JPH02217847A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To improve the stability against the fluctuation in processing conditions by incorporating a DIR compd. into the photosensitive material and incorporating a formalin scavenger and 5-pyrazolone magenta coupler therein. CONSTITUTION:This photosensitive material is constituted by having at least blue photosensitive, green photosensitive and red photosensitive silver halide emulsion layers on a base. The photosensitive material contains the DIR compd. and contains the formalin scavenger; in addition, at least the green photosensitive layer is constituted of a single layer and contains the 5-pyrazolone magenta coupler. The DIR compd. refers to a development restrainer or compd. which eliminates the compd. capable of releasing the development restrainer by reaction with the oxidant of a color developing agent. The silver halide color photographic sensitive which has the excellent preservable property of gradations even when placed in a gaseous formalin condition or in spite of a fluctuation in development processing conditions is obtd. in this way.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application J] The present invention relates to a negative silver halide color photographic material suitable for full-color photography.

[Prior Art] Currently, the so-called negative-positive method, in which color photographs are taken using color negative film and enlarged onto color paper to produce color prints, is widely used.

One reason for this is that color negative film has a very wide exposure latitude, so the probability of failure is very low, and even ordinary users without specialized knowledge can easily take color photographs. It's true.

[Having a wide exposure latitude] means that in the so-called characteristic curve where the horizontal axis is the exposure amount and the vertical axis is the color density,
This means that the gradation is good over a wide exposure ffi range from shadow areas with a low exposure amount to highlight areas with a high exposure amount.

If this gradation is poor, the color reproducibility and tone reproducibility of the dye image will deteriorate.

Color negative film is a photosensitive material that requires strict control of gradation throughout the color reversal film, and for this reason, currently commercially available color negative films for photography have different photosensitive layers for blue, green, and red light. The result is a multilayer structure of multiple emulsion layers having a high-speed layer containing silver halide grains with a large grain size and a low-speed layer containing silver halide grains with a small grain size, and further reaction with an oxidized form of a developing agent. So-called DIR compounds, which produce development inhibitors, are used.

This technology is unique to color negative film;
In particular, DIR compounds are not only sensitive (the sharpness of dye images,
It also improves graininess and color reproducibility, and is essential for color negative films.

[Problems to be Solved by the Invention] As mentioned above, a color negative film has a multilayer structure having a plurality of emulsion layers containing silver halide grains of different grain sizes,
Furthermore, since the gradation is strictly controlled using DIR compounds,
The storage stability of photosensitive materials is poor in a formalin gas atmosphere.
It has drawbacks such as poor stability against fluctuations in processing conditions, resulting in deterioration of gradation, and deterioration of color reproducibility and tone reproducibility. However, compared to color reversal films, color negative films are developed in a variety of laboratories, so they are developed under widely varying processing conditions. Therefore, color negative films are required to have particularly high stability against fluctuations in processing conditions.

As a technique for improving such gradation stability, for example, as described in JP-A No. 60-244944, silver halide emulsions having the same average grain size are chemically sensitized, and then each emulsion is given a molar A method is known in which sensitizing dyes are added at different ratios and mixed again.

However, this method is unfavorable because dye adsorption equilibrium occurs between particles during the stagnation period leading up to coating.

[Objective of the Invention 1 The object of the present invention is to provide a silver halide color photographic light-sensitive material that has excellent gradation stability even when placed in a formalin gas atmosphere and under fluctuations in development processing conditions. It's about doing.

[Means for Solving the Problems] The object of the present invention is to provide a silver halide color photographic light-sensitive material having at least blue-sensitive, green-sensitive and red-sensitive silver halide emulsion layers on a support. The halogen compound has a DIR compound, a formalin scavenger, at least the green-sensitive emulsion layer is composed of a single layer, and contains a 5-virazolone magenta coupler. This can be achieved using silver oxide color photographic materials.

The present invention will be explained in more detail below.

The DIR compound used in the light-sensitive material of the present invention is a compound that reacts with an oxidized form of a color developing agent to release a compound capable of releasing a phenomenon inhibitor or a development inhibitor.

The compound capable of releasing the development inhibitor described above may be one that releases the development inhibitor imagewise or non-imagewise.

Examples of the imagewise release include those caused by reaction with an oxidized product of a developing agent. An example of a device that emits in a non-imagewise manner is one that utilizes TIMEI, which will be described later.

The DIR compound used in the present invention has the following general formula % Formula % General formula (D-1) AY (1) In the formula, A represents a coupler residue. The layer represents 1 or 2, Y is bonded to the coupling position of the coupler residual NA and reacts with the oxidized form of the color developing agent, resulting in fnI! ! 2 represents a development inhibitor &1I711 group or a group capable of releasing a development inhibitor, typically represented by the following general formulas (D-2) to (D-2
0).

General formula (D-2) General formula (D-5) General formula (D-(3) General formula (D-7> General formula CD -8+ General formula (D-9) Rd.

In general formulas (D-2) to (D-7), Rds is a hydrogen atom, a halogen atom, or an alkyl, alkoxy,
Acylamino, alkoxycarbonylxycarbonyl N-alkylcarbamoyllubamoyloxy, sulfamoyl, N-alkylcarbamoyloxy, hydroxy, alkoxycarbonylamino, alkylthio, arylthio, aryl, heterocycle, cyano, alkylsulfonyl or aryloxycarbonylamino represents a group. n represents O, 1 or 2, and when n is 2, each Rd+ may be the same or different.

The total number of carbon atoms contained in n Rds in (D-2) to (D-5) and (D-7) is O to 10, and the carbon contained in Rdt in general formula (D-6) is The number is 0-15.

X in the above general formula (D-6) represents an oxygen atom or a sulfur atom.

In general formula (D-8), Rd2 represents an alkyl group, an aryl group or a heterocyclic group.

In general formula (D-9), Rd3 represents a hydrogen atom or a polygroup of alkyl, cycloalkyl, aryl, or heterocycle, and Rds represents a hydrogen atom, a halogen atom, or an alkyl, cycloalkyl, aryl, acylamino, alkoxycarbonylamino, Represents a polygroup of aryloxycarbonylaminonesulfonamide, cyanide, heterocycle, alkylthio or amine.

When Rdl, Rd2, Rd3 or Rds represents an alkyl group, this alkyl group may have a substituent and may be straight or branched.

When Rdl, Rd2, Rda or Rds represents an aryl group, the aryl group includes those having a substituent.

When Rdl, Rd2, Rd3 or Rds represents a heterocyclic group, this heterocyclic group includes those having a substituent. The heteroatom is selected from a nitrogen atom, an oxygen atom, and a sulfur atom, and the heterocyclic group is preferably a 5- or 6-membered monocyclic ring or a fused ring containing at least one of the above heteroatoms, such as pyridyl. , quinolyl, furyl, benzothiazolyl, oxacylyl, imidazolyl, thiazolyl, triazolyl, benzotriazolyl, imide, oxazine, and the like.

In general formula (D-8), the number of carbon atoms contained in Rd2 is O to 15.

In the above general formula (D-9), the total number of carbon atoms contained in Rda and Rds is 0 to 15.

General formula (D-10> - (TIME), -INHIBIT In the formula, TIMEM is a group that binds to the coupling position of the coupler residue represented by A and can be cleaved by reaction with an oxidized form of a color developing agent, It is a group that can be cleaved from a coupler and then sequentially cleaved to finally release an INHtBrT group with appropriate control.

n is 1 to 3, and when n is 2 or 3, each TIME group may be the same or different. The INHIBIT group is a group that becomes a development inhibitor upon release (for example, a group represented by the general formulas (D-2) to (D-9)).

In the general formula (D-10>), the TIME group is typically represented by the following general formulas (D-11) to (Cl-19).

General formula (D-11) General formula (D-12) General formula (D-13) niti, - (Rds)f General formula<D-14) General formula (D-15) General formula (D-16) υ General formula (D-171 the law of nature General formula (D-18) General formula (D-19) Rd.

1<d, FCd.

In general formulas (D-11) to (D-15) and (D-18), Rds is a hydrogen atom, a halogen atom, or alkyl, cycloalkyl, alkenyl, aralkyl, alkoxy, alkoxycarbonyl, anilino, acylamino, ureido, cyano , nitro, sulfonamide, sulfamoyl, carbamoyl, 7-lyl, carboxy, sulfo, hydroxy or alkanesulfonyl, represented by general formulas (D-11) to (D-13>, (D-15)
In (D-18), Rds may combine with each other to form a condensed ring, and the general formulas (D-11), (D-14)
, (D-15) and (D-19), Rds represents 8 groups of alkyl, alkenyl, aralkyl, cycloalkyl, heterocycle or aryl, and the general formula (D-1
6) and (D-17), Rd7 represents a hydrogen atom or 8 groups of alkyl, alkenyl, aralkyl, cycloalkyl, heterocycle, or aryl, and has the general formula (
Rda and Rds in D-19) each represent a hydrogen atom or an alkyl group (preferably an alkyl group having 1 to 4 carbon atoms), and have the general formula CD-11), (D-15) to
k in (D-18) represents an integer of 0, 1 or 2, and general formulas (D-11) to (D-13), (D-15)
, l in (D-18) represents an integer of 1 to 4, - in general formula (0-16) represents an integer of 1 or 2, and 2. When R is 2 or more, each Rds and Rd7 may be the same or different, and n in the general formula (D-19> is 2 to 4
represents an integer of n Rda and Rd9 may be the same or different, and represent an integer of general formulas (D-16) to (D-1
B in 8) represents an oxygen atom or -N- (R (fs represents the same meaning as Rda defined above), and B in the general formula (D-16
) represents that it may be a single bond or a double bond, and in the case of a single bond, ■ is 2, and in the case of double viscosity, m is 1.

General formula (D-20) →T1S R+T2 'jtr-I N HI B
In the I T formula, T1 is 5R-fT2+r-INl-11B
The component that cleaves IT was 5RH8RfT2h-INHI.
After BIT is generated, by reaction with the oxidized form of the developing agent, T2 becomes (T2+-r NH[B
A component that cleaves INHIBIT, and INHIBIT is a development inhibitor! and bi represent O or 1, respectively.

The component represented by SR may be one that produces the above-mentioned component by reaction with the oxidized form of the developing agent, such as a coupler component that reacts with the oxidized form of the developing agent and a coupler component that reacts with the oxidized form of the developing agent. Examples include redox components that undergo redox reactions.

Coupler components include acylacetanilides, 5-
Pyrazolones, pyrazoloazoles, phenols, naphthols, acetophenones, indanones, carbamoylacetanilides, 2 (5H)-imidacylones, 5-isoxacilones, uracils, homophthalimides, oxacilones, 2.5 -Thiadiazoline-
In addition to 1,1-dioxides, triazolothiadiazines, indoles, yellow couplers, magenta couplers, and cyan couplers, those that produce various dyes or those that do not produce dyes may be used.

+T1\S R-(-T2 +r-I N HI B
IT is preferably bonded to the active site of component A in general formula (D-1).

Also, if SR is a coupler component, SR is -+T +
The fusuma cleaved from J- is coupled with +T1 and +T2 to function as couplers for the first time.

For example, when the coupler component is a phenol or naphthol, the oxygen atom of the hydroxyl group is the oxygen atom of the hydroxyl group at the 5-position of the tautomer, or the nitrogen atom at the 2-position is the tautomer. , also, acetophenones,
In indanones, the oxygen atom of the hydroxyl group of the tautomer bonds with +T1-37-, and -+T2-+1f
-I NHIB IT is preferably bound to the active site of the coupler.

When SR is a redox component, examples include hydroquinones, catechols, pyrogallols, aminophenols (e.g. (p-aminophenols,
O-aminophenols), naphthalene diols (e.g. 1,2-naphthalene diols, 1,4-naphthalene diols, 2,6-naphthalene diols), or aminonaphthols (e.g. 1,2-aminonaphthols) , 1.4-aminonaphthols, 2.6-aminonaphthols), and the like.

Also, if SR is a redox component, SR is 1 + 11 yen -
is cleaved from , and for the first time combines with +T1-+7- and +T2+r-■NHIBIT to function as a redox component.

Examples of the groups represented by T1 and T2 include those represented by the aforementioned general formulas (D-11) to (D-19).

Examples of the development inhibitor represented by INHIBIT include those represented by the aforementioned general formulas (D-2) to (D-9>).

Among the DIR compounds, preferred are those in which Y has the general formula (D-
2), (D-3), (D-8), (D-10) or (D
-20), and (D-10>, (D
-20), INHIBIT has the general formula (D-2)
, (D-3), (D-6) (especially X of general formula CD-6>
is an oxygen atom) or (D-8) is preferred.

Examples of the coupler component represented by A in general formula (D-1) include yellow image forming coupler residues, magenta image forming coupler residues, cyan color image forming coupler residues, and colorless coupler residues.

Preferred DIR compounds used in the present invention include the following compounds, but these are limited to: Specific examples of DIR compounds that can be used in the present invention are U.S. Pat. Nos. 4,234,678 and 3,227,5
No. 54, No. 3,617,291, No. 3,958,99
No. 3, No. 4,149.886, No. 3,933,50
No. 0, JP 57-56837, 51-13239, U.S. Pat. No. 2,072,363, JP 2,070,26
No. 6, Research Disclosure t' - December 1981
It is described in Monthly No. 21228, etc.

DIR compound is 0.0001 per mole of silver halide
It is preferable to use ~0.1 mol, especially 0.001 mol.
It is preferable to use ~0.05 mol.

The DIR compound may be added at any place where it can affect the development of silver halide in an emulsion layer consisting of a single layer, preferably in the silver halide emulsion layer, and more preferably in the emulsion layer consisting of a single layer. A silver halide emulsion layer and/or an emulsion layer having the same photosensitivity as the emulsion layer.

The formalin scavenger used in the present invention is a compound that reacts with formaldehyde gas, and is particularly preferably represented by the following general formula [S].

General formula [8] General formula [3-II ■ R+-A-R2 Here, R1 and R2 represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an acyl group, a carbamoyl group, an iminomethyl group, or an amino group, The above 8 groups include those having a substituent, R1 and R2 include those forming a ring, and when R1 and R2 do not form a ring, these R
At least one of 1 and R2 is an acyl group, a carbamoyl group, or a general formula [8-III] R7-NH-Ra -NH-C-Rs general formula [8-r
V] Among the formalin scavengers represented by the general formula [8], preferred ones are those represented by the general formula [8-II, [8-[1, [
It is a compound represented by S-IIll or [3-IV].

General formula [8-II (H2N-C-NH Qi R3 ■ Ro Here, R3 represents a divalent alkyl group, R41R5 and R7 are a hydrogen atom, an alkenyl group, an alkyl group, or -〇-R'(R' is an alkyl group.

), R6 represents a hydrogen atom, an alkyl group, or an amino group, R9 represents an alkyl group, and 8 groups include those having substituents, and here R4 and R6 and R7 and R9 form a ring. Including those who do. The substituent includes an amino group, a hydrocarbon residue, or an -OR" group (R" is a hydrocarbon residue)
can be mentioned.

R8 represents a carbonyl group, -C(-NH)- group, and RI
O represents a hydrogen atom, an alkyl group, a cyclohexyl group, a phenyl group, an aralkyl group, an alkoxyl group, an aryloxyl group, a carbamoyl group, an alkoxycarbonyl group, and a cyano group, and these eight groups include those having a substituent. Rat represents a hydrogen atom, an alkyl group, a cyclohexyl group, a phenyl group, an aralkyl group, a petero ring residue, a benzoyl group, a sulfone alkyl group, a sulfone aryl group, a carboxyalkyl group, a carbamoyl group, a thiocarbamoyl group, and 8 groups are substituted. Including those with groups.

Particularly preferred formalin scavengers are shown below, but are limited to (S-1) (S-2) (S-3) (S-4) 82NCNHNH2 (S-S) Hz N CN HC2Hs (S-17) (S-19) (S-21) (S-18) (S-ZO) (S-22) (S-12) (S-16) (S-29) ( S-13) (S-30) Among the formalin scavengers shown here, for example, (
S-1>, (S-2'), (S-5), (S-6), (
S-7) and (S-8) are commercially available compounds, and (S-7> to (S-16) are disclosed in British Patent No. 717,2
No. 87, U.S. Patent No. 2,731.412, U.S. Patent No. 3,187
,004, JP-A-58-79248, etc., (S-19) can be synthesized by the method described in Be1lSt.
ein Handbuch der 0rC1ani
SCherChea+ie l-198, (1921)
, che*1sche der Berichte
54. B, 1802-1833.2441-24
77° (1921), Bulletin of t
he chemical 3ocietyOr Jap
an-39, 1559-1567, 1734-1738
(1966) and others. Also, (S-28) is German patent 148
, No. 108.

The formalin scavenger used in the present invention is 21
The above may be used in combination.

The formalin scavenger used in the present invention is a protective layer, a silver halide emulsion layer, an intermediate layer, a filter layer, an antihalation layer, a silver halide color photographic light-sensitive material,
It can be used by being included in at least one of the other layers. It is preferable to add the magenta coupler to a silver halide emulsion layer containing the magenta coupler or a layer farther from the support than the layer, and it is preferable to add it to a layer in which no dye is formed than to a layer in which a dye is formed by development.

In order to add the formalin scavenger used in the present invention to these layers, it can be added directly to the coating solution, or added to a low boiling point Il solvent such as water or alcohol that does not affect the silver halide color photographic light-sensitive material. It can also be added after combing. It is also possible to dissolve the formalin scavenger of the present invention in a high boiling point organic solvent, emulsify and disperse the solution in an aqueous solution, and then add the solution.

The amount of formalin scavenger used in the present invention is 5X per 1f of silver halide color photographic light-sensitive material.
10-5 mol to 1 mol is suitable, preferably IX 10-4 mol to 5X10-1 mol,
More preferably 5X10-3 mol to 1X10
−'Mole.

The pyrazolone magenta coupler used in the present invention is
It is represented by the following general formula [I].

General formula [I] These are monovalent groups such as honamido groups and divalent groups such as alkylene groups, and in the case of divalent groups, X forms 21 bodies.

Specific examples are given below.

In the formula, Cp represents a pyrazolone coupler residue, the fist represents a coupling position of the coupler, and X represents a hydrogen atom or a hydrogen atom when a dye is formed by coupling with an oxidized product of an aromatic primary amine color developing agent. Represents a leaving group.

mmi represented by X is, for example, a halogen atom, an alkoxy group, an aryloxy group, a hetero Represents the atomic group necessary to form a 5- to 6-membered ring with 1 atom), acylamimu L sulfexdene atom: salt, bromine, 7-alkoxy group, OC, l-1s -OCH, CONHCH, CH, OCH .

7 reel oxy fl -5CHtCOOCIHs.

-3CHtCH2OC,H,.

Arylthio group: Heterorinthio group: heterocyclic oxy group Acyloxy group: alkylthio group -SCH3゜ 18C1Hsl -SC,H,,.

-801, H2S.

-4 Kai: Pyrazolyl group.

imidazolyl group.

Triazolyl group.

Sulfonamide group: Alkylene group Niazylamide group NHCO(CF2CFz)2H In the present invention, particularly great effects are observed when X is a hydrogen atom.

As a pyrazolone magenta coupler, the following general formula [M
-1] and [M-2] are preferred.

General formula [M-1] General formula [M-2] In the above general formulas [M-1] and [M-2], R2 represents a hydrogen atom or a substituent, R3 represents a substituent, and X represents a general formula [ 2 represents 1 to 5, and when l is 2 or more, each R2 may be the same or different.

Examples of the substituent represented by R2 include a halogen atom,
Examples include 8 groups such as alkyl, cycloalkyl, aryl, and heterocycle bonded directly or via divalent atoms or groups.

Examples of the above divalent atoms or groups include oxygen atoms,
Examples include nitrogen atom, sulfur atom, carbonylamino, aminocarbonyl, sulfonylamino, aminosulfonyl, amino, carbonyl, carbonyloxy, oxycarbonylleylene, thiocarbonylamino, sulfonyl, and sulfonyloxy.

Further, the alkyl, cycloalkyl, aryl, and heterocycle as examples of the substituent represented by R2 include those having a substituent. #illf substituents include, for example, halogen atom, nitro, cyano, alkyl, alkenyl, cycloalkyl, aryl, alkoxy, aryloxy, alkoxycarbonyl, aryloxycarbonyl,
Examples include carboxy, sulfo, sulfamoyl, carbamoylamino, ureido, urethane, sulfonamide, heterocycle, arylsulfonyl, alkylsulfonyl, arylthio, alkylthio, alkylamino, anilino, hydroxy, imide, and acyl.

Examples of R3 include polygroups such as alkyl, cycloalkyl, aryl, and heterocycle, including those having substituents, and examples of such substituents include substituents possessed by the polygroups listed as examples of R2. The following are examples.

As the leaving group for X, an alkylthio group and an aryl exemplified compound lene group are particularly preferred.

Specific examples of the pyrazolone-based magenta coupler used in the present invention are listed below, but are limited to - seconds M-9 M-17
(Weight ratio) M-21 M-22! ('-1 then L to Uυi rσ X : y : z = 50 : 25 : 25
(Weight ratio) In the present invention, the amount of magenta coupler added is preferably 2X10-5 to ix i O-3 mol/f, more preferably 5X10-5 to 1X
It is 10-3 mol/f.

The term "a photosensitive emulsion layer is a single layer" means that a plurality of layers having the same type of coupler contained in the emulsion layer, grain size of silver halide grains, halogen composition and crystal habit, and ratio of coupler and silver halide are used. It also includes cases where emulsion layers having the same photosensitivity are arranged as a continuous layer.

Here, "having the same photosensitivity" or "same photosensitivity" may mean that they are the same in terms of, for example, blue sensitivity, green sensitivity, and red sensitivity, and it is not necessary that the spectral sensitivity characteristics be exactly the same. .

In the present invention, the green-sensitive layer is a single layer, but it is more preferable that the blue-sensitive and green-sensitive silver halide emulsion layers are both single layers, particularly the blue-sensitive, green-sensitive and red-sensitive silver halide layers. Preferably, all of the photosensitive silver halide emulsion layers are each a single layer.

When the photosensitive layer has a single-layer structure, the number of coated layers of photosensitive material is reduced compared to the conventional single-layer structure, making it possible to achieve WIII. Therefore, production efficiency and sharpness are improved,
Graininess is also improved. The film thickness after drying is preferably 20 to 3 μl, particularly preferably 15 to 5 μl.

Exposure latitude is the width of the amount of received light that produces significantly different exposure effects, and is the exposure range from highlights to deep shadows in the characteristic curve, as described in Photo Chemistry, page 393 (
Shashin Kogyo Shuppansha, 1982).

In other words, the slope of the tangent at the foot and shoulder of the characteristic curve, where the horizontal axis is logH and the vertical axis is transmission density, is 0.22.
This is a difference of 10QH between points.

The light-sensitive material of the present invention preferably has an exposure latitude of 3.0 or more, and preferably 3.0 to 3.0 or more, as measured by the above method.
8.0 is particularly preferred.

As a means for widening the exposure latitude of a single silver halide emulsion layer to 3.0 or more, a method of mixing and using silver halide grains having different sensitivities can be used. Specifically, examples include a method in which silver halide grains having different grain sizes are mixed and used, and a method in which a desensitizer is contained in at least a portion of the silver halide grains.

Silver halide grains with different grain sizes used in combination to obtain a wide exposure latitude have an average grain size of 0.2.
A combination of silver halide grains having a maximum average grain size of ~2.0 μm and silver halide grains having a minimum average grain size of 0.05 to 1.0 μm is preferable, and furthermore, a combination of silver halide grains having a minimum average grain size of 0.05 to 1.0 μm is preferable. One or more types of silver halide grains having the following may be combined.

Further, the average grain size of the silver halide grains having the maximum average grain size is 1.5 to 4% of the average grain size of the silver halide grains having the minimum average grain size.
Preferably, it is 0 times.

In order to obtain a wide exposure latitude, it is possible to mix and use silver halide grains with different average grain sizes. If used, the difference in average grain size can be reduced without changing the sensitivity of silver halide grains, and furthermore, it is possible to mix and use silver halide grains having the same average grain size and different sensitivities.

That is, by using silver halide grains containing a desensitizer, a wide exposure latitude can be obtained even if the coefficient of variation of the entire grain is made small.

Therefore, when exposed to the same environment, these silver halide grains having a small coefficient of variation are preferred because their photographic performance is stabilized against changes over time and fluctuations in development processing. Furthermore, from the viewpoint of production technology, it becomes possible to chemically sensitize a mixed system of silver halide grains having different sensitivities in the same batch.

Various desensitizers can be used, such as metals, ions, antifoggants, stabilizers, and desensitizing dyes.

In the present invention, a metal ion doping method is preferred. Metal ions used for doping include groups Ib, mb, [la, ll1b, and
Examples include metal ions of group b, group Va, and group II. Preferred metal ions include Au, Zn, Cd, T1
．． Sc, Y, Bi, Fe.

Ru, Os, Rh, Ir, Pd, Pr, S*.

Examples include Yb metal ions. Particularly preferably Rh
, Ru, Os, lr. These metal ions can be used, for example, as halide complex salts, etc., and can also be used as AQ X! during doping. The pH of the a-turbid system is preferably 5 or less.

In addition, the doping amount of these metal ions varies depending on the type of metal ion, the particle size of the silver halide grains, the doping position of the metal ion, the desired sensitivity, etc.
1Q-17 to 10-2 mol is preferred, more preferably 10-12 to 10-3 mol, particularly 10-
9 to 10-4 mol is preferred.

Furthermore, by selecting the type of metal ion, the doping position and the doping lamp, various different sensitivity qualities can be imparted to the silver halide grains.

If the doping amount is less than 10-2 mol/1 mol AQX mol, it will hardly affect the growth of the particles.
Silver halide grains with a narrow grain size distribution can be prepared even under the same grain growth conditions and even under the same batch growth.

It is also possible to chemically sensitize silver halide grains with different doping conditions by mixing them in a predetermined ratio to form the same batch after preparing them for practical use. Each silver halide grain receives a sensitizing effect based on its properties, and an emulsion having a wide exposure latitude can be obtained depending on the sensitivity difference and mixture ratio.

The antifoggants or stabilizers include azoles (e.g., benzthiazolium salts, indazoles, triazoles, benztriazoles, benzimidazoles, etc.), heterocyclic mercapto compounds (e.g., mercaptotetrazoles, mercaptothiazoles, mercapto Thiadiazoles, mercaptobenzthiazoles, mercaptobenzimidazoles, mercaptopyrimidines, etc.) Azaindenes (e.g., tetraazaindenes, pentaazaindenes, etc.) Nucleic acid decomposition products (e.g., adenine, guanine, etc.), benzenethiosulfonic acids, thioketo Examples include compounds.

Examples of desensitizing dyes include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holoporacyanine dyes, hemicyanine dyes, styryl dyes, and hemioxonol dyes.

The location of the desensitizer is preferably mixed inside the silver halide grains from the viewpoint of storage stability of the photosensitive material, stagnation stability of the coating solution, etc., and even if its distribution is uniform, , even if it is localized in the center or middle part of the particle,
It may gradually decrease from the center of the particle toward the outside.

From the viewpoint of production efficiency, it is preferable that the seed particles be localized in the center of the particles, and if a method using seed particles with a small coefficient of variation is used, the steps after particle growth can be performed in the same batch.

In the light-sensitive material of the present invention, at least one green-sensitive layer contains desensitizer-containing AQX particles, preferably the blue-sensitive layer and the green-sensitive layer, and most preferably all the light-sensitive layers are desensitized. This is the case in which the agent-containing At)X particles are contained.

Also, the ratio S/? of the standard deviation (S) of the grain size to the average grain size (division) of the entire silver halide grains contained in each silver halide emulsion layer? The coefficient of variation defined by ' is preferably 0.4 or less, more preferably 0.33 or less, even more preferably 0.25 or less, particularly preferably 0.20 or less.

The average grain size (r) is the grain size (in the case of cubic silver halide grains, the length of its side, or in the case of grains with a shape other than a cube, when converted to a cube having the same volume) When the number of particles of ri (length of one side) is ni, it is defined by the following formula.

r-Σni -rtΣni Further, the standard deviation (S) is defined by the following formula.

The relationship between particle size distribution is [Empirical relationship between sensitometric distribution and particle size distribution in photography] The Photographic Journal, LXX TX (1949) 330
This can be determined by the method described in the article by Tribel and Smith on pages ~338.

The silver halide emulsion used in the light-sensitive material of the present invention includes:
Any conventional silver halide emulsion can be used, but silver halide containing substantially iodine in the halogen composition (for example, silver iodobromide, silver iodochlorobromide) is preferred;
Silver iodobromide is particularly preferred in terms of sensitivity. The iodine content is preferably 1 mol% or more and 20 mol% or less, particularly 3.5
It is preferably mol % or more and 12 mol % or less.

The emulsion can be chemically sensitized by conventional methods, and can be optically sensitized to a desired wavelength range using a sensitizing dye.

Antifoggants, stabilizers, etc. can be added to the silver halide emulsion. It is advantageous to use gelatin as the binder for the emulsion a.

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

A coupler is used in the emulsion layer of a light-sensitive material for color photography.

Furthermore, by coupling with a colored coupler having a color correction effect, a competing coupler, and an oxidized form of a developing agent, a developer, a silver halide solvent, a toning agent, a hardening agent, an antifoggant, and a chemical sensitizer can be obtained. Compounds that release photographically useful fragments such as spectral sensitizers, spectral sensitizers, and desensitizers can be used.

The photosensitive material can be provided with auxiliary layers such as a filter layer, an antihalation layer, and an antiirradiation layer. These layers and/or the emulsion layer may contain dyes that are washed out or bleached from the light-sensitive material during the development process.

A formalin scavenger-1 fluorescent whitening agent, a matting agent, a lubricant, an image stabilizer, a surfactant, a color fog preventive agent, a development accelerator, a development retardant, a bleach accelerator, etc. can be added to the photosensitive material.

As a support, paper laminated with polyethylene, etc.
Polyethylene terephthalate film, baryta paper, cellulose triacetate, etc. can be used.

The photosensitive material of the present invention is particularly useful as a negative photosensitive material.

To obtain a dye image using the photosensitive material of the present invention, an exposure pattern,
Commonly known color photographic processing can be performed.

[Example] Next, the present invention will be specifically explained with reference to Examples.

Real lJl! Prior to the examples, silver halide emulsions used in the examples were prepared.

Preparation of monodispersed emulsion A gelatin aqueous solution is charged into a reaction vessel, and the p in the reaction vessel is
While controlling Ag and I)H, silver nitrate aqueous solution, potassium iodide aqueous solution and potassium bromide aqueous solution were added simultaneously while controlling the addition time, and then precipitation desalination was performed using IIH coagulating gelatin and gelatin was added. Seed emulsion NE-1 was prepared.

Seed emulsion NE-2 was also prepared in the same manner as above except that Ka R11Ole was added to the reaction vessel.

The seed emulsion and its contents are shown in Table-1.

Table 1 The above seed emulsion and gelatin aqueous solution were put into a reaction vessel, and while controlling the I) Afll and pH in the reaction vessel, an ammoniacal silver nitrate aqueous solution, a potassium iodide aqueous solution, and a potassium bromide aqueous solution were added during grain growth. It was added in proportion to the surface area, and at the appropriate particle size it was replaced with potassium bromide solution and subsequently added. In the same way as the seed emulsion, precipitation and desalting were performed, and gelatin was added and redispersed to give a pAg of 7.8 and a pH of
, o emulsion was obtained.

In this way, the inside of the grain becomes a silver iodobromide emulsion EM with a relatively high content.
-1 to EM-4 were prepared.

Table 2 shows the emulsion and its contents.

Table 2 Example 1 Material N 0.101 Multilayer color photosensitive material having a multilayer structure having the following composition on a subbed cellulose acetate support N 0.10
1 to 105 were created.

The coating amount is the amount expressed in Q/f units converted to silver for silver halide and colloidal silver, and the amount expressed in Q/f units for additives and gelatin.
The coupler and DIR compounds are expressed in moles per mole of silver halide in the same layer. The emulsion contained in each color-sensitive emulsion layer contained equimolar amounts of -1NE-1 and NE-2 made of sodium thiosulfate and chloroauric acid.

C-3 cc-i Cσ JV-1 V-2 Sensitizing dye I Sensitizing dye ■ Sensitizing dye
1, R-2, 1L-2, G-1, G-2゜YC, B-L
8-2. They shall be indicated by the abbreviations Pro-1 and Pro-2.

In addition to the above ingredients, a surfactant is added as a coating aid to each layer, and G-1, G-2, YC, B-1, 8-2, P
Formalin scavenger shown in Table 3 was added to ro-1.

Samples Nos. 108 to 110 of NO, 106 to 110 (of the present invention) are sample No. 101 except for G-2, and the emulsions contained in G-1 are combined with EM-1 and E.
In place of the equimolar mixture of M-2, the amount of emulsion, gelatin and TCP contained in G-1 was increased by 30%, and the formalin scavenger shown in Table 3 was added to G-1, YC,
Samples n N 0.106 to 110 were prepared in the same manner except that the sample was added to 8-1, 8-2, and Pro-1. (The amounts of the sensitizing dye, coupler, and DIR compound in G-1 per mole of silver halide are the same as those in samples No. and Lol.) No. 111 to 115 (light preparation sample No. 11)
1 to 115, the emulsion contained in G-1 of sample No. 106 was replaced with the emulsion shown in Table 3, and the formalin scavenger shown in Table 3 was used as G-1, YC.

Sample No. except for addition to B-1, B-2, and Pro-1
Samples Nos. 0.111 to 115 were prepared in the same manner as , 106.

Sample No. 116 117 (comparison) Sample No.
116 is sample N except that the couplers M-18 and CM-1 contained in G-1 and G-2 of sample N 0.105 are replaced with the following pyrazolotriazole magenta coupler MG-1.
It was produced in the same manner as 0.105.

Sample No. 117 is Sample No. Sample No. 110, except that the couplers M-18 and CM-1 contained in G-1 of 110 are replaced with the following pyrazolotriazole magenta coupler MG-1.
It was produced in the same manner as 0.110.

The amount of formalin scavenger added to the top layer is the total amount added to each layer.

*The emulsions of samples No. 111 to No. 01114 are equimolar mixtures of EM-2 and EM-3.

C-1 Each sample was divided into two parts, and the preservation of gradation in a formalin gas atmosphere was evaluated. Place the following on one of the two divided samples]!
! ! 1 and the other was subjected to the following treatment 2.

Treatment 1 A liquid containing 300 cc of a 35% glycerin aqueous solution was placed at the bottom, and the sample was held at 30° C. for 3 days in a closed container filled with air equilibrated with this.

Treatment 2 A solution containing 5 cc of 40% formaldehyde aqueous solution per 300 cc of 35% glycerin aqueous solution was placed at the bottom, and a sealed container filled with air equilibrated with this was placed at 30°C for 30 minutes.
Retain samples for days.

Thereafter, wedge exposure was performed according to a conventional method, and the following development treatment was performed.

Processing process (38℃) Color development 3 minutes 15 seconds Bleaching 6 minutes 30 seconds Water
Wash for 3 minutes and 15 seconds
Arrive 6 minutes 30 seconds Wednesday
Washing Stabilize for 3 minutes and 15 seconds
Drying for 1 minute and 30 seconds The composition of the treatment liquid used in each treatment step is shown below.

Color developing solution 4-amino-3-methyl-N-ethyl-N-(β-hydroxyethyl) Aniline sulfate 4.75Q anhydrous sodium sulfite 4.25 (J hydroxylamine 1/2 sulfate'PIJ salt 2. 0g Anhydrous potassium carbonate 37.50 Potassium bromide 1.30 Nitrilotriacetic acid 3
Sodium salt (monohydrate) 2.59 Potassium hydroxide 1.0g Add water to make 12. (DH-10,02) Bleach solution ethylenediaminetetraacetate iron (I[I) ammonium 1! 100. Oa
Ethylenediaminetetraacetic acid diammonium salt 10.0 (ammonium monobromide 150, Og ice vinegar @
10.0 () Add water to make 11, and adjust to pH 6.0 using aqueous ammonia.

Fixing solution Ammonium thiosulfate 175.0 g Anhydrous ammonium sulfite, 8.6 g Sodium metasulfite 2.3 g Water is added to make one solution, and the pH is adjusted to o using acetic acid.

Sou JJL member formalin (37% aqueous solution) 1.51Q
Konidax (manufactured by Konica Corporation) 7. Add 51Q water to make one volume.

In this way, treatment 1 (no contact with formalin gas)
The gradation storage stability of the sample subjected to the treatment (M standard) and the sample subjected to treatment 2 (contacted with formalin gas) was evaluated. (The evaluation method will be described later.) The results for the green photosensitive layer are shown in Table 4.

Next, sample Nos. 0.101 to 111 were divided into two parts, one part was subjected to the wedge exposure and development process in the same manner as above, and the other part was subjected to the wedge exposure and the pH of the color developing solution in the above processing step.
After developing in the same manner except that the value was changed to 10.5, the gradation storage stability was evaluated in the same manner as above.

The results for the green photosensitive layer are shown in Table 4.

A method for evaluating gradation preservation will be explained using figures.

FIG. 1 shows a reference characteristic curve (broken line) and a characteristic curve to be evaluated (solid line). Minimum concentration +0 in Figure 1
．． From the exposure point giving a density of 1, Δ1oaH-+ 3.0
Each exposure point between the exposure points (Δ1O between each exposure point (IIH
The point gamma value of -(1,15) is shown in FIG. From FIG. 2, the absolute value Δγ of the difference in point gamma at each exposure point between the reference characteristic curve and the characteristic curve to be evaluated is determined. The preservation of gradation was expressed by the value (ΔT) obtained by multiplying the average value of Δγ by 1000 and the value Σ obtained by multiplying the standard deviation σ of Δγ by 1000.

That is, the larger the value of Δγ, the larger the difference in point gamma between the two characteristic curves, and the larger the value of Σ, the more uneven the change in gradation becomes.I'? The storage stability of Iim is shown in Table 4. As is clear from Table 4, the sample of the present invention has a characteristic curve with a characteristic curve ranging from highlight to shadow with respect to fluctuations in storage and processing in a formalin gas atmosphere. It was found that the tone displacement was small and the gradation preservation was good.

Sample using pyrazolotriazole coupler <NO,
Nos. 116 and 117) have a satisfactory level of gradation preservation under a formalin gas atmosphere, but are significantly inferior in gradation preservation against processing variations.

In addition, in the case of the Bilane 0 triazole coupler, no significant improvement in gradation preservation was observed even when the green-sensitive layer was made into a single layer. However, when a 5-pyrazolone coupler was used, by forming the green-sensitive layer into a single layer, the gradation preservation under formalin gas conditions and the gradation preservation against processing variations were significantly improved. This was unexpected even for the inventors.

Among the samples of the present invention, samples containing emulsions doped with Rh ions inside the grains (N 0.111 to 115) had a narrow particle size distribution of silver halide grains in the green-sensitive layer, which had an improvement effect on processing fluctuations. It was found that this is preferable because it has a large value. Furthermore, sample No. 115 was prepared in the preparation of an emulsion.
It is also preferable in terms of production efficiency because physical ripening and chemical ripening can each be performed once.

In addition, G-1 coupler (M-18
) M-21, M-19, M-22, M-32, M-3
The effects of the present invention were also observed for each sample in which .

In addition, formalin scavenger-8 for sample NO, lit
The effects of the present invention were also observed for each sample using 5-28 and 5-30 instead of -1.

In addition, each sample in which DIR compound Riichi 42 of 8-2 of Trial I N 0.106 was replaced with D-4,0-29, and sample No. 0.1
13, G-1, D (R compound D-26, D-2, D-6
, each sample replaced with D-10, sample N.

DIR compound D-23 of R-1 of 115 is D-17゜D
The effects of the present invention were also observed for each sample in which samples were replaced with -19 and D-21.

Also, K3 Rh Cj! RLI Cf13 instead of s
゜Qs Emulsions prepared by using a seed emulsion prepared by adding C13, Pb (NO3)2 in place of NE-2 were used as EM-3 for samples N 0.111 to N0.114, and for sample N 0.115. The effects of the present invention were also observed for each sample used in place of EM-4.

[Effect of the invention 1] As is clear from the above results, the present invention has produced a silver halide color that has excellent gradation preservation even when placed in a formalin gas atmosphere and against fluctuations in development processing conditions. We were able to provide photographic materials.

[Brief explanation of the drawing]

Figure 1 is a diagram showing the characteristic curves of the standard (broken line) and evaluation target (solid line) photographic materials, and Figure 2 is the standard (broken line).
and a diagram showing the point gamma of the photographic light-sensitive material to be evaluated (solid line).

Claims (1)

[Claims] A silver halide color photographic material comprising at least blue-sensitive, green-sensitive and red-sensitive silver halide emulsion layers on a support, which contains a DIR compound, a formalin scavenger, and A silver halide color photographic light-sensitive material, wherein at least the green-sensitive emulsion layer is composed of a single layer and contains a 5-pyrazolone magenta coupler.