JP2000309720A - Organic compound, silver halide emulsion using same as photosensitive dye, and silver halide photographic material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a silver halide emulsion improved in spectral sensitization, photographic characteristics, sensitivity, and storage stability by including a specified organic compound in a silver halide photographic emulsion. SOLUTION: An organic compound represented by the formula is included so that the coverage with a monomolecular film on the surface of each photosensitive particle in a silver halide photographic emulsion may be 40-90%, desirably, 50-80%. In the formula, R1 to R4 are each an aliphatic group; R5 is a substituent or a group of non-metallic atoms necessary to form, together with R1 or R2, a five- or six-membered fused ring; V1 to V4 are H atoms or optionally substituted groups, provided that at least one of them is an aromatic group; M1 is an ion necessary to counterbalance the total charge of the molecule; and m1 is a number necessary to counterbalance the charge of the molecule. In this way, it is possible to obtain an excellent green-sensitive silver halide emulsion stabilized against the low-temperature stagnation of a silver halide emulsion and against the stagnation of a coating fluid, reduced in fluctuation and deterioration in sensitivity, having good long-term stability of a raw film, and reduced in stain with residual color.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel compound, a silver halide photographic emulsion using the same as a photosensitive dye (hereinafter, also referred to as a silver halide emulsion or simply an emulsion) and a silver halide photographic material (hereinafter, referred to as an emulsion). More specifically, the present invention relates to a silver halide photographic light-sensitive material having high sensitivity, no dye contamination, and excellent storage stability and production stability.

[0002]

2. Description of the Related Art The addition of a certain dye to a photosensitive silver halide emulsion broadens the photosensitive wavelength range of the silver halide emulsion.
It is well known that spectral sensitization is performed optically.

A large number of dyes used for this purpose have been known in the art. For example, the theory of the photographic process, 4th edition (1977, Macmillan, Inc.) , N .;
Y. ) P. 194-234, "The Cyanine Soy and Related Compounds" by Francis M. Harmer (1964, John Willy and
Sands, N. Y. ), Dem Stammer, "The Chemistry of Heterocyclic Compounds, Vol. 30," p. 441 to (1977, John Willy and Sons, NY) and various dyes classified as styryl dyes, hemicyanine dyes, cyanine dyes, merocyanine dyes, xanthene dyes, etc. By selecting and combining the lengths of the heterocyclic nucleus or aromatic ring and the conjugated chain, and the substituents, a dye having an arbitrary absorption maximum wavelength in the near ultraviolet to near infrared region is derived.

These dyes called photosensitive dyes or sensitizing dyes must not only extend the photosensitive wavelength range of the silver halide emulsion but also satisfy the following conditions.

1) The spectral sensitization range is appropriate.

2) High spectral sensitization efficiency.

3) No adverse interaction with other additives, for example, stabilizers, antifoggants, coating aids, high-boiling solvents, etc.

4) To not adversely affect the characteristic curve such as fogging and gamma change.

5) The silver halide photographic light-sensitive material containing a sensitizing dye should not change its photographic performance such as fog when aged (especially when stored under high temperature and high humidity).

6) The added photosensitive dye does not diffuse into layers having different photosensitive wavelength ranges and does not cause color turbidity.

7) After the development and fixing, the photosensitive dye is not removed after washing with water to cause no color contamination.

In recent years, with the technical progress of electronic image recording materials, competition in the field of photography has been made. In order to maintain the superiority of silver halide photographic materials, for example, graininess, sharpness, etc. There is an increasing demand for further improvement of image characteristics represented by characteristics, sensitivity, gradation, reproducibility of color tone and the like and rapid processing. That is, in a color photosensitive material having excellent color reproducibility, the green light sensitivity is higher and the photosensitive maximum is 5
It is desired to have a spectrum waveform spread in the range of 30 to 550 nm, and in the case of X-ray sensitive materials, high green light sensitivity in accordance with emission of 545 nm emission line and low residual color contamination concentration after processing derived from photosensitive dyes are required. Is required.

Regarding green sensitization, dyes alone include, for example, US Pat. Nos. 2,647,053, 2,521,705, and 2,072,908; Oxacarbocyanine dyes described in JP-A-012,825 and the like, and JP-B-38-7828.
No. 43-14497 or British Patent No. 815,
172; U.S. Pat. Nos. 2,778,823;
739,149, 2,912,329 and 3,656,959, and the like, and benzimidazolocarbocyanine dyes described in British Patent No. 1,011.
The oxathiacarbocyanine described in 2,825 is known.

Further, for example, Japanese Patent Publication No. 43-22884
No. 44-32753, No. 46-11627, No. 48-25652, Japanese Patent Application Laid-Open No. 46-38694, and the like, a technique combining a specific dye is known. -23931, 57-14834
JP-B-55-14411 and JP-B-56-27864, U.S. Pat. Nos. 3,580,724 and 3,
No. 840,373 and German Patent No. 2,127,671 describe a technique of combining an oxacarbocyanine dye with a benzimidazolooxacarbocyanine dye or an oxathiacarbocyanine dye, and
-4936, JP-A-50-87636 and 54-8
No. 0118, No. 59-116646, No. 59-116
647, 62-191847, U.S. Pat. Nos. 2,688,545 and 3,397,060,
Nos. 3,663,210 and 3,841,609
Nos., British Patent Nos. 1,231,079 and 1,54
No. 2,062 discloses a technique in which an oxacarbocyanine dye and a benzimidazolocarbocyanine dye are combined.

By the way, for rapid processing, the processing time of each processing step such as development, fixing, washing, and drying is shortened.
The load in each process increases. For example, if the development time is simply shortened, the density of the conventional light-sensitive material is reduced, that is, the sensitivity is lowered and the gradation is deteriorated. Also, if the fixing time is shortened, the fixation of silver halide is incomplete and the image quality is deteriorated. Become. Furthermore, the reduction of each processing time is achieved by developing, fixing,
Since the dyes are not sufficiently eluted in each of the water washing treatment steps, color contamination due to the residual dye remains (residual color) and the image quality deteriorates. Therefore, in order to solve such a problem, for example, it is necessary to reduce the amount of silver, increase the developing speed and the fixing speed, reduce the amount of dye, and promote the detachment and / or decoloration of dye. .

On the other hand, in recent years, many techniques using tabular silver halide grains have been disclosed as means for achieving high sensitivity. Tabular silver halide grains have the same volume and a larger surface area than normal crystal grains, so that the amount of photosensitive dye adsorbed on the grain surface can be increased, and spectral sensitivity and image sharpness can be improved. . However, increasing the amount of the dye is undesirable because it results in an increase in the residual color in rapid processing.

If the spectral sensitization can be performed with high sensitivity, the amount of the dye can be expected to be reduced. However, the spectral sensitization by the combination of the dyes described above has little interaction with the photographic additive and is useful as a technique for giving a low fog density. However, no remarkable effect of increasing the color sensitization sensitivity was observed, and the dye amount could not be reduced.

Techniques for improving these problems include, for example, European Patent No. 506,584 and JP-A-5-88293.
And JP-A-5-93975 disclose techniques for using specific benzimidazolocarbocyanines having good decolorization performance as spectral sensitizing dyes.

In Japanese Patent Application Laid-Open No. 5-61148, oxacarbocyanine and benzimidazolocarbocyanine are combined in a specific ratio with a silver halide emulsion having a silver iodide content of 1 mol% or less. It discloses that the chemical sensitization with a tellurium compound is performed to improve the rapid processing property and the residual color. However, although the residual color and the speed of development are improved, they are still insufficient to meet the recent demand levels for various performances, especially when the photosensitive material is stored for a long time under high humidity and high temperature. However, there is a disadvantage that the sensitivity is greatly reduced.

[0020]

Accordingly, a first object of the present invention is to provide a novel compound as a photosensitive dye and a halogenated compound which is spectrally sensitized by using it as a sensitizing dye and has improved photographic characteristics. A second object of the present invention is to provide a silver light-sensitive material, in which a novel compound is combined with a green light-sensitive carbocyanine dye to provide a high-sensitivity, reduced residual color stain, and improved storage stability performance. Provided is a photosensitive material.

[0021]

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

1. A compound represented by the following general formula [I].

[0023]

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[In the formula, R _{1 to} R ₄ each represent an aliphatic group, and R ₅ represents a substituent or a 5- or 6-membered condensed ring with R ₁ or R _2. Represents a non-metallic atomic group. V _{1 to} V ₄ each represent a hydrogen atom or a substitutable group, and at least one of V _{1 to} V ₄ is an aromatic ring group. M ₁ represents an ion required to offset the total charge of the molecule, and m 1 represents a number required to neutralize the charge in the molecule. ] 2. A light-sensitive silver halide photographic emulsion comprising the compound represented by the formula [I].

3. A silver halide photographic emulsion comprising a compound represented by the following general formula [II] and a compound represented by the following general formula [III].

[0026]

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[Wherein, R _{11 to} R ₁₄ each represent an aliphatic group, and at least one of R ₁₂ and R ₁₄ substitutes for a sulfo group or a carboxy group. R ₁₅ represents a substituent or a group of non-metallic atoms necessary for forming a 5- or 6-membered condensed ring with R ₁₁ or R ₁₂ . V ₁₁ ~V ₁₈ each represents a hydrogen atom or a substitutable group. M ₁₁ represents an ion required to offset the total charge of the molecule, m11 represents a number necessary for neutralizing the molecular charge. ]

[0028]

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[In the formula, each of R _{21 to} R ₂₄ represents an aliphatic group, and at least one of R ₂₂ and R ₂₄ replaces a sulfo group or a carboxy group. V _{21 to} V ₂₄ are each a hydrogen atom or a substitutable group, and are selected such that the sum of Hammett σp values added for the groups V _{21 to} V ₂₄ is larger than 0.7. M ₂₁ represents an ion required to offset the total charge of the molecule, m21 represents a number necessary for neutralizing the molecular charge. ] 4. A silver halide photographic emulsion comprising a compound represented by the general formula [II] and a compound represented by the following general formula [IV].

[0030]

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[In the formula, Y ₃₁ represents an oxygen atom, a sulfur atom, a selenium atom or a —N (R ₃₄ ) — group, R ₃₃ represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group;
₃₁ , R ₃₂ and R ₃₄ each represent an aliphatic group, and R ₃₁ and R ₃₂
At least one group replaces a sulfo group or a carboxy group. V _{31 to} V ₃₈ each represent a hydrogen atom or a substitutable group, and V ₃₁ and V ₃₂ , V ₃₂ and V ₃₃ , V ₃₃ and V ₃₄ , V ₃₅
And V ₃₆ , V ₃₆ and V ₃₇ , and V ₃₇ and V ₃₈ , respectively, may be bonded to form a condensed ring. M ₃₁ represents an ion required to offset the total charge of the molecule, m31 represents a number necessary for neutralizing the molecular charge. ] 5. A silver halide photographic emulsion comprising a compound represented by the above general formula [II], a compound represented by the above general formula [III], and a compound represented by the above general formula [IV].

6. 3. A silver halide photographic light-sensitive material comprising at least one layer containing the silver halide photographic emulsion described in 2 above.

[7] 3. A silver halide photographic light-sensitive material comprising at least one layer containing the silver halide photographic emulsion described in 3 above.

8. 5. A silver halide photographic material comprising at least one layer containing the silver halide photographic emulsion described in 4 above.

9. It has at least one layer containing the silver halide photographic emulsion according to the above item 5,
Silver halide photographic material.

Hereinafter, the present invention will be described more specifically.

Formulas [I], [II], [III] and [I
V], R ₁ , R ₂ , R ₃ , R ₄ , R
_{11, R 12, R 13,} R 14, R 21, R 22, R 23, R 24,
As the aliphatic group represented by R ₃₁ , R ₃₂ and R ₃₄ , for example, a branched or straight-chain alkyl group having 1 to 10 carbon atoms (eg, methyl, ethyl, propyl, butyl, pentyl, iso-pentyl) , 2-ethyl-hexyl, octyl, decyl and the like), an alkenyl group having 2 to 10 carbon atoms (for example, ethenyl, 2-propenyl, 3-butenyl, 1-methyl-3-propenyl, 3-pentenyl, 1
-Methyl-3-butenyl, 4-hexenyl, etc.),
An alkynyl group having 2 to 10 carbon atoms (for example, 2-propynyl, 3-butynyl, 3-pentynyl, 2-methyl-
Each group such as 3-butynyl) and an aralkyl group having 7 to 10 carbon atoms (for example, each group such as benzyl and phenethyl).

R₁, R_Two, R_Three, R_Four, R₁₁, R₁₂, R₁₃,
R₁₄, R_{twenty one}, R_{twenty two}, R_{twenty three}, R_{twenty four}, R ₃₁, R₃₂And R₃₄so
The aliphatic groups shown further include a halogen atom (eg,
Nitrogen, chlorine, bromine, etc.), alkoxy (eg
For example, methoxy group, ethoxy group, etc.), aryloxy group
(For example, phenoxy group, p-tolyloxy group, etc.),
Ano group, carbamoyl group (for example, carbamoyl group, N
-Methylcarbamoyl group, N, N-tetramethylenecar
Bamoyl group, N- (2,2,3,3-tetrafluoro
Phenylpropylcarbamoylmethyl group), sulfamo
Yl group (for example, sulfamoyl group, N, N-3-oxo
Sapentamethyleneaminosulfonyl group, etc.), methanesulfur
Honyl group, alkoxycarbonyl group (for example, ethoxy
Carbonyl group, butoxycarbonyl group, etc.), aryl group
(For example, phenyl group, carboxyphenyl group, etc.),
Sil group (eg, acetyl group, benzoyl group, etc.)
Amino group (eg, acetylamino, benzoylamido
And sulfonamide groups (for example, methanesulfone
Amide, butanesulfonamide group, etc.), sulfo group, car
Boxy group, phosphono group, sulfate group, hydroxy
Group, sulfinyl group (for example, trifluoromethanes
Rufinyl, methanesulfinyl group, etc.), sulfonylua
Minocarbonyl group (for example, methanesulfonylamino
Rubonyl, ethanesulfonylaminocarbonyl group, etc.),
Acylaminosulfonyl group (for example, acetamidosulfur
Honyl, methoxyacetamidosulfonyl group, etc.)
Aminocarbonyl group (for example, acetamidocarboni
, Methoxyacetamidocarbonyl group, etc.), sulfy
Nylaminocarbonyl group (for example, methanesulfinyl
Aminocarbonyl, ethanesulfinylaminocarboni
, Etc.).

R ₂ , R ₄ , R ₁₂ , R ₁₄ , R ₂₂ , R ₂₄ , R ₃₁
And the aliphatic group represented by R ₃₂ include, for example, a sulfo group, a carboxy group, a phosphono group, a sulfate group, a hydroxy group, a sulfino group, and a sulfonylaminocarbonyl group (eg, methanesulfonylaminocarbonyl, ethanesulfonylaminocarbonyl group, etc.) An acylaminosulfonyl group (eg, acetamidosulfonyl, methoxyacetamidosulfonyl group, etc.), an acylaminocarbonyl group (eg, acetamidocarbonyl, methoxyacetamidocarbonyl group, etc.), a sulfinylaminocarbonyl group (eg, methanesulfinylaminocarbonyl, ethanesulfinylamino It is preferably substituted with a water-solubilizing group such as a carbonyl group. 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, and ω-sulfo. Propoxycarbonylmethyl, ω-sulfopropylaminocarbonylmethyl, 3-sulfinobutyl, 3-phosphonopropyl, hydroxyethyl, N-methanesulfonylcarbamoylmethyl, 4-sulfo-3-butenyl, 2-carboxy-2-propenyl , O-sulfobenzyl, p-sulfophenethyl, p-carboxybenzyl and the like.

As the substituents represented by R ₅ and R ₁₅ ,
For example, an alkyl group (eg, a methyl group, an ethyl group, a butyl group, an iso-butyl group, etc.), an alkenyl group (a 2-propenyl group, a 1-propenyl group, a 1-methyl-3-butenyl group, etc.), an aralkyl group ( For example, a benzyl group, a phenethyl group, etc., a cycloalkyl group (eg, cyclopropyl group, cyclopentyl group, cyclohexyl group, etc.), a halogen atom (eg, fluorine atom, chlorine atom, bromine atom, iodine atom), an aryl group (eg, , Phenyl group, naphthyl group, etc.), heterocyclic group (for example, pyridyl group, pyrrolyl group, indolyl group, imidazolyl group, thiazolyl group,
A pyrimidinyl group), an acyl group (eg, an acetyl group,
Benzoyl group), cyano group, trifluoromethyl group,
Alkoxy group (for example, methoxy group, ethoxy group, etc.),
Aryloxy group (eg, phenoxy group, naphthoxy group, etc.), acyl group (eg, acetyl group, etc.), acyloxy group (eg, acetyloxy group, benzoyloxy group), acylamino group (eg, acetylamino group, benzoylamino group) Groups), an alkoxycarbonyl group, and a group such as a methoxycarbonyl group and an ethoxycarbonyl group.

As the 5- or 6-membered condensed ring which can be formed by R ₁ or R ₂ and R ₅ and R ₁₁ or R ₁₂ and R ₁₅ , for example, 1,2,3-trihydropyrrolo [1 , 2
-A] benzimidazole ring, 1,2,3,4-tetrahydropyrido [1,2-a] benzimidazole ring and the like.

Examples of the alkyl group represented by R ₃₃ include a methyl group, an ethyl group, a butyl group and an iso-butyl group, and examples of the aryl group include a phenyl group and a naphthyl group. As the heterocyclic group, for example, a furyl group, a thienyl group, a pyridyl group, a pyrrolyl group,
Examples include an indolyl group, an imidazolyl group, a thiazolyl group, and a pyrimidinyl group. Each of these groups may have a substituent, and the substituent can be selected from the groups described in the description of the aliphatic group represented by R _{1 to} R ₃₄ ,
Specifically, 2-methoxyethyl group, benzyl group, p-
Tolyl group, m-chlorophenyl group, o-carboxyphenyl group, 5-methyl-2-furyl group, 4-methoxy-2
-Thienyl group, 1,3-bis (2-methoxyethyl)-
Form a 6-hydroxy-2,4-diketo-1,2,3,4, tetrahydro-5-pyrimidyl group and the like.

V ₁ , V ₂ , V ₃ , V ₄ , V ₁₁ , V ₁₂ , V ₁₃ ,
_{V 14, V 15, V 16} , V 17, V 18, V 21, V 22, V 23, V
_{24, V 31, V 32,} V 33, V 34, V 35, V 36, V 37 and V
Examples of the displaceable group represented by ₃₈ include an alkyl group (for example, a methyl group, an ethyl group, a butyl group, an iso-
Butyl group, t-pentyl group, etc., alkenyl group (2-propenyl group, 1-propenyl group, 1-methyl-3-butenyl group, etc.), aralkyl group (eg, benzyl group, phenethyl group, etc.), alkoxy group ( For example, methoxy group, ethoxy group, isopropyl group, etc., alkylthio group (eg, methylthio group, ethylthio group, etc.), aryloxy group (eg, phenoxy group, 2-naphthoxy group, etc.), arylthio group (eg, phenylthio group, A 1-naphthylthio group, etc.), a halogen atom (eg, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc.), an aryl group (eg,
Phenyl group, naphthyl group, etc.), heterocyclic group (for example, 2-
Furyl group, 2-thienyl group, pyridyl group, pyrrolyl group,
An indolyl group, an imidazolyl group, a thiazolyl group, a pyrimidinyl group, an acyl group (eg, an acetyl group, a benzoyl group, etc.), a cyano group, a trifluoromethyl group, a sulfonyl group (eg, a methanesulfonyl group, a benzenesulfonyl group, etc.), Sulfinyl group (eg, trifluoromethanesulfinyl, methanesulfinyl group, benzenesulfinyl group, etc.), sulfamoyl group (eg, sulfamoyl group, N-phenylsulfamoyl group, morpholinosulfamoyl group, etc.), carbamoyl group (eg,
Carbamoyl group, N, N-dimethylcarbamoyl group, morpholinocarbamoyl group, etc.), acylamino group (eg, acetylamino group, benzoylamino group, etc.), sulfonylamino group (eg, methanesulfonylamino group,
Benzenesulfonylamino group, etc., alkoxycarbonyl group (for example, methoxycarbonyl group, ethoxycarbonyl group, trifluoroethoxycarbonyl group, etc.). These groups may be further substituted with groups such as a hydroxyl group and a carboxyl group in addition to the groups described above.

For V ₁ -V ₄ , at least one group is an aromatic ring group, which also includes a heteroaryl ring,
Preferred groups include, for example, phenyl group, cyano-substituted phenyl group (for example, groups such as 4-cyanophenyl and 3-cyanophenyl), and halogen-substituted phenyl group (for example, 4
-Chlorophenyl, 4-bromophenyl, etc.), 2
-Furyl, 2-thienyl, pyridyl, pyrrolyl and the like.

The groups V _{21 to} V ₂₄ are selected so that when the Hammett σp values of the substituents are added, the sum is larger than 0.7, and more preferably, the range is 0.86 to 1.80. .

V ₃₁ and V ₃₂ , V ₃₂ and V ₃₃ , V ₃₃ and V ₃₄ , V
Examples of the condensed ring which can be formed by ₃₅ and V ₃₆ , V ₃₆ and V ₃₇ , and V ₃₇ and V ₃₈ include, for example, a 6-membered saturated or unsaturated carbocyclic group, and a 5- or 6-membered Heterocyclic groups include, for example, naphtho [2,1-d] imidazole, naphtho [1,2-d] imidazole, naphtho [2,3-d] imidazole, 1-aza-4,5,6 together with the azole ring.
-Trihydrobenzo [h, i] indolizine, naphtho [2,1-d] oxazole, naphtho [1,2-d] oxazole, naphtho [2,3-d] oxazole, 6,
It forms 7,8,9-tetrahydronaphtho [1,2-d] oxazole, thieno [1,2-f] benzimidazole and the like. On these condensed rings, any of the groups mentioned above for V _{1 to} V ₃₈ can be substituted.

The Hammett σp value used in the above general formula [III] is a substituent constant determined from the electronic effect of the substituent on the hydrolysis of ethyl benzoate by Hammett et al., And is described in Journal of Organic Chemistry. Vol.23, p420-427 (1958), Experimental Chemistry Course Vol.14, Maruzen Publishing Co., Ltd., Physical Organic Chemistry (McGraw Hill Book)
Company: 1940), Drag Design VII (Acad)
emic Press New York: 1976
) And the structure-activity relationship of drugs (Nankodo: 1979).

M ₁ , M ₁₁ , M ₂₁ and M ₃₁ each represent a cation or an acid anion. Specific examples of the cation include a proton, an organic ammonium ion (for example, triethylammonium, triethanolammonium, pyridinium, 1- Each ion such as ethylpyridinium),
Inorganic cations (for example, cations such as lithium, sodium, potassium, and calcium) are mentioned. Specific examples of acid anions include, for example, halogen ions (for example, chloride ion, bromine ion, iodine ion, etc.), p-toluenesulfonic acid Ion, perchlorate ion, boron tetrafluoride ion, sulfate ion and the like. m1, m11, m2
1 and m31 become 0 when each compound forms an inner salt and the charge is neutralized.

The compound of the present invention represented by the general formula [I] is a benzimidazolocarbocyanine having a substituent at the α-position on the methine chain, or a substituent at the α-position and the N-position of the methine chain. Form a 5- or 6-membered ring between
Trihydropyrrolo [1,2-a] benzimidazole nucleus or 1,2,3,4-tetrahydropyrido [1,
2-a] a benzimidazolocarbocyanine structure having a benzimidazole nucleus as at least one basic nucleus, wherein at least one aromatic group is substituted on the condensed benzene ring of the imidazole nucleus. Things.

1,2,3-trihydropyrrolo [1,2-
a) benzimidazole nucleus or 1,2,3,4-tetrahydropyrido [1,2-a] benzimidazolocarbocyanine dye having at least one basic nucleus is, for example, disclosed in U.S. Pat. 93
No. 1,156, the compound of the general formula [I] according to the present invention is not specifically described in this patent, and these compounds are used in a silver halide emulsion. It was not expected that the disadvantage that fogging would easily occur in the case of the above was improved, and that the effect of suppressing the progress of fog under long-term storage conditions could be obtained.

These compounds can be applied not only to silver halide photographic systems but also to non-silver-salt photosensitive systems such as diazo photosensitive materials and PS plate materials as photosensitive dyes utilizing their light absorption.

As shown in the description of the general formula, the compound represented by the general formula [II] has a substituent at the α-position of the methine group and has a carboxyl group on the nitrogen of the azole ring of the dye nucleus. Is a compound having at least one substituent having a group or a sulfo group. However, when these are used in combination with the general formula [III] or the general formula [IV], a preferable photographic effect, that is, a drawback that fogging easily occurs. The above-mentioned U.S. Patent and other known documents have not described any improvement or an effect of suppressing the progress of fog under long-term storage conditions.

Specific examples of the photosensitive dye represented by formula (I) or (II) are shown below, but the photosensitive dye used in the present invention is not limited to these compounds.

[0054]

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[0055]

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[0056]

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[0057]

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[0058]

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[0059]

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Next, the general formula [II] used in the present invention
Specific examples of the photosensitive dye represented by the formula (I) are given below.

[0061]

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[0062]

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[0063]

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[0064]

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Next, the above-mentioned general formula [IV] used in the present invention
Specific examples of the photosensitive dye represented by

[0066]

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[0067]

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[0068]

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[0069]

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[0070]

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[0071]

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Other examples of the dye represented by the general formula [IV] of the present invention include the compounds described in JP-A-4-9040, such as II-3, II-4, II-6 and II. -7, II-
8, II-10, II-13, II-14, II-16, II-1
7, II-18, II-20, II-21, II-24 to II-4
4 and the like can be similarly used.

The photosensitive dyes represented by the general formulas [I] to [IV] according to the present invention merely show one state of the resonance structure, and are imidazo in the ultimate structure of the resonance system. The lilidene structure can have an imidazolium structure, the pyrroleimidazolylidene structure can have a pyrroleimidazolium structure, the pyridoimidazolylidene structure can have a pyridoimidazolium ion structure, and the oxazolylidene structure can have an oxazolium structure.

The photosensitive dyes represented by the general formulas [I] to [IV] according to the present invention include, for example, British Patent No. 955,96
No. 1, U.S. Pat. Nos. 2,739,149 and 3,932
No. 1,156, Japanese Patent Publication No. 43-10251,
Nos. 43-10252 and 44-16589, JP-A-5-88293, JP-A-6-230501, and JP-A-6-29
No. 8731, Ann. , 596, 209 (19
55); Org. Chem. , 24, 420 (19
55); Chem. Soc. , 1955, 327
5, Zh. Obshch. Khim. , 1962, 3
2, 1581-1586, by FM Hammer, Cyanindice Rerated Compounds IV, V, VI
Chapters 89-199. (Jhon Wiley & So
ns, New York, London 1964); M. Sturmer (Heterocyclic Compounds Special Topics in Heterocyclic Chemistry) Chapter VIII IV. 482-515 (Jhon Wiley & Sons, New York)
k, London 1977) and the like.

The compounds represented by the above general formulas [I] to [IV] (hereinafter also referred to as the compounds of the present invention and the photosensitive dyes of the present invention) used in the present invention can be prepared by a conventionally known method. It can be added to an emulsion. For example,
Protonation dissolution addition method, dispersion addition with a surfactant, dispersion addition to a hydrophilic substrate, addition as a solid solution, or a water-soluble solvent dissolving the dye described in Research Disclosure No. 21802, etc. (For example, low-boiling solvents such as water, methanol, ethanol, propyl alcohol, acetone, and fluorinated alcohols, and high-boiling solvents such as dimethylformamide, methylcellosolve, and phenylcellosolve) alone or in a mixed solvent thereof. It is added to the emulsion by arbitrarily selecting and using a method of adding the compound. The amount of the compounds represented by the general formulas (I) to (IV) varies depending on the kind of the dye and the structure, composition, ripening condition, purpose, purpose and the like of the silver halide. It is preferable that the coverage of the monomolecular layer on the surface of the conductive particles be 40% or more and 90% or less, and more preferably 50% to 80%.

The compound of the present invention represented by the general formulas (I) to (IV) may be added at any stage during the emulsion production process from physical ripening to completion of chemical ripening. During ripening, prior to the addition of the chemical sensitizer in the chemical ripening step, or immediately after the addition of the chemical sensitizer,
Addition of the compound of the present invention has an effect of obtaining higher spectral sensitivity and is preferably used.

These photosensitive dyes may be added to the emulsion at the same time or separately at different times, and the order and time interval may be arbitrarily determined depending on the purpose.

The spectral sensitivity of the photosensitive dye used in the present invention can be further increased by using a compound having another supersensitizing effect. Examples of the compound having such a supersensitizing effect include a compound having a pyrimidinylamino group or a triazinylamino group, an aromatic organic formaldehyde condensate, a calixarene derivative, a halogenated benzotriazole derivative, a bispyridinium compound, Aromatic heterocyclic quaternary salt compound, electron-donating compound, polymer containing aminoarylidenemalononitrile unit, hydroxytetrazaindene derivative, 1,3-oxadiazole derivative, amino-1,2,3,4- Thiatriazole derivatives and the like. The timing of addition of these supersensitizers is not particularly limited, and they can be arbitrarily added according to the timing of the addition of the photosensitive dye. The amount of addition is selected in the range of 1 × 10 ^-6 to 1 × 10 ^-1 mol per mol of silver halide, and it is used in a molar ratio of 1/10 to 10/1 with the photosensitive dye.

The silver halide composition used in the silver halide emulsion of the silver halide photographic light-sensitive material of the present invention includes:
It is arbitrarily selected from silver iodobromide, silver bromide, silver chlorobromide, silver chloroiodobromide, silver chloride and silver chloroiodide. The shape of the silver halide grains used in the present invention may be any shape. Cubic, octahedral, tetradecahedral, spherical or aspect ratio 3
Although any of the above tabular crystals, potatoes and the like can be used, tabular crystals are particularly preferred.

Hereinafter, tabular grains will be described as typical examples of the silver halide grains of the present invention.

The tabular silver halide grains preferably used in the present invention are crystallographically classified as twins. Twins are silver halide crystals having one or more twin planes in one grain, and the classification of twin morphology is based on the report by Klein and Moiser in Photographies Correspondents (Photographisches Korresp).
ondenz), Vol. 99, p. 99, and Vol. 100, p. 57.

The tabular silver halide grains preferably used in the present invention mainly have an even number of parallel twin planes, and these twin planes may or may not be parallel to each other. However, it is particularly preferable to have two twin planes.

The tabular silver halide grains used in the present invention have an average ratio (average aspect ratio) of grain diameter / thickness (aspect ratio) of 2 or more. The average aspect ratio of the tabular silver halide grains used in the present invention is preferably from 2 to 12, more preferably from 3 to 8.
It is.

The outer wall of the crystal of the tabular silver halide grains according to the present invention may consist essentially of the {111} plane or the {100} plane. In addition, it may have both the {111} plane and the {100} plane. In this case, 50% or more of the particle surface is the {111} plane, more preferably 60% to 90% is the {111} plane, and particularly preferably 70 to 95% is the {111} plane. It is preferable that the plane other than the {111} plane is mainly the {100} plane. This surface ratio utilizes the difference in the adsorption dependency between the {111} plane and the {100} plane in the adsorption of the sensitizing dye [T. Tani, J .; Ima
ging Sci. 29, 165 (1985)].

The tabular silver halide grains according to the present invention include:
It may be polydisperse or monodisperse, but is preferably monodisperse. Specifically, (standard deviation of particle size / average particle size) × 100 = 25% or less when the width of distribution is defined by the relative standard deviation (coefficient of variation) expressed by the width (%) of particle size distribution Is preferably 20% or less, more preferably 15% or less.
It is as follows.

In the present invention, the tabular silver halide grains are preferably hexagonal. Hexagonal tabular grains (hereinafter also referred to as hexagonal tabular grains) are defined as the main plane (｛1
(11 ° plane) is hexagonal, and the maximum adjacency ratio is 1.0 to 2.0. Here, the maximum adjacent side ratio is the ratio of the length of the side having the maximum length to the length of the side having the minimum length forming a hexagon. In the present invention, the hexagonal tabular grains have a maximum adjacent side ratio of 1.0 to 1.0.
If it is 2.0, it is also preferable that the corner is rounded. The length of a side having a rounded corner is represented by the distance between the intersection of the extended straight line portion of the side and the extended straight line portion of the adjacent side. It is also preferred that the tabular grains are further rounded and are substantially circular.

In the present invention, it is preferable that at least one half of each side forming the hexagon of the hexagonal tabular grain is substantially a straight line. In the present invention, the adjacent side ratio is 1.
More preferably, it is 0 to 1.5.

The silver halide grains according to the present invention may have dislocation lines. The dislocation is described, for example, in J. Mol. F. Hamil
ton, Photo. Sci. Eng, 57 (1967)
And T. Shiozawa, J .; Soc. Photo. S
ci. Japan, 35, 213 (1972) and can be observed by a direct method using a low-temperature transmission electron microscope. That is, the silver halide grains taken out so as not to apply enough pressure to generate dislocations from the emulsion are placed on a mesh for observation with an electron microscope, and the sample is prepared so as to prevent damage (printout, etc.) by an electron beam. Observation is performed by a transmission method in a state of cooling. At this time,
The thicker the particles, the more difficult it is for the electron beam to pass,
High pressure type (200 kV for 0.25 μm thick particles)
The above can be observed more clearly using an electron microscope.

From the photographs of the particles obtained by such a method, the position and number of dislocations for each particle can be determined. The dislocation position of the silver halide grains according to the present invention is 0.58 from the center of the halide grains toward the outer surface.
It is desirable that it occurs in the region from L to 1.0 L, but more preferably in the region from 0.80 L to 0.98 L. The direction of the dislocation line is approximately from the center toward the outer surface, but often meanders.

In the present invention, the center of the silver halide grains is defined by dispersing silver halide microcrystals in a methacrylic resin in the same manner as in the method described in the abstract of Inoue et al. Solidified, ultrathin sections with a microtome, with the largest cross-sectional area and 90%
Focusing on the sliced sample having the above cross-sectional area, this is the center of a circle when a circumscribed circle that is the smallest with respect to the cross section is drawn. In the present invention, the distance L from the center to the outer surface is defined as the distance between the point at which the line intersects the outer periphery of the particle when a straight line is drawn outward from the center of the circle and the center of the circle.

Regarding the number of dislocations in the silver halide grains according to the present invention, it is desirable that at least 50% (number) of grains containing one or more dislocations be present, and the ratio (number) of tabular grains having dislocation lines be present. Is higher.

In the present invention, the particle diameter is a diameter when a projected image of a particle is converted into a circular image having the same area. The projected area of a grain can be determined from the sum of the grain areas. In each case, a silver halide crystal sample distributed on a sample table to such an extent that no grain overlap occurs can be obtained by observing the sample with an electron microscope.

The average projected area diameter of the tabular silver halide grains in the present invention is represented by a circle equivalent diameter of the projected area of the grains, and is preferably 0.30 μm or more, more preferably 0.30 μm to 5 μm. More preferably 0.40μ
m to 2 μm.

The particle size can be obtained by projecting the particles at a magnification of 10,000 to 70,000 times with an electron microscope and measuring the projected area on the print.

The average particle size (φi) is expressed by n
And when the frequency of particles having a particle size φi is ni, it can be obtained by the following equation.

Average particle size (φi) = Σnidi / n (The number of measured particles is indiscriminately 1.000 or more.) The particle thickness is obtained by obliquely observing the sample with an electron microscope. Can be. The preferred thickness of the tabular grains preferably used in the present invention is 0.03 to 1.0.
μm, and more preferably 0.05 to 0.5 μm.

The ratio (b / a) of the longest distance (a) between two or more parallel twin planes of the silver halide grains of the present invention and the thickness (b) of the grains is preferably 5 or more. ,
It is preferable that the ratio is 50% (number) or more.

The tabular silver halide grains preferably used in the present invention may have a uniform composition, but may contain at least two silver halide grains having substantially different halogen compositions.
Grains having a core / shell structure having a two-layer structure may be contained in the photosensitive silver halide emulsion layer.

The silver halide grains of the present invention may be so-called halogen conversion type (conversion type) grains. The halogen conversion amount is from 0.2 mol% to the silver amount.
It is preferably 2.0 mol%, and the conversion may be performed during physical ripening or after physical ripening. As a method of halogen conversion, an aqueous halogen solution or fine silver halide particles having a smaller solubility product with silver than the halogen composition of the grain surface before the halogen conversion is usually added. The particle size at this time is preferably 0.2 μm or less, more preferably 0.02 μm or less.
０．１0.1 μm.

The silver halide grains of the present invention are preferably grown by, for example, a method of depositing silver halide on a seed crystal as described in Examples of JP-A-60-138538.

In the method for producing a silver halide photographic emulsion according to the present invention, in which a water-soluble silver salt solution and a water-soluble halide solution are supplied to a protective colloid in order to obtain a tabular silver halide emulsion, A) Silver iodide content of 0 to 5 mol%
From the initial stage of the formation of silver halide precipitates,
The core particles forming step to maintain the pBr of the mother liquor to 2.5 to -0.7 is provided, (b) Following the nucleic particle generation step, 10 ^-5 mol per mol of silver halide of the silver halide solvent in the mother liquor ~
Providing a seed grain forming step of forming silver halide seed grains containing 2.0 mol and being substantially monodisperse spherical twins,
Alternatively, following the core particle generation step, the temperature of the mother liquor is set to 40 to
A seed grain forming step of raising the temperature to 80 ° C. to form silver halide twin seed grains is provided. (C) Then, a water-soluble silver salt solution and a water-soluble halide solution and / or halogenated fine particles are added to form seed grains. Is preferably used. Here, the mother liquor is a liquid (including a silver halide emulsion) which is used for preparing a silver halide emulsion up to a completed photographic emulsion.

The silver halide grains formed in the grain forming step are twin grains composed of 0 to 5 mol% of silver iodide.

A water-soluble silver salt may be added for the purpose of adjusting the ripening during the seed particle forming step used in the present invention. The seed grain growing step for enlarging the silver halide seed grains is carried out during the precipitation of silver halide and during the Ostwald ripening.
It is achieved by controlling Ag, pH, temperature, concentration of silver halide solvent and silver halide composition, and addition rate of silver salt and halide solution.

In preparing the emulsion according to the present invention, a known silver halide solvent such as ammonia, thioether, thiourea or the like may be present during the step of forming seed grains and growing the seed grains.

In order to obtain tabular silver halide grains according to the present invention, conditions for enlarging the produced seed grains include, for example, JP-A-51-39027 and JP-A-55-14232.
No. 9, 58-113928, 54-48521 and 58-49938, a water-soluble silver salt solution and a water-soluble halide solution are added by a double jet method, and the addition speed is controlled by the particle enlargement. A method may be used in which the nucleus formation does not occur and the Ostwald ripening does not occur, and the temperature is gradually changed. As another condition for enlarging the seed particles, the Abstracts of the 58th Annual Meeting of the Photographic Society of Japan 1983
As seen in the section, add silver halide fine particles and dissolve,
A method of enlarging by recrystallization may also be used.

For growth, an aqueous silver nitrate solution and an aqueous halide solution can be added by a double jet method, but the iodine can also be supplied into the system as silver iodide.
The addition rate is such that no new nuclei are generated, and the rate at which the size distribution does not spread due to Ostwald ripening,
That is, it is preferable to add in a range of 30 to 100% of the rate at which new nuclei are generated.

In producing the silver halide emulsion of the present invention, stirring conditions during production are extremely important. As the stirrer, an apparatus described in JP-A-62-160128 in which an additive liquid nozzle is installed in the liquid near the mother liquor suction port of the stirrer is particularly preferably used. In this case, the rotation speed of the stirring is preferably set to 400 to 1200 rpm.

The silver iodide content and the average silver iodide content of the silver halide grains of the present invention were determined by the EPMA method (Electro
n Probe Micro Analyzer). According to this method, a sample in which emulsion grains are well dispersed so as not to be in contact with each other is prepared, and elemental analysis of a part smaller than X-ray analysis by electron beam excitation in which an electron beam is irradiated can be performed. By this method, the halogen composition of each grain can be determined by determining the characteristic X-ray intensity of silver and iodine emitted from each grain. If the silver iodide content is determined for at least 100 grains by the EPMA method, the average silver iodide content can be determined from the average thereof.

In the preparation of the photosensitive silver halide emulsion of the present invention, the seed emulsion has two or more twin planes in which 50% or more of the total projected area of the seed grains are parallel to each other. It is preferable that both the coefficient of variation and the coefficient of variation of the longest distance (at) between twin planes of the seed particles are 35% or less.

Even if the variation coefficient of only the thickness of the seed grains or only (at) is set to 35% or less, it is not possible to suppress the variation coefficient of the twin plane distance (a) of the grown grains to 35% or less. No, it is necessary that both be established at the same time.

This is probably because twin planes are generally formed at the stage of nucleation, but some are formed during growth.

Furthermore, the silver halide grains according to the present invention can be produced in the course of forming and / or growing grains by cadmium salts, zinc salts, lead salts, thallium salts, iridium salts (including complex salts), rhodium salts (including complex salts). At least one metal ion selected from the group consisting of a complex salt and an iron salt (including a complex salt) to add these metal elements inside the particles and / or in the particle surface layer. By placing the particles in a suitable atmosphere, reduction sensitization nuclei can be provided inside the grains and / or on the surface of the grains.

The effect of the reducing agent added at a desired point in time of particle formation is to add an oxidizing agent such as hydrogen peroxide (water) and its adduct, peroxoacid salt, ozone, and I ₂ at a desired point in time. It is preferable to deactivate and suppress or stop the reducing agent. The oxidizing agent can be added at any time during the period from the formation of silver halide grains to the chemical sensitization step.

In the silver halide emulsion of the silver halide photographic light-sensitive material according to the present invention, unnecessary soluble salts may be removed at the end of the growth of silver halide grains, or may remain contained. When removing the salts, use Lisa
H Disclosure (hereinafter abbreviated as RD) 17643
It can be performed based on the method described in Item II.

The silver halide emulsion layer containing the group of grains in the present invention may contain grains of various shapes as long as the effects of the present invention are not impaired.

The silver halide emulsion of the present invention can be subjected to chemical sensitization. Chemical sensitization is performed under process conditions such as pH,
There is no particular limitation on the pAg, temperature, time, etc., and the reaction can be performed under conditions generally used in the art. For chemical sensitization, sulfur sensitization using a compound containing sulfur capable of reacting with silver ions or active gelatin, selenium sensitization using a selenium compound, tellurium sensitization using a tellurium compound, a reducing substance Reduction sensitization method used, gold and other, noble metal sensitization method using noble metal and the like can be used alone or in combination, among them, selenium sensitization method, tellurium sensitization method, reduction sensitization method and the like are preferably used, In particular, a selenium sensitization method is preferably used.

In the case of selenium sensitization, the selenium sensitizer used comprises a wide variety of selenium compounds. For example, U.S. Patent Nos. 1,574,944, 1,602,592, 1,623,499, and JP-A-60-150046.
No., JP-A-4-25832, JP-A-4-109240,
And selenium compounds described in JP-A-4-147250 and the like. Useful selenium sensitizers include colloidal selenium metal, isoselenocyanates (eg, allyl isoselenocyanate), selenoureas (eg, N,
N-dimethylselenourea, N, N, N'-triethylselenourea, N, N, N'-trimethyl-N'-heptafluoroselenourea, N, N, N'-trimethyl-N'-
Heptafluoropropylcarbonylselenourea, N,
N, N'-trimethyl-N'-4-nitrophenylcarbonylselenourea, etc., selenoketones (eg, selenoacetone, selenoacetophenone, etc.), selenoamides (eg, selenoacetamide, N, N-dimethylselenobenzamide, etc.) , Selenocarboxylic acids and selenoesters (eg, 2-selenopropionic acid, methyl-3-selenobutyrate, etc.), selenophosphates (eg, tri-p-triselenophosphate, etc.),
Selenides (such as diethyl selenide and diethyl diselenide) and phosphine selenides (such as triphenylphosphine selenide, pentafluorophenyl-diphenylphosphine selenide, and tris (m-chlorophenyl) phosphine selenide). Can be Particularly preferred selenium sensitizers are selenoureas, selenamides, and phosphine selenides.

The amount of the selenium sensitizer varies depending on the selenium compound used, silver halide grains, chemical ripening conditions and the like, but is generally from 10 ^-8 mol to 10 mol per mol of silver halide.
^Use about ^-4 moles. Depending on the properties of the selenium compound used, water or methanol, a method of dissolving in a single or mixed solvent of an organic solvent such as ethanol, or a method of pre-mixing with a gelatin solution and adding,
The compound can be added by a method disclosed in JP-A-4-140739, that is, a method of adding a mixed solution with a polymer soluble in an organic solvent in the form of an emulsified dispersion.

The temperature of chemical ripening using a selenium sensitizer is 4
A range from 0 to 90C is preferred. More preferably, it is 45 ° C or more and 80 ° C or less. The pH is 4-9 and the pAg is 6-
A range of 9.5 is preferred.

For tellurium sensitizers and sensitization methods, see US Pat. Nos. 1,623,499 and 3,320,069.
No. 3,772,031 and No. 3,531,28
9, No. 3,655,394, and British Patent No. 235
No. 211, No. 1, 121, 496, No. 1, 29
No. 5,462, No. 1,396,696, Canadian Patent No. 800,958, JP-A-4-204640, JP-A-4-330430 and the like.

Examples of useful tellurium sensitizers are telluroureas (eg, N, N-dimethyltellurourea, tetramethyltellurourea, N-carboxyethyl-N, N'-dimethyltellurourea, N, N'- Dimethyl-N'-phenyltellurourea), phosphine tellurides (eg, tributylphosphine telluride, tricyclohexylphosphine telluride, triisopropylphosphine telluride, butyl-diisopropylphosphine telluride, dibutylphenylphosphine telluride), telluramides ( Examples thereof include telluroacetamide, N, N-dimethyltellurobenzamide), telluroketones, telluroesters, and isotellurocyanates. The technology for using the tellurium sensitizer is based on the technology for using the selenium sensitizer.

By placing the silver halide emulsion in a suitable reducing atmosphere, so-called reduction sensitization can be performed on the grain surface. Preferred examples of the reducing agent include thiourea dioxide and ascorbic acid and derivatives thereof. Other preferred reducing agents include hydrazine,
Examples thereof include polyamines such as diethylenetriamine, dimethylamine borane, and sulfite.

The amount of the reducing agent to be added depends on the type of reduction sensitizer, the particle size of silver halide grains, the composition and crystal habit, the temperature of the reaction system, p.
It is preferable to change the temperature depending on environmental conditions such as H and pAg. For example, in the case of thiourea dioxide, a preferable result can be obtained by using about 0.01 to 2 mg per mol of silver halide as a rough guide. In the case of ascorbic acid, the range is preferably about 50 mg to 2 g per mol of silver halide.

As conditions for reduction sensitization, the temperature is about 40 to 7
0 ° C., time is about 10 to 200 minutes, pH is about 5 to 11, p
Ag is preferably in the range of about 1-10.

As the water-soluble silver salt, silver nitrate is preferable. By adding a water-soluble silver salt, so-called silver ripening, which is a kind of reduction sensitization technique, is performed. The pAg during silver ripening is suitably from 1 to 6, and preferably from 2 to 4. Conditions such as temperature, pH, and time are preferably in the above-described reduction sensitization condition range. As a stabilizer for a silver halide photographic emulsion containing silver halide grains subjected to reduction sensitization, the following general stabilizers can be used. For example, the stabilizer is disclosed in JP-A-57-82831. Antioxidants and / or V.I. S. Gahle
r's dissertation [Zeithlift fur wiss
enshaftliche Photographi
e Bd. 63, 133 (1969)] and JP-A-54
Good results are often obtained when thiosulfonic acids described in US Pat. No. -1019 are used in combination. These compounds may be added at any stage of the emulsion production process from the crystal growth to the preparation process immediately before coating.

In the present invention, fine grains of silver iodide may be added to the silver halide emulsion during the process from chemical ripening to coating. Here, the process from chemical ripening to coating includes during chemical ripening and means that fine grain silver iodide is added to the process from coating to coating. Further, the fine grain silver iodide used in the present invention may be either cubic γ-AgI or hexagonal β-AgI, or a mixture thereof.

The addition timing of the fine grain silver iodide in the present invention may be any of the steps from the chemical ripening step to immediately before coating, but is preferably the chemical ripening step.

The term "chemical ripening step" used herein refers to a period from the point when the physical ripening and desalting operations of the emulsion of the present invention are completed to the point when a chemical sensitizer is added and then the operation for stopping the chemical ripening is performed. Point between. The addition of the fine grain silver iodide may be carried out several times at intervals, or another chemically-ripened emulsion may be added after the addition of the fine grain silver iodide. The temperature of the emulsion of the present invention when adding fine grain silver iodide is preferably in the range of 30 to 80 ° C, more preferably 40 to 6 ° C.
A range of 5 ° C. is particularly preferred.

The silver halide light-sensitive material according to the present invention includes:
Various photographic additives can be used. Known additives include, for example, RD17643 (Dec. 1978)
18716 (November 1979) and 308
119 (Dec. 1989). The types of compounds and the locations described in these three RDs are listed below.

[0130]

[Table 1]

The emulsion of the silver halide photographic light-sensitive material according to the present invention may contain a developing agent such as aminophenol, ascorbic acid, pyrocatechol or the like in an emulsion layer or other layers.
A developing agent such as hydroquinone, phenylenediamine or 3-pyrazolidone may be included.

The support which can be used in the silver halide photographic light-sensitive material of the present invention includes, for example, the aforementioned RD17
643 on page 28 and RD308119 on page 1009. Suitable supports include polyethylene terephthalate film, cellulose triacetate, cellulose nitrate, polyethylene terephthalate, polyesters such as polyethylene-2,6-naphthalate, polyolefins such as polyethylene, polystyrene, baryta paper, paper laminated with polyethylene, etc.
Glass, metal and the like can be mentioned.

These supports may optionally be used, for example,
An undercoating process such as corona discharge treatment and installation of a subbing polymer adhesive layer is performed.

The hydrophilic protective colloid used for preparing the silver halide photographic light-sensitive material of the present invention may be a gelatin derivative such as acetylated gelatin or phthalated gelatin, in addition to the gelatin used in ordinary silver halide emulsions. , Water-soluble cellulose derivatives and other synthetic or natural hydrophilic polymers.

In the silver halide photographic light-sensitive material of the present invention, various techniques and additives known in the art can be used as necessary. For example, in addition to the photosensitive silver halide emulsion layer, auxiliary layers such as a protective layer, a filter layer, an antihalation layer, a crossover light cut layer, and a backing layer can be provided. Sensitizers, noble metal sensitizers, couplers, high boiling solvents, antifoggants, stabilizers, development inhibitors, bleach accelerators, fixing accelerators, color mixture inhibitors, formalin scavengers, colorants, hardeners, surfactants Agents, thickeners, plasticizers, slippers, ultraviolet absorbers, anti-irradiation dyes, filter light-absorbing dyes, polymer latex, heavy metals, antistatic agents, matting agents and the like can be incorporated by various methods.

The above-mentioned additives are described in more detail in RD17643 (December 1978),
431 (August 1979), 18716 (November 1979) and 308119 (December 1989).

Next, the processing method for the silver halide photographic light-sensitive material of the present invention will be described.

The silver halide photographic light-sensitive material according to the present invention provides a method for processing a silver halide photographic light-sensitive material in which the total processing time is 15 seconds to 90 seconds. The method for developing a silver halide photographic light-sensitive material of the present invention is performed by an automatic processor, and the steps from development to drying are completed within 90 seconds. That is, the time from when the tip of the photosensitive material starts to be immersed in the developing solution to when the tip comes out of the drying zone through a processing step (so-called Dry)
(Dry to dry time) is within 90 seconds, more preferably within 60 seconds.

Specifically, the development time is 5 seconds to 45 seconds, preferably 8 seconds to 30 seconds. Development temperature is 25 ° C to 50 ° C
Is preferable, and 30 ° C to 40 ° C is more preferable.

The fixing temperature and time are about 20 ° C. to 50 ° C. and 6 hours.
The time is preferably from 20 seconds to 20 seconds, and more preferably from 6 seconds to 15 seconds at 30 ° C to 40 ° C. The drying time may be generally 35 to 100 ° C., preferably 40 to 80 ° C., or a drying zone provided with heating means by far-infrared rays may be provided in the automatic developing machine.

An automatic developing machine equipped with a mechanism for applying water or a rinsing liquid of an acidic solution having no fixing ability to the photosensitive material during each of the developing, fixing and washing steps (Japanese Patent Application Laid-Open No.
-264953) may be used. Further, a device capable of adjusting a developing solution and a fixing solution may be incorporated.

To develop the silver halide photographic light-sensitive material of the present invention, for example, T.I. H. The Theory of the Photographic Process by James 4
Edition (The Theory of the Photo)
graphic Process, fourth Ed
ition) pages 291-334 and Journal of the American Chemical Society (Journ)
al of the American Chemica
l Society) 73, 3,100 (195
1), JP-A-4-15641, JP-A-4-16841
Developers such as those described in No. can be used effectively.
Dihydroxybenzenes, such as hydroquinone, para-aminophenols, such as p-aminophenol, N-
Examples of 3-pyrazolidones such as methyl-p-aminophenol and 2,4-diamiphenol include 1-phenyl-3-pyrazolidones, 1-phenyl-3-pyrazolidone, 1-phenyl-4-methyl-4 -Hydroxymethyl-3-pyrazolidone, 5,5-dimethyl-1-phenyl-3-pyrazolidone and the like are preferably used in combination.

The preferred amount of the above-mentioned paraaminophenols and 3-aminopyrazolidones is 0.004 mol / liter, more preferably 0.04 to 0.12.
Mol / l.

The total molar number of dihydroxybenzenes, paraaminophenols, and 3-pyrazolidones contained in all the components of the developing solution is preferably 0.1 mol / liter or less.

Preservatives may include sulphites, such as potassium sulphite, sodium sulphite, reductones, such as piperidinohexose reductone, which are preferably 0.2 to 1 mol / l, more preferably Preferably, 0.3 to 0.6 mol / liter is used. Also, the addition of a large amount of ascorbic acids leads to processing stability.

The alkaline agent includes a pH adjusting agent such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium tertiary phosphate and potassium tertiary phosphate. Further, borate described in JP-A-61-28708, saccharose, acetoxime, 5-sulfosalicylic acid, phosphate described in JP-A-60-93439,
A buffer such as a carbonate may be used. The content of these chemicals should be adjusted to a pH of the developer of 9.0 to 13, preferably pH 1
Choose to be 0-12.5.

Examples of solubilizers include polyethylene glycols and esters thereof. Examples of sensitizers include
For example, a development accelerator, a surfactant and the like such as a quaternary ammonium salt can be contained.

The silver sludge inhibitor is disclosed in JP-A-56-1.
No. 06244, silver stain inhibitor, JP-A-3-5
The sulfides and disulfide compounds described in Japanese Patent Application No. 1844, and the cysteine derivatives or triazine compounds described in Japanese Patent Application No. 4-92947 are preferably used.

As the organic inhibitor, azole organic antifoggants such as indazole, imidazole, benzimidazole, triazole, benzotriazo, tetrazole and thiadiazole compounds are used.

The inorganic inhibitors include sodium bromide, potassium bromide, potassium iodide and the like. In addition,
L. F. A. Menson, "Photographic Processing Chemistry," Focal Press (19
66), pages 226-229, U.S. Pat.
No. 015, No. 2,592,364, JP-A-48-6
No. 4933 may be used. Chelating agents for concealing calcium ions mixed in tap water used in the treatment liquid include chelating agents having a chelate stabilization constant of 8 or more with iron described in JP-A-1-193853 as an organic chelating agent. It is preferably used. Examples of the inorganic chelating agent include sodium hexametaphosphate, calcium hexametaphosphate, and polyphosphate. The development temperature is preferably 25 to 50 ° C, more preferably 30 to 50 ° C.
４０40 ° C. The development time is 5 to 90 seconds, more preferably 8 to 60 seconds. Processing time is Dry to
Dry for preferably 20 to 210 seconds, more preferably 3 seconds.
0 to 90 seconds.

The replenishment of the processing solution replenishes the amount corresponding to the processing agent fatigue and oxidation fatigue. As a replenishment method, Japanese Patent Application Laid-Open No. 55-126
No. 243, replenishment by feeding speed,
Japanese Patent Application Laid-Open No. 1-14991
Area replenishment controlled by the number of continuously processed sheets described in No. 56 may be used, and a preferable replenishment amount is 500 to 150 cc.
/ M ² .

As the fixing solution composition used in the method for processing a silver halide photographic light-sensitive material according to the present invention, a usual acidic hardening solution can be used.

Specific examples of the present invention will be described below, but the present invention is not limited to the following examples unless the gist of the present invention is exceeded.

[0154]

EXAMPLES Example 1 (Synthesis of Compound I-7) << Synthesis of Intermediate >> Synthesis of Intermediate 1: "Synthesis of 4-pyrrolidino-3-nitrobenzotrifluoride" 4-trifluoromethyl-2-nitro -46 g of chlorobenzene and 35 g of pyrrolidine were added to 100 ml of ethanol, and the mixture was heated under reflux for 2 hours. After the reaction, the solvent was distilled off, and the remaining crystals were collected by filtration and washed with water. Recrystallization from ethanol gave Intermediate 1. Yield 52 g (98% yield). Melting point 58
° C.

Synthesis of Intermediate 2: "Synthesis of 5-trifluoromethyl-1,2-trimethylenebenzimidazole" 40 g of Intermediate 1 was dissolved in 250 ml of acetic acid, and catalytically reduced using 5% palladium on carbon as a catalyst. did. After removing the catalyst, 84 ml of 34.5% aqueous hydrogen peroxide was carefully added and reacted at 80 to 86 ° C. Acetic acid was distilled off, and the residue was neutralized with a 10% aqueous sodium carbonate solution to obtain crude crystals. Recrystallization from ethanol gave Intermediate 2. Yield 25 g (70% yield). 145-149 ° C.

Synthesis of Intermediate 3: "Synthesis of 5-trifluoromethyl-1,2-trimethylene-3-ethylbenzimidazolium = p-toluenesulfonate" 1.1 g of intermediate 2 and methyl p-toluene After combining 1.1 g of sulfonate and reacting at 130 ° C. for 30 minutes,
The generated crystals were washed with acetone to obtain Intermediate 3. Yield 1.6 g (78% yield).

Synthesis of Intermediate 4: "3- (1-ethyl-2)
Synthesis of -methyl-5-phenyl-3-benzimidazolio) propanesulfonate 4.5 g of 1-ethyl-2-methyl-5-phenylbenzimidazole and 3 g of 1,3 propane sultone with 6 g of sulfolane Crystals formed by reacting at 120 ° C. for 20 minutes are collected by filtration, washed with acetone, and 6.8 g of Intermediate 4
was gotten. Melting point 292-293 [deg.] C (decomposition).

Synthesis of Intermediate 5: "3- (1-ethyl-2)
-Synthesis of (2-anilinoethenyl) -5-phenylbenzimidazolio) propanesulfonate "6.8 g of intermediate 4 and 4.6 g of diphenylformamidine and 2 ml of m-cresol were combined for 140 to 15
After heating and reacting at 0 ° C. for 4 hours, acetone was added to the generated crystals, which was filtered, washed with acetone, ethanol, and water, and dried to obtain 7.6 g of Intermediate 5. Melting point 290 ° C or higher.

Synthesis of Intermediate 6: "3- (1-ethyl-2)
Synthesis of-(2- (N-acetyl) anilinoethenyl) -5-phenylbenzimidazolio) propane sulfonate 7.6 g of Intermediate 5, 30 ml of acetic anhydride and 7 ml of triethylamine are combined and reacted at 90 to 100 ° C. for 15 minutes. After that, acetone was added, the crystals were collected by filtration, washed with acetone, and the crude crystals were recrystallized from methanol to obtain 7.4 g of Intermediate 6. Melting point 290 ° C or higher.

<< Synthesis of Compound of the Present Invention >> Synthesis Example 1 (Synthesis of Compound I-7) 1 g of Intermediate 3 and 1.2 g of Intermediate 6 were combined with 3 ml of dimethyl sulfoxide (abbreviated as DMSO) and 1,8-diazabicyclo [ [5,4,0] undec-7-ene (abbreviated as DBU) in a mixed solution of 0.8 ml and reacted at 93 ° C. for 5 minutes. Ethanol was added to obtain crude crystals, which were recrystallized from methanol to obtain a dye. Yield 1.1 g (yield 75
%). λmax: 506 nm (in methanol). ε = 1
84,000 (in methanol).

Example 2 (Synthesis of Compound I-11) Compound I-11 was obtained in the same manner as in Example 1.

Λmax: 508 nm (in methanol).
ε = 199,000 (in methanol).

Example 3 (Synthesis of Compound I-17) Compound I-17 was obtained in the same manner as in Example 1.

Λmax: 510 nm (in methanol).
ε = 213,000 (in methanol).

Example 4 (Preparation of Seed Emulsion-1) Seed emulsion (T-
1) was prepared.

A1 ossein gelatin 100 g potassium bromide 2.05 g 11.5 l with water B1 ossein gelatin 55 g potassium bromide 65 g potassium iodide 1.8 g 0.2N sulfuric acid 38.5 ml 2.6 l with water C1 ossein gelatin 75g Potassium bromide 950g Potassium iodide 27g Water 3.0l D1 Silver nitrate 95g Water 2.7l E1 Silver nitrate 1410g Water 3.2l A1 solution with reactor temperature kept at 60 ° C, B1 solution and D1
One solution was added by a controlled double jet method over 30 minutes, and then, C1 and E1 solutions were added by a controlled double jet method over 105 minutes, and both were stirred at 500 rpm. The flow rate was such that no new nuclei were generated with the growth of the particles, and so-called Ostwald ripening was performed. During the addition of the silver ion solution and the halide ion solution, the pAg was adjusted to 8.3 ± 0.05 using a potassium bromide solution, and the pH was adjusted to 2.0 ± 0.1 using sulfuric acid.

After the addition was completed, the pH was adjusted to 6.0, and then, to remove excess salts, precipitation and desalting were performed using an aqueous solution of Demol N (manufactured by Kao Atlas) and an aqueous solution of magnesium sulfate.

When the obtained seed emulsion was observed with an electron microscope, it was a cubic monodisperse emulsion having an average particle diameter of 0.27 μm and a particle size distribution of 17% and a slightly cubic shape.

Preparation of Em-1 A monodisperse core / shell emulsion was prepared using the above seed emulsion (T-1) and the following seven kinds of solutions.

A2 ossein gelatin 10 g ammonia water (28%) 28 ml glacial acetic acid 3 ml seed emulsion (T-1) 0.119 mol equivalent Equivalent to 600 ml with water B2 ossein gelatin 0.8 g potassium bromide 5 g potassium iodide 3 g water C2 Ossein gelatin 2 g Potassium bromide 90 g Finished to 240 ml with water D2 Silver nitrate 9.9 g Ammonia water (28%) 7.0 ml Finished to 110 ml with water E2 Silver nitrate 130 g Ammonia water (28%) 100 ml 240 ml with water F2 Potassium bromide 94 g Finished to 165 ml with water G2 Silver nitrate 9.9 g Ammonia water (28%) 7.0 ml Finished to 110 ml with water A2 solution was kept at 40 ° C. and stirred at 800 rpm with a stirrer. The pH of solution A2 was adjusted to 9.90 using acetic acid,
Seed emulsion-1 was ingested, dispersed and suspended, and then the G2 solution was added at a constant speed over 7 minutes to adjust the pAg to 7.3. Further, B
Solution 2 and solution D2 were added simultaneously over 20 minutes. The pAg at this time was kept constant at 7.3. PH = 8.83, pA using potassium bromide solution and acetic acid over a further 10 minutes
After adjusting g = 9.0, C2 solution and E2 solution were simultaneously added to 30 g.
It was added over a minute.

At this time, the flow rate ratio at the time of addition and at the end of addition was 1:10, and the flow rate was increased with time.
In addition, the pH is decreased from 8.83 to 8.00 in proportion to the flow rate ratio. When the C2 solution and the E2 solution are added in only 2/3 of the total amount, the F2 solution is additionally injected, and it takes 8 minutes. Added quickly. At this time, the pAg increased from 9.0 to 11.0. Further, acetic acid was added to adjust the pH to 6.0.

After the addition, to remove excess salts, precipitation and desalting were carried out in the same manner as in the seed emulsion described above.
An emulsion Em-1 having an average silver iodide content of about 2 mol% at pH 5.85 at 8.5 and 40 ° C. was obtained.

When the obtained emulsion was observed with an electron microscope, it was a rounded tetrahedral monodisperse core / shell type emulsion having an average particle size of 0.55 μm and a particle size distribution of 14%.

(Preparation of Seed Emulsion-2) Seed emulsion (T-2) was prepared as follows.

A3 ossein gelatin 24.2 g water 9657 ml polypropyleneoxy-polyethyleneoxy-disuccinate sodium salt (10% aqueous ethanol) 6.78 ml potassium bromide 10.8 g 10% nitric acid 114 ml B3 2.5N silver nitrate aqueous solution 2825 ml C3 bromide Potassium 824 g Potassium iodide 23.5 g Finished to 2825 ml with water D3 1.75 N aqueous potassium bromide solution Silver transfer control amount at 35 ° C below JP-B-58-58288 and 58-5828
Using a mixing stirrer described in No. 9, 464.3 ml of each of the solution B3 and the solution C3 was added to the solution A3 by a simultaneous mixing method.
Nucleation was performed by adding over a minute.

After stopping the addition of the solution B3 and the solution C3, it takes 60 minutes to raise the temperature of the solution A3 to 60 ° C., adjust the pH to 5.0 with a 3% KOH aqueous solution, and then again. The solution B3 and the solution C3 were added at a flow rate of 55.4 ml / min for 42 minutes by the simultaneous mixing method. The silver potential (measured with a silver ion selective electrode using a saturated silver-silver chloride electrode as a reference electrode) during the temperature rise from 42 ° C. to 60 ° C. and re-mixing with the solutions B3 and C3 was +8 mV using the solution D3. And +16 mV.

After the addition was completed, the pH was adjusted with a 3% aqueous KOH solution.
Was immediately adjusted to 6, and desalting and washing were immediately performed.

In this seed emulsion, 90% or more of the total projected area of the silver halide grains is composed of hexagonal tabular grains having a maximum adjacent side ratio of 1.0 to 2.0, and the thickness of the hexagonal tabular grains is 0.06 μm.
m and the average particle size (in terms of circular diameter) were confirmed to be 0.59 μm by an electron microscope.

Preparation of Em-2 A tabular emulsion Em-2 was prepared using the above seed emulsion-2 and the following three kinds of solutions.

A4 ossein gelatin 5.26 g Polypropylene oxy-polyethylene oxy-disacnate sodium salt (10% aqueous ethanol) 1.4 ml Seed emulsion (T-2) 0.094 mol equivalent Equivalent to 569 ml with water B4 ossein gelatin 15. 5 g Potassium bromide 114 g Potassium iodide 3.19 g Finish up to 658 ml with water C4 Silver nitrate 166 g Finish up to 889 ml with water Add solution B4 and solution C4 to solution A4 vigorously stirred at 60 ° C.
It was added by the double jet method in 7 minutes. During this time, the pH was kept at 5.8 and the pAg was kept at 8.7 throughout. B4 liquid and C4
The addition rate of the liquid was linearly increased so as to be 6.4 times at the beginning and at the end.

After completion of the addition, precipitation and desalting were carried out in the same manner as in Em-1 to remove excess salts, and pAg 8.5, 40
At pH 5.85 at an average silver iodide content of about 2.0
A mole% emulsion was obtained.

When the obtained emulsion was observed with an electron microscope, 82% of the projected area was tabular silver halide grains having an average grain size of 0.98 μm, a grain size distribution of 18%, and an average aspect ratio of 4.5. there were.

Preparation of Em-3 A tabular emulsion Em-3 having a core / shell structure was prepared using the seed emulsion (T-2) and the following four solutions.

A5 ossein gelatin 11.7 g Polypropylene oxy-polyethylene oxy-disuccinate sodium salt (10% ethanol solution) 1.4 ml Seed emulsion (T-2) Equivalent to 0.1 mol Equivalent to 550 ml with water B5 ossein gelatin 5. 9 g Potassium bromide 4.6 g Potassium iodide 3.0 g Finished to 145 ml with water C5 Silver nitrate 10.1 g Finished to 145 ml with water D5 Ossein gelatin 6.1 g Potassium bromide 94 g Finished to 304 ml with water E5 Silver nitrate 137 g Watered 304 ml The solution B5 and the solution C5 were added to the solution A5 which was vigorously stirred at 70 ° C. in 58 minutes by a double jet method. Next, D5 solution and E5 solution were added to the same solution by a double jet method for 48 minutes. During this time, the pH was kept at 5.8 and the pAg was kept at 8.7.
After completion of the addition, desalting and precipitation were carried out in the same manner as in the case of emulsion Em-2.
At 0 ° C., an emulsion having a pAg of 8.5 and a pH of 5.85 and an average silver iodide content of about 2.0 mol% was obtained.

Observation of the obtained emulsion with an electron microscope revealed that 81% of the projected area had a mean particle size of 0.96 μm, the size distribution was 18%, and the tabular halogen had an average aspect ratio of 4.5. It was silver halide particles.

The emulsions Em-1 to Em-3 were respectively heated to 60 ° C., and a predetermined amount of the spectral sensitizing dye shown in Table 2 was added as a dispersion of fixed fine particles. Was added, and after 60 minutes, a silver iodide fine grain emulsion was added, followed by ripening for 2 hours in total. At the end of ripening, 4-hydroxy-6-methyl-1,
An appropriate amount of 3,3a, 7-tetrazaindene (TAI) was added. The additives other than the spectral sensitizing dye and the amounts added are shown below.

(Presentation of Sensitizer) Potassium thiocyanate 95 mg Chloroauric acid 2.5 mg Sodium thiosulfate 2.0 mg Pentafluorophenyl-diphenylphosphine selenide 2.0 mg Silver iodide fine particles 850 mg Stabilizer (TAI) 1 g Spectral sensitization A solid fine particle dispersion of a dye is disclosed in JP-A-5-297.
No. 496, prepared by the method according to the method.
That is, a predetermined amount of the spectral sensitizing dye is added to water whose temperature has been previously adjusted to 27 ° C., and a high-speed stirrer (dissolver) is used at 3.500 rpm
For 30-120 minutes at room temperature.

Next, the additives described below were added to the thus spectrally sensitized emulsion to prepare an emulsion coating solution sample. In addition, a protective layer coating solution was also prepared according to a prescription as described below, and these were coated to obtain a coating sample No. Nos. 1 to 21 were produced.

In order to examine the stagnation property of the above-mentioned coating solution sample after preparation, a reference coating solution left at 40 ° C. for 30 minutes and a coating solution left at 40 ° C. for 8 hours to form a coating solution were formed. .

(Coating) The obtained coating solution was prepared in such a manner that the amount of silver per side of the support was 2.0 g / m ² and the amount of gelatin added was 3.1 g.
/ M ² and so as to perform double-sided simultaneous coating on a support using two slide hopper type coaters, and dried to obtain samples. The support was 175 μm thick and had a glycidyl methacrylate of 50 wt.
%, 10% by weight of methyl acrylate, and 40% by weight of butyl methacrylate. The following filter dye (solid dispersion) was added to an aqueous dispersion of the copolymer obtained by diluting the copolymer to a concentration of 10% by weight. And a solution prepared by dispersing gelatin and applying as an undercoat liquid was used.

[0191]

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The additives added to the above emulsion are as follows. The amount of addition is shown per 1 mol of silver halide.

1,1-Dimethylol-1-bromo-1-nitromethane 70 mg t-butylcatechol 400 mg polyvinylpyrrolidone (molecular weight 10,000) 1.0 g styrene-maleic anhydride copolymer 2.5 g nitrophenyl-triphenylphospho Numium chloride 50 mg Ammonium 1,3-dihydroxybenzene-4-sulfonate 2.0 g C ₄ H ₉ OCH ₂ CH (OH) CH ₂ N (CH ₂ COOH) ₂ 1.5 g 1-phenyl-5-mercaptotetrazole 15 mg

[0194]

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Protective layer solution A protective layer coating solution was prepared according to the following formulation. The additives are shown in an amount per liter of the coating solution.

Lime-treated inert gelatin 68 g Acid-treated gelatin 2.0 g Sodium-i-amyl-n-decylsulfosuccinate 1.0 g Polymethyl methacrylate (a matting agent having an area average particle size of 3.5 μm) 1.1 g Silicon dioxide particles (Matting agent having an area average particle size of 1.2 μm) 0.5 g (CH ₂ ＣＨCHSO ₂ C ₂ H ₄ CONHCH ₂ ) ₂ (hardening agent) 500 mg C ₄ F ₉ SO ₃ K 2.0 mg C ₁₂ H ₂₅ CONH (CH ₂ CH ₂ O) ₅ H 2.0 g

[0197]

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[0198]

[Table 2]

Next, the coating amount sample No. 1-1 to N
o. Each of 1-21 was allowed to stand under the following two conditions, and a substitute experiment for preservability was performed.

Condition A: Reference sample left at 23 ° C. and 55% RH or less for 4 days Condition B: Storage test sample left at 40 ° C. and 80% RH or less for 4 days Each sample was subjected to two intensifying screens KO- 250 (manufactured by Konica Corporation)
The tube was exposed to X-rays at a tube voltage of 80 kVp and a tube current of 100 mA for 0.05 seconds through an aluminum wedge. Next, an automatic developing machine SRX-502 (Konica Corporation)
And processed with a developing solution and a fixing solution having the following formulation.

(Developer Formulation) Part-A (for 12 liter finishing) Potassium hydroxide 450 g Potassium sulfite (50% solution) 2280 g Diethylenetriaminepentaacetic acid 120 g Sodium hydrogen bicarbonate 132 g 5-methylbenzotriazole 1.2 g 1-phenyl-5 -Mercaptotetrazole 0.2 g Hydroquinone 340 g Part-B (for finishing 12 L) Glacial acetic acid 170 g Triethylene glycol 185 g 1-Phenyl-3-pyrazolidone 22 g 5-Nitroindazole 0.4 g Starter Glacial acetic acid 120 g Potassium bromide 225 g Add water Finish to 1.0 liter (fixer solution formulation) Part-A (for 18 liter finishing) Ammonium thiosulfate (70 wt / vo 1%) 6000 g Sodium sulfite 110 g Sodium acetate trihydrate 4 50 g sodium citrate 50 g gluconic acid 70 g 1- (N, N-dimethylamino) -ethyl-5-mercaptotetrazole 18 g Part-B aluminum sulfate 800 g To prepare a developing solution, Part A and Part B were simultaneously added to about 5 l of water and stirred. Add water while dissolving and finish to 12 liters.
The pH was adjusted to 10.40 with glacial acetic acid. This is used as a developer. The starter described above is used for 20 of the developer.
ml / l was added to adjust the pH to 10.26 to prepare a working solution.

The fixing solution was prepared by adding Part A, P
ArtB was added at the same time, and water was added while stirring and dissolving.
and the pH was adjusted to 4.4 using sulfuric acid and NaOH. This was used as a fixing replenisher.

Incidentally, the processing temperature and the processing time were respectively set to the developing 3
8 ° C 15 seconds, fixing 35 ° C, 15 seconds, water washing 20 ° C, 10
Seconds, drying at 50 ° C., and the total processing time was 45 seconds by dry to dry.

<Evaluation of Sensitivity> The processed sample was subjected to PDA-
After measuring the developed silver concentration with a Konica 65 (manufactured by Konica Corporation) and determining the characteristic curve, the sensitivity was determined by the reciprocal of the exposure amount giving a density of fog +1.0. It was expressed as a relative value with the sensitivity of 1-1 being 100.

<Evaluation of stagnation and storage property> The stagnation property was determined by aging a coating solution for 30 minutes at a temperature of 40 ° C., and setting the sensitivity of the sample stored under the storage condition A to 40 ° C. The sample applied after 8 hours of aging was used as the SCA, and the value of ΔSp (SiA / SCA) was used as a measure of sensitivity variation due to stagnation after preparation of the coating solution.

Further, the sensitivity of the sample stored under the above-mentioned storage condition B was changed to S by applying the sample aged at 40 ° C. for 8 hours.
CB and the sensitivity of the sample stored under the storage condition A was SC
As A, the value of ΔSs (SCA / SCB) was used as a measure of the sensitivity fluctuation of the storage property. Further, ΔFs (FCB-FCA) was obtained from each of the fogs at that time, and was used as a measure of fog fluctuation of the storage stability. The smaller the value of ΔSp and ΔSs approaches 1, and the smaller the value of ΔFs, the more excellent the production stability (stagnation) and storage stability with time.

<Evaluation of Residual Color> The unexposed sample, which was applied after being aged at 40 ° C. for 30 minutes and stored under the storage condition A, was processed in the above-described processing step, and the residual color of the obtained sample was measured. It was visually evaluated on a 5-point scale. Those having no residual color are ranked as the highest rank "5". Hereinafter, "4" according to the degree of occurrence of the residual color,
"3", "2", and "1" were evaluated by sequentially lowering the rank. “2” and “1” are levels that are not practically preferable. Table 3 shows the above results.

[0208]

[Table 3]

As is clear from Table 3, the sample of the present invention showed little change in sensitivity due to the stagnation of the coating solution, and had good storage stability of the raw film over time. Furthermore, the samples of the present invention also showed little residual color contamination by the dye.

Example 5 Preparation of Emulsion Em-4 With reference to the description of JP-A-5-34851, a seed emulsion having two parallel twin planes (T-
3) was prepared.

Solution A10 Ossein gelatin 80.0 g Potassium bromide 47.4 g HO (C ₂ H ₄ O) _m (CH (CH ₃ ) CH ₂ O) _19.8 (C ₂ H ₄ O) _n H (m + n = 9) .77) 10% by weight methanol solution 0.48 g with water 8000 ml solution B10 silver nitrate 1200 g with water 1600 ml solution C10 ossein gelatin 32.2 g potassium bromide 790 g potassium iodide 70.34 g with water 1600 ml solution D10 ammonia water 470 ml Using a stirrer described in JP-A-62-160128, 4
Solution B10 and solution C10 were added to solution A10 vigorously stirred at 0 ° C. by a double jet method for 7.7 minutes,
Nucleation was performed. During this time, pBr was kept at 1.60.

Then, the temperature was lowered to 20 ° C. over 35 minutes. Furthermore, solution D10 was added for 1 minute, and aging was performed for 5 minutes. Potassium bromide concentration during aging is 0.03 mol / l, ammonia concentration is 0.66 mol
/ L.

After the completion of the ripening, the pH was adjusted to 6.0 and desalting was carried out according to a conventional method. When the seed emulsion particles were observed with an electron microscope, the average grain size was 0.225 μm, and the ratio of two twin planes was 75% by number of all the grains.

Next, two solutions were prepared using the following seven types of solutions.
Monodisperse emulsion Em-4 having a plate shape having two parallel twin planes
Was prepared.

Solution A11 69.0 g of ossein gelatin 3268 ml of distilled water HO (C ₂ H ₄ O) m [CH (CH ₃ ) CH ₂ O] _19.8 (C ₂ H ₄ O) _n H (m + n = 9.77) 2.50 ml of 10% by weight methanol solution of seed emulsion (T-3) Equivalent to 0.141 mol Make up to 3500 ml with distilled water.

Solution B11 0.5N silver nitrate aqueous solution 959.0 ml Solution C11 Potassium bromide 52.88 g Ossein gelatin 35.55 g Make up to 959 ml with distilled water.

Solution D11 3.5N aqueous silver nitrate solution 4745.0 ml Solution E11 Potassium bromide 1863.8 g Ossein gelatin 179.0 g Make up to 4475 ml with distilled water Solution F11 3% by weight gelatin and silver iodide particles (average particle size) Emulsion (preparation method is shown below) * 2492.0 g * To 5000 ml of a 6.0% by weight gelatin solution containing 0.06 mol of potassium iodide, 7.06 mol of silver nitrate and 2,000 ml of an aqueous solution containing 7.06 mol of potassium iodide were added over 10 minutes. The temperature during the formation of the fine particles was controlled at 40 ° C. After the formation of the particles, the pH was adjusted to 6.0 using an aqueous solution of sodium carbonate. The finished weight was 12.53 kg.

Solution G11 1.75N Potassium bromide aqueous solution required amount Solution A11 was added to the reaction vessel, and while vigorously stirring,
Solutions B11 to F11 were added by a double jet method according to the combinations shown in Table 4, seed crystals were grown, and a core / shell type silver halide emulsion was prepared. However, solution B
11, starting from the start of addition of C11 and F11.
After 95 minutes, the pH was adjusted to 7.2 using 10% potassium hydroxide. As a result, reduction sensitization was performed inside the grains.

Here, (1) solution B11, solution C11 and solution F11 addition rates, (2) solution D11 and solution E1
The addition rate of the solution F11 and the solution F11, and (3) the addition rate of the solution D11 and the solution 1E1 were changed in a function-wise manner with time so as to match the critical growth rate of the silver halide grains, and the growing seed was changed. An appropriate addition rate was controlled so that generation of small particles other than crystals and polydispersion due to Ostwald ripening did not occur.

The solution temperature in the reaction vessel was controlled at 75 ° C. and the pAg was controlled at 8.8 throughout the entire region of the crystal growth. Solution p for control of pAg
11 was added.

Table 4 also shows the amount of silver added at that time with respect to the addition time of the reaction solution and the silver iodide content of the silver halide phase forming the surface.

After grain growth, a desalting treatment was carried out according to the method described in JP-A-5-72658, and then an aqueous gelatin solution was added to redisperse the mixture.
Was adjusted to 8.06.

The silver halide grains contained in the obtained silver halide emulsion had an average grain size of 1.42 μm (diameter in terms of projected area circle), 85% of grains having an aspect ratio of 3.0 or more, and a grain size distribution of 14.0. % Tabular silver halide grains.

[0224]

[Table 4]

Preparation of Emulsion Em-5 A monodisperse spherical seed emulsion (T-
4) was prepared.

Solution A12 Ossein gelatin 80 g Potassium bromide 47.4 g Polyisopropylene-polyethyleneoxy-disuccinate sodium salt (10% methanol solution) 20 ml Make up to 8000 ml with water.

Solution B12 Silver nitrate 1200 g Make up to 1600 ml with water.

Solution C12 Ossein gelatin 32.2 g Potassium bromide 840 g Make up to 1600 ml with water.

Solution D12 Ammonia water 470 ml To solution A12 stirred vigorously at 40 ° C., solution B12 and solution C12 were added by a double jet method over 11 minutes,
Nucleation was performed. During this time, pBr was kept at 1.60. Thereafter, the temperature was lowered to 30 ° C. over 12 minutes, and ripening was further performed for 18 minutes. Further, the solution D12 was added for 1 minute, and subsequently ripening was performed for 5 minutes. During aging, the concentration of potassium bromide was 0.07 mol / l, and the concentration of ammonia was 0.63 mol / l.

After the completion of the ripening, the pH was adjusted to 6.0 and desalting was carried out according to a conventional method to obtain a spherical seed emulsion (T-4). When this seed emulsion was observed with an electron microscope, it was a spherical emulsion having two twin planes parallel to each other and an average grain size of 0.318 μm.

Next, Emulsion Em-5 was prepared using the following seven kinds of solutions.

Solution A13 Ossein gelatin 268.2 g Distilled water 4000 ml Polyisopropylene-polyethyleneoxy-disuccinate sodium salt (10% methanol solution) 1.5 ml Seed emulsion (T-4) 0.286 mol equivalent 28% by weight Aqueous ammonia solution 528.0 ml 56% by weight acetic acid aqueous solution 795.0 ml 0.001 mol of iodine-containing methanol solution 50.0 ml Distilled water to 5930.0 ml.

Solution B13 3.5N aqueous ammonium nitrate solution (adjusted to pH 9.0 with ammonium nitrate) Solution C13 3.5N aqueous potassium bromide solution containing 4.0% by weight gelatin Solution D13 3% by weight gelatin And a fine grain emulsion comprising silver iodide grains (average grain size: 0.05 μm) (Preparation method is shown below *) 0.844 mol * 6.0% by weight of a 6.0% by weight gelatin solution containing 0.06 mol of potassium iodide 5000 m To 1, 2,000 ml of a solution containing 7.06 mol of silver nitrate and 2,000 ml of a water solution containing 7.06 mol of potassium iodide were added over 10 minutes. During the formation of fine particles, the pH was controlled at 2.0 using nitric acid, and the temperature was controlled at 40 ° C. After particle size formation, the pH was adjusted to 6.0 using aqueous sodium carbonate solution.

Solution E13 2.20 mol of a fine grain emulsion composed of silver iodobromide grains (average grain size: 0.04 μm) containing 1 mol% of silver iodide and prepared in the same manner as the above silver iodide fine grain emulsion. However, the temperature during the formation of fine particles was controlled at 3.0 ° C.) Solution F13 1.75 N aqueous potassium bromide solution G13 56% by weight acetic acid aqueous solution Solution A13 kept at 70 ° C. in a reaction vessel, solution B1
3. The solution C13 and the solution D13 are mixed with the
After 63 minutes of addition, solution E1 was subsequently added.
3 was added alone at a constant speed for 12 minutes, and the seed crystal was
Grown up.

Here, the addition rates of the solution B13 and the solution C13 were changed in a function with respect to time so as to match the critical growth rate, and the addition rate was increased due to the generation of small particles other than the growing seed crystal and Ostwald ripening. The addition was performed at an appropriate rate so as not to disperse. The solution D13, that is, the silver iodide fine grain emulsion was supplied by changing the rate ratio (molar ratio) with the aqueous ammoniacal silver nitrate solution with respect to the particle size as shown in Table 5 to obtain a core / shell type halogen having a multiple structure. A silver halide emulsion was prepared.

Further, by using the solution F13 and the solution G13, pAg and pH during the crystal growth were controlled as shown in Table 5. However, at the time of the addition of 82.6 minutes, the pH was adjusted to 8.4 using a 10% aqueous sodium hydroxide solution, whereby reduction sensitization was performed inside the grains. Note that p
Ag and pH were measured using a silver sulfide electrode and a glass electrode according to a conventional method. After the formation of the particles, see JP-A-5-348.
After desalting according to the method described in No. 51, gelatin was added and the mixture was redispersed.
g was adjusted to 8.06.

When the obtained emulsion grains were observed by an electron microscope, it was found that the twin grains were composed of 100% twin grains and had an aspect ratio of 1.2 to 1.6 having two or more parallel twin planes and a twin ratio of 8
It consisted of slightly distorted octahedral twin monodisperse particles having a distribution of 5%, a distribution width of 10% and an average particle size of 1.0 μm.

[0238]

[Table 5]

Preparation of Emulsion Em-6 In the preparation of Emulsion Em-4, solutions B11, C11, F
Emulsion Em-6 not subjected to reduction sensitization was prepared in the same manner except that potassium hydroxide, which was added 114.95 minutes after the addition of 11, was not added.

Preparation of Emulsions A-1 and A-2 A part of Emulsion Em-4 was divided into two parts and dissolved by heating at 55 ° C.
After adjusting the pH to 5.80, sensitizing dye (sd-1) 1.03 × 10 ⁻⁴ mol / mol of silver halide.
1, (sd-2) 7.1 × 10 ⁻⁵ mol / l, (sd−
3) 8.0 × 10 ⁻⁵ mol / l, one of which is 1: 1 of methanol and 2,2,3,3-tetrafluoropropanol
A 0.5 w / v% concentration dye solution (* I: solution added) of the mixed solvent and a 0.5 w / v% concentration dye dispersion solution (* II: solid dispersion addition) were added to the other. Twenty minutes after the addition of the sensitizing dye, 5 × 10 ^-6 mol of sodium thiosulfate pentahydrate was added per mol of silver halide, followed by 1.42 × 10 ^-6 mol of chloroauric acid and 3.15 ammonium thiocyanate. × 10 ^-4 mol was added and aged for an appropriate time.

At the end of aging, a stabilizer (ST-1) was added.
Emulsion A-1 (* I: solution added) and emulsion A-2 (* II: solid dispersion added) were obtained by cooling and solidifying, respectively.

* I (solution addition): methanol and 2,2
A predetermined amount of a dye was added to a 1: 1 mixed solution of 3,3-tetrafluoropropanol so that the dye was adjusted to 0.5 w / v%.

* II (solid dispersion added): The dye was previously heated at 27 ° C.
, And a predetermined amount of a dispersion aqueous solution obtained by stirring at a high speed with a dissolver was adjusted to a concentration of 0.5 w / v%.

ST-1: 4-hydroxy-6-methyl-
1,3,3a, 7-tetrazaindene

[0245]

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<< Preparation of Emulsions B-1 to V-2 >> Except that the prepared emulsions and sensitizing dyes shown in Tables 6 and 7 were used,
Emulsion B was prepared in the same manner as in the preparation of emulsions A-1 and A-2.
-1 to N-2 were prepared. However, the amounts of the various additives (sodium thiosulfate, chloroauric acid) were determined in emulsions A-1 and A-1.
The optimum amount is applied to each emulsion in the range of 0.75 to 1.5 times the amount used when preparing No. -2, and the ripening time is also optimum (the best result is obtained in the evaluation of fog sensitivity). It was adjusted to become.

[0247]

[Table 6]

[0248]

[Table 7]

(Preparation of Coating Samples 201 to 244) The emulsions A-1 to V-2 obtained as described above were sequentially coated on a triacetyl cellulose film support which had been subjected to a subbing process according to the following coating formulation. It dried and the application samples 201-244 were produced.

Coating Formulation First Layer: Green-Sensitive Silver Halide Emulsion Layer Emulsion (described in Tables 6 and 7) 2.5 g / m ² magenta coupler (m-1) 0.01 mol / mol Ag Colored magenta coupler (cm-1) 0.005 mol / molAg DIR compound (d-1) 0.0002 mol / molAg high boiling point solvent (TCP) 0.02 g / m ² Second layer: yellow filter layer Yellow colloidal silver 0.08 g / m ² hardener ( HI) 10 mg / g gelatin

[0251]

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TCP: tricresyl phosphate H-1: 2,4-dichloro-6-hydroxy-s-triazine sodium <Sensitometry evaluation> Green light was applied to the coated samples 201 to 242 obtained as described above. 1/200 second using
After the step wedge exposure of 3.2 CMS, processing is performed in the following processing steps to determine a characteristic curve, and the relative sensitivity (reciprocal of the exposure amount that gives a density of fog density + 0.10, expressed as a relative value with sample 206 being 100) I asked.

Processing step (38 ° C.) Color development (2 minutes 50 seconds) → Bleaching (6 minutes 30 seconds) → Washing (3 minutes 15 seconds) → Fixing (6 minutes 30 seconds) → Washing (3 minutes 15 seconds)
Sec) → stabilization (1 minute 30 seconds) → drying The composition of the processing solution used in each processing step is as follows.

Color developing solution 4-Amino-3-methyl-N-ethyl-N- (β-hydroxyethyl) aniline / sulfate 4.75 g Sodium sulfite anhydrous 4.25 g Hydroxylamine 1/2 sulfate 2.0 g Anhydrous potassium carbonate 37.5 g Sodium bromide 1.3 g Nitrilotriacetic acid trisodium salt (monohydrate) 2.5 g Potassium hydroxide 1.0 g Water is added to 1 liter, and the pH is adjusted to 10.0.

Bleaching solution Iron ammonium salt of ethylenediaminetetraacetic acid 100.0 g Diammonium salt of ethylenediaminetetraacetic acid 10.0 g Ammonium bromide 150.0 g Glacial acetic acid 10.0 g Water was added to 1 liter, and the pH was adjusted to 6.0 using aqueous ammonia. Adjust to 0.

Fixing solution Ammonium thiosulfate 175.0 g Anhydrous sodium sulfite 8.5 g Sodium metasulfite 2.3 g Water was added to 1 liter, and the pH was adjusted to 6.0 with acetic acid.

Stabilizer Formalin (37% aqueous solution) 1.5 ml Konidax (manufactured by Konica Corporation) 7.5 ml Make up to 1 liter by adding water.

<Evaluation of Storage Stability> Each sample was stored at 40 ° C.
After forcibly deteriorating at 0% RH for one week, exposure and development were carried out in the same manner as in the sensitometric evaluation. The same day sample used in the sensitometry evaluation was used to measure the concentration fluctuation at the concentration position giving Dmin + 0.3, and the difference was determined by the difference (S
(Immediate-S aging).

Therefore, the smaller the value, the better the storage stability.

S Immediate: Same day sample concentration S Time: 1 week Concentration of forcedly degraded sample

[0261]

[Table 8]

[0262]

[Table 9]

As is clear from Tables 8 and 9, the samples of the present invention show excellent effects in both sensitivity and storage stability. In comparison, none of the comparative samples shows an effect superior in both sensitivity and storage stability.

Further, it can be seen that there is a large difference in the storage stability of the comparative sample due to the difference in the method of adding the dye.

In Comparative Samples 201 and 202, the green light sensitivity and storage stability were good.
In No. 06, the storage performance was good, but in each of these samples, contamination having a maximum absorption near 550 nm remained, and remarkable staining was observed, particularly in a high aspect emulsion having good photographic characteristics, and was inferior.

Example 6 Polyethylene was laminated on one side of a paper support and polyethylene on the other side was laminated with polyethylene containing titanium oxide. Each layer having the following structure was replaced with a polyethylene layer containing titanium oxide. The multilayered silver halide color photographic material sample 301 was prepared. However, the coating solution was prepared as follows.

Coating solution for the first layer: 26.7 g of yellow coupler (Y-1), 10.0 g of dye image stabilizer (ST-1), dye image stabilizer (ST-1)
-2) 6.67 g, additive (HQ-1) 0.67 g, anti-irradiation dye (AI-3) 0.34 g, high boiling organic solvent (DNP) 0.67 g and ethyl acetate 60 ml
To dissolve the solution, and add 20% surfactant (SU-
1) 220 m of 10% gelatin aqueous solution containing 7 ml
The resulting mixture was emulsified and dispersed using an ultrasonic homogenizer to prepare a yellow coupler dispersion. This dispersion was treated under the following conditions with a blue-sensitive silver halide emulsion (8.68 g of silver).
Was contained to prepare a first layer coating solution.

The coating solutions for the second to seventh layers were prepared in the same manner as the coating solution for the first layer.

Further, (H) was added to the second and fourth layers as a hardening agent.
-1) and (H-2) were added to the seventh layer. Surfactants (SU-2) and (SU-3) were added as coating aids to adjust the surface tension.

The amount of addition is shown in g / m ² . However, silver halide emulsions were shown in terms of silver.

Layer Structure Coating Amount 7th Layer Gelatin 1.0 (Protective Layer) Silica (Average Particle Size 3 μm) 0.03 Color Mixing Prevention Agent (HQ-2) 0.002 Color Mixing Prevention Agent (HQ-3) 0 0.002 color mixture inhibitor (HQ-4) 0.004 color mixture inhibitor (HQ-5) 0.02 high boiling point organic solvent (DIDP) 0.005 compound (F-1) 0.002 sixth layer gelatin 0.4 (Intermediate layer) UV absorber (UV-1) 0.1 UV absorber (UV-2) 0.04 UV absorber (UV-3) 0.16 Color mixing inhibitor (HQ-5) 0.04 High boiling point Organic solvent (DNP) 0.2 High boiling organic solvent (PVP) 0.03 Anti-irradiation dye (AI-2) 0.02 Anti-irradiation dye (AI-4) 0.01 Fifth layer Gelatin 1. 3 (Red sensitive layer) Spectroscopy with sensitizing dye (RS-1) Sensitized red-sensitive silver chlorobromide emulsion (Br 5 mol%, Cl 95 mol%) 0.21 cyan coupler (C-1) 0.17 cyan coupler (C-2) 0.25 color-mixing inhibitor (HQ -1) 0.02 HBS-1 0.2 High boiling organic solvent (DOP) 0.2 Anti-irradiation dye (AI-1) 0.01 4th layer Gelatin 0.94 (Intermediate layer) UV absorber ( UV-1) 0.28 UV absorber (UV-2) 0.09 UV absorber (UV-3) 0.38 Color mixture inhibitor (HQ-5) 0.10 High boiling organic solvent (DNP) 0.4 Third layer Gelatin 1.2 (green-sensitive layer) Green-sensitive silver chlorobromide emulsion spectrally sensitized with a sensitizing dye (GS-1) (Br 5 mol%, Cl 95 mol%) 0.35 Magenta coupler ( M-1) 0.23 color image stabilizer (ST-3) 0.20 color image Stabilizer (ST-4) 0.17 High-boiling organic solvent (DIDP) 0.13 High-boiling organic solvent (DBP) 0.13 Anti-irradiation dye (AI-3) 0.01 Second layer gelatin 1. 2 (Intermediate layer) Color mixture inhibitor (HQ-2) 0.03 Color mixture inhibitor (HQ-3) 0.03 Color mixture inhibitor (HQ-4) 0.05 Color mixture inhibitor (HQ-5) 0.23 High Boiling point organic solvent (DIDP) 0.13 Compound (F-1) 0.002 First layer Gelatin 1.2 (Blue-sensitive layer) Blue-sensitive silver chlorobromide spectrally sensitized with sensitizing dye (BS-1) Emulsion (Br 5 mol%, Cl 95 mol%) 0.26 Yellow coupler (Y-1) 0.80 Color image stabilizer (ST-1) 0.30 Color image stabilizer (ST-2) 20 color mixing inhibitor (HQ-1) 0.02 anti-irradiation dye (AI-3) 0.01 High boiling organic solvent (DNP) 0.02 Back layer Gelatin 6.0 Silica (average particle size 3 μm) 0.1 The silver halide emulsions used in the present invention each have a distribution width of 10% or less. Was obtained. Each emulsion was subjected to optimal chemical ripening in the presence of sodium thiosulfate, chloroauric acid and ammonium thiocyanate, and a stabilizer (4-hydroxy-6-methyl-1,3,3a, 7-
Tetrazaindene and 1- (3-acedamido) phenyl-5-mercaptotetrazole) were added.

The structure of the compound used is shown below.

PVP: polyvinylpyrrolidone DBP: dibutyl phthalate DOP: dioctyl phthalate DNP: dinonyl phthalate DIDP: diisodecyl phthalate HQ-1: 2,5-di-t-octylhydroquinone HQ-2: 2,5-di-s- Dodecylhydroquinone HQ-3: 2,5-di-s-tetradecylhydroquinone HQ-4: 2-s-dodecyl-5-s-tetradecylhydroquinone SU-1: i-propyl-naphthalene-sodium sulfonate SU-2 : Di (2-ethylhexyl) sodium sulfosuccinate SU-3: di (2,2,3,3,4,4,4) sulfosuccinate
5,5-octafluoropentyl) sodium H-1: (CH ₂ ＣＨCHSO ₂ C ₂ H ₄ CONHCH ₂ ) ₂ H-2: sodium 2,4-dichloro-6-hydroxy-s-triazine sodium

[0274]

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[0275]

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[0276]

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[0277]

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[0278]

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[0279]

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Next, Comparative Samples 302 to 304 and Inventive Sample 305 were prepared in the same manner as Sample 301 except that the sensitizing dye (GS-1) in the third layer was changed as shown in Table 10 in the preparation of the sample. To 317. The addition amount of the sensitizing dye was adjusted to be the same molar amount as the addition amount in Sample 301.

[0281]

[Table 10]

The obtained coating amount sample No. 301-No.
Each of the samples 317 was left under the following two conditions, and an experiment for substituting storage was performed.

Condition A: Reference sample left at 23 ° C. and 55% RH or less for 4 days Condition B: Storage test sample left at 40 ° C. and 80% RH or less for 4 days After exposure to wedges for 2 seconds and color development according to the following processing steps, the magenta color density was measured using an optical densitometer (PDA-65 manufactured by Konica) to obtain a characteristic curve.

Processing Step Temperature Time Color Development 35.0 ± 0.3 ° C. 45 seconds Bleaching and Fixing 35.0 ± 0.5 ° C. 45 seconds Stabilization 30-34 ° C. 90 seconds Drying 60-80 ° C. 60 seconds Color developing solution Pure water 800 ml Triethanolamine 10 g N, N-diethylhydroxylamine 5 g Potassium bromide 0.02 g Potassium chloride 2 g Potassium sulfite 0.3 g 1-Hydroxyethylidene-1,1-diphosphonic acid 1.0 g Ethylenediaminetetraacetic acid 1 0.0 g catechol-3,5-disulfonic acid disodium salt 1.0 g diethylene glycol 10 g N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate 4.5 g fluorescent brightener (4 1,4'-diaminostilbene sulfonic acid derivative) 1.0 g Potassium carbonate 27 g The total volume is made up to 1 l and the pH is adjusted to 10.10.

Bleaching-fixing solution Ethylenediaminetetraacetic acid ammonium ferric ammonium dihydrate 60 g Ethylenediaminetetraacetic acid 3 g Ammonium thiosulfate (70% aqueous solution) 100 ml Ammonium sulfite (40% aqueous solution) 27.5 ml Water was added to bring the total amount to 1 l. PH is adjusted to 5.7 with glacial acetic acid.

Stabilizing solution 5-chloro-2-methyl-4-isothiazolin-3-one 0.2 g 1,2-benzisothiazolin-3-one 0.3 g ethylene glycol 1.0 g 1-hydroxyethylidene-1,1 -Diphosphonic acid 2.0 g o-Phenylphenol sodium 1.0 g Ethylenediaminetetraacetic acid 1.0 g Ammonium hydroxide (20% aqueous solution) 3.0 g Fluorescent brightener (4,4'-diaminostilbenesulfonic acid derivative) 1.5 g The total volume is adjusted to 1 liter by adding water, and the pH is adjusted to 7.0 with sulfuric acid and potassium hydroxide.

<Evaluation of sensitivity> Fog of characteristic curve + 1.0
Is determined by the reciprocal of the exposure amount giving the density of Sample No. 301
Was expressed as a relative value with the sensitivity of 100 as 100.

<Evaluation of Storage Property> ΔSs (SCA / SCB) where SCB is the sensitivity of the sample stored under the storage condition B and SCA is the sensitivity of the sample stored under the storage condition A.
The value of was used as a measure of the sensitivity variability of preservation. Further, ΔFs (FCB-FCA) was obtained from each of the fogs at that time, and was used as a measure of fog fluctuation of the storage stability. ΔSs value is 1
And the smaller the value of ΔFs, the better the storage stability with time.

<Evaluation of Residual Color> The unexposed sample stored under the storage condition A was processed in the above-mentioned processing step, and the residual color of the obtained sample was visually evaluated in five steps. Those having no residual color were ranked as the highest rank "5", and the ranks were sequentially lowered to "4", "3", "2", and "1" according to the degree of occurrence of the residual color. “2” and “1” are levels that are not practically preferable. Table 11 shows the above results.

[0290]

[Table 11]

From the results shown in Table 11, it can be seen that all of the samples of the present invention using the compound of the present invention have higher green light sensitivity than the comparative sample and are excellent in fog and residual color contamination. I understand.

[0292]

According to the present invention, a green-sensitive silver halide photographic emulsion having a stable low-temperature stagnation property and a stagnation property of a coating solution and free from fluctuation in sensitivity can be obtained as demonstrated in the examples. , Was beneficial in manufacturing. Further, according to the present invention, it was possible to obtain an excellent green-sensitive silver halide photographic light-sensitive material in which the raw film had good storage stability over time, had little residual color contamination, and was excellent.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 2H023 CA07 4H056 CA01 CA03 CC02 CC08 CE03 CE06 CE07 DD03 DD04 DD06 DD19 DD23 DD30 FA05

Claims (9)

[Claims] 1. An organic compound represented by the following general formula [I]. Embedded image [Wherein, R _{1 to} R ₄ each represent an aliphatic group, and R ₅ represents a substituent or a non-metal required for forming a 5- or 6-membered condensed ring with R ₁ or R _2. Represents an atomic group. V _{1 to} V ₄ each represent a hydrogen atom or a substitutable group, and at least one of V _{1 to} V ₄ is an aromatic ring group. M ₁ represents an ion required to offset the total charge of the molecule, and m 1 represents a number required to neutralize the charge in the molecule. ] 2. A silver halide photographic emulsion comprising the compound represented by the above general formula [I]. 3. A silver halide photographic emulsion comprising a compound represented by the following general formula [II] and a compound represented by the following general formula [III]. Embedded image Wherein each R ₁₁ to R ₁₄ represents an aliphatic group, R ₁₂ and R
_At least one of ₁₄ groups replaces a sulfo group or a carboxy group. R ₁₅ represents a substituent or a group of non-metallic atoms necessary for forming a 5- or 6-membered condensed ring with R ₁₁ or R ₁₂ . V ₁₁ ~V ₁₈ each represents a hydrogen atom or a substitutable group. M ₁₁ represents an ion required to offset the total charge of the molecule, m11 represents a number necessary for neutralizing the molecular charge. [Chemical formula 3] Wherein each R ₂₁ to R ₂₄ represents an aliphatic group, R ₂₂ and R
_At least one group of ₂₄ replaces a sulfo group or a carboxy group. V _{21 to} V ₂₄ are each a hydrogen atom or a substitutable group, and are selected such that the sum of Hammett σp values added for the groups V _{21 to} V ₂₄ is larger than 0.7.
M ₂₁ represents an ion required to offset the total charge of the molecule;
m21 represents the number required to neutralize the intramolecular charge. ] 4. A silver halide photographic emulsion comprising a compound represented by the general formula [II] and a compound represented by the following general formula [IV]. Embedded image [In the formula, Y ₃₁ represents an oxygen atom, a sulfur atom, a selenium atom or a —N (R ₃₄ ) — group, R ₃₃ represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, and R ₃₁ and R ₃₂ And R ₃₄ each represents an aliphatic group, and at least one of R ₃₁ and R ₃₂ replaces a sulfo group or a carboxy group. V ₃₁
To V ₃₈ each represent a hydrogen atom or a substitutable group;
₃₁ and V ₃₂ , V ₃₂ and V ₃₃ , V ₃₃ and V ₃₄ , V ₃₅ and V ₃₆ , V ₃₆
And V ₃₇ , and V ₃₇ and V ₃₈ may be bonded to form a condensed ring. M ₃₁ represents an ion required to offset the total charge of the molecule, m31 represents a number necessary for neutralizing the molecular charge. ] 5. The compound represented by the general formula [II], the compound represented by the general formula [III], and the compound represented by the general formula [I
V] A silver halide photographic emulsion comprising a compound represented by the formula: 6. A silver halide photographic light-sensitive material comprising at least one layer containing the silver halide photographic emulsion according to claim 2. 7. A silver halide photographic material comprising at least one layer containing the silver halide photographic emulsion according to claim 3. 8. A silver halide photographic light-sensitive material comprising at least one layer containing the silver halide photographic emulsion according to claim 4. 9. A composition comprising at least one layer containing the silver halide photographic emulsion according to claim 5.
Silver halide photographic material.