JPH04346341A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To enhance raw property preservability and processing stability by containing at least one kind of a specific Magenta coupler and at least one kind of a specific compound in at least one of green-sensitive silver halide emulsion layers. CONSTITUTION:At least one kind of a Magenta coupler expressed by a formula I and a formula II and at least one kind of a compound expressed by a formula III are contained in at least one of green-sensitive silver halide emulsion layers. Here, R1 represents a hydrogen atom, alkyl group, or aryl group; R2, R3 and R4 represent a hydrogen atom, alkyl group, and aryl group; J represents a methylene group, oxygen atom, and sulpher atom; X1, X2 represent a hydrogen atom, or a group separable due to reaction with an oxidant of a color developing agent; Z1, Z2 represent a non-metallic atom group necessary for forming a nitrogen containing heterocyclic ring; R40, R50, and R60 respectively represent a fatty group or aromatic group; and (l), (m) and (n) respectively represent 0 or 1 while these three can not simultaneously take the value 1.

Description

[Detailed description of the invention]

0001

[Industrial Application Field] The present invention relates to a silver halide color photographic light-sensitive material, and more specifically, the present invention relates to a silver halide color photographic material that has little variation between printers, has good shelf life, and has good processing stability. Regarding photographic materials.

0002

[Background of the invention] Silver halide color photographic materials include
Usually, yellow couplers, cyan couplers, and magenta couplers are used in combination. Among these, 5-pyrazolone magenta couplers are widely used as magenta couplers. 5-pyrazolone magenta couplers have various problems in color reproduction because the dye formed by development has sub-absorption near 430 nm. New magenta couplers have been researched to solve this problem, such as U.S. Pat. No. 3,725,065 and U.S. Pat.
, No. 761, No. 3,758,309, No. 3,725,
Pyrazolotriazole couplers such as those disclosed in No. 067 have been developed.

[0003] These couplers have many advantages such as low side absorption, good color reproducibility, excellent color development, and also excellent storage stability in the presence of formalin. are doing.

However, when these pyrazolotriazole couplers are used in color negative films and printed on paper, the hue of the finished color paper may vary due to differences in printer equipment (hereinafter referred to as printers) used. It was found that there was a discrepancy between printers (hereinafter referred to as inter-printer variation).

[0005] Although this phenomenon has been observed in other conventional couplers, the degree of the phenomenon was extremely small and was not a problem. However, it has been found that when a pyrazolotriazole coupler is used, the difference in hue of the finished color paper due to differences in printers becomes a non-negligible level.

[0006] This phenomenon is thought to be mainly due to the following reasons. That is, when printing from color negative film to color paper using a printer, the printer first measures (1) the blue density, green density, and red density of the color negative film, and (2) measures the blue density, green density, and red density of the color negative film.
) These measured values are then converted into an exposure amount for the color paper, and (3) the color paper is exposed with this exposure amount. Various printers are commercially available and in use on the market, and depending on the model of these printers, the spectral sensitivity of the detector used for photometry (1) may differ, and due to the spectral absorption characteristics of the coloring dye in the color negative film, For example, a hue shift may occur because the half-width is too small or the spectral absorption characteristics vary depending on the concentration.

Many of the above-mentioned pyrazolotriazole magenta couplers have spectral absorption characteristics that vary greatly depending on concentration, and this is one of the reasons why the variation between printers increases when pyrazolotriazole magenta couplers are used for negative films. It is thought that there is one.

[0008] Therefore, it has been desired to develop a technique that provides excellent gradation properties and reduces printer-to-printer variation in silver halide color photographic light-sensitive materials containing pyrazolotriazole-based magenta couplers.

Furthermore, it has become clear that photographic materials containing these pyrazolotriazole couplers have a problem in that their photographic performance tends to change during long-term storage after production. In recent years, industry demands for improving the photographic performance of silver halide color photographic materials have become increasingly strict.
There is a strong demand for products that have so-called homogeneity, with little difference in sensitivity over time or between lots.Moreover, with the recent trend toward silver-saving and thinning of silver halide color photographic materials, Since the change in performance becomes large, it is desired to develop a silver halide color photographic light-sensitive material that shows little change in photographic performance during storage over time, that is, has good shelf life.

[0010] These pyrazolotriazole-based magenta couplers are also effective against variations in the development process, especially in the p of the color developing solution.
It was found that silver halide photographs have the disadvantage of large changes in color density due to H fluctuations, and have little change in color density even when processed with color developing solutions of different pH, that is, silver halide photographs with good processing stability. The development of photosensitive materials was desired.

[0011]

OBJECTS OF THE INVENTION The present invention relates to a silver halide color photographic light-sensitive material, and more specifically, it provides a silver halide photographic light-sensitive material that has little variation between printers, good shelf life, and good processing stability. It's about doing.

0012

SUMMARY OF THE INVENTION The above objects of the present invention are achieved by the following silver halide color photographic light-sensitive material.

(1) A silver halide color photographic light-sensitive material having photographic constituent layers including a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, and a red-sensitive silver halide emulsion layer on a support, At least one of the green-sensitive silver halide emulsion layers contains at least one magenta coupler represented by the following general formula [M-I] and a magenta coupler represented by the following general formula [M-I].
1. A silver halide color photographic material containing at least one magenta coupler represented by [-II] and at least one compound represented by the following general formula [I].

[0014]

embedded image [In the formula, R1 represents a hydrogen atom, an alkyl group, or an aryl group. R2, R3 and R4 are hydrogen atoms, alkyl groups,
Represents an aryl group. Further, R2, R3 and R4 may be bonded together to form a saturated or unsaturated ring. At least two of R2, R3 and R4 are not hydrogen atoms. J represents a methylene group, an oxygen atom, or a sulfur atom. X1 and X2 represent a hydrogen atom or a group that can be separated by reaction with an oxidized product of a color developing agent. Z1 and Z2 represent a group of nonmetallic atoms necessary to form a nitrogen-containing heterocycle, and the ring formed by Z1 and Z2 may have a substituent. ] General formula [I]

[0015]

embedded image [In the formula, R40, R50 and R60 each represent an aliphatic group or an aromatic group, and l, m and n each represent 0 or 1. However, l, m and n are never 1 at the same time. ] (2) In a silver halide color photographic light-sensitive material having a photographic constituent layer including a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, and a red-sensitive silver halide emulsion layer on a support, the green At least one of the magenta couplers represented by the general formula [M-I] described in (1) above is contained in at least one layer of the sensitive silver halide emulsion layer;
A halogen characterized by containing at least one magenta coupler represented by the general formula [M-II] described in 1) and at least one compound represented by the following general formula [II] Silver chemical color photographic material. General formula [II] RA-NHSO2-RB [wherein RA and RB are each a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, an aryl group, a heterocyclic group, an alkoxy group, and an aryl group. oxy group, heterocyclic oxy group, or

0
016]

Represents [Chemical 7]. Here, RC and RD each represent a hydrogen atom, an alkyl group or an aryl group. RA and RB may be the same or different. ] (3) In a silver halide color photographic light-sensitive material having a photographic constituent layer including a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, and a red-sensitive silver halide emulsion layer on a support, the green At least one of the magenta couplers represented by the general formula [M-I] described in (1) above is contained in at least one layer of the sensitive silver halide emulsion layer, and at least one magenta coupler represented by the general formula [M-II] described in the above (1) is added. ] A silver halide color photographic light-sensitive material characterized by containing at least one magenta coupler represented by the following formula [AI] and at least one compound represented by the following general formula [A-I]. General formula [A-I]

[0017]

embedded image [In the formula, J represents a divalent organic group, and Y represents an alkyl group, a cycloalkyl group, an aryl group, an alkenyl group, an alkynyl group, a cycloalkenyl group, or a heterocyclic group. ]below,
The present invention will be explained in detail.

First, the magenta coupler represented by the general formula [M-I] of the present invention will be explained in detail.

In the general formula [M-I], R1 represents a hydrogen atom, an alkyl group, or an aryl group.

The alkyl group represented by R1 preferably has 1 to 32 carbon atoms, and may be linear or branched.

The aryl group represented by R1 is preferably a phenyl group.

In the general formula [M-I], J represents a methylene group, an oxygen atom, or a sulfur atom.

Groups that can be separated by reaction with the oxidized product of the color developing agent represented by X1 include, for example, halogen atoms (chlorine atom, bromine atom, fluorine atom, etc.), alkoxy, aryloxy, heterocyclic oxy, acyloxy, sulfonyl. oxy, alkoxycarbonyloxy, aryloxycarbonyl, alkyloxalyloxy, alkoxyoxalyloxy, alkylthio, arylthio, heterocyclic thio, alkyloxythiocarbonylthio, acylamino, sulfonamide, nitrogen-containing heterocycle bonded by N atom,
Examples include alkyloxycarbonylamino, aryloxycarbonylamino, carboxyl, etc.
Preferred is a halogen atom, especially a chlorine atom.

[0024] Examples of the nitrogen-containing heterocycle formed by Z1 include a pyrazole ring, imidazole ring, triazole ring, and tetrazole ring.

More specifically, those represented by the general formula [M-I] include, for example, the following general formulas [M-Ia] to [M-If]
Represented by

[0026]

embedded image In the general formulas [M-Ia] to [M-If], R1
is synonymous with R1 in general formula [M-I], and R11
~R17 represents a hydrogen atom or a substituent.

The substituents represented by R11 to R17 are not particularly limited, but typically include alkyl, aryl, anilino, acylamino, sulfonamide, alkylthio,
Examples include arylthio, alkenyl, cycloalkyl, and other groups; in addition, halogen atoms, cycloalkenyl, alkynyl, heterocycle, sulfonyl, sulfinyl, phosphonyl, acyl, carbamoyl, sulfamoyl, cyano, alkoxy, aryloxy, heterocycle Oxy, siloxy, acyloxy, carbamoyloxy, amino, alkylamino, imide, ureido, sulfamoylamino, alkoxycarbonylamino, aryloxycarbonylamino, alkoxycarbonyl, aryloxycarbonyl, heterocyclic thio groups, and spiro compound residues. Also included are groups, bridged hydrocarbon compound residues, and the like.

The alkyl group represented by R11 to R17 preferably has 1 to 32 carbon atoms, and may be linear or branched.

The aryl group represented by R11 to R17 is preferably a phenyl group.

[0030] Examples of the acylamino group represented by R11 to R17 include an alkylcarbonylamino group and an arylcarbonylamino group.

Examples of the sulfonamide group represented by R11 to R17 include an alkylsulfonylamino group and an arylsulfonylamino group.

Examples of the alkyl component and aryl component in the alkylthio group and arylthio group represented by R11 to R17 include the alkyl group and aryl group represented by R11 to R17 above.

The alkenyl group represented by R11 to R17 preferably has 2 to 32 carbon atoms, and the cycloalkyl group preferably has 3 to 12 carbon atoms, particularly 5 to 7 carbon atoms.
Alkenyl groups may be linear or branched.

The cycloalkenyl group represented by R11 to R17 preferably has 3 to 12 carbon atoms, particularly 5 to 7 carbon atoms.

Examples of the sulfonyl group represented by R11 to R17 include an alkylsulfonyl group and an arylsulfonyl group; examples of the sulfinyl group include an alkylsulfinyl group and an arylsulfinyl group; examples of the phosphonyl group include an alkylphosphonyl group and an alkoxyphosphonyl group; Nyl group, aryloxyphosphonyl group, arylphosphonyl group, etc.; As an acyl group, an alkylcarbonyl group, an arylcarbonyl group, etc.; As a carbamoyl group, an alkylcarbamoyl group, an arylcarbamoyl group, etc.; As a sulfamoyl group, an alkylsulfonyl group, etc. Famoyl group, arylsulfamoyl group, etc.; Acyloxy group includes alkylcarbonyloxy group, arylcarbonyloxy group, etc.; Carbamoyloxy group includes alkylcarbamoyloxy group, arylcarbamoyloxy group, etc.; ureido group includes alkyl Ureido group, aryl ureido group, etc.; Examples of sulfamoylamino group include alkylsulfamoylamino group, arylsulfamoylamino group, etc.; Preferably, 5- to 7-membered heterocyclic group; specifically, 2-furyl group, 2-thienyl group, 2-pyrimidinyl group, 2-benzothiazolyl group, etc.; As the heterocyclic oxy group, one having a 5- to 7-membered heterocycle is preferable, for example, 3,4,5,6- Tetrahydropyranyl-2-oxy group, 1-phenyltetrazole-5
-oxy group, etc.; As the heterocyclic thio group, a 5- to 7-membered heterocyclic thio group is preferable, such as 2-pyridylthio group, 2-benzothiazolylthio group, 2,4-diphenoxy-1,3,5- Triazole-6-thio group, etc.; Siloxy group includes trimethylsiloxy group, triethylsiloxy group, dimethylbutylsiloxy group, etc.; imide group includes succinimide group, 3-heptadecylsuccinimide group, phthalimide group, glutarium group. Imide group, etc.; spiro compound residues include spiro[3.3]heptan-1-yl, etc.; bridged hydrocarbon compound residues include bicyclo[2.2.
1] Heptan-1-yl, tricyclo[3.3.1.1
3,7]decane-1-yl, 7,7-dimethyl-bicyclo[2.2.1]heptan-1-yl, and the like.

The above general formula [M-Ia] to general formula [M-I
Particularly preferable among the magenta couplers represented by [M-Ia] to [M-Ib] are magenta couplers represented by formulas [M-Ia] to [M-Ib].

The most preferred substituents R11 to R17 on the heterocycle are those represented by the following general formula [M-Ig]. General formula [M-Ig] R18-CH2- In the formula, R18 has the same meaning as R11 to R17 above. R1
Preferred as 8 is a hydrogen atom or an alkyl group.

Typical specific examples of the magenta coupler represented by the general formula [M-I] according to the present invention are shown below.

[0039]

[Chemical formula 10]

[0040]

[Chemical formula 11]

[0041]

[Chemical formula 12]

[0042]

[Chemical formula 13]

[0043]

[Chemical formula 14]

[0044]

[Chemical formula 15]

[0045]

[Chemical formula 16]

[0046]

[Chemical formula 17]

[0047]

[Chemical formula 18]

[0048]

embedded image Next, the magenta coupler represented by the general formula [M-II] of the present invention will be explained in detail.

In the general formula [M-II], R2, R3
and R4 represents a hydrogen atom, an alkyl group, or an aryl group. Furthermore, two or three of R2, R3, and R4 may be bonded together to form a saturated or unsaturated ring. At least two of R2, R3, and R4 are not hydrogen atoms.

The alkyl groups represented by R2, R3 and R4 preferably have 1 to 32 carbon atoms, and may be linear or branched. The aryl group represented by R2, R3 and R4 is preferably a phenyl group.

[0051] Examples of the saturated or unsaturated ring formed by bonding two or three of R2, R3 and R4 include cycloalkane, cycloalkene, heterocycle, benzene ring, and bridged hydrocarbon ring. .

In the general formula [M-II], X2, Z2
has the same meaning as X1 and Z1 in the general formula [M-I].

More specifically, those represented by the general formula [M-II] include, for example, the following general formulas [M-IIa] to [M-I
If].

[0054]

embedded image In the general formulas [M-IIa] to [M-IIf],
R21 to R27 have the same meanings as R11 to R17 above.

Typical specific examples of the magenta coupler represented by the general formula [M-II] according to the present invention are shown below.

[0056]

[C21]

[0057]

[C22]

[0058]

[C23]

[0059]

[C24]

[0060]

[C25]

[0061]

[C26]

[0062]

embedded image Magenta coupler (hereinafter referred to as
magenta coupler [M-I]) and the general formula [M-I
The magenta coupler represented by I] (hereinafter referred to as magenta coupler [M-1I]) was published in the Journal of the Chemical Society.
Perkin I (1977), 2047-20
52, U.S. Patent No. 3,725,067, JP-A-59-9
No. 9437, No. 58-42045, No. 59-1625
No. 48, No. 59-171956, No. 60-33552
No. 60-43659, No. 60-172982,
It can be synthesized by referring to No. 60-190779, No. 62-209457, No. 63-307453, etc.

The magenta coupler [M-I] of the present invention is
Usually, it can be used in a range of 1.times.10@-3 mol to 1 mol, preferably 1.times.10@-2 mol to 8.times.10@-1 mol per mol of silver halide.

Furthermore, the magenta coupler of the present invention [M-II
] can be used in a range of 1 x 10-3 mol to 1 mol, preferably 1 x 10-2 mol to 8 x 10-1 mol, per mol of silver halide.

In the present invention, magenta coupler [M-I] and magenta coupler [M-II] are used together, and the molar ratio of magenta coupler [M-I] and magenta coupler [M-II] is 10:1 to 1. :5 is preferable, 5:1 to 1:3
is even more preferable. The couplers of the invention can be used in conjunction with other types of magenta couplers.

Next, the compound represented by the general formula [I] of the present invention will be explained.

Examples of the aliphatic groups represented by R40, R50 and R60 include alkyl groups having 1 to 32 carbon atoms, alkenyl groups, alkynyl groups, cycloalkyl groups, cycloalkenyl groups, and the like. The alkyl group, alkenyl group and alkynyl group may be linear or branched. Furthermore, these aliphatic groups include those having substituents.

Examples of aromatic groups represented by R40, R50 and R60 include aryl groups (for example, phenyl groups, etc.)
, aromatic heterocyclic group (e.g. pyridyl group, furyl group, etc.)
etc. Furthermore, these aromatic groups include those having substituents.

R40, R50 and R60 are each preferably an alkyl group or an aryl group;
50 and R60 may be the same or different, and R4
The total number of carbon atoms of 0, R50 and R60 is preferably 6 to 50.

There are no particular restrictions on the substituents for the aliphatic or aromatic groups represented by R40, R50 and R60, but
Preferred examples include an alkoxy group, an aryloxy group, an acyl group, an acyloxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, a sulfamoyl group, an acylamino group, and an amino group.

[0071] l, m and n each represent 0 or 1, but l, m and n are never 1 at the same time. That is, at least one of the aliphatic groups or aromatic groups represented by R40, R50 and R60 is directly bonded to the phosphorus atom. Preferably, l, m and n are all 0.

Typical specific examples of the compound represented by the general formula [I] of the present invention are shown below, but the present invention is not limited thereto.

[0073]

[C28]

[0074]

[C29]

[0075]

[C30]

[0076]

[Chemical formula 31]

[0077]

[C32]

[0078]

[Chemical formula 33]

[0079]

[C34]

[0080]

[C35]

[0081]

[C36]

[0082]

embedded image The compound represented by the general formula [I] of the present invention is
It also includes compounds described on pages 4 to 5 of Publication No. 19049.

Some of the compounds represented by the general formula [I] of the present invention are commercially available, but for example, JP-A-56-19
Publication No. 049; Specification of British Patent No. 694,772; Journal of the American Chemical Society, 1957, Volume 79, Page 6524 [J. Am
．． Chem. Soc. , 79, 6524 (1957)]
; Journal of Organic Chemistry, 1
960, Volume 25, Page 1000 [J. Org. Ch
em. , 25, 1000 (1960)]; Organic Synthesis, 1951, Volume 31, Page 33 [Or
g. Synth. , 31, 33 (1951)].

Next, to explain the compound represented by the general formula [II], the alkyl groups represented by RA and RB have 1 to 32 carbon atoms, alkenyl groups, and alkynyl groups have 2 to 32 carbon atoms. Examples of the cycloalkyl group, cycloalkenyl group, and cycloalkenyl group include those having 3 to 12 carbon atoms. The alkyl group, alkenyl group, and alkynyl group may be linear or branched. Moreover, these groups also include those having substituents.

The aryl group represented by RA and RB is preferably a phenyl group, including those having substituents.

The heterocyclic groups represented by RA and RB are preferably 5- to 7-membered, and may be fused, and these groups also include those having substituents.

The alkoxy groups represented by RA and RB include those having substituents, such as 2-ethoxyethoxy group, pentadecyloxy group, 2-dodecyloxyethoxy group, phenethyloxyethoxy group, and the like.

Further, as the aryloxy group, a phenyloxy group is preferable, and the aryl nucleus may be substituted, such as a phenoxy group, a pt-butylphenoxy group, a m-pentadecylphenoxy group, and the like.

Furthermore, the heterocyclic oxy group preferably has a 5- to 7-membered heterocycle, and the heterocycle may further have a substituent, for example, 3,4,5,6-tetrahydro Examples include pyranyl-2-oxy group and 1-phenyltetrazol-5-oxy group.

Particularly preferred among the non-color-forming compounds of the present invention are compounds represented by the following general formula [III]. General formula [III] RE-NHSO2-RF In the formula, RE and RF are each an alkyl group or an aryl group, and these groups also include substituted groups. More preferably, at least one of RE and RF is an aryl group. Most preferably, RE and RF are both aryl groups, particularly preferably phenyl groups. Here, when RE is a phenyl group, it is particularly preferable that the Hammett's σp value of the substituent at the para position of the sulfonamide group is −0.4 or more.

The alkyl group and aryl group represented by RE or RF are RA or RB of the general formula [II]
It has the same meaning as the alkyl group and aryl group represented by.

[0092] Furthermore, the non-chromogenic compound of the present invention may form a dimer or more multimer in RA or RB,
Further, RA and RB may be combined with each other to form a 5- to 6-membered ring.

The total number of carbon atoms in the non-color-forming compound of the present invention is preferably 8 or more, particularly preferably 12 or more.

Typical examples of the non-chromogenic compounds of the present invention are shown below.

[0095]

[C38]

[0096]

[C39]

[0097]

[C40]

[0098]

[C41]

0099

[C42]

[0100]

[C43]

[0101]

[C44]

[0102]

[C45]

[0103]

[C46]

[0104]

[C47]

[0105]

[C48]

[0106]

[C49]

[0107]

[C50]

[0108]

[C51]

[0109]

embedded image The non-chromogenic compound represented by the general formula [II] of the present invention is
For example, it can be synthesized by conventionally known methods such as the method described in Japanese Patent Application No. 61-20589.

The amount of the non-color-forming compound represented by the general formula [II] of the present invention is preferably 5 to 500 mol%, more preferably 10 to 300 mol%, based on the coupler.

[0111] Some of the non-chromogenic compounds represented by the general formula [II] of the present invention are disclosed in JP-A-57-76543 and JP-A-57-76543.
-179842, 58-1139, 62-17
It is described in various publications such as No. 8258.

Next, the general formula [A-I] according to the present invention
The compound represented by will be explained.

Examples of the divalent organic group represented by J' include an alkylene group, an alkenylene group, a cycloalkylene group, an arylene group, a heterocyclic group, and a -J''-NH- group (J'' is an arylene group. ), and these groups may have a substituent.

The alkyl group, cycloalkyl group, aryl group, alkenyl group, alkynyl group, and cycloalkenyl group represented by Y preferably have a carbon atom number in the range of 1 to 32. These alkyl groups, alkenyl groups and alkynyl groups may be linear or branched. Moreover, these groups include those having substituents.

The heterocyclic group represented by Y is preferably a nitrogen-containing heterocyclic group, such as a pyrrolyl group, a pyrazolyl group, an imidazolyl group, a pyridyl group, a pyrrolinyl group, an imidazolidinyl group, an imidazolinyl group, a piperazinyl group,
Examples include piperidinyl groups. These heterocyclic groups also include those having substituents.

Typical specific examples of the compound represented by the general formula [A-I] are shown below.

[0117]

[C53]

[0118]

[C54]

[0119]

embedded image In the present invention, magenta coupler [M-I], magenta coupler [M-II], and compounds represented by general formula [I], general formula [II], and general formula [A-I] are used. In order to incorporate the silver halide into the emulsion layer, a conventional method is used, for example, a mixture of a high boiling point solvent such as dibutyl phthalate or tricresyl phosphate, and a low boiling point solvent such as butyl acetate or ethyl acetate. After dissolving magenta coupler [M-I] and magenta coupler [M-II], either alone or in combination, they are mixed with an aqueous gelatin solution containing a surfactant, and then mixed with a high-speed rotary mixer, a colloid mill, or an ultraviolet mixer. A method can be adopted in which the material is emulsified and dispersed using a sonic disperser and then directly added to the emulsion. Alternatively, after setting the emulsified dispersion, it may be shredded, washed with water, and then added to the emulsion.

In the present invention, the magenta coupler [M-I] and the magenta coupler [M-II] according to the present invention may be separately dispersed by the above-mentioned dispersion method and added to the silver halide emulsion. , a method in which both compounds are simultaneously dissolved, dispersed, and added to an emulsion is preferred.

As the silver halide emulsion used in the light-sensitive material of the present invention, any conventional silver halide emulsion can be used. 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. Gelatin is advantageously used as binder for the emulsion.

The emulsion layer and other hydrophilic colloid layers can be hardened, and can also contain a plasticizer and a dispersion (latex) of a water-insoluble or sparingly soluble synthetic polymer. Couplers are used in the emulsion layer of color photographic materials.

Furthermore, by coupling with a colored coupler having a color correction effect, a competitive coupler, and an oxidized form of a developing agent, a development accelerator, a bleach accelerator, a developer, a silver halide solvent, a toning agent, a hardener, etc. Compounds that release photographically useful fragments such as film agents, fogging agents, antifogging agents, chemical sensitizers, spectral sensitizers, and desensitizers can be used.

The photosensitive material may be provided with auxiliary layers such as a filter layer, an antihalation layer, and an antiirradiation layer. In these layers and/or in the emulsion layer,
Dyes that are washed out or bleached from the light-sensitive material during processing may also be included. Photosensitive materials include formalin scavengers, fluorescent whitening agents, matting agents, lubricants, image stabilizers, surfactants, color fog preventive agents, development accelerators,
Development retarders and bleach accelerators can be added.

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

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

[0128]

[Examples] Next, the present invention will be specifically explained with reference to Examples, but the present invention is not limited thereto.

In all the examples below, the amount added in the silver halide photographic light-sensitive material was 1 m2 unless otherwise specified.
Show the winning one. Furthermore, silver halide and colloidal silver are shown in terms of silver. Example 1 One side (front side) of a triacetyl cellulose film support was subjected to a subbing process, and then the following composition was applied to the opposite side (back side) of the support across the support from which the subbing process was applied. The layers were created sequentially starting from the support side. Back side 1st layer Alumina sol AS-100 (aluminum oxide)
0.8g (manufactured by Nissan Chemical Industries, Ltd.) Second layer on the back: diacetyl cellulose
100m
g stearic acid

10mg Silica fine particles (average particle size 0.2μm
) 50
A multilayer color photographic material 101 was prepared by sequentially forming layers having the compositions shown below on the surface of a triacetyl cellulose film support subjected to mg subbing processing, starting from the support side. 1st layer; antihalation layer (HC) black colloidal silver
0.1
5g Ultraviolet absorber (UV-1)
0.20g
Colored cyan coupler (CC-1)
0.02g High boiling point solvent (O
il-1)
0.20g High boiling point solvent (Oil-
2)
0.20g gelatin

1.6g second layer; intermediate layer (IL-
1) Gelatin

1.3g third layer; low sensitivity red-sensitive emulsion layer (R-L) Silver iodobromide emulsion (average grain size 0.3 μm) (average iodine content 2.0 mol%)

0.4g Silver iodobromide emulsion (average grain size 0.4μm) (average iodine content 8.0mol%)


0.3g Sensitizing dye (S-1)
3.2×10-4 (mol/silver 1 mol)
Sensitizing dye (S-2) 3.2×
10-4 (mol/silver 1 mol) Sensitizing dye (S-3)
0.2 x 10-4 (mol/silver 1
Mol) Cyan coupler (C-1)
0.50g
Cyan coupler (C-2)
0.13g colored cyan coupler (CC-1)
0.07g DIR compound (D-
1)
0.006g DIR compound (D-2
)
0.01g High boiling point solvent (Oil-1)

0.55g gelatin

1.0g 4th layer; High sensitivity red-sensitive emulsion layer (R-H) Silver iodobromide emulsion (average grain size 0.7 μm) (
Average iodine content 7.5 mol%)

0.9g
Sensitizing dye (S-1) 1.7×
10-4 (mol/silver 1 mol) Sensitizing dye (S-2)
1.6 x 10-4 (mol/silver 1
Mol) Sensitizing dye (S-3)
0.1×10-4 (mol/silver 1 mol) Cyan coupler (C-2)
0.23g colored cyan coupler (CC-1)
0.03g DIR compound (D-2)

0.02g High boiling point solvent (Oil-1)
0.2
5g gelatin

1.0g 5th layer; intermediate layer (IL-2) gelatin

0.8g 6th layer; low-sensitivity green-sensitive emulsion layer (GL) Silver iodobromide emulsion (average grain size 0.4 μm) (average iodine content 8.0 mol%)

0.6g Silver iodobromide emulsion (average grain size 0.3 μm) (average iodine content 2.0 mol%)


0.2g Sensitizing dye (S-4)
6.7 x 10-4 (mol/1 mol of silver)
Sensitizing dye (S-5) 0.8x
10-4 (mol/silver 1 mol) Magenta coupler (M
-I-4)
0.50g colored magenta coupler (CM-
1) 0.10g
DIR compound (D-3)
0.02g High boiling point solvent (Oil-2)
0.7g gelatin

1.0g 7th layer;
High-sensitivity green-sensitive emulsion layer (GH) Silver iodobromide emulsion (average grain size 0.7 μm) (average iodine content 7.5 mol%)


0.9g Sensitizing dye (S-6)
1.1 x 10-4 (mol/silver 1 mol) Sensitizing dye (S-7) 2.0 x 1
0-4 (mol/silver 1 mol) Sensitizing dye (S-8)
0.3 x 10-4 (mol/silver 1 mol) Magenta coupler (M-I-4)
0.25g colored magenta coupler (CM-1)
0.04g DIR compound (D-3)

0.004g High boiling point solvent (Oil-2)

0.35g gelatin

1.0g 8th layer; Yellow filter layer (YC) Yellow colloidal silver

0.1g additive (HS-1)

0.07g additive (HS-2)

0.07g Additive (SC-1)

0.12g High boiling point solvent (Oil-2)
0.
15g gelatin

1.0g 9th layer; low sensitivity blue sensitive emulsion layer (BL)
Silver iodobromide emulsion (average grain size 0.3 μm) (average iodine content 2.0 mol%)

0.25g Silver iodobromide emulsion (average grain size 0.4 μm) (average iodine content 8.0
mole%)

0.25g Sensitizing dye (S-9)
5.8 x 10-4 (mol/silver 1
Mol) Yellow coupler (Y-1)
0.6g
Yellow coupler (Y-2)
0.32g DIR compound (D-1)
0.003g DIR compound (D-2)
0.006g High boiling point solvent (
Oil-2)
0.18g gelatin

1.3g 10th layer; Highly sensitive blue-sensitive emulsion layer (B-H) Silver iodobromide emulsion (average grain size 0.8 μm) (average iodine content 8.5 mol%)


0.5g Sensitizing dye (S-10)
3 x 10-4 (mol/1 mol of silver) Sensitizing dye (S-11) 1.2 x 10-4 (mol/1 mol of silver) Yellow coupler (Y-1)
0.1
8g yellow coupler (Y-2)
- 0.10
g High boiling point solvent (Oil-2)
0.05g
gelatin
1.
0g 11th layer; 1st protective layer (PRO-1) Silver iodobromide emulsion (average grain size 0.08 μm)
0.3g UV absorber (U
V-1)
0.07g Ultraviolet absorber (UV-2
)
0.10g additive (HS-1)

0.2g additive (HS-2)

0.1g High boiling point solvent (Oil-1)
0
．． 07g High boiling point solvent (Oil-3)
0.07
g Gelatin

0.8g 12th layer; 2nd protective layer (PRO-2) Compound A

0.04g Compound B

0.004g Polymethyl methacrylate (average particle size 3μm) 0.02g
Methyl methacrylate: Ethyl methacrylate:
Copolymer of methacrylic acid = 3:3:4 (weight ratio) (average particle size: 3 μm) 0.13 g The silver iodobromide emulsion used in the 10th layer was prepared in the following manner.

[0130] Monodispersed silver iodobromide grains (silver iodide content: 2 mol %) having an average grain size of 0.33 μm were used as seed crystals to prepare by a double jet method.

[0131] Solution <G-1> was heated to a temperature of 70°C and a pAg of 7.
8. While keeping the pH at 7.0 and stirring well, a seed emulsion equivalent to 0.34 mol was added. (Formation of internal high iodine phase - core phase) Then <H-1>
and <S-1> were added at an accelerated flow rate (the final flow rate was 3.6 times the initial flow rate) over a period of 86 minutes while maintaining a flow ratio of 1:1. (Formation of external low iodine phase - shell phase) Subsequently, pAg1
<H-2> and <S- while keeping the pH at 0.1 and pH 6.0.
2> was added at an accelerated flow rate (end flow rate 5.2 times the initial flow rate) at a flow rate ratio of 1:1 over a period of 65 minutes.

[0132] pAg and pH during particle formation were controlled using an aqueous potassium bromide solution and a 56% acetic acid aqueous solution. After the particles were formed, they were washed with water by a conventional flocculation method, and then gelatin was added to redisperse them, and the pH and pAg were adjusted to 5.8 and 8.06, respectively, at 40°C.

The obtained emulsion had an average grain size of 0.80 μm,
It was a monodisperse emulsion containing octahedral silver iodobromide grains with a distribution width of 12.4% and a silver iodide content of 8.5 mol%. <G-1> Ossein gelatin
100.0g
Compound-I
2
5.0ml 28% ammonia aqueous solution
440.
0ml 56% acetic acid aqueous solution
660
．． Finish with 0ml water
50
00.0ml <H-1> Ossein gelatin
82.4
g potassium bromide
151
．． 6g potassium iodide

Finish with 90.6g water

1030.5ml <S-1> Silver nitrate
3
09.2g 28% ammonia aqueous solution
Equivalent Finish with water
1030.5
ml<H-2> Ossein gelatin
302.1g
potassium bromide
770.
0g potassium iodide

Finish with 33.2g water
3
776.8ml <S-2> Silver nitrate
113
3.0g 28% ammonia aqueous solution
equivalent weight
finish with water
3776.8m
l In the same manner, the average grain size of the seed crystal, temperature, pAg, p
The above emulsions having different average grain sizes and silver iodide contents were prepared by varying H, flow rate, addition time, and halide composition.

All of them were core/shell type monodisperse emulsions with a distribution width of 20% or less. Each emulsion was subjected to optimal chemical ripening in the presence of sodium thiosulfate, chloroauric acid and ammonium thiocyanate, and the sensitizing dye, 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene ,
1-phenyl-5-mercaptotetrazole was added.

[0135]

[C56]

[0136]

[C57]

[0137]

[C58]

[0138]

[C59]

[0139]

[C60]

[0140]

[C61]

[0141]

[C62]

[0142]

[C63]

[0143]

[C64]

[0144]

embedded image The above-mentioned photosensitive material 101 further contains the compound Su-1,
Su-2, viscosity modifier, hardener H-1, H-2, stabilizer ST-1, antifoggant AF-1, AF-2 (weight average molecular weight 10,000 and 1,100,000) ), dyes AI-1, AI-2 and compound DI-1 (9
．． 4mg/m2).

[0145] In the multilayer color photographic material 101,
A multilayer color photographic material was prepared in the same manner as the multilayer color photographic material 101 except that the magenta coupler M-I-4 and the high boiling point solvent Oil-2 in the sixth and seventh layers were changed as shown in Table 1. Photosensitive materials 102 to 110 were created.

[0146] Photosensitive material 101 prepared as above
-110 were exposed to white light through a step wedge for sensitometry, and then processed under the following conditions to determine the fog and sensitivity of the green photosensitive layer.

[0147] *The amount of replenishment is the value per 1 m2 of photosensitive material.

The following color developing solution, bleaching solution, fixing solution, stabilizing solution and their replenisher were used. <Color developer> Water

800ml potassium carbonate

30g sodium bicarbonate
2.5g potassium sulfite
3.0g sodium bromide
1.3g
potassium iodide
1.2
mg hydroxylamine sulfate
2.5g
sodium chloride
0
．． 6g 4-amino-3-methyl-N-ethyl-
N-(β-hydroxyethyl) aniline sulfate
4.5g diethylenetriaminepentaacetic acid
3.0g potassium hydroxide
Add 1.2g water and 1
liter and adjust the pH to 10.06 using potassium hydroxide or 20% sulfuric acid. <Color developer replenisher> Water

800ml potassium carbonate

35g sodium bicarbonate
3g potassium sulfite
5g
sodium bromide
0.4
g Hydroxylamine sulfate
3.1g
4-amino-3-methyl-N-ethyl-N-(β
-hydroxyethyl) aniline sulfate

6.3g potassium hydroxide

2g diethylenetriaminepentaacetic acid
Add 3.0 g of water to make 1 liter, and use potassium hydroxide or 20% sulfuric acid to make a solution.
Adjust to H10.18. <Bleach solution> Water

700ml 1,3-diaminopropanetetraacetic acid iron(III) ammonium

125
g ethylenediaminetetraacetic acid

2g sodium nitrate

40g ammonium bromide

150g glacial acetic acid

Add 40 g of water to make 1 liter, and adjust to pH 4 using aqueous ammonia or glacial acetic acid.
Adjust to 4. <Bleach replenisher> Water

700ml 1,3-diaminopropanetetraacetic acid iron(III) ammonium

175g ethylenediaminetetraacetic acid
2g sodium nitrate
50g ammonium bromide
200g
glacial acetic acid

56g pH 4.0 using aqueous ammonia or glacial acetic acid.
After adjusting to 0, add water to make 1 liter. <Fixer> Water

800ml ammonium thiocyanate
120g ammonium thiosulfate

150g sodium sulfite

15g ethylenediaminetetraacetic acid
After adjusting the pH to 6.2 using 2g ammonia water or glacial acetic acid, add water to make 1 liter. <Fixer replenisher> Water

800ml ammonium thiocyanate
150g ammonium thiosulfate

180g sodium sulfite

20g ethylenediaminetetraacetic acid
After adjusting the pH to 6.5 using 2g ammonia water or glacial acetic acid, add water to make 1 liter. <Stabilizing liquid and stable replenishing liquid> Water

900ml 66

2.0g

[0149]

[Chemical 66] Dimethylol urea
0.
5g hexamethylenetetramine
0.2g
1,2-benzisothiazolin-3-one
0.1g siloxane (UCC L-77)
0.1g ammonia water

Add 0.5 ml of water to make 1 liter, and then adjust the pH to 8.5 using aqueous ammonia or 50% sulfuric acid. [Evaluation of raw storage stability] A sample of the photosensitive materials 101 to 110 prepared was left in an atmosphere of 40° C. and 80% relative humidity for 7 days to undergo forced deterioration, and then exposed to light in the same manner as above and subjected to the same development treatment. I did it. The fog and sensitivity of the green photosensitive layer of the obtained sample were measured, and the increase in fog (ΔFog) compared to the sample without forced deterioration and the increase in fog after forced deterioration when the sensitivity of the sample without forced deterioration was taken as 100. The relative sensitivity of the samples was determined. [Evaluation of processing stability] Photosensitive materials 101 to 110 were exposed to white light through a sensitometric step wedge in the same manner as above, and then the pH of the color developer was adjusted to 10.4 and 10.0. The same processing was performed using different color developing solutions, and the gamma fluctuation values in the linear portion of the green density characteristic curve were compared.

The gamma variation value is the rate of change in gamma value B at pH 10.4 with respect to gamma value A at pH 10.0, and was determined by the following formula.

[0151] Gamma variation value = {(B/A)-1}×10
0 The smaller the gamma variation value, the smaller the change. [Evaluation of variations between different types of printers] Photosensitive materials 101-11
0 was uniformly exposed to white light, and the same development process as above (however, the pH of the color developing solution was adjusted to 10.18) was performed. Using these developed samples, each was printed in gray with a reflection density of 0.5 using Printer A to create print samples 101A to 110A.

Next, each sample was printed under the same printing conditions as Printer A using Printer B, which has a different spectral sensitivity of the detector in the green region from Printer A, to create print samples 101B to 110B. For the obtained print samples 101B to 110B, 10 panelists visually evaluated the deviation from gray of each print sample, that is, the variation between different types of printers. The above results are also shown in Table 2.

[0153]

[Table 1]

[0154]

[Table 2] As is clear from Table 2, photosensitive material 101 other than the present invention exhibits an increase in fog and a severe decrease in sensitivity when subjected to forced deterioration, and also has a gamma fluctuation value when the pH of the color developer changes. is large, and the variation between different types of printers is also very large.

In contrast, photosensitive materials 102-1 of the present invention
No. 10 exhibits a small increase in fog and a small decrease in sensitivity when subjected to forced deterioration, and has good shelf life. Furthermore, the gamma variation value when the pH of the color developer changes is small, and the variation between different types of printers is also small, and very good performance is obtained. Example 2 In the multilayer color photographic material 101 prepared in Example 1, the magenta coupler M-I-4 and the high boiling point solvent Oil-2 in the sixth and seventh layers were changed as shown in Table 3. Multilayer color photographic materials 111 to 120 were prepared in the same manner as multilayer color photographic material 101 except for the above.

[0156] Photosensitive material 111 prepared as above
-120, raw storage stability, processing stability, and variation between different printers were evaluated in the same manner as in Example 1. The results are also shown in Table 4.

[0157]

[Table 3]

[0158]

[Table 4] As is clear from Table 4, photosensitive material 101 other than the present invention exhibits an increase in fog and a severe decrease in sensitivity when subjected to forced deterioration, and also has a gamma fluctuation value when the pH of the color developer changes. is large, and the variation between different types of printers is also very large.

On the other hand, the photosensitive materials 111-1 of the present invention
No. 20 exhibits good shelf life with little increase in fog or decrease in sensitivity when subjected to forced deterioration. Furthermore, the gamma variation value when the pH of the color developer changes is small, and the variation between different types of printers is also small, and very good performance is obtained. Example 3 In the multilayer color photographic material 101 prepared in Example 1, the sixth
A multilayer color photographic material 121 was produced in the same manner as the multilayer color photographic material 101 except that the magenta coupler M-I-4 and the high boiling point solvent Oil-2 in the first and seventh layers were changed as shown in Table 5. ~130 were created.

[0160] Photosensitive material 121 prepared as above
~130, raw storage stability, processing stability, and variation between different types of printers were evaluated in the same manner as in Example 1. The results are also shown in Table 6.

[0161]

[Table 5]

[0162]

[Table 6] As is clear from Table 6, photosensitive material 101 other than the present invention exhibits an increase in fog and a severe decrease in sensitivity when subjected to forced deterioration, and also has gamma fluctuation values when the pH of the color developer changes. is large, and the variation between different types of printers is also very large.

On the other hand, the photosensitive materials 121-1 of the present invention
No. 30 exhibits good shelf life with little increase in fog or decrease in sensitivity when subjected to forced deterioration. Furthermore, the gamma variation value when the pH of the color developer changes is small, and the variation between different types of printers is also small, and very good performance is obtained.

[0164]

According to the present invention, it is possible to provide a silver halide photographic material that exhibits little variation between printers, good shelf life, and good processing stability.

Claims (3)

[Claims] 1. A silver halide color photographic light-sensitive material having photographic constituent layers including a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, and a red-sensitive silver halide emulsion layer on a support, comprising: At least one magenta coupler represented by the following general formula [M-I] and a magenta coupler represented by the following general formula [M-I] are included in at least one layer of the green-sensitive silver halide emulsion layer.
At least one kind of magenta coupler represented by II],
and at least one of the compounds represented by the following general formula [I]
A silver halide color photographic light-sensitive material characterized by containing seeds. embedded image [In the formula, R1 represents a hydrogen atom, an alkyl group, or an aryl group. R2, R3 and R4 are hydrogen atoms, alkyl groups,
Represents an aryl group. Further, R2, R3 and R4 may be bonded together to form a saturated or unsaturated ring. At least two of R2, R3 and R4 are not hydrogen atoms. J represents a methylene group, an oxygen atom, or a sulfur atom. X1 and X2 represent a hydrogen atom or a group that can be separated by reaction with an oxidized product of a color developing agent. Z1 and Z2 represent a group of nonmetallic atoms necessary to form a nitrogen-containing heterocycle, and the ring formed by Z1 and Z2 may have a substituent. ] General formula [I] [In the formula, R40, R50 and R60 each represent an aliphatic group or an aromatic group, and l, m and n each represent 0 or 1. However, l, m and n are never 1 at the same time. ] 2. A silver halide color photographic light-sensitive material having a photographic constituent layer comprising a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, and a red-sensitive silver halide emulsion layer on a support, At least one layer of the green-sensitive silver halide emulsion layer contains the general formula [M
-I], at least one magenta coupler represented by the general formula [M-II] according to claim 1, and the following general formula [II].
] A silver halide color photographic material containing at least one compound represented by the following. General formula [II] RA-NHSO2-RB [wherein RA and RB are each a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, an aryl group, a heterocyclic group, an alkoxy group, and an aryl group. Represents an oxy group, a heterocyclic oxy group, or [Formula 3]. Here, RC and RD each represent a hydrogen atom, an alkyl group or an aryl group. RA and RB may be the same or different. ] 3. A silver halide color photographic light-sensitive material having a photographic constituent layer comprising a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, and a red-sensitive silver halide emulsion layer on a support, At least one of the green-sensitive silver halide emulsion layers has the general formula [M-I] according to claim 1.
At least one magenta coupler represented by the following, at least one magenta coupler represented by the general formula [M-II] according to claim 1, and a compound represented by the following general formula [A-I] A silver halide color photographic material containing at least one of the following. General formula [A-I] [Formula, J' represents a divalent organic group, Y represents an alkyl group,
Represents a cycloalkyl group, aryl group, alkenyl group, alkynyl group, cycloalkenyl group, and heterocyclic group. ]