JPH07199392A - Silver halide photographic emulsion - Google Patents

Abstract

PURPOSE:To enhance spectral sensitivity in the green wavelength region, especially, its shorter wavelength region by using a specified cyanine dye for at least one of cyanine dyes. CONSTITUTION:The photographic silver halide emulsion is spectrally sensitized with the cyanine dyes including at least one kind of cyanine dye represented by the formula I or II in which each of R<1> and R<2> is a 1-10 C aliphatic group; R<3> is H, alkyl, aryl, or a heterocyclic group; each of R<4>-R<7> is H, halogen, alkoxy, or the like or a heterocyclic group; Z<1> is a nonmetallic atomic group necessary to form an oxazole, oxazoline, or condensed oxazole ring; M<1> is an ion necessary to neutralize the total intramolecular charge; n<1> is a number necessary to neutralize it; each of R<11>-R<13> is a specified aliphatic group; each of V<1> and V<2> is H, alkyl, or the like; and each of R<14> and R<17> is H or halogen or the like.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention has improved spectral sensitivity in the green wavelength region, particularly in the green short wavelength region, and has good storage stability.
The present invention also relates to a silver halide photographic emulsion used in a silver halide photographic light-sensitive material (hereinafter abbreviated as light-sensitive material) in which residual color contamination of a light-sensitive dye is reduced.

[0002]

2. Description of the Related Art When a certain dye is added to a light-sensitive silver halide photographic emulsion (hereinafter referred to as a halogenated emulsion or simply an emulsion), the light-sensitive wavelength range of the silver halide emulsion is expanded to optically It is well known that sensitization is performed.

A large number of compounds have been conventionally known as dyes used for this purpose. For example, for example, "The Theory of the Photographic Process", 4th Edition, written by TJ James, (1977, Macmillan). Company, N.
Y. ) P.194-234, "The Cyanine Soybean and Related Compounds" by Francis M. Harmer (1964, Joon Willy and Sons,
N. Y. ), D. M. Starmer, "The Chemistry of Heterocyclic Compounds 30."
Volume "p.441- (1977, Joon Willy & Sons, NY), and various dyes such as hemicyanine dyes, cyanine dyes, merocyanine dyes, and xanthene dyes are known.

These spectral sensitizing dyes must not only expand the photosensitive wavelength range of the silver halide emulsion, but must also satisfy the following conditions.

1) Appropriate spectral sensitization range 2) High spectral sensitization efficiency 3) Between other additives such as stabilizers, antifoggants, coating aids, high boiling point solvents, etc. 4) Do not adversely affect the characteristic curve such as fogging or gamma change. 5) When a silver halide photographic material containing a sensitizing dye is aged (especially at high temperature and high humidity). Do not change the photographic performance such as fog when stored below) 6) The added photosensitive dye does not diffuse into layers of different photosensitive wavelength range to cause color turbidity 7) Develop and fix Dye does not escape from the light-sensitive material to cause color contamination. However, the spectrally sensitizing dyes disclosed hitherto have not yet reached the level of satisfying all of these various conditions.

By the way, it is known that human eyes have the highest sensitivity to green light, and that a delicate balance of green light sensitivity has a great influence on color. Therefore, in particular, in the green light sensitivity of the color photographic light-sensitive material, it is required that the spectral sensitivity is appropriate in addition to the sufficiently high sensitivity.

In the light-sensitive material for photographing, the spectral sensitivity of the green light-sensitive layer for realizing good color reproducibility is 50
It is said that spectral sensitization is performed over the range of 0 to 600 nm, and the centroid wavelength of the spectral maximum is about 540 nm. That is, in order to realize the proper spectral sensitivity distribution, 500-540
The region multiplied by nm also needs to be spectrally sensitized as high as the long-wave side.

Conventionally, many patents have been disclosed regarding green spectral sensitization, and as dyes alone, for example, US Pat. Nos. 2,072,908, 2,647,053, and British Patent 1,012,
Oxacarbocyanine dyes described in Japanese Patent No. 825, etc., Japanese Examined Patent Publication No. 38-7828, No. 43-14497 or British Patent No. 815,172, U.S. Patent Nos. 2,778,823, 2,739,149.
Nos. 2,912,329 and 3,656,959, etc., and oxathiacarbocyanines described in British Patent No. 1,012,825 are known. Furthermore, for example, Japanese Examined Patent Publication Nos. 43-4936 and 43-22.
884, 44-32753, 46-11627, 48-25652,
Japanese Patent Application Laid-Open Nos. 46-38694 and 57-14834 disclose techniques for supersensitizing a combination of an oxacarbocyanine dye and another dye. However, according to these, although the green sensitivity is high, the spectral sensitivity region is shifted to a long wave, so that good color reproducibility cannot be obtained.

Examples of the sensitizing dye that spectrally sensitizes a wavelength region shorter than 550 nm include, for example, JP-B-44-14030 and JP-A-51-312.
No. 28 benzimidazolooxacarbocyanine dyes, U.S. Pat.Nos. 2,072,908, 2,231,658 and other cyanine dyes described in the specification, or, for example, U.S. Pat.
No. 3,748, No. 2,519,001, No. 3,480,439, etc., the dimethine merocyanine dyes described in the specification are known, but when these dyes are used alone, the sensitivity in the green short-wave region, especially at 540 nm or shorter There is a problem that a photographic emulsion having a high sensitivity cannot be obtained and fog tends to occur when an attempt is made to increase the sensitivity, and the storage stability tends to be deteriorated. In addition, for example, US Pat.
The oxacarbocyanine dyes described in the specifications of 2,521,959, 2,647,054 and the like have a photosensitivity maximum in the range of 530 to 540 nm, but they also have a drawback that they have a low reaching sensitivity and have a significant residual color stain. The oxacarbocyanine dye disclosed in JP-A-63-163843, in which a sulfoalkyl group is substituted at the N-position, shifts the photosensitivity maximum by a short wave as compared with a conventional oxacarbocyanine dye, and is excellent in improving photographic properties. However, the color sensitization sensitivity on the shorter wavelength side than 540 nm is insufficient, and further improvement has been demanded.

Further, as another problem, the development processing time has been shortened, and nowadays, the washing with water and the recycling of the processing liquid have been introduced, so that the dyes are more likely to remain, and as a result, the products of the light-sensitive material are manufactured. There is a problem that the value is remarkably reduced, and improving the residual color contamination performance of the photosensitive dye is an important improvement item. However, generally, a photosensitive dye having a low residual color stainability is weakly adsorbed to silver halide grains, and is desorbed from silver halide grains when exposed to high temperature and high humidity in a film coating, for example, to lower the sensitivity. Invite. Therefore, there has been a demand for a photosensitive dye which is excellent in residual color contamination and has good storage stability in a photosensitive material.

[0011]

SUMMARY OF THE INVENTION It is, therefore, a first object of the present invention to provide a silver halide photographic emulsion having enhanced spectral sensitivity in the green wavelength region, particularly in the green short wavelength region. The second object is to provide a silver halide photographic light-sensitive material with reduced residual color contamination. A third object is to provide a silver halide photographic emulsion having improved storage stability.

[0012]

The above objects of the present invention have been achieved by the following constitutions.

1. In a silver halide photographic emulsion spectrally sensitized with at least two cyanine dyes, at least one of the cyanine dyes is represented by the following general formula [I] or general formula [II]. Silver halide photographic emulsion.

[0014]

[Chemical 4]

In the formula, R ¹ and R ² each have 1 or more carbon atoms.
Represents an aliphatic group of 10 or less, R ³ represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, and R ⁴ , R ⁵ , R ⁶
And R ⁷ each represents a hydrogen atom, a halogen atom, an alkoxy group, an aryloxy group, an aralkyl group, an alkyl group, an aryl group or a heterocyclic group. However, either one of R ¹ and R ² is a group in which a water-solubilizing group is substituted.

Z ¹ is an oxazole ring, an oxazoline ring,
It represents a group of non-metal atoms necessary for forming a condensed oxazole ring.

M ¹ represents an ion necessary to cancel the total charge of the molecule, and n ¹ represents a number necessary to neutralize the charge in the molecule.

[0018]

[Chemical 5]

In the formula, R ¹¹ , R ¹² and R ¹³ each represent an aliphatic group having 1 to 10 carbon atoms, and V ¹ and V ² each represent a hydrogen atom, an alkyl group, an alkylthio group or an electron-withdrawing group. Represents a group, R ¹⁴ , R ¹⁵ , R ¹⁶ and R ¹⁷ are each a hydrogen atom,
It represents a halogen atom, an alkoxy group, an aryloxy group, an aralkyl group, an alkyl group, an aryl group or a heterocyclic group. However, one of R ¹¹ and R ¹² is a group in which a water-solubilizing group is substituted, and ^one of V ¹ and V ² is an electron-withdrawing group.

M ² represents an ion necessary to cancel the total charge of the molecule, and n ² represents a number necessary to neutralize the charge in the molecule.

2. The silver halide photographic emulsion according to the above 1, wherein at least one kind of cyanine dyes other than the cyanine dyes represented by the general formula [I] or [II] is represented by the following general formula [III].

[0022]

[Chemical 6]

In the formula, Z ² and Z ³ represent a non-metal atom group necessary for forming a 5- or 6-membered heterocycle, and each may be the same or different. Here, R ²¹ and R ²² may be the same or different and each represents an alkyl group or a substituted alkyl group. L ¹ , L ² and L ³ represent a methine group or a substituted methine group. p and q represent 0 or 1. m represents 0, 1, 2 and when m is 2, each -L ² = L ³
The-may be the same or different. X ^1- represents an anion.
k represents 0 or 1.

3. In the general formula [III], m is 0.
Or the silver halide photographic emulsion as described in 2 above, which is 1.

4. ^{3. The} silver halide photographic emulsion as described in 2 above, wherein in the general formula [III], Z ² and / or Z ³ represents a group of non-metal atoms necessary for forming a substituted or unsubstituted oxazole ring.

5. ^{3. The} silver halide photographic emulsion as described in 2 above, wherein in the general formula [III], Z ² and / or Z ³ represents a group of non-metal atoms necessary for forming a substituted or unsubstituted thiazole ring.

6. ^{3. The} silver halide photographic emulsion as described in 2 above, wherein in the general formula [III], Z ² and / or Z ³ represents a group of non-metal atoms necessary for forming a substituted or unsubstituted imidazole ring.

7. A silver halide photographic light-sensitive material containing at least one silver halide photographic emulsion among the above-mentioned 1 to 6 silver halide photographic emulsions.

The present invention will be described in more detail below.

General formulas [I] and [I used in the present invention
In the compound represented by I], the aliphatic group having 1 to 10 carbon atoms represented by R ¹ , R ² , R ¹¹ , R ¹² and R ¹³ includes, for example, a branched group having 1 to 10 carbon atoms. Or a straight-chain alkyl group (for example, each group such as methyl, ethyl, propyl, butyl, pentyl, iso-pentyl, 2-ethyl-hexyl, octyl, decyl), an alkenyl group having 3 to 10 carbon atoms (for example, 2 -Propenyl, 3-butenyl, 1-methyl-3-propenyl, 3-pentenyl, 1-methyl-3-butenyl, 4-hexenyl, etc.), aralkyl groups having 7 to 10 carbon atoms (eg, benzyl, phenethyl) Each group) and the like.

The groups represented by R ¹ , R ² , R ¹¹ , R ¹² and R ¹³ further include a halogen atom (eg fluorine atom, chlorine atom, bromine atom etc.), an alkoxy group (eg methoxy group,
Ethoxy group etc.), aryloxy group (eg phenoxy group, p-tolyloxy group etc.), cyano group, carbamoyl group (eg carbamoyl group, N-methylcarbamoyl group, N,
N-tetramethylenecarbamoyl group etc.), sulfamoyl group (eg sulfamoyl group, N, N-3-oxapentamethyleneaminosulfonyl group etc.), methanesulfonyl group, alkoxycarbonyl group (eg ethoxycarbonyl group,
Butoxycarbonyl group etc.), aryl group (eg phenyl group, carboxyphenyl group etc.), acyl group (eg acetyl group, benzoyl group etc.), acylamino group (eg acetylamino, benzoylamino group etc.), sulfonamide group (eg methane) Sulfonamide, butanesulfonamide group, etc.), sulfonylaminocarbonyl group (eg, methanesulfonylaminocarbonyl, ethanesulfonylaminocarbonyl group, etc.), acylaminosulfonyl group (eg, acetamidosulfonyl, methoxyacetamidosulfonyl group, etc.), acylaminocarbonyl group ( For example, acetamidocarbonyl, methoxyacetamidocarbonyl group, etc., sulfinylaminocarbonyl group (eg, methanesulfinylaminocarbonyl, ethanesulfinylaminocarbo group) It may be substituted with a substituent Le group) and the like.

The water-soluble group which substitutes either one of R ¹ and R ² and one of R ¹¹ and R ¹² includes an acidic group (eg, sulfo group, phosphono group, sulfate group, sulfino group, etc.). , An alkali ion dissociable group (eg, carboxy group, sulfonylaminocarbonyl group (eg, methanesulfonylaminocarbonyl, ethanesulfonylaminocarbonyl group, etc.), acylaminosulfonyl group (eg, acetamidosulfonyl, methoxyacetamidosulfonyl group, etc.), acylaminocarbonyl group (Eg, acetamidocarbonyl, methoxyacetamidocarbonyl group, etc.), sulfinylaminocarbonyl group (eg, methanesulfinylaminocarbonyl, ethanesulfinylaminocarbonyl group, etc.), hydrophilic group (eg, hydroxy, ethylene) Preferred examples include various groups such as a glycol group and the like), a basic group (for example, a trimethylammonium group, a benzyldimethylammonium group and the like), an acid ion dissociable group (a dimethylamine group, a diethylamine group and the like).

Specific examples of the aliphatic group substituted with these water-solubilizing groups include carboxymethyl, carboxyethyl, sulfoethyl, sulfopropyl, sulfobutyl, sulfopentyl, 3-sulfobutyl, 6-sulfo-3-oxahexyl, ω-sulfopropoxycarbonylmethyl, ω-
Sulfopropylaminocarbonylmethyl, 3-sulfinobutyl, 3-phosphonopropyl, hydroxyethyl, N-
Each group such as methanesulfonylcarbamoylmethyl, 4-sulfo-3-butenyl, 2-carboxy-2-propenyl, o-sulfobenzyl, p-sulfophenethyl, p-carboxybenzyl and the like can be mentioned.

R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ¹⁴ , R ¹⁵ ,
Examples of the alkyl group represented by R ¹⁶ and R ¹⁷ include linear or branched groups (for example, methyl, ethyl, iso-propyl, t-butyl, iso-butyl, t-pentyl, hexyl and the like groups). To be R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ¹⁴ , R ¹⁵ ,
Examples of the aralkyl group represented by R ¹⁶ and R ¹⁷ include groups such as benzyl and phenethyl, and examples of the aryl group include phenyl, p-tolyl, p-chlorophenyl,
Examples of the heterocyclic group include p-methoxyphenyl and the like. Examples of the heterocyclic group include 2-thienyl, 2-furyl, 1,3-bis (2-methoxyethyl) -6-hydroxy-2,4-dioxo-1. , 2,3,4-Tetrahydro-5-pyrimidyl, 5-hydroxy-3-methyl-1-
Each group such as phenyl-4-pyrazolyl may be mentioned.

Examples of the halogen atom represented by R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ¹⁴ , R ¹⁵ , R ¹⁶ and R ¹⁷ include each atom such as fluorine, chlorine and bromine, and an alkoxy group. Examples thereof include groups such as methoxy, ethoxy and propoxy, and examples of the aryloxy group include groups such as phenoxy, p-tolyloxy, m-chlorophenoxy and p-methoxyphenyloxy.

R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ¹⁴ , R ¹⁵ ,
The alkyl group, aralkyl group, aryl group, alkoxy group and aryloxy group represented by R ¹⁶ and R ¹⁷ may have a substituent at any position, and examples thereof include a halogen atom (fluorine atom, chlorine atom, bromine atom). Atom, iodine atom), trifluoromethyl group, alkoxy group (for example, unsubstituted alkyl groups such as methoxy, ethoxy and butoxy, substituted alkoxy groups such as 2-methoxyethoxy and benzyloxy), hydroxy group, cyano group, Aryloxy group (eg, substituted or unsubstituted groups such as phenoxy or tolyloxy), or aryl group (eg, substituted or unsubstituted groups such as phenyl or p-chlorophenyl), styryl group, heterocyclic group (eg, furyl, Groups such as thienyl), carbamoyl groups (eg, groups such as carbamoyl and N-ethylcarbamoyl), sulfamoyl groups For example sulfamoyl, N, N-
Each group such as dimethylsulfamoyl), an acylamino group (each group such as acetylamino, propionylamino, benzoylamino), an acyl group (each group such as acetyl, benzoyl), an alkoxycarbonyl group (such as ethoxycarbonyl) Group), sulfonamide group (eg, each group of methanesulfonylamide, benzenesulfonamide, etc.), sulfonyl group (eg, group of methanesulfonyl, butanesulfonyl, p-toluenesulfonyl, etc.), carboxy group, etc. .

In the general formula [I], the oxazole nucleus represented by Z ¹ is a condensed oxazole nucleus in which a condensed ring is formed by a monocyclic ring, a carbon ring, a benzene ring or a naphtho ring, and specific examples of these oxazole rings are shown. Specific examples include, for example, oxazolidine, oxazoline, oxazole, 4,5-trimethylene oxazole, 4,5,6,7-tetrahydrobenzoxazole, benzoxazole, naphtho [1,2-d] oxazole, naphtho [2,3 -d] oxazole, naphtho [2,1-
d] Oxazole and the like can be mentioned.

These rings may have a substituent at any position, for example, an alkyl group (for example, each group such as methyl, ethyl, isopropyl, t-pentyl, etc.), a halogen atom (fluorine atom, chlorine atom, Bromine atom, iodine atom, etc.),
Trifluoromethyl group, alkoxy group (eg, unsubstituted alkoxy group such as methoxy, ethoxy, butoxy, 2-
Substituted alkoxy groups such as methoxyethoxy and benzyloxy), alkylmercapto groups (eg, methylmercapto, ethylmercapto, etc.), hydroxy groups, cyano groups, aryloxy groups (eg, phenoxy, tolyloxy, etc., substituted or unsubstituted) Groups), or aryl groups (eg, substituted or unsubstituted groups such as phenyl and p-chlorophenyl), styryl groups, heterocyclic groups (eg, groups such as furyl and thienyl), carbamoyl groups (eg, carbamoyl, N-
Each group such as ethylcarbamoyl), a sulfamoyl group (for example, a group such as sulfamoyl, N, N-dimethylsulfamoyl), an acylamino group (for example, a group such as acetylamino, propionylamino, benzoylamino), an acyl group (for example, Each group such as acetyl, benzoyl), an alkoxycarbonyl group (for example, a group such as ethoxycarbonyl),
Any group such as a sulfonamide group (for example, each group such as methanesulfonylamide and benzenesulfonamide), a sulfonyl group (for example, each group such as methanesulfonyl, butanesulfonyl, p-toluenesulfonyl) and a carboxy group can be substituted.

In the general formula [II], examples of the alkylthio group represented by V ¹ and V ² include groups such as methylthio and ethylthio.

The electron-withdrawing group represented by V ¹ and V ² is selected from substituents having a positive Hammett σp value, and examples thereof include a halogen atom (eg, fluorine atom, chlorine atom, bromine atom) and cyano. Group, carbamoyl group (eg, carbamoyl group, N-methylcarbamoyl group, N, N-tetramethylenecarbamoyl group, etc.), sulfamoyl group (eg, sulfamoyl group, N, N-3-oxapentamethyleneaminosulfonyl group, etc.), methanesulfonyl Examples include substituents such as a group, an alkoxycarbonyl group (eg, ethoxycarbonyl group, butoxycarbonyl group, etc.), an acyl group (eg, acetyl group, benzoyl group, etc.), and a trifluoromethyl group.

Regarding the σp value, Chemical Review 17/125
~ 136 (1935), Substituent Constants for Correlation Analysis in Chemistry and Biology, 69-161 (1979)
(Published by John Wiley and Sons), Ranges
Handbook of Chemistry 12th Edition Volume 3, 134-137
It can be selected by referring to the publications such as page (1979).

M ¹ and M ² represent a cation or an acid anion, and specific examples of the cation include a proton and an organic ammonium ion (eg triethylammonium,
Examples of the acid anion include halogen ions (eg, chlorine ion, bromine ion, iodine ion, etc.), and inorganic cations (eg, lithium, sodium, calcium, etc. cations). , P-toluenesulfonate ion, perchlorate ion, boron tetrafluoride ion, sulfate ion and the like.

N ¹ and n ² are 0 when an intramolecular salt is formed and the charge is neutralized.

The novel photosensitizing dye according to the present invention has a structure having an oxazolidine nucleus substituted with a water-soluble group as at least one basic nucleus, and in the limiting structure of the resonance system, an oxazoliridenium structure and an oxazolidine structure are included. It can be taken.

Of the compounds represented by the general formulas [I] and [II], compounds having at least two water-soluble groups in the molecule are preferable.

In the general formula [I], ^{one of} the water-soluble groups substituting for R ¹ and R ² is a sulfo group in that both effects of color sensitization sensitivity and reduction of residual color stain are satisfied. A compound in which the other group is an alkali ion dissociable group is particularly preferable, and in the general formula [II], one of the water-soluble groups substituting for R ¹¹ and R ¹² is a sulfo group and the other group is an alkali ion dissociable group. A compound that is a functional group is particularly preferable.

Specific examples of the photosensitive dyes represented by the general formulas [I] and [II] are shown below, but the sensitizing dyes used in the present invention are not limited to these compounds.

[0048]

[Chemical 7]

[0049]

[Chemical 8]

[0050]

[Chemical 9]

[0051]

[Chemical 10]

[0052]

[Chemical 11]

The 2-oxazoline nucleus according to the present invention is, for example,
J.Org.Chem., 23 (1958) 72, J.Am.Chem.Soc., 72 (1950) 557
7, ibid.77 (1955) 636,640, can be synthesized by referring to the method described in Pharmaceutical Journal 74 (1954) 1293 and the like.The compound of the present invention can be synthesized, for example, by F.M. -It can be easily synthesized by referring to a conventionally known method described in "Soybean and related compounds" (1964, published by Inter Science Publishers).

The addition amount of the compound according to the present invention varies greatly depending on the conditions used and the type of emulsion, but preferably 1 × 10 ^{−6 to} 5 × 10 ⁻³ mol per mol of silver halide,
More preferably, it is in the range of 2 × 10 ⁻⁶ to 2 × 10 ⁻³ mol.

The compounds represented by the above formulas [I] and [II] used in the present invention can be added to the silver halide emulsion by a conventionally known method. For example,
Japanese Patent Application Laid-Open Nos. 50-80826 and 50-80827, Protonated Dissolution Addition Method, U.S. Patent No. 3,822,135, Japanese Patent Application Laid-Open No. 50-11
A method of dispersing and adding together with a surfactant described in 419, U.S. Pat.Nos. 3,676,147, 3,469,987, 4,247,627, JP-A-51-59942, 53-16624, 53-102732.
No. 53-102733, No. 53-137131, a method of dispersing and adding to a hydrophilic substrate, a method of adding as a solid solution described in East German Patent No. 143,324, or Research Disclosure 21,802, Japanese Patent Publication 50-40659, JP-A-59-148
A water-soluble solvent that dissolves a dye typified by No. 053 (for example, a low-boiling solvent such as water, methanol, ethanol, propyl alcohol, acetone, and fluorinated alcohol, a high-boiling solvent such as dimethylformamide, methylcellosolve, and phenylcellosolve). A solvent having a boiling point) or a method of adding it after dissolving it in a mixed solvent thereof can be arbitrarily selected and added to the emulsion. The compound of the present invention represented by the general formulas [I] and [II] may be added at any stage in the emulsion production process from physical ripening to completion of chemical ripening, and immediately before coating. Preferably, it is added between the physical ripening and the end of chemical ripening.

Addition of the compound according to the present invention during the physical ripening or prior to the addition of the chemical sensitizer in the chemical ripening step or immediately after the addition of the chemical sensitizer has the effect of obtaining a higher spectral sensitivity. And is preferably used.

In the present invention, the general formula [I] or [I
Preferred cyanine dyes used for cyanine dyes other than the cyanine dyes represented by I] include the following general formula [III].

[0058]

[Chemical 12]

In the formula, Z ² and Z ³ represent a group of non-metal atoms necessary for forming a 5- or 6-membered heterocycle, and each may be the same or different. Here, R ²¹ and R ²² may be the same or different and each represents an alkyl group or a substituted alkyl group. L ¹ , L ² and L ³ represent a methine group or a substituted methine group. p and q represent 0 or 1. m represents 0, 1, 2 and when m is 2, each -L ² = L ³
The-may be the same or different. X ^1- represents an anion.
k represents 0 or 1.

The 5- or 6-membered heterocyclic ring formed by Z ₂ and Z ₃ includes those condensed with other rings, and examples thereof include the following.

Thiazole nucleus (eg thiazole, 4-methylthiazole, 4-phenylthiazole, 4,5-dimethylthiazole, 4,5-diphenylthiazole etc.), benzothiazole nucleus (eg benzothiazole, 4-chlorobenzothiazole, 5 -Chlorobenzothiazole, 6-chlorobenzothiazole, 5-nitrobenzothiazole, 4-methylbenzothiazole, 5-methylbenzothiazole, 6-methylbenzothiazole, 5-bromobenzothiazole, 6-bromobenzothiazole, 5-iodo Benzothiazole, 5-phenylbenzothiazole, 5-methoxybenzothiazole, 6-methoxybenzothiazole, 5-ethoxybenzothiazole, 5-ethoxycarbonylbenzothiazole, 5-
Carboxybenzothiazole, 5-phenethylbenzothiazole, 5-fluorobenzothiazole, 5-chloro-6-methylbenzothiazole, 5,6-dimethylbenzothiazole, 5-hydroxy-6-methylbenzothiazole, tetrahydrobenzothiazole, 4- Phenylbenzothiazole etc.), naphthothiazole nucleus (eg naphtho [2,1-d]
Thiazole, naphtho [1,2-d] thiazole, naphtho [2,3
-d] thiazole, 5-methoxynaphtho [1,2-d] thiazole, 7-ethoxynaphtho [2,1-d] thiazole, 8-methoxynaphtho [2,1-d] thiazole, 5-methoxynaphtho [2 , 3
-d] thiazole etc.), thiazoline nucleus (eg thiazoline, 4-methylthiazoline, 4-nitrothiazoline etc.),
Oxazole nucleus (eg oxazole, 4-methyloxazole, 4-nitroxazole, 5-methyloxazole, 4-phenyloxazole, 4,5-diphenyloxazole, 4-ethyloxazole, etc.), benzoxazole nucleus (benzoxazole, 5-chloro) Benzoxazole, 5-methylbenzoxazole, 5-bromobenzoxazole, 5-fluorobenzoxazole, 5-phenylbenzoxazole, 5-methoxybenzoxazole,
5-nitrobenzoxazole, 5-trifluoromethylbenzoxazole, 5-hydroxybenzoxazole,
5-carboxybenzoxazole, 6-methylbenzoxazole, 6-chlorobenzoxazole, 6-nitrobenzoxazole, 6-methoxybenzoxazole, 6-hydroxybenzoxazole, 5,6-dimethylbenzoxazole, 4,6-dimethylbenzo Oxazole, 5-ethoxybenzoxazole, etc.), naphthoxazole nucleus (eg, naphtho [2,1-d] oxazole, naphtho [1,2-
d] oxazole, naphtho [2,3-d] oxazole, 5-nitronaphtho [2,1-d] oxazole, etc.), oxazoline nucleus (eg, 4,4-dimethyloxazoline), selenazole nucleus (eg, 4-methylselenazole) , 4-nitroselenazole, 4-phenylselenazole, etc.), benzoselenazole nucleus (eg benzoselenazole, 5-chlorobenzoselenazole, 5-nitrobenzoselenazole, 5-methoxybenzoselenazole, 5-hydroxybenzo) Selenazole, 6-nitrobenzoselenazole, 5-chloro-6-nitrobenzoselenazole, etc.), naphthoselenazole nucleus (eg naphtho [2,1-d] selenazole, naphtho [1,2-
d] selenazole, etc., 3,3-dialkylindolenine nucleus (eg, 3,3-dimethylindolenine, 3,3-diethylindolenine, 3,3-dimethyl-5-cyanoindolenine, 3,3
-Dimethyl-6-nitroindolenine, 3,3-dimethyl-5-nitroindolenine, 3,3-dimethyl-5-methoxyindolenine, 3,3,5-trimethylindolenine, 3,3-dimethyl-5
-Chloroindolenine, etc.), imidazole nucleus {eg 1
-Alkylimidazole, 1-alkyl-4-phenylimidazole, 1-alkylbenzimidazole, 1-alkyl-5
-Chlorobenzimidazole, 1-alkyl-5,6-dichlorobenzimidazole, 1-alkyl-5-methoxybenzimidazole, 1-alkyl-5-cyanobenzimidazole, 1-alkyl-5-fluorobenzimidazole, 1-alkyl -5-trifluoromethylbenzimidazole, 1-
Alkyl-6-chloro-5-cyanobenzimidazole, 1-alkyl-6-chloro-5-trifluoromethylbenzimidazole, 1-alkylnaphtho [1,2-d] imidazole, 1-aryl-5,6-dichloro Benzimidazole, 1-aryl-
5-chlorobenzimidazole, 1-arylimidazole, 1-arylbenzimidazole, 1-aryl-5-chlorobenzimidazole, 1-aryl-5,6-dichlorobenzimidazole, 1-aryl-5-methoxybenzimidazole, 1 -Aryl-5-cyanobenzimidazole, 1
-Arylnaphtho [1,2-d] imidazole, wherein the alkyl group has 1 to 8 carbon atoms, for example, an unsubstituted alkyl group such as methyl, ethyl, propyl, isopropyl, butyl, or a hydroxyalkyl group (for example, 2- Hydroxyethyl, 3-hydroxypropyl, etc.) are preferred. Particularly preferred are methyl group and ethyl group. The above aryl is
Represents phenyl, halogen (eg chloro) substituted phenyl, alkyl (eg methyl) substituted phenyl, alkoxy (eg methoxy) substituted phenyl and the like. 1-pyridine nucleus (eg 2-pyridine, 4-pyridine, 5-methyl-2-pyridine, 3-methyl-4-pyridine etc.), quinoline nucleus (eg 2
-Quinoline, 3-methyl-2-quinoline, 5-ethyl-2-quinoline, 6-methyl-2-quinoline, 6-nitro-2-quinoline, 8-fluoro-2-quinoline, 6-methoxy-2-quinoline , 6-hydroxy-2-quinoline, 8-chloro-2-quinoline, 4-quinoline,
6-ethoxy-4-quinoline, 6-nitro-4-quinoline, 8-chloro-4-quinoline, 8-fluoro-4-quinoline, 8-methyl-4-
Quinoline, 8-methoxy-4-quinoline, isoquinoline, 6-
Nitro-1-isoquinoline, 3,4-dihydro-1-isoquinoline, 6-nitro-3-isoquinoline, etc., imidazo [4,5-
b] quinoxaline nuclei (eg 1,3-diethylimidazo [4,5
-b] quinoxaline, 6-chloro-1,3-diallylimidazo [4,5-b] quinoxaline, etc.), oxadiazole nucleus,
Thiadiazole nucleus, tetrazole nucleus, pyrimidine nucleus and the like can be mentioned.

Of the methine groups and substituted methine groups represented by L ¹ , L ² and L ³ , the substituents include, for example, alkyl groups (eg methyl, ethyl etc.), aryl groups (eg phenyl etc.), aralkyl. A group (eg, benzyl group) or a halogen (eg, chloro, bromo, etc.) alkoxy group (eg, methoxy, ethoxy, etc.) and the like, and the substituents of the methine chain may form a 4- to 6-membered ring.

Examples of the optionally substituted alkyl group represented by R ²¹ and R ²² include alkyl groups having 1 to 18 carbon atoms, preferably 1 to 7 carbon atoms, and particularly preferably 1 to 4 carbon atoms. Typically, an unsubstituted alkyl group (eg methyl,
Ethyl, propyl, isopropyl, butyl, isobutyl, hexyl, octyl, dodecyl, octadecyl etc.), substituted alkyl groups such as aralkyl groups (eg benzyl, 2-phenylethyl etc.), hydroxyalkyl groups (eg 2-hydroxyethyl, 3- Hydroxypropyl, etc., carboxyalkyl group (eg, 2-carboxyethyl, 3-carboxypropyl, 4-carboxybutyl, carboxymethyl, etc.), alkoxyalkyl group (eg,
2-methoxyethyl, 2- (2-methoxyethoxy) ethyl, etc.), sulfoalkyl group (for example, 2-sulfoethyl, 3-sulfopropyl, 3-sulfobutyl, 4-sulfobutyl, 2-
[3-sulfopropoxy] ethyl, 2-hydroxy-3-sulfopropyl, 3-sulfopropoxyethoxyethyl, etc.), sulfatoalkyl group (eg, 3-sulfatopropyl, 4-sulfatobutyl, etc.), heterocycle-substituted alkyl A group (for example, 2- (pyrrolidin-2-one-1-yl) ethyl, tetrahydrofurfuryl, etc.), 2-acetoxyethyl, carbomethoxymethyl, 2-methanesulfonylaminoethyl,
There are allyl groups.

Specific examples of the photosensitive dyes represented by the general formula [III] are shown below, but the sensitizing dyes usable in the present invention are not limited to these compounds.

[0065]

[Chemical 13]

[0066]

[Chemical 14]

[0067]

[Chemical 15]

[0068]

[Chemical 16]

[0069]

[Chemical 17]

[0070]

[Chemical 18]

[0071]

[Chemical 19]

[0072]

[Chemical 20]

[0073]

[Chemical 21]

[0074]

[Chemical formula 22]

[0075]

[Chemical formula 23]

[0076]

[Chemical formula 24]

[0077]

[Chemical 25]

[0078]

[Chemical formula 26]

[0079]

[Chemical 27]

[0080]

[Chemical 28]

[0081]

[Chemical 29]

[0082]

[Chemical 30]

[0083]

[Chemical 31]

[0084]

[Chemical 32]

The method of addition, the timing of addition and the amount of addition to the silver halide emulsion of the general formula [III] are in accordance with the general formula [I] and the general formula [II].

The light-sensitive dye used in the present invention can be further combined with a compound which brings about a supersensitizing effect to obtain further spectral sensitivity. Examples of such a compound having a supersensitizing effect include, for example, U.S. Pat.
6,927, 3,511,664, 3,615,613, 3,615,632
No. 3,635,721, etc., JP-A-3-15042, 3-11
Compounds having a pyrimidinylamino group or a triazinylamino group described in 0545 and 4-255841, and British Patent No.
1,137,580, aromatic organic formaldehyde condensates described in JP-A-61-169833, etc., calixarene derivatives described in JP-A-4-184332, halogenated benzotriazole derivatives described in U.S. Pat. Bispyridinium compounds described in JP-A-59-142541 and JP-A-59-188641, quaternary aromatic heterocyclic compounds described in JP-A-59-191032, electron-donating compounds described in JP-A-60-79348 ,
US Pat. No. 4,307,183 described polymer containing aminoarylidene malononitrile units, JP-A-4-149937 described hydroxytetrazaindene derivative, US Pat.
615,633 1,3-oxadiazole derivative described in,
Examples thereof include amino-1,2,3,4-thiatriazole derivatives described in US Pat. No. 4,780,404. The timing of addition of these supersensitizers is not particularly limited, and can be arbitrarily added according to the timing of addition of the above-mentioned photosensitive dye. The addition amount is selected in the range of 1 × 10 ^-6 to 1 × 10 ^-1 mol per mol of silver halide, and the addition amount is 1/100 to 100/1 with the photosensitive dye.

In the present invention, silver halide emulsions described in Research Disclosure No. 308119 (hereinafter abbreviated as RD308119) can be used. The following shows the locations.

[Item] [Page of RD308119] Iodine composition 993 IA item Production method 993 I-A item and 994 E item Crystal habit Normal crystal 993 I-A item Twin 933 I-A Epitaxial 933 I- Item A Halogen composition is uniform 993 IB item is not uniform 933 IB item Halogen conversion 994 I-C item Halogen substitution 994 I-C item Metal-containing 994 I-D item Monodisperse 995 I-F item Solvent addition 995 IF item Latent image forming position Surface 995 IG item Internal 995 IG item Applicable photographic material Negative 995 IH item Positive (including internal fog particles) 995 IH item Mixing emulsion 995 I- Item J Desalting 995 II-A In the present invention, a silver halide emulsion which has been physically and chemically ripened is used. Further, the silver halide emulsion of the present invention may be used in combination with a spectral sensitizer other than the photosensitive dye of the present invention. Additives used in such processes are Research Disclosure No.17643, No.18716 and No.308.
119 (hereinafter abbreviated as RD17643, RD18716 and RD308119, respectively). The following shows the locations.

[Item] [Page of RD308119] [RD17643] [RD18716] Chemical sensitizer 996 III-A Item 23 648 Spectral sensitizer 996 IV-AA, B, C, D, E, H, I, J Item 23-24 648-9 Supersensitizer 996 IV-AE, J Item 23-24 648-9 Antifoggant 998 VI 24-25 649 Stabilizer 998 VI 24-25 649 Known photographs that can be used in the present invention Additives are also described in Research Disclosure above. The following shows the locations.

[Items] [Page of RD308119] [RD17643] [RD18716] Color turbidity inhibitor 1002 VII-I 25 650 Dye image stabilizer 1001 VII-J 25 Whitening agent 998 V 24 UV absorber 1003 VIII C , XIII C Item 25-26 Light absorber 1003 VIII 25-26 Light scattering agent 1003 VIII Filter dye 1003 VIII 25-26 Binder 1003 IX 26 651 Antistatic agent 1006 XIII 27 650 Hardener 1004 X 26 651 Plasticizer 1006 XII 27 650 Lubricant 1006 XII 27 6
50 Activators / Coating aids 1005 XI 26 to 27 650 Matting agent 1007 X VI Developer (contained in light-sensitive material) 1011 XX-B Various couplers can be used in the invention, and specific examples thereof are , Research Disclosure, supra. The relevant locations are shown below.

[Item] [Page of RD308119] [RD17643] [RD18716] Yellow coupler 1001 VII-D item VII C to G item Magenta coupler 1001 VII-D item VII C to G item Cyan coupler 1001 VII-D item VII C Item G Colored coupler 1002 VII-G item VII G item DIR coupler 1001 VII-F item VII F item BAR coupler 1002 VII-F Other useful residue releasing coupler 1001 VII-F item Alkali-soluble coupler 1001 VII-E Item The additives used in the present invention can be added by the dispersion method described in RD308119 XIV.

In the present invention, the above-mentioned RD17643, page 28, RD
The supports described in 18716 pages 647-8 and RD308119 XIX can be used.

The light-sensitive material of the present invention includes the above-mentioned RD308119VII.
An auxiliary layer such as a filter layer or an intermediate layer described in the section -K can be provided.

The light-sensitive material of the present invention is the above-mentioned RD308119VII-K.
Various layer configurations such as the forward layer, the reverse layer, and the unit configuration described in the section can be adopted.

The present invention can be applied to various color light-sensitive materials represented by color negative films for general use or movies, color reversal films for slides or televisions, and color positive films.

In these color light-sensitive materials, the total thickness of all hydrophilic colloid layers on the emulsion layer side is preferably 24 μm or less, more preferably 20 μm or less, and 18 μm or less.
The following are more preferable. The film swelling speed T _1/2 is preferably 30 seconds or less, more preferably 20 seconds or less. The film thickness means a film thickness measured at 25 ° C. and 55% relative humidity (2 hr), and the film swelling rate T _1/2 can be measured according to a method known in the art.

The film swelling speed T _1/2 can be adjusted by adding a hardening agent to gelatin as a binder or changing the aging condition after coating. or,
The swelling rate is preferably 150 to 400%. The swelling rate is calculated from the maximum swollen film thickness under the above-mentioned conditions by the formula:
It can be calculated according to (film thickness) / film thickness.

The color light-sensitive material is the same as RD17643 28, 2 described above.
The development can be carried out by a usual method described on page 9 and RD18716, page 615, left column to right column.

When the color light-sensitive material is used in the form of a roll, it is preferable that it is housed in a cartridge. The most common cartridge is the current 135 format Patrone. In addition, the cartridges proposed in the following patents can also be used.

No. 58-67329, JP-A-58-181035,
U.S. Pat.No. 4,221,479, Japanese Patent Laid-Open Nos. 1-231045 and 2-199451
U.S. Pat.Nos. 4,846,418, 4,848,693, 4,832,27
No. 5.

The present invention can also be applied to the "small photographic roll film cartridge and film camera" filed on January 31, 1992 (Toshihiko Yagi et al.).

The light-sensitive material of the present invention has the above-mentioned RD17643 28 to 29.
RD18716, page 615 and RD308119, XIX.

[0103]

EXAMPLES Specific examples of the present invention will be described below, but the embodiments of the present invention are not limited to these.

In the following examples, the addition amount in the light-sensitive material is the number of grams per 1 m ² unless otherwise specified.
The silver halide and colloidal silver are shown in terms of silver, and the sensitizing dye is shown in the number of moles per mole of silver.

Example 1 (Preparation of Twin Crystal Emulsion T-1) By the following method.
An emulsion with two parallel twin planes was prepared.

A ossein gelatin 80.0 g potassium bromide 47.4 g polyisopropylene-polyethyleneoxy-disuccinate sodium salt (10% methanol solution) 0.48 ml water 8000.0 ml B silver nitrate 1200.0 g water 1600.0 ml C ossein Gelatin 32.2 g Potassium bromide 790.0 g Potassium iodide 70.34 g Water 1600.0 ml D Ammonia water 470.0 ml Solution A and solution C were vigorously stirred at 40 ° C, and solution B and solution C were added in 7.7 minutes by the double jet method. Generated. During this time, pBr was kept at 1.60.

Thereafter, the temperature was lowered to 30 ° C. over 30 minutes.
Further, the liquid D was added in 1 minute, followed by aging for 5 minutes. The concentration of potassium bromide during aging was 0.03 mol / liter, and the concentration of ammonia was 0.66 mol / liter.

After completion of aging, the pH was adjusted to 6.0 and desalting was carried out according to a conventional method. When the seed emulsion grains were observed with an electron microscope, they were hexagonal tabular grains having two twin planes parallel to each other.

The average grain size of the seed emulsion grains is 0.217 μm, 2
The parallel twin plane ratio was 75% in terms of the number ratio of all grains.

(Preparation of Emulsion EM-1 of the Present Invention) An octahedral twin monodisperse emulsion EM-1 having two parallel twin planes according to the present invention was prepared using the following seven kinds of solutions. .

(Solution A) Ocein gelatin 61.0 g Distilled water 1963.0 ml Polyisopropylene-polyethyleneoxy-disuccinate sodium salt (10% methanol solution) 2.5 ml Seed emulsion (T-1) 0.345 mol 28 wt% ammonia solution 308.0 ml 56 wt% acetic acid aqueous solution 358.0 ml 0.003 Methanol solution containing 1 mol of iodine 33.7 ml Distilled water up to 3500.0 ml.

(Solution B) 3.5N ammoniacal silver nitrate aqueous solution (pH adjusted to 9.0 with ammonium nitrate) (Solution C) 3.5N potassium bromide aqueous solution (Solution D) 3 wt% gelatin and silver iodide grains ( 1.40 mol fine grain emulsion (*) * consisting of average grain size of 0.05 μm) The preparation method is shown below.

To 5000 ml of a 6.0 wt% gelatin solution containing 0.06 mol of potassium iodide, 2000 ml of an aqueous solution containing 7.06 mol of silver nitrate and 2000 ml of 7.06 mol of potassium iodide were added for 10 minutes. The pH during fine particle formation was controlled to 2.0 using nitric acid, and the temperature was controlled to 40 ° C. After particle formation, the pH was adjusted to 6.0 using an aqueous sodium carbonate solution.

(Solution E) Fine grains composed of silver iodobromide grains (average grain size 0.04 μm) containing 2 mol% of silver iodide, prepared in the same manner as the silver iodide fine grain emulsion described in Solution D. Emulsion 3.68 mol However, the temperature during the formation of fine particles was controlled at 30 ° C.

(Solution F) 1.75N potassium bromide aqueous solution (Solution G) 56 wt% acetic acid aqueous solution Solution A kept at 70 ° C. in a reaction vessel was mixed with Solution B, Solution C and Solution D for 128 minutes by the simultaneous mixing method. After the addition over a period of time, solution E was then added singly at a constant rate over a period of 7 minutes to grow a seed crystal to 0.806 μm.

Here, the addition rates of solution B and solution C were changed in a function-like manner with respect to time so as to be commensurate with the critical growth rate, and a large number of small particles other than the growing seed crystal were generated and Ostwald ripening was performed to increase the number. It was added at an appropriate addition rate so as not to disperse. The solution D, that is, the silver iodide fine grain emulsion supply, has a multiple structure by changing the rate ratio (molar ratio) with the aqueous ammoniacal silver nitrate solution with respect to the particle size (addition time) as shown in Table 1. A core / shell type silver halide emulsion was prepared.

By using solutions F and G, pAg and pH during crystal growth were controlled as shown in Table 1. In addition,
The pAg and pH were measured using a silver sulfide electrode and a glass electrode according to a conventional method.

After grain formation, desalting treatment was carried out by a conventional method, and then gelatin was added to redisperse the mixture, and the pH was adjusted to 40 ° C.
5.80 and pAg were adjusted to 8.06. From the scanning electron micrograph of the obtained emulsion grains, the average grain size was 0.806 μm and the distribution was wide.
It was confirmed to be a 12.0% octahedral twin monodisperse emulsion.

[0119]

[Table 1]

After optimal chemical sensitization of EM-1 with sodium thiosulfate, chloroauric acid and ammonium thiocyanate, the sensitizing dye was added as shown in Table 2 for 25 minutes at 50 ° C. for 15 minutes. Adsorbed. Each emulsion is then 4-hydroxy
-6-methyl-1,3,3a, 7-tetrazaindene and 1-phenyl-
Stabilized by adding 5-mercaptotetrazole.

Further, the following magenta coupler (M-1)
Is dissolved in ethyl acetate and tricresyl phosphate and emulsified and dispersed in an aqueous solution containing gelatin, and general photographic additives such as extenders and hardeners are added to prepare a coating solution, and the undercoating is performed. Samples 101 to 125 were prepared by coating and drying on the prepared cellulose triacetate support by a conventional method.

[0122]

[Table 2]

Samples 101 to 125 were each divided into three parts to form samples I, II and III, and sample I was subjected to wedge exposure according to a conventional method and immediately subjected to development processing according to the following processing steps. Further, Sample II was subjected to wedge exposure in the same manner as Sample I, and then left in an atmosphere of 40 ° C. and 80% RH for 7 days, and then subjected to the same development processing. However, for sample I and II, the wedge exposure is performed by Kodak's Ratten filter CC-40G and CC
-50G was used as a filter and exposed. And the sample
For III, a residual color test described later was conducted.

(Treatment Process) Treatment Process Treatment Time Treatment Temperature Replenishment Amount * Color development 3 minutes 15 seconds 38 ± 0.3 ° C 780ml Bleach 45 seconds 38 ± 2.0 ° C 150ml fixation 1 minute 30 seconds 38 ± 2.0 ° C 830ml stability 1 Min 38 ± 5.0 ℃ 830ml Dry 1 minute 55 ± 5.0 ℃-* Replenishment amount is the value per 1m ² of light-sensitive material.

The following color developing solutions, bleaching solutions, fixing solutions, stabilizing solutions and their replenishers were used.

(Color Developer and Color Replenisher) Developer Replenisher Water 800 ml 800 ml Potassium carbonate 30 g 35 g Sodium hydrogen carbonate 2.5 g 3.0 g Potassium sulfite 3.0 g 5.0 g Sodium bromide 1.3 g 0.4 g Potassium iodide 1.2 mg-hydroxyl Amine sulfate 2.5g 3.1g Sodium chloride 0.6g-4-Amino-3-methyl-N-ethyl-N- (β-hydroxylethyl) aniline sulfate 4.5g 6.3g Diethylenetriaminepentaacetic acid 3.0g 3.0g Potassium hydroxide 1.2 g 2.0 g Add water to make 1 liter, and use potassium hydroxide or 20% sulfuric acid to adjust the color developer to pH 10.06 and the replenisher to pH 10.18.
Adjust to.

(Bleaching solution and bleach replenishing solution) Bleaching solution replenishing solution Water 700 ml 700 ml 1,3-Diaminopropanetetraacetic acid iron (III) ammonium 125 g 175 g Ethylenediaminetetraacetic acid 2 g 2 g Sodium nitrate 40 g 50 g Ammonium bromide 150 g 200 g Glacial acetic acid 40 g 56 g Water is added to make 1 liter, and the bleaching solution is adjusted to pH 4.4 and the replenisher is adjusted to pH 4.0 using ammonia water or glacial acetic acid.

(Fixing Solution and Fixing Replenishing Solution) Fixing Solution Replenishing Solution Water 800 ml 800 ml Ammonium thiocyanate 120 g 150 g Ammonium thiosulfate 150 g 180 g Sodium sulfite 15 g 20 g Ethylenediaminetetraacetic acid 2 g 2 g Ammonia water or glacial acetic acid was used as a fixing solution at pH 6.2 After adjusting the replenisher to pH 6.5, add water to make 1 liter.

(Stabilizer and stable replenisher) Water 900 ml p-Octylphenol ethylene oxide 10 mol adduct 2.0 g Dimethylolurea 0.5 g Hexamethylenetetramine 0.2 g 1,2-Benzisothiazolin-3-one 0.1 g Siloxane (UCC L -77) 0.1g Ammonia water 0.5ml After adding water to make 1 liter, ammonia water or 50%
Adjust to pH 8.5 with sulfuric acid.

The sensitivity of each sample is represented by the reciprocal of the exposure amount that gives an optical density of fog density + 0.15, and is shown as a relative value with the sensitivity of Sample I of Sample No. 101 as 100.

The residual color test was carried out from the bleaching step of the above-mentioned processing step with Sample III being unexposed and visually evaluated in 5 steps. The highest rank is "5" when no residual color is seen, and "4" or "3" depending on the degree of occurrence of residual color.
"2" and "1" and their ranks shall be sequentially lowered and evaluated.

The results are shown in Table 3.

[0133]

[Table 3]

From Table 3, it can be seen that the samples of the present invention are highly sensitive to the green short wavelength region and have high storage stability when left to stand under high temperature and high humidity. Also, it can be seen that the residual color is suppressed low.

Example 2 The EM-1 used in Example 1 was divided into 10 parts, and several sensitizing dyes shown in Table 4 were added, followed by sodium thiosulfate,
Chloroauric acid and ammonium thiocyanate were added for optimum chemical sensitization at 50 ° C, and then 4-hydroxy-6-methyl-1,
Aging was stopped by adding 3,3a, 7-tetrazaindene and 1-phenyl-5-mercaptotetrazole.

These emulsions are designated A to J and they are listed in Table 4.
Shown in.

[0137]

[Table 4]

On the undercoated cellulose triacetate film support, a multi-layer color light-sensitive material consisting of each layer having the following composition was prepared and designated as sample No. 201. Incidentally, the amount of additive is indicated in grams per photosensitive material 1 m ^2, a silver halide emulsion and colloidal silver are indicated in terms of silver value. Further, the sensitizing dye is shown by the number of moles per mole of silver halide contained in the same layer.

First Layer: Antihalation Layer (HC) Black Colloidal Silver 0.16 UV Absorber (UV-1) 0.30 Gelatin 1.70 Second Layer: Intermediate Layer (IL-1) Gelatin 0.80 Third Layer: Low Sensitivity Red Sensitive Layer (RL) Silver iodobromide emulsion (average grain size 0.30 μm) 0.40 Sensitizing dye (S-1) 1.2 × 10 ^-4 Sensitizing dye (S-2) 0.2 × 10 ^-4 Sensitizing dye (S-3) 2.0 × 10 ^-4 Sensitizing dye (S- ⁴ ) 1.2 × 10 ^-4 Cyan coupler (C-1) 0.33 Colored cyan coupler (CC-1) 0.05 High boiling point solvent (Oil-1) 0.30 Gelatin 0.55 Fourth layer: Medium sensitivity red-sensitive layer (RM) Silver iodobromide emulsion (average particle size 0.40 μm) 0.48 Sensitizing dye (S-1) 1.5 × 10 ^-4 Sensitizing dye (S-2) 0.2 × 10 ^-4 Sensitizing dye (S─3) 2.5 × 10 ^-4 sensitizing dye (S─4) 1.5 × 10 ^-4 cyan coupler (C─1) 0.30 colored cyan coupler (CC─1) 0.05 high-boiling solvent (Oil─1) 0.40 peptidase Chin 0.60 Fifth Layer: High Sensitivity Red-Sensitive Layer (RH) Silver iodobromide emulsion (average grain size 0.51 .mu.m) 0.66 Sensitizing dye (S─1)
1.0 × 10 ^-4 sensitizing dye (S-2) 0.2 × 10 ^-4 sensitizing dye (S-3) 1.7 × 10 ^-4 sensitizing dye (S- ⁴ ) 1.0 × 10 ^-5 cyan coupler (C-2) ) 0.10 Colored cyan coupler (CC-1) 0.01 DIR compound (D-1) 0.02 High boiling point solvent (Oil-1) 0.15 Gelatin 0.53 6th layer: Intermediate layer (IL-2) Gelatin 0.80 7th layer: Low sensitivity green Sensitive layer (GL) Silver iodobromide emulsion (average grain size 0.40 μm) 0.60 Silver iodobromide emulsion (average grain size 0.30 μm) 0.40 Sensitizing dye (S-1) 0.6 × 10 ^-4 Sensitizing dye (S-- 5) 5.1 × 10 ^-4 Magenta coupler (M-1) 0.55 Colored magenta coupler (CM-1) 0.17 DIR compound (D-2) 0.03 High boiling point solvent (Oil-2) 0.70 Gelatin 1.56 Eighth layer: High sensitivity green Sensitive layer (GH) Silver halide emulsion A 0.60 Magenta coupler (M-1) 0.06 Magenta coupler (M-2) 0.02 Colored magenta coupler (CM-2) ) 0.02 DIR compound (D-3) 0.002 High boiling point solvent (Oil-2) 0.15 Gelatin 0.45 9th layer: Yellow filter layer (YC) Yellow colloidal silver 0.08 Formalin scavenger (HS-1) 0.20 Color stain inhibitor (HS-) 2) 0.15 High boiling point solvent (Oil-2) 0.19 Gelatin 0.80 Layer 10: Low sensitivity blue sensitive layer (BL) Silver iodobromide emulsion (average grain size 0.40 μm) 0.18 Silver iodobromide emulsion (average grain size 0.30 μm) ) 0.35 Sensitizing dye (S-9) 5.1 × 10 ^-4 Sensitizing dye (S-10) 2.0 × 10 ^-4 Yellow coupler (Y-1) 0.58 Yellow coupler (Y-2) 0.30 High boiling solvent (Oil 2) 0.15 gelatin 1.20 11th layer: high-sensitivity blue-sensitive layer (BH) silver iodobromide emulsion (average grain size 0.88 μm) 0.45 sensitizing dye (S-9) 2.8 × 10 ^-4 sensitizing dye (S-10 ) 1.0 × 10 ^-4 Yellow coupler (Y-1) 0.10 High boiling point solvent (Oil-2) 0.04 Gelatin 0.50 12th layer: 1st protective layer (Pro- 1) Silver iodobromide emulsion (average grain size 0.07 μm) 0.30 UV absorber (UV-1) 0.07 UV absorber (UV-2) 0.10 High boiling point solvent (Oil-2) 0.07 High boiling point solvent (Oil-3) 0.07 Formalin scavenger (HS-1) 0.25 gelatin 0.80 13th layer: 2nd protective layer (Pro-2) Alkali-soluble matting agent (average particle size 2 μm) 0.13 Polymethylmethacrylate (average particle size 3 μm) 0.02 Gelatin 0.50 Above In addition to the above composition, coating aid Su-1, dispersion aid Su-2, hardeners H-1, H-2, dyes AI-1, AI
-2, stabilizer ST-1, antifoggant AF-1, two kinds of AF-2 having molecular weights of 10,000 and 20,000, and preservative DI-1 were appropriately added.

The structures of the compounds used to prepare the above samples are shown below.

Oil-1: dioctyl phthalate Oil-2: tricresyl phosphate Oil-3: dibutyl phthalate Su-1: dioctyl sodium sulfosuccinate Su-2: sodium tri-i-propylnaphthalene sulfonate HS-1: 1- (3-sulfophenyl) -3-methyl-5-imino-2
-Pyrazoline HS-2: 2-sec-octadecyl-5-methylhydroquinone H-1: 2,4-dichloro-6-hydroxy-s-triazine / sodium H-2: bis (vinylsulfonylmethyl) ether

[0142]

[Chemical 33]

[0143]

[Chemical 34]

[0144]

[Chemical 35]

[0145]

[Chemical 36]

[0146]

[Chemical 37]

[0147]

[Chemical 38]

[0148]

[Chemical Formula 39]

Eighth Layer Silver Halide Emulsion A of Sample No. 201
Instead of the above, Sample Nos. 202 to 210 were prepared by replacing the silver halide emulsions B to J, respectively.

Sample Nos. 201 to 210 are each divided into two and I
V and V, and sample IV is wedge exposed according to the usual method,
Immediately, the same development processing as in Example 1 was performed. Also, sample V
Is a sample after being left in an atmosphere of 40 ° C and 80% RH for 14 days
Wedge exposure was performed in the same manner as IV, and the same development processing was performed.

The sensitivity of each sample is such that the green density is the fog density +
Expressed as the reciprocal of the exposure dose that gives an optical density of 0.15, Sample No. 2
The value is shown as a relative value with the sensitivity of Sample IV of 01 being 100.

The results are shown in Table 5.

[0153]

[Table 5]

Table 5 shows that the samples of the present invention have high sensitivity and high storage stability under high temperature and high humidity.

[0155]

The silver halide photographic emulsion according to the present invention comprises
It has high spectral sensitivity, reduced residual color contamination, and excellent storage stability.

Claims (7)

[Claims] 1. A silver halide photographic emulsion spectrally sensitized with at least two cyanine dyes, wherein at least one of the cyanine dyes has the following general formula [I]:
Alternatively, a silver halide photographic emulsion represented by the general formula [II]. [Chemical 1] [In the formula, each of R ¹ and R ² represents an aliphatic group having 1 to 10 carbon atoms, R ³ represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, and R ⁴ , R ⁵ , R ⁶ and R ⁷ each represent a hydrogen atom, a halogen atom, an alkoxy group, an aryloxy group, an aralkyl group, an alkyl group, an aryl group or a heterocyclic group. However, either one of R ¹ and R ² is a group in which a water-solubilizing group is substituted. Z ¹ is an oxazole ring,
It represents a group of non-metal atoms necessary for forming an oxazoline ring or a condensed oxazole ring. M ¹ represents an ion necessary to cancel the total charge of the molecule, and n ¹ represents the number necessary to neutralize the charge in the molecule. ] [Chemical 2] [In the formula, R ¹¹ , R ¹² and R ¹³ each represent an aliphatic group having 1 to 10 carbon atoms, and V ¹ and V ² each represent a hydrogen atom, an alkyl group, an alkylthio group or an electron-withdrawing group. Represents
R ¹⁴ , R ¹⁵ , R ¹⁶ and R ¹⁷ are each a hydrogen atom, a halogen atom, an alkoxy group, an aryloxy group, an aralkyl group,
It represents an alkyl group, an aryl group or a heterocyclic group. However,
One of R ¹¹ and R ¹² is a group in which a water-solubilizing group is substituted, and ^one of V ¹ and V ² is an electron-withdrawing group. M ² represents an ion necessary for canceling the total charge of the molecule, and n ² represents a number necessary for neutralizing the charge in the molecule. ] 2. The halogen according to claim 1, wherein at least one kind of cyanine dyes other than the cyanine dyes represented by the general formula [I] or [II] is represented by the following general formula [III]. Silver halide photographic emulsion. [Chemical 3] [In the formula, Z ² and Z ³ represent a non-metal atom group necessary for forming a 5- or 6-membered heterocycle, and each may be the same or different. Here, R ²¹ and R ²² may be the same or different and each represents an alkyl group or a substituted alkyl group. L ¹ , L ² and L ³ represent a methine group or a substituted methine group. p and q represent 0 or 1. m represents 0, 1, 2, m is the time for 2 each -L ² = L ³ - may be the same or different. X ^1- represents an anion. k represents 0 or 1. ] 3. The silver halide photographic emulsion according to claim 2, wherein m is 0 or 1 in the general formula [III]. 4. The general formula [III], wherein Z ² and / or Z ³ represents a group of non-metal atoms necessary for forming a substituted or unsubstituted oxazole ring. Silver halide photographic emulsion. 5. The general formula [III], wherein Z ² and / or Z ³ represents a group of non-metal atoms necessary for forming a substituted or unsubstituted thiazole ring. Silver halide photographic emulsion. 6. The compound according to claim ² , wherein Z ² and / or Z ³ in the general formula [III] represents a group of non-metal atoms necessary for forming a substituted or unsubstituted imidazole ring. Silver halide photographic emulsion. 7. At least one of claims 1 to 6
A silver halide photographic light-sensitive material comprising two silver halide photographic emulsions.