JPS6374058A - Silver halide color photographic sensitive material with regulated pka of coupler - Google Patents

Abstract

PURPOSE:To obtain the titled material having coloring stability with respect to a change in pH at the time of developing, by incorporating a pyrazolotriazole magenta coupler having a specific acid dissociation constant (pKa) and a DIR coupler which has a specific pKa and is capable of releasing a development restrainer or its precursor by reacting with an oxidant of a developing agent to the titled material. CONSTITUTION:The titled material comprises the pyrazolotriazole magenta coupler having pKa of 8.0-10.0 and the DIR coupler which has pKa of 7.0-9.0 and is capable of releasing the development restrainer or its precursor by reacting with the oxidant of the developing agent. And, the titled material is color photographically processed to obtain a dye image, after exposing said material. Thus, the titled material having an improved color-reproducibility and capable of obtaining a stabilized coloring with respect of the change of processing condition, especially, the change of pH at the time of development, is obtd.

Description

[Detailed Description of the Invention] [Industrial Field of Application] The present invention has excellent color reproducibility and J! [! The present invention relates to a silver halide color photographic light-sensitive material that can provide stable color density against fluctuations in conditions, especially fluctuations in pl+.

[Prior art]

In recent years, there has been a demand for higher image quality in color photographs for amateur use, and there is a particularly strong need for improved color reproducibility.

As a means of improving color reproducibility, research has been actively conducted on spectral sensitivity controllers, introduction of diffusive DIR couplers, and improvement of couplers, among others.
No. 59-171956, No. 60-98434,
IJ azole-based magenta couplers (see in Japanese Patent No. 61-120152 and Japanese Patent No. 61-120154) are characterized by no secondary absorption, and are attracting attention as a technology for improving color reproducibility.

In addition, D releases a diffusive inhibitor during development and exhibits a development effect (IIE) between silver halide emulsion layers with different color sensitivities.
Techniques for improving color reproducibility using IR couplers are also attracting attention. Such techniques can be found in Japanese Patent Application Laid-Open No. 59-131934, Japanese Patent Application No. 60-93411, etc.

On the other hand, competition for quick processing services for color photographs in DPE finishing has intensified, and color prints that previously took several days to be delivered to users are now being delivered within a day or even within a few hours.

For this reason, there is no time for reprinting color prints, etc., and the problem of deterioration in pre-21 quality has become apparent, and there is a strong demand for color photographic materials that can provide stable color development even against fluctuations in color development processing.

However, the Virazolotosoazole type Magenta Cabra and the old R
Kabra significantly lowers the stability of color density in color development, and improvements have been desired.

[Purpose of the invention]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a silver halide color photographic material which has excellent color reproducibility and can provide stable color development against fluctuations in processing conditions, particularly fluctuations in I+ during development.

[Structure of the invention]

The object of the present invention is to have an acid dissociation constant (pKa) of 8.0 to 10.
Pyrazolotriazole magenta coupler having a pKa of 7.0≦pKa≦9.0 and having a pKa of 7.0 to 9, which reacts with an oxidized form of a developing agent to release a development inhibitor or its precursor. This is achieved by a silver halide color photographic light-sensitive material characterized by containing a DIR coupler of .0.

The pKa of the pyrazolotriazole magenta cabra according to the present invention is 8.0 to 10.0, but preferably 8.5.
≦pKa≦9,9, particularly preferably 9.0≦pKa≦9
．． It is 8.

The pKa of DIR Kabra, which reacts with the oxidized form of the developing agent to release the development inhibitor or its precursor, is O-9.0, but preferably 7.2≦pt (a≦
8.8, particularly preferably 7.4≦pKa≦8.6.

Next, the magenta color forming coupler and [)I in the present invention
A method for measuring the pKa (acid dissociation constant) of an R coupler will be described.

Generally, the pKa of Kabra is J, C, S, Perkin
ll −809(19)3) and same < 1766
(1973), J, Pbot, Sci, *22.49
(1974) E, Pelizzrtti (3N,
rtalia)yG, 5aini(Toino Uni
v,) and J,Pbot,Sci,, 13,248
(1965) B, P. Brand (ICI), it has been determined by spectrophotometry or neutralization drop using the appropriate solution III & (water-organic solvent mixture).

The pKa of Kabra in the present invention is a value measured by spectrophotometry. That is, since there is generally a difference in absorbance between Kabra and the coupler anion, the pH that gives the inflection point of the curve obtained by plotting the absorbance against pl+ of the coupler solution is taken as the pKa of the Kabra.

Specifically, 2-butoxyethyl 7-ol:water=
A mixed solution of 30:70 was used, and the coupler concentration was lXl.
Choose a concentration that is easy to measure, from about 0-5 to 1X10-'M.

Spectroscopic absorption measurements can be performed by adding anhydrous potassium carbonate 38/1 to the coupler solution and adjusting the pH of the solution with hydrochloric acid and potassium hydroxide.

Depending on the Kabra, there are multiple protons that can be dissociated, and multiple pKa values can be measured using the above measurement method.

The pKa value in the present invention is a measured value, among these plural pKa values, related to the 7-ionization of the coupler core that can generate a dye by a coupling reaction with an oxidized product of a color developing agent.

The pyrazolotriazole magenta cabra used in the present invention is generally represented by the following general formula (1).

In the magenta coupler represented by general formula (1), Z represents a nonmetallic atomic group necessary to form a nitrogen-containing heterocycle, and the ring formed by Z may have a substituent. .

X represents a hydrogen atom or a substituent that can be separated by reaction with an oxidized product of a color developing agent.

Moreover, R1 represents a hydrogen atom or a substituent.

Furthermore, the magenta coupler is preferably a coupler represented by the following general formula (2) or (3).

General formula (2) General formula (3) above R
Examples of the substituents represented by 3 and R2 include a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, an aryl group, a heterocyclic group, an acyl group, a sulfonyl group, a sulfinyl group, a phosphonyl group, Carbamoyl group, sul77moyl group, anano group, spiro compound residue, bridged hydrocarbon compound residue, alkoxy group, aryloxy group, heterocyclic oxy group, siloxy group, acyloxy group, carbamoyloxy group, ami7
group, 7 acylamide groups, sulfonamide group, imide group, ureido group, 7 sulfonylamide groups, 7 alkoxycarbonylamide groups, 7 aryloxycarbonylamide groups, alkoxycarbonyl group, aryloxycarbonyl group,
Examples include an alkylthio group, an arylthio group, and a heterocyclic thio group.

Examples of substituents that can be removed by reaction with the oxidized product of the color developing agent represented by Examples include groups substituted via.

Examples of groups substituted via a carbon atom include carbo (R1'
is the same as the above R, Z' is the same as the above Z,
Rz' and Rco' each represent a hydrogen atom, an a17-al group, an alkyl group, or a heterocyclic group, such as a group represented by ), a hydroxymethyl group, and a triphenylmethyl group.

I! ! Examples of groups substituted through diatomic atoms include alkoxy groups, aryloxy groups, heterocyclic oxy groups, acyloxy groups, sulfonyloxy groups, alkoxycarbonyloxy groups, aryloxycarbonyloxy groups, alkyloxalyloxy groups, and alkoxyoxalyloxy groups. Examples include groups.

R1 represents a ru group, an aryl group, a heterocyclic group, a sulfamoyl group, a carbamoyl group, an anru group, a sulfonyl group, an aryloxycarbonyl group, an alphkidicarbonyl group, and R1
' and Rs' may be combined to form a heterocycle. However, R1' and R5' are not both hydrogen atoms.

Examples of the group substituted via a sulfur atom include a furkylthio group, an arylthio group, a heterocyclic thio group, and an alkyloxythiocarbonylthio group.

In the formula, R1 represents alkylene, and R2 represents an alkyl, cycloalkyl or aryl group.

The alkylene represented by R1 preferably has 2 or more carbon atoms in the straight chain portion, more preferably 3 to 6 carbon atoms, and does not matter whether the straight chain has 9 branches or not. Also, this alkylene is r! It may have an i substituent. Preferred substituents include phenyl.

Preferred specific examples of alkylene represented by R' are shown below.

Shi++3 C2115C
The alkyl group represented by tH+sR2 has one straight chain branch.

Specific examples include methyl, ethyl, propyl, 1so-propyl, butyl, 2-ethylhexyl, octyl, dodecyl, tetradecyl, hexaacyl, oftagyl, 2-hexyldecyl, and the like.

The cycloalkyl group represented by R2 preferably has 5 to 6 members, such as cyclohexyl.

The alkyl and cycloalkyl represented by R2 may have a substituent, and examples thereof include those exemplified as the substituent for R1 above.

Specific examples of the aryl represented by R2 include phenyl and naphthyl. The aryl group may have a substituent. Examples of the substituent include linear or branched alkyl, as well as those exemplified as the substituent for R1 described above.

Moreover, when there are two or more substituents, those substituents may be the same or different.

When used for negative image formation, R3 preferably satisfies the following conditions 1 and more preferably satisfies the following conditions 1 and 2 regarding the substituents on the heterocycles in general formulas (1) to (3). This is the case.

Condition 1: The root atom directly connected to the heterocycle is a carbon atom.

Condition 2: At least two hydrogen atoms are bonded to the carbon atom.

The most preferred substituent R1 on the multi-ring is represented by the following general formula (4).

General formula (4) % formula % In the formula, R12 is a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group,
Alkynyl group, aryl group, heterocyclic group, acyl group, sulfonyl group, sulfinyl group, phosphonyl group, carbamoyl group, sulf77moyl group, sia7 group, spiro compound residue, bridged hydrocarbon compound residue, alkoxy group, Aryloxy group, heterocyclic oxy group, siloxy group, acyloxy group, carbamoyloxy group, ami 7 group, acylami 7
group, sulfonamide group, imide group, ureido group, sul7
7 moyl amide groups, 7 alfkidicarbonyl amine groups, 7 aryloxycarbonyl amine groups, alkoxycarbonyl group, aryloxycarbonyl group, alkylthio group,
Represents an arylthio group or a heterocyclic thio group.

The group represented by R12 may have a substituent, and R+
Specific examples of the group represented by 2 and substituents that the group may have include specific examples of the group represented by R in the above-mentioned general formula (1) and the V substituent.

Preferred as R1□ is a hydrogen atom or an alkyl group.

The coupler was also published in the Journal of the Chemical Society.
ical 5ociety)y Perkin
) f (1977), 2047-2052, U.S. Patent No. 3,725,067, JP-A-59-99437,
No. 58-42045, No. 59-162548, No. 5
No. 9-171956, No. 60-33552, No. 60-
No. 43659, No. 60-172982 and No. 60-1
It can be synthesized by referring to No. 90779 and the like.

The couplers of the present invention are usually lXl0 per mole of silver halide.
-'mol-1 mol, preferably lXl0-2 mol-8X
A range of 10-' moles can be used.

The coupler of the present invention can also be used in combination with other types of magenta couplers.

Specific examples of compounds used in the present invention are shown below with their pKa
and Comparative Examples, and the Comparative Examples are marked with this mark.

M-3 Zero M-4 M-5 Kyo C/ M-8 C/ I 9.6 Next, the DIR cover used in the present invention will be explained.

DIR couplers are used for the purpose of improving image sharpness and image graininess by binding the oxidized product of an aromatic primary amine developer and releasing a development inhibitor or its precursor during development. .

DIR Cobra has two types: one in which the inhibitor is directly bonded to the coupling position, and the other in which the inhibitor is bonded to the coupling position via a divalent group, and the intramolecular nucleophilicity at the base circle released by the coupling reaction. Those bound in such a way that the inhibitor is released by reaction, intramolecular electron transfer reaction, etc. (timing DIR
(referred to as kaput) is included. Furthermore, inhibitors that are diffusible after release and those that are not so diffusible may be used alone or in combination depending on the purpose.

Din Kabra used in the present invention has a pKa of 7.0 to 9.
．． 0, but structurally preferred is a compound having the diffusivity represented by the following general formula (1).However, if the DIR Kabra has a quaternary pKa range, the general formula [
Even compounds not included in 1) will not cause the plant to wither.

General formula (1) In general formula (1), Ro, R2 and R3 each represent a hydrogen atom or a lower alkyl group, R1 represents a lower furkyl group, and R6 represents a hydrogen atom, an acylamide group, a sulfonamide group, or a carbamoyl group. represents an amino group or a sul7amoylamino group, n represents an integer from 1 to 4, and TI
ME represents a timing group that allows the compound represented by the above general formula [1] to react with an oxidized form of a color developing agent, thereby releasing PUG together with PIG, and PUG represents a photographically useful group. represent.

The above R1, R2, R1, R1, R3, T of general formula (1)
ll4E and PuG are detailed below.

R3 is a hydrogen atom or a lower alkyl group having 1 to 4 carbon atoms (
For example, it represents a methyl group, an ethyl group, a propyl group, a butyl group, etc.).

R2 and R are each a hydrogen atom or a lower furkyl group having 1 to 4 carbon atoms (e.g., methyl group, ethyl group, propyl group, 1so-pro and ru group, butyl group, 1so-butyl group, 5ec-butyl group, etc.) represents. This alkyl group may have a substituent such as a hydroxyl group, an alkylthio group (for example, /tilthio group), or an alfkyl dicarbonyl group (for example, a methoxycarbonyl group, an ethoxycarbonyl group, etc.).

R1 represents a lower alkyl group having carbon r&1 to 4 (eg, methyl group, ethyl group, propyl group, 1so-propyl group, butyl group, '1sO-butyl group, 5ee-butyl group, etc.). This alkyl group may be substituted with a hydroxyl group or an alkoxy group (eg, methoxy group, ethoxy group, etc.).

When R3 is other than a hydrogen atom, an aliphatic sulfonamide group having 1 to 4 carbon atoms or an acylamide 7 group is preferable, and this aliphatic group may be substituted with a 7 atoms.

Examples of timing groups represented by TIME include those that release PUC through an intramolecular nucleophilic substitution reaction as disclosed in U.S. Pat. No. 57-1
Electron s along the conjugated chain disclosed in No. 54234 etc. l! Examples include those that release PUG by IJ reaction.

Others: JP-A-57-188035, JP-A No. 58-987
No. 28, No. 59-208834, No. 60-7429, No. 60-214358, No. 60-237446,
Also included is the timing group disclosed in No. 60-237447.

TIME useful in the present invention includes the following general formula (II),
It includes, but is not limited to, CI [[], [■]].

General formula (II) In the formula, X represents a benzene ring which may have a substituent. Y represents 10-1-S-1-N-, and the compound represented by the general formula (1) ( (hereinafter referred to as 1-7toll coupler group), and is bonded to the coupling position of R
6, R7 and Rs represent a hydrogen atom, a furkyl group or an aryl group. Further, the R6 10- group is substituted with R7 at the ortho position or the rose position with respect to Y, and is bonded to the heteroatom contained in puc.

General formula (Ill) In the formula, Y%Rs and Ry each have the same meaning as in general formula (II). R6 is a hydrogen atom, an alkyl group, an aryl group, an acyl group, a sulfonyl group, an alkoxycarbonyl group, or a heterocyclic residue, and RIo is a hydrogen atom, an alkyl group, an aryl group, a heterocyclic residue, an alkoxy group, or an ami7 group. , acid amide group,
Indicates a sulfonamide group, carboxy, alkoxycarbonyl group, carbamoyl group, cyano, and the timing group is represented by Y in general formula [I] as in general formula CI+).
The coupling of the 1-7 toll coupler group represented by 6 is combined.

Next, an example of a timing group that releases PIJG by an intramolecular nucleophilic substitution reaction is shown by general formula (IV).

General formula [■] In the Nu -E formula, Nu is a nucleophilic group having an electron-rich oxygen, sulfur or nitrogen atom, and is a 1-
It is bonded to the coupling position of the 7 toll coupler group.
E is an electrophilic group having an electron-poor carbonyl group, thiocarbonyl group, phosphinyl group or thiophosphinyl group, and is bonded to the heteroelectron of PuG.

X has a steric relationship with Nu and E, and has the general formula (1
) After Nu is released and removed from the 1-7 toll coupler group represented by It is a bonding group that can

The photographically useful group PuG can be any group that is to be made available in an image-like pattern within a photographic element.

Specific examples of photographically useful groups include development inhibitors, development accelerators, whitening inhibitors, bleach accelerators, developers, fixing agents, silver halide solvents, and silver-complexing agents. , hardeners, tanning agents, toning agents, fogging agents, antifoggants, chemical or optical sensitizers, destabilizing agents, photographic dyes or their precursors, couplers (e.g., competitive couplers, color-forming couplers, development inhibitors). Dllt-coupler), etc.

The most preferred of these photographically useful groups are development inhibitors, typical examples of which are U.S. Pat.
No. 227,554, No. 3,384,657, No. 3,6
15.

No. 506, No. 3 + f No. 317, 291, No. 3,733,
201 and British Patent No. 1,450,479, etc., mercaptotetrazole group, selnotetrazole group, mercaptobenzothiazole group, selenobenzothiazole group, mercaptobenzoxazole group, selenobenzoxazole group, mercaptobenzimidazole group, Examples include selenobenzimidazole group, benzotriazole group, benzonoazole group, and iodine atom.

Next, specific examples of DIR couplers satisfying at least 7.0≦pKa≦9.0 are illustrated below along with their pKa and comparative examples. Comparative examples are marked with this mark.

:Example DIR Kabulani D2
pKaol(O2 D-41pKaol4 D-5 book II N'-N4N D-6ne pK
anl+ NIICOC112C112COOI+D -8pKa l NIICOCI+.

Infant D-10pKa D 13
pKanI+ D-14011 These DIR converters are U.S. Pat. No. 4,234.678, U.S. Pat.
No. 3,958,993, No. 4,149,886, No. 3,933,500, JP-A-57-56837, 5
1-13239, U.S. Patent No. 2,072,363, U.S. Patent No. 2,070°266, Research Disclosure 1
It can be easily synthesized by the method described in No. 12821228/981.

The diffusible DIR coupler according to the invention has a
．． It is preferable to use 0.0001 to 0.1 mol, particularly preferably 0.0001 to 0.05 mol.

In the present invention, any commonly used silver halide can be used, but silver bromide, silver iodobromide, and silver chloroiodobromide are particularly preferred. Light-sensitive silver halide emulsion The halogenated particles used in this process may be obtained by any of the acid method, neutral method, and ammonia method.The particles may be grown all at once, or may be grown after forming seed particles. The method for producing and growing good type 0 particles may be the same or different.

In the photosensitive silver halide emulsion, halide ions and silver ions may be mixed simultaneously, or one may be mixed in a liquid in which the other is present. Also, while considering the critical growth rate of silver halide crystals, mix halide ions and silver ions in a pl+ tank.

+1 AI? By this method (I), silver halide grains having a regular crystal shape and a nearly uniform grain size can be obtained. Conversion methods may be used at any step in the formation of the 88x to change the halogen composition of the particles.

Known silver halide solvents such as ammonia, thioether, thiourea, etc. can be present during the growth of photosensitive silver halide grains.

Photosensitive silver halide grains are produced through the process of grain formation and/or
Or, in the I & Lengthening process, at least one selected from cadmium salts, zinc salts, lead salts, talitum salts, iridium salts (including complex salts), romium salts (including complex salts), and iron salts (including complex salts) is used. By adding metal ions to the particles, these metal elements can be contained inside the particles and/or on the particle surfaces, and by placing them in an appropriate reducing atmosphere, reduction sensitization can be created inside the particles and/or on the particle surfaces. Can be granted.

Silver halide used in the present invention? Unnecessary soluble salts may be removed from the L agent after the growth of silver halide grains is completed, or the L agent may be left in the L agent. When removing the salts, Research Disclosure (R
esearch Disclosure (hereinafter abbreviated as RD) based on the method described in Section 1 of No. 17643.

The photosensitive silver halide grains may have a uniform silver halide composition distribution within the grain, or may be core/shell grains in which the silver halide IIL composition differs between the interior of the grain and the surface layer.

The photosensitive silver halide grains may be grains in which a latent image is mainly formed on the surface, or may be grains in which a latent image is mainly formed inside the grain.

The photosensitive silver halide grains may have regular crystal shapes such as cubes, octahedrons, and tetradecahedrons, or may have modified R11 crystal shapes such as spherical or plate shapes. good.

These particles may have a composite phase of crystalline form, or particles of various crystalline forms may be mixed.

The grain size of silver halide grains is 0.05 to 30
μ, preferably 0.1 to 20 μ can be used.

The photosensitive silver halide emulsion may have any grain size distribution, and may be an emulsion with a wide grain size distribution (referred to as a polydisperse emulsion), or an emulsion with a narrow grain size distribution (referred to as a polydisperse emulsion). It is called a dispersed emulsion.The monodispersed emulsion referred to here refers to one in which the standard deviation of the grain size distribution divided by the average grain size is 0.20 or less.The grain size is spherical. In the case of silver halide, the diameter is shown; in the case of particles having a shape other than spherical, the diameter is shown when the projected image is converted into a circular image of the same area.) may be used alone or in combination. Further, a polydisperse emulsion and a JII dispersion emulsion may be mixed and used.

The silver halide emulsion may be a mixture of two or more separately formed silver halide emulsions.

The photosensitive silver halide emulsion can be chemically sensitized by a conventional method.

Light-sensitive silver halide emulsions can be optically sensitized to a range of wavelengths using dyes known in the photographic industry as sensitizing dyes.

Silver halide emulsions are used during the manufacturing process of photosensitive materials, during storage,
Alternatively, for the purpose of preventing fog during photographic processing or maintaining stable photographic performance, photographs may be taken during chemical ripening, at the end of chemical ripening, and/or after chemical ripening and before coating a silver halide emulsion. Compounds known in the industry as antifoggants or stabilizers can be added.

It is advantageous to use gelatin as a binder (or protective colloid) for silver halide emulsions, but gelatin derivatives, graft polymers of gelatin and other polymers, other proteins, sugar derivatives, cellulose derivatives, single Alternatively, hydrophilic colloids such as synthetic hydrophilic polymeric substances such as copolymers may also be used.

The photographic emulsion layer and other hydrophilic floid layers of the light-sensitive material using the silver halide emulsion of the present invention are prepared by adding a hardening agent to crosslink the binder (or protective colloid) and increase the film strength.
Hardening can be achieved by using one species or two or more species.

A hardening agent can harden a photosensitive material to the extent that it is not necessary to add a hardening agent to the processing solution, and can be added, but it is also possible to add a hardening agent to the processing solution.

A plasticizer can be added to the silver halide emulsion layer and/or other hydrophilic colloid layer of the light-sensitive material for the purpose of increasing flexibility. Preferred plasticizers are the compounds described in RD 17643, Section 2, A.

A dispersion (latex) of a water-insoluble or poorly soluble synthetic polymer can be contained in the photographic emulsion layer or other hydrophilic colloid layer of a light-sensitive material for the purpose of improving dimensional stability.

The emulsion layer of the light-sensitive material contains a dye that forms a dye through a coupling reaction with an oxidized product of an aromatic primary amine developer (for example, p-phenylenenoamine derivative, aminophenol derivative, etc.) during color development processing. Forming couplers are used.

The dye-forming coupler has a color correction effect, and by coupling with the oxidized form of the developing agent, it can be used as a development inhibitor, development accelerator, bleach accelerator, developer, silver halide solvent, and toning agent. Compounds that release photographically useful 7-ragments such as hardeners, fogging agents, antifogging agents, chemical sensitizers, spectral sensitizers, and desensitizers are included.

A colorless coupler (also called a competitive coupler) which undergoes a coupling reaction with an oxidized aromatic GI-grade amine developer but does not form a dye can also be used in combination with a dye-forming coupler.

Dye-forming couplers, colored couplers, DIR compounds, image stabilizers that do not need to be adsorbed on the surface of silver halide crystals,
Among color capri inhibitors, ultraviolet absorbers, optical brighteners, etc.
Various methods can be used to incorporate hydrophobic compounds into photosensitive materials, such as solid dispersion, latex dispersion, and oil-in-water emulsion dispersion. It can be selected as appropriate.

When the dye-forming coupler, colored coupler, DIR coupler, image stabilizer, anti-color cast agent, ultraviolet absorber, optical brightener, etc. have an acid group such as carboxylic acid or sulfonic acid, hydrophilic colloid is used as an alkaline aqueous solution. It can also be introduced inside.

The oxidized form of the developing agent or the electron transfer agent migrates between the emulsion layers of the light-sensitive material (between the same color-sensitive layers and/or between different color-sensitive layers), causing color turbidity, deterioration of sharpness, and graininess. A color cast inhibitor can be used to prevent the color from becoming noticeable.

An image stabilizer can be used in the photosensitive material to prevent deterioration of the dye image. Compounds that can be preferably used are those described in Section 2 J of RD17643.

Hydrophilic colloid layers such as protective layers and intermediate layers of photosensitive materials contain ultraviolet absorbers to prevent fogging due to discharge caused by charging of photosensitive materials due to friction, etc., and to prevent deterioration of images due to ultraviolet rays. good.

In order to prevent deterioration of magenta dye-forming couplers and the like due to formalin during storage of the light-sensitive material, formalin scumbennoya can be used in the light-sensitive material.

When containing dyes, ultraviolet absorbers, etc. in the hydrophilic colloid layer of a photosensitive material, they may be mordanted with a mordant such as a cationic polymer.

Compounds that change the developability, such as development accelerators and development retardants, and bleaching accelerators can be added to the silver halide emulsion layer and/or other water-developable colloid layers of the light-sensitive material. Acceleration of development,
Black and white developing agents and/or breaker thereof may be used for other purposes.

The emulsion layer of a photographic light-sensitive material is made of polyalkylene oxide or its ethers, derivatives such as amines, thioether compounds, thiomol hepta-olins, quaternary ammonium compounds, It may also contain turethane derivatives, urea derivatives, imidazole derivatives, etc. (1.

A fluorescent whitening agent can be used in the photosensitive material for the purpose of emphasizing the whiteness of the white background and making the coloration of the white background less noticeable.

The photosensitive material can be provided with auxiliary layers such as a filter layer, an antihalation layer, an antiirradiation layer, and the like.

These layers and/or the emulsion layer may contain dyes that are leached from the light-sensitive material or bleached during the development process.

A matting agent can be added to the silver halide emulsion I4 and/or other hydrophilic colloid layer of the light-sensitive material for the purpose of reducing the gloss of the light-sensitive material, improving the ease of writing, and preventing the light-sensitive materials from sticking together.

A lubricant can be added to the photosensitive material to reduce sliding friction.

An antistatic agent can be added to the photosensitive material for the purpose of preventing static electricity.

The photographic emulsion layer and/or other hydrophilic colloid layer of the light-sensitive material may be coated with coating properties, antistatic properties, slipperiness properties, emulsification dispersion,
Various surfactants can be used for the purpose of preventing adhesion and improving photographic properties (development acceleration, film hardening, sensitization, etc.).

The support used in the photosensitive material of the present invention includes α-olefin polymers (e.g., polyethylene, polypropylene,
Flexible reflective supports such as paper laminated with (ethylene/butene copolymer) *, synthetic paper, semi-synthetic or synthetic polymers such as cellulose acetate, cellulose nitrate, polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate, polyamide, etc. films, flexible supports with reflective layers on these films, glass, metals, F
This includes liil vessels, etc.

After subjecting the support surface to corona discharge, ultraviolet irradiation, flame treatment, etc. as necessary, the photosensitive material can be used directly or on the surface of the support for adhesion, antistatic properties, dimensional stability, abrasion resistance, hardness, and halation. It may be applied through one or more subbing layers to improve protection, friction properties, and/or other properties.

When coating the photosensitive material, a thickener may be used to improve coating properties. In addition, for example, hardeners (such as hardeners), which are so reactive that if added to the coating solution in advance will cause delification before coating, should be mixed using a static mixer etc. immediately before coating. is preferred.

As coating methods, extrusion coating and curtain coating, which allow two or more types of layers to be applied simultaneously, are particularly useful, but packet coating may also be used depending on the purpose. Further, the coating speed can be arbitrarily selected.

The present invention can be preferably applied to color negative films, color reversal films, and the like.

To obtain a dye image using the photosensitive material of the present invention, after exposure,
Perform any color photographic processing known in the art.

〔Example〕

Specific examples of the present invention will be described below, but the embodiments of the present invention are not limited thereto.

In all the examples below, the amount added in the silver halide photographic material is per I+12 unless otherwise specified. In addition, halogenated coins and colloidal silver are shown in terms of silver.

A multilayer color photographic element sample 1 was prepared by sequentially forming each layer having the composition shown below on a tria-7tylcellulose film support from the support side.

Sample-1 (comparison) 1st M: antihalation layer (+IC-1>gelatin layer containing black colloidal silver).

Second layer; Intermediate layer (1,L,) Gelatin layer containing an emulsified dispersion of 2.5-not-t-octylhydroquinone.

3rd N: Low sensitivity red-sensitive silver halide emulsion layer (RL-1)
Monodispersed emulsion consisting of^gBrl with an average grain size (r) of 0.40 μm and ΔF11 of 6 mol% (ILL12--silver coating weight 1.8 g/m2)
Sensitizing color 'AI --- 5 x 10-5 moles per mole of silver Sensitizing dye ---- 0.8X 10-5 moles per mole of ffi Cyankabra (C-1) --- 1 mole of silver Colored cyan coupler (CC-1) ---0.005 mole per mole of silver DIR coupler (D-14) ---0.003 mole per mole of silver 4th layer ; High-sensitivity red-sensitive silver halide IL agent πI (It
l+-1) Average particle size (r) 0.8/'m+8g17.
Monodispersed emulsion (emulsion ■) consisting of 8 gcrl containing o mol % - silver coating weight 1.3 g/+a2
Sensitizing dye I-1 - 2.5X 10-' mol sensitizing dye for 1 mol silver -
--- 0゜sx io-'Morsian Kabra per 1 mole of silver (C-2) --- 0.007 moles Cyankabra per 1 mole of silver (C-3) --- For 1 mole of silver 0.027 mol Colored Cyan Kabra (CC-1)---0.0015 mol per mol of silver Dllt Cabra (D-14)---0.001 mol per mol of silver 5th layer; Middle 111 layer (1, L,) Same as f52 layer, gelatin layer.

fjS6 layer; low-sensitivity green-sensitive silver halide emulsion 1 (GL
-1) Sensitizing dye ■-1- 2. OX 10-5 molar sensitized color code -
-- 1.0 per mole of silver. OX 10-5 mole magenta coupler (M -1) --- 0.090 mole per mole of silver Colored magenta coupler (CM-1) --- 0.004 mole per mole of silver DIR coupler (D -12) --- 7th layer: 0.005 mol per mol of silver; high-sensitivity green-sensitive silver halide emulsion layer (Gl+-1
) Emulsion-m-11 coated silver amount 1.4g/Yari2 sensitizing dye ■-
-- 1.2X 10-5 mol sensitizing dye per ml mol ■-
--0.8X 10-S mole magenta coupler (M-1) for 1 mole of silver---! Colored Magenta Coupler (CM-1)---0.002 mol per mol of silver DIR Cafura (D-12)---o per mol of silver; ooiomol Pt58 layer; Yellow filter layer (VC-1) Gelatin layer containing an emulsified dispersion of yellow colloidal silver and 2,5-di-t-octylhydroquinone.

9th layer: low sensitivity i7 sensitive silver halide emulsion layer (IIL-
1) 8g containing 16 mol% of average particle size 0.48μ
Monodispersed emulsion (emulsion ■) consisting of llr l...silver coating amount 0.9g/L02
Sensitizing dye■ --- 1.3X 10"' mole per mole of silver Yellow coupler (Y -1) --- 0.29 mole per mole of silver 10th layer; High sensitivity blue-sensitive emulsion N (n11-1) Average particle size: 0.8μ gloss, containing 8g [lrl
Monodispersed emulsion (emulsion ■) consisting of...silver coating amount 0.5ε/r
2 sensitized color cord V --- 1.0% per mole of silver. OX 10-5 mol Yellow coupler (Y -1) --- 0.08 mol per mol of silver DIR coupler (D -15) --- 0.0030 mol per mol of silver 11th layer; 1 protective layer (Pro-1) Silver iodobromide (Heg
11 mol% average particle size 0.07 μm) Trowel coating jlO, 5 g
/m2 Gelatin layer containing ultraviolet absorbers UV-I, UV-2.

12th layer; second protective layer (Pro-2) polymethyl methacrylate particles (diameter 1.5μ, a) and formalin scavennoya (HS-
1) Gelatin layer containing.

In addition to the above composition, each layer contains gelatin. curing agent (H-1) and (H-2) and surfactants were added.

The compounds contained in each layer of Sample 1 are as follows.

Sensitizing dye I; anhydro-5,5'-dichloro-9-
Ethyl-3,3'-no(3-sulfobrovir)thiacarbocyanine hydroxide sensitizing dye ■; Anhydro-9-ethyl-3,3'-no(3-sulfopropyl)-4,5,4',5 '-Dibenzothiacarbocyanine hydroxide sensitizing dye ■ 1 anhydro-5,5'-diphenyl-9
-Ethyl-3,3'-C(3-sulfopropyl)oxacarbocyanine hydroxide sensitizing dye; 6'-Dibenzoxacarbocyanine hydroxide sensitizing dye ■; Anhydro-3,3'-di(3-sulfopropyl)-4,5-benzo-5'-methoxythiacyanine anhydro', no'll C- 1 0 ■ C! p 1V-1 C+0g(t) 1V-2 ts-1 nN.

((C11□=CH5O, C11□)zccI(2SO
□(C1+2)2 ]2N(CI!2)2sOJ In sample 1! ff16ffi, sample 2 ~ by changing the [11R coupler and magenta coupler contained in the 7th tear]
15 was created. Table 1 shows the contents of the sample at this time.

Values in parentheses indicate pKa. Each sample No. 1 to 15 thus prepared was exposed to sea urchin light using white light, blue light, green light, and red light, and then subjected to the following development treatment.

Processing process (38°C) Color development 3 minutes 15 seconds bleaching 6 minutes 30 seconds washing with water
Fixed for 3 minutes and 15 seconds
Wash with water for 6 minutes and 30 seconds
3 minutes 15 seconds stabilization 1 minute 3
0 second drying The composition of the treatment liquid used in each treatment step is as follows.

[Color developer]

4-7 minnow 3-methyl-N-ethyl-N-(β-hydroxyethyl)-aniline f, 41m
4.75g anhydrous sodium sulfite 4
．． 25Fi hydroxylamine ψ1/2 sulfuric acid jl
2.0g anhydrous potassium carbonate
37.5g Sodium Bromide Wam
1.38 Nitrilotriacetic acid trisodium salt (monohydrate) 2.5g Potassium hydroxide 1.0g Add water to make 11. (pH 10,0) [Bleach solution] Ethylenedi7minetetraacetic acid iron ammonium salt 100.0g Ethylenedi7minetetraacetic acid diammonium salt 10.0g Ammonium bromide 150.0g Ice vinegar FIZ, 10. O1
! Add 1 water to make 1 volume, and use ammonia water to make pl+
=6.0.

[Fixer]

Aqueous ammonia thiosulfate 175.0g Anhydrous sodium sulfite 8.58 Sodium metasulfite 2.3g Add water to make 11, and adjust to pl+=6.0 using acetic acid.

[Stabilizing liquid]

Formalin (37% water soluble 1Lt) 1
．． 5 bells! Konidax (manufactured by Konishiroku Photo Industry Co., Ltd.)
7.5mj! Add water to make 11.

From the sensitometric curve obtained at this time, the ratio γR/γN of the gamma (γR) during red exposure and the gamma (γN) during white exposure is calculated, and the interlayer effect (IIE) that affects the red sensitivity from the green sensitive layer is calculated. It was evaluated and used as a measure of color reproducibility.

Next, other samples Nos. 1 to 15 were wedge exposed using white light, and the pH of the color development step of the aforementioned processing steps was adjusted to 9.
．． I changed it to 7 and 10.3 and the process failed.

From the sensitometric curve obtained at this time, γ (gamma)
Find γH=γ10.3/γ10.0, γL=γ9.7
/γ10.0, and the variation in photographic characteristics with respect to processing changes was evaluated.

(γ9.7, γ10.0, γ10.3 is the pH of color development.
are 9.7.10.0.10.3 respectively).

The results at this time are shown in Table-2.

"＼ 1, Shimoyosada 2, / Table 2 From the results in Tables 2 to 2, the samples of the present invention have excellent color reproducibility and stable characteristics against changes in development processing conditions. I found out.

〔Effect of the invention〕

Not only the structure of the compound used in the present invention but also the action of the compound! ! ! By conducting a thorough screening, it was shown that it is possible to construct technology from a new perspective, free from structure.

Applicant: Roku Konishi Photo Industry Co., Ltd. Santo Ago Aji City Shoho September IO date 1, 1986, Indication of the case 3, Person making the amendment Connection with the case (related) Patent applicant address: Nishi-Shinjuku, Shinjuku-ku, Tokyo 1-26-2 Konishiroku Photo Industry Co., Ltd., 1 Sakura-cho, Hino-shi, Tokyo 191 Japan (Tel: 0425-83-152)
1. ) Patent Part 4, Area Weight of Amendment Order Vol. 5, "Detailed Description of the Invention" column of the Specification aI subject to amendment.

6. Contents of amendment The detailed description of the invention is amended as follows.

Page 3, line 16' l) K u is 7.0≦pKa≦
9.0" is deleted.

Claims (1)

[Claims] A pyrazolotriazole magenta coupler having an acid dissociation constant (pKa) of 8.0 to 10.0 and a pK that reacts with an oxidized form of a developing agent to release a development inhibitor or its precursor.
A silver halide color photographic material containing a DIR coupler in which a is 7.0 to 9.0.