US3769026A - Spectrally sensitized silver halide photographic emulsion - Google Patents

Spectrally sensitized silver halide photographic emulsion Download PDF

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Publication number
US3769026A
US3769026A US00184604A US3769026DA US3769026A US 3769026 A US3769026 A US 3769026A US 00184604 A US00184604 A US 00184604A US 3769026D A US3769026D A US 3769026DA US 3769026 A US3769026 A US 3769026A
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Prior art keywords
silver halide
halide photographic
photographic emulsion
dye
group
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Expired - Lifetime
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US00184604A
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English (en)
Inventor
A Sato
K Shiba
H Takei
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Fujifilm Holdings Corp
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Fuji Photo Film Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
    • C09B23/02—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups
    • C09B23/06—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups three >CH- groups, e.g. carbocyanines
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
    • C09B23/10—The polymethine chain containing an even number of >CH- groups
    • C09B23/105—The polymethine chain containing an even number of >CH- groups two >CH- groups
    • 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

Definitions

  • the photographic sensitive materials are required to have high sensitivity at the specific wavelengths different from each other according to the purpose for use.
  • sensitizing dyes bring about the lowering of the sensitivity of the emulsion in the intrinsic sensitivity region thereof, i.e., desensitization, while they bring about spectral sensitization. Therefore, it is quite advantageous to use at least two kinds of sensitizing dyes, which are in a supersitizing relation to each other and do not accompany desensitizing actron.
  • the object of this invention is to lower the desensitizing action and to raise both the sensitivity intrinsic to silver halide and the panchromatically sensitized spectral sensitivity by using at least two kinds of sensitizing dyes.
  • the second object of this invention is to improve the image quality of the spectrally sensitized photographic sensitive material.
  • the sensitizing dyes affect the development of the photographic emulsion and, in many cases, lower the quality of the photographic image.
  • cationic dyes affect the infectious development, which is employed for photographic plate making, and deteriorate the dot quality obtained. Therefore, it is also the object of this invention to obtain high panchromatic sensitivity by supersensitization using a restricted cyanine dye and another merocyanine dye, which have little effect on infectious development, and to obtain good dot quality, which is difircult to obtain by supersensitization using more than two kinds of cyanine dyes together.
  • Merocyanine dyes are generally adsorbed Hat on silver halide to prohibit the formation of the J aggregate of the carbocyanine dye and, as a result thereof, lower the red sensitivity extremely.
  • One of the characteristics of this invention is the discovery of a method for strengthening the formation of the J aggregate of the restricted carbocyanine by strictly selecting the chemical structure of the merocyanine dye.
  • Theobject of ,this invention is accomplished by'the combined use of at least one sensitizing carbocyanine dye having two heterocyclic nuclei selected from the group consisting of a benzothiazole nucleus,-a benzoselenazolenucleus, a fi-naphthoselenaz ole nucleus, and a B-naphthothiazole nucleus, the m'eso-position of said dye being substituted with a methyl or ethyl group and, preferably, at least one of the N-substituents of said heterocyclic nuclei being a sulfoalkyl group or a carboxy alkyl groupvMore specifically, weare speaking of sensitizing dyes of the following general formula (I), and at least one merocyanine dye, wherein a tetrazole derivative nucleus and a merocyanine nucleus-are connected through a dimethine chain, more specifically, sens
  • R and R each represents a lower alkyl group, such as methyl, ehtyl, propyl, gamma-sulfopropyl-, gamma-sulfobutyl, delta-sulfobutyl, beta-hydroxyethyl, beta-carboxyethyl, allyl group, etc.;
  • A represents a lower alkyl group, preferably a methyl or an ethyl group;
  • Z and Z each represents the 1 non-metallic atoms necessary to complete a benzothiazole; benzoselenazole, beta-naphthoselenazole, or betanaphthothiazole nucleus, which may be substituted with a halogen atom, such as chlorine, bromine, etc., a lower alkyl group, such as methyl, ethyl, etc., an alkoxy group, such as methoxy, ethoxy, etc., an alko x
  • the cyanine dyes of this invention having the general formula (I) have their maximum sensitization part between 595 and 690 nm, and many of them have high red sensitivity. Some of the sensitizing dyes having the general formula (11) have their maximum sensitization part between 460 and 560 um, and others do not exhibit remarkable spectral sensitization action, even when used together with a silver iodide emulsion.
  • the red sensitivity arising from the sensitizing dye of the general formula (I) is further raised, thewhite light sensitivity is remarkably raised and the silver halide photographic emulsion, which almost does not cause intrinsic desensitization, can be obtained by the combined use of at least one of the sensitizing dyes of the general formula (1) and at least one of the sensitizing dyes of the general formula (11), which have the said characteristics.
  • the combination of meso-methyl-carbocyanine being one of the sensitizing dyes represented by the general formula (I), and the sensitizing dye of the general formula (ll) wherein Z is sulfur, remarkably raises the white light sensitivity and red sensitivity, and brings about remarkable maximum sensitization around 630 nm.
  • the sensitizing dyes of the general formula (1) do not deteriorate the dot quality obtained by the infectious development employed for the sensitive material for print plate making in proportion to the fact that they strongly and spectrally supersensitize to the relatively long wavelength of 690 nm.
  • the application of the known supersensitizing art using cyanine dyes together in order to raise the spectral sensitivity badly deteriorates the dot quality.
  • the application of the supersensitizing art described in the specification of US. Pats. Nos. 2,533,426, 2,688,545, and 2,751,298, the specification of German Pat. No. 1,547,641, the specification of German Patent Prepublication No. 1,813,001, Japanese Patent Publication No. 16169/68 and No. 4132/68 are disadvantageous because of the reason described above.
  • the merocyanine dye represented by the general formula rather strengthens the infectious development, and is useful to obtain good dot quality. Accordingly, the supersensitizing art of this invention is useful espe cially for the panchromatic sensitization of the sensitive material for printing plates which are to be subjected to the treatment of infectious development.
  • the spectral sensitization method of this invention is useful for the spectral sensitization of the gelatinosilver-halide photographic emulsion. It is also useful for the emulsion containing a hydrophilic polymer, other than gelatin, such as agar collodion, water-soluble cellulose derivatives, polyvinyl alcohol, polyvinyl- -pyrrolidone copolymer and other synthesized hydrophilic resin, natural hydrophilic polymer, gelatin derivatives, and the like.
  • a hydrophilic polymer other than gelatin, such as agar collodion, water-soluble cellulose derivatives, polyvinyl alcohol, polyvinyl- -pyrrolidone copolymer and other synthesized hydrophilic resin, natural hydrophilic polymer, gelatin derivatives, and the like.
  • the photographic emulsion to be used in this invention is suitably a mixed silver halide comprising at least two of silver chloride, silver bromide and silver iodide.
  • the sensitizing dye according to this invention is introduced into a photographic emulsion according to a conventional method.
  • dyes are dissolved in a solvent, such as methanol, ethanol, water, cellosolve, water-soluble ketones, etc., and added to an emulsion.
  • dyes may also be dissolved in an oil, slightly soluble in water, then added to water or a hydrophilic colloid to disperse the same.
  • the mol ratio of the sensitizing carbocyanine to the sensitizing merocyanine to be contained in the emulsion can vary widely from 9:1 to 1:9 depending upon the effects desired.
  • the amount of each of the dyes is preferably in the range of from 1 X 10" to l X 10 mol per mol of silver according to the character of the emulsion employed.
  • the photographic emulsion of this invention can be subjected to further hypersensitization and other supersensitization in the known manner.
  • conventional additives such as chemical sensitizers,
  • stabilizers may be contained in the photographic emulsion of this invention in a conventional manner.
  • the photographic emulsion of this invention may be coated in a common manner on a suitable support, such as a glass plate, film of a cellulose derivative, film of a synthetic resin, Baryta paper, resin-coated paper, etc.
  • a suitable support such as a glass plate, film of a cellulose derivative, film of a synthetic resin, Baryta paper, resin-coated paper, etc.
  • a silver halide photographic emulsion was prepared 'by adding separately the dye of this invention illustrated before and to be used in this invention independently to a silver bromoiodide emulsion (AglzAgBr 7 molsz93 mols).
  • a silver halide photographic emulsion containing both the earbocyanine dye and the merocyanine dye was prepared.
  • the white light sensitivity and the red light sensitivity obtained by the combined use of the sensitizing dyes of this invention are far higher than those obtained by the independent use thereof.
  • the sensitizing effect obtained by the combination of at least one of the carbocyanine dyes and at least one of the merocyanine dyes is not deteriorated if an orthochromatic sensitizing dye already known, such as that of 11 or 12, is further used together.
  • the orthochromatic sensitizing dyes used together with the sensitizing dyes employed in this invention are, for example, 2,2- cyanine and pseudo-type cyanine (e.g., 2'-thiacyanine) having the following chemical structures, but are not solely limited to these.
  • a silver halide photographic emulsion comprising a supersensitizing combination of at least one sensitizing carbocyanine dye having two heterocyclic nuclei selected from the group consisting of a benzothiazole nucleus, a benzoselenazole nucleus, a B-naphthoselenazole nucleus and a B-naphthothiazole nucleus, the meso-position of said dye being substituted with a member selected from the group consisting of a methyl and an ethyl group, and at least one merocyanine dye in which a tetrazole derivative nucleus and a merocyanine nucleus are connected through a dimethine chain.
  • R, and R each represents a lower alkyl group
  • A represents a member selected from the group con sisting of a methyl and an ethyl group
  • Z and Z
  • ring selected from the group consisting of a benzothiazole nucleus, a benzoselenazole nucleus, a fi-naphthoselenazole nucleus, and a B-naphthothiazole nucleus;
  • R and R each represents a lower alkyl group
  • B represents a member selected from the group consisting of a lower alkyl and an aryl group
  • Z, and Z of formula (I) are nonmetallic atoms necessary to complete a member selected from the group consisting of a benzothiazole and a B-naphthothiazole nucleus.
  • A'of formula (I) is a'methyl group and Z of formula (II) is a sulfur atom.
  • the orthochromatic sensitizing dye is selected from the group consisting of a 2,2'-cyanine dye and a pseudo-type cyanine dye.
  • the silver halide photographic emulsion of claim v1 wherein the carbocyanine dye is selected from the group consisting of and the merocyanine dye is selected from the group 6 consi t ing of H I V ⁇ 102E933 21 22 10.
  • the silver halide photographic emulsion of claim and 7, wherein the orthochromatic sensitizing dye is selected from the group consisting of N CHCHS :l S zHa O ⁇ N -S V7 7 C H;CH CHI I 10 13.
  • the silver halide photographic material compris- 12.
  • the silver halide photographic emulsion comprisin a l r ntai i th ilv r h lid l i f ing a supersensitizing combination of claim 1 V. V.V. mm 7 16.
  • the silver halide photographic emulsion of claim 5 s 1, wherein the mol ratio of said carbocyanine dye to said merocyanine dye ranges from 9:1 to l:9.' I 17.
  • each of said cyanine and merocyanine dye LL is present in an amount of l X l()' to I X l0 mol pcr nmsommcnma mol of Silven (HDaSOa'

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (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)
US00184604A 1970-09-28 1971-09-28 Spectrally sensitized silver halide photographic emulsion Expired - Lifetime US3769026A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP45084532A JPS4842500B1 (enrdf_load_stackoverflow) 1970-09-28 1970-09-28

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US (1) US3769026A (enrdf_load_stackoverflow)
JP (1) JPS4842500B1 (enrdf_load_stackoverflow)
CA (1) CA988771A (enrdf_load_stackoverflow)
DE (1) DE2148425B2 (enrdf_load_stackoverflow)
FR (1) FR2108036B1 (enrdf_load_stackoverflow)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030219685A1 (en) * 2002-03-13 2003-11-27 Agfa-Gevaert Method for preparation of a photothermographic material with increased photosensitivity
EP1750173A1 (en) 2005-08-04 2007-02-07 Fuji Photo Film Co., Ltd. Silver halide photosensitive material and packaged body containing the same

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS60119483U (ja) * 1984-01-23 1985-08-12 高山　彬弘 遊戯具

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2430558A (en) * 1945-10-26 1947-11-11 Eastman Kodak Co Photographic emulsion sensitized with combination of merocyanine dye and a monomethinecyanine, a trimethinecyanine, a dimethinehemicyanine, or a styryl dye
DE1019418B (de) * 1954-01-21 1957-11-14 Hoechst Ag Verfahren zur Herstellung von Sensibilisierungsfarbstoffen

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2430558A (en) * 1945-10-26 1947-11-11 Eastman Kodak Co Photographic emulsion sensitized with combination of merocyanine dye and a monomethinecyanine, a trimethinecyanine, a dimethinehemicyanine, or a styryl dye
DE1019418B (de) * 1954-01-21 1957-11-14 Hoechst Ag Verfahren zur Herstellung von Sensibilisierungsfarbstoffen

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030219685A1 (en) * 2002-03-13 2003-11-27 Agfa-Gevaert Method for preparation of a photothermographic material with increased photosensitivity
US7067243B2 (en) * 2002-03-13 2006-06-27 Agfa Gevaert Method for preparation of a photothermographic material with increased photosensitivity
EP1750173A1 (en) 2005-08-04 2007-02-07 Fuji Photo Film Co., Ltd. Silver halide photosensitive material and packaged body containing the same

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Publication number Publication date
DE2148425B2 (de) 1973-10-18
CA988771A (en) 1976-05-11
DE2148425A1 (de) 1972-07-20
DE2148425C3 (enrdf_load_stackoverflow) 1974-05-16
FR2108036A1 (enrdf_load_stackoverflow) 1972-05-12
FR2108036B1 (enrdf_load_stackoverflow) 1973-05-11
JPS4842500B1 (enrdf_load_stackoverflow) 1973-12-13

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