupler of the structure shown below was formed into two dispersions by means of a high speed rotary mixer.
  • the relative speed, fog and RMS graininess at a color density value of about 1.0 of the film samplesafter the C1 C1 color development treatments were as shown in Table 1 l.
  • the RMS (root means square) graininess referred to herein is a value of 1,000 times the standard deviation of density values measured when a uniformly ex- 31 posed and developed sample was scanned by means of a micro-densiwmeter having a micasuring head of 25 I (Provided that the coupler dispersions had such comdlametel) positions as set forth below in which the amounts TABLE 1 Amount of Amount of compound (1) compound ([1) per mole of per mole of Relative Sninplt' AgX AgX speed Fog RMS Control snmplu 100 0.13 116 111-1, 0.15 g... as 0.11 113 Sample of the present invention. [1 1, 0.15 g. ⁇ II -4, 0.05 g 110 0. lo
  • the coupler dispersions were individually mixed with either of the aforesaid emulsions as shown in Table 2, and then 120 ml. of 1 percent formalin and 300 ml. of 5 percent saponin were added to each emulsion. Subsequently, the emulsions were individually coated on a cellulose triacetate film base to a dry thickness of 5 pt, and then dried to prepare film samples. These film samples were subjected to the same development treatments as in Example 1. The results obtained were as set forth in Table 2.
  • Sample of the present 0.2 g. 2 97 0.10 76 invention As is clear from Table 2, it is understood that in the case of the color photographic material, the resulting image is greatly improved in graininess without any substantial degradation in speed.
  • Coupler 47 g. 2,5'Di(t)-octyl hydroquinone 3 g. Tricresyl phosphate 20 g. Ethyl acetate 130 g. 5% Alkanol B 100 ml 3% Gelatin 2,000 ml.
  • EXAMPLE 4 A high speed silver iodobromide emulsion (containing 4.0 mole percent of Ag], and g. of gelation per mole of AgX) was subjected to second ripening, and then charged with l .4 g. (per mole of AgX) of 5- methyl-7-hydroxy-l ,3,4-triazaindolizine and 0.2 g. (per mole of AgX) of a spectral sensitizing dye of the following structure:
  • Coupler 57 g. (per mole of AgX) of a coupler of the structure shown below was formed into an alkali dispersion. Coupler:
  • EXAMPLE 1 A high speed silver iodobromide emulsion (containing 5.0 mole percent of Ag], and 180 g. of gelatin per mole of AgX) was subjected to second ripening, and then spectrally sensitized by addition of 0.2 g. (per mole of AgX) of the same spectral sensitizing dye as in Example 3. Subsequently, the emulsion was divided into several emulsions, which were then individually charged with one or two of compounds (I) and (II) as shown in Table 5. Thereafter, couplers l and 2 of the structures shown below were formed into a dispersion by means of a high speed rotary mixer.
  • Coupler dispersion had the composition as set forth below in which the amounts of individual components are per mole of AgX.
  • composition of dispersion is composition of dispersion:
  • Coupler I [0 g Coupler 2 4 g. 2,5 Di-(t)-octyl hydroquinone 0.5 g. Tricresyl phosphate 20 g. Ethyl acetate 30 g. 5% Alkanol B 15 ml. 2% Gelatin 400 ml.
  • a light-sensitive silver halide color photographic material comprising one or more layers, at least one of which is a coupler-containin g layer and incorporated in said eouper-containing layer or in a layer adjacent thereto at least one compound of the formula (I),
  • R is a lower alkyl group; R is a lower alkyl, lower alkenyl or aryl group; Z represents a non metallic atom group necessary to complete a 5- or 6- membered heterocyclic ring nucleus; Z represents a non'metallic atom group necessary to complete a 5- membered ring; and n is 0 or 1, and at least one compound of the formula (II),
  • R4 N-C--SH wherein R R and R are individually a hydrogen atom, or an alkyl, alkenyl, aryl or aralkyl group, and R and R may be the same or different.
  • a light-sensitive silver halide color photographic material as claimed in claim I wherein said compound (I) and said compound (ll) are individually incorporated into two different layers which are adjacent to each other.

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  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Organic Chemistry (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
  • Plural Heterocyclic Compounds (AREA)
US00126360A 1970-03-20 1971-03-19 Light-sensitive color photographic material Expired - Lifetime US3753719A (en)

Applications Claiming Priority (1)

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JP45023143A JPS4923367B1 (en(2012)) 1970-03-20 1970-03-20

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JP (1) JPS4923367B1 (en(2012))
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GB (1) GB1324046A (en(2012))

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4097284A (en) * 1974-11-26 1978-06-27 Fuji Photo Film Co., Ltd. Method for supersensitizing silver halide photographic emulsions
US4202695A (en) * 1971-12-09 1980-05-13 Agfa-Gevaert N.V. Photographic Lippmann emulsions
US4221864A (en) * 1977-02-01 1980-09-09 Konishiroku Photo Industry Co., Ltd. Light-sensitive silver halide photographic materials
US4243748A (en) * 1979-05-29 1981-01-06 E. I. Du Pont De Nemours And Company Light-sensitive silver halide reproduction material
US4960689A (en) * 1987-06-05 1990-10-02 Fuji Photo Film Co., Ltd. Color photographic light-sensitive material and method of developing the same
US20090102355A1 (en) * 2005-09-10 2009-04-23 Winscom Christopher J Display element

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4707488A (en) * 1985-02-11 1987-11-17 Smithkline Beckman Corporation Dopamine-β-hydroxylase inhibitors and use thereof
DE19507913C2 (de) * 1995-03-07 1998-04-16 Agfa Gevaert Ag Farbfotografisches Silberhalogenidmaterial

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3367780A (en) * 1963-08-19 1968-02-06 Eastman Kodak Co Direct-print photographic silver halide emulsions
US3397987A (en) * 1965-05-24 1968-08-20 Eastman Kodak Co Photographic emulsion containing mercapto development anti-foggants
US3457078A (en) * 1964-03-11 1969-07-22 Agfa Ag Supersensitized silver halide emulsions
US3480439A (en) * 1964-10-15 1969-11-25 Agfa Gevaert Ag Light-sensitive materials optically sensitized with chloropropylsulfonic acid substituted merocyanines
US3563754A (en) * 1966-11-23 1971-02-16 Eastman Kodak Co Photographic process
US3580723A (en) * 1968-12-12 1971-05-25 Konishiroku Photo Ind Light-sensitive silver halide photographic emulsion
US3615644A (en) * 1968-02-24 1971-10-26 Agfa Gevaert Ag Optically sensitized silver halide emulsions

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3367780A (en) * 1963-08-19 1968-02-06 Eastman Kodak Co Direct-print photographic silver halide emulsions
US3457078A (en) * 1964-03-11 1969-07-22 Agfa Ag Supersensitized silver halide emulsions
US3480439A (en) * 1964-10-15 1969-11-25 Agfa Gevaert Ag Light-sensitive materials optically sensitized with chloropropylsulfonic acid substituted merocyanines
US3397987A (en) * 1965-05-24 1968-08-20 Eastman Kodak Co Photographic emulsion containing mercapto development anti-foggants
US3563754A (en) * 1966-11-23 1971-02-16 Eastman Kodak Co Photographic process
US3615644A (en) * 1968-02-24 1971-10-26 Agfa Gevaert Ag Optically sensitized silver halide emulsions
US3580723A (en) * 1968-12-12 1971-05-25 Konishiroku Photo Ind Light-sensitive silver halide photographic emulsion

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4202695A (en) * 1971-12-09 1980-05-13 Agfa-Gevaert N.V. Photographic Lippmann emulsions
US4097284A (en) * 1974-11-26 1978-06-27 Fuji Photo Film Co., Ltd. Method for supersensitizing silver halide photographic emulsions
US4221864A (en) * 1977-02-01 1980-09-09 Konishiroku Photo Industry Co., Ltd. Light-sensitive silver halide photographic materials
US4243748A (en) * 1979-05-29 1981-01-06 E. I. Du Pont De Nemours And Company Light-sensitive silver halide reproduction material
US4960689A (en) * 1987-06-05 1990-10-02 Fuji Photo Film Co., Ltd. Color photographic light-sensitive material and method of developing the same
US20090102355A1 (en) * 2005-09-10 2009-04-23 Winscom Christopher J Display element

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GB1324046A (en) 1973-07-18
DE2113199A1 (de) 1971-10-07
DE2113199B2 (de) 1978-02-02
JPS4923367B1 (en(2012)) 1974-06-15
DE2113199C3 (de) 1978-10-12

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