JPH06186702A - Silver halide color reversal photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain the silver halide color reversal photographic sensitive material high in sharpness and sensitivity and maximum density by incorporating a silver salt of a dye in one of photographic constituent layers and a specified cyan coupler in one of those. CONSTITUTION:This color reversal photographic sensitive material has the photographic constituent layers including red-, green-, and blue-sensitive silver halide emulsion layers on a substrate, an at least one of the constituent layers contains at least one kind of the silver salt of the dye and at least one of the constituent layers contains at least one of the cyan couplers represented by formula in which each of R1 and R2 is alkyl, aryl, aralkyl, or the like, and each optionally substituted; and X is H or a group to be released by reaction with the oxidation product of a developing agent. The silver salt of the dye is a silver salt or a silver complex formed by reaction of the dye with the silver ions and the dye is an organic compound having absorption in the visible spectrum.

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 reversal photographic light-sensitive material, and more specifically, it has high sharpness,
The present invention relates to a silver halide color reversal photographic material having high sensitivity and high maximum density.

[0002]

2. Description of the Related Art It has been well known that a silver halide color photographic light-sensitive material is provided with a coloring layer such as an antihalation layer or a filter layer in order to improve image sharpness. Although such colored layers often contain water-soluble dyes, these known dyes are often not completely photochemically inactive and often have a detrimental effect on the photosensitive layer of the photographic material: It resulted in a decrease in sensitivity and maximum density.

Further, in the industry, silver halide color reversal photographic light-sensitive materials having higher and higher image quality have been demanded in recent years, and in particular, silver halide color reversal photographic light-sensitive materials have low image quality, particularly low sharpness. It's a problem.

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 of the present inventors, the sensitivity of the emulsion layer was remarkably lowered and the maximum density was largely lowered. 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 therefore an object of the present invention to provide a silver halide color reversal photographic material having high sharpness, high sensitivity and high maximum density.

[0006]

The above objects of the present invention have been achieved by the following silver halide color reversal photographic light-sensitive material.

A silver halide color reversal 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 support. At least one of the silver salts of the dye is contained in at least one of the constituent layers, and at least one of the photographic constituent layers is represented by the general formula [C-I].
A silver halide color reversal photographic light-sensitive material comprising at least one cyan coupler represented by "Chemical Formula 1".

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

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.

The above dyes are represented by the following general formula [I]
Examples thereof include dyes represented by [V].

[0013]

[Chemical 2]

[Wherein R ¹ and R ² represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group or a heterocyclic group,
X ₁ and X ₂ represent an oxygen atom and a sulfur atom. L _{1 to} L ₅ represent a methine group, and n ₁ and n ₂ represent integers of 0 to 2. See also E ₁
Represents a group having an acidic nucleus. ]

[0015]

[Chemical 3]

[Wherein R ³ and R ⁴ have the same meanings as R ¹ and R ² in the general formula [I], and X ₃ and X ₄ have the same meanings as X ₁ and X ₂ in the general formula [I]. . L _{6 to} L ₉ represent a methine group,
n _3, n _4, n ₅ represents an integer of 0 to 2. R ⁵ represents an alkyl group or an alkenyl group, and Q ₁ represents a non-metal atom group necessary for forming a 5- or 6-membered heterocycle. ]

[0017]

[Chemical 4]

[Wherein R ⁶ and R ⁷ have the same meanings as R ¹ and R ² in the general formula [I], and X ₅ and X ₆ have the same meanings as X ₁ and X ₂ in the general formula [I]. . R ⁸ to R ¹⁰ is a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a halogen atom, a cyano group, a sulfo group, -COR ^11, -CON
(R ¹¹ ) (R ¹² ), —N (R ¹¹ ) (R ¹² ), —OR ¹¹ ,
-SOR ¹¹ , -SO ₂ R ¹¹ , -SO ₂ N (R ¹¹ )
^{(R 12), - N (} R 11) COR 12, -N (R 11) SO 2
^{R 12, -N (R 11)} CON (R 12) (R 13), - S
R ¹¹ and —COOR ¹¹ are represented, and R ^{11 to} R ¹³ represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, or a heterocyclic group. ]

[0019]

[Chemical 5]

[Wherein R ¹⁴ and R ¹⁵ have the same meanings as R ¹ and R ² in the general formula [I], and X ₇ and X ₈ have the same meanings as X ₁ and X ₂ in the general formula [I]. . L ₁₀ ~L ₁₂ represents a methine group, n ₆ represents an integer of 0 to 2. R ^{16 to} R ¹⁸ are represented by the general formula [I
It is synonymous with R ⁸ to R ¹⁰ in the II]. ]

[0021]

[Chemical 6]

[Wherein R ¹⁹ and R ²⁰ have the same meanings as R ¹ and R ² in the general formula [I], and X ₉ and X ₁₀ have the same meanings as X ₁ and X ₂ in the general formula [I]. . W ₁ represents an aryl group or a heterocyclic group. Examples of the alkyl group represented by R ¹ and R ² in the above general formula include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, and a tert-group.
Examples thereof include a butyl group, a cyclopentyl group and a cyclohexyl group. These alkyl groups may be further substituted with a hydroxyl group, a cyano group, a sulfo group, a carboxyl group, a halogen atom, an alkoxy group, an aryloxy group, an aryl group, an alkoxycarbonyl group, an aryloxycarbonyl group or the like.

Examples of the aryl group represented by R ¹ , R ² and W ₁ include a phenyl group and a naphthyl group. These groups can be substituted with an alkyl group represented by R ¹ or R ² , and a group similar to the substituent represented as the substituent of the alkyl group.

Examples of the heterocyclic group represented by R ¹ , R ² and W ₁ include pyridyl group, thiazolyl group, oxazolyl group, imidazolyl group, furyl group, pyrrolyl group, pyrazinyl group, pyrimidinyl group, pyridazinyl group, Examples thereof include a purinyl group, a selenazolyl group, a sulforanyl group, a piperidinyl group, a pyrazolyl group and a tetrazolyl group. These groups can be substituted with an alkyl group represented by R ¹ or R ² , and a group similar to the substituent represented as the substituent of the alkyl group.

Examples of the alkenyl group represented by R ¹ and R ² include a vinyl group and an allyl group. These groups can be substituted with an alkyl group represented by R ¹ and R ² , and a group similar to the substituent represented as the substituent of the alkyl group.

Examples of the group having an acidic nucleus represented by E ₁ in the general formula [I] include skeletons described in JP-A 61-281235, page 11, line 20 to page 14, line 15. And a group represented by the following formulas 1 to 4.

[0027]

[Chemical 7]

[In the formula, R ²¹ and R ²² have the same meanings as R ¹ and R ² in the above general formula [I]. Further, X ₁₁ and X ₁₂ have the same meanings as X ₁ and X ₂ in the general formula [I]. ]

[0029]

[Chemical 8]

[Wherein R ²³ has the same meaning as R ¹ and R ² in the above general formula [I], and R ²⁴ and R ²⁵ represent the above general formula [II]
It is synonymous with R ⁸ to R ¹⁰ in I]. ]

[0031]

[Chemical 9]

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

[0033]

[Chemical 10]

[Wherein 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 ,
^{-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-61-282.
Heterocycles described on pages 23 to 26 of 832 and

[0037]

[Chemical 11]

[In the formula, R ³³ has the same meaning as R ¹ and R ² in the general formula [I], and R ³⁴ has the same meaning as R ^{8 to} R ¹⁰ in the general formula [III]. l ₁ represents an integer of 0 to 3. ] The heterocycle represented by these can be mentioned.

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

[0040]

[Chemical 12]

[0041]

[Chemical 13]

[0042]

[Chemical 14]

[0043]

[Chemical 15]

[0044]

[Chemical 16]

[0045]

[Chemical 17]

[0046]

[Chemical 18]

[0047]

[Chemical 19]

Further, examples of the dye used in the present invention include dyes represented by the following general formula [I '] to general formula [V'].

[0049]

[Chemical 20]

[In the general formulas [I '] to [V'], R ³⁵ represents an alkyl group or an alkenyl group, and R ³⁶ and R ³⁷ represent an alkyl group, an alkenyl group, an aryl group, a heterocyclic group or a halogen. Atom, cyano group, sulfo group, -COR ³⁸ ,
^{-CON (R 38) (R 39} ), - N (R 38) (R 39), -
OR ³⁸ , -SOR ³⁸ , -SO ₂ R ³⁸ , -SO ₂ N (R ³⁸ )
^{(R 39), - N (} R 38) COR 39, -N (R 38) SO 2
^{R 39, -N (R 38)} CON (R 39) (R 40), - S
R ^38, represents a -COOR ^38, R ³⁸ ~R ⁴⁰ represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, 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

[0052]

[Chemical 21]

(In the general formulas [A ₁ ] to [A ₄ ] and the general formulas [A ′ ₁ ] to [A ′ ₄ ], R ⁴¹ , R ⁴² ,
R ⁴⁴ and R ⁴⁶ represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group or a heterocyclic group, R ⁴³ represents an alkyl group,
Alkenyl group, aryl group, heterocyclic group, cyano group, -C
OR ⁴⁷ , -CON (R ⁴⁷ ) (R ⁴⁸ ), -N (R ⁴⁷ ) (R
⁴⁸ ), -OR ⁴⁷ , -SOR ⁴⁷ , -SO ₂ R ⁴⁷ , -SO ₂ N
^{(R 47) (R 48)} , - N (R 47) COR 48, -N
^{_{(R 47) SO 2 R 48}} , -N (R 47) CON (R 48) (R
^49), - SR ^47, represents a -COOR ^47, R ⁴⁷ ~R ⁴⁹ represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group. R ⁴⁵ has the same meaning as R ³⁶ and R ³⁷ . X ₁₃ represents an oxygen atom, a sulfur atom, a selenium atom, or = NR ⁵⁰ . R ⁵⁰ has the same meaning as R ⁴¹ . X ₁₄ , X ₁₅ and X ₁₆ represent an oxygen atom and a sulfur atom. ) L represents a methine group, and E
Represents a group having an acidic nucleus. Q ₂ represents a group of non-metal atoms necessary for forming a heterocycle. W ₂ represents an aryl group or a heterocyclic group. n ₇ and n ₈ represent an integer of 0 to 3, n ₉
And n ₁₀ represents an integer of 0 to 2, l ₂ and l ₃ is an integer of 0 to 3. The compounds represented by formulas [I '] to [V'] will be described.

Examples of the alkyl group represented by R ^{35 to} R ⁵⁰ include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, tert-butyl group, cyclopentyl group, cyclohexyl group and the like. To be These alkyl groups may be further substituted with a hydroxyl group, a cyano group, a sulfo group, a carboxyl group, a halogen atom, an alkoxy group, an aryloxy group, an aryl group, an alkoxycarbonyl group, an aryloxycarbonyl group or the like.

Examples of the aryl group represented by R ^{36 to} R ⁵⁰ and W ₂ include a phenyl group and a naphthyl group. These groups are alkyl groups represented by R ^{35 to} R ⁵⁰ ,
And a substituent similar to the substituent represented as the substituent of the alkyl group.

Examples of the heterocyclic group represented by R ^{36 to} R ⁵⁰ and W ₂ include pyridyl group, thiazolyl group, oxazolyl group, imidazolyl group, furyl group, pyrrolyl group, pyrazinyl group, pyrimidinyl group, pyridazinyl group, Examples thereof include a purinyl group, a selenazolyl group, a sulforanyl group, a piperidinyl group, a pyrazolyl group and a tetrazolyl group. These groups can be substituted with an alkyl group represented by R ^{35 to} R ⁵⁰ and a group similar to the substituent represented as the substituent of the alkyl group.

Examples of the alkenyl group represented by R ^{35 to} R ⁵⁰ include a vinyl group and an allyl group. These groups can be substituted with an alkyl group represented by R ^{35 to} R ⁵⁰ , and a group similar to the substituent represented as the substituent of the alkyl group.

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

[0059]

[Chemical formula 22]

[0060] wherein, R ⁵⁴ has the same meaning as R ^41, R ^52,
R ⁵³ represents a hydrogen atom and the group shown above as R ³⁶ . ]

[0061]

[Chemical formula 23]

[In the formula, R ⁵⁴ has the same meaning as R ⁴¹ , and R ⁵⁵ represents a hydrogen atom and the group shown above as R ³⁶ . ]

[0063]

[Chemical formula 24]

[In the formula, R ⁵⁶ has the same meaning as R ⁴² , and R ⁵⁷ has the same meaning as R ⁴³ . Examples of the heterocycle formed by Q ₂ in the general formula [II ′] include, for example, JP-A-61-282832.
The heterocycles described on pages 23 to 26 of the publication and

[0065]

[Chemical 25]

[In the formula, R ⁵⁸ has the same meaning as R ⁴¹ , and R ⁵⁹ has the same meaning as R ³⁶ . l ₄ is an integer of 0 to 3. ] The heterocycle represented by these can be mentioned.

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

[0068]

[Chemical formula 26]

[0069]

[Chemical 27]

[0070]

[Chemical 28]

[0071]

[Chemical 29]

[0072]

[Chemical 30]

[0073]

[Chemical 31]

Furthermore, examples of the dye used in the present invention include dyes represented by the following general formula [VI] (hereinafter referred to as methine compounds).

[0075]

[Chemical 32]

[In the formula, Dye represents an atom group having a methine dye structure, and J represents a divalent linking group having a skeleton of an atom or an atomic group selected from a carbon atom, a nitrogen atom, an oxygen atom and a sulfur atom. , Sal represents a group forming a sparingly soluble salt with silver ion, l ₅ is 1 or 2, and m ₁ is 0 or 1.
, N ₁₁ represents 1, 2, 3 or 4. ] General formula [VI]
In, the group represented by Dye represents an atomic group having a methine dye structure, and includes, for example, cyanine, merocyanine,
It is a group having a dye structure in which a methine chain such as merostyryl, styryl, oxonol, and triarylmethane has a conjugated double bond. Specific examples of these dyes include, for example, cyanine dyes described in JP-A-63-202665,
JP-A-52-29727, JP-A-63-34539, U.S. Pat.No. 2,94
4,896, merocyanine dyes described in No. 3,148,187 etc., JP-A-59-211041, JP-A No. 62-185758, the merostyryl dyes described in JP-A No. 50-145125, JP-A-55-3310.
No. 3, No. 55-120660, No. 63-264745, U.S. Patent No.
Oxonol dyes described in 4,187,275 and the like, JP-A-59-5
The triarylmethane dyes described in No. 5437 and the like, and further, “Theory of Photographic” edited by TH James.
Process "D Mills, 1977, Macmillan, DMSturmer" T
he Chemistry of Heterocyclic Compounds ”ed.A. Weis
sberger and ECTaylor, selected from those described in publications such as 1977.

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, arylene groups, alkenylene groups, sulfonyl groups, sulfinyl groups, ether groups, thioether groups, carbonyl groups, -N.
( ^R60 )-group ( ^R60 is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group), -N =
It is a divalent linking group having 20 or less carbon atoms, which is formed by combining one or more groups and one or more divalent heterocyclic groups, and may have a substituent. Typical examples of the substituent include a halogen atom, an alkyl group, an aralkyl group, an alkoxy group, an alkoxycarbonyl group, an alkylthio group,
Any group such as a hydroxyl group, a carboxyl group, a sulfo group, a sulfonyl group, a carbamoyl group, an acyl group, an acylamide group, a sulfonamide group, a cyano group, an amino group and a ureido group is selected.

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. As a preferable group, a general formula (V
The groups represented by III) and (IX) or the groups represented by the general formula (II) to the general formula (VI) described in JP-A-2-225476 are mentioned.

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

[0080]

[Chemical 33]

[0081]

[Chemical 34]

[0082]

[Chemical 35]

[0083]

[Chemical 36]

[0084]

[Chemical 37]

[0085]

[Chemical 38]

[0086]

[Chemical Formula 39]

[0087]

[Chemical 40]

[0088]

[Chemical 41]

[0089]

[Chemical 42]

[0090]

[Chemical 43]

[0091]

[Chemical 44]

The methine compound according to the present invention can be dyed from an intermediate raw material in which a sparingly soluble silver salt-forming group represented by Sal is substituted in advance, or a method in which a methine dye structure moiety represented by Dye and a Sal moiety are bonded. However, it can be selected and synthesized arbitrarily. Various known binding reactions can be used to introduce the Sal group, for example, an addition reaction to an unsaturated group such as a vinyl group or a carbonyl group, an active hydrogen substituent such as an amino group or a hydroxyl group, and an 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 Rea
ctions ”Vol, 1,3,12 John Wiley & Sons (New York L
ondon), “The Chemistry of Functional Groups” John
Wiley & Sons (New York London), LFFieser and M.Fie
ser, “Advanced Organic Chemistry” Maruzen (1962)
Many books 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 a silver halide photographic light-sensitive material.

In the present invention, the amount of the 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 yellow coupler represented by the general formula [C-I] of the present invention will be described.

In the general formula [C-I], R ₁ and R ₂
Represents an alkyl group, an aryl group, an aralkyl group, or an amino group, and examples of the alkyl group include a methyl group, an ethyl group, a propyl group, and an n-octyl group. The alkyl group may further have a substituent, and examples of the substituent include a halogen atom (chlorine, fluorine etc.), an alkoxy group (methoxy group etc.), an aryloxy group (phenoxy group, naphthyloxy group etc.), Examples thereof include an alkyl group (ethyl group, i-propyl group, n-butyl group, etc.).

Examples of the aryl group include a phenyl group and a naphthyl group, which may further have a substituent.

Examples of the aralkyl group include a benzyl group, which may have a substituent. Examples of these substituents include the groups described above as the substituents of the alkyl group.

The amino group may be unsubstituted or may have a substituent, and examples of the substituent include an alkyl group (such as a methyl group) and an aryl group (such as a phenyl group).

X represents a hydrogen atom or a group capable of splitting off in the coupling reaction with the oxidation product of the color developing agent.

For example, a halogen atom (eg, fluorine,
(Chlorine, bromine) thiocyan group, optionally substituted alkyloxy group, aryloxy group or heterocyclic oxy group,
Examples thereof include an alkylthio group, an arylthio group, a heterocyclic thio group, an acyloxy group, a sulfonamide group, an alkylsulfonyl group, an arylsulfonyl group, an acyl group, a heterocyclic group, a phosphonyloxy group and an arylazo group. As a more specific example, U.S. Pat.
No. 4, JP-A-47-37425, JP-B-48-36894, JP-A 50-1
No. 0135, No. 50-117422, No. 50-120334, No. 50-130441
No. 51, No. 51-108841, No. 52-18315, No. 53-105226,
54-14736, 54-48237, 55-32071, 55-65957
No. 56-1938, No. 56-12643, and No. 56-27147.

Of these, preferable X includes a hydrogen atom, a fluorine atom, a chlorine atom, an alkyloxy group, an aryloxy group, a heterocyclic oxy group, an alkylthio group, an arylthio group and a heterocyclic thio group. Particularly preferable X includes an alkyloxy group and an aryloxy group.

The cyan coupler represented by the general formula [C-I] is more preferably the cyan coupler represented by the following general formula [C-II] or [C-III].

[0104]

[Chemical formula 45]

In the general formula [C-II], R ₃ has the same meaning as R _{1 in the} general formula [C-I], but it is preferably an alkyl group which may have a substituent.

In the general formula [C-II], R ₇ represents a substituent, preferably an aryl group which may have a substituent.

In the general formulas [C-II] and [C-III], R ₄ , R ₅ , R ₈ and R ₉ represent a hydrogen atom or an alkyl group which may have a substituent.

In the general formulas [C-II] and [C-III], R ₆ and R ₁₀ represent a substituent, and examples of the substituent include a halogen atom, a cyano group, an amino group, an alkyl group, a sulfonyl group and an alkoxy group. Examples thereof include groups, but alkyl groups are preferable. Further, l and m represent an integer of 0 to 5,
Alternatively, when m is 2 or more, R _{6 and} R ₁₀ may be the same or different.

In the general formulas [C-II] and [C-III], X ₁ and X ₂ have the same meanings as X in the general formula [C-I].

Specific examples of the cyan coupler represented by the general formula [C-I] are shown below, but the invention is not limited thereto.

[0111]

[Chemical formula 46]

[0112]

[Chemical 47]

[0113]

[Chemical 48]

[0114]

[Chemical 49]

[0115]

[Chemical 50]

The cyan couplers represented by the general formula [C-I] of the present invention can be easily synthesized by the method described in Japanese Patent Application Nos. 57-221487 and 58-38438.

The cyan coupler represented by the general formula [C-I] according to the present invention may be used alone or in combination of two or more, and may be used in combination with another type of cyan coupler.

In the present invention, the cyan coupler is
Usually, it can be used 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.

The silver halide emulsion used in the present invention is
It may be any of silver chloride, silver iodobromide, silver chlorobromide, silver chloroiodobromide and silver chloroiodide.

The state of distribution of silver iodide and silver bromide in the silver halide grains is not particularly limited, and they may be localized at the central part, surface or in the middle of the grains, or they are 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 containing either one.

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. , At least one selected from the group consisting of rhodium salts (or complex salts) and iron salts (or complex salts) may be added to the metal ions to allow these metal elements to be contained inside the particles and / or on the surface of the particles. 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 remain contained. 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, JP-B-44-15748, US Pat. No. 3,904,415, US Pat. No. 3,930,867, US Pat. No. 3,984,249, US Pat. No. 4,054,457, and US Pat.
067,740, RD12008, 13452, 13564
Issue, "The Theory of the Photographic" by TH James
Process "(4th Ed. Macmillan. 1977) 67-76 etc. is preferable.

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

The red-sensitive, green-sensitive and blue-sensitive silver halide emulsion layers according to the present invention may each have a single layer structure, or may have a two-layer structure of a high sensitivity layer and a low sensitivity layer. Further, it may have a three-layer structure of a high sensitivity layer, a medium sensitivity layer, and a low sensitivity layer. It is preferably a two-layer structure or more.

The total amount of silver in the photosensitive layer is 0.2 to 10 g / m ²
Is preferable, and particularly preferably 1 to 8 g / m ² .

The dry total film thickness is 8 to 30 at 23 ° C. and 55% RH.
μm is preferable, and particularly preferably 10 to 25 μm.

Antifoggants, stabilizers and the like can be added to the silver halide emulsion. It is advantageous to use gelatin as the binder of the emulsion.

The emulsion layer and other hydrophilic colloid layers may be hardened and may contain a plasticizer and a dispersion (latex) of a water-insoluble or sparingly soluble synthetic polymer.

A coupler is used in the emulsion layer of the color photographic light-sensitive material. Further development reaction, bleaching accelerator, developer by coupling with colored coupler, competing coupler and oxidant of developing agent, which has the effect of correction,
It is possible to use compounds that release photographically useful fragments such as silver halide solvents, toning agents, hardeners, fogging agents, antifoggants, chemical sensitizers, spectral sensitizers and desensitizers. it can.

Formalin scavengers, fluorescent whitening agents, matting agents, slip agents, image stabilizers, surfactants, color fog inhibitors, development accelerators, development retarders and bleaching accelerators can be added to the light-sensitive material.

As the support, paper laminated with polyethylene or the like, baryta paper, polyethylene terephthalate film containing white content, cellulose triacetate film or the like can be used.

To obtain a dye image using the light-sensitive material of the present invention, a generally known color reversal photographic process can be carried out after exposure.

[0140]

EXAMPLES Next, specific examples of the present invention will be described, but embodiments of the present invention are not limited to these.

In all the following examples, the addition amount in the silver halide photographic light-sensitive material is the number of grams per 1 m ² unless otherwise specified. Also, silver halide and colloidal silver are shown in terms of silver.

Example 1 One side (surface) of triacetyl cellulose film support
Was subjected to an undercoating treatment, and then the support was sandwiched therebetween, and a layer having the following composition was sequentially formed from the support side on the surface (rear surface) opposite to the surface subjected to the undercoating treatment.

Backside first layer Alumina sol AS-100 (aluminum oxide) 0.8 (manufactured by Nissan Chemical Industries, Ltd.) Backside second layer diacetyl cellulose 100 Stearic acid (average particle size 0.2 μm) 10 Silica fine particles (average particle size 0.2 μm) 50 Onto the surface of an undercoated cellulose triacetate film support, each layer having the following composition was sequentially coated from the support side to prepare a comparative sample 101 of a multilayer color light-sensitive material.

First Layer (Antihalation Layer) Black Colloidal Silver 0.24 Ultraviolet Absorber U-1 0.14 Ultraviolet Absorber U-2 0.072 Ultraviolet Absorber U-3 0.072 Ultraviolet Absorber U-4 0.072 High Boiling Solvent O-1 0.31 High boiling solvent O-2 0.098 Poly-N-vinylpyrrolidone 0.15 Gelatin 2.02 Second layer (intermediate layer) High boiling solvent O-3 0.011 Gelatin 1.17 Third layer (low sensitivity red sensitive layer) Red sensitizing dye S-1, Silver iodobromide emulsion spectrally sensitized with S-2 (AgI 3.0 mol%, average grain size 0.3 μm) 0.60 Coupler C-12 0.37 High boiling point solvent O-2 0.093 Poly-N-vinylpyrrolidone 0.074 Gelatin 1.35 4 layers (high-sensitivity red-sensitive layer) Silver iodobromide emulsion spectrally sensitized with red sensitizing dyes S-1 and S-2 (AgI 2.5 mol%, average grain size 0.60 μm) 0.60 Coupler C-12 0.85 High Boiling point solvent O-2 0.21 Poly-N-vinylpyrrolidone 0.093 Gelatin 1.56 Fifth layer (intermediate layer) Color mixing inhibitor AS-1 0.20 High boiling point solvent O-3 0.25 Matting agent MA-1 0.0091 Gelatin 1.35 Sixth layer (low sensitivity green sensitive layer) Spectral sensitization with green sensitizing dye S-3 Sensitized silver iodobromide emulsion (AgI 3.0 mol%, average particle size 0.3 μm) 0.70 Coupler M-1 0.31 Coupler M-2 0.076 High boiling point solvent O-3 0.059 Poly-N-vinylpyrrolidone 0.074 Gelatin 1.29 7th layer (High-sensitivity green-sensitive layer) Silver iodobromide emulsion spectrally sensitized with green sensitizing dye S-3 (AgI 3.0 mol%, average particle size 0.8 μm) 0.70 Coupler M-1 0.80 Coupler M-2 0.19 Color mixture prevention Agent AS-1 0.055 High boiling point solvent O-3 0.16 Poly-N-vinylpyrrolidone 0.12 Gelatin 1.91 8th layer (intermediate layer) Gelatin 0.90 9th layer (yellow filter layer) Color mixture inhibitor AS-1 0.068 High boiling point solvent O- 3 0.085 Matting agent MA-1 0.012 Gelatin 0.68 10th layer (low-sensitivity blue-sensitive layer) Silver iodobromide emulsion spectrally sensitized with blue sensitizing dye S-4 (AgI 3.0 mol%, average particle size 0.3 μm) 0.70 Coupler Y-1 0.86 Image stabilizer G -1 0.012 High boiling point solvent O-3 0.22 Poly-N-vinylpyrrolidone 0.078 Compound F-1 0.020 Compound F-2 0.040 Gelatin 1.09 11th layer (high sensitivity blue sensitive layer) Spectral sensitization with blue sensitizing dye S-4 Silver iodobromide emulsion (AgI 3.0 mol%, average particle size 0.85 μm) 0.70 coupler Y-1 1.24 image stabilizer G-1 0.017 high boiling solvent O-3 0.31 poly-N-vinylpyrrolidone 0.10 compound F-1 0.039 Compound F-2 0.077 Gelatin 1.73 12th layer (protective layer-1) Non-photosensitive fine grain silver iodobromide (silver iodide 1.0 mol%, 0.08 μm) 0.075 UV absorber U-1 0.048 UV absorber U-2 0.024 UV absorber U-3 0.024 UV absorber U-4 0.024 High boiling point solvent O-1 0.13 High boiling point solvent O-2 0.13 Compound F-1 0.075 Compound F-2 0.15 Gelatin 1.2 13th layer (protective layer-2) Sliding agent WAX-1 0.041 Matting agent MA-2 0.0090 Matting agent MA-3 0.051 Surfactant SU -1 0.0036 Gelatin 0.55 (Note: The weight average molecular weight of poly-N-vinylpyrrolidone used in each layer is 350,000. ) In this sample 101, in addition to the above composition, gelatin hardeners H-1 and H-2 were used.
H-3, compound DI-1, stabilizer ST-1, and antifoggant AF-1 were added as required.

The silver halide emulsions used in the respective light-sensitive layers were all monodisperse emulsions having a distribution of 20% or less. Each emulsion was desalted and washed with water, and then subjected to optimum chemical ripening in the presence of sodium thiosulfate, chloroauric acid and ammonium thiocyanate to spectrally sensitize the silver halide emulsion used for each photosensitive layer. Each sensitizing dye, 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene, 1-phenyl-5-mercaptotetrazole was added.

The distribution width (%) = (particle size standard deviation / average particle size) × 100.

The structural formulas of the compositions used in the above samples are shown below.

[0148]

[Chemical 51]

[0149]

[Chemical 52]

[0150]

[Chemical 53]

[0151]

[Chemical 54]

[0152]

[Chemical 55]

[0153]

[Chemical 56]

Further, as to Sample 101, Samples 102 to 12 were prepared in the same manner as in Sample 101 except that the comparative dyes shown in Table 1 or the silver salts of the dyes of the present invention were added to the layers shown in Table 1.
Created 0. 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 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 cc. Of water, and 10 cc. 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 cc. Of a 3% aqueous gelatin solution, 0.01 mol of the silver salt of the dye obtained above and the surfactant Triton X-200 (Ro
hm & Haas) 6.7% solution (3 cc.), glass beads (diameter 1 mm) 200 g, and a medium stirring mill (Aquamizer QA-5, manufactured by Hosokawa Micron Co., Ltd.) for 2 hours to obtain a dye. A silver salt dispersion was obtained.

White exposure was applied to the above samples 101 to 120 through a step wedge for sensitometric measurement,
The following development processing was performed.

Processing step Processing time Processing temperature First development 6 minutes 38 ° C Water washing 2 minutes 38 ° C Inversion 2 minutes 38 ° C Color development 6 minutes 38 ° C adjustment 2 minutes 38 ° C Bleach 6 minutes 38 ° C fixing 4 minutes 38 ℃ Washing with water 4 minutes 38 ℃ Stability 1 minute Normal temperature Drying The composition of the processing solution used in the above processing step is as follows.

First developer sodium tetrapolyphosphate 2 g sodium sulfite 20 g hydroquinone monosulfonate 30 g sodium carbonate (monohydrate) 30 g 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone 2 g potassium bromide 2.5 g thiocyan Potassium acid salt 1.2 g Potassium iodide (0.1% solution) 2 cc Water was added to make 1000 cc (pH 9.60).

Inversion solution Nitrilotrimethylenephosphonic acid hexasodium salt 3 g Stannous chloride (dihydrate) 1 g p-Aminofunole 0.1 g Sodium hydroxide 8 g Glacial acetic acid 15 cc Water was added to make 1000 cc (pH 5.75).

Color developer Sodium tetrapolyphosphate 3 g Sodium sulfite 7 g Sodium triphosphate (dihydrate) 36 g Potassium bromide 1 g Potassium iodide (0.1% solution) 90 cc Sodium hydroxide 3 g Citrazinate 1.5 g N-ethyl-N- (β-Methanesulfonamidoethyl) -3-methyl-4-aminoaniline / sulfate 11 g 2,2-ethylenedithiodiethanol 1 g Water was added to make 1000 cc (pH 11.70).

Preparation Solution Sodium sulfite 12 g Sodium ethylenediaminetetraacetate (dihydrate) 8 g Thioglycerin 0.4 cc Glacial acetic acid 3 cc Water was added to make 1000 cc (pH 6.15).

Bleaching solution Sodium ethylenediaminetetraacetate (dihydrate) 2 g Ethylenediaminetetraacetate iron (III) ammonium (dihydrate) 120 g Ammonium bromide 100 g Water was added to make 1000 cc (pH 5.56).

Fixing solution Ammonium thiosulfate 80 g Sodium sulfite 5 g Sodium bisulfite 5 g Water was added to make 1000 cc (pH 6.60).

Stabilizer Formalin (37% by weight) 5cc Conidax (manufactured by Konica Corporation) 5cc Water was added to make 1000cc (pH 7.00).

The sensitivity of each photosensitive emulsion was measured using sensitometry for the sample after the above processing. Sample 10 sensitivity
The value is shown as a relative value with 1 being 100.

Image sharpness was also measured.

The sharpness was shown by determining the MTF of the dye image and the relative value of the MTF at 30 lines / mm (Sample 101 being 100).

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. Table 1 together with the results
Shown in.

[0170]

[Table 1]

[0171]

[Chemical 57]

As is clear from Table 1, sample 101 containing no anti-irradiation dye has high sensitivity but insufficient sharpness. On the other hand, the conventionally used water-soluble dyes AI-1 to AI-3 are added to the eighth layer, the fifth layer, and the first layer, respectively.
In Samples 102 to 104 added to the layers, the sharpness is improved, but the sensitivity of each of the sensitive layers is significantly lowered. On the other hand, in the samples 105 to 120 of the present invention in which the silver salt of the dye of the present invention was added to the first layer, the fifth layer and the eighth layer, the sharpness was significantly reduced with a relatively small decrease in sensitivity. Is recognized.

Example 2 The cyan couplers shown in Table 2 were used instead of C-12 in the third and fourth layers of Sample 101, and the dyes shown in Table 2 were added to the fifth layer and / or the first layer. After subjecting Samples 201 to 220 to wedge exposure with white light, development processing was performed by the same processing steps as in Example 1 above.

The sensitivity, maximum density and sharpness of the red-sensitive emulsion layer were determined for each of the samples after the above processing. The sensitivity was measured in the same manner as in Example 1, and an optical densitometer (PDA-65 manufactured by Konica) was used to measure the maximum density.

The sensitivity is shown as a relative value when the sample 201 is 100, and the MTF is shown as a relative value when the sample 201 is 100. Further, the maximum concentration is shown as a relative value with the sample 201 being 100.

The results are shown in Table 2.

[0177]

[Table 2]

[0178]

[Chemical 58]

As is clear from Table 2, Samples 201 and 203 which do not contain the anti-irradiation dye have high sensitivity but insufficient sharpness. On the other hand, Sample 202 and Sample 2 in which a water-soluble dye that has been conventionally used is added to the fifth layer
Although the sharpness is improved in 04, the sensitivity is greatly reduced, and particularly in Sample 204, it is remarkable. Samples 205 and 20
At 6, the maximum density (Dmax) decreases (that is, the fog increases).

On the other hand, all of Samples 207 to 220 of the present invention using the silver salt of the dye of the present invention and containing the cyan coupler of the present invention in the third and fourth layers have a relatively small sensitivity decrease. Significant improvement in sharpness is recognized in and, and there is little fog.

[0181]

The silver halide color reversal photographic light-sensitive material of the present invention has excellent sharpness, high sensitivity and low fog.

Claims (1)

[Claims] 1. A blue-sensitive silver halide emulsion layer on a support,
In a silver halide color reversal photographic light-sensitive material having a photographic constituent layer containing a green-sensitive silver halide emulsion layer and a red-sensitive silver halide emulsion layer, at least one silver salt of a dye is contained in at least one of the photographic constituent layers. And in at least one of the photographic constituent layers, the following general formula [C-I]
A silver halide color reversal photographic light-sensitive material containing at least one cyan coupler represented by: [Chemical 1] [Wherein R ₁ and R ₂ are each an alkyl group, an aryl group,
It represents an aralkyl group or an amino group, and these also include those having a substituent. X represents a hydrogen atom or a group capable of splitting off upon reaction with an oxidized product of a developing agent. ]