JPH07253630A - Direct positive silver halide color photographic sensitive material and formation of direct positive color image - Google Patents

Abstract

PURPOSE:To provide a direct positive silver halide color photographic sensitive material capable of obtaining a color proof improved in white ground and dot reproducibility and to provide a direct positive color image forming method small in the amt. of waste liquid and preferable to environment protection. CONSTITUTION:This direct positive silver halide color photographic sensitive material has a photosensitive silver halide emulsion layer which is not preliminarily fogged and contains inner latent image type silver halide particles and a compd. expressed by formula on a supporting body. The swelling degree of photographic layers in the side of the supporting body where the photosensitive silver halide emulsion layer is formed is 80-200%. In the formula, Z01 and Z02 are nonmetal atoms necessary to form five or six-member nitrogen-contg. heterorings, L1 is a methyn carbon, R01 is -J2-COOH, J1 and J2 are alkylene groups, l1 and l2 are integers of 0 or 1, and nn is an odd integer of >=3.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a direct positive silver halide color photographic light-sensitive material utilizing internal latent image type silver halide grains, and in particular, residual (also referred to as residual color) of a sensitizing dye after development processing. The present invention relates to a direct positive silver halide color photographic light-sensitive material excellent in white background of formed images.

[0002]

2. Description of the Related Art In recent years, an emulsion containing an internal latent image type silver halide grain has been used to carry out a fog treatment (nucleation treatment) after image exposure.
Direct surface silver halide color photographic light-sensitive material (hereinafter also referred to as light-sensitive material) to directly obtain a positive image by performing surface development while performing fog processing after performing image development and then image development, or image exposure, The simplicity of the treatment process has been accepted and it has been used for color copying and color proofing. In this case, a good positive image having a high maximum image density and a low minimum image density can be obtained, that is, it is desired that the halftone dot reproducibility is excellent in the case of a color proof. It has a great influence, and further improvement is required.

A factor that deteriorates the white background is that the sensitizing dye contained in the light-sensitive material remains in the light-sensitive material after processing, resulting in what is called a residual color. It's becoming a big problem. As a method for improving the problem of residual color, for example, Japanese Patent Laid-Open No. 3-1456
37, the addition of a compound that reduces residual color is described, but the effect is not sufficient, and improvement is eagerly desired.

On the other hand, the demand for reduction of waste liquid for photographic processing has been increasing year by year in consideration of the environment. In fact, in order to reduce the amount of waste liquid, the replenishment amount of various processing liquids is reduced and running processing is performed with a concentrated processing liquid. The problem of residual color becomes remarkable when the replenishment amount of the developing solution is reduced.

The emulsion containing an internal latent image type silver halide grain is a halogenated compound having a photosensitive nucleus mainly inside the silver halide crystal grain and forming a latent image inside the grain upon exposure. An emulsion containing silver particles.

[0006]

SUMMARY OF THE INVENTION Accordingly, the first object of the present invention is to provide a direct positive silver halide color photographic light-sensitive material in which the white background is improved and a good positive image can be obtained.

Secondly, there is provided a direct positive silver halide color photographic light-sensitive material capable of obtaining a color proof having an improved white background, a hue close to that of an ink of a printed matter, and an improved dot reproducibility. To do.

Thirdly, it is an object of the present invention to provide a direct positive color image forming method in which a white background is improved, a good positive image is obtained, and the amount of waste liquid is small, which is preferable from the viewpoint of environmental protection.

[0009]

The above-mentioned object of the present invention comprises an internal latent image type silver halide grain which is not previously fogged on a support and a compound represented by the above general formula [D] (Chemical formula 1). Direct positive halogen having a photosensitive silver halide emulsion layer to be used, and the swelling degree of the photographic constituent layer on the side having the photosensitive silver halide emulsion layer on the support is in the range of 80 to 200%. A silver halide color photographic light-sensitive material, the light-sensitive material containing at least one selected from the compounds represented by the above formulas [I] to [IV] (Chemical Formula 2), and the light-sensitive silver halide emulsion layer , After the color development processing, the yellow image forming layer,
At least one selected from those forming a magenta image forming layer and a cyan image forming layer, and a yellow image forming layer,
Internal latent image type silver halide grains having a spectral sensitivity region common to the spectral sensitivity regions of the respective internal latent image type silver halide grains contained in the magenta image forming layer and the cyan image forming layer are used as the yellow image forming layer and magenta. An image, at least one of the cyan image forming layers and / or an image forming layer other than the above, and a light reflecting layer containing at least one white pigment on the side of the image forming layer on the support, The ratio of the amount of the white pigment contained in the light reflecting layer to the amount of the binder contained in the light reflecting layer is 20% or more by weight, and after direct exposure of this direct positive silver halide color photographic light-sensitive material, In a direct positive color image forming method including a step of processing with a color developing solution, the replenishing amount of the color developing solution is
The problem is solved by 700 ml / light-sensitive material being 1 m ² or less.

The present invention will be described in detail below.

The compound of the general formula [D] will be described below.

The alkylene group represented by J ₁ and J ₂ is a linear or branched alkylene group having 1 to 6 carbon atoms (eg methylene, ethylene, propylene, 1,3-butylene, 1,4-butylene). , Each group such as pentylene), and these groups may be substituted with groups such as a hydroxy group, a fluorine atom, a chloro atom and a cyano group.

The 5- or 6-membered nitrogen-containing heterocyclic group formed by Z ₀₁ and Z ₀₂ is known as a nucleus constituting a cyanine dye, and examples thereof include oxazole, oxazolidine, oxazoline, benzoxazole and benzo. Oxazoline, naphtho [1,2-d] Oxazole, naphtho [1,2-d]
Oxazoline, naphtho [2,1-d] oxazole, naphtho [2,
1-d] oxazoline, naphtho [2,3-d] oxazole, naphtho [2,3-d] oxazoline, 1,3-dioxolo [4,5-f] benzoxazole, 1,3-dioxolo [4,5 -f] benzoxazoline, 1,3-dioxolo [4,5-e] benzoxazole, 1,3
-Dioxolo [4,5-e] benzoxazoline, isoxazole, isoxazoline, benzisoxazole, benzisoxazoline, thiazole, thiazolidine, thiazoline, benzothiazole, benzothiazoline, naphtho [1,2-d] thiazole, naphtho [ 1,2-d] thiazoline, naphtho [2,1-d] thiazole, naphtho [2,1-d] thiazoline, naphtho [2,3-d] thiazole, naphtho [2,3-d] thiazoline, 1, 3-
Dioxolo [4,5-f] benzothiazole, 1,3-dioxolo
[4,5-f] benzothiazoline, 1,3-dioxolo [4,5-e] benzothiazole, 1,3-dioxolo [4,5-e] benzothiazoline, thieno [2,3-d] thiazole, Thieno [2,3-d] thiazoline, thieno [3,2-d] thiazole, thieno [3,2-d] thiazoline, thieno [2,3-e] benzothiazole, thieno [2,3-e] benzo Thiazoline, thieno [3,2-e] benzothiazole, thieno [3,2-e] benzothiazoline, pyrroline, pyrrolidine, 3,3-dimethylindole, 3,3-dimethylindolenin, tetrazole, imidazole, imidazolidine, Imidazoline, benzimidazole, benzimidazoline, naphtho [2,1-d] imidazole, naphtho [2,1-d] imidazoline, selenazole, selenazolidine, selenazoline, benzoselenazole, benzoselenazoline, naphtho
[1,2-d] selenazole, naphtho [1,2-d] selenazoline, naphtho [2,1-d] selenazole, naphtho [2,1-d] selenazoline, naphtho [2,3-d] selenazole, naphtho [2,3-d] selenazoline, tellurazole, tellrazoline, benzoterrazole, benzoterrazoline, pyridine, 2-quinoline, 4-
Examples include quinoline. These nitrogen-containing heterocycles may have a substituent at any position, specifically, alkyl groups (for example, methyl, ethyl, t-pentyl, trifluoromethyl, fluoromethyl, ω-trifluoroethyl, hydroxymethyl). , Each group such as cyanomethyl), a heterocyclic group (for example, each group such as pyridyl (2-, 4-), furyl (2-), thienyl (2-), sulforanyl, tetrahydrofuryl, piperidinyl), a halogen atom ( For example, each atom of fluorine, chlorine, bromine, iodine, etc.), an alkoxy group (eg, methoxy,
Each group such as ethoxy), aryloxy group (for example, phenoxy, p-tolyloxy, etc.), cyano group, carbamoyl group (for example, carbamoyl, N-methylcarbamoyl, N, N-tetramethylenecarbamoyl, etc.) ), Sulfamoyl groups (eg, sulfamoyl, N, N-3-oxapentamethyleneaminosulfonyl, etc.), aryl groups (eg, phenyl, carboxyphenyl, p-tolyl, p-hydroxyphenyl, p-methoxyphenyl, etc.) Groups), acyl groups (eg, groups such as acetyl and benzoyl), hydroxy groups, cyano groups, styryl groups, acylamino groups (eg, groups such as acetylamino, propionylamino, benzoylamino), sulfonamide groups (Eg, each group of methanesulfonylamide, benzenesulfonamide, etc.), sulfonyl (E.g., methanesulfonyl, each group such as p- toluenesulfonyl), include any group such as a carboxy group.

The methine carbon represented by L ₁ may be substituted, and examples of the substituted group include a lower alkyl group (eg, each group such as methyl, ethyl and propyl),
Lower alkoxy group (for example, each group such as methoxy and ethoxy), aryl group (for example, each group such as phenyl and p-fluorophenyl), aralkyl group (for example, each group such as benzyl and phenethyl), heterocyclic group ( Examples thereof include groups such as thienyl and furyl), cyano groups, and halogen atoms (eg, atoms such as fluorine and chlorine).

Further, between the adjacent methine carbon atom,
Alternatively, a ring can be formed by bonding to a methine carbon atom placed at one position.

The odd integer n ₁ defining the number of methine chains is selected from the range of 3 to 15, but is preferably the odd number of 3 to 7.

The compounds of the present invention are, for example,
Hama, "Cyanine Soybean and Relayed
Compounds "(1964, published by Inter Science Publishers), edited by S. Kofei," Rod Chemistry of Carbon Compounds 2nd Edition B ", Japanese Patent Publications 35-5892, 38-7828, etc. It can be easily synthesized by referring to the conventionally known method.

Specific examples of the compound represented by the general formula [D] are shown below, but the compound used in the present invention is not limited thereto.

[0019]

[Chemical 3]

[0020]

[Chemical 4]

[0021]

[Chemical 5]

[0022]

[Chemical 6]

[0023]

[Chemical 7]

[0024]

[Chemical 8]

Next, the compounds represented by the general formulas [I] to [IV] will be described.

Substituents having a substituent constant σ _P defined by Hammett of +0.20 or more according to these compounds are specifically sulfonyl, sulfinyl, sulfonyloxy,
Sulfamoyl, phosphoryl, carbamoyl, acyl,
Examples include groups such as acyloxy, oxycarbonyl, carboxyl, cyano, nitro, halogen-substituted alkoxy, halogen-substituted aryloxy, pyrrolyl, tetrazolyl, etc., and halogen atoms.

The sulfonyl group is alkylsulfonyl, arylsulfonyl, halogen-substituted alkylsulfonyl, halogen-substituted arylsulfonyl, etc .; Sulfinyl group is alkylsulfinyl, arylsulfinyl, etc .; Sulfonyloxy group is alkylsulfonyloxy, arylsulfonyloxy. Etc .; as the sulfamoyl group, N, N-dialkylsulfamoyl, N,
N-diaryl sulfamoyl, N-alkyl-N-aryl sulfamoyl and the like; phosphoryl groups include alkoxyphosphoryl, aryloxyphosphoryl, alkylphosphoryl, arylphosphoryl and the like; carbamoyl groups include N, N-dialkylcarbamoyl, N, N-diarylcarbamoyl, N-alkyl-N-arylcarbamoyl and the like; acyl groups such as alkylcarbonyl and arylcarbonyl; acyloxy groups such as alkylcarbonyloxy; oxycarbonyl groups such as alkoxycarbonyl and aryloxy Carbonyl, etc .; Halogen-substituted alkoxy groups, α-halogen-substituted alkoxy, etc .; Halogen-substituted aryloxy groups, tetrafluoroaryloxy, pentafluoroaryloxy, etc .; Pyrrolyl groups, 1-pyrrolyl, etc. Examples of the tetrazolyl group include 1-tetrazolyl and the like.

In addition to the above substituents, trifluoromethyl group, heptafluoroisopropyl group, nonylfluoro-t
-Butyl group, tetrafluoroaryl group, pentafluoroaryl group and the like are also preferably used.

In the general formula [I], among the substituents represented by R ₁ or R ₂ , the substituents other than the electron-withdrawing group include various ones and are not particularly limited. , Alkyl, aryl, anilino, acylamino,
Sulfonamide, alkylthio, arylthio, alkenyl, cycloalkyl, cycloalkenyl, alkynyl, heterocycle, alkoxy, aryloxy, heterocycleoxy, siloxy, amino, alkylamino, imide, ureido, sulfamoylamino, alkoxycarbonylamino, aryl Examples include oxycarbonylamino, alkoxycarbonyl, aryloxycarbonyl, heterocyclic thio, thioureido, hydroxyl and mercapto groups, spiro compound residues and bridged hydrocarbon compound residues.

The alkyl group preferably has 1 to 32 carbon atoms and may be linear or branched. A phenyl group is preferred as the aryl group.

The acylamino group is an alkylcarbonylamino group or an arylcarbonylamino group; the sulfonamide group is an alkylsulfonylamino group or an arylsulfonylamino group; the alkyl component of the alkylthio group or the arylthio group, and the aryl component is the above alkyl group or aryl. Groups.

The alkenyl group has 2 to 32 carbon atoms, and the cycloalkyl group has 3 to 12 carbon atoms, especially 5 to
7 is preferable, and the alkenyl group may be linear or branched. The cycloalkenyl group is preferably one having 3 to 12 carbon atoms, particularly 5 to 7 carbon atoms.

The ureido group is an 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 preferably has a 5- to 7-membered heterocycle,
For example, 3,4,5,6-tetrahydropyranyl-2-oxy group, 1-
Phenyltetrazole-5-oxy group, etc .; The heterocyclic thio group is preferably a 5- to 7-membered heterocyclic thio group, for example, 2-pyridylthio group, 2-benzothiazolylthio group, 2,4-diphenoxy-1,3 , 5-triazole-6-thio group, etc .; as siloxy groups, trimethylsiloxy group, triethylsiloxy group,
Dimethylbutylsiloxy group, etc .; Imido group as succinimide group, 3-heptadecyl succinimide group, phthalimido group, glutarimide group, etc .; Spiro compound residue as spiro [3.3] heptan-1-yl etc .; Arashi Bridge Hydrocarbon compound residues include bicyclo [2.2.1] heptan-1-yl, tricyclo [3.3.1.1 ^3.7 ] decan-1-yl, 7,7-dimethyl-bicyclo
[2.2.1] Heptan-1-yl and the like can be mentioned.

These groups may further contain a substituent such as a long chain hydrocarbon group or a diffusion resistant group such as a polymer residue.

In the general formula [I], the group capable of splitting off upon reaction with the oxidation product of the color developing agent represented by X ₁ is, for example, a halogen atom (hydrochloric acid, bromine, fluorine, etc.), alkoxy, aryloxy, or heterocycle. Oxy, acyloxy, sulfonyloxy, alkoxycarbonyloxy, aryloxycarbonyl, alkyl oxalyloxy, alkoxy oxalyloxy, alkylthio, arylthio, heterocyclic thio, alkoxythiocarbonylthio, acylamino, sulfonamide, nitrogen-containing N-bonded Examples thereof include heterocyclic groups, alkoxycarbonylamino, aryloxycarbonylamino, and carboxyl groups. Among these, preferred are a hydrogen atom and alkoxy, aryloxy, alkylthio, arylthio,
It is a nitrogen-containing heterocyclic group bonded at the N atom.

In the general formula [I], examples of the nitrogen-containing 5-membered heterocycle formed by Z ₁ include a pyrazole ring, an imidazole ring, a benzimidazole ring, a triazole ring and a tetrazole ring. The nitrogen-containing 5-membered heterocycle may be condensed with a benzene ring or the like.

More specifically, the compound represented by the general formula [I] is represented by the following general formulas [I] -1 to [I] -7.

[0038]

[Chemical 9]

[0039] In the above general formula, (I) at least one of R ₁ and R ₁₁ in -1, [I] in -2 R ₁ and R
_At least one of ₁₂ , at least one of R ₁ , R ₁₃ and R ₁₄ in [I] -3, at least one of R ₁ , R ₁₅ and R ₁₆ in [I] -4 R ₁ and R in [I] -5
_At least one of ₁₇ , R ₁ in [I] -6, [I]-
At least one of R ₁ and R _{18 in} 7 is an electron-withdrawing group having σ _P of 0.20 or more.

X ₁ has the same meaning as X ₁ in the formula [I], and p represents an integer of 0-4.

In the general formulas [I] -1 to [I] -7, among R ₁ and R _{11 to} R ₁₈ , those not having an electron-withdrawing group with σ _P of 0.20 or more are hydrogen atoms or substituents. And R ₁₈ which is not an electron-withdrawing group is not particularly limited as a substituent, and specifically, in the general formula [I], R ₁ or R ₂
When is a group other than an electron-withdrawing group, those mentioned as the substituent represented by R ₁ or R ₂ can be mentioned.

Next, the compound represented by the general formula [II] will be described.

This compound has a structure in which it is condensed with a pyrazole ring to form a hetero 6-membered ring, and the substituent represented by R ₃ is not particularly limited, and typically, alkyl, aryl, anilino, Examples thereof include groups such as acylamino, sulfonamide, alkylthio, arylthio, alkenyl, and cycloalkyl. In addition to these, a halogen atom and cycloalkenyl, alkynyl, heterocycle, sulfonyl,
Sulfinyl, phosphonyl, acyl, carbamoyl, sulfamoyl, cyano, alkoxy, sulfonyloxy, aryloxy, heterocycleoxy, siloxy, acyloxy, carbamoyloxy, amino, alkylamino, imide, ureido, sulfamoylamino, alkoxycarbonylamino, aryl Examples also include oxycarbonylamino, alkoxycarbonyl, aryloxycarbonyl, heterocyclic thio, thioureido, carboxyl, hydroxyl, mercapto, nitro, sulfonic acid groups, spiro compound residues, bridged hydrocarbon compound residues and the like.

The alkyl group represented by R ₃ is preferably one having 1 to 32 carbon atoms, which may be linear or branched, and the aryl group is preferably a phenyl group.

As the acylamino group represented by R ₃ ,
Alkylcarbonylamino group, arylcarbonylamino group, etc .; sulfonamide group, such as alkylsulfonylamino group, arylsulfonylamino group, etc .; alkylthio group, alkyl component in arylthio group, aryl component is alkyl group represented by R ₃ above, aryl Groups.

The alkenyl group represented by R ₃ has 2 to 32 carbon atoms, and the cycloalkyl group has 3 to 32 carbon atoms.
12, particularly 5 to 7, are preferable, and the alkenyl group may be linear or branched. The cycloalkenyl group preferably has 3 to 12 carbon atoms, and more preferably 5 to 7 carbon atoms.

The sulfonyl group represented by R ₃ 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 aryl. Oxyphosphonyl group, arylphosphonyl group, etc .; Acyl group, alkylcarbonyl group, arylcarbonyl group, etc .; Carbamoyl group, alkylcarbamoyl group, arylcarbamoyl group, etc .; Sulfamoyl group, alkylsulfamoyl group, arylsulfamoyl group Moyl group, etc .; Acyloxy group as alkylcarbonyloxy group, arylcarbonyloxy group, etc .; Carbamoyloxy group as alkylcarbamoyloxy group, arylcarbamoyloxy group, etc .; The idide group is an alkylureido group, an arylureido group, or the like; the sulfamoylamino group is an alkylsulfamoylamino group, an arylsulfamoylamino group, or the like; and the heterocyclic group is preferably a 5- to 7-membered group. 2-furyl group, 2-thienyl group,
2-pyrimidinyl group, 2-benzothiazolyl group, 1-pyrrolyl group, 1-tetrazolyl group, etc .;
Those having a 7-membered heterocycle are preferred, 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-Penzothiazolylthio group, 2,4-diphenoxy-1,3,5-
Triazole-6-thio group, etc .; siloxy group, trimethylsiloxy group, triethylsiloxy group, dimethylbutylsiloxy group, etc .; imide group, succinimide group, 3-
Heptadecyl succinimide group, phthalimide group, glutarimide group, etc .; Spiro compound residue is spiro [3.3]
Heptan-1-yl, etc .; bridged hydrocarbon compound residues include bicyclo [2.2.1] heptan-1-yl, tricyclo [3.3.1.1
^3.7 ] decan-1-yl, 7,7-dimethyl-bicyclo [2.2.1] heptan-1-yl and the like.

The above groups may further have a substituent such as a long chain hydrocarbon group or a diffusion resistant group such as a polymer residue.

Examples of the group represented by X ₂ which can be removed by the reaction with the oxidation product of the color developing agent include the same groups as X _{1 in the} general formula [I].

In the general formula [II], the nitrogen-containing hetero 6-membered ring formed by Z ₂ is preferably 6π electron system or 8π
It is an electronic system, and contains 1 to 4 including at least one -NH-
At least one carbonyl group containing 6 nitrogen atoms and contained in the 6-membered ring represents a group such as> C = O or> C = S. Further, the at least one sulfonyl group contained in the 6-membered ring represents a —SO ₂ — group. The nitrogen-containing hetero 6-membered ring may be condensed with a benzene ring or the like in addition to the pyrazolol ring.

As a preferred specific example, the following general formula [I
Examples thereof include compounds represented by I] -1 to [II] -6.

[0052]

[Chemical 10]

In the formula, R ₃ , R ₂₁ , R ₂₂ , R ₂₃ , R ₂₄ , R
_25, R _26, R ₂₇ and R ₂₈ has the same meaning as R ₁ in the general formula [I], X ₂ has the same meaning as X ₁ in the general formula (I), formula (II) -1 and [ II] -5, n is 0
Represents an integer of 4 and, when n is an integer of 2 to 4, a plurality of R ₂₁
And R ₂₆ may be the same or different.

R ₂₄ , R ₂₅ , R ₂₇ and R ₂₈ in the general formulas [II] -4 and [II] -6 have the same meanings as R ₂ in the general formula [I], but R ₂₄ and R ₂₇ are hydroxyl groups. It is never the basis.

In the general formula [III], R ₄ and R ₅ represent an electron-withdrawing group having a Hammett's substituent constant σ _P of 0.20 or more. These electron-withdrawing groups include R in the general formula [I]. _{The same} groups as the electron-withdrawing groups of ₁ and R ₂ can be mentioned. However, the sum of the σ _P values of R ₄ and R ₅ is 0.65 or more.

Examples of the nitrogen-containing 5-membered heterocyclic ring formed by Z ₃ include a pyrazole ring, an imidazole ring and a tetrazole ring. These nitrogen-containing 5-membered heterocycles may have a substituent.

More specifically, the compound represented by the general formula [III] is represented by the following general formulas [III] -1 to [III] -8.

[0058]

[Chemical 11]

In the formula, R ₄ , R ₅ and X ₃ are represented by the general formula [III]
Are synonymous with each. R ₃₁ represents a hydrogen atom or a substituent, and R ₃₂ represents an electron-withdrawing group having a Hammett's substituent constant σ _P of 0.20 or more.

The substituent represented by R ₃₁ is represented by the general formula [II]
The same group as R ₃ of R can be mentioned, and the electron withdrawing group represented by R ₃₂ can be the same as the electron withdrawing group of R ₁ and R ₂ in the general formula [I].

Of these, general formulas [III] -1, [III]
-2 or a compound represented by [III] -3 is preferable, and a compound represented by [III] -2 is particularly preferable.

In the general formula [IV], R ₆ and R ₇ represent a hydrogen atom or a substituent, and these substituents include the same groups as R _{3 in the} general formula [II].

Z ₄ in the general formula [IV] represents a non-metal atom group necessary for forming a nitrogen-containing 6-membered heterocycle. However, the heterocycle has at least one dissociative group. As the four divalent linking groups for constituting the nitrogen-containing 6-membered heterocycle, for example, -NH-, -N (R)-, -N =, -CH (R)-,-
CH =, - C (R) =, - CO -, - S -, - SO -, - SO 2 - and the like (R is a substituent group, include the substituents exemplified in R ₃₁ is as an example Be). As the dissociative group, for example, −
Examples thereof include those having an acidic proton such as NH- and -CH (R)-, and those having a pKa value of 3 to 12 in water are preferable. The nitrogen-containing 6-membered complex may have a substituent.

Preferred specific examples include the following general formula [IV]
Examples thereof include compounds represented by -1 to [IV] -6.

[0065]

[Chemical 12]

In the formula, R ₆ , R ₇ and X ₄ are each represented by the general formula [IV]
Are synonymous with each. R ₄₁ and R ₄₂ are respectively
R ₄₃ represents a hydrogen atom or a substituent, and R ₄₃ represents an electroattractive group having a Hammett's substituent constant σ _P value of 0.20 or more.

Specific examples of the substituents of R ₄₁ and R ₄₂ are the same as those of R _{3 in the} general formula [II], and specific examples of the electron-withdrawing group represented by R ₄₃ are R ₁ in the general formula [I]. And the electron withdrawing group of R ₂ .

Examples of the group represented by X ₄ which can be eliminated by the reaction with the oxidized product of the color developing agent include the same groups as X _{1 in the} general formula [I].

Specific examples of the compounds of the general formulas [I] to [IV] are shown below, but the invention is not limited thereto.

[0070]

[Chemical 13]

[0071]

[Chemical 14]

[0072]

[Chemical 15]

[0073]

[Chemical 16]

[0074]

[Chemical 17]

[0075]

[Chemical 18]

[0076]

[Chemical 19]

[0077]

[Chemical 20]

The compounds having these electron-withdrawing groups are
JP-A 64-554, 64-555, 64-557 and 1-
It can be easily synthesized according to the method described in No. 105251 and the like.

In the present invention, these compounds can be used in the range of 1 × 10 ^-3 mol to 1 mol, preferably 1 × 10 ^-1 mol to 8 × 10 ^-1 mol per mol of silver halide.

In the present invention, the degree of swelling of the hydrophilic colloid layer on the side of the light-sensitive material having the light-sensitive silver halide emulsion layer is determined as follows. That is, the hydrophilic colloid layer on the back surface side of the photosensitive material having a specific area is peeled and removed. The weight at this time is W ₀ . Put the above sample in pure water at 38 ℃.
Immerse for a minute to remove excess water and measure the weight immediately. Let this weight be W ₁ . The hydrophilic colloid layer on the emulsion layer side is peeled off and the weight is measured. Let this weight be W ₂ .

The degree of swelling can be calculated by ((W ₁ -W ₀ ) / (W ₀ -W ₂ )) × 100 [%].

In the present invention, the swelling degree of the hydrophilic colloid layer on the side having the photosensitive silver halide emulsion layer is 80 to
Within the range of 200%. Particularly preferably, it is 110 to 170%.

In the present invention, means for adjusting the degree of swelling to a desired value include adjustment of the amount of the hardener, selection of the type of hardener, selection of coating liquid conditions such as pH, and coating. Examples include selection of conditions for subsequent heating and / or humidification of the photosensitive material.

Hardeners that can be preferably used in the present invention include, for example, US Pat. No. 2,732,303 and British Patent 932,998.
, French Patent No. 1,296,928, Japanese Patent Publication No. 47-6151 and the like, active halogen type hardeners, for example Japanese Patent Publication No. Sho 49-13563.
No. 49-73122, No. 51-4463, No. 52-21059,
Examples thereof include active vinyl type hardeners described in JP-A-53-41221, JP-A-53-57257, US Pat. No. 3,490,911 and the like.

Specific examples of the hardener which can be preferably used in the present invention are shown below.

(Active Halogen Type Hardener)

[0087]

[Chemical 21]

(Active vinyl type hardener)

[0089]

[Chemical formula 22]

In addition to the above-mentioned patents, these compounds have active halogen type compounds in Japanese Patent Publication Nos. 47-33380 and 54-2541.
And British Patent No. 932,978, and Japanese Patent Publications Nos. 47-24259, 50-35807 and JP-A-49-24435 for active vinyl type.
No. 59-18944, French Patent No. 1,491,807 and the like.

The addition amount of these hardeners varies depending on the kind of hydrophilic colloid such as gelatin used, physical characteristics, photographic characteristics of the photographic light-sensitive material, processing conditions, etc., but the hydrophilic colloid in the coating solution is generally used. In the range of 0.05 to 20% by weight, the range is more preferably 0.1 to 10% by weight. In that case, if necessary, it can be used in combination with another hardener within a range that does not impair the effects of the present invention. Further, the timing of addition may be any stage of adjusting the coating liquid.

An internal latent image type silver halide having a common part with the spectral sensitivity region of each internal latent image type silver halide grain contained in the yellow image forming layer, magenta image and cyan image forming layer used in the present invention. Particles include, for example, blue light, green light when the yellow image forming layer contains a blue color sensitive emulsion, the magenta image forming layer contains a green color sensitive emulsion, and the cyan image forming layer contains a red color sensitive emulsion. It is necessary to have color sensitivity to all red light. When the yellow image forming layer contains a green color sensitive emulsion, the magenta image forming layer contains a red color sensitive emulsion, and the cyan image forming layer contains an infrared color sensitive emulsion, green light, red light, infrared light It is necessary that all of them have color sensitivity. The silver halide grains may be contained in any image forming layer, but are contained in each of the yellow image forming layer, the magenta image forming layer and the cyan image forming layer, or contained in the black image forming layer. Preferably.

In one embodiment of the present invention, a yellow image forming layer containing a blue color sensitive emulsion, a magenta image forming layer containing a green color sensitive emulsion, and a cyan image forming containing a red color sensitive emulsion. There is a light-sensitive material in which a layer and a black image-forming layer containing an emulsion having sensitivity to all of blue light, green light and red light are formed on a support.

Here, in order to form a black image, a black coupler may be used, or a yellow coupler,
You may mix and use a magenta coupler and a cyan coupler.

In another embodiment, a yellow image forming layer containing a blue color sensitive emulsion, a magenta image forming layer containing a green color sensitive emulsion, and a cyan image forming layer containing a red color sensitive emulsion. In addition, there is a light-sensitive material which independently has a yellow image forming layer, a magenta image forming layer, and a cyan image forming layer each containing an emulsion having sensitivity to all of blue light, green light and red light. .

Further, as another embodiment, a yellow image forming layer and a green color sensitive emulsion containing a blue color sensitive emulsion and an emulsion having color sensitivity to all light of blue light, green light and red light. And a magenta image forming layer containing an emulsion having sensitivity to all blue light, green light and red light, a red-sensitive emulsion and sensitivity to all light of blue light, green light and red light There is a light-sensitive material having a cyan image forming layer containing an emulsion having

These light-sensitive materials may have an intermediate layer, a filter layer and a protective layer, if necessary, in addition to the above-mentioned image forming layer.

The non-pre-fogged internal latent image type silver halide grains according to the present invention are silver halide grains which mainly form a latent image inside the silver halide grains and have most of the photosensitive nuclei inside the grains. It is a particle. Particularly preferably, a part of the sample coated on the transparent support so that the coated silver amount is in the range of about 1 to 3.5 g / m ² is exposed to light for a certain period of time of about 0.1 to about 1 second. When developed for 4 minutes at 20 ° C. using the surface developer A described below, which is exposed to the intensity scale and contains substantially no silver halide solvent, and which develops only the surface image of the grain, the same emulsion sample Part of the same is exposed to light and the image inside the grain is developed.
It is an emulsion showing a maximum density which is not larger than 1/5 of the maximum density obtained when developed for a minute. More preferably, the maximum concentration obtained using Surface Developer A is Internal Developer B
It is not more than 1/10 of the maximum concentration obtained in.

(Surface developer A) Metol 2.5 g L-ascorbic acid 10.0 g Sodium metaborate (tetrahydrate) 35.0 g Potassium bromide 1.0 g Water was added to 1000 ml (internal developer B) Metol 2.0 g Sodium sulfite ( Anhydrous) 90.0 g Hydroquinone 8.0 g Sodium carbonate (monohydrate) 52.5 g Potassium bromide 5.0 g Potassium iodide 0.5 g Water was added to 1000 ml Also, the internal latent image type silver halide emulsion in the present invention can be prepared by various methods. Those that are prepared are included. For example, conversion type silver halide emulsions described in U.S. Pat.No. 2,592,250, or U.S. Pat.Nos. 3,206,316 and 3,3.
Internally chemically sensitized silver halide emulsions described in 17,322 and 3,367,778, or U.S. Pat.
Nos. 3,447,927 and 3,531,291, a silver halide emulsion containing a polyvalent metal ion described therein, or a dopant described in U.S. Pat.No. 3,761,276 to weakly chemically sensitize the grain surface. Silver halide emulsion, or
No. 50-8524, No. 50-38525 and No. 53-2408, silver halide emulsions having a laminated structure, and others.
And the silver halide emulsions described in JP-A No. 614 and 55-127549.

The internal latent image type silver halide grain in the present invention is a silver halide having an arbitrary halogen composition, for example, silver bromide, silver chloride, silver chlorobromide, silver chloroiodide, silver iodobromide or salt. It may be silver iodobromide. The grains containing silver chloride have excellent developability and are suitable for rapid processing.

The shape of the particles may be any of a cube, an octahedron, a tetrahedron composed of a mixture of (100) planes and (111) planes, a shape having a (110) plane, a spherical shape, a tabular shape and the like. An average particle size of 0.05 to 3 μm can be preferably used. The grain size distribution may be a monodisperse emulsion having uniform grain size and crystal habit, or a polydisperse emulsion having no grain size or crystal habit.
It is preferably a monodisperse silver halide emulsion.

In the present invention, a particularly preferred highly monodisperse emulsion is one in which the breadth of distribution defined by (grain size standard deviation / mean grain diameter) × 100 = breadth of distribution (%) is 20% or less. is there. Here, the frequency n _i of the average particle size r _m particles having a particle size r _i
And r _i ³ and the product n _i × r _i ³ are defined as the maximum particle size r _i (three significant digits and the least significant digit are rounded to four).
The term "particle size" used herein means the diameter of spherical silver halide grains, or the diameter of a projected image converted into a circular image of the same area in the case of grains having a shape other than spherical. .
(The number of particles measured shall be 1000 or more indiscriminately).

A monodisperse emulsion is prepared by adding a water-soluble silver salt solution and a water-soluble halogen salt solution to pAg and p in a gelatin solution containing seed grains.
It can be obtained by adding by the double jet method under the control of H 2. In determining the addition rate, refer to JP-A-54
-48521 and 58-49938 can be referred to. As a method for obtaining a more advanced monodisperse emulsion, a growth method in the presence of a tetrazaindene compound disclosed in JP-A-60-122935 can be applied.

In the present invention, at least one layer of a light-reflecting layer containing a white pigment is provided on the image forming layer side of the support, and the amount of the white pigment contained in the light-reflecting layer is the binder of the light-reflecting layer. It is preferable that the ratio to the attached amount is 20% or more by weight.

The light-reflecting layer according to the present invention may contain a white pigment in the polyolefin resin coating layer provided on the surface of the support, or a hydrophilic colloid containing the white pigment provided on the support. It may be a layer.

The polyolefin resin coating layer as the light-reflecting layer in the present invention more preferably contains 20 to 40% by weight of a white pigment with respect to the amount of the binder. When a resin that cures with actinic rays such as ultraviolet rays and electron beams is used as a binder, a white pigment having a relatively high content can be contained.

In the present invention, a hydrophilic colloid layer containing a white pigment can be preferably used as the light reflecting layer. In that case, it is more preferable that the white pigment is contained in an amount of 30 to 70% by weight with respect to the amount of the binder in the light reflecting layer.

As the white pigment, an inorganic and / or organic white pigment can be used, and an inorganic white pigment is preferable. Inorganic white pigments include sulfates of alkaline earth metals such as barium sulfate, carbonates of alkaline earth metals such as calcium carbonate, finely divided silicic acid, silicas of synthetic silicates, calcium silicate, alumina, hydrated alumina. , Titanium oxide, zinc oxide, talc, clay and the like. Among these, preferably barium sulfate, calcium carbonate, titanium oxide, more preferably barium sulfate,
Titanium oxide. Titanium oxide may be rutile type or anatase type, and the one whose surface is coated with metal oxide such as hydrous alumina oxide or hydrous ferrite is also used.

In addition, various additives such as colored pigments, fluorescent whitening agents and antioxidants may be added.

The amount of white pigment applied is preferably 0.5 to 50.
in the range of g / m ^2, more preferably in the range of from 1 to 20 g / m ^2.

In the present invention, color development is carried out continuously while replenishing the color developing replenisher with the developing tank. The replenishing amount of the color developing replenisher is preferably 700 ml or less, and more preferably 400 ml or less per 1 m ² of the light-sensitive material.

The yellow image forming layer, the magenta image forming layer, the cyan image forming layer and the black image forming layer of the present invention are laminated and coated on a support, but the order from the support may be any order. One preferred embodiment is, for example, from the side closer to the support, a cyan image forming layer, a magenta image forming layer,
It becomes a yellow image forming layer and a black image forming layer. In addition to these, an intermediate layer, a filter layer, a protective layer and the like can be arranged as required.

The light-sensitive material having a silver halide emulsion layer according to the present invention forms a positive image directly by subjecting it to imagewise exposure or developing it in the presence of a fogging agent.

A wide variety of compounds can be used as the fog agent, and it is sufficient that the fog agent is present during the development processing. For example, in the constituent layers other than the support of the light-sensitive material (in particular, the silver halide emulsion layer). Medium)), or in a developing solution or a processing solution prior to the development processing. The amount used can be varied over a wide range according to the purpose. The preferable amount added is 1 mole per mol of silver halide when it is added to the silver halide emulsion layer.
~ 1500 mg, preferably 10-1000 mg. When added to a processing solution such as a developing solution, the preferable addition amount is 0.01 to 5 g /
1, particularly preferably 0.05 to 1 g / l.

Examples of the fogging agent used in the present invention include hydrazines described in US Pat. Nos. 2,563,785 and 2,588,982 or hydrazides or hydrazine compounds described in US Pat. No. 3,227,552; US Pat.
5, 3,718,479, 3,719,494, 3,734,738 and 3,759,901, heterocyclic quaternary nitrogen salt compounds; and silver halides such as acylhydrazinophenylthioureas described in U.S. Pat. No. 4,030,925. Examples thereof include compounds having an adsorption group on the surface. Further, these fogging agents can be used in combination. For example, RD1516 described above
No. 2 describes that a non-adsorption type fogging agent is used in combination with an adsorption type fogging agent, and this combination technique is also effective in the present invention. In the present invention, both an adsorption type and a non-adsorption type can be used, or they can be used in combination.

As the developer that can be used in the developer used for developing the light-sensitive material of the present invention, a conventional silver halide developer such as polyhydroxybenzenes such as hydroquinone, aminophenols and 3-pyrazolidone can be used. , Ascorbic acid and its derivatives, reductones, phenylenediamines and the like, or mixtures thereof. Specifically, hydroquinone, aminophenol, N-methylaminophenol, 1-phenyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, 1-
Phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, ascorbic acid, N, N-diethyl-p-phenylenediamine, diethylamino-o-toluidine, 4-amino-3-methyl-N-ethyl-N- ( β-methanesulfonamidoethyl) aniline, 4-amino-3-methyl-N-ethyl-N- (β-hydroxyethyl) aniline, 4-amino-N-ethyl-N- (β-hydroxyethyl) aniline, etc. Can be mentioned. It is also possible to incorporate these developers in the emulsion in advance so that they act on the silver halide during the immersion in the high pH aqueous solution.

The developer used in the present invention may further contain a specific antifoggant and development inhibitor, or these developer additives may be optionally incorporated in the constituent layers of the photographic light-sensitive material. Is also possible.

Known photographic additives such as compounds described in Research Disclosure (RD) 17643 and RD18716 can be used in the light-sensitive material of the present invention.

In the silver halide emulsion layer of the light-sensitive material of the present invention, a dye-forming coupler capable of forming a dye by a coupling reaction with an oxidized product of a color developing agent can be used.
The dye-forming couplers are usually selected so that a dye that absorbs the light of the light-sensitive spectrum of the emulsion layer is formed for each emulsion layer. A magenta dye forming coupler is used in the sensitive emulsion layer and a cyan dye forming coupler is used in the red sensitive emulsion layer. However, the color light-sensitive material may be produced by a method different from the above combination depending on the purpose.

It is desirable that these dye-forming couplers have a group called a ballast group having 8 or more carbon atoms, which makes the coupler non-diffusible, in the molecule. Further, these dye-forming couplers are required to reduce 4 molecules of silver ions in order to form 1 molecule of dye, but even if they are 4 equivalents, only 2 molecules of silver ions need to be reduced. Either equivalence may be used. Releases a development inhibitor along with development, releases a development inhibitor at the same time as a DIR coupler that improves image sharpness and image graininess, and produces a colorless compound through a coupling reaction with an oxidized product of a developing agent. DIR compounds may be used. In addition, a colorless coupler (also referred to as a competing coupler) which undergoes a coupling reaction with an oxidized product of an aromatic primary amine developer but does not form a dye can be used in combination with the dye-forming coupler.

Known acylacetanilide type couplers can be preferably used as the yellow dye-forming coupler. Among these, benzoylacetanilide compounds and pivaloylacetanilide compounds are advantageous.

As the magenta dye-forming coupler, known 5-pyrazolone-based couplers, pyrazolobenzimidazole-based couplers, pyrazoloaryl-based couplers, acylacetonitrile-based couplers, indazolone-based couplers and the like can be used.

As the cyan dye forming coupler, known phenol type, naphthol type or imidazole type couplers can be used. Typical examples include phenol-based couplers substituted with an alkyl group, an acylamino group, or a ureido group, naphthol-based couplers formed from a 5-aminonaphthol skeleton, and 2-equivalent naphthol-based couplers having an oxygen atom introduced as a leaving group. To be done.

RD16 is a black dye-forming coupler.
226, JP-A-52-42725, JP-A-53-46029, JP-A-54-9924 and the like can be used.

The support which can be used in the light-sensitive material of the present invention is, for example, the above-mentioned RD17643, page 28, RD18716.
Those described on page 647 can be mentioned. These may be subjected to a treatment for enhancing adhesiveness, antistatic property and the like.

[0126]

EXAMPLES The present invention will be described in detail below with reference to examples, but the present invention is not limited thereto.

Example 1 << Preparation of Emulsion EM-1 >> An equimolar silver nitrate aqueous solution and potassium bromide aqueous solution were simultaneously added to a gelatin aqueous solution at 50 ° C. for 30 minutes by the double jet method to give an average particle size of 0.35.
An emulsion consisting of μm octahedral silver bromide grains was obtained. To this emulsion, 5.5 mg of sodium thiosulfate and 2.5 mg of potassium chloroaurate were added per mol of silver, and the mixture was chemically ripened at 70 ° C. for 80 minutes. Next, using this emulsion as a core, an aqueous silver nitrate solution and an aqueous potassium bromide solution were simultaneously added to obtain an average particle size of 0.50 μm.
To obtain a core / shell type octahedral silver bromide emulsion. After desalting with water, 1.5 mg of sodium thiosulfate and 1.0 mg of potassium chloroaurate per mol of silver were added to this emulsion, and the emulsion was added at 50 ° C at 50 ° C.
Directly positive silver halide emulsion EM-
Got 1.

<< Preparation of Emulsion EM-1B >> Sensitizing dye BD-1 shown below was added to Emulsion EM-1 at 2.4 × 1 per mol of emulsion.
Blue sensitizing emulsion EM-1 was prepared by adding 0 ^-4 mol for color sensitization.
B was obtained.

<< Preparation of Emulsion EM-1G >> Emulsion EM-1 was added with sensitizing dye GD-1 shown below at 1.6 × 1 per mol of emulsion.
^0-4 mol was added for color sensitization to obtain a green color-sensitive emulsion EM-1.
Got G.

On the front side of a paper support (thickness: 220 μm) laminated on both sides with polyethylene, the following first to tenth layers were multilayer-coated to prepare a color light-sensitive material sample 1-1.

The numbers represent the coating amount (g / m ² ).
However, the silver halide emulsion is shown in terms of silver.

10th Layer (UV Absorbing Layer) Gelatin 0.78 UV Absorbing Agent (UV-1) 0.065 UV Absorbing Agent (UV-2) 0.195 Solvent (SO-2) 0.10 Colloidal Silica 0.03 9th Layer (Blue Photosensitive Layer) Gelatin 1.14 Emulsion EM-1B 0.40 Yellow coupler (YC-1) 0.656 Anti-stain agent (AS-2) 0.02 Solvent (SO-1) 0.656 Inhibitor (ST-1, ST-2, T-1) 8th layer (intermediate) Layer) Gelatin 0.54 Anti-color mixing agent (AS-1) 0.055 Solvent (SO-2) 0.072 7th layer (Yellow colloid silver layer) Gelatin 0.42 Yellow colloid silver 0.04 Anti-color mixing agent (AS-1) 0.04 Solvent (SO-2) 0.049 Polyvinylpyrrolidone (PVP) 0.047 Sixth layer (intermediate layer) Gelatin 0.54 Anti-color mixing agent (AS-1) 0.055 Solvent (SO-2) 0.072 Fifth layer (green photosensitive layer) Gelatin 1.14 Emulsion EM-1G 0.40 Maze Ta coupler (MC-1) 0.20 Anti-staining agent (AS-2) 0.0152 Solvent (SO-1) 0.248 Inhibitor (ST-1, ST-2, T-1) 4th layer (intermediate layer) Gelatin 0.75 Anti-color mixing agent (AS-1) 0.055 Solvent (SO-2) 0.072 Third layer (red photosensitive layer) Gelatin 1.10 Emulsion EM-1 0.24 Cyan coupler (CC-1: CC-2 = 1: 1) 0.352 Solvent (SO-1) 0.248 Anti-stain agent (AS-2) 0.012 Inhibitor (ST-1, ST-2, T-1) Second layer (intermediate layer) Gelatin 0.55 First layer (antihalation layer) Gelatin 0.75 Black colloidal silver 0.07 Color mixture prevention Agent (AS-1) 0.04 Solvent (SO-2) 0.049 Note that SA-1 and SA-2 were used as coating aids, and H-1 was used as a hardening agent.

T-1: 4-hydroxy-6-methyl-1,3,3a, 7
-Tetrazaindene SA-1: sulfosuccinic acid di (2-ethylhexyl) ester / sodium SA-2: sulfosuccinic acid di (2,2,3,3,4,4,5,5-octafluoropentyl) ester -Sodium H-1: 2,4-dichloro-6-hydroxy-S-triazine-sodium AS-1: 2,5-di-t-octylhydroquinone AS-2: 2,5-di-t-butylhydroquinone SO -1: Trioctyl phosphate SO-2: Dioctyl phthalate ST-1: 1- (3-acetamido) phenyl-5-mercaptotetrazole ST-2: N-benzyladenine

[0134]

[Chemical formula 23]

[0135]

[Chemical formula 24]

[0136]

[Chemical 25]

Next, after the emulsion EM-1 was prepared, the sensitizing dyes shown in Table 1 were added in an amount of 1.6 × 10 ^-4 mol per mol of the emulsion, and the mixture was ripened at 55 ° C. for 30 minutes for color sensitization. , A red color-sensitive emulsion was obtained. These emulsions were used as the emulsion EM- of the third layer of Sample 1-1.
Samples 1-2 to 1-21 were prepared in the same manner as Sample 1-1, except that the amount of H-1 added was changed to 1. The swelling degree shown in Table 1 was obtained by changing the addition amount of H-1.

Samples 1-1 to 1-obtained in this way
21 was exposed to white light for 0.5 seconds through an optical wedge.

Each exposed sample was developed according to the following processing step-1. However, the fog exposure was carried out while being immersed in the developing solution, and the entire surface of the photosensitive material was uniformly exposed through a layer of the developing solution having a thickness of 3 mm.

Processing Step-1 Temperature Time Tank Capacity Immersion (Developer) 37 ° C 12 seconds Fog exposure-12 seconds Development 37 ° C 95 seconds 10l Bleaching fixing 35 ° C 45 seconds 5l Stabilization 25-30 ° C 90 seconds 5l × 2 Dry 60-85 ℃ 40 seconds Composition of processing solution (color developer) Benzyl alcohol 15.0ml Cerium (III) sulfate 0.015g Ethylene glycol 8.0ml Potassium sulfite 2.5g Potassium bromide 0.6g Sodium chloride 0.2g Potassium carbonate 25.0g T-1 0.1g Hydroxylamine sulfate 5.0g Diethylenetriamine pentaacetate 2.0g N-Ethyl-N- (β-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate 4.5g Optical brightener (4,4'- Diaminostilbene disulfonic acid derivative) 1.0 g Potassium hydroxide 2.0 g Diethylene glycol 15.0 ml Add water to bring the total volume to 1000 ml, and adjust to pH 10.15.

(Bleach-fixing solution) Diethylenetriamine 5 ferric ammonium acetate 90.0 g Diethylenetriamine 5 acetic acid 3.0 g Ammonium thiosulfate (70% aqueous solution) 180.0 ml Ammonium sulfite (40% aqueous solution) 27.5 ml 3-Mercapto-1,2,4- Triazole 0.15g Adjust the pH to 7.1 with potassium carbonate or glacial acetic acid and add water to make the total volume 1000ml. (Stabilizing solution) o-Phenylphenol 0.3g Potassium sulfite (50% aqueous solution) 12.0ml Ethylene glycol 10.0g 1-Hydroxyethylidene-1,1-diphosphonic acid 2.5g Bismuth chloride 0.2g Zinc sulfate 7-hydrate 0.7g Hydroxylation Ammonium (28% aqueous solution) 2.0g Polyvinylpyrrolidone (K-17) 0.2g Fluorescent brightener (4,4'-diaminostilbenedisulfonic acid derivative) 2.0g Add water to make 1000ml and add ammonium hydroxide or sulfuric acid. Adjust to pH 7.5.

The stabilization treatment was a countercurrent system with a two tank structure.

The maximum cyan density of the sample after the treatment and the residual color density obtained by subtracting the magenta stain density of Sample 1-1 (blank sample containing no sensitizing dye) from the magenta stain density of each sample were evaluated. . The results obtained are shown in Table 1.

[0144]

[Table 1]

As is clear from the results shown in Table 1, it was found that the samples of the present invention provided good positive images with little residual color.

Example 2 In Samples 1-4 and 1-9 of Example 1, the cyan couplers (CC-1, CC-2) in the third layer were replaced with the cyan couplers shown in Table 2 in equimolar amounts. Others were made in the same manner as Samples 2-1 to 2-6.

The results of evaluation of the obtained sample in the same manner as in Example 1 are shown in Table 2.

[0148]

[Table 2]

As is clear from the results of Table 2, Samples 2-3 to 2-6 in which the cyan coupler was changed in the samples of the present invention.
It was found that the residual color was less, and a more favorable positive image was obtained.

Example 3 << Preparation of emulsion EM-1K1 >> Sensitizing dye B was added to emulsion EM-1.
D-1 is 2.4 × 10 ^-4 mol per mol of emulsion, GD-1 is
1.4 × 10 ^-4 mol and 1.2 × 10 ^-4 mol of RD-1 were added for color sensitization to obtain a blue-sensitive, green-sensitive and red-sensitive emulsion EM.
-1K1 was obtained.

In Sample 1-4 of Example 1, emulsion EM
-1K1 in the 3rd layer 0.06g per 1 m ² (silver conversion), 5th
Sample 3-1 was prepared in the same manner except that 0.08 g was added to the layer and 0.10 g was added to the ninth layer.

Next, an emulsion EM-1K2 was prepared in the same manner as in the emulsion EM-1K1 except that D-15 was added instead of the sensitizing dye RD-1.

In Sample 1-9 of Example 1, emulsion EM
-1K2 in the 3rd layer 0.06g per 1 m ² (silver conversion), 5th
Sample 3-2 was prepared in the same manner except that 0.08 g was added to the layer and 0.10 g was added to the ninth layer.

The results of evaluation of the obtained sample in the same manner as in Example 1 are shown in Table 3.

[0155]

[Table 3]

As is clear from the results of Table 3, blue light,
It has been found that the samples of the present invention produce a good positive image with less residual color even in a light-sensitive material containing an emulsion having color sensitivity to both green light and red light.

Example 4 Samples 4-1 and 4-2 were prepared in the same manner as in samples 1-1 and 1-4 of Example 1 except that the first layer was changed as follows.

First Layer Gelatin 1.50 Titanium Oxide 1.50 The results of evaluating the obtained sample in the same manner as in Example 1 are shown in Table 4.

[0159]

[Table 4]

As is clear from the results shown in Table 4, even in the light-sensitive material having a white pigment layer, the sample of the present invention produces a good positive image with little residual color.

Example 5 Samples 1-4 and 1-9 of Example 1 were subjected to a running process in which the replenishing amount of the color developing solution was 600 ml / m ² , and the replenishing amount of the color developing solution was changed immediately after the running process was started. The sample after being processed to 3 times the developing tank capacity was evaluated in the same manner as in Example 1. The replenishing amounts of the bleach-fixing solution and the stabilizing solution were the same as those for the color developing solution. The results thus obtained are shown in Table 5.

[0162]

[Table 5]

As is clear from the results shown in Table 5, it was found that the samples of the present invention gave a good positive image with little residual color even in the development process in which the replenishing amount of the color developing solution was small.

[0164]

According to the present invention, it is possible to provide a direct positive silver halide color photographic light-sensitive material and a direct positive color image forming method in which a good positive image can be obtained with less residual color of the sensitizing dye.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Office reference number FI Technical display location G03C 7/00 540 550 7/20 7/38 7/407 7/44

Claims (5)

[Claims] 1. A photosensitive silver halide emulsion layer containing an internal latent image type silver halide grain which is not previously fogged and a compound represented by the following general formula [D], on a support,
A direct positive silver halide color photographic light-sensitive material characterized in that the degree of swelling of the photographic constituent layer on the side having the light-sensitive silver halide emulsion layer on the support is in the range of 80 to 200%. [Chemical 1] [In the formula, Z ₀₁ and Z ₀₂ each represent a nonmetallic atom group necessary for forming a 5- or 6-membered nitrogen-containing heterocycle, and L ₁
Represents methine carbon. R ₀₁ represents a —J ₂ —COOH group. J
₁ and J ₂ each represent an alkylene group. l ₁ and l ₂ each represent an integer of 0 or 1, and n ₁ represents an odd integer of 3 or more. ] 2. The direct positive silver halide color photographic light-sensitive material according to claim 1, containing at least one selected from compounds represented by the following general formulas [I] to [IV]. [Chemical 2] [In the formula, R ₁ represents a hydrogen atom or a substituent, and R ₂ represents a substituent. m represents the number of substituents R ₂ . When m is 0, R ₁ represents an electron-withdrawing group having a Hammett substituent constant σ _P of 0.20 or more, and when m is 1 or 2, at least one of R ₁ and R ₂ is a Hammett substituent. Represents an electron-withdrawing group having a constant σ _P of 0.20 or more. Z ₁ represents a group of non-metallic atoms necessary for forming a nitrogen-containing hetero 5-membered ring. R ₃ represents a hydrogen atom or a substituent, Z ₂ is condensed with —NH— to the pyrazole ring,
It represents a group of non-metal atoms necessary for forming a nitrogen-containing hetero 6-membered ring. R ₄ and R ₅ represent electron withdrawing groups having a Hammett's substituent constant σ _P of 0.20 or more. However, the sum of the σ _P values of R ₄ and R ₅ is 0.65 or more. Z ₃ represents a group of non-metal atoms necessary for forming a nitrogen-containing 5-membered heterocycle. R ₆ and R ₇ represent a hydrogen atom or a substituent, and Z ₄ represents a non-metal atom group necessary for forming a nitrogen-containing 6-membered heterocycle. X ₁ , X ₂ , X ₃ and X ₄ each represent a hydrogen atom or a group capable of leaving by a coupling reaction with an oxidant of a color developing agent. ] 3. The photosensitive silver halide emulsion layer according to claim 1, which is at least one selected from a yellow image forming layer, a magenta image forming layer and a cyan image forming layer after color development processing, The internal latent image type silver halide grains having a spectral sensitivity region common to the spectral sensitivity regions of the respective internal latent image type silver halide grains contained in the yellow image forming layer, the magenta image forming layer and the cyan image forming layer are used. The direct positive silver halide color photographic light-sensitive material according to claim 1 or 2, which is contained in at least one layer of an image forming layer, a magenta image and a cyan image forming layer and / or an image forming layer other than these. 4. At least 1 on the side of the image forming layer on the support.
Layer having a light reflecting layer containing a white pigment, wherein the ratio of the amount of the white pigment contained in the light reflecting layer to the amount of the binder contained in the light reflecting layer is 20% or more by weight. 4. The direct positive silver halide color photographic light-sensitive material according to claim 1. 5. A direct positive color image forming method comprising a step of treating the direct positive silver halide color photographic light-sensitive material according to claim 1 with a color developing solution after imagewise exposure, and replenishing the color developing solution. A direct positive color image forming method, characterized in that the amount is 700 ml / m ² or less of the light-sensitive material.