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US4097284A Expired / Lapsed US ⏱️ 0.0 years remaining

Method for supersensitizing silver halide photographic emulsions

Assignee: Fujifilm Holdings Corp
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Filing: 1976-10-27
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Granted: 1978-06-27
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Expires: 1996-10-27
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Abstract

Abstract A method for spectrally sensitizing a silver halide photographic emulsion with a supersensitizing combination as hereinafter described, wherein the combination of a trimethinecyanine dye and a nitrogen-containing heterocyclic compound having a mercapto group, which is capable of producing a slightly soluble silver salt by reacting with a silver ion, is incorporated in the emulsion in a supersensitizing amount.

Inventors

  • 👤 Tadaaki Tani

Bibliographic Details

Application Number —
Jurisdiction US
Data Source google_patents
Last Synchronized 2026-11-03 23:24
CPC Classifications
G; G03; G03C; G03C1/00; G03C1/005; G03C1/06; G03C1/08; G03C1/28

Claims Analysis

Total Claims: 16
Claim 1
Independent Claim 318 words
A method for spectrally sensitizing a silver halide photographic emulsion, which is characterized by the presence of the combination of (1) a trimethinecyanine dye of formula (II): ##STR6## wherein Y 1 and Y 2 each represents a sulfur atom, a selenium atom, or an oxygen atom; R 11 and R 21 each represents an alkyl group, a hydroxyalkyl group, a carboxyalkyl group, a sulfoalkyl group or a sulfoalkoxyalkyl group where any alkyl moiety has 1 to 8 carbon atoms; W 1 and W 2 each represents an alkyl group containing 1 to 4 carbon atoms, a phenyl group, an aralkyl group, an alkoxy group containing 1 to 4 carbon atoms, a hydroxy group, a halogen atom, a cyano group, a carboxy group, an alkoxycarbonyl group, the alkyl moiety thereof having up to 4 carbon atoms, or a trifluoromethyl group; q and r each represents zero or an integer ranging from 1 to 4; R 0 represents a hydrogen atom, an alkyl group containing up to 4 carbon atoms, a hydroxyalkyl group, a carboxyalkyl group, a cyano group, an aralkyl group or a phenyl group; p represents 0 or 1 and X.sup.⊖ represents an inorganic or organic acid anion which forms a salt together with the dye moiety, wherein when the dye moiety forms an internal salt p is 0 and in other cases p is 1, and (2) a nitrogen-containing heterocyclic compound free of any acidic groups and having at least one mercapto group, which is capable of producing a silver salt which is less soluble in water than silver chloride upon reaction with silver ion, the combination being present in said emulsion in a supersensitizing amount, said heterocyclic compound comprising a heterocyclic ring selected from the group consisting of a 1, 2, 4-triazole ring, a 1, 3, 4-thiadiazole ring and a triazolotriazole ring, said nitrogen-containing heterocyclic compound having an acid dissociation constant pKa of 3.5 or more.
Claim 2
Independent Claim 318 words
A method for spectrally sensitizing a silver halide photographic emulsion, which is characterized by the presence of the combination of (1) a trimethinecyanine dye of formula (II): ##STR6## wherein Y 1 and Y 2 each represents a sulfur atom, a selenium atom, or an oxygen atom; R 11 and R 21 each represents an alkyl group, a hydroxyalkyl group, a carboxyalkyl group, a sulfoalkyl group or a sulfoalkoxyalkyl group where any alkyl moiety has 1 to 8 carbon atoms; W 1 and W 2 each represents an alkyl group containing 1 to 4 carbon atoms, a phenyl group, an aralkyl group, an alkoxy group containing 1 to 4 carbon atoms, a hydroxy group, a halogen atom, a cyano group, a carboxy group, an alkoxycarbonyl group, the alkyl moiety thereof having up to 4 carbon atoms, or a trifluoromethyl group; q and r each represents zero or an integer ranging from 1 to 4; R 0 represents a hydrogen atom, an alkyl group containing up to 4 carbon atoms, a hydroxyalkyl group, a carboxyalkyl group, a cyano group, an aralkyl group or a phenyl group; p represents 0 or 1 and X.sup.⊖ represents an inorganic or organic acid anion which forms a salt together with the dye moiety, wherein when the dye moiety forms an internal salt p is 0 and in other cases p is 1, and (2) a nitrogen-containing heterocyclic compound free of any acidic groups and having at least one mercapto group, which is capable of producing a silver salt which is less soluble in water than silver chloride upon reaction with silver ion, the combination being present in said emulsion in a supersensitizing amount, said heterocyclic compound comprising a heterocyclic ring selected from the group consisting of a 1, 2, 4-triazole ring, a 1, 3, 4-thiadiazole ring and a triazolotriazole ring, said nitrogen-containing heterocyclic compound having an acid dissociation constant pKa of 3.5 or more.
Claim 3
Dependent Claim 34 words
The method of claim 1, wherein the amount of said nitrogen-containing heterocyclic compound free of any acidic groups is from about 10 -5 mol to about 10 -2 mol per mol of silver halide.
Claim 4
Dependent Claim 24 words
The method of claim 1, wherein the amount of said heterocyclic compound is 10 -3 mol to 0.0035 mol per mol of silver halide.
Claim 5
Dependent Claim 33 words
The method of claim 2, wherein the ratio of said nitrogen-containing heterocyclic compound free of any acidic groups to the trimethinecyanine dye of formula (I) (molar) is from about 40/1 to about 1/10.
Claim 6
Dependent Claim 12 words
The method of claim 4, wherein said ratio is 5/1 to 1/5.
Claim 7
Dependent Claim 20 words
The method of claim 1, wherein said nitrogen-containing heterocyclic compound has an acid dissociation constant pKa Of 3.5 to 10.
Claim 8
Dependent Claim 14 words
The method of claim 1, wherein said nitrogen-containing heterocyclic compound has the formula: ##STR7##
Claim 9
Dependent Claim 14 words
The method of claim 1, wherein said nitrogen-containing heterocyclic compound has the formula: ##STR8##
Claim 10
Dependent Claim 322 words
A photographic light-sensitive element comprising a support carrying thereon a least one silver halide photographic emulsion which comprises a supersensitizing amount of a combination of (1) a trimethinecyanine dye of formula (II): ##STR9## wherein Y 1 and Y 2 each represents sulfur atom, a selenium atom, or an oxygen atom; R 11 and R 21 each represents an alkyl group, a hydroxyalkyl group, a carboxyalkyl group, a sulfoalkyl group or a sulfoalkoxyalkyl group where any alkyl moiety has 1 to 8 carbon atoms; W 1 and W 2 each represents an alkyl group containing 1 to 4 carbon atoms, a phenyl group, an aralkyl group, an alkoxy group containing 1 to 4 carbon atoms, a hydroxy group, a halogen atom, a cyano group, a carboxy group, an alkoxycarbonyl group, the alkyl moiety thereof having up to 4 carbon atoms, or a trifluoromethyl group; q and r each represents zero or an integer ranging from 1 to 4; R 0 represents a hydrogen atom, an alkyl group containing up to 4 carbon atoms, a hydroxyalkyl group, a carboxyalkyl group, a cyano group, an aralkyl group or a phenyl group; p represents 0 or 1 and X.sup.⊖ represents an inorganic or organic acid anion which forms a salt tOgether with the dye moiety, wherein when the dye moiety forms an internal salt p is 0 and in other cases p is 1, and (2) a nitrogen-containing heterocyclic compound free of any acidic groups and having a least one mercapto group, which is capable of producing a silver salt which is less soluble in water than silver chloride upon reaction with silver ion, the combination being present in said emulsion in a supersensitizing amount, said heterocyclic compound comprising a heterocyclic ring selected from the group consisting of a 1, 2, 4-triazole ring, a 1, 3, 4-thiadiazole ring and a triazolotriazole ring, said nitrogen-containing heterocyclic compound having an acid dissociation constant pKa of 3.5 or more.
Claim 11
Dependent Claim 322 words
A photographic light-sensitive element comprising a support carrying thereon a least one silver halide photographic emulsion which comprises a supersensitizing amount of a combination of (1) a trimethinecyanine dye of formula (II): ##STR9## wherein Y 1 and Y 2 each represents sulfur atom, a selenium atom, or an oxygen atom; R 11 and R 21 each represents an alkyl group, a hydroxyalkyl group, a carboxyalkyl group, a sulfoalkyl group or a sulfoalkoxyalkyl group where any alkyl moiety has 1 to 8 carbon atoms; W 1 and W 2 each represents an alkyl group containing 1 to 4 carbon atoms, a phenyl group, an aralkyl group, an alkoxy group containing 1 to 4 carbon atoms, a hydroxy group, a halogen atom, a cyano group, a carboxy group, an alkoxycarbonyl group, the alkyl moiety thereof having up to 4 carbon atoms, or a trifluoromethyl group; q and r each represents zero or an integer ranging from 1 to 4; R 0 represents a hydrogen atom, an alkyl group containing up to 4 carbon atoms, a hydroxyalkyl group, a carboxyalkyl group, a cyano group, an aralkyl group or a phenyl group; p represents 0 or 1 and X.sup.⊖ represents an inorganic or organic acid anion which forms a salt tOgether with the dye moiety, wherein when the dye moiety forms an internal salt p is 0 and in other cases p is 1, and (2) a nitrogen-containing heterocyclic compound free of any acidic groups and having a least one mercapto group, which is capable of producing a silver salt which is less soluble in water than silver chloride upon reaction with silver ion, the combination being present in said emulsion in a supersensitizing amount, said heterocyclic compound comprising a heterocyclic ring selected from the group consisting of a 1, 2, 4-triazole ring, a 1, 3, 4-thiadiazole ring and a triazolotriazole ring, said nitrogen-containing heterocyclic compound having an acid dissociation constant pKa of 3.5 or more.
Claim 12
Dependent Claim 20 words
The element of claim 9 wherein said nitrogen-containing heterocyclic compound has an acid dissociation constant pKa of 3.5 to 10.
Claim 13
Dependent Claim 29 words
The element of claim 10, wherein the amount of said nitrogen-containing heterocyclic compound is from about 10 -5 mol to about 10 -2 mol per mol of silver halide.
Claim 14
Dependent Claim 29 words
The element of claim 11, wherein the ratio of said nitrogen-containing heterocyclic compound to the trimethine cyanine dye of formula (II) (molar) is from about 40/1 to about 1/10.
Claim 15
Dependent Claim 14 words
The element of claim 9, wherein said nitrogen-containing heterocyclic compound has the formula: ##STR10##
Claim 16
Dependent Claim 14 words
The element of claim 9, wherein said nitrogen-containing heterocyclic compound has the formula: ##STR11##

References Cited (Backward Citations)

US3457078A Cited
US3637393A Cited
US3753719A Cited
US3895948A Cited
US3776738A Cited

USPTO Annuity & Maintenance Windows

Annuity Stage Window Opens Payment Deadline Surcharge Period Until Estimated Fee Status
3.5 Years (Year 4) 1981-06-26 1981-12-26 1982-06-27 $2000.00 Window Closed / Lapsed
7.5 Years (Year 8) 1985-06-26 1985-12-26 1986-06-27 $3760.00 Window Closed / Lapsed
11.5 Years (Year 12) 1989-06-26 1989-12-26 1990-06-27 $7700.00 Window Closed / Lapsed

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