Silver bromoiodide photographic emulsion with improved green sensitivity

Claim 2

The photographic emulsion as claimed in claim 1 comprising silver bromoiodide mixed crystals with about 0.01 to about 1.0 mol percent of iodide ions adsorbed on the surface thereof.

Claim 3

The photographic emulsion as claimed in claim 1, wherein the green sensitizing dye is an anionic dye.

Claim 4

The photographic emulsion as claimed in claim 1, wherein the green sensitizing dye is a cationic dye without an iodide ion as a counter anion.

Claim 5

The photographic emulsion as claimed in claim 1, wherein the amount of said iodide ions added is at least 0.05 mol percent based on silver halide and the green sensitizing dye is a cationic dye with an iodide ion as a counter anion.

Claim 6

The photographic emulsion aS claimed in claim 1, wherein the amount of said iodide ions added is within the range of from 0.05 to 0.3 mol percent based on silver halide.

Claim 7

The photographic emulsion as claimed in claim 1, wherein at least two of said dyes are used in combination.

Claim 8

The photographic emulsion as claimed in claim 1, wherein the halogen atom in A1, A3 or B1 is chlorine, bromine, iodine or fluorine; wherein the alkoxy group is methoxy or ethoxy, the amino group is amino, methylamino or dimethylamino, the acylamido group is acetoamido or propionamido, the acyloxy group is acetoxy, the alkoxycarbonyl group is methoxycarbonyl, ethoxycarbonyl, propioxycarbonyl or butoxycarbonyl in A2, A4, B2, B3 or B4; the lower alkyl group is methyl, ethyl or isopropyl in A2 or A4; wherein the lower aklyl group is methyl, ethyl or n-propyl, and the aryl group is phenyl or tolyl in R4 wherein the alkyl group is methyl, ethyl or n-propyl, the hydroxyalkyl group is 2-hydroxyethyl, 3-hydroxypropyl or 4-hydroxybutyl, the acetoxyalkyl group is 2-acetoxyethyl, 3-acetoxypropyl or 4-acetoxybutyl, the alkoxyalkyl group is 2-methoxyethyl or 3-methoxypropyl, the alkyl group containing a carboxy group is carboxymethyl, 2-carboxyethyl, 3-carboxypropyl, 4-carboxybutyl or 2-(2-carboxyethoxy)ethyl, the alkyl group containing a sulfo group is 2-sulfoethyl, 3-sulfopropyl, 4-sulfobutyl, 2-hydroxy-3-sulfopropyl, 2-(3-sulfopropoxy) ethyl, 2-acetoxy-3-sulfopropyl, 3-methoxy-2-(3-sulfopropoxy)propyl, 2-(2-(3-sulfopropoxy)-ethoxy) ethyl, p-sulfobenzyl, p-sulfobenzyl or p-sulfophenethyl in R1, R2, R3, R4 or R5; wherein the lower alkyl group is methyl, ethyl or trifluoromethyl, the aryl group is phenyl or tolyl, the carbamoyl group is carbamoyl, methylcarbamoyl, phenylcarbamoyl, dimethylcarbamoyl, diethylcarbamoyl, morpholinocarbamoyl or piperidinocarbamoyl, the alkyl sulfonyl group is methyl sulfonyl, the alkylaminosulfonyl group is methylaminosulfonyl, ethylaminosulfonyl, dimethylaminosulfonyl, morpholinosulfonyl, piperidinosulfonyl or pyrrolidinosulfonyl in B2, B3 or B4; wherein the alkyl group in R7 or R8 is methyl, ethyl or vinylmethyl; wherein the alkyl group is R9 is methyl or ethyl; and wherein the alkylene group, which joins together R5 and R6, is dimethylene or trimethylene.

Claim 9

The photographic emulsion as claimed in claim 1, wherein said green sensitizing dye is a cyanine dye selected from the group:

Claim 10

The photographic emulsion as claimed in claim 1, wherein more than one green sensitizing dye is used, the dyes comprising a combination of:

Claim 11

The photographic emulsion as claimed in claim 1, wherein the amount of green sensitizing dye is within the range of from 10 4 to 2 X 10 2 moles per 1 mole of silver halide.

Claim 12

The photographic emulsion as claimed in claim 1, wherein the emulsion comprises a hydrophilic colloid selected from the group gelatin, phthalated gelatin, polyacrylic amide, polyvinyl alcohol and polyvinyl pyrrolidone.

Claim 13

The photographic emulsion as claimed in claim 1, further containing a coupler.

Claim 14

The photographic light-sensitive silver halide material which comprises a support having thereon at least one layer comprising a photographic emulsion as claimed in claim 1.

Claim 15

In a process for spectrally sensitizing a negative-working silver bromoiodide photographic emulsion of the developing out type which is subjected to only one exposure followed by wet-developing, said emulsion containing at least one green sensitizing dye which effects the green sensitization of said emulsion, the improvement comprising adsorbing at least 0.1 mol percent iodide ions on the surface of the silver halide grains in the emulsion, said iodide being in addition to iodine present in said silver iodobromide, whereby the emulsion is intensely sensitized to green without substantially deteriorating its photographic properties wherein said green sensitizing dye is represented by one of the following general formulae

Claim 16

The process as claimed in claim 16, wherein bromide ion in an amount of from 1 to 30 times of the molar concentration of the iodide ion added is also adsorbed on the surface of silver bromoiodide grains contained in the emulsion.

Claim 17

The process as claimed in claim 16, wherein said emulsion comprises silver bromoiodide mixed crystals with about 0.01 to about 1.0 mol percent of iodide ions adsorbed on the surface thereof.

Claim 18

The process as claimed in claim 16, wherein the amount of said iodide ions added is within the range of from 0.05 to 0.3 mol percent based on silver halide.

Claim 19

The process as claimed in claim 16, wherein at least two of said dyes are used in combination.

Claim 20

The process as claimed in claim 16, wherein the halogen atom in A1, A3 or B1 is chlorine, bromine, iodine or fluorine; wherein the alkoxy group is methoxy or ethoxy, the amino group is amino, methylamino or dimethylamino, the acylamido group is acetoamido or propionamido; the acyloxy group is acetoxy, the alkoxycarbonyl group is methoxycarbonyl, ethoxycarbonyl, propioxycarbonyl or butoxycarbonyl in A2, A4, B2, B3 or B4; the lower alkyl group is methyl, ethyl or isopropyl in A2 or A4; wherein the lower alkyl group is methyl, ethyl or n-propyl, and the aryl group is phenyl or tolyl in R4 wherein the alkyl group is methyl, ethyl or n-propyl, the hydroxyalkyl group is 2-hydroxyethyl, 3-hydroxypropyl or 4-hydroxybutyl, the acetoxyalkyl group is 2-acetoxyethyl, 3-acetoxypropyl or 4-acetoxybutyl, the alkoxyalkyl group is 2-methoxyethyl or 3-methoxypropyl, the alkyl group containing a carboxy group is carboxymethyl, 2-carboxyethyl, 3-carboxypropyl, 4-carboxybutyl or 2-(2-carboxyethoxy)ethyl, the alkyl group containing a sulfo group is 2-sulfoethyl, 3-sulfopropyl, 4-sulfobutyl, 2-hydroxy-3-sulfopropyl, 2-(3-sulfopropoxy) ethyl, 2-acetoxy-3-sulfopropyl, 3-methoxy-2-(3-sulfopropoxy)propyl, 2-(2-(3-sulfopropoxy)-ethoxy) ethyl, p-sulfobenzyl, p-sulfobenzyl or p-sulfophenethyl in R1, R2, R3, R4 or R5; wherein the lower alkyl group is methyl, ethyl or trifluoromethyl, the aryl group is phenyl or tolyl, the carbamoyl group is carbamoyl, methylcarbamoyl, phenylcarbamoyl, dismethylcarbamoyl, diethylcarbamoyl morpholinocarbamoyl or piperidinocarbamoyl, the alkyl sulfonyl group is methyl sulfonyl, the alkylaminosulfonyl group is methylaminosulfonyl, ethylaminosulfonyl, dimethylaminosulfonyl, morpholinosulfonyl, piperidinosulfonyl or pyrrolidinosulfonyl in B2, B3 or B4; wherein the alkyl group in R7 or R8 is methyl, ethyl or vinylmethyl; wherein the alkyl group in R9 is methyl or ethyl; and wherein the alkylene group, which joins together R5 and R6, is dimethylene or trimethylene.

Claim 21

The process as claimed in claim 16, wherein said green sensitizing dye is a cyanine dye selected from the group:

Claim 22

The process as claimed in claim 16, wherein more than one green sensitizing dye is used, the dyes comprising a combination of:

Claim 23

The process as claimed in claim 16, wherein the amount of green sensitizing dye is within the range of from 10 4 to 2 X 10 2 moles per 1 mole of silver halide.

Claim 24

The photographic emulsion of claim 1 which has been chemically ripened.

Claim 25

The process of claim 16, wherein said photographic emulsion has been chemically ripened.

Claim 26

The photographic emulsion of claim 1, wherein more than 1 green sensitizing dye is used, the spectral absorption regions of the green sensitizing dyes differing from each other.

Claim 27

The process of claim 16, wherein more than 1 green sensitizing dye is used, the spectral absorption regions of the green sensitizing dyes differing from each other.

Claim 28

The photographic emulsion as claimed in claim 1 wherein said silver bromoiodide mixed crystals contain about 0.5 to about 10 mol percent of iodide ions based on the total silver halide.

Claim 29

The process as claimed in claim 16, wherein said silver bromoiodide mixed crystals used contain about 0.05 to about 10 mol percent of iodide ions based on the total silver halide.

Claim 30

The photographic emulsion as claimed in claim 1 wherein the green sensitizing dye is cationic.

Claim 31

The process as claimed in claim 16, wherein the green sensitizing dye is cationic.