US3867149A - Fogged, direct-positive silver halide photographic material containing a rhodium salt desensitizer and a bispyrazolone dye stabilizer - Google Patents

Fogged, direct-positive silver halide photographic material containing a rhodium salt desensitizer and a bispyrazolone dye stabilizer Download PDF

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Publication number
US3867149A
US3867149A US354842A US35484273A US3867149A US 3867149 A US3867149 A US 3867149A US 354842 A US354842 A US 354842A US 35484273 A US35484273 A US 35484273A US 3867149 A US3867149 A US 3867149A
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US
United States
Prior art keywords
dye
silver halide
direct
light
pyrazolone
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Expired - Lifetime
Application number
US354842A
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English (en)
Inventor
Tetsuo Furuya
Hidehiko Ishikawa
Hideo Kanisawa
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Konica Minolta Inc
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Konica Minolta Inc
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Publication of US3867149A publication Critical patent/US3867149A/en
Assigned to KONICA CORPORATION reassignment KONICA CORPORATION RELEASED BY SECURED PARTY (SEE DOCUMENT FOR DETAILS). Assignors: KONISAIROKU PHOTO INDUSTRY CO., LTD.
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Expired - Lifetime legal-status Critical Current

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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
    • G03C1/485—Direct positive emulsions
    • G03C1/48515—Direct positive emulsions prefogged
    • G03C1/48523—Direct positive emulsions prefogged characterised by the desensitiser
    • G03C1/4853—Direct positive emulsions prefogged characterised by the desensitiser polymethine dyes
    • 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
    • Y10S430/141—Direct positive material

Definitions

  • ABSTRACT A direct positive light sensitive silver halide material containing fogged silver halide grains and a rho-- dium salt as a desensitizer to increase the reversal speed, which material comprises a bis-pyrazolone dye having an absorption maximum in the range from 590 to 690 mu, said bis-pyrazolone dye having a methine chain connecting two pyrazolone nuclei thereof, said methine chain consisting of 5 unsubstituted methine groups.
  • This invention relates to a light-sensitive silver halide photographic material. More particularly, the invention pertains to a solarization type direct-positive lightsensitive material.
  • a direct-positive light-sensitive material utilizing Harschel effect a so-called Harschel type direct-positive light-sensitive material
  • a directpositive light-sensitive material utilizing solarization a so-called solarization type direct-positive light-sensitive material
  • the solarization type directpositive light-sensitive material is of such a type that moderately pre-fogged nuclei effect subtraction due to excess exposure to give a direct-positive image, and hence is essentially different from the Harschel type direct-positive light-sensitive material which utilizes the phenomenon that pre-fogged nuclei effect subtraction due to red light or infrared light.
  • the solarization type directpositive lightsensitive material has moderately been pre-fogged by application of light or by adoption of such chemical means as using a fogging agent, and it is well known that subtraction of the fog is promoted by use of a desensitize'r to increase the reveral speed of the lightsensitive material. It is also well known that when a rhodium salt is used as the desensitizer in the above case, there is obtained a solarization .type direct-positive light-sensitive material which is relatively high in speed.
  • the solarization type direct-positive light-sensitive material containing a rhodium salt as the desensitizer is low in safeness to darkroom light and hence is inconvenient in handling.
  • This tendency is particularly marked when the said light-sensitive material has been optically sensitized by incorporation of a sensitizing dye or the like and has been made higher in speed by interaction of said dye with the rhodium salt. Consequently, the lightsensitive material is deteriorated in safeness to a darkroom light of orange to red color, which is ordinarily used in a darkroom, with the result that the density is lowered.
  • a principal object of the present invention is to provide a solarization type direct-positive light-sensitive material which is not only high in speed but also has en-.
  • the above-mentioned object can successfully be accomplished by incorporating into at least one'of the photographic layers, e.g., protective layer, inter layer, emulsion layer, sub layer or backing layer, ofa solarization type direct-positive lightsensitive material containing a rhodium salt as a desensitizer, a certain dye in a proportion of 1 to 500 mg. per 100cm of the lightsensitive material.
  • the photographic layers e.g., protective layer, inter layer, emulsion layer, sub layer or backing layer, ofa solarization type direct-positive lightsensitive material containing a rhodium salt as a desensitizer, a certain dye in a proportion of 1 to 500 mg. per 100cm of the lightsensitive material.
  • the dye used in the present invention is required to have an absorption maximum in the range from 590 to 690 mu. In case a dye having an absorption maximum exceeding the said range has been used, the light-' sensitive material is insufficient in safeness to darkroom light, while in case a dye having an absorption maximum smaller than said range has been used, the light-sensitive material gives an image which is unsatisfactory in photographic property.
  • the amount of the dye used in the present invention should be in the range from 1 to 500 mg. per 100 cm of the effective area of the light-sensitive material. If the amount of the dye is out of said range, either the photographic property or the safeness to darkroom light is unsatisfactory.
  • dyes usable in the present 40 invention are not limited to these.
  • the dye used in the present'invention is preferably such that it is water-soluble and leaves no stains after development.
  • the dye is dissolved in a proper solvent such as water, methanol, ethanol or acetone, and then incorporated into any of the photographic layers of a solarization type direct-positive light-sensitive material.
  • the dye is preferably incorporated into the protective layer or the like layer which is upper than the light-sensitive layer. If necessary, however, the dye is incorporated into the backing layer, sub layer or the like layer which is lower than the light-sensitive layer.
  • the dye may be incorporated into the light-sensitive layer or into the inter layer or the like layer adjacent to the light-sensitive layer.
  • the amount of the dye to be incorporated is l to 500 mg., preferably about 5 to mg., per 100 cm of the effective area of the light-sensitive material.
  • the solarization type direct-positive light-sensitive material according to the present invention which is prepared'in the above manner not only has excellent speed and safeness to darkroom light but also is excellent in other photographic properties.
  • the rhodium salt used in the present invention is a water-soluble rhodium salt suchas rhodium chloride or rhodium bromide which is used as a desensitizer.
  • the rhodium salt is added at the time of emulsification or physical ripening of silver halide, and is ordinarily used in a proportion within the range from about 0.5 to 400 mg. per mole of silver halide.
  • the silver halide may be any of such silver halides as silver chlorobromide, silver bromide, silver chloroiodobromide and silver iodobromide, and the silver halide emulsion may be prepared according to any of acid process, neutral process and ammonia process. In this case, gelatin is ordinarily used as the protective colloid. Alternatively,
  • hydrophilic protective colloid such as albumin, polyvinyl alcohol and the like may be used either singly or in admixture with gelatin or in the form of a mixture of two or more.
  • the silver halide emulsion is fogged according to an ordinary procedure with a reducing agent such as stannous chloride, formaldehyde or thiourea dioxide, or with a salt of a metal high in potential than silver such as potassium chloroaurate, or with a combination of the two.
  • a reducing agent such as stannous chloride, formaldehyde or thiourea dioxide
  • a salt of a metal high in potential than silver such as potassium chloroaurate
  • the reducing agent is used in a proportion of about-0.05 to 400 mg.
  • the salt ofa metal higher in potential than silver is used in'a proportion of about 0.5 to 100 mg., per mole of silver halide.
  • the light-sensitive material according to the present invention may contain various photographic additives, e.g., a hardener such as formaldehyde, glyoxal or such substituted fatty acid as mucobromic acid, an extender such as saponin, a stabilizer, couplers, etc. More pref-
  • a hardener such as formaldehyde, glyoxal or such substituted fatty acid as mucobromic acid
  • an extender such as saponin
  • a stabilizer such as a stabilizer, couplers, etc.
  • More pref- The thus prepared sample was allowed to stand with the emulsion sideup and at a distance of l m. under a 20W darkroom lamp with a red filter for such a period oftime as shown in Table l. Thereafter,the sample was subjected to ordinary development (using, for example, the D72 developer produced by Kodak Co.) and then measured in density to obtain the results as set forth in Table 1.
  • the light-sensitive material is optically sensitized with any of such spectral sensitizersas cyanine and mero'cyanine dyes.
  • the emulsion was thus treated emulsion was incorporated with a hard ripened at 50C. for 40 minutes and then charged with ener and a surface active agent to form an emulsion the liquid IV. After 10 minutes, the emulsion was 'ad- (A), and the other half of the emulsion was incorpousted to a pH of 8.8 by addition of alk and 5 cc. of rated with an ortho-sensitizing dye 3.,3'-9-triethyloxa 4 percent formaldehyde solution was added thereto. acarbocyanine iodide, a hardener and a surface active After fogging y incubation at C. for 15 m nutes, 50 agent.
  • each of the emulsions (A) and (B) was coated the emulsion was neutralized to a pH of 6.0 by addition on a transparent support. Subsequently, a protective of acid. Subsequently, the emulsion was incorporated layer-forming solution incorporated with each of such with an ortho-sensitizing dye 3,3-9-triethyloxacardyes as shown in Table 2 was coated on the resulting bocya riine iodide, each of such dye as shown in Table emulsion layer and then dried to prepare a sample. The l, a hardener and a surface active agent, coated on a thus prepared sample was treated in the same manner transparent support and then dried to prepare a samas in Example 1 and then measured in density to obtain pl the results as set forth in Table 2.
  • a direct-positive light-sensitive silver halide material containing fogg ed silver halide grains and a rhodium salt as a desensitizer to increase the reversal speed which material comprises a bis-pyrazolone dye having an absorption maximum in the range from 590 to 690 mp., which dye is present in an amount of l to 500 mg. per 100 cm of the effective area of said sensitive material, said bis-pyrazolone dye having a methine chain connecting two pyrazolone nuclei thereof, said methine chain consisting of 5 unsubstituted methine groups.
  • a direct-positive light-sensitive material according to claim 1, wherein said bis-pyrazolone dye is selected from the following compounds:

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
US354842A 1972-05-04 1973-04-26 Fogged, direct-positive silver halide photographic material containing a rhodium salt desensitizer and a bispyrazolone dye stabilizer Expired - Lifetime US3867149A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP47043679A JPS495616A (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html) 1972-05-04 1972-05-04

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US3867149A true US3867149A (en) 1975-02-18

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US (1) US3867149A (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
JP (1) JPS495616A (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
DE (1) DE2322275A1 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
GB (1) GB1434612A (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4269914A (en) * 1979-04-16 1981-05-26 Eastman Kodak Company Ultrasonographic elements containing multiple layers and processes for their use
US4301242A (en) * 1977-02-26 1981-11-17 Agfa-Gevaert Aktiengesellschaft Emulsion mixture for color reversal (reflection viewing) material
US5684024A (en) * 1996-01-25 1997-11-04 Viropharma Incorporated Pyrazole dimers compositions and methods for treating influenza
US6670475B2 (en) * 1996-09-30 2003-12-30 Fuji Photo Film Co., Ltd. Information recording medium

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS59154439A (ja) * 1983-02-21 1984-09-03 Fuji Photo Film Co Ltd 直接反転ハロゲン化銀写真感光材料

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2717833A (en) * 1952-05-12 1955-09-13 Sperry Rand Corp Direct positive emulsions
US3576636A (en) * 1967-12-23 1971-04-27 Konishiroku Photo Ind Light-sensitive silver halide direct-positive photographic emulsion
US3656961A (en) * 1969-01-25 1972-04-18 Fuji Photo Film Co Ltd Direct positive silver halide photographic light-sensitive elements
US3738846A (en) * 1970-04-14 1973-06-12 Fuji Photo Film Co Ltd Fogged direct positive silver halide emulsion containing a sulfonatedtriphenylmethane dye

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2717833A (en) * 1952-05-12 1955-09-13 Sperry Rand Corp Direct positive emulsions
US3576636A (en) * 1967-12-23 1971-04-27 Konishiroku Photo Ind Light-sensitive silver halide direct-positive photographic emulsion
US3656961A (en) * 1969-01-25 1972-04-18 Fuji Photo Film Co Ltd Direct positive silver halide photographic light-sensitive elements
US3738846A (en) * 1970-04-14 1973-06-12 Fuji Photo Film Co Ltd Fogged direct positive silver halide emulsion containing a sulfonatedtriphenylmethane dye

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4301242A (en) * 1977-02-26 1981-11-17 Agfa-Gevaert Aktiengesellschaft Emulsion mixture for color reversal (reflection viewing) material
US4269914A (en) * 1979-04-16 1981-05-26 Eastman Kodak Company Ultrasonographic elements containing multiple layers and processes for their use
US5684024A (en) * 1996-01-25 1997-11-04 Viropharma Incorporated Pyrazole dimers compositions and methods for treating influenza
US6670475B2 (en) * 1996-09-30 2003-12-30 Fuji Photo Film Co., Ltd. Information recording medium
US20040115560A1 (en) * 1996-09-30 2004-06-17 Fuji Photo Film Co., Ltd. Information recording medium
US6849316B2 (en) 1996-09-30 2005-02-01 Fuji Photo Film Co., Ltd. Information recording medium

Also Published As

Publication number Publication date
DE2322275A1 (de) 1973-11-22
GB1434612A (en) 1976-05-05
JPS495616A (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html) 1974-01-18

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AS Assignment

Owner name: KONICA CORPORATION, JAPAN

Free format text: RELEASED BY SECURED PARTY;ASSIGNOR:KONISAIROKU PHOTO INDUSTRY CO., LTD.;REEL/FRAME:005159/0302

Effective date: 19871021