US3743510A - Optical super-sensitized silver halide emulsion - Google Patents

Optical super-sensitized silver halide emulsion Download PDF

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Publication number
US3743510A
US3743510A US00074483A US3743510DA US3743510A US 3743510 A US3743510 A US 3743510A US 00074483 A US00074483 A US 00074483A US 3743510D A US3743510D A US 3743510DA US 3743510 A US3743510 A US 3743510A
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United States
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group
ethyl
series
silver halide
dye
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US00074483A
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English (en)
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M Sawahara
N Hinata
Y Nakazawa
N Tsuji
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Fujifilm Holdings Corp
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Fuji Photo Film Co Ltd
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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

Definitions

  • a dye sensitization is ob- A sensitized photographic silver halide e u s on is pr tained which is higher than the sum of each sensitization pared by lncorporating a dye of the gen ral formula 8613 obtained by individual addition. This phenomenon is out below and a Formalin condensate into the silver hacalled super-sensitization and the additive used for this lide emulsion. purpose is called a super sensitizing agent.
  • the polyhydroxybenzene is one having from group, a 2-hydroxy-1-su1fopropyl group, a 2-(3-sulfo- 1 to 3 hydroxyl groups on the benzene nucleus. Further, propoxy)-ethy1 group, a 2 acetoxy 1 sulfopropyl the novolak-type condensate of a substituted or an ungroup, 3 methoxy 2 (3 sulfopropoxy)-propyl group, substituted polyhydroxybenzene and Formalin is herein- 2 (2 (3 sulfopropoxy)ethoxy)ethyl group, 2-hyvafter called simply Formalin condensate.
  • Objects of the present invention are thus: to provide group; an aryl group; a substituted aryl group; or an an optical supersensitized emulsion; to provide such a aralkyl group
  • R represents an alkyl group or an aryl supersensitized combination where reduction of sensitivity group, R represents a hydrogen atom, an alkyl group or during storage is prevented; and where the formation of an allyl group, Y and Y each represents an atomic group fog is reduced.
  • the sensitizing dye of Formula I can be represented by the following general formula:
  • R and R each represents an alkyl group, such APPLICATIONS as, a methyl group, an ethyl group, fl-hydroxyethyl group, fl-sulfobutyl group, a 2-hydroxy-1-sulfopropyl group, a Th1s application is a continuation-in-part of US. Ser.
  • the present invention relates to an improved opticalfi-sulfobutyl group, a 2-hydroxy-1-sulfopropyl group, a sensitized photographic silver halide emulsion and more 2 (3 sulf0propoXy)-ethyl group, a 2-acetoxy-1-sulfoparticularly to a so-called super optical sensitized silver propyl group, 3 methoxy 2 (3 s
  • R represents an alkyl group or an aryl silver halide emulsions that by adding a sensitizing dye group
  • R represents a hydrogen atom, an alkyl group or Field of the invention Description of the prior art an allyl group
  • Q represents an oxygen atom or a sulfur atom
  • X represents an anion
  • n is 1 or 2, said It being 1 when the dye forms an intramolecular salt, an n 11 and n each is or 1.
  • Y and Y each represents an atomic group necessary for forming a heterocyclic ring.
  • Y and Y may, for example, represent the atomic group necessary to complete a heterocyclic ring of the pyridines series (e.g. 2-pyr1dme, 2-pyridine), the tetrazole series (e.g. tetrazole, 4-methyltetrazole, 4-ethyltetrazole), the thiazole series (e.g.
  • benzothiazole 4-chlorobenzothiazole, S-chlorobenzothiazole, 6 chlorobenzothiazole, 7 chlorobenzothiazole, S-methylbenzothiazole, G-methylbenzothiazole, bromo benzothiazole, S-phenylbenzothiazole, S-rnethoxybenzothiazole, 6-methoxybenzothiazole, S-ethoxybenzothiazole, 5, 6 dimeth'oxybenzothiazole, S-hydroxybenzothiazole, 6- hydroxybenzothiazole), the naphtho[1,2]thiazole series, the naphtho[2,3]thiazole series, the naphtho[2,1]thiazole series, the oxazole series (e.g.
  • oxazole 4-methyloxazole, 5- methyloxazole, 4-phenyloxazole, 4,5-diphenyloxazole, 4- ethyloxazole, 4,5-dimethyloxazole, S-phenyloxazole), the benzoxazole series (e.g.
  • benzoxazole 5-chlorobenzoxazole, S-methylbenzoxazole, S-phenylbenzoxazole, 6-meth ylbenzoxazole, 5,6 dimethylbenzoxazole, '5 methoxybenzoxazole, S-ethoxybenzoxazole, S-hydroxybenzoxazole, 6-hydroxybenzoxazole), the naphtho[1,2]oxazole series, the naphtho[2,3]oxazole series, the naphtho[2,1]oxazole series, the selenazole series (e.g. 4 methylselenazole, 4- phenylselenazole, th'e benzselenazole series e.g.
  • benzselenazole 5-chlorobenzselenazole, S-methylbenzselenazole, S-methoxybenzselenazole, 5 hydroxybenzselenazole, 5- phenylbenzselenazole), the naphthol[l,2] selenazole series, the naphtho[2,l]selenazole series, the thiazoline series (e.g. thiazoline, 4-1nethylthiazoline), the oxazolino series (e.g. oxazoline), the quinoline series such as the Z-quinoline series (e.g.
  • l-isoquinoline 4-dihydro-1-isoquinoline
  • 3-isoquinoline e.g. 3-isoquinoline
  • the benzimidazole series e.g. 1,3- diethylbenzimidazole, 1,3-diethyl-S-chlorobenzimidazole, 1,3-diethyl 5, 6 dichlorobenzimidazole, 1-ethyl-3phenylbenzimidazole, the 3,3'-dialkylindolenine series (e.g. 3,3-dimethylindolenine, 3,3',5-trimethylindolenine, 3,3',7- trimethylindolenine) etc.
  • the 3,3'-dialkylindolenine series e.g. 3,3-dimethylindolenine, 3,3',5-trimethylindolenine, 3,3',7- trimethylindolenine
  • the substituted or unsubstituted polyhydroxybenzene used in the present invention is shown by the following general formula:
  • R and R each represents OH, OM, 0R NH S N(R6)2, NZHNH or -NHNHR (where R Presents an alkyl group having 1-8 carbon atoms, an allyl Hp or an :aralkyl group and M represents an alkali metal or an alkaline earth metal), and I1 and n each represents an integer of from 1 to 3, inclusive.
  • Typical ples of poly hydtnoxybenzenes shown by the above formulas are p-dic xytlirenzene, o-dioxybenzene p-hydroxybenzoic acid, p-hy, hmxybemne sulfonic acid, o-hydroxy benzoic acid, O-lrydv rpxybsnzem sulfonic acid, m-hydroxy benzoic acid, m-hydroxybenzene sulfonic acid, a-resorcinic acid, fl-resorcinic acid, 'y-resorcinic acid, 3,5-dihydroxybenzene sulfonic acid, 2,4 dihydroxybenzene sulfonic acid, 2,6-dihydroxybenzene sulfonic acid, 2,5-dihydroxy benzoic acid, 2,5-dihydroxy benzoic acid, 2,5-dihydroxybenzene sulfonic acid, pyrogallo
  • amides or hydrazides of the above mentioned carboxylic acids or sulfonic acids and the alkyl( 1-8 carbon atoms)-, aralkylor allyl-derivatives of their amides or hydrazides are effectively employed in the present invention.
  • the esters of the above-mentioned carboxylic acids and the sulfonic acids can also be etfectively used in this invention.
  • the condensate of the above-mentioned substituted or unsubstituted polyhydroxybenzene and formaldehyde may be prepared by a conventional novolak-type method for producing a phenol-formaldehyde resin.
  • it may be prepared generally as follows: The poly-substituted hydroxybenzene is dispersed in water, and after the addition of concentrated hydrochloric acid and 37% Formalin, the dispersion is stirred for 30 to minutes at 100 C. Thereafter, if necessary, hydrochloric acid is supplemented followed by continuation of heating and stirring. After the reaction is finished, the product is poured into cold water and the thus precipitated product is collected and purified to provide the condensate.
  • the thus precipitated product is recovered by filtration, re-dissolved in 1000 parts of methanol while the product is in a semi-dried state, and then recrystallized with water.
  • the product is recovered by filtration and dried to provide the objective condensate.
  • the above-mentioned method or slightly modified methods can be applied.
  • the condensate obtained by the above-mentioned methods has about 2-10 units in a condensation unit (degree of polymerization) as is general with novolak resins.
  • a condensate having 2-10 units, in degree of polymerization, is effective in the present invention, but a condensate having from 2-5 units in degree of polymerization, or having a molecular weight of from about 300 to 800 is particularly desirable.
  • Formalin condensate of the present invention is added to a silver halide emulsion containing sensitizing dye (I), a very excellent super-sensitization can be obtained without lowering the sensitivity.
  • sensitizing dyes (I) have such drawbacks that when they are incorporated in photographic light-sensitive materials, the sensitivity thereof is lowered during storage, but by incorporating the dye together with the Formalin condensate in accordance with the present invention, the reduction in sensitivity during storage can be remarkably prevented. Moreover, the formation of fog in the emulsion caused by the presence of sensitivity dye (I) can be reduced by the addition of the Formalin condensate to an emulsion containing the sensitizing dye (I).
  • the concentration of the sensitizing dye (I) in silver halide emulsion be 0.002-02 g./gram molecule of silver halide and the concentration of the Formalin condensate in said emulsion be 0.1-2.0 g./ gram molecule of silver halide. Furthermore, a particularly effective concentration ratio of the sensitizing dye (I) to the Formalin condensate is from 1:5 to 1:500.
  • the sensitizing dye (I) may be added to the emulsion by any method widely known in the field.
  • the Formalin condensate may be incorporated in the emulsion as a solution thereof in water or an organic solvent such as methanol or ethanol. It is convenient to incorporate the sensitizing dye (1) and the Formalin condensate into the emulsion directly before coating.
  • the sensitizing dye (I) may be added to the emulsion before or after the addition of the Formalin condensate, or a mixture of the sensitizing dye (I) and the Formalin condensate may be added to the emulsion. They may also :be added to the emulsion after water-washing and during ripening.
  • gelatino silver halide emulsions are generally employed, but materials other than gelatin having no bad influences on the photographic light-sensitive materials, such as resinous materials or cellulose derivatives, may be used.
  • the silver halide used in the emulsion of this invention may be silver chloride, silver bromide, silver bromo-iodide, silver bromo-chloride, silver bromo-chlorodide, and the like.
  • the silver halide emulsion used in this invention may also contain the usual additives, such as chemical sensitizing, hardening agents, antifoggants, wetting agents, stabilizers, plasticizers, development promoters, an antibronzing agent, couplers, fluorescent whitening agents, anti-air foggants, and the like.
  • the silver halide emulsion of this invention may be applied by conventional methods to a suitable support, such as, a glass plate, a cellulose derivative film, a synthetic resin film or a 'baryta paper.
  • the sensitivity is shown by M.U.D. (the reciprocal of exposure necessary for giving fog +0.1 in optical density), the sensitivity in the case of incorporating only the sensitizing dye in the emulsion is defined to be 100, and the sensitivity in the case of incorporating the novolaktype condensate together with the sensitizing dye in the emulsion is shown by comparison with the defined sensitivity.
  • sensitizing dyes and the Formalin condensates used in the present invention should not be limited to the following formulae shown in Table 1.
  • the product was precipitated by the addition of 5 ml. of an aqueous 20% solution of sodium perchlorate.
  • the precipitate was filtered under suction, and washed with water, and recrystallized from methanol.
  • the melting point of the dye was 251 C. (accompanied with decomposition).
  • sensitizing dyes used in this invention may be prepared by processes similar to the above-mentioned processes.
  • the melting points of the sensitizing dyes used in the examples of this invention are shown in Table 4.
  • Example 14-23 a silver bromo-iodide emulsion was used in Examples 14-23, while a silver chlorobromide emulsion was used in Examples 15-45.
  • the film was exposed through a Fuji -No. 3 filter [trademark] (made by Fuji Photo Film Co., and transmitting light having a wave length longer than 500 millimicrons) and then developed.
  • the materials of Ex. 14-23 were developed for 10 minutes at 20 C. using the composition of Table 3, and Ex. 24-45 for six minutes at 20 C. using the composition of Table 2.
  • the dye separated from the solution was collected on the filter under suction, washed with acetone and then recrystallized from methanol.
  • the melting point of the product was 266 C. (accompanied by decomposition).
  • sensitizing dyes used in this invention may be prepared by process similar to the above-mentioned process and/or the process set forth in US. Pat. No. 2,947,630.
  • R and R each is a member selected from the group consisting of an alkyl group, a substituted alkyl group selected from the group consisting of a hydroxyalkyl group, an acetoxyalkyl group, an alkylsulfate group, a carboxyalkyl group, a carboxyalkoxyalkyl group, a sulfoalkyl group, a hydroxysulfoalkyl group, a sulfoalkoxyalkyl group, an acetoxysulfoalkyl group, an alkoxysulfoalkoxyalkyl group, a sulfoalkoxyalkoxyalkyl group, and a hydroxysulfoalkoxyalkyl group, an allyl group, an aryl group, and an aralkyl group; R is a member selected from the group consisting of an alkyl group and an allyl group; R is a member selected from the group consisting of a hydrogen atom
  • n 1 6 and n is 1 or 2, said n being 1 when the dye forms an intramolecular salt, and (2) at least one condensate of formaldehyde and a member selected from the group consisting of polyhydroxybenzenes of the formulae 4) OH COR; S 2R5 wherein R and R each is a member selected from the group consisting of OH, OM, 0R NH NHR N(R NHNH and --NHNHR where R represents a member selected from the group consisting of an alkyl group having from 1 to 8 carbon atoms, an allyl group, and an aralkyl group, and M is a member selected from the group consisting of an alkali metal and an alkaline earth metal; and n; and m each is an integer of from 1 to 3 inclusive.
  • a photographic light-sensitive element comprising a support bearing at least one silver halide emulsion containing (l) a sensitizing dye selected from those represented by the following general formula:
  • R and R each is a member selected from the group consisting of an alkyl group, substituted alkyl group selected from the group consisting of a hydroxyalkyl group, an acetoxyalkyl group, an alkylsulfate group, a carboxyalkyl group, a carboxyalkoxyalkyl group, a sulfoalkyl group, a hydroxysulfoalkyl group, a sulfoalkoxyalkyl group, an acetoxysulfoal-kyl group, an alkoxysulfoalkoxyalkyl group, a sulfoalkoxyalkoxyalkyl group, and a hydroxysulfoalkoxyalkyl group, an allyl group, an aryl group, and an aralkyl group; R is a member selected from the group consisting of an alkyl group and an allyl group; R is a member selected from the group consisting of a hydrogen atom,
  • concentration of said sensitizing dye in said silver halide emulsion is from 0.002 to 0.2 gram per gram molecule of silver halide and the concentration of said condensate is from 0.1 to 2.0 grams per gram molecule of silver halide.
  • concentration ratio of said sensitizing dye to said condensate in the silver halide emulsion is from 1:5 to 1:500.

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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)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
  • Thiazole And Isothizaole Compounds (AREA)
  • Plural Heterocyclic Compounds (AREA)
US00074483A 1965-12-30 1970-09-22 Optical super-sensitized silver halide emulsion Expired - Lifetime US3743510A (en)

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BE (1) BE691993A (enrdf_load_stackoverflow)
DE (1) DE1547862C3 (enrdf_load_stackoverflow)
FR (1) FR1583164A (enrdf_load_stackoverflow)
GB (1) GB1137580A (enrdf_load_stackoverflow)

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
USB360719I5 (enrdf_load_stackoverflow) * 1970-08-13 1975-01-28
US3909274A (en) * 1972-01-04 1975-09-30 Minnesota Mining & Mfg Silver halide emulsion containing trinuclear rhodanine nucleus dyes soluble in low-molecular weight alcohols
EP0143424A2 (en) 1983-11-25 1985-06-05 Fuji Photo Film Co., Ltd. Heat-developable light-sensitive materials
EP0204175A1 (en) 1985-05-09 1986-12-10 Fuji Photo Film Co., Ltd. Silver halide color photographic materials
EP0210660A2 (en) 1985-07-31 1987-02-04 Fuji Photo Film Co., Ltd. Image forming process
EP0239363A2 (en) 1986-03-25 1987-09-30 Konica Corporation Light-sensitive silver halide photographic material feasible for high speed processing
US4710631A (en) * 1984-08-28 1987-12-01 Fuji Photo Film Co., Ltd. Temperature compensation for a semiconductor light source used for exposure of light sensitive material
EP0253390A2 (en) 1986-07-17 1988-01-20 Fuji Photo Film Co., Ltd. Photographic support and color photosensitive material
US4770961A (en) * 1985-10-30 1988-09-13 Mitsubishi Paper Mills, Ltd. Light sensitive materials for lithographic printing plates
US4940657A (en) * 1988-01-21 1990-07-10 Mitsubishi Paper Mills Limited Photographic spectral sensitizing dye
WO1996013755A1 (en) 1994-10-26 1996-05-09 Eastman Kodak Company Photographic emulsions of enhanced sensitivity
JP2731715B2 (ja) 1992-12-21 1998-03-25 イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー 写真エレメント製造のための改良された方法

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3915715A (en) * 1970-08-13 1975-10-28 Eastman Kodak Co Silver halide photographic materials containing a high weight ratio of gold to sulfur sensitizers and a sensitizing methine dye
USB360719I5 (enrdf_load_stackoverflow) * 1970-08-13 1975-01-28
US3909274A (en) * 1972-01-04 1975-09-30 Minnesota Mining & Mfg Silver halide emulsion containing trinuclear rhodanine nucleus dyes soluble in low-molecular weight alcohols
EP0143424A2 (en) 1983-11-25 1985-06-05 Fuji Photo Film Co., Ltd. Heat-developable light-sensitive materials
US4710631A (en) * 1984-08-28 1987-12-01 Fuji Photo Film Co., Ltd. Temperature compensation for a semiconductor light source used for exposure of light sensitive material
EP0204175A1 (en) 1985-05-09 1986-12-10 Fuji Photo Film Co., Ltd. Silver halide color photographic materials
EP0210660A2 (en) 1985-07-31 1987-02-04 Fuji Photo Film Co., Ltd. Image forming process
US4770961A (en) * 1985-10-30 1988-09-13 Mitsubishi Paper Mills, Ltd. Light sensitive materials for lithographic printing plates
EP0239363A2 (en) 1986-03-25 1987-09-30 Konica Corporation Light-sensitive silver halide photographic material feasible for high speed processing
EP0253390A2 (en) 1986-07-17 1988-01-20 Fuji Photo Film Co., Ltd. Photographic support and color photosensitive material
US4940657A (en) * 1988-01-21 1990-07-10 Mitsubishi Paper Mills Limited Photographic spectral sensitizing dye
JP2731715B2 (ja) 1992-12-21 1998-03-25 イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー 写真エレメント製造のための改良された方法
WO1996013755A1 (en) 1994-10-26 1996-05-09 Eastman Kodak Company Photographic emulsions of enhanced sensitivity

Also Published As

Publication number Publication date
FR1583164A (enrdf_load_stackoverflow) 1969-10-24
DE1547862B2 (de) 1973-07-12
BE691993A (enrdf_load_stackoverflow) 1967-05-29
DE1547862A1 (de) 1969-11-27
GB1137580A (en) 1968-12-27
DE1547862C3 (de) 1974-02-07

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