JP2000112055A - Silver halide photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a silver halide photographic sensitive material improved in fog without deteriorating storage stability and spectrally sensitized to high sensitivity by incorporating at least one kind of specified methine dyes. SOLUTION: This silver halide photographic sensitive material contains at least one of a methine dyes represented by formulae I and II in which Z1 is a nonmetallic atomic group necessary to form a 5- or 6-membered N- containing hetero ring together with an N atom, each of Z2 and Z3 is a non-metallic atomic group necessary to form a condensed carbon ring or hetero rings, Q is a nonmetallic atomic group necessary to form an acid nucleus, each of Y1 and Y2 is 0 or S atom or the like, each of M1 and M2 is a pair ion for neutralizing a charge in the molecule, each of n1 and n2 is the number of >=0 necessary to neutralize the charge, each of L1-L5 is methine group or a substituted methine group, (s) is 0 or 1. (t) is an integer of 0-3 and each of A1 and A2 is an aliphatic group or the like.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a silver halide photographic material using a novel methine dye.

[0002]

2. Description of the Related Art Silver halide color photographic light-sensitive materials are said to be mature products having a very high degree of perfection. However, further required performance is high sensitivity, high image quality, and minimization of performance fluctuation due to storage conditions. In the future, it is necessary to take into account rapid processing suitability that has advanced development progress and the like, and the required level has been increasing in recent years.

[0003] In particular, in terms of high sensitivity, due to recent technological advances in digital cameras, in order to maintain the superiority of silver halide photosensitive materials, fog is kept low while maintaining high feasibility while maintaining low fog. Sensitivity must be improved. Techniques for increasing the sensitivity of silver halide emulsions, i.e., sensitization techniques, relate to a method for producing a silver halide emulsion, to chemical sensitization of a silver halide emulsion, to spectral sensitization of a silver halide emulsion, to halogenation, Various methods are known, such as those relating to the design method of silver halide photosensitive materials and those relating to the development process of silver halide photosensitive materials. Spectral sensitization technology that expands the photosensitive area of silver halide uses information efficiently. It is indispensable to keep a record.

[0004] Spectral sensitization is carried out by adsorbing certain cyanine dyes or merocyanine dyes onto a silver halide crystal and transmitting light energy having a wavelength absorbed by the dye to a photosensitive silver halide crystal as a carrier. Is being done.

[0005] These spectral sensitizing dyes must not only extend the photosensitive wavelength range of the silver halide emulsion but also satisfy the following conditions.

1) Spectral sensitization range is appropriate 2) Spectral sensitization efficiency is high 3) Between other additives such as stabilizers, antifoggants, coating aids, high boiling solvents, etc. 4) No adverse effect on the characteristic curve such as fog or gamma change 5) When a silver halide photographic material containing a sensitizing dye is aged (especially high temperature and high humidity) 6) Do not change the photographic performance such as fog during storage under the conditions. 6) The added photosensitive dye does not diffuse to layers in different photosensitive wavelength ranges to cause color turbidity. 7) Develop and fix. However, the spectral sensitizing dyes disclosed heretofore have not yet reached levels that sufficiently satisfy all of these conditions.

[0007] In particular, regarding spectral sensitizing dyes in the infrared region, US Pat. No. 4,536,473 and European Patent No.
Various dyes have been studied as described in the specification. However, these sensitizing dyes did not have a sharp peak in the infrared region, had low-sensitivity absorption, and were inferior in the storage stability of raw samples. In order to improve these disadvantages, Japanese Patent Application Laid-Open
In JP-A-72660, a sensitizing dye in which an unsubstituted alkynyl group or a substituted or unsubstituted alkenyl group is introduced on the nitrogen atom of the azole ring forming the dye has been developed and attempted to be improved.

Further, Japanese Patent Application Laid-Open Nos. 5-45775 and 8-328
In Japanese Patent No. 189, an improvement is introduced by introducing a branched alkyl group and a branched aryl group, and in Japanese Patent Application Laid-Open No. 9-022086, an improvement is attempted by introducing a branched sulfoalkyl group. As for the feeling, it was not sufficiently improved.

In recent years, in order to generate a final image,
A so-called dry photosensitive material that does not use a liquid developer has been desired from the viewpoint of workability with no liquid preparation and environmental protection without waste liquid. However, silver images obtained from heat-developable silver halide photographic materials have lower sensitivity and blackness than silver images obtained from silver halide photographic materials obtained by liquid development. Was required.

On the other hand, in recent years, with the rapid increase in the amount of information,
Large-capacity optical recording media are in the spotlight. In order to manufacture an organic optical recording medium capable of recording information easily and at high density with an inexpensive semiconductor laser, a new long-wavelength absorbing dye that efficiently absorbs light in the red to near-infrared region has been desired.

[0011]

SUMMARY OF THE INVENTION An object of the present invention is to provide a silver halide light-sensitive material which is improved in fog without deteriorating storage stability and which is spectrally sensitized with high sensitivity. is there.

[0012]

The object of the present invention is to provide: (1) a silver halide containing at least one methine dye represented by the following general formula (I) or (II): Photosensitive material.

[0013]

Embedded image [In the formula, Z ₁ represents a group of nonmetallic atoms necessary to form a 5- or 6-membered nitrogen-containing heterocyclic ring together with a nitrogen atom, and may be a single ring or a condensed ring. Good. Z ₂ and Z ₃ each represent a group of nonmetallic atoms necessary to form a condensed carbocyclic or heterocyclic ring. Q represents a group of nonmetallic atoms necessary to form an acidic nucleus. Y ₁ and Y ₂
Is oxygen, sulfur, selenium, tellurium,> N
Represents Rp. Rp represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group. M ₁ ,
M ₂ represents a charge neutralizing counter ion, and n ₁ and n ₂ each represent a number of 0 or more necessary to neutralize the charge in the molecule. L ₁ ,
L ₂ , L ₃ , L ₄ and L ₅ represent a methine group or a substituted methine group. Further, each methine group may form a ring with another methine group, or may form a ring with an auxochrome.

S represents an integer of 0 or 1, t is 0,
Represents an integer of 1, 2, or 3.

A ₁ and A _{2 each} represent an aliphatic group or a substituent represented by the following general formula (III). However, neither A ₁ nor A ₂ is an aliphatic group. A ₃ represents a substituent represented by the following general formula (III).

[0016]

Embedded image(In the general formula (III), R on the secondary carbon atom a is
Represents a group represented by any of the general formulas (i) to (vi),
Rb is represented by any of the general formulas (i) to (vi)
Group or aliphatic, cyano, amino, alkylsulfo
Nil, arylsulfonyl, acyl, acylamino, a
Represents each group of lucoxycarbonyl. m₁Is an integer greater than or equal to 0
Represents A)₁, A_TwoIs a substitution represented by the general formula (III)
When it is a group, A₁And A_TwoRa and Rb in
Each may be the same or different.

[0017]

Embedded image (In the general formulas (i) to (vi), R ₁ , R ₃ , R ₄ , R
₇ , R ₈ and R ₉ represent a hydrogen atom or a substituent, and R ₂ ,
R ₅ , R ₆ and R ₁₀ represent a substituent. (2) A silver halide photographic light-sensitive material containing at least one methine dye represented by the following general formula (Ia) or (II-a).

[0018]

Embedded image [In the formula, Z ₁ represents a group of nonmetallic atoms necessary to form a 5- or 6-membered nitrogen-containing heterocyclic ring together with a nitrogen atom, and may be a single ring or a condensed ring. Good. Z ₂ and Z ₃ each represent a group of nonmetallic atoms necessary to form a condensed carbocyclic or heterocyclic ring. Q represents a group of nonmetallic atoms necessary to form an acidic nucleus. Y ₁ and Y ₂
Is oxygen, sulfur, selenium, tellurium,> N
Represents Rp. Rp represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group. M ₁ ,
M ₂ represents a charge neutralizing counter ion, and n ₁ and n ₂ each represent a number of 0 or more necessary to neutralize the charge in the molecule. L ₁ ,
L ₂ , L ₃ , L ₄ and L ₅ represent a methine group or a substituted methine group. Further, each methine group may form a ring with another methine group, or may form a ring with an auxochrome.

S represents an integer of 0 or 1, t is 0,
Represents an integer of 1, 2, or 3.

A ₁ and A _{2 each} represent an aliphatic group or a substituent represented by the following general formula (III). However, neither A ₁ nor A ₂ is an aliphatic group. A ₃ represents a substituent represented by the following general formula (III).

[0021]

Embedded image(In the general formula (III), R on the secondary carbon atom a is
Represents a group represented by any of formulas (vii) and (viii)
And Rb is represented by any of the general formulas (vii) and (viii).
Groups, or aliphatic, cyano, amino, alkyl
Sulfonyl, arylsulfonyl, acyl, acylamido
And each group of alkoxycarbonyl. m₁Is 0 or more
Represents an integer. A)₁, A_TwoIs a substitution represented by the general formula (III)
When it is a group, A₁And A_TwoRa and Rb in
Each may be the same or different.

[0022]

Embedded image (In the general formulas (vii) to (viii), R ₁₁ and R ₁₂ represent substituents.)] (3) It contains at least one methine dye represented by the following general formula (Ib) A silver halide photographic light-sensitive material comprising:

[0023]

Embedded image [In the formula, Z ₁ represents a group of nonmetallic atoms necessary to form a 5- or 6-membered nitrogen-containing heterocyclic ring together with a nitrogen atom, and may be a single ring or a condensed ring. Good. Z ₂ represents a nonmetallic atom group necessary for forming a condensed carbocyclic or heterocyclic ring. Y ₁ represents an oxygen atom, a sulfur atom, a selenium atom, a tellurium atom, and> NRp. R
p represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group. M ₁ represents a charge neutralizing counter ion, and n ₁ represents a number of 0 or more necessary to neutralize the charge in the molecule. L ₁ , L ₂ and L ₃ represent a methine group or a substituted methine group. Further, each methine group may form a ring with another methine group, or may form a ring with an auxochrome.

S represents an integer of 2 or 3.

A ₁ and A _{2 each} represent an aliphatic group or a substituent represented by the following general formula (III). However, neither A ₁ nor A ₂ is an aliphatic group.

[0026]

Embedded image(In the general formula (III), R on the secondary carbon atom a is
Represents a group represented by any of the general formulas (i) to (vi),
Rb is represented by any of the general formulas (i) to (vi)
Group or aliphatic, cyano, amino, alkylsulfo
Nil, arylsulfonyl, acyl, acylamino, a
Represents each group of lucoxycarbonyl. m₁Is an integer greater than or equal to 0
Represents A)₁, A_TwoIs a substitution represented by the general formula (III)
When it is a group, A₁And A_TwoRa and Rb in
Each may be the same or different.

[0027]

Embedded image (In the general formulas (i) to (vi), R ₁ , R ₃ , R ₄ , R
₇ , R ₈ and R ₉ represent a hydrogen atom or a substituent, and R ₂ ,
R ₅ , R ₆ and R ₁₀ represent a substituent. (4) A silver halide photographic material comprising at least one methine dye represented by the following general formula (Ic).

[0028]

Embedded image [In the formula, Z ₁ represents a group of nonmetallic atoms necessary to form a 5- or 6-membered nitrogen-containing heterocyclic ring together with a nitrogen atom, and may be a single ring or a condensed ring. Good. Z ₂ represents a nonmetallic atom group necessary for forming a condensed carbocyclic or heterocyclic ring. Y ₁ represents an oxygen atom, a sulfur atom, a selenium atom, a tellurium atom, and> NRp. R
p represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group. M ₁ represents a charge neutralizing counter ion, and n ₁ represents a number of 0 or more necessary to neutralize the charge in the molecule. L ₁ , L ₂ and L ₃ represent a methine group or a substituted methine group. Further, each methine group may form a ring with another methine group, or may form a ring with an auxochrome.

S represents an integer of 2 or 3.

A ₁ and A _{2 each} represent an aliphatic group or a substituent represented by the following general formula (III). However, neither A ₁ nor A ₂ is an aliphatic group.

[0031]

Embedded image(In the general formula (III), R on the secondary carbon atom a is
Represents a group represented by any of formulas (vii) and (viii)
And Rb is represented by any of the general formulas (vii) and (viii).
Groups, or aliphatic, cyano, amino, alkyl
Sulfonyl, arylsulfonyl, acyl, acylamido
And each group of alkoxycarbonyl. m₁Is 0 or more
Represents an integer. A)₁, A_TwoIs a substitution represented by the general formula (III)
When it is a group, A₁And A_TwoRa and Rb in
Each may be the same or different.

[0032]

Embedded image (In the general formulas (vii) to (viii), R ₁₁ and R ₁₂ represent substituents.)] (5) Contains at least one methine dye described in any of the above (1) to (4). A heat-developable silver salt photographic light-sensitive material,

Hereinafter, the present invention will be described in detail.

In the conventionally known sensitizing dyes, the higher the efficiency of the formation of aggregates, the higher the spectral sensitizing ability, and as a result, the higher the storage stability and the lower the fog. It is well known that the formation efficiency of the aggregate, particularly the J aggregate, increases as the number of stereoisomers of the sensitizing dye decreases.

The feature of the novel methine dye of the present invention is that the alkyl group on the nitrogen atom of the azole ring forming the dye is branched to suppress the rotation of the methine chain and reduce the number of metastable stereoisomers. By reducing and further selecting the groups represented by the general formulas (i) to (viii) on the secondary carbon atom of the branched group, the intermolecular interaction at the time of forming an aggregate is strengthened. Thus, it is considered that the formation efficiency of the aggregate is increased, and the effect of the present invention can be obtained.

Formulas (I), (II), (Ia), (I
-B), (I-c) , ( in II-a), Z ₁ represents a nonmetallic atomic group necessary for forming a nitrogen-containing heterocyclic 5- or 6-membered together with the nitrogen atom, a single ring Or a condensed ring. Z ₂ and Z ₃ each represent a group of nonmetallic atoms necessary to form a condensed carbocyclic or heterocyclic ring. Q represents a group of nonmetallic atoms necessary to form an acidic nucleus. Y ₁ and Y ₂ represent an oxygen atom, a sulfur atom, a selenium atom, a tellurium atom, and> NRp. Rp represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group. M ₁ and M ₂ represent a charge neutralizing counter ion, and n ₁ and n ₂ represent a number of 0 or more necessary for neutralizing the charge in the molecule. L ₁ , L ₂ , L ₃ , L ₄ and L ₅
Represents a methine group or a substituted methine group. Further, each methine group may form a ring with another methine group,
Also, a ring may be formed with the auxiliary chromophore.

A₁, A_TwoIs an aliphatic group or a general formula (II
Represents a substituent represented by I). However, A₁, A_TwoBoth sides
Is not an aliphatic group, and A₁, A_TwoBoth
When it is a substituent represented by the general formula (III), A₁Passing
And A_TwoR in a and Rb are the same or different
It may be. A_ThreeIs the position represented by the general formula (III)
Represents a substituent.

Hereinafter, the present invention will be described in more detail.

Formulas (I), (II), (Ia), (I
In b), (Ic) and (II-a), the nucleus formed by Z ₁ includes a thiazole nucleus and a thiazole nucleus (for example, 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, 6-methylthiobenzothiazole, 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, a naphthothiazole nucleus (for example, Naft [2
1-d] thiazole, naphtho [1,2-d] thiazole, naphtho [2,3-d] thiazole, 5-methoxyxinaphtho [1,2-d] thiazole, 7-ethoxynaphtho [2,1-d] thiazole , 8-methoxynaphtho [2,
1-d] thiazole, 5-methoxynaphtho [2,3-
d] Thiazole)}, thiazoline nucleus (for example, thiazoline, 4-methylthiazoline, 4-nitrothiazoline),
Oxazole nucleus ｛Oxazole nucleus (eg, oxazole, 4-methyloxazole, 4-nitrooxazole, 5-methyloxazole, 4-phenyloxazole, 4,5-diphenyloxazole, 4-ethyloxazole), benzoxazole nucleus (eg, benzoxazole) Oxazole, 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 (for example, 4,4-dimethyloxazoline), selenazole Nucleus ｛selenazole nucleus (for example, 4-methyl selenazole, 4-nitro selenazole, 4-phenyl selenazole), benzo selenazole nucleus (for example, benzo selenazole, 5-chlorobenzo selenazole, 5-nitrobenzo selenazole) , 5-methoxybenzoselenazole, 5
-Hydroxybenzoselenazole, 6-nitrobenzoselenazole, 5-chloro-6-nitrobenzoselenazole, 5,6-dimethylzenzoselenazole), naphthoselenazole nucleus (for example, naphtho [2,1-d]) Selenazole, naphtho [1,2-d] selenazole)}, selenazoline nucleus (eg, selenazoline, 4-methylselenazoline), tellurazole nucleus ｛tellurazole nucleus (eg, tellurazole, 4-methyltellurazole, 4-phenyltellurazole) Benzotellurazole nucleus (for example, benzotellurazole, 5-chlorobenzotellurazole, 5-methylbenzotellurazole, 5,6-dimethylbenzotellurazole, 6-methoxybenzotellurazole), naphthotellurazole nucleus (for example, Naphtho [2,1-d] tellurazole, naphtho [ , 2-d] tellurazole)}, tellurazoline nucleus (for example, tellurazoline, 4-methyltellurazoline), 3,3-dialkylindolenine nucleus (for example, 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-trimethylindolenine, 3,3-dimethyl-5-chloroindolenine), imidazole nucleus Imidazole nucleus (eg, 1-alkylimidazole, 1-alkyl-4-phenylimidazole, 1-arylimidazole), Benzimidazole nucleus (eg, 1-alkylbenzimidazole, 1-alkyl-5-chlorobenzimidazole, 1-alkyl -5,6-dichlorobenzimidazole, 1-alkyl-5-methoxybenzimidazole,
1-alkyl-5-cyanobenzimidazole, 1-alkyl-5-fluorobenzimidazole, 1-alkyl-5-trifluoromethylbenzimidazole, 1-
Alkyl-6-chloro-5-cyanobenzimidazole, 1-alkyl-6-chloro-5-trifluoromethylbenzimidazole, 1-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, 1-alkylnaphtho [1,2-d] imidazole, 1-arylnaphtho [1,2-d] imidazole) (an alkyl group having 1 to 8 carbon atoms Stuff,
For example, an unsubstituted alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, and a butyl group and a hydroxyalkyl group (for example, a 2-hydroxyethyl group and a 3-hydroxypropyl group) are preferable. Particularly preferred are a methyl group and an ethyl group. The aryl group includes a phenyl group, a halogen (for example, chloro) -substituted phenyl group, an alkyl (for example, methyl) -substituted phenyl group, and an alkoxy (for example, methoxy) -substituted phenyl group. )}, Pyridine nucleus (for example, 2-pyridine, 4-pyridine, 5-methyl-2-pyridine, 3-methyl-4-
Pyridine), quinoline nucleus ｛quinoline nucleus (for example, 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 nucleus (for example, 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] quinoxalin), oxadiazole nucleus, thiadiazole nucleus, tetrazole nucleus and pyrimidine nucleus.

The nucleus formed by Z ₁ 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.

The fused ring formed together with the azole ring by Z ₂ and Z ₃ includes, for example, benzoxazole,
4,5,6,7-tetrahydrobenzoxazole, naphtho [1,2-d] oxazole, naphtho [2,3-
d] oxazole, benzothiazazole, 1,3-dioxolo [4,5-f] benzoxazole, 4,5
6,7-tetrahydrobenzothiazole, naphtho [1,
2-d] thiazole, naphtho [2,3-d] thiazole, 1,3-dioxolo [4,5-f] benzothiazole, benzoselenazole, naphtho [1,2-d] selenazole, benzotellurazole and the like And fused rings.

These condensed rings may have a substituent at any position on the ring, such as a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom). , Trifluoromethyl group, alkoxy group (for example, unsubstituted alkyl group such as methoxy group, ethoxy group, butoxy group, substituted alkoxy group such as 2-methoxyethoxy group, benzyloxy group), hydroxy group, cyano group, aryloxy Groups (eg, substituted phenoxy group, tolyloxy group, etc., unsubstituted aryloxy groups), aryl groups (eg, substituted phenyl group, p-chlorophenyl group, etc., unsubstituted aryl groups), styryl groups, heterocyclic groups (For example, furyl group, thienyl group, etc.), carbamoyl group (for example, carbamoyl group, N-ethylcarbamoyl group, etc.), sulfamoi Group (for example, a sulfamoyl group,
N, N-dimethylsulfamoyl group, etc.), acylamino group (eg, acetylamino group, propionylamino group, benzoylamino group, etc.), acyl group (eg, acetyl group, benzoyl group, etc.), alkoxycarbonyl group (eg, Arbitrary groups such as an ethoxycarbonyl group), a sulfonamide group (eg, a methanesulfonylamide group, a benzenesulfonamide group), a sulfonyl group (eg, a methanesulfonyl group, a p-toluenesulfonyl group), and a carboxy group. Can be

Q represents a group of non-metallic atoms necessary for forming a cyclic group by linking to a keto group adjacent to a methine group-bonding site. The acidic nucleus formed by Q is an acidic ring nucleus used in known merocyanine dyes, and specifically, isoxazolone-based (for example, 2-isoxazoline-5)
Oxazolidine type (for example, 2-thio-oxazolidine-2,4-dione, 2,4-oxazolidinedione, oxazolidin-4-one, 2-oxazoline-4-one, etc.), and thiazolidine type (for example, 2-thio-thiazolidine-2,4-dione, 2,4-thiazolidinedione, thiazolidine-4-one, 2-thiazoline-
4-one etc.), imidazolidine-based (for example, 2-thio-
Imidazolidine-2,4-dione, 2,4-imidazolidindione, imidazolidine-4-one, 2-imidazolidin-4-one, etc., selenazolidine type (for example, 2
-Thio-selenazolidine-2,4-dione, 2,4-selenazolidinedione, selenazolidine-4-one, 2-
Selenazolin-4-one etc.), pyridine type (e.g. tetrahydropyridine-2,4-dione, tetrahydropyridin-2,6-dione etc.), pyrimidine type (e.g.
Tetrahydropyrimidine-2,4-dione, tetrahydropyrimidine-2,6-dione, hexahydropyrimidine-2,4,6-trione, 2-thio-hexahydropyrimidine-2,4,6-trione, etc.), pyrazolines (Pyrazolin-5-one, pyrazolidine-3,5-dione, etc.), carbocyclic systems (eg cyclopentane-2,5-
Dione, cyclohexane-2,6-dione, cyclohexene-2,6-dione, etc.), pyrazolopyridines (for example, pyrazolo [3,4-b] pyridine-3,6-dione etc.), pyrazolopyrimidines ( For example, pyrazolo [1,
5-a] pyrimidin-2-one, etc.), pyrazolo [2,3
-A] imidazol-6-one etc.).

These acidic nuclei may have a substituent at an arbitrary position. Examples of the substituent include an unsubstituted aryl group, a substituted or unsubstituted alkyl group and a heterocyclic group. Group, hydroxy group, alkoxy group, aryloxy group, alkoxycarbonyl group, aryloxycarbonyl group, ureido group, carbamoyl group, carbamoyloxy group, alkoxycarbonylamino group, aryloxycarbonylamino group, cyano group, acyl group, carboxy group , A phosphoryl group, an amide group, an imide group,
Examples thereof include a sulfonyl group, a sulfinyl group, a sulfamoylamino group, a sulfamoyl group, and a sulfonamide group.

M ₁ and M ₂ represent charge neutralizing counter ions, and function to neutralize charges in the molecule. As the counter ion, a cation or an acid anion is used. Specific examples of the cation include a proton, an organic ammonium ion (eg, each ion such as triethylammonium and triethanolammonium), and an inorganic cation (eg, lithium, sodium, calcium). And specific examples of the acid anion include, for example, a halogen ion (for example, chloride ion, bromine ion, iodine ion, etc.), p-toluenesulfonic acid ion, perchlorate ion, and tetrafluoride. Boron ions and the like.

N ₁ and n ₂ are numbers necessary for neutralizing the charge in the molecule, and become 0 when an internal salt is formed and the charge is neutralized.

L₁, L _Two, L_Three, L_Four, L_FiveReplace with
Examples of the substituent of the methine group include, for example,
A substituted alkyl group (for example, a methyl group, an ethyl group,
Ruboxyethyl group), substituted or unsubstituted aryl group
(E.g., phenyl group, o-carboxyphenyl group),
Heterocyclic group (for example, barbituric acid), halogen atom
(Eg, fluorine, chlorine, bromine), alcohol
Xy group (for example, methoxy group, ethoxy group), amino group
(For example, N, N-diphenylamino group, N-methyl-
N-phenylamino group, N-methylpiperazino group),
Alkylthio group (for example, methylthio group, ethylthio group)
And the like.

Also, L₁, L _Two, L_Three, L_Four, L_FiveRepresented by
The substituent of a substituted methine group forms a ring with another methine group.
And it may form a ring with an auxiliary chromophore. Ma
Further, these rings may further have a substituent. This
These substituents include a substituted or unsubstituted alkyl group
(For example, methyl, ethyl, propyl, chloro
Benzyl group), substituted or unsubstituted aryl
Groups (eg, phenyl group, p-chlorophenyl group), c
Halogen atom (eg, chlorine atom, fluorine atom), hydro
Xy group, alkoxy group (for example, methoxy group, ethoxy
Group) and other monovalent and divalent groups.

Next, A ₁ , A ₂ and A ₃ will be described.

As the aliphatic group represented by A ₁ and A ₂ , a linear or branched alkyl group (eg, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, an iso-
Pentyl group, 2-ethyl-hexyl group, octyl group, decyl group, etc.), alkenyl group (eg, 2-propenyl group, 3-butenyl group, 1-methyl-3-propenyl group,
3-pentenyl group, 1-methyl-3-butenyl group, 4-
Hexenyl group) and an aralkyl group (eg, benzyl group, phenethyl group, etc.).

In the general formula (III) represented by A ₁ , A ₂ and A ₃ , Ra is on a secondary carbon atom, and
It is a group represented by (vi) or (vii) or (viii).

In the groups represented by formulas (i) to (viii), R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ ,
R ₁₀ , R ₁₁ and R ₁₂ will be described.

As the substituents represented by R ₁ and R ₉ , an alkyl group (for example, methyl group, ethyl group, n-propyl group, n-pentyl group, etc.), an aryl group (phenyl group, etc.)
Is mentioned. Preferred as R ₁ and R ₉ are a hydrogen atom.

R_Two, R_Five, R₆, R _Ten, R ₁₁, R₁₂Represented by
Examples of the substituent include an alkyl group (for example, a methyl group,
Ethyl group, n-propyl group, n-pentyl group, isobutyl
Group), an aryl group (eg, a phenyl group), an ara
Alkyl group (for example, benzyl group, phenethyl group, etc.),
Lucenyl group (for example, 3-butenyl group, 2-propenyl
And the like).

As the substituent represented by R ₃ , R ₄ , R ₇ , and R ₈ , an alkyl group (for example, a methyl group, an ethyl group, an n-
Propyl group, n-pentyl group, etc.) and aryl group (phenyl group, etc.). It is preferable that one of R ₃ and R ₄ or R ₇ and R ₈ is a hydrogen atom.

R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ ,
The substituents represented by R ₈ , R ₉ , R ₁₀ , R ₁₁ , R ₁₂ , R _b , R _d , and R _f may further have a substituent, and these substituents include, for example, Halogen atom (eg, fluorine atom, chlorine atom, bromine atom, etc.), alkoxy group (eg, methoxy group, ethoxy group, etc.), aryloxy group (eg, phenoxy group, p-tolyloxy group, etc.), cyano group, carbamoyl group (For example, carbamoyl group, N
-Methylcarbamoyl group, N, N-tetramethylenecarbamoyl group, etc.), sulfamoyl group (eg, sulfamoyl group, N, N-3-oxapentamethyleneaminosulfonyl group, etc.), methanesulfonyl group, alkoxycarbonyl group (eg, ethoxy group) Carbonyl group, butoxycarbonyl group, etc.), aryl group (eg, phenyl group, carboxyphenyl group, etc.), acyl group (eg, acetyl group, benzoyl group, etc.), acylamino group (eg, acetylamino, benzoylamino group, etc.), And a sulfonamide group (for example, a methanesulfonamide, a butanesulfonamide group, and the like).

As the group represented by Rb, Ra is
Group represented by an aliphatic group (A₁, A_TwoWith the aliphatic groups described in
It is synonymous. ), Cyano group, amino group, alkyl sulfo
Nyl group, arylsulfonyl group, acyl group (acetyl
Group, benzoyl group, etc.), acylamino group (acetylamino
Groups, benzoylamino groups, etc.), alkoxycarbonyl
Groups. The alkyl component of these groups, aryl
The component and the alkoxy component include the above R_Two, R_Five, R₆,
R _Ten, R ₁₁, R₁₂Alkyl in the substituent represented by
Group, an aryl group, and an alkoxy group.

A preferred group represented by Rb is R
a and an aliphatic group represented by a.

M ₁ represents an integer of 0 or more. m ₁ is preferably ₁ , 2 or 3. More preferably, 1
It is.

The compounds represented by the following general formulas (I), (II) and (I-
Specific examples of a), methine dyes represented by (Ib), (Ic) and (II-a) (hereinafter referred to as methine dyes of the present invention) are shown below. It is not limited to this.

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The methine dye of the present invention can be prepared by a known method described in, for example, FM Haama, “Cyanine Soybeans and Related Compounds” (published by Inter Science Publishers, 1964). And can be easily synthesized.

Hereinafter, specific synthesis examples will be given, but other methine dyes of the present invention can be synthesized by the same method. <Synthesis of Dye IA-1> 12.0 g of 2-methyl-5-chloro-benzothiazole and 9.2 g of 1-iodo-2-ethoxybutane were added to 100 ml of m-cresol, and reacted by heating at 140 ° C. for 2.5 hours. Thereafter, acetone was added, and the obtained crystals were recrystallized from methanol to obtain 15.0 g of (Intermediate 1).

(Intermediate 1) 1.2 g of triethyl orthopropionate 0.48 g of triethylamine 0.4 g of pyridine 1
The mixture was added to 0 ml and heated under reflux for 90 minutes. The reaction mixture was poured into diisopropyl ether to precipitate, and the supernatant phase was decanted. Add a small amount of ethanol to the precipitate to dissolve it,
The crystals were left to crystallize in a refrigerator. The crystals were recrystallized from methanol to give 0.32 g of a dye [λmax = 554 nm / ε.
= 1.34 × 10 ⁵ (ethanol)].

The product was identified as the target product (IA-1) by NMR spectrum and mass spectrum.

The methine dye of the present invention can be added to a silver halide emulsion by a conventionally known method. For example, JP-A-50-80826, the protonation dissolution addition method described in JP-A-50-80827, U.S. Pat.No. 3,822,135, and dispersed together with a surfactant described in JP-A-50-11419. Addition method, U.S. Pat.No.3,676,147, 3,469,987
No. 4,247,627, JP-A-51-59942, JP-A-53-16624, JP-A-53-102732, JP-A-53-1027.
No. 33, a method of dispersing and adding to a hydrophilic substrate described in JP-A No. 53-137131, a method of adding as a solid solution described in East German Patent No. 143,324, a research method
JP-A-21,802, JP-B-50-40659, JP-A-59-148
Water-soluble solvents for dissolving dyes represented by Japanese Patent No. 053 (for example, methanol, ethanol, propyl alcohol,
Low-boiling solvents such as acetone and fluorinated alcohol, and high-boiling solvents such as dimethylformamide, methylcellosolve and phenylcellosolve) alone or in the form of a solution in which they are dissolved in a mixed solvent. In the emulsion.

The methine dye of the present invention may be added at any stage during the emulsion production process from physical ripening to completion of chemical ripening, but is added between physical ripening and completion of chemical ripening. Is preferred. The addition of the methine dye of the present invention during physical ripening, or prior to the addition of the chemical sensitizer in the chemical ripening step, or immediately after the addition of the chemical sensitizer, has the effect of obtaining higher spectral sensitivity. Is preferable.

The addition amount of the methine dye of the present invention varies greatly depending on the conditions used and the type of emulsion, but the coverage of the monomolecular layer on the surface of the photosensitive grains in the silver halide emulsion is 4%.
It is preferable to set the addition amount to be 0% or more and 90% or less, and it is more preferable to set the coverage of the monomolecular layer in the range of 50% to 80%.

The monolayer coverage is relatively determined based on the amount of saturated adsorption when an adsorption isotherm is created at 50 ° C., as an amount corresponding to a coverage of 100%.

In the silver halide emulsion according to the present invention, the methine dye of the present invention and a conventionally known sensitizing dye may be used in combination. The ratio of using both of them can be arbitrarily selected in an amount that gives a desired sensitivity. Further, a dye which does not itself have a spectral sensitizing effect, or a compound which does not substantially absorb visible light, and which contains a supersensitizer which enhances the sensitizing effect of the sensitizing dye may be contained in the emulsion. Good. Conventionally known sensitizing dyes include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes, hemioxonol dyes, oxonol, merostyril, and polymethine dyes containing streptocyanin. Can be mentioned.

The silver halide emulsion of the present invention can be obtained by sulfur sensitization,
Chalcogen sensitization such as selenium sensitization and tellurium sensitization, reduction sensitization, and noble metal sensitization can be used alone or in appropriate combination for chemical sensitization. The conditions of the chemical sensitization step, for example, pH, pAg, temperature, time and the like are not particularly limited, and can be performed under conditions generally performed in the art.

For the sulfur sensitization, an unstable sulfur compound can be used, and specific examples thereof include 1,3-diphenylthiourea, triethylthiourea, and 1-ethyl-3- (2-thiazolyl) thiourea. It is preferable to use thiourea derivatives, rhodanine derivatives, dithicarbamic acids, polysulfide organic compounds, thiosulfates, elemental sulfur and the like.
In addition, as the elemental sulfur, α-sulfur belonging to the orthorhombic system is preferable.

In addition, US Pat. No. 1,574,944,
2,410,689, 2,278,947, 2,728,
No. 668, 3,501,313, 3,656,955, West German Application Publication (OLS) 1,422,869, JP-A-56-24937, JP-A 55-45016, etc. A sensitizer can be used.

Unstable selenium compounds can be used for selenium sensitization. For example, selenium sensitization is described in US Pat. Nos. 1,574,944, 1,602,592,
623,499 specification, JP-A-60-150046, JP-A-4-25
Nos. 832, 4-109240 and 4-147250.

Useful selenium sensitizers include colloidal selenium metal, isoselenocyanates (eg, allyl isoselenocyanate, etc.), and selenoureas (eg, N,
N-dimethylselenourea, N, N, N'-triethylselenourea, N, N, N'-trimethyl-N'-heptafluoropropylselenourea, N, N, N'-trimethyl-N'-heptafluoropropyl Carbonylselenourea, N, N, N'-trimethyl-N'-4-nitrophenylcarbonylselenourea, etc., selenoketones (eg, selenoacetone, selenoacetophenone, etc.), selenoamides (eg, selenoacetamide, N, N- Dimethylselenobenzamide, etc.), selenocarboxylic acids and selenoesters (for example, 2-selenopropionic acid,
Methyl-3-selenobutyrate, etc.), selenophosphates (eg, tri-p-triselenophosphate, etc.), selenides (dimethyl selenide, triphenylphosphine selenide, pentafluorophenyl-).
Diphenylphosphine selenide).
Particularly preferred selenium sensitizers are selenoureas, selenamides, and selenides.

Specific examples of the techniques for using these selenium sensitizers are described, for example, in US Pat. Nos. 1,574,944 and 1,602,559.
No. 92, No. 1,623,499, No. 3,297,466, No. 3,297,447, No. 3,320,069, No. 3,
408,196, 3,408,197, 3,442,653
No. 3,420,670, No. 3,591,385, French Patent No. 2,693,038, No. 2,093,209, Japanese Patent Publication No. 52-34491, No. 52-34492,
No. 53-295, No. 57-22090, JP-A-59-180536, No. 59-185330, No. 59-181337, No. 59-1
No. 87338, No. 59-192241, No. 60-150046, No. 60-151637, No. 61-246738, JP-A-3-
No. 4221, No. 3-24537, No. 3-111838, No. 3
Nos. -116132, 3-148648, 3-237450, 4-16838, 4-25832, 4-32831, 4-96059, 4- No. 109240, 4-14073
No. 8, No. 4-140739, No. 4-147250, No. 4-1
No. 84331, No. 4-190225, No. 4-91729,
No. 4-195035, UK Patent No. 255,846, 86
1,984, HESpencer et al., Journal of Photograp
hic science, vol. 31, 158-169 (1983).

An unstable tellurium compound can be used for tellurium sensitization. As for tellurium sensitizers and sensitization methods, for example, U.S. Patent Nos. 1,623,499 and 3,320,0
No. 69, No. 3,772,031, No. 3,531,289, No. 3,655,394, British Patent No. 235,211, No. 1,121,469, No. 1,295,462, No. 1,
No. 396,696, Canadian Patent No. 800,958, and JP-A-4-20464. Specific examples of tellurium sensitizers include phosphine tellurides (eg, butyl-diisopropylphosphine telluride, tributylphosphine telluride, etc.) and telluroureas (eg, N, N-dimethylethylene tellurourea). , N, N-
Diphenylethylene tellurourea), telluramides and the like.

For precious metal sensitization, Research Disclosure Magazine 3
Noble metal salts such as gold, platinum, palladium, iridium and osmium described in Vol. 07, No. 307105, etc. can be used. Useful gold sensitizers include, for example, chloroauric acid, gold thiosulfate, gold thiocyanate, U.S. Pat.
Organic gold compounds disclosed in JP-A-6,5,049,485, JP-B-44-15748, JP-A-1-47537, JP-A-4-70650 and the like can be mentioned. The noble metal sensitization is preferably combined with another chalcogen sensitization.

In the various sensitization methods described above, the method of adding the sensitizer can be selected according to the properties of the compound used.
The method disclosed in Japanese Patent Application Laid-Open No. 4-140739 discloses a method of dissolving in water or an organic solvent such as methanol singly or in a mixed solvent, or adding the solution by premixing with a gelatin solution. Alternatively, it may be added in the form of an emulsified dispersion of a mixed solution with an organic solvent-soluble polymer.

The silver halide emulsion of the present invention can be subjected to chemical sensitization in the presence of a silver halide solvent. As silver halide solvents that can be used, U.S. Pat.
No. 271,157, No. 3,574,628, JP-A-54-101
No. 9, JP-A-54-158917, organic thioethers described in JP-A-54-158917, JP-A-53-82408, JP-A-55-77737,
Thiourea derivatives described in JP-A-55-2982 and the like; silver halide solvents having a thiocarbonyl group sandwiched between an oxygen or sulfur atom and a nitrogen atom described in JP-A-53-144319; Examples thereof include imidazoles, sulfites, thiocyanates and the like described in JP-A-54-100717.

The reduction sensitization is carried out according to Research Disclosure Magazine 307
For example, a reducing compound described in Vol. 307105, JP-A-7-78685, or the like can be used. Specific examples of these reducing compounds include aminoiminomethanesulfinic acid (also known as thiourea dioxide), borane compounds (eg, dimethylamine borane, etc.), hydrazine compounds (eg, hydrazine, p-tolylhydrazine, etc.), Examples include polyamine compounds (eg, diethylenetriamine, triethylenetetramine, etc.), stannous chloride, silane compounds, reductones (eg, ascorbic acid, etc.), sodium sulfite, aldehyde compounds, hydrogen gas, and the like. Further, Japanese Patent Application Nos. 8-277938, 8-251486, and 8-182035 can be subjected to reduction sensitization in an atmosphere containing a high pH or excess silver ion as disclosed in the specification of JP-A-8-182035. Good.

The silver halide emulsion used in the present invention is:
Various antifoggants and stabilizers can be contained for the purpose of preventing fogging during the production process, storage or processing of the photosensitive material and stabilizing photographic performance. As these antifoggants and stabilizers, specifically, for example, tetrazaindenes, azoles, benzothiazolium salts, nitroindazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, Mercaptothiazoles, mercaptobenzimidazoles, aminotriazoles, benzotriazoles, nitrobenzotriazoles, mercaptotetrazole, mercaptopyrimidines, mercaptotriazines, thioketo compounds, and also benzenethiosulfinic acid, benzenesulfinic acid, benzenesulfone Examples thereof include acid amide, hydroquinone derivative, aminophenol derivative, gallic acid derivative, and ascorbic acid derivative.

Various photographic additives can be used in the silver halide light-sensitive material of the present invention. These photographic additives include, for example, Research Disclosure (RD) No. 17643 (December 1978) and No. 1
8716 (November 1979) and No. 308119
(December 1989). The photographic additives and the locations described in these three RDs are listed below.

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The silver halide photographic light-sensitive material of the present invention may contain a developing agent, for example, aminophenol, ascorbic acid, pyrocatechol, hydroquinone, phenylenediamine or 3-pyrazolidone in the emulsion layer or other layers. .

The support which can be used in the silver halide photographic light-sensitive material of the present invention includes, for example, the aforementioned RDN
and o.17643, page 28, and RD No.308119, page 1009.

As a binder for the emulsion layer or other layers, gelatin is advantageously used. These emulsion layers and other hydrophilic colloid layers can be hardened and can contain a plasticizer and a dispersion (latex) of a water-insoluble or poorly soluble synthetic polymer.

When the silver halide photographic material of the present invention is a color photographic material, a coupler is used in the emulsion layer.

Further, a development accelerator, a bleaching accelerator, a developer, and a coupling agent having an effect of color correction with a colored coupler, a competitive coupler, and an oxidized form of a developing agent are coupled.
Use of compounds that release photographically useful fragments such as silver halide solvents, toning agents, hardeners, fogging agents, antifoggants, chemical sensitizers, spectral sensitizers and desensitizers. it can.

In the silver halide photographic light-sensitive material of the present invention,
Auxiliary layers such as a filter layer, an antihalation layer, and an antiirradiation layer can be provided. In these layers and / or the emulsion layers, dyes which flow out of the light-sensitive material or are bleached during the development processing may be contained.

In the silver halide photographic light-sensitive material of the present invention,
Matting agents, lubricants, image stabilizers, surfactants, color fogging inhibitors, development accelerators, development retarders and bleaching accelerators can be added.

As the support, paper laminated with polyethylene or the like, polyethylene terephthalate film, baryta paper, cellulose triacetate or the like can be used.
An undercoat layer may be provided on the surface of the support to improve the adhesion of the coating layer, or corona discharge, ultraviolet irradiation, or the like may be applied.

In order to obtain a dye image using the silver halide photographic light-sensitive material of the present invention, a generally known color photographic processing is performed after exposure.

Next, the heat-developable silver halide photographic material of the present invention will be described.

In the present invention, the photosensitive silver halide used in the heat-developable silver salt photographic light-sensitive material can be prepared by any method known in the field of photographic technology such as a single jet method and a double jet method, for example, using a Lippmann emulsion. The emulsion is prepared in advance as an emulsion such as an emulsion prepared by an ammonia method, a thiocyanate or a thioether-ripened emulsion, and then mixed with other components for use in the present invention.

In this case, in order to sufficiently bring the organic silver salt into contact with the photosensitive silver halide, for example, as a protective polymer for preparing a photosensitive silver halide emulsion, US Pat.
No. 6,564, 3,706,565, 3,713,833, 3,748,143, means using a polymer other than gelatin such as polyvinyl acetal described in British Patent No. 1,362,970, British Patent No. 1,354,18
Means for enzymatically decomposing gelatin used in a light-sensitive silver halide emulsion as described in US Pat. No. 6,697,098, or interfacial light-sensitive silver halide grains as described in U.S. Pat.No. 4,076,539. By preparing in the presence of the activator, various means such as a means for omitting the use of the protective polymer can be applied.

The photosensitive silver halide used in the heat-developable silver salt photographic light-sensitive material of the present invention may also contain a halogenating agent and an organic silver salt-forming component, as described in British Patent 1,447,454. By injecting a silver ion solution into a mixed solution in which the organic silver salt is coexisted, the organic silver salt can be generated almost simultaneously.

As still another method, a photosensitive silver halide-forming component is allowed to act on a previously prepared solution or dispersion of an organic silver salt or a sheet material containing an organic silver salt to convert a part of the organic silver salt. There is also a method of converting to light-sensitive silver halide. The photosensitive silver halide thus formed effectively contacts the organic silver salt and exhibits a preferable action.
The above-mentioned photosensitive silver halide forming component is a compound capable of forming a photosensitive silver halide by reacting with an organic silver salt.
Which compounds correspond to photosensitive silver halide-forming components and are effective can be determined by mixing an organic silver salt and the compound to be tested, heating if necessary, and then applying X-ray diffraction to the silver halide. It can be determined by examining the presence of a unique diffraction peak.

The photosensitive silver halide forming components confirmed to be effective by such a test include inorganic halides, onium halides, halogenated hydrocarbons, N-halogen compounds, and other halogen-containing compounds. For specific examples thereof, U.S. Pat.No. 4,009,039, 3,457,075, 4,003,749,
The details are described in British Patent Nos. 1,498,956 and 1,498,956 and JP-A-53-27027 and JP-A-53-25420, examples of which are shown below.

(1) Inorganic halide: for example, MX _n
(M represents H, NH ₄ and a metal atom, X represents Cl, Br and I, n represents 1 when M is H and NH ₄ , and M represents When it is a metal atom, it represents its valence, for example, lithium, sodium, potassium, cesium, magnesium,
Calcium, strontium, barium, zinc, cadmium, mercury, tin, antimony, chromium, manganese, iron,
Cobalt, nickel, rhodium, cerium, etc.). Halogen molecules such as bromine water are also effective.

(2) Onium halides: quaternary ammonium halides such as trimethylphenylammonium bromide, cetylethyldimethylammonium bromide and trimethylbenzylammonium bromide; and quaternary phosphoniums such as tetraethylphosphonium bromide Halide; tertiary sulfonium halide such as trimethylsulfonium iodide;

(3) Halogenated hydrocarbons: for example, iodoform, bromoform, carbon tetrabromide, 2-bromo-
2-methylpropane and the like.

(4) N-halogen compound: For example, N-halogen compound
Chlorosuccinimide, N-bromosuccinimide, N
-Bromophthalimide, N-bromoacetamide, N-
Iodosuccinimide, N-bromophthalazon, N-bromooxazolinone, N-chlorophthalazone, N-bromoacetanilide, N, N-dibromobenzenesulfonamide, N-bromo-N-methylbenzenesulfonamide, 1,3-dibromo -4,4-dimethylhydantoin, N-bromourazole and the like.

(5) Other halogen compounds contained: For example, triphenylmethyl chloride, triphenylmethyl bromide, 2-bromoacetic acid, 2-bromoethanol, benzophenone dichloride and the like can be mentioned.

These photosensitive silver halide forming components include:
A small amount is used stoichiometrically with respect to the organic silver salt. Usually, the range is from 0.001 mol to 0.7 mol, preferably from 0.03 mol to 0.1 mol, per 1 mol of the organic silver salt.
Set to 5 moles. The photosensitive silver halide forming component is 2
The above may be used in combination.

Various conditions such as a reaction temperature, a reaction time and a reaction pressure in the step of converting a part of the organic silver salt to the photosensitive silver halide using the photosensitive silver halide forming component may be selected from a wide range. The reaction temperature can be appropriately selected and set according to the purpose of the reaction.
C., the reaction time is preferably 0.1 second to 72 hours, and the reaction pressure is preferably set to the atmospheric pressure. This reaction is preferably performed in the presence of a polymer used as a binder described below. The amount of the polymer used at this time is 0.01 to 100 parts by weight, preferably 0.1 to 10 parts by weight, per 1 part by weight of the organic silver salt.

The light-sensitive silver halide prepared by the above-mentioned various methods may be, for example, a sulfur-containing compound, a gold compound, a platinum compound, a palladium compound, a silver compound, a tin compound, a chromium compound or a combination thereof.
Can be chemically sensitized. For the procedure of this chemical sensitization, for example, US Pat. No. 4,036,650, British Patent No. 1,518,850, JP-A-51-22430,
Nos. 78319 and 51-81124. Further, in an embodiment in which a part of the organic silver salt is converted into photosensitive silver halide by a photosensitive silver halide forming component, a low molecular weight amide compound as described in U.S. Pat. By doing so, sensitization can be achieved.

The organic silver salt used in the heat-developable silver salt photographic light-sensitive material of the present invention includes: (1) a silver salt of an organic compound having an imino group: for example, a silver salt of a saccharin or a silver salt of a benzotriazole , Silver salts of phthalazinones, silver salts of benzoxadiones, silver salts of imidazoles, silver salts of tetraazaindenes, silver salts of pentaazaindenes, and the like. (2) Organic compounds having a mercapto group or a thione group: For example, silver salts of 2-mercaptobenzoxazoles, silver salts of mercaptooxadiazoles, silver salts of 2-mercaptobenzothiagals, silver salts of 2-mercaptobenzimidazoles, silver salts of 2-mercaptobenzimidazoles , 3-mercapto-4-phenyl-1,
Silver salts of 2,4-triazoles and the like (3) Silver salts of organic compounds having a carboxyl group: For example, silver salts of aliphatic carboxylic acids, silver salts of aromatic carboxylic acids (for example, silver benzoate, silver phthalate) , Silver phenylacetate, silver salt of 4'-n-octadecyloxydiphenyl-4-carboxylic acid, etc.).

For more specific examples of these organic silver salts and examples of organic silver salts other than those described above, see, for example, US Pat. Nos. 3,457,075, 3,549,379, and 3,785,
No. 830, No. 3,933,507, No. 4,009,039 and British Patent No. 1,230,642 or JP-A-50-
No. 93139, No. 50-99719, No. 52-141222 and No. 53-36224, and are also used in the present invention by appropriately selecting from these known organic silver salts. can do. For example, when a silver halide or silver dye photosensitive complex is used as a photocatalyst, a material which is relatively stable to light is selected from the above known organic silver salts. Preferable examples thereof include silver salts of long-chain aliphatic carboxylic acids having 10 to 40 carbon atoms, particularly 18 to 33 carbon atoms. Specific examples thereof include silver laurate, silver myristate, silver palmitate, and silver stearate. , Silver arachidate, silver behenate, silver glycerate, silver pentacosanoate, silver cellotate, silver heptacosanoate, silver montanate, silver melissinate, silver laccelate and the like.

Such an organic silver salt is described, for example, in US Pat.
457,075, 3,458,544, 3,700,458
No. 3,839,049, No. 3,960,908, British Patent No. 1,173,426 or JP-A-49-5262.
No. 6, No. 51-122011, and No. 52-14122, and can be synthesized by various known methods. In particular, when forming an organic silver salt, the polymers described in U.S. Pat.No. 3,700,458 or JP-A-53-32015, and U.S. Pat.
The presence of the metal-containing compound described in JP-A-13224 is preferable because the grain morphology, grain size and / or photographic properties of the organic silver salt can be improved. The preferable range of the use amount of these coexisting components is 0.1 g to 1000 g, particularly 1 g to 500 g for polymers, and 1 g to 500 g for 1 mol of the produced organic silver salt.
It is 0 ^-6 mol to 10 ^-1 mol.

As the organic silver salt, those having a major axis of 0.01 μm to 10 μm, particularly preferably 0.1 μm to 5 μm are preferably used.

In the present invention, the organic silver salt is 1 m ² of the support.
It is used in a range of 0.1 g to 4 g, preferably 0.2 g to 2.5 g in terms of silver amount. This range is a range of an amount necessary and sufficient to give an appropriate image density, and if used below this range, the pixel density becomes insufficient, and even if used more than this range, the image density does not increase, On the contrary, the cost increases.

A reducing agent is used in the heat-developable silver salt photographic light-sensitive material of the present invention. Examples of these reducing agents include reducing agents commonly used in heat-developable silver salt photographic materials.
For example, monophenols, polyphenols having two or more phenol groups, mononaphthols, bisnaphthols, polyhydroxybenzenes having two or more hydroxyl groups, polyhydroxynaphthalenes having two or more hydroxyl groups, ascorbin Acids, 3-pyrazolidones,
Pyrazolin-5-ones, pyrazolines, phenylenediamines, hydroxylamines, hydroquinone monoethers, hydroxamic acids, hydrazides, amide oximes, N-hydroxyureas and the like. More specifically, for example, U.S. Patent No. 3,615,533,
3,679,426, 3,672,904, 3,751,
No. 252, No. 3,782,949, No. 3,801,321, No. 3,794,488, No. 3,893,863, No.
3,887,376, 3,770,448, 3,819,38
No. 2, No. 3,773,512, No. 3,839,048, No. 3,887,378, No. 4,009,039, No. 4,
No. 021,240, British Patent No. 1,486,148 or Belgian Patent No. 786,086 and JP-A-50-36143
No. 50-36110, No. 50-116023, No. 50-361
No. 99719, No. 50-140113, No. 51-51933,
JP-A-51-23721, JP-A-52-84727 or JP-B-51
There is a reducing agent specifically exemplified in JP-35851-A, and the present invention can be appropriately selected from such known reducing agents and used. As a selection method, it is considered that the simplest method is to actually prepare a heat-developable photographic light-sensitive material and evaluate the photographic properties to determine the superiority of the reducing agent used.

When silver aliphatic carboxylate is used as the organic silver salt, a preferable reducing agent is a polyphenol in which two or more phenol groups are linked by an alkylene group or sulfur, particularly a hydroxy-substituted position of the phenol group. At least one alkyl group (eg, methyl group, ethyl group, propyl group, t
Polyphenols in which two or more phenol groups substituted by an -butyl group, a cyclohexyl group, or an acyl group (eg, an acetyl group, a propionyl group, etc.) are linked by an alkylene group or sulfur (for example, 1,1
-Bis (2-hydroxy-3,5-dimethylphenyl)
-3,5,5-trimethylhexane, 1,1-bis (2
-Hydroxy-3-t-butyl-5-methylphenyl)
Methane, 1,1-bis (2-hydroxy-3,5-di-
t-butylphenyl) methane, 2,6-methylenebis (2-hydroxy-3-t-butyl-5-methylphenyl-4-methylphenol, 6,6'-benzylidene-
Bis (2,4-di-t-butylphenol), 6,6 ′
-Penzylidene-bis- (2-t-butyl-4-methylphenol), 6,6'-pendylidene-bis (2,4
-Dimethylphenol), 1,1-bis (2-hydroxy-3,5-dimethylphenyl) -2-methylpropane, 1,1,5,5-tetrakis (2-hydroxy-
3,5-dimethylphenyl) -2,4-ethylpentane, 2,2-bis (4-hydroxy-3,5-dimethyl) propane, 2,2-bis (4-hydroxy-3,5
-Di-t-butylphenyl) propane and the like.
3,589,903, 4,021,249 or British Patent 1,486,148 and JP-A-51-51933,
No. 50-36110, No. 50-116023, No. 52-84727 or Japanese Patent Publication No. 51-35727) (polyphenol compounds described in US Pat. No. 3,672,904). -Naphthols (for example, 2,2'-
Dihydroxy-1,1'-binaphthyl, 6,6'-dibromo-2,2'-dihydroxy-1,1'-binaphthyl, 6,6'-dinitro-2,2'-dihydroxy-
1,1'-binaphthyl, bis (2-hydroxy-1-naphthyl) methane, 4,4'-dimethoxy-1,1'-dihydroxy-2,2'-binaphthyl, etc.); U.S. Pat.
Sulfonamidophenols or sulfonamidonaphthols described in 3,801,321 (e.g., 4-benzenesulfonamidophenol, 2-benzenesulfonamidophenol, 2,6-dichloro-)
4-benzenesulfonamidophenol, 4-benzenesulfonamidonaphthol, etc.).

The amount of the reducing agent used in the heat-developable silver salt photographic light-sensitive material of the present invention varies depending on the kind of the organic silver salt, the reducing agent, and other additives. 0.05 to 10 mol, preferably 0.1 to 10 mol, per mol.
1-3 moles are suitable. Moreover, within the range of this amount, two or more of the above-mentioned reducing agents may be used in combination. The reducing agent is incorporated in the heat-developable silver halide photographic material.

In the heat-developable silver salt photographic light-sensitive material of the present invention, it is desirable to use an additive (hereinafter, referred to as a color toning agent) called a color tone, a color tone imparting agent or an activator toner together with the above-mentioned components. . The color tone agent has a function of participating in the process of forming a redox silver (image) between the organic silver salt and the reducing agent to make the resulting image dark, particularly black.

As the color toning agent, a great variety of compounds are already known, and most of them are compounds having an imino group, a mercapto group or a thione group. An appropriate color tone agent is selected according to the type of the organic silver salt and the reducing agent to be used from among them. The phthalazinones ( For example, phthalazinone, 2-
Acetylphthalazinone, 2-carbamoylphthalazinone, etc.), 2-pyrazolin-5-ones (eg, 3-methyl-2-pyrazolin-5-one), quinazolinones (eg, quinazolinone, 4-methylquinazolinone) ), Pyrimidines (eg, 6-methyl-2,4-dihydroxypyrimidines), 1,2,5-triazines (eg, 3-methyl-4,6-dihydroxy-).
1,2,5-triazine, etc.), phthalazinediones (eg, phthalazinedione), cyclic imides (eg, succinimides, phthalimides or urazoles, benzoxazinediones, benzothiazinediones, Heterocyclic compounds having an imino group such as phthalimides). These color tones may be used in combination of two or more, for example, benzoxazine diones in combination with phthalazinone as described in JP-A-53-1020 and JP-A-53-55115, By using benzothiazine diones or phthalimides in combination, it is possible to prevent deterioration of the color tone effect due to storage under high temperature and high humidity.

Further, as described in US Pat. Nos. 3,847,612 and 3,994,732, phthalic acid, naphthoic acid or phthalamidic acid can be used in combination with imidazoles or phthalazines as color toning agents. .

When a toning agent is used, it is used in an amount of 0.0001 mol to 2 mol per mol of the organic silver salt.
A range from 0.0005 mol to 1 mol is preferred.

Each component used in the heat-developable silver salt photographic light-sensitive material of the present invention is dispersed in at least one kind of colloid as a binder. Suitable binders include hydrophobic polymer materials, and in some cases, hydrophilic polymer materials may be used in combination. Also,
A hydrophilic polymer material can be used alone.

The polymer material used as the binder is preferably one which gives a transparent or translucent and colorless, white or light-colored layer or layer when applied or cast.

As the binder, for example, natural polymer materials such as proteins such as gelatin, cellulose derivatives, polysaccharides such as dextran or gum arabic, and synthetic polymer materials are used. Among them, polyvinyl butyral, Polyvinyl acetate, ethyl cellulose, vinylidene chloride-vinyl chloride copolymer,
Polymethyl methacrylate, vinyl chloride-vinyl acetate copolymer, cellulose acetate butyrate, gelatin or polyvinyl alcohol is particularly preferably used. Two or more of these polymer materials may be used in combination.

The binder is used in an amount sufficient to support the components dispersed therein, that is, in an effective range as the binder.

The range can be appropriately determined by those skilled in the art. As an example, when at least an organic silver salt is dispersed and supported, the weight ratio to the organic silver salt is 10: 1 to 1:10, particularly 4: 1. Used in the range of 1 to 4.

In the composition containing each component of the heat-developable silver salt photographic light-sensitive material of the present invention, when the binder used gives a film having a self-supporting property, the respective components can be used according to a known casting method. Although the film may be formed as a supported film, it is usually applied on various supports selected from a wide range of materials in one or more divided layers to complete the photothermographic material. Examples of the material of the support include various polymer materials, glass, wool cloth, cotton cloth, paper, and metal (for example, aluminum). When used as an information recording material, the material is flexible from the viewpoint of handling. What can be processed into a sheet or a roll is suitable.

Accordingly, as a support used in the heat-developable silver salt photographic light-sensitive material of the present invention, a plastic film (for example, a cellulose acetate film, a polyester film, a polyethylene terephthalate film, a polyamide film, a polyimide film, a triacetate film or a polycarbonate film) Or paper (other than ordinary paper, for example, photographic base paper, printing base paper such as coated paper or art paper, baryta paper, resin (coated) paper, as described in Belgian Patent No. 784,615). Paper sized with a suitable polysaccharide, a pigment paper containing a pigment such as titanium dioxide, or a paper sized with polyvinyl alcohol).

[0145]

EXAMPLES Hereinafter, the present invention will be described specifically with reference to examples, but the present invention is not limited to these examples.

Example 1 (Preparation of silver halide photographic light-sensitive material sample I-1) Polyethylene containing titanium oxide on a paper support laminated with polyethylene on one side and polyethylene containing titanium oxide on the other side On the side of the layer, each layer having the constitution shown in Tables 2 and 3 was applied, and silver halide photographic light-sensitive material sample I was coated.
-1 was produced.

The coating solution for each layer was prepared as follows. First layer coating solution Yellow coupler (EY-1) 26.7 g, dye image stabilizer (ST-1) 10.0 g, dye image stabilizer (S
T-2) 6.67 g, stain inhibitor (HQ-1) 0.
Ethyl acetate (60 ml) was added to and dissolved in 67 g and 6.67 g of a high boiling point organic solvent (DNP). The ultrasonic homogenizer was added to 220 ml of a 10% aqueous gelatin solution containing 7 ml of a 20% aqueous solution of a surfactant (SU-2). The mixture was emulsified and dispersed to prepare a yellow coupler dispersion.

This dispersion was treated with a blue-sensitive silver chlorobromide emulsion (Em-
B) (containing 8.67 g of silver), and an anti-irradiation dye (AIY-1) was further added to prepare a first layer coating solution.

The coating solutions for the second to seventh layers were prepared in the same manner as the coating solution for the first layer. As a hardener, (HH-1) was added to the second and fourth layers, and (HH-2) was added to the seventh layer. Surfactants (SU-1) as coating aids,
(SU-3) was added to adjust the surface tension.

[0150]

[Table 2]

[0151]

[Table 3] The structural formula of the compound used in each layer is shown below.

[0152]

Embedded image

[0153]

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[0154]

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[0155]

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[0156]

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[0157]

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The blue-sensitive silver chlorobromide emulsion (Em-
B), a green-sensitive silver chlorobromide emulsion (Em-G) and a red-sensitive silver chlorobromide emulsion (Em-R) are shown below. Blue-sensitive silver chlorobromide emulsion (Em-B) Monodisperse cubic emulsion having an average particle size of 0.85 µm, a coefficient of variation of 0.07, and a silver chloride content of 99.5 mol% Sodium thiosulfate 0.8 mg / mol AgX gold chloride Acid 0.5 mg / mol AgX Stabilizer STAB-1 6 × 10 ^-4 mol / mol AgX sensitizing dye BS-1 4 × 10 ^-4 mol / mol AgX sensitizing dye BS-2 1 × 10 ^-4 mol / mol AgX

Green-sensitive silver chlorobromide emulsion (Em-G) Monodispersed cubic emulsion having an average particle size of 0.43 μm, a coefficient of variation of 0.08, and a silver chloride content of 99.5 mol% 1.5 mg / mol of sodium thiosulfate AgX chloroauric acid 1.0 mg / mol AgX Stabilizer STAB-1 6 × 10 ^-4 mol / mol AgX Sensitizing dye GS-1 4 × 10 ^-4 mol / mol AgX

Red-sensitive silver chlorobromide emulsion (Em-R) Monodisperse cubic emulsion having an average particle size of 0.50 μm, a coefficient of variation of 0.08, and a silver chloride content of 99.5 mol% 1.8 mg / mol of sodium thiosulfate AgX chloroauric acid 2.0 mg / mol AgX stabilizer STAB-1 6 × 10 ⁻⁴ mol / mol AgX sensitizing dye RS-1 1 × 10 ⁻⁴ mol / mol AgX The coefficient of variation is calculated by the following equation 1.

[0161]

(Equation 1) Here, ri represents the particle size of each particle, and ni represents the number thereof. The particle size refers to the diameter of spherical silver halide grains, and the diameter of a projected image converted to a circular image of the same area for cubic or non-spherical shaped particles.

The blue-sensitive silver chlorobromide emulsion (Em
-B) shows the structural formulas of the compounds used for preparing the green-sensitive silver chlorobromide emulsion (Em-G) and the red-sensitive silver chlorobromide emulsion (Em-R).

[0163]

Embedded image (Preparation of silver halide photographic light-sensitive material samples I-2 and I-3) Photosensitive dye (sensitizing dye BS-) of blue-sensitive silver chlorobromide emulsion (Em-B) used for the first layer of sample I-1 1), the photosensitive dye (sensitizing dye GS-1) of the green-sensitive silver chlorobromide emulsion (Em-G) used in the third layer, and the red-sensitive silver chlorobromide emulsion (Em-R) used in the fifth layer ) Of the photosensitive dye (sensitizing dye RS-1)
Sample I- except that equimolar amounts of the photosensitive dyes shown in Table 4 were used
Samples I-2 and 1-3 were prepared in the same manner as Sample No. 1.

[0164]

[Table 4]

[0165]

Embedded image

The obtained sample was exposed to a wedge and subjected to color development processing according to the following processing steps, and the sensitivity, fog, and storage stability (fog) of the first, third and fifth layers were evaluated as follows. Table 5 shows the obtained results.

Color development processing Processing time Temperature Time Color development 35.0 ± 0.3 ° C. 45 seconds Bleaching and fixing 35.0 ± 0.5 ° C. 45 seconds Stabilization 30-34 ° C. 90 seconds Drying 60-80 ° C. 60 seconds

Color developing solution Tank solution Replenisher Pure water 800 ml 800 ml Triethanolamine 10 g 18 g N, N-diethylhydroxylamine 5 g 9 g Potassium chloride 2.4 g 1-hydroxyethylidene-1,1-diphosphonic acid 1.0 g 1.8 g N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate 5.4 g 8.2 g Fluorescent whitening agent (4,4′-diaminostilbenesulfonic acid derivative) 1.0 g 8 g Potassium carbonate 27 g 27 g Water was added to make the total volume 1 liter. The pH of the tank solution was 10.10, and the pH of the replenisher was 10.6.
Adjust to 0.

Bleaching / fixing solution (tank solution and replenisher are the same) Ferric ammonium ammonium diaminetetraacetate dihydrate 60 g Ethylenediaminetetraacetic acid 3 g Ammonium thiosulfate (70% aqueous solution) 100 ml Ammonium sulfite (40% aqueous solution) 27.5 ml In addition, bring the total volume to 1 liter and adjust the pH to 5.7 with potassium carbonate or glacial acetic acid.

Stabilizing solution (the tank solution and the replenishing solution are the same) 5-chloro-2-methyl-4-isothiazolin-3-one 1.0 g ethylene glycol 1.0 g 1-hydroxyethylidene-1,1-diphosphonic acid 2 1.0 g Ethylenediaminetetraacetic acid 1.0 g Ammonium hydroxide (20% aqueous solution) 3.0 g Fluorescent whitening agent (4,4'-diaminostilbenesulfonic acid derivative) 1.5 g Water was added to bring the total volume to 1 liter. Adjust the pH to 7.0 with potassium hydroxide.

<< Evaluation of Sensitivity >> The sensitivity of the first layer is expressed by blue density,
The sensitivity of the third layer is green density, and the sensitivity of the fifth layer is red density,
The exposure amount (E) giving an optical density of fog +0.15 was obtained, and -logE was calculated to obtain the sensitivity. Table 5 shows the relative values with the sensitivity of Sample I-1 taken as 100.

<< Evaluation of Fog >> The first layer was measured for blue density, the third layer was measured for green density, and the fifth layer was measured for red density. Fog was evaluated based on the minimum density value of a characteristic curve obtained.

<< Evaluation of Storage Property (△ Fog) >> Temperature of 23 ° C.
Sample A which was conditioned for 24 hours under the condition of a relative humidity of 65%, sealed in a resin can, and aged at 55 ° C. for 3 days.
Of the first layer (blue), the third layer (green), and the fifth layer (red) of the sample B stored in the refrigerator, according to the evaluation of the fog, and the difference (the fog of the sample B) -Fog of sample A) was evaluated for storage stability.

[0174]

[Table 5]

As is clear from Table 5, the compound of the present invention achieved lower fog and higher sensitivity than the comparative sample. In addition, the fog during storage was smaller and improved as compared with the comparative compound. Example 2 [Preparation of seed emulsion] Using a stirrer described in JP-A-62-160128, K-5 solution was added to A-5 solution which was vigorously stirred at 30 ° C, and then F-5 solution was added. And the solution G-5 were added by a double jet method over 2 minutes to produce silver halide nuclei.

Thereafter, the J-5 solution was added, the temperature was raised to 68 ° C. over 41 minutes, and the H-5 solution was further added, followed by aging for 7 minutes. Thereafter, the solution I-5 was further added, and one minute later, the pH was adjusted to 4.7 with the solution L-5, and immediately desalting was carried out by an ordinary method. When this seed emulsion was observed with an electron microscope, the average grain size (grain size in terms of projected area circle) having two twin planes parallel to each other was 0.31 μm, and the grain size distribution was 16%.
Was obtained.

(E-5 solution) Deionized alkali-treated gelatin (average molecular weight 15,000) 244.0 g Potassium bromide 156.6 g HO (CH ₂ CH ₂ O) _m (CH (CH ₃ ) CH ₂ O) _19.8 (CH 34.0L with 10% methanol solution 0.48mL water _{2 CH 2 O) n H (} m + n = 9.77)

(F-5 solution) 1200 g of silver nitrate 3716 mL with water (G-5 solution) Deionized alkali-treated gelatin (average molecular weight 15,000) 31.6 g 906.0 g of potassium bromide 4.0 L with water (H-5 solution) Ammonia water (28%) 299 mL (I-5 solution) Water 8.0 L (J-5 solution) Ossein gelatin 400.0 g With water 4832 mL (K-5 solution) Potassium bromide 69.2 g Water 386 mL (L- 5 solution) 56% by weight acetic acid aqueous solution 1000 mL

[Preparation of Emulsion Em-1]
Solution 6 was added, and while stirring vigorously, Solution I-6, J-6
Solution and K-6 solution were added by the simultaneous mixing method according to the combination shown in Table 6 to grow a seed crystal, thereby preparing a core / shell type silver halide emulsion.

In the growth of the seed crystal, the first addition is
The solution temperature in the reaction vessel was controlled at 75 ° C., and the pAg was controlled at 8.8. Next, the solution temperature in the reaction vessel was reduced to 60 ° C. in 15 minutes, and the N-6 solution was added in 4 minutes,
After the K-6 solution was added in an amount equivalent to 2% of the total silver used, a second addition was performed. The second addition was performed while controlling the solution temperature in the reaction vessel to 60 ° C., the pAg to 9.8, and the pH to 5.8. The control of pAg and pH is L
Solution -6 and solution M-6 were added.

The addition rates of the liquid I-6, the liquid J-6, and the liquid K-6 are changed in a function-wise manner with respect to the addition time in consideration of the critical growth rate. Outbreaks,
The deterioration of the particle size distribution due to Ostwald ripening between the growing particles is prevented.

After the particles are formed, desalting treatment is performed according to the method described in JP-A-5-72658, and then gelatin is added and dispersed, and pAg 8.06 at 40 ° C., pH
5.8 emulsion Em-1 was obtained.

When the silver halide grains in this emulsion Em-1 were observed with an electron microscope, the average grain size was 1.30 μm.
m, hexagonal tabular monodispersed silver halide grains having a particle size distribution of 17% and an average aspect ratio of 8.0. The hexagonal tabular silver halide grains had dislocation lines in the fringe portions.

(H-6 solution) Ossein gelatin 223.6 g HO (CH ₂ CH ₂ O) _m (CH (CH ₃ ) CH ₂ O) _19.8 (CH ₂ CH ₂ O) _n H (m + n = 9.77) ) 10% methanol solution 3.6 mL seed emulsion 0.774 mol equivalent 5904 mL with water

(I-6 solution) 3.5N silver nitrate aqueous solution 6490 mL (J-6 solution) 3.5N potassium bromide aqueous solution 7500 mL (K-6 solution) 3.0% by weight of gelatin and silver iodide fine particles (average grain size) Necessary amount of fine grain emulsion SMC-1 consisting of 0.05 μm in diameter

(L-6 solution) 1.75N aqueous solution of potassium bromide required amount (M-6 solution) 56% by weight aqueous acetic acid solution required amount (N-6 solution) 3.5N aqueous solution of potassium bromide 500mL

The fine grain emulsion SM used in the K-6 solution is described below.
The preparation method of C-1 is shown.

6.0 containing 0.06 mol of potassium iodide
Five liters of a 5% by weight aqueous solution of gelatin was vigorously stirred, and 2 liters of a 7.06 mol aqueous solution of silver nitrate and 2 liters of a 7.06 mol aqueous solution of potassium iodide were added thereto over 10 minutes. During this time, the pH was adjusted to 2.0 using nitric acid and the temperature was adjusted to 4
It was controlled at 0 ° C. After the preparation of the particles, the pH was adjusted to 5.0 using an aqueous sodium carbonate solution.

The average grain size of the fine silver iodide particles in the obtained fine grain emulsion SMC-1 was 0.05 μm.

[0190]

[Table 6]

[Preparation of Emulsions A to H] After raising the temperature of Emulsion Em-1 to 58 ° C., 4.8 × 10 ^-4 mol / mol Ag of each of the photosensitive dyes shown in Table 7 was added, and after 20 minutes, Sodium thiosulfate pentahydrate 5 × 10 ⁻⁶ mol / mol Ag, chloroauric acid 3.2 × 10 ⁻⁶ mol / mol Ag, potassium thiocyanate 3.5 × 10 ⁻⁴ mol / mol Ag, triphenylphosphine Selenide was added at 2.5 × 10 ⁻⁶ mol / mol Ag and aged for 1/100 second to optimize sensitivity.

At the end of the ripening, the stabilizer ST-1 and the antifoggant AF-1 were added, and the temperature was lowered.
~ Emulsion H was prepared.

[Preparation of Samples 201 to 208] Emulsions A to H were added to ethyl acetate and tricresyl phosphate.
Magenta coupler M-1 dissolved in OIL-1
Is dispersed in an aqueous solution containing gelatin, a dispersing aid (SU-1), a spreading agent (SU-2), a hardening agent (H
-1, H-2) was added to prepare a coating solution, and the obtained coating solution was applied on a subbed cellulose triacetate support by a conventional method and dried to prepare Samples 201 to 208. . Note that samples 201 to 208 were provided with a surface protective layer as a second layer.

The compositions of the first and second layers are shown below.

First Layer: Green-Sensitive Silver Halide Emulsion Layer Emulsion Silver coating amount 1.5 g / m ² Magenta coupler (M-1) 0.33 g / m ² Tricresyl phosphate (OIL-1) 0.50 g / m ² gelatin 3.5 g / m ² Second layer: surface protective layer PM-1 0.15 g / m ² PM-2 0.04 g / m ² gelatin 0.65 g / m ²

[0196]

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[0197]

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The obtained sample was wedge-exposed with green light,
The color development processing was performed according to the following processing steps, and the sensitivity, fog, and storage stability (△ fog) were evaluated as follows. Table 7 shows the obtained results.

(Processing step) Processing step Processing time Processing temperature Replenishment amount * Color development 3 minutes 15 seconds 38 ± 0.3 ° C. 780 ml Bleaching 45 seconds 38 ± 2.0 ° C. 150 ml Fixing 1 minute 30 seconds 38 ± 2. 0 ° C. 830 ml Stability 60 seconds 38 ± 5.0 ° C. 830 ml Drying 1 minute 55 ± 5.0 ° C.-* The replenishing amount is a value per 1 m ² of the photosensitive material.

The following color developing solutions, bleaching solutions, fixing solutions, stabilizing solutions and replenishers were used. Color developing solution and color developing replenisher Developer replenisher Water 800 ml 800 ml Potassium carbonate 30 g 35 g Sodium bicarbonate 2.5 g 3.0 g Potassium sulfite 3.0 g 5.0 g Sodium bromide 1.3 g 0.4 g Potassium iodide 2 mg-hydroxylamine sulfate 2.5 g 3.1 g sodium chloride 0.6 g-4-amino-3-methyl-N-ethyl-N- (β-hydroxylethyl) aniline sulfate 4.5 g 6.3 g diethylenetriamine Acetic acid 3.0 g 3.0 g Potassium hydroxide 1.2 g 2.0 g Water was added to make 1 liter, and potassium hydroxide or 20 g was added.
% Sulfuric acid and pH 10.06 in a color developer.
The pH of the replenisher is adjusted to 10.18.

Bleach and Bleach Replenisher Bleach Replenisher Water 700 ml 700 ml 1,3-diaminopropanetetraacetic acid iron (III) ammonium 125 g 175 g ethylenediaminetetraacetic acid 2 g 2 g sodium nitrate 40 g 50 g ammonium bromide 150 g 200 g glacial acetic acid 40 g 56 g water And adjust to pH 4.4 in the bleaching solution and pH 4.0 in the replenisher using ammonia water or glacial acetic acid.

Fixer Solution and Fixer Replenisher Fixer Replenisher Water 800 ml 800 ml Ammonium thiocyanate 120 g 150 g Ammonium thiosulfate 150 g 180 g Sodium sulfite 15 g 20 g Ethylenediaminetetraacetic acid 2 g 2 g Use ammonia water or glacial acetic acid to add p to the fixing solution.
After adjusting the pH of H6.2 to pH 6.5 in the replenisher, water is added to make 1 liter.

Stabilizing Solution and Stabilizing Replenisher Water 900 ml p-octylphenol ethylene oxide 10 mol adduct 2.0 g dimethylolurea 0.5 g hexamethylenetetramine 0.2 g 1,2-benzoisothiazolin-3-one 0.1 g siloxane (UCC L-77) 0.1 g ammonia water 0.5 ml After adding water to make 1 liter, add ammonia water or 5
Adjust to pH 8.5 with 0% sulfuric acid.

<< Evaluation of Sensitivity >> Green density is fog +0.1
The exposure amount (E) giving an optical density of 5 was obtained, and -logE was calculated to obtain the sensitivity. Table 7 shows the relative values with the sensitivity of Sample No. 201 being 100.

<< Evaluation of Fog >> Fog was evaluated based on the minimum density value of a characteristic curve obtained by measuring green density.

<< Evaluation of Storage Property (△ Fog) >> Temperature of 23 ° C.
-Sample C which was conditioned for 24 hours under the condition of a relative humidity of 65%, sealed in a resin can, and aged at 55 ° C for 3 days.
Fog of the sample D stored in the refrigerator was determined according to the fog evaluation described above, and the difference (the fog of the sample D) was determined.
The storage stability was evaluated by fog of Sample C).

[0207]

[Table 7]

[0208]

Embedded image

As is clear from Table 7, when the compound of the present invention was used, lower fog and higher sensitivity could be achieved as compared with the case where Comparative 3 and Comparative 4 were used. In addition, storage stability was also improved.

Example 3 [Preparation of photothermographic material] A silver halide / silver behenate complete soap was prepared by the method described in US Pat. No. 3,839,049. To 50 g of the above silver behenate, 200 g of methyl ethyl ketone, 100 g of toluene, 25 g of polyvinyl butyral (PVB), 200 m of isopropanol
l, and using a homogenizer, 3000 rpm, 3
The mixture was stirred for 0 minute to prepare a dispersion. Next, 30 ml of calcium bromide (5% MeOH solution) and 10 g of polyvinylpyrrolidone were added, and the mixture was stirred for 1 hour. Further, 2 ml of a 0.025% methanol solution of the photosensitive dye described in Table 8 and 0.5% of phthalazinone were used. 10 ml of methanol solution, 2,2'-methylenebis- (6-t-butyl-4-ethylphenol)
A coating solution was prepared by adding 10 ml of a 10% acetone solution of (reducing agent).

The obtained coating solution was coated on a subbed 180 μm thick polyethylene terephthalate (PET) support made of a vinyl chloride-vinyl acetate copolymer and the amount of silver was 1 g.
/ M ² and dried to obtain photothermographic material samples 301 to 305.

The obtained light-sensitive material was subjected to sensitometric exposure, and was heat-developed at 120 ° C. for 10 seconds using a heat roller. A characteristic curve was obtained.

<< Evaluation of Fog and Sensitivity >> Fog was evaluated based on the minimum density value of the characteristic curve.

Further, an exposure amount (E) giving an optical density of fog + 0.15 was obtained from the characteristic curve, and -logE was calculated to obtain the sensitivity. Table 8 shows that the sensitivity of Sample 301 was 100
The relative values are shown as follows.

[0215]

[Table 8] From Table 8, it was found that the heat-developable silver salt photographic material sample of the present invention had high sensitivity and was also excellent in heat fog.

[0216]

The silver halide light-sensitive material and the heat-developable silver salt photographic light-sensitive material of the present invention have improved fog without deterioration in storage stability and are spectrally sensitized with high sensitivity.

Continued on the front page (51) Int.Cl. ⁷ Identification FI FI Theme Court II (Reference) G03C 1/498 503 G03C 1/498 503 (72) Inventor Tatsuo Tanaka 1 Sakuramachi, Hino City, Tokyo Konica Corporation ( 72) Inventor ▲ Daibu Shinichi 1 Sakuracho, Hino-shi, Tokyo Konica Corporation (72) Inventor Fumio Ishii 1 Sakuracho, Hino-shi, Tokyo Konica Corporation F-term (reference) 2H023 CA07 CA08 2H123 AB00 AB03 AB23 AB25 BB00 BB23 CB00 CB03 DA06 4H056 CA01 CA02 CA05 CB01 CC02 CC08 CE03 CE06 DD06 DD19 DD23 DD28 DD29 FA05

Claims (5)

[Claims] 1. A compound represented by the following general formula (I) or (II)
Characterized by containing at least one methine dye
Silver halide photographic material. Embedded image[Wherein, Z₁Is a 5- or 6-membered nitrogen containing nitrogen atom
Represents a group of non-metallic atoms necessary to form a heterocyclic ring.
Or a condensed ring. Z_TwoPassing
And Z_ThreeIs a condensed carbocyclic or heterocyclic ring
Represents a group of nonmetallic atoms necessary to form Q is an acidic nucleus
Represents a group of nonmetallic atoms necessary to form Y₁And Y_Two
Is oxygen, sulfur, selenium, tellurium,> N
Represents Rp. Rp is a hydrogen atom, a substituted or unsubstituted al
Represents a killed group or a substituted or unsubstituted aryl group. M₁,
M_TwoRepresents a charge neutralizing counter ion, and n₁, N_TwoIs the electron in the molecule
Represents the number of zero or more necessary to neutralize the load. L₁,
L_Two, L_Three, L_FourAnd L_FiveRepresents a methine group or a substituted methine group
Represent. Also, each methine group forms a ring with another methine group.
And may form a ring with an auxiliary chromophore.
No. s represents an integer of 0 or 1, and t represents 0, 1, 2, or
Represents an integer of 3. A₁, A_TwoIs an aliphatic group or
Represents a substituent represented by the general formula (III). However, A₁,
A_TwoAre not aliphatic groups. A_ThreeIs one of the following
Represents a substituent represented by the general formula (III). Embedded image(In the general formula (III), R on the secondary carbon atom a is
Represents a group represented by any of the general formulas (i) to (vi),
Rb is represented by any of the general formulas (i) to (vi)
Group or aliphatic, cyano, amino, alkylsulfo
Nil, arylsulfonyl, acyl, acylamino, a
Represents each group of lucoxycarbonyl. m₁Is an integer greater than or equal to 0
Represents A)₁, A_TwoIs a substitution represented by the general formula (III)
When it is a group, A₁And A_TwoRa and Rb in
Each may be the same or different. Embedded image(In the general formulas (i) to (vi), R₁, R_Three, R_Four, R
₇, R₈, R₉Represents a hydrogen atom or a substituent;_Two,
R_Five, R₆, R_TenRepresents a substituent. )] 2. A compound represented by the following general formula (Ia) or (II-a)
Containing at least one methine dye represented by
Characteristic silver halide photographic material. Embedded image[Wherein, Z₁Is a 5- or 6-membered nitrogen containing nitrogen atom
Represents a group of non-metallic atoms necessary to form a heterocyclic ring.
Or a condensed ring. Z_TwoPassing
And Z_ThreeIs a condensed carbocyclic or heterocyclic ring
Represents a group of nonmetallic atoms necessary to form Q is an acidic nucleus
Represents a group of nonmetallic atoms necessary to form Y₁And Y_Two
Is oxygen, sulfur, selenium, tellurium,> N
Represents Rp. Rp is a hydrogen atom, a substituted or unsubstituted al
Represents a killed group or a substituted or unsubstituted aryl group. M₁,
M_TwoRepresents a charge neutralizing counter ion, and n₁, N_TwoIs the electron in the molecule
Represents the number of zero or more necessary to neutralize the load. L₁,
L_Two, L_Three, L_FourAnd L_FiveRepresents a methine group or a substituted methine group
Represent. Also, each methine group forms a ring with another methine group.
And may form a ring with an auxiliary chromophore.
No. s represents an integer of 0 or 1, and t represents 0, 1, 2, or
Represents an integer of 3. A₁, A_TwoIs an aliphatic group or
Represents a substituent represented by the general formula (III). However, A₁,
A_TwoAre not aliphatic groups. A_ThreeIs one of the following
Represents a substituent represented by the general formula (III). Embedded image(In the general formula (III), R on the secondary carbon atom a is
Represents a group represented by any of formulas (vii) and (viii)
And Rb is represented by any of the general formulas (vii) and (viii).
Groups, or aliphatic, cyano, amino, alkyl
Sulfonyl, arylsulfonyl, acyl, acylamido
And each group of alkoxycarbonyl. m₁Is 0 or more
Represents an integer. A)₁, A_TwoIs a substitution represented by the general formula (III)
When it is a group, A₁And A_TwoRa and Rb in
Each may be the same or different. Embedded image(In the general formulas (vii) to (viii), R₁₁, R₁₂Is
Represents a substituent. )] 3. A methine color represented by the following general formula (Ib):
Halogen containing at least one element selected from the group consisting of
Silver halide photographic material. Embedded image[Wherein, Z₁Is a 5- or 6-membered nitrogen containing nitrogen atom
Represents a group of non-metallic atoms necessary to form a heterocyclic ring.
Or a condensed ring. Z_TwoIs
Each form a fused or carbocyclic or heterocyclic ring
Represents the group of non-metallic atoms necessary for Y₁Is an oxygen atom, sulfur
Represents a yellow atom, a selenium atom, a tellurium atom,> NRp. R
p is a hydrogen atom, a substituted or unsubstituted alkyl group,
Or an unsubstituted aryl group. M₁Is charge neutralization vs. ion
N₁Is required to neutralize intramolecular charge
Represents a number of 0 or more. L₁, L_TwoAnd L_ThreeIs a methine group or
Represents a substituted methine group. In addition, each methine group is
May form a ring with the methine group of
A ring may be formed. s represents an integer of 2 or 3. A
₁, A_TwoIs represented by an aliphatic group or the following general formula (III)
Represents a substituent. However, A₁, A_TwoAre both aliphatic groups
Never be. Embedded image(In the general formula (III), R on the secondary carbon atom a is
Represents a group represented by any of the general formulas (i) to (vi),
Rb is represented by any of the general formulas (i) to (vi)
Group or aliphatic, cyano, amino, alkylsulfo
Nil, arylsulfonyl, acyl, acylamino, a
Represents each group of lucoxycarbonyl. m₁Is an integer greater than or equal to 0
Represents A)₁, A_TwoIs a substitution represented by the general formula (III)
When it is a group, A₁And A_TwoRa and Rb in
Each may be the same or different. Embedded image(In the general formulas (i) to (vi), R₁, R_Three, R_Four, R
₇, R₈, R₉Represents a hydrogen atom or a substituent;_Two,
R_Five, R₆, R_TenRepresents a substituent. )] 4. A methine color represented by the following general formula (Ic):
Halogen containing at least one element selected from the group consisting of
Silver halide photographic material. Embedded image[Wherein, Z₁Is a 5- or 6-membered nitrogen containing nitrogen atom
Represents a group of non-metallic atoms necessary to form a heterocyclic ring.
Or a condensed ring. Z_TwoIs
Each form a fused or carbocyclic or heterocyclic ring
Represents the group of non-metallic atoms necessary for Y₁Is an oxygen atom, sulfur
Represents a yellow atom, a selenium atom, a tellurium atom,> NRp. R
p is a hydrogen atom, a substituted or unsubstituted alkyl group,
Or an unsubstituted aryl group. M₁Is charge neutralization vs. ion
N₁Is required to neutralize intramolecular charge
Represents a number of 0 or more. L₁, L_TwoAnd L_ThreeIs a methine group or
Represents a substituted methine group. In addition, each methine group is
May form a ring with the methine group of
A ring may be formed. s represents an integer of 2 or 3. A
₁, A_TwoIs represented by an aliphatic group or the following general formula (III)
Represents a substituent. However, A₁, A_TwoAre both aliphatic groups
Never be. Embedded image(In the general formula (III), R on the secondary carbon atom a is
Represents a group represented by any of formulas (vii) and (viii)
And Rb is represented by any of the general formulas (vii) and (viii).
Groups, or aliphatic, cyano, amino, alkyl
Sulfonyl, arylsulfonyl, acyl, acylamido
And each group of alkoxycarbonyl. m₁Is 0 or more
Represents an integer. A)₁, A_TwoIs a substitution represented by the general formula (III)
When it is a group, A₁And A_TwoRa and Rb in
Each may be the same or different. Embedded image(In the general formulas (vii) to (viii), R₁₁, R₁₂Is
Represents a substituent. )] 5. A heat-developable silver salt photographic material comprising at least one methine dye according to claim 1.