JP2000273332A - Arylidene compound, azomethine compound, and silver halide photographic material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an arylidene compound being easily removed in photographic processing and improved in diffusion resistance and stability. SOLUTION: There is provided an arylidene compound of the formula (wherein L1 is mono-, tri-, penta-, or hepta-methine; Z is cyano or carbamoyl; R1, R2, R5, and R6 are each H, a halogen, cyano, an aliphatic group, an aromatic group, -O-R11, -CO-R12, or the like; R11 and R12 are each H, an aliphatic group, or an aromatic group; R3 and R4 are each H, an aliphatic group, an aromatic group, -CO-R21, or -SO2R22; R21 and R22 are each an aliphatic group or an aromatic group; R7 and R8 are each a halogen, cyano, an aliphatic group, -O-R31, -CO-R32, -CO-O-R23, or the like; R31 to R33 are each H, an aliphatic group, or an aromatic group; m is 0-5; a plurality of R7s may be different from each other when m is 2 or greater; n is 0-4; a plurality of R8s may be different from each other when n is 2 or greater; and R1 and R2, R2 and R3, R3 and R4, R4 and R5, R5 and R6, two R7s, or two R8s are may be bonded to each other to form a ring.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to an arylidene compound and an azomethine compound. Furthermore, the present invention
The present invention also relates to a silver halide photographic material containing an arylidene compound or an azomethine compound as a dye.

[0002]

2. Description of the Related Art An arylidene compound and an azomethine compound are used as dyes for dyeing fibers, or added to paints or silver halide photographic materials.
In the use of a silver halide photographic material, a dye is added to a silver halide photographic emulsion layer or a non-photosensitive hydrophilic colloid layer in order to absorb light in a specific wavelength range. Dyes used in silver halide photographic materials include the following (1) to
It is required to satisfy the condition (5).

(1) Appropriate spectral absorption The specific absorption wavelength range is determined according to the purpose of use of the dye. (2) Photochemically Inactive Dyes must not adversely affect the performance of silver halide photographic materials, especially silver halide emulsion layers.
Specifically, a reduction in sensitivity, regression of a latent image and fogging must not occur. (3) Decolorization or removal in photographic processing Dyes function in principle in image exposure. If the dye whose function has been terminated is not bleached or removed from the silver halide photographic light-sensitive material, the dye will color the image. Therefore, the dye must be decolorized or removed by a photographic processing solution (a developing solution or a bleaching solution). (4) Diffusion resistance Since the dye functions in a specific layer of the silver halide photographic material, a problem arises when the dye is diffused into another layer. For example, when a dye added to the non-photosensitive hydrophilic colloid layer for the purpose of preventing halation diffuses into the silver halide emulsion layer, the sensitivity of the silver halide emulsion layer is reduced. (5) Stability No discoloration or fading should occur during storage of the dye, for example, during storage as a solution of the dye or as a silver halide photographic material.

Of the above conditions (1) to (5),
It is said that it is particularly difficult to achieve both (3) and (4). In general, dyes that satisfy (3) and are easy to decolor or remove easily diffuse into other layers, and dyes that hardly diffuse and satisfy (4) are difficult to discolor or remove. In order to satisfy the conditions (3) and (4), silver halide photographic materials in which a dye containing a weak acidic group (eg, carboxyl) is added in the form of solid fine particles have been proposed. Since the weak acidic group does not dissociate in the coating solution (generally acidic to neutral) of the layer of the silver halide photographic material, the dye does not dissolve in the coating solution. Therefore, the dye can be added in the form of solid fine particles that are hardly diffused into other layers. Then, in the photographic processing solution (generally alkaline), the dye is dissolved in the photographic processing solution because the weak acidic group is dissociated. Therefore, the dye can be easily removed from the silver halide photographic material by the photographic processing solution. A silver halide photographic material containing an arylidene dye or an azomethine dye in the form of a solid fine particle dispersion is disclosed in
No. 7931, No. 4-37841, No. 4-37842
And JP-A-4-45436.

[0005]

SUMMARY OF THE INVENTION The inventor of the present invention has
No. 7931, No. 4-37841, No. 4-37842
And azomethine dyes described in JP-A-5-45436 and JP-A-4-45436, it was found that the stability of (5) needs to be improved. An object of the present invention is to provide an arylidene compound and an azomethine compound which can be used as a dye having excellent stability. Another object of the present invention is to provide a silver halide photographic material containing a dye which is easily removed in photographic processing and has excellent diffusion resistance and stability.

[0006]

An object of the present invention is to provide an arylidene compound of the following (1) to (3),
The azomethine compound of (7) and the following (4), (5),
This was achieved by the silver halide photographic light-sensitive materials of (8) and (9). (1) An arylidene compound represented by the following formula (I).

[0007]

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Where L¹Is monomethine, trimethine,
Pentamethine or heptamethine; Z is cyano
Or carbamoyl; R¹, R^Two, R^FiveAnd R
⁶Is independently a hydrogen atom, a halogen atom,
, An aliphatic group, an aromatic group, -OR¹¹, -CO-R¹²,
-CO-OR¹³, -NR¹⁴R^Fifteen, -NHCO-R¹⁶,
-NH-CO-OR¹⁷, -SO_Two-R¹⁸Or -NH
-SO_Two-R¹⁹And R¹¹, R¹², R¹³, R¹⁴, R
^Fifteen, R¹⁶, R¹⁷, R¹⁸And R¹⁹Are, independently of each other,
A hydrogen atom, an aliphatic group or an aromatic group;^Threeand
R^FourIs independently a hydrogen atom, an aliphatic group, an aromatic
Group, -CO-R^{twenty one}Or -SO_Two-R^{twenty two}And R^{twenty one}
And R^{twenty two}Is independently an aliphatic group or an aromatic group
A group; R⁷And R⁸Are, independently,
Atom, cyano, aliphatic group, aromatic group, -OR³¹, −
CO-R³², -CO-OR³³, -NR³⁴R³⁵, -NH
CO-R³⁶, -NH-CO-OR³⁷, -SO_Two-R³⁸
Or -NH-SO_Two-R ³⁹And R³¹, R³², R
³³, R³⁴, R³⁵, R³⁶, R³⁷, R³⁸And R³⁹Is it
Each independently represents a hydrogen atom, an aliphatic group or an aromatic group.
M is 0, 1, 2, 3, 4, or 5;
If two or more, multiple R⁷May be different; n
Is 0, 1, 2, 3 or 4 and n is 2 or more.
If multiple R⁸May be different; and R¹When
R^Two, R^TwoAnd R^Three, R^ThreeAnd R^Four, R^FourAnd R ^Five, R^FiveAnd R
⁶, Two R⁷Or two R⁸Are linked to each other
Can be formed.

(2) The arylidene compound according to (1), wherein in the formula (I), L ¹ is trimethine. (3) formula (I), R ¹ and R ⁶ are each independently a hydrogen atom, an alkyl group or an alkoxy group; R ² and R ⁵ is a hydrogen atom; R ³ and R
⁴ are each independently a hydrogen atom, an alkyl group or an aryl group; and R ² and R ³ or R ⁴ and R ⁵
Are arylidene compounds according to (1), which can be bonded to each other to form a ring. (4) A silver halide photographic material having a support, a silver halide emulsion layer and a non-photosensitive hydrophilic colloid layer, wherein the silver halide emulsion layer or the non-photosensitive hydrophilic colloid layer has the formula (I) A silver halide photographic material comprising an arylidene dye represented by the formula: (5) The silver halide photographic material as described in (4), wherein the arylidene dye represented by the formula (I) is dispersed in the form of solid fine particles in a silver halide emulsion layer or a non-photosensitive hydrophilic colloid layer. . (6) An azomethine compound represented by the following formula (II).

[0010]

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Wherein Z is cyano or carbamoyl
Yes; R¹, R^Two, R^FiveAnd R⁶Are independent
, Hydrogen atom, halogen atom, cyano, aliphatic group, aromatic
Group, -OR¹¹, -CO-R¹², -CO-OR¹³,
-NR¹⁴R^Fifteen, -NHCO-R ¹⁶, -NH-CO-O-
R¹⁷, -SO_Two-R¹⁸Or -NH-SO_Two-R¹⁹In
What, R¹¹, R¹², R¹³, R¹⁴, R^Fifteen, R¹⁶, R¹⁷, R
¹⁸And R¹⁹Are each independently a hydrogen atom or an aliphatic group
Or an aromatic group;^ThreeAnd R^FourIs German
First, a hydrogen atom, an aliphatic group, an aromatic group, -CO-R^{twenty one}Ma
Or -SO_Two-R ^{twenty two}And R^{twenty one}And R^{twenty two}Is it
Each independently an aliphatic or aromatic group;⁷And
And R⁸Are each independently a halogen atom, cyano,
Aliphatic group, aromatic group, -OR³¹, -CO-R³², -CO
-OR³³, -NR³⁴R³⁵, -NHCO-R³⁶, -NH
-CO-OR³⁷, -SO_Two-R³⁸Or -NH-SO
_Two-R³⁹And R³¹, R³², R³³, R³⁴, R³⁵, R
³⁶, R³⁷, R³⁸And R³⁹Are each independently a hydrogen source
M is 0, 1,
2, 3, 4 or 5, when m is 2 or more, plural
R⁷May be different; n is 0, 1, 2, 3 or
Or 4 and n is 2 or more, a plurality of R⁸Is different
And R¹And R^Two, R^TwoAnd R^Three, R
^ThreeAnd R^Four, R^FourAnd R^Five, R^FiveAnd R⁶, Two R⁷Or
Two R⁸Can combine with each other to form a ring.

(7) In the formula (II), R ¹ and R ⁶
Are each independently a hydrogen atom, an alkyl group or an alkoxy group; R ² and R ⁵ are hydrogen atoms;
R ³ and R ⁴ are each independently a hydrogen atom, an alkyl group or an aryl group; and R ² and R ³ or R ⁴ and R ⁵ can combine with each other to form a ring (6)
The azomethine compound according to the above. (8) A silver halide photographic material having a support, a silver halide emulsion layer and a non-photosensitive hydrophilic colloid layer, wherein the silver halide emulsion layer or the non-photosensitive hydrophilic colloid layer has the formula (II) A silver halide photographic material comprising an azomethine dye represented by the formula: (9) The silver halide photographic material as described in (8), wherein the azomethine dye represented by the formula (II) is dispersed in the form of solid fine particles in a silver halide emulsion layer or a non-photosensitive hydrophilic colloid layer. .

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION The arylidene compound is represented by the following formula (I).

[0014]

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In the formula (I), L¹Is monomethine,
Trimethine, pentamethine or heptamethine.
L¹Is monomethine, trimethine or pentamethine
Preferably, it is monomethine or trimethine.
More preferably, and most preferably trimethine.
preferable. Monomethine, trimethine, pentamethine and
And heptamethine may have a substituent. One
When introducing a substituent, place it in the middle (meso) methine.
It is preferred to attach a substituent. Also, two substituents
Is bonded to form a 5- or 6-membered unsaturated aliphatic ring (cyclo
A pentene ring or a cyclohexene ring). Place
Examples of substituents include halogen, cyano, nitro, aliphatic
Group, aromatic group, heterocyclic group, -OR⁴¹, -SR⁴², −
CO-R⁴³, -CO-OR⁴⁴, -NR⁴⁵R ⁴⁶, -CO
-NR⁴⁷R⁴⁸, -NH-CO-R⁴⁹, -NH-CO-N
HR⁵⁰, -NH-CO-OR⁵¹, -SO_Two-R⁵²,
-SO_Two-NR⁵³R⁵⁴, -NH-SO _Two-R⁵⁵, -CO
-NH-SO_Two-R⁵⁶And -SO_Two-NH-CO-R
⁵⁷Is included. R⁴¹, R⁴², R⁴³, R⁴⁴, R⁴⁵, R⁴⁶,
R⁴⁷, R⁴⁸, R⁴⁹, R⁵⁰, R⁵¹, R⁵², R⁵³, R⁵⁴, R
⁵⁵, R⁵⁶And R⁵⁷Are each independently a hydrogen atom,
It is an aliphatic group or an aromatic group. Aliphatic groups, aromatic groups and
And heterocyclic groups, R¹, R^Two, R^FiveAnd R⁶of
The definition will be described later.

In the formula (I), Z is cyano or carbamoyl.

In the formula (I), R ¹ , R ² , R ⁵ and R ⁶ each independently represent a hydrogen atom, a halogen atom,
Cyano, aliphatic group, aromatic group, -OR ¹¹ , -CO-R
^{12, -CO-O-R 13} , -NR 14 R 15, -NHCO-R
¹⁶ , -NH-CO-OR ¹⁷ , -SO ₂ -R ¹⁸ or-
Is NH-SO ₂ -R ^19. R ¹¹ , R ¹² , R ¹³ , R ¹⁴ ,
R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ and R ¹⁹ are each independently a hydrogen atom, an aliphatic group or an aromatic group. R ¹ and R ⁶ are preferably each independently a hydrogen atom, a halogen atom, an aliphatic group or —O—R ¹¹ ,
It is more preferably a hydrogen atom, a chlorine atom, a fluorine atom, an alkyl group, a substituted alkyl group, an alkoxy group or a substituted alkoxy group, and is preferably a hydrogen atom, a chlorine atom, a fluorine atom, an alkyl group having 1 to 10 carbon atoms, A substituted alkyl group having 1 to 10 atoms, 1 to 1 carbon atoms
More preferably, it is an alkoxy group having 0 or a substituted alkoxy group having 1 to 10 carbon atoms, and a hydrogen atom,
Most preferably, it is an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 8 carbon atoms. R
² and R ⁵ are each independently preferably a hydrogen atom or an aliphatic group, more preferably a hydrogen atom or an alkyl group, and more preferably a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. Is more preferable,
Most preferably, it is a hydrogen atom.

In the present specification, the aliphatic group is an alkyl
Group, substituted alkyl group, alkenyl group, substituted alkenyl
Group, alkynyl group, substituted alkynyl group, aralkyl group
And substituted aralkyl groups. Alkyl groups are branched
May be provided. The number of carbon atoms in the alkyl group is 1
It is preferably from 20 to 20, preferably from 1 to 18.
More preferred. The alkyl portion of the substituted alkyl group is
The same applies to the above alkyl group. Alkenyl groups are branched
It may be. The number of carbon atoms in the alkenyl group is 2 to
It is preferably 20 and preferably 2 to 18.
More preferred. The alkenyl part of the substituted alkenyl group is
The same as the above alkenyl group. Alkynyl groups are branched
May be provided. The number of carbon atoms in the alkynyl group is 2
From 20 to 20, preferably from 2 to 18
Is more preferred. Alkynyl moiety of substituted alkynyl group
Is the same as the above alkynyl group. Aralkyl groups and
And the alkyl part of the substituted aralkyl group is
Is the same as Aralkyl and substituted aralkyl groups
The aryl moiety is the same as the following aryl group. Substitution
Alkyl group, substituted alkenyl group, substituted alkynyl group and
Examples of substituents on the alkyl portion of the substituted aralkyl group include
Logen atom, cyano, nitro, heterocyclic group, -OR⁶¹,
-SR⁶², -CO-OR⁶³, -NR⁶⁴R⁶⁵, -CO
-NR⁶⁶R⁶⁷, -SO_Two-R⁶⁸And -SO_Two-NR⁶⁹
R⁷⁰Is included. R⁶¹, R⁶², R ⁶³, R⁶⁴, R⁶⁵,
R⁶⁶, R⁶⁷, R⁶⁸, R⁶⁹And R⁷⁰Are independent
And a hydrogen atom, an aliphatic group or an aromatic group. Substitution
Examples of the substituent of the aryl portion of the aralkyl group include the following substituents
This is the same as the example of the substituent of the reel group.

In the present specification, the aromatic group means an aryl group and a substituted aryl group. The aryl group is preferably phenyl or naphthyl, and phenyl is particularly preferred. The aryl part of the substituted aryl group is the same as the above-mentioned aryl group. Examples of the substituent of the substituted aryl group include a halogen atom, cyano, nitro, an aliphatic group, a heterocyclic group, -OR ⁷¹ , -SR ⁷² , -CO-OR ⁷³ ,
^{-NR 74 R 75, -CO-NR} 76 R 77, include -SO ₂ -R ⁷⁸ and -SO ₂ -NR ⁷⁹ R ^80. R ⁷¹ , R ⁷² , R
⁷³ , ^R74 , ^R75 , ^R76 , ^R77 , ^R78 , ^R79 and R
⁸⁰ is each independently a hydrogen atom, an aliphatic group or an aromatic group.

In the present specification, a heterocyclic group is a 5-membered or
Preferably contains a 6-membered saturated or unsaturated heterocycle
No. Aliphatic ring, aromatic ring or other heterocyclic ring
It may be condensed. Examples of heteroatoms in a heterocycle include:
B, N, O, S, Se and Te are included. Heterogeneous
As the children, N, O and S are preferable. Heterocycle is charcoal
Elementary atoms have a free valence (monovalent) (heterocyclic groups are carbon
Bond at an element atom). Saturated heterocycle
Include pyrrolidine ring, morpholine ring, 2-bora-
1,3-dioxolane ring and 1,3-thiazolidine ring
Is included. Examples of the unsaturated heterocyclic ring include an imidazole ring,
Thiazole ring, benzothiazole ring, benzoxazo
Ring, benzotriazole ring, benzoselenazole ring,
Contains pyridine, pyrimidine and quinoline rings
You. The heterocyclic group may have a substituent. Substituent
Examples include halogen atoms, cyano, nitro, aliphatic groups, aromatic
Aromatic group, heterocyclic group, -OR⁸¹, -SR⁸², -CO-
OR⁸³, -NR⁸⁴R⁸⁵, -CO-NR⁸⁶R⁸⁷, -SO
_Two-R⁸⁸And -SO_Two-NR⁸⁹R⁹⁰Is included.
R⁸¹, R⁸², R⁸³, R⁸⁴, R⁸⁵, R⁸⁶, R⁸⁷, R ⁸⁸, R
⁸⁹And R⁹⁰Are each independently a hydrogen atom or an aliphatic group
Or an aromatic group.

In the formula (I), R ³ and R ⁴ each independently represent a hydrogen atom, an aliphatic group, an aromatic group,
—R ²¹ or —SO ₂ —R ²² . R ²¹ and R
²² is each independently an aliphatic group or an aromatic group. R ³ and R ⁴ are each independently preferably a hydrogen atom, an aliphatic group or an aromatic group, more preferably a hydrogen atom, an alkyl group or an aryl group, and more preferably a hydrogen atom or an alkyl group. And more preferably a hydrogen atom or an alkyl group having 1 to 18 carbon atoms.

In the formula (I), R⁷And R⁸Is
Each independently halogen atom, cyano, aliphatic group, aromatic
Group, -OR³¹, -CO-R³², -CO-OR³³,
-NR³⁴R³⁵, -NHCO-R³⁶, -NH-CO-O-
R³⁷, -SO_Two-R³⁸Or -NH-SO_Two-R³⁹In
You. R³¹, R³², R³³, R³⁴, R³⁵, R³⁶, R³⁷, R ³⁸
And R³⁹Are each independently a hydrogen atom or an aliphatic group.
Or an aromatic group. R⁷And R⁸Are independent
Is preferably an aliphatic group, and an alkyl group.
More preferably, alkyl having 1 to 8 carbon atoms
More preferably, it is a group.

In the formula (I), m is 0, 1, 2,
3, 4 or 5. When m is 2 or more, a plurality of R ⁷
May be different. m is 0, 1, 2, 3, or 4
Is preferably 0, 1, 2 or 3, more preferably 0, 1 or 2, and still more preferably 0 or 1.
Most preferably, it is 0. In the formula (I), n
Is 0, 1, 2, 3 or 4. When n is 2 or more, a plurality of R ⁸ may be different. n is 0, 1,
It is preferably 2 or 3, more preferably 0, 1 or 2, further preferably 0 or 1, and most preferably 0.

In the formula (I), R ¹ and R ² , R ² and R
^3, R ³ and R ^4, R ⁴ and R ^5, R ⁵ and R ^6, two R ⁷
Alternatively, two R ⁸ can be bonded to each other to form a ring.
Combinations forming a ring include R ² and R ³ or R ⁴ and R
It is preferably ⁵ . The ring formed by combining R ¹ and R ² , R ⁵ and R ⁶ , two R ⁷ or two R ⁸ with each other is preferably a 5- or 6-membered ring. The ring is
Aromatic ring (eg, benzene ring) or unsaturated heterocyclic ring (eg,
A pyridine ring, an imidazole ring, a thiazole ring, and a pyrimidine ring). The ring formed by combining R ² and R ³ or R ⁴ and R ⁵ is preferably a 5- or 6-membered ring. Examples of the ring include a tetrahydroquinoline ring and a dihydroindole ring. R ³
And R ⁴ are bonded to each other to form a 5-membered ring or 6-membered ring.
It is preferably a membered ring. Examples of the ring include a pyrrolidine ring, a piperidine ring and a morpholine ring.

The azomethine compound is represented by the following formula (II).

[0026]

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In the formula (II), Z is cyano or carbamoyl.

In the formula (II), R ¹ , R ² , R ⁵ and R ⁶ each independently represent a hydrogen atom, a halogen atom,
Cyano, aliphatic group, aromatic group, -OR ¹¹ , -CO-R
^{12, -CO-O-R 13} , -NR 14 R 15, -NHCO-R
¹⁶ , -NH-CO-OR ¹⁷ , -SO ₂ -R ¹⁸ or-
Is NH-SO ₂ -R ^19. R ¹¹ , R ¹² , R ¹³ , R ¹⁴ ,
R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ and R ¹⁹ are each independently a hydrogen atom, an aliphatic group or an aromatic group. R ¹ and R ⁶ are preferably each independently a hydrogen atom, a halogen atom, an aliphatic group or —O—R ¹¹ ,
It is more preferably a hydrogen atom, a chlorine atom, a fluorine atom, an alkyl group, a substituted alkyl group, an alkoxy group or a substituted alkoxy group, and is preferably a hydrogen atom, a chlorine atom, a fluorine atom, an alkyl group having 1 to 10 carbon atoms, A substituted alkyl group having 1 to 10 atoms, 1 to 1 carbon atoms
More preferably, it is an alkoxy group having 0 or a substituted alkoxy group having 1 to 10 carbon atoms, and a hydrogen atom,
Most preferably, it is an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 8 carbon atoms. R
² and R ⁵ are each independently preferably a hydrogen atom or an aliphatic group, more preferably a hydrogen atom or an alkyl group, and more preferably a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. Is more preferable,
Most preferably, it is a hydrogen atom.

In the formula (II), R ³ and R ⁴ each independently represent a hydrogen atom, an aliphatic group, an aromatic group,
—R ²¹ or —SO ₂ —R ²² . R ²¹ and R
²² is each independently an aliphatic group or an aromatic group. R ³ and R ⁴ are each independently preferably a hydrogen atom, an aliphatic group or an aromatic group, more preferably a hydrogen atom, an alkyl group or an aryl group, and more preferably a hydrogen atom or an alkyl group. And more preferably a hydrogen atom or an alkyl group having 1 to 18 carbon atoms.

In the formula (II), R⁷And R⁸Is
Each independently halogen atom, cyano, aliphatic group, aromatic
Group, -OR³¹, -CO-R³², -CO-OR³³,
-NR³⁴R³⁵, -NHCO-R³⁶, -NH-CO-O-
R³⁷, -SO_Two-R³⁸Or -NH-SO_Two-R³⁹In
You. R³¹, R³², R³³, R³⁴, R³⁵, R³⁶, R³⁷, R ³⁸
And R³⁹Are each independently a hydrogen atom or an aliphatic group.
Or an aromatic group. R⁷And R⁸Are independent
Is preferably an aliphatic group, and an alkyl group.
More preferably, alkyl having 1 to 8 carbon atoms
More preferably, it is a group.

In the formula (II), m is 0, 1, 2,
3, 4 or 5. When m is 2 or more, a plurality of R ⁷
May be different. m is 0, 1, 2, 3, or 4
Is preferably 0, 1, 2 or 3, more preferably 0, 1 or 2, and still more preferably 0 or 1.
Most preferably, it is 0. In the formula (II), n
Is 0, 1, 2, 3 or 4. When n is 2 or more, a plurality of R ⁸ may be different. n is 0, 1,
It is preferably 2 or 3, more preferably 0, 1 or 2, further preferably 0 or 1, and most preferably 0.

In the formula (II), R ¹ and R ² , R ² and R
^3, R ³ and R ^4, R ⁴ and R ^5, R ⁵ and R ^6, two R ⁷
Alternatively, two R ⁸ can be bonded to each other to form a ring.
Combinations forming a ring include R ² and R ³ or R ⁴ and R
It is preferably ⁵ . The definition and examples of the ring to be formed are the same as those in formula (I).

Examples of the arylidene compound represented by the formula (I) and the azomethine compound represented by the formula (II) will be given below.

[0034]

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The arylidene compound and the azomethine compound are disclosed in JP-A-52-135335 and JP-A-3-7335.
No. 931 can be synthesized with reference to the methods described therein.

When the arylidene compound and the azomethine compound are used as dyes, they are preferably in the form of a solid dispersion. A solid dispersion is obtained by dispersing fine powder (fine crystal particles) of a dye in an appropriate dispersion medium. Examples of the dispersion medium include water and alcohol. A dispersing device may be used. Examples of the dispersing device include a ball mill, a vibration ball mill, a planetary ball mill, a sand mill, a colloid mill,
Includes jet mills and roller mills. ) Can be prepared mechanically. Further, a dispersant may be used. After dissolving the dye in a suitable solvent using a dispersing agent, it can be added to a poor solvent for the dye to precipitate microcrystals. Alternatively, the pH can be adjusted to dissolve the dye, and then the pH can be changed to obtain fine crystals of the dye. A layer containing a dye can be formed from a coating solution obtained by adding a suitable binder to a solid dispersion of the dye. Alternatively, a layer may be formed from a coating solution in which a dye salt is dissolved in a solvent, and then the layer may be acidified to precipitate the dye as solid fine particles. The degree of acidity depends on the dissociable group (carboxyl) of the dye.
Is determined according to the pKa of In order to make the layer containing the dye acidic, an acidic substance may be primed under the layer or an acidic substance may be applied on the layer.

As the binder for the layer containing the dye, a hydrophilic natural or synthetic polymer is preferably used. Proteins or polysaccharides are used as natural polymers. Examples of proteins include gelatin, albumin, casein and derivatives thereof. Gelatin derivatives also include gelatin graft polymers. Examples of polysaccharides include cellulose, dextrin, sodium alginate, pectin, starch, gum arabic and derivatives thereof. Cellulose derivatives include hydroxyethylcellulose, hydroxymethylcellulose, hydroxypropylcellulose, carboxymethylcellulose, ethylcellulose, methylcellulose, nitrocellulose and cellulose sulfate. Starch derivatives include carboxymethyl starch. Examples of synthetic polymers include polyalkylene oxide, polyvinyl alcohol, polyvinyl alcohol partial acetal,
Modified polyvinyl alcohol polyvinyl butyral, poly-N-vinylpyrrolidone, polyethyl oxazoline, polyvinyl methyl oxazolidone, polyacrylic acid, polymethacrylic acid, acryloylmethylpropanesulfonic acid copolymer, polymethacrylic acid, maleic acid and its esters and Includes amide copolymers, polyacrylamide, polyvinylimidazole and polyvinylpyrazole. For the modified polyvinyl alcohol, see JP-A-7-
No. 219113 describes this. Other synthetic polymers are described in EP 678770 A2. Natural or synthetic polymers can also function as the following dispersants.

As the dispersant, a surfactant can be used. Examples of the surfactant include anionic surfactants (U.S. Pat. Nos. 4,060,25 and 5,104,776, European Patent EP 678,771 A2, JP-A-62-215272, JP-A-63-11935, and JP-A-63-1935).
-60446, JP-A-1-201655, 4-1
25548 and 4-324858), nonionic surfactants, amphoteric surfactants (described in U.S. Pat. No. 3,542,581 and European Patent No. 569074A1) or fluorine-containing surfactants (European Patent 6
02428 A1).
Anionic or nonionic surfactants are preferred. Two or more surfactants may be used in combination. Natural or synthetic polymers can also function as dispersants. Examples of the polymer which functions as a dispersant include polymers having a low molecular weight (preferably 1500 to 2000) (Japanese Patent Application Laid-Open Nos. 60-158637 and 7-13300).
And nonionic polymers (described in US Pat. No. 3,860,425) are preferably used.
The amount of the dispersant used is preferably 1 to 200% by weight of the amount of the dye.

The fine particles of the dye are 0.005 to 10 μm
Having an average particle size of 0.01 to 1 μm.
More preferably, it has an average particle size of O.m. More preferably, it has an average particle size of O1 to 0.5 μm, most preferably 0.01 to 0.1 μm.

When a dye (preferably, solid fine particles thereof) is added to a silver halide photographic material, it is added to a silver halide emulsion layer or a non-photosensitive hydrophilic colloid layer depending on the purpose of use of the dye. The non-photosensitive hydrophilic colloid layer to which the dye is added includes an antihalation layer and a filter layer. The antihalation layer is provided between the support and the silver halide emulsion layer or on the surface of the support opposite to the silver halide emulsion layer (back surface). The yellow filter layer is provided between the blue-sensitive silver halide emulsion layer and the green-sensitive silver halide emulsion layer. The magenta filter layer is provided between the green-sensitive silver halide emulsion layer and the red-sensitive silver halide emulsion layer. In the present invention, when the non-photosensitive layer is provided as a functional layer as described above (antihalation layer, yellow filter layer, magenta filter layer), the dye represented by the formula (I) is preferably provided on all of these layers (preferably, , A solid dispersion thereof).

A silver halide photographic light-sensitive material contains an arylidene dye or an azomethine dye at 5.0 × / m ^2.
Preferably, it is contained in the range of 10 ^{-5 to} 5.0 g.
More preferably, it is contained in the range of 0 × 10 ^{−4 to} 2.0 g, and more preferably, it is contained in the range of 5.0 × 10 ^{−3 to} 1.0 g. Two or more dyes may be used in combination in the same layer. One dye may be used in multiple layers. The arylidene dye represented by the formula (I) may be used in combination with a known dye.

The silver halide emulsion layer and the non-photosensitive hydrophilic colloid layer of the silver halide photographic material are both prepared using a hydrophilic colloid. As a hydrophilic colloid, gelatin is typical. As the silver halide emulsion, a silver bromide emulsion, a silver iodobromide emulsion, a silver iodochlorobromide emulsion, a silver chlorobromide emulsion or a silver chloride emulsion is preferably used. The silver halide grains may be fine grains of 0.1 μm or less or large grains having a projected area diameter of up to 10 μm. The grain size distribution of the silver halide grains in the emulsion is such that the total weight of silver halide grains having a grain size within ± 20% of the average grain size is 60% of the total weight of all silver halide grains. %, More preferably 80% or more. Monodisperse emulsions having a uniform particle size distribution are described in US Pat.
No. 5394 and British Patent No. 1413748.

The shape of the silver halide grains may be a regular crystal form (eg, cubic, octahedral, tetradecahedral) or an irregular crystal form (eg, spherical, tabular). May be a crystal form having crystal defects (eg, twin planes) or a composite form thereof. In silver halide emulsions containing tabular grains, tabular grains having an aspect ratio (equivalent circle diameter of AgX grains / grain thickness) of 3 or more account for at least 50% (per projected area) of all silver halide grains in the emulsion. Preferably it is present. For tabular grains and their preparation methods, see Gatoff, Gutoff, Photographic Science and Engi.
neering), Vol. 14, pp. 248-257 (1970)
And U.S. Pat. Nos. 4,434,226 and 44,143.
Nos. 10, 443,048 and 4,439,520, and British Patent No. 2,121,157.

The silver halide photographic emulsion is described in Research Disclosure (RD) No. 17643 (Jan.
Feb., pp. 22-23, "I. Emulsion prepar
No. 18716 (Jan. 1979)
No. 307105 (January, 1989)
Jan.), pp. 863-865, Grafkid, "Physics and Chemistry of Photography", published by Paul Montel (P. Glafkides, Chemie)
et Physique Photographique, Paul Montel, 1967), Duffin's Photographic Emulsion Chemistry, published by Focal Press (G.
F. Duffin, Photographic Emulsion Chemistry, Focal P
ress, 1966) and Zerikman et al., "Production and coating of photographic emulsions", published by Focal Press (VLZelikman et al., M.
aking and Coating Photographic Emulsion, Focal Pre
ss, 1964).

Emulsions comprising ordinary silver halide grains are:
By performing nucleation and particle growth by the double jet method while maintaining pAg supersaturated to such an extent that renucleation does not occur, particles of a desired size can be obtained. Also, a method of adding an aqueous solution of potassium iodide-gelatin and an aqueous solution of ammonium silver nitrate to an aqueous solution of gelatin containing silver halide grains while changing the addition rate as a function of time (described in JP-A-54-48521). )
May be used to produce an emulsion. In this case, a highly monodisperse silver halide emulsion can be obtained by appropriately selecting the time function of the addition rate, pH, pAg or temperature. For more information on these terms, see Photographic Science and Engineering
(Photographic Science and Engineering), Volume 6,
159-165 (1962), Journal of Photograph Science
ic Science), 12, 242-251 (1964),
And U.S. Pat. No. 3,655,394, British Patent 14137
No. 48 is described in each specification.

The crystal structure of the silver halide grains may be uniform, or the interior and exterior may have different halogen compositions. The particles having a different halogen composition may have a layered structure. Particles composed of different halogen compositions are disclosed in British Patent No. 1,027,146 and US Pat.
No. 68 and No. 4444877. Further, silver halides having different compositions may be bonded to the grains by epitaxial bonding. Compounds other than silver halide, such as rodan silver and lead oxide, may be bonded to the silver halide grains. The silver halide grains preferably have a distribution or structure relating to the halogen composition therein. For example, a core-shell type or double structure type particle having a halogen composition in which the inside and the surface of the particle are different (Japanese Patent Publication No. 43-13162, Japanese Patent Application Laid-Open No. 60-22284).
No. 5, No. 61-75337, and No. 61-215540) are preferable. Silver halides having a different composition on the surface of grains having a triple structure (described in JP-A-60-222844), multi-layered grains having more than that, and a core-shell double-structured grain, instead of a simple double-structured grain. May be used.

In order to impart a structure to the inside of the particle, not only the above-described wrapping structure but also a particle having a so-called bonding structure may be prepared. The bonding type particles are described in JP-B-58-24772 and JP-A-58-108526.
And JP-A-59-16254 and JP-A-59-133540 and EP199290A2. The crystal to be bonded has a different halogen composition from that of the host crystal. The crystal to be bonded is generated by bonding to an edge, a corner, or a plane of the host crystal. Such a junction crystal can be formed regardless of whether the host crystal has a uniform halogen composition or a core-shell structure. A silver salt compound that does not have a rock salt structure, such as rodan silver or silver carbonate, can be combined with silver halide to form a junction structure. Further, a non-silver salt compound such as PbO can also form a junction structure.

In a silver iodobromide grain having a core-shell type structure in which the halogen composition inside is different, even if the silver composition having a high silver iodide content in the core portion and a low silver iodide content in the shell portion is low. Conversely, the composition may have a low silver iodide content in the core portion and a high shell portion. Similarly, for silver iodobromide grains having a junction structure, even if the host crystal has a high silver iodide content and the junction crystal has a relatively low silver iodide content, the opposite halogen composition It may be.
Further, in a grain having a different halogen composition inside, a boundary portion having a different halogen composition is a clear boundary,
It may be an unclear boundary where a mixed crystal is formed due to a composition difference. Further, a continuous structural change may be positively introduced into the particles. Silver halide emulsions may be subjected to a treatment for imparting roundness to grains (European Patent Nos. 0136727B1 and 006)
4412B1) or a modification treatment of the particle surface (described in German Patent No. 2306447C2 and Japanese Patent Application Laid-Open No. 60-221320).

The silver halide emulsion is generally of the surface latent image type. However, an internal latent image type emulsion may be used by selecting a developing solution or developing conditions. The internal latent image type emulsion is described in JP-A-59-133542. Further, a shallow internal latent image type emulsion covered with a thin shell (described in JP-A-63-264740) can also be used. A silver halide solvent may be used to promote ripening of the silver halide emulsion. It is also known that aging is promoted when an excessive amount of halogen ions is present in the reactor. Therefore, ripening can be promoted only by introducing a solution of a halide salt into the reactor instead of the silver halide solvent. Ripening agents other than the silver halide solvent may be used. The ripening agent can be incorporated in its entirety in the dispersion medium in the reactor before adding the silver salt and the halide salt. It can also be introduced into the reactor together with one or more halide salts, silver salts or protective colloids. Furthermore, the ripening agent can be introduced into the reactor independently of the halide salt and silver salt during the stage of addition to the reactor.

As the ripening agent other than the halogen ion, ammonia, an amine compound, or a thiocyanate salt (for example, ammonium thiocyanate salt and alkali metal thiocyanate salt, particularly sodium or potassium thiocyanate salt) can be used. The silver halide emulsion is usually used after chemical sensitization (chalcogen sensitization, noble metal sensitization or reduction sensitization). Silver halide grains doped with a polyvalent metal ion in an amount of 1 × 10 ⁻⁴ mol / mol Ag or more do not show the effect of doping in an unripened state, and exhibit a remarkable effect when chemically sensitized. Depending on the composition, structure, and shape of the particles,
Or it depends on the use of the emulsion. There are cases where a chemical sensitizing nucleus is embedded inside the grain, where the chemical sensitizing nucleus is embedded at a position shallow from the grain surface, and where a chemical sensitizing nucleus is formed on the grain surface. When a chemical sensitization nucleus is formed near the surface, the effect of doping is remarkable. That is, doping with a polyvalent metal ion is more effective in a surface latent image type emulsion than in an internal latent image type emulsion.

Chemical sensitization was described by TH (James),
The Photographic Process, 4th Edition, Macmillan, 1977 (TH James, The Theory of the
Photographic Process, 4th ed, Macmillan, 1977) 67
This can be done using active gelatin as described on pages 76-76. Also, Research Disclosure 1
20, April 1974, 12010, Research Disclosure, 34, June 1975, 1345
2, U.S. Pat. Nos. 2,642,361 and 3,297,446;
Nos. 3772031, 3857711, 3901
No. 714, No. 3904415, No. 4266018,
As described in GB 1315755, pAg 5-10, pH 5-8 and temperature 30-80.
Chemical sensitization can be performed at ° C.

In the chalcogen sensitization, a sulfur, selenium or tellurium compound is used as a sensitizer. Noble metal sensitization
Gold, platinum, palladium or iridium compounds are used as sensitizers. A plurality of sensitizers may be used in combination. Gold sensitization may be performed in combination with a gold compound and a thiocyanate compound. As a sulfur sensitizer,
Hypo, thiourea compounds and rhodanine compounds are used. For sulfur sensitizers, see US Pat.
No. 1, No. 4,266,018 and No. 4,054,457. Chemical sensitization can also be performed in the presence of a chemical sensitization aid. The chemical sensitization aid has a function of suppressing fog in the process of chemical sensitization and increasing sensitivity. Examples of the chemical sensitizer include azaindene, azapyrididine and azapyrimidine. Chemical sensitization aids (or chemical sensitization improvers) are described in US Pat.
No. 31038, No. 3411914, No. 3555757
And JP-A-58-126526, and the aforementioned "Emulsion Chemistry" by Duffin, pp. 138-143.

The present invention is effective for both color photographic materials and black-and-white photographic materials. Typical color photographic light-sensitive materials are color paper, film for color photography, and color reversal films. Representative black-and-white photographic materials include X-ray films, black-and-white photographing films, and printing light-sensitive materials. A color photographic light-sensitive material generally has a multilayer structure and comprises a plurality of silver halide emulsion layers and a plurality of non-photosensitive hydrophilic colloid layers. Non-photosensitive hydrophilic colloid layer, a protective layer provided on the emulsion layer, an intermediate layer provided between a plurality of emulsion layers,
There is an undercoat layer provided between the emulsion layer and the support and a backing layer provided on the back side of the support (the side on which no emulsion layer is provided). The layer to which the dye is added is determined according to the function of the dye. When the dye functions as a filter, the dye is added to the protective layer or the intermediate layer. When functioning as an antihalation dye, the dye is added to the undercoat or backing layer. When functioning as an anti-irradiation dye, the dye is added to the silver halide emulsion layer.

There are no particular restrictions on the additives of the silver halide photographic light-sensitive material. For example, Research Disclosure, Volume 176, Item 1
7643 (RD17643) and 187, Item 18716 (RD18716). RD17643 and RD18716
Are described below.

{Type of Additive RD17643 RD18716} ─────────────────────────────── Chemical sensitizer page 23 648 right column Sensitivity enhancer 648 right column Spectral sensitizer Sensitizer, supersensitizer 23 to 24 pages 648 right column to 649 right column Whitening agent 24 fogging inhibitor, stabilizer 24 to 25 pages 649 right column Light absorber, filter dye, ultraviolet absorption 25 to 26 page 649 right column to 650 left column Stain inhibitor 25 page 650 page left column to 650 right column Dye image stabilizer 25 page Hardening agent 26 page 651 left column Binder 26 page 651 left column Plasticizer, lubricant page 27, page 650, left column Coating aid, surfactant, pages 26 to 27, page 650, right column STATI Anti-blocking agent Page 27 650 Right column ────────────────────────────────────

A dye may be added to a silver halide photographic light-sensitive material for thermal development. A silver halide photographic light-sensitive material for heat development is disclosed in US Pat.
0660A2, JP-A-59-218443.
Nos. 60-133449 and 61-238056. However, the present invention is particularly effective in ordinary wet development processing. Regarding the wet development processing using an automatic developing machine, see JP-A-3-13937 (pages 20 to 21, 25, 30 to 33, 40, 45).
Pp. 46-52, 53-53) and 3-171136 (1.
Pages 8 to 19) and JP-A-6-43583 (page 27).

The color photographic light-sensitive material is generally subjected to a developing process, a bleach-fixing process or a fixing process, a washing process or a stabilizing process after image exposure. The replenishment amount of the developing solution and the fixing solution is 25 to 200 m per 1 m ² of the photosensitive material.
1 is preferable, 30 to 180 ml is more preferable, and 60 to 150 ml or less is most preferable. The development processing time is preferably within 5 minutes, more preferably from 5 to 60 seconds, and most preferably from 5 to 30 seconds. In the water washing process, two or more tanks are generally countercurrently washed to save water. As the stabilizing treatment, a multi-stage countercurrent stabilizing treatment (described in JP-A-57-8543) can be employed instead of the washing step.

The color developing solution used for developing the color photographic light-sensitive material is preferably an alkaline aqueous solution containing an aromatic primary amine-based color developing agent as a main component. Aminophenol compounds are also useful as color developing agents, but p-phenylenediamine compounds are preferably used. Examples of p-phenylenediamine compounds include 3-
Methyl-4-amino-N, N-diethylaniline, 3-
Methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-
Methyl-4-amino-N-ethyl-N-β-methoxyethylaniline and their sulfates, hydrochlorides or p
-Toluenesulfonate is included. When the reversal process is performed, color development is usually performed after black and white development.
Black-and-white developers include dihydroxybenzenes (eg, hydroquinone) and 3-pyrazolidones (eg, 1-phenyl-).
3-pyrazolidone) or aminophenols (eg, N
-Methyl-p-aminophenol). The pH of the color developer and the black-and-white developer is
Generally it is 9-12.

The silver halide emulsion layer after development is usually subjected to a bleaching treatment. The bleaching process may be performed simultaneously with the fixing process (bleach-fixing process), or may be performed individually. In order to further speed up the processing, the order of the bleach-fixing after the bleaching may be used. In both the bleaching solution and the bleach-fixing solution, the use of an iron (III) aminopolycarboxylate complex salt is particularly effective. The pH of the bleaching solution or the bleach-fixing solution using the aminopolycarboxylic acid iron (III) complex salt is usually 5.5 to 8
It is. However, for faster processing, a lower p
H can also be processed.

In the bleaching solution, the bleach-fixing solution and the prebath thereof, a bleaching accelerator can be used if necessary.
Useful bleach accelerators are compounds having a mercapto group or a disulfide group. The bleaching accelerator may be added to a silver halide photographic light-sensitive material. As a fixing agent, thiosulfate is generally used. The silver halide photographic material generally undergoes a washing step or a stabilizing step after desilvering. The amount of rinsing water in the rinsing step is set according to various conditions (characteristics and application of the photosensitive material, rinsing water temperature, number of stages of the rinsing tank, replenishment method such as countercurrent or forward flow). The relationship between the number of washing tanks and the amount of water in the multistage countercurrent method is described in the Journal of the Society of Motion Picture an.
d Television Engineers Vol. 64, p. 248-25
3 (May 1955).

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[Embodiment 1]

[0153]

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Synthesis of Compound (3) 96.0 g of Compound (1) and toluene 3 were placed in a three-necked flask.
While stirring at room temperature, 97.7 ml of triethylamine was added dropwise over 5 minutes. After dropping,
Compound (2) 17 while heating and stirring at an internal temperature of 100 ° C.
4.9 g was added dropwise over 25 minutes. After completion of the dropwise addition, the mixture was continuously heated and stirred for 4 hours. Then, toluene was distilled off with an aspirator, the mixture was cooled to an internal temperature of 80 ° C. with water, and 300 ml of acetonitrile was added. After continuing cooling and stirring for 1 hour as it was, the precipitated crystals were separated by suction filtration and dried to obtain 184.4 g of compound (3) (yield: 93).
%).

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Synthesis of Compound (4) 70.8 g of Compound (3) and 210 ml of isopropyl alcohol were placed in a three-necked flask, and 59.3 ml of piperidine was added dropwise thereto over 10 minutes while stirring under reflux with heating. Subsequently, 36.1 ml of ethyl cyanoacetate was added dropwise over 10 minutes, and then the mixture was heated and stirred under reflux for 10 hours.
Cooled to room temperature. 500 ml of ethyl acetate and 5 ice
Then, 210 ml of concentrated hydrochloric acid was added with stirring, and the mixture was stirred for 1 hour. The precipitated crystals were filtered by suction and dried to obtain 68.1 g of the desired compound (4).
Was obtained (yield: 82%).

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Synthesis of arylidene compound (I-25) 166 g of compound (4) and compound (5) were placed in a three-necked flask.
96 g and 700 ml of acetic acid were added, and 330 ml of acetic anhydride was added dropwise at an internal temperature of 95 ° C. over 30 minutes. After heating and stirring for 3 hours after the completion of the dropwise addition, the mixture was cooled to room temperature, and the precipitated crystals were collected by suction filtration. The obtained crystals are methanol,
After washing with acetone, water and methanol in this order, 428 g of an arylidene compound (I-25) was obtained as a methanol wet cake. The dye content was 56% and the reaction yield was 98%.

[Example 2]

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Synthesis of azomethine compound (II-5) 166 g of compound (4) and 700 m
l, and 70 ml of triethylamine was added dropwise over 50 minutes while stirring and cooling with ice. After completion of the dropwise addition, 110 g of the compound (6) was added over 15 minutes, and 52 ml of acetic anhydride was further added dropwise over 30 minutes. After completion of the dropwise addition, the ice bath was removed and stirring was continued for 5 hours. The precipitated crystals were filtered by suction and washed in the order of methanol, acetone, water and methanol to obtain 554 g of an azomethine compound (II-5) as a methanol wet cake. The dye content was 41% and the reaction yield was 95%.

[Embodiment 3]

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Synthesis of Compound (7) 45 ml of sulfuric acid was placed in a three-necked flask, and 33.2 g of Compound (4) was added over 5 minutes while stirring at room temperature.
After completion of the addition, the mixture was heated and stirred at an internal temperature of 85 ° C. for 4 hours, and then poured into 500 g of ice while stirring, and the stirring was continued for 2 hours. The precipitated crystals were collected by suction filtration, washed with water and acetonitrile in that order, and dried to obtain compound (7) 3.
0.8 g was obtained (yield: 88%).

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Synthesis of arylidene compound (I-36) 104.5 g of compound (7), 57.5 g of compound (5) and 700 ml of acetic acid were placed in a three-necked flask, and 169 ml of acetic anhydride was added thereto while stirring under heating and reflux. It was added dropwise over 30 minutes. After completion of the dropwise addition, the mixture was continuously stirred for 5 hours, then concentrated using an aspirator, 500 ml of ethanol was added, and the mixture was allowed to cool to room temperature with stirring. The precipitated crystals are filtered by suction, washed with a solvent in the order of ethanol, acetone, water, and ethanol, and the arylidene compound (I-
357 g of 36) was obtained as an ethanol wet cake. The dye content was 42% and the reaction yield was 99%.

[Embodiment 4]

[0168]

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Synthesis of Compound (9) 192.0 g of Compound (8) and 500 ml of toluene were placed in a three-necked flask, and 195.4 ml of triethylamine was added dropwise over 5 minutes while stirring at room temperature. After completion of the dropwise addition, compound (2) 349.
8 g was added dropwise over 15 minutes. After completion of the dropwise addition, heating and stirring were continued for 4 hours. Then, toluene was distilled off using an aspirator, and the mixture was further heated and stirred at an internal temperature of 140 ° C. for 2 hours. Thereafter, the internal temperature was cooled to 80 ° C. with water cooling, and 800 ml of acetonitrile was added. Allow it to cool for one hour,
After continued stirring, the precipitated crystals were separated by suction filtration,
Drying gave 337.2 g of compound (9) (yield: 8).
5%).

[0170]

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Synthesis of Compound (10) Compound (9) (120.4 g) and n-butyl alcohol (350 ml) were placed in a three-necked flask, and piperidine (100.8 ml) was added dropwise with stirring over 30 minutes while heating under reflux. Subsequently, 61.3 ml of ethyl cyanoacetate was added dropwise over 10 minutes, followed by heating under reflux for 10 hours and cooling to room temperature. 700 ml of ethyl acetate and 1 piece of ice
000 g, and 360 ml of concentrated hydrochloric acid was added with stirring, followed by stirring for 1 hour. The precipitated crystals were collected by suction filtration and dried, and 108.7 g of the compound (10) was dried.
Was obtained (yield: 77%).

[0172]

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Synthesis of arylidene compound (I-26) 84.0 g of compound (10), 48.0 g of compound (5) and 350 ml of acetic acid were placed in a three-necked flask, and 165 ml of acetic anhydride was added thereto while stirring under heating and reflux. It was added dropwise over 30 minutes. After completion of the dropwise addition, the mixture was further stirred under heating and reflux for 3 hours, cooled to room temperature, and the precipitated crystals were collected by suction filtration. The obtained crystals are methanol, acetone,
After washing with water and methanol in this order, the arylidene compound (I
-26) was obtained as a methanol wet cake (272 g). The dye content was 44% and the reaction yield was 98%.

[Embodiment 5]

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Synthesis of Azomethine Compound (II-8) 33.2 g of compound (4) and 170 ml of methanol were placed in a three-necked flask, and 14.0 ml of triethylamine was added dropwise with stirring under cooling with ice over 5 minutes. After completion of the dropwise addition, 27.3 g of the compound (11) was added over 5 minutes, and 10.4 ml of acetic anhydride was further added dropwise over 30 minutes. After the completion of the dropwise addition, the ice bath was removed and stirring was continued for 4 hours. The precipitated crystals were filtered by suction and washed in the order of methanol, acetone, water and methanol to obtain 118 g of an azomethine compound (II-8) as a methanol wet cake. The dye content was 42% and the reaction yield was 90%.

Example 6 (Preparation of Solid Fine Particle Dispersion of Dye) In a 700 ml pot mill, 21.7 ml of water, 3 ml of a 5% by weight aqueous solution of sodium p-octylphenoxyethoxyethoxyethanesulfonate and p-octylphenoxypolyethylene were added. 0.5 wt% aqueous solution of oxyethylene ether (degree of polymerization 10) 0.5
g), 5.0 g of arylidene dye (I-25) and 500 ml of zirconium oxide beads (diameter: 1 mm) were added, and a vibration ball mill (BO type, manufactured by Chuo Koki Co., Ltd.)
For 2 hours. After the dispersion, the contents were taken out, added to 8 g of a 12.5% by weight aqueous solution of gelatin, and the beads were removed by filtration to obtain a gelatin dispersion of an arylidene dye (I-25). The average particle size of the dye fine particles is 0.4
It was 1 μm.

(Preparation of silver halide photographic light-sensitive material) A silver halide color photographic light-sensitive material having the following layer constitution (described in Example 1 of JP-A-11-38568) was prepared, and
To the layer (second antihalation layer), a solid fine particle dispersion of an arylidene dye (I-25) was added as an antihalation dye. The amount added was 0.1 as the amount of dye applied.
It was 0 g / m ² . Further, the composition of the second layer (second antihalation layer) is shown. The composition of the layers other than the second layer is the same as that of a general silver halide color photographic light-sensitive material.

１６ Sixteenth layer (second protective layer) No. 15 Layer (first protective layer) Fourteenth layer (highly sensitive blue-sensitive silver halide emulsion layer) 13th layer (low-sensitive blue-sensitive silver halide emulsion layer) 12th layer (yellow filter layer) 11th layer (highly sensitive green) Sensitive silver halide emulsion layer) 10th layer (medium-speed green-sensitive silver halide emulsion layer) 9th layer (low-sensitivity green-sensitive silver halide emulsion layer) 8th layer (inter-image effect layer) 7th layer (intermediate) Layer) 6th layer (high-speed red-sensitive silver halide emulsion layer) 5th layer (medium-speed red-sensitive silver halide emulsion layer) 4th layer (low-speed red-sensitive silver halide emulsion layer) Third layer (intermediate layer) ) Second layer (second antihalation layer) First layer (first antihalation layer) Undercoat layer Support (triacetylcellulose) Film)

の of the second layer (second antihalation layer) Composition コ ロ イ ド Black colloidal silver 0.066 g / m ² Gelatin 0.407 g / m ² following magenta couplers 0.050 g / m ² following cyanine dye 0.002 g / m ² tricresyl phosphate (high-boiling organic solvent) 0.074 g / m ² solid particulate arylidene dyes (I-1) 0 .015 g / m ² ────────────────────────────────────

[0181]

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[0182]

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(Evaluation of silver halide photographic light-sensitive material) The silver halide photographic light-sensitive material was exposed to white light through an optical wedge, and then processed by the following method using an automatic developing machine. The automatic developing machine was adjusted in advance, and the processing was performed until the cumulative replenishment amount of the solution became three times the capacity of the mother liquor tank.

工程 Step Processing Time Processing Temperature ──────色 Color development 3 minutes and 15 seconds 38 ° C Bleaching 3 minutes and 00 seconds 38 ° C Rinse with water 30 seconds 24 ° C fixed 3 minutes 00 seconds 38 ° C water washing (1) 30 seconds 24 ° C water washing (2) 30 seconds 24 ° C stable 30 seconds 38 ° C drying 4 minutes 20 seconds 55 ° C ────────── ──────────────────────────

組成 Color developing solution composition─────── ───────────────────────────── Diethylenetriaminepentaacetic acid 1.0 g 1-hydroxyethylidene-1,1-diphosphonic acid 2.0 g Sulfurous acid Sodium 4.0 g Potassium carbonate 30.0 g Potassium bromide 1.4 g Potassium iodide 1.5 mg Hydroxylamine sulfate 2.4 g 4- [N-ethyl-N- (β-hydroxyethyl) amino] -2-methylaniline Sulfate 4.5g Add water 1 liter pH (adjusted with potassium hydroxide and sulfuric acid) 10.05０．０５ ──────────

{Bleach-fixing solution composition} ───────────────────────────── Ferric sodium ethylenediaminetetraacetate trihydrate 100.0 g Disodium ethylenediaminetetraacetate 10. 0 g 3-mercapto-1,2,4-triazole 0.03 g ammonium bromide 140.0 g ammonium nitrate 30.0 g ammonia water (27%) 6.5 ml water was added to add 1 liter pH (adjusted with ammonia water and nitric acid) 6.0 ────────────────────────────────────

<< Composition of Fixing Solution >>二 Ethylenediaminetetraacetic acid disodium salt 0.5 g Ammonium sulfite 20.0 g Ammonium thiosulfate aqueous solution (700 g / liter) ) 295 ml Acetic acid (90%) 3.3 g 1 liter by adding water pH (adjusted with ammonia water and acetic acid) 6.7 ───────────────────── ───────────────

組成 Fixing solution composition──────── ──────────────────────────── p-nonylphenoxy polyglycidol (glycidol average polymerization degree: 10) 0.2 g ethylenediaminetetraacetic acid 05g 1,2,4-triazole 1.3g 1,4-bis (1,2,4-triazol-1-ylmethyl) piperazine 0.75g hydroxyacetic acid 0.02g hydroxyethylcellulose 0.1g 1,2-benzisothiazoline- 3-one 0.05g 1 liter pH 8.5 with water ──

After the processing, the density of the silver halide photographic light-sensitive material was measured, and the density (DR (min)) of the fog portion of the red-sensitive silver halide emulsion layer was read as a relative value to the result of Comparative Example 1 described later. The decolorization of the dye was evaluated. The lower the density of the fogged portion, the better the decolorization of the dye. Further, the sensitivity of the red-sensitive silver halide emulsion layer was adjusted to fog +0.
It was expressed by the logarithm of the reciprocal of the exposure amount giving the density of 2, and evaluated by a relative value to the result of Comparative Example 1 described later. The higher the relative sensitivity, the better the diffusion resistance of the dye.
The migration from the antihalation layer to the red-sensitive silver halide emulsion layer does not lower the sensitivity of the red-sensitive silver halide emulsion layer. Further, the reflection spectrum of the silver halide photographic light-sensitive material before exposure was measured in a visible region of 400 to 700 nm under an infrared lamp. Next, put the silver halide photographic material in a dark box,
A forced deterioration test was performed for 10 days at a temperature of 50 ° C. and a relative humidity of 80%. Then, visible range 400-7 under infrared light
The reflection spectrum at 00 nm was measured. Wavelength 550nm
At the wavelength of 650 nm, the following absorbance ratio was determined to evaluate the stability of the dye. Dye stability (absorbance ratio) = 100 × absorbance before test / absorbance after test.

Examples 7 to 13 The arylidene dyes (I
-25) Instead of 5.0 g, an arylidene dye (I-2)
6), (I-28), (I-36), (I-38), azomethine dyes (II-1), (II-4) and (II-1)
A solid fine particle dispersion of a dye was prepared in the same manner as in Example 6, except that 3) was used in the same amount. The average particle size of the fine particles is shown in Table 1. A silver halide photographic material was prepared and evaluated in the same manner as in Example 6, except that the prepared solid fine particle dispersion was used. The results are shown in Table 1.

Comparative Examples 1 to 5 The arylidene dyes (I-
25) Instead of 5.0 g, the following oxonol dye (X
-1), (X-2), arylidene dye (Y-1),
A solid fine particle dispersion of the dye was prepared in the same manner as in Example 6, except that the same amounts of (Y-2) and the azomethine dye (Z-1) were used. The average particle size of the fine particles is shown in Table 1. The arylidene dye (Y-1) is disclosed in
No. 37841, the arylidene dye (Y-2) corresponds to the compound 4 described in the same publication, and the azomethine dye (Z-1) corresponds to the compound I-1 described in Japanese Patent Application Laid-Open No. 4-45436. I do. A silver halide photographic material was prepared and evaluated in the same manner as in Example 6, except that the prepared solid fine particle dispersion was used. The results are shown in Table 1.

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Table 1 Table 1- Red-sensitive silver halide dyes Emulsion layer dye stability Photosensitive material Dye Average particle size Fog density Relative sensitivity 550nm 650nm ─────────────────────────────── ───── Example 6 (I-25) 0.41 μm −0.14 +0.08 94 98 Example 7 (I-26) 0.33 μm −0.09 +0.06 90 96 Example 8 (I −28) 0.40 μm −0.12 +0.06 88 91 Example 9 (I−36) 0.38 μm −0.11 +0.09 9699 Example 10 (I−38) 0.44 μm −0.07 +0.06 94 95 Example 11 (II-1) 0.49 μm −0.06 +0.08 94 93 Example 12 (II-4) 0.30 μm −0.08 +0.06 89 90 Example 13 (II-13) 0.52 μm −0.08 +0.05 93 98 Comparative Example 1 (X-1) 0.44 μm 0 (reference) 0 (reference) 76 65 Comparative Example 2 (X-2) 0.24 μm +0.24 −0.04 59 44 Comparative Example 3 (Y-1) 0.39 μm +0.05 −0.10 83 70 Comparative Example 4 (Y-2) 0. 28 μm + 0.18−0.14 80 66 Comparative Example 5 (Z−1) 0.43 μm + 0.26−0.11 78 70 ──────────────────── ────────────────

[Example 14] (Preparation of silver halide photographic light-sensitive material) An X-ray light-sensitive material having the following layer constitution (described in Example 5 of JP-A-3-7931) was prepared, and the dye layer was prepared. The solid fine particle dispersion of the arylidene dye (I-25) prepared in 1 was added.

──────────────────────────────────── Surface protective layer X-ray-sensitive silver halide emulsion Layer Dye layer (gelatin 0.12 g / m ² and solid particulate dye 50 mg / m ² ) Support (175 μm thick blue-dyed polyethylene terephthalate) Dye layer (gelatin 0.12 g / m ² and solid particulate dye) 50 mg / m ² ) X-ray-sensitive silver halide emulsion layer Surface protective layer ───

(Evaluation of silver halide photographic light-sensitive material) A silver halide photographic light-sensitive material was sandwiched between two screens (G-3, manufactured by Fuji Photo Film Co., Ltd.), and X-ray exposure was performed through a 10 cm water phantom. went. The silver halide photographic material was processed by an automatic processor (FPM-4000, manufactured by Fuji Photo Film Co., Ltd.). The sensitivity was 100% for the sample in which the solid particulate dye was not added to the dye layer.
Was determined. Sharpness (MTF) is 30μ
The measurement was performed with an aperture of mx 500 μm, and the evaluation was performed at a portion where the optical density was 1.0 using an MTF value where the spatial frequency was 1.0 cycle / mm. Further, the unexposed photographic light-sensitive material was processed by an automatic developing machine, and the degree of residual color was evaluated on a scale of A to E. A is a state in which no residual color is recognized, E is a state in which strong residual color is recognized, and BD are intermediate states. Table 2 shows the above results.

Examples 15 to 22 The arylidene dye (I-25) was used in place of 5.0 g of the arylidene dye (I-25).
-27), (I-34), (I-41), (I-4
Example 1 except that the same amounts of the azomethine dyes (II-2), (II-8) and (II-12) were used respectively.
In the same manner as in the above, a solid fine particle dispersion of the dye was prepared. Table 2 shows the average particle diameter of the fine particles. The prepared solid fine particle dispersion and the arylidene dye (I) prepared in Example 9 were prepared.
Example 1 except that the solid fine particle dispersion of -36) was used.
In the same manner as in Example 4, a silver halide photographic light-sensitive material was prepared and evaluated. The results are shown in Table 2.

[0202]

[Table 2] Table 2 感光 Photosensitive material Dye Average particle size Relative Sensitivity MTF residual color 色 Example 14 (I-25) 0. 36 μm 96 0.88 A Example 15 (I-27) 0.44 μm 94 0.88 A Example 16 (I-34) 0.48 μm 94 0.87 A Example 17 (I-36) 0.38 μm 94 0.88 A Example 18 (I-41) 0.32 μm 95 0.87 A Example 19 (I-49) 0.38 μm 93 0.88 A Example 20 (II-2) 0.44 μm 94 88 A Example 21 (II-8) 0.40 μm 94 0.87 A Example 22 (II-12) 0.33 μm 93 0.88 A ──── ────────────────────────────────

Example 23 (Preparation of a silver halide photographic light-sensitive material) A silver halide color photographic light-sensitive material having the following layer constitution (described in Example 7 of JP-A-3-7931) was prepared, and antihalation was performed. The solid fine particle dispersion of the arylidene dye (I-25) prepared in Example 1 was added to the layer. The amount added was 0.10 g / m ² as the coating amount of the dye.

７ Seventh layer (protective layer) Sixth layer (protective layer) UV-absorbing layer) Fifth layer (infrared-sensitive cyan-color-forming silver halide emulsion layer) Fourth layer (ultraviolet-absorbing layer) Third layer (infrared-sensitive magenta-coloring silver halide emulsion layer) Second layer (color-mixing prevention layer) First layer (infrared-sensitive yellow-colored silver halide emulsion layer) Antihalation layer (0.8 g of gelatin and 77 mg of solid particulate dye) Support (paper laminated on both sides with polyethylene) ──────────────────────────

(Evaluation of the silver halide photographic light-sensitive material) After the silver halide photographic light-sensitive material was exposed to an image, it was developed with a color paper processor. As a result, an image having good resolving power and good edge cut was obtained.

Examples 24-28 The arylidene dye (I-25) was replaced with 5.0 g of the arylidene dye (I-25).
-30), (I-35) and (I-51) were prepared in the same manner as in Example 1 except that the same amounts were used, to prepare solid fine particle dispersions of dyes. Except for using the prepared solid fine particle dispersion, the solid fine particle dispersion of the arylidene dye (I-36) prepared in Example 9, and the solid fine particle dispersion of the azomethine dye (II-12) prepared in Example 22, A silver halide photographic light-sensitive material was prepared and evaluated in the same manner as in Example 23. As a result, images with good resolving power and good edge cut were obtained.

[0207]

The arylidene compound and azomethine compound of the present invention have excellent stability as dyes, are easily removed in photographic processing, and have excellent diffusion resistance.

 ────────────────────────────────────────────────── ─── Continued on the front page (72) Inventor Yoshiharu Yabuki 210 Nakanakanuma, Minamiashigara, Kanagawa Prefecture Fuji Photo Film Co., Ltd. F-term (reference) 2H023 CE00 FD01 4H056 CA01 CE03 DD04 FA05

Claims (9)

[Claims] 1. An arylidene represented by the following formula (I):
Compound. Embedded imageWhere L¹Means monomethine, trimethine, pentamethine
Or heptamethine; Z is cyano or carb
Moyl; R¹, R^Two, R^FiveAnd R⁶Is
Independently hydrogen, halogen, cyano, aliphatic
Group, aromatic group, -OR¹¹, -CO-R¹², -CO-O
-R¹³, -NR¹⁴R^Fifteen, -NHCO-R¹⁶, -NH-C
OOR¹⁷, -SO_Two-R¹⁸Or -NH-SO_Two−
R¹⁹And R¹¹, R¹², R¹³, R¹⁴, R^Fifteen, R¹⁶,
R¹⁷, R¹⁸And R¹⁹Is independently a hydrogen atom,
An aliphatic group or an aromatic group;^ThreeAnd R^FourIs
Each independently represents a hydrogen atom, an aliphatic group, an aromatic group, -CO
-R^{twenty one}Or -SO_Two-R^{twenty two}And R^{twenty one}And R^{twenty two}
Are each independently an aliphatic or aromatic group;
R⁷And R⁸Are each independently a halogen atom,
Ano, aliphatic group, aromatic group, -OR³¹, -CO-
R³², -CO-OR³³, -NR³⁴R³⁵, -NHCO-
R³⁶, -NH-CO-OR³⁷, -SO_Two-R³⁸Or
-NH-SO_Two-R ³⁹And R³¹, R³², R³³, R
³⁴, R³⁵, R³⁶, R³⁷, R³⁸And R³⁹Is German
A hydrogen atom, an aliphatic group or an aromatic group;
Is 0, 1, 2, 3, 4, or 5, and m is 2 or more
In the case of⁷May be different; n is 0,
1, 2, 3 or 4, when n is 2 or more, plural
R⁸May be different; and R¹And R^Two, R
^TwoAnd R^Three, R^ThreeAnd R^Four, R^FourAnd R ^Five, R^FiveAnd R⁶,two
R⁷Or two R⁸Are bonded to each other to form a ring
Wear. 2. The arylidene compound according to claim 1, wherein in the formula (I), L ¹ is trimethine. 3. In the formula (I), R ¹ and R ⁶ are
R ² and R ⁵ are each independently a hydrogen atom, an alkyl group or an alkoxy group; R ³ is a hydrogen atom;
And R ⁴ are each independently a hydrogen atom, an alkyl group or an aryl group; and R ² and R ³ or R
⁴ and R ^5, arylidene compound of claim 1 which can bond to each other to form a ring. 4. A support, a silver halide emulsion layer and a non-sensitive
Silver halide photographic light-sensitive material having photo-hydrophilic colloid layer
A silver halide emulsion layer or a non-photosensitive hydrophilic
Arylidene dyeing wherein the colloid layer is represented by the following formula (I):
Silver halide photographic light-sensitive material, characterized in that it contains a silver halide photographic material. Embedded imageWhere L¹Means monomethine, trimethine, pentamethine
Or heptamethine; Z is cyano or carb
Moyl; R¹, R^Two, R^FiveAnd R⁶Is
Independently hydrogen, halogen, cyano, aliphatic
Group, aromatic group, -OR¹¹, -CO-R¹², -CO-O
-R¹³, -NR¹⁴R^Fifteen, -NHCO-R¹⁶, -NH-C
OOR¹⁷, -SO_Two-R¹⁸Or -NH-SO_Two−
R¹⁹And R¹¹, R¹², R¹³, R¹⁴, R^Fifteen, R¹⁶,
R¹⁷, R¹⁸And R¹⁹Is independently a hydrogen atom,
An aliphatic group or an aromatic group;^ThreeAnd R^FourIs
Each independently represents a hydrogen atom, an aliphatic group, an aromatic group, -CO
-R^{twenty one}Or -SO_Two-R^{twenty two}And R^{twenty one}And R^{twenty two}
Are each independently an aliphatic or aromatic group;
R⁷And R⁸Are each independently a halogen atom,
Ano, aliphatic group, aromatic group, -OR³¹, -CO-
R³², -CO-OR³³, -NR³⁴R³⁵, -NHCO-
R³⁶, -NH-CO-OR³⁷, -SO_Two-R³⁸Or
-NH-SO_Two-R ³⁹And R³¹, R³², R³³, R
³⁴, R³⁵, R³⁶, R³⁷, R³⁸And R³⁹Is German
A hydrogen atom, an aliphatic group or an aromatic group;
Is 0, 1, 2, 3, 4, or 5, and m is 2 or more
In the case of⁷May be different; n is 0,
1, 2, 3 or 4, when n is 2 or more, plural
R⁸May be different; and R¹And R^Two, R
^TwoAnd R^Three, R^ThreeAnd R^Four, R^FourAnd R ^Five, R^FiveAnd R⁶,two
R⁷Or two R⁸Are bonded to each other to form a ring
Wear. 5. The silver halide photograph according to claim 4, wherein the arylidene dye represented by the formula (I) is dispersed in the form of solid fine particles in a silver halide emulsion layer or a non-photosensitive hydrophilic colloid layer. Photosensitive material. 6. An azomethine compound represented by the following formula (II):
Compound. Embedded imageWherein Z is cyano or carbamoyl;¹,
R^Two, R^FiveAnd R⁶Is independently a hydrogen atom,
Halogen atom, cyano, aliphatic group, aromatic group, -OR
¹¹, -CO-R¹², -CO-OR¹³, -NR¹⁴R^Fifteen,
-NHCO-R ¹⁶, -NH-CO-OR¹⁷, -SO_Two
-R¹⁸Or -NH-SO_Two-R¹⁹And R¹¹, R
¹², R¹³, R¹⁴, R^Fifteen, R¹⁶, R¹⁷, R¹⁸And R
¹⁹Are each independently a hydrogen atom, an aliphatic group or an aromatic
Group; R^ThreeAnd R^FourIs, independently of each other, hydrogen
Atom, aliphatic group, aromatic group, -CO-R^{twenty one}Or -SO
_Two-R ^{twenty two}And R^{twenty one}And R^{twenty two}Are independent
Is an aliphatic or aromatic group;⁷And R
⁸Is independently a halogen atom, cyano, aliphatic
Group, aromatic group, -OR³¹, -CO-R³², -CO-O
-R³³, -NR³⁴R³⁵, -NHCO-R³⁶, -NH-C
OOR³⁷, -SO_Two-R³⁸Or -NH-SO_Two−
R³⁹And R³¹, R³², R³³, R³⁴, R³⁵, R³⁶,
R³⁷, R³⁸And R³⁹Is independently a hydrogen atom,
M is 0, 1, 2, or an aliphatic or aromatic group;
3, 4, or 5, when m is 2 or more, a plurality of R
⁷May be different; n is 0, 1, 2, 3, or
4, when n is 2 or more, a plurality of R⁸Is different
And R¹And R^Two, R^TwoAnd R^Three, R^ThreeWhen
R^Four, R^FourAnd R^Five, R^FiveAnd R⁶, Two R⁷Or two
R⁸Can combine with each other to form a ring. 7. In the formula (II), R ¹ and R ⁶ are
R ² and R ⁵ are each independently a hydrogen atom, an alkyl group or an alkoxy group; R ³ is a hydrogen atom;
And R ⁴ are each independently a hydrogen atom, an alkyl group or an aryl group; and R ² and R ³ or R
⁴ and R ^5, arylidene compound of claim 1 which can bond to each other to form a ring. 8. A support, a silver halide emulsion layer and a non-sensitive
Silver halide photographic light-sensitive material having photo-hydrophilic colloid layer
A silver halide emulsion layer or a non-photosensitive hydrophilic
Azomethine dye whose colloid layer is represented by the following formula (II)
A silver halide photographic light-sensitive material comprising: Embedded imageWherein Z is cyano or carbamoyl;¹,
R^Two, R^FiveAnd R⁶Is independently a hydrogen atom,
Halogen atom, cyano, aliphatic group, aromatic group, -OR
¹¹, -CO-R¹², -CO-OR¹³, -NR¹⁴R^Fifteen,
-NHCO-R ¹⁶, -NH-CO-OR¹⁷, -SO_Two
-R¹⁸Or -NH-SO_Two-R¹⁹And R¹¹, R
¹², R¹³, R¹⁴, R^Fifteen, R¹⁶, R¹⁷, R¹⁸And R
¹⁹Are each independently a hydrogen atom, an aliphatic group or an aromatic
Group; R^ThreeAnd R^FourIs, independently of each other, hydrogen
Atom, aliphatic group, aromatic group, -CO-R^{twenty one}Or -SO
_Two-R ^{twenty two}And R^{twenty one}And R^{twenty two}Are independent
Is an aliphatic or aromatic group;⁷And R
⁸Is independently a halogen atom, cyano, aliphatic
Group, aromatic group, -OR³¹, -CO-R³², -CO-O
-R³³, -NR³⁴R³⁵, -NHCO-R³⁶, -NH-C
OOR³⁷, -SO_Two-R³⁸Or -NH-SO_Two−
R³⁹And R³¹, R³², R³³, R³⁴, R³⁵, R³⁶,
R³⁷, R³⁸And R³⁹Is independently a hydrogen atom,
M is 0, 1, 2, or an aliphatic or aromatic group;
3, 4, or 5, when m is 2 or more, a plurality of R
⁷May be different; n is 0, 1, 2, 3, or
4, when n is 2 or more, a plurality of R⁸Is different
And R¹And R^Two, R^TwoAnd R^Three, R^ThreeWhen
R^Four, R^FourAnd R^Five, R^FiveAnd R⁶, Two R⁷Or two
R⁸Can combine with each other to form a ring. 9. The silver halide photograph according to claim 8, wherein the azomethine dye represented by the formula (II) is dispersed in the form of solid fine particles in a silver halide emulsion layer or a non-photosensitive hydrophilic colloid layer. Photosensitive material.