US3679428A - Spectrally sensitized photographic emulsions - Google Patents

Spectrally sensitized photographic emulsions Download PDF

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Publication number
US3679428A
US3679428A US57607A US3679428DA US3679428A US 3679428 A US3679428 A US 3679428A US 57607 A US57607 A US 57607A US 3679428D A US3679428D A US 3679428DA US 3679428 A US3679428 A US 3679428A
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United States
Prior art keywords
alkyl group
group
substituted
alkyl
complete
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Expired - Lifetime
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US57607A
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English (en)
Inventor
Keisuke Shiba
Motohiko Tsubota
Akira Sato
Tadashi Ikeda
Akira Ogawa
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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
    • 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

  • R is an alkyl group having from l to 4 carbon atoms
  • R3 and R4 which may be the same or different, each represents an alkyl group, an allyl group and an alkyl group substituted by hydroxy, alkoxy, carboxy, sulfo or mixtures thereof
  • Z3 and Z4, which may be the same or dilerent each represents a non-metallic atomic group necessary to complete a benzothiazole or a benzoselenazole nucleus, which may be substituted by halogen, phenyl, alkoxyphenyl, hydroxyphenyl, carboxyphenyl, an alkyl hafving from l to 4 carbon atoms, hydroxyl, alkoxy, carboxyl, carboxylic acid ester, carbamoyl or alkyl carbamoyl groups;
  • X2 is an acid anion and m is 1 or 2.
  • This invention relates to a spectrally sensitized silver halide photographic emulsion and more particularly, it is concerned with a high sensitivity silver halide photographic emulsion which is supersensitized, by the use of a combination of at least two sensitizing dyes over the absorption light wavelength region of each of the sensitizing dyes.
  • the spectral sensitization over the visible region is required for light-sensitive materials for photography in general, but having a high spectral sensitivity up to very long wavelengths is not always preferred from the viewpoint of tone reproduction.
  • Two or more sensitizing dyes are generally used in combination in order to obtain the most suitable distribution of spectral sensitivity.
  • the spectral sensitivity obtained in the case of using two or more sensitizing dyes in combination to regulate the spectral sensitivity distribution is often lower than in the case of using each of them individually.
  • the spectral sensitizing action is alfected not only by the chemical structure of the sensitizing dye but also by the properties of the silver halide emulsion employed, for example, the crystal habit of the silver halide line crystals, the particle size, the halogen composition, the hydrogen ion concentration and the silver ion concentration.
  • additives present in the emulsion such as, for example, inhibitors, stabilizers, sensitizers, hardeners, binders, precipitators, plasticizers, color formers and photographic dyes, have many influences thereupon, many of them acting so as to weaken the special sensitizing action.
  • the spectral sensitizing action obtained by adding one sensitizing dye is superadditively strengthened by also adding therewith another sensitizing dye or organic compound, in particular, an aromatic compound.
  • Another sensitizing dye or organic compound in particular, an aromatic compound.
  • the action of this type is known as supersensitization.
  • the use of a cyanine dye alone scarcely gives a maximum sensitivity over relatively long wavelengths, such as 625 mm. to 640 mm.
  • It is therefore an object of the present invention to nd the spectral sensitization capable of raising the spectral sensitivity of a photographic light-sensitive material, in particular, to a wavelength region of 625 to 640 mm.
  • Such a technique is very important for improving the productivity in making photographic light-sensitive materials.
  • R represents a hydrogen atom or a lower alkyl group, such as methyl or ethyl
  • R1 and R2 which may be the same or different, are selected from groups of the alkyl series, such as alkyl .groups (e.g., methyl, ethyl and propyl), allyl groups and substituted alkyl groups (e.g.,
  • R1 and R2 being a substituted alkyl group of the type indicated;
  • Z1 represents a non-metallic atomic group necessary to complete a heterocyclc nucleus of the naphthothiazole series (e.g., a-naphthothiazole, -naphthothiazole, 5methoxy naphthothiazole, S-ethoxy--naphthothiazole, 8-methoxya-naphthothiazole, 7 methoxy a naphthothiazole), the naphthoselenazole series (e.g., a-naphthoselenazole or naplithoselenazole), or the naphthox
  • R5 represents a lower alkyl group, such as ethyl or butyl
  • R3 and R4, which may be the same or dilerent each represents groups of the alkyl series, such as alkyl groups (e.g., methyl, ethyl and butyl), allyl groups and substituted alkyl groups (e.g., Z-,hydroxyethyL Z-methoxyethyl, carboxymethyl, 3-carboxypropyl, 4-carboxybutyl, 3- sulfopropyl, 4-su1fobutyl, 3-sulfoisobutyl, 2-(3-sulfopropoxy)ethyl and 2hydroxy3sulfopropyl);
  • Z3 and Z4, which may be the same ordiiferent each represents a non-metallic atomic group necessary to complete a benzothiazole or a benzoselenazole nucleus which may be substituted by a group capable of promoting the alky
  • the gure represents spectrograms of samples containing a dye of Formula I, a dye of Formula II and a combination thereof, respectively.
  • the sensitizing dye represented by Formula I the nitrogen atom in the cyanine dye nuclei consisting of the naphthothiazole, naphthoselenamle, naphthoxazole or naphthoimidazole nucleus is substituted by at least one substituted Ialkyl group as described above, and that the cyanine dye represented by Formula II is liable to form a relatively strong J-aggregate.
  • the supersensitizing action over the whole wavelength region which the dyes absorb is obtained and the spectral sensitivity distribution is regulated relatively optional by the use of, in combination, the sensitizing dye characterized by the chemical structure of Formula I and the cyanine dye represented by Formula II in suitable amounts.
  • the spectral sensitivity within a wavelength region of 625 mm. to 640 mm. can be raised.
  • a further feature of the presentrinvention consists in the advantage that theV supersensitization given by the sensitizing dye of Formula I'serves to markedly improve the stability and reproducivity of the spectral sensitivity obtained.
  • the sensitizing dyes of the present invention are dissolved in .an aqueous solution or in a water-soluble organic solvent such as methanol, ethanol, acetone, methyl Cellosolve or pyridine and then added to a silver halide emulsion separately or as a mixture thereof.
  • lStirrng by ultrasonic Waves may be applied during the dissolving of the' sensitizing dyes.
  • the amount of addition, order of addition land addition procedure may be varied with the production process of the light-sensitive material.
  • the amount of Vaddition of the sensitizing dyes is preferably from 1 10 mole to 5 X10-4 mole per mole of silver halide, the molar n is coated onto a suitable support, for examle, a cellulose derivative lm, a polyethylene terephthalate lm, a polycarbonate film, baryta paper, resin coated paper, synthetic paper, resin laminated paper or a glass sheet.
  • sensitizing dyes -according tothe present invention are given below, these compounds being merely illustrative 'and not limiting in nature.
  • Sensitizing dyes represented by Formulae I and II were separately dissolved in methanol to give a predetemined concentration (shown in Table I).
  • a predetermined amount (shown in Table I) of each of the sensitizing dye H Co 0 a l/ N OCH solutions was added to the emulsion with agitation. After H minute, 7 ml. of each emulsion was applied to a glass Ems o i 5 sheet of cabinet size and dried to obtain a sample.
  • the sensitizing dyes represented by Formulae I and II Metol g 2 may be synthesized in any known manner.
  • Anhydrous sodium sulte g 100 dyes IA, IB, IIA, IIB, IIC, IID and IIE can be readily 4Hydroquinone g-- 5 synthesized by the methods disclosed in U.S. Pat. No. Borax g y 2 2,503,776, German Pats. Nos. 929,080 and 1,072,765 and Water to make 1000 ml.
  • curve 1 is a spectrogram of the sample obtained by adding 20 ml. of sensitizing dye (IA) of No. 1 in Table I;
  • curve 2 is va spectrogram of the sample obtained by adding 10 ml. of sensitizing dye (IIA) of No. 2 in Table I; and curve 3 is a spectrogram of the sample obtained by adding a mixture of 20 ml. of dye (IA) and 10 ml. of dye (IIA) according to the present invention.
  • R is a hydrogen atom or an alkyl group having from 1 to 4 carbon atoms
  • Z1 is a Lnon-metallic ⁇ atomic group necessary to ⁇ complete a heterocyclic nucleus of the naphthothiazole, naphthoselenazole or naphthoxazole series
  • Z2 is a non-metallic group necessary to complete a nucleus of the napthoselenazole, naphthoxazole, naphthoimidazole or benzimidazole series
  • X1 is an acid anion and n is 1 or 2, and at least one sensitizing dye represented by the following Formula II:
  • R is a hydrogen atom or an alkyl group having from 1 to 4 carbon atoms
  • R1 and R1 which may be the same or diterent, each represents analkyl group, an allyl group and an alkyl group substituted by hydroxy, carboxy, ⁇ sulfo or mixtures thereof, at least one of R1 and R2 being a substituted alkyl group
  • Z1 is a non-metallic atomic group necessary to complete a heterocyclic nucleus of the naphthothiazole, or naphthoselenazole series
  • Z1 is a non-metallic group necessary to complete a nucleus of the naphthoselenazole, naphthoimidazole or benzimidazole series
  • X1- is an :acid anion and n is 1 or 2, and at least one sensitizing dye represented by the following Formula II:
  • R5 is an alkyl group having from l to 4 carbon atoms
  • R3 and R1 each represents a member selected from the group consisting of sulfo alkyl and hydroxyalkyl groups
  • Z3 and Z4 which may be the same or different, each represents a non-metallic atomic group necessary to complete a benzothiazole or a benzoselenazole nucleus, which may be substituted by halogen, phenyl, Aalkoxyphenyl, hydroxyphenyl, carboxyphenyl, an alkyl having from l to 4 carbon atoms, hydroxyl, alkoxy, carboxyl, carboxylic acid ester, carbamoyl or alkyl carbamoyl groups;
  • X1 is an acid anion and m is 1 or 2.

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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)
  • Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
  • Plural Heterocyclic Compounds (AREA)
US57607A 1969-07-23 1970-07-23 Spectrally sensitized photographic emulsions Expired - Lifetime US3679428A (en)

Applications Claiming Priority (1)

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JP44058180A JPS4825653B1 (da) 1969-07-23 1969-07-23

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US (1) US3679428A (da)
JP (1) JPS4825653B1 (da)
BE (1) BE753807A (da)
CA (1) CA971813A (da)
DE (1) DE2036641C3 (da)
FR (1) FR2053101B1 (da)
GB (1) GB1321427A (da)

Cited By (28)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3770449A (en) * 1970-09-24 1973-11-06 Fuji Photo Film Co Ltd Spectrally sensitized silver halide photographic emulsion
US3808008A (en) * 1970-09-10 1974-04-30 Fuji Photo Film Co Ltd Spectrally sensitized silver halide photographic emulsion
US3907575A (en) * 1972-10-27 1975-09-23 Fuji Photo Film Co Ltd Spectrally sensitized silver halide photographic emulsion
US3922170A (en) * 1972-07-20 1975-11-25 Fuji Photo Film Co Ltd Spectrally sensitized silver halide photographic emulsion
US3967967A (en) * 1973-12-06 1976-07-06 Fuji Photo Film Co., Ltd. Spectrally sensitized silver halide photographic emulsion
US3977882A (en) * 1972-07-20 1976-08-31 Fuji Photo Film Co., Ltd. Spectrally sensitized silver halide photographic emulsion
DE2615971A1 (de) * 1975-04-14 1976-10-28 Konishiroku Photo Ind Lichtempfindliches farbphotographisches silberhalogenid-aufzeichnungsmaterial
US4028115A (en) * 1975-08-26 1977-06-07 Fuji Photo Film Co., Ltd. Silver halide photographic emulsion sensitized to red with four carbocyanine dyes
DE2711267A1 (de) * 1976-03-15 1977-09-22 Fuji Photo Film Co Ltd Photographische silberhalogenidemulsion
US4277353A (en) * 1980-01-07 1981-07-07 Exxon Research & Engineering Co. Oil-soluble substituted mono and bicyclic oxazolidines, their preparation and use as additives for functional fluids
US4282108A (en) * 1980-01-07 1981-08-04 Exxon Research & Engineering Co. Oil-soluble spiro-[cycloalkane-oxazolidines], their preparation and use as additives and chelating agents for functional fluids
US4369118A (en) * 1980-12-29 1983-01-18 Exxon Research & Engineering Co. Process of inhibiting haze in lubricating oil compositions
EP0143424A2 (en) 1983-11-25 1985-06-05 Fuji Photo Film Co., Ltd. Heat-developable light-sensitive materials
EP0147854A2 (en) 1983-12-29 1985-07-10 Fuji Photo Film Co., Ltd. Silver halide photographic light-sensitive materials
EP0209118A2 (en) 1985-07-17 1987-01-21 Konica Corporation Silver halide photographic material
EP0218266A2 (en) 1984-05-02 1987-04-15 Fuji Photo Film Co., Ltd. Silver halide color photographic light-sensitive material
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
EP0256537A2 (en) 1986-08-15 1988-02-24 Fuji Photo Film Co., Ltd. Color print and a method for producing the same
EP0562476A1 (en) 1992-03-19 1993-09-29 Fuji Photo Film Co., Ltd. A silver halide photographic emulsion and a photographic light-sensitive material
EP0563708A1 (en) 1992-03-19 1993-10-06 Fuji Photo Film Co., Ltd. Silver halide photographic emulsion and light-sensitive material using the same
WO1996013755A1 (en) 1994-10-26 1996-05-09 Eastman Kodak Company Photographic emulsions of enhanced sensitivity
US5582957A (en) * 1995-03-28 1996-12-10 Eastman Kodak Company Resuspension optimization for photographic nanosuspensions
EP0777153A1 (en) 1995-11-30 1997-06-04 Fuji Photo Film Co., Ltd. Silver halide color photographic light-sensitive material
EP1624337A2 (en) 2004-08-02 2006-02-08 Fuji Photo Film Co., Ltd. Silver halide holographic sensitive material and system for taking holographic images by using the same
EP1691237A2 (en) 2005-02-15 2006-08-16 Fuji Photo Film Co., Ltd. Holographic recording material and holographic recording method
EP1750173A1 (en) 2005-08-04 2007-02-07 Fuji Photo Film Co., Ltd. Silver halide photosensitive material and packaged body containing the same
EP1914594A2 (en) 2004-01-30 2008-04-23 FUJIFILM Corporation Silver halide color photographic light-sensitive material and color image-forming method

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5228659B2 (da) * 1973-04-23 1977-07-28

Cited By (29)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3808008A (en) * 1970-09-10 1974-04-30 Fuji Photo Film Co Ltd Spectrally sensitized silver halide photographic emulsion
US3770449A (en) * 1970-09-24 1973-11-06 Fuji Photo Film Co Ltd Spectrally sensitized silver halide photographic emulsion
US3922170A (en) * 1972-07-20 1975-11-25 Fuji Photo Film Co Ltd Spectrally sensitized silver halide photographic emulsion
US3977882A (en) * 1972-07-20 1976-08-31 Fuji Photo Film Co., Ltd. Spectrally sensitized silver halide photographic emulsion
US3907575A (en) * 1972-10-27 1975-09-23 Fuji Photo Film Co Ltd Spectrally sensitized silver halide photographic emulsion
US3967967A (en) * 1973-12-06 1976-07-06 Fuji Photo Film Co., Ltd. Spectrally sensitized silver halide photographic emulsion
DE2615971A1 (de) * 1975-04-14 1976-10-28 Konishiroku Photo Ind Lichtempfindliches farbphotographisches silberhalogenid-aufzeichnungsmaterial
US4028115A (en) * 1975-08-26 1977-06-07 Fuji Photo Film Co., Ltd. Silver halide photographic emulsion sensitized to red with four carbocyanine dyes
DE2711267A1 (de) * 1976-03-15 1977-09-22 Fuji Photo Film Co Ltd Photographische silberhalogenidemulsion
US4152163A (en) * 1976-03-15 1979-05-01 Fuji Photo Film Co., Ltd. Silver halide photographic emulsion containing cyanine and hemicyanine sensitizing dyes
US4277353A (en) * 1980-01-07 1981-07-07 Exxon Research & Engineering Co. Oil-soluble substituted mono and bicyclic oxazolidines, their preparation and use as additives for functional fluids
US4282108A (en) * 1980-01-07 1981-08-04 Exxon Research & Engineering Co. Oil-soluble spiro-[cycloalkane-oxazolidines], their preparation and use as additives and chelating agents for functional fluids
US4369118A (en) * 1980-12-29 1983-01-18 Exxon Research & Engineering Co. Process of inhibiting haze in lubricating oil compositions
EP0143424A2 (en) 1983-11-25 1985-06-05 Fuji Photo Film Co., Ltd. Heat-developable light-sensitive materials
EP0147854A2 (en) 1983-12-29 1985-07-10 Fuji Photo Film Co., Ltd. Silver halide photographic light-sensitive materials
EP0218266A2 (en) 1984-05-02 1987-04-15 Fuji Photo Film Co., Ltd. Silver halide color photographic light-sensitive material
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
EP0209118A2 (en) 1985-07-17 1987-01-21 Konica Corporation Silver halide photographic material
EP0239363A2 (en) 1986-03-25 1987-09-30 Konica Corporation Light-sensitive silver halide photographic material feasible for high speed processing
EP0256537A2 (en) 1986-08-15 1988-02-24 Fuji Photo Film Co., Ltd. Color print and a method for producing the same
EP0563708A1 (en) 1992-03-19 1993-10-06 Fuji Photo Film Co., Ltd. Silver halide photographic emulsion and light-sensitive material using the same
EP0562476A1 (en) 1992-03-19 1993-09-29 Fuji Photo Film Co., Ltd. A silver halide photographic emulsion and a photographic light-sensitive material
WO1996013755A1 (en) 1994-10-26 1996-05-09 Eastman Kodak Company Photographic emulsions of enhanced sensitivity
US5582957A (en) * 1995-03-28 1996-12-10 Eastman Kodak Company Resuspension optimization for photographic nanosuspensions
EP0777153A1 (en) 1995-11-30 1997-06-04 Fuji Photo Film Co., Ltd. Silver halide color photographic light-sensitive material
EP1914594A2 (en) 2004-01-30 2008-04-23 FUJIFILM Corporation Silver halide color photographic light-sensitive material and color image-forming method
EP1624337A2 (en) 2004-08-02 2006-02-08 Fuji Photo Film Co., Ltd. Silver halide holographic sensitive material and system for taking holographic images by using the same
EP1691237A2 (en) 2005-02-15 2006-08-16 Fuji Photo Film Co., Ltd. Holographic recording material and holographic recording method
EP1750173A1 (en) 2005-08-04 2007-02-07 Fuji Photo Film Co., Ltd. Silver halide photosensitive material and packaged body containing the same

Also Published As

Publication number Publication date
FR2053101B1 (da) 1973-05-25
DE2036641C3 (de) 1981-02-12
CA971813A (en) 1975-07-29
GB1321427A (en) 1973-06-27
JPS4825653B1 (da) 1973-07-31
DE2036641A1 (de) 1972-01-27
BE753807A (fr) 1970-12-31
FR2053101A1 (da) 1971-04-16
DE2036641B2 (de) 1974-01-10

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