JPH1048767A - Silver halide photographic sensitive material and its processing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide the silver halide photographic sensitive material high in sensitivity and rapid processing aptitude and suitable for processing in an automatic developing machine small in a replenishing rate for a processing solution and in a discharging amount of waste solutions. SOLUTION: The silver halide emulsion in the photosensitive material has a silver chloride content of 20-100mol% and contains flat silver halide grains having an aspect ratio of >=2 in >=50% of the projection areas of the total silver halide grains and the emulsion contains the compound represented by the formula in which each of Ra and Rb is an H atom or an aliphatic or aryl or heterocyclic group by each is not an H atom at the same time; each of La and Lb is a methine group; each of k1 and k2 is an integer of 0-5; each of L1 and L2 is a methine group; p1 0 or 1; Z1 is an atomic group necessary to form a 5- or 6-membered N-containing hetero-cyclic group; M1 is a counter ion necessary to balance a charge in the molecule; m1 is an integer necessary to balance it; and Q is a methine dye forming atomic group.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic material and a processing method thereof.

[0002]

2. Description of the Related Art There is a great demand for rapid processing accompanying the recent increase in processing of silver halide light-sensitive materials. For example, the same tendency is observed in the field of medical X-ray films. That is, the number of X-ray photography increases due to an increase in the number of diagnostics such as health examinations and an increase in the number of examination items for improving diagnostic accuracy. Such a development process is strongly desired. However, in order to enable the above-mentioned rapid and large-scale processing, it is necessary to reduce the replenishment of the processing solution and to shorten the time of each step of development, fixing, washing and drying.
In such systems, Br ^-, I ^- in accordance (1) fatigue and developer, and (2) residual color due to inhibition of dye desorption, (3) problems fixing failure or the like can not be ignored. Br ^-, I ^- in order to reduce fatigue and development inhibiting effect of the developer by the longer it must increase the replenishment rate. Further, Br ^-, I ^- the dye adsorption is strengthened by, for example, JP-A-2-68,540
As described in detail in the above item, the residual color due to the spectral sensitizing dye is increased. To prevent this, the fixing / washing time must be increased. The same applies to fixing failure.

On the other hand, various studies have been made on tabular grains having a high silver chloride content in rapid processing and low replenishment processing. For example, examples of tabular grains having a {111} plane as a main plane include JP-B Nos. 64-8326 and 64-8326.
No. 25, No. 64-8324, JP-A-1-250943
No., Japanese Patent Publication No. 3-14328, Japanese Patent Publication No. 4-81782
JP-A-5-40298, JP-A-5-39459, JP-A-5-12696, and JP-A-63-213836, JP-A-6-213836.
JP-A-3-218938, JP-A-63-281149, and JP-A-62-218959. Further, tabular grains having a {100} plane as a main plane are described in JP-A-5-20.
No. 4073, JP-A-51-88017 and JP-A-63-88017.
No. 24238 and the like. In particular, JP-A-6-0593
No. 60 describes a {100} flat plate containing silver chloride. However, these silver chloride tabular grains did not provide high color sensitization sensitivity as compared with those using silver bromide or silver iodide.

The sensitizing dyes conventionally used include:
Since the adsorption to silver chloride is not strong, the sensitizing dye is adsorbed at a high temperature (50 ° C. or higher) to prevent the sensitizing dye from desorbing from the silver halide grains (especially at high humidity) in the light-sensitive material Although a method of causing the sensitizing dye to be adsorbed before the chemical sensitization for increasing the sensitivity is widely known, these methods are insufficient. Further, a method of adding a small amount of a dye having a lower oxidation potential to improve the color sensitization rate has been known in the art as a super sensitization technique since ancient times. P
ROCESS 4th edition Chapter 10 and JP-A-2-47647
This method is effective particularly for dyes whose reduction potential is lower than the conduction band edge of the silver halide used. However, these methods also had insufficient effects with the conventionally used sensitizing dyes.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a silver halide photographic light-sensitive material which has high sensitivity, is excellent in rapid processing suitability, and is suitable for processing in an automatic developing machine with low replenishment and low waste liquid. Things.

[0006]

In the prior art, it has been extremely difficult to sensitize a high silver chloride emulsion suitable for rapid and low replenishment processing in the spectral sensitization region. On the other hand, the present inventors have found a means for obtaining high sensitivity and rapid development progress even in a silver halide emulsion having a high silver chloride content.
Means for Solving the Problems The present inventors have made intensive studies on the above-described problems and newly found that the following method is particularly effective.

(1) In a silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support, the silver halide emulsion has a silver chloride content of from 20 mol% to 100 mol%. And at least 50% of the total projected area in the emulsion is occupied by tabular silver halide grains having an aspect ratio of 2 or more, and the emulsion layer contains at least one compound represented by the following general formula (I). A silver halide photographic material.

[0008]

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In the formula (I), R_aAnd R_bIs water
Represents an atom, an aliphatic group, an aryl group, or a heterocyclic group.
You. Where R_aAnd R_bAre simultaneously hydrogen atoms
Absent. L _aAnd L_bEach represents a methylene group. k₁
Is an integer from 0 to 5, k_TwoRepresents an integer of 0 to 5. L₁ as well as
L_Two Each represents a methine group. p₁ Represents 0 or 1
You. Z ₁ Is to form a 5- or 6-membered nitrogen-containing heterocycle
Represents the required atomic group. M₁ Represents a charge-balancing counter ion,
m₁ Is an integer of 0 or more necessary to neutralize the electric charge of the molecule.
Represent. Q represents a group of atoms necessary to form a methine dye.
You.

(2) The compound represented by the general formula (I) described in (1) is a compound represented by the following general formula (II), (III) or (IV) The silver halide photographic material according to claim 1, wherein

[0011]

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In the formula (II), L ₃ , L ₄ , L ₅ , L ₆ , L
_7, L ₈ and L ₉ each represents a methine group. p ₂ and p ₃ each represent 0 or 1. n ₁ is 0, 1, 2,
Or 3 is represented. Z ₂ and Z ₃ each represent an atom group necessary for forming a 5- or 6-membered nitrogen-containing heterocyclic ring. M ₂
Represents a charge balancing counter ion, and m ₂ represents an integer of 0 or more necessary to neutralize the charge of the molecule. R ₁ and R ₂ each represent an alkyl group. However, at least one of R ₁ and R ₂ is an alkyl group represented by the following Rz.

[0013]

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In Rz, R _a , R _b , L _a , L _b ,
k ₁ and k ₂ have the same meanings as in the general formula (I).

[0015]

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In the formula (III), L_Ten, L₁₁, L₁₂, And L
₁₃Each represents a methine group. p_Four Represents 0 or 1.
n_Two Represents 0, 1, 2 or 3. Z_Four And Z_Five Each
Necessary to form a 5- or 6-membered nitrogen-containing heterocycle.
Represents a child group. M_Three Represents a charge-balancing counter ion, m_Three Is a minute
Represents an integer of 0 or more necessary to neutralize the charge of the child. R
_Four Represents an alkyl group, an aryl group, or a heterocyclic group. R
_Three Is an alkyl group represented by Rz.

[0017]

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In the formula (IV), L ₁₄ , L ₁₅ , L ₁₆ , L ₁₇ , L
₁₈ , L ₁₉ , L ₂₀ , L ₂₁ and L ₂₂ each represent a methine group. p ₅ and p ₆ each represent 0 or 1. n ₃ and n ₄ represent 0, 1, 2, or 3, respectively. Z ₆ , Z ₇
And Z ₈ each represent an atom group necessary for forming a 5- or 6-membered nitrogen-containing heterocyclic ring. M ₄ represents a charge balancing counter ion, and m ₄ represents an integer of 0 or more necessary to neutralize the charge of the molecule. R ₅ and R ₇ each represent an alkyl group. R ₆ represents an alkyl group, an aryl group or a heterocyclic group. However, at least one of R ₅ and R ₇ is an alkyl group represented by Rz.

(3) The compound represented by the general formula (I) is
2. The silver halide photographic material according to claim 1, which is a compound represented by formula (II) described in (2).

(4) _Ra is an aryl group or a heterocyclic group, and R _b is a hydrogen atom.
The silver halide photographic material according to any one of (3) and (3).

(5) In a silver halide photographic material having at least one silver halide emulsion layer on a support, the silver halide emulsion has a silver chloride content of from 20 mol% to 100 mol%. And at least 50% of the total projected area in the emulsion is occupied by tabular silver halide grains having an aspect ratio of 2 or more, and the emulsion layer contains at least one compound represented by the following general formula (V). A silver halide photographic material.

[0022]

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In the formula (V), R ₈ and R ₉ represent an alkyl group. Z ₉ and Z ₁₀ represent a group of nonmetal atoms necessary for forming an aromatic ring. Q ₁ represents an alkyl group having 3 or more carbon atoms. X represents an ion necessary to balance the charges. m ₅ is 0 or 1 and 0 when an inner salt is formed.

(6) The halogen according to any one of (1) to (5), wherein the tabular silver halide grain emulsion is a tabular grain having a {100} plane as a main plane. Silver halide photographic material.

(7) Any of (1) to (6), wherein the compound represented by any one of formulas (I) to (V) is added to the emulsion before the addition of the chemical sensitizer. 4. The silver halide photographic light-sensitive material according to item 1.

(8) The tabular silver halide grain emulsion comprises:
The silver halide photographic material according to any one of (1) to (7), which is chemically sensitized with a selenium compound.

[0027] (9) tabular silver halide surface of grain emulsions Br ^-, I ^-, SCN ^-, characterized in that it is conversion by at least one (1) to
(8) The silver halide photographic light-sensitive material according to any one of the above (8).

[0028] (10) tabular silver halide surface of grain emulsion I ^- and Br ^- are conversions result, the particles of the total silver iodide content of the case, 0 total silver.
The silver halide photographic light-sensitive material according to any one of (1) to (9), wherein the content is 6 mol% or less.

(11) A silver halide photographic light-sensitive material characterized by processing the silver halide photographic light-sensitive material according to any one of (1) to (10) with a developer containing ascorbic acid or a derivative thereof. Material treatment method.

[0030]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail. In the present invention, the silver chloride content is 20 mol% or more and 1
The following describes the tabular silver halide grains of not more than 00 mol%.

In a silver halide emulsion containing at least a dispersion medium and silver halide grains, 50% to 100%, preferably 60%, of the total projected area of the silver halide grains.
A tabular silver halide emulsion having an aspect ratio (diameter / thickness) of 2 or more, more preferably 70 to 100%, more preferably 70 to 100%. The Cl ^- content is 20 mol% or more and 100 mol%.
Hereinafter, it is preferably 30 mol% to 100 mol%, more preferably 40 mol% to 100 mol%, and still more preferably 50 mol% to 100 mol%. The thickness of the tabular grains is 0.35 μm or less, preferably 0.05 to 0.3 μm, more preferably 0.05 to 0.3 μm.
0.25 μm is more preferred. The aspect ratio is 2 or more,
Preferably it is 2-25, More preferably, it is 5-20.
Here, the diameter refers to the diameter of a circle having an area equal to the projected area of the tabular grains, and the thickness refers to the distance between two principal planes.

With regard to the nucleation of the emulsion of the present invention having the {111} plane as the main plane, see JP-B 64-8326.
Nos. 64-8325, 64-8324, JP-A-1-250943, JP-B-3-14328, JP-B-4-81782, JP-B-5-40298, and 5-3
No. 9459, No. 5-112696 and JP-A-63-213.
No. 836, No. 63-218938, No. 63-2811
No. 49, JP-A-62-218959, etc., and tabular grains having a {100} plane as a main plane are described in JP-A-5-204073 and JP-A-51-20773.
No. 88017 and JP-A-63-24238. In the present invention, any of the nucleation methods described therein can be used.

Physical properties in the presence of the silver halide fine grains of the present invention
Aging (fine particles dissolve and substrate particles grow)
The method of crystal growth is preferably used. This is described below.
Will be described. 0.001 μm or more in the fine grain emulsion addition method.
15 μm diameter or less, preferably 0.001 μm or more and 0.1
μm diameter or less, more preferably 0.06 to 0.006 μm
AgX fine-grain emulsion was added, and Ostwald ripened.
The tabular grains are grown. The fine grain emulsion is continuously
Can be added or can be added continuously
You. The fine grain emulsion was mixed with A in a mixer provided near the reaction vessel.
gNO_Three Solution and X ^-Continuously prepared by feeding a salt solution,
It can be added immediately to the reaction vessel immediately,
Continuous or after preparing in batches in another container in advance
It can be added continuously. The fine grain emulsion is liquid
Can be added or added as a dry powder
You can also. The dry powder is mixed with water just before the addition,
It can also be added after shaping. 1 second for the added fine particles
It is preferable to add in such a manner that it disappears within 20 minutes from
And 10 seconds to 10 minutes is more preferable. Longer disappearance time
Aging occurs between the fine particles, and the particle size increases
Not preferred. Therefore, it is better not to add all at once
preferable. The fine particles are substantially free of a large amount of twin particles.
Is preferred. The term “multiple twin particles” refers to one particle
Refers to particles having two or more twin planes. Substantially included
If no, the ratio of the number of multiple twin particles is 0% to 5%,
Preferably 0% or more and 1% or less, more preferably 0% or more
0.1% or less. Furthermore, single twin particles are also substantially
It is preferable not to include it. Furthermore, screw dislocations
It is preferable not to include it. Here, we do not substantially include
Follow the above rules.

The halogen composition of the fine particles is AgCl, Ag
BrCl, AgBr, AgBrl (I ^- content is 0 mol%
Not less than 10 mol%, preferably not less than 0 mol% and not more than 5 mol%
The following is more preferred. ) And mixed crystals of two or more thereof. For other details, the description in JP-A-6-59360 can be referred to. The total amount of the fine grains added is required to be 20% or more of the total silver halide amount.
It is 40% or more and 98% or less, more preferably 50% or more and 98% or less. The Cl content of the fine particles is 10 mol%
It is preferably at least 100 mol%, more preferably at least 50 mol% and at most 100 mol%.

As the dispersion medium for nucleation, ripening and growth, conventionally known dispersion mediums for AgX emulsions can be used. In particular, the methionine content is preferably 0 to 50 μmol / g, more preferably 0 to 50 μmol / g. Gelatin of ３０30 μmol / g can be preferably used. When the gelatin is used during ripening and growth, thinner tabular grains having a uniform diameter size distribution are preferably formed. In addition, Tokiko Sho 52
-16365, The Photographic Society of Japan, 29 (1), 1
7, 22 (1966), same 30 volumes (1), 10, 19
(1967), Vol. 30 (2), 17 (1967)
), 33 (3), 24 (1967) can be preferably used as a dispersion medium. The pH at the time of growth by adding fine particles needs to be 2.0 or more, but is preferably 6 or more and 10 or less. More preferably, p
H6 or more and 9 or less. Also, pCl needs to be 1.0 or more, but is preferably 1.6 or more. More preferably, it is 2.0 or more and 3.0 or less. These growth conditions are particularly preferable for tabular grains having a {100} plane as a main plane. Here, pCl is defined as pCl = −log [Cl ⁻ ] with respect to the activity [Cl ⁻ ] of Cl ions in the solution. Written by THJames THE THEORY OF THE RHOTO
This is described in detail in GRAPHIC PROCESS, 4th edition, Chapter 1.

When the pH becomes 2.0 or less, for example, in the case of tabular grains having a {100} plane as a main plane, the lateral growth is suppressed, the aspect ratio is reduced, and the covering power of the emulsion is reduced. Tends to be low and the sensitivity is low. When the pH is 2.0 or higher, an emulsion having a high lateral growth rate and a high aspect ratio and a high covering power can be obtained, but the fog is high and the sensitivity is easily lowered. p
When Cl is 1.0 or less, the growth in the vertical direction is promoted, the aspect ratio is reduced, the covering power of the emulsion is low, and the sensitivity is lowered. When the pCl is 1.6 or more, the aspect ratio is increased to increase the covering power, but the fog is high and the sensitivity is easily reduced. At this time, when the substrate grains are grown with silver halide fine grains, the fog is low even at a pH of 6 or more and / or a pCl of 1.6 or more, resulting in a high sensitivity, a high aspect ratio, and a high covering power.

The tabular grains of the present invention are preferably silver halide grains having dislocation lines. Tabular grain dislocations are described, for example, in JF Hamilton, Phot. Sci. Eng., 1
1, 57, (1967) and T. Shiozawa, J. Soc. Pho
t. Sci. Japan, 35, 213, (1972) can be observed by a direct method using a low-temperature transmission electron microscope. That is, silver halide grains taken out with care not to apply enough pressure to generate dislocations from the emulsion are placed on a mesh for observation with an electron microscope,
Observation is performed by a transmission method in a state where the sample is cooled so as to prevent damage (eg, printout) due to an electron beam. At this time, the thicker the particle, the more difficult it is for an electron beam to pass. Therefore, a clearer observation can be obtained by using a high-pressure electron microscope (200 kV or more for particles having a thickness of 0.25 μm). From the photograph of the particles obtained by such a method, the position and number of dislocations for each particle when viewed from the direction perpendicular to the main plane can be determined.

The silver halide grains of the present invention may be obtained by using the obtained grains as host grains and forming epitaxial grains at the edges and / or corners of the grains.
Alternatively, the particles may be used as a substrate, and AgX layers having a different halogen composition from the substrate may be laminated to produce various known particles having various particle structures.

The monodispersity of the emulsion of the present invention is preferably 30% or less, and more preferably 5% or more and 25%, considering the degree of monodispersity based on the variation coefficient defined by the method described in JP-A-59-745481. % Or less is preferable. In particular, when used for a high-sensitivity photosensitive material, the content is preferably 5% or more and 15% or less.

In the course of silver halide grain formation or physical ripening, cadmium salt, zinc salt, lead salt, thallium salt, iridium salt or its complex salt, rhodium salt or its complex salt, iron salt or its complex salt, etc. are allowed to coexist. Is also good. In addition, a mode in which impurity ions are doped in the whole AgX particles, a mode in which impurities are doped in specific locations in the AgX particles, and a mode in which impurities are localized and doped within 0.1 μm from the particle surface can be exemplified. The doping concentration in this case is 10
^-8 to 10 ^-1 mol / mol AgX is preferred, and 10 ^-7 to 10 mol / mol is preferred.
^-2 mol / mol AgX is more preferred. Refer to Research Disclosure, Vol. 307, Item 3071 for details of specific examples of impurity ion compounds and the method of doping the AgX phase.
05, November, 1989, US Patent 5,166,045
Nos. 4,933,272, 5,164,292 and 51
No. 32203, No. 4269927, No. 4847191
Nos. 4933272, 4981781, 50
No. 24931, JP-A-4-305644 and 4-32
No. 1024, No. 1-183647, No. 2-20853
Nos., 1-285941 and 3-118536 can be referred to.

The photographic emulsion used in the present invention can contain various compounds for the purpose of preventing fog during the production process, storage or photographic processing of the photographic material or stabilizing photographic performance. Azoles such as benzothiazolium salts, nitroindazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles , Benzotriazoles, nitrobenztriazoles, mercaptotetrazoles (especially 1
-Phenyl-5-mercaptotetrazole); mercaptopyrimidines; azaindenes such as triazaindenes, tetraazaindenes (especially 4-hydroxy-substituted (1,3,3a, 7) tetraazaindenes), and pentaaza Many compounds known as antifoggants or stabilizers, such as indenes and the like; benzenethiosulfonic acid, benzenesulfinic acid, benzenesulfonamide, etc. can be added. For example, those described in U.S. Pat. Nos. 3,954,474 and 3,982,947 and JP-B-52-28,660 can be used.

The emulsion of the present ^{invention, Br -, I -, SCN} -
Conversion of the emulsion surface with ions enhances dye adsorption and can be preferably used. The technique of converting the particle surface with I ^- ions or the like to enhance dye adsorption is a technique widely known in the art. However, if the conversion is attempted with silver iodide fine particles or iodide ions or its release agent to form a thin surface layer of silver iodide on silver chloride tabular grains, the solubility difference between silver iodide and silver chloride is large, A uniform conversion could not be performed. Therefore, it was unexpected that excellent adsorption was obtained in the present invention.

Each ion may be used alone or in combination. The conversion by each ion is performed, for example, by the salt (KBr, KI, KSCN, N
aBr, NaI, NaSCN, etc.) can be added as a solid or as an aqueous solution or as a gelatin dispersion. In addition, when coexisting with the substrate particles, the silver salt of fine particles (Ag
(Br, AgI, AgSCN, AgBrI, etc.). When added in the form of fine particles, the fine particles preferably have an average equivalent sphere diameter of 0.1 μm or less.
Those having a size of not more than 05 μm are more preferred. The fine particles are
A silver nitrate aqueous solution and an alkali halide or alkali thiocyanate aqueous solution of an arbitrary composition are supplied and adjusted continuously by a mixer provided near the reaction vessel, and can be immediately added to the reaction vessel, or can be added to another vessel in advance. It can also be added after adjusting batchwise. If necessary, the fine particles may contain ions or compounds of heavy metals such as iridium, rhodium, platinum, and yellow blood salt.

The amount of ions used for the conversion is preferably from 0.01 mol% to 3 mol% based on the total silver amount.
Especially I ^- ion 0.0 conversions
1 mol% to 0.6 mol% seems to be preferred, but more preferably 0.01 mol% to 0.3 mol%.

[0045] In the present invention, the surface I ^- and Br ^-
The grains having a total silver iodide content of preferably 0.01 mol% to 0.6 mol%, more preferably 0.01 mol% to 0.6 mol%, based on the total silver amount.
0.3 mol%.

The halogen conversion time of the present invention is as follows.
It is preferable to perform halogen conversion at least before addition of the spectral sensitizing dye.

Hereinafter, the compounds used in the present invention are described in detail. Although any methine dye can be formed by Q, preferred examples include a cyanine dye, a merocyanine dye, a rhodocyanine dye, a trinuclear merocyanine dye, an allopolar dye, a hemicyanine dye, and a styryl dye. These methine dyes are described in FM Harmer, Heterocyclic Compounds-Cyanine Dy
es and Related Compounds), John Wiley & Sons-New York,
London, 1964. In the general formula (I), when a cyanine dye is formed by Q, it can be represented by the following resonance formula.

[0048]

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Formulas (I), (II), (III) and (IV)
Wherein the 5- or 6-membered nitrogen-containing heterocyclic ring represented by Z ₁ , Z ₂ , Z ₃ , Z ₄ , Z ₆ and Z ₈ is a thiazoline nucleus, thiazole nucleus, benzothiazole nucleus, oxazoline nucleus, oxazole Nucleus, benzoxazole nucleus, selenazoline nucleus, selenazole nucleus, benzoselenazole nucleus,
3,3-dialkylindolenine nucleus (for example, 3,3-dimethylindolenine), imidazoline nucleus, imidazole nucleus, benzimidazole nucleus, 2-pyridine nucleus, 4-pyridine nucleus, 2-quinoline nucleus, 4-quinoline nucleus, -Isoquinoline nucleus, 3-isoquinoline nucleus, imidazo [4,5-
b] A quinoxaline nucleus, an oxadiazole nucleus, a thiadiazole nucleus, a tetrazole nucleus and a pyrimidine nucleus. Preferred are a benzoxazole nucleus, a benzothiazole nucleus, a benzimidazole nucleus and a quinoline nucleus, and more preferred are a benzoxazole nucleus and a benzothiazole nucleus. In the general formula (II), Z ₁ and Z ₂ are particularly preferably a benzoxazole nucleus.

Z ₁ , Z ₂ , Z ₃ , Z ₄ , Z ₆ and Z ₈
Assuming that the above substituent is V, the substituent represented by V is not particularly limited. For example, a halogen atom (for example, chlorine, bromine, iodine, fluorine), a mercapto group, a cyano group,
Carboxyl group, phosphate group, sulfo group, hydroxy group,
A carbamoyl group having 1 to 10 carbon atoms, preferably 2 to 8 carbon atoms, more preferably 2 to 5 carbon atoms (eg, methylcarbamoyl, ethylcarbamoyl, morpholinocarbonyl), 0 to 10 carbon atoms, preferably 2 to 8 carbon atoms More preferably, a sulfamoyl group having 2 to 5 carbon atoms (eg, methylsulfamoyl, ethylsulfamoyl, piperidinosulfonyl), a nitro group, 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, more preferably An alkoxy group having 1 to 8 carbon atoms (for example, methoxy, ethoxy, 2-methoxyethoxy, 2-phenylethoxy), having 6 to 20 carbon atoms, preferably 6 to 1 carbon atoms;
2, more preferably an aryloxy group having 6 to 10 carbon atoms (eg, phenoxy, p-methylphenoxy, p-
Chlorophenoxy, naphthoxy), having 1 to 20 carbon atoms,
Preferably, it is an acyl group having 2 to 12 carbon atoms, more preferably 2 to 8 carbon atoms (eg, acetyl, benzoyl, trichloroacetyl), 1 to 20 carbon atoms, preferably 2 to 12 carbon atoms, more preferably 2 to 12 carbon atoms. 8 acyloxy groups (eg, acetyloxy, benzoyloxy), having 1 to 20 carbon atoms, preferably 2 to 1 carbon atoms.
2, more preferably an acylamino group having 2 to 8 carbon atoms (eg, acetylamino), a sulfonyl group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms (eg, methanesulfonyl, ethane Sulfonyl, benzenesulfonyl, etc.), having 1 to 2 carbon atoms
0, preferably a sulfinyl group having 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms (for example, methanesulfinyl, benzenesulfinyl), 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 10 carbon atoms
To 8 sulfonylamino groups (for example, methanesulfonylamino, ethanesulfonylamino, benzenesulfonylamino, etc.), an amino group,

A substituted amino group having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms (eg, methylamino, dimethylamino, benzylamino, anilino, diphenylamino); 1
5, preferably an ammonium group having 3 to 10 carbon atoms, more preferably 3 to 6 carbon atoms (for example, trimethylammonium group, triethylammonium group), 0 to 15 carbon atoms, preferably 1 to 10 carbon atoms, more preferably carbon atom A hydrazino group having a number of 1 to 6 (for example, a trimethylhydrazino group);
To 10, more preferably a ureido group having 1 to 6 carbon atoms (e.g., a ureide group, an N, N-dimethylureido group);
0, more preferably an imide group having 1 to 6 carbon atoms (eg, succinimide group), an alkyl or arylthio group having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms (eg, methylthio, Ethylthio, carboxyethylthio, sulfobutylthio,
Phenylthio etc.), an alkoxycarbonyl group having 2 to 20 carbon atoms, preferably 2 to 12 carbon atoms, more preferably 2 to 8 carbon atoms (eg, methoxycarbonyl, ethoxycarbonyl, benzyloxycarbonyl), and 6 to 20 carbon atoms, preferably An aryloxycarbonyl group having 6 to 12 carbon atoms, more preferably 6 to 8 carbon atoms (for example, phenoxycarbonyl);

An unsubstituted alkyl group having 1 to 18 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms (eg, methyl, ethyl, propyl, butyl), and 1 to 18 carbon atoms, preferably 1 to 1 carbon atoms
0, more preferably a substituted alkyl group having 1 to 5 carbon atoms (hydroxymethyl, trifluoromethyl, benzyl,
Carboxyethyl, ethoxycarbonylmethyl, acetylaminomethyl, and here an unsaturated hydrocarbon group having 2 to 18 carbon atoms, preferably 3 to 10 carbon atoms, more preferably 3 to 5 carbon atoms (for example, vinyl group, ethynyl group, 1-cyclohexenyl group, benzylidine group, benzylidene group) are also included in the substituted alkyl group. ), Having 6 to 20 carbon atoms, preferably 6 to 1 carbon atoms.
5, more preferably a substituted or unsubstituted aryl group having 6 to 10 carbon atoms (for example, phenyl, naphthyl, p-carboxyphenyl, p-nitrophenyl, 3,5-dichlorophenyl, p-cyanophenyl, m-fluorophenyl, p-tolyl), an optionally substituted heterocyclic group having 10 to 20 carbon atoms, preferably 2 to 10 carbon atoms, more preferably 4 to 6 carbon atoms (eg, pyridyl, 5-methylpyridyl, thienyl, furyl, morpholino) , Tetrahydrofurfuryl). Further, a structure in which a benzene ring or a naphthalene ring is condensed can be employed. Further, V may further substitute on these substituents.

Z ₁ , Z ₂ , Z ₃ , Z ₄ , Z ₆ and Z ₈
Preferred as the substituent of the above-mentioned alkyl group, aryl group, alkoxy group, halogen atom, acyl group, cyano group, sulfonyl group, and benzene ring condensation, more preferably alkyl group, aryl group, halogen atom,
An acyl group, a sulfonyl group, and a benzene ring fused,
Particularly preferred are a methyl group, a methoxy group, a chlorine atom, a bromine atom, an iodine atom, and a benzene ring condensation.

In the general formula (I), R _a and R _b represent a hydrogen atom, an aliphatic group, an aryl group, or a heterocyclic group.
However, _Ra and _Rb are not simultaneously hydrogen atoms. Specifically, the following are mentioned. Examples of the aliphatic group having 1 or more carbon atoms include unsubstituted alkyl groups having 1 to 16 carbon atoms, preferably 2 to 8 carbon atoms, more preferably 2 to 4 carbon atoms (eg, ethyl, butyl, pentyl), and carbon atoms. Number 1 to 20, preferably 3 to 1 carbon atoms
0, more preferably includes an aliphatic group or an unsaturated aliphatic group V mentioned is substituted as a substituent, such as Z ₁ in the substituted aliphatic group (e.g., above 3 to 7 carbon atoms. Further, specifically Represents an allyl group, a vinyl group, a benzyl group, a hydroxyethyl group, a carboxyethyl group, etc.),
An unsubstituted aryl group having 6 to 20 carbon atoms, preferably 6 to 10 carbon atoms, more preferably 6 to 8 carbon atoms (for example, a phenyl group or 1-naphthyl group);
Preferably 10, more preferably from 6 carbon atoms and an aryl group V is substituted cited as substituents, such as Z ₁ of the substituted aryl group (e.g., above 8 to 6 carbon atoms. Specifically p- methoxy A phenyl group, a p-methylphenyl group, a p-chlorophenyl group, etc.), having 1 to 20 carbon atoms, preferably 3 to 1 carbon atoms.
0, more preferably an unsubstituted heterocyclic group having 4 to 8 carbon atoms (eg, 2-furyl group, 2-thienyl group, 2-pyridyl group), 1 to 20 carbon atoms, preferably 3 to 1 carbon atoms.
0, more preferably include heterocyclic group V mentioned as substituents is substituted, such as Z ₁ substituted Hajime Tamaki (e.g., the aforementioned 8 from 4 carbon atoms. Specifically 5-methyl-2
-Thienyl group, 4-methoxy-2-pyridyl group and the like. As the aliphatic group, those having 2 or more carbon atoms are preferable. More preferred are an ethyl group, an allyl group, a vinyl group and a benzyl group, and particularly preferred are an allyl group, a vinyl group and a benzyl group.

[0055] As L _a and L _b, unsubstituted methylene group,
Or a substituted methylene group (for example, a methylene group substituted by V mentioned as a substituent such as Z ₁ above. Specific examples include a methyl-substituted methylene group, an ethyl-substituted methylene group, a phenyl-substituted methylene group, and a hydroxy group. And a group-substituted methylene group.) Preferably, it is an unsubstituted methylene group.

K ₁ represents an integer of 0 to 5, and k ₂ represents an integer of 0 to 5. The total of k ₁ and k ₂ is preferably 1 or more and 5 or less.
k ₁ is preferably 1, 2, or 3. More preferably, it is 2. k ₂ is preferably 0 or 1. More preferably, it is 0. When k ₁ and k ₂ are 2 or more, L _a and L _b are repeated, but need not be the same.

In the general formula (I), R _a , R _b , L _a , L _b ,
Examples of k ₁ , k ₂ and Rz are shown below. Incidentally, it shows a preferred embodiment in order Rz ₇ from Rz _1, most preferably from Rz _7.

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R in the general formulas (II), (III) and (IV)
₁ , R ₂ , R ₃ , R ₅ and R ₇ each represent an alkyl group. Examples of the alkyl group represented by R ₁ and R ₂ include, for example, an unsubstituted alkyl group having 1 to 18, preferably 1 to 7, and particularly preferably 1 to 4 carbon atoms (eg, methyl, ethyl, propyl, isopropyl, butyl) , Isobutyl, hexyl, octyl, dodecyl, octadecyl), a substituted alkyl group having 1 to 18, preferably 1 to 7, and particularly preferably 1 to 4 carbon atoms (for example, V mentioned as the substituent such as Z ₁ described above is preferred) Preferably, the alkyl group is a substituted alkyl group, preferably an aralkyl group (eg, benzyl, 2-phenylethyl), an unsaturated hydrocarbon group (eg, an allyl group), a hydroxyalkyl group (eg,
2-hydroxyethyl, 3-hydroxypropyl), carboxyalkyl group (for example, 2-carboxyethyl,
3-carboxypropyl, 4-carboxybutyl, carboxymethyl), an alkoxyalkyl group (for example, 2-
Methoxyethyl, 2- (2-methoxyethoxy) ethyl), aryloxyalkyl group (eg, 2-phenoxyethyl, 2- (1-naphthoxy) ethyl), alkoxycarbonylalkyl group (eg, ethoxycarbonylmethyl, 2-benzyloxycarbonyl) Ethyl), an aryloxycarbonylalkyl group (for example, 3-phenoxycarbonylpropyl), an acyloxyalkyl group (for example, 2
-Acetyloxyethyl), acylalkyl group (eg, 2-acetylethyl), carbamoylalkyl group (eg, 2-morpholinocarbonylethyl), sulfamoylalkyl group (eg, N, N-dimethylcarbamoylmethyl), sulfoalkyl group (eg, , 2-sulfoethyl,
3-sulfopropyl, 3-sulfobutyl, 4-sulfobutyl, 2- [3-sulfopropoxy] ethyl, 2-hydroxy-3-sulfopropyl, 3-sulfopropoxyethoxyethyl), sulfatoalkyl group (for example, 3-
Furfatopropyl, 4-flufatobutyl), a heterocyclic-substituted alkyl group (for example, 2- (pyrrolidin-2-one-
1-yl) ethyl, tetrahydrofurfuryl), methanesulfonylcarbamoylmethyl group and the like.
The alkyl group of R ₁ , R ₂ , R ₃ , R ₅ and R ₇ is preferably the above-mentioned carboxyalkyl group, sulfoalkyl group and Rz, more preferably the above-mentioned sulfoalkyl group and Rz.

Z ₅ represents a group of atoms necessary to form an acidic nucleus, but can take the form of an acidic nucleus of any general merocyanine dye. The acidic nucleus referred to here is, for example, “The Theory of the Photographic Process” edited by James (The Theory of the Ph.D.).
otographic Process) 4th edition, Macmillan Publishing Co., 19
77, 198 pages. Specifically, U.S. Patent Nos. 3,567,719 and 3,575,869.
No. 3,804,634, 3,837,862
No. 4,002,480, 4,925,777
And JP-A-3-167546.

It is preferred that the acidic nucleus forms a 5- or 6-membered nitrogen-containing heterocyclic ring composed of carbon, nitrogen and chalcogen (typically oxygen, sulfur, selenium and tellurium) atoms. Include the following nuclei: 2-pyrazolin-5-one, pyrazolidine-3,5-dione, imidazolin-5-one, hydantoin, 2 or 4-thiohydantoin, 2-iminooxazolidin-4-one, 2-oxazoline-5-one, 2- Thiooxazoline-2,4-dione, isoxazolin-5-one, 2
Thiazoline-4-one, thiazolidine-4-one, thiazolidine-2,4-dione, rhodanine, thiazolidine-2,4-dithione, isorhodanine, indan-
1,3-dione, thiophen-3-one, thiophen-
3-one-1,1-dioxide, indoline-2-one, indoline-3-one, 2-oxoindazolinium, 3-oxoindazolinium, 5,7-dioxo-
6,7-dihydrothiazolo [3,2-a] pyrimidine,
Cyclohexane-1,3-dione, 3,4-dihydroisoquinolin-4-one, 1,3-dioxane-4,6-
Dione, barbituric acid, 2-thiobarbituric acid, chroman-2,4-dione, indazolin-2-one, pyrido [1,2-a] pyrimidine-1,3-dione, pyrazolo [1,5-b Quinazolone, pyrazolo [1,5-
a] Benzimidazole, pyrazolopyridone, 1,2,2
3,4-tetrahydroquinoline-2,4-dione, 3-
Oxo-2,3-dihydrobenzo [d] thiophene-
1,1-dioxide, 3-dicyanomethine-2,3-
Core of dihydrobenzo [d] thiophene-1,1-dioxide.

Z ₅ is preferably hydantoin, 2 or 4-thiohydantoin, 2-oxazoline-5-one, 2-thiooxazoline-2,4-dione, thiazolidine-2,4-dione, rhodanine, thiazolidine-.
2,4-dithione, barbituric acid and 2-thiobarbituric acid, more preferably hydantoin, 2 or 4-thiohydantoin, 2-oxazoline-5-one, rhodanine, barbituric acid, 2-thiobarbitic acid Tool acid. Particularly preferred are 2 or 4-thiohydantoin, 2-oxazolin-5-one and rhodanine.

The 5- or 6-membered nitrogen-containing heterocyclic ring formed by Z _{7 is obtained} by removing an oxo group or a thioxo group from the heterocyclic ring represented by Z ₅ . Preferably hydantoin, 2 or 4-thiohydantoin, 2-oxazolin-5-one, 2-thiooxazoline-2,4-
Dione, thiazolidine-2,4-dione, rhodanine,
Thiazolidine-2,4-dithione, barbituric acid, 2
-Thiobarbituric acid is obtained by removing an oxo group or a thioxo group, more preferably hydantoin,
2 or 4-thiohydantoin, 2-oxazoline-5
-One, rhodanine, barbituric acid, 2-thiobarbituric acid from which an oxo group or a thioxo group has been removed, particularly preferably 2 or 4-thiohydantoin;
It is obtained by removing an oxo group or a thioxo group from 2-oxazolin-5-one or rhodanine.

Examples of the alkyl group represented by R ₄ and R ₆ include the unsubstituted alkyl group and the substituted alkyl group mentioned as examples of R ₁ and the like, and similar ones are preferable. Moreover, it has 6 to 20 carbon atoms, preferably 6 carbon atoms.
To 10, more preferably an unsubstituted aryl group having 6 to 8 carbon atoms (eg, phenyl group, 1-naphthyl group), 6 to 20 carbon atoms, preferably 6 to 10 carbon atoms, more preferably 6 to 8 carbon atoms. A substituted aryl group (for example, an aryl group substituted by V mentioned as a substituent such as Z ₁ described above. Specific examples include a p-methoxyphenyl group,
p-methylphenyl group, p-chlorophenyl group and the like. ), Having 1 to 20 carbon atoms, preferably 3 carbon atoms
To 10, more preferably an unsubstituted heterocyclic group having 4 to 8 carbon atoms (eg, 2-furyl, 2-thienyl, 2-pyridyl, 3-pyrazolyl, 3-isoxazolyl, 3
-Isothiazolyl, 2-imidazolyl, 2-oxazolyl, 2-thiazolyl, 2-pyridazyl, 2-pyrimidyl, 3-pyrazyl, 2- (1,3,5-triazolyl), 3- (1,2,4-triazolyl) , 5-tetrazolyl), a substituted heterocyclic group having 1 to 20 carbon atoms, preferably 3 to 10 carbon atoms, more preferably 4 to 8 carbon atoms (for example, the above-mentioned V as a substituent such as Z ₁ is substituted. Heterocyclic groups, specifically, 5-methyl-2
-Thienyl group, 4-methoxy-2-pyridyl group and the like. ). Preferred as R ₄ and R ₆ are methyl, ethyl, 2-sulfoethyl, 3-sulfopropyl, 3-sulfobutyl, 4-sulfobutyl, carboxymethyl, phenyl, 2-pyridyl, 2-thiazolyl, more preferably ethyl, 2-sulfoethyl, carboxymethyl, phenyl and 2-pyridyl.

L ₁ , 0065 ₃ , L ₄ , L ₅ , L ₆ , L
_{7, L 8, L 9,} L 10, L 11, L 12, L 13, L 14,
L ₁₅ , L ₁₆ , L ₁₇ , L ₁₈ , L ₁₉ , L ₂₀ , L ₂₁ , and L ₂₂
Each independently represents a methine group. The methine group represented by L _{1 to} L ₂₂ may have a substituent. Examples of the substituent include a substituted or unsubstituted C ₁ to C 15, preferably C ₁ to C 10, more preferably C ₁ to C 10 carbon atom. An alkyl group of the formulas 1 to 5 (eg, methyl, ethyl, 2-carboxyethyl), a substituted or unsubstituted C 6 to C 2
0, preferably an aryl group having 6 to 15 carbon atoms, more preferably 6 to 10 carbon atoms (eg, phenyl, o-carboxyphenyl), substituted or unsubstituted 3 to 20 carbon atoms, preferably 4 to 15 carbon atoms, More preferably, it is a heterocyclic group having 6 to 10 carbon atoms (for example, N, N-diethylbarbituric acid group), a halogen atom (for example, chlorine, bromine, fluorine, iodine), 1 to 15 carbon atoms, preferably 1 to 15 carbon atoms. 10, more preferably an alkoxy group having 1 to 5 carbon atoms (eg, methoxy, ethoxy), an alkylthio group having 1 to 15, preferably 1 to 10, more preferably 1 to 5 carbon atoms (eg, methylthio, ethylthio) ), An arylthio group having 6 to 20 carbon atoms, preferably 6 to 15 carbon atoms, and more preferably 6 to 10 carbon atoms (eg, Phenylthio), from 0 carbon atoms 1
5, preferably an amino group having 2 to 10 carbon atoms, more preferably 4 to 10 carbon atoms (for example, N, N-diphenylamino, N-methyl-N-phenylamino, N-methylpiperazino) and the like. Further, a ring may be formed with another methine group, or a ring may be formed with an auxochrome. Here auxochrome and, for example, a heterocyclic ring, and the like represented by Z ₁ to Z _8.

N ₁ , n ₂ and n ₃ are preferably 0 or 1, and more preferably 1. n ₄ is preferably 0 or 1, and more preferably 0. n
_{When 1 to} n ₄ are 2 or more, the methine group is repeated but need not be the same.

M ₁ , M ₂ , M ₃ and M ₄ are included in the formula to indicate the presence of a cation or an anion when necessary to neutralize the ionic charge of the dye. I have. Typical cations include hydrogen ions (H ⁺ ), inorganic cations such as alkali metal ions (eg, sodium ion, potassium ion, lithium ion), alkaline earth metal ions (eg, calcium ion), and ammonium ions (eg, Organic ions such as ammonium ion, tetraalkylammonium ion, pyridinium ion, and ethylpyridinium ion. The anion may be either an inorganic anion or an organic anion, such as a halogen anion (eg, a fluorine ion, a chloride ion, an iodine ion), a substituted arylsulfonate ion (eg, a p-toluenesulfonic acid ion, a p-chloroion ion). Benzenesulfonic acid ion), aryl disulfonic acid ion (for example, 1,3-benzenesulfonic acid ion, 1,5-naphthalenedisulfonic acid ion,
2,6-naphthalenedisulfonic acid ion), alkyl sulfate ion (eg, methyl sulfate ion), sulfate ion, thiocyanate ion, perchlorate ion, tetrafluoroborate ion, picrate ion, acetate ion, trifluoromethanesulfonic acid ion Is mentioned. Further, another dye having a charge opposite to that of the ionic polymer or the dye may be used. m ₁ , m ₂ , m ₃ , and m ₄ represent the numbers required to balance the charges and are 0 when forming a salt in the molecule. m ₁ , m ₂ , m ₃ and m ₄ are preferably 0 or more and 6 or less, more preferably 0 or more and 4 or less, and particularly preferably 0 or more and 1 or less. p ₁ ,
p ₂ , p ₃ , p ₄ , p ₅ , and p ₆ are each independently 0
Or represents 1. Preferably it is 0.

In the general formula (V), R ₈ and R ₉ are preferably an unsubstituted alkyl group having 18 or less carbon atoms (eg, methyl, ethyl, propyl, butyl, pentyl, octyl, decyl, dodecyl, octadecyl), or Substituted alkyl group ｛As the substituent, for example, a carboxy group, a sulfo group, a cyano group, a halogen atom (for example, fluorine, chlorine, or bromine), a hydroxy group, an alkoxycarbonyl group having 8 or less carbon atoms (for example, methoxycarbonyl, ethoxy Carbonyl, phenoxycarbonyl, benzyloxycarbonyl), an alkoxy group having 8 or less carbon atoms (eg, methoxy, ethoxy, benzyloxy, phenethyloxy), a monocyclic aryloxy group having 10 or less carbon atoms (eg, phenoxy, p-tolyloxy) An acyloxy group having 3 or less carbon atoms (eg, For example, acetyloxy, propionyloxy), an acyl group having 8 or less carbon atoms (eg, acetyl, propionyl, benzoyl, mesyl), a carbamoyl group (eg, carbamoyl, N, N-dimethylcarbamoyl, morpholinocarbonyl, piperidinocarbonyl), and a sulfamoyl group (Eg sulfamoyl, N,
N-dimethylsulfamoyl, morpholinosulfonyl,
Piperidinosulfonyl), an alkylsulfonylcarbamoyl group having 8 or less carbon atoms (eg, methanesulfonylcarbamoyl), an alkylcarbonylsulfamoyl group having 8 or less carbon atoms (eg, acetylsulfamoyl), 1 carbon atom
And an alkyl group having 18 or less carbon atoms, which is substituted with an aryl group having 0 or less (eg, phenyl, 4-chlorophenyl, 4-methylphenyl, α-naphthyl). Preferably, a carboxyalkyl group (eg, 2-carboxyethyl group, carboxymethyl group), a sulfoalkyl group (eg, 2-sulfoethyl group, 3-sulfopropyl group,
-Sulfobutyl group, 3-sulfobutyl group) and methanesulfonylcarbamoylmethyl group. Most preferably,
A sulfoalkyl group having 2 to 4 carbon atoms (specifically, a sulfoethyl group, a sulfopropyl group, a 3-sulfobutyl group, and a 4-sulfobutyl group). X represents an ion necessary for balancing the charges, m is 0 or 1, respectively, and 0 when an internal salt is formed. Examples of the oxazole ring fused to the aromatic ring formed by Z ₉ and Z ₁₀ include the following.

Benzoxazole nucleus (benzoxazole, 5-chlorobenzoxazole, 5-methylbenzoxazole, 5-bromobenzoxazole, 5-fluorobenzoxazole, 5-phenylbenzoxazole, 5-methoxybenzoxazole, 5-nitrobenzo Oxazole, 5-trifluoromethylbenzoxazole, 5-hydroxybenzoxazole, 5-
Carboxybenzoxazole, 6-methylbenzoxazole, 6-chlorobenzoxazole, 6-nitrobenzoxazole, 6-methoxybenzoxazole, 6-hydroxybenzoxazole, 5,6-dimethylbenzoxazole, 4,6-dimethylbenzoxazole, 5-ethoxybenzoxazole), naphthooxazole nucleus (for example, naphtho [2,1-d] oxazole, naphtho [1,2-d] oxazole, naphtho [2,3-d] oxazole, 5-nitronaphtho [2
1-d] oxazole). The present invention is particularly effective when it has a substituted or unsubstituted benzoxazole nucleus.

As the optionally substituted alkyl group represented by Q ₁ , for example, an alkyl group having 3 to 18, preferably 3 to 7, particularly preferably 3 to 4 carbon atoms (for example, propyl, isopropyl, Butyl group, isobutyl group, hexyl group, octyl group, dodecyl group, octadecyl group), hydroxyalkyl group (eg, 2-hydroxypropyl group, 3-hydroxypropyl group), carboxyalkyl group (eg, 3-carboxypropyl group, 4
-Carboxybutyl group), an alkoxyalkyl group (for example, 3-methoxypropyl group, 3- (2-methoxyethoxy) propyl group), a sulfoalkyl group (for example, 2-
Sulfoethyl group, 3-sulfopropyl group, 3-sulfobutyl group, 4-sulfobutyl group, 3- [3-sulfopropoxy] ethyl group, 2-hydroxy-3-sulfopropyl group, sulfatoalkyl group (for example, 3-sulfoalkyl group) A fatopropyl group, a 4-sulfatobutyl group), a heterocyclic-substituted alkyl group (for example, a 2- (pyrrolidin-2-one-1-yl) propyl group, a 3-morpholinopropyl group), a 3-acetoxypropyl group, Methoxypropyl group, methanesulfonylaminopropyl group, allyl group), halogenated alkyl group (eg, 4-bromobutyl, 3-bromopropyl, 3-chloropropyl), arylalkyl group (eg, phenylpropyl), acylalkyl group (eg, Acetylpropyl), most preferably a propyl group.

The general formulas (I) and (II) of the present invention are described below.
Specific examples of the compounds (III), (IV) and (V) are shown below, but the present invention is not limited thereto. Since the general formulas (II), (III) and (IV) are subordinate concepts of the general formula (I), specific examples of the general formula (I) include:
Compounds excluding these subordinate compounds were listed. Specific examples of the compound of the general formula (II)

[0072]

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[0073]

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[0074]

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[0075]

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[0076]

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[0077]

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[0078]

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[0079]

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[0080]

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[0081]

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[0082]

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Specific examples of the compound of the general formula (III)

[0084]

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[0085]

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[0086]

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Specific examples of the compound of the general formula (IV)

[0088]

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[0089]

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[0090]

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Specific examples of the compound of the general formula (I)

[0092]

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[0093]

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Specific examples of the compound of the general formula (V)

[0095]

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[0096]

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[0097]

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[0098]

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[0099]

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[0100]

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In the most preferred embodiment of the compound represented by formula (V) of the present invention, the 5-position substituted (chloro,
(Phenyl, methyl, bromo, iodo, etc.) An oxacarbocyanine dye having a benzoxazole ring, at least one of R ₈ and R ₉ is a sulfoalkyl group, and Q ₁ is a propyl group or a butyl group.

The compounds represented by the general formulas (I) to (V) according to the present invention are described in "Heterocyclic Compounds-Heterocyclic Compounds-Cyanine Soybeans and Relativized Compounds" by FM Harmer.
nds-Cyanine Dyes and Related Compounds), John Wiley & Sons-
New York, London, 1964, DM
DMSturmer, Heterocyclic Compounds-Special Topics In, Heterocyclic Compounds-Sp
ecial topics in heterocyclic chemistry), 18
Chapter 14, Sections 482-515, John Wiley & Sons, Inc.-New York, London, 1977, "Rodd's Chemistry."
of Carbon Compounds) '' 2nd.Ed.vol.IV.partB.197
7th edition, Chapter 15, Chapters 369-422, Elsevier
Science Public Company, Inc. (Elsevie
r Science Publishing Company Inc.), New York, and the like.

Synthesis Example (Synthesis of Compound II-1) Compound II-1 was synthesized according to the following scheme.

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A) Synthesis of 1-ethyl-1,3-propane sultone 68 g (1.09 mol) of ethylene glycol and 343.2 g of propylsulfonyl chloride (2.406 mol)
l) and 650 ml of dichloromethane were cooled with dry ice / acetone while stirring, and triethylamine 335.
4 ml (2.406 mol) was added dropwise over 25 minutes. The internal temperature was kept at -10C or lower. Furthermore, at room temperature 4
After stirring for an hour, the reaction solution was added to water 11, and the dichloromethane layer was extracted. The extract was dried over magnesium sulfate, and the solvent was distilled off under reduced pressure to obtain 287 g of a colorless liquid (A). Yield 96
%. 200 g (0.729 mol) of (A) and tetrahydrofuran 21 were stirred and cooled to −78 ° C., and 464 ml of a normal butyl lithium (1.65 mol / l) solution.
(0.765 mol) was added dropwise over 30 minutes. Furthermore, after stirring at -15 ° C for 1 hour, the reaction solution was added to ethyl acetate 31 / water 1.51, and the ethyl acetate layer was extracted.
The extract was dried over magnesium sulfate, and the solvent was distilled off under reduced pressure.
53 g of propane sultone (115-122 ° C / 2 mmH
g, yield 48%).

B) Synthesis of quaternary salt 4 g of 5-phenyl-2-methylbenzoxazole
(0.019 mol) and 3.4 g (0.023 mol) of 1-ethyl-1,3-propanesultone were heated and stirred on a 150 ° C. oil bath for 2 hours. While stirring the reaction solution, 50 ml of ethyl acetate was added, and after the reaction solution reached room temperature,
The obtained crystals were separated by absorption filtration and dried.
(B) (colorless powder, yield 6.75 g, yield 99%, melting point 265-270 ° C)

C) Synthesis of Compound (II-1) 6.75 g (0.019 mol) of (B), 17 ml of orthopropionic acid ethyl ester (0.0845 mol)
l), 11 ml of acetic acid and 11 ml of pyridine at 140 ° C.
Heat and stir on an oil bath, then add 7 ml of triethylamine.
(0.05 mol), and the mixture was heated and stirred for 2 hours. While stirring the reaction mixture, 100 ml of ethyl acetate was added. After the reaction mixture reached room temperature, the obtained crystals were separated by suction filtration. The obtained crystals were dissolved in 50 ml of methanol, a solution of 0.9 g of potassium acetate / 20 ml of methanol was added, and the obtained crystals were separated by suction filtration. Further, after adding 50 ml of methanol and dissolving by heating under reflux, the crystals were subjected to gravity filtration, and the solvent of the filtrate was added to about 20 ml.
The mixture was distilled off under normal pressure and allowed to cool to room temperature. The precipitated crystals were separated by suction filtration and dried. (II-1) (red powder, yield 0.85 g, yield 11.4%, λmax = 5
02 nm, ε = 143000 (methanol), melting point 220
Decomposed above ℃)

Synthesis Example 2 (Synthesis of Compound II-2) Compound II-2 was synthesized according to the following scheme.

[0109]

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A) Synthesis of 1-phenyl-1,3-propane sultone The synthesis was carried out in the same manner as in Synthesis Example 1a) except that benzylsulfonyl chloride was used instead of propylsulfonyl chloride.

B) Synthesis of quaternary salt 2.5 g of 5-phenyl-2-methylbenzoxazole
(0.012 mol) and 2.6 g (0.013 mol) of 1-phenyl-1,3-propane sultone at 150 ° C.
The mixture was heated and stirred on an oil bath for 4 hours. After stirring the reaction mixture, 50 ml of ethyl acetate was added. After the reaction mixture reached room temperature, the obtained crystals were separated by suction filtration and dried. (C) (colorless powder, yield 4.84 g, yield 100)
C) Synthesis of compound (II-2) A method similar to that of Synthesis Example 1 c) except that (C) was used instead of (B) and sodium acetate was used instead of potassium acetate. To obtain (II-2). (Red powder, yield 7%, λm
ax = 505 nm, ε = 146000 (methanol),
Melting point 195-200 ° C)

The addition amount of the compounds represented by the general formulas (I) to (V) (sensitizing dye) is 0.5 per mol of silver halide.
The range is preferably from × 10 ⁻⁶ mol to 1.0 × 10 ⁻² mol. More preferably, it is in the range of 1.0 × 10 ⁻⁵ mol to 5.0 × 10 ⁻³ mol. The compounds (sensitizing dyes) represented by the general formulas (I) to (V) may be added in the process of forming silver halide grains or in the process of chemical sensitization, or may be added at the time of coating. Particularly, as a method for adding the compounds (sensitizing dyes) represented by formulas (I) to (V) during the formation of silver halide emulsion grains, US Pat. Nos. 4,225,666 and 4,8
28,972 and JP-A-61-103,149. A method of adding a sensitizing dye in a desalting step of a silver halide emulsion is disclosed in European Patent 2
91, 339-A and JP-A-64-52,137 can be referred to. The method of adding a sensitizing dye in the chemical sensitization step can be referred to JP-A-59-48,756. In the present invention, before adding a chemical sensitizer such as a selenium sensitizer, a sulfur sensitizer, or a gold sensitizer, the compounds represented by the general formulas (I) to (V) of the present invention (sensitized) It is most preferable to add a dye to the emulsion.

The compound (sensitizing dye) represented by formulas (I) to (V) of the present invention may be added in a form dissolved in water or a solvent such as methanol. A dispersion of a sensitizing dye which is mechanically pulverized and dispersed into fine particles of 1 μm or less in an aqueous system under conditions substantially free of an organic solvent and / or a surfactant by the method described in No. 45217 or the like may be used. .

As a method for increasing the spectral sensitization sensitivity of the compounds (sensitizing dyes) represented by formulas (I) to (V) of the present invention, a method using two or more sensitizing dyes in combination is known. ing. When two or more sensitizing dyes are used in combination, the spectral sensitivity tends to be an intermediate effect of using each sensitizing dye alone or is often reduced, but when a particular combination is used. In some cases, the spectral sensitivity is significantly increased as compared with the case where each sensitizing dye is used alone. Usually, this phenomenon is called a supersensitizing effect of the sensitizing dye. TH Jam for supersensitization
es "The Theory of the Photogra
phy Process "(4th edition, Macmillan, Ne
w York, 1977), Chapter 10 (W. West and PB Gilma
n Co-author). When such a combination is used, the spectral sensitizing wavelength may be in the middle of the spectral sensitizing wavelength obtained when each sensitizing dye is used alone, or may be simply a combination, but the spectral sensitizing wavelength when used alone is used. There may be a shift in spectral sensitization to wavelengths that cannot be predicted from the sensitivity characteristics. By using a combination of sensitizing dyes in this way, a higher spectral sensitivity can be obtained than when each sensitizing dye is used alone, and a sensitizing wavelength range suitable for the intended use of the photographic material is obtained. Finding a combination of sensitizing dyes has been a major problem in the technique of spectral sensitization of silver halide photographic emulsions.
The combination of sensitizing dyes used to obtain supersensitization requires a remarkable selectivity between the dyes. Significantly affected. That is, it is difficult to predict a combination of sensitizing dyes that provide a supersensitizing effect only from the chemical structural formula.

As the supersensitizer, a dye which does not itself have a spectral sensitizing effect or a substance which does not substantially absorb visible light can be used. For example, anomistyryl compounds substituted with a nitrogen-containing heterocyclic group (for example, those described in U.S. Pat. Nos. 2,933,390 and 3,635,721), and aromatic organic acid formaldehyde condensate (for example, 743,510), cadmium salts, azaindene compounds and the like.
U.S. Pat. Nos. 3,615,613 and 3,615,641
Nos. 3,617,295 and 3,635,721 are particularly useful.

The emulsion of the present invention is preferably selenium-sensitized. Here, selenium sensitization is performed by a conventionally known method. That is, usually, an unstable selenium compound and / or a non-unstable selenium compound is added,
It is preferably carried out by stirring the emulsion at 40 ° C. or higher for a certain period of time. Selenium sensitization using an unstable selenium sensitizer described in JP-B-44-15748 is preferably used. Specific unstable selenium sensitizers include aliphatic isoselenocyanates such as allyl isoselenocyanate, selenoureas, selenoketones, selenoamides,
There are selenocarboxylic acids and esters, selenophosphates. Particularly preferred unstable selenium compounds are shown below.

I. Colloidal metal selenium II. Organic selenium compounds (a selenium atom is double-bonded to a carbon atom of an organic compound by a covalent bond) a isoselenocyanates, for example, aliphatic isoselenocyanates such as allyl isoselenocyanate b selenoureas (enol type For example, methyl, ethyl, propyl, isopropyl, butyl, hexyl octyl, dioctyl, tetramethyl, N- (β-carboxyethyl) -N ′, N′-dimethyl, N, N-dimethyl, diethyl, dimethyl, etc. Aliphatic selenoureas having one or more aromatic groups such as phenyl and tolyl; heterocyclic selenoureas having heterocyclic groups such as pyridyl and benzothiazolyl c selenoketones such as selenoacetone; Selenoacetophenone, selenoketo with alkyl group bonded to> C = Se Selenoamides such as selenoacetamide e selenocarboxylic acids and esters such as 2-selenopropionic acid, 3-selenobutyric acid, methyl-3-selenobutyrate and the like III. Others a selenides such as diethyl selena Id, diethyl diselenide,
B Selenophosphates, for example, tri-p-tolylselenophosphate, tri-n-butylselenophosphate, etc.

The preferred types of unstable selenium compounds have been described above, but these are not limitative. Those skilled in the art will note that an unstable selenium compound as a sensitizer of a photographic emulsion is not so important as long as selenium is unstable, and the structure of the selenium sensitizer molecule is not important. It is generally understood that the moieties carry selenium and have no role other than to cause them to be present in the emulsion in an unstable manner. In the present invention, an unstable selenium compound having such a broad concept is advantageously used. Tokiko Sho 46-
No. 4553, Japanese Patent Publication No. 52-34492 and Japanese Patent Publication No. 5
Selenium sensitization using the non-labile selenium sensitizer described in 2-34491 is also used. Non-labile selenium compounds include, for example, selenous acid, potassium selenocyanide, selenazoles, quaternary ammonium salts of selenazoles, diaryl selenide, diaryl diselenide, 2-thioselenazolidinedione, 2-selenooxolidine And thione and derivatives thereof. Japanese Patent Publication No. 52-38408
The non-labile selenium sensitizer and thioselenazolidinedione compound described in the above item are also effective.

These selenium sensitizers are dissolved in water or an organic solvent such as methanol or ethanol alone or in a mixed solvent, and added during chemical sensitization. Preferably, it is added before the start of chemical sensitization. The selenium sensitizer used is not limited to one, and two or more of the above-described selenium sensitizers can be used in combination. It is preferable to use a combination of an unstable selenium compound and a non-unstable selenium compound. The addition amount of the selenium sensitizer used in the present invention varies depending on the activity of the selenium sensitizer used, the type and size of silver halide, the ripening temperature and time, but preferably 1 mol of silver halide. 1 × 10 ^-8 per
More than mole. More preferably, 1 × 10 ⁻⁷ mol or more 1
× 10 ^-5 mol or less. The temperature for chemical ripening when using a selenium sensitizer is preferably 45 ° C. or higher. More preferably, it is 50 ° C. or more and 80 ° C. or less. pAg and p
H is optional. For example, the effects of the present invention can be obtained in a wide range of pH from 4 to 9.

Chemical sensitization is more effective when performed in the presence of a silver halide solvent. Examples of the silver halide solvent that can be used in the present invention include U.S. Pat.
Nos. 271,157, 3,531,289, 3,574,628, JP-A-54-1019, and 5
(A) Organic thioethers described in JP-A-4-158917, JP-A-53-82408 and JP-A-55-7773.
(B) thiourea derivatives described in JP-A Nos. 7-55-2982, etc .; and (c) thiocarbonyl groups sandwiched between an oxygen or sulfur atom and a nitrogen atom described in JP-A-53-144319. Silver halide solvent having
(D) imidazoles described in -100717,
(E) sulfite, (f) thiocyanate and the like. Particularly preferred solvents include thiocyanate and tetramethylthiourea. The amount of the solvent used varies depending on the kind. For example, in the case of thiocyanate, the preferred amount is 1 × 10 ⁻⁴ mol to 1 × 10 ⁻² mol per mol of silver halide.

The silver halide photographic emulsion of the present invention can achieve higher sensitivity by using gold sensitization in combination with chemical sensitization.
Low fog can be achieved. It is preferable to further use sulfur sensitization if necessary. Sulfur sensitization is usually carried out at a high temperature, preferably at 40 ° C, by adding a sulfur sensitizer.
The above is carried out by stirring the emulsion for a certain time.
The gold sensitization is usually carried out by adding a gold sensitizer and stirring the emulsion at a high temperature, preferably at 40 ° C. or higher for a certain period of time. Known sulfur sensitizers can be used for the sulfur sensitization. For example, thiosulfate,
Allyl thiocarbamide thiourea, allyl isothiocyanate, cystine, p-toluene thiosulfonate, rhodanine and the like can be mentioned. Other US Patent No. 1,57
No. 4,944, No. 2,410,689, No. 2,2
No. 78,947, No. 2,728,668, No. 3,
Nos. 501,313 and 3,656,955, German Patent 1,422,869, JP-B-56-2
No. 4,937, JP-A-55-45016 and the like can also be used. The sulfur sensitizer may be added in an amount sufficient to effectively increase the sensitivity of the emulsion. This amount, pH, temperature, varies over a range of equivalent under various conditions such as the size of the silver halide grains, the silver halide per mol 1 × 10 ^-7 mol, 5 × 10 ^-5 Molar or less is preferred.

As the gold sensitizer for gold sensitization, the oxidation number of gold may be +1 or +3, and a gold compound usually used as a gold sensitizer can be used. Representative examples include chloroaurate, potassium chloroaurate, auric trichloride, potassium auric thiocyanate, potassium iodooleate, tetracyano auric acidide, ammonium aurothiocyanate, pyridyl trichlorogold, and the like. Although the amount of the gold sensitizer to be added varies depending on various conditions, the standard is preferably 1 × 10 ⁻⁷ mol or more and 5 × 10 ⁻⁵ mol or less per mol of silver halide.

In chemical ripening, there is no particular limitation on the timing and order of addition of a silver halide solvent and a gold sensitizer used in combination with a selenium sensitizer or tellurium sensitizer. The compounds can be added simultaneously (preferably) or during the course of chemical ripening, or at different times. In addition, the above compound is water or an organic solvent that can be mixed with water,
For example, it may be dissolved in a single solution or a mixed solution of methanol, ethanol, acetone or the like and added.

The method of reduction sensitization used in the present invention may be, for example, stannous chloride, aminoiminomethanesulfinic acid, hydrazine derivatives, borane compounds, Reduction sensitization can be performed using a silane compound or a polyamine compound. Further, the pH of the emulsion was 7 or more or the pAg was 8.3.
Reduction sensitization can be achieved by holding and aging the following. Further, reduction sensitization can be achieved by introducing a single addition portion of silver ions during grain formation. However, from the viewpoint of reducing the influence on grain formation and crystal growth and performing controlled reduction sensitization, reduction sensitization using ascorbic acid and its derivatives or thiourea dioxide is preferred. Used amount of the reduction sensitizer may vary depending reducing agent species 10 ^-7 mol to 10 ^-2
A mol / mol Ag amount is preferably used. Reduction sensitization is
It may be carried out at any point during grain formation, and may be carried out at any time after grain formation but before chemical sensitization.

In the present invention, tellurium sensitization can also be preferably used. As tellurium sensitizers, U.S. Pat.
623,499, 3,320,069, 3,7
72,031; British Patent No. 235,211;
121,496, 1,295,462, 1,3
96,696; Canadian Patent No. 800,958; Journal of Chemical Society Chemicals.
Communication (J.Chem.Soc.Chem.Commun.) 635 (1
980), ibid 1102 (1979), ibid 645 (1979), and the compounds described in Journal of Chemical Society Parkin Transaction (J. Chem. Soc. Perkin Trans.) 1, 2191 (198). Is preferred.

Specific examples of tellurium sensitizers include colloidal tellurium, telluroureas (for example, allyl tellurourea,
N, N-dimethyltellurourea, tetramethyltellurourea, N-carboxyethyl-N ′, N′-dimethyltellurourea, N, N′-dimethylethylenetellurourea, N,
N'-diphenylethylene tellurourea), isotellurocyanates (e.g. allyl isotellurocyanate), telluro ketones (e.g. telluroacetone, telluroacetophenone), telluroamides (e.g. telluroacetamide, N, N-dimethyltellurobenzamide), tellurohydrazide (Eg, N, N ′, N′-trimethyltellurobenzhydrazide), telluroester (eg, t-butyl-t-hexyltelluroester), phosphine tellurides (eg, tributylphosphine telluride, tricyclohexylphosphine telluride, triisopropyl) Phosphine telluride, butyl-diisopropylphosphine telluride, dibutylphenylphosphine telluride) and other tellurium compounds (for example, the negatively charged tellurium described in GB 1,295,462). Doion containing gelatin, Potassium nitrosium telluride, Potassium nitrosium tellurocyanate diisocyanate, tellurocarbonyl penta isethionate, sodium salt, allyl tellurocyanate)
And the like.

The amount of the tellurium sensitizer used in the present invention varies depending on the silver halide grains used, the conditions of chemical ripening, and the like, but is generally 10 ^-8 per mol of silver halide.
It is used in an amount of about 10 ⁻² mol, preferably about 10 ^{−7 to} 5 × 10 ⁻³ mol.

The conditions for chemical sensitization in the present invention include:
Although there is no particular limitation, the pAg is 6 to 11, preferably 7 to 10, and the temperature is 40 to 95 ° C, preferably 45 to 85 ° C.

In the present invention, it is preferable to use a noble metal sensitizer such as gold, platinum, palladium or iridium in combination. In particular, it is preferable to also perform gold sensitization agent include chloroauric acid, potassium chloroaurate, potassium aurithiocyanate, gold sulfide, gold selenide, and the like, per mol of silver halide, 10 ^{- About 7} to 10 ^-2 mol can be used.

In the present invention, it is preferable to further use a sulfur sensitizer in combination. Specific examples thereof include known unstable sulfur compounds such as thiosulfates (eg, hypo), thioureas (eg, diphenylthiourea, triethylurea, allylthiourea), rhodanines and the like. About 10 ^-7 to 10 ^-2 mol per mol can be used.

The emulsion layer of the silver halide photographic light-sensitive material of the present invention may contain ordinary silver halide grains in addition to the tabular silver halide grains. In this case, the silver halide may be any of silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide and silver chloride. They are,
P. Glafkides Chimie et Physique Photographique (
Paul Montel 1967), GFDuffin Photo
graphic Emulsion Chemistry (The Focal Press 19
66), Making and Coating P by VLZelikman et al
hotographic Emulsion (The Focal Press 1964
Year)). That is, any of an acidic method, a neutral method, an ammonium method and the like may be used, and a method of reacting a soluble silver salt and a soluble halide may be any of a one-side mixing method, a double-mixing method, a combination thereof and the like. . Method of forming grains in excess of silver ions (so-called reverse mixing method)
Can also be used. As one type of the double jet method, a method in which pAg in a liquid phase in which silver halide is formed is kept constant, that is, a so-called controlled double jet method can be used. The swelling ratio of the light-sensitive material of the present invention is preferably 150% or more. The light-sensitive material of the present invention may have an emulsion layer on one surface or an emulsion on both surfaces, but a light-sensitive material having an emulsion layer on both surfaces (especially an X-ray light-sensitive material) is preferred. In that case: It is preferable that the amount of silver applied to both sides is 3.5 g or less per 1 m ² .

In the present invention, it is also preferable to carry out chemical sensitization in the presence of a nucleic acid or a decomposition product thereof before completion of chemical sensitization. Regarding nucleic acids or their degradation products,
No. 67541 can be used. The nucleic acid used in the present invention includes deoxyribonucleic acid (DN)
A) and ribonucleic acid (RNA), and examples of the nucleic acid degradation products include those undergoing degradation and simple substances such as adenine, guanine, uracil, cytosine, and thymine.
In particular, adenine is a preferred nucleolytic product. These can be used alone or in combination. In this case, it goes without saying that the nucleic acid and the nucleic acid degradation product may be used in combination. The amount of the nucleic acid or the decomposition product thereof varies depending on the type of the nucleic acid decomposition product, but is in the range of 20 mg or more, preferably 100 mg to 1 g per mol of silver halide. As described above, when these nucleic acids or nucleic acid degradation products are used alone or in combination of two or more, the total amount of additions described above is sufficient.

The silver halide photographic light-sensitive material of the present invention preferably contains a polymer latex, colloidal silica, and a polyhydric alcohol. These compounds,
Regarding the amount and method of use, refer to Japanese Patent Application No. 8-9688.
No. 3 can be used.

In the silver halide photographic light-sensitive material of the present invention, the hydrophilic colloid layer may contain a water-soluble dye as a filter dye or for various purposes such as prevention of irradiation. With respect to examples of the compound of the water-soluble dye, its use amount, and its use method, those described in Japanese Patent Application No. 8-96883 can be used.

In the present invention, the hydrophilic colloid layer other than the photosensitive silver halide emulsion layer and the surface protective layer may contain a non-elutable solid fine particle dispersion dye as a position detection dye. With respect to examples of the compounds of the dyes, their amounts and methods of use, those described in Japanese Patent Application No. 8-96883 can be used.

There are no particular restrictions on other various additives used in the light-sensitive material of the present invention.
Japanese Patent No. 68539 can be used. Item Applicable section 1. 1. From the lower right column, page 8, lower line 6 of JP-A-2-68539, from the line of its preparation From the same line, page 10, upper right column, line 12, 2. Chemical sensitization method, page 10, line 13 from the upper right column to line 16 from the lower left column. Antifoggant / Stable From page 10, lower left column, line 17 to page 11, upper left column 7, agent line and from page 3, lower left column, line 2 to page 4, lower left column. 4. Spectral sensitizing dyes, page 4, lower right column, line 4 to page 8, lower right column. 5. Surfactant / Electrostatic Protection Line 11 on page 11, upper left column to line 9, Stopper on page 12, upper left column. 6. Matting agent, slip agent, page 12, top left column, line 10 to top right column, line 10. Plasticizer Same as page 14, lower left column, line 10 to lower right column, line 1. 7. Hydrophilic colloid, page 12, line 11, upper right column to line 16, lower left column. 8. Hardener From page 12, lower left column, line 17 to page 13, upper right column, line 6; 9. Supporting substance: From page 7, line 7 to line 20 in the upper right column. 10. Dyes and mordants From page 13, lower left column, line 1 to page 14, lower left column, line 9.

The silver halide photographic light-sensitive material of the present invention is not particularly limited, but is preferably used for the following light-sensitive materials. Color negative photosensitive material for general photography, black-and-white negative photosensitive material for general photography, color paper photosensitive material for printing, black-and-white paper photosensitive material for printing, X-ray photosensitive material for medical direct shooting,
It can be preferably used for medical indirect X-ray sensitive materials, photographic materials for laser light sources, photosensitive materials for printing, microfilms and the like.

A preferred method for processing the light-sensitive material of the present invention is described below. In the development processing of the light-sensitive material of the present invention, processing with a developing solution containing ascorbic acid or a derivative thereof is preferable.

The replenishment rate of the developer is 0.1 ml or more and 10 ml / 4.
It is preferably not more than 0, more preferably 0.
It is 1 ml or more and 5 ml / 4 or less, and in this case, the effect of the present invention is greatly exhibited. Ascorbic acid or a derivative thereof used in the developer of the present invention includes a compound represented by formula (I) of JP-A-5-165161 and examples of compounds I-1 to I-8 and II- described therein. 9 to II-12 are particularly preferred. The ascorbic acids used in the developer used in the present invention include an endiol type (Endiol), an enaminol type (Enaminol), an endamine type (Endiamin), a thiol-enol type (Thiol-Enol) and an enamine-thiol type (Enamin-Thiol). ) Is generally known as a compound. Examples of these compounds are described in U.S. Pat. No. 2,688,5.
49 and JP-A-62-237443. Methods for synthesizing these ascorbic acids are also well known, and are described, for example, in Tsuguo Nomura and Hirohisa Omura, "Reducton Chemistry" (Uchida Lao Tsuruhoshinsha 1969). The ascorbic acids used in the present invention can be used in the form of an alkali metal salt such as a lithium salt, a sodium salt and a potassium salt. These ascorbic acids are used in an amount of 1 to 100 g, preferably 5 to 80 g per liter of the developer.
It is preferable to use g.

In the present invention, it is particularly preferable to use 1-phenyl-3-pyrazolidones or p-aminophenols together with ascorbic acids. 3 used in the present invention
1-phenyl-3 as a pyrazolidone-based developing agent
-Pyrazolidone, 1-phenyl-4,4-dimethyl-3
-Pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, 1-phenyl-4,
4-dihydroxymethyl-3-pyrazolidone, 1-phenyl-5-methyl-3-pyrazolidone, 1-p-aminophenyl-4,4-dimethyl-3-pyrazolidone, 1-
p-tolyl-4,4-dimethyl-3-pyrazolidone, 1
-P-tolyl-4-methyl-4-hydroxymethyl-3
-Pyrazolidone and the like. Examples of the p-aminophenol-based developing agent used in the present invention include N-methyl-p-aminophenol, p-aminophenol, N- (β-hydroxyethyl) -p-aminophenol, and N- (4-hydroxyphenyl). There are glycine, 2-methyl-p-aminophenol, p-benzylaminophenol and the like, among which N-methyl-p-aminophenol is preferable. The amount of the 3-pyrazolidone or p-aminophenol developing agent is usually 0.001 mol / l to 1.2.
It is preferably used in an amount of mol / liter.

The alkaline agents used for setting the pH include sodium hydroxide, potassium hydroxide, sodium carbonate,
It contains pH adjusters such as potassium carbonate, tribasic sodium phosphate and tribasic potassium phosphate. Examples of the sulfite preservative used in the developer of the present invention include sodium sulfite, potassium sulfite, lithium sulfite, ammonium sulfite, sodium bisulfite, and potassium metabisulfite. The sulfite is preferably at least 0.01 mol / l, particularly preferably at least 0.02 mol / l. The upper limit is preferably up to 2.5 mol / l. In addition, LFA Mason, "Photographic Processing Chemistry", Focal Press (1966), 22
6 to 229, U.S. Pat. Nos. 2,193,015 and 2,592,364 and JP-A-48-64933 may be used.

In general, a boric acid compound (for example, boric acid or borax) is often used as a pH buffer or the like in a developer, but a boric acid compound is contained in an ascorbic acid-containing developer of the present invention. Is preferably not substantially contained.
If the ascorbic acid-containing developer contains a boric acid compound, the effects of the present invention cannot be obtained even when combined with the packaging material having a low oxygen permeability of the present invention. The relationship between the presence or absence of the boric acid compound and the effect in the system of the present invention was completely unexpected.

The preparation of the treating agent used in the present invention is described in JP-A-61-177132 and JP-A-3-134666.
And JP-A-3-67258. As a method of replenishing the developer as a processing method of the present invention, a method described in JP-A-5-216180 can be used. When developing processing for 100 seconds or less by dry to dry, in order to prevent development unevenness peculiar to rapid processing, a rubber roller as described in JP-A-63-151943 is provided at the outlet of the developing tank. It is applicable to a roller, or the discharge flow rate for stirring a developer in a developer tank is set to 10 m / min or more as described in JP-A-63-151944. As described in the specification of JP-A-63-264758, it is more preferable to perform stronger stirring at least during development processing than during standby.

Hereinafter, preferred embodiments for processing the light-sensitive material of the present invention will be described. 1. A processing method in which the developer is a one-part concentrated developer. 2. A processing method, wherein a total processing time (Dry to Dry) is 20 seconds to 100 seconds. 3. A processing method, wherein the heating means of the roller portion in contact with the photosensitive material in a stage preceding the drying section of the automatic developing apparatus is at 70 ° C. or higher.

4. A processing method, wherein the automatic developing apparatus has a mechanism in which a developer and a fixing solution cartridge are simultaneously used when a chemical mixer is incorporated in the automatic developing apparatus. 5. The opening ratio of the developing tank of the automatic developing processor is 0.04
A processing method characterized by being not more than cm ⁻¹ . 6. A processing method characterized in that a developing concentrated solution and a fixing concentrated solution are composed of one part, and each concentrated solution and water are diluted into a working solution in each tank and supplied as a replenisher (just before mixing dilution method). 7. A processing method, wherein the containers for the developing concentrated solution and the fixing concentrated solution are integrated packaging materials. 8. A processing method using an automatic developing machine provided with a rinsing tank and a rinsing roller (crossover roller) between the developing tank and the fixing tank and between the fixing tank and the washing tank.

9. A processing method characterized by using an automatic developing machine provided with a stock tank of water for supplying various water rust preventive agents (antibacterial agents) to a washing tank and a rinsing tank. 10. A processing method characterized by using an automatic developing machine in which a solenoid valve is installed at a drain of a washing tank. 11. A developer, wherein 70 mol% or more of all cations in the developer are potassium ions. 12. A developer, wherein the developer is a powder. 13. A processing method characterized in that the developing solution and the fixing solution are of a working solution type. 14. A processing method, wherein the washing tank of the automatic development processing apparatus has a multi-chamber tank and a multi-stage countercurrent washing method.

[0147]

Hereinafter, the present invention will be described with reference to Examples.
The present invention is not limited to these. Example 1 "Preparation of {100} high silver chloride tabular emulsion A" 1582 ml of an aqueous gelatin solution (19.5 g of gelatin-1 (deionized alkali-treated bone gelatin having a methionine content of about 40 μmol / g) and HNO ₃ Containing 7.8 ml of 1N solution, p
H4.3), NaCl-1 solution (NaCl in 100 ml)
13 ml of 10 g) was added, and while maintaining the temperature at 40 ° C., 62.4 ml of the Ag-1 solution (containing 20 g of AgNO _{3 in} 100 ml) and the X-1 solution (containing 7.05 g of NaCl in 100 ml) were added. 15.6 ml at the same time. After stirring for 3 minutes, Ag-2 solution (A in 100 ml)
gNO ₃ containing 2 g) and X-2 solution (KBr in 100 ml)
1.4g) at 20.6ml / min at 80.6ml / min. After stirring for 3 minutes, Ag-1 solution and X-1
The solution was simultaneously mixed and added in 46.8 ml at 62.4 ml / min. After stirring for 2 minutes, 203 ml of an aqueous gelatin solution (113 g of gelatin, 1.3 g of NaCl, including a 1N solution of NaOH to adjust the pH to 6.0) was added, and pCl was added to 1.
After adjusting the temperature to 8, the temperature was raised to 75 ° C., and the pCl was adjusted to 1.8, followed by aging for 42 minutes. AgCl fine grain emulsion (average grain diameter 0.1 μm) was converted to 2.68 × 10 ^-2 mol / min Ag
It was added at a Cl addition rate for 20 minutes. After aging for 10 minutes after the addition, a precipitant was added, the temperature was lowered to 35 ° C., and the precipitate was washed by settling. An aqueous gelatin solution was added, and the pH was adjusted to 6.0 at 60 ° C. A transmission electron micrograph image (hereinafter referred to as TEM) of a replica of the particles was observed. The resulting emulsion was silver chlorobromide {100} tabular grains containing 0.44 mol% of AgBr based on silver. The shape characteristic values of the particles were as follows. (Total projected area of tabular grains having an aspect ratio of 2 or more / total A)
gX grain projected area sum) × 100 = a ₁ = 90% (average aspect ratio of tabular grains (average diameter / average thickness)) = a ₂ = 9.3 Here, the average aspect ratio means a total tabular shape. It is the average of the aspect ratio of the particles. (Average diameter of tabular grains) = a ₃ = 1.67 μm (average thickness) = a ₄ = 0.18 μm

"{100} AgBrCl Tabular emulsion B
1560 ml of aqueous gelatin solution (gelatin-
1 (methionine content of about 40 μmol / g of deionized
Lucari-treated bone gelatin) 19.5 g, H_TwoSO_Four1N liquid
7.8 ml, pH 4.3), NaCl-1 solution (1
13 ml of NaCl (containing 10 g of NaCl in 00 ml)
While maintaining the temperature at 40 ° C, Ag-1 solution (A in 100 ml)
gNO_Three20 g) and X-1 solution (Na in 100 ml).
(Including 3.44 g of Cl and 7 g of KBr).
Simultaneous addition of 31.2 ml was added at a rate of ml / min. P at this time
Ag was 7.13. After stirring for 3 minutes, Ag-2
Liquid (AgNO in 100 ml_Three2g) and liquid X-2
(Containing 9.84 g of KBr in 100 ml).
56.4 ml was mixed simultaneously at 14 ml / min. P at this time
Ag was 9.22. After stirring for 3 minutes, Ag-1
135.2 ml of the solution was added over 1 minute and 5 seconds, and simultaneously X-
93.6 ml of one solution was added, and the addition was completed in 45 seconds. this
The pAg at that time was 6.81. After stirring for 2 minutes,
224 ml of ratine aqueous solution (13 g of oxidized gelatin, pH
(Including 1N NaOH solution) to adjust pH to 5.5).
Then, the temperature was raised to 75 ° C., and pCl was set to 1.8.
After aging for 10 minutes. Then, the disulfide compound-A
Of 1 × 10 per mol of silver halide ^{ー 4}Mole was added.
Ag-3 solution (AgNO in 100 ml)_ThreeTo 21.0
X-3 solution (containing 4 g of NaCl in 100 ml).
34 g, KBr 7.36 g and average molecular weight 15,000
(Including 5.1 g of low molecular weight gelatin)
Mixer placed next to the reaction vessel at the same time in 866 ml / min
To make a fine particle emulsion,
An emulsion was added. The average size of the particles at this time is
It was 0.03 μm. After aging for 10 minutes after addition,
A precipitant was added, the temperature was lowered to 35 ° C., and the precipitate was washed by settling. Zera
An aqueous solution of tin was added, and the pH was adjusted to 6.0 at 60 ° C.

[0149]

Embedded image

The replica of the particles was observed by a transmission electron microscope (hereinafter referred to as TEM). The resulting emulsion is
Silver chlorobromide {100} tabular grains containing 51.5 mol% of AgBr based on silver. The shape characteristic values of the particles were as follows. a ₁ = 94%, a ₂ = 9.3, a ₃ = 1.67 μm, a
₄ = 0.18 μm

"Preparation of {111} Silver Chloride Tabular Emulsion C" Silver chloride tabular grains were prepared as follows.

[0152]

Embedded image

[0153]

To the solution (1) maintained at 35 ° C., the solution (2) and the solution (3) were simultaneously added over 1 minute with stirring.
The temperature of the solution was raised to 50 ° C. over 15 minutes. At this point, grains corresponding to about 5.7% of the total silver were formed. Next, the solution (4) and the solution (5) were simultaneously added over 24 minutes, and further, the solution (6) and the solution (7) were simultaneously added over 40 minutes to obtain a silver chloride tabular emulsion. Gelatin 30g and H ₂ was washed with water and desalted by precipitation the emulsion
O, 2.0 g of phenoxyethanol and 0.8 g of sodium polystyrene sulfonate as a thickener.
Was added thereto, and the mixture was redispersed with sodium hydroxide to pH 6.0. The emulsion thus obtained has a ₁ = 90% and a ₃ =
This is a silver chloride tabular emulsion having a {111} plane as a main plane, having a main surface of 1.55 μm, a ₄ = 0.18 μm, a ₂ = 8.6, and a coefficient of variation of a circle-equivalent projected area diameter of 19%.

[Preparation of {111} AgBr Tabular Particles D] 6.0 g of potassium bromide and 7.0 g of low-molecular-weight gelatin having an average molecular weight of 15,000 were added to 1 liter of water.
37cc of silver nitrate aqueous solution while stirring into a container maintained at ℃
38 cc of an aqueous solution containing (4.00 g of silver nitrate) and 5.9 g of potassium bromide was added over 37 seconds by the double jet method. Next, 18.6 g of gelatin was added and the temperature was raised to 70 ° C., and 89 cc of an aqueous silver nitrate solution (9.80 g of silver nitrate) was added to 22 g of the aqueous solution.
It was added over a minute. Here, 7 cc of a 25% aqueous ammonia solution was added, the mixture was physically aged at the same temperature for 10 minutes, and then 6.5 cc of a 100% acetic acid solution was added. Subsequently, an aqueous solution of 153 g of silver nitrate and an aqueous solution of potassium bromide were added to pAg
Controlled double jet method while keeping at 8.5
Added over 5 minutes. Next, 15 cc of a 2N potassium thiocyanate solution was added. After physical ripening at the same temperature for 5 minutes, the temperature was lowered to 35 ° C. a ₁ = 95%, a _{2
= 8.1, a 3 = 1.50μm,} a 4 = 0.185μ
Monodispersed pure silver bromide tabular grains having a m and a variation coefficient of diameter of 18.5% were obtained. Thereafter, soluble salts were removed by a sedimentation method. The temperature was raised again to 40 ° C., and 30 g of gelatin, 2.35 g of phenoxyethanol and 0.8 g of sodium polystyrenesulfonate as a thickener were added, and the mixture was adjusted to pH 5.90 and pAg 8.00 with sodium hydroxide and silver nitrate solution.

"Preparation of {111} silver chlorobromide tabular grains E" In the preparation of AgBr tabular grains D, pAg8.
When growing by the control double jet method while keeping at 5, the potassium bromide solution was used as a mixed solution of potassium bromide and potassium chloride, and the particle shape such as the aspect ratio and the particle size became almost the same as the tabular particles D. Thus, a silver chlorobromide tabular emulsion E having a {111} plane as a main plane having a silver chloride content of 24% was prepared. Other conditions were the same as those for producing tabular grains D.

[Preparation of Cubic Monodispersed Silver Chlorobromide Particles F] 32 g of gelatin was dissolved in 1 liter of water, and 0.3 g of potassium bromide and 5 g of sodium chloride were placed in a vessel heated to 53 ° C.
And compound [I]

[0158]

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After adding 46 mg, 444 ml of an aqueous solution containing 80 g of silver nitrate and 452 ml of an aqueous solution containing 45 g of potassium bromide and 5.5 g of sodium chloride are added over about 20 minutes by the double jet method, and then containing 80 g of silver nitrate. 400 ml of an aqueous solution and 415 ml of an aqueous solution containing 46.4 g of potassium bromide, 5.7 g of sodium chloride and potassium hexachloroiridate (III) (10 ^-7 mol / mol silver)
Is added by a double jet method over about 25 minutes to obtain a cubic monodispersed silver chlorobromide particle having an average grain size (projected area diameter) of 0.34 μm (coefficient of variation of projected area diameter of 10).
%).

The emulsion was desalted by a coagulation method, and 62 g of gelatin and 1.75 g of phenoxyethanol were added.
Adjusted to pH 6.5 and pAg 8.5.

"Chemical sensitization" Next, while stirring the emulsions A to F,
Optimum chemical sensitization was performed while maintaining the temperature at 56 ° C. Ma
Thiosulfonate compound-1 in 1 mole of silver halide
6 × 10 per^-5Mole equivalents, then average sphere phase etc.
AgBr fine particles having a diameter of 0.05 μm were converted into 1 mole of silver halide.
Aging for about 5 minutes
0.2 mol% per mol of silver halide
Of a 1% KI aqueous solution was added. After another 3 minutes,
1 x 10 urea^-6Mol / mol Ag and add for 22 minutes
It was kept as it was and subjected to reduction sensitization. Next, 4-hydroxy
C-6-methyl-1,3,3a, 7-tetraazaindene
1.5 x 10 per mole of silver halide^{ー 4}Mole equivalent
And the dispersion of sensitizing dye SD-1 was added to sensitizing dye SD-
1 × 1 × 10 5 per mole of silver halide ^{ー 3},
Sensitizing dye SD-2 was added at 1.2 × / mol of silver halide.
10^-FiveMoles of sensitizing dye SD-3 in 1 mole of silver halide.
2.4 × 10 per le^-FourMolar equivalents were added simultaneously. Pull
Continue to add sodium thiosulfate per mole of silver halide
5 × 10^-6Molar equivalent of selenium compound-1 with silver halide
1 × 10 per mole^-6After adding mole equivalent, chloroauric acid is added.
2.7 × 10 per mole of silver halide^-6Mole equivalent
And potassium thiocyanate per mole of silver halide
1.8 × 10^-3Mole equivalents were added. In addition, nucleic acids (Sanyo
Pulp Co., Ltd .: trade name RNA-F)
67 mg / l. Then add chloroauric acid
20 minutes after the addition, the sodium sulfite is replaced with silver halide.
3.2 × 10 per mole^-FourAddition of moles and further aging
80 minutes after the addition of the chloroauric acid, the water-soluble mercap
Compound 1 was added and cooled to 35 ° C. Thus the emulsion
Adjustment (chemical ripening) was completed.

[0162]

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<Preparation of Dispersion of Sensitizing Dye SD-1> Water 5
For 0 ml, 1 g of the sensitizing dye SD-1 was added at pH 7.0 ±.
0.5, 50-65 ° C, 20
The particles were mechanically dispersed in solid fine particles of 1 μm or less at 00 to 2500 rpm, 50 g of 10% gelatin was added, and the mixture was cooled after mixing.

Further, instead of the dispersion of the sensitizing dye SD-1, emulsions having sensitizing dyes as shown in Tables 1 and 2 were prepared. The amount of the sensitizing dye added was such that the number of moles per mole of silver halide was the same as that of the sensitizing dye SD-1. A sensitizing dye was prepared by adding a dye microcrystal dispersion in the same manner as described above.

[0165]

[Table 1]

[0166]

[Table 2]

"Preparation of Coated Sample" (Preparation of Emulsion Coated Layer) The following chemicals were added to the chemically sensitized emulsion per mole of silver halide to prepare an emulsion coating solution. -Gelatin (including gelatin in the emulsion) 111 g-Dextran (average molecular weight 39,000) 21.5 g-Trimethylolpropane 9.0 g-Sodium polyacrylate (average molecular weight 400,000) 5.1 g-Sodium polystyrene sulfonate ( Average molecular weight 600,000) 1.2 g Hardener 1,2-bis (vinylsulfonylacetamido) ethane Addition amount is adjusted so that the swelling ratio becomes 170%. Compound-I 42.1 mg Compound-II 10.3 g Compound-III 0.11 g Compound-IV 8.5 mg Compound-V 0.43 g Compound-VI 4 mg Compound-VII 57.4 mg Compound-VIII 20 mg Compound-IX 30 mg Polymer latex Lx-1 0.4 g Colloidal silica particles Diameter 0.014μm 0.5g adjusted to pH 6.1 with NaOH

[0168]

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[0169]

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Dye emulsion A was added to the above coating solution so that Dye-I was 10 mg / m ² per one side.

[0171]

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(Preparation of Dye Emulsion A)
0g and 62.8 g of the following high boiling point organic solvent-I, -II
Was dissolved at 60 ° C. in 62.8 g and ethyl acetate 333 g. Next, 65 cc of a 5% aqueous solution of sodium dodecyl sulfonate, 94 g of gelatin and 581 cc of water were added, and the mixture was emulsified and dispersed at 60 ° C. for 30 minutes with a dissolver. Then p-
2 g of methyl hydroxybenzoate and 6 liters of water were added, and the temperature was lowered to 40 ° C. Next, using an ultrafiltration laboratory module ACP1050 manufactured by Asahi Kasei, the mixture was concentrated until the total amount became 2 kg, and 1 g of methyl p-hydroxybenzoate was added to obtain a dye emulsion A.

[0173]

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(Preparation of Coating Solution for Surface Protective Layer) A coating solution for surface protective layer was prepared such that each component had the following coating amount. Gelatin 0.780 g / m ² · Sodium polyacrylate (average molecular weight 400,000) 0.035 g / m ² · Sodium polystyrenesulfonate (average molecular weight 600,000) 0.0012 g / m ² · methacrylate: methyl methacrylate: styrene = 7: a copolymer of 76:17 (average particle size 4.0μm) 0.074g / m ² · coating aids -I 0.014g / m ² · coating aids -II 0.036g / m ² · coating aids -III 0.0069 g / M ² · Coating aid-IV 0.0032 g / m ² · Coating aid -V 0.0012 g / m ² · Compound-X 0.0008 g / m ² · 4-hydroxy-6-methyl-1,3,3a, 7 -Tetraazaindene 0.0057 g / m ² · Compound-XI 0.0007 g / m ² · Proxel 0.0010 g / m ² (adjusted to pH 6.8 with NaOH)

[0175]

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(Preparation of Dye Intermediate Layer Coating Solution for Infrared Position Detection) Gelatin 0.50 g / m ² · Benzoisothiazolone 1.4 mg / m ² · Sodium polyacrylate (average molecular weight 41,000) 17 mg / m ^2. Dispersion of infrared dye compound-I (as dye solid content) 20 mg / m ²

[0177]

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(Preparation of Support) (1) Preparation of Dye Dispersion B for Undercoat Layer The following Dye-II was ball-milled by the method described in JP-A-63-197943.

[0179]

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434 ml of water and Triton X200
(Registered trademark) surfactant (TX-200 (registered trademark))
791 ml of a 6.7% aqueous solution was placed in a 2 liter ball mill. 20 g of the dye were added to this solution. 400 ml (2 mm diameter) beads of zirconium oxide (ZrO ₂ ) were added, and the contents were ground for 4 days. Thereafter, 160 g of 12.5% gelatin was added. After defoaming, the ZrO ₂ beads were removed by filtration. Observation of the obtained dye dispersion showed that the particle size of the crushed dye was 0.05 to
It has a wide field up to 1.15 μm, with an average particle size of 0.37 μm. Furthermore, dye particles having a size of 0.9 μm or more were removed by centrifugation. Thus, a dye dispersion B was obtained.

(2) Preparation of Support A corona discharge was carried out on a biaxially stretched polyethylene terephthalate film having a thickness of 175 μm, and the coating amount of the first undercoating liquid having the following composition was 4.9 cc / m ^2. And dried at 185 ° C. for 1 minute. Next, a first undercoat layer was similarly provided on the opposite surface. The polyethylene terephthalate used contained the following dye.・ Dye-III 0.04 wt% ・ Dye-IV 0.02 wt% ・ Dye-V 0.02 wt%

[0182]

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First undercoating liquid • Butadiene-styrene copolymer latex solution (solid content 40% butadiene / styrene weight ratio = 31/69) 158 cc • 2,4-dichloro-6-hydroxy-s-triazine sodium salt 4 % Solution 41 cc ・ Distilled water 801 cc * The following compound is contained in the latex solution as an emulsifying dispersant at 0.4 wt% based on the solid content of the latex.

[0184]

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(3) Coating of undercoat layer A second undercoat layer having the following composition was coated on the first undercoat layer on both sides of the above both sides, one side at a time, so that the coating amount was as described below. To the wire bar coder method,
Dried at 155 ° C.・ Gelatin 80 mg / m ²・ Dye dispersion B (as a dye solid content) 8 mg / m ²・ Coating aid-VI 1.8 mg / m ²・ Proxel 0.27 mg / m ²・ Mat agent Average particle size 2.5 μm 2.5 mg / m ^{2 of} polymethyl methacrylate

[0186]

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(Preparation of photographic material) On the support prepared as described above, a coating solution for the emulsion layer, surface protective layer and dye intermediate layer for infrared position detection was coated on both sides by a simultaneous extrusion method. The dye interlayer for infrared position detection was located between the emulsion layer and the support. The amount of silver applied on one side is 1.50 g / m ^2.
And Thus, coating samples 1 to 42 were prepared.

(Evaluation of photographic performance) The photographic material was brought into close contact with both sides using an X-ray AD system screen HGM manufactured by FUJIFILM Corporation, exposed for 0.05 seconds from both sides, and exposed to X-rays. Sensitometry was performed. The adjustment of the exposure amount was performed by changing the distance between the X-ray tube and the cassette. After the exposure, the film was subjected to automatic developing machine processing using the following developing solution and fixing solution.

(Processing) Automatic developing machine: CEPROS manufactured by FUJIFILM Corporation
Dry to Dry 30 seconds using -30. Preparation of Concentrate <Developer> Parts A potassium hydroxide 330 g potassium sulfite 630 g sodium sulfite 255 g potassium carbonate 90 g boric acid 45 g diethylene glycol 180 g diethylenetriaminepentaacetic acid 30 g 1- (N, N-diethylamine) ethyl -5-mercaptotetrazole 0.75 g hydroquinone 450 g 4-hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone 60 g Add water 4125 ml

Parts agent B Diethylene glycol 525 g 3,3'-dithiobishydrocinnamic acid 3 g Glacial acetic acid 102.6 g 2-nitroindazole 3.75 g 1-phenyl-3-pyrazolidone 34.5 g Water was added to add 750 ml.

Parts agent C Glutaraldehyde (50 wt / wt%) 150 g Potassium bromide 15 g Potassium metabisulfite 105 g Add water 750 ml

<Fixing solution> Ammonium thiosulfate (70 wt / vol%) 3000 ml Ethylenediaminetetraacetic acid / disodium / dihydrate 0.45 g Sodium sulfite 225 g Boric acid 60 g 1- (N, N-diethylamine) -ethyl-5 -Mercaptotetrazole 15 g Tartaric acid 48 g Glacial acetic acid 675 g Sodium hydroxide 225 g Sulfuric acid (36N) 58.5 g Aluminum sulfate 150 g Add water 6000 ml pH 4.68

(Preparation of Processing Solution) The above-mentioned developer concentration solution was filled into the following containers for each part. In this container, the respective partial containers of the parts agents A, B, and C are connected together by the container itself. The above-mentioned fixer concentration was also filled in the same type of container. First, as a starter in the developing tank,
Aqueous solution 30 containing 54 g of acetic acid and 55.5 g of potassium bromide
0 ml was added. Insert the processing agent container upside down and insert it into the perforation blade of the processing liquid stock tank mounted on the side of the automatic processing machine, break the sealing film of the cap, and transfer each processing agent in the container to the stock tank. Filled. These processing agents were filled in the developing tank and the fixing tank of the automatic processing machine at the following ratios by operating the pumps respectively installed in the automatic processing apparatus. Also,
Each time the photosensitive material was processed, the processing solution stock solution and water were mixed at this ratio and replenished to the processing tank of the automatic processing machine.

Developing solution Part solution A 51 ml Part solution B 10 ml Part solution C 10 ml Water 125 ml pH 10.50 Fixing solution Concentrate 80 ml Water 120 ml pH 4.62 The washing tank was filled with tap water.

Further, as an anti-scale agent, 0.4 g of actinobacteria supported on perlite having an average particle diameter of 100 μm and an average pore diameter of 3 μm was covered with a polyethylene bottle (the bottle opening was covered with a 300-mesh nylon cloth. 3 pieces of water and bacteria can be distributed from the cloth), two of them are placed at the bottom of the washing tank and one is placed at the bottom of the washing tank (0.2 liter). Each sunk.

(Evaluation of Fixing Ability) Using the above-mentioned processing solution and an automatic processing machine, photographic materials 1 to 42 were processed in 4-cut sizes without exposure. Whether the film was fixed or not was evaluated by visually observing the processed film.

(Evaluation of residual color)
It was cut to 5 cm × 25.4 cm, treated with washing water at 5 ° C., and the degree of residual color of the photographic material was visually evaluated according to the following criteria. A: Almost no residual color. ：: Slight residual color but not bothersome. Δ: Remains color but practically acceptable. ×: Many residual colors are not possible. The results are shown in Table 3.

[0198]

[Table 3]

[0199]

[Table 4]

The sensitivity is represented by the reciprocal of the exposure amount that gives a density of Fog + 1.0. As shown in Tables 3 and 4, only the emulsion of the present invention had sensitivity,
It can be seen that the fixing property and the residual color are simultaneously excellent.

Example 2 The photographic light-sensitive material prepared in Example 1 was processed with the following developing solution. (Preparation of Concentrated Developing Solution) Concentrated developing solution A having the following formulation and using sodium erythorbate as a developing agent was prepared. Diethylenetriaminepentaacetic acid 8.0 g Sodium sulfite 20.0 g Sodium carbonate monohydrate 52.0 g Potassium carbonate 55.0 g Sodium erythorbate 60.0 g 4-hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone 13.2 g 3,3'-diphenyl -3,3'-dithiopropionic acid 1.44 g Diethylene glycol 50.0 g Development accelerator-1 1.0 g Development accelerator-21.0 g Adjust the pH to 10.4 with sodium hydroxide.

[0202]

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(Adjustment of developer replenisher)
It was diluted twice and used as a developing replenisher.

(Preparation of developing mother liquor) 2 liters of the above concentrated developing solution was diluted with water to 4 liters, and a starter solution having the following composition was added at 60 ml per liter of the diluted developing solution.
The developing solution of 9.5 was used as a developing mother liquor. Starter solution Potassium bromide 11.7 g Acetic acid (90%) 12.0 g Add water to make 60 ml

(Preparation of concentrated fixing solution) A concentrated fixing solution having the following formulation was prepared. Water 0.5 l Ethylenediaminetetraacetic acid dihydrate 0.05 g sodium thiosulfate 290.0 g sodium bisulfite 98.0 g sodium hydroxide 2.9 g Adjust the pH to 5.2 with NaOH, and add water to make 1 liter.

(Adjustment of Fixing Replenisher)
It was diluted twice and used as a fixing replenisher.

(Preparation of fixing mother liquor) 2 L of the above concentrated fixing solution was diluted with water to make 4 L. pH was 5.4.

(Processing of photographic material) Fuji Photo Film Co., Ltd. in which the photographic material was improved to a drive system and an aperture ratio of 0.02.
An automatic developing machine of SEPROS 30 manufactured by the company was modified, and processing was carried out using the above-mentioned developing mother liquor and fixing mother liquor while replenishing the developing replenisher and the fixing replenisher with 80 ml per m ² of the light-sensitive material. Process temperature Processing time Insertion -2 seconds Current image 35 ° C 8 seconds Fixed 35 ° C 8 seconds Rinse 18 ° C 5 seconds Squeeze 2 seconds Dry 55 ° C 5 seconds Total (Dry to Dry) 30 seconds Light-sensitive material of the present invention And that the processing solution exhibited excellent photographic performance.

Example 3 <Emulsion Layer Coating Solution> Each of the chemically sensitized emulsions prepared in Example 1 was added with the following chemicals per mole of silver halide to prepare a coating solution. 72.0 mg of 2,6-bis (hydroxyamino) -4-diethylamino-1,3,5-triazine 3.9 g of dextran (average molecular weight 39,000) Potassium polystyrene sulfonate (average molecular weight 600,000) 0 0.7 g Compound-I 7.0 mg Sodium hydroquinone monosulfonate 8.2 g Snowtex C (Nissan Chemical Co., Ltd.) 10.5 g Ethyl acrylate / methacrylic acid (97/3) copolymer latex 7 g. Gelatin The amount of the emulsion layer coated was adjusted to 2.6 g / m ² . Hardener (1,2-bis (vinylsulfonylacetamido) ethane) The swelling ratio was adjusted to 230%.

<Preparation of Coating Solution for Surface Protective Layer> Coating solution b-1 was prepared so that each component had the following coating amount.・ Gelatin 650 mg / m ²・ Sodium polyacrylate (average molecular weight: 400,000) 18 mg / m ²・ Butyl acrylate / methacrylic acid (4/6) copolymer latex (average molecular weight: 120,000) 120 mg / m ² coating aids -I 18 mg / m ² · coating aids -II 45 mg / m ² · coating aids -IV 0.9 mg / m ² and coating aids -V 0.61 mg / m ² and coating aids -VII 26 mg / m ² · Compound-X 1.3 mg / m ² · Polymethyl methacrylate (average particle size 2.5 µm) 87 mg / m ² · Proxel 0.5 mg / m ² · Polystyrene sulfonate (average molecular weight 600,000) 0.9 mg / m ² (adjusted to pH 7.4 with NaOH)

[0211]

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(Preparation of Coating Solution for Back Surface) <Antihalation Layer> (1) Preparation of Dye Dispersion L A solution prepared by dissolving 2.5 g of each of Dye-I and high-boiling organic solvents-I and II in 50 cc of ethyl acetate was used. 90 g of an 8% aqueous gelatin solution containing 1.5 g of sodium dodecylbenzenesulfonate and 0.18 g of methyl p-hydroxybenzoate was added.
The mixture was mixed at 0 ° C. and stirred at a high speed with a homogenizer. After completion of the high-speed stirring, the mixture was subjected to a reduced pressure treatment at 60 ° C. using an evaporator to remove 92 wt% of ethyl acetate. As a result, a dye dispersion L having an average particle size of 0.18 μm was obtained. (2) Adjustment of coating liquid The coating liquid was adjusted so that each component had the following coating amount. Gelatin 2.0 g / m ² · phosphoric acid 5.2 mg / m ² · Snowtex C (Nissan Chemical (Co.)) 0.5 g / m ² · ethyl acrylate / methacrylic acid (97/3) copolymer latex 0.5 g / m ² .Proxel 4.2 mg / m ² .Dye Dispersion L 8.0 g / m ² .Dye-VI 75 mg / m ² .Dye -VII 50 mg / m ² .Dye -VIII 50 mg / m ² · Hardener 1,2-bis (vinylsulfonylacetamido) ethane 40 mg / m ²

[0213]

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<Surface Protective Layer> A coating solution was prepared so that each component had the following coating amount.・ Gelatin 1000 mg / m ²・ Polymethyl methacrylate (average particle size 3.5 μm) 20 mg / m ² (average particle size 0.75 μm) 81 mg / m ²・ Coating aid-I 20 mg / m ²・ Coating Auxiliary agent-II 40 mg / m ² · Coating auxiliary agent-IV 6 mg / m ² · Coating auxiliary agent-V 9 mg / m ² · Coating auxiliary agent-VIII 1.7 mg / m ² · Coating auxiliary agent-IX 13 mg / m ² · Proxel 1.3 mg / m ² · Potassium polystyrene sulfonate (average molecular weight 600,000) 2 mg / m ² · NaOH 2.5 mg / m ²

[0215]

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(Adjustment of support) Biaxially stretched thickness 18
A corona discharge is performed on a 3 μm polyethylene terephthalate film, and a first undercoating liquid having the following composition is applied by a wire bar coater so as to have a coating amount of 5.1 cc / m ^2, and dried at 175 ° C. for 1 minute. did. Next, a first undercoat layer was similarly provided on the opposite surface. The polyethylene terephthalate used contained Dye-III at 0.04 wt%. • Butadiene-styrene copolymer latex solution (solid content 40% butadiene / styrene weight ratio = 31/35) 79 cc • 2,4-dichloro-6-hydroxy-s-triazine sodium salt 4% aqueous solution 20.5 cc • Distillation Water 900.5 cc * The following emulsifying dispersant was used in the latex solution at 0.4 wt% based on the solid content of the latex.

(Preparation of Photographic Material) After the back surface antihalation layer and the surface protective layer were coated on the support prepared as described above, the emulsion layer and the surface protective layer were coated on the opposite sides by simultaneous extrusion. Applied. The amount of silver coated on the emulsion surface was 2.7 g / m ² .

(Evaluation of photographic performance) The photographic material was emitted on a CRT (light-emitting body P-45) for a medical multi-camera with a concentration gradient and exposed for 1 second from the emulsion surface side. As a result, it was confirmed that the photographic material of the present invention and the processing solution exhibited excellent photographic performance.

Example 4 The X-ray film S manufactured by Fuji Photo Film Co., Ltd. was combined with the emulsions of Example 1 and further combined with emulsions each having an appropriate grain size by adjusting the grain size of each emulsion.
Same sensitivity as HRA30, UR-1, UR-2, UR-3 /
Photosensitive materials having the same gradation were prepared by the same coating method as in Example 1. Further, when the photographic light-sensitive material was evaluated in the same manner as in Example 1, it was found that the photographic light-sensitive material of the present invention was excellent in sharpness improvement by reduction of crossover light, granularity, processing stability, and the like. I understand. When the crossover light was evaluated by the method described in JP-A-1-172828, the crossover light of the photographic light-sensitive material of the present invention was 9% or less.

[0220]

The light-sensitive material of the present invention has high sensitivity and excellent rapid processing suitability, and is suitable for low replenishment and low waste liquid processing in an automatic developing machine.

────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] October 30, 1996

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] Claim 1

[Correction method] Change

[Correction contents]

Embedded image In the formula (I), R _a and R _b each represent a hydrogen atom, an aliphatic group, an aryl group, or a heterocyclic group. Where _Ra
And R _b are not hydrogen atoms at the same time. L _a and L _b each represent a methylene group. k ₁ is an integer of 0 to 5, k ₂ is an integer of 0-5. L ₁ and L ₂ each represent a methine group. p ₁ represents 0 or 1. Z ₁ represents an atom group necessary for forming a 5- or 6-membered nitrogen-containing heterocyclic ring. M ₁ represents a charge balancing counter ion, and m ₁ represents an integer of 0 or more necessary to neutralize the charge of the molecule. Q represents an atomic group necessary for forming a methine dye.

[Procedure amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0008

[Correction method] Change

[Correction contents]

[0008]

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[Procedure amendment 3]

[Document name to be amended] Statement

[Correction target item name] 0048

[Correction method] Change

[Correction contents]

[0048]

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──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification number Agency reference number FI Technical indication location G03C 1/06 502 G03C 1/06 502 1/09 1/09 1/18 1/18 1/26 1/26 5/30 5/30

Claims (11)

[Claims] 1. A silver halide photographic material having at least one silver halide emulsion layer on a support,
The silver halide emulsion has a silver chloride content of at least 20 mol%
At least 50% of the total projected area of the emulsion is not more than 00 mol%, and tabular silver halide grains having an aspect ratio of 2 or more are occupied by the emulsion layer. Silver halide photographic material comprising at least one compound represented by the formula: Embedded image In the formula (I), R _a and R _b each represent a hydrogen atom, an aliphatic group, an aryl group, or a heterocyclic group. Where _Ra
And R _b are not hydrogen atoms at the same time. L _a and L _b each represent a methylene group. k ₁ is an integer of 0 to 5, k ₂ is an integer of 0-5. L ₁ and L ₂ each represent a methine group. p ₁ represents 0 or 1. Z ₁ represents an atom group necessary for forming a 5- or 6-membered nitrogen-containing heterocyclic ring. M ₁ represents a charge balancing counter ion, and m ₁ represents an integer of 0 or more necessary to neutralize the charge of the molecule. Q represents an atomic group necessary for forming a methine dye. 2. The compound represented by the general formula (I) according to claim 1.
Is a compound represented by the following general formula (II), general formula (III), or
Characterized by being a compound represented by the general formula (IV)
The silver halide photographic light-sensitive material according to claim 1. Embedded imageIn the formula (II), L_Three , L_Four , L_Five , L₆ , L₇ , L₈ as well as
L₉ Each represents a methine group. p_Two , And p_Three Is it
Represents 0 or 1, respectively. n₁ Represents 0, 1, 2, or 3
You. Z_Two And Z_Three Is a 5- or 6-membered nitrogen-containing heterocyclic ring, respectively.
Represents an atomic group necessary to form M_Two Is the charge balance
Represents a counter ion, m_Two Is required to neutralize the molecular charge
Represents an integer of 0 or more. R₁ And R_Two Is each archi
Represents a hydroxyl group. Where R₁ And R_Two At least one of
Is an alkyl group represented by the following Rz. Embedded imageIn Rz, R_a, R_b, L_a, L_b, K₁And k_TwoIs
It has the same meaning as in formula (I). Embedded imageIn the formula (III), L_Ten, L₁₁, L₁₂, And L₁₃Are each
Represents a methine group. p_FourRepresents 0 or 1. n_Two Is 0,
Represents 1, 2 or 3. Z_Four And Z_Five Is 5 or 6 respectively
Lists the atoms required to form a 10-membered nitrogen-containing heterocycle.
You. M_Three Represents a charge-balancing counter ion, m_Three Is the molecular charge
Represents an integer of 0 or more necessary to neutralize R_Four Is al
Represents a kill group, an aryl group, or a heterocyclic group. R_Three Is before
And an alkyl group represented by Rz. Embedded imageIn the formula (IV), L₁₄, L_Fifteen, L₁₆, L₁₇, L₁₈, L₁₉, L
₂₀, L_{twenty one}And L_{twenty two}Each represents a methine group. p_Five ,
And p₆ Represents 0 or 1, respectively. n_Three And n _Four Is it
Represents 0, 1, 2, or 3, respectively. Z₆ , Z₇ And Z₈ Is
Necessary to form a 5- or 6-membered nitrogen-containing heterocycle, respectively.
Represents key atoms. M_Four Represents a charge-balancing counter ion, m
_Four Represents an integer of 0 or more necessary to neutralize the molecular charge.
You. R_FiveAnd R₇ Each represents an alkyl group. R₆ Is
Represents an alkyl group, an aryl group or a heterocyclic group. However,
R_Five And R₇ At least one of them is represented by the aforementioned Rz.
Is an alkyl group. 3. The silver halide photographic light-sensitive material according to claim 1, wherein the compound represented by formula (I) is the compound represented by formula (II) according to claim 2. 4. The method according to claim 1, wherein R _a is an aryl group or a heterocyclic group, and R _b is a hydrogen atom.
4. The silver halide photographic light-sensitive material according to any one of items 3. 5. A silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support,
The silver halide emulsion has a silver chloride content of at least 20 mol%
In the emulsion layer, at least 50% of the total projected area of the emulsion is occupied by tabular silver halide grains having an aspect ratio of 2 or more. The emulsion layer is represented by the following general formula (V). Silver halide photographic material comprising at least one compound represented by the formula: Embedded image In the formula (V), R ₈ and R ₉ represent an alkyl group. Z ₉ ,
Z ₁₀ represents a group of non-metallic atoms necessary for forming an aromatic ring. Q ₁ represents an alkyl group having 3 or more carbon atoms. X
Represents an ion necessary for balancing electric charges. m
₅ is 0 or 1 and 0 when an internal salt is formed. 6. The method according to claim 1, wherein said tabular silver halide grain emulsion is # 10.
The silver halide photographic material according to any one of claims 1 to 5, wherein the photographic material is a tabular grain having a main plane of 0 ° plane. 7. The emulsion according to claim 1, wherein the compounds of the formulas (I) to (V) are added to the emulsion before the addition of the chemical sensitizer. Silver halide photographic material. 8. The silver halide photographic material according to claim 1, wherein said tabular silver halide grain emulsion is chemically sensitized with a selenium compound. 9. tabular silver halide surface of grain emulsions Br ^-, I ^-, SCN - claimed in any one of claims 1-8, characterized in that it is conversion by at least one Silver halide photographic material. 10. The surface of the tabular silver halide grain emulsion is converted by I ⁻ and Br ⁻ ,
The silver halide photographic light-sensitive material according to any one of claims 1 to 9, wherein the total silver iodide content of the grains in that case is 0.6 mol% or less of the total silver amount. 11. The processing of a silver halide photographic light-sensitive material, characterized in that the silver halide photographic light-sensitive material according to claim 1 is processed with a developer containing ascorbic acid or a derivative thereof. Method.