JPH0545773A - Silver halide photographic emulsion - Google Patents

Abstract

PURPOSE:To obtain the silver halide photographic sensitive material high in sensitivity and small in drop of sensitivity during storage by incorporating a specified mechine compound having a polycyclic aromatic compound. CONSTITUTION:The silver halide photographic sensitive material contains at least one of the mechine compounds represented by formula I in which MNET is an atomic group having the mechine compound structure; Q is a divalent bonding group comprising at least one of C, N, S, and 0 atoms or atomic groups of them; Ar is an >=8 atoms aromatic polycyclic group: k1 is an integer of Si1: k2 is or 1; and k3 is an integer of >=5. It IS preferred for the mechine compound to have an oxidation-reduction potential of 0.60V vs SCE or baser than this.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a silver halide emulsion containing a novel methine compound. More specifically, it relates to a silver halide emulsion having improved sensitivity fluctuation due to natural storage.

[0002]

2. Description of the Related Art Conventionally, in the production of a silver halide light-sensitive material, a technique of adding a sensitizing dye to a silver halide emulsion to expand the light-sensitive wavelength range of the silver halide emulsion and optically sensitizing it is well known. Has been. A large number of compounds have been conventionally known as spectral sensitizing dyes used for such a purpose. For example, “The Theory of the Photographic.”, Edited by TJ James (TH James).
Process "(The Theory of the PhotographicProces
s) (3rd edition), 1966, Macmillan
, N, Y, pages 198 to 228, cyanine dyes, merocyanine dyes, xanthene dyes and the like. When these sensitizing dyes are usually applied to silver halide emulsions, they must not only expand the photosensitive wavelength range of the silver halide emulsion, but also satisfy the following conditions. (1) The spectral sensitization range is appropriate. (2) The sensitization efficiency is good and a sufficiently high sensitivity can be obtained. (3) Fog should not occur. (4) Variation in sensitivity due to temperature change during exposure is small. (5) No adverse interaction with other additives such as stabilizers, antifoggants, coating aids, color formers, etc. (6) The sensitivity should not change when the silver halide emulsion containing the sensitizing dye is stored. In particular, the sensitivity should not fluctuate when stored under high temperature and high humidity. (7) The added sensitizing dye should not diffuse into other photosensitive layers and cause color turbidity (color mixing) after development processing. The above-mentioned various conditions have important meanings when preparing a silver halide emulsion in a silver halide photographic light-sensitive material. However, in spite of various attempts, the reduction in sensitivity during raw sample storage has not been prevented to a sufficiently satisfactory level.

[0003]

SUMMARY OF THE INVENTION The object of the present invention is to have a high feeling and to prevent fog from increasing during storage under high temperature and / or high humidity, and to have little change in sensitivity (that is, excellent raw storage stability). To provide a silver halide photographic light-sensitive material.

[0004]

The above objects of the present invention have been achieved by a silver halide emulsion characterized by containing at least one compound represented by formula (I). General formula (I)

[0005]

[Chemical 2]

In the formula (I), MET represents an atom group having a methine compound structure, and Q represents a divalent atom or an atomic group containing at least one of a carbon atom, a nitrogen atom, a sulfur atom and an oxygen atom. Represents a linking group, and Ar represents a group having aromaticity and having a polycyclic compound composed of 8 or more atoms. k ₁ represents an integer of 1 or more, and k ₂
Represents 0 or 1, k ₃ represents an integer of 5 or more, or
Or k ₁ represents an integer of 3 or more, and k ₂ represents 0 or 1
And k ₃ represents 1, 2, 3, or 4. More preferably, the methine dye represented by the general formula (I) has an oxidation potential of 0.60 (VvsSCE) or less, and more preferably 0.45 (VvsS).
CE) or less base. Further, as a preferable structure, MET has a hexamethine merocyanine structure or a heptamethine cyanine structure.

The present invention will be described in more detail below.

In the general formula (I), the group represented by MET is a nitrogen-containing heterocycle usually called a basic nucleus and another group.
Cyanine structure that is formed by conjugating two nitrogen-containing heterocycles by conjugated double bonds so that they can be conjugated to each other, or in the heterocycle and basic nucleus called acidic nucleus, carbonyl group and base in acidic nucleus Merocyanine structure formed by coupling with a conjugated double bond so that the nitrogen atom in the sex nucleus can be conjugated with each other, or a rhodacyanine structure having these structures, an oxonol structure, a hemicyanine structure,
It represents a styryl structure, a benzylidene structure, or the like. Examples of these polymethine dyes include, for example, “The Theory of the Photographic Process” 1977 edited by TH James.
, Macmillan, Chapter 8, DMSturmer "The Chemis
try of Heterocyclic Compounds "ed.A. Weissberger and
ECTaylor, 1977, John Wiley and Sons (New
(York) etc.

Q represents a divalent linking group consisting of an atom or an atomic group containing at least one of a carbon atom, a nitrogen atom, a sulfur atom and an oxygen atom. Preferably, an alkylene group (for example, a methylene group, an ethylene group, a propylene group,
Butylene group, pentylene group), arylene group (for example,
Phenylene group, naphthylene group), alkenylene group (for example, ethenylene group, propenylene group), sulfonyl group,
Sulfinyl group, thioether group, ether group, carbonyl group, -N (R ¹ )-(R ¹ represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group), divalent heterocycle A group (eg 6-chloro-1,
3,5-triazine-2,4-diyl group, pyrimidine-
2,4-diyl group, quinoxaline-2,3-diyl group)
Represents a divalent linking group having 20 or less carbon atoms, which is formed by combining one or more of k ₁ represents an integer of 1 or more, k ₂ represents 0 or 1, and k ₃ represents an integer of 5 or more. k ₁ is preferably 1 or 2, and k ₃ is preferably 5 or 6. more preferably a k ₁ and more preferably 5 as 1, k _3. Alternatively, k ₁ represents an integer of 3 or more, k ₂ represents 0 or 1, and k ₃ represents 1, 2, 3 or 4. Preferably, k ₁ is 1, and k ₃ is preferably 1. Next, Ar will be described. The definition of aromaticity is "Iwanami Physics and Chemistry Dictionary 3rd Edition, Supplement," edited by Tamamushi Bunichi, published by Iwanami Shoten (198).
1 year publication) P-1258, 1259. A
Specific examples of the polycyclic compound represented by r are shown below.

[0010]

[Chemical 3]

[0011]

[Chemical 4]

[0012]

[Chemical 5]

[0013]

[Chemical 6]

[0014]

[Chemical 7]

[0015]

[Chemical 8]

The substituent of these polycyclic compounds Ar is preferably a hydrogen atom, a substituted or unsubstituted alkyl group (eg, methyl, ethyl, propyl, butyl, hydroxyethyl, trifluoromethyl, benzyl, sulfopropyl, Diethylaminoethyl, cyanopropyl, adamantyl, p-chlorophenethyl, ethoxyethyl, ethylthioethyl, phenoxyethyl, carbamoylethyl, carboxyethyl, ethoxycarbonylmethyl, acetylaminoethyl), unsubstituted or substituted alkenyl groups (eg allyl, styryl). ), An unsubstituted or substituted aryl group (eg, phenyl, naphthyl, p-carboxyphenyl, 3,5-dicarboxyphenyl, m-sulfophenyl, p-acetamidophenyl, 3-caprylamidophenyl, p Sulfamoylphenyl, m-hydroxyphenyl, p-nitrophenyl, 3,5-dichlorophenyl, p-anisyl, o-anisyl, p-cyanophenyl, p-N-methylureidophenyl, m-fluorophenyl, p-tolyl. , M-tolyl), optionally substituted heterocycle residue (eg pyridyl, 5-methyl-2)
-Pyridyl, thienyl), halogen atoms (eg chlorine,
(Bromine, fluorine), mercapto group, cyano group, carboxyl group, sulfo group, hydroxy group, carbamoyl group, sulfamoyl group, amino group, nitro group, optionally substituted alkoxy group (eg, methoxy, ethoxy, 2-methoxyethoxy) , 2-phenylethoxy), optionally substituted aryloxy group (eg, phenoxy, p-methylphenoxy, p-chlorophenoxy), acyl group (eg, acetyl, benzoyl), acylamino group (eg, acetylamino, caproylamino). , Sulfonyl groups (eg methanesulfonyl, benzenesulfonyl), sulfonylamino groups (eg methanesulfonylamino, benzenesulfonylamino), substituted amino groups (eg diethylamino, hydroxyamino), alkyl or arylthio groups (eg In methylthio, carboxyethylthio, sulfo butyl thio, phenylthio), an alkoxycarbonyl group (e.g., methoxycarbonyl), an aryloxycarbonyl group (e.g. phenoxycarbonyl)
And these substituents further include a divalent linking group Q.
Alternatively, it may be bonded to MET by a single bond. Further, on these substituents, further alkyl group, alkenyl group, aryl group, hydroxy group, carboxyl group, sulfo group, nitro group, cyano group, halogen atom, alkoxy group, aryloxy group, alkoxycarbonyl group, acyl group, It may be substituted with an acylamino group, a sulfoneamino group, a carbamoyl group, a sulfamoyl group, or the like.
In addition, at least one of these substitutions may be bonded to MET through a divalent linking group Q or a single bond. Ar
Is at least one substituent or a single bond (Q) _k1 −
It is associated with (MET) _k2 . Preferred is the case where they are bound via Q.

The oxidation potential was measured by phase discrimination type second harmonic alternating current polarography. The details are described below. Acetonitrile (spectral grade) dried in 4A-1 / 16 molecular sieves was used as a solvent, and normal tetrapropylammonium perchlorate (a special reagent for polarograph) was used as a supporting electrolyte. The sample solution was prepared by dissolving the red-sensitive sensitizing dye in acetonitrile containing 0.1 M of supporting electrolyte in a concentration of 10 ^-3 to 10 ^-5 mol / liter. It was deoxygenated for 15 minutes or more with ultra-high purity argon gas (99.999%). The working electrode was a rotating platinum electrode, the reference electrode was a saturated calomel electrode (SCE), and the counter electrode was platinum. The reference electrode and the sample solution were connected by a Luggin tube filled with acetonitrile containing 0.1 M supporting electrolyte, and Vycor glass was used for the liquid junction. When the tip of the Lugin tube and the tip of the rotating platinum electrode are 5 mm to 8 mm apart, 2
It was measured at 5 ° C. In addition, the measurement of the oxidation potential by the phase discrimination type oni harmonic AC voltammetry described above is performed in the “Journal of Imaging Science” (Journal of Imaging Science).
Imaging Science), Volume 30, pp. 27-35 (198
6 years).

The hexamethine merocyanine structure preferably used as the MET in the present invention is represented by the general formula (II), and the heptamethine cyanine structure is represented by the general formula (III). General formula (II)

[0019]

[Chemical 9]

General formula (III)

[0021]

[Chemical 10]

Wherein Z ₁ , Z ₂ and Z ₃ are 5 or 6
Represents the atomic group necessary to form a nitrogen-containing heterocycle of the member.
D and D'represent an atomic group necessary for forming an acyclic or cyclic acidic nucleus. R ₁ , R ₂ and R ₃ represent an alkyl group. L ₁ , L ₂ , L 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 and L ₂₁ represent a methine group or a substituted methine group. Further, it may form a ring with another methine group, or may form a ring with an auxiliary chromophore. n ₁ , n ₂ , n ₃ and n ₄ represent 0 or 1. M ₁ and M ₂ represent charge neutralizing counterions, and m ₁
And m ₂ are 0 necessary for neutralizing the charge in the molecule.
The above is the number.

M represented by the general formulas (II) and (III)
ET is substituted with at least 5 or 1 Ar each via a divalent linking group Q or via a single bond. The general formulas (II) and (III) will be described in more detail below. R ₁ , R ₂ , R ₃ and R ₄ are preferably unsubstituted alkyl groups having 18 or less carbon atoms (eg methyl, ethyl, propyl, butyl, pentyl, octyl, decyl, dodecyl, octadecyl) or substituted alkyl groups. {As a substituent, for example, a carboxy group, a sulfo group, a cyano group, a halogen atom (eg, fluorine, chlorine, bromine), a hydroxy group, an alkoxycarbonyl group having 8 or less carbon atoms (eg, methoxycarbonyl, ethoxycarbonyl, 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), 3 carbon atoms. The following acyloxy groups (eg acetyloxy) , Propionyloxy), no more than 8 acyl group carbons (e.g., acetyl,
Propionyl, benzoyl, mesyl), carbamoyl groups (eg carbamoyl, N, N-dimethylcarbamoyl, morpholinocarbonyl, piperidinocarbonyl),
A sulfamoyl group (eg, sulfamoyl, N, N-dimethylsulfamoyl, morpholinosulfonyl, piperidinosulfonyl), an aryl group having 10 or less carbon atoms (eg, phenyl, 4-chlorophenyl, 4-methylphenyl, α-naphthyl) And a substituted alkyl group having 18 or less carbon atoms}. Preferably, an unsubstituted alkyl group (eg, methyl group, ethyl group, n-propyl group, n-
Butyl group, n-pentyl group, n-hexyl group), carboxyalkyl group (for example, 2-carboxyethyl group, carboxymethyl group), sulfoalkyl group (for example, 2-sulfoethyl group, 3-sulfopropyl group, 4-sulfobutyl group) Group, 3-sulfobutyl group). (M ₁ ) _m1 and (M ₂ ) _m2 are included in the formula to indicate the presence or absence of a cation or anion when required to neutralize the ionic charge of the dye. There is. Whether a dye is a cation, an anion, or has a net ionic charge depends on its auxochrome and substituents. Typical cations are inorganic or organic ammonium and alkali metal ions, while the anions can be either inorganic or organic anions, for example halogen anions (e.g. fluoride ions, (Chlorine ion, bromine ion, iodine ion), substituted aryl sulfonate ion (for example, p-toluene sulfonate ion, p-chlorobenzene sulfonate ion), aryl disulfonate ion (for example, 1,3-benzenedisulfonate ion, 1, 5-naphthalene disulfonate ion, 2,6-naphthalene disulfonate ion), alkyl sulfate ion (for example, methyl sulfate ion), sulfate ion, thiocyanate ion, perchlorate ion, tetrafluoroborate ion, picrate ion,
Examples thereof include acetate ion and trifluoromethanesulfonate ion.

Preferred are ammonium ion, iodine ion and p-toluenesulfonate ion. Z ₁ ,
The nucleus formed by Z ₂ and Z ₃ includes a thiazole nucleus (thiazole nucleus (eg, thiazole, 4-methylthiazole, 4-phenylthiazole, 4,5-dimethylthiazole, 4,5-diphenylthiazole), benzothiazole nucleus) (For example, benzothiazole, 4-chlorobenzothiazole, 5-chlorobenzothiazole, 6-chlorobenzothiazole, 5-nitrobenzothiazole,
4-methylbenzothiazole, 5-methylthiobenzothiazole, 5-methylbenzothiazole, 6-methylbenzothiazole, 6-methylthiobenzothiazole, 5
-Bromobenzothiazole, 6-bromobenzothiazole, 5-iodobenzothiazole, 5-phenylbenzothiazole, 5-methoxybenzothiazole, 6-methoxybenzothiazole, 5-ethoxybenzothiazole, 5-ethoxycarbonylbenzothiazole, 5- Carboxybenzothiazole, 5-phenethylbenzothiazole, 5-fluorobenzothiazole, 5-chloro-
6-methylbenzothiazole, 5,6-dimethylbenzothiazole, 5,6-dimethoxybenzothiazole,
5,6-dimethylthiobenzothiazole, 5-hydroxy-6-methylbenzothiazole, tetrahydrobenzothiazole, 4-phenylbenzothiazole), naphthothiazole nucleus (for example, naphtho [2,1-d] thiazole, naphtho [1, 2-d] thiazole, naphtho [2,3]
-D] thiazole, 5-methoxynaphtho [1,2-d]
Thiazole, 7-ethoxynaphtho [2,1-d] thiazole, 8-methoxynaphtho [2,1-d] thiazole,
5-methoxynaphtho [2,3-d] thiazole)}, thiazoline nucleus (eg, thiazoline, 4-methylthiazoline, 4-nitrothiazoline), oxazole nucleus {oxazole nucleus (eg, oxazole, 4-methyloxazole, 4- Nitroxazole, 5-methyloxazole, 4-phenyloxazole, 4,5-diphenyloxazole, 4-ethyloxazole), benzoxazole nucleus (for example, benzoxazole, 5-chlorobenzoxazole, 5-methylbenzoxazole, 5
-Bromobenzoxazole, 5-fluorobenzoxazole, 5-phenylbenzoxazole, 5-methoxybenzoxazole, 5-nitrobenzoxazole, 5-trifluoromethylbenzoxazole, 5-
Hydroxybenzoxazole, 5-carboxybenzoxazole, 6-methylbenzoxazole, 6-chlorobenzoxazole, 6-nitrobenzoxazole, 6-methoxybenzoxazole, 6-hydroxybenzoxazole, 5,6-dimethylbenzoxazole, 4, 6-dimethylbenzothiazole, 5-ethoxybenzoxazole), naphthoxazole nucleus (for example, naphtho [2,1-d] oxazole, naphtho [1,
2-d] oxazole, naphtho [2,3-d] oxazole, 5-nitronaphtho [2,1-d] oxazole)}, oxazoline nucleus (eg, 4,4-dimethyloxazoline), selenazole nucleus {eg selenazole nucleus (eg, selenazole nucleus , 4-methylselenazole, 4-nitroselenazole, 4-phenylselenazole), benzoselenazole nucleus (for example, benzoselenazole, 5-chlorobenzoselenazole, 5-nitrobenzoselenazole, 5-methoxybenzoselena) Zole, 5-hydroxybenzoselenazole, 6-nitrobenzoselenazole, 5-chloro-
6-nitrobenzoselenazole, 5,6-dimethylbenzoselenazole), naphthoselenazole nucleus (for example, naphtho [2,1-d] selenazole, naphtho [1,2-
d] selenazole)}, selenazoline nucleus (eg, selenazoline, 4-methylselenazoline), tellurazole nucleus {terrazole nucleus (eg, tellurazole, 4-methylterrazole, 4-phenylterrazole), benzoterrazole nucleus (eg, Benzoterrazole, 5-chlorobenzoterrazole, 5-methylbenzoterrazole, 5,6-dimethylbenzotelrazole, 6-methoxybenzoterrazole), naphthoterrazole nucleus (for example, naphtho [2,1-d]) Tellurazole, naphtho [1,
2-d] terrazole)}, a tellrazoline nucleus (for example,
Tellrazoline, 4-methylterrazoline), 3,3-dialkylindolenine nucleus (eg, 3,3-dimethylindolenine, 3,3-diethylindolenine, 3,3-
Dimethyl-5-cyanoindolenine, 3,3-dimethyl-6-nitroindolenine, 3,3-dityl-5-nitroindolenine, 3,3-dimethyl-5-methoxyindolenine, 3,3,5- Trimethyl indolenine, 3,
3-dimethyl-5-chloroindolenine), imidazole nucleus {indazole nucleus (e.g., 1-alkylimidazole, 1-alkyl-4-phenylimidazole, 1-
Aryl imidazole), benzimidazole nuclei (for example, 1-alkylbenzimidazole, 1-alkyl-
5-chlorobenzimidazole, 1-alkyl-5,6
-Dichlorohenzoimidazole, 1-alkyl-5-methoxybenzimidazole, 1-alkyl-5-cyanobenzimidazole, 1-alkyl-5-fluorobenzimidazole, 1-alkyl-5-trifluoromethylbenzimidazole, 1-alkyl -6-chloro-5
-Cyanobenzimidazole, 1-alkyl-6-chloro-5-trifluoromethylbenzimidazole, 1-
Allyl-5,6-dichlorobenzimidazole, 1-allyl-5-chlorobenzimidazole, 1-arylbenzimidazole, 1-aryl-5-chlorobenzimidazole, 1-aryl-5,6-dichlorobenzimidazole, 1- Aryl-5-methoxybenzimidazole, 1-aryl-5-cyanobenzimidazole), naphthoimidazole nucleus (for example, -alkylnaphtho [1,2-d] imidazole, 1-arylnaphtho [1,2-d] imidazole) The above-mentioned alkyl groups are those having 1 to 8 carbon atoms, for example, unsubstituted alkyl groups such as methyl, ethyl, propyl, isopropyl and butyl, and hydroxyalkyl groups (eg 2-hydroxyethyl, 3-hydroxypropyl). preferable. Particularly preferred are methyl group and ethyl group. The above aryl group is
Represents phenyl, halogen (eg chloro) substituted phenyl, alkyl (eg methyl) substituted phenyl, alkoxy (eg methoxy) substituted phenyl. }, A pyridine nucleus (eg, 2-pyridine, 4-pyridine, 5-methyl-
2-pyridine, 3-methyl-4-pyridine), quinoline nucleus {quinoline nucleus (eg, 2-quinoline, 3-methyl-
2-quinoline, 5-ethyl-2-quinoline, 6-methyl-2-quinoline, 6-nitro-2-quinoline, 8-fluoro-2-quinoline, 6-methoxy-2-quinoline, 6
-Hydroxy-2-quinoline, 8-chloro-2-quinoline, 4-quinoline, 6-ethoxy-4-quinoline, 6-
Nitro-4-quinoline, 8-chloro-4-quinoline, 8
-Fluoro-4-quinoline, 8-methyl-4-quinoline, 8-methoxy-4-quinoline, 6-methyl-4-quinoline, 6-methoxy-4-quinoline, 6-chloro-4
-Quinoline), isoquinoline nuclei (eg 6-nitro-
1-isoquinoline, 3,4-dihydro-1-isoquinoline, 6-nitro-3-isoquinoline)}, imidazo [4,5-b] quinoxaline nucleus (for example, 1,3-diethylimidazo [4,5-b]) Quinoxaline, 6-chloro-1,3-diallylimidazo [4,5-b] quinoxaline), oxadiazole nucleus, thiadiazole nucleus, tetrazole nucleus and pyrimidine nucleus.

The nucleus formed by Z ₁ , Z ₂ and Z ₃ is preferably a benzothiazole nucleus, a naphthothiazole nucleus, a benzoxazole nucleus, a naphthoxazole nucleus, a benzimidazole nucleus, a 2-quinoline nucleus or a 4-quinoline nucleus. is there. Z ₅ represents an atomic group necessary for forming a 5- or 6-membered ring. This ring may be further substituted. As the substituent, a substituted or unsubstituted alkyl group (for example, methyl, ethyl, propyl, chloroethyl,
Benzyl), substituted or unsubstituted aryl groups (eg phenyl, p-chlorophenyl), halogen atoms (eg chlorine atom, fluorine atom), hydroxy groups, alkoxy groups (eg methoxy, ethoxy) and other monovalent and divalent A substituent is mentioned. L _{1 to} L ₁₄ are a methine group or a substituted methine group (eg, a substituted or unsubstituted alkyl group (eg, methyl group, ethyl group, 2-carboxyethyl group), a substituted or unsubstituted aryl group (eg,
Phenyl group, o-carboxyphenyl group), heterocyclic group (eg barbituric acid), halogen atom (eg chlorine atom, bromine atom), alkoxy group (eg methoxy group, ethoxy group), amino group (eg N, N) -Diphenylamino group, N-methyl-N-phenylamino group, N-
Those substituted with a methylpiperazino group), an alkylthio group (for example, a methylthio group, an ethylthio group), etc.}
And may form a ring with another methine group,
Alternatively, a ring can be formed with the auxiliary chromophore. An unsubstituted methine group is preferred.

D and D'represent the atomic groups necessary to form the acidic nucleus, but can take the form of the acidic nucleus of any common merocyanine dye. D in preferred form
Is a thiocarbonyl group or a carbonyl group, and D'represents the remaining atomic groups necessary for forming an acidic nucleus.
D and D'may together form a 5- or 6-membered heterocycle consisting of carbon, nitrogen and chalcogen (typically oxygen, sulfur, selenium and tellurium) atoms. Preferably, the next nucleus is completed. 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-thiooxazolidine-2 ，
4-dione, isoxazolin-5-one, 2-thiazolin-4-one, thiazolidin-4-one, thiazolidine-2,4-dione, rhodamine, thiazolidine-2,
4-dithione, isorhodanine, indan-1,3-dione, thiophen-3-one, thiophen-3-one-
1,1-dioxide, indoline-2-one, indoline-3-one, indazoline-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, indazoline-
2-one, or pyrido [1,2-a] pyrimidine-
1,3-dione nucleus. More preferably, 3-alkyl rhodamine, 3-alkyl-2-thiooxazolidine-
They are 2,4-dione and 3-alkyl-2-thiohydantoin. The substituent bonded to the nitrogen atom contained in the nucleus is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, preferably 1 to 7 carbon atoms, particularly preferably 1 to 4 carbon atoms (for example, methyl, ethyl, propyl, isopropyl, butyl). , Isobutyl, hexyl, octyl, dodecyl, octadecyl), substituted alkyl groups (eg aralkyl groups (eg benzyl, 2-
Phenylethyl), hydroxyalkyl groups (eg 2
-Hydroxyethyl, 3-hydroxypropyl), carboxyalkyl group (eg, 2-carboxyethyl, 3
-Carboxypropyl, 4-carboxybutyl, carboxymethyl), an alkoxyalkyl group (for example, 2-methoxyethyl, 2- (2-methoxyethoxy) ethyl), a sulfoalkyl group (for example, 2-sulfoethyl,
3-sulfopropyl, 3-sulfobutyl, 4-sulfobutyl, 2- [3-sulfopropoxy] ethyl, 2-hydroxy-3-sulfopropyl, 3-sulfopropoxyethoxyethyl), sulfatoalkyl group (for example, 3-
Sulfatopropyl, 4-sulfatobutyl), heterocyclic-substituted alkyl groups (eg 2- (pyrrolidin-2-one-
1-yl) ethyl, tetrahydrofurfuryl, 2-morpholinoethyl), 2-acetoxyethyl, carbomethoxymethyl, 2-methanesulfonylaminoethyl}, allyl group, aryl group (for example, phenyl, 2-naphthyl),
A substituted aryl group (eg, 4-carboxyphenyl, 4
-Sulfophenyl, 3-chlorophenyl, 3-methylphenyl) and a heterocyclic group (for example, 2-pyridyl, 2-thiazolyl) are preferable. More preferably, an unsubstituted alkyl group (for example, methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl), a carboxyalkyl group (for example, carboxymethyl, 2-carboxyethyl, sulfoalkyl group ( For example, 2-sulfoethyl).

L ₁ , L ₂ , L 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 and L ₂₁ are methine groups or substituted methine groups (eg, substituted or unsubstituted alkyl groups (eg, methyl group, ethyl group, 2-carboxyethyl group)) A substituted or unsubstituted aryl group (eg, phenyl group, o-carboxyphenyl group), heterocyclic group (eg, barbituric acid), halogen atom (eg, chlorine atom, bromine atom), alkoxy group (eg, methoxy group, Ethoxy group), amino group (for example, N, N-diphenylamino group, N-methyl-N-phenylamino group, N-
Those substituted with a methylpiperazino group), an alkylthio group (for example, a methylthio group, an ethylthio group), etc.}
And may form a ring with another methine group,
Alternatively, a ring can be formed with the auxiliary chromophore. L ₂ and L
It is preferable that one of ₄ , L ₃ and L ₅ forms a ring with each other. Also, L ₁₂ and L ₁₄ , L ₁₃ and L ₁₅ , L
It is preferable that one of ₁₄ and L ₁₆ forms a ring with each other. Particularly preferred ring structures for L ₂ and L ₄ , L ₁₂ and L ₁₄ , and L ₁₄ and L ₁₆ are shown below.

[0028]

[Chemical 11]

Particularly preferred ring structures for L ₃ and L ₅ and L ₁₃ and L ₁₅ are shown below.

[0030]

[Chemical formula 12]

[0031]

[Chemical 13]

That is, when L ₃ and L ₅ and L ₁₃ and L ₁₅ form a ring structure, L ₄ and L ₁₄ are preferably an unsubstituted methine group, an unsubstituted alkyl group (eg methyl), an alkoxy group. Groups (eg methoxy), amino groups (eg N, N-diphenylamino), methine groups substituted with halogen atoms (eg chlorine) or methine substituted with an acidic nucleus as represented by D and D ′ above. It is a base. The other L is preferably an unsubstituted methine group.

Further, in the general formulas (II) and (III), at least five or _one- (Q) _l2- Ar is substituted, and the substitution position is, for example, the general formula (II) or (III) a 5- or 6-membered nitrogen-containing heterocycle represented by Z ₁ , Z ₂ and Z ₃ , an acidic nucleus represented by D and D ′, an alkyl group represented by R ₁ , R ₂ and R ₃ , or Any of the methine groups represented by L _{1 to} L ₂₁ may be used.
Substitution to the nitrogen atom of the acidic nucleus represented by R ₁ , R ₂ and R ₃ , or D and D ′ is preferable. As the spectral sensitizing dye used in the present invention, other cyanine dyes,
A merocyanine dye, a composite merocyanine dye or the like is used. In addition, complex cyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes, and hemioxonol dyes are used. As the cyanine dye, a simple cyanine dye, a carbocyanine dye, a dicarboxylic cyanine dye, and a tricarbocyanine dye are used. Typical examples of the methine compound represented by the general formula (I) are shown below, but the invention is not limited thereto.

[0034]

[Chemical 14]

[0035]

[Chemical 15]

[0036]

[Chemical 16]

[0037]

[Chemical 17]

[0038]

[Chemical 18]

[0039]

[Chemical 19]

[0040]

[Chemical 20]

[0041]

[Chemical 21]

The polymethine dye represented by the general formula (I) used in the present invention can be synthesized according to the methods described in the following documents. a) FM Harmer, “Heterocyclic Compounds-Cyanine Die and Relative Compounds- (Heterocyclic Compo
unds-Cyanine dyes and related compounds −) ”(John Wiley & Sons, Inc.-New York, London-, 1964) b) DMSturmer-“ Heterocyclic Compounds ” -Special Topics in Heterocyclic Chemistry- (Hetero
cyclic Compounds-Special topics in heterocyclic c
hemistry-) "Chapter 8 Section 4, pp. 482-515 (John Wiley & Sons, Inc.-New York, London-, 1977) c) Jurnal Organich Escoi Himmy (Zh.O.
rg.Khim.) Vol. 17, No. 1, pp. 167-169 (198)
1), Vol. 15, No. 2, pp. 400-407 (1979)
, Vol. 14, No. 10, pp. 2214-2221 (19)
1978), Vol. 13, No. 11, pp. 2440-2443 (1977), Vol. 19, No. 10, pp. 2134-214.
Page 2 (1983), Ukr.Khim.Zh. Vol. 40, No. 6, No. 6
Pp. 25-629 (1974), Kimi. Geterotsikl.soe (Khim. Geterotsikl.soe)
din.) No. 2, pp. 175-178 (1976), Russian Patents 420643 and 341823, JP-A-59-
217761, U.S. Patents 4334000, 367.
No. 1648, No. 3623881, No. 3573921
No., European Patents 288261A1 and 102781A2
No. 102781A2, Japanese Patent Publication No. 49-46930
issue. US Pat. Nos. 3,582,344, 2,734,
900, AI Tolmachev (TITolmachev)
Dokl.Akad.Nauk SSSR, No. 177, 869-872
It can be synthesized based on the method described on page (1967).

For the bond forming reactions including the ether bond forming reaction, the amide bond forming reaction and the ester bond forming reaction of the-(Q) _k2- Ar moiety, a method known in organic chemistry can be used. . Ie M
Method for connecting polycyclic moieties represented by ET and Ar, method for synthesizing polymethine dye, and method for linking polycyclic moieties represented by Ar to intermediates, and then carrying out pigmentation reaction, conversely polycyclic moieties represented by Ar After connecting the synthetic raw materials and intermediates of the part to the polymethine dye part, Ar
Any method such as a method for synthesizing the polycyclic moiety represented by can be used, and the polycyclic portion can be appropriately selected and synthesized. Regarding the synthetic reaction for these linkages, for example, edited by The Chemical Society of Japan, New Experimental Chemistry Course 14, Synthesis and Reaction of Organic Compounds, Volumes I to V,
Maruzen, Tokyo (1977), Yoshiro Ogata, Organic Reaction Theory, Maruzen, Tokyo (1962) LFFieserand M. Fieser, Advan
Many books on organic synthesis such as ced Organic Chemistry, Maruzen, Tokyo (1962) can be referred to.

The silver halide emulsion which can be used in the present invention is
It may contain any of silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide and silver chloride. The silver halide grain may have a regular crystal such as a cube, an octahedron, a tetrahedron, and a rhombodecahedral, or an irregular crystal such as a sphere or a plate. It may have a shape or a composite of these crystal shapes. It may consist of a mixture of particles of various crystal forms.
The plate-like particles have a thickness of 0.5 μm or less,
The diameter is preferably 0.3 micron or less, and the diameter is preferably 0.
Tabular grains having a grain size of 6 microns or more and having an average aspect ratio of 5 or more occupy 50% or more of the total projected area are preferable. The silver halide grains may have different phases in the inside and the surface layer, or may be composed of a uniform phase. Further, it may be a grain in which a latent image is mainly formed on the surface (for example, a negative emulsion) or a grain in which a latent image is mainly formed inside the grain (for example, an internal latent image type emulsion).
The preferred silver halide emulsions in the present invention are described in detail below.

As the silver halide emulsion used in the present invention, those composed of silver chlorobromide or silver chloride containing substantially no silver iodide can be preferably used. Here, "containing substantially no silver iodide" means that the silver iodide content is 1 mol%.
Hereinafter, it is preferably 0.2 mol% or less. The halogen composition of the emulsion may be different or the same between grains, but if an emulsion having the same halogen composition between grains is used, it is easy to make the properties of each grain uniform. Regarding the halogen composition distribution inside the silver halide emulsion grains, the so-called uniform structure grains having the same composition in any portion of the silver halide grains, or the core inside the silver halide grains and the shell surrounding it (Shell) [a single layer or a plurality of layers] particles having a so-called laminated structure having a different halogen composition or a structure having a portion having a different halogen composition inside or on the surface of the particle (edge of the particle when present on the particle surface, It is possible to appropriately select and use particles having a structure in which parts having different compositions are bonded to a corner or a surface. In order to obtain high sensitivity, it is advantageous to use either of the latter two particles rather than the particles having a uniform structure, and it is also preferable from the viewpoint of pressure resistance. When the silver halide grains have the above structure, the boundary between different portions in the halogen composition is an unclear boundary because a mixed crystal is formed due to the composition difference even if the boundary is clear. It may also be one that positively has a continuous structural change.

A so-called high silver chloride emulsion having a high silver chloride content is preferably used for a light-sensitive material suitable for rapid processing. In the present invention, the silver chloride content of the high silver chloride emulsion is 9
0 mol% or more is preferable, and 95 mol% or more is more preferable. In such a high silver chloride emulsion, a structure having a silver bromide localized phase in the inside and / or on the surface of the silver halide grain in a layered or non-layered manner as described above is preferable. The halogen composition of the localized phase preferably has a silver bromide content of at least 10 mol%, and preferably 20 mol%.
It is more preferable that the number exceeds. These localized phases can be present inside the grains, on the edges, corners, or on the surface of the grains, and one preferable example is the one epitaxially grown at the corners of the grains. On the other hand, in order to suppress the sensitivity decrease as much as possible when the light-sensitive material is subjected to pressure, even in a high-silver chloride emulsion having a silver chloride content of 90 mol% or more, grains having a uniform structure with a small distribution of halogen composition in the grains are formed. It is also preferably used. It is also effective to further increase the silver chloride content of the silver halide emulsion for the purpose of reducing the replenishment amount of the developing solution. In such a case, an almost pure silver chloride emulsion having a silver chloride content of 98 mol% to 100 mol% is also preferably used. The average grain size of the silver halide grains contained in the silver halide emulsion used in the present invention (the grain size is determined by the diameter of a circle equivalent to the projected area of the grain and the number average thereof is taken) is 0.1 μ to 2 μ. Is preferred. In addition, their particle size distributions are coefficient of variation (standard deviation of particle size distribution divided by average particle size) 2
So-called monodisperse particles of 0% or less, preferably 15% or less are preferable. At this time, for the purpose of obtaining a wide latitude, it is also preferable to use the above monodisperse emulsion by blending it in the same layer, or to perform multi-layer coating. The shape of silver halide grains contained in a photographic emulsion is one having a regular crystal form such as a cube, a tetradecahedron or an octahedron, an irregular shape such as a sphere or a plate.
lar) having a crystalline form, or having a complex form thereof can be used. It may also be a mixture of those having various crystal forms. In the present invention, it is preferable that 50% or more, preferably 70% or more, and more preferably 90% or more of the particles having the above-mentioned regular crystal form are contained in the present invention.

In addition to these, an emulsion having tabular grains having an average aspect ratio (diameter in terms of circle / thickness) of 5 or more, preferably 8 or more as a projected area exceeding 50% of all grains is also preferably used. it can. The silver chlorobromide emulsion used in the present invention is a Chimie et Phisique by P. Glafkides.
Photographique (Paul Montel, 1967), GF
Photographic Emulsion Chemistry (Focal Pre by Duffin
ss, 1966), by VL Zelikman et al Makinga
nd Coating Photographic Emulsion (Focal Press, 1964) and the like. That is, any method such as an acidic method, a neutral method, or ammonia may be used, and as a method of reacting the soluble silver salt and the soluble halogen salt, any method such as a one-sided mixing method, a simultaneous mixing method, and a combination thereof is used. May be. It is also possible to use a method of forming particles in an atmosphere in which silver ions are excessive (so-called reverse mixing method).
As one form of the simultaneous mixing method, a method of keeping pAg in a liquid phase where silver halide is formed constant, that is, a so-called controlled double jet method can be used. According to this method, a silver halide emulsion having a regular crystal form and a substantially uniform grain size can be obtained. In the silver halide emulsion used in the present invention, various polyvalent metal ion impurities can be introduced in the process of emulsion grain formation or physical ripening. Examples of compounds used include salts of cadmium, zinc, lead, copper, thallium, etc., or Group VIII elements iron, ruthenium, rhodium,
Examples thereof include salts or complex salts of palladium, osmium, iridium, platinum and the like. Particularly, the above Group VIII elements can be preferably used. The addition amount of these compounds is wide depending on the purpose, but is preferably 10 ^-9 to 10 ^-2 mol with respect to the silver halide.

The silver halide emulsion used in the present invention is
Usually, it is chemically and spectrally sensitized. Regarding the chemical sensitization method, sulfur sensitization typified by the addition of an unstable sulfur compound, noble metal sensitization typified by gold sensitization, reduction sensitization, or the like can be used alone or in combination. Compounds used for chemical sensitization are described in JP-A-62-21.
Those described in the lower right column on page 18 to the upper right column on page 22 of Japanese Patent No. 5272 are preferably used. Spectral sensitization is carried out for the purpose of imparting spectral sensitization in a desired light wavelength range to the emulsion of each layer in the light-sensitive material of the present invention. In the present invention, it is preferable to add a dye that absorbs light in a wavelength range corresponding to the desired spectral sensitivity-a spectral sensitizing dye. Examples of the spectral sensitizing dye used at this time include F.
Heterocyclic compounds-Cyanine dyes and by M. Harmer
related compounds (John Wiley & Sons New York, Lo
Examples thereof include those described in Ndon Publishing Co., 1964). As specific examples of the compound and the spectral sensitization method, those described in JP-A-62-215272, page 22, upper right column to page 38 are preferably used.
The silver halide emulsion used in the present invention prevents fogging during the manufacturing process, storage or photographic processing of a light-sensitive material,
Alternatively, various compounds or precursors thereof can be added for the purpose of stabilizing photographic performance. As specific examples of these compounds, those described on pages 39 to 72 of the above-mentioned JP-A No. 62-215272 are preferably used.

The emulsion used in the present invention is a so-called surface latent image type emulsion in which a latent image is mainly formed on the grain surface. When a semiconductor laser is used as a light source for digital exposure in the present invention, it is necessary to efficiently spectrally sensitize the infrared region. Particularly, the methine compounds represented by the general formulas (II) and (III) are preferable for spectral sensitization in the region of 700 nm or more. Since infrared sensitization uses sensitization of the sensitizing dye in the M band, the spectral sensitivity distribution is generally broader than that in the J band. Therefore, it is preferable to provide a coloring layer containing a dye in the colloid layer on the photosensitive surface side of the predetermined photosensitive layer to correct the spectral sensitivity distribution. This colored layer is effective in preventing color mixing due to the filter effect.

To contain the spectral sensitizing dyes in the silver halide emulsion, they may be dispersed directly in the emulsion, or water, methanol, ethanol, propanol, methyl cellosolve, 2,2,3. It may be added to the emulsion by dissolving it in a solvent such as 1,3-tetrafluoropropanol alone or in a mixed solvent. In addition, Japanese Patent Publication No.
No. 89, Japanese Patent Publication No. 44-27555, Japanese Patent Publication No. 57-22
As described in 089 etc., an acid or a base is allowed to coexist to prepare an aqueous solution, or US Pat. No. 3,822,135 and US Pat.
As described in No. 006025 and the like, an aqueous solution or colloidal dispersion in which a surfactant coexists may be added to the emulsion. Alternatively, the emulsion may be dissolved in a solvent which is substantially immiscible with water such as phenoxyethanol and then dispersed in water or a hydrophilic colloid to add to the emulsion. As described in JP-A-53-102733 and JP-A-58-105141, the dispersion may be directly dispersed in a hydrophilic colloid, and the dispersion may be added to the emulsion. The time of addition to the emulsion may be any stage of emulsion preparation known to be useful so far. In other words, before preparing the silver halide emulsion grains, during grain formation, immediately after grain formation, before entering the washing step, before chemical sensitization, during chemical sensitization, immediately after chemical sensitization, until the emulsion is cooled and solidified. You can choose from either. Most commonly, it is carried out after the completion of chemical sensitization and before the application, but is described in US Pat.
It is also possible to add spectral sensitization simultaneously with chemical sensitization by adding it at the same time as the chemical sensitizer as described in JP-A No. 28969 and No. 4225666.
It may be carried out prior to chemical sensitization as described in No. 8 or it may be added before the completion of silver halide grain precipitation to initiate spectral sensitization. It is also possible to add the spectral sensitizing dyes separately, as taught in U.S. Pat. No. 4,225,666, i.e. some prior to chemical sensitization and the rest after chemical sensitization. It is possible and can be at any time during silver halide grain formation including the method taught in US Pat. No. 4,183,756. Of these, it is particularly preferable to add a sensitizing dye before the emulsion washing step or before chemical sensitization. The addition amount of these spectral sensitizing dyes is wide depending on the case, and is 0.5 × 10 ⁻⁶ mol to 1 mol of silver halide.
The range of 1.0 × 10 ^-2 mol is preferable. More preferably, it is in the range of 1.0 × 10 ⁻⁶ mol to 5.0 × 10 ⁻³ mol. In the red or infrared sensitization in the present invention, the M band type sensitization is particularly described in JP-A-2-157749.
Supersensitization with the compounds described on page 3, lower right column, line 3 to page 22, lower right column, lower line 3 is effective.

The constitution of the light-sensitive material of the present invention will be described. The light-sensitive material of the present invention has at least three silver halide emulsion layers on a support, at least two of which are 670 layers.
It is preferable to have the spectral sensitivity maximum at nm or more.
This photosensitive layer contains at least one coupler which develops a color by a coupling reaction with an oxidation product of an aromatic amine compound.
It is preferable to contain seeds. For full-color hard copy, at least three types of silver halide photosensitive layers having different color sensitivities are provided on a support, and each layer is yellow by a coupling reaction with an oxidant of an aromatic amine compound. It preferably contains either a magenta or a coupler capable of forming a cyan color. These three different spectral sensitivities can be arbitrarily selected according to the wavelength of the light source used for digital exposure, but from the viewpoint of color separation, the closest spectral sensitivity maximum is at least 30 nm.
It is preferable that they are separated from each other. At least three types of photosensitive layers (λ1, λ2, λ3) having different maximum spectral sensitivities.
The corresponding relationship with the color forming couplers (Y, M, C) contained in is not particularly limited. That is, 3 × 2 = 6 combinations are possible. Also, there is no particular restriction on the order of coating from the support side of the photosensitive layer having at least three kinds of maximum spectral sensitivity, but from the viewpoint of rapid processing, the longest wavelength spectral sensitivity including silver halide grains having the largest average size is obtained. In some cases, it is preferable that the photosensitive layer has a top layer. Therefore, there are 36 possible combinations of the three different spectral sensitivities, the three color forming couplers and the layer order. The present invention can be effectively used for all the 36 types of light-sensitive materials. In the present invention, it is particularly preferable to use a semiconductor laser as a light source for digital exposure. In this case, among at least three types of silver halide photosensitive layers having different color sensitivities,
It is preferable that at least one type of photosensitive layer has a spectral sensitivity maximum at 730 nm or more, and at least two types of layers have a spectral sensitivity maximum in a long wavelength region of 670 nm or more. Also in this case, there are no restrictions on the spectral sensitivity maximum, the color forming coupler, and the layer order. Table 1 shows specific examples of the digital exposure light source, the spectral sensitivity maximum, and the color forming coupler, but the present invention is not limited thereto.

[0052]

[Table 1]

The exposure in the present invention will be described. The photosensitive material in the present invention is intended to be used for scanning digital exposure in which an image is exposed by moving a high-density beam light such as a laser or an LED relative to the photosensitive material. Therefore, the exposure time of the silver halide in the light-sensitive material is the time required to expose a certain minute area. As this minute area, the minimum unit for controlling the light amount from each digital data is generally used and is called a pixel. Therefore, the exposure time per pixel changes depending on the size of this pixel. The size of this pixel depends on the pixel density and is in a practical range of 50 to 2000 dpi. When the exposure time is defined as the time for exposing the pixel size when the pixel density is 400 dpi, the preferable exposure time is 10
^-4 seconds or less, more preferably 10 ^-6 seconds or less.
In the light-sensitive material according to the present invention, a hydrophilic colloid layer is added in order to improve the sharpness of an image, etc.
No. 0,337,490A2, pages 27 to 76, the dyes which can be decolorized by treatment (among others, oxonol dyes) have an optical reflection density at 680 nm of 0.70 or more. 12% by weight or more (more preferably 14% by weight or more) of titanium oxide surface-treated with a dihydric or tetrahydric alcohol (eg, trimethylolethane) in the water resistant resin layer of the support. It is preferably contained.

Colloidal silver and dyes are used in the light-sensitive material of the present invention to prevent irradiation and halation, particularly to separate the spectral sensitivity distribution of each light-sensitive layer and ensure safety against safelight. Examples of such dyes include U.S. Pat. Nos. 506,385 and 1,17.
7,429, 1,131,884, 1,33
8,799, 1,385,371, 1,46
7,214, 1,433,102, 1,55
3,516, JP-A-48-85,130, 49-
114, 420, 52-117, 123, 55.
-161,233, 59-111,640, JP-B-39-22,069, 43-13,168, 62-273527, U.S. Pat. No. 3,247,127.
Oxonol dyes having a pyrazolone nucleus, a barbituric nucleus or a barbituric acid nucleus described in U.S. Pat. Nos. 3,469,985 and 4,078,933, and US Pat.
No. 533,472, No. 3,379,533, British Patent No. 1,278,621, JP-A-1-134447,
Other oxonol dyes described in JP-A-1-183652, British Patent Nos. 575,691 and 680,63
1, No. 599,623, No. 786,907, No. 9
No. 07,125, No. 1,045,609, U.S. Pat. No. 4,255,326, JP-A-59-211,043 and the like, and JP-A-50-100,116.
No. 54-118,247, British Patent No. 2,01.
Azomethine dyes described in U.S. Pat. Nos. 4,598,750 and 031, anthraquinone dyes described in U.S. Pat. No. 2,865,752, U.S. Pat. No. 2,538,00.
No. 9, No. 2,688,541, No. 2,538,008
No., British Patent Nos. 584,609 and 1,210,25
No. 2, JP-A Nos. 50-40,625 and 51-3,62.
No. 3, No. 51-10, 927, No. 54-118, 24
No. 7, Japanese Patent Publication No. 48-3,286, No. 59-37, 30
Arylidene dyes described in No. 3 and the like, Japanese Patent Publication No. 28-
3,082, 44-16,594, 59-2
Styryl dyes described in US Pat. No. 8,898, British Patent Nos. 446,538, 1,335,422, and Japanese Patent Laid-Open No.
9-228,250 and the like, triarylmethane dyes, British Patent Nos. 1,075,653 and 1,15.
No. 3,341, No. 1,284,730, No. 1,47
5,228,807, 1,542,807 and the like, merocyanine dyes, US Pat. No. 2,843,486,
Examples thereof include cyanine dyes described in JP-A-3,294,539, JP-A-1-291247 and the like. In order to prevent the diffusion of these dyes, the following methods can be mentioned. For example, a ballast group is added to the dye to make it resistant to diffusion. Further, for example, a method in which a hydrophilic polymer having a charge opposite to that of the dissociated anionic dye is allowed to coexist in a layer as a mordant and the dye is localized in a specific layer by interaction with dye molecules is disclosed in US Pat. No. 564, No. 4,124,3
No. 86, No. 3,625,694 and the like.
Further, a method of dyeing a specific layer using a water-insoluble dye solid is disclosed in JP-A-56-12639 and JP-A-55-155.
No. 350, No. 55-155351, No. 63-2783.
No. 8, 63-197943, European Patent No. 15,60.
No. 1 and the like. In addition, a method of dyeing a specific layer using fine particles of a metal salt having a dye adsorbed thereto is disclosed in US Pat.
719,088, 2,496,841, 2,4
96,843, JP-A-60-45237 and the like.

Further, in the light-sensitive material according to the present invention, it is preferable to use a color image storability improving compound as described in European Patent EP 0,277,589A2 together with a coupler. In particular, it is preferably used in combination with a pyrazoloazole coupler. That is, the compound (F) that chemically bonds to the aromatic amine-based developing agent remaining after the color development processing to form a chemically inactive and substantially colorless compound and / or the aroma remaining after the color development processing. The simultaneous use of the compound (G), which forms a chemically inactive and substantially colorless compound by chemically bonding with an oxidant of a group amine color developing agent, for example, in storage after processing. It is preferable in order to prevent the occurrence of stains and other side effects due to the formation of a coloring dye due to the reaction of the coupler with the residual color developing agent in the film or its oxidation product. Further, in the light-sensitive material according to the present invention, in order to prevent various molds and bacteria which propagate in the hydrophilic colloid layer and deteriorate the image, JP-A-63-27124 is used.
It is preferable to add a mildew-proofing agent as described in JP-A-7. The support used in the light-sensitive material according to the present invention may be a white polyester-based support for a display or a support provided with a layer containing a white pigment on the support having a silver halide emulsion layer. You may use. Further, in order to improve the sharpness, it is preferable to apply an antihalation layer on the silver halide emulsion layer-coated side or the back side of the support. In particular, the transmission density of the support is 0.35 to 0. so that the display can be viewed with both reflected light and transmitted light.
It is preferable to set it in the range of 8. The exposed light-sensitive material may be subjected to conventional black-and-white or color development processing, but in the case of a color light-sensitive material, it is preferable to perform bleach-fix processing after color development for the purpose of rapid processing. Particularly when the above high silver chloride emulsion is used, the pH of the bleach-fixing solution is preferably about 6.5 or less, more preferably about 6 or less for the purpose of promoting desilvering. Silver halide emulsions and other materials (additives etc.) and photographic constituent layers (layer arrangement etc.) applied to the light-sensitive material according to the present invention, and processing methods and processings applied for processing the light-sensitive material. Examples of additives include the following patent publications, particularly European Patent Publication EP 0,355,660A.
What is described in the specification of No. 2 (Japanese Patent Application No. 1-107011) is preferably used.

[0056]

[Table 2]

[0057]

[Table 3]

[0058]

[Table 4]

[0059]

[Table 5]

[0060]

[Table 6]

Further, as a cyan coupler, JP-A-2-
In addition to the diphenylimidazole type cyan coupler described in Japanese Patent No. 33144, European Patent EP 0,333,085
The 3-hydroxypyridine type cyan couplers described in A2 specification (among these, couplers (42) listed as specific examples, which are 4-equivalent couplers with a chlorine leaving group to make them 2-equivalent, couplers (6) and (9) is particularly preferable) and cyclic active methylene cyan couplers described in JP-A-64-32260 (coupler examples 3, 8, and 34 listed as specific examples are particularly preferable) are also preferably used. .. The processing temperature of the color developer applicable to the present invention is 20 to 50 ° C, preferably 30 to 45 ° C. The processing time is preferably substantially 20 seconds or less. It is preferable that the replenishing amount is small, but ^{20 to} 600 ml is appropriate per 1 m ^{2 of} the light-sensitive material, preferably 50 to 300.
ml. It is more preferably 60 to 200 ml, most preferably 60 to 150 ml. In the present invention, it is preferable that the development time is substantially within 20 seconds. The term "substantially 20 seconds" as used herein means that the photosensitive material is stored in the next tank from the time when the photosensitive material enters the developer tank. It means the time until it enters, and it also includes the transit time in the air from the developer tank to the next tank. The preferred pH of the washing step or stabilizing step is 4 to 1
It is 0, and more preferably 5-8. The temperature can be set variously depending on the use and characteristics of the light-sensitive material, but generally 30 to
The temperature is 45 ° C, preferably 35 to 42 ° C. The time can be set arbitrarily, but a shorter time is preferable from the viewpoint of reducing the processing time. Preferably 10 to 45 seconds, more preferably 10 to 45 seconds.
40 seconds. The smaller the replenishment amount, the more preferable from the viewpoint of running cost, reduction of discharge amount, handleability and the like. A specific preferable amount of replenishment is 0.5 to 50 times, preferably 2 to 15 times the amount carried from the prebath per unit area of the light-sensitive material. Alternatively, it is 300 ml or less, preferably 150 ml or less per 1 m ^{2 of the} light-sensitive material. The replenishment may be performed continuously or intermittently. The liquid used in the washing and / or stabilizing step can be further used in the previous step. An example of this is that the overflow of washing water reduced by the multi-stage countercurrent method is caused to flow into the bleach-fixing bath of the preceding bath, and the bleach-fixing bath is replenished with a concentrated liquid to reduce the amount of waste liquid. Next, the drying process that can be used in the present invention will be described. A drying time of 20 to 40 seconds is desired in order to complete an image by the ultra-rapid processing of the present invention. As a means for shortening the drying time, as a means on the side of the light-sensitive material, it is possible to improve by reducing the amount of water taken into the film by reducing the amount of a hydrophilic binder such as gelatin. Further, from the viewpoint of reducing the carry-in amount, it is also possible to accelerate the drying by absorbing the water with a squeeze roller or a cloth immediately after leaving the washing bath. As a means of improvement from the dryer, as a matter of course, it is possible to accelerate the drying by increasing the temperature or increasing the drying air. Further, the drying can be accelerated by adjusting the blowing angle of the drying air to the light-sensitive material or by removing the exhausted air.

[0062]

【Example】

Example 1 (Preparation of Emulsion A) 3.3 g of sodium chloride was added to a 3% aqueous solution of lime-processed gelatin, and 3.2 ml of N, N'-dimethylimidazolidine-2-thione (1% aqueous solution) was added. An aqueous solution containing 0.2 mol of silver nitrate, 0.2 mol of sodium chloride and 15 μg of rhodium trichloride.
And was mixed with an aqueous solution containing at 50 ° C. with vigorous stirring. Subsequently, an aqueous solution containing 0.780 mol of silver nitrate and an aqueous solution containing 0.780 mol of sodium chloride and 4.2 mg of potassium ferrocyanide are stirred vigorously at 56 ° C.
Was added and mixed. Five minutes after the addition of the silver nitrate aqueous solution and the alkali halide aqueous solution was completed, the silver nitrate was further added to 0.0
An aqueous solution containing 20 mol, and 0.015 mol of potassium bromide,
An aqueous solution containing 0.005 mol of sodium chloride and 0.8 mg of potassium hexachloroiridium (IV) ate was added and mixed at 40 ° C. with vigorous stirring. Then, a copolymer of isobutene maleic acid 1-sodium salt was added, and the mixture was washed by sedimentation and desalting. Further, 90.0 g of lime-processed gelatin was added to adjust the pH and pAg of the emulsion to 6.2 and 6.5, respectively. Further, sulfur sensitizer (triethylthiourea) 1 × 10 ^-5 mol / molAg and chloroauric acid 1 × 10
^-5 mol / molAg and nucleic acid 0.2 g / molAg were added, and optimal chemical sensitization was performed at 50 ° C. Regarding the obtained silver chlorobromide (A), the particle shape, particle size and particle size distribution were determined from electron micrographs. All of these silver halide grains are cubic and have a grain size of 0.52 μm.
The coefficient of variation was 0.08. The particle size is represented by the average value of the diameter of the circle equivalent to the projected area of the particle, and the particle size distribution is the standard deviation of the particle size divided by the average particle size. The halogen composition of the emulsion grains was then determined by measuring the X-ray diffraction from the silver halide crystals. The diffraction angle from the (200) plane was measured in detail using a monochromatic Cuk α ray as a radiation source. A diffraction line from a crystal having a uniform halogen composition gives a single peak, whereas a diffraction line from a crystal having a localized phase having a different composition gives a plurality of peaks corresponding to those compositions. By calculating the lattice constant from the diffraction angle of the measured peak, the halogen composition of silver halide constituting the crystal can be determined. The measurement results of this silver chlorobromide emulsion (A) are silver chloride 1
70% silver chloride (30% silver bromide) in addition to the main peak of 00%
It was possible to observe a broad diffraction pattern having a center at the center and skirting around 60% of silver chloride (40% of silver bromide).

(Preparation of Photosensitive Material B) After corona discharge treatment was applied to the surface of a paper support laminated on both sides with polyethylene, a gelatin subbing layer containing sodium dodecylbenzenesulfonate was provided, and various photographic constituent layers were further coated. A multilayer color photographic paper having the following layer structure was prepared. The coating liquid was prepared as follows. Preparation of coating solution for the first layer Yellow coupler (ExY) 19.1 g and color image stabilizer (Cpd-1) 4.4 g and color image stabilizer (Cpd-)
7) 0.7 g of ethyl acetate 27.2 cc and solvent (So
lv-3) and (Solv-7) 4.1 g each
The solution was added and dissolved, and the solution was dissolved in 10% sodium dodecylbenzenesulfonate (8 cc) in 10% gelatin aqueous solution 185.
cc was emulsified and dispersed to prepare an emulsified dispersion. On the other hand, the silver chlorobromide emulsion (A) has the following red-sensitive sensitizing dye (Dye-
An emulsion containing 1) was prepared. The above emulsified dispersion and this emulsion were mixed and dissolved to prepare a first coating solution having the following composition. The coating solutions for the second to seventh layers were prepared in the same manner as the coating solution for the first layer. As a gelatin hardening agent for each layer, 1-oxy-3,5-dichloro-s-triazine sodium salt was used. In addition, Cpd-
10 and Cpd-11 were added so that the total amount would be 25.0 mg / m ² and 50.0 mg / m ² , respectively. The following were used as the spectral sensitizing dye for each layer.

[0064]

[Chemical formula 22]

[0065]

[Chemical formula 23]

[0066]

[Chemical formula 24]

When (Dye-2) or (Dye-3) is used, the following compounds are used in an amount of 1.8 per mol of silver halide.
× 10 ⁻³ mol was added.

[0068]

[Chemical 25]

Further, 1- (5-methylureidophenyl) -5-mercaptotetrazole was added to the yellow color-forming emulsion layer, the magenta color-forming emulsion layer and the cyan color-forming emulsion layer in an amount of 8.0 × 10 ^-4 per mol of silver halide. Mol added. The following dyes were added to the emulsion layer to prevent irradiation.

[0070]

[Chemical formula 26]

[0071]

[Chemical 27]

(Layer Structure) The composition of each layer is shown below. Numbers represent coating amount (g / m ² ). The silver halide emulsion represents the coating amount in terms of silver. Support Polyethylene laminated paper [Polyethylene on the first layer side contains a white pigment (TiO ₂ ) and bluish dye (ultraviolet)] First layer (red sensitive yellow color forming layer) Silver chlorobromide emulsion (A) 0. 30 gelatin 1.86 yellow coupler (ExY) 0.82 color image stabilizer (Cpd-1) 0.19 solvent (Solv-3) 0.18 solvent (Solv-7) 0.18 color image stabilizer (Cpd-) 7) 0.06 Second layer (color mixing prevention layer) Gelatin 0.99 Color mixing inhibitor (Cpd-5) 0.08 Solvent (Solv-1) 0.16 Solvent (Solv-4) 0.08 Third layer ( Infrared-sensitive magenta coloring layer) Silver chlorobromide emulsion (A) 0.12 Gelatin 1.24 Magenta coupler (ExM) 0.23 Color image stabilizer (Cpd-2) 0.03 Color image stabilizer (Cpd- 3) 0.16 color image stabilizer Cpd-4) 0.02 color image stabilizer (Cpd-9) 0.02 solvent (Solv-2) 0.40 fourth layer (ultraviolet absorbing layer) gelatin 1.58 ultraviolet absorber (UV-1) 0. 47 Anti-Color Mixing Agent (Cpd-5) 0.05 Solvent (Solv-5) 0.24 Fifth Layer (Infrared Sensitive Cyan Coloring Layer) Silver Chlorobromide Emulsion (A) 0.23 Gelatin 1.34 Cyan Coupler (ExC) 0.32 Color image stabilizer (Cpd-2) 0.03 Color image stabilizer (Cpd-4) 0.02 Color image stabilizer (Cpd-6) 0.18 Color image stabilizer (Cpd-7) ) 0.40 Color image stabilizer (Cpd-8) 0.05 Solvent (Solv-6) 0.14 Sixth layer (UV absorbing layer) Gelatin 0.53 UV absorber (UV-1) 0.16 Color mixing prevention Agent (Cpd-5) 0.02 Solvent (Solv-5) 0.08 Layer (protective layer) Gelatin 1.33 Polyvinyl acrylic modified copolymer of an alcohol (modification degree 17%) 0.17 Liquid paraffin 0.03

[0073]

[Chemical 28]

[0074]

[Chemical 29]

[0075]

[Chemical 30]

[0076]

[Chemical 31]

[0077]

[Chemical 32]

[0078]

[Chemical 33]

[0079]

[Chemical 34]

[0080]

[Chemical 35]

[0081]

[Chemical 36]

As shown in Table 7, sample Nos. 1 and 2 are the first layer of the light-sensitive material (yellow color-developing layer), sample Nos. 3 to 6 are the third layer of the light-sensitive material (magenta color-developing layer), and sample Nos. 7 to 12
Was prepared in the same manner as in Photosensitive material a except that the spectral sensitizing dye used was changed to the fifth layer (cyan color forming layer) of photosensitive material a. The following were used as comparative sensitizing dyes.

[0083]

[Table 7]

[0084]

[Chemical 37]

[0085]

[Chemical 38]

Each of the coated samples was divided into three parts, and one set was sealed in an oxygen-impermeable bag substituted with argon gas, and -3
Stored at 0 ° C. The other set was stored at 80% RH and 50 ° C. for 3 days. The other set was stored under an oxygen partial pressure of 10 atm at room temperature for 7 days.

The prepared light-sensitive material was exposed using the following two types of exposure devices. (1) Photosensitizer (FWH type, manufactured by Fuji Photo Film Co., Ltd.,
670n for this light source using the color temperature of the light source 3200K)
Gradient exposure for sensitometry was applied for 10 seconds through a vapor deposition interference filter of m, 750 nm, and 830 nm. (2) Semiconductor laser AlGaInP (oscillation wavelength, about 670n
m), semiconductor laser GaAlAs (oscillation wavelength, about 750n
m) and GaAlAs (oscillation wavelength, about 830 nm). The laser light is a device capable of sequentially scanning and exposing on a color photographic paper that moves in a direction perpendicular to the scanning direction by a rotating polyhedron. Using this device, the light amount is changed to change the relationship D between the density (D) and the light amount (E) of the photosensitive material.
−logE was calculated. The light quantity of the semiconductor laser was controlled by combining a pulse width modulation method that modulates the light quantity by changing the energization time to the semiconductor laser and an intensity modulation method that modifies the light quantity by changing the energization quantity. This scanning exposure is performed at 400 dpi, and the average exposure time per pixel at this time is about 10 ⁻⁷ seconds. After the exposure, the development processing shown below was performed. (Development Treatment) The exposed sample was used after being subjected to continuous treatment (running) using a paper processor until replenishment with twice the tank capacity for color development in the next treatment step. Processing process Temperature Time Replenisher ^* Tank capacity Color development 35 ℃ 45 seconds 161ml 17 liter Bleach fixing 30-35 ℃ 45 seconds 215ml 17 liters Rinse 30-35 ℃ 20 seconds-10 liters Rinse 30-35 ℃ 20 seconds -10 liters Rinse 30-35 ℃ 20 seconds 350ml 10 liters Dry 70-80 ℃ 60 seconds * Replenishment amount per 1 m ² of light-sensitive material. (A three-tank countercurrent flow system from rinse to) was used. The composition of each treatment liquid is as follows. Color developer Tank solution Replenisher Water 800ml 800ml Ethylenediamine-N, N, N ', N'-tetramethylenephosphonic acid 1.5g 2.0g Potassium bromide 0.015g-Triethanolamine 8.0g 12.0g Sodium chloride 1.4g-Potassium carbonate 25 g 25 g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline sulfate 5.0 g 7.0 g N, N-bis (carboxymethyl) hydrazine 4.0 g 5.0 g N, N- Di (sulfoethyl) hydroxylamine ・ 1Na 4.0g 5.0g Optical brightener (WHITEX 4B, Sumitomo Chemical Co., Ltd.) 1.0g 2.0g Water is added 1000ml 1000ml pH (25 ℃) 10.05 10.45 Bleach-fixing solution (tank solution and replenisher) Is the same) Water 400 ml Ammonium thiosulfate (70 g / l) 100 ml Sodium sulfite 17 g Ethylenediaminetetraacetic acid iron (III) ammonium 55 g Ethylenediaminetetraacetic acid disodium 5 g Ammonium bromide 40 g Water added 1000 ml pH (25 ° C) 6.0 Rinse solution (tank solution and replenisher are the same) Ion-exchanged water (calcium and magnesium are 3 ppm or less each)

The results obtained are shown in Table 7. The sensitivity is
The results with a sensitometer are shown. Similar results were obtained using a semiconductor laser. Sensitivity was defined as the reciprocal of the exposure amount required to develop a color obtained by adding a fog density to a cyan density of 0.5. In argon gas substitution and storage at −30 ° C., sample number 2 shows the relative sensitivity of each sample when the sensitivity of sample number 1 is 100. Further, the sample numbers 4 to 6 have the sensitivity of the sample number 3 as 100, and the sample numbers 8 to 12 have the sample number 7
The relative sensitivity when the sensitivity of 100 is set to 100 is shown. Also,
The sensitivity when the sample was stored at 85% RH and 50 ° C. and the oxygen partial pressure was 10 atm, and the relative sensitivity was the relative value when the sensitivity of each sample was 100 at the argon gas displacement of −30 ° C. As shown.

Example 2 The light-sensitive material of Example 1 was tested in the same manner as in Example 1 except that the following developing treatment (II) was carried out using the above-mentioned automatic processor. The results obtained were those of Example 1. It was similar. Processing of Photosensitive Material: Development Processing (II) The photosensitive material was subjected to the following development processing (II) by using the automatic developing machine. Processing process Development process (II) Color developer 38 ℃ 20 seconds Bleach-fix 38 ℃ 20 seconds Rinse 38 ℃ 7 seconds Rinse 38 ℃ 7 seconds Rinse 38 ℃ 7 seconds Rinse 38 ℃ 7 seconds Rinse 38 ℃ 7 seconds Dry 65 ℃ 15 Seconds (Rinse → 5 tanks countercurrent type) (The above processing time is from the time the photosensitive material enters one processing solution to the time when it exits this processing solution and enters the next processing solution. The ratio of the aerial time in the processing time is usually 5% to 40% in the embodiment of the present invention, though the ratio of the aerial time in the processing time usually differs depending on the size of the processor. The composition of the liquid is as follows. Color developer Tank solution Replenisher Water 700ml 700ml Sodium triisopropylnaphthalene- (β) sulfonate 0.1g 0.1g Ethylenediaminetetraacetic acid 3.0g 3.0g 1,2-dihydroxybenzene-4,6-disulfonic acid disodium salt 0.5g 0.5g Triethanolamine 12.0g 12.0g Potassium chloride 6.5g None Potassium bromide 0.03g None Sodium sulfite 0.1g 0.1g Potassium carbonate 27.0g 27.0g 4-Amino-N-ethyl-N- (3-hydroxypropyl)- 3-Methylaniline 12.8 g 27.8 g Disodium-N, N-bis (sulfonate ethyl) hydroxylamine 10.0 g 13.0 g Optical brightener (UVITEX-CK manufactured by Ciba-Geigy) 2.0 g 6.0 g Water was added to 1000 ml 1000 ml pH ( 25 ° C.) 10.05 10.95 The replenishing amount of the above replenishing solution was 35 ml per 1 m ² of the light-sensitive material. Bleach-fixing solution Tank solution Replenishing solution Water 400ml 400ml Ammonium thiosulfate (70%) 100ml 250ml Ethylenediaminetetraacetic acid 3.4g 8.5g Ethylenediaminetetraacetic acid iron (III) ammonium dihydrate 73.0g 183g Ammonium sulfite 40g 100g Ammonium bromide 20.0g 50.0 g Nitric acid (67%) 9.6 g 24 g Water was added to 1000 ml 1000 ml pH (25 ° C) 5.80 5.10 The replenishing amount of the above replenisher was 35 ml per 1 m ² of the light-sensitive material. Rinse solution: Ion-exchanged water was used for both the tank solution and the replenisher, and the replenishment rate was 60 ml / m ² .

Example 3 The photosensitive material of Example 1 was tested in the same manner as in Example 1 except that the following developing treatment (III) was carried out using the above-mentioned automatic processor. It was similar. Development process (III) Processing process Replenishment amount per 1 m ^{2 of} light-sensitive material Color development 38.5 ℃ 45 seconds 35ml Bleach fixing 38 ℃ 20 seconds 35ml Rinse 38 ℃ 12 seconds Rinse 38 ℃ 12 seconds Rinse 38 ℃ 12 seconds 105ml Dry 65 ℃ 15 seconds (Rinse → 3 tank countercurrent system) The processing solution composition of the above-mentioned development processing (V) is as follows. Color developer Tank solution Replenisher Water 700ml 700ml Sodium triisopropylnaphthalene (β) sulfonate 0.1g 0.1g Ethylenediaminetetraacetic acid 3.0g 3.0g 1,2-dihydroxybenzene-4,6-disulfonic acid disodium salt 0.5g 0.5 g Triethanolamine 12.0g 12.0g Potassium chloride 6.5g None Potassium bromide 0.03g None Potassium carbonate 27.0g 27.0g Sodium sulfite 0.1g 0.1g Disodium-N, N-bis (sulfonate ethyl) hydroxylamine 10.0g 13.0g N -Ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline sulfate 5.0 g 11.5 g Optical brightener (manufactured by Ciba Geigy) UVITEV-CK 2.0 g 6.5 g

Example 4 A gold / sulfur sensitized tabular silver iodobromide emulsion prepared according to the method disclosed in Example-1 of JP-A-60-131,533 (mean diameter: 0. 82 μm, average diameter / thickness 11.2, pAg 8.2, pH 6.5) at 40 ° C. with addition of the compounds shown in Table 8 and then 2,4-dichloro-6-hydroxy- as a gelatin hardening agent. 1,3,5-
The sodium salt of triazine was added and coated on a cellulose triacetate support. At this time, a protective layer containing gelatin containing a surfactant and the above-mentioned gelatin hardening agent as a main component was simultaneously coated on the emulsion layer. Each of the samples prepared in this way was divided into three, and one set was -30 ° C.
The other one is stored under natural conditions for one year each, and the remaining one is stored at -30 ° C after exposure to 80% R for 3 days before exposure.
After being stored under H at 50 ° C., these three sets of samples are transmitted with light having a wavelength longer than 520 nm with an FWH sensitometer (ultraviolet absorption filter device, tungsten light source, color temperature 2854 ° K) manufactured by Fuji Photo Film Co., Ltd. Exposure for sensitometry was performed through a sharp cut filter, development was performed with a developing solution described later, bleaching, washing with water, and drying. The treated sample was measured for fog density and sensitivity using a densitometer manufactured by Fuji Photo Film Co., Ltd. Sensitivity is 0.2 for fog density
It is expressed by the reciprocal of the required amount of light to give the added concentration, and in Table 8, each sample stored at −30 ° C.
The relative value of the sensitivity of the corresponding sample when 0 was shown. Composition of developer Metol 2.5 g 1-Ascorbic acid 10.0 g Potassium bromide 1.0 g Nabox 35.0 g Water added 1.0 liter (pH 9.8) As shown in Table 8, the present invention is , Sensitivity increase / decrease is little over time. In particular, polymethine dyes C-9, C-10, (14) and (2 having E _OX less base than 0.60 V _VS SCE
0) shows a tendency that this desensitization is larger than that of the polymethine dyes C-7, C-8 and (2), which have a higher E _OX than 0.60 V _VS SCE. It is remarkable in C-9 and C-10. However, the polymethine dye of the present invention has a smaller desensitization than C-9 and C-10, and is a very useful technique.

[0092]

[Table 8]

[0093]

[Chemical Formula 39]

[0094]

[Chemical 40]

Example 5 A cubic silver bromide emulsion was prepared according to the method disclosed in JP-A-1-223,441 and Example-1. The silver bromide grains of the obtained silver bromide emulsion were monodisperse grains having an average side length of 0.74 μm (variation coefficient 10.6%). This emulsion at 40 ° C
The pH was adjusted to 6.3 and the pAg was adjusted to 8.4, and chloroauric acid and sodium thiosulfate were added at 55 ° C. for aging, and gold / sulfur sensitization was performed so as to be optimum. Then, the compounds shown in Table 9 were added at 40 ° C., and 0.1 g of sodium salt of 2-hydroxy-4,6-dichloro-1,3,5-triazine was added to 1 g of the emulsion, and dodecylbenzenesulfonic acid was added to the emulsion. After adding 0.1 g of the sodium salt of 1., a protective layer was provided on the polyethylene terephthalate film base and coated in the same manner as in Example-8. The prepared coating sample is divided into three,
One set is at -30 ° C, the other is 80% RH, 50 ° C for 3 days, and the remaining one is at an oxygen partial pressure of 10 atm at room temperature.
After storage for each day, exposure for sensitometry was carried out in the same manner as in Example 4, development processing was performed, and sensitivity was determined. Sensitivity was expressed as the reciprocal of the amount of light required to give a density obtained by adding 0.2 to the fog density. The results are shown in Table 9, and Table 9 shows relative values of sensitivities of other corresponding samples when the sensitivity of each sample stored at −30 ° C. was set to 100.

[0096]

[Table 9]

[0097]

[Chemical 41]

[0098]

[Chemical 42]

From the results shown in Table 9, it can be understood that the present invention causes less reduction in sensitivity even under such storage conditions. Furthermore, as in sample numbers 9-3 and 9-7, the compound V-
1 or V-2 in combination, 80% RH, 50
When it is placed under high temperature and high humidity of ℃, the sensitivity is less decreased. On the other hand, sample number 9-11 using IV-1 in combination
80% R compared to 9-10 which did not add it to
Even when placed in a high temperature and high humidity condition of H and 50 ° C. and an oxygen partial pressure of 10 atm, the decrease in sensitivity is further suppressed. The effects of these compounds are similarly expressed on the polymethine dyes outside the present invention, but when combined with the polymethine dyes of the present invention, it is considered that the decrease in sensitivity is significantly suppressed even under these storage conditions. be able to.

Example 6 An aqueous solution of 1 kg of AgNO _{3 in} an aqueous solution containing 72 g of gelatin and 16 g of NaCl, 161 g of KBr and NaC.
1205 g of an aqueous solution were added simultaneously at a constant rate for 32 minutes. (Br = 23 mol%) At this time, rhodium chloride and K ₃ IrCl _{6 were} added in the first 10 minutes.
And were added so as to be 5 × 10 ⁻⁷ mol / Ag mol, respectively. Then the soluble salts were removed and gelatin was added. Next, pH was adjusted to 6.0 and pAg was adjusted to 7.5, chloroauric acid and hypo were added, and chemical sensitization was performed at 60 ° C. The chemical sensitization time was selected to give the highest sensitivity. To this emulsion was added 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene as a stabilizer and phenoxyethanol as a preservative.

1 kg of each of the emulsions thus obtained was used. As shown in Table 1, each of the sensitizing dyes of the general formula (I)
110 ml of 5% solution, 0.5% methanol solution of V-1 6
0 ml, 35 ml of 0.5% V-2 methanol solution, IV-1
Of 42% of 0.5% methanol solution, hydroquinone 100 mg / m ² , polyethyl acrylate latex as plasticizer 25% gelatin binder ratio, 2-bis (vinylsulfonylacetamide) ethane 85 mg / m as hardener. ^{2 was} added and coated on a polyester support to give silver of 3.7 g / m ² . 2.0 for gelatin
It was g / m ² . 0.8 g / m ² of gelatin, 40 mg / m ^{2 of} polymethyl methacrylate having an average particle size of 2.5 μ as a matting agent, and 30 mg of colloidal silica having an average particle size of 4 μ.
/ M ² , silicone oil 80 mg / m ² , dodecylbenzenesulfonic acid sodium salt 80 mg / m ² as a coating aid, a surfactant having the following structural formula, polyethyl acrylate latex 150 mg / m ² and 1,1′-disulfobutyl-
3,3,3 ', 3'-Tetramethyl-5,5'-disulfoindotricarbocyanine potassium salt 6 mg / m ² was applied as a protective layer. On the opposite side of the polyester support of these samples, a back layer and a back protective layer having the following compositions are provided.

(Back layer) Gelatin 2.4 g / m ² dodecylbenzenesulfonic acid sodium salt 60 mg / m ² dye 80 mg / m ² 〃 30 mg / m ² 1,1′-disulfobutyl-3,3,3 ′, 3 ′ - tetramethyl-5,5'-surrender ho indotricarbocyanines potassium salt 80 mg / m ² 1,3-divinyl-sulfonyl-2-propanol 60 mg / m ² polyvinyl - potassium benzenesulfonate 30 mg / m ² (back protective layer ) Gelatin 0.75 mg / m ² polymethylmethacrylate (average particle size 3.5 μ) 40 mg / m ² sodium dodecylbenzenesulfonate 20 mg / m ² Surfactant 2 mg / m ² Silicone oil 100 mg / m ² C ₈ F _{17 SO 2 N (C 3 H 7} ) -CH 2 COOK

[0103]

[Chemical 43]

[0104]

[Chemical 44]

Each of the samples thus prepared was divided into 3 parts, one set was stored at -30 ° C, the other set was stored under natural conditions for 1 year, and the remaining set was stored at -30 ° C. Exposure 3
After being stored at 80% RH and 50 ° C. for the day before, these three sets were subjected to scanning exposure using a semiconductor laser emitting light at 780 nm. Next, using a developing solution and a fixing solution having the following composition, an automatic developing machine FG manufactured by Fuji Photo Film Co., Ltd.
Sensitometry was performed by developing at 38 ° C. for 14 seconds at −310 PTS, fixing, washing with water, and drying. The reciprocal of the exposure dose giving a density of 3.0 was taken as the sensitivity, and Table 10 shows the relative values of the corresponding samples when each sample stored at −30 ° C. was taken as 100. Developer formulation Water 720 ml Ethylenediaminetetraacetic acid disodium salt 4 g Sodium hydroxide 44 g Sodium sulfite 45 g 2-Methylimidazole 2 g Sodium carbonate 26.4 g Boric acid 1.6 g Potassium bromide 1 g Hydroquinone 36 g Diethylene glycol 39 g 5-Methyl-benzotriazole 0. 2g Pyrazone 0.7g Add water 1 liter Fixer formulation Ammonium thiosulfate 170g Sodium sulfite (anhydrous) 15g Boric acid 7g Glacial acetic acid 15ml Potassium alum 20g Ethylenediaminetetraacetic acid 0.1g Tartaric acid 3.5g Add water 1 liter

[0106]

[Table 10]

[0107]

[Chemical 45]

Table 10 shows that the sensitizing dye of the present invention has high storage stability.

[0109]

EFFECTS OF THE INVENTION From Examples 1, 2, 3, 4, 5, and 6, the dyes of the present invention have high sensitivity and can be used under severe conditions.
You can see that it is very stable. In the present invention, especially the sensitizing dye for infrared light is extremely unstable, and the commercially available infrared light silver halide light-sensitive material had to be stored at a low temperature in a refrigerator, etc. It has been attempted to improve the stability by improving the stability in combination with various other compounds, but the sensitizing dye itself can improve the stability in this way as in the present invention. Is extremely significant.

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

[Procedure amendment]

[Submission date] November 13, 1991

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0009

[Correction method] Change

[Correction content]

Q represents a divalent linking group consisting of an atom or an atomic group containing at least one of a carbon atom, a nitrogen atom, a sulfur atom and an oxygen atom. Preferably, an alkylene group (for example, a methylene group, an ethylene group, a propylene group,
Butylene group, pentylene group), arylene group (for example,
Phenylene group, naphthylene group), alkenylene group (for example, ethenylene group, propenylene group), sulfonyl group,
Sulfinyl group, thioether group, ether group, carbonyl group, -N (R ¹ )-(R ¹ represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group), a heterocyclic divalent A group (eg 6-chloro-1,
3,5-triazine-2,4-diyl group, pyrimidine-
2,4-diyl group, quinoxaline-2,3-diyl group)
Represents a divalent linking group having 20 or less carbon atoms, which is formed by combining one or more of k ₁ represents an integer of 1 or more, k ₂ represents 0 or 1, and k ₃ represents an integer of 5 or more. Preferably, k ₁ is 1 or 2, and k ₃ is preferably 5 or 6. more preferably a k ₁ and more preferably 5 as 1, _{k 3.} Alternatively, k ₁ represents an integer of 3 or more, k ₂ represents 0 or 1, and k ₃ represents 1, 2, 3 or 4. Preferably, k ₁ is 3, and k ₃ is preferably 1. Next, Ar will be described. The definition of aromaticity is "Iwanami Physics and Chemistry Dictionary 3rd Edition, Supplement," edited by Tamamushi Bunichi, published by Iwanami Shoten (198).
1 year publication) P-1258, 1259. A
Specific examples of the polycyclic compound represented by r are shown below.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0016

[Correction method] Change

[Correction content]

The substituent of these polycyclic compounds Ar is preferably a hydrogen atom, a substituted or unsubstituted alkyl group (eg, methyl, ethyl, propyl, butyl, hydroxyethyl, trifluoromethyl, benzyl, sulfopropyl, Diethylaminoethyl, cyanopropyl, adamantyl, p-chlorophenethyl, ethoxyethyl, ethylthioethyl, phenoxyethyl, carbamoylethyl, carboxyethyl, ethoxycarbonylmethyl, acetylaminoethyl), unsubstituted or substituted alkenyl groups (eg allyl, styryl). ), An unsubstituted or substituted aryl group (eg, phenyl, naphthyl, p-carboxyphenyl, 3,5-dicarboxyphenyl, m-sulfophenyl, p-acetamidophenyl, 3-caprylamidophenyl, p Sulfamoylphenyl, m-hydroxyphenyl, p-nitrophenyl, 3,5-dichlorophenyl, p-anisyl, o-anisyl, p-cyanophenyl, p-N-methylureidophenyl, m-fluorophenyl, p-tolyl. , M-tolyl), optionally substituted heterocycle residue (eg pyridyl, 5-methyl-2)
-Pyridyl, thienyl), halogen atoms (eg chlorine,
(Bromine, fluorine), mercapto group, cyano group, carboxyl group, sulfo group, hydroxy group, carbamoyl group, sulfamoyl group, amino group, nitro group, optionally substituted alkoxy group (eg, methoxy, ethoxy, 2-methoxyethoxy) , 2-phenylethoxy), optionally substituted aryloxy group (eg, phenoxy, p-methylphenoxy, p-chlorophenoxy), acyl group (eg, acetyl, benzoyl), acylamino group (eg, acetylamino, caproylamino). , Sulfonyl groups (eg methanesulfonyl, benzenesulfonyl), sulfonylamino groups (eg methanesulfonylamino, benzenesulfonylamino), substituted amino groups (eg diethylamino, hydroxyamino), alkyl or arylthio groups (eg In methylthio, carboxyethylthio, sulfo butyl thio, phenylthio), an alkoxycarbonyl group (e.g., methoxycarbonyl), an aryloxycarbonyl group (e.g. phenoxycarbonyl)
And these substituents further include a divalent linking group Q.
Alternatively, it may be bonded to MET by a single bond. Further, on these substituents, further alkyl group, alkenyl group, aryl group, hydroxy group, carboxyl group, sulfo group, nitro group, cyano group, halogen atom, alkoxy group, aryloxy group, alkoxycarbonyl group, acyl group, It may be substituted with an acylamino group, a sulfoneamino group, a carbamoyl group, a sulfamoyl group, or the like.
In addition, at least one of these substitutions may be bonded to MET through a divalent linking group Q or a single bond. Ar
Is at least one substituent or a single bond (Q) _k2
-(MET) is bound to _k1 . Preferred is the case where they are bound via Q.

[Procedure 3]

[Document name to be amended] Statement

[Name of item to be corrected] 0025

[Correction method] Change

[Correction content]

The nucleus formed by Z ₁ , Z ₂ and Z ₃ is preferably a benzothiazole nucleus, a naphthothiazole nucleus, a benzoxazole nucleus, a naphthoxazole nucleus, a benzimidazole nucleus, a 2-quinoline nucleus or a 4-quinoline nucleus. is there.

[Procedure amendment 4]

[Document name to be amended] Statement

[Name of item to be corrected] 0027

[Correction method] Change

[Correction content]

L ₁ , L ₂ , L 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 and L ₂₁ represent a methine group or a substituted methine group {eg, a substituted or unsubstituted alkyl group (eg, methyl group,
Ethyl group, 2-carboxyethyl group), substituted or unsubstituted aryl group (eg, phenyl group, o-carboxyphenyl group), heterocyclic group (eg, barbituric acid),
Halogen atom (eg chlorine atom, bromine atom), alkoxy group (eg methoxy group, ethoxy group), amino group (eg N, N-diphenylamino group, N-methyl-N)
-Phenylamino group, N-methylpiperazino group), alkylthio group (eg, methylthio group, ethylthio group), and the like}, and may form a ring with another methine group, or It is also possible to form a ring with the chromophore. L ₂ and L ₄ , L ₃ and L ₅ , L ₄ and L ₆
At least one of them preferably forms a ring with each other. Further, L ₁₂ and L ₁₄ , L ₁₃ and L ₁₅ , L ₁₄
It is preferable that one of L ₁₆ and L ₁₆ forms a ring with each other. L ₂ and L ₄ , L ₄ and L ₆ , L ₁₂ and L ₁₄ , L ₁₄
Particularly preferable ring structures as L ₁₆ and L ₁₆ are shown below.

[Procedure Amendment 5]

[Document name to be amended] Statement

[Name of item to be corrected] 0033

[Correction method] Change

[Correction content]

Further, in the general formulas (II) and (III), at least 5 or 1- (Q) _kz-
Ar is substituted, and the substitution position is, for example, a 5- or 6-membered nitrogen-containing heterocycle represented by Z ₁ , Z ₂ and Z ₃ in the general formulas (II) and (III), and D and D ′. It may be any of the acidic nucleus represented, the alkyl group represented by R ₁ , R ₂ and R ₃ , or the methine group represented by L _{1 to} L ₂₁ . Preferably R ₁ , R ₂ and R ₃ ,
Alternatively, it is the substitution of the nitrogen atom of the acidic nucleus represented by D and D '. As the spectral sensitizing dye used in the present invention, other cyanine dyes, merocyanine dyes, complex merocyanine dyes and the like are used. In addition, complex cyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes, and hemioxonol dyes are used. As the cyanine dye, a simple cyanine dye, a carbocyanine dye, a dicarboxylic cyanine dye, and a tricarbocyanine dye are used. Typical examples of the methine compound represented by the general formula (I) are shown below, but the invention is not limited thereto.

[Procedure Amendment 6]

[Document name to be amended] Statement

[Name of item to be corrected] 0053

[Correction method] Change

[Correction content]

The exposure in the present invention will be described. The light-sensitive material of the present invention is preferably used for scanning digital exposure in which an image is exposed by moving a high-density beam light such as laser or LED relative to the light-sensitive material. Therefore, the exposure time of the silver halide in the light-sensitive material is the time required to expose a certain minute area. As this minute area, the minimum unit for controlling the light amount from each digital data is generally used and is called a pixel. Therefore, the exposure time per pixel changes depending on the size of this pixel. The size of this pixel depends on the pixel density, and as a practical range,
It is 50 to 2000 dpi. When the exposure time is defined as the time for exposing the pixel size when the pixel density is 400 dpi, the exposure time is preferably 10 ⁻⁴ seconds or less, more preferably 10 ⁻⁶ seconds or less. In the light-sensitive material according to the present invention, a hydrophilic colloid layer is added in order to improve the sharpness of an image, European Patent EP0,
337,490A2, pages 27 to 76, wherein a dye that can be decolorized by treatment (among others, an oxonol dye) is added so that the optical reflection density at 680 nm of the light-sensitive material becomes 0.70 or more. 12% by weight or more (more preferably 14% by weight or more) of titanium oxide surface-treated with a dihydric or tetravalent alcohol (eg, trimethylolethane) or the like is added to the water resistant resin layer of the support. Is preferred.

[Procedure Amendment 7]

[Document name to be amended] Statement

[Correction target item name] 0088

[Correction method] Change

[Correction content]

The results obtained are shown in Table 7. The sensitivity is
The results with a sensitometer are shown. Similar results were obtained using a semiconductor laser. Sensitivity was defined as the reciprocal of the exposure amount required to develop the color obtained by adding the fog density to each coupler color density of 0.5. In argon gas substitution and storage at −30 ° C., sample number 2 shows the relative sensitivity of each sample when the sensitivity of sample number 1 is 100. Sample Nos. 4-6
Indicates the relative sensitivity when the sensitivity of Sample No. 3 is 100 and the sensitivity of Sample No. 8 to 100 is 100. The sensitivity when the sample was stored at 85% RH and 50 ° C and the oxygen partial pressure was 10 atm was the relative sensitivity when the sensitivity of each sample was 100 at the argon gas displacement of -30 ° C. It is shown as a relative value.

[Procedure Amendment 8]

[Document name to be amended] Statement

[Correction target item name] 0101

[Correction method] Change

[Correction content]

1 kg of the thus obtained emulsion was taken,
As shown in Table 10, 110 ml of a 0.05% solution of the sensitizing dye of the general formula (I), 60 ml of 0.5% methanol solution of V-1 and 0.5% methanol solution of V-2 35
ml, 42 ml of a 0.5% methanol solution of IV-1 was added, and then hydroquinone 100 mg / m ² , polyethyl acrylate latex as a plasticizer 25% in gelatin binder ratio, and 2-bis (vinylsulfonylacetamide) as a hardener. 85 mg / m ^{2 of} ethane was added and coated on a polyester support so as to give silver of 3.7 g / m ² . The gelatin was 2.0 g / m ² . 0.8 g / m ² of gelatin, 40 mg / m ^{2 of} polymethyl methacrylate having an average particle diameter of 2.5 μ as a matting agent,
Colloidal silica having an average particle diameter of 4μ 30 mg / m ² , silicone oil 80 mg / m ² , dodecylbenzenesulfonic acid sodium salt 80 mg / m ² as a coating aid, a surfactant having the following structural formula, polyethyl acrylate latex 150 mg / m ² And 1,1'-disulfobutyl-
3,3,3 ', was applied 3'-tetramethyl-5,5'-di-sulfo indotricarbocyanines potassium salt 6 mg / ^{m 2} as a protective layer. On the opposite side of the polyester support of these samples, a back layer and a back protective layer having the following compositions are provided.

[Procedure Amendment 9]

[Document name to be amended] Statement

[Correction target item name] 0104

[Correction method] Change

[Correction content]

[0104]

[Chemical 44]

Claims (4)

[Claims] 1. A silver halide photographic emulsion comprising at least one methine compound represented by formula (I). General formula (I): In the formula (I), MET represents an atom group having a methine compound structure, and Q represents a divalent linking group consisting of an atom or an atomic group containing at least one of a carbon atom, a nitrogen atom, a sulfur atom and an oxygen atom. Wherein Ar represents a group having a polycyclic compound having aromaticity and composed of 8 or more atoms, k ₁ represents an integer of 1 or more, and k ₂ represents 0 or 1
And k ₃ represents an integer of 5 or more. 2. A silver halide photographic emulsion according to claim 1, wherein the methine compound represented by the general formula (I) has an oxidation potential of 0.60 (VvsSCE) or less. 3. In the methine compound represented by the general formula (I), k ₃ is 1, 2, 3 or 4, and k ₁ is 3.
The silver halide photographic emulsion according to claim 1, which is an integer of the above. 4. The oxidation potential of the methine compound represented by the general formula (I) according to claim 3 is 0.60 (VvsSC).
The silver halide photographic emulsion according to claim 3, which is E) or less base.