US3764327A - Color photographic light sensitive material - Google Patents

Color photographic light sensitive material Download PDF

Info

Publication number
US3764327A
US3764327A US00211101A US3764327DA US3764327A US 3764327 A US3764327 A US 3764327A US 00211101 A US00211101 A US 00211101A US 3764327D A US3764327D A US 3764327DA US 3764327 A US3764327 A US 3764327A
Authority
US
United States
Prior art keywords
color
polymer
silver halide
photographic
gelatin
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
US00211101A
Other languages
English (en)
Inventor
T Nagae
N Tsuji
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 US3764327A publication Critical patent/US3764327A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

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
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/04—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with macromolecular additives; with layer-forming substances
    • G03C1/053—Polymers obtained by reactions involving only carbon-to-carbon unsaturated bonds, e.g. vinyl polymers

Definitions

  • R represents an alkyl group preferably having 1 to 4 carbon atoms and x, y, and z are numbers satisfying the following conditions:
  • the present invention relates to a color photographic light-sensitive material, and more particularly to an improvement in the color density of reversal color images.
  • the present invention relates to a novel color photographic material which improved the dye density in color images that were color-developed with color developers containing couplers.
  • Coupler-in-developer type color photographic lightsensitive materials are ordinarily processed in the following manner after exposure.
  • the element is subjected to a black & white development, subjected to red exposure from the back side of the photographic material, developed with a cyan color developer containing a cyan coupler and an aromatic amino photographic developing agent, subjected to a purple exposure from the photographic emulsion layer side thereof, developed with a yellow color developer containing a yellow coupler and an aromatic amino photographic developing agent, and then developed with a magenta color developer containing a magenta coupler and an aromatic amino photo graphic developing agent.
  • the present invention relates to a novel color photographic material improving the density of reversal color images in the cyan color development, yellow color development, and magenta color development, and particularly to an improvement in the color density of the magenta color image.
  • the densities of reversal color images can be increased a more effective color reproducing system can be made.
  • the thickness of the emulsion layers can be reduced, which provides such merits that the sharpness of the color images can be improved and the amount of silver halide incorporated in the emulsion layers can be reduced.
  • a gelatino silver halide emulsion layer containing a polymer as described below as a binder is processed by a color developer containing a color coupler.
  • R represents an alkyl group preferably having 1 to 4 carbon atoms and x, y, and z are numbers satisfythe following conditions:
  • Preferred range 40x90 60x 10y60 20y40 05 S40 10z40 and x+y +z 100.
  • preferred polymers have a mean molecular Weight in the range of from about 5,000 to about 500,000, particularly from about 10,000 to about 100,000. Molecular weights outside the above-mentioned range are also operable to the present invention. Examples of such polymer are illustrated below, but the polymers used in this invention are not to be limited to them.
  • the term polymer used hereafter means copolymer" and should not be limited so-called block copolymers.
  • the polymers used in this invention are not watersoluble but are soluble in alcohols such as methanol, ethanol, and water-alcohol mixtures.
  • the polymer is thus usually added to a photographic emulsion as a solution of an alcohol or a water-alcohol mixture.
  • gelatino photographic emulsion according to the invention implies a photographic emulsion may also contain a hydrophilic organic colloid other than gelatin as the binder of silver halide.
  • the hydrophilic organic colloid other than gelatin there is gelatin derivatives, and natural or synthetic resin or polymer usually employed in the art of photographic emulsion manufacturing, such as cellulose, polyvinyl alcohol, etc.
  • the polymers used in this invention may be added to a gelatino photographic emulsion or may replace a part of the gelatin.
  • the polymer may be added in any stage before coating, but is preferably added between postripening and coating.
  • a suitable amount of polymer is in the range of from about 1% by weight to about 90% by Weight of the total amount of gelatin and the polymer in the gelatino silver halide emulsion.
  • the invention is applied to a gelatino silver iodobromide emulsion but the present invention may be applied to various gelatino silver halide emulsions such as silver bromide silver chlorobromide, silver iodochlorobromide and the like.
  • the silver halide emulsion used in this invention may be sensitized by a compound having labile sulfur, such as sodium thiosulfate or an allylthiourea; by a thiocyanat-e aurite salt; by a reduction sensitizer such as an amino compound or stannous chloride (see The Theory of the Photographic Process, 3rd ed., 113-116 (1966), published by McMillan Company); by a polyalkylene oxide derivative; or by combinations thereof.
  • a compound having labile sulfur such as sodium thiosulfate or an allylthiourea
  • a thiocyanat-e aurite salt such as an amino compound or stannous chloride
  • dyes capable of sensitizing in the wave length region of from 500 millimicrons to 700 millimicrons can be added thereto such as 1,1'-diethyl- 2,2 cyanine iodide, 3,3 diethyl 9 methylcarbocyanine iodide, etc. (ibid., pp. 199-232).
  • the silver halide emulsion may contain a stabilizer such as 4-hydroxy 6 methyl 1,3,3a,7 tetraazaindene (ibid., pp. 344-346), a hardening agent such as formaldehyde or mucobromic acid (ibid., pp. 54-60), and a wetting agent such as saponin or sodium alkylbenzenesulfonate.
  • a stabilizer such as 4-hydroxy 6 methyl 1,3,3a,7 tetraazaindene (ibid., pp. 344-346)
  • a hardening agent such as formaldehyde or mucobromic acid (ibid., pp. 54-60)
  • a wetting agent such as saponin or sodium alkylbenzenesulfonate.
  • each of the cyan, magenta, and yellow color developers contains at least one color developing agent and the ditfusible couplers which will be coupled into cyan, magenta, and yellow respectively.
  • the color developingagent there may be used the well-known p-phenylenediamine derivatives such asMA- amino-N,N-diethylaniline, 4. amino-N,N-diethyl-3-methylaniline, 4 amino-3-methyl-N-methyl-N-(fl-methylsulfoneamidoethyl)aniline, 4-amino 3 methyl-N-ethyl-N- (fi-hydroxyethyl) aniline, etc. (ibid., p. 387).
  • p-phenylenediamine derivatives such asMA- amino-N,N-diethylaniline, 4. amino-N,N-diethyl-3-methylaniline, 4 amino-3-methyl-N-methyl-N-(fl-methylsulfoneamidoethyl)aniline, 4-amino 3 methyl-N-ethyl-N- (fi-hydroxyethyl) aniline, etc. (ibid., p. 387
  • ditfusiblecyan coupler used in' this invention there can be used the well-known phenolic couplers such as 2-chloro-1-naphthol, 2,4 dichloro-l-naphthol, 2-(oacetamido-fl-phenethyl) 1 hydroxynaphthamide, etc. (ibid., p. 387).
  • the dilfusible magenta coupler there can be used the well known open chain methylenic couplers such as acylacetonitrile, Z-cyanoethylbenzofuran, and benzylacetonitrile or cyclic methylene couplers such as 1-phenyl-3- (4-chlorobenzamido) 5 pyrazolone, 1 phenyl-3-(3- nitrobenzoylamino) 5 pyrazolone, l-( 2,4,6-trichlorophenyl) -3- (4-nitroanilino -5-pyrazo1one, etc.
  • the open chain methylenic couplers such as acylacetonitrile, Z-cyanoethylbenzofuran, and benzylacetonitrile or cyclic methylene couplers such as 1-phenyl-3- (4-chlorobenzamido) 5 pyrazolone, 1 phenyl-3-(3- nitrobenzoylamino
  • the diffusible yellow couplers there can be used the well-known acylacetoamide open chain methylenic conplers such as 2 acetanilide, 2 aceto-2',4'-dichloroacetanilide, 2-benzoylacetanilide, 2 benz0yl-2-methoxyacetanilide, etc. (ibid., p. 389 and G. H. Brown et al'., Journal of The American Chemical Society, vol. 79, 2919-2927 (1957)
  • the following examples illustrate preferred modes of the invention in great detail.
  • EXAMPLE 1 A high-speed gelatin silver iodobromide reversal color photographic emulsion (silver iodide content 3.5 mol percent) that had been subjected to a sulfur sensitization and a gold sensitization was melted by heating and applied on to cellulose triacetate film base in an amount of about 15 mg./ cm. (as silver halide).
  • the binder for the silver iodobromide in the emulsion thus coated was gelatin which contained polymer 2 described above in various ratios.
  • the emulsion layer was exposed using an NSG II-type sensitometer and'subjected' to the following proces sings:
  • compositions of the processing baths used in the above processings were as shown below.
  • N-methyl-p-aminophenol sulfate g. S Anhydrous sodium sulfite, g 4 79 Hydroquinone, g. 2 Sodium carbonate (monohydrate), g. 40 Potassium bromide, g. 3.5 Potassium thiocyanate, g. 2.0 0.1% potassium iodide, cc. 12.5 Sodium hydroxide, g. 1.0
  • the ratio of binder (gelatin 100% by weight) to silver iodobromide in the gelatin silver halide emulsion was S/ 11 by weight. The results obtained are shown in Table 1.
  • V EXAMPLE 2 The same procedure as in Example 1 was carried out i using polymer 2 in various ratios as the polymer to be mixed with gelatin. The results obtained are shown in the following table.
  • EXAMPLE 3 Thesameprocedure as in Example 1 was carried out using polymer 2, polymer 6 and polymer 7 respectively as the polymer to be mixed with gelatin. The results obtained are shown in the following table.
  • EXAMPLE 4 Using the same processings as in Example 1, a cyan color developing process (27 C., 5 min.) was carried out in place of the magenta color development using the same color photographic film as prepared in Example 1. Moreover, in the same procedure a yellow color development (27 C., 5 min.) was carried out in place of the magenta color development. The results of the both cases are shown in Table 4 and Table 5 respectively.
  • compositions of the cyan color developer and the yellow color developer used were as shown below.
  • Potassium bromide g. 20 0.1% potassium iodide, cc. 20 Potassium thiocyanate, g. 3.0
  • Anhydrous sodium sulfite g. 10 Sodium carbonate (monohydrate), g. 30 Sodium hydroxide, g. 2.0 S-nitrobenzimidazole nitrate, g. 0.5 2,4-dichl0ro-1-naphthol, g. 2.0 4-amino-3methyl-N,N'-diethylaniline hydrochloride, g. 3.0
  • a color photographic light-sensitive material of the coupler-in-developer type comprising support having thereon at least one of a red-sensitive gelatin silver halide emulsion layer, a green-sensitive gelatino silver halide emulsion layer, or a blue-sensitive gelatino silver halide emulsion layer
  • gelatino silver halide emulsion layer containing the polymer is a magenta color forming-emulsion layer.
  • the polymer is a member selected from the group consisting of f on -03 CH CH CH C 5 jun r. /'20 a jar LOOK 0003B; ONE: (mean molecular weight: 10,000) and ONHz OOH wherein the ratio of said constituents is wherein R represents an alkyl group preferably having 1 to 4 carbon atoms and x, y, and z are numbers satisfying the following conditions:

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
US00211101A 1970-12-26 1971-12-22 Color photographic light sensitive material Expired - Lifetime US3764327A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP45118983A JPS4943889B1 (enrdf_load_stackoverflow) 1970-12-26 1970-12-26

Publications (1)

Publication Number Publication Date
US3764327A true US3764327A (en) 1973-10-09

Family

ID=14750092

Family Applications (1)

Application Number Title Priority Date Filing Date
US00211101A Expired - Lifetime US3764327A (en) 1970-12-26 1971-12-22 Color photographic light sensitive material

Country Status (4)

Country Link
US (1) US3764327A (enrdf_load_stackoverflow)
JP (1) JPS4943889B1 (enrdf_load_stackoverflow)
DE (1) DE2164249A1 (enrdf_load_stackoverflow)
GB (1) GB1341750A (enrdf_load_stackoverflow)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3907572A (en) * 1973-01-30 1975-09-23 Mitsubishi Paper Mills Ltd Color photographic photosensitive emulsion and color photographic material
US4145221A (en) * 1977-11-08 1979-03-20 Gaf Corporation Synthetic polymer latices in photographic silver halide emulsions containing multivalent metal salts
US4710456A (en) * 1984-09-12 1987-12-01 Fuji Photo Film Co., Ltd. Silver halide photographic material
US5436124A (en) * 1993-04-02 1995-07-25 Eastman Kodak Company Photographic elements containing particular color couplers in combination with polymeric stabilizers
US5709983A (en) * 1995-08-31 1998-01-20 Eastman Kodak Company Nonaqueous solid particle dye dispersions
CN108625223A (zh) * 2018-04-13 2018-10-09 保定市乐凯化学有限公司 一种彩色相纸用水溶性防褪色剂及其制备方法

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3907572A (en) * 1973-01-30 1975-09-23 Mitsubishi Paper Mills Ltd Color photographic photosensitive emulsion and color photographic material
US4145221A (en) * 1977-11-08 1979-03-20 Gaf Corporation Synthetic polymer latices in photographic silver halide emulsions containing multivalent metal salts
US4710456A (en) * 1984-09-12 1987-12-01 Fuji Photo Film Co., Ltd. Silver halide photographic material
US5436124A (en) * 1993-04-02 1995-07-25 Eastman Kodak Company Photographic elements containing particular color couplers in combination with polymeric stabilizers
US5709983A (en) * 1995-08-31 1998-01-20 Eastman Kodak Company Nonaqueous solid particle dye dispersions
CN108625223A (zh) * 2018-04-13 2018-10-09 保定市乐凯化学有限公司 一种彩色相纸用水溶性防褪色剂及其制备方法
CN108625223B (zh) * 2018-04-13 2020-09-11 保定市乐凯化学有限公司 一种彩色相纸用水溶性防褪色剂及其制备方法

Also Published As

Publication number Publication date
GB1341750A (en) 1973-12-25
DE2164249A1 (de) 1972-07-06
JPS4943889B1 (enrdf_load_stackoverflow) 1974-11-25

Similar Documents

Publication Publication Date Title
US4565774A (en) Method for the formation of dye image
CA1106384A (en) Thiazolyl couplers, coupler compositions and photographic elements suited to forming integral sound tracks
US3622318A (en) Photographic materials and processes
US4026707A (en) Silver halide photographic emulsion sensitized with a mixture of oxacarbocyanine dyes
US3935016A (en) Silver halide color photographic materials containing 3-anilino-5-pyrazolone couplers
JPH0670709B2 (ja) 増加した露出ラチチュードを有する写真プリント材料
US4863846A (en) Silver halide photographic light-sensitive material
US3769024A (en) Light-sensitive silver halide photographic material with sensitizing dye combination
JPS6026339A (ja) ハロゲン化銀カラ−写真感光材料
US3756821A (en) Process for the formation of color photographic images
US3536487A (en) Photographic elements and processes for producing therein interimage effects with diffusible 4 - thiazoline-2-thione
US3764327A (en) Color photographic light sensitive material
US3834908A (en) Color silver halide photographic materials containing bis-pyrazolone color couplers
US3695882A (en) High-speed fine grain light-sensitive material
US3730724A (en) Silver halide color photographic element containing a magenta color coupler and a carboxy substituted thiazoline compound
US3206310A (en) Modification of colloidal metals and metal sulfides to reduce action as a nucleus for physical development
US5804359A (en) Photographic silver halide materials
US3706556A (en) Method for preventing color mixing in multiple layer-type reversal color photographic light-sensitive materials
US3940271A (en) Color photographic light-sensitive material
US3591385A (en) Silver halide emulsions sensitized with a combination of sulfur and selenium for color photography
EP0237256A2 (en) Method for processing silver halide photographic light-sensitive materials
JPH02216147A (ja) ハロゲン化銀カラー写真感光材料
US3536486A (en) High temperature processing of exposed photographic elements
US3844784A (en) Reversal multi-layer color photographic materials
US3741765A (en) Process for developing silver halide color photographic light-sensitive materials at high temperature