US3663210A - Light-sensitive silver halide supersensitized photographic material - Google Patents

Light-sensitive silver halide supersensitized photographic material Download PDF

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Publication number
US3663210A
US3663210A US28711A US3663210DA US3663210A US 3663210 A US3663210 A US 3663210A US 28711 A US28711 A US 28711A US 3663210D A US3663210D A US 3663210DA US 3663210 A US3663210 A US 3663210A
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Prior art keywords
dye
silver halide
light
emulsion
group
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Expired - Lifetime
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US28711A
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English (en)
Inventor
Shui Sato
Eiichi Sakamoto
Shizuo Saito
Kaiichiro Sakazume
Tokuzo Kaneko
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Konica Minolta Inc
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Konica Minolta Inc
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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
    • 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
    • G03C1/08—Sensitivity-increasing substances
    • G03C1/28—Sensitivity-increasing substances together with supersensitising substances
    • G03C1/29—Sensitivity-increasing substances together with supersensitising substances the supersensitising mixture being solely composed of dyes ; Combination of dyes, even if the supersensitising effect is not explicitly disclosed

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  • ABSTRACT A light-sensitive silver halide photographic material which contains at least one layer of silver halide emulsion including a combination of at least one benzimidazolo-carbocyanine dye represented by the general formula (CH O(CH OH; R and R are individually a C, to C -alkyl hydroxyalkyl, or sulfoalky group; Y and Y: are individually a C1 to C4-alkyl group, ethoxyethyl group or an aryl group; X- is a negative group; and n is l or 2: and at least one benzoxazolo-carbocyanine dye represented by the general formula wherein R5 and Rs are individually a C to C -alky
  • This invention relates to a light-sensitive silver halide photographic material containing 2 or more sensitizing dyes in combination. More particularly, the invention is concerned with a lightsensitive silver halide photographic material containing at least one layer of a silver halide emulsion which has been highly sensitized by the combination of a certain kind of benzimindazolo-carbocyanine and a certain kind of benzoxazolo-carbocyanine.
  • the intrinsic light-sensitive wavelength region of a silver halide emulsion is ordinarily limited to a short wavelength region of ultraviolet light or blue light. It is well known that as a means for the spectral sensitization of such silver halide emulsion, the use of a certain kind of cyanine sensitizing dye is extremely effective.
  • the sensitizing dyes employed not only contribute to the increase in color sensitizing effects but also satisfy such conditions as mentioned below.
  • these conditions are important when the supersensitization process is applied to green light-sensitive emulsions for light-sensitive color photographic materials. That is, it is desirable that the sensitizing dyes have such spectral sensitization region as to attain the best color reproductivity when used in light-sensitive color photographic materials, and have a high speed green light-sensitivity.
  • the sensitizing dyes are required to be such that they should not be lowered in speed by interaction with a magenta color image-forming component, i.e. a magenta coupler, which couples with an oxidation product of a color developer using p-phenylenediamine or the like, to give a color image.
  • a magenta color image-forming component i.e. a magenta coupler, which couples with an oxidation product of a color developer using p-phenylenediamine or the like, to give a color image.
  • An object of the present invention is to provide a light-sensitive silver halide photographic material supersensitized by use of sensitizing dyes capable of satisfying all the above-mentioned conditions.
  • Another object is to provide a best green light-sensitive color photographic material containing sensitizing dyes, which can show a sensitization maximum at the wavelength region intermediate between the spectral sensitization maxima of individual sensitizing dyes.
  • the supersensitizing dyes employed in the present invention are represented by the following formulas (l) and (II):
  • R, and R are individually a C, to C,-alkyl or substituted alkyl group
  • R and R are individually a C, to C alkyl, hydroxyalkyl or sulfoalkyl group, or a derivative thereof
  • Y, and Y are individually a C, to C -alkyl, a substituted alkyl, aryl or substituted aryl group
  • X' is a negative group (anion); and n is l or 2.
  • Typical examples of the dye represented by the formuld ll) are as follows:
  • sensitizing dyes usable in the present invention are not limited only to those mentioned above.
  • the combination according to the present invention-which comprises at least one of the sensitizing dyes of the aforesaid formula (I) and at least one of the sensitizing dyes of the formula (II) has excellent characteristics as mentioned previously and can impart ideal green-light sensitivity to silver halide emulsions. Accordingly, the combination of the present invention is desirably applied to green lightsensitive emulsions for internal color photographic materials which contain a magenta dye-forming coupler, or to orthomatic type emulsions for light-sensitive black-white photographic materials.
  • the location of spectral sensitization maximum of the silver halide photographic emulsion in accordance with the present invention may be varied by varying the kinds and proportions of the sensitizing dyes represented by the aforesaid formulas. These sensitizing dyes are dissolved in a water-miscible organic solvent such as methanol or ethanol and then the resulting solution is added to a silver halide emulsion. Alternatively, the sensitizing dyes are formed into organic solvent solutions, which are then added either singly or in admixture to a silver halide emulsion.
  • the addition of the sensitizing dyes to a photographic emulsion is most preferably made after completion of the second ripening, though the addition may sometimes be made at any stage'during the preparation of said emulsion.
  • the amounts of the sensitizing dyes to be added vary depending on the kind of the silver halide emulsion. Ordinarily, however, the amounts thereof per kg. of the silver halide emulsion are such that the amountof the benzimidazolocarbocyanine dye of the formula (I) is l mg. to 200 mg., while the amount of the benzoxazolo-carbocyanine dye of the formula (ll) is 2 mg. to 400 mg., and the ratio ofthe dye (l) to the dye (ll) is preferably in the range of 4:1 to 1:20. However, the amounts thereof are not always limited to those mentioned above but may be varied as occasion demands.
  • the silver halide emulsion employed in the present invention may be any of silver iodobromide, silver bromide, silver chloride, silver chlorobromide and silver chloroiodide emulsions. These emulsions may have been subjected to chemical sensitization using noble metal sensitizers, sulfur sensitizers, reductive sensitizers or polyalkylene oxide derivatives. Further, they may be incorporated according to ordinary procedure with such additives as stabilizers, surface active agents, hardeners, etc.
  • the thus prepared emulsion was divided into several portions, and each portion was incorporated with a methanol solution or methanol solutions of such two sensitizing dyes as shown in Table 1.
  • Each of the thus treated emulsions was stirred at about 40 C. for 20 minutes to stabilize the color sensitization thereof and then coated on a film base, followed by drying to obtain an orthomatic type photographic material.
  • the samples prepared in the above manner were subjected to KS-l type Sensitometer (manufactured by Konishiroku Photo Industrial Co.), exposed to a 160 lux day light lamp ,400 K.) through a green filter having a transmission maximum at 525 mu, and then developed at 20 C. for 5 minutes with a developer of the following composition:
  • Dye of exemplillcation (17) (30 mg). 8 Dye of exempllfication (7) (60 mg.) 85 0. 05 680 Dye ol' exempliflcation (7) (20 mg.) 9 plus 190 0.08 570 dye of exemplification (18) (40 mg). Dye of exemplification (7) (30 mg.). 10 plus 175 0. 07
  • 1, 2 and 3 show, respectively, the spectral sensitivity curves of the sample (5), the sample (ll) and the sample (6) according to the present invention. From these drawings, it is recognized that the sample in accordance with the present invention has an excellent sensitization maximum which cannot be attained in the case where the sensitizing dye is used singly, and, from Table l and from the drawing, it is understood that the sample according to the present invention has excellent photographic properties.
  • EXAMPLE 2 A silver iodobromide emulsion for high speed negative which had been adjusted to the optimum speed according to the gold and sulfur sensitization process was divided into portions of each 1 kg. in amount, and each portion was incorporated with a 0.1 percent methanol solution of each of the sensitizing dyes shown in Table 2. The thus treated emulsion was stirred at 40 C. for about 20 minutes and then charged with 35 ml. of a 0.5 percent aqueous solution of 4-hydroxy-6- methyll ,3,3a,7-tetrazaindene as a stabilizer.
  • each of the thus obtained emulsions was immediately coated on a film base, followed by drying to prepare an immediately-coated sample.
  • each of the emulsions was allowed to stand at 40 C. for 3 hours and then emulsions a combination of methanol solutions of the sensitizing dyes as shown in Table 3, adding in the same manner as in Example 2 l-(2,4,6-trichlorophenyl)-3-[3-(2,4-di-tert.- amylphenoxyacetamide)benzamide] as a magenta coupler,
  • Dye oi exeinplilication (19) iiig.). Dye of exemplitieatioii (1) (40 mg.) 15 plus 100 0.03 185 0.04 185 0.04 190 0,04
  • Dye of exemplifieation (20) (40 mg.)
  • Dye of exeinplilieation (11) (40 mg.) l7... plus 170 0.03 170 0.03 175 0.03 170 0.03
  • the light-sensitive silver halide in asilveriodobromide negative emulsion sensitized according photographic materials according to the present invention are to the gold and sulfur sensitization process, and then adjusting high in green light-sensitivity even when used in the presence the resulting mixture to pH 6.8. of a magenta coupler, and are not fogged nor deteriorated in
  • the multi-layer color photographic materials obtained in color sensitization even when allowed to stand or stored under the above were exposed the Same manner as a p 1, severe conditions. developed at 22 C. for l0 minutes with the aforesaid color EXAMPLE 3 developer, bleached and fixed according to ordinary I I procedures, and then subjected to sensitometry.
  • the t us orme i m was t in Dye f amplification (3) (20 mgjnn coated with gelatine and then coated with a green light-sensi- 23 g g cxempllficatm" (3) (20 0 n5 tive color photographic emulsion prepared by dividing the Dy0 ofcmmpjmcauon (19) (40 mm H same high speed silver iodobromide emulsion as in Example 1 24 Control y mg.) p on l into portion of 1 kg. in amount, adding to each of the divided dye (ll) (40 mph).
  • Table 3 shows the fact that the combinations of the dyes according to the present invention are more excellent in speed of magenta layer as green light-sensitivity and lower in residual color property than the combination of the dyes used as controls, and give excellent light-sensitive multi-layer color photographic materials.
  • EXAMPLE 4 A reversal color photographic silver iodobromide emulsion containing 3 mol of silver iodide which had been treated with a gelatine coagulant was subjected to second ripening according to gold and sulfur sensitization. After completion of the ripening, the emulsion was divided into several portions of each 1 kg. in amount. To each portion of the divided emulsions were added in combination methanol solutions of the sensitizing dyes shown in Table 4. Each of the emulsions was stirred at 40 C. for 20 minutes to thoroughly stabilize the color sensitization thereof, and then an optimum amount of a stabilizer was added thereto.
  • Metol N-methyl-p-aminophenol sulfate
  • Potassium bromide Potassium thiocyanate Water to make u. ---mouioiu MOGQ FOQ P iter.
  • the developed sample was subjected to second exposure by use of a white light, and then developed at C. for 12 minutes with a developer of the following composition:
  • the light-sensitive reversal color photographic materials according to the present invention have excellent photographic properties as compared with the control sample.
  • a light-sensitive silver halide photographic material characterized by containing at least one layer of a silver halide emulsion incorporated with a combination of at least one benzimidazolo-carbocyanine dye represented by the general wherein R, and R are individually a C, to C,-alkyl or a group wherein R,and R are individually a C, to C.,-alkyl or substituted alkyl group; R and R, are individually a C, to C.,-alkyl, hydroxyalkyl, or sulfoalkyl group, or a derivative thereof; Y, and Y, are individually a C,'to C -alkyl, substituted alkyl, aryl or substituted aryl group; X is a negative group; and n is l or 2;

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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
US28711A 1969-04-19 1970-04-15 Light-sensitive silver halide supersensitized photographic material Expired - Lifetime US3663210A (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3765899A (en) * 1969-03-14 1973-10-16 Konishiroku Photo Ind Light-sensitive super-sensitized silver halide photographic emulsion
US3854955A (en) * 1972-01-14 1974-12-17 Fuji Photo Film Co Ltd Supersensitized silver halide photographic emulsions
US3861920A (en) * 1974-01-02 1975-01-21 Polaroid Corp Super-sensitizing dye combination in silver halide emulsions
DE2500048A1 (de) * 1974-01-02 1975-07-10 Polaroid Corp Photographische silberhalogenidemulsion

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS59116647A (ja) * 1982-12-13 1984-07-05 Konishiroku Photo Ind Co Ltd ハロゲン化銀写真感光材料

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3397060A (en) * 1964-10-19 1968-08-13 Eastman Kodak Co Supersensitization of green-sensitive silver halide emulsions

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3397060A (en) * 1964-10-19 1968-08-13 Eastman Kodak Co Supersensitization of green-sensitive silver halide emulsions

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3765899A (en) * 1969-03-14 1973-10-16 Konishiroku Photo Ind Light-sensitive super-sensitized silver halide photographic emulsion
US3854955A (en) * 1972-01-14 1974-12-17 Fuji Photo Film Co Ltd Supersensitized silver halide photographic emulsions
US3861920A (en) * 1974-01-02 1975-01-21 Polaroid Corp Super-sensitizing dye combination in silver halide emulsions
DE2500048A1 (de) * 1974-01-02 1975-07-10 Polaroid Corp Photographische silberhalogenidemulsion

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DE2018687A1 (de) 1970-11-05

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