US3635721A - Spectrally sensitized photographic silver halide emulsions - Google Patents

Spectrally sensitized photographic silver halide emulsions Download PDF

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Publication number
US3635721A
US3635721A US687469A US3635721DA US3635721A US 3635721 A US3635721 A US 3635721A US 687469 A US687469 A US 687469A US 3635721D A US3635721D A US 3635721DA US 3635721 A US3635721 A US 3635721A
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US
United States
Prior art keywords
group
silver halide
halide emulsion
member selected
emulsion
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
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US687469A
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English (en)
Inventor
Akiro Sato
Hiroshi Misu
Keisuke Shiba
Masanao Hinata
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Fujifilm Holdings Corp
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Fuji Photo Film Co Ltd
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Publication of US3635721A publication Critical patent/US3635721A/en
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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
    • 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
    • C09B23/0016—Methine or polymethine dyes, e.g. cyanine dyes substituted on the polymethine chain the substituent being a halogen atom
    • 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
    • C09B23/08—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups more than three >CH- groups, e.g. polycarbocyanines
    • C09B23/083—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups more than three >CH- groups, e.g. polycarbocyanines five >CH- groups

Definitions

  • SIPIECWALLW SIENMTHZIEIW PHOTOORAPHHC siwmi HALWE IEMFULEHUNS [72] Inventors: Alitiro Soto; lllliroslhi Misti; lifieisulte Shilm;
  • a photographic silver halide emulsion composition comprising a sensitizing dye shown by general formula (I) alkyl group; X represents an anion, n stands for 1 or 2; and m stands for l or 2, and a compound shown by general formula R3-Z( INHA-NH-I TZR3 V Y 14 R4 (ll) S 03M S 03M S 03M @CONH S aM wherein M represents a member selected from the group consisting of a hydrogen atom, an alkali metal, ammonium. and an amino group.
  • the sensitivity of a definite emulsion sensitized by a definite sen sitizing dye can be varied by changing the properties of the emulsion. For instance, the sensitivity of a silver halide emulsion can be increased by increasing the silver ion concentration or by reducing the hydrogen ion concentration or by a combination thereof.
  • the silver halide emulsion sensitized in such a way has the disadvantage that the preservability thereof is generally bad.
  • supersensitizing action that is, a phenomenon of increasing the sensitivity of a silver halide emulsion by incorporating in the emulsion a compound along with a sensitizing dye without changing the properties of the emulsion as mentioned above, e.g., without changing the silver ion concentration and the hydrogen ion concentration of the emulsion.
  • the compound which is used together with the sen sitizing dye is generally called a supersensitizer.
  • a mesosubstituted dicarbocyanine As the spectral sensitizer for a photographic silver halide emulsion, there are usually used dicarbocyanines. Among them, a mesosubstituted dicarbocyanine has a merit in that the formation of fog in a silver halide emulsion sensitized by it is very low as compared with the case of using mesounsubstituted dicarbocyanines. In some cases, however, the addition of the mesosubstituted dicarbocyanine to a silver halide emulsion is accompanied by a reduction in sensitivity. Particularly in the case of using a dicarbocyanine, the mesoposition of which has been substituted with a halogen, the sensitivity of the silver halide emulsion containing the dicarbocyanine is reduced markedly.
  • an object of the present invention is to provide a photographic silver halide emulsion in which a mesosub stituted carbocyanine and a specific supersensitizer, as mentioned below, have been incorporated to improve the sensitivity thereof and reduce the formation of fogs.
  • Another object of the present invention is to provide a photographic light-sensitive element having high sensitivity and low fog.
  • Y and Y each represents a nonmetallicatomic group necessary for forming a heterocyclic ring.
  • R and R each represents an alkyl group, such as, an ethyl group, a propyl group, and the like; a substituted alkyl group, such as, a 2-hydroxyethyl group, a Z-methoxyethyl group, a carboxymethyl group, a Zcarboxyethyl group, a 3- carboxypropyl group, a 4-carboxybutyl group, a 2-sulfoethyl group
  • R represents a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and the like; or an alkyl group such as a methyl group, an ethyl group, a'propyl group and the like;
  • X represents an anion;
  • n is l or 2; and
  • m is l (in the case of forming an intramolecular salt) or2;
  • R and R each represents a halogen atom, a hydroxyl group, an alkoxyl group, an aryloxyl group, an arylthio group, an aryl group, an amino group, an alkylamino group, an arylamino group, or an aralkylamino group; and
  • A represents a group selected from the following:
  • the compounds in which Z is 1I t l 1atis, the compounds hav' ing an S-triazine nucleus may be prepared by known methods.
  • those compounds wherein R and R are halogen atoms or various amino groups, or the compounds wherein R or R is bonded to the pyrimidine nucleus by an ether bond or a thioether bond may be prepared by procedures of the type shown in the following examples. 7
  • the addition amount of the mesosubstituted carbocyanine sensitizing dye used in the present invention is suitably from about 0.002 to 0.2 g. per one gram molecule of silver halide contained in the silver halide emulsion and the addition amount of the super-sensitizer having general formula (11) is suitably from about 0.05 to 10 g. per one gram of silver halide in the silver halide emulsion.
  • the suitable ratio of sensitizing dye (l) to compound (11) is from about 1:2 to 1:200.
  • Sensitizing dye (1) may be added to a silver halide emulsion by any method well known in this field.
  • Compound (11) may be added to a silver halide emulsion as a solution of the compound in an organic solvent, such as methanol or ethanol.
  • Sensitizing dye (l) and compound (11) are added to a silver halide emulsion prior to coating.
  • Sensitizing dye (1) may be added to a silver halide emulsion before or after the addition of com pound (11) or may be added together with the latter.
  • the silver halide emulsion of this invention various silver salts may be used such as silver chloride, silver bromide, silver iodide, silver iodobromide, silver chlorobromide, silver chloroiodobromide and the like.
  • the usual additives such as a chemical sensitizer, a hardening agent, an antifoggant, a wetting agent, a stabilizer, a plasticizer, a development accelerator, and an antibronzing agent.
  • the silver halide emulsion of this invention may contain a coupler capable of forming dye by color development such as a cyan coupler without affecting the merits of the addition of the compounds of this invention.
  • the photographic silver halide emulsion may be applied to a suitable support, such as a glass plate, a film of a cellulose derivative, a synthetic resin film, a baryta-coated paper and the like.
  • a suitable support such as a glass plate, a film of a cellulose derivative, a synthetic resin film, a baryta-coated paper and the like.
  • sensitizing dye Compound (11) Red (mm/gram mol of (mg/gram mol of sensi- Ag halide) Ag halide) tivity Fog [-8 (12) 100 0. 04 l-H (12; .l l-ili $300) 135 0. 04 l-X (l2 ll-ll 301)) 229 0. 04 l-i (u) 100 0. 04 l-l g1! ll-lH (300) [74 0. 04 l-[ il) I H1 (300) 27!) (l. ()4 l 4 (10). 100 0.04 1 10) ll-IH E300) lili 0. 04 l-4 10) ll-(l 300) 809 (l. 04 l-3 11) 100 0.
  • 04 I-7 (9) 11-11 (300) 347 0. 04 I-7 (9) 11-12 (300) 275 0. 04 I-7 9) 11-13 (300) 372 0. 04 I-7 (9) 11-14 (300) 288 0. 04 I-7 E9) 11-15 (300) 601 0. 04 I-7 9) II16 300) 316 0. 04 1-7 (9) 11-17 (300) 275 0. 04 I-7 59) 11-20 (300) 178 0. 04 I-7 9) 1I-21 (300) 191 0. 04 I-6 (9) 100 0. 05 Hi (9) I16 (300) 130 0. 04 [-2 E13) 100 0. 06 1-2 13) 11-6 (300) 316 0. 04 I-2 213) 11-22 (300) 204 0. 04 I-S 12) 100 0. 04 I-8 (12) 11-23 (300) 204 0. 04 I-7 (9) 100 0. 04 I-7 135 0. 04
  • a photographic silver halide emulsion composition comprising a silver halide and a sensitizing dye shown by the following formula wherein Z represents a member selected from the group consisting of CH and N; R and R each represents a member selected from the group consisting of a halogen atom, a hydroxyl group, an alkoxyl group, an aryloxy group, an arylthio group, an aryl group, an amino group, an alkylamino group, an arylamino group and an aralkylamino group; and A represents a memberselected from the group consisting of:
  • M represents a member selected from the group consisting of a hydrogen atom, an alkali metal, ammonium, and an amino group.
  • Y and Y each represents a nonmetallic atomic group necessary for forming a heterocyclic ring
  • R and R each represents a member selected-from the group consisting of an alkyl group, a substituted alkyl group, an aryl group, an allyl group and an aralkyl group
  • R represents an alkyl group
  • X represents an anion
  • n stands for l or 2
  • m stands for l or 2, and from about 0.05 to grams per 1 gram molecule of said silver halide of a compound shown by the formula wherein Z represents a member selected from the group consisting of CH and N; R and R each represents a member selected from the group consisting of a halogen atom, a hydroxyl group, an alkoxyl group, an arylorty group, an
  • A represents a member selected from the group consisting of:
  • M represents a member selected from the group consisting of a hydrogen atom, an alkali metal, ammonium, and an amino group, wherein the weight ratio of said sensitizing dye .to said compound varies from I :2 to 1:200.

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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)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Nitrogen Condensed Heterocyclic Rings (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
US687469A 1966-12-03 1967-12-04 Spectrally sensitized photographic silver halide emulsions Expired - Lifetime US3635721A (en)

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JP7925566 1966-12-03

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US3635721A true US3635721A (en) 1972-01-18

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US (1) US3635721A (is")
BE (1) BE707403A (is")
DE (1) DE1597589C2 (is")
FR (1) FR1564517A (is")
GB (1) GB1211735A (is")

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3887380A (en) * 1970-06-02 1975-06-03 Fuji Photo Film Co Ltd Direct positive silver halide photographic emulsion
US3941778A (en) * 1973-02-21 1976-03-02 Sandoz Ltd., (Sandoz Ag) Bis(triazinylamino) stilbene compounds
US4046572A (en) * 1975-06-30 1977-09-06 Fuji Photo Film Co., Ltd. Silver halide photographic light sensitive material
EP0124795A2 (en) 1983-04-11 1984-11-14 Fuji Photo Film Co., Ltd. Silver halide photographic emulsion
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
US4677053A (en) * 1983-04-15 1987-06-30 Yuji Mihara Silver halide photographic 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
EP0253390A2 (en) 1986-07-17 1988-01-20 Fuji Photo Film Co., Ltd. Photographic support and color photosensitive material
US5017466A (en) * 1989-05-24 1991-05-21 Fuji Photo Film Co., Ltd. Color-forming aminopyrimidine couplers and silver halide color photographic light-sensitive materials containing the coupler
WO1996013755A1 (en) 1994-10-26 1996-05-09 Eastman Kodak Company Photographic emulsions of enhanced sensitivity
US5580711A (en) * 1993-03-02 1996-12-03 Konica Corporation Silver halide photographic light-sensitive material
EP0749038A1 (en) 1995-06-16 1996-12-18 Minnesota Mining And Manufacturing Company Light-sensitive photographic materials comprising tabular silver halide grains and azodicarbonamide derivatives
EP0843209A1 (en) 1996-11-13 1998-05-20 Imation Corp. Silver halide emulsion manufacturing method
JP2007512259A (ja) * 2003-11-24 2007-05-17 プロメティック、バイオサイエンシーズ、インコーポレーテッド 化合物、その化合物を含む組成物、その化合物を利用した自己免疫疾患の治療方法

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6440651B1 (en) * 2000-10-05 2002-08-27 Eastman Kodak Company Concentrated photographic fixer additive and fixing compositions and method of photographic processing

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2933390A (en) * 1955-10-12 1960-04-19 Eastman Kodak Co Supersensitization of photographic silver halide emulsions
SU168596A3 (is") * 1963-04-28 1965-03-19

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE551712A (is") * 1955-10-12

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2933390A (en) * 1955-10-12 1960-04-19 Eastman Kodak Co Supersensitization of photographic silver halide emulsions
SU168596A3 (is") * 1963-04-28 1965-03-19

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Hamer, The Cyanine Dyes and Related Compounds, (1964), p. 207. *

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3887380A (en) * 1970-06-02 1975-06-03 Fuji Photo Film Co Ltd Direct positive silver halide photographic emulsion
US3941778A (en) * 1973-02-21 1976-03-02 Sandoz Ltd., (Sandoz Ag) Bis(triazinylamino) stilbene compounds
US4046572A (en) * 1975-06-30 1977-09-06 Fuji Photo Film Co., Ltd. Silver halide photographic light sensitive material
EP0124795A2 (en) 1983-04-11 1984-11-14 Fuji Photo Film Co., Ltd. Silver halide photographic emulsion
US4677053A (en) * 1983-04-15 1987-06-30 Yuji Mihara Silver halide photographic materials
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
EP0253390A2 (en) 1986-07-17 1988-01-20 Fuji Photo Film Co., Ltd. Photographic support and color photosensitive material
US5017466A (en) * 1989-05-24 1991-05-21 Fuji Photo Film Co., Ltd. Color-forming aminopyrimidine couplers and silver halide color photographic light-sensitive materials containing the coupler
US5580711A (en) * 1993-03-02 1996-12-03 Konica Corporation Silver halide photographic light-sensitive material
WO1996013755A1 (en) 1994-10-26 1996-05-09 Eastman Kodak Company Photographic emulsions of enhanced sensitivity
EP0749038A1 (en) 1995-06-16 1996-12-18 Minnesota Mining And Manufacturing Company Light-sensitive photographic materials comprising tabular silver halide grains and azodicarbonamide derivatives
EP0843209A1 (en) 1996-11-13 1998-05-20 Imation Corp. Silver halide emulsion manufacturing method
JP2007512259A (ja) * 2003-11-24 2007-05-17 プロメティック、バイオサイエンシーズ、インコーポレーテッド 化合物、その化合物を含む組成物、その化合物を利用した自己免疫疾患の治療方法

Also Published As

Publication number Publication date
BE707403A (is") 1968-04-16
DE1597589A1 (de) 1970-08-13
GB1211735A (en) 1970-11-11
DE1597589C2 (de) 1982-04-01
FR1564517A (is") 1969-04-25

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