EP0486216B1 - Light-sensitive silver halide photographic material - Google Patents

Description

FIELD OF THE INVENTION

The present invention relates to a light-sensitive silver halide photographic material. More particularly, it relates to a light-sensitive silver halide photographic material that can form a dye image having been improved in fastness to light and also having been prevented from being stained.

BACKGROUND OF THE INVENTION

Dye images obtained using light-sensitive silver halide photographic materials (hereinafter often "light-sensitive material(s)") are desired not to undergo discoloration or fading even after they have been subject to light for a long time or stored in an environment of high temperature and high humidity. They are also desired to be free from yellowing (hereinafter "Y-stain") that may occur at their non-image portions because of light, humidity or heat.

A metal complex having a singlet oxygen quenching rate constant kq of not less than 3 x 10⁷ M^-1s^-1 is used to improve the fastness to light of dye images, as disclosed in Japanese Patent Publications Open to Public Inspection (hereinafter referred to as "Japanese Patent O.P.I. Publication(s)") No. 262740/1986, No. 267049/1986, No. 175754/1987, No. 187348/1987, No. 182741/1987, No. 183459/1987, etc.

Japanese Patent O.P.I. Publication No. 958/1990 also discloses that the storage stability can be improved when a compound with kq of not less than 1 x 10⁷ M^-1s^-1 is made present in a heat-developable color light-sensitive element having a dye-providing compound capable of forming or releasing a diffusible dye, corresponding or reverse corresponding with the reaction in which a light-sensitive silver halide, a binder and a silver halide are reduced to silver.

Sole use of the compound having the above kq, however, can not be said to be satisfactory for preventing the fading and discoloration of color images against light.

On account of the problem on color reproduction quality, pyrazoloazole couplers improved in the prevention of unpreferable secondary absorption inherent in 5-pyrazolone couplers conventionally used as magenta dye forming couplers have been recently developed and put into use.

Such pyrazoloazole magenta couplers have been advantageous in that the Y-stain at the non-image portions may hardly occur against light, heat and humidity, but on the other hand disadvantageous in that the azomethin dye formed has a very low fastness to light and also tends to undergo the discoloration by light, to seriously damage the performances of, in particular, light-sensitive color photographic materials for printing. No satisfactory effect has been obtainable even when the compound having the above kq is solely used together with any of these couplers.

Japanese Patent O.P.I. Publication No. 3995/1991 discloses a technique by which the fastness to light is improved and the Y-stain due to light, humidity and heat is prevented from occurring, by using a pyrazoloazole coupler in combination with an amine compound and a phenol compound. Nevertheless, no satisfactory effect of preventing fading for a long period of time was found to be obtained even by this method.

In addition, in recent years, emulsions layers are desired to be made smaller in layer thickness from the viewpoints of cost, sharpness, etc. As a measure for settling this matter, it has been proposed to decrease the amount of gelatin used as a binder. The decreasing of the amount of gelatin, however, causes the problem that the storage stability of dye images is deteriorated.

Meanwhile, in continuous methods wherein light-sensitive materials are running processed, they are commonly running processed while the respective processing solutions are replenished using replenishing solutions. In such instances, a large quantity of overflowing solution is produced with supply of the replenishing solutions, causing a great problem from the viewpoints of environmental pollution and cost.

Thus, it is strongly desired in recent years to decrease the amount of replenishment of color developing solution (i.e., to achieve low-replenishment). When, however, conventional light-sensitive color photographic material are continuously processed using a low-replenished color developing solution, the deterioration of storage stability of dye images has clearly come into question.

SUMMARY OF THE INVENTION

Accordingly, a first object of the present invention is to provide a light-sensitive silver halide photographic material that can form a dye image causing less discoloration against light.

A second object of the present invention is to provide a light-sensitive material that has prevented the Y-stain at the non-image portions from occurring against light, heat and humidity.

A third object of the present invention is to provide a light-sensitive material that is free from the secondary absorption of magenta dyes and has been improved in color reproduction quality.

The above objects of the present invention can be achieved by a light-sensitive silver halide photographic material comprising a support carrying a silver halide emulsion layer containing a dye forming coupler, characterised in that the silver halide emulsion layer contains a compound having a singlet oxygen-quenching ability with a quenching rate constant Kq of not less than 1 X 10⁸ M^-1 s^-1 and having the Formula II-a-2;

wherein Y' is a group of non-metallo atoms necessary to complete a heterocyclic ring having from 5 to 8 members; R¹⁰ is an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, a heterocyclic group, an acyl group. a bridged hydrocarbon group, an alkylsulfonyl group or an arylsulfonyl group; R¹¹ and R¹³ are each an electron donating group having a Hammett's σ p value of not more than 0; and R¹² and R¹⁴ are each hydrogen atoms; and a compound represented by the Formula R;

wherein R¹⁵ is a substituent and l is an integer in the range 0 to 5; provided that the value of Kq is determined as follows:
   singlet oxygen is produced from 3-(1,4-epidioxyl-4-methyl-1,4-dihydro-1-naphthyl)proprionic acid in ethanol as solvent at 35 C; 2,5-diphenyl-3,4-benzofuran (DPBF), as a standard substance for quenching, is made present together with the substance to be measured; then both the substances are brought into competitive reaction with the singlet oxygen the changes with time of light absorption at the absorption wavelength of the DPBF (λ max: 411 nm) are followed up to determine the Kq.

The present invention can be particularly effective when the dye forming coupler comprises a couple represented by the following Formula M-I

In the formula, Z represents a group of non-metal atoms necessary to complete a nitrogen-containing heterocyclic ring. The ring formed by X may have a substituent.

X represents a hydrogen atom or a group capable of being split off upon reaction with an oxidized product of a color developing agent.

R represents a hydrogen atom or a substituent.

DETAILED DESCRIPTION OF THE INVENTION

The kq is determined by the measurement according to the method disclosed in Daifuku, Mukai et al., Ehime University, the Faculty of Science, SUMMARY COLLECTIONS OF THE 22ND OXIDATION FORUM, page 7.

More specifically, singlet oxygen is produced from 3-(1,4-epidioxyl-4-methyl-1,4-dihydro-1-naphthyl)propionic acid (EP) in an ethanol solvent at 35°C according to the Inoue et al's Method disclosed in Tetrahedron Letter, 41, pp.2177-2181 (1985). Using 2,5-diphenyl-3,4-benzofuran (DPBF) as a standard substance for quenching, a substance to be measured is made present together with this substance. Both the substances are brought into competitive reaction with the singlet oxygen, and changes with time of light absorbance at the absorption wavelength (λmax: 411 nm) of the DPBF are followed up to determine the kq.

wherein Y' represents a group of non-metallo atoms necessary to complete a heterocyclic ring having from 5 to 8 members; R¹⁰ represents an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, a heterocyclic group, an acyl group, a bridged hydrocarbon group, an alkylsulfonyl group or an arylsulfonyl group.

R¹¹ to R¹⁴ each represent an electron donative group having a Hammett's σp value of not more than 0.

The alkyl group represented by R¹⁰ may preferably be a straight-chain or branched alkyl group having 1 to 24 carbon atoms, as exemplified by groups such as methyl, ethyl, isopropyl, t-butyl, 2-ethylhexyl, dodecyl, t-octyl and benzyl.

The cycloalkyl group may preferably be a cycloalkyl group having 5 to 24 carbon atoms, as exemplified by groups such as cyclopentyl and cyclohexyl.

The alkenyl group may preferably be an alkenyl group having 3 to 24 carbon atoms, as exemplified by groups such as aryl and 2,4-pentadienyl.

The aryl group may include, for example, groups such as phenyl and naphthyl.

The heterocyclic group may include, for example, groups such as pyridyl, imidazolyl and thiazolyl.

The acyl group may include, for example, groups such as acetyl and benzoyl.

The bridged hydrocarbon group may include, for example, groups such as bicyclo[2.2.1]heptyl.

The alkylsulfonyl group may include, for example, groups such as dodecylsulfonyl and headecylsulfonyl. The arylsulfonyl group may include, for example, groups such as phenylsulfonyl.

These groups may each include those having a substituent. For example, the substituent of the alkyl group may include a halogen atom and groups such as hydroxyl, alkoxyl, aryl, acylamino, sulfonamide, aryloxy, alkylthio, carbamoyl, sulfamoyl, alkylsulfonyl, nitro, cyano, arylsulfonyl, carboxyl, amino, arylamino, alkylamino, alkoxycarbonayl, acyl and acyloxy. The substituent of the group represented by R¹⁰ except for the alkyl group may include the substituents described above and an alkyl group.

R¹⁰ preferably represents an alkyl group.

R¹¹ to R¹⁴ each represent an electron donative group having a Hammett's σp value of not more than 0. R¹² and R¹⁴ each represent a hydrogen atom.

Typical examples of these compounds are shown below. The compounds usable in the present invention are by no means limited by these.

The kq of the compound having a singlet oxygen quenching rate constant kq of not less than 1 x 10⁸ M^-1 s^-1may preferably be within the range of from 1 x 10⁸ M^-1 s^-1to 1 x 10⁹ M^-1s^-1.

The compound having a radical-scavenging ability may preferably be a compound having a radical-scavenging rate constant Ks of 10^-1 to 2 x 10⁴ M^-1 s^-1.

The above Ks is determined by the measurement according to the method disclosed in Mukai et al., Bull. Chem. Soc. Jpn., 59, pp.3113-3116.

More specifically, 2,6-di-t-butyl-4-(4'-methoxyphenyl)phenoxyl radical (PhO·) is mixed in an ethanol solvent at 25.0°C. Using a stopped-flow spectrophotometer, changes with time at the maximum absorption wavelength (λmax: 375 nm) of the PhO· are followed up to determine the Ks.

The quenching compound having the above ks of 10^-1 to 2 x 10⁴ M^-1 s^-1 has the structure of the following Formula R.

In the formula, R¹⁵ represents a substituent that can be substituted on the benzene ring, and ℓ represents an integer of 0 to 5. When ℓ is 2 or more, a plurality of R¹⁵ may be the same or different one another, and R¹⁵'s may mutually combine to form a ring.

The group represented by R¹⁵ in Formula R may preferably include an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, an acylamino group, a sulfonamide group, an alkylamino group, an alkylthio group, an arylthio group, an alkoxycarbonyl group, an aryloxycarbonyl group, a halogen atom and a group -OR¹⁶.

Here, R¹⁶ represents an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, a heterocyclic group or a group

wherein R^16a, R^16b and R^16c may be the same or different one another, and each represent an alkyl group, an alkenyl group, an aryl group, an alkoxyl group, an alkenoxy group or an aryloxy group.

The alkyl group represented by R¹⁵ may include a straight-chain or branched alkyl group having 1 to 24 carbon atoms as exemplified by groups such as methyl, ethyl, i-propyl, t-butyl, octyl, 2-ethylhexyl, dodecyl, tetradecyl, hexadecyl, eicocyl and benzyl.

The cycloalkyl group represented by R¹⁵ may include a cycloalkyl group having 5 to 24 carbon atoms as exemplified by groups such as cyclopentyl and cyclohexyl.

The alkenyl group may include an alkenyl group having 2 to 24 carbon atoms as exemplified by groups such as ethenyl, propenyl, butenyl, octenyl, decenyl and oleyl.

The aryl group represented by R¹⁵ may include a phenyl group and a naphthyl group.

The halogen atom may include, for example, atoms such as fluorine, chlorine, bromine and iodine.

The acylamino group may include, for example, groups such as acetylamino and benzoylamino.

The sulfonamide group may include, for example, groups such as methylsulfonylamino and benzenesulfonylamino.

The alkyl component that constitutes the alkylamino group and alkylthio group may include the same as those of the alkyl group previously described.

The aryl component that constitutes the arylthio group may include the same as those of the aryl group previously described.

The alkoxycarbonyl group may include, for example, groups such as methoxycarbonyl, ethoxycarbonyl, benzyloxycarbonyl. The aryloxycarbonyl group may include, for example, a phenoxycarbonyl group.

In Formula R, among the respective substitutents, the alkyl group, the cycloalkyl group, the aryl group or the heterocyclic group, or a group having any of these groups even in part, may further has a substituent.

For example, the substituent for the alkyl group or cycloalkyl group may include a halogen atom and groups such as hydroxyl, alkoxyl, alkylthio, acylamino, sulfonamide, aryl, aryloxy, carboxyl, amino, alkylamino, arylamino, carbamoyl, sulfamoyl, alkylsulfonyl, arylsulfonyl, nitro, cyano, alkoxycarbonyl, acyl and acyloxy.

The substituents other than the alkyl group may include the substituents set forth above and an alkyl group.

The substitutents the aryl group and heterocyclic group may have may include a halogen atom and groups such as alkyl, aryl, alkoxyl, aryloxy, alkylthio, arylthio, acyl, acylamino, sulfonamide, carbamoyl, sulfamoyl, ureido, alkoxycarbonyl, amino, sulfonyl, nitro, cyano and carboxyl.

When ℓ is two or more, the ring that may be formed by any mutual combination of a plurality of R¹⁵ may include an indane ring, a cumarane ring, a naphthalene ring and a chromane ring. The spiro ring may include a spirobiindane ring, a spirobicumaran ring and a spirobichroman group.

These compounds include the compounds disclosed in the patent publications as set forth in the description on Formula I.

However, when R¹⁵ is a hydroxyl group, the compound represented by Formula R is not preferable because of its properties that it reacts with an oxidized product of a developing agent to inhibit the dye formation of the dye forming coupler.

Of the compound represented by Formula R, preferred compounds are those represented by the following Formulas R-a and R-b.

In the formula, R¹⁵ and R^15' each have the same definition for R¹⁵ in Formula R, and A represents a divalent connecting group. Letter symbols a and a' each represent an integer of 0 to 4. In the case when a or a' is two or more, a plurality of R¹⁵ or R^15' may be the same or different one another. R¹⁵ and R^15' may also combine to form a ring.

In the formula, R^15' and R^15" each have the same definition for R¹⁵ in Formula R, and may be the same or different each other. Letter symbols b and b' each represent an integer of 0 to 3. In the case when b or b' is two or more, a plurality of R^15' or R^15" may be the same or different one another, and may also combine to form a ring. B and B' each represent a group of non-metal atoms necessary to complete a heterocyclic ring of 5 to 7 members together with the carbon atoms and C=C.

Of the compound represented by Formula R-a, particularly preferred compounds are those with the structures represented by the following Formulas R-a-1 and R-a-2 .

In the formula, R¹⁵ and R^15' may be the same or different each other, and each have the same definition for R¹⁵ in Formula R. Letter symbols a' and a" each represent an integer of 0 to 4. The letter symbol A represents a divalent connecting group.

In the formula, R¹⁶, R^16' , a', a" and A have the same definitions for R¹⁶, R^16' , a', a" and A, respectively, in Formula R-a-1.

In the above Formulas R-a-1 and R-a-2, the substituents represented by R¹⁶ and R^16' may include the groups detailed for R¹⁵ in Formula R.

The A represents a divalent connecting group, as exemplified by an alkylene group,

etc.
wherein R¹⁷ represents a hydrogen atom or a substituted or unsubstituted alkyl group or phenyl group in all instances.

The alkylene group may have a single or plural number of substituent(s). Such substituent(s) may include, for example, an aryl group, a cyano group, a halogen atom, a heterocyclic group, a cycloalkyl group, an alkoxyl group, a hydroxyl group and an aryloxy group.

This alkylene group may also be those in which the alkylene chain itself constitutes a cycloalkyl ring, as in the following:

The A may also include those in which the above divalent connecting groups are arbitrarily connected in plurality.

The compound represented by Formula R-b will be described below in greater detail.

Of the compound represented by Formula R-b, particularly preferred compounds may include structures represented by Formula R-b-1 or R-b-2.

In the formula, R¹⁵, R^15' , b and b' have the same definitions for R¹⁵, R^15' , b and b', respectively, in

R¹⁸, R^18' , R¹⁹ and R^19' each represent a hydrogen atom, a substituted or unsubstituted aliphatic group, a substituted or unsubstituted aromatic group or a substituted or unsubstituted heterocyclic group.

In the formula, R^15' , R^15", b, b' and D have the same definitions for R^15' , R^15", b, b' and D, respectively, in Formula R-b-1.

Typical examples of the compound represented by Formula R are shown below. The compounds usable in the present invention are by no means limited by these.

The compound having a radical-scavenging ability is not the same as the compound having a singlet oxygen quenching rate constant kq of not less than 1 x 10⁸ M^-1 s^-1.

The compound having a radical-scavenging ability may preferably have a radical-scavenging rate constant Ks in the range of from 10^-1 M^-1 s^-1 to 2 x 10⁴ M^-1 s^-1, and more preferably from 10^-1 M^-1 s^-1to 10³ M^-1 s^-1.

In the coupler represented by Formula M-1 as previously set forth,

Z represents a group of non-metal atoms necessary to complete a nitrogen-containing heterocyclic ring. The ring formed by said Z may have a substitutent.

X represents a hydrogen atom or a group capable of being split off upon reaction with an oxidized product of a color developing agent.

R represents a hydrogen atom or a substituent. There are no particular limitations on the substituent represented by R. It may typically include groups such as alkyl, aryl, anilino, acylamino, sulfonamide, alkylthio, arylthio, alkenyl and cycloalkyl. Besides these, it may also include a halogen atom, groups such as cycloalkenyl, alkynyl, a heterocyclic ring, 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, a spiro compound residual group, and a bridged hydrocarbon compound residual group.

The alkyl group represented by R may preferably include those having 1 to 32 carbon atoms, which may be either straight-chain or branched.

The aryl group represented by R may preferably include a phenyl group.

The acylamino group represented by R may include an alkylcarbonylamino group and an arylcarbonylamino group.

The sulfonamide group represented by R may include an alkylsulfonylamino group and an arylsulfonylamino group.

The alkyl component or aryl component in the alkylthio group or arylthio group represented by R may include the alkyl group or aryl group represented by R.

The alkenyl group represented by R may preferably include those having 2 to 32 carbon atoms; and the cycloalkyl group, those having 3 to 12 carbon atoms, and particularly 5 to 7 carbon atoms. The alkenyl group may be either straight-chain or branched.

The cycloalkenyl group represented by R may preferably include those having 3 to 12 carbon atoms, and particularly preferably 5 to 7 carbon atoms.

The sulfonyl group represented by R may include an alkylsulfonyl group and an arylsulfonyl group;

the sulfinyl group may include an alkylsulfinyl group and an arylsufinyl group;

the phosphonyl group may include an alkylphosphonyl group, an alkoxyphosphonyl group, an aryloxyphosphonyl group and an arylphosphonyl group;

the acyl group may include an alkylcarbonyl group and an arylcarbonyl group;

the carbamoyl group may include an alkylcarbamoyl group and an arylcarbamoyl group;

the sulfamoyl group may include an alkylsulfamoyl group and an arylsulfamoyl group;

the acyloxy group may include an alkylcarbonyloxy group and arylcarbonyloxy group;

the carbamoyloxy group may include an alkylcarbamoyloxy group and an arylcarbamoyloxy group;

the ureido group may include an alkylureido group and an arylureido group;

the sulfamoylamino group may include an alkylsulfamoylamino group and an arylsulfamoylamino group;

the heterocyclic group may preferably include those of 5 to 7 members, specifically including a 2-furyl group, a 2-thienyl group, a 2-pyrimidinyl group and a 2-benzothiazolyl group;

the heterocyclic oxy group may preferably include those having a heterocyclic ring of 5 to 7 members, including, for example, a 3,4,5,6-tetrahydropyranyl-2-oxy group and a 1-phenyltetrazole-5-oxy group;

the heterocyclic thio group may preferably include a heterocyclic thio group of 5 to 7 members, including, for example, a 2-pyridylthio group, a 2-benzothiazolylthio group and a 2,4-diphenoxy-1,3,5-triazole-6-thio group;

the siloxy group may include a trimethylsiloxy group, a triethylsiloxy group and a dimethylbutylsiloxy group;

the imido group may include a succinimido group, a 3-heptadecylsuccinimido group, a phthalimido group and a glutalimido group;

the spiro compound residual group may include spiro[3.3]heptan-1-yl; and

the bridged hydrocarbon compound residual group may include bicylo[2.2.1]heptan-1-yl, tricyclo[3.3.1.1^3.7] decan-1-yl and 7,7-dimethyl-bicyclo[2.2.1]heptan-1-yl.

The group represented by X, capable of being split off through the reaction with an oxidized product of a color developing agent, may include, for example, a halogen atom such as a chlorine atom, a bromine atom or a fluorine atom, and groups such as alkoxy, aryloxy, heterocyclic oxy, acyloxy, sulfonyloxy, alkoxycarbonyloxy, aryloxycarbonyl, alkyloxalyloxy, alkoxyoxalyloxy, alkylthio, arylthio, heterocyclic thio, alkyloxythiocarbonylthio, acylamino, sulfonamido, a nitrogen-containing heterocyclic ring bonded with a N atom, alkyloxycarbonylamino, aryloxycarbonylamino, carboxyl, and

wherein R₁' has the same definition for the above R, and Z', the same definition for the above Z; and R₂' and R₃' each represent a hydrogen atom, an aryl group, an alkyl group or a heterocyclic group. It may preferably include a nitrogen-containing heterocyclic group substituted via a nitrogen atom, or a halogen atom, in particular, a chlorine atom.

The nitrogen-containing heterocyclic group formed by Z or Z' may include a pyrazole ring, an imidazole ring, a triazole ring or a tetrazole ring, and the substituent the above ring may have may include those described for the above R.

The coupler represented by Formula M-I is more specifically represented, for example, by the following Formulas M-II to M-VII.

In the above Formulas M-II to M-VII, R₁ to R₈ and X have the same definitions for the above R and X, respectively.

Among Formula M-I, preferred is the one represented by Formula M-VIII shown below.

In the formula, R₁, X and Z₁ have the same definitions for R, X and Z, respectively, in Formula M-I.

Among the magenta couplers represented by Formulas M-II to M-VII, particularly preferred magenta couplers are the magenta couplers represented respectively by Formulas M-II and M-III.

Among the substituents on the above heterocyclic ring, at least one of them may preferably be a substituent represented by the following Formula M-IX. Particularly preferably, R₁ is the substituent of Formula M-IX.

In the formula, R₉, R₁₀ and R₁₁ each have the same definitions for the above R.

Any two of the above R₉, R₁₀ and R₁₁, for example, R₉ and R₁₀, may also combine to form a saturated or unsaturated ring as exemplified by cycloalkane, cycloalkene and a heterocyclic ring, and the ring thus formed and R₁₁ may further combine to form a bridged hydrocarbon compound residual group.

Particularly preferred in Formula M-IX are (i) the case when at least two of R₉ to R₁₁ are alkyl groups, and (ii) the case when one of R₉ to R₁₁, for example, R₁₁, is a hydrogen atom, and other two, R₉ and R₁₀, combine to form cycloalkyl together with the route carbon atom.

Still particularly preferred in (i) is the case when any two of R₉ to R₁₁ are alkyl groups and the remaining one is a hydrogen atom or an alkyl group.

The substituent the ring formed by Z in Formula M-I or the ring formed by Z₁ in Formula M-VIII may have, and R₂ to R₈ in Formulas M-II to M-VI may preferably include those represented by Formula M-X shown below. Formula M-X   -R₁₂-SO₂-R₁₃

In the formula, R₁₂ represents an alkylene group, and R₁₃ represents an alkyl group, a cycloalkyl group or an aryl group.

The alkylene group represented by R₁₂ may preferably have two or more, more preferably 3 to 6, carbon atoms at the straight-chain moiety, and may be straight-chain or branched.

Typical examples of the compounds are shown below.

In addition to the above typical examples of the compounds employed in the present invention, examples of the compounds which can be used in the present invention may also be the compounds shown as Nos. 1 to 4, 6, 8 to 17, 19 to 24, 26 to 43, 45 to 59, 61 to 104, 106 to 121, 123 to 162 and 164 to 223 among the compounds disclosed in Japanese Patent O.P.I. Publication No. 166339/1987, pages 66 to 122.

The magenta coupler represented by the above Formula M-I can be readily synthesized by those skilled in the art, by making reference to Journal of the Chemical Society, Perkin I (1977), 2047-2052, U.S. Patent No. 3,725,067, Japanese Patent O.P.I. Publications No. 99437/1984, No. 42045/1983, No. 162548/1984, No. 171956/1984, No. 33552/1985, No. 43659/1985, No. 172982/1985 and No. 190779/1985, etc.

The magenta couplers can be used usually in the range of from 1 x 10^-3 mol to 1 mol, and preferably from 1 x 10^-2 mol to 8 x 10^-1 mol, per mol of silver halide.

The use couplers can also be used in combination with magenta couplers of different types.

Based on the magenta coupler represented by Formula M-I, the compound having a singlet oxygen quenching rate constant kq of not less than 10⁸ M^-1s^-1and the compound having a radical-scavenging ability may each preferably be used in an amount of from 5 mol % to 400 mol %, and more preferably from 10 mol % to 250 mol %.

The compound having kq of not less than 10⁸ M^-1s^-1 and the compound having a radical-scavenging ability may be used in their total amount of from 10 mol % to 500 mol %, and more preferably from 20 mol % to 400 mol %, based on the magenta coupler represented by Formuia M-I.

The compound having kq of not less than 10⁸ M^-1 s^-1 and the compound having a radical-scavenging ability, according to the present invention, may preferably be used in a proportion of from 0.1 to 10, and more preferably in the range of from 0.25 to 4.0, in molar ratio of the former to the latter.

The magenta coupler represented by Formula M-I, the compound having kq of not less than 10⁸ M s^-1s^-1and the compound having a radical-scavenging ability (serving as stabilizing agents) are used in the same layer. They may also be used in such a way that the stabilizing agents are used in a layer adjoining to the layer in which the coupler is present.

The magenta coupler represented by Formula M-I, the compound having kq of not less than 10⁸ M^-1s^-1 and the compound having a radical-scavenging ability, according to the present invention can be added to the light-sensitive material by various methods such as the solid-state dispersion, the latex dispersion and the oil-in-water emulsification dispersion.

For example, according to the oil-in-water emulsification dispersion, hydrophobic additives such as the magenta coupler may usually be dissolved in a high-boiling organic solvent having a boiling point of 150°C or more or a water-insoluble polymeric compound, optionally together with a low-boiling and/or water-soluble organic solvent to effect emulsification dispersion in a hydrophilic binder such as an aqueous gelatin solution using a surface active agent, and thereafter the resulting emulsion may be added to the intended hydrophilic colloid layer.

The light-sensitive material of the present invention can be applied to, for example, color negative and positive films and color photographic papers. The present invention can be remarkably effective particularly when applied to color photographic papers used for direct viewing.

The silver halide used in the present invention may include any silver halides such as silver chloride, silver bromide, silver iodide, silver chlorobromide, silver iodobromide and silver chloroiodide.

Silver halide grains preferably used in the present invention may preferably have a silver chloride content of not less than 90 mol %, a silver bromide content of not more than 10 mol % and a silver iodide content of not more than 0.5 mol %. They may more preferably be silver chlorobromide grains having a silver bromide content of from 0.1 mol % to 2 mol %.

The silver halide grains may be used alone, or may also be used in combination with other silver halide grains having different composition. They may also be used in combination with silver halide grains having a silver chloride content of not more than 90 mol %.

In the silver halide emulsion layer containing silver halide grains having a silver chloride content of not less than 90 mol %, the silver halide grains having a silver chloride content of not less than 90 mol % are held in a proportion of not less than 60 % by weight, and preferably not less than 80 % by weight, in the whole silver halide grains contained in the emulsion layer.

The composition of silver halide grains may be uniform throughout a grain, from its inside to its outer portion, or may be different between the inside and outer portion of a grain. In the case when the composition of the grain is different between the inside and the outer portion, the composition may change continuously or discontinuously.

There are no particular limitations on the grain size of the silver halide grains according to the present invention. Taking account of the rapid processing performance and speed, and also other photographic performances, it may be preferably in the range of from 0.2 µm to 1.6 µm, and more preferably from 0.25 µm to 1.2 µm. The above grain size can be measured by various methods generally used in the present technical field. Typical methods are described in Loveland, "Grain Size Analytical Methods", A.S.T.M. Symposium on Light Microscopy, 1955, pp.94-122, or Mees and James, "The Theory of The Photographic Process", 3rd Ed., 2nd Chapter, Macmillan Publishing Co., Inc. (1966).

This grain size can be measured by use of the projected area or diameter approximate value of a grain. If the grains are of substantially uniform shape, the grain size distribution can be represented fairly accurately as the diameter or projected area.

The grain size distribution of the silver halide grains according to the present invention may be polydisperse or monodisperse. Prefered are monodisperse silver halide grains wherein, in the grain size distribution of the silver halide grains, its coefficient of variation is 0.22 or less, and preferably 0.15 or less. Here, the coefficient of variation is a coefficient indicating the breadth of the grain size distribution, and can be defined by the following formula: Coefficient of variation (S/r) = Standard deviation of grain size distribution Average grain size Standard deviation (S) of grain size distribution = Σ(r - ri)2ni Σni Average grain size (r) = ΣniriΣni

Here, ri represents the grain size of the individual grains; and ni, its number. The grain size herein mentioned indicates the diameter when a silver halide grain is spherical; and, when it is cubic or of the form other than the spherical, the diameter obtained by calculating a projected image thereof as a round image having the same area.

In the present invention, the silver halide grains used in emulsions may be those obtained by any of the acid method, the neutral method and the ammoniacal method. The grains may be grown at one time, or may be grown after making seed grains.

The method of making seed grains and the method of growing them may be the same or different.

The manner by which soluble silver salts are reacted with readily soluble halogen salts may be any of those including the normal precipitation, the reverse precipitation, the double-jet precipitation, and the combination of any of these. Preferred are grains obtained by the double-jet precipitation. As one manner of the double-jet precipitation, it is also possible to use the pAg-controlled double-jet precipitation described in Japanese Patent O.P.I. Publication No. 48521/1979.

If necessary, a silver halide solvent such as thioethers may also be used. A mercapto group-containing compound, a nitrogen-containing heterocyclic compound or a compound like a spectral sensitizer may also be used by adding them at the time the silver halide grains are formed or after the formation of grains has been completed.

As the silver halide grains used in the present invention, those of any shape can be used. A preferable example thereof is a cube having { 100} face as a crystal surface. It is also possible to prepare grains of the shape such as an octahedron, a tetradecahedron or a dodecahedron, according to the methods as disclosed in publications such as U.S. Patents No. 4,183,756 and No. 4,225,666, Japanese Patent O.P.I. Publication No. 26589/1980, Japanese Patent Publication No. 42737/1980, and The Journal of Photographic Science, 21, 39 (1973), and put them into use. Grains with twin planes may also be used.

The silver halide grains used in the present invention may be comprised of grains having a single shape, or comprised of a mixture of grains having various shapes.

In the present invention, to the silver halide grains used in emulsions, metal ions may be added using a cadmium salt, a zinc salt, a lead salt, a thallium salt, an iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof, an iron salt or a complex salt thereof, in the course the grains are formed and/or in the course they are grown, whereby they can be incorporated in the insides of the grains and/or the surfaces thereof. Alternatively, the silver halide grains may be placed in a reducing atmosphere, whereby reduction sensitization nuclei can be imparted to the insides of the grains and/or the surfaces of the grains.

From emulsions containing the silver halide grains, excess soluble salts may be removed after the growth of the silver halide grains has been completed, or they may remain unremoved. In the case when the slats are removed, they can be removed by the method described in Research Disclosure No. 17643.

In the present invention, the silver halide grains used in emulsions may be those in which a latent image is mainly formed on the surfaces, or those in which it is formed in the insides of grains. It is preferred to use grains in which the latent image is mainly formed on the surfaces.

In the present invention, the emulsions are chemically sensitized by conventional methods. More specifically, the sulfur sensitization making use of a compound containing sulfur capable of reacting with silver ions or an active gelatin, the selenium sensitization making use of a selenium compound, the reduction sensitization making use of a reducing substance and the noble metal sensitization making use of a compound of noble metal such as gold or the like can be used alone or in combination.

The emulsions can also be spectrally sensitized to the desired wavelength region, using a spectral sensitizer. The spectral sensitizer that can be used may include cyanine dyes, merocyanine dyes, composite cyanine dyes, composite merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxanol dyes.

The dye forming couplers used in the light-sensitive silver halide photographic material of the present invention are usually so selected that the dye capable of absorbing spectrum light to which an emulsion layer is sensitive is formed with respect to each emulsion layer. Thus, a yellow dye forming coupler is used in a blue-sensitive emulsion layer, a magenta dye forming coupler in a green-sensitive emulsion layer, and a cyan dye forming coupler in a red-sensitive emulsion layer. However, depending on the purpose, the light-sensitive silver halide photographic material may be prepared by a method in which the couplers are used in the manner different from the above combination.

In the present invention, as the yellow dye forming coupler, acylacetoanilide couplers can be preferably used. In particular, benzoyl acetanilide compounds and pivaroyl acetanilide compounds are advantageous, and those particularly preferably usable are the exemplary compounds Y-1 to Y-146 disclosed in Japanese Patent O.P.I. Publication No. 85631/1988, the exemplary compounds Y-1 to Y-98 disclosed in Japanese Patent O.P.I. Publication No. 97951/1988, the exemplary compounds I-1 to I-50 disclosed in Japanese Patent O.P.I. Publication No. 298943/1990, and the exemplary compounds Y-1 to Y-24 disclosed in Japanese Patent Application No. 316996/1987.

In the present invention, in addition to the magenta coupler represented by Formula M-I previously set forth, a magenta coupler represented by the following Formula M-II may also be used in combination.

In the formula, Ar represents an aryl group; X represents a halogen atom, an alkoxyl group or an alkyl group; and R represents a group capable of being substituted on the benzene ring. The letter symbol n represents 1 or 2. In the case when n is 2, the groups R's may be the same or different. Y represents a group capable of being split off upon reaction with an oxidized product of an aromatic primary amine color developing agent.

In Formula M-II, the group represented by Y, capable of being split off upon reaction with an oxidized product of an aromatic primary amine color developing agent may include, for example, a halogen atom, an alkoxyl group, an aryloxy group, an acyloxy group, an arylthio group, an alkylthio group, and -N Z' wherein Z' represents a group of atoms necessary to complete a ring of 5 or 6 members formed by an atom selected from a carbon atom, an oxygen atom, a nitrogen atom and a sulfur atom, together with the nitrogen atom. Here, Y does not represent a hydrogen atom.

Examples of the group represented by Y are shown below.

Halogen atom: Atoms such as chlorine, bromine and fluorine.

Alkoxyl group: An ethoxy group, a benzoyloxy group, a methoxyethylcarbamoylmethoxy group, a tetradecylcarbamoylmethoxy group, etc.

Aryloxy group: A phenoxy group, a 4-methoxyphenoxy group, a 4-nitrophenoxy group, etc.

Acyloxy group: An acetoxy group, a myristoyloxy group, a benzoyloxy group, etc.

Arylthio group: a phenylthio group, a 2-butoxy-5-octylphenylthio group, a 2,5-dihexyloxyphenylthio group, etc.

Alkylthio group: A methylthio group, an octylthio group, a hexadecylthio group, a benzylthio group, a 2-(diethylamino)ethylthio group, an ethoxycarbonylmethylthio group, an ethoxydiethylthio group, a phenoxyethylthio group, etc.

-N Z': A pyrazolyl group, an imidazolyl group, a triazolyl group, a tetrazolyl group, etc.

The coupler represented by Formula M-II may include, for example, the exemplary compounds No. 218 to No. 244 disclosed in Japanese Patent O.P.I. Publication No. 52138/1988. It may further include those disclosed in U.S. Patents No. 2,600,788, No. 3,061,432, No. 3,062,653, No. 3,127,269, No. 3,311,476, No. 3,152,896, No. 3,419,391, No. 3,519,429, No. 3,555,318, No. 3,684,514, No. 3,888,680, No. 3,907,571, No. 3,928,044, No. 3,930,861, No. 3,930,866 and No. 3,933,500, Japanese Patent O.P.I. Publications No. 29639/1974, No. 111631/1974, No. 129538/1974, No. 13041/1975, No. 58922/1977, No. 62454/1980, No. 118034/1980, No. 38043/1981, No. 35858/1982, No. 2953/1985, No. 23855/1985, No. 60644/1985, British Patent No. 1,247,493, Belgian Patents No. 789,116 and 792,525, West German Patent No. 21 56 111, Japanese Patent Examined Publications No. 60479/1971 and No. 36577/1982.

The cyan coupler used in the present invention may include naphthol type, phenol type and imidazole type compounds.

The cyan coupler particularly preferably used in the present invention may include cyan couplers represented by the following Formulas C-I and C-II.

In the formula, R_c1 represents an alkyl group having 2 to 6 carbon atoms.

R_c2 represent a ballast group. Z_c represents an atom or group capable of being split off upon reaction with an oxidized product of a color developing agent.

The alkyl group represented by R_c1 may be straight-chain or branched, and may include those having a substituent.

The ballast group represented by R_c2 is an organic group having the size and shape that impart to coupler molecules a bulkiness large enough for the coupler to be substantially undiffusible from the layer to which the coupler is applied, to other layer.

A group preferred as the ballast group is a group represented by the following formula:

R_c3 represents an alkyl group having 1 to 12 carbon atoms, Ar_c represents an aryl group such as a phenyl group. This aryl group includes those having a substituent.

The cyan coupler represented by Formula C-I can be exemplified by the exemplary compounds PC-1 to PC-19 disclosed in Japanese Patent O.P.I. Publication No. 156748/1989, page 30, right upper column to page 31, left upper column, the exemplary compounds C-1 to C-28 disclosed in Japanese Patent O.P.I. Publication No. 249151/1987, and also the cyan couplers as disclosed in Japanese Patent Examined Publication No. 11572/1974, Japanese Patent O.P.I. Publications No. 3142/1986, No. 9652/1986, No. 9653/1986, No. 390465/1986, No. 50136/1986, No. 99141/1986 and No. 105545/1986. Examples are by no means limited to these.

In the formula, R^c1 represents an alkyl group or an aryl group. R^c2 represents an alkyl group, a cycloalkyl group, an aryl group or a heterocyclic group. R^c3 represents a hydrogen atom, a halogen atom, an alkyl group or an alkoxyl group. R^c3 and R^c1 may also combine to form a ring. Z^c represents a hydrogen atom or a group capable of being split off upon reaction with an oxidized product of a color developing agent.

In the cyan coupler represented by the above Formula C-II, the alkyl group represented by R^c1 may preferably be an alkyl group having 1 to 32 carbon atoms, these of which may be straight-chain or branched, and may also include those having a substituent.

The aryl group represented by R^c1 may preferably be a phenyl group, and may include those having a substituent.

The alkyl group represented by R^c2 may preferably be an alkyl group having 1 to 32 carbon atoms. Such alkyl group may be straight-chain or branched, and may include those having a substituent.

The cycloalkyl group represented by R^c2 may preferably be a cycloalkyl group having 3 to 12 carbon atoms. Such cycloalkyl group may include those having a substituent.

The aryl group represented by R^c2 may preferably be a phenyl group, and may include those having a substituent.

The heterocyclic group represented by R^c2 may preferably be a heterocyclic ring of 5 to 7 members, and may include those having a substituent. It may also be of a condensed form.

R^c3 represents a hydrogen atom, a halogen atom, an alkyl group or an alkoxyl group, where the alkyl group and the alkoxyl group may include those having a substituent. R^c3 may preferably be a hydrogen atom.

The ring formed by the combination of R^c1 and R^c3 may preferably include rings of 5 or 6 members, which can be exemplified by the following:

The group represented by Z^c, capable of being split off upon reaction with an oxidized product of a color developing agent may include a halogen atom, an alkoxyl group, an aryloxy group, an acyloxy group, a sulfonyloxy group, an acylamino group, a sulfonylamino group, an alkoxycarbonyoxy group, an aryloxycarbonyloxy group and an imide group, all of which may include those having a substituent. It may preferably be a halogen atom, an aryloxy group or an alkoxyl group.

Of the cyan couplers described above, a particularly preferred one is a cyan coupler represented by the following Formula C-II-A.

In the formula, R_A1 represents a phenyl group substituted with at least one halogen atom. Such a phenyl group may include a phenyl group further having a substituent other than the halogen atom. R_A2 has the same definition for R^c1 in Formula C-II previously described. X_A represents a halogen atom, an aryloxy group or an alkoxyl group, and may include those having a substituent.

Typical examples of the cyan coupler represented by Formula C-II are the exemplary compounds C-1 to C-25 disclosed in Japanese Patent O.P.I. Publication No. 96656/1985, the exemplary compounds PC-II-1 to PC-II-31 disclosed in Japanese Patent O.P.I. Publication No. 156748/1989, pages 32, left lower column to page 34, left upper column, and besides the 2,5-diacylamino cyan couplers as disclosed in Japanese Patent O.P.I. Publication No. 178962/1987, page 7, right lower column to page 9, left lower column, Japanese Patent O.P.I. Publication No. 225155/1985, page 7, left lower column to page 10, right lower column, Japanese Patent O.P.I. Publication No. 222853/1985, page 6, left upper column to page 8, right lower column, and Japanese Patent O.P.I. Publication No. 185335/1984, page 6, left lower column to page 9, left upper column. They can be synthesized according to the method disclosed in these publications.

Hydrophobic compounds such as the dye forming couplers as described above may usually be dissolved in a high-boiling organic solvent having a boiling point of about 150°C or above or a water-insoluble polymeric compound, optionally together with a low-boiling and/or water-soluble organic solvent to effect emulsification dispersion in a hydrophilic binder such as an aqueous gelatin solution using a surface active agent by the use of a dispersion means such as a homogenizer, a colloid mill, a flow-jet mixer and an ultrasonic apparatus, and thereafter the resulting emulsion may be added to the intended hydrophilic colloid layer. The step of removing the low-boiling organic solvent at the same time of carrying out the dispersion may also be inserted.

In the present invention, a solvent with a dielectric constant of less than 6.0 may preferably be used as the high-boiling organic solvent.

Any compounds can be used as the high-boiling organic solvent preferably used in the present invention so long as they are compounds with a dielectric constant of less than 6.0. No particular limitation may be required for its lower limit. In a preferred embodiment, the compounds may have a dielectric constant of 1.9 or more. They can be exemplified by esters such as phthalate and phosphate, organic acid amides, ketones and hydrocarbon compounds having dielectric constant of less than 6.0.

In the present invention, it is preferred to use a high-boiling organic solvent having a vapor pressure of preferably not more than 0.5 mmHg at 100°C. It is more preferred to use phthalates or phosphates among such high-boiling organic solvents. The organic solvent may be comprised of a mixture of two or more kinds. In this instance, the mixture may have the dielectric constant of less than 6.0. The dielectric constant herein referred to indicates a dielectric constant measured at 30°C.

The phthalate advantageously used in the present invention may include a compound represented by the following Formula HA.

In the formula, R_H1 and R_H2 each represent an alkyl group, an alkenyl group or an aryl group, provided that the total sum of the carbon atom number of the groups represented by R_H1 and R_H2 is from 9 to 32. More preferably, the total sum of the carbon atom number is from 16 to 24.

The alkyl group represented by R_H1 and R_H2 in the above Formula HA may be straight-chain or branched. The aryl group represented by R_H1 and R_H2 may include a phenyl group, a naphthyl group, etc., and the alkenyl group, a hexenyl group, a heptenyl group, an octadecenyl group, etc. These alkyl group, alkenyl group and aryl group may each have a substituent or substituents.

In the present invention, the phosphate advantageously used in the present invention may include a compound represented by the following Formula HB.

In the formula, R_H3, R_H4 and R_H5 each represent an alkyl group, an alkenyl group or an aryl group, provided that the total sum of the carbon atom number of the groups represented by R_H3, R_H4 and R_H5 is from 24 to 54.

The alkyl group, alkenyl group and aryl group may each have a substituent or substituents. Preferably, R_H3, R_H4 and R_H5 are each an alkyl group, which may include a nonyl group, a n-decyl group, a sec-decyl group, a sec-dodecyl group and a t-octyl group.

The above high-boiling organic solvent can be exemplified by the exemplary organic solvents 1 to 22 disclosed in Japanese Patent O.P.I. Publication No. 166331/1987, page 41.

The polymer used for dispersing the couplers, which is insoluble in water and soluble in an organic solvent, may include the following:

(1) Vinyl polymers and copolymers.

(2) Condensation polymers of polyhydric alcohols with polybasic acids.

(3) Polyesters obtained by ring-opening polymerization.

(4) Others: Polycarbonate resins, polyurethane resins, polyamide resins, etc.

There are no particular limitations on the number average molecular weight of these polymers. It may preferably be not more than 200,000, and more preferably from 5,000 to 100,000. The proportion of the polymer to the hydrophobic compounds such as couplers may preferably be 1:20 to 20:1, and more preferably 1:10 to 10:1.

Examples of the polymer preferably used are shown below. Copolymers are shown together with their weight ratios.

(PO-1) Poly(N-t-butylacrylamide)

(PO-2) N-t-butylacrylamide/methyl methacrylate copolymer (60:40)

(PO-3) Polybutyl methacrylate

(PO-4) Methyl methacrylate/styrene copolymer (90:10)

(PO-5) N-t-butylacrylamide/2-methoxyethyl acrylate copolymer (55:45)

(PO-6) ω-Methoxypolyethylene glycol acrylate (addition molar number n = 9)/N-t-butylacrylamide copolymer (25:75)

(PO-7) 1,4-Butanediol-adipic acid polyester

(PO-8) Polypropiolactam

As the binder (or protective colloid) used in the light-sensitive silver halide photographic material of the present invention, it is advantageous to use gelatin. Besides gelatin, it is also possible to use hydrophilic colloids such as gelatin derivatives, graft polymers of gelatin with other macromolecules, proteins, sugar derivatives, cellulose derivatives, and homopolymer or copolymer synthetic hydrophilic polymeric substances.

In the light-sensitive silver halide photographic material of the present invention, it is also possible to optionally use additives such as hardening agents, color contamination preventives, image stabilizers, ultraviolet absorbents, plasticizers, latexers, surface active agents, matting agents, lubricants and antistatic agents.

The gelatin coated on a support of the light-sensitive material of the present invention may preferably be in an amount of less than 7 g/m² in total. No particular limitation is required for its lower limit. In general, it may preferably be not less than 3 g/m² in view of physical properties or photographic performance. The amount of gelatin can be determined in terms of the weight of gelatin containing 11.0 % of water, according to the method of measuring water content as described in the PAGI method.

The gelatin contained in the light-sensitive material of the present invention is hardened using a hardening agent. There are no particular limitations on the hardening agent that can be used. It may include hardening agents known in the photographic industrial field, as exemplified by aldehyde type hardening agents, active vinyl type hardening agents, active halogen type hardening agents, epoxy type hardening agents, ethyleneimine type hardening agents, methane sulfonate type hardening agents, carbodiimide type hardening agents, isooxazole type hardening agents, and polymeric hardening agents.

The present invention can be particularly effective when the light-sensitive material of the present invention is used in direct-view light-sensitive materials such as color photographic papers or color copying light-sensitive materials on which there are severe demands for image storage stability.

In the light-sensitive material of the present invention, images can be formed by carrying out color development processing known in the present industrial field.

In the present invention, the color developing agent used in the color developing solution may include aminophenol derivatives and p-phenylenediamine derivatives widely used in various color photographic processes.

To the color developing solution applied in the processing of the light-sensitive material of the present invention, known developing solution component compounds can be added in addition to the primary aromatic amine color developing agent previously mentioned.

The color developing solution may have a pH value of not less than 9, and preferably from about 10 to about 13.

Color developing may be carried out at a temperature of usually not lower than 15°C, and generally in the range of from 20°C to 50°C.

For rapid processing, the color developing may preferably be carried out at 30°C or above.

Development processing may generally be carried out in 10 seconds to 4 minutes. When the rapid processing is intended, the processing may preferably be carried out in the range of from 10 seconds to 1 minute. When more rapid processing is required, the processing may preferably be carried out in the range of from 10 seconds to 30 seconds.

In instances in which the light-sensitive material of the present invention is running processed while continuously supplying a color developing solution replenisher, the color developing solution may preferably be replenished in an amount of from 20 ml to 150 ml, more preferably from 20 ml to 120 ml, and still more preferably from 20 ml to 100 ml, per 1 m² of the light-sensitive material. The present invention can be more effective when such low-replenishment running processing is carried out.

After the color developing has been completed, the light-sensitive material of the present invention is subjected to bleach-fixing.

After the bleach-fixing has been completed, the light-sensitive material is usually subjected to washing or stabilizing, or both of them in combination.

EXAMPLES

Specific examples of the present invention will be given below. Embodiments of the present invention are by no means limited to these.

Structures of additives used in the examples are shown together in the last.

Example 1 (Preparation of silver halide emulsions)

Six kinds of silver halide emulsions shown below were prepared by neutral and double-jet precipitation.

Emulsion No.	AgCl	AgBr	Av. grain size	Chemical sensitizer	Spectral sensitizer
	(mol%)	(mol%)	(µm)
Em-1	10	90	0.67	Sodium thiosulfate	SD-1
Em-2	30	70	0.46	"	SD-2
Em-3	30	70	0.43	"	SD-3
Em-4	99.5	0.5	0.67	Sodium thiosulfate + Sodium chloroaurate	SD-1
Em-5	99.5	0.5	0.46	"	SD-2
Em-6	99.5	0.5	0.43	"	SD-3

The respective silver halide emulsions were chemically sensitized. After completion of the sensitization, STB-1 was added as an emulsion stabilizer in an amount of 2 x 10^-4 mol per mol of silver halide.

(Preparation of light-sensitive silver halide color photographic materials)

On a laminated support comprising a paper support one side of which was coated with polyethylene and the first layer side on the other side of which was coated with polyethylene containing titanium oxide, layers with the constitution as shown below were formed by coating to give a multilayer light-sensitive silver halide color photographic material. Coating solutions were prepared in the following way.

First layer coating solution:

To a mixture of 26.7 g of a yellow coupler (Y-1), 0.67 g of an anti-stain agent (HQ-1) and 13.3 g of a high-boiling organic solvent (DNP), 60 ml of ethyl acetate was added to effect dissolution. The resulting solution was emulsifyingly dispersed in 200 ml of an aqueous 10 % gelatin solution containing 10 ml of 10 % sodium alkylnaphthalenesulfonate, using a homogenizer to produce a yellow coupler dispersion.

The dispersion thus obtained was mixed together with a blue-sensitive silver chlorobromide emulsion (Em-1, 10 g in terms of silver) and a coating gelatin solution to give a first-layer coating solution.

Second-layer to seventh-layer coating solutions were also prepared in the same manner as the first-layer coating solution.

As hardening agents, a compound (H-1) was added to the second and fourth layers, and (H-2) to the seventh layer. As coating aids, surface active agents (SU-2), (SU-3) were added to make adjustment of surface tension.

Layer	Constitution	Amount
		(g/m2)
Seventh layer (Protective layer)	Gelatin	1.00
Sixth layer (UV absorbing layer)	Gelatin	0.40
	Ultraviolet absorbent (UV-1)	0.10
	Ultraviolet absorbent (UV-2)	0.04
	Ultraviolet absorbent (UV-3)	0.16
	Anti-stain agent (HQ-1)	0.01
	DNP	0.20
	PVP	0.03
Fifth layer (Red-sensitive layer)	Gelatin	1.30
	Red-sensitive silver chlorobromide
	emulsion (Em-3)	0.21
	Cyan coupler (C-1)	0.24
	Cyan coupler (C-2)	0.08
	Dye image stabilizer (ST-1)	0.20
	Anti-stain agent (HQ-1)	0.01
	HBS-1	0.20
	DOP	0.20
Fourth layer (UV absorbing layer)	Gelatin	0.94
	Ultraviolet absorbent (UV-1)	0.28
	Ultraviolet absorbent (UV-2)	0.09
	Ultraviolet absorbent (UV-3)	0.38
	Anti-stain agent (HQ-1)	0.03
	DNP	0.40
Third layer (Green-sensitive layer)	Gelatin	1.40
	Green-sensitive silver chlorobromide
	emulsion (Em-2)	0.17
	Magenta coupler (MM-1)	0.35
	Dye image stabilizer (1) (as shown in
	Table 1)	0.20
	Dye image stabilizer (2) (as shown in
	Table 1)	0.20
	DNP	0.20
Second layer (Intermediate layer)	Gelatin	1.20
	Anti-stain agent (HQ-2)	0.12
	DIDP	0.15
First layer	Gelatin	1.20
(Blue-sensitive layer)	Blue-sensitive silver chlorobromide
	emulsion (Em-1)	0.26
	Yellow coupler (Y-1)	0.80
	Dye image stabilizer (ST-1)	0.30
	Dye image stabilizer (ST-2)	0.20
	Anti-stain agent (HQ-1)	0.02
	DNP	0.20
Support	Polyethylene-laminated paper

The amounts of silver halide emulsions added are expressed in terms of silver.

DOP:

Dioctyl phthalate

DNP:

Dinonyl phthalate

DIDP:

Diisodecyl phthalate

PVP

Polyvinyl pyrrolidone

The dye image stabilizers (1) and (2) were changed as shown in Table 1 to produce samples 102 to 140.

Samples thus obtained were subjected to wedge exposure using green light by means of a sensitometer KS-7 (manufactured by Konica Corporation), and were processed according to the following color processing steps. After the processing was completed, evaluation was made on the items shown later.

Processing steps	Time	Temp.
Color developing	3 min. 30 sec.	33°C
Bleach-fixing	1 min. 30 sec.	33°C
Washing	3 min.	33°C

Formulation of color developing solution
N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-
aminoaniline sulfate	4.9 g
Hydroxylamine sulfate	2.0 g
Potassium carbonate	25.0 g
Sodium bromide	0.6 g
Anhydrous sodium sulfite	2.0 g
Benzyl alcohol	13.0 ml
Polyethylene glycol (average degree of polymerization: 400)	3.0 ml
Made up to 1 liter by adding water, and adjusted to pH 10.0 using sodium hydroxide.

Formulation of bleach-fixing solution
Ferric sodium ethylenediaminetetraacetate	6.0 g
Ammonium thiosulfate	100 g
Sodium bisulfite	10 g
Sodium metabisulfite	3 g
Made up to 1 liter by adding water, and adjusted to pH 7.0 using ammonia water

On the samples 101 to 140 thus processed, densities were measured using a densitometer (Type KD-7R, manufactured by Konica Corporation) under the following conditions.

The above samples having been processed were stored for 2 weeks under sunlight (on an exposure stand) to examine fastness to light of dye images.

The fastness to light of dye images was evaluated on the following items.

- Retention -

Percentage of the dye remaining after light fastness tests, with respect to the initial density 1.0.

- Degree of discoloration -

A value obtained by subtracting the (yellow density)/(magenta density) before light fastness tests from the (yellow density)/(magenta density) after light fastness tests started at the initial density 1.0. The larger this value is, the more the color tends to change from magenta to a yellowish tone.

Results obtained are shown in Table 1.

Sample No.	Dye image stabilizer (1)	Kq (M-1 s-1)	Dye image stabilizer (2)	Ks M-1 s-1	Retention (2 w.) (%)	Discoloration
101(X)	-	-	-	-	65	0.59
102(X)	-	-	Cp.RH-1	0	67	0.14
103(X)	-	-	Ex.R-47	3x10 1	81	0.17
104(X)	-	-	Ex.R-29	8	78	0.18
105(X)	-	-	Ex.R-1	3x10	80	0.16
106(X)	-	-	Ex.R-23	1x102	79	0.18
107(X)	-	-	Ex.R-4	5x103	77	0.17
108(X)	Cp.QH-1	2x106	-	-	68	0.18
109(X)	Cp.QH-1	2x106	Cp.RH-1	0	70	0.19
110(X)	Cp.QH-1	2x106	Ex.R-47	3x10 1	85	0.14
111(X)	Cp.QH-1	2x106	Ex.R-29	8	82	0.13
112(X)	Cp.QH-1	2x106	Ex.R-1	3x10	83	0.13
113(X)	Cp.QH-1	2x106	Ex.R-23	1x102	82	0.14
114(X)	Cp.QH-1	2x106	Ex.R-4	5x102	80	0.16
115(X)	Cp.QH-2	8x107	-	-	79	0.17
X: Comparative Example, Y: Present Invention
Cp.: Comparative, Ex.: Exemplary

Sample No.	Dye image stabilizer (1)	Kq (M-1s-1)	Dye image stabilizer (2)	Ks (M-1s-1)	Retention (2 w.) (%)	Discoloration
116(X)	Cp.QH-2	8x107	Cp . RH-1	0	80	0.19
117(X)	Cp.QH-2	8x107	Ex.R-47	3x10-1	88	0.07
118(X)	Cp.QH-2	8x107	Ex.R-29	8	89	0.08
119(X)	Cp.QH-2	8x107	Ex.R-1	3x10	88	0.08
120(X)	Cp.QH-2	8x107	Ex.R-23	1x102	89	0.07
121(X)	Cp.QH-2	8x107	Ex.R-4	5x103	84	0.10
122(X)	EX.Q-48	1x108	-	-	77	0.16
123(X)	EX.Q-48	1x108	Cp.RH-1	0	78	0.15
124(X)	EX.Q-48	1x108	Ex.R-47	3x10-1	94	0.05
125(X)	EX.Q-48	1x108	Ex.R-29	8	92	0.05
126(X)	EX.Q-48	1x108	Ex.R-1	3x10	93	0.06
127(X)	EX.Q-48	1x108	Ex.R-23	1x102	92	0.05
128(X)	EX.Q-48	1x108	Ex.R-4	5x103	90	0.08
X: Comparative Example, Y: Present Invention

Sample No.	Dye image stabilizer (1)	Kq (M-1 s-1)	Dye image stabilizer (2)	Ks (M-1 s-1)	Retention (2 w.) (%)	Discoloration
133(Y)	Ex.Q-34	7x108	Ex.R-47	3x10-1	92	0.06
134(Y)	Ex.Q-34	7x108	Ex.R-29	8	89	0.07
135(Y)	Ex.Q-34	7x108	Ex.R-1	3x10	91	0.05
136(Y)	Ex.Q-34	7x108	Ex.R-23	1x102	92	0.06
X: Comparative Example, Y: Present Invention

As is clear from the results shown in Table 1, improvements have been achieved, but less effectively, in both the dye retention and the prevention of discoloration in the light fastness tests when the compound according to the present invention having the radical-scavenging ability is used alone. Improvements have been also achieved, but less effectively, in both the dye retention and the prevention of discoloration in the light fastness tests when the compound according to the present invention having the singlet oxygen quenching rate constant kq of not less than 10⁸ M^-1s^-1 is used alone. In the instances in which the compound according to the present invention having the radical-scavenging ability and the comparative compound QH-1 with kq of 2 x 10⁶ M^-1s^-1 are used in combination (Samples 108 to 114), improvements can be seen compared with the instances in which they are not used in combination, but the effect is unsatisfactory.

On the other hand, in the instances where the compound according to the present invention having the radical-scavenging ability and the compound according to the present invention having the kq of not less than 10⁸ M^-1s^-1 are used at the same time (Samples 124 to 140), improvements have been achieved in both the dye retention and the prevention of discoloration in the light fastness tests, to the extent that can not be expected when the compound having the radical-scavenging ability and the compound having the kq of not less than 10⁸ M^-1s^-1 are respectively used alone (Samples 102 to 107 and 122).

Improvements are also found to have been particularly remarkably achieved in both the dye retention and the prevention of discoloration in the light fastness tests when the compound having the radical-scavenging rate constant Ks of 10^-1 to 10³ M^-1s^-1 and the compound having the kq of not less than 10⁸ M^-1s^-1 are used at the same time.

Example 2

Multilayer light-sensitive silver halide color photographic materials were produced in the same manner as in Example 1 except that the blue-sensitive silver chlorobromide emulsion Em-1 in the first layer, the green-sensitive silver chlorobromide emulsion Em-2 in the third layer and the red-sensitive silver chlorobromide emulsion Em-3 in the fifth layer were replaced with Em-4, Em-5 and Em-6, respectively.

Samples thus obtained were subjected to wedge exposure in the same manner as in Example 1, and were processed according to the following color processing steps. Thereafter, evaluation similar to that in Example 1 was also made.

Results obtained are shown in Table 2.

Processing steps	Temp.	Time
Color developing	35.0 ±0.3°C	45 sec.
Bleach-fixing	35.0 ±0.5°C	45 sec.
Stabilizing	30 to 34°C	90 sec.
Drying	60 to 80°C	60 sec.

Bleach-fixing solution
Ferric ammonium ethylenediaminetetraacetate dihydrate	60 g
Ethylenediaminetetraacetic acid	3 g
Ammonium thiosulfate (aqueous 70 % solution)	100 ml
Ammonium sulfite (aqueous 40 % solution)	27.5 ml
Made up to 1 liter by adding water, and adjusted to pH 6.2 using potassium carbonate or glacial acetic acid.

Stabilizing solution
5-Chloro-2-methyl-4-isothiazolin-3-on	1.0 g
Ethylene glycol	1.0 g
1-Hydroxyethylidene-1,1-diphosphonic acid	2.0 g
Ethylenediaminetetraacetic acid	1.0 g
Ammonium hydroxide (aqueous 20 % solution)	3.0 g
Ammonium sulfite	3.0 g
Fluorescent brightening agent (4,4'-diaminostilbene disulfonic acid derivative)	1.5 g
Made up to 1 liter by adding water, and adjusted using to pH 7.0 sulfuric acid or potassium hydroxide.

Color developing solution
Pure water	800 ml
Triethanolamine	10 g
N,N-diethylhydroxyamine	5 g
Potassium bromide	0.02 g
Potassium chloride	2 g
Potassium sulfite	0.3 g
1-Hydroxyethylidene-1,1-diphosphonic acid	1.0 g
Ethylenediaminetetraacetic acid	1.0 g
Disodium catechol-3,5-diphosphonate	1.0 g
N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate	4.5 g
Fluorescent brightening agent (4,4'-diaminostilbene disulfonic acid derivative)	1.0 g
Potassium carbonate	27 g
Made up to 1 liter in total by adding water, and adjusted to pH 10.10.

Sample No.	Dye image stabilizer (1)	Kq (M-1s-1)	Dye image stabilizer (2)	Ks (M-1s-1)	Retention (2 w.) (%)	Discoloration
201(X)	-	-	-		64	0.60
202(X)	-	-	Cp.RH-1	0	66	0.13
203(X)	-	-	Ex.R-47	3x10-1	80	0.16
204(X)	-	-	Ex.R-29	8	78	0.17
205(X)	-	-	Ex.R-1	3x10	80	0.17
206(X)	-	-	Ex.R-23	1x102	80	0.16
207(X)	-	-	Ex.R-4	5x103	76	0.16
208(X)	Cp.QH-1	2x106	-	-	67	0.18
209(X)	Cp.QH-1	2x106	Cp.RH-1	0	69	0.20
210(X)	Cp.QH-1	2x106	Ex.R-47	3x10-1	84	0.13
211(X)	Cp.QH-1	2x106	Ex.R-29	8	81	0.14
212(X)	Cp.QH-1	2x106	Ex.R-1	3x10	82	0.13
213(X)	Cp.QH-1	2x106	Ex.R-23	1x102	82	0.14
214(X)	Cp.QH-1	2x106	Ex.R-4	5x103	80	0.15
215(X)	Cp.QH-2	8x107	-	-	78	0.19
X: Comparative Example, Y: Present Invention

Sample No.	Dye image stabilizer (1)	Kq (M-1s-1)	Dye image stabilizer (2)	Ks (M-1 s-1)	Retention (2 w.) (%)	Discoloration
216(X)	Cp.QH-2	8x107	Cp.RH-1	0	80	0.18
217(X)	Cp.QH-2	8x107	Ex.R-47	3x10 -1	88	0.07
219(X)	Cp.QH-2	8x107	Ex.R-1	3x10	87	0.08
220(X)	Cp.QH-2	8x107	Ex.R-23	1x102	88	0.08
221(X)	Cp.QH-2	8x107	Ex.R-4	5x103	84	0.11
222(X)	Ex.Q-48	1x108	-	-	78	0.15
223(X)	Ex.Q-48	1x108	Cp.RH-1	0	79	0.14
224(Y)	Ex.Q-48	1x108	Ex.R-47	3x10 1	93	0.04
225(Y)	Ex.Q-48	1x108	Ex.R-29	8	93	0.05
226(Y)	Ex.Q-48	1x108	Ex.R-1	3x10	93	0.06
227(Y)	Ex.Q-48	1x108	Ex.R-23	1x102	92	0.05
228(Y)	Ex.Q-48	1x108	Ex.R-4	5x103	91	0.07
X: Comparative Example, Y: Present Invention

Sample No.	Dye image stabilizer (1)	Kq (M-1 s-1)	Dye image stabilizer (2)	Ks (M-1 s-1)	Retention (2 w.) (%)	Discoloration
233(Y)	Ex.Q-34	7x108	Ex.R-47	3x10-1	92	0.06
234(Y)	Ex.Q-34	7x108	Ex.R-29	8	90	0.08
235(Y)	Ex.Q-34	7x108	Ex.R-1	3x10	91	0.06
236(Y)	Ex.Q-34	7x108	Ex.R-23	1x102	92	0.07
X: Comparative Example, Y: Present Invention

As is clear from Table 2, improvements have been achieved in both the dye retention and the prevention of discoloration in the light fastness tests even when the silver halide emulsion having a silver chloride content of 99.5 % is used and the rapid processing is carried out in the developing time of 45 seconds, if the compound according to the present invention having the radical-scavenging ability and the compound having the kq of not less than 10⁸ M^-1s^-1 are used as dye image stabilizers at the same time.

Example 3

The dye image stabilizers (1) and (2) in Example 2 were replaced as shown in Table 3. The light-sensitive materials obtained were subjected to wedge exposure in the same manner as in Example 1, and were processed according to the color development processing steps like those in Example 2. Thereafter, the light-sensitive materials thus processed were stored for a month under sunlight, and then the same evaluation as in Example 1 was made.

Results obtained are shown in Table 3.

Sample No.	Dye image stabilizer (1)	Kq (M-1 s-1)	Dye image stabilizer (2)	Ks (M-1s-1)	Retention (1 m.) (%)	Discoloration
301(X)	-	-	-	-	48	0.90
302(X)	Cp.QH-2	8x107	-	-	53	0.54
303(X)	Cp.QH-2	8x107	Cp.RH-1	0	56	0.52
304(X)	Cp.QH-2	8x107	Ex.R-47	3x10 -1	65	0.46
305(X)	Cp.QH-2	8x107	Ex.R-29	8	63	0.45
306(X)	Cp.QH-2	8x107	Ex.R-1	3x10 2	62	0.44
307(X)	Cp.QH-2	8x107	Ex.R-23	1x10	63	0.43
308(X)	Cp.QH-2	8x107	Ex.R-4	5x103	62	0.45
309(X)	Ex.Q-48	1x108	-	-	56	0.42
310(X)	Ex.Q-48	1x108	Cp.RH-1	0	57	0.43
311(Y)	Ex.Q-48	1x108	Ex.R-47	3x10-1	78	0.32
312(Y)	Ex.Q-48	1x108	Ex.R-29	8	77	0.31
313(Y)	Ex.Q-48	1x108	Ex.R-1	3x10	78	0.32
314(Y)	Ex.Q-48	1x10-8	Ex.R-23	1x102	77	0.34
315(Y)	Ex.Q-48	1x108	Ex.R-4	5x103	74	0.32
X: Comparative Example, Y: Present Invention

Sample No.	Dye image stabilizer (1)	Kq (M-1s-1)	Dye image stabilizer (2)	Ks (M-1s-l)	Retention (1 m.) (%)	Discoloration
316(Y)	Ex.Q-34	7x108	Ex.R-47	3x10 -1	77	0.32
317(Y)	Ex.Q-34	7x108	Ex.R-29	8	75	0.33
318(Y)	Ex.Q-34	7x108	Ex.R-1	3x10	77	0.35
319(Y)	Ex.Q-34	7x108	Ex.R-23	1x102	78	0.32
X: Comparative Example, Y: Present Invention

As is clear from Table 3, improvements have been achieved, but less effectively, in both the dye retention and the prevention of discoloration in the light fastness tests continued for as long as one month, when the comparative compound QH-2 with kq of 8 x 10⁷ M^-1s^-1 and the compound having the radical-scavenging ability are used at the same time.

On the other hand, in the instances where the compound according to the present invention having the kq of not less than 10⁸ M^-1s^-1 and the compound having the radical-scavenging ability are used at the same time, surprising improvements have been achieved in both the dye retention and the prevention of discoloration.

From the above results, it is understood that a superior fastness to light can be promised when the compound according to the present invention having the kq of not less than 10⁸ M^-1s^-1 and the compound having the radical-scavenging ability are used at the same time.

Example 4

The magenta coupler MM-1 and the dye image stabilizers (1) and (2) in Example 2 were replaced as shown in Table 4. The same evaluation as in Example 1 was made.

Results obtained are shown in Table 4.

Sample No.	Dye image stabilizer (1)	Kq (M-1s-1)	Dye image stabilizer (2)	Ks (M-1 s-1)	[1]	[2] (%)	[3]
401(X)	-	-	-	-	MM-1	64	0.59
402(X)	Cp.QH-2	8x107	-	-	MM-1	79	0.20
403(X)	Cp.QH-2	8x107	Cp.RH-1	0	MM-1	80	0.19
404(X)	Cp.QH-2	8x107	Ex.R-47	3x10 -1	MM-1	88	0.07
405(X)	Cp.QH-2	8x107	Ex.R-23	1x102	MM-1	89	0.08
406(X)	EX.Q-48	1x108	-	-	MM-1	79	0.16
407(X)	EX.Q-48	1x108	Cp.RH-1	0	MM-1	80	0.15
408(Y)	EX.Q-48	1x108	Ex.R-47	3x10 -1	MM-1	95	0.04
409(Y)	EX.Q-48	1x108	Ex.R-23	1x10-2	MM-1	92	0.06
410(X)	EX.Q-48	1x108	-	-	MM-2	73	0.55
411(X)	EX.QH-2	8x107	-	-	MM-2	81	0.17
412(X)	Cp.QH-2	8x107	Cp.RH-1	0	MM-2	84	0.16
413(X)	Cp.QH-2	8x107	Ex.R-47	3x10 -1	MM-2	91	0.06
414(X)	Cp.QH-2	8x107	Ex.R-23	1x102	MM-2	91	0.07
415(X)	EX.Q-48	1x108	-	-	MM-2	81	0.13
[1]: Magenta coupler, [2]: Retention (2 weeks)
[3]: Discoloration
X: Comparative Example, Y: Present Invention

Sample No.	Dye image stabilizer (1)	Kq (M-1 s-1)	Dye image stabilizer (2)	Ks (M-1 s-1)	[1]	[2] (%)	[3]
416(X)	EX.Q-48	1x108	Cp.RH-1	0	MM-2	82	0.12
417(Y)	EX.Q-48	1x108	Ex.R-47	3x10 -1	MM-2	94	0.04
418(Y)	EX.Q-48	1x108	Ex.R-23	1x10-2	MM-2	92	0.04
419(X)	EX.Q-48	1x108	-	-	MM-3	71	0.57
420(X)	Cp.QH-2	8x107	-	-	MM-3	81	0.17
421(X)	Cp.QH-2	8x107	Cp.RH-1	0	MM-3	84	0.16
422(X)	Cp.QH-2	8x107	Ex.R-47	3x10 -1	MM-3	90	0.05
423(X)	Cp.QH-2	8x107	Ex.R-23	1x10-2	MM-3	90	0.06
424(X)	EX.Q-48	1x108	-	-	MM-3	80	0.13
425(X)	EX.Q-48	1x108	Cp.RH-1	0	MM-3	80	0.14
426(Y)	EX.Q-48	1x108	Ex.R-47	3x10 -1	MM-3	95	0.04
427(Y)	EX.Q-48	1x108	Ex.R-23	1x10-2	MM-3	93	0.04
428(X)	EX.Q-48	1x108	-	-	MM-4	66	0.58
429(X)	EX.QH-2	8x107	-	-	MM-4	80	0.19
430(X)	Cp.QH-2	8x107	Cp.RH-1	0	MM-4	80	0.17
[1]: Magenta coupler, [2]: Retention (2 weeks)
[3]: Discoloration
X: Comparative Example, Y: Present Invention

Sample No.	Dye image stabilizer (1)	Kq (M-1 s-1)	Dye image stabilizer (2)	Ks (M-1 s-1)	[1]	[2] [%]	[3]
431(X)	Cp.QH-2	8x107	Ex.R-47	3x10-1	MM-4	88	0.06
432(X)	Cp.QH-2	8x107	Ex.R-23	1x102	MM-4	88	0.07
433(X)	EX.Q-48	1x108	-	-	MM-4	80	0.14
434(X)	EX.Q-48	1x108	Cp.RH-1	0	MM-4	80	0.13
435(Y)	EX.Q-48	1x108	Ex.R-47	3x10 -1	MM-4	94	0.05
436(Y)	EX.Q-48	1x108	Ex.R-23	1x102	MM-4	93	0.06
[1]: Magenta coupler, [2]: Retention (2 weeks)
[3]: Discoloration
X: Comparative Example, Y: Present Invention

As is clear from Table 4, improvements have been achieved in both the dye retention and the prevention of discoloration in the light fastness, when the magenta coupler was replaced with the 5-pyrazolone coupler MM-2 and when the compound according to the present invention having the kq of not less than 10⁸ M^-1s^-1 and the compound having the radical-scavenging ability are used at the same time.

Also when the pyrazolotriazole couplers MM-1, MM-3 and MM-4 are used, which have a superior color reproduction quality to conventionally used 5-pyrazolone couplers but have an inferior fastness to light, improvements have been achieved particularly in both the dye retention and the prevention of discoloration in the light fastness when the compound according to the present invention having the kq of not less than 10⁸ M^-1s^-1 and the compound having the radical-scavenging ability are used at the same time.

Example 5

Samples produced in Example 3 were subjected to wedge exposure in the same manner as in Example 1, and thereafter processed according to the following processing steps until a color developing solution was replenished with a color developing solution replenisher in the amount three times the tank capacity of the color developing solution.

Processing steps	Temp.	Time
Color developing	35.0 ±0.3°C	45 sec.
Bleach-fixing	35.0 ±0.3°C	45 sec.
Stabilizing	30 to 34°C	90 sec.
Drying	60 to 80°C	60 sec.

Processing solutions each had the composition as shown below.

The color developing solution was replenished in an amount of 160 ml in the case of A, 110 ml in the case of B or 80 ml in the case of C, per 1 m² of the light-sensitive silver halide photographic material.

Color developing solution

(a) Pure water

(b) Triethanolamine

(c) N,N-diethylhydroxyamine

(d) Potassium chloride

(e) 1-Hydroxyethylidene-1,1-diphosphonic acid

(f) N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate

(g) Fluorescent brightening agent (4,4'-diaminostilbene disulfonic acid derivative)

(h) Potassium carbonate

(i) By adding water, made up to:

(j) pH

Tank solution	Replenishing solution
	A	B	C	A	B	C
(a)	800 ml	800 ml	800 ml	800 ml	800 ml	800 ml
(b)	10 g	10 g	10 g	13 g	15 g	18 g
(c)	5 g	5 g	5 g	7 g	8 g	9 g
(d)	2 g	2.2 g	2.4 g	0.1 g	-	-
(e)	1.0 g	1.0 g	1.0 g	1.3 g	1.5 g	1.8 g
(f)	5.0 g	5.2 g	5.4 g	7.2 g	7.6 g	8.2 g
(g)	1.0 g	1.0 g	1.0 g	1.3 g	1.5 g	1.8 g
(h)	27 g	27 g	27 g	27 g	27 g	27 g
(i)	1 lit	1 lit	1 lit	1 lit	1 lit	1 lit
(j)	10.10	10.10	10.10	10.10	10.10	10.10

Bleach-fixing solution
(Common to the tank solution and the replenishing solution)
Ferric ammonium ethylenediaminetetraacetate dihydrate	60 g
Ethylenediaminetetraacetic acid	3 g
Ammonium thiosulfate (aqueous 70 % solution)	100 ml
Ammonium sulfite (aqueous 40 % solution)	27.5 ml
Made up to 1 liter in total by adding water, and adjusted to pH 5.7 using potassium carbonate or glacial acetic acid.

Stabilizing solution
(Common to the tank solution and the replenishing solution)
5-Chloro-2-methyl-4-isothiazolin-3-on	1.0 g
Ethylene glycol	1.0 g
1-Hydroxyethylidene-1,1-diphosphonic acid	2.0 g

Ethylenediaminetetraacetic acid	1.0 g
Ammonium hydroxide (aqueous 20 % solution) Fluorescent brightening agent (4,4'-diaminostilbene	3.0 g
disulfonic acid derivative)	1.5 g
Made up to 1 liter in total by adding water, and adjusted to pH 7.0 using sulfuric acid or potassium hydroxide.

Using the samples having been continuously processed, evaluation was made in the following way.

On the samples 501 to 542, densities were measured using a densitometer (Type KD-7R, manufactured by Konica Corporation) under he following conditions.

The above samples having been processed were stored for 2 weeks under sunlight (on an exposure stand) to examine the fastness to light of dye images.

The fastness to light of dye images was evaluated on the following items.

- Retention -

Percentage of the dye remaining after light fastness tests, with respect to the initial density 1.0.

- Stain -

An increase in green density at the minimum density portions of dye images with respect to its initial density.

Results obtained are shown in Table 5.

Sample No.	Dye image stabilizer (1)	Kq (M-1 s-1)	Dye image stabilizer (2)	Ks (M-1 s-1)	[1]	[2] (%)	[3]
501(X)	-	-	-	-	A	64	0.15
502(X)	Cp.QH-2	8x107	-	-	A	79	0.08
503(X)	Cp.QH-2	8x107	Cp.RH-1	0	A	80	0.07
504(X)	Cp.QH-2	8x107	Ex.R-47	3x10-1	A	88	0.05
505(X)	Cp.QH-2	8x107	Ex.R-29	8	A	88	0.06
506(X)	Cp.QH-2	8x107	Ex.R-23	1x102	A	88	0.05
507(X)	EX.Q-48	1x108	-	-	A	77	0.08
508(X)	EX.Q-48	1x108	Cp.RH-1	0	A	78	0.08
509(Y)	EX.Q-48	1x108	Ex.R-47	3x10 -1	A	93	0.05
510(Y)	EX.Q-48	1x108	Ex.R-29	8	A	92	0.04
511(Y)	EX.Q-48	1x108	Ex.R-23	1x102	A	91	0.04
515(X)	-	-	-	-	B	62	0.18
[1]: Processing, [2]: Retention (2 weeks)
[3]: Discoloration
X: Comparative Example, Y: Present Invention

Sample No.	Dye image stabilizer (1)	Kq (M-1 s-1)	Dye image stabilizer (2)	Ks (M-1 s-1)	[1]	[2] (%)	[3]
516(X)	Cp.QH-2	8x107	-	-	B	73	0.11
517(X)	Cp.QH-2	8x107	Cp.RH-1	0	B	76	0.10
518(X)	Cp.QH-2	8x107	Ex.R-47	3x10 -1	B	84	0.07
519(X)	Cp.QH-2	8x107	Ex.R-29	8	B	83	0.09
520(X)	Cp.QH-2	8x107	Ex.R-23	1x102	B	84	0.07
521(X)	Ex.Q-48	1x108	-	-	B	73	0.10
522(X)	Ex.Q-48	1x108	Cp.RH-1	0	B	75	0.09
523(Y)	Ex.Q-48	1x108	Ex.R-47	3x10-1	B	92	0.05
524(Y)	Ex.Q-48	1x108	Ex.R-29	8	B	91	0.06
525(Y)	Ex.Q-48	1x108	Ex.R-23	1x102	B	89	0.04
529(X)	-	-	-	-	C	60	0.23
530(X)	Cp.QH-2	8x107	-	-	C	70	0.15
[1]: Processing, [2]: Retention (2 weeks)
[3]: Discoloration
X: Comparative Example, Y: Present Invention

Sample No.	Dye stabilizer (1)	Kq (M-1 s-1 )	Dye image stabilizer (2)	Ks (M-1 s-1 )	[1]	[2] (%)	[3]
531(X)	Cp.QH-2	8x107	CP.RH-1	0	C	73	0.16
532(X)	CP.QH-2	8x107	Ex.R-47	3x10-1	C	81	0.11
533(X)	Cp.QH-2	8x107	Ex.R-29	8	C	80	0.12
534(X)	Cp.QH-2	8x107	Ex.R-23	1x102	C	81	0.13
535(X)	Ex.Q-48	1x108	-	-	C	70	0.12
536(X)	Ex.Q-48	1x108	CP.RH-1	0	C	72	0.10
537(Y)	Ex.Q-48	1x108	Ex.R-47	3x10-1	C	91	0.05
538(Y)	Ex.Q-48	1x108	Ex.R-29	8	C	89	0.06
539(Y)	Ex.Q-48	1x108	Ex.R-23	1x102	C	88	0.05
[1]: Processing, [2]: Retention (2 weeks)
[3]: Discoloration
X: Comparative Example, Y: Present Invention

As is clear from Table 5, the decreasing of the amount of the replenishing solution causes a great deterioration of the fastness to light in the light fastness tests and also results in a lowering of the dye retention. However, unexpectedly great improvements have been achieved when the compound according to the present invention having the kq of not less than 10⁸ M^-1s^-1 and the compound having the radical-scavenging ability are used at the same time.

Example 6

The amounts of gelatin as used in the first to seventh layers in Example 3 were changed as shown below, and also the dye image stabilizers (1) and (2) were replaced as shown in Table 6. Processing was carried out in the same manner as in Example 2, and evaluation was also made in the same manner as in Example 1.

Amount of gelatin (g/m2)
	Samples 601 to 609	Samples 610 to 618
Seventh layer	1.00	0.80
Sixth layer	0.40	0.35
Fifth layer	1.30	1.10
Fourth layer	0.94	0.90
Third layer	1.40	1.20
Second layer	1.20	1.00
First layer	1.20	1.00
Total	7.44	6.35

Results obtained are shown in Table 6.

Sample No.	Dye image stabilizer (1)	Kq (M-1s-1)	Dye image stabilizer (2)	Ks (M-1s-1)	[1] (g/m2)	[2] (%)	[3]
601(X)	-	-	-	-	7.44	64	0.61
602(X)	Cp.QH-2	8x107	-	-	7.44	77	0.20
603(X)	Cp.QH-2	8x107	Cp.RH-1	0	7.44	80	0.19
604(X)	Cp.QH-2	8x107	Ex.R-47	3x10-1	7.44	87	0.07
605(X)	Cp.QH-2	8x107	Ex.R-23	1x102	7.44	88	0.08
606(X)	Ex.Q-48	1x108	-	-	7.44	79	0.16
607(X)	Ex.Q-48	1x108	Cp.RH-1	0	7.44	79	0.14
608(Y)	Ex.Q-48	1x108	Ex.R-47	3x10-1	7.44	93	0.05
609(Y)	Ex.Q-48	1x108	Ex.R-23	1x102	7.44	92	0.05
610(X)	Ex.Q-48	1x108	-	-	6.35	60	0.68
611(X)	Ex.QH-2	8x107	-	-	6.35	73	0.24
612(X)	CP.QH-2	8x107	Cp.RH-1	0	6.35	76	0.22
613(X)	CP.QH-2	8x107	Ex.R-47	3x10-1	6.35	81	0.10
614(X)	CP.QH-2	8x107	Ex.R-23	1x102	6.35	81	0.11
615(X)	Ex.Q-48	1x108	-	-	6.35	72	0.18
616(X)	Ex.Q-48	1x108	Cp.RH-1	0	6.35	76	0.17
617(Y)	Ex.Q-48	1x108	Ex.R-47	3x10-1	6.35	92	0.05
618(Y)	Ex.Q-48	1x108	Ex.R-23	1x102	6.35	90	0.06
[1]: Amount of gelatin, [2]: Retention (2 weeks)
[3]: Discoloration
X: Comparative Example, Y: Present Invention

As is clear from Table 6, the decreasing of the amount of gelatin causes a great deterioration of the fastness to light in the light fastness tests and also results in a lowering of the dye retention. However, unexpectedly great improvements have been achieved when the compound according to the present invention having the kq of not less than 10⁸ M^-1s^-1 and the compound having the radical-scavenging ability are used at the same time.

As having been described above, the present invention has made it possible to provide a light-sensitive silver halide photographic material improved in the fastness to light, of dye images and the prevention of stain on account of the feature that the compound having a singlet oxygen quenching rate constant kq of not less than 10⁸ M^-1s^-1 is contained and also the compound having a radical-scavenging ability is contained.

Claims (6)

1. A light-sensitive silver halide photographic material comprising a support carrying a silver halide emulsion layer containing a dye forming coupler, characterised in that the silver halide emulsion layer contains a compound having a singlet oxygen-quenching ability with a quenching rate constant Kq of not less than 1 X 10⁸ M^-1 s^-1 and having the Formula II-a-2;

   

   wherein Y' is a group of non-metallic atoms necessary to complete a heterocyclic ring having from 5 to 8 members; R¹⁰ is an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, a heterocyclic group, an acyl group, a bridged hydrocarbon group, an alkylsulfonyl group or an arylsulfonyl group; R¹¹ and R¹³ are each an electron donating group having a Hammet's p value of not more than 0; and R¹² and R¹⁴ are each hydrogen atoms; and a compound represented by the Formula R;

   

   wherein R¹⁵ is a substituent and 1 is an integer in the range 0 to 5; provided that the value of Kq is determined as follows: singlet oxygen is produced from 3-(1,4-epidioxyl-4-methyl-1,4-dihydro-1-naphthyl)proprionic acid in ethanol as solvent at 35 C; 2,5-diphenyl-3,4-benzofuran (DPBF), as a standard substance for quenching, is made present together with the substance to be measured; then both the substances are brought into competitive reaction with the singlet oxygen the changes with time of light absorption at the absorption wavelength of the DPBF (λmax: 411 nm) are followed up to determine the Kq.
2. A light-sensitive silver halide photographic material according to claim 1, characterised in that the compound represented by the Formula R has a radical-scavenging rate constant ks of from 1 X 10^-1 to 2 X 10⁴ M^-1s^-1.
3. A light-sensitive silver halide photographic material according to claim 1, characterised in that the compound represented by the Formula R has one of the formulae R-a or R-b;

   

   wherein R¹⁵ and R^15' each have the same definition for R¹⁵ in Formula R; A represents a divalent connecting group; a and a' each represent an integer of 0 to 4. provided. when a or a' is 2 or more. a plurality of R¹⁵ and R^15' may be the same or different from one another. and R¹⁵ and R^15' may combine to form a ring;

   

   wherein R^15' and R^15" each have the same definition for R¹⁵ in Formula R; b and b' each represent an integer of 0 to 3, provided, when b or b' is 2 or more, a plurality of R^15' or R^15" may be the same or different one another, and may combine to form a ring; B and B' each represent a group of non-metal atoms necessary to complete a heterocyclic ring of 5 to 7 members together with the carbon atoms and C=C.
4. A photographic material of claim 1, wherein said dye-forming coupler is represented by the following Formula M-I:

   

   wherein Z represents a group of non-metal atoms necessary to complete a nitrogen-containing heterocyclic ring; X represents a hydrogen atom or a group capable of being split off upon reaction with an oxidized product of a color developing agent; and R represents a hydrogen atom or a substituent.
5. A photographic material of claim 8, wherein said dye-forming coupler is represented by the following Formula M-II through M-VII:

   

   

   

   

   

   

   wherein R₁ through R₈ and X have the same definitions tor R and X, respectively, in Formula M-I.
6. A photographic material of claim 1, wherein said silver halide emulsion layer contains silver halide grains having a silver chloride content of not less than 90 mol%.