EP0296785A2

EP0296785A2 - Reversal silver halide light-sensitive photographic material having improved stability against processing

Info

Publication number: EP0296785A2
Application number: EP88305621A
Authority: EP
Inventors: Toshihiko Kimura; Masaru Iwagaki; Atsuo Ezaki
Original assignee: Konica Minolta Inc
Current assignee: Konica Minolta Inc
Priority date: 1987-06-21
Filing date: 1988-06-21
Publication date: 1988-12-28
Also published as: JPS6477056A; EP0296785A3

Abstract

A reversal silver halide light-sensitive photographic material having improved stability against processing is disclosed. The photographic material comprises a support and photographic component layers including at least two silver halide emulsion layers having different spectral sensitivity from each other, in which at least one layer of the silver halide emulsion layers contains a pyrazoloazole-type magenta coupler, and at least one layer of the photographic component layer contains a compound which is capable of releasing either a development inhibitor or a compound capable of releasing a development inhibitor.

Description

FIELD OF THE INVENTION

The present invention relates to a color reversal silver halide light-sensitive photographic material, and more particularly to a color reversal light-sensitive material which is improved so that its photographic characteristics are hardly affected by fluctuation in processing and which is excellent in the color reproducibility.

BACKGROUND OF THE INVENTION

For color reversal light-sensitive materials, various characteristics are required, and above all, in the noticeable high-quality-image-oriented trend in recent years, importance is attached particularly to the color reproducibility. In color reversal light-sensitive materials, since it is practically impossible to apply to them the technique of compensating the formed dyes' secondary absorptions by such colored couplers as used in color negative materials, the color-forming materials in themselves are required to form high color-purity dyes. For example, pyrazoloazole-type magenta couplers, since their secondary absorption is extremely small, are advantageous in the color reproducibility.
Another desirable characteristic for the color reversal light-sensitive material is that the material be stable against fluctuations in color developing conditions.
As for the processing of a color reversal light-sensitive material, as described in 'The Theory of the Photographic Process,' edited by T. H. James, 4th ed., p. 336 (Macmillan), its process comprises the steps of the first development for black-and-white developing, optically or chemically fogging the residual silver halide, color development in the presence of couplers, bleaching, and fixing. The residual silver halide remaining undeveloped in the first development, after being fogged, is used for color development;― thus the color reversal process is complex as compared to color negative materials, and this complexity is considered to result in increasing fluctuations in the developing conditions (including e.g., pH of the developer solution) of the color reversal light-sensitive material, thereby making its photographic characteristics increasingly unstable.
It has been found as a result of our investigation that the use of the aforementioned pyrazoloazole-type magenta coupler, which is satisfactory in the color reproducibility, particularly emphasizes the influence by such fluctuations in the processing. Such the behavior of the pyrazoloazole-type coupler is a significant drawback to its practical use.

SUMMARY OF THE INVENTION

It is therefore a first object of the present invention to provide a color reversal light-sensitive material which is improved so that its photographic characteristics are hardly affected by fluctuations in processing.
It is a second object of the present invention to provide a color reversal light-sensitive material which is excellent in the color reproducibility.
The above objects of the present invention are accomplished by a reversal silver halide photographic light-sensitive material comprising a support and, provided thereon, photographic component layers including at least two silver halide emulsion layers different in the spectral sensitivity from each other, in which at least one layer of the silver halide emulsion layers contains a pyrazoloazole-type magenta coupler, and at least one layer of the photographic component layers contains a compound which is capable of releasing a development inhibitor (hereinafter referred to as 'DIR compound').
Japanese Patent Publication Open to Public Inspection (hereinafter referred to as Japanese Patent O.P.I. Publica tion) No. 262158/1985 discloses the use of both of pyrazoloazole-type magenta coupler and a DIR compound capable of releasing a diffusible inhibitor component. This publication describes the improvement of color reproducibility, but makes no mention of improving photographic characteristics so as to be stable against fluctuations in color reversal processing. Accordingly, the improvement to make the photographic characteristics stable against fluctuations in processing, which is one of the objects of the present invention, cannot be expected at all to be accomplished by those techniques alone which have hitherto been disclosed.

DETAILED DESCRIPTION OF THE INVENTION

The foregoing pyrazoloazole-type magenta coupler according to the present invention has the following Formula [M-I]:
wherein Z is a group of non-metal atoms necessary to form a nitrogen-containing heterocyclic ring, provided that the ring to be formed by the Z may be allowed to have a substituent; X is a hydrogen atom or a group capable of being split off upon reaction with the oxidation product of a color developing agent; and R is a hydrogen atom or a substituent.
The substituent represented by the R, although not specially restricted, is typified by alkyl, aryl, anilino, acylamino, sulfonamido, alkylthio, arylthio, alkenyl, cycloalkyl and the like groups, and in addition, by a halogen atom and those groups including cycloalkenyl, alkinyl, heterocyclic, sulfonyl, sulfinyl, phosphonyl, acyl, carbamoyl, sulfamoyl, cyano, alkoxy, aryloxy, heterocyclic oxy, siloxy, acyloxy, carbamoyloxy, amino, alkylamino, imido, ureido, sulfamoylamino, alkoxycarbonylamino, aryloxycarbonylamino, alkoxycarbonyl, aryloxycarbonyl and heterocyclic thio groups, and spiro compound residue, cross-linked hydrocarbon compound residue and the like.
The alkyl group represented by the R is preferably a straight-chain or branched-chain alkyl group having from 1 to 32 carbon atoms.
The aryl group represented by the R is preferably a phenyl group.
The acylamino group represented by the R is preferably an alkylcarbonylamino group, arylcarbonylamino group or the like.
The sulfonamido group represented by the R is such as an alkylsulfonylamino group, arylsulfonylamino group, or the like.
The alkyl and aryl constituents of the alkylthio and arylthio groups are the same as the above alkyl and aryl groups, respectively, represented by the foregoing R.
The alkenyl group represented by the R is one having from 2 to 32 carbon atoms, and the cycloalkyl group is one having from 3 to 12 carbon atoms, and particularly preferably from 5 to 7 carbon atoms. The alkenyl group may be either straight-chain or branched-chain.
The cycloalkenyl group represented by the R is one having from 3 to 12 carbon atoms, and more preferably from 5 to 7 carbon atoms.
The sulfonyl group represented by the R is such as an alkylsulfonyl group, arylsulfonyl group or the like.
The sulfinyl group is such as an alkylsulfinyl group, arylsulfinyl group or the like.
The phosphonyl group is such as an alkylphosphonyl group, alkoxyphosphonyl group, aryloxyphosphonyl group, arylphosphonyl group or the like.
The acyl group is such as an alkylcarbonyl group, arylcarbonyl group or the like.
The carbamoyl group is such as an alkylcarbamoyl group, arylcarbamoyl group or the like.
The sulfamoyl group is such as an alkylsulfamoyl group, arylsulfamoyl group or the like.
The acyloxy group is such as an alkylcarbonyloxy group, arylcarbonyloxy group or the like.
The carbamoyloxy group is such as an alkylcarbamoyloxy group, arylcarbamoyloxy group or the like.
The ureido group is such as an alkylureido group, arylureido group or the like.
The sulfamoylamino group is such as an alkylsulfamoylamino group, arylsulfamoylamino group or the like.
The heterocyclic group is preferably a 5- to 7-member heterocyclic group such as a 2-furyl group, 2-thienyl group, 2-pyrimidinyl group, 2-benzothiazolyl group or the like.
The heterocyclic oxy group is preferably one having a 5- to 7-member heterocyclic ring, such as a 3,4,5,6-tetrahydropyranyl-2-oxy group, 1-phenyltetrazole-5-oxy group or the like.
The heterocyclic thio group is preferably a 5- to 7-member heterocyclic thio group such as a 2-pyridylthio group, 2-benzothiazolylthio group, 2,4-diphenoxy-1,3,5-triazole-6-thio group or the like.
The siloxy group is such as a trimethylsiloxy group, triethylsiloxy group, dimethylbutylsiloxy group or the like.
The imido group is such as a succinic acid imido group, 3-heptadecyl-succinic acid imido group, phthalimido group, glutarimido group or the like.
The spiro compound residue is such as spiro[3.3]heptan-1-yl, or the like.
The cross-linked hydrocarbon compound residue is such as bicyclo[2.2.1]heptan-1-yl, tricyclo[3.3.1.1³ʼ⁷]decan-1-yl, 7,7-dimethyl-bicyclo[2.2.1]heptan-1-yl, or the like.
The group represented by the X, which is capable of being split off upon reaction with the oxidation product of a color developing agent, is, for example, a halogen atom (such as chlorine, bromine, fluorine) or an alkoxy group, aryloxy group, heterocyclic oxy group, acyloxy group, sulfonyloxy group, alkoxycarbonyloxy group, aryloxycarbonyl group, alkyloxalyloxy group, alkoxyoxalyloxy group, alkylthio group, arylthio group, heterocyclic thio group, alkyloxythiocarbonylthio group, acylamino group, sulfonamido group, nitrogen-containing heterocyclic group combined by a nitrogen atom, alkyloxycarbonylamino group, aryloxycarbonylamino group, carboxyl group, or group having the formula:
wherein R₁′ is as defined in the foregoing R; Z′ is as defined in the foregoing Z; R₂′ and R₃′ each is a hydrogen atom, an aryl, alkyl or heterocyclic group; and preferably a halogen atom, and more preferably a chlorine atom.
The nitrogen-containing heterocyclic ring formed by the Z or Z′ is such as a pyrazole ring, imidazole ring, triazole ring or tetrazole ring, which each may have a substituent. Examples of the substituent include those represented by the foregoing R.
The compounds having Formula [M-I], more particularly, include those represented by, e.g., the following Formulas [M-II] through [M-VII]:
In the above Formulas [M-II] through [M-VII], R₁ through R₈ and X are as defined in the foregoing R and X, respectively, wherein the R₅ and R₆ may form a ring together, examples of which ring include, e.g., a benzene ring.
Further, preferred among the compounds having Formula [M-I] are those having the following Formula [M-VIII]:
wherein R₁, X and Z₁ are as defined in the R, X and Z, respectively, of Formula [M-I].
Particularly preferred among the magenta couplers having Formulas [M-II] through [M-VII] are those magenta couplers having Formula [M-II].
Preferred as the substituent which the ring formed by the Z of Formula [M-I] or the ring formed by the Z₁ of Formula [M-VIII] may have or as the R₂ through R₈ of Formulas [M-II] through [M-VI] are those having the following Formula [M-IX]:

Formula [M-IX]

-R¹-(NH)n-SO₂-R²
wherein R¹ is an alkylene group, R² is an alkyl group, cycloalkyl group or aryl group, and n is an integer of 0 or 1.
The alkylene group represented by the R¹ is an either straight-chain or branched-chain alkylene group of which the straight-chain portion has preferably not less than 2 carbon atoms, and more preferably from 3 to 6 carbon atoms.
The cycloalkyl group represented by the R² is preferably a 5- or 6-member cycloalkyl group.
When used for positive image formation, the most preferred as the substituent R or R₁ to the above-mentioned heterocyclic ring are those having the following Formula [M-X]:
wherein R₉, R₁₀ and R₁₁ are as defined in the foregoing R.
Two out of the R₉, R₁₀ and R₁₁, e.g., R₉ and R₁₀, may combine with each other to form a saturated or unsaturated ring such as, e.g., cycloalkane, cycloalkene, heterocyclic ring, and further the formed ring may also combine with the R₁₁ to constitute a cross-linked organic hydrocarbon compound residue.
The preferred case of Formula [M-X] is where (i) at least two of the R₉ through R₁₁ are alkyl groups, or (ii) one of the R₉ through R₁₁, e.g., the R₁₁, is a hydrogen atom and the other two, both R₉ and R₁₀, combine together with the immediate carbon atom to form a cycloalkyl group.
Further, the case (i) is more preferably where two of the R₉ through R₁₁ are alkyl groups and the other one is a hydrogen atom or an alkyl group.
When used for negative image formation, the most preferred as the substituent R or R₁ to the foregoing heterocyclic ring are those having the following Formula [M-XI]:

Formula [M-XI]

R₁₂-CH₂-
wherein R₁₂ is as defined in the foregoing R. The R₁₂ is preferably a hydrogen atom or an alkyl group.
The following are examples of the compound of this invention.
In addition to the above examples of the compounds according to this invention, other examples of the compounds usable in this invention also include those compounds Nos. 1 through 4, 6, 8 through 17, 19 through 24, 26 through 43, 45 through 59, 61 through 104, 106 through 121, 123 through 162, and 164 through 223 disclosed in pages 66 through 122 of Japanese Patent O.P.I. Publication No. 9791/1986.
These couplers can be synthesized by making reference to the Journal of the Chemical Society, Perkin, I (1977), 2047-2052, U.S. Patent No. 3,725,067, Japanese Patent O.P.I. Publication Nos. 99437/1984, 42045/1983, 162548/1984, 171956/1984, 33552/1985, 43659/1985, 172982/1985 and 190779/1985.
The coupler of this invention may be used in the amount range of normally from 1 x 10⁻³ mole to 1 mole per mole of silver halide, and more preferably from 1x10⁻² mole to 8x10⁻¹ mole.
The coupler of this invention may be used in combination with different other magenta coupler.
In this invention, the DIR compound implies a compound which, upon reaction with the oxidation product of a color developing agent, splits off a development inhibitor or a compound capable of releasing a development inhibitor. Preferred ones of such DIR compounds are diffusible DIR compounds.
The diffusible DIR compound in this invention is a com pound wherein the development inhibitor or compound capable of releasing a development inhibitor to be split off upon reaction with the oxidation product of a color developing agent has a diffusibility of not less than 0.34 according to the evaluation method that will be mentioned hereinafter, and of preferably not less than 0.40.
The diffusibility is evaluated in accordance with the following method:
On a transparent support is coated a layer of the following composition, whereby light-sensitive material Samples (I) and (II) are prepared.

Sample (I): Sample having a green-sensitive silver halide emulsion layer

A gelatin coating liquid containing green-sensitized silver iodobromide (containing 6 mole% silver iodide, average grain size 0.48 µm) and 0.07 mole per mole of silver of the following coupler is coated so that the coating weight of silver is 1.1g/m² and that of gelatin is 3.0g/m², and on this layer is further coated a gelatin coating liquid, as a protective layer, containing silver iodobromide neither chemically sensitized nor optically sensitized (containing 2 mole% silver iodide, average grain size 0.08 µm) so that the coating weight of silver is 0.1g/m² and that of gelatin is 0.8g/m².

Sample (II): Sample of the same composition as that of Sample (I) except that the silver iodobromide is removed from the protective layer of Sample (I).

The above respective layers contain a gelatin hardener and surfactant in addition to the above-mentioned components.
Each of Samples (I) and (II) is exposed through an optical wedge to white light, and then processed in accordance with the following procedure. For the processing there are used two different developer solutions: one containing a various development inhibitor in an amount enough to restrain the sensitivity of Sample (II) to 60% (-Δlog E = 0.22) and the other containing no development inhibitor.

Processing steps (at 38°C)

Color developing 2 min. 40 sec.
Bleaching 6 min. 30 sec.
Washing 3 min. 15 sec.
Fixing 6 min. 30 sec.
Washing 3 min. 15 sec.
Stabilizing 1 min. 30 sec.
Drying
The compositions of the processing solutions used in the respective processing steps are as follows:

Color Developer Solution

4-Amino-3-methyl-N-ethyl-N-(β-hydroxyethyl)-aniline sulfate 4.75g
Anhydrous sodium sulfite 4.25g
Hydroxylamine 1/2 sulfate 2.0 g
Anhydrous potassium carbonate 37.5 g
Sodium bromide 1.3 g
Trisodium nitrilotriacetate, monohydrated 2.5 g
Potassium hydroxide 1.0 g
Water to make 1 liter.

Bleaching Bath

Iron-ammonium ethylenediaminetetraacetate 100.0 g
Diammonium ethylenediaminetetraacetate 10.0 g
Ammonium bromide 150.0 g
Glacial acetic acid 10.0 ml
Water to make 1 liter. Use aqueous ammonia to adjust the pH to 6.0.

Fixing Bath

Ammonium thiosulfate 175.0 g
Anhydrous sodium sulfite 8.5 g
Sodium metasulfite 2.3 g
Water to make 1 liter. Use acetic acid to adjust the pH to 6.0.

Stabilizing Bath

Formalin (aqueous 37% solution) 1.5 ml
Koniducks (product of Konishiroku Photo Industry Co., Ltd.) 7.5 ml
Water to make 1 liter
If the speeds of Sample (I) and Sample (II) when no development inhibitor is added are regarded as S₀ and S₀′, respectively, and if the speeds of Sample (I) and Sample (II) when a development inhibitor is added are regarded as S_I and S_II, respectively, then the fall in the speed of Sample (I) is expressed as ΔS=S₀-S_I, the fall in the speed of Sample (II) as ΔS₀=S₀′-S_II, and the diffusibility as ΔS/ΔS₀, provided that every speed is expressed in logarithm of reciprocal of exposure (-log E) at a point of fog density plus 0.3.
The diffusibility values of several development inhibitors obtained according to the above method are shown in the following table.
In the present invention, the DIR compound is desirable to be one the group released from which has a diffusibility falling under the foregoing range, but any other DIR compounds may also be used.
Formulas of examples representative of the DIR compound will be given below:

Formula (D-1)

A-(Y)m
wherein A is a coupler residue, m is an integer of 1 or 2, Y is a group that is bound to the coupler residue A in its coupling position and is capable of being split off upon reaction with the oxidation product of a color developing agent and also is a development inhibiting group or a group capable of releasing a development inhibitor.
In Formula (D-1), the Y is typified by those having the following Formulas (D-2) through (D-19):
In Formulas (D-2) through (D-7) =, Rd₁ is a hydrogen atom, a halogen atom or an alkyl, alkoxy, acylamino, alkoxycarbonyl, thiazolidinylidenamino, aryloxycarbonyl, acyloxy, carbamoyl, N-alkylcarbamoyl, N,N-dialkylcarbamoyl, nitro, amino, N-arylcarbamoyloxy, sulfamoyl, N-alkylcarbamoyloxy, hydroxy, alkoxycarbonylamino, alkylthio, arylthio, aryl, heterocyclic, cyano, alkylsulfonyl or aryloxycarbonylamino group; n is an integer of 0, 1 or 2, provided that when n is equal to 2, the Rd₁s may be either the same or different, and the total number of carbon atoms contained in the n number of Rd₁s is from zero to 15.
In Formula (D-6), X is an oxygen atom or a sulfur atom.
In Formula (D-8), Rd₂ is an alkyl, aryl or heterocyclic group.
In Formula (D-9), Rd₃ is a hydrogen atom or an alkyl, cycloalkyl, aryl or heterocyclic group; Rd₄ is a hydrogen atom, a halogen atom or an alkyl, cycloalkyl, aryl, acylamino, alkoxycarbonylamino, aryloxycarbonylamino, alkanesulfonamido, cyano, heterocyclic, alkylthio or amino group.
When the Rd₁, Rd₂, Rd₃ or Rd₄ represents an alkyl group, the alkyl group includes those having a substituent, which may be either straight-chain or branched-chain.
When the Rd₁, Rd₂, Rd₃ or Rd₄ represents an aryl group, the aryl group includes those having a substituent.
When the Rd₁, Rd₂, Rd₃ or Rd₄ represents a heterocyclic group, the heterocyclic group includes those having a substituent and is desirable to be of a single 5- or 6-member single ring or condensed rings containing at least one hetero atom selected from the group consisting of nitrogen, oxygen and sulfur atoms, and is one selected from, e.g., pyridyl, quinolyl, furyl, benzothiazolyl, oxazolyl, imidazolyl, thiazolyl, triazolyl, benzotriazolyl, imido, oxazino and the like groups.
The number of carbon atoms contained in the Rd₂ of Formulas (D-6) and (D-8) is from zero to 15.
In the above Formula (D-9), the total number of carbon atoms contained in both Rd₃ and Rd₄ is from zero to 15.

Formula (D-10)

-TIME-INHIBIT
wherein the TIME group is bound to the A in its coupling position and is a group which is cleavable upon reaction with the oxidation product of a color developing agent and which, after being cleaved from the coupler, is capable of appropriately controlling and releasing the INHIBIT group. The INHIBIT group is a group to become a development inhibitor as a result of the above release (such as a group represented by one of those Formulas (D-2) through (D-9)).
The -TIME-INHIBIT group of Formula (D-10), more particularly, includes those groups having the following Formulas (D-11) through (D-19):
In Formulas (D-11) through (D-15) and (D-18), RD₅ is a hydrogen atom, a halogen atom or an alkyl, cycloalkyl, alkenyl, aralkyl, alkoxy, alkoxycarbonyl, anilino, acylamino, ureido, cyano, nitro, sulfonamido, sulfamoyl, carbamoyl, aryl, carboxy, sulfo, hydroxy or alkanesulfonyl group, and in Formulas (D-11) through (D-13), (D-15) and (D-18), the Rd₅s may combine with one another to form a condensed ring. In Formulas (D-11), (D-14), (D-15) and (D-19), the Rd₅ represents an alkyl, alkenyl, aralkyl, cycloalkyl, heterocyclic or aryl group, and in Formulas (D-16) and (D-17), Rd₇ represents a hydrogen atom or an alkyl, alkenyl, aralkyl, cycloalkyl, heterocyclic or aryl group. In Formula (D-19), Rd₈ and Rd₉ each is a hydrogen atom or an alkyl group (preferably an alkyl group having from 1 to 4 carbon atoms). In Formulas (D-11) and (D-15) through (D-18), k is an integer of 0, 1 or 2; in Formulas (D-11) through (D-13), (D-15) and (D-18), 1 is an integer of from 1 to 4; in Formula (D-16), m is an integer of 1 or 2, provided that when the m is 2, the Rd₇s may be either the same or different; in Formul (D-19), n is an integer of from 2 to 4, provided that the n number of Rd₈s and of Rd₉s may be either the same or different; in Formulas (D-16) through (D-18), B is an oxygen atom or a -

(wherein the Rd₆ is as already defined); and in Formula (D-16), the ----- implies either a single bond or double bond, provided that in the case of a single bond, the m is 2, while in the case of a double bond, the m is 1, and the INHIBIT group has the same meaning as defined in Formulas (D-2) through (D-9) except for the number of carbon atoms.
In the INHIBIT group, the total number of carbon atoms contained in the Rd₁ in one molecule of each of Formulas (D-2) through (D-7) is from 0 to 32; the number of carbon atoms contained in the Rd₂ of Formula (D-8) is from 1 to 32; and the total number of carbon atoms contained in both Rd₃ and Rd₄ of Formula (D-9) is from 0 to 32.
Preferred among DIR compounds are those in which the Y is represented by Formula (D-2), (D-3) or (D-10). In the (D-10), the INHIBIT is preferably Formula (D-2), (D-6) (particularly when the X of (D-6) is an oxygen atom) or (D-8) (particularly when the Rd₂ of Formula (D-8) is a hydroxyaryl or an alkyl having from 1 to 3 carbon atoms).
In Formula (D-1), the coupler component represented by the A includes a yellow color image forming coupler residue, a magenta color image forming coupler residue, a cyan color image forming coupler residue and a colorless coupler residue.
Diffusible DIR compounds suitably usable in this invention include the following compounds, but the invention is not limited thereto.
Including these compounds, examples of the DIR compounds usable in this invention are disclosed in U.S. Patent Nos. 4,234,678, 3,227,554, 3,617,291, 3,958,993, 4,149,886, 3,933,500, Japanese Patent O.P.I. Publication Nos. 56837/1982 and 13239/1976, U.S. Patent Nos. 2,072,363 and 2,070,266, Research Disclosure 21,228, Dec. 1981, and the like.
The DIR compound is to be used in an amount of preferably from 0.0001 to 0.1 mole per mole of silver halide, and more preferably from 0.001 to 0.05 mole.
In the present invention, any various DIR compounds may be used, but above all they are desirable to be diffusible DIR compounds. The use of the diffusible DIR compound enables to prevent such troubles of uneven color development and silver retention as seen in the layer to which is applied a nondiffusible DIR compound, considered due mainly to the not-uniform presence of an inhibitor released therefrom, and also enables to increase IIE (interimage effect).
The layer into which the DIR compound is to be incorporated is allowed to be an emulsion layer containing a pyrazoloazole-type magenta coupler of this invention, but the DIR compound may also be contained together with a light-sensitive silver halide in a layer which does substantially not contain any color-forming couplers.
In the present invention, the DIR compound is preferably contained in a DIR layer. The DIR layer is a layer containing both DIR compound and light-sensitive silver halide emulsion, and preferably a layer forming no substantial color image, wherein the 'forming no substantial color image' implies that the maximum density of the DIR layer after being processed is not more than 0.3 in terms of a transmission density in the case of a transmission-type photographic material or in terms of a reflection density in the case of a reflective-type photographic material, preferably not more than 0.2, and more preferably not more than 0.1. The light-sensitive silver halide to be contained in the DIR layer forming no substantial color image may be any arbitrary silver halide such as, e.g., silver chloride, silver bromide, silver iodide, silver chlorobromide, silver iodobromide or silver chloroiodobromide. Grain sizes of such the silver halide may fall under the range of from 0.05 to 2 µm, and preferably from 0.1 to 1.5 µm. The coating weight of the silver halide is from 0.01 g/m² to 3.0 g/m² in silver equivalent, and preferably from 0.05 g/m² to 1.5 g/m².
The coating weight of the gelatin of the DIR layer forming no substantial color image is from 0.1 g/m² to 3.0 g/m², and preferably from 0.2 g/m² to 2.0 g/m².
The position of the DIR layer forming no substantial color image, although not specially restricted, is desirable to be in the proximity of a silver halide emulsion layer different in the color sensitivity from the silver halide of the DIR layer. The DIR layer may be either a single layer or comprised of two or more layers provided on a support and, in the case of two or more layers, they are desirable to be different in the color sensitivity from each other.
The silver halide to be used in those layers other than the DIR layer forming no substantial color image may be silver bromide, silver iodobromide, silver chloride, silver chlorobromide, silver chloroiodobromide, or the like, but the silver iodide content of these silver halides is preferably not more than 6 mole%, and particularly preferably from 1 to 3 mole%.
The processing stability improving effect of this invention can be highly expected particularly when the silver iodide content is as small as this.
To the silver halide emulsion may be added an antifogging agent, stabilizing agent and the like. As the binder for the emulsion, gelatin may be advantageously used.
The emulsion layer and other hydrophilic colloid layer may be hardened, and may also contain a plasticizer and water-insoluble or less-soluble synthetic polymer dispersed product (latex).
In emulsion layers of the color light-sensitive material, couplers are used. Further, competing couplers having a color-compensating effect and compounds capable of releasing photographically useful fragments, in their coupling reaction with the oxidation product of a color developing agent, such as development accelerators, developing agents, silver halide solvents, color toning agents, hardening agents, fogging agents, antifogging agents, chemical sensitizers, spectrally sensitizing agents, desensitizers, and the like, may also be used.
The light-sensitive material may be provided with auxiliary layers such as filter layers, antihalation layer, antiirradiation layer, and the like. These auxiliary layers and/or emulsion layers may contain a dye which, in development, is either dissolved out into the developer solution or bleached.
To the light-sensitive material may also be added a matting agent, lubricant, image stabilizer, formalin scavenger, ultraviolet absorbing agent, brightening agent, surface active agent, development accelerator, development retarder, and the like.
The light-sensitive material may use as its support a polyethylene-laminated paper, polyethylene terephthalate film, baryta paper, cellulose triacetate film or the like.
To obtain a dye image by using the light-sensitive material of this invention, the conventionally known color reversal developing process may take place.
That is, the exposed silver halide portion of the light-sensitive material is black-and-white developed in the first development process, and the rest unexposed is then fogged by being exposed to light or by being processed in a fogging bath and subsequently color-developed to thereby form a dye image.

EXAMPLES

Examples of the present invention will now be described below, but the invention is not limited by the examples.

EXAMPLE 1

On a both-side-polyethylene-coated paper support were provided the following Layers 1 through 8, whereby a color reversal light-sensitive material Sample No.1-1 was prepared. The coating weights of the respective components are given in g/m² except that the coating amounts of the following sensitizing dyes and couplers are shown in moles per mole of silver halide. As for silver halide, its coating weight is given in silver equivalent. (The same shall apply to the succeeding examples)

Layer 1 (antihalation layer)

Black colloidal silver 0.05
Gelatin 0.20

Layer 2 (red-sensitive layer)

Cyan Coupler A 0.34
Cyan Coupler B 0.17
Red-sensitive silver iodobromide emulsion (containing 3 mole% silver halide, average grain size 0.6 µm) 0.30
Gelatin 2.0

Layer 3 (first intermediate layer)

Anti-color-mixing agent E 0.08
Gelatin 1.0

Layer 4 (green-sensitive layer)

Magent Coupler C 0.28
DIR compound (D-23) 0.02
Green-sensitive silver iodobromide emulsion (containing 3 mole% silver iodide, average grain size 0.7 µm) 0.30
Gelatin 2.0

Layer 5 (second intermediate layer)

Yellow colloidal silver 0.15
Anti-color-mixing agent E 0.08
Gelatin 1.0

Layer 6 (blue-sensitive layer)

Yellow Coupler D 0.60
Blue-sensitive silver iodobromide emulsion (containing 3 mole% silver iodide, average grain size 0.8 µm) 0.35
Gelatin 2.0

Layer 7 (ultraviolet absorbing layer)

Ultraviolet absorbing agent UV-1 0.2
Ultraviolet absorbing agent UV-2 0.2
Ultraviolet absorbing agent UV-3 0.2
Ultraviolet absorbing agent UV-4 0.2
Gelatin 2.0

Layer 8 (protective layer)

Gelatin 1.0
Provided that the color reversal light-sensitive material also contains a high-boiling solvent, antidiscoloration agent, surface active agent, hardening agent and antiirradiation agent in addition to the above components.
Further, Samples 1-2 through 1-6 were prepared in the same manner as is Sample 1-1 except that the Magenta Coupler C and the DIR Compound D-23 of Sample 1-2 were replaced by equimolar amounts of those magenta couplers and DIR compounds as given in Table 1.
Each of these light-sensitive material Samples 1-1 through 1-6 was exposed through an optical stepwedge with a magenta filter (Wratten No.32, product of Eastman Kodak Company) to a light source of 3200°K, and then subjected to Processing A in the following order:

[Processing A]

First developing (monochromatic) 1 min. 15 sec. at 38°C
Washing 1 min. 30 sec.
Exposure to light for fogging 2 min. 15 sec.
Second developing (color developing) 2 min. 15 sec. at 38°C
Washing 45 sec.
Bleach-fix 2 min. at 38°C
Washing 2 min. 15 sec.

First Developer Solution

Potassium sulfite 30.0 g
Sodium thiocyanate 1.0 g
Sodium bromide 2.4 g
Potassium iodide 8.0 ml
Potassium hydroxide (48%) 6.2 ml
Potassium carbonate 14.0 g
Sodium hydrogencarbonate 12.0 g
1-Phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone 1.5 g
Hydroquinonemonosulfonate 23.3 g
Water to make 1 liter (pH=9.65)

Second Developer Solution

Benzyl alcohol 14.6 ml
Ethylene glycol 12.6 ml
Anhydrous potassium carbonate 26.0 g
Potassium hydroxide 1.4 g
Sodium sulfite 1.6 g
3,6-dithiaoctane-1,8-diol 0.24g
Hydroxylamine sulfate 2.6 g
4-N-ethyl-N-β-(methanesulfonamidoethyl)-2-methyl-p-phenylenediamine sesquisulfate 5.0 g
Water to make 1 liter (pH=10.45)

Bleach-Fix Bath

Ferric-ammonium ethylenediaminetetraacetate 1.56 mole solution 115.0 ml
Sodium metabisulfite 15.4 g
Ammonium thiosulfate (58%) 126.0 ml
1,2,4-triazolo-3-thiol 0.4 g
Water to make 1 liter (pH=6.5)
Also, Processing B took place in quite the same manner as in Processing A except that the pH of the second developer solution of Processing A was adjusted to 10.1.
The reflection density measured through a blue filter and the reflection density through a red filter when an exposure was made to give a reflection density of 1.0 of the magenta image measured through a green filter, which has been obtained by Processing A, are shown in Table 1. The smaller the values, the better. Also, the reflection Dmax (maximum density) values of the magenta dye images obtained by measuring through a green filter, which have been obtained by Processings A and B, are given in Table 1, wherein the closer the value obtained in Processing B is to that in Processing A, the better.
As is apparent from Table 1, samples having the constructions according to this invention enable to obtain clear magenta images with little changes in the magenta Dmax due to fluctuations in processing, whereas Comparative Samples 1-1 through 1-3 are inferior in the color reproduction with significant changes in the density due to processing.

EXAMPLE 2

In the same manner as in Example 1, the following Layers 1 through 12 were coated on a both-side-polyethylene-coated paper support, whereby a color reversal light-sensitive material Sample 2-1 was prepared.

Layer 1 (antihalation layer)

Black colloidal silver 0.05
Gelatin 0.20

Layer 2 (red-sensitive layer)

Cyan Coupler A 0.34
Cyan Coupler B 0.17
Red-sensitive silver iodobromide emulsion (containing 3 mole% silver iodide, average grain size 0.6 µm) 0.30
Gelatin 2.0

Layer 3 (first intermediate layer)

Anti-color-mixing agent E 0.08
Gelatin 1.0

Layer 4 (green-sensitive DIR layer)

Green-sensitive silver bromide emulsion (average grain size 0.7 µm) 0.10
DIR Compound D-23 0.10
Gelatin 2.0

Layer 5 (second intermediate layer)

Anti-color-mixing agent E 0.08
Gelatin 1.0

Layer 6 (green-sensitive layer)

Magenta Coupler C 0.28
Green-sensitive silver iodobromide emulsion (containing 3 mole% silver iodide, average grain size 0.7 µm) 0.30
Gelatin 2.0

Layer 7 (third intermediate layer)

Anti-color-mixing agent E 0.08
Gelatin 1.0

Layer 8 (red-sensitive DIR layer)

Red-sensitive silver bromide emulsion (average grain size 0.6 µm) 0.10
DIR Compound D-23 0.10
Gelatin 2.0

Layer 9 (fourth intermediate layer)

Yellow colloidal silver 0.15
Anti-color-mixing agent E 0.08
Gelatin 1.0

Layer 10 (blue-sensitive layer)

Yellow coupler 0.60
Blue-sensitive silver iodobromide emulsion (containing 10 mole% silver iodide, average grain size 0.8 µm) 0.35
Gelatin 2.0

Layer 11 (ultraviolet absorbing layer)

Layer 12 (protective layer)

Gelatin 1.0
Provided that the color reversal light-sensitive material contains a high-boiling solvent, antidiscoloration agent, surface active agent, hardening agent and antiirradiation dye in addition to the above components.
Further, Samples 2-2 through 2-5 were prepared in the same manner as in the above sample except that the DIR compound of both Layers 4 and 8 and the magenta coupler of Layer 6 were replaced by equimolar amounts of those as given in Table 2.
Each of the obtained samples was exposed and then subjected to Processings A and B in the same manner as in Example 1. The obtained results are shown in Table 2.
As is apparent from Table 2, the samples according to this invention are excellent in the magenta color reproduction, and show little changes in the magenta Dmax densities measured through a green filter.

EXAMPLE 3

In the present example, the adding amounts of the sensitizing dyes and couplers will be shown in moles per mole of silver halide unless otherwise stated.
On a subbed triacetyl cellulose film support were coated the following compositions-having layers in order from the support side, whereby a multilayer color light-sensitive material Sample 3-1 was prepared.

Layer 1 (antihalation layer)

Ultraviolet Absorbing Agent-1 0.3
Ultraviolet Absorbing Agent-2 0.4
Black colloidal silver 0.24
Gelatin 2.7

Layer 2 (intermediate layer)

2,5-di-t-octyl-hydroquinone 0.1
Gelatin 1.0

Layer 3 (low-speed red-sensitive silver halide emulsion)

AgBrI emulsion (Emulsion-1) having an average grain size of 0.35 µm, containing 2.5 mole% AgI 0.5
Sensitizing Dye-1 7.6x10⁻⁴
Coupler C-1 0.1
Gelatin 0.9

Layer 4 (high-speed red-sensitive silver halide emulsion)

AgBrI emulsion (Emulsion-2) having an average grain size of 0.75 µm, containing 2.5 mole% AgI 0.8
Sensitizing Dye-1 3.2x10⁻⁴
Coupler C-1 0.2
Gelatin 1.75

Layer 5 (intermediate layer)

2,5-di-octyl-hydroquinone 0.1
Gelatin 0.9

Layer 6 (low-speed green-sensitive silver halide emulsion)

Emulsion-1 1.0
Sensitizing Dye-2 6.6x10⁻⁴
Sensitizing Dye-3 0.6x10⁻⁴
Coupler M-1 0.05
Gelatin 0.8

Layer 7 (high-speed green-sensitive silver halide emulsion)

Emulsion-2 1.0
Sensitizing Dye-2 2.76x10⁻⁴
Sensitizing Dye-3 0.23x10₋₄
Coupler M-1 0.15
Gelatin 1.5

Layer 8 (intermediate layer)

The same as Layer 5

Layer 9 (yellow filter layer)

Yellow colloidal silver 0.1
Gelatin 0.9
2,5-di-t-octyl-hydroquinone 0.1

Layer 10 (low-speed blue-sensitive silver halide emulsion)

AgBrI emulsion (Emulsion-3) having an average grain size of 0.6 µm, containing 2.5 mole% AgI 0.4
Coupler Y-1 0.3
Gelatin 1.3

Layer 11 (high-speed blue-sensitive silver halide emulsion)

AgBrI emulsion (Emulsion-4) having an average grain size of 1.0 µm, containing 2.5 mole% AgI 0.8

Layer 12 (first protective layer)

Ultraviolet Absorbing Agent-1 0.3
Ultraviolet Absorbing Agent-2 0.4
Gelatin 1.2
2,5-di-t-octyl-hydroquinone 0.1

Layer 13 (second protective layer)

Non-light-sensitive fine-grained silver halide emulsion comprising AgBrI having an average grain size of 0.08 µm, containing 1 mole% AgI 0.3
Polymethyl methacrylate particles (diameter 1.5 µm)
Gelatin 0.7
To the above layers were at need added Gelatin Hardening Agent-1 and surface active agent-1 in addition to the above compositions, and tricresyl phosphate was used as a coupler solvent.
Further, Samples 3-2 to 3-5 were prepared in the same manner as in Sample 3-1 except that the equimolar amounts of the magenta couplers and DIR compounds as shown in Table 3 were used.
The thus obtained Samples 3-1 to 3-5 were each exposed through an optical wedge to a magenta light (with a CC-90 filter, produced by Kodak), and then subjected to the following Processing C:
The compositions of the processing solutions which were applied to the above processing steps are as follows:

First Developer Solution

Sodium tetrapolyphosphate 2.0 g
Sodium sulfite 20.0 g
Hydroquinone monosulfate 30.0 g
Sodium carbonate, monohydrated 30.0 g
1-Phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone 2.0 g
Potassium bromide 2.5 g
Potassium thiocyanate 1.2 g
Potassium iodide (0.1 % solution) 2.0 ml
Water to make 1000 ml

Reversal Processing Bath

Hexasodium nitrilotrimethylenesulfonate 3.0 g
Stannous chloride, dihydrated 1.0 g
p-Aminophenol 0.1 g
Sodium hydroxide 8.0 g
Glacial acetic acid 15.0 ml
Water to make 1000 ml

Color Developer Solution

Sodium tetrapolyphosphate 2.0 g
Sodium sulfite 7.0 g
Sodium tertiary phosphate, dihydrated 36.0 g
Potassium bromide 1.0 g
Potassium iodide (0.1 % solution) 90.0 ml
Sodium hydroxide 3.0 g
Citrazinic acid 1.5 g
N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate 11.0 g
2,2-ethylenedithiodiethanol 1.0 g
Water to make (pH=11.85) 1000 ml

Compensating Bath

Sodium sulfite 12.0 g
Sodium ethylenediaminetetraacetate, dihydrated 8.0 g
Thioglycerol 0.4 ml
Glacial acetic acid 3.0 ml
Water to make 1000 ml

Bleaching Bath

Sodium ethylenediaminetetraacetate, dihydrated 2.0 g
Iron(II)-ammonium ethylenediaminetetraacetate, dihydrated 120.0 g
Potassium bromide 100.0 g
Water to make 1000 ml

Fixing Bath

Ammonium thiosulfate 80.0 g
Sodium sulfite 5.0 g
Sodium hydrogensulfite 5.0 g
Water to make 1000 ml

Stabilizing Bath

Formalin (37 % by weight) 5.0 ml
Koniducks (produced by Konishiroku Photo Ind. Co., Ltd.)
5.0 ml
Water to make 1000 ml
Regarding the yellow, magenta and cyan color densities of the above processed samples, the yellow and cyan densities at the time of the magenta density being 1.5 were measured by using a densitometer 'Status A', manufactured by X-RITE Co., and the results are given in Table 3.
Further, Processing D also took place in quite the same manner as in the above Processing C except that the pH of the color developer solution of Processing C was adjusted to 11.55. The Dmax densities of the magenta color obtained by measuring through a green filter are shown in Table 3.
As is apparent from Table 3, Samples 3-4 and 3-5 for this invention show highly pure color reproduction with their yellow and cyan color formations restrained when exposed to the magenta light as compared with Comparative Samples 3-1 through 3-3.
Also, similar effects were displayed in those samples where DIR compounds D-6, D-17 and D-27 were used.

EXAMPLE 4

In quite the same manner as in Example 1, a color reversal light-sensitive material Sample No.4-1 was prepared by coating the following Layers 1 through 15 on a polyethylene-coated paper support.

Layer 1 (antihalation layer)

Black colloidal silver 0.05
Gelatin 0.20

Layer 2 (first red-sensitive layer)

Cyan Coupler A 0.14
Cyan Coupler B 0.07
Red-sensitive silver iodobromide emulsion having an average grain size of 0.4 µm, containing 3 mole% silver iodide 0.14
Gelatin 1.0

Layer 3 (second red-sensitive layer)

Cyan Coupler A 0.20
Cyan Coupler B 0.10
Red-sensitive silver iodobromide emulsion having an average grain size of 0.6 µm, containing 3 mole% silver iodide 0.16
Gelatin 1.0

Layer 4 (intermediate layer)

Anti-Color-Mixing Agent E 0.08
Gelatin 1.0

Layer 5 (green-sensitive DIR layer)

Green-sensitive silver iodobromide emulsion having an average grain size of 0.6 µm, containing 3 mole% silver iodide 0.10
DIR Compound D-23 0.08
Gelatin 1.0

Layer 6 (first intermediate layer)

Gelatin 1.0
Anti-Color-Mixing Agent E 0.08

Layer 7 (first green-sensitive layer)

Magent Coupler C 0.14
Green-sensitive silver iodobromide emulsion having an average grain size of 0.5 µm, containing 3 mole% silver iodide 0.15
Gelatin 1.0

Layer 8 (second green-sensitive layer)

Magenta Coupler C 0.14
Green-sensitive silver iodobromide emulsion having an average grain size of 0.9 µm, containing 3 mole% silver iodide 0.15
Gelatin 1.0

Layer 9 (intermediate layer)

Anti-Color-Mixing Agent E 0.08
Gelatin 1.0

Layer 10 (red-sensitive DIR layer)

Red-sensitive silver iodobromide emulsion having an average grain size of 0.6 µm, containing 3 mole% silver iodide 0.10
DIR Compound D-23 0.08
Gelatin 1.0

Layer 11 (second intermediate layer)

Yellow colloidal silver 0.15
Anti-Colo-Mixing Agent E 0.08
Gelatin 1.0

Layer 12 (first blue-sensitive layer)

Yellow Coupler D 0.40
Blue-sensitive silver iodobromide emulsion having an average grain size of 0.5 µm, containing 3 mole% silver iodide 0.15
Gelatin 0.70

Layer 13 (second blue-sensitive layer)

Layer 14 (ultraviolet absorbing layer)

Layer 15 (protective layer)

Gelatin 1.0
Provided that the sample contains a high-boiling solvent, antidiscoloration agent, hardening agent and antiirradiation agent in addition to the above compositions.
Subsequently, Samples 4-2 through 4-7 were prepared in the same manner except that the couplers and DIR compounds in Layers 5, 7, 8 and 10 were replaced as shown in Table 4, provided that in Samples 4-5 and 4-7, the DIR compound contained in Layers 7 and 8 is D-23 in an amount equivalent to 0.02g/m².
Each of these samples was subjected to Processings A and B in similar manner to Example 1, and the yellow density and cyan density at the time of magenta light exposure were measured. The results are as given in Table 4. Data of stability against processings are also shown in the table.
As is apparent from Table 4, the samples of the constructions according to this invention are excellent in the magenta color reproduction as well as in the stability of photographic characteristics against processing.

Claims

1. A reversal silver halide light-sensitive photographic material comprising a support and, provided thereon, photographic component layers including at least two silver halide emulsion layers having different spectral sensitivity from each other, wherein at least one layer of the silver halide emulsion layers contains a pyrazoloazole-type magenta coupler, and at least one layer of the photographic component layers contains a compound which is capable of releasing either a development inhibitor or a precursor thereof.

2. The reversal silver halide light-sensitive photographic material of claim 1, wherein the pyrazoloazole-type magenta coupler has the formula [M-I];

wherein Z is a group of non-metal atoms necessary to complete a nitrogen-containing heterocyclic ring which may have a substituent; X is a hydrogen atom or a group capable of being split off upon reaction with the oxidation product of a color developing agent; and R is a hydrogen atom or a substituent.

3. The reversal silver halide light-sensitive photographic material of claim 1, wherein the compound is one capable of releasing either a diffusible development inhibitor or a precursor thereof.

4. The reversal silver halide light-sensitive photographic material of claim 1, wherein the compound is incorporated into at least one of the silver halide light-sensitive emulsion layer.

5. The reversal silver halide light-sensitive photographic material of claim 4, wherein the compound is incorporated in the silver halide light-sensitive emulsion layer containing a the pyrazoloazole-type magenta coupler.

6. The reversal silver halide light-sensitive photographic material of claim 5, wherein the pyrazoloazole-type magenta coupler has the formula [M-I];

7. The reversal silver halide light-sensitive photographic material of claim 4, wherein the compound is incorporated into at least one of the silver halide light-sensitive emulsion layer which does not substantially form a dye image in the color development.

8. The reversal silver halide light-sensitive photographic material of claim 7, wherein the support is either a transparent support or a reflective support and the transmission color density in the case of a transparent support or the reflection color density in the case of a reflective support to be formed in the layer containing the compound in the color development is not more than 0.3.

9. The reversal silver halide light-sensitive photographic material of claim 8, wherein the transmission color density or the reflection color density to be formed in the layer containing the compound in the color development is not more than 0.2.

10. The reversal silver halide light-sensitive photographic material of claim 8, wherein the transmission color density or the reflection color density to be formed in the layer containing the compound in the color development is not more than 0.1.

11. The reversal silver halide light-sensitive photographic material of claim 7, wherein the silver halide light-sensitive emulsion layer which does not substantially form a dye image in the color development is provided adjacent to another light-sensitive emulsion layer which has different spectral sensitivity.

12. The reversal silver halide light-sensitive photographic material of claim 1, wherein the amount of pyrazoloazole magenta coupler to be contained is 1 x 10⁻³ to 1 mole per 1 mole of silver halide.

13. The reversal silver halide light-sensitive photographic material of claim 12, wherein the amount is 1 x 10⁻² to 8 x 10⁻² mole per 1 mole of silver halide.

14. The reversal silver halide light-sensitive photographic material of claim 4, wherein the amount of the compound to be contained is 1 x 10⁻⁴ to 1 x 10⁻¹ mole per 1 mole of silver halide.

15. The reversal silver halide light-sensitive photographic material of claim 14, wherein the amount is 1 x 10⁻³ to 5 x 10⁻² mole per 1 mole of silver halide.