JPH05181225A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To enhance sharpness and sensitivity and to reduce fog by incorporating a silver salt of a dye in a photographic constituent layer and a homopolymer or copolymer soluble in organic solvents but insoluble in water in a blue- sensitive silver halide emulsion layer. CONSTITUTION:The photographic sensitive material is provided with the silver halide emulsion layers including blue-sensitive, green-sensitive, and red-sensitive layers on a reflective support and one of the photographic constituent layers contains at least one of the silver salt of the dye, and this blue-sensitive silver halide emulsion layer contains the polymer or copolymer insoluble in water but soluble in organic solvents, and one of the silver halide emulsion layers contains at least one of the compounds represented by formula I in which each of R1-R3 is an aliphatic or aromatic group; and each of (l), (m), and (n) is 0 or 1. The silver salt of a dye means the silver salt or silver complex salt formed by reaction between the dye and a silver ion, and the dye is an organic compound having absorption in the visible spectra (380-700nm).

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide color photographic light-sensitive material, and more particularly to a silver halide color photographic light-sensitive material having high sharpness, high sensitivity, little fog and good raw storability. ..

[0002]

BACKGROUND OF THE INVENTION It is well known in the art to provide a coloring layer such as an antihalation layer or a filter layer in a silver halide photographic light-sensitive material in order to improve image sharpness. Although such colored layers often contain water-soluble dyes, these known dyes are often not completely photochemically inert and often have a detrimental effect on the light-sensitive layers of photographic materials, i.e. fog. And increased sensitivity.

Further, in the industry, silver halide color photographic light-sensitive materials having higher and higher image quality have been desired in recent years.
In particular, in the so-called color negative / positive system in which a final image is obtained by photographing with a silver halide photographic light-sensitive material for color negative and printing on a silver halide photographic light-sensitive material for color photographic paper, a silver halide photographic light-sensitive material for color negative On the other hand, there is a problem in that the image quality of a silver halide photographic light-sensitive material for color photographic paper, especially sharpness, is low.

Therefore, an attempt was made to improve the sharpness of the image by adding a large amount of a water-soluble dye. According to the experiments conducted by the present inventors, the sensitivity of the emulsion layer was remarkably lowered and the fog density was greatly increased. It was revealed that the storability deteriorated and the effect of improving the sharpness of the image was small.

[0005]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a silver halide color photographic light-sensitive material having high sharpness, high sensitivity, little fog and good raw storability.

[0006]

The above object of the present invention is achieved by the following silver halide color photographic light-sensitive material. (1) A silver halide color photographic light-sensitive material having a photographic constituent layer including a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, and a red-sensitive silver halide emulsion layer on a reflective support. In the photographic constituent layer, and at least one of water-insoluble and organic solvent-soluble homopolymers or copolymers in the blue-sensitive silver halide emulsion layer. And a silver halide color photographic light-sensitive material. (2) A silver halide color photographic light-sensitive material having a photographic constituent layer comprising a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, and a red-sensitive silver halide emulsion layer on a reflective support. The photographic constituent layer of No. 1 contains at least one silver salt of a dye, and the red-sensitive silver halide emulsion layer contains at least one of water-insoluble and organic solvent-soluble homo- or copolymers. And a silver halide color photographic light-sensitive material. (3) A silver halide color photographic light-sensitive material having a photographic constituent layer including a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, and a red-sensitive silver halide emulsion layer on a reflective support. In the photographic constituent layer, and in any one of the silver halide emulsion layers contains at least one compound represented by the following general formula [I]. A silver halide color photographic light-sensitive material.

[0007]

[Chemical 2][In the formula, R ₁, R₂And R₃Is an aliphatic group or
Represents an aromatic group, and l, m and n each represent 0 or 1.
You ] (4) Blue-sensitive silver halide emulsion layer, green on reflective support
Sensitive silver halide emulsion layer and red-sensitive silver halide emulsion
Silver halide color photographic feeling having photographic constituent layers including layers
In optical materials, silver salt of dye is added to either photographic constituent layer.
Containing at least one of
At least one heterocyclic antifoggant in the silver halide emulsion layer
Silver halide color photographic light-sensitive material characterized by containing
material. (5) Blue-sensitive silver halide emulsion layer, green on reflective support
Sensitive silver halide emulsion layer and red-sensitive silver halide emulsion
Silver halide color photographic feeling having photographic constituent layers including layers
In optical materials, silver salt of dye is added to either photographic constituent layer.
Containing at least one of
Characterized in that the layer contains at least one optical brightener
And a silver halide color photographic light-sensitive material. (6) Blue-sensitive silver halide emulsion layer, green on reflective support
Sensitive silver halide emulsion layer and red-sensitive silver halide emulsion
Silver halide color photographic feeling having photographic constituent layers including layers
In optical materials, silver salt of dye is added to either photographic constituent layer.
Containing at least one of
The layer is covered with at least one vinyl sulfone hardener.
Halogen characterized by containing cross-linked gelatin
Silver halide color photographic light-sensitive material.

The present invention will be described in detail below.

First, the silver salt of the dye of the present invention will be described.

In the present invention, the silver salt of the dye represents a silver salt or a silver complex formed by the reaction of the dye with silver ions, and the dye is an organic compound having an absorption in the visible spectrum (380 to 700 nm). Represent

The preferred dyes capable of forming the silver salt of the dye used in the present invention will be described below, but the present invention is not limited thereto.

Examples of the dye include the dyes represented by the following general formulas [I] to [V].

[0013]

[Chemical 3][In the formula, R¹, R²Is a hydrogen atom, alkyl group, alkenyl
A group, an aryl group or a heterocyclic group, X₁, X₂Is oxygen source
Represents a child and a sulfur atom. L ₁~ L_FiveRepresents a methine group, n
₁, N₂Represents an integer of 0 to 2. Also E₁Has an acidic nucleus
Represents the group ]

[0014]

[Chemical 4][In the formula, R³, R^Four Is R in the general formula [I]¹, R²Same as
Righteous and X₃, X_FourIs X in the general formula [I]₁, X ₂When
Are synonymous. L₆~ L₉Represents a methine group, n₃~ N_FiveIs 0
Represents an integer of 2; R^FiveIs an alkyl group or an alkenyl group
Represent, Q₁Required to form a 5- or 6-membered heterocycle
Represents a non-metallic atomic group. ]

[0015]

[Chemical 5][In the formula, R⁶, R⁷Is R in the general formula [I]¹, R²Same as
Righteous and X_Five, X₆Is X in the general formula [I]₁, X₂When
Are synonymous. R⁸~ R^TenIs a hydrogen atom, alkyl group,
Kenyl group, aryl group, heterocyclic group, halogen atom, sia
Group, sulfo group, -COR¹¹, -CON (R¹¹)
(R¹²), -N (R¹¹) (R¹²),-OR¹¹, -SOR
¹¹, -SO₂R¹¹, -SO₂N (R¹¹) (R¹²), -N
(R¹¹) COR¹², -N (R¹¹) SO₂R¹², -N (R
¹¹) CON (R¹²) (R¹³), -SR¹¹, -COOR¹¹
Represents R¹¹~ R¹³ Is a hydrogen atom, alkyl group, alkene
Represents a phenyl group, an aryl group, or a heterocyclic group. ]

[0016]

[Chemical 6][In the formula, R¹⁴, R¹⁵Is R in the general formula [I]¹, R²When
Synonymous and X₇, X₈Is X in the general formula [I]₁, X₂
Is synonymous with. L_Ten~ L₁₂Represents a methine group, n₆Is 0
Represents an integer of 2; R¹⁶~ R¹⁸Is in the general formula [III]
R⁸ ~ R^Ten Is synonymous with. ]

[0017]

[Chemical 7][In the formula, R¹⁹, R²⁰Is R in the general formula [I]¹, R²When
Synonymous and X₉, X_TenIs X in the general formula [I]₁, X
₂Is synonymous with. W₁Represents an aryl group or a heterocyclic group
You ] In the above general formula, R¹ , R² As an alkyl group represented by
Are, for example, methyl group, ethyl group, propyl group, iso
Propyl group, n-butyl group, tert-butyl group, cyclope
And a cyclohexyl group. these
The alkyl group may be a hydroxy group, a cyano group or a sulfo group.
Groups, carboxyl groups, halogen atoms (eg fluorogen
Child, chlorine atom, bromine atom), alkoxy group (for example,
Toxy group, ethoxy group), aryloxy group (for example,
Phenoxy group, 4-sulfophenoxy group, 2,4-dis
Ruphophenoxy group), aryl groups (eg phenyl)
Group, 4-sulfophenyl group, 2,5-disulfophenyl
Group), an alkoxycarbonyl group (eg, methoxycarl)
Bonyl group, ethoxycarbonyl group), aryl oxyca
Due to a carbonyl group (eg, phenoxycarbonyl group), etc.
May be replaced.

R¹ , R² And W₁And an aryl group represented by
Include, for example, a phenyl group and a naphthyl group.
It These groups are R¹ , R² An alkyl group represented by
And a group similar to the substituent represented as the substituent of the alkyl group.
Therefore, it can be replaced.

R¹ , R² And W₁As a heterocyclic group represented by
Are, for example, pyridyl group, thiazolyl group, oxazoli
Group, imidazolyl group, furyl group, pyrrolyl group, pyrazine
Nyl group, pyrimidinyl group, pyridazinyl group, purinyl
Group, selenazolyl group, sulforanyl group, piperidinyl
Group, pyrazolyl group, tetrazolyl group and the like. This
These groups are R¹ , R² An alkyl group represented by
By a group similar to the substituent shown as the substituent of the kill group,
Can be replaced.

R¹ , R² As an alkenyl group represented by
Are, for example, a vinyl group and an allyl group. this
These groups are R¹ , R² And an alkyl group represented by
Group represented by a substituent similar to
Can be exchanged.

Examples of the group having an acidic nucleus represented by E ₁ in the general formula [I] include skeletons described in JP-A No. 61-281235, page 11, line 20 to page 14, line 15. And a group represented by the following formulas 1 to 4.

[0022]

[Chemical 8][In the formula, R^{twenty one}, R^{twenty two}Is R in the general formula [I]¹,
R²Is synonymous with. Also, X₁₁, X ₁₂In the general formula [I]
X in₁, X₂Is synonymous with. ]

[0023]

[Chemical 9] [In the formula, R ²³ has the same meaning as R ¹ and R ² in the general formula [I], and R ²⁴ and R ²⁵ represent R ⁸ in the general formula [III].
~ Is synonymous with R ¹⁰ . ]

[0024]

[Chemical 10] [In the formula, R ²⁶ has the same meaning as R ¹ and R ² in the general formula [I], and R ²⁷ represents R ^{8 to} R ¹⁰ in the general formula [III].
Is synonymous with. ]

[0025]

[Chemical 11] [In the formula, R ²⁸ has the same meaning as R ¹ and R ² in the above general formula [I], and R ²⁹ represents an alkyl group, an aryl group, an alkenyl group, a heterocyclic group, a cyano group, —COR ³⁰ , or —CON.
^{(R 30) (R 31)} , - N (R 30) (R 31), - OR 30,
-SOR ³⁰ , -SO ₂ R ³⁰ , -SO ₂ N (R ³⁰ )
^{(R 31), - N (} R 30) COR 31, -N (R 30) SO 2
^{R 31, -N (R 30)} CON (R 31) (R 32), - S
R ^30, represents a -COOR ^30. R ^{30 to} R ³² have the same meaning as R ^{11 to} R ¹³ in the general formula [III]. Examples of the alkyl group, alkenyl group, aryl group, and heterocyclic group include the same groups as those described above for R ¹ and R ² .

In the above description, all the groups having an acidic nucleus represented by E ₁ are represented by keto type, but it is clear from a chemical point of view that enol type can be obtained by tautomerism.

The 5- or 6-membered heterocycle formed by Q ₁ in the general formula [II] is, for example, JP-A-61-28.
Heterocycles described on pages 23 to 26 of 2832 and

[0028]

[Chemical 12][In the formula, R³³ Is R in the general formula [I]¹ And R²When
Synonymous, R³⁴ Is R in the general formula [III]⁸ ~ R
^TenIs synonymous with. l₁Represents an integer of 0 to 3. ]]
The heterocyclic ring can be mentioned.

Representative specific examples of the compounds represented by the general formulas [I] to [V] are shown below.

[0030]

[Chemical 13]

[0031]

[Chemical 14]

[0032]

[Chemical 15]

[0033]

[Chemical 16]

[0034]

[Chemical 17]

[0035]

[Chemical 18]

[0036]

[Chemical 19]

[0037]

[Chemical 20]

[0038]

[Chemical 21]

[0039]

[Chemical formula 22]

[0040]

[Chemical formula 23]Further, the dye used in the present invention has the following general formula
[I '] ~ General formula [V ’] Dyes represented by
You can

[0041]

[Chemical formula 24][General formula [I '] ~ General formula [V ′], R³⁵ A
R represents a alkyl group or an alkenyl group, and R³⁶ And R³⁷ Is Archi
Group, alkenyl group, aryl group, heterocyclic group, halogen
Atom, cyano group, sulfo group, -COR³⁸ , -CON (R
³⁸ ) (R³⁹ ), -N (R³⁸ ) (R³⁹ ),-OR³⁸ , -S
OR³⁸ , -SO₂R³⁸ , -SO₂N (R³⁸ ) (R³⁹ ),-
N (R³⁸ ) COR³⁹ , -N (R³⁸ ) SO₂R³⁹ , -N
(R³⁸ ) CON (R³⁹ ) (R⁴⁰ ), -SR³⁸ , -COO
R³⁸ Represents R³⁸ ~ R⁴⁰ Is a hydrogen atom, alkyl group,
It represents a alkenyl group, an aryl group or a heterocyclic group.

A is a group represented by the following general formula [A ₁ ] to general formula [A ₄ ] and A'is a group represented by the following general formula [A ' ₁ ] to general formula [A' ₄ ]. Represents.

[0043]

[Chemical 25](General formula [A₁] ~ General formula [A_Four] And the general formula [A ′₁]
~ General formula [A '_Four], R⁴¹ , R⁴² , R⁴⁴ and
R⁴⁶ Is a hydrogen atom, alkyl group, alkenyl group, aryl
Group, a heterocyclic group, R⁴³ Is an alkyl group, alkenyl
Group, aryl group, heterocyclic group, cyano group, -COR⁴⁷ ,-
CON (R⁴⁷ ) (R⁴⁸ ), -N (R⁴⁷ ) (R⁴⁸ ), -O
R⁴⁷ , -SOR⁴⁷ , -SO₂R⁴⁷ , -SO₂N (R⁴⁷ )
(R⁴⁸ ), -N (R⁴⁷ ) COR⁴⁸ , -N (R⁴⁷ ) SO₂
R⁴⁸ , -N (R⁴⁷ ) CON (R⁴⁸ ) (R⁴⁹ ), -S
R⁴⁷ , -COOR⁴⁷ Represents R⁴⁷ ~ R⁴⁹ Is a hydrogen atom,
Shows alkyl, alkenyl, aryl and heterocyclic groups.
You R⁴⁵ Is R³⁶ And R³⁷ Is synonymous with. X₁₃Is oxygen source
Child, sulfur atom, selenium atom, = NR^Fifty Represents R^Fifty
Is R⁴¹ Is synonymous with. X₁₄, X₁₅And X₁₆Is an oxygen atom,
Represents a sulfur atom. ) L represents a methine group, and E represents a group having an acidic nucleus.
Q₂Represents the group of non-metal atoms required to form a heterocycle.
You W₂Represents an aryl group or a heterocyclic group. n₇And n₈Is
Represents an integer of 0 to 3, n₉And n_TenRepresents an integer from 0 to 2
Then l₂And l₃Represents an integer of 0 to 3. ] The compounds represented by the general formulas [I '] to [V'] are
And explain.

R above³⁵ ~ R^Fifty As an alkyl group represented by
Are, for example, methyl group, ethyl group, propyl group, iso
Propyl group, n-butyl group, tert-butyl group, cyclope
And a cyclohexyl group. these
The alkyl group may be a hydroxy group, a cyano group or a sulfo group.
Groups, carboxyl groups, halogen atoms (eg fluorogen
Child, chlorine atom, bromine atom), alkoxy group (for example,
Toxy group, ethoxy group), aryloxy group (for example,
Phenoxy group, 4-sulfophenoxy group, 2,4-dis
Ruphophenoxy group), aryl groups (eg phenyl)
Group, 4-sulfophenyl group, 2,5-disulfophenyl
Group), an alkoxycarbonyl group (eg, methoxycarl)
Bonyl group, ethoxycarbonyl group), aryl oxyca
Due to a carbonyl group (eg, phenoxycarbonyl group), etc.
May be replaced.

R³⁶ ~ R^Fifty And W₂An aryl group represented by
Examples of include a phenyl group and a naphthyl group.
It These groups are R³⁵ ~ R^Fifty An alkyl group represented by
And a group similar to the substituent represented as the substituent of the alkyl group
Can be replaced by

R³⁶ ~ R^Fifty And W₂And a heterocyclic group represented by
Are, for example, pyridyl group, thiazolyl group, oxazol group.
Ryl group, imidazolyl group, furyl group, pyrrolyl group, pyra
Dinyl group, pyrimidinyl group, pyridazinyl group, purinyl
Group, selenazolyl group, sulforanyl group, piperidinyl
Group, pyrazolyl group, tetrazolyl group and the like. This
These groups are R³⁵ ~ R^Fifty An alkyl group represented by
A group similar to the substituent shown as the substituent of the alkyl group is used.
Can be replaced.

R³⁵ ~ R^Fifty As an alkenyl group represented by
Are, for example, a vinyl group and an allyl group. this
These groups are R³⁵ ~ R^Fifty An alkyl group represented by
By a group similar to the substituent shown as the substituent of the kill group,
Can be replaced.

Examples of the group having an acidic nucleus represented by E in the general formula [I '] include bones described in JP-A No. 61-281235, page 11, line 20 to page 14, line 15. Examples thereof include a group having a nucleus, a group having a nucleus represented by the general formula [A ′ ₁ ] to the general formula [A ′ ₄ ] and a group represented by the following formulas 6 to 8.

[0049]

[Chemical formula 26][In the formula, R⁵¹ Is R⁴¹ Is synonymous with R⁵² , R⁵³ Is hydrogen
Child and R first³⁶ Represents the group shown as. ]

[0050]

[Chemical 27][In the formula, R⁵⁴ Is R⁴¹ Is synonymous with R⁵⁵ Is a hydrogen atom and
R first³⁶ Represents the group shown as. ]

[0051]

[Chemical 28][In the formula, R⁵⁶ Is R⁴² Is synonymous with R⁵⁷ Is R⁴³ Synonymous with
is there. ] In the general formula [II ′], Q₂A heterocycle formed by
For example, see pages 23 to 26 of JP-A-61-282832.
Listed heterocycle and

[0052]

[Chemical 29][In the formula, R⁵⁸ Is R⁴¹ Is synonymous with R⁵⁹ Is R³⁶ Synonymous with
is there. l_FourIs an integer of 0 to 3. ] Heterocycle represented by
Can be mentioned.

Typical specific examples of the compounds represented by the general formulas [I '] to [V'] are shown below.

[0054]

[Chemical 30]

[0055]

[Chemical 31]

[0056]

[Chemical 32]

[0057]

[Chemical 33]

[0058]

[Chemical 34]

[0059]

[Chemical 35]

[0060]

[Chemical 36]

[0061]

[Chemical 37]

[0062]

[Chemical 38] Further, as the dye used in the present invention, the following general formula [V
Examples thereof include dyes represented by I] (hereinafter referred to as methine compounds). General formula [VI]

[0063]

[Chemical Formula 39] [In the formula, Dye represents an atomic group having a methine dye structure, J represents a divalent linking group having an atom or an atomic group selected from a carbon atom, a nitrogen atom, an oxygen atom, and a sulfur atom as a skeleton, and Sal is Represents a group which forms a sparingly soluble salt with silver ion, l ₅ represents 1 or 2, m ₁ represents 0 or 1 and n ₁₁ represents 1, 2, 3 or 4. In the general formula [VI], the group represented by Dye represents an atom group having a methine dye structure, and includes, for example, cyanine, merocyanine, merostyryl, styryl, oxonol,
A group having a dye structure in which a methine chain such as triarylmethane is conjugated with a double bond. Specific examples of these dyes include, for example, JP-A-63-202665, cyanine dyes described in Soviet Patent No. 653,257, JP-A-5
2-29727, 52-60825, 52-135335, 56-2
7146, 56-29226, 59-10944, 59-15934
No. 59-111847, No. 63-34539, U.S. Pat.
44,896, 3,148,187 and other merocyanine dyes, JP-A-59-211041, 59-211042, 60-
135936, 60-135937, 61-204630, 61-20
5934, 62-56958, 62-70830, 62-92949
No. 62-185758 and the like, merostyryl dyes,
JP-A-50-145125, 55-33103, 55-120660
No. 55, No. 55-161233, No. 62-185755, No. 63-139949
No. 63-231445, No. 63-264745, U.S. Pat.
187,275, British Patent 1,521,083, Belgian Patent 869,
Oxonol dyes described in Japanese Patent No. 677, JP-A-59-5
No. 5437, 59-228250 publication, U.S. Patent No. 4,115,126,
Examples thereof include triarylmethane dyes described in JP-A-4,359,574, and further, “Theory of P” edited by TH James.
hotographic Process "1977, published by Macmillan, FMH
armer "Heterocyclic compounds Cyanine dyes and
related compounds ”John Wiley & Sons (New York
London) 1964, DMSturmer “The Chemistry
of Heterocyclic Compounds ”ed.A. Weissberger and
ECTaylor, 1977, “The Chemistry of Syntheti
c Dyes "Academic Press (New York London) Vol.II,
1952, Vol.IV, 1971 and other publications listed in the book.

J represents a divalent linking group having a skeleton of an atom or atomic group selected from carbon atom, nitrogen atom, oxygen atom and sulfur atom. Preferred groups are alkylene groups (eg,
Methylene group, ethylene group, propylene group, pentylene group etc.), arylene group (eg phenylene group etc.), alkenylene group (eg ethylene group, propenylene group etc.), sulfonyl group, sulfinyl group, ether group, thioether group, carbonyl group Group, -N (R ⁶⁰ ) -group (R ⁶⁰
Is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group), a -N = group, a heterocyclic divalent group (for example, a triazine-2,4-diyl group, a pyrimidine-).
2,4-diyl group, thiazole-2,4-diyl group, benzoxazole-2,5-diyl group, etc.), or a divalent linking group having 20 or less carbon atoms , May have a substituent. Examples of the substituent include common ones, and a halogen atom (for example,
Fluoro atom, chlorine atom, bromine atom, etc.), alkyl group (eg, methyl group, ethyl group, isopropyl group, butyl group, etc.), aralkyl group (eg, benzyl group, phenethyl group, etc.), alkoxy group (eg, methoxy group) , Ethoxy group, etc.), alkoxycarbonyl group (eg, ethoxycarbonyl group), alkylthio group, hydroxy group, carboxy group, sulfo group, sulfonyl group (eg, methanesulfonyl group, p-toluenesulfonyl group, etc.), carbamoyl group ( For example, N-methylcarbamoyl group, morpholinocarbonylamino group, etc.), acyl group (eg, acetyl group, benzoyl group, etc.), acylamide group (eg,
Acetamide group, etc.), sulfonamide group (eg, methanesulfonamide group, butanesulfonamide group, etc.), cyano group, amino group (eg, ethylamino group, dimethylamino group, etc.), ureido group, etc. To be done.

L ₅ is 1 or 2, m ₁ is 0 or 1,
n ₁₁ represents 1, 2, 3 or 4. Sal represents a group forming a sparingly soluble salt with silver ion, and examples thereof include a mercapto group, an acetylene group, a thiocarbonyl group, a thioamide group,
Thiourethane group, thioureido group (for example, 3-ethylthioureido group, 3-phenylthioureido group, etc.) or a saturated or unsaturated 5- to 7-membered heterocyclic group containing at least one nitrogen atom in the ring. Examples include ring residues. Preferred groups include groups represented by formulas (VIII) and (IX) described in JP-A-2-97937, or JP-A-2-225
Examples thereof include groups represented by the general formula (II) to the general formula (VI) described in Japanese Patent No. 476.

Next, specific examples of the methine compound according to the present invention will be shown.

[0067]

[Chemical 40]

[0068]

[Chemical 41]

[0069]

[Chemical 42]

[0070]

[Chemical 43]

[0071]

[Chemical 44]

[0072]

[Chemical 45]

[0073]

[Chemical 46]

[0074]

[Chemical 47]

[0075]

[Chemical 48]

[0076]

[Chemical 49]

[0077]

[Chemical 50]

[0078]

[Chemical 51]

[0079]

[Chemical 52]

[0080]

[Chemical 53]

[0081]

[Chemical 54]

[0082]

[Chemical 55]

[0083]

[Chemical 56]

[0084]

[Chemical 57] The methine compound according to the present invention may be either a method of dyeing from an intermediate raw material in which a sparingly soluble silver salt forming group represented by Sal is substituted in advance, or a method of binding a methine dye structure moiety represented by Dye and a Sal moiety, It can be arbitrarily selected and synthesized. Various known binding reactions can be used to introduce the Sal group, for example, addition reaction to unsaturated groups such as vinyl group and carbonyl group, active hydrogen substituent such as amino group and hydroxy group, and acid derivative. Or a halogen derivative. In conducting these reactions, "New Experimental Chemistry Course 14" edited by the Chemical Society of Japan, synthesis and reaction of organic chemistry,
Volumes I to V, Maruzen (1962), "Organic Reactions" Vo
l, 1,3,12 John Wiley & Sons (New York London),
"The Chemistry of Functional Groups" John Wiley &
Sons (New York London), LFFieser and M.Fieser,
Many books such as "Advanced Organic Chemistry" Maruzen (1962) can be referred to.

These methine dyes according to the present invention are reacted with an aqueous solution of a soluble silver salt to form a difficult silver salt, which is dispersed and added to the silver halide photographic light-sensitive material.

In the present invention, the amount of silver salt of the dye of the present invention is preferably 0.001 to 1 g / m ² , and more preferably 0.005 to 1 g / m ^2.
0.2 g / m ² is preferred.

Next, the water-insoluble and organic solvent-soluble homo- or copolymer according to the present invention will be explained.

As the water-insoluble and organic solvent-soluble homopolymer or copolymer (hereinafter referred to as the copolymer of the present invention), various compounds can be used. For example, those shown below can be preferably used. .. (1) Vinyl-based Polymer and Copolymer The monomer forming the vinyl-based polymer and copolymer of the present invention will be described more specifically.

Acrylic acid ester: For example, methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, tert-butyl acrylate, isobutyl acrylate, sec-butyl acrylate, amyl acrylate, hexyl acrylate, 2-ethylhexyl. Acrylate, octyl acrylate, tert-octyl acrylate, 2-chloroethyl acrylate, 2-bromoethyl acrylate, 4-chlorobutyl acrylate, cyanoethyl acrylate, 2-acetoxyethyl acrylate, dimethylaminoethyl acrylate, benzyl acrylate, methoxybenzyl acrylate, 2 -Chlorocyclohexyl acrylate, cyclohexyl acrylate, furfuryl acrylate Relate, tetrahydrofurfuryl acrylate, phenyl acrylate, 5-hydroxypentyl acrylate, 2,2-dimethyl-3-
Hydroxypropyl acrylate, 2-methoxyethyl acrylate, 3-methoxybutyl acrylate, 2-
Ethoxyethyl acrylate, 2-iso-propoxyethyl acrylate, 2-butoxyethyl acrylate,
2- (2-methoxyethoxy) ethyl acrylate, 2
-(2-butoxyethoxy) ethyl acrylate, ω-
Methoxy polyethylene glycol acrylate (additional mol number n = 9), 1-bromo-2-methoxyethyl acrylate, 1,1-dichloro-2-ethoxyethyl acrylate; Methacrylic acid ester: for example, methyl methacrylate, ethyl methacrylate, n-propyl Methacrylate, isopropyl methacrylate, n-butyl methacrylate, tert-butyl methacrylate, isobutyl methacrylate, sec-butyl methacrylate, amyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, chlorobenzyl methacrylate, octyl methacrylate, sulfopropyl methacrylate, N-ethyl- N-phenylaminoethyl methacrylate, 2- (3-phenylpropyloxy) eth Methacrylate, dimethylaminoethyl phenoxyethyl methacrylate, furfuryl methacrylate, tetrahydrofurfuryl methacrylate, phenyl methacrylate, cresyl methacrylate, naphthyl methacrylate, 2-hydroxyethyl methacrylate,
4-hydroxybutyl methacrylate, triethylene glycol monomethacrylate, dipropylene glycol monomethacrylate, 2-methoxyethyl methacrylate, 3-methoxybutyl methacrylate, 2-acetoxyethyl methacrylate, 2-acetoacetoxyethyl methacrylate, 2-ethoxyethyl methacrylate,
2-iso-propoxyethyl methacrylate, 2-butoxyethyl methacrylate, 2- (2-methoxyethoxy) ethyl methacrylate, 2- (2-ethoxyethoxy) ethyl methacrylate, 2- (2-butoxyethoxy) ethyl methacrylate, ω-methoxy Polyethylene glycol methacrylate (addition mol number n = 6); Vinyl esters: for example, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl caproate, vinyl chloroacetate,
Vinyl methoxyacetate, vinyl phenylacetate, vinyl benzoate, vinyl salicylate; Acrylamide: for example, acrylamide, methylacrylamide, ethylacrylamide, propylacrylamide, butylacrylamide, tert-butylacrylamide, cyclohexylacrylamide, benzylacrylamide, hydroxymethylacrylamide, methoxyethyl. Acrylamide, dimethylaminoethyl acrylamide, phenyl acrylamide, dimethyl acrylamide, diethyl acrylamide, β-cyanoethyl acrylamide, N- (2-acetoacetoxyethyl) acrylamide, diacetone acrylamide; methacrylamides: for example, methacrylamide, methyl methacrylamide, ethyl Methacrylate , Methacrylamide, butyl methacrylamide, tert-
Butyl methacrylamide, cyclohexyl methacrylamide, benzyl methacrylamide, hydroxymethyl methacrylamide, methoxyethyl methacrylamide, dimethylaminoethyl methacrylamide, phenyl methacrylamide, dimethyl methacrylamide, diethyl methacrylamide, β-cyanoethyl methacrylamide, N
-(2-acetoacetoxyethyl) methacrylamide; olefins: for example, dicyclopentadiene, ethylene, propylene, 1-butene, 1-pentene, vinyl chloride, vinylidene chloride, isoprene, chloroprene, butadiene, 2,3-dimethylbutadiene. Styrenes: for example, styrene, methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene,
Isopropylstyrene, chloromethylstyrene, methoxystyrene, chlorostyrene, dichlorostyrene, bromostyrene, vinylbenzoic acid methyl ester; crotonic acid ester: for example, butyl crotonic acid, hexyl crotonic acid; itaconic acid diester: for example, dimethyl itaconic acid, Diethyl itaconic acid, dibutyl itaconic acid; maleic acid diesters: for example, diethyl maleate, dimethyl maleate, dibutyl maleate; fumaric acid diesters: for example, diethyl fumarate, dimethyl fumarate, dibutyl fumarate; ..

The following are examples of other monomers.

Allyl compounds: for example, allyl acetate, allyl caproate, allyl laurate, allyl benzoate;
Vinyl ethers: for example, methyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, methoxyethyl vinyl ether, dimethylaminoethyl vinyl ether; vinyl ketones: for example, methyl vinyl ketone, phenyl vinyl ketone, methoxy. Ethyl vinyl ketone; Vinyl heterocyclic compounds: for example, vinyl pyridine, N-vinyl imidazole, N-vinyl oxazolidone, N-vinyl triazol, N-vinyl pyrrolidone; glycidyl esters: for example, glycidyl acrylate, Glycidyl methacrylate; unsaturated nitriles: for example, acrylonitrile, methacrylonitrile; and the like.

The polymer used in the present invention may be a homopolymer of the above-mentioned monomers, or may be a copolymer composed of two or more kinds of monomers, if necessary. Further, the polymer used in the present invention may contain a monomer having an acid group to the extent that it does not become water-soluble (preferably 20%).
% Or less. ), Those not containing at all are preferred.

Examples of the monomer having an acid group include acrylic acid; methacrylic acid; itaconic acid; maleic acid; monoalkyl itaconate (for example, monomethyl itaconate); monoalkyl maleate (for example, monomethyl maleate); citracone. Acid; Styrenesulfonic acid; Vinylbenzylsulfonic acid; Acryloyloxyalkylsulfonic acid (eg, acryloyloxymethylsulfonic acid); Methacryloyloxyalkylsulfonic acid (eg, methacryloyloxymethylsulfonic acid, methacryloyloxyethylsulfonic acid, methacryloyloxypropylsulfone) Acid); acrylamidoalkylsulfonic acid (for example, 2-acrylamido-2-methylethanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, 2-ac Lamido-2-methylbutanesulfonic acid); methacrylamideamidoalkylsulfonic acid (for example, 2-methacrylamide-2-methylethanesulfonic acid, 2-methacrylamide-2-methylpropanesulfonic acid, 2-methacrylamide-2-methyl). Butanesulfonic acid); acryloyloxyalkyl phosphate (eg, acryloyloxyethyl phosphate, 3
-Acryloyloxypropyl-2-phosphate);
Methacryloyloxyalkyl phosphates (eg,
Methacryloyloxyethyl phosphate, 3-methacryloyloxypropyl-2-phosphate) and the like can be mentioned.

The acid group-containing monomer may be a salt of an alkali metal (eg, Na, K, etc.) or ammonium ion.

As the monomer forming the polymer used in the present invention, acrylate type, methacrylate type, acrylamide type and methacrylamide type are preferable.

The polymer formed from the above monomers can be obtained by a solution polymerization method, a bulk polymerization method, a suspension polymerization method and a latex polymerization method. As the initiator used for these polymerizations, a water-soluble polymerization initiator and a lipophilic polymerization initiator are used.

Examples of the water-soluble polymerization initiator include persulfates such as potassium persulfate, ammonium persulfate and sodium persulfate, 4,4'-azobis-4cyanosodium valerate, 2,2'-azobis (2 Water-soluble azo compounds such as -amidinopropane) hydrochloride and hydrogen peroxide can be used.

Examples of the lipophilic polymerization initiator include azobisisobutyronitrile and 2,2'-azobis (2,4-
Dimethylvaleronitrile), 2,2'-azobis (4-
Methoxy-2,4-dimethylvaleronitrile), 1,
1'-azobis (cyclohexanone-1-carbonitrile), dimethyl 2,2'-azobisisobutyrate, 2,2 '
And lipophilic azo compounds such as diethyl azobisisobutyrate, benzoyl peroxide, lauryl peroxide, diisopropyl peroxydicarbonate and di-tert-butyl peroxide. (2) The polyester resin polyhydric alcohol obtained and a polyhydric alcohol and a polybasic acid are _{condensed, HO-R 1 -OH (R} 1 is the number of carbon atoms
2 to about 12 hydrocarbons, especially glycols having an aliphatic hydrocarbon) comprising structure or polyalkylene glycols are effective, as the polybasic acid, HOOC-R ₂ -COO
Those having H (R ₂ represents a mere bond or a hydrocarbon having 1 to 12 carbon atoms) are effective.

Specific examples of the polyhydric alcohol include ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, trimethylolpropane, 1,4.
-Butane diol, isobutylene diol, 1,5-pentane diol, neopentyl glycol, 1,6-hexane diol, 1,7-heptane diol, 1,8-
Octanediol, 1,9-nonanediol, 1,10
-Decanediol, 1,11-undecanediol,
Examples thereof include 1,12-dodecanediol, 1,13-tridecanediol, 1,14-tetradecanediol, glycerin, diglycerin, triglycerin, 1-methylglycerin, erythritol, mannitol and sorbit.

Specific examples of the polybasic acid include oxalic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, corkic acid, azelaic acid, sebacic acid, nonanedicarboxylic acid,
Decanedicarboxylic acid, undecanedicarboxylic acid, dodecanedicarboxylic acid, fumaric acid, maleic acid, itaconic acid,
Examples thereof include citraconic acid, phthalic acid, isophthalic acid, terephthalic acid, tetrachlorophthalic acid, metaconic acid, isohymeric acid, cyclopentadiene-maleic anhydride adduct, and rosin-maleic anhydride adduct. (3) Polyester obtained by ring-opening polymerization method These polyesters include β-propiolactone and ε-
It is obtained from caprolactone, dimethylpropiolactone and the like. (4) Others Polycarbonate resin obtained by polycondensation of glycol or dihydric phenol with carbonic acid ester or phosgene, polyurethane resin obtained by polyaddition of polyhydric alcohol and polyisocyanate, or polyvalent amine and polybasic acid The polyamide resin etc. which are obtained are mentioned.

The number average molecular weight of the polymer used in the present invention is not particularly limited, but it is preferably 200,000 or less, more preferably 5,000 or more and 100,000 or less.

Specific examples of the polymer used in the present invention are shown below, but the invention is not limited thereto. (The composition of the copolymer is shown by weight ratio.) P-1) Poly (N-sec-butylacrylamide) P-2) Poly (N-tert-butylacrylamide) P-3) Diacetone acrylamide-methyl methacrylate copolymer Polymer (25:75) P-4) Polycyclohexylmethacrylate P-5) N-tert-butylacrylamide-methylmethacrylate copolymer (60:40) P-6) Poly (N, N-dimethylacrylamide) P- 7) Poly (tert-butyl methacrylate) P-8) Polyvinyl acetate P-9) Polyvinyl propionate P-10) Polymethyl methacrylate P-11) Polyethyl methacrylate P-12) Polyethyl acrylate P-13) Vinyl acetate -Vinyl alcohol copolymer (90:10) P-14) Poly n-butyl acrylate -15) Poly n-butyl methacrylate P-16) Polyisobutyl methacrylate P-17) Polyisopropyl methacrylate P-18) Polyoctyl acrylate P-19) n-Butyl acrylate-acrylamide copolymer (95: 5) P-20 ) Stearyl methacrylate-acrylic acid copolymer (90:10) P-21) Methyl methacrylate-vinyl chloride copolymer (70:30) P-22) Methyl methacrylate-styrene copolymer (90:10) P-23 ) Methyl methacrylate-ethyl acrylate copolymer (50:50) P-24) n-butyl methacrylate-methyl methacrylate-styrene copolymer (50:20:30) P-25) Vinyl acetate-acrylamide copolymer (8
5:15) P-26) Vinyl chloride-vinyl acetate copolymer (65: 3
5) P-27) Methyl methacrylate-acrylonitrile copolymer (65:35) P-28) n-butyl methacrylate-pentyl methacrylate-N-vinyl-2-pyrrolidone copolymer (3
8:38:24) P-29) Methyl methacrylate-n-butyl methacrylate-isobutyl-methacrylate-acrylic acid copolymer (37: 29: 25: 9) P-30) n-butyl methacrylate-acrylic acid (95: 5) P-31) Methyl methacrylate-acrylic acid copolymer (95: 5) P-32) Benzyl methacrylate-acrylic acid copolymer (93: 7) P-33) n-butyl methacrylate-methyl methacrylate-benzyl methacrylate -Acrylic acid copolymer (35: 35: 25: 5) P-34) n-butyl methacrylate-methyl methacrylate-benzyl methacrylate copolymer (40:30:
30) P-35) Diacetone acrylamide-methyl methacrylate copolymer (50:50) P-36) Methyl vinyl ketone-isobutyl methacrylate copolymer (55:45) P-37) Ethyl methacrylate-n-butyl acrylate copolymer Polymer (70:30) P-38) Diacetone acrylamide-n-butyl acrylate copolymer (60:40) P-39) Methyl methacrylate-stearyl methacrylate-diacetone acrylamide copolymer (40: 4)
0:20) P-40) n-butyl acrylate-stearyl methacrylate-diacetone acrylamide copolymer (70:
20:10) P-41) Stearyl methacrylate-methyl methacrylate-acrylic acid copolymer (50:40:10) P-42) Methyl methacrylate-styrene-vinyl sulfonamide copolymer (70:20:10) P- 43) Methyl methacrylate-phenyl vinyl ketone copolymer (70:30) P-44) n-butyl acrylate-methyl methacrylate-n-butyl methacrylate copolymer (35:35:
30) P-45) n-butyl methacrylate-N-vinyl-
2-Pyrrolidone Copolymer (90:10) P-46) Polypentyl Acrylate P-47) Cyclohexyl Methacrylate-Methyl Methacrylate-n-Propyl Methacrylate Copolymer (37:29:34) P-48) Polypentyl Methacrylate P -49) Methyl methacrylate-n-butyl methacrylate copolymer (65:35) P-50) Vinyl acetate-vinyl propionate copolymer (75:25) P-51) n-butyl methacrylate-3-acryloxy Butane-1-sodium sulfonate copolymer (9
7: 3) P-52) n-butyl methacrylate-methyl methacrylate-acrylamide copolymer (35:35:30) P-53) n-butyl methacrylate-methyl methacrylate-vinyl chloride copolymer (37:36:27) ) P-54) n-butyl methacrylate-styrene copolymer (82:18) P-55) tert-butyl methacrylate-methyl methacrylate copolymer (70:30) P-56) poly (N-tert-butylmethacryl) Amide) P-57) N-tert-butylacrylamide-methylphenylmethacrylate copolymer (60:40) P-58) Methylmethacrylate-acrylonitrile copolymer (70:30) P-59) Methylmethacrylate-methylvinyl Ketone copolymer (38:72) P-60) Methyl methacrylate-styrene copolymer (75:25) P-6 ) Methyl methacrylate-hexyl methacrylate copolymer (70:30) P-62) Butyl methacrylate-acrylic acid copolymer (85:15) P-63) Methyl methacrylate-acrylic acid copolymer (80:20) P- 64) Methyl methacrylate-acrylic acid copolymer (98: 2) P-66) Methyl methacrylate-N-vinyl-2-
Pyrrolidone Copolymer (90:10) P-67) n-Butyl Methacrylate-Vinyl Chloride Copolymer (90:10) P-68) n-Butyl Methacrylate-Styrene Copolymer (70:30) P-69) 1,4-Butanediol-adipic acid polyester P-70) Ethylene glycol-sebacic acid polyester P-71) Polycaprolactam P-72) Polypropiolactam P-73) Polydimethylpropiolactone P-74) N-tert- Butylacrylamide-dimethylaminoethylalamide copolymer (85:15) P-75) N-tert-butylmethacrylamide-vinylpyridine copolymer (95: 5) P-76) Dimethyl maleenate-n-butyl acrylate Copolymer (65:35) P-77) N-tert-butylacrylamide-2-methoxyethyl acrylate The polymer (55:45)

In the present invention, the copolymer of the present invention is present in lipophilic fine particles in a state of coexisting with a coupler which forms a dye by coupling with an oxidation product of an aromatic primary amine developing agent. It is preferable to use it as a dispersion. The dispersion is obtained by dissolving at least one of the coupler and the copolymer of the present invention in a substantially water-insoluble high-boiling point organic solvent and emulsifying and dispersing it in a hydrophilic protective colloid.

Here, the substantially water-insoluble high-boiling point organic solvent is a compound immiscible with water having a melting point of 100 ° C. or lower and a boiling point of 140 ° C. or higher, such as a phenol derivative, a phthalic acid ester or a phosphoric acid ester. And the like, organic acid amides, carbamates, kents and the like. These are U.S. Pat.Nos. 2,322,027, 2,353,262, and 2,
No. 533,514, No. 2,801,170, No. 2,801,171, No.
No. 2,835,579, No. 2,852,383, No. 2,870,012, No. 2,991,171, No. 3,287,134, No. 3,554,755,
No. 3,676,137, No. 3,676,142, No. 3,700,454
No. 3,748,141, No. 3,779,765 and No. 3,83
No. 7,863 is described in each specification.

Further, in order to assist the above-mentioned dissolution, a low boiling point organic solvent or an organic solvent miscible with water can be used.

As the low boiling point organic solvent, ethyl acetate, butyl acetate, cyclohexanone, isobutyl alcohol,
Examples thereof include methyl ethyl ketone and methyl cellosolve.

Examples of the water-miscible organic solvent include methyl alcohol, ethyl alcohol, acetone, phenoxyethanol, tetrahydrofuran, dimethylformamide and the like.

These low-boiling point organic solvents and water-miscible organic solvents can be removed by a method such as washing with water or by coating and drying.

The organic solvents described above can be used in combination of two or more kinds.

To emulsify and disperse in a hydrophilic protective colloid to obtain lipophilic fine particles, a dispersing aid such as a surfactant is used, and a stirrer, homogenizer, colloid mill, flow jet mixer, ultrasonic device, etc. are used. Spread. A step of removing the low boiling point organic solvent at the same time as the dispersion may be added.

An aqueous gelatin solution is preferably used as the hydrophilic protective colloid.

The average particle size of the lipophilic fine particles is preferably 0.04 μ to 2 μ, more preferably 0.06 μ to 0.4 μ. Particle size is Coulter model N4 manufactured by Coulter UK
Etc. can be measured.

In the above, the mixing ratio of the coupler, homo- or copolymer, high-boiling solvent and low-boiling solvent or auxiliary solvent such as water-miscible organic solvent is such that the coupler, homo- or copolymer, high-boiling solvent It may be selected so that the solution prepared by dissolving it in the auxiliary solvent has a viscosity suitable for being easily dispersed in the hydrophilic colloid. The value at this time varies depending on the solubility of the coupler used, the type of the polymer and the degree of polymerization, and cannot be uniformly determined.For example, the ratio of the polymer to the coupler (weight ratio) is 1:10 to 5: 1. , Preferably 1: 3
~ 2: 1.

The ratio (weight ratio) of the high boiling point solvent to the coupler used is 1:20 to 5: 1, preferably 1:10 to.
It is 2: 1. The ratio (weight ratio) of the low boiling point solvent to the polymer is 1:10 to 10: 1, preferably 1: 4 to 5: 1.

In the present invention, when the above-mentioned dispersion is contained in a silver halide emulsion layer, a blue-sensitive layer having a yellow coupler and a red-sensitive layer having a cyan coupler are usually used.

In the dispersion, a compound which does not need to be adsorbed on the surface of the silver halide crystal, such as an image stabilizer, an antifoggant, a UV absorber, a brightening agent and an oil-soluble dye, is simultaneously added. It can also be dispersed.

It is preferable to simultaneously disperse the image stabilizers described in JP-A-59-125732 and JP-A-62-96944.

Next, the compound represented by the general formula [I] according to the present invention (hereinafter referred to as the compound [I] of the present invention) will be explained.

Examples of the aliphatic group represented by R ₁ , R ₂ and R ₃ include an alkyl group having 1 to 32 carbon atoms, an alkenyl group,
Examples thereof include an alkynyl group, a cycloalkyl group and a cycloalkenyl group. The alkyl group, alkenyl group and alkynyl group may be linear or branched. Further, these aliphatic groups also include those having a substituent.

Examples of the aromatic group represented by R ₁ , R ₂ and R ₃ include an aryl group (eg phenyl group etc.), an aromatic heterocyclic group (eg pyridyl group, furyl group etc.) and the like. .. Further, these aromatic groups include those having a substituent.

R ₁ , R ₂ and R ₃ are preferably each an alkyl group or an aryl group, R ₁ , R ₂ and R ₃ may be the same or different, and R ₁ , R ₂ and R ₃ The total number of carbon atoms of is preferably 6 to 50.

The substituent of the aliphatic group or aromatic group represented by R ₁ , R ₂ and R ₃ is not particularly limited, but is preferably an alkoxy group, an aryloxy group, an acyl group, an acyloxy group, an alkoxycarbonyl. Group, aryloxycarbonyl group, carbamoyl group, sulfamoyl group, acylamino group, amino group and the like.

L, m and n each represent 0 or 1.

The typical examples of the compound [I] of the present invention are shown below, but the present invention is not limited thereto.

[0125]

[Chemical 58]

[0126]

[Chemical 59]

[0127]

[Chemical 60]

[0128]

[Chemical formula 61]

[0129]

[Chemical formula 62]

[0130]

[Chemical 63]

[0131]

[Chemical 64]

[0132]

[Chemical 65]

[0133]

[Chemical 66]

[0134]

[Chemical 67]

[0135]

[Chemical 68]

[0136]

[Chemical 69]

[0137]

[Chemical 70] The compound [I] of the present invention can be obtained, for example, from JP-B-48-32727,
JP-A-53-13923, JP-A-54-119235, JP-A-54-119921
No. 59-119922, No. 55-25057, No. 55-36869,
It can be synthesized by the method described in these publications, including the phosphate ester high boiling point solvent described in each publication such as JP-A-56-81836, JP-A-56-19049, and British Patent 694,772.

The compound [I] of the present invention is preferably used in an amount of 5 to 500 mol%, more preferably 10 to 300 mol%, based on the coupler used.

The compound [I] of the present invention may be used alone or in combination of two or more kinds. The compound [I] of the present invention is preferably used in the same layer as the coupler, and most preferably, it is present in the same hydrophobic organic phase (for example, oil phase) in the same layer. Specifically, the compound [I] of the present invention and a coupler are
If necessary, a high-boiling organic solvent is used, and if necessary, a low-boiling and / or water-soluble organic solvent is also used in combination to simultaneously dissolve, and emulsification is performed using a surfactant in a hydrophilic binder such as an aqueous gelatin solution. After dispersion, it is preferably added to the desired hydrophilic colloid layer.

Next, the heterocyclic fogging inhibitor according to the present invention will be described.

The heterocyclic antifoggant means a heterocyclic ring selected from compounds used for the purpose of preventing fog during the manufacturing process of a light-sensitive material, storage or photographic processing, or stabilizing photographic performance. We have what we have.

Examples of the heterocycle include imidazole, triazole, tetrazole, thiadiazole, oxadiazole, pyridine, pyrimidine, benzimidazole, benzotriazole, indazole, benzothiazole, benzoxazole and azaindenes.

These heterocyclic nuclei may be substituted with a general organic group, and examples of the organic group include an alkyl group, an allyl group, a heterocyclic group, an acyl group, an alkoxy group, a carboxyl group, an alkoxycarbonyl group, Examples thereof include amino group, amide group, carbamoyl group, ureido group, sulfo group, sulfonamide group, sulfamoyl group, alkylthio group, mercapto group, hydroxyl group, nitro group and halogen atom.

Specific examples of the heterocyclic fogging inhibitor (hereinafter referred to as the inhibitor of the present invention) preferably used in the present invention are shown below, but the present invention is not limited thereto.

[0145]

[Chemical 71]

[0146]

[Chemical 72]

[0147]

[Chemical formula 73]

[0148]

[Chemical 74]

[0149]

[Chemical 75]

[0150]

[Chemical 76]

[0151]

[Chemical 77]

[0152]

[Chemical 78]

[0153]

[Chemical 79] Some of these compounds are commercially available, for example, U.S. Pat.No. 3,259,976, JP-A-57-14836, and JP-A-57-167023.
No. 58-95728, No. 59-68732 and the like.

In order to incorporate the inhibitor of the present invention into the silver halide emulsion layer of the present invention, water or an organic solvent optionally miscible with water (eg, methanol, ethanol, etc.) is used.
It may be added after it is dissolved in. The inhibitor of the present invention may be used alone, or may be used in combination with another inhibitor of the present invention or a fog inhibitor other than the present invention.

The inhibitor of the present invention may be added before the formation of silver halide grains, during the formation of silver halide grains, after the completion of silver halide grain formation and before the start of chemical ripening, during the chemical ripening, and during the chemical ripening. At the end of aging, any time from the end of chemical aging to the time of coating may be used. Preferably, it is added during chemical ripening, at the end of chemical ripening, or after the end of chemical ripening and before coating. The addition may be carried out all at once or may be added in a plurality of times.

It may be added at the time of preparation of the silver halide emulsion or directly in the silver halide emulsion coating solution, or may be added to the coating solution for the adjacent non-photosensitive hydrophilic colloid layer and applied in the multilayer coating. May be incorporated into the silver halide emulsion layer according to the present invention.

The addition amount is not particularly limited, but is usually 1 × 10 ^-6 mol to 1 × 10 ^-1 mol, preferably 1 × 10 ^-5 mol to 1 × 10 ^-2 mol per mol of silver halide. It is added in the range of.

Next, the fluorescent whitening agent according to the present invention will be described.

The fluorescent whitening agent used in the present invention is a substance which absorbs ultraviolet light and emits fluorescent light which is usually bluish to make an object appear whiter. Any compound may be used as long as it is mainly used for increasing the whiteness of the background after the processing of photographic paper.
K.VeenRataramann, “Chemistry of Synthetic Dyes” (the Chemis
try of Synthetic Dyes) The compounds described in Volume V, Chapter 8 can be used. More specifically, stilbene compounds, coumarin compounds, biphenyl compounds,
Examples thereof include benzoxazolyl compounds, naphthalimide compounds, pyrazoline compounds, and carbostyryl compounds.

The water-soluble fluorescent whitening agent and the oil-soluble fluorescent whitening agent will be described separately according to their solubility.

Water-soluble fluorescent whitening agents are described, for example, in US Pat.
Stilbene whitening agents having a water-soluble group as described in 3,390, JP-B-48-30495 and JP-A-55-135833 are mainly used.

Of these, a water-soluble diaminostilbene compound is particularly preferably used, and it is more preferable that it has a sulfo group as a water-soluble group.

Fluorescent brightening agents including 4,4'-diaminostilbenedisulfonic acid derivatives are described in, for example, "Fluorescent brightening agent" (published in August 1976) edited by Chemical Industry Association. It can be synthesized by the usual method.

The water-soluble fluorescent whitening agent of the present invention may be added to the light-sensitive material as an aqueous solution as it is, or for the purpose of preventing the fluorescent whitening agent from flowing out of the layer during processing. JPA
56-32547, as described in European Patent 0024380B1, the molecular structure may be improved so that it does not easily flow out, but most preferably, it is described in JP-B-34-7127 or Research Disclosure No. 17159. As described above, a method of adding to a photosensitive material together with a water-soluble polymer such as polyvinylpyrrolidone or polyvinyl alcohol is used.

As the oil-soluble fluorescent whitening agent used in the present invention, substituted stilbenes and substituted coumarins described in British Patent 786,234 and substituted thiophenes described in US Pat. No. 3,135,762 are particularly useful. , Other Special Public Sho
Fluorescent brighteners such as those disclosed in JP-A-45-37376 and JP-A-50-126732 can be advantageously used.

The oil-soluble fluorescent whitening agent used in the present invention is mainly added to the light-sensitive material as an emulsion dispersion or a latex dispersion. For example, the method of emulsification and dispersion can be adjusted by dissolving in a high-boiling point organic solvent or a water-insoluble polymer and emulsifying and dispersing. Specifically, there is a method in which a brightening agent is dissolved in a high-boiling organic solvent as exemplified in British Patent 1,072,915, and this is emulsified and dispersed in a hydrophilic colloid such as gelatin together with a surfactant. As the high-boiling-point solvent, amide compounds, benzoic acid esters, substituted paraffins and the like can be used in addition to phthalic acid esters and phosphoric acid esters.

Instead of the above high boiling point organic solvent, a water-insoluble polymer such as polyurethane or polyacrylic acid ester can be used to prepare an emulsion dispersion in the same manner as described above.

The latex dispersion may be prepared by dissolving an oil-soluble fluorescent whitening agent in a monomer in advance and polymerizing it to obtain a latex dispersion, or impregnating a hydrophobic polymer with an auxiliary solvent. There is also a method of forming a latex dispersion by the method described in JP-A-50-12.
6732, Japanese Patent Publication No. 51-47043, U.S. Pat.
3,359,102, 3,558,316, and 3,788,854.

Examples of the compound of the fluorescent whitening agent according to the present invention are shown below, but the present invention is not limited to these.

[0170]

[Chemical 80]

[0171]

[Chemical 81]

[0172]

[Chemical formula 82]

[0173]

[Chemical 83]

[0174]

[Chemical 84]

[0175]

[Chemical 85]

[0176]

[Chemical formula 86]

[0177]

[Chemical 87]

[0178]

[Chemical 88]

[0179]

[Chemical 89]

[0180]

[Chemical 90] The amount of the fluorescent whitening agent used in the present invention depends on the finished light-sensitive material.
0.1 to 200 mg / m ² is preferably added so as to be present,
Most preferably, it is used in the range of 1 to 100 mg / m ² .

The fluorescent whitening agent of the present invention may be added to either a silver halide emulsion layer (photosensitive layer) or a non-photosensitive hydrophilic colloid layer (protective layer, intermediate layer, undercoat layer, etc.). it can.

Next, the vinyl sulfone type hardener according to the present invention will be described.

The vinyl sulfone type hardener used in the present invention is, for example, aromatic compounds described in German Patent No. 1,100,942 and US Pat. No. 3,490,911, JP-B-44-29622, and JP-A-44-29622. 47-25373, 47-24259
Heteroatom-bonded alkyl compounds as described in JP-B-49-24435, sulfonamides and ester compounds as described in JP-B-47-8736, and JP-A-49-24435.
1,3,5-tris [β-
(Vinylsulfonyl) -propionyl] -hexahydro-s-triazine or JP-B-50-35807, JP-A-5-35807
The compounds include alkyl compounds as described in 1-44164 and the like and compounds described in JP-A-59-18944 and the like.

The vinyl sulfone type hardener which is preferably used in the present invention is represented by the following general formula [HI].

[0185]

[Chemical Formula 91] In the general formula [H-I], L is an m-valent linking group, may be substituted, X is -CH = CH ₂ or -CH ₂
It is any of CH ₂ Y, and Y represents a group which is substituted by a nucleophilic group or which can be eliminated by a base in the form of HY (eg, a halogen atom, a sulfonyloxy group, a sulfuric acid monoester, etc.). ..

M represents an integer of 2-10.

The m-valent linking group L is, for example, an alkylene group,
Arylene groups or these groups, and -O-, -N (R¹ ) −, −
CO−, −SO−, −SO₂−, −SO₃−, −SO₂N (R¹ ) −, −CO
O−, −CON (R¹ ) −, −N (R¹ ) CON (R¹ ) −, −N (R¹ ) CO₂-In
By combining one or more of the bonds shown
It is a formed m-valent group. R¹Is a hydrogen atom, or 1
An alkyl group or aralkyl group having 15 carbon atoms
Represent Also, -N (R¹ ) −, −SO₂N (R¹ ) −, −CON (R¹ ) −, −
N (R¹ ) CO₂When two or more-are included, those R¹Comrade concludes
They may be combined to form a ring. Further, L has a substituent
Also, as a substituent, a hydroxy group, an alkoxy group,
Carbamoyl group, sulfamoyl group, alkyl group, ari
Examples include a diol group and the like. Also, the substituent is 1
One or more X³-SO₂Further substituted by a group represented by
It may be. X³Has the same meaning as X described above.

The following are typical examples of L. However, a to v in the examples are integers of 1 to 6, and only d may be 0. Of these, d, k, l
And p are preferably 1 to 3, and the above d of a to v,
Other than k, l and p are preferably 1 or 2. R ¹ is preferably a hydrogen atom or an alkyl group having a monovalent to hexavalent carbon atom, particularly preferably a hydrogen atom, a methyl group or an ethyl group.

[0189]

[Chemical Formula 92] Specific examples of X include the following.

[0190]

[Chemical formula 93] Among these, especially

[0191]

[Chemical 94] Is preferred.

Representative examples of the vinyl sulfone type hardener according to the present invention are shown below.

[0193]

[Chemical 95]

[0194]

[Chemical 96]

[0195]

[Chemical 97]

[0196]

[Chemical 98]

[0197]

[Chemical 99]

These vinyl sulfone type hardeners are dissolved in water or an organic solvent and used in an amount of 0.005 to 20% by weight, preferably 0.02 to 10% by weight, based on gelatin.

For addition to the photographic layer, a batch method, an in-line addition method or the like is adopted.

The layer in which these hardeners are added to the photographic layer is not particularly limited, and the object of the present invention can be achieved by adding them to, for example, one uppermost layer, one lowermost layer or all layers. You can

Since the above-mentioned hardener has a high diffusibility in the photographic constituent layers, when all the photographic constituent layers are simultaneously coated,
Before being hardened even if it is added to any of the constituent layers that are simultaneously coated, or even when it is simultaneously coated while exhibiting the hardenability, almost all layers of the photographic constituent layer are finally coated. It is possible to harden the film almost uniformly.

When all the layers constituting the photographic constituent layer are coated in several times, the present invention can be used in the constituent layer of the blue-sensitive silver halide emulsion layer containing the yellow coupler of the present invention or a constituent layer above the emulsion layer. It is preferable to add the vinyl sulfone type hardener.

The silver halide photographic light-sensitive material of the present invention exhibits the effects of the present invention sufficiently when it is used as a color photographic paper for direct viewing.

The silver halide photographic light-sensitive material of the present invention including this color photographic paper may be either monochromatic or polychromatic. In the case of a multi-color silver halide photographic light-sensitive material, a silver halide emulsion layer and a non-light-sensitive layer usually containing yellow, magenta and cyan couplers as photographic couplers in order to perform color reduction subtraction. Has a structure in which it is laminated on the support in an appropriate number of layers and in an order of layers, but the number of layers and the order of layers may be appropriately changed depending on the priority performance and the purpose of use.

Examples of the yellow dye image-forming coupler which can be used in the present invention include acylacetanilide type couplers such as benzoylacetanilide type and pivaloylacetanilide type couplers, which are described in US Pat.
No. 501, No. 4,022,620, No. 4,326,024, No. 4,40
1,752, 4,248,961, 3,973,968, 4,3
No. 14,023, No. 4,511,649, Japanese Patent Publication No. 58-10739, British Patent Nos. 1,425,020, 1,476,760, etc.

Preferred yellow dye image-forming couplers for use in the present invention include the couplers represented by the following general formula [Y-I].

[0207]

[Chemical 100] [In the formula, R ^A represents an alkyl group or a cycloalkyl group,
R ^B represents an alkyl group, a cycloalkyl group, an aryl group or an acyl group, and R ^C represents a group capable of substituting on the benzene ring. n represents 0 or 1. X ^A represents a group capable of splitting off upon coupling with an oxidized product of a developing agent, and Y ^A represents an organic group. In the general formula [Y-I], examples of the alkyl group represented by R ^A include a methyl group, an ethyl group, an isopropyl group, a t-butyl group, a dodecyl group and the like. The alkyl group represented by R ^A also includes those having a substituent, and examples of the substituent include a halogen atom,
Examples thereof include an aryl group, an alkoxy group, an aryloxy group, an alkylsulfonyl group, an acylamino group and a hydroxy group.

R^AAs a cycloalkyl group represented by
Is a cyclopropyl group, cyclohexyl group, adamantchi
And the like. R^A Preferably,
It is an alkyl group, and a t-butyl group is particularly preferable.

In the general formula [Y-I], examples of the alkyl group and cycloalkyl group represented by R ^B include the same groups as those described for R ^A , and the aryl represented by R ^B Examples of the group include a phenyl group. The alkyl group, cycloalkyl group, and aryl group represented by R ^B include those having the same substituents as the groups described in the description of R ^A. Examples of the acyl group represented by R ^B include an acetyl group, a propionyl group, a butyryl group, a hexanoyl group and a benzoyl group. R
^B is preferably an alkyl group or an aryl group,
An alkyl group is more preferable, and a lower alkyl group having 5 or less carbon atoms is further preferable.

In the general formula [Y-I], R^C Represented by
Groups that can be substituted on the benzene ring include halogen atoms
(Eg chlorine atom), alkyl group (eg ethyl group, i
-Propyl group, t-butyl group), alkoxy group (for example,
Methoxy group), aryloxy group (eg phenyloxy)
Si group), an acyloxy group (eg, methylcarbonyloxy)
Si group, benzoyloxy group), acylamino group (for example,
Acetamide group, phenylcarbonylamino group), cal
Vamoyl group (for example, N-methylcarbamoyl group, N-phenyl group)
Phenylcarbamoyl group), alkylsulfonylamino group
(Eg ethylsulfonylamino group), arylsulfo
A nylamino group (for example, a phenylsulfonylamino group),
Sulfamoyl group (eg N-propylsulfamoyl
Group, N-phenylsulfamoyl group) and imide group (eg
Examples include succinimide group and glutarimide group)
Be done. n represents 0 or 1.

In the general formula [Y-I], Y^A Is an organic group
Is represented, but is not limited to, preferably the following general formula [Y-
II]. General formula [Y-II] -J-R^D  In the formula, J is -N (R^E ) −CO−, −CON (R^E ) −, −COO−, −N
(R^E ) −SO₂-Or-SO₂−N (R^E ) -Represents. R^D And R
^E Is a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group
Represents

R^D And R^E As an alkyl group represented by
Is a methyl group, an ethyl group, an isopropyl group, t-butyl
Group, dodecyl group and the like. Also R^D And R^E Table
Examples of the aryl group include phenyl group and naphthyl group.
Groups and the like. These R^D And R^E Represented by
The alkyl group and the aryl group include those having a substituent.
Get caught The substituent is not particularly limited, but
As a representative, halogen atoms (chlorine atom, etc.),
Kill group (ethyl group, t-butyl group, etc.), aryl group (phenyl group)
Phenyl group, p-methoxyphenyl group, naphthyl group, etc.),
Alkoxy group (ethoxy group, benzyloxy group, etc.),
Reeloxy group (phenoxy group, etc.), alkylthio group
(Ethylthio group etc.), arylthio group (phenylthio group
Etc.), an alkylsulfonyl group (β-hydroxyethyls
(Rufonyl group, etc.), Arylsulfonyl group (Phenylsulfur group)
And a acylamino group, for example,
Alkylcarbonylamino group (acetamido group, etc.),
Reel carbonylamino group (phenylcarbonylamino
Groups etc.); carbamoyl groups such as alkyl groups, aryl
Those in which a group (preferably a phenyl group) is substituted
Specifically, N-methylcarbamoyl group, N-phen
Nylcarbamoyl group and the like; Acyl group such as acetyl group and the like
Arylcarbons such as alkylcarbonyl groups and benzoyl groups of
Rubonyl group; sulfonamide group such as alkylsulfone
Nylamino group, arylsulfonylamino group, specifically
Is methylsulfonylamino group, benzenesulfonamide
Groups, etc .; sulfamoyl groups such as alkyl groups, aryl
Those substituted with a group (preferably a phenyl group), etc.
Specifically, N-methylsulfamoyl group, N-phenyl
Phenylsulfamoyl group, etc .; Hydroxy group; Nitrile
Group; etc. are also mentioned.

-J-R^D Is particularly preferred as a group represented by
As -NHCOR ′^D Is mentioned. Where R '^D Is
Represents a functional group, preferably a straight chain or branched chain having 1 to 30 carbon atoms
Alkyl groups such as methyl group, ethyl group, n-propy
Group, isopropyl group, t-butyl group, n-pentyl group,
n-hexyl group, 2-ethylhexyl group, n-octyl
Group, n-decyl group, linear and branched dodecyl group, tridecane group
Syl group, tetradecyl group, pentadecyl group, hexadecyl group
Group, heptadecyl group, octadecyl group, nonadecyl group
Group, eicosyl group, docosyl group, tetracosyl group, hex
A sacosyl group is mentioned. Among these alkyl groups,
Particularly preferred is an alkyl group having 8 to 20 carbon atoms.

X in the general formula [Y-I]^A Is a developing agent
Represents a group that splits off during the coupling reaction with the oxidant.
Examples of these groups include the following general formula [Y-III] or
Or a group represented by the general formula [Y-IV].
A group represented by the general formula [Y-IV] is preferred. General formula [Y-III] -OR^F  In the general formula [Y-III], R^F Has a substituent
Represents an aryl group or a heterocyclic group.

[0215]

[Chemical 101]In the general formula [Y-IV], Z^A In collaboration with the nitrogen atom
The non-metallic atomic groups necessary to form a 5- or 6-membered ring are listed below.
You Here, the atomic groups necessary to form the non-metallic atomic group and
For example, methylene, methine, substituted methine,> C =
O,> NR^G (R^G Is the R^E Synonymous with), -N =, -O
−, −S−, −SO₂-And the like.

Yellow represented by the above general formula [Y-I]
The coupler is R^A , R^C Or Y^A To form a screw body
You may.

Next, specific examples of the yellow coupler represented by the formula [Y-I] are shown.

[0218]

[Chemical 102]

[0219]

[Chemical 103]

[0220]

[Chemical 104]

[0221]

[Chemical 105]

[0222]

[Chemical formula 106]

[0223]

[Chemical formula 107]

[0224]

[Chemical 108]

[0225]

[Chemical 109]

[0226]

[Chemical 110]

[0227]

[Chemical 111]

[0228]

[Chemical 112] Yellow couplers represented by the general formula [Y-I] are disclosed in JP-A-63-123047, Japanese Patent Application Nos. 2-245949 and 2-96.
It can be easily synthesized by the method described in Japanese Patent No. 774.

The yellow coupler represented by the general formula [Y-I] can be used alone or in combination of two or more, and can also be used in combination with another type of yellow coupler.

These yellow couplers can be used usually in the range of about 1 × 10 ^-3 mol to about 1 mol, preferably 1 × 10 ^-2 mol to 8 × 10 ^-1 mol per mol of silver halide. ..

As the magenta dye image-forming coupler which can be used in the present invention, 5-pyrazolone type, pyrazoloazole type, pyrazolinobenzimidazole type, indazolone type and cyanoacetyl type 4-equivalent or 2-equivalent magenta dye image Forming couplers, which include:
For example, U.S. Patent Nos. 2,600,788, 3,061,432, and
No. 3,062,653, No. 3,127,269, No. 3,311,476, No. 3,152,896, No. 3,419,391, No. 3,519,429,
No. 3,558,318, No. 3,684,514, No. 3,705,896
No. 3, No. 3,888,680, No. 3,907,571, No. 3,928,04
No. 4, No. 3,930,861, No. 3,930,816, No. 3,933,5
00, JP-A-49-29639, JP-A-49-111631, JP-A-49-129
538, 51-112341, 52-58922, 55-62454
No. 55-118034, No. 56-38643, No. 56-135841
No. 46, Japanese Patent Publication No. 46-60479, No. 52-34937, No. 55-29421
No. 55-35696, British Patent No. 1,247,493, Belgian Patent No. 792,525, and West German Patent No. 2,156,111 described as preferred magenta dye image-forming couplers used in the present invention are as follows. Examples thereof include couplers represented by the general formula [MI].

[0232]

[Chemical 113] In the general formula [I], Z represents a nonmetallic atom group necessary for forming a nitrogen-containing heterocycle, and the ring formed by the Z may have a substituent. X represents a hydrogen atom or a group capable of splitting off upon reaction with an oxidized product of a color developing agent. Also R
Represents a hydrogen atom or a substituent.

The substituent represented by R is not particularly limited, but typical examples thereof include alkyl, aryl, anilino, acylamino, sulfonamide, alkylthio, arylthio, alkenyl and cycloalkyl groups. In addition, halogen atom and cycloalkenyl, alkynyl, heterocycle, sulfonyl, sulfinyl, phosphonyl, acyl, carbamoyl, sulfamoyl, cyano,
Alkoxy, aryloxy, heterocyclic oxy, siloxy, acyloxy, carbamoyloxy, amino, alkylamino, imide, ureido, sulfamoylamino, alkoxycarbonylamino, aryloxycarbonylamino, alkoxycarbonyl, aryloxycarbonyl, heterocyclic thio Each group, a spiro compound residue, a bridged hydrocarbon compound residue and the like are also included.

The alkyl group represented by R preferably has 1 to 32 carbon atoms, and may be linear or branched.

The aryl group represented by R is preferably a phenyl group.

Examples of the acylamino group represented by R include an alkylcarbonylamino group and an arylcarbonylamino group.

As the sulfonamide group represented by R,
Examples thereof include an alkylsulfonylamino group and an arylsulfonylamino group.

Examples of the alkyl component and aryl component in the alkylthio group and arylthio group represented by R include the alkyl group and aryl group represented by R above.

The alkenyl group represented by R has 2 to 32 carbon atoms, and the cycloalkyl group has 3 to 1 carbon atoms.
2, especially 5 to 7, are preferable, and the alkenyl group may be linear or branched.

The cycloalkenyl group represented by R is preferably one having 3 to 12 carbon atoms, particularly 5 to 7 carbon atoms.

The sulfonyl group represented by R is an alkylsulfonyl group, an arylsulfonyl group, etc .; The sulfinyl group is an alkylsulfinyl group, an arylsulfinyl group, etc .; The phosphonyl group is an alkylphosphonyl group, an alkoxyphosphonyl group, an aryloxy group. Phosphonyl group, arylphosphonyl group, etc .; Acyl group, alkylcarbonyl group, arylcarbonyl group, etc .; Carbamoyl group, alkylcarbamoyl group, arylcarbamoyl group, etc .; Sulfamoyl group, alkylsulfamoyl group, arylsulfamoyl group Groups and the like; acyloxy groups such as alkylcarbonyloxy groups and arylcarbonyloxy groups; and carbamoyloxy groups such as alkylcarbamoyloxy groups and arylcarbamoyloxy groups; The de group alkylureido group,
Aryl ureido group, etc .; Sulfamoylamino group is alkylsulfamoylamino group, arylsulfamoylamino group, etc .; Heterocyclic group is preferably 5 to 7-membered, specifically, 2-furyl group, 2-thienyl group, 2
-Pyrimidinyl group, 2-benzothiazolyl group, etc .; The heterocyclic oxy group is preferably one having a 5- to 7-membered heterocycle, for example, 3,4,5,6-tetrahydropyranyl-
2-oxy group, 1-phenyltetrazole-5-oxy group, etc .; As the heterocyclic thio group, a 5- to 7-membered heterocyclic thio group is preferable, for example, 2-pyridylthio group, 2-benzothiazolylthio group, 2 , 4-diphenoxy-1,3,5-triazole-6-thio group etc .; trimethylsiloxy group, triethylsiloxy group, dimethylbutylsiloxy group etc. as siloxy group; succinimide group as imide group,
3-heptadecyl succinimide group, phthalimide group,
Glutarimide group etc .; Spiro [3.3] heptan-1-yl etc. as spiro compound residue; Bicyclo [2.2.1] heptan-1-yl, tricyclo [3] as bridged hydrocarbon compound residue 3.1.1 ^3,7 ] decan-1-yl, 7,7-dimethyl-bicyclo [2.2.1] heptan-1-yl and the like can be mentioned.

Examples of the group capable of splitting off upon reaction with the oxidant of the color developing agent represented by X include a halogen atom (chlorine atom, bromine atom, fluorine atom, etc.) and alkoxy, aryloxy, heterocyclic oxy, acyloxy, sulfonyl. Oxy, alkoxycarbonyloxy, aryloxycarbonyl, alkyl oxalyloxy, alkoxy oxalyloxy, alkylthio, arylthio, heterocyclic thio, alkyloxythiocarbonylthio, acylamino, sulfonamide, nitrogen-containing heterocyclic ring bonded by N atom,
Alkyloxycarbonylamino, aryloxycarbonylamino, carboxyl,

[0243]

[Chemical 114](R ₁'Is synonymous with R above and Z'is synonymous with Z above.
Yes, R₂'And R₃'Is a hydrogen atom, an aryl group, an alkyl group
Represents a group or a heterocyclic group. ) And other groups,
Preferred is a halogen atom, especially a chlorine atom.

Examples of the nitrogen-containing heterocycle formed by Z or Z ′ include a pyrazole ring, an imidazole ring, a triazole ring and a tetrazole ring. The ones mentioned are mentioned.

What is represented by the general formula [MI] is more specifically represented by, for example, the following general formulas [M-II] to [M-VII].

[0246]

[Chemical 115] In the general formulas [M-II] to [M-VII], R _{1 to} R ₈
And X have the same meanings as R and X described above.

Further, among the general formulas [MI], preferred are those represented by the following general formula [M-VIII].

[0248]

[Chemical formula 116] In the formula, R ₁ , X and Z ₁ are R in the general formula [MI],
It is synonymous with X and Z.

Among the magenta couplers represented by the above general formulas [M-II] to [M-VII], the magenta couplers represented by the general formula [M-II] are particularly preferable.

Most preferred as the substituents R and R ₁ on the heterocycle are those represented by the following general formula [M-IX].

[0251]

[Chemical 117] In the formula, R ₉ , R ₁₀ and R ₁₁ have the same meanings as R above.

Two of R ₉ , R ₁₀ and R ₁₁ mentioned above, for example, R ₉ and R ₁₀ are combined to form a saturated or unsaturated ring (eg cycloalkane, cycloalkene, heterocycle). Alternatively, R ₁₁ may be bonded to the ring to form a bridged hydrocarbon compound residue.

Of the general formula [M-IX], preferred is
(I) when at least two of R _{9 to} R ₁₁ are alkyl groups, (ii) one of R _{9 to} R ₁₁ such as R ₁₁ is a hydrogen atom and the other two R ₉ and R _{9 When 10} joins to form a cycloalkyl with the root carbon atom.

Further preferred among (i) are R ₉ to
This is the case where two of R ₁₁ are alkyl groups and the other one is a hydrogen atom or an alkyl group.

In addition, Z is represented by the formula [MI].
Formed ring and Z in the general formula [M-VIII]₁By
Substituents that the ring formed may have,
-II] to R in [M-VI]₂~ R₈As below general
Those represented by the formula [MX] are preferable. General formula [MX] -R ₁₂-SO₂-R ₁₃ Where R ₁₂Is an alkylene group, R ₁₃Is an alkyl group,
Represents an alkyl group or an aryl group.

R ₁₂The alkylene group represented by is preferably
The number of carbon atoms in the straight chain portion is 2 or more, more preferably 3 to 6
And may be linear or branched.

R ₁₃The cycloalkyl group represented by
Those having 5 to 6 members are preferable.

Typical specific examples of the compound according to the present invention are shown below.

[0259]

[Chemical 118]

[0260]

[Chemical 119]

[0261]

[Chemical 120]

[0262]

[Chemical 121]

[0263]

[Chemical formula 122]

[0264]

[Chemical 123]

[0265]

[Chemical formula 124]

[0266]

[Chemical 125]

[0267]

[Chemical formula 126]

[0268]

[Chemical 127]

[0269]

[Chemical 128]

[0270]

[Chemical formula 129]

[0271]

[Chemical 130]

In addition to the above, as specific examples of the magenta coupler used in the present invention, among the compounds described on pages (18) to (32) of JP-A-62-166339, N
o.1 to 4, 6, 8 to 17, 19 to 24, 26 to 43, 45 to 59, 61 to 10
4, 106-121, 123-162, 164-223 can be mentioned.

Further, the coupler is a journal of the chemical society (Journal of the Chemical Society).
Society), Perkin I (1977), 2047
2052, U.S. Pat.No. 3,725,067, JP-A-59-99437,
58-42045, 59-162548, 59-171956, 60
-33552, 60-43659, 60-172982, 60-19
No. 0779, No. 62-209457, No. 63-307453, etc. can be referred to for synthesis.

These magenta couplers are usually halogen-containing.
1 x 10 per mol of silver chloride^-3Mol ~ 1 mol, preferably 1 x 10
^-2Mol ~ 8 x 10^-1 It can be used in the molar range.

Preferred cyan dye image-forming couplers for use in the present invention include couplers represented by the following general formula [CI].

[0276]

[Chemical 131] [In the formula, R _A represents an alkyl group having 2 to 6 carbon atoms. R _B represents a ballast group. Z _A represents a hydrogen atom or an atom or group capable of splitting off upon reaction with an oxidized product of a color developing agent. The alkyl group represented by R _A may be linear or branched and includes those having a substituent. The ballast group represented by R _B is an organic group having a size and shape that provides the coupler molecule with sufficient bulk to prevent the rapplers from substantially spreading to the other layers from the layer to which the coupler is applied. is there.

The preferred ballast group is represented by the following general formula.

[0278]

[Chemical 132] _RC represents an alkyl group having 1 to 12 carbon atoms, Ar represents an aryl group such as a phenyl group, and the aryl group includes those having a substituent.

Next, specific examples of the coupler represented by the general formula [C-I] are shown, but the couplers are not limited to these.

[0280]

[Chemical 133]

[0281]

[Chemical 134]

[0282]

[Chemical 135]

Specific examples of the cyan coupler that can be used in the present invention including these are described in JP-B-49-11572.
No. 61-3142, 61-9652, 61-9653,
61-39045, 61-50136, 61-99141, 61
-105545 etc.

These cyan couplers are generally used in an amount of 1 × 10 ⁻³ to 1 mol, preferably 1 × 10 ³ mol per mol of silver halide.
It can be used in the range of ^-2 mol to 8 x 10 ^-1 mol.

The silver halide emulsion used in the silver halide photographic light-sensitive material of the present invention (hereinafter referred to as the silver halide emulsion of the present invention) includes silver bromide, silver iodobromide and iodochloride as silver halides. Any silver halide emulsion such as silver, silver chlorobromide and silver chloride can be used, but it is preferable to use a high chloride silver halide emulsion.

In the present invention, the high chloride silver halide emulsion means a silver chlorobromide, silver chloroiodobromide, silver chloroiodide or silver chloride emulsion having 90 mol% or more of silver chloride. The content of silver iodide is preferably 1 mol% or less, and more preferably contains no silver iodide. The content of silver bromide is preferably 5 mol% or less, more preferably 2 mol% or less, and most preferably 1 to 0.01 mol%.

The distribution of silver iodide and silver bromide in the silver halide grains is not particularly limited, and they may be localized at the center, on the surface or in the middle of the grains, or distributed on average. May be.

As a method for preparing silver halide grains, any of an acidic method, a neutral method, an ammonia method and the like is preferably used. Further, a silver halide solvent other than the ammonia method may be used. The grains may be grown at one time, or may be grown after forming seed grains. The method of forming seed particles and the method of growing seed particles may be the same or different.

The silver halide emulsion may be formed by mixing halide ions and silver ions at the same time, or by mixing the other in a liquid in which either one is present.

The silver halide emulsion according to the present invention may be a mixture of two or more kinds of silver halide emulsions formed separately.

The grain size distribution of the silver halide grains used in the present invention may be polydisperse or monodisperse.
Monodispersion is preferred.

The silver halide grains used in the silver halide emulsion of the present invention are cadmium salt, zinc salt, lead salt, thallium salt, iridium salt (or complex salt) during the grain forming process and / or growing process. , A rhodium salt (or complex salt) and an iron salt (or complex salt) may be used to add a metal ion to allow these metal elements to be contained inside the particle and / or on the surface of the particle. By placing in an appropriate reducing atmosphere,
Alternatively, reduction sensitizing nuclei can be imparted to the grain surface.

In the silver halide emulsion of the present invention, unnecessary soluble salts may be removed after the completion of the growth of silver halide grains, or may be contained therein. When removing the salts, Research Disclosure (Resear
ch Disclosure, hereinafter abbreviated as RD) No. 17643, Item II.

The average grain size of the silver halide grains of the present invention (in the case of spherical grains, the diameter thereof, and in the case of cubic or non-spherical grains, converted into a circular image having the same area as the projected image thereof) The diameter) is preferably 5 μm or less, and particularly preferably 1 μm or less.

The silver halide emulsion of the present invention can be chemically sensitized by a conventional method.

Further, for example, British Patent Nos. 618,061, 1,315,755, 1,396,696,
JP-B-44-15748, U.S. Pat.Nos. 1,574,944, 1,623,499, 1,623,499,
No. 1,673,522, No. 2,278,947, and No.
No. 2,399,083, No. 2,410,689, No. 2,41
9,974, 2,448,060, 2,487,85
No. 0, No. 2,518,698, No. 2,521,926, No. 2,642,361, No. 2,694,637, No. 2,728,668, No. 2,739,060,
No. 2,983,610, No. 3,021,215, and No.
No. 3,026,203, No. 3,297,446, No. 3,29
No. 7,447, No. 3,361,564, No. 3,411,91
No. 4, No. 3,554,757, No. 3,565,631, No. 3,565,633, No. 3,591,385, No. 3,656,955, No. 3,761,267,
No. 3,772,031 specification, No. 3,857,711 specification, no.
3,891,446, 3,001,714, 3,90
4,415, 3,930,867, 3,984,24
No. 9, No. 4,054,457, No. 4,067,740, RD12008, No. 13452, No. 13564, THJam
es “The Theory of the Photographic process”
(4th Ed. Macmillan. 1977) pages 67 to 76, etc. are preferably chemically sensitized.

The silver halide emulsion of the present invention can be optically sensitized to a desired wavelength region by using a dye known as a sensitizing dye in the photographic industry.

The silver halide photographic light-sensitive material of the present invention comprises
Anti-foggant, hardener, plasticizer, polymer latex, ultraviolet absorber, formalin scavenger, mordant, development accelerator, development retarder, optical brightener, matting agent,
Lubricants, antistatic agents, surfactants and the like can be optionally used.

The silver halide photographic light-sensitive material of the present invention can form an image by being subjected to various color development treatments.

[0300]

EXAMPLES Next, the present invention will be explained based on examples.
Embodiments of the present invention are not limited to these. Example 1 On a paper support having polyethylene laminated on one side and polyethylene containing titanium oxide on the other side, each layer having the constitution shown in Tables 1 and 2 below is a polyethylene layer containing titanium oxide. To prepare a multilayer silver halide color photographic light-sensitive material sample 1. The coating liquid was prepared as follows. First layer coating liquid 26.7 g of yellow coupler (YA), 10.0 g of dye image stabilizer (ST-1), dye image stabilizer (ST-2) 6.
To 67 g, 0.67 g of the additive (HQ-1) and 6.67 g of the high boiling point organic solvent (DNP), 60 ml of ethyl acetate was added and dissolved, and this solution contained 7 ml of a 20% aqueous solution of the surfactant (SU-1) 10 % Gelatin aqueous solution 220 ml was emulsified and dispersed using an ultrasonic homogenizer to prepare a yellow coupler dispersion. This dispersion was mixed with a blue-sensitive silver chlorobromide emulsion (containing 8.68 g of silver) prepared under the following conditions to prepare a coating solution for the first layer.

The coating solutions for the second to seventh layers were prepared in the same manner as the coating solution for the first layer. Moreover, (H-1) was added to the 2nd layer, the 4th layer, and the 7th layer as a hardening agent. Surfactants (SU-2) and (SU-3) are added as coating aids,
The surface tension was adjusted. The addition amount in the silver halide photographic light-sensitive material is the number of grams per 1 m ² unless otherwise specified.

[0302]

[Table 1]

[0303]

[Table 2]

[0304]

[Chemical 136]

[0305]

[Chemical 137]

[0306]

[Chemical 138]

[0307]

[Chemical 139] (Preparation of silver halide emulsion) Three kinds of silver halide emulsions shown in Table 3 were prepared by the neutral method and the simultaneous mixing method.

[0308]

[Table 3] To each silver halide emulsion, after chemical sensitization, STB-1 shown below as an emulsion stabilizer was added in an amount of 5 × 10 ⁻³ mol per mol of silver halide.

[0309]

[Chemical 140]

Next, to Sample 1, the comparative dyes shown in Table 4 or the silver salts of the dyes of the present invention were added to the layers shown in Table 4, and the cyan layer of the fifth layer in the layer structure of Sample 1 was added. The coupler and the high boiling point organic solvent were changed as shown in Table 4, and further,
Samples 2 to 22 were prepared in exactly the same manner as in Sample 1 except that the polymer of the present invention was added as shown in Table 4 when the coupler dispersion was prepared. Comparative dyes AI-1, AI-
2 was prepared as an aqueous solution, and the silver salt of the dye of the present invention was prepared by the following method and added as a dispersion.

0.01 mol of dye and 1.01 g of triethylamine
(0.01 mol) was dissolved in 1000 ml of water, and 10 ml of a 1 mol / liter silver nitrate aqueous solution was added dropwise with stirring. The resulting precipitate was collected by filtration, washed with water, and dried to obtain the desired silver salt of the dye.

To 70 ml of a 3% aqueous gelatin solution, 0.01 mol of the silver salt of the dye obtained above and the surfactant Triton X-200 (Roh
m & Haas) 6.7% solution (3 ml), glass beads (diameter 1 mm) 200 g, and a medium stirring mill (Aquamizer QA-5, Hosokawa Micron Co., Ltd.) 2
A silver salt dispersion of the dye was obtained by pulverizing for a period of time.

[0313]

[Table 4]

Two sets of the obtained samples 1 to 22 were prepared. The first set uses a sensitometer KS-7 type (manufactured by Konica Corporation) after wedge exposure with red light and then processed according to the following color development processing steps. (Company PDA-65 type) was used to measure the fog density and sensitivity of the red photosensitive emulsion layer,
The same day performance was evaluated.

Further, the second set of the two sets prepared above of the obtained light-sensitive material was allowed to stand in a high temperature and high humidity (50 ° C., 80% RH) atmosphere for 3 days, and thereafter, the same wedge as described above was used. The resulting dye image was subjected to exposure and color development processing, and the fog density and sensitivity of the red light-sensitive emulsion layer were measured to evaluate the storage stability over time.

Table 5 shows the results of evaluation of the same day performance and storability over time.

Processing Step Temperature Time Color development 35.0 ± 0.3 ° C. 45 seconds Bleach fixing 35.0 ± 0.5 ° C. 45 seconds Stabilization 30-34 ° C. 90 seconds Dry 60-80 ° C. 60 seconds Color developer 800 ml Triethanolamine 10 g N, N-diethylhydroxylamine 5 g Potassium bromide 0.02 g Potassium chloride 2 g Potassium sulfite 0.3 g 1-Hydroxyethylidene-1,1-diphosphonic acid 1.0 g Ethylenediaminetetraacetic acid 1.0 g Catechol-3,5-disulfonic acid disodium salt 1.0 g Diethylene glycol 10g N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate 4.5g Optical brightener (4,4'-diaminostilbene sulfonic acid derivative) 1.0g Potassium carbonate 27g Water was added. Adjust the total volume to 1 liter and adjust the pH to 10.10. Bleach-fixing solution Ethylenediaminetetraacetic acid ammonium ferric dihydrate 60g Ethylenediaminetetraacetic acid 3g Ammonium thiosulfate (70% aqueous solution) 100ml Ammonium sulfite (40% aqueous solution) 27.5ml Add water to bring the total volume to 1 liter and add potassium carbonate or glacial acetic acid. Adjust pH to 5.7 with. Stabilizing solution 5-chloro-2-methyl-4-isothiazolin-3-one 0.2 g 1,2-benzisothiazolin-3-one 0.3 g ethylene glycol 1.0 g 1-hydroxyethylidene-1,1-diphosphonic acid 2.0 g o -Sodium phenylphenol 1.0 g Ethylenediaminetetraacetic acid 1.0 g Ammonium hydroxide (20% aqueous solution) 3.0 g Optical brightener (4,4'-diaminostilbene sulfonic acid derivative) 1.5 g Water was added to bring the total volume to 1 liter, and sulfuric acid was added. Or adjust the pH to 7.0 with potassium hydroxide.

Samples 1 to 22 were decomposed and exposed with red light through a MTF measuring wedge, and processed in the same steps as described above.

With respect to each of the samples after the above treatment, the MTF (Modulation Transfer Function) of the red photosensitive layer was determined by a microdensitometer, and the MTF values at a spatial frequency of 5 lines / mm were compared.

It is well known to those skilled in the art to judge the sharpness of an image by MTF.
of the photographic process "4th edition Macmil
lan.1977 pp. 612-614. The results are also shown in Table 5
Shown in.

[0321]

[Table 5]

As is clear from Table 5, Sample 1 containing no anti-irradiation dye has high sensitivity but insufficient sharpness. On the other hand, the samples 2 and 3 to which the water-soluble dye which has been used conventionally is improved in sharpness, but the sensitivity is significantly decreased in all cases, and the sample 4 to which the silver salt of the dye is added has improved sharpness. However, the sensitivity is small, but the fog during storage with time is large and the raw storability is deteriorated.

On the other hand, Samples 5 to 22 according to the present invention
Shows no deterioration in sensitivity, has good raw storability, and is significantly improved in sharpness. Example 2 In comparison with Sample 1 of Example 1, the comparative dyes shown in Table 6 or silver salts of the dyes of the present invention were added to the layers shown in Table 6, and the first layer of the layer constitution of Sample 1 was added. Samples 23 to 23 were prepared in the same manner as in Sample 1 except that the yellow coupler and the high boiling point organic solvent were changed as shown in Table 6, and the polymer of the present invention was added as shown in Table 6 when the coupler dispersion was prepared.
45 was created. The comparative dyes AI-1 to AI-3 were prepared as an aqueous solution, and the silver salt of the dye of the present invention was prepared in the same manner as in the method of Example 1 and added as a dispersion liquid.

[0324]

[Table 6]

Each of the obtained samples 23 to 45 was replaced with 2
I prepared it. The first set used a sensitometer KS-7 type (manufactured by Konica Corporation) after wedge exposure with blue light and then processed according to the color development processing step of Example 1 to obtain an optical densitometer ( Konica Corporation PDA-65 type)
Was used to measure the fog density and sensitivity of the blue photosensitive emulsion layer, and the performance on the same day was evaluated.

Further, the second of the two prepared sets of the above light-sensitive materials was left in a high temperature and high humidity (50 ° C., 80% RH) atmosphere for 3 days, and then the same wedge as described above was used. The resulting dye image was subjected to exposure and color development processing, and the fog density and sensitivity of the blue-sensitive emulsion layer were measured to evaluate the storage stability over time.

Table 7 shows the evaluation results of the performance on the same day and the storability over time.

Samples 23 to 45 were decomposed and exposed with blue light through a wedge for measuring MTF.
The treatment was performed by the same steps as described above.

For each of the samples after the above treatment, the MTF (Modulation Transfer Function) of the blue photosensitive layer was determined by a microdensitometer, and the MTF values at a spatial frequency of 5 lines / mm were compared. The results are also shown in Table 7.

[0330]

[Table 7] As is clear from Table 7, Samples 28 to 45 according to the present invention
It can be seen that there is little or no decrease in sensitivity, the raw storage stability is good, and the sharpness is excellent. Example 3 (Preparation of silver halide emulsion) Three kinds of silver halide emulsions shown in Table 8 were prepared by the neutral method and the simultaneous mixing method.

[0331]

[Table 8] To each silver halide emulsion, after chemical sensitization, STB-1 shown below as an emulsion stabilizer was added in an amount of 5 × 10 ⁻³ mol per mol of silver halide.

[0332]

[Chemical 141]

(Sample 4 of silver halide color photographic light-sensitive material)
Preparation of 6) Next, the following layers 1 to 7 were sequentially coated (simultaneous coating) on a paper support whose both surfaces were coated with polyethylene to prepare a silver halide color photographic light-sensitive material sample 46.
(In the following examples, the addition amount is shown per 1 m ² of the light-sensitive material.) Layer 1 ... Gelatin (1.2 g) and 0.29 g (in terms of silver, the same applies hereinafter) of a blue-sensitive silver halide emulsion ( Em-1) and 0.75g
Yellow coupler (YA) and 0.015 g of 2,5-
Dioctyl hydroquinone (HQ-1) dissolved 0.3
A layer containing g of the high boiling organic solvent DNP (dinonyl phthalate). Layer 2 ... 0.2 g of high boiling organic solvent DOP (dioctyl phthalate) in which gelatin (0.9 g) and 0.04 g of HQ-1 are dissolved and 0.03 g of anti-irradiation dye (AI-
1), a layer containing 0.02 g of (AI-2). Layer 3: Gelatin (1.4 g), 0.2 g green light-sensitive silver halide emulsion (Em-2) and 0.5 g magenta coupler (M-
1), 0.25g light stabilizer (ST-2) and 0.01g HQ
A layer containing 0.3 g of a high boiling point organic solvent DOP in which -1 was dissolved and 6 mg of the following filter dye (AI-1). Layer 4: Gelatin (1.2 g) and 0.6 g UV absorber (UV
-1) and 0.3 g of a high boiling organic solvent DNP in which 0.05 g of HQ-1 was dissolved. Layer 5 ... Gelatin (1.4 g), 0.20 g of red-sensitive silver halide emulsion (Em-3) and 0.54 g of cyan coupler (C-
1), a layer containing 0.01 g of HQ-1 and 0.3 g of ST-1 dissolved in 0.3 g of a high boiling organic solvent DOP. Layer 6 ... A layer containing gelatin (1.1 g) and 0.3 g of a high boiling organic solvent DOP in which 0.2 g of UV-1 was dissolved. Layer 7: A layer containing gelatin (1.0 g) and 0.05 g of sodium 2,4-dichloro-6-hydroxytriazine.

[0334]

[Chemical 142]

[0335]

[Chemical 143]

Next, for the sample 46, the AI added to the layer 2 was used.
-1 and AI-2 were changed to the silver salts of the dyes shown in Table 9, and further the couplers and high boiling point organic solvents of Layer 1, Layer 2 and Layer 3 were changed as shown in Table 9 to give Samples 47 to 58. Created.

The above samples 46 to 58 thus obtained were each subjected to 2
I prepared it. The first set is a sensitometer KS-7 type (manufactured by Konica Corporation), which is subjected to wedge exposure with white light and then processed according to the following color development processing step. Measure the fog density and sensitivity of each photosensitive emulsion layer using a PDA-65 type manufactured by the company,
The same day performance was evaluated.

Further, the second of the two prepared sets of the above-mentioned light-sensitive materials was left in a high temperature and high humidity (50 ° C., 80% RH) atmosphere for 3 days, and then the same wedge as described above was used. Exposure and color development were performed, and the resulting dye image was measured for fog density of each photosensitive emulsion layer to evaluate the storage stability over time.

Tables 9 and 10 show the results of sensitivity on the same day and the amount of fog increase after storage with time.

Further, the samples 46 to 58 were subjected to decomposition exposure with blue light, green light and red light through a MTF measuring wedge, and processed by the same steps as described above.

For each sample after the above treatment, each MTF
(Modulation Transfer Function) is calculated with a microdensitometer, and MTF at a spatial frequency of 5 lines / mm
The values were compared. The results are also shown in Tables 9 and 10.

[0342]

[Table 9]

[0343]

[Table 10]

As can be seen from Tables 9 and 10, the samples 49 to 58 according to the present invention have high sensitivity, little increase in fog even after storage over time, and excellent sharpness. Example 4 A silver halide color photographic light-sensitive material sample 59 was prepared by sequentially coating the following layers on a polyethylene-laminated paper support from the support side. Layer 1 ... 1.2 g / m ² gelatin, 0.32 g / m ² (silver equivalent, the same applies below) blue-sensitive silver halide emulsion (silver chloride content 99.7
Mol%, sodium thiosulfate 2 mg / 1 mol silver halide as a chemical sensitizer, and SD-1 0.9 mmol / silver halide 1 mol as a spectral sensitizer. ), 0.50 g / m ²
0.75 g / m ² dissolved in dinonyl phthalate (DNP)
A layer containing a yellow coupler (YA). Layer 2 ... An intermediate layer comprising 0.7 g / m ² of gelatin, 40 mg / m ² of anti-irradiation dye (AI-1) and 20 mg / m ² of (AI-2). Layer 3: 1.25 g / m ² gelatin, 0.22 g / m ² green-sensitive silver halide emulsion (silver chloride content 99 mol%, sodium thiosulfate 2 mg / 1 mol silver halide and spectral sensitizer as chemical sensitizer) SD-2 0.7 mmol / silver halide 1 as sensitizer
Contains moles. ), 0.62 g / m ² of magenta coupler (MA) dissolved in 0.30 g / m ² of dioctyl phthalate (DOP) and 0.25 g / m ² of ST-1. Layer 4 ... An intermediate layer consisting of 1.2 g / m ² of gelatin. Layer 5: 1.40 g / m ² gelatin, 0.20 g / m ² red-sensitive silver halide emulsion (silver chloride content 99 mol%, sodium thiosulfate 2 mg / silver halide 1 mol and spectral sensitizer as chemical sensitizer) containing SD-3 0.2 mmol / mole silver halide as a sensitive agent.), containing 0.20 g / m ² of dioctyl phthalate (DOP) was dissolved in a 0.45 g / m ² of cyan coupler (C-a) layer. Layer 6 ... A layer containing 0.5 g / m ² of gelatin.

As a hardening agent, 2,4-dichloro-
Layer 6-hydroxy sodium 6-hydroxy-s-triazine
0.017 g per 1 g of gelatin was added to each of Nos. 1 and 6.

[0346]

[Chemical 144]

[0347]

[Chemical 145]

Next, with respect to Sample 59, the heterocyclic fog inhibitors shown in Tables 11 and 12 were added to each of the silver halide emulsion layers of Layer 1, Layer 3 and Layer 5 in an amount of 0.5 mmol / mol of silver halide. The silver salts of the dyes of the present invention were added to the layers shown in Tables 11 and 12, and the couplers of Layer 1, Layer 3 and Layer 5 were added to Table 11
Samples 60 to 72 were prepared in the same manner as sample 59 except that the couplers shown in Table 12 were changed to equimolar amounts.

The above Samples 59 to 72 thus obtained were each subjected to 2
I prepared it. The first set was subjected to wedge exposure with white light using a sensitometer KS-7 type (manufactured by Konica Corporation), and then processed according to the color development processing step of Example 1, and an optical densitometer ( Konica Corporation PDA-65 type)
Was used to measure the fog density and sensitivity of each photosensitive emulsion layer to evaluate the performance on the same day.

Further, the second of the two prepared sets of the above-mentioned light-sensitive materials was left in a high temperature / high humidity (50 ° C., 80% RH) atmosphere for 3 days, and then the same wedge as described above was used. Exposure and color development were performed, and the resulting dye image was measured for fog density of each photosensitive emulsion layer to evaluate the storage stability over time.

Tables 11 and 12 show the results of the sensitivity on the same day and the fog increase after storage with time.

[0352]

[Table 11]

[0353]

[Table 12]

As is clear from Tables 11 and 12, the comparative samples 61 and 62 using the silver salt of the dye are significantly fogged after storage with time, whereas the samples of the present invention greatly reduce fog after storage with time. It can be seen that it has excellent photographic performance without lowering the sensitivity as in Comparative Sample 60. Example 5 Silver halide color photographic light-sensitive material samples 71 to 85 were prepared by sequentially coating the following layers from the support side on a polyethylene-supported paper support. Layer 1 ... 1.2 g / m ² gelatin, 0.32 g / m ² (silver equivalent, the same applies below) blue-sensitive silver halide emulsion (average grain size 0.70 μ
m, silver chloride content 97 mol%, sodium thiosulfate 2 mg / 1 mol silver halide as chemical sensitizer and SD-1 0.9 mmol / 1 mol silver halide as spectral sensitizer. ), And a layer containing 1.0 mmol / m ² of the yellow coupler shown in Table 13 dissolved in 0.50 g / m ² of dioctyl phthalate. Layer 2 ... Intermediate layer containing 0.7 g / m ² gelatin, irradiation dyes shown in Tables 13 and 14. Layer 3: 1.25 g / m ² gelatin, 0.22 g / m ² green-sensitive silver halide emulsion (average grain size 0.45 μm, silver chloride content 99 mol%, sodium thiosulfate 2 mg / halogenated as chemical sensitizer) Containing 1 mol of silver and 0.7 mmol of SD-2 / 1 mol of silver halide as a spectral sensitizer), 0.30 g / m ²
0.8 mmol / m ² magenta coupler shown in Table 13 and 0.25 g / m ² ST-dissolved in dioctyl phthalate.
A layer containing 1. Layer 4 ... An intermediate layer made of 1.2 g / m ² of gelatin. Layer 5: 1.40 g / m ² gelatin, 0.20 g / m ² red-sensitive silver halide emulsion (average grain size 0.50 μm, silver chloride content 99 mol%, sodium thiosulfate 2 mg / halogenated as a chemical sensitizer) It contains 1 mol of silver and 0.2 mmol of SD-3 as a spectral sensitizer / 1 mol of silver halide.), 0.20 g / m 2.
A layer containing 0.9 mmol / m ² of the cyan coupler shown in Table 13 dissolved in ² of tri-n-octyl phosphate. Layer 6 ... A layer containing 0.5 g / m ² of gelatin, 55 mg / m ² of the fluorescent brightening agent shown in Tables 13 and 14, and 150 mg / m ² of polyvinylpyrrolidone (average molecular weight 100,000).

As a hardening agent, 2,4-dichloro-
Layer 6-hydroxy sodium 6-hydroxy-s-triazine
0.017 g per 1 g of gelatin was added to each of Nos. 1 and 6.

[0356]

[Chemical formula 146]

[0357]

[Chemical 147]

Samples 71 to 85 prepared in this way
After being subjected to wedge exposure according to a conventional method, development processing was performed in the same manner as in Example 1.

For each processed sample, the fog of each photosensitive emulsion layer was measured, and the whiteness of the unexposed portion was visually evaluated. The results are shown in Table 13.

Samples 71 to 85 were subjected to decomposition exposure with blue light, green light, and red light through an MTF measuring wedge, and were processed by the same steps as described above.

With respect to each of the samples after the above treatment, the MTF (Modulation Transfer Function) of the red photosensitive layer was obtained by a microdensitometer, and the MTF values at a spatial frequency of 5 lines / mm were compared. The results are also shown in Table 13.

[0362]

[Table 13]

As is clear from Table 13, the samples according to the present invention have good whiteness, little fog, and further improved sharpness. Example 6 The present invention was applied to a color paper here. That is,
Silver halide color photographic light-sensitive materials 86 to 108 were prepared by sequentially coating the following layers from the support side on a paper support laminated on both sides with polyethylene.

Layer 1 ... 1.2 g / m ² gelatin, 0.32 g / m ²
A blue-sensitive silver chlorobromide emulsion (in terms of silver, the same applies hereinafter) (silver chloride content 99.3 mol%), 1.0 mmol / m ² dissolved in 0.50 g / m ² of dioctyl phthalate, yellow shown in Tables 14 and 15 Layer containing coupler. Layer ² ... 0.70g / m 2 of gelatin, Table 14, anti-irradiation dye and 40 mg / m ² of dioctyl phthalate were dissolved in a 40 mg / m ² of color turbidity preventing agent shown in Table 15 (AS-1)
The middle layer consisting of. Layer 3: 1.25 g / m ² of gelatin, 0.25 g / m ² of green-sensitive silver chlorobromide emulsion (silver chloride content 99.5 mol%), 0.8 mmol of Table 14 dissolved in 0.30 g / m ² of dioctyl phthalate. ,
A layer containing a magenta coupler shown in Table 15. Layer 4 ... 1.20g / m ² of gelatin and 40 mg / m ² of dioctyl phthalate were dissolved in a 40 mg / m ² of color turbidity inhibitor (AS-
An intermediate layer consisting of 1). Gelatin layer ^{5 ... 1.20g / m 2, 0.30g} / m 2 of red-sensitive silver chlorobromide emulsion (silver content 99.7 mol% chloride), 0.20g / m ² of 0.9 mmol dissolved in dioctyl phthalate Table 14 ,
A layer containing a cyan coupler shown in Table 15. Layer 6 0.30 g / m ² of UV absorber (U) dissolved in 1.00 g / m ² of gelatin and 0.20 g / m ² of dioctyl phthalate.
A layer containing V-1). Layer 7 ... A layer containing 0.50 g / m ² of gelatin.

[0365]

[Chemical 148]

The hardeners shown in Tables 14 and 15 were added to Layers 2, 4 and 7 at 0.1 mmol / g of gelatin.

Each of the obtained samples was left to stand for 3 days and
After storing at 55 ° C and 80% relative humidity for 3 days, the sensitometer KS-
After wedge exposure using type 7 (manufactured by Konica Corporation),
After processing according to the same color development process as in Example 1, the sensitivity (S) and fog (Fog) of each photosensitive emulsion layer are measured using an optical densitometer (PDA-65 type manufactured by Konica Corporation).
Was measured. The results are also shown in Tables 14 and 15.

For samples 86 to 108, MTF
Decomposition exposure was performed with blue light, green light, and red light through the measurement wedge, and the same process as above was performed.

For each sample after the above treatment, the MTF (Modulation Transfer Function) of each photosensitive emulsion layer was determined by a microdensitometer, and the spatial frequency was 5 lines /
The MTF values in mm were compared. The results are also shown in Table 14 and Table 1.
5 shows.

[0370]

[Chemical 149]

[0371]

[Table 14]

[0372]

[Table 15]

As is clear from Tables 14 and 15, the samples 92 to 108 according to the present invention have good photographic performance.
It can be seen that the fog is low and the sensitivity is not deteriorated even when stored at 80 ° C and 80 ° C. Further, the sample of the present invention is M
It can be seen that it has a high TF value and excellent sharpness.

[0374]

The silver halide photographic light-sensitive material of the present invention comprises
It has high sharpness, high sensitivity, little fog, and good raw storability.

Continuation of the front page (51) Int.Cl. ⁵ Identification code Office reference number FI technical display location G03C 1/46 7/392 A

Claims (6)

[Claims] 1. A silver halide color photographic light-sensitive material having a photographic constituent layer comprising a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, and a red-sensitive silver halide emulsion layer on a reflective support. One of the photographic constituent layers contains at least one silver salt of a dye, and the blue-sensitive silver halide emulsion layer contains at least one water-insoluble and organic solvent-soluble homo- or copolymer. A silver halide color photographic light-sensitive material characterized by: 2. A silver halide color photographic light-sensitive material having a photographic constituent layer comprising a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, and a red-sensitive silver halide emulsion layer on a reflective support. One of the photographic constituent layers contains at least one silver salt of a dye, and the red-sensitive silver halide emulsion layer contains at least one water-insoluble and organic solvent-soluble homo- or copolymer. A silver halide color photographic light-sensitive material characterized by: 3. A blue-sensitive silver halide emulsion on a reflective support.
Layers, green-sensitive silver halide emulsion layers, and red-sensitive halogenated layers
Silver halide color having photographic constituent layers including silver emulsion layer
In a photographic light-sensitive material, a dye is used in any of the photographic constituent layers.
Containing at least one of the silver salts of
A compound represented by the following general formula [I] in the silver halide layer
A halogen containing at least one of
Silver halide color photographic light-sensitive material. [Chemical 1][In the formula, R ₁, R₂And R₃Is an aliphatic group or
Represents an aromatic group, and l, m and n each represent 0 or 1.
You ] 4. A silver halide color photographic light-sensitive material having a photographic constituent layer comprising a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, and a red-sensitive silver halide emulsion layer on a reflective support. Halogenation characterized in that any photographic constituent layer contains at least one silver salt of a dye, and any silver halide emulsion layer contains at least one heterocyclic fog inhibitor. Silver color photographic light-sensitive material. 5. A silver halide color photographic light-sensitive material having a photographic constituent layer comprising a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, and a red-sensitive silver halide emulsion layer on a reflective support. A silver halide color photographic light-sensitive material characterized in that any photographic constituent layer contains at least one silver salt of a dye, and any photographic constituent layer contains at least one fluorescent whitening agent. material. 6. A silver halide color photographic light-sensitive material having a photographic constituent layer including a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, and a red-sensitive silver halide emulsion layer on a reflective support. One of the photographic constitutional layers contains at least one silver salt of a dye, and one of the photographic constitutional layers contains gelatin crosslinked with at least one vinylsulfone hardener. Silver halide color photographic light-sensitive material.