US3890155A - Radiation-sensitized fine-grained silver halide photographic sensitive material - Google Patents

Radiation-sensitized fine-grained silver halide photographic sensitive material Download PDF

Info

Publication number
US3890155A
US3890155A US350579A US35057973A US3890155A US 3890155 A US3890155 A US 3890155A US 350579 A US350579 A US 350579A US 35057973 A US35057973 A US 35057973A US 3890155 A US3890155 A US 3890155A
Authority
US
United States
Prior art keywords
emulsion
silver halide
grain size
micron
base
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
US350579A
Other languages
English (en)
Inventor
Yasuharu Nakamura
Yoshiyuki Nakazawa
Tohru Sueyoshi
Akira Sato
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 US3890155A publication Critical patent/US3890155A/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
    • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • G03C1/08—Sensitivity-increasing substances
    • G03C1/10—Organic substances
    • G03C1/12—Methine and polymethine dyes
    • G03C1/14—Methine and polymethine dyes with an odd number of CH groups

Definitions

  • ABSTRACT A radiation-sensitive silver halide photographic emulsion containing silver halide crystals whose mean grain size is not greater than 0.2 micron or at least 90% in number of which are not greater than 0.25 micron in grain size and at least one sensitizing base represented by the following general formula (1);
  • the present invention relates to a radiationsensitized silver halide photographic emulsion and, more particularly, to a silver halide photographic emulsion containing fine-grained silver halide crystals sensitized with certain cyanine bases.
  • Electron beam-recording enables one to record with high density, but in order to obtain an image of high quality, it is firstly necessary to minimize the grain size of the silver halide in the light-sensitive material as much as possible. However, a reduction in the grain size of the silver halide generally results in a reduction in the sensitivity to electrons. Therefore, a novel sensitizing method becomes necessary. Secondly, it is of importance to reduce the surface charge of the lightsensitive material irradiated with electrons to form a distinct image. For this purpose, it is necessary to raise the velocity of electron beam recording to reduce the amount of irradiation with electrons. From this viewpoint, a light-sensitive material having high sensitivity to electron beam is also required.
  • Another object of the invention is to provide a highly radiation-sensitive photographic emulsion providing improved image quality.
  • Another object of the invention is to provide a photographic emulsion having an extended light-sensitive wave-length region.
  • Another object of the invention is to provide a silver halide photographic emulsion which solves the abovedescribed problems.
  • the inventors havefound that when a silver halide photographic emulsion containing silver halide crystals whose mean grain size is not greater than 0.2 micron, or at least in number of which are not greater than 0.25 micron in grain size, is spectrally sensitized with a certain cyanine base, not only is the light-sensitive wave-length region extended, but also the sensitivity in the absorption wave-length region intrinsic to silver halide is remarkably enhanced, and that the sensitivity of a silver halide photographic emulsion to electrons can be markedly raised by incorporating one or more of such bases in the emulsion.
  • the effect discovered in the present invention is absolutely different from the Capri blue effect in that even when a silver halide photographic emulsion containing silver halide crystals of a specific grain size is subjected to sulfur sensitization, reduction sensitization or gold sensitization, the light sensitivity of the emulsion in the absorption wave-length range intrinsic to silver halide can be simultaneously enhanced when the emulsion is spectrally sensitized with a cyanine base represented by the later described formula.
  • benzimidazolocarbocyanines such as a halogen atom, (e.g., fluorine atom, chlorine atom, bromine atom, etc.), a trifluoromethyl group, an alkylsulfonyl group, wherein the alkyl moiety preferably has up to 4 carbon atoms (e.g., methylsulfonyl group), an aminosulfonyl group (e.g., sulfo- 1O nyl, methylaminosulfonyl, morpholinosulfonyl, pyrrolidinosulfonyl group, etc.), a cyano group, a carboxyl group, an alkoxycarbonyl group, wherein the alkyl moiety preferably has up to 3 carbon atoms (e.g., methoxycarbonyl, ethoxycarbonyl group, etc.), an acyl group (e.g., an aliphatic atom, e.
  • the alkyl moiety preferably has up to 3 carbon atoms (e.g., beta-cyanoethyl, gamma-cyanopropyl, deltacyanobutyl, etc.), carbamoylalkyl, wherein the alkyl moiety preferably has up to 4 carbon atoms (e.g., betacarbamoylethyl, gamma-carbamoylpropyl, deltacarbamoylbutyl, beta-N-ethylcarbamoylethyl, gamma-N-ethylcarbamoylpropyl, delta-N-methylcarbamoylbutyl, etc.), sulfamoylalkyl wherein the alkyl moiety preferably has up to 4 carbon atoms (e.g., gamma-sulfamoylpropyl, delta-sulfamoylbutyl,
  • Y represents an oxygen atom, a sulfur atom, a selenium atom or an N---R group and Y represents a sulfur atom, a selenium atom or an NR group, where R and R each represents an alkyl group (i.e.,
  • n 1 or 2.
  • R and R contains as a substituent a sulfo group or a carboxyl group, for example, a gamma- 1 .11 CH Crl Cl1 SO
  • Y represents a sulfur atom or a NR group
  • Z Z R R R and n each have the same meanings as defined in general formula (1).
  • the sensitizing bases represented by general formula (I) can be synthesized by refluxing a compound repre- C C ⁇ (V) sented by the following general formula (IV) and a 2 1- 2 compound represented by the following general for- 50 mula (V) in alcohol in the presence of triethylamine according to a method described in the textbook by F. R M. Hamer (The Chemistry of Heterocyclic Com- 2 pounds: The Cyanine Dyes And Related Compounds, lnterscience Publishers): 55
  • synthesis is under the following reaction conditions: molar ratio of reactants: stoichiometric amount; temperature: on a water bath; time: within 1 hour; pres sure: atmospheric; amount of alcohol: sufficient to dissolve reactants; triethylamine: as shown in the Synthesis example.
  • the present invention not only is the lightsensitive wave-length region of a silver halide photographic emulsion extended, but the light sensitivity in the absorption wave-length region intrinsic to silver halides is remarkably enhanced as well.
  • gelatino-silver halide photographic emulsion This effect is particularly conspicuous with a gelatino-silver halide photographic emulsion.
  • the present invention is effective also in silver halide photographic emulsions containing other synthetic or natural hydrophilic high molecular weight polymer binders which do not harm photographic properties such as gelatin derivatives (e.g., acetylated gelatin, malonated gelatin, phthaloylated gelatin, etc.), a water-soluble cellulose derivative (e.g., hydroxyethyl cellulose, carboxymethyl cellulose, etc.) hydrophilic polymers (e.g., polyvinyl alcohol, polyvinyl pyrrolidone, polystyrene sulfonic acid, polyacrylamide) and the like.
  • the ratio by weight of silver halide to hydrophilic binder is preferred to be within a range of from about A to about 4/1.
  • the sensitizing effect in the absorption range intrinsic to silver halide in the invention depends greatly upon the grain size of the silver halide crystals used. That is, in silver halide photographic emulsions having the same halogen composition andd the same base, the effect varies depending upon the grain size of the silver halide crstals. In a silver halide photographic emulsion containing silver halide crystals whose mean grain size is greater than 0.2 micron, e.g., 0.6 micron, there is observed little or no sensitizing effect.
  • the sensitization ratios are shown in terms of relative ratios based on the sensitivity value of a silver halide photographic emulsion containing no Base (5), which value is taken as l.
  • the mean grain size can be determined in a Conventional manner, e.g., measuring the projected area as described in The Photographic Journal, vol. LXXIX, pp.330-338 (1939).
  • the radiation-sensitive silver halide used in the invention can be any of silver chloride, silver bromide, silver chlorobromide, silver bromoiodide and silver chlorobromoiodide.
  • an excellent effect is exhibited in the case of silver bromide and silver bromoiodide.
  • one or several bases represented by the general formula (I) can be added in a conventional manner to a silver halide emulsion.
  • the emulsion can be previously chemically sensitized in a conventional manner, such as by gold sensitization (e.g., see U.S. Pat. Nos. 2,540,085; 2,597,856; 2,597,9l5; 2,399,083, etc.) by Group VIII metal ion sensitization, sulfur sensitization (e.g., see U.S. Pat. Nos.
  • the base(s) can be added to a silver halide photographic emulsion as a solution prepared by dissolving the bases in a suitable solvent such as methanol, ethanol, methyl cellosolve, etc.
  • a suitable solvent such as methanol, ethanol, methyl cellosolve, etc.
  • the amount of the base(s) incorporated can be varied over a wide range, for example, of from about 1X10 to about 1X10 mol/mol Ag.
  • compositional bounds set out above are not mandatory in the present invention. However, as one begins to use much lower concentrations of the sensitizing dye the sensitizing effect gradually reduced. On the other hand, using greater amounts of sensitizing dye does not appreciably increase or conversely decreases the sensitizing effect and is economically wasteful.
  • the silver halide photographic emulsion of the invention can further be supersensitized or hypersensitized.
  • the sensitizing effect of the present invention can be obtained, in one embodiment, by adding the sensitizing base to a silver halide photographic emulsion prepared in a usual manner immediately before applying the emulsion to a support.
  • similar effects can be obtained by adding the sensitizing base during physical ripening or chemical ripening, etc. There is no restriction as to the stage of the addition of the base.
  • additives such as other chemical sensitizing agents, a stabilizer, an anti-fogging agent, a toning agent, a hardener, a surface active agent, a thickener, a plasticizer, a lubricant, a development accelerator, a color coupler, a brightening agent or the like can be added in a conventional manner and in conventional amounts.
  • EXAMPLE 1 To g of a chemically repened gelatino silver bromoiodide Br: 99 mol I:1 mol emulsion (gelatino: silver halide 1:1 by weight) containing silver halide crystals of 0.07 micron or 0.6 micron (for comparison) in mean grain size (prepared in a known manner) were added, respectively, methanol solutions of bases in the amounts shown in Table 2. Chemical sensitization was performed with triethyl thiourea and potassium chloroaurate. mg. triethyl thiourea per mole of silver, 1 mg. potasium chloroaurate per mol of silver. 7 milliliters of the thus produced silver halide photographic emulsions were applied to cabinet-sized glass plates and dried to prepare samples.
  • the photographic sensitivity is relatively Also, in the case of silver halide crystals of grains at shown by determining the irradiation amount required least 90% in number of which are not greater than 0.25 for the foog-free photographic density to go up to 0.5 micron in grain size, a markedly high sensitization ratio while taking the (sensitivity value of a sensitizing basewas similarly obtained. free emulsion as 100.
  • Sensiti- Sensiti zation Mean zation Mean ratio grain ratio Sensi- Amount of grain (in the size (in the tizing mol of base added size jm i (for intrinsic base (mol of base (present absorp compaabsorp-.
  • the photographic emulsions of the invention of fine grain size provide high image quality and have a high sensitivity to electrons beams without a substantial increase in fog. Therefore, it can be said that substantial technical progress has been attained by the present invention.
  • Z and Z each represent the atoms necessary to form a benzene ring
  • Y represents an oxygen atom, a sulfur atom, a selenium atom or a NR group
  • Y represents a sulfur atom, a selenium atom or a N--R group
  • R and R which may be the same or different each represents an alkyl group
  • R represents a hydrogen atom or an alkyl group
  • n represents 1 or 2
  • Y represents a sulfur atom or N-R and Z Z R R R and n each have the following meaning: Z and Z each represent the atoms necessary to form a benzene ring; R and R which may be the same or different, each represents an alkyl groups, R represents a hydrogen atom or an alkyl group, and n represents l or 2.
  • sensitizing base is selected from the class consisting of the following bases:
  • An electron beam-sensitive photographic emulsion 8 The emulsion as claimed in claim 3 wherein the as claimed in claim 3 wherein the sensitizing base is seamount of base(s) is about 1X10 to about 1X10 lected from the class consisting of the following bases: mol/mol of silver in the emulsion.
  • amount of base(s) is about 1X10 to about lXlO 11.
  • emulsion comprises gelatin as a hydrophilic binder.
  • Z, and Z each represent the atoms necessary to form a benzene ring wherein the Z benzene ring is unsubstituted or if substituted is substituted with halogen, trifluoromethyl, alkyl sulfonyl, where the alkyl moiety has up to 4 carbon atoms, aminosulfonyl, where the alkyl moiety has up to 4 carbon atoms, cyano carboxyl, alkoxycarbonyl, where the alkoxy moiety has up to 3 carbon atoms, acyl, or one or more thereof, and the Z benzene ring is unsubstituted or if substituted is substituted with an alkyl group of up to 4 carbon atoms, a halogen atom, an alkoxy group where the alkyl moiety has up to 3 carbon atoms, or one or more thereof, Y represents an oxygen atom, a sulfur atom, a selenium atom or a l IR group, R
  • R represents an alkyl group of up to 4 carbon atoms.
  • R represents an alkyl group with up to 4 carbon atoms.

Landscapes

  • 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)
US350579A 1972-04-12 1973-04-12 Radiation-sensitized fine-grained silver halide photographic sensitive material Expired - Lifetime US3890155A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP3667672A JPS5434330B2 (enrdf_load_stackoverflow) 1972-04-12 1972-04-12

Publications (1)

Publication Number Publication Date
US3890155A true US3890155A (en) 1975-06-17

Family

ID=12476444

Family Applications (1)

Application Number Title Priority Date Filing Date
US350579A Expired - Lifetime US3890155A (en) 1972-04-12 1973-04-12 Radiation-sensitized fine-grained silver halide photographic sensitive material

Country Status (2)

Country Link
US (1) US3890155A (enrdf_load_stackoverflow)
JP (1) JPS5434330B2 (enrdf_load_stackoverflow)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6291203B1 (en) * 1995-11-13 2001-09-18 Molecular Probes, Inc. Cyanine dyes that stain cells and mitochondria
US20050208534A1 (en) * 2003-12-05 2005-09-22 Dallwig Jason A Methine-substituted cyanine dye compounds
US7598390B2 (en) 2005-05-11 2009-10-06 Life Technologies Corporation Fluorescent chemical compounds having high selectivity for double stranded DNA, and methods for their use

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6389842A (ja) * 1986-10-02 1988-04-20 Konica Corp 減力処理特性にすぐれた製版用ハロゲン化銀写真感光材料

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2393743A (en) * 1941-04-18 1946-01-29 Eastman Kodak Co Organic cyanine base
US2918369A (en) * 1956-06-15 1959-12-22 Gen Aniline & Film Corp Non-ionic benzimidazole cyanine dyes containing in alpha-position a cyano group on the methenyl chain
US3090782A (en) * 1958-03-04 1963-05-21 Bayer Ag Process for the production of cyanine dyestuffs
US3706566A (en) * 1969-03-07 1972-12-19 Fuji Photo Film Co Ltd Photographic emulsion containing optically dye-sensitized silver halide grains of less than 0.2 micron
US3706570A (en) * 1969-05-17 1972-12-19 Fuji Photo Film Co Ltd Spectrally sensitized negative emulsion containing silver halide grains of less than 0.18 micron

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2393743A (en) * 1941-04-18 1946-01-29 Eastman Kodak Co Organic cyanine base
US2918369A (en) * 1956-06-15 1959-12-22 Gen Aniline & Film Corp Non-ionic benzimidazole cyanine dyes containing in alpha-position a cyano group on the methenyl chain
US3090782A (en) * 1958-03-04 1963-05-21 Bayer Ag Process for the production of cyanine dyestuffs
US3706566A (en) * 1969-03-07 1972-12-19 Fuji Photo Film Co Ltd Photographic emulsion containing optically dye-sensitized silver halide grains of less than 0.2 micron
US3706570A (en) * 1969-05-17 1972-12-19 Fuji Photo Film Co Ltd Spectrally sensitized negative emulsion containing silver halide grains of less than 0.18 micron

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6291203B1 (en) * 1995-11-13 2001-09-18 Molecular Probes, Inc. Cyanine dyes that stain cells and mitochondria
US8470529B2 (en) 2003-12-05 2013-06-25 Life Technologies Corporation Methine-substituted cyanine dye compounds
US20050208534A1 (en) * 2003-12-05 2005-09-22 Dallwig Jason A Methine-substituted cyanine dye compounds
US10005908B2 (en) 2003-12-05 2018-06-26 Life Technologies Corporation Methine-substituted cyanine dye compounds
US9403985B2 (en) 2003-12-05 2016-08-02 Life Technologies Corporation Methine-substituted cyanine dye compounds
US7776529B2 (en) 2003-12-05 2010-08-17 Life Technologies Corporation Methine-substituted cyanine dye compounds
US20100317543A1 (en) * 2003-12-05 2010-12-16 Life Technologies Corporation Methine-substituted cyanine dye compounds
US9040561B2 (en) 2003-12-05 2015-05-26 Life Technologies Corporation Methine-substituted cyanine dye compounds
US7943777B2 (en) 2005-05-11 2011-05-17 Life Technologies Corporation Fluorescent chemical compounds having high selectivity for double stranded DNA, and methods for their use
US8865904B2 (en) 2005-05-11 2014-10-21 Life Technologies Corporation Fluorescent chemical compounds having high selectivity for double stranded DNA, and methods for their use
US20110217699A1 (en) * 2005-05-11 2011-09-08 Life Technologies Corporation Fluorescent Chemical Compounds Having High Selectivity for Double Stranded DNA, and Methods for Their Use
US9115397B2 (en) 2005-05-11 2015-08-25 Life Technologies Corporation Fluorescent chemical compounds having high selectivity for double stranded DNA, and methods for their use
US9366676B2 (en) 2005-05-11 2016-06-14 Life Technologies Corporation Fluorescent chemical compounds having high selectivity for double stranded DNA, and methods for their use
US20100143917A1 (en) * 2005-05-11 2010-06-10 Life Technologies Corporation Fluorescent chemical compounds having high selectivity for double stranded dna, and methods for their use
US7598390B2 (en) 2005-05-11 2009-10-06 Life Technologies Corporation Fluorescent chemical compounds having high selectivity for double stranded DNA, and methods for their use

Also Published As

Publication number Publication date
JPS48104521A (enrdf_load_stackoverflow) 1973-12-27
JPS5434330B2 (enrdf_load_stackoverflow) 1979-10-26

Similar Documents

Publication Publication Date Title
US3537858A (en) Reversal silver halide emulsions
US3679428A (en) Spectrally sensitized photographic emulsions
US3666480A (en) Spectrally sensitized silver halide photographic emulsion
US3137578A (en) Photographic emulsions containing 2-heterocyclic benzimidazole antifoggants
US3676147A (en) Method of spectrally sensitizing photographic silver halide emulsions
US3615635A (en) Silver halide photographic emulsion
US4576905A (en) Photographically useful chalcogenazoles, chalcogenazolines, and chalcogenazolinium and chalcogenazolium salts
US3656959A (en) Photographic silver halide emulsion
US3501311A (en) Direct positive silver halide emulsions containing carbocyanine dyes having a nitro-substituted 3h-indole nucleus
US3706566A (en) Photographic emulsion containing optically dye-sensitized silver halide grains of less than 0.2 micron
US3632349A (en) Silver halide supersensitized photographic emulsion
US3890155A (en) Radiation-sensitized fine-grained silver halide photographic sensitive material
US3541089A (en) Method of preparing chain-substituted trimethine indole dyestuffs
US3922170A (en) Spectrally sensitized silver halide photographic emulsion
US3988513A (en) Silver halide emulsions for recording electron rays
US3969116A (en) Silver halide photographic sensitive element for flash exposure
US3615517A (en) Direct-positive silver halide emulsion containing halogen conductor and electron acceptor developed with polyhydroxy benzene
US3687676A (en) Desensitizers in unfogged silver halide systems
US2848329A (en) Supersensitization with bis-heterocyclic bases
US3933505A (en) Fogged, direct positive silver halide emulsion containing a nitro-substituted fluorene desensitizer
US3669672A (en) Supersensitized silver halide photographic emulsion
US3585195A (en) Stabilization of aqueous solutions of certain acid substituted spectral sensitizing dyes
US3745015A (en) Spectral sensitization of photodevelopable silver halide emulsions
US3567456A (en) Photographic direct-reversal emulsions
US3702251A (en) Light-sensitive silver halide photographic emulsion for microfilm use