US3632349A - Silver halide supersensitized photographic emulsion - Google Patents

Silver halide supersensitized photographic emulsion Download PDF

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Publication number
US3632349A
US3632349A US27035A US3632349DA US3632349A US 3632349 A US3632349 A US 3632349A US 27035 A US27035 A US 27035A US 3632349D A US3632349D A US 3632349DA US 3632349 A US3632349 A US 3632349A
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United States
Prior art keywords
group
silver halide
nucleus
emulsion
sensitizing
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Expired - Lifetime
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US27035A
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English (en)
Inventor
Keisuke Shiba
Akira Sato
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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
    • C09B23/0008—Methine or polymethine dyes, e.g. cyanine dyes substituted on the polymethine chain
    • 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

  • A is a thienyl group, a furyl group or a thienyl group substituted by a halogen atom, an alkyl group or an alkylcarboxyl group
  • R, and R are individually selected from the group consisting of an alkyl group, an aryl group and an alkyl group substituted by a hydroxyl group, an alkoxyl group, a carboxyl group, a sulfo group, a carboxyalkoxyl group or a sulfoalkoxyl group; at least one of R and R being a sulfosubstituted alkyl group
  • Z is an atomic group necessary to complete a naphthothiazole nucleus or a naphthoselenazole nucleus, and Z is an atomic group necessary to complete a naphthothiazole nucleus, a naphthoselenazole nucleus, a benzothiazole nucleus or
  • This invention relates to a spectrally sensitized silver halide photographic emulsion and more particularly, to an emulsion whose spectral sensitivity in the red region is raised by the use of a combination of at least two kinds of sensitizing dyes.
  • spectral sensitization In order to extend the light-sensitive wavelength region of a light-sensitive material further to the long wavelength side, one adds some sensitizing dye to the silver halide emulsion. This is termed spectral sensitization.
  • the spectral sensitization effect depends upon the chemical structure of the sensitizing dye employed, its state in emulsion and various properties of the emulsion such as the crystal habit of the silver halide, the halogen composition, the silver ion concentration and the hydrogen ion concentration. It is also affected by fog inhibitors coexistent in the emulsion, stabilizers, flocculating agents, hardeners, binders and plasticizers.
  • two or more sensitizing dyes are used in order to sensitize to a predetermined wavelength region according to their use. In many cases, however, the sensitization produced by the use of two or more sensitizing dyes is less than the sum of the sensitizations of the components. This is known as antisensitization. On the other hand, sometimes the use of two or more sensitizing dyes in special combination gives a sensitization greater than the sum of the individual effects. This is known as supersensitization.
  • a severe selection is required for such a combination of two or more sensitizing dyes having a supersensitizing action. Since even a slight difference in chemical structure has a large effect on the supersensitization, it is a view common to all photographic engineers that a combination of sensitizing dyes showing supersensitizing action cannot readily be expected from the chemical structure only of the dyes. It has been very difficult to find a combination of two or more sensitizing dyes showing a supersensitizing action.
  • a color sensitive material is ordinarily composed of at least three light-sensitive emulsion layers: a blue-sensitive emulsion layer, a green-sensitive emulsion layer and a red-sensitive emulsion layer.
  • the distribution of spectral sensitivity of each emulsion layer is a principal factor in determining the color reproduction characteristics of the light-sensitive material.
  • the spectral light-sensitive wavelength regions of the blue, green and red-sensitive emulsion layers, respectively must be separated sufficiently.
  • the red-sensitive emulsion must have a high sensitivity in the red region and a low sensitivity in the green region, because a dye sensitizing throughout the whole visible region is generally used therefor.
  • the maximum sensitizing wavelength should be within a range of from 640 to 650 my. and the sensitivity of longer wavelengths should be up to at least 690 mp. to which the visible sensitivity extends.
  • the sensitizing dye used in the red-sensitive emulsion layer must be prevented from diffusing into another adjacent emulsion layer and sensitizing the same.
  • care should be taken to avoid the lowering of a high spectral sensitivity with the passage of time and while being allowed to stand in a state of liquid emulsion.
  • R is an alkyl group having one to four carbon atoms, such as methyl and ethyl groups
  • R and R are individually an alkyl group such as a methyl, ethyl or propyl group, an allyl group or a substituted alkyl group such as 2-hydroxyethyl, 2- methoxyethyl, carboxymethyl, 2-carboxyethyl, 3-carboxypropyl, 4-carboxybutyl, 3-sulfopropyl, 4-sulfobutyl, 3-sulfoisobutyl, 2-carboethoxyethyl, 2-(3-sulfopropoxy)ethyl, 2[2- (3-sulfopropoxy)]ethoxyethyl and 2-hydroxy-l-sulfopropyl groups
  • Z, and Z are the same or different atomic groups necessary for forming a benzothiazole or benzoselenazole nucleus
  • n is l
  • A is a thienyl group, a furyl group or a substituted thienyl group such as 2,5-dichloro-3-thienyl, 5-methyl-2-thienyl or 2-methyl-5-carboxy-3-thienyl;
  • R and R are individually an alkyl group, an allyl group or an alkyl group substituted by a group selected from the group consisting of hydroxy, alkoxy, carboxy, sulfo, carboxy alkoxy and sulfoalkoxy, at least one of R and R being a substituted alkyl group containing a sulfo group;
  • 2 is an atomic group necessary for forming a naphthothiazole or a naphthoselenazole nucleus
  • Z is an atomic group necessary for forming a naphthothiazole, naphthoselenazole, benzothiazole or benzoselenazole nucleus.
  • FIGURE shows the sensitization effects of employing a dye of formula I alone, a dye of formula II alone and a combination of dyes of formulas I and II, respectively.
  • At least one of the two heterocyclic nuclei of the cyanine dye is a naphthoselenazole or a naphthothiazole nucleus
  • at least one sulfo-substituted alkyl group on the resonating terminal nitrogen atom in the heterocyclic nucleus there is either an aryl group, a thienyl group, a furyl group or a substituted thienyl group in the meso position.
  • the sensitizing dye represented by general formula II shows a very weak spectral (ID) 8 S sensitizing action only when used alone, but a remarkably high (13H; spectral sensitivity when used together with the sensitizing dye represented by general formula l.
  • the present invention is thus different in this 1:1 N respect from that described in Japanese Pat. Publication No. ($39105 5 ((iJHMOH 4933/ l 968. in accordance with the present invention, further- (HA) more, the particular dye employed is prevented from diffusing 15 S S S into an adjacent emulsion layer whereby the red sensitivity is not given, and accordingly the color reproduction is improved.
  • the sensitizing dye represented by general formula I is a carbocyanine dye whose J-band appears easily.
  • the sensitizing dyes used in the present invention are added to the silver halide emulsion separately or in admixture in the form of a solution in water or in a water-soluble organic solvent such as methanol, ethanol, acetone or pyridine.
  • the amount added and the order of addition to the silver halide (II C) emulsion may be varied as desired.
  • the amount of Se 3 the sensitizing dye added is preferably from 1X 10' to lXlO ⁇ Zl mole per mole of silver halide and the weight ratio of sensitiz- J;
  • sensitizing dye ll to sensitizing dye l is from l00:l to 1:10, preferably Cl from 20:] to lzl. rtz N & Hg) 03- Any of the following may be used as the silver halide emul- 4O tiling sion in the present invention: silver chloride, silver chlorobromide, silver bromide and silver iodobromide.
  • the sensitizing dyes of the present invention may be incorporated into the (H D) silver halide emuision together with a fog inhibitor, a stabil- 45 izer, a chemical sensitizer, a hardener, a coupler, a plasticizer, 8 Se a photographic dye and a coating agent. 2
  • sensitizing dyes used in the present inven- Clix may be synthesized by any known method, for example, that disclosed in U.S. Pat. No. 2,503,776 or German Pat. No. 929,080.
  • the sensitizing dye of general formula Il may be synthesized by any known method, for example, that disclosed in U.S. Pat. No. 2,060,383, U.S. Pat. No. 2,756,227 or U.S. Pat. No. 2,503,776.
  • EXAMPLE 1 Five hundred grams of a silver iodobromide gelatin emulsion (silver iodobromide content 4.0 mole percent) prepared in a conventional manner was taken and rendered molten in a thermostat at 40 C. As shown in table 1, a predetermined amount of the sensitizing dye represented by general formula l and a predetermined amount of the sensitizing dye represented by general formula II were mixed in solution and added thereto with agitation.
  • the emulsion was allowed to stand in the thermostat at 37 C. while stirring for 10 minutes, then uniformly coated onto a glass sheet support in a proportion of 7.0 ml. per cabinet size, set and dried to obtain a light-sensitive sample.
  • the sample was cut and subjected to light-wedge exposure using a red light from a light source having a color temperature of 5,400 K. obtained by adapting a Davis-Gibson conversion filter to a light source having a color temperature of 2,666 K. and using a K-7 filter (made by Fuji Photo Film Co, Ltd.) permitting wavelengths longer than about 600 mg.
  • the exposed sensitive sample was developed at C. for 10 minutes with a developer having the following composition, stopped, fixed and washed with water to obtain a strip. Measurement of the density thereof was carried out by the use of an S-type densitometer made by Fuji Photo Film Co., Ltd. to determine the relative red sensitivity. The optical density point at which the sensitivity was determined was a point of (fog density +0.10). The results are shown in table 1.
  • sensitizing Amount used sensitizing Amount used, sensitizing Amount used, Rel. red ASE dye ml. (mole cone.) dye ml. (mole cone.) sensitivity Fog mu. Note 10 (1x10 0.11 650 20 0.13 650 Curve (1) in figure.
  • Sensltizln (mole tizln (mole sensilowed by a series of developing processings to obtain a spec dye 8 com.) dye 8 cont) mm, Fog xsmun trogram.
  • Curve 1 is a curve obtained by using 20 ml. of a E) 20 (5)00) 85 0410 20 40 100 0.10 solution of (I A) having a mole concentration of 5X10 curve 105 0.10 2 is a curve obtained by using 1 ml.
  • curve 3 is a curve ob- 0: 15 (ii iii tained byjointly using (l A) and (ll B).
  • sens tizing dye A w is l i d i shown Fl was used for compaflson B laddmo" to l.
  • R is an alkyl group having from one to four carbon atoms
  • R and R are individually selected from the group consisting of an alkyl group, an allyl group and an alkyl group substituted by a hydroxyl group, an alkoxyl group, a carboxyl group, a sulfo group, a carboxyalkoxyl group, or a sulfoalkoxyl group
  • A is a thienyl group, a fury] group or a thienyl group coupler B substituted by a halogen atom, an alkyl group or an alkyl car- OH boxyl group;
  • R and R are individually selected from the A group consisting of an alkyl group, an aryl group and an alkyl CONHCnHz-r group substituted by a hydroxyl group, an alkoxyl group, a
  • sensitizing dyes represented by formulas l and ll water to 1,000 ml. are:
  • sensitizing dyes represented by formulas l and ll are: 5
  • sensitizing dyes represented by formulas l and ll are:
  • a color sensitive material comprising a support having thereon at least one layer containing the photographic silver halide emulsion as in claim 1.

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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)
  • Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
  • Nitrogen- Or Sulfur-Containing Heterocyclic Ring Compounds With Rings Of Six Or More Members (AREA)
  • Plural Heterocyclic Compounds (AREA)
US27035A 1969-04-09 1970-04-09 Silver halide supersensitized photographic emulsion Expired - Lifetime US3632349A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP44027421A JPS4824540B1 (de) 1969-04-09 1969-04-09

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US (1) US3632349A (de)
JP (1) JPS4824540B1 (de)
DE (1) DE2017053C3 (de)
FR (1) FR2043121A5 (de)
GB (1) GB1293125A (de)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3836370A (en) * 1971-03-09 1974-09-17 Minnesota Mining & Mfg Merocyaninic dyes and their use in silver halides photographic emulsions containing the same
US4028115A (en) * 1975-08-26 1977-06-07 Fuji Photo Film Co., Ltd. Silver halide photographic emulsion sensitized to red with four carbocyanine dyes
US4135933A (en) * 1975-06-20 1979-01-23 Fuji Photo Film Co., Ltd. Silver halide photographic emulsion
US5418126A (en) * 1992-11-19 1995-05-23 Eastman Kodak Company Furan or pyrrole substituted dye compounds and silver halide photographic elements containing such dyes
US5601963A (en) * 1996-06-28 1997-02-11 Polaroid Corporation Silver halide emulsions
US6066443A (en) * 1994-05-18 2000-05-23 Eastman Kodak Company Blue sensitizing dyes with heterocyclic substituents
EP1750173A1 (de) 2005-08-04 2007-02-07 Fuji Photo Film Co., Ltd. Lichtempfindliches Silberhalogenidmaterial und dieses enthaltender verpackter Gegenstand
CN111100627A (zh) * 2019-12-20 2020-05-05 中国科学院化学研究所 荧光探针及其应用

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CH660595A5 (de) * 1984-09-27 1987-05-15 Ciba Geigy Ag Cyaninfarbstoffe, verfahren zu ihrer herstellung und ihre verwendung als sensibilisatoren in photographischen materialien.

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2704720A (en) * 1954-07-20 1955-03-22 Eastman Kodak Co Photographic supersensitizing combinations comprising thienylcarbocyanine dyes
US3432303A (en) * 1965-05-24 1969-03-11 Eastman Kodak Co Silver halide emulsions containing dye combinations for supersensitization

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2704720A (en) * 1954-07-20 1955-03-22 Eastman Kodak Co Photographic supersensitizing combinations comprising thienylcarbocyanine dyes
US3432303A (en) * 1965-05-24 1969-03-11 Eastman Kodak Co Silver halide emulsions containing dye combinations for supersensitization

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3836370A (en) * 1971-03-09 1974-09-17 Minnesota Mining & Mfg Merocyaninic dyes and their use in silver halides photographic emulsions containing the same
US4135933A (en) * 1975-06-20 1979-01-23 Fuji Photo Film Co., Ltd. Silver halide photographic emulsion
US4028115A (en) * 1975-08-26 1977-06-07 Fuji Photo Film Co., Ltd. Silver halide photographic emulsion sensitized to red with four carbocyanine dyes
US5418126A (en) * 1992-11-19 1995-05-23 Eastman Kodak Company Furan or pyrrole substituted dye compounds and silver halide photographic elements containing such dyes
US6066443A (en) * 1994-05-18 2000-05-23 Eastman Kodak Company Blue sensitizing dyes with heterocyclic substituents
US5601963A (en) * 1996-06-28 1997-02-11 Polaroid Corporation Silver halide emulsions
WO1998000756A1 (en) * 1996-06-28 1998-01-08 Polaroid Corporation Silver halide emulsions
EP1750173A1 (de) 2005-08-04 2007-02-07 Fuji Photo Film Co., Ltd. Lichtempfindliches Silberhalogenidmaterial und dieses enthaltender verpackter Gegenstand
CN111100627A (zh) * 2019-12-20 2020-05-05 中国科学院化学研究所 荧光探针及其应用

Also Published As

Publication number Publication date
DE2017053B2 (de) 1973-10-04
GB1293125A (en) 1972-10-18
JPS4824540B1 (de) 1973-07-21
DE2017053C3 (de) 1974-05-09
FR2043121A5 (de) 1971-02-12
DE2017053A1 (de) 1970-10-29

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