US3713835A - Light-sensitive supersensitized silver halide photographic material - Google Patents

Light-sensitive supersensitized silver halide photographic material Download PDF

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Publication number
US3713835A
US3713835A US00079941A US3713835DA US3713835A US 3713835 A US3713835 A US 3713835A US 00079941 A US00079941 A US 00079941A US 3713835D A US3713835D A US 3713835DA US 3713835 A US3713835 A US 3713835A
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Prior art keywords
silver halide
combination
anhydro
light
group
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Expired - Lifetime
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US00079941A
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English (en)
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S Saito
K Sakazume
S Sato
E Sakamoto
T 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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  • h l M1929 graphic emulsion layer thereof a combination of sensitizing dyes comprising at least one compound (X na-1 wherein R, and R are individually a lower alkyl group which may be in etherated form; R and R are individually a lower alkyl group, a hydroxyalkyl group or a sulfoalkyl group; Y, and Y are individually a lower alkyl group which may be in'etherated form, or
  • X is an anion (that is an acid anion); and n is an integer of 1 or 2, with at least one compound represented by the general formula (11),
  • R is a lower alkyl group; and A is an alkylene group, or a combination of said compounds with at least one compound represented by the general formula (111),
  • R is a lower alkyl group
  • R is a lower alkyl group, a hydroxyalkyl group, a carboxyalkyl group or a sulfoalkyl group
  • Y is a hydrogen atom, a lower alkyl group or a lower alkoxy group
  • Z is S or Se:
  • X is a negative group; and
  • n is an integer of l or 2.
  • This invention relates to a light-sensitive silver halide photographic material incorporated with a combination of sensitizing dyes. More particularly, the invention pertains to a light-sensitive silver halide photographic material characterized by containing in the silver halide photographic emulsion layer thereof a combination of at least one compound represented by the general formula (I),
  • R is a lower alkyl group; and A is an alkylene group, or a combination of said compounds with at least one compound represented by the general formula (III),
  • R is a lower alkyl group
  • R is a lower alkyl group, a hydroxyalkyl group, a carboxyalkyl group or a sulfoalkyl group
  • Y is a hydrogen atom, a lower alkyl group or a lower alkoxy group
  • Z is S or Se
  • X is a negative group
  • n is an integer of l or 2.
  • the light-sensitive wavelength region inherent to a silver halide emulsion is ordinarily limited to the wavelength region of such a short wave as ultraviolet light or blue light. It is well known that as a means for the spectral sensitization of such a silver halide emulsion, the use of a certain cya nine dye is quite effective. It is also well known that a combination of said sensitizing dye with a certain other sensitizing dye or with an organic compound is incorporated into a silver halide emulsion to impart to the emulsion a light sensitivity which is greater than thetotal sum of the light-sensitivities of the individual compounds. Such effect is called super-sensitization, and many such combinations have already been reported.
  • the combination should be proper in spectral sensitization area.
  • the combination should have no detrimental interaction with other photographic additives and should provide stable photographic properties even when emulsions incorporated with the combination are allowed to stand or films or printing papers containing the combination are stored for a long period of time.
  • the combination should not .leave any color stain or fog in films or printing papers after development treatment.
  • the combination is required to satisfy the condition that even when used together with a magenta color image-forming agent, i.e. a magenta coupler, which couples with the oxidation product of a color developing agent containing p-phenylenediamine or the like in order to obtain a color image, the combination should not bring about a decrease of color sensitivity due to interaction with said magenta coupler.
  • a magenta color image-forming agent i.e. a magenta coupler
  • none of the known combinations of sensitizing dyes can satisfy the above-mentioned conditions. I
  • An object of the present invention is to provide a light-sensitive silver halide photographic material which has been subjected to supersensitization using a combination of sensitizing dyes capable of satisfying all the above-mentioned conditions.
  • the spectral maximum values of individual sensitizing dyes can be brought, by combination use of the sensitizing dyes, to a unified and collective spectral maximum value, and the optimum green sensitivity can be obtained.
  • Another object of the invention is to provide a lightsensitive silver halide photographic material having a high green light sensitivity which does not form any optical fog even when treated under a safety light having a wavelength of more than 600 mp
  • a safety light having a wavelength of more than 600 mp
  • sensitizing dyes represented by the abovementioned formulas are ortho-type sensitizing, dyes.
  • the sensitizing dye of the general formula (I) is a green-sensitive dye which, when used singly,
  • the sensitizing dye represented by the general formula (ll) or (III) is a green-sensitive sensitizing dye which shows a color sensitization maximum in a short wavelength region (wavelength 550 mp. 560 my).
  • the long and short wavelength portions in the green sensitive area are supersensitized to obtain a green color sensitivity of a high degree as well as to attain green sensitization having a new color sensitization maximum which cannot be attained when the sensitizing dyes are used singly.
  • the combination used in the present invention is an excellent supersensitizing agent which has no detrimental interaction with other additives to be added to photographic emulsions and which leaves no color stain in films after development treatment.
  • the distribution of color sensitization maxima of silver halide-emulsions according to the present invention may vary depending on the kind and proportions of the sensitizing dyes represented by the aforesaid general formulas.
  • These sensitizing dyes may be added to a silver halide photographic emulsion after dissolving the dyes in a water-miscible organic solvent such as methanol or ethanol.
  • the sensitizing dyes may be added individually after dissolving each of the Anhydrous sodium sulfite dyes in such anorganic solvent as mentioned above.
  • the sensitizing dyes may be added to a silver halide photographic emulsion at any stage.
  • the sensitizing dyes may be added to a silver halide photographic emulsion at any stage.
  • the dyes are preferably added immediately after completion of the second ripening.
  • the amounts of the sensitizing dyes vary depending on the kind of the silver halide emulsion used. Ordinarily, however, the total amount of the compounds of the general formulas (I), (ll) and (III) is in the range of 1 mg. to 100 mg. per kg. of the silver halide emulsion, wherein the weight ratio of the compound of the general formula emulsions, which may have been sensitized by means of noble metal sensitizers, sulfur sensitizers, reduction sensitizers or polyalkylene oxide type sensitizers. Further, the emulsions may be incorporated according to a known procedure with such additives as stabilizers, surface active agents and hardeners.
  • EXAMPLE 1 A silver iodobromide emulsion containing 3 mol percent of silver iodide which has been added with a gelatine coagulant was subjected to second ripening according to gold and sulfur sensitization to prepare a high speed negative photographic emulsion. This emulsion was divided into several portions, which were then incorporated with one or more of methanol solutions of such sensitizing .dyes' as shown in Table 1. Each of the thus treated emulsions was allowed to stand at about 40C. for minutes and then coated on a film base, followedby drying, to prepare a green-sensitive lightsensitive photographic material.
  • Metol N-methyl-p-aminophenol. sulfate
  • Potassium bromide Water to make g. 29. g. g.
  • the relative speed is a value calculated by assuming as 100 the green sensitization of the sample prepared by using the exemplified dye (3) singly.
  • FIGS. 1, 2 and 3 are spectral sensitivity curves of the samples (1), (2) and (11), and FIGS. 4 and 5 are spectral sensitivity curves of the present samples (4) and 12), respectively.
  • EXAMPLE 2 The same emulsions as in Example 1 were individually incorporated with each of such combinations of dyes as shown in Table 2. After sufficiently stabilizing the color sensitization thereof, the emulsions were individually added with a suitable amount of 4-hydroxy--methyl-l,3,3a,7-tetrazaindene and then coated on a film base, followed by drying, to prepare green-sensitive light-sensitive materials.
  • the thus prepared samples were individually subjected to incubation test at a high temperature and a high, humidity to obtain such results as shown in Table 2.
  • the exposure and the development were effected in the same manner as in Example 1.
  • the relative speed is a value calculated by assuming as 100 the relative speed of the control sample developed immediately after preparation, and the residual color is the .optical density measured by a sensitometer of the sample which has been freed from fog.
  • Control dye ('B) 3 mg. 14 Compound (1) 3mg. 160 0.03 0.02 150 0.03
  • EXAMPLE 3 A high speed color negative silver iodobromide emulsion containing 5 mol percent of silver iodide was spectrally sensitized by addition of 50 mg. per kg. of the emulsion of anhydro-S ,5 '-dichloro-9-ethyl-3,3 '-disulfopropyl thiacarbocyanine as a red-sensitive sensitizing dye.
  • 4-chlorol -hydroxy-2-(n)-octyl naphthamide as a cyan coupler was dissolved at an elevated temperature in a mixture of di-(n)-butyl phthalate and ethyl acetate, and the resulting solution was dispersed in a gelatine solution by use of sodium alkylbenzenesulfonate to prepare a dispersion.
  • a definite amount of the thus prepared dispersion was added to the above-mentioned emulsion.
  • This emulsion was adjusted to pH 6.3 and then coated on a film base so as to form a layer of 5 microns in thickness, and then gelatine was thinly coated on the said layer.
  • Example 2 Thereafter, the same high speed silver iodobromide emulsion as in Example 2 was divided into portions of 1 kg. in weight, and each of the divided emulsions was combined with one or more of methanol solutions of such sensitizing dyes as shown in Table 3.
  • l-(2,4,6-trichlorophenyl)-3- [3-(2,4-di-tert-amyl phenoxyacetamide) benzamide]- S-pyrazolbne as a magenta coupler was dispersed in the same manner as in the case of the cyan coupler.
  • the emulsion was adjusted to pH 6.8 and then coated on the aforesaid gelatine layer so as to form a layer of 6 microns in thickness, and a yellow filter layer was further applied onto the thus formed la er.
  • 2-dodecyloxybenzoyl acetanilide as a yellow coupler was dispersed in the same manner as in the case of the aforesaid cyan coupler in a silver iodobromide negative emulsion, which had been sensitized according to gold and sulfur sensitization.
  • This emulsion was adjusted to pH 6.8 and then coated on the above-mentioned yellow filter layer so as to form a layer of 5 microns in thickness.
  • Example 2 The thus obtained multi-layered light-sensitive color photographic materials were exposed in the same manneras in Example 1, developed at 22C. for l0 minutes with a color developer having such a composition as shown below, and then subjected to bleaching, fixing and color sensitometry according to ordinary procedures.
  • Table 3 clearly shows that the light-sensitive silver halide photographic materials according to the present invention (the samples l8, l9 and 20) are high in green sensitivity and less in fog and gamma, even when used as multi-layered color photographic materials containing magenta couplers.
  • EXAMPLE 4 A reversal color photographic silver iodobromide emulsion containing 3 mol percent 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 portions of 1 kg. in weight, and the divided emulsions were individually incorporated witheach of such combinations of sensitizing -dyes as shown in Table 4. Each emulsion was allowed to stand with stirring at about 40C.
  • the thus treated sample was subjected to sensitometry and measured in residual color to obtain the results as shown in Table 4.
  • the relative speed in the table is a value calculated by assuming as 100 the relative speed in green sensitivity of the control sample used in Example 2.
  • Control dye (B) 5 mg. 100 0. l0 22 Compound (4) 7.5 mg.
  • control dyes (A) and (B) were the same as those used in Example 2.
  • R and R are individually a lower alkyl group which may be substituted by an alkoxy or hydroxyalkoxy group; R, and R are individually a lower alkyl group, a hydroxyalkyl group or a sulfoalkyl group; Y
  • Y are individually a lower alkyl group which may zs u mtsqlzy, an al xy qthydxexya kex so p or an aryl group;
  • X is an anion; and
  • n is an integer of 1 or 2, with at least one compound represented by the general formula (II),
  • y-n-propyl)-benzimidazolo-carbocyanine hydroxide anhydro-5,5'-dichloro-3,3'-di(sulphobutyl)-9-ethyloxacarbocyanine hydroxide and 3-carboxyethyl-l-ethyl- 6'-methyl-selena-2'-cyanine iodide.

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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)
US00079941A 1969-10-13 1970-10-12 Light-sensitive supersensitized silver halide photographic material Expired - Lifetime US3713835A (en)

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JP44081151A JPS4828293B1 (de) 1969-10-13 1969-10-13

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Cited By (8)

* 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
US3849147A (en) * 1969-06-25 1974-11-19 Fuji Photo Film Co Ltd Silver halide supersensitized photographic emulsion
US3930860A (en) * 1972-12-29 1976-01-06 Fuji Photo Film Co., Ltd. Spectrally sensitized color photographic materials suitable for high temperature rapid development
US3933510A (en) * 1972-09-04 1976-01-20 Fuji Photo Film Co., Ltd. Spectrally sensitized silver halide photographic emulsion
US3969116A (en) * 1971-01-19 1976-07-13 Fuji Photo Film Co., Ltd. Silver halide photographic sensitive element for flash exposure
USH899H (en) 1986-03-25 1991-03-05 Konishiroku Photo Industry Co., Ltd. Light-sensitive silver halide photographic material feasible for high speed
US5077183A (en) * 1987-12-24 1991-12-31 Agfa Gevaert Aktiengesellschaft Color photographic recording material and a process for the preparation of a photographic silver halide emulsion
US6479226B2 (en) * 2000-04-27 2002-11-12 Konica Corporation Silver halide color photographic light sensitive material

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5036975B2 (de) * 1971-10-18 1975-11-28
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
US4725529A (en) 1985-04-30 1988-02-16 Konishiroku Photo Industry Co., Ltd. Developing inhibitor arrangment in light-sensitive silver halide color photographic materials
AU590563B2 (en) 1985-05-16 1989-11-09 Konishiroku Photo Industry Co., Ltd. Method for color-developing a silver halide color photographic light-sensitive material

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2688545A (en) * 1953-05-28 1954-09-07 Eastman Kodak Co Supersensitization of photographic emulsions with benzimidazolocarbocyanine dyes
US2751298A (en) * 1954-08-23 1956-06-19 Eastman Kodak Co Supersensitization of photographic emulsions with benzimidazolocyanine dyes
US3348949A (en) * 1963-04-19 1967-10-24 Ilford Ltd Photographic light-sensitive materials
US3397060A (en) * 1964-10-19 1968-08-13 Eastman Kodak Co Supersensitization of green-sensitive silver halide emulsions

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2688545A (en) * 1953-05-28 1954-09-07 Eastman Kodak Co Supersensitization of photographic emulsions with benzimidazolocarbocyanine dyes
US2751298A (en) * 1954-08-23 1956-06-19 Eastman Kodak Co Supersensitization of photographic emulsions with benzimidazolocyanine dyes
US3348949A (en) * 1963-04-19 1967-10-24 Ilford Ltd Photographic light-sensitive materials
US3397060A (en) * 1964-10-19 1968-08-13 Eastman Kodak Co Supersensitization of green-sensitive silver halide emulsions

Cited By (8)

* 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
US3849147A (en) * 1969-06-25 1974-11-19 Fuji Photo Film Co Ltd Silver halide supersensitized photographic emulsion
US3969116A (en) * 1971-01-19 1976-07-13 Fuji Photo Film Co., Ltd. Silver halide photographic sensitive element for flash exposure
US3933510A (en) * 1972-09-04 1976-01-20 Fuji Photo Film Co., Ltd. Spectrally sensitized silver halide photographic emulsion
US3930860A (en) * 1972-12-29 1976-01-06 Fuji Photo Film Co., Ltd. Spectrally sensitized color photographic materials suitable for high temperature rapid development
USH899H (en) 1986-03-25 1991-03-05 Konishiroku Photo Industry Co., Ltd. Light-sensitive silver halide photographic material feasible for high speed
US5077183A (en) * 1987-12-24 1991-12-31 Agfa Gevaert Aktiengesellschaft Color photographic recording material and a process for the preparation of a photographic silver halide emulsion
US6479226B2 (en) * 2000-04-27 2002-11-12 Konica Corporation Silver halide color photographic light sensitive material

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Publication number Publication date
GB1297655A (de) 1972-11-29
DE2049967A1 (de) 1971-05-19
DE2049967B2 (de) 1974-06-12
DE2049967C3 (de) 1975-01-30
JPS4828293B1 (de) 1973-08-31

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