JPS593737B2 - Multilayer color photosensitive material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a color photosensitive material with improved color reproducibility and improved uniformity of finishing quality during development.
In particular, the present invention relates to a color photosensitive material in which development unevenness 10 does not occur during high-temperature development.

Usually, color photographic materials include an emulsion layer (BL) containing a yellow coupler and mainly sensitive to positive color light, an emulsion layer (GL) containing a magenta coupler and mainly sensitive to green light,
The emulsion layer (RL) has a built-in cyan coupler and is mainly sensitive to 15 red light, the intermediate layer (ML), the filter layer (FL) that absorbs ultraviolet rays and visible light in a specific wavelength range, and the antihalation layer (AHL). ), a protective layer (PL), and a light-sensitive emulsion layer (20) whose spectral sensitivity distribution is changed depending on the purpose using various couplers are known to be provided. Various efforts have been made to improve color reproducibility. First, the interlayer effect
Organic compounds are applied that enhance the geeffects. For example, it is known that an organic heterocyclic compound having an oxo or thioxo group can be used. For example, German Published Patent Specification No. 2,043,943;
Compounds described in No. 043, 944 and the like are used.

Second, compounds having a mercapto group or thioether bond, such as '■O2-mercaptobenzotriazole,
β-hydroxyethylisothiouronium nitrate, 2,
3-dimethylthiazolium salt, 1-(2-mercaptoethyl)-1,4,4-trimethylpipecidinium salt or 2-thioxobenzotriazole 15, etc., e.g., U.S. Pat. No. 3,536,487, U.S. Pat. Compounds described in Defensive Publications T909, No. 022, T909, No. 023, etc. can be used. Third, a power coupler is used. Fourth, an uncolored coupler for interlayer color correction is used. For example, JP-A-50-2
No. 537, especially JP-A No. 49-122335 and Special Publication No. 4 of the 1970s.
Compounds described in Japanese Patent Application No. 6-222514 and the like are used. Fifth, as described in JP-A No. 49-122335, in a multilayer structure, the halogen composition of the photosensitive silver halide emulsion itself used in each layer is controlled, especially the silver iodide emulsion. Concentration distribution is controlled. The effect of the fifth measure is generally smaller than those mentioned above. Sixthly, a hydroquinone derivative for interlayer color correction is used. Compounds such as those shown in JP-A-49-129536 are used. These ideas are
Although it can represent an improved effect regarding excellent color reproduction, on the other hand, there are serious deficiencies.

The first defect is the so-called interlayer effect, in which a development inhibitor is released from the development starting point in response to image development and diffuses into the adjacent layer, suppressing the development of the adjacent layer.
interimage effects or under
Not only do cutinterimage effects appear, but the released inhibitor passes through the photosensitive emulsion layers and oozes into the developer, further inhibiting development over an unnecessarily wide range and inducing uneven development. The latter defect actually results in deterioration of image quality after development. Therefore,
In order to exhibit the improvement effect of achieving the expected best color reproduction, it is necessary to limit the range of action of the released development inhibitor to only between the light-sensitive emulsion layers that mutually give an interlayer effect. be. The first improvement in color reproduction mentioned above.
, the second, third, fourth and sixth devices, especially when the fourth device is applied, this defect is likely to appear, and about 30
It becomes more noticeable when rapid development is performed at a high temperature of ℃ or higher. On the other hand, when the fifth technique is applied, it is known that an advantageous multilayer effect such as development at high temperature appears. The second defect is that when the first, second, fourth, and sixth methods of improving color reproduction described above are applied, the image quality obtained with a tired developer is lower than that of a fresh developer. This is a significant deterioration in image quality compared to the image quality that can be obtained. On the other hand, it is known that when the fifth technique is applied, the multilayer effect becomes noticeable, such as by using a fatigued developer. When the photosensitive materials using these first, second, third, fourth and sixth devices are developed,
The deleterious effect on image quality caused by the development inhibitor released into the developer is different from when the photosensitive material with the fifth technique is developed. It is known that most of the iodine ions are captured in undeveloped silver halide grains by a conversion reaction, and only a small amount leaches into the developer. An object of the present invention is to improve the defects that appear when the above-described first, second, third, fourth, and sixth ideas are applied. In particular, it is an object of the present invention to provide a multilayer color photosensitive material that has improved color reproducibility and is suitable for high-temperature rapid processing at temperatures higher than 30° C. without causing uneven development. Other objects of the invention will be apparent from the description. These objects include a photosensitive emulsion layer containing an interlayer color correction coupler represented by the following general formula 0 and at least one coupler selected from yellow couplers, magenta couplers and cyan couplers on a support; Above the emulsion layer or between the emulsion layer and the support, there is provided an adsorbed colloid layer of an organic development inhibiting compound separated from the interlayer color correction coupler containing silver halide grains which are not substantially developed by color development. This is achieved by a color image forming method characterized by developing the prepared multilayer color photosensitive material at a high temperature of 3θ°C or higher.

General formula a] Cp-Z In the formula, Cp represents a coupler residue that undergoes a coupling reaction with an oxidized product of a primary aromatic amine color developer, and Z represents a 1-triazole ring, a 1-diazole ring, or a 2-benzotriazole ring. a heterocyclic group, an arylmonothio group, a tetrazolethio group, a triazinylthio group, a triazolylthio group, an oxazolylthio group, an imidazolylthio group, an oxadiazolylthio group, a thiadiazolylthio group, a benzothiazolylthio group, a pyrimidylthio group, or Hail pyridinylthio group.

According to a preferred embodiment of the present invention, the multilayer color light-sensitive material has at least two light-sensitive emulsion layers on a support that provide images of substantially different hues by color development, and at least one of these light-sensitive emulsion layers is An organic development inhibitor containing a coupler for interlayer color correction, and containing silver halide grains above the containing emulsion layer or between the containing emulsion layer and the support, which are not substantially developed by color development. It has an adsorbent colloid layer.

The interlayer color correction coupler (ICC-coupler) in the present invention is a coupler as defined in Japanese Patent Application Laid-Open No. 50-2537.
layereffects), and as a result ``
A coupler having the function of "color correction" (COlOurCOrectiOn), preferably JP-A-49-12233
This is a coupler shown in No. 5, and one part of it is the so-called "
DIR-coupler.

Particularly useful are the residues represented by the general formula [1a]. General Formula [1a] In the formula, V represents a benzene-based aromatic ring or a heteroaromatic ring containing at least one nitrogen atom, and L represents methine or a derivative group thereof.

V may be substituted with groups such as amino, acylamino, halogen, alkyl, nitro, alkoxy, alkylthio, aryl, and the like. When the development-suppressing leaving group (Z in general formula 0) in the interlayer color correction coupler is a mercapto residue, the mercapto group strongly adsorbs to the photosensitive silver halide through a chemical bond. The effect is relatively weak, but rather the effect of suppressing intralayer development is relatively strong.

On the other hand, in-situ inhibited leaving groups such as the general formula [1a]
In the case of the residue represented by , the interlayer color correction effect appears relatively strong. In this case, the useful effect of providing the organic development inhibitor adsorbing colloid layer according to the present invention is particularly noticeable. The adsorbed colloid layer (ADL) of an organic development inhibitor according to the present invention refers to an organic promoter of multilayer effect that is released from the ICC/coupler during development or is adsorbed in advance to silver halide grains in the light-sensitive emulsion layer. It is a colloid layer that has the function of adsorbing and fixing development-inhibiting residues released from the agent during development of particles and preventing them from being released during development. ,
It is a colloid layer that has the function of adsorbing and removing it from the developer, and the function of appropriately controlling the diffusion of released development-inhibiting residues.

Therefore, the colloid layer (ADL) according to the invention is preferably provided above or below the light-sensitive emulsion layers. This colloidal layer contains silver halide particles, and may also contain a compound having adsorption power such as colloidal silica.
The silver halide grains are preferably fine grains and contain a small amount of iodide ions in order to increase adsorption power and adsorption capacity. In particular, ultrafine particles with an average particle diameter of less than 0.2 microns are preferred. In order to maintain strong adsorption in the developer, the silver halide grains are preferably not developed or dissolved. Therefore, preferably 1 particle is not chemically ripened.
Silver iodobromide grains containing less than 0 moles of silver iodide are preferred. Silver chloride particles are rather less preferred. One of the features of the present invention is the arrangement of the organic development inhibitor adsorption colloid layer ADL.

First, it is provided in the emulsion layer in which the ICC coupler is used and on top of the emulsion layer where the weight effect is to be imparted. In this case, the development inhibitor released from the lower photosensitive emulsion layer is captured to control the range in the plane direction over which the development inhibitor acts, thereby preventing uneven development. Secondly, it is provided below the photosensitive emulsion layer, that is, closer to the support. In this case, the development inhibitor released from the light-sensitive emulsion layer is captured, and the development inhibitor continues to diffuse, thereby controlling the effect from spreading too much in the plane direction. This prevents uneven development. Further, when the ADL is provided on the back side of the support, it is possible to capture the development inhibitor released into the developer and prevent contamination of the developer. In both the first and second cases, the silver halide grains used in ADL are fine grains, preferably having an average grain size of 0.2 microns or less, and are silver iodobromide or silver bromide, which are difficult to dissolve in color development. I like it. Preferably, the coating is used at a coating rate of 0.19 to 5 y/m. The inventors discovered that if the action range of the development inhibitor released during development in the plane direction is too wide, it may cause "uneven development".
That is, it has been found that unnatural hue unevenness occurs in minute images like Mackie lines. This is improved by the installation of the ADL according to the invention. According to the present invention, not only the occurrence of "uneven development" which is the first object of the present invention is prevented, but also the uniformity of the development process is significantly improved as a result.

This is because the release of organic development inhibitors into the developer solution, which is a decisive factor in the contamination of the developer solution, is prevented. Another feature of the present invention is high temperature development.

High temperature development according to the present invention refers to development at temperatures above about 30°C, preferably from about 30°C to 40°C, and even at temperatures of 60°C or higher. Tokuko Sho 45-288
No. 36 and French Patent No. 2,132,675, the iodide ions released during development are extremely easy to convert silver chloride in silver halide grains in the commonly used adjacent layer into silver bromide through a conversion reaction. It is known that it is trapped and normally difficult to be released into the developing solution. In particular, at high temperatures, the conversion reaction is accelerated and almost no release into the developing solution occurs. A monothio-type leaving group as shown in U.S. Pat. No. 3,227,554 also chemically adsorbs with the commonly used silver halide in the adjacent layer to form silver mercaptide, and at high temperatures this chemical adsorption is promoted and transferred to the developer. emissions tend to decrease. However, in general, couplers for interlayer color correction, especially couplers with a leaving group represented by the general formula [a], have a weaker adsorption power to silver halide used in the light-sensitive emulsion layer than iodo ions or mercapto compounds, and can be developed at high temperatures. Instead, it becomes more easily diffused and released into the developer. In this case, the effect of installing the adsorbent colloid layer (ADL) according to the present invention is particularly noticeable. The couplers used in the present invention are usefully 4-equivalent couplers and 2-equivalent couplers, particularly couplers represented by the following general formulas (1V1, (V1 and 3).

General formula [] In the formula, R3 is an alkyl group selected from primary, secondary and tertiary groups (e.g. methyl, propyl, n-
butyl, tert-butyl, hexyl, 2-hydroxyethyl, 2-phenylethyl, pentadecyl, etc.) alkoxy groups (e.g. methoxy, ethoxy, benzyloxy), aryloxy groups (e.g. phenoxy), aryl groups (e.g. phenyl, 2,4 -di-Tert-phenyl, etc.), heterocyclic residues (quinolinyl, pyridyl,
benzofuranyl, oxazolyl, etc.), amino groups (e.g. methylamino, diethylamino, phenylaminotolylamino, 4-(3-sulfobenzamino)anilino,
2-chloro-5-acylaminoanilino, 2-chloro-
5-alkoxycarbonylanilino, 2-trifluoromethylphenylamino, etc.), acylamino groups (e.g. ethylcarboxamide, alkylcarboxamide, arylcarboxamide, benzothiazolylcarboxamide, sulfamide, heterocyclic sulfamide, etc.), ureido group (For example, alkyl ureido, aryl ureido, heterocyclic ureido, etc.)

R4 is an aryl group (e.g. naphthyl, phenyl, 2,4
, 6-trichlorophenyl, 2-chloro-4,6-dimethylphenyl, 2,6-dichloro-4-methoxyphenyl, 4-methylphenyl, 4-acylaminophenyl,
4-alkylaminophenyl, 4-trifluoromethylphenyl, 3,5-dipromophenyl, etc.), heterocyclic groups (e.g. benzofuranylbenzothiazolyl, quinolinyl, etc.), primary, secondary, It represents an alkyl group selected from tertiary groups (eg, methyl, ethyl, t-butyl, benzyl, etc.). Z1 is a group from which a hydrogen atom can be separated during color development, such as a thiocyano group, an acyloxy group, an aryloxy group, an alkoxy group, an alkoxycarbonyloxy group, an aryloxycarbonyl group, an oxy group, an aryloxycarbonyloxy group, and a disubstituted amino group. group, acyl (sulfonyl, carbonyl) amino group, arylazo group, heterocyclic azo group, etc., for example, as described in U.S. Pat.
, No. 419,391, No. 3,252,924, No. 3,
No. 311,476, No. 3,227,505, JP-A-4
These are groups described in No. 9-129538 and No. 50-13041. General formula [V] In the formula, R5 is an alkyl group selected from primary, secondary and tertiary alkyl groups (e.g. tert-butyl, 1,1
- dimethyl propyl, 1,1-dimethyl-1-methoxyphenoxymethyl, etc.) aryl groups (e.g. phenyl, alkyl phenyl, 2-methyl phenyl, 3
-Octadecylphenyl, alkoxyphenyl, 2-
Methoxyphenyl, 4-methoxyphenyl, halofenyl, 2-chloro-5-alkylcarbamide phenyl, 2-chloro-5-[α-(2,4-di-Tert
-aminophenoxy)butyramide] phenyl, 2-
methoxy-5-alkylamidophenyl, 2-chloro-5-sulfoamidophenyl, etc.), R6 is a phenyl group (e.g. 2-chlorophenyl, 2-halo-5
-alkylamide phenyl, 2-chloro-5-[α-
(2,4-Di-Tert-amylphenoxy)acetamide]phenyl, 2-chloro-5-(4-methylphenylsulfamide)phenyl, 2-methoxy-5-
(2,4-di-Tert-amylphenoxy)acetamidophenyl, etc.).

Z2 is a group from which a hydrogen atom can be separated during color development, such as a halogen atom, especially a fluorine atom, an acyloxy group, an aryloxy group, a carbonyloxy group of a hair aromatic ring, a sulfimide group, an alkylsulfoxy group, an arylsulfoxy group, Represents a phthalimide group, dioxoimidazolidinyl group, dioxoxazolidinyl group, dioxothiazolidinyl group, dioxomorpholino group, etc., and includes, for example, U.S. Pat. Nos. 3,227,550 and 3,253,924.
No. 3,277,155, No. 3,265,506, No. 3,408,194, No. 3,415,652,
French Patent No. 1,411,384, British Patent No. 944,49
No. 0, No. 1,040,710, No. 1,118,028
No., German Published Patent (0LS) No. 2,057,941,
These are described in JP-A No. 2,163,812, JP-A No. 2,213,461, JP-A No. 2,219,917, and JP-A-49-122335. General 2 [] General formula [] 0H In the formula, R7 is a substituent used in a cyan coupler. For example, carbamyl groups (e.g. alkylcarbamyl, phenyl)
sulfamyl groups (e.g. alkylsulfamyl, arylsulfamyl, phenylsulfamyl, heterocyclic sulfamyl, etc.) alkoxy Represents a carbonyl group, aryloxycarbonyl group, etc.

R8 represents an alkyl group, an aryl group, a heterocyclic group, an amino group, a carboxamide group (eg, an alkylcarboxamide, an arylcarboxamide, etc.), a sulfonamide group, a sulfamyl group, a carbamyl group, or the like. R,,RlO
Rll represents the group defined for R8, a halogen atom, an alkoxy group, or the like. Z3 is a group from which a hydrogen atom can be separated during color development, such as a halogen atom, a thiocyano group, a cycloimide group (e.g. maleimide, succinimide,
, 2-dicarboximide, etc.) represents an arylazo group, a heterocyclic azo group, etc. In order to make the coupler resistant to diffusion, a group containing a hydrophobic residue having 8 to 32 carbon atoms is introduced into the coupler molecule.

Such residues are called ballast groups. The ballast group can be directly attached to the coupler skeleton structure, or may include an imino bond, an ether bond, a carbonamide bond, a sulfonamide bond,
They are linked via a ureido bond, ester bond, imide bond, carbamoyl bond, sulfamoyl bond, etc. Some examples of ballast groups are as described in the coupler examples of the invention. Specific examples of the ballast group are as follows. (1) Alkyl group and alkenyl group v≦64≦IlVijJ Prefecture Todoroki 88'ゞ1166
00()Alkoxyalkyl group, for example, Japanese Patent Publication No. 39-27
(4) Alkylaryl groups (acylamidoalkyl groups such as those described in U.S. Pat. No. 3,337,344 and U.S. Pat. No. 3,418)
For example, -CH-
CH=CH-Cl6H33 (4) An alkyl group substituted with an ester group, for example, -CH-Cl6H33ω) (7) An alkyl group substituted with an aryl group or a heterocyclic group, for example, (to) an aryloxyalkoxycarbonyl group Substituted Aryl Group Next, typical examples of materials used in the present invention are shown.

It is not limited to this. (Yellow coupler) (1) α-{3-[α-( 2,4-di-1 Tert
-Amylphenoxy)butyramide]benzoyl}-2
-methoxyacetanilide (2) α-acetoxy-α-
3-[γ-(2,4-di-tert-alumiphenoxy)butyramide]benzoyl 2-methoxyacetanilide (3) N-(4-anisoylacetamidobenzenesulfonyl)-N-benzyl-N-toluidine (4) α -(2,4-dioxo-5,5dimethyloxazolidinyl)α-pivaloyl-2-chloro5-{
α(2,4-di-Tert-amylphenoxy)butyramide}acetanilide (5)α-(4-carboxyphenoxy)-α-pivaloyl-2-chloro-
5{α(2,4-di-Tert-amylphenoxy)butyramide}acetanilide (6)α{3(1-benzyl-2,4-dioxo)hydantoin}-α-bivaloyl-2-chloro-5{α-( 2,4-Ji Ter
t-amylphenoxy)butyramide}acetanilide (7) α-(4-methoxybenzoyl)-α-(3
,5-dioxomorpholino)-5-{γ-(2,4-di-tert-amylphenoxy)butyramide}-2
-Chloroacetanilide (magenta coupler) (8) 1-(2,4,6-trichlorophenyl)-3-[3-(2,4-di-Tert-amylphenoxyacetamide)benzamide]-5-pyrazolone (9) 1-(2,4,6-trichlorophenyl)-
3-{3[α-(2,4-di-Tert-amylphenoxy)acetamide]benzamide}-4-acetoxy-5-pyrazolone Qll-(2,4,6-trichlorophenyl)-3-tridecylamide- 4-(4-hydroxyphenyl)azo-5-pyrazolone C [1]
1-(2,4,6-trichlorophenyl)-3-[(
2-chloro-5-tridecanoylamino)anilino]-
5-Pyrazolone Q Co 1-(2,4,6-trichlorophenyl)-3-(2-chloro-5-tetradecyloxycarbonyl)anilino-4-(1-naphthylazo)-5-pyrazolone QEl(2, 4-dichloro-6-methoxyphenyl)-3[(2-chloro-
5-tridecanoylamino)anilino]-4-benzyloxycarbonyloxy-5-pyrazolone 1-
(2,4,6-trichlorophenyl)-3-[3-
{(2,4-di-Tert-amylphenoxy)acetamide}benzamide]-4-piperidino-5-pyrazolone Q$ 1-(2,4,6-trichlorophenyl)-3-[2-chloro-5-{ α-(2,4-di-T
ertamylphenoxy)butyramide}alinino]-
4-N-phthalimido-5-pyrazolone (16) 1-
(2,4,6-trichlorophenyl)-3-(2-chloro-5-tetradecylaminoanilino-4-(3-methyl-4-hydroxyphenylazo)-5-pyrazolone (cyan coupler) 5) 1-Hydroxy-N-[γ(2,4-di-Te
rt-amylphenoxypropyl)]-2-naphthamide 1-hydroxy-4-[2-hexyldecyloxycarbonyl)phenylazo]-2-[N-(1-naphthyl)]naphthamide 011-hydroxy-4- Chloro-N[α-(2,4-di-Tert-amylphenoxy)butyl]-2-naphthamide 1205-methyl-4
,6-dichloro-2-[α-(3-n-pentadecylphenoxy)butylamino]phenolC2Dl-hydroxy-4-(2-ethyloxycarbonylphenylazo)-N-(2-ethylamyl)- 2-Naphthamide (
Uncolored coupler for interlayer color correction) α-benzoyl-α-(2-benzothiazolylthio)4-[N-(γ-phenylpropyl)-N-(
4-triyl)sulfamyl]acetanilide Q3l-
14-[γ-(2,4-di-Tert-amylphenoxybutyramide)phenyl]-3-piperidinyl-4
-(1-phenyl-5-tetrazolylthio)-5 pyrazolone (24) 1-(2,4,6-trichlorophenyl)-3-{4-[α-(2,4-di-Tert-amylphenoxy)butyramide ]Anilino}14-(1
-phenyl-5-tetrazolylthio)-5-pyrazone C95) 1-[4-{α-(2,4-di-Tert-
amylphenoxy)acetamide}phenyl]-3-methyl-4-(5-1- or 6-bromo-1-benztriazolyl)-5-pyrazolone (1) 5-methoxy-2-[
α-(3-n-pentadecylphenoxy)butyramide]-4-(1-phenyl-5-tetrazolylthio)phenol (27)N-{α-(2,4-di-Tert-
amylphenoxy) aritethyl}-ω-(1-phenyl-5-tetrazolylthio)-m-aminoacetophenone (sub)α-vivaloyl-α-(5- or 6-bromo-1-
benztriazolyl)-5-[α-(2,4-di-T
ert-amylphenoxy)propionamide]-2-
Chloro-acetanilide (support) α-(4-methonacybenzoyl)-α-(5- or 6-nitro-1-benztriazolyl)-5-{γ-(2,4-di-t-amylphenoxy) butyramide}-2-chloroacetanilide (to) α-(4-stearyloxybenzoyl)-α-
(5- or 6-bromo-1-benztriazolyl)-
2-Methoxyacetanilide (301-hydroxy-4
-(1-phenyltetrazolylthio)-N-{(
2-chloro-5-hexadecyloxy)-phenyl}-
2-naphthamide (to) 1-benzyl-3-(2-chloro-5-tetradecanamide-anilino)-4-(5
1- or 6-methyl-1-benztriazolyl)-5-
Pyrazolone (to) 1-[4-{α-(2,4-di-t)
-amylphenoxy)acetamido}phenyl]-3-ethoxy-4-(5- or 6-bromo-1-benztriazolyl)-5-pyrazolone The couplers according to the invention contain water-soluble groups, such as carboxyl groups, hydroxy groups, They are broadly divided into Fischia type 1 couplers, which have sulfo groups, etc., and hydrophobic couplers.

Conventionally known methods of adding or dispersing couplers to emulsions and methods of adding them to gelatin or hydrophilic colloids are applicable. For example, high-boiling organic solvents - dibutyl phthalate, tricresyl phosphate, fatty oils that are liquid at room temperature,
A method of mixing and dispersing wax, higher fatty acids and their esters with couplers, for example, US Patent No. 2,304,9
No. 39, No. 2,322,027, etc., a method of mixing and dispersing the coupler with a low-boiling organic solvent or a water-soluble organic solvent, and a method of dispersing the coupler in combination with a high-boiling organic solvent. methods, such as U.S. Patent 2,80
No. 1,170, No. 2,801,171, No. 2,949
, No. 360, when the coupler itself has a sufficiently low melting point (for example, 75°C or less), it can be used alone or in combination with other couplers, such as a forced lard coupler and an uncolored coupler. For example, the method described in German Patent No. 1,143,707 is applied.

Dispersion aids include commonly used anionic surfactants (e.g. sodium alkylbenzene sulfonate, sodium dioctyl sulfosuccinate, sodium dodecyl sulfate, sodium alkylnaphthalene sulfonate,
Fishery type 1 couplers, etc.), amphoteric surfactants (eg, N-tetradecyl-N,N-dipolyethylene-α-betaine, etc.), and nonionic surfactants (eg, sorbitan monolaurate, etc.) are used.

The coupler is usually used in a molar amount of 1/100 to 1/2 times the amount of silver halide. The interlayer color correction coupler may be used alone or mixed with other couplers, and is used in an amount of 50 mol % or less, preferably 20 mol % or less, based on the total amount of the coupler used in the light-sensitive material according to the present invention. The silver halide emulsion used in the light-sensitive emulsion layer in the present invention includes not only silver chloride and silver bromide but also mixed silver halides such as silver chlorobromide, silver iodobromide, silver chloroiodobromide, etc., in addition to silver chloride and silver bromide. They are finely dispersed in hydrophilic polymers such as, and range from uniform particle size to wide particle size distribution, and the average particle size ranges from about 0.1 micron to about 3 microns.
Those having a wide range of dispersion down to microns are selected depending on the intended use of the photosensitive material.

These silver halide emulsions can be prepared, for example, by a mixing method such as a single or double jet method or a controlled double jet method, and further by a thermal formation method such as an ammonia method, a neutral method, an acid method, or the like. The silver halide emulsion used in the light-sensitive emulsion layer in the present invention is produced by a commonly used chemical sensitization method.

For example, U.S. Patent Nos. 2,399,083 and 2,597
, 856 and 2,597,915; reduction sensitization as described in U.S. Pat. No. 2,487,850 and 2,521,925; and U.S. Pat. Nos. 1,623,499 and 2,410.
, 689, and U.S. Pat. Nos. 2,448,060 and 2,566,245.
The sensitization method using different metal ions, or the sensitization method using a combination thereof, as described in No. 2, No. 2,566,263, can be applied. Spectral sensitization methods normally used for color light-sensitive materials can also be applied.

In addition, commonly used stabilizers such as 4-hydroxy-1,3,3a,7-tetrazaindene derivatives, antifoggants such as mercapto compounds and benzotriazole derivatives, coating aids, curing agents, and wetting agents. and sensitizers, such as U.S. Pat. No. 2,271,623;
Onium derivatives such as quaternary ammonium described in No. 88,226 and No. 2,234,864, and US Pat.
, 708, 16, No. 2, No. 2,531,832, No. 2
, No. 533,990, No. 3,210,191, No. 3,
The polyalkylene oxide derivatives described in No. 158,484 can be included. In addition, a filter layer, a mordant dyeing layer, and a colored layer containing a hydrophobic dye can be included as an anti-irradiation dye or as a layer component of the color light-sensitive material according to the present invention.
The photosensitive emulsion used in the present invention is coated on various supports.

For example, cellulose acetate film, polyethylene terephthalate film, polyethylene film, polypropylene film, glass dry plate, baryta paper, resin laminated paper, synthetic paper, etc. are used. The photographic light-sensitive material of the present invention is developed using a commonly used color developer containing a paraphelenediamine derivative, a para-aminophenol derivative, or the like as a color developing agent.

Suitable paraphenylenediamine derivatives are, for example, p-amino-N-ethyl-N-β-(methanesulfamidoethyl)-m-toluidine sesquisulfate monohydrate, diethylamino-p-phenylenediamine sesquisulfide, p- These include amino-N,N-diethyl-m-toluidine hydrochloride, p-amino-N-ethyl-N-β-hydroxyethylaniline sesquisulfate monohydrate, and the like. Also, known color negative photosensitive materials, color negative or positive photosensitive materials for movies, color paper, and developers for instant color photosensitive materials can be used.
．． Written by GOrdOn “The British Journa”
lOfPhOtOgraphy”November 15, 1954
Articles published on 558 pages or more, published on September 9, 1955, less than 440 pages, published on January 6, 1956, less than 2 pages, etc.
．． Written by Horwitz, published in the same magazine on April 22, 1960 2
12 pages and below, E. Written by Gehret, published on March 4, 1960, page 122 and below, published on May 7, 1965, page 396
Pages below, J. Written by Meech, published on April 3, 1959, page 182 and below, and West German Patent Publication Specification (0LS) 2
, 238,051 and the like is used. Next, examples will be shown. Although the present invention is not limited thereto, aspects of the present invention and
Other purposes may be understood. Example 1 On a transparent cellulose triacetate film support, as shown in FIG. 1, the first layer, second layer, third layer, fourth layer,
and the fifth layer were applied in this order to obtain sample A.

The composition and preparation of the coating liquid used for each layer are as follows. First layer (BL): Silver iodobromide emulsion 11Cp (silver content;
0.52 mol, iodide content: 6 mol%), 100y of coupler (4) and 100y of dibutyl phthalate.
Sodium dodecylbenzenesulfonate is dissolved in 200 d of ethyl acetate and dissolved in 1 Kp of 10% gelatin solution.
600 f of emulsion 1 obtained by emulsifying and dispersing using g! was added and applied.

The silver coating amount of the first layer was 0.6f1/M2. Second layer (GL): Silver iodobromide emulsion 1K prepared by a conventional method!
．． (silver content: 0.6 mol, iodine content: 6 mol%),
2 x 10-4 moles of sensitizing dye 1 and 6 x 10-4 moles of sensitizing dye
Spectral sensitization was performed using 5 mol.

60g of color (8) and 40f1 of coupler (25) were combined with 100d of tricresyl phosphate and 2g of ethyl acetate.
007n1 and emulsified and dispersed in 10% gelatin solution 1KP using sodium dodecylbenzenesulfonate 4f1, 600y of emulsion H was added to the above emulsion. The silver coverage of the second layer was 0.99/M2. Third
Layer (ADL): Ultrafine grain silver iodobromide emulsion 1K2 (silver amount; 0
．． 5 mol, iodine content: 2 mol%, average particle size: 0.
05μ) was applied to a film thickness of 3μ (silver coating amount: 2.1y/M2).

4th layer (RL): 1 KP of silver iodobromide emulsion (same as the 1st layer) and 4 sensitizing dyes.
Spectral sensitization was carried out with 10-5 moles of X and 1 x 10-5 moles of sensitizing element.

This is 100f of coupler (17)! Emulsion 4509 obtained in the same manner as the emulsion was added. The amount of silver applied in the 4th layer is 1.7f! /M2. Fifth layer (PL): Gelatin protective layer In addition to the above composition, each coating solution contains appropriate amounts of sodium poly-vinylbenzenesulfonate as a thickener, sodium dodecylbenzenesulfonate as a surfactant, and a gelatin hardener. added.

Materials used to make sample A; Sensitizing dye 1; Anthitro 92-ethyl-5,5'-dichloro-3,
32-disulfopropyloxacarbocyanine sodium salt sensitizing dye; amphitrow 5,6,5',62-tetrachloro-1,
12-diethyl-3,32-disulfopropoxyethoxyethylimidazolocarbocyanine hydroxide sodium salt sensitizing dye; amphitrow 5,52-dichloro-3,3'-disulfopropyl-9-ethylthiacarbocyanine hydroxide Pyridinium salt sensitizing dye; a third layer of anthithro 9-ethyl-3,32-di-(3-sulfopropyl)-4,5,4',52-dibenzothiacarbocyanine hydroxide triethylamine salt Sample A was applied in the same manner. Sample B was obtained in the same manner as Sample A except that the thickness of the gelatin layer did not contain an emulsion.

After exposing samples A and B in stages with a green light source,
Apply uniform exposure with a red light source and perform the following processing step (1)
Development processing was carried out at 38°C.

1. Color development 3 minutes 15 seconds 2. Bleach 6 minutes 30 seconds 3. Wash with water 3 minutes 15 seconds 4. Fixation 6 minutes 30 seconds 5. Wash with water 3 minutes 15 seconds 6. Stable 3 minutes 15 seconds The treatment liquid composition used in each step was as follows.

Color developer Sodium nitrilotriacetate 1.0g Sodium sulfite 4.0f! Sodium carbonate 30.0g Potassium bromide
1.49 Hydroxylamine sulfate 2.494-(N-ethyl-N
-βhydroxyethylamino)-2-methyl-aniline sulfate 4.59 in water
1e Bleach liquid ammonium bromide 160.0f! Ammonia water (28%) 25.0d Ethylenediamine monotetraacetic acid sodium iron salt 13
0f! Glacial acetic acid 14d Water 1e Fixer Sodium tetrapolyphosphate 2.0f! Sodium sulfite 4.0f! Ammonium thiosulfate (70%) 175.0ml Sodium bisulfite 4.69 in water
1e Stabilized liquid formalin (40%)
8.0d with water
11 Sample A obtained by developing as described above,
The red light transmission density (curves 1 and 3) and the green light transmission density (curves 2 and 4) of B were measured and compared.

FIG. 4 shows the measurement results for sample A and FIG. 5 shows the measurement results for sample B. In Sample B, the green light density increases with the exposure amount, and the red light density decreases accordingly. On the other hand, in sample A having the ADL of the present invention, the green light density is the same as sample B, but no decrease in red light density is observed. from now,
In sample B, 5-bromobenztriazole is generated from the coupler 25 in the second layer during color development, and diffuses into the fourth layer to suppress the development of the fourth layer, but in sample A, the third It can be seen that in the layer (ADL) the 5-bromobenztriazole is trapped and substantially prevented from diffusing into the fourth layer, thus achieving the purpose of the present invention. On the other hand, each of Samples A and B was uniformly exposed to light using a red light source under the same conditions as described above, and was further exposed to 500% light using a green light source.
A line exposure of micron width x 10 mm length was given.

This was developed under the following conditions A, d, and c. a・
...at 24°C for 15 minutesb...at 30°C for 7 minutesc...at 38°C for 4 minutes Regarding sample B, bl::. Only in the strips developed under condition c, uneven development of purple to magenta colors occurred around the blue image.

However, with respect to sample A, uneven development did not occur in any case. Example 2 A multilayer color photosensitive material E as shown in FIG. 3 was prepared on a cellulose triacetate support, consisting of each layer having the composition shown below.

1st layer: Antihalation layer (AHL) Gelatin layer containing black colloidal silver 2nd layer: Intermediate layer (ML) Gelatin layer containing 2,5-di-t-octylhydroquinone emulsified dispersion 3rd layer: 1st red Sensitive emulsion layer (RL,) Silver iodobromide emulsion (8 mol% iodine) ... Silver coating amount 1.29/M2 Sensitizing dye 1 (as shown in Example 1) ... ...6 x 10-5 mol sensitizing dye (as shown in Example 1) per mol silver...1.5 x 10-5 mol coupler (17) per mol silver... ...0.09 mol coupler (18) for 1 mol of silver 0.02 mol for 1 mol of silver 4th layer: 2nd layer
Red-sensitive emulsion layer (RL,) Silver iodobromide emulsion (8 mol% iodine)...Silver coating amount 1.19/M2
Sensitizing dye 1 3 x 10-5 mol sensitizing dye per 1 mol silver 〃 1.2 x 10-5 mol coupler (30
) 〃 0.02 mole capra one (18) 〃
0.06 molar coupler (17)
0.08 mol 5th layer: Same as middle layer (ML) 2nd layer.

6th layer: 1st green-sensitive emulsion layer (GLl) Silver iodobromide emulsion (8 mol% iodine) ... Silver coating amount 1.4 f1/M
2 Sensitizing dye (as shown in Example 1)...Silver 1
3 x 10-5 mole per mole sensitizing dye (as shown in Example 1)...1 x 10-5 mole coupler (8) per mole silver 0.05 mole coupler (30) per mole silver ) 〃 0.002 mol coupler (31) 〃 0.001 mol 7th layer: Second green-sensitive emulsion layer (GL2) Silver iodobromide emulsion (6 mol% iodine) Silver coating amount 1.59/M2 sensitizing dye 2.5 x 10-5 moles of sensitizing dye per mole of silver
〃 0.8X10-5 molar coupler (8)
〃 0.004 molar coupler (16)
〃 0.02 molar coupler (31) 〃
0.0003 mol 8th layer: (YFL) A gelatin layer containing an emulsified dispersion of yellow colloidal silver and 2,5-di-t-octylhydroquinone in an aqueous gelatin solution. 9th layer: 1st blue-sensitive emulsion layer (BLl). Silver bromide emulsion (6 mol% iodine) Silver coating amount 1f! /M2 coupler (4) 0.25 mol coupler (30) 0.01 mol per mol of silver 10th layer: 2nd
Blue-sensitive emulsion layer (BL2) Silver iodobromide emulsion (6 mol % iodine) Silver coating amount 1.1 V/M2 coupler (4) 0.06 mol coupler (30) per 1 mol silver 0.002 mol No. 11 Layer: A
DL: Ultra-fine grain silver iodobromide emulsion 1Kp (silver content: 0.6 mol, iodine content: 14 mol%, average grain size: 0.03μ
) was applied to a film thickness of 3 μm (silver coating amount: 2.3 f!/M2).

12th layer: Protective layer (PL) Gelatin layer containing polymethyl methacrylate particles (diameter approximately 1.5μ) In addition to the above composition, appropriate amounts of gelatin hardener, surfactant, and thickener were added to each layer. .

Sample F was obtained in the same manner as Sample E except that the 11th layer of Sample E was a gelatin layer containing no silver halide.

Samples E and F were cut to a width of 351 gt, uniformly exposed to white light, and subjected to treatment (1).

In sample F, as the amount of processing increased, the red light density, green light density, and blue light density decreased significantly.
It was found that Sample E, which has the ADL of the present invention, showed significantly less decrease in concentration and achieved the object of the present invention. Example 3 On the back side of the cellulose triacetate film support of Sample F obtained in Example 3, particles having an average particle size of 0.15
ADL containing micron silver bromide particles with a silver coverage of 5.59
/M2 to obtain sample G.

According to Example 2, the width is 351i! It was cut into 1-inch pieces, uniformly exposed to white light, and subjected to treatment (1). As the amount of processing increased, the color density decreased, but compared to sample F, sample G showed a smaller degree of decrease. Example 4 ADL was coated on a cellulose triacetate film support using the same coating solution as used for sample A in Example 1.
, BL, GL, RL, and PL layers were provided in this order to prepare sample H.

According to Example 1, after uniform exposure with a red light source, line exposure was given with a green light source. ``Development unevenness'' obtained by developing under the conditions (C)0) above was significantly smaller in Sample H than in Sample B. The present invention is applicable to all color photosensitive materials using ICC-couplers. There will be.

It is particularly useful for color photographic materials that require high fidelity in color reproduction, such as color negative materials, color reversal materials, color transparent positive materials, and color papers. It is also useful for color X-ray photosensitive materials, color microphotosensitive materials, etc. when uniformity of development finish quality or contamination of the developer is considered a problem. Next, preferred embodiments of the present invention will be illustrated.

(1) In the claims, RL, GL<! :． B
The photosensitive emulsion layer unit consists of L photosensitive emulsion layer units, and an ultrafine grain emulsion layer having a grain size of 0.2 microns or less is provided on each layer. (
2) A coupler represented by general formula [1] is used as the ICC coupler.

(3) General formulas [1] and [1a] as ICC couplers
We use a coupler represented by and.

(4) In (1), the general formula [
1] is used.

(5) In (1), couplers represented by general formulas [1] and [1a] are used as ICC-couplers. (6) In the claims, the photosensitive emulsion layer unit is composed of RL, GL, and BL, and the ADL is provided in one layer of colloid yellow or in close proximity to the FL.

(7) In the claims, the ADL is coated with an emulsion containing ultrafine silver iodomonobromide or silver bromide grains having an average grain size of less than 0.1 micrometer in a silver amount of 0.1 to 5y/Mr. use (8) It consists of a photosensitive emulsion layer unit of RL, GL and BL, and the ADL is provided below these, especially above the AHL.

(9) In the claims, the ADL also serves as a protective layer.

AO) In (9), an ultrafine emulsion with an average particle size of 0.1 micron or less and a polymer latex or colloidal silica are used together in ADL.

In the scope of the (self) claims, it is also used as ADL8FL. (Self) In the claims, ultrafine particles having an average grain size of 0.2 microns or less are present in a light-sensitive emulsion layer above or below a light-sensitive emulsion layer containing an ICC-coupler or an organic accelerator for interlayer effect. Mix the emulsion and use it also as ADL.

(Own) In the scope of the claims, development is performed at a temperature of 30° C. or higher to form a color image.

Claims (1)

[Scope of Claims] 1. A photosensitive emulsion layer containing an interlayer color correction coupler represented by the following general formula [I] and at least one coupler selected from yellow couplers, magenta couplers, and cyan couplers on a support. and adsorption of an organic development inhibiting compound released from the interlayer color correction coupler containing silver halide grains that are not substantially developed by color development above the emulsion layer or between the emulsion layer and the support. A color image forming method characterized by developing a multilayer color photosensitive material having a colloid layer at a high temperature of 30° C. or higher. General formula [I] Cp-Z In the formula, Cp represents a coupler residue that undergoes a coupling reaction with the oxidized product of a primary aromatic amine color developer, and Z represents a 1-triazole ring, a 1-diazole ring, or a 2-benzotriazole ring. Heterocyclic group with a ring, arylmonothio group, tetrazolethio group, triazinylthio group, triazolithio group, oxazolylthio group, imidazolylthio group, oxadiazolylthio group, thiadiazolylthio group, benzothiazolylthio group, pyrimidylthio group group or pyridinylthio group.