JPH0740127B2 - Direct positive color image forming method - Google Patents

Description

The present invention relates to a direct positive color image forming method.

(Prior Art) Photographic methods for obtaining direct positive images without the need for reversal processing steps or negative films are well known.

The conventionally used methods for producing a positive image using a direct positive silver halide photographic light-sensitive material, except for special ones, can be mainly classified into two types in consideration of practical usefulness. it can.

One type uses a fogged silver halide emulsion in advance and directly obtains a positive image after development by destroying fog nuclei (latent image) in the exposed area by utilizing solarization or Herschel effect. is there.

The other type is to directly obtain a positive image by using an unfogged internal latent image type silver halide emulsion and performing surface development after image exposure and after fogging or fogging. .

The above-mentioned internal latent image type silver halide photographic emulsion is a type of silver halide photographic emulsion in which a silver halide grain has a photosensitive nucleus mainly inside and a latent image is mainly formed inside the grain by exposure. Say.

This latter type method is generally more sensitive than the former type method and is suitable for applications requiring high sensitivity, and the present invention relates to this latter type.

Various techniques have been known so far in this technical field. For example, US Patent Nos. 2592250 and 2466957.
No. 2497875, No. 2588982, No. 3317322,
3761266, 3761276, 3796577 and British Patents 1151363, 1150553 (1011062), Research Disclosure RD15162 (November 1976), 1
No. 7643 (December 1978) Main items are those described in each specification.

By using these known methods, a photographic light-sensitive material having a relatively high sensitivity as a direct positive type can be produced.

Further, for details of the mechanism for forming a direct positive image, for example,
The James of The Theory of the Photogra Process
phic Proccss) 4th edition, Chapter 7, pages 182 to 193 and US Patent 3,
761,276, etc.

That is, the fog nuclei are selectively generated only on the surface of the silver halide grains in the unexposed portion due to the surface desensitizing effect caused by the so-called internal latent image generated inside the silver halide by the first imagewise exposure, Then, a normal so-called surface development treatment is applied to the photographic image (direct positive image) on the unexposed area.
Is believed to be formed.

As described above, as a means for selectively generating fog nuclei, a method of giving a second exposure to the entire surface of the photosensitive layer, which is generally called "light fog method" (for example, British Patent 1,151,363)
And a nucleating agent called "chemical fogging"
gent) method is known. This latter method is described, for example, in "Research Disclosure".
(Research Disclosure) Vol. 151, No. 15162 (November 1976)
Monthly issue), pages 76-78.

To form a positive color image directly, after the internal latent image type silver halide light-sensitive material is subjected to a fogging treatment or a surface color development processing is performed while performing the fogging treatment, bleaching, fixing (or bleach-fixing) treatment is then performed. Can be achieved. After the bleaching / fixing treatment, washing and / or stabilizing treatment is usually performed.

(Problems to be Solved by the Invention) In such a method, in direct positive image formation, the developing time is slower than that in the case of a normal negative type, and thus it takes a long processing time. Since it takes a longer processing time, lowering the pH of the developer is not preferable. Therefore, using a low pH developer, yet with a high maximum image density,
Moreover, it is difficult to obtain a direct positive image having a low minimum image density.

On the other hand, as a means to solve the problem of processing time,
There is a method of increasing the pH to shorten the treatment time.

However, in general, there is a problem that the minimum image density of the direct positive image obtained when the pH is high is increased. Further, under high pH conditions, the developing agent is apt to be deteriorated by air oxidation, resulting in a problem that the developing activity is remarkably lowered. Compounds exhibiting a nucleating action even at a pH of 12 or less are proposed in JP-A-52-69613, U.S. Pat.Nos. 3,615,615 and 3,850,638, but there is a problem that the minimum image density also increases in these compounds, and Further, these nucleating agents have a drawback that they act on silver halide during the storage of the light-sensitive material before processing or the nucleating agents themselves decompose and eventually reduce the maximum image density after processing.

Other means for increasing the developing speed of direct positive image formation include the following.

U.S. Pat. No. 3,227,552 describes the use of hydroquinone derivatives to increase the development speed at moderate concentrations.

Further, JP-A-60-170843 describes that a mercapto compound having a carboxylic acid group or a sulfonic acid group is added to increase the maximum image density. However, the effect of adding these compounds is small. Moreover, the pH of the developer is
12.0, the stability of the developer is still insufficient.

In JP-A-55-134848, the minimum image density is lowered by processing with a processing solution (pH 12.0) containing a tetrazaindene compound in the presence of a nucleating agent to prevent the formation of a reversal negative image. It is stated to do.

However, no matter which method is used or a combination of them is used, a technique for stably obtaining a minimum image density satisfying a high maximum image density while processing in a short time has been found. There wasn't.

Further, in order to increase the sensitivity of the direct positive type photosensitive material, it is generally necessary to increase the silver halide grain size, but there is a problem that the minimum density of the obtained image increases when the size is increased, In this field, a technique capable of suppressing the minimum image density even if the sensitivity is increased is desired.

It is therefore an object of the present invention to treat pre-fogged internal latent image type silver halide light-sensitive materials with a particularly low pH color developing solution to obtain a high maximum color density and a particularly low minimum image density. It is an object of the present invention to provide a light-sensitive material capable of forming a positive color image quickly and stably.

Another object of the present invention is to provide a light-sensitive material that directly forms a positive color image having a low minimum image density even if the size of silver halide grains is increased to increase the sensitivity.

Also, to provide a light-sensitive material that directly forms a positive color image in which the maximum image density and the minimum image density do not easily change from the optimum values and the color reproducibility does not change even when the temperature and pH of the color developing solution change. is there.

Further, to provide a light-sensitive material that directly forms a positive color image in which the maximum image density and the minimum image density hardly change from the optimum values and the color reproducibility does not easily change even when the color development time changes with respect to the standard time. It is in.

(Means for Solving Problems) The above-mentioned object is a core / shell type silver halide grain which is an internal latent image type which is not previously fogged and whose shell portion is gold sensitized, and the following general formula [I]. A light-sensitive material having at least one photographic emulsion layer containing at least one pyrazoloazole-based magenta coupler selected from the group of compounds represented by It has been found to be achieved by a direct positive color image-forming method characterized in that development is carried out with a surface color developing solution having a pH of 10.0 to 11.0 after and / or while performing fog treatment with an agent.

General formula [I] (In the formula, R ₁ represents a hydrogen atom or a substituent, and X represents a hydrogen atom or a group capable of splitting off by a coupling reaction with an oxidized product of an aromatic primary amine developer. Za, Zb and Zc.
Represents methine, substituted methine, = N- or -NH-,
One of the Za-Zb bond and the Zb-Zc bond is a double bond, and the other is a single bond.

When Zb-Zc is a carbon-carbon double bond, it includes the case where it is part of an aromatic ring. Furthermore, the case where R ₁ or X forms a dimer or higher multimer is also included. Also, Za, Zb or
When Zc is a substituted methine, it also includes the case where the substituted methine forms a dimer or higher multimer. In the present invention, a specific pyrazoloazole-based magenta coupler is contained in a light-sensitive material together with a core / shell type silver halide grain having a shell portion sensitized with gold, and color development is performed in the presence of a specific nucleating agent. In addition to the well-known effect that the treatment makes it possible to obtain a high density with a small amount of coated silver because the hue of magenta becomes clear because the secondary absorption is small when the color is developed and the color development is good. Surprisingly, in a system using an internal latent image type silver halide emulsion, a positive color image can be directly obtained by processing with a low pH developer of pH 10.0 to 11.0, and at the same time, the minimum image density obtained is reduced. Was found.

The pyrazoloazole type magenta coupler used in the present invention is a compound represented by the above general formula [I].

In the general formula [I], a multimer means one having two or more groups represented by the general formula [I] in one molecule, and a bis compound and a polymer coupler are also included in this. Here, the polymer coupler is a monomer having a portion represented by the general formula [I] (preferably one having a vinyl group,
Hereinafter, a homopolymer composed of only a vinyl monomer) may be used, or a copolymer may be prepared together with a non-color forming ethylene-like monomer that does not couple with an oxidation product of an aromatic primary amine developing agent.

The compound represented by the general formula [I] is a 5-membered ring-5-membered ring condensed nitrogen heterocyclic type coupler, and its coloring mother nucleus shows isoelectronic aromaticity with naphthalene, and is generally called azapentalene. It has a structure. Among the couplers represented by the general formula [I], preferred compounds are 1H-imidazo [1,2-b] pyrazoles, 1H-pyrazolo [1,5-b] pyrazoles, 1H-pyrazolo [5,1-c ] [1,2,4] Triazoles, 1H-pyrazolo [1,5-b] [1,2,4] triazoles, 1H-pyrazolo [1,5-d] tetrazole and 1
H-pyrazolo [1,5-a] benzimidazoles,
They are represented by the general formulas [II], [III], [IV], [V], [VI] and [VII], respectively. Of these, the general formula [II],
The compounds represented by [IV] and [V] are preferable, and particularly preferable compounds are [II] and [V].

Substituents R ₂ , R ₃ and R ₄ in the general formulas [II] to [VII] are hydrogen atom, halogen atom, alkyl group, aryl group, heterocyclic group, cyano group, alkoxy group, aryloxy group, heterocycle Oxy group, acyloxy group, carbamoyloxy group, silyloxy group, sulfonyloxy group, acylamino group, anilino group, ureido group, imide group, sulfamoylamino group, carbamoylamino group, alkylthio group, arylthio group, heterocyclic thio group, Alkoxycarbonylamino group, aryloxycarbonylamino group,
Represents a sulfonamide group, a carbamoyl group, an acyl group, a sulfamoyl group, a sulfonyl group, a sulfinyl group, an alkoxycarbonyl group or an aryloxycarbonyl group, and X represents a hydrogen atom, a halogen atom, a carboxy group, or an oxygen atom, a nitrogen atom or a sulfur atom. Represents a group capable of coupling off with a group bonded to the carbon at the coupling position via.

The case where R ₂ , R ₃ , R ₄ or X becomes a divalent group to form a bis form is also included. Further, when the portion represented by the general formulas [II] to [VII] is in the vinyl monomer, R ₂ , R ₃
Alternatively, R ₄ represents a simple bond or a linking group, and the moiety represented by the general formulas [II] to [VII] is bonded to the vinyl group via this.

More specifically, R ₂ , R ₃ and R ₄ are a hydrogen atom, a halogen atom (eg, chlorine atom, bromine atom, etc.), an alkyl group (eg, methyl group, propyl group, t-butyl group, trifluoromethyl group, Tridecyl group, 3- (2,4-di-t
-Amylphenoxy) propyl group, 2-dodecyloxyethyl group, 3-phenoxypropyl group, 2-hexylsulfonyl-ethyl group, cyclopentyl group, benzyl group,
Etc.), aryl groups (eg, phenyl group, 4-t-butylphenyl group, 2,4-di-t-amylphenyl group, 4-
Tetradecanamidophenyl group, etc.), heterocyclic group (eg, 2-furyl group, 2-thienyl group, 2-pyrimidinyl group, 2-benzothiazolyl group, etc.), cyano group, alkoxy group (eg, methoxy group, ethoxy group, 2-methoxyethoxy group, 2-dodecyloxyethoxy group, 2-methanesulfonylethoxy group, etc.), aryloxy group (for example, phenoxy group, 2-methylphenoxy group, 4
-T-butylphenoxy group, etc.), heterocyclic oxy group (eg, 2-benzimidazolyloxy group, etc.), acyloxy group (eg, acetoxy group, hexadecanoyloxy group, etc.), carbamoyloxy group (eg, N
-Phenylcarbamoyloxy group, N-ethylcarbamoyloxy group, etc.), silyloxy group (eg, trimethylsilyloxy group, etc.), sulfonyloxy group (eg, dodecylsulfonyloxy group, etc.), acylamino group (eg, acetamide group, Benzamide group, tetradecanamide group, α- (2,4-di-t-amylphenoxy) butyramide group, γ- (3-t-butyl-4-hydroxyphenoxy) butyramide group, α- {4- (4
-Hydroxyphenylsulfonyl) phenoxy} decanamide group, etc.), anilino group (for example, phenylamino group, 2-chloroanilino group, 2-chloro-5-tetradecaneamidoanilino group, 2-chloro-5-dodecyloxycarbonylanilino). Group, N-acetylanilino group, 2
-Chloro-5- {α- (3-t-butyl-4-hydroxyphenoxy) dodecanamide} anilino group, etc.), ureido group (for example, phenylureido group, methylureido group, N, N dibutylureido group, Etc.), imide group (for example, N-succinimide group, 3-benzylhydantoinyl group, 4- (2-ethylhexanoylamino) phthalimide group, etc.), sulfamoylamino group (for example, N,
N-dipropylsulfamoylamino group, N-methyl-
N-decylsulfamoylamino group, etc., alkylthio group (eg, methylthio group, octylthio group, tetradecylthio group, 2-phenoxyethylthio group, 3-phenoxypropylthio group, 3- (4-t-butyl) Phenoxy) propylthio group, etc.), arylthio group (eg,
Phenylthio group, 2-butoxy-5-t-octylphenylthio group, 3-pentadecylphenylthio group, 2-carboxyphenylthio group, 4-tetradecanamidophenylthio group, etc., heterocyclic thio group (for example, 2 -Benzothiazolylthio group, etc.), alkoxycarbonylamino group (eg, methoxycarbonylamino group, tetradecyloxycarbonylamino group, etc.), aryloxycarbonylamino group (eg, phenoxycarbonylamino group, 2,4-di- -Tert-butylphenoxycarbonylamino group, etc.), sulfonamide group (eg, methanesulfonamide group, hexadecanesulfonamide group, benzenesulfonamide group, p-toluenesulfonamide group, octadecanesulfonamide group, 2-methyloxy- group) 5-t-butylbenze Sulfonamido group, etc.), carbamoyl group (eg, N-ethylcarbamoyl group, N,
N-dibutylcarbamoyl group, N- (2-dodecyloxyethyl) carbamoyl group, N-methyl-N-dodecylcarbamoyl group, N- {3- (2,4-di-tert-amylphenoxy) propyl} carbamoyl group, Etc.), an acyl group (eg, acetyl group, (2,4-di-tert-amylphenoxy) acetyl group, benzoyl group, etc.), a sulfamoyl group (eg, N-ethylsulfamoyl group, N,
N-dipropylsulfamoyl group, N- (2-dodecyloxyethyl) sulfamoyl group, N-ethyl-N-dodecylsulfamoyl group, N, N-diethylsulfamoyl group, etc.), sulfonyl group (for example, Methanesulfonyl group, octanesulfonyl group, benzenesulfonyl group, toluenesulfonyl group, etc.), sulfinyl group (for example,
Octansulfinyl group, dodecylsulfinyl group, phenylsulfinyl group, etc.), alkoxycarbonyl group (eg, methoxycarbonyl group, butyloxycarbonyl group, dodecylcarbonyl group, octadecylcarbonyl group, etc.), aryloxycarbonyl group (eg, phenyloxy Carbonyl group, 3-pentadecyloxy-
Carbonyl group, etc., and X is a hydrogen atom, a halogen atom (eg, chlorine atom, bromine atom, iodine atom, etc.),
Carboxyl group, or a group linked by an oxygen atom (for example, acetoxy group, propanoyloxy group, benzoyloxy group, 2,4-dichlorobenzoyloxy group, ethoxyoxaloyloxy group, pyrvinyloxy group, cinnamoyloxy group, Phenoxy group, 4-cyanophenoxy group, 4-methanesulfonamidophenoxy group, 4-methanesulfonylphenoxy group, α-naphthoxy group, 3-pentadecylphenoxy group, benzyloxycarbonyloxy group, ethoxy group, 2-cyanoethoxy group , A benzyloxy group, a 2-phenethyloxy group, a 2-phenoxyethoxy group, a 5-phenyltetrazolyloxy group, a 2-benzothiazolyloxy group, and the like), a group linked by a nitrogen atom (for example, benzenesulfonamide) Group, N-ethyltoluenesulfonamide group Heptafluorobutanamide group, 2,3,4,5,6-pentafluorobenzamide group, octanesulfonamide group, p-cyanophenylureido group, N, N-diethylsulfamoylamino group, 1-piperidyl group, 5 , 5-Dimethyl-2,4-dioxo-3-oxazolidinyl group, 1-benzyl-ethoxy-3-hydantoinyl group, 2N-1,1-dioxo-3 (2H) -oxo-
1,2-benzisothiazolyl group, 2-oxo-1,2-dihydro-1-pyridinyl group, imidazolyl group, pyrazolyl group, 3,5-diethyl-1,2,4-triazol-1-yl,
5- or 6-bromo-benzotriazol-1-yl, 5-methyl-1,2,3,4-triazol-1-yl group, benzimidazolyl group, 3-benzyl-1-hydantoinyl group, 1-benzyl- 5-hexadecyloxy-
3-hydantoinyl group, 5-methyl-1-tetrazolyl group, 4-methoxyphenylazo group, 4-pivaloylaminophenylazo group, 2-hydroxy-4-propanoylphenylazo group, etc.), and sulfur atom A group (for example, a phenylthio group, a 2-carboxyphenylthio group,
2-methoxy-5-t-octylphenylthio group, 4-
Methanesulfonylphenylthio group, 4-octanesulfonamidophenylthio group, 2-butoxyphenylthio group, 2- (2-hexanesulfonylethyl) -5-tert
-Octylphenylthio group, benzylthio group, 2-cyanoethylthio group, 1-ethoxycarbonyltridecylthio group, 5-phenyl-2,3,4,5-tetrazolylthio group,
2-benzothiazolylthio group, 2-dodecylthio-5-
Thiophenylthio group, 2-phenyl-3-dodecyl-1,
2,4-triazolyl-5-thio group).

When R ₂ , R ₃ , R ₄ or X is a divalent group to form a bis derivative, the divalent group can be described in more detail. A substituted or unsubstituted alkylene group (eg, methylene group, ethylene group, 1,10-decylene _{group, -CH 2 CH 2 -O-CH} 2 CH 2 -,
Etc.), a substituted or unsubstituted phenylene group (for example, 1,4-
Phenylene group, 1,3-phenylene group, -NHCO-R ₂ -CONH- group (R ₂ represents a substituted or unsubstituted alkylene group or a phenylene group.

When the one represented by the general formulas [II] to [VII] is in the vinyl monomer, the linking group represented by R ₂ , R ₃ or R ₄ is an alkylene group (a substituted or unsubstituted alkylene group , For example, methylene group, ethylene group, 1,10-decylene group, CH ₂ CH ₂ OCH ₂ CH ₂ —, etc., phenylene group (substituted or unsubstituted phenylene group, for example, 1,4-phenylene group, 1,3-phenylene group, -NHCO-, -CONH-, -O-, OCO- and aralkylene groups (for example, Etc.) and groups that are established by combining those selected from the above.

The vinyl group in the vinyl monomer has the general formula [II]
In addition to those represented by [VII], those having a substituent are also included. A preferable substituent is a hydrogen atom, a chlorine atom, or a lower alkyl group having 1 to 4 carbon atoms.

Acrylic acid, α is used as the non-color-forming ethylene-like monomer that does not couple with the oxidation product of the aromatic primary amine developing agent.
-Chloroacrylic acid, α-alacrylic acid (eg, methacrylic acid) and esters or amides derived from these acrylic acids (eg, acrylamide, n-butylacrylamide, t-butylacrylamide, diacetoneacrylamide, methacrylamide) , Methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, t-butyl acrylate, iso-butyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, lauryl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate And β-hydroxymethacrylate), methylenedibisacrylamide, vinyl esters (eg vinyl acetate, vinyl propionate) And vinyl laurate),
Acrylonitrile, methacrylonitrile, aromatic vinyl compounds (eg, styrene and its derivatives, vinyltoluene, divinylbenzene, vinylacetophenone and sulfostyrene), itaconic acid, citraconic acid, crotonic acid, vinylidene chloride, vinyl alkyl ethers (eg vinyl Ethyl ether), maleic acid, maleic anhydride, maleic acid ester, N-vinyl-2-
Pyrrolidone, N-vinyl pyridine, and 2- and 4
-Vinyl pyridine and the like. It also includes the case where two or more non-color-forming ethylenically unsaturated monomers used here are used together.

Examples of compounds of the couplers represented by the general formulas [II] to [VII], synthetic methods, and the like are described in the following documents.

The compound of the general formula [II] is described in Japanese Patent Application No. 58-23434, and the compound of the general formula [III] is described in Japanese Patent Application No. 58-151354.
The compound of V] is disclosed in Japanese Patent Publication No. 47-27411, the compound of the general formula [V] is disclosed in Japanese Patent Applications 58-45512 and 59-27745, and the compound of the general formula [VI] is disclosed in Japanese Patent Application No. 58-27412. -142801 etc. and the compound of the general formula [VII] are respectively described in U.S. Pat. No. 3,061,432 and the like.

Further, JP-A-58-42045, Japanese Patent Application Nos. 58-88940 and 58-5292.
The highly chromogenic ballast groups described in 3, 58-52924 and 58-52927 are applicable to any of the compounds represented by the above general formulas [II] to [VII].

Specific examples of the pyrazoloazole-based coupler used in the present invention are shown below, but the invention is not limited thereto.

These couplers are generally used in an amount of 1 × 10 ⁻³ to 5 × 10 ⁻¹ mol, preferably 5 × 10 ⁻² mol per mol of silver in the emulsion layer.
Mol to 5 × 10 ^-1 mol.

Two or more types of the above-mentioned couplers and the like can be used in combination in the same layer in order to satisfy the characteristics required for the light-sensitive material.
It can also be used in combination with other magenta couplers.

To introduce the coupler into the silver halide emulsion layer, a known method such as the method described in US Pat. No. 2322027 is used. For example, phthalic acid alkyl ester (dibutyl phthalate, dioctyl phthalate, etc.), phosphoric acid ester (diphenyl phosphate, triphenyl phosphate, tricresyl phosphate, dioctyl butyl phosphate), citric acid ester (eg acetyl citrate tributyl), Benzoic acid esters (eg, octyl benzoate), alkylamides (eg, diethyllaurylamide), fatty acid esters (eg, dibutoxyethyl succinate, diethyl azelate), trimesic acid esters (eg, tributyl trimesate), etc., or a boiling point of about Organic solvents at 30 ° C to 150 ° C, for example, lower alkyl acetates such as ethyl acetate and butyl acetate,
It is dissolved in ethyl propionate, secondary butyl alcohol, methyl isobutyl ketone, β-ethoxyethyl acetate, methyl cellosolve acetate, etc., and then dispersed in a hydrophilic colloid. The high boiling point organic solvent and the low boiling point organic solvent may be mixed and used.

The pre-fogged internal latent image type silver halide emulsion used in the present invention is an emulsion in which the surface of silver halide grains is not pre-fogged and which contains a silver halide mainly forming a latent image inside the grains. However, more specifically, the silver halide emulsion is added to a transparent support in a silver amount of 0.5.
~ 3 g / m ^{2 was} applied, and this was exposed to light for a fixed time of 0.01 to 10 seconds.
The maximum density measured by a usual photographic density measuring method when developed at 5 ° C for 5 minutes was 20 times in a developing solution B (surface type developing solution) prepared by coating the same amount as the above and exposing the same in a silver halide emulsion. It is preferable to have a density which is at least 5 times higher than the maximum density obtained when developed at 6 ° C. for 6 minutes,
More preferably, it has a concentration at least 10 times greater.

Internal developer A Metol 2g Sodium sulfite (anhydrous) 90g Hydroquinone 8g Sodium carbonate (monohydrate) 52.5g KBr 5g KI 0.5g Water is added 1 Surface developer B Metol 2.5g l-Ascorbic acid 10g NaBO ₂ 4H ₂ O 35 g KBr 1 g Water is added 1 As a specific example of the internal latent emulsion, for example, British Patent No. 1011062
And U.S. Patent Nos. 2592250, 2456943, and Japanese Patent Publication
Examples thereof include conversion type silver halide emulsions and emulsions having a shell attached thereto as described in the specifications of JP-A-58-54379 and JP-A-58-70221. Examples of core / shell type silver halide emulsions include , JP-A-53-60222, 53-66218
No. 53, No. 53-66727, No. 55-127549, No. 57-136641, No.
58-70221, 59-208540, 59-216136, 60-10764
1, No. 60-247237, No. 61-2148, No. 61-3137, Japanese Patent Publication No. 56-18939, No. 58-1412, No. 58-1415, No. 58-6935
No. 58-108528, Japanese Patent Application No. 61-3642, U.S. Pat.
No. 3, No. 3317322, No. 3761266, No. 3761276, No. 3850
No. 637, No. 3923513, No. 4035185, No. 4395478, No. 45
The emulsions described in 04570, European Patent 0017148, Research Disclosure RD16345, pages 45 to 46, and 23510, page 236, and the like can be mentioned. As the composition of silver halide, in addition to silver chloride and silver bromide, mixed silver halides such as silver chlorobromide, silver chloroiodobromide and silver iodobromide are typical. The silver halide preferably used in the present invention contains no silver iodide or contains silver (iodo) bromide having a molar ratio of 3% or less.
It is (iodo) silver chloride or (iodo) silver bromide. Average grain size of silver halide grains (the grain diameter is the grain size for spherical or near-sphere grains, and the ridge length is the grain size for cubic grains).
Is preferably 2 μ or less and 0.1 μ or more, and particularly preferably 1 μ or less and 0.15 μ or more. The particle size distribution may be narrow or wide, but it is ± 40% of the average particle size in terms of number of particles or weight to improve graininess and sharpness.
Within (more preferably within ± 30%, most preferably within ± 20%
It is preferred to use in the present invention so-called "monodisperse" silver halide emulsions having a narrow grain size distribution such that 90% or more, especially 95% or more of all grains fall within the range (%). In order to satisfy the target gradation of the light-sensitive material, the emulsion layers having substantially the same color sensitivity have different grain sizes.
One or more kinds of monodisperse silver halide emulsions or a plurality of grains having the same size but different sensitivities can be mixed in the same layer or multi-layered in different layers. Further, two or more kinds of polydisperse silver halide emulsions or a combination of monodisperse emulsions and polydisperse emulsions can be mixed or laminated and used.

The silver halide grains used in the present invention may have a rcgular crystal such as a cube, an octahedron, a dodecahedron or a tetrahedron, or an irregular shape such as a sphere. It may have an (irregular) crystal form, or may have a composite form of these crystal forms. Further, tabular grains may be used, and an emulsion in which tabular grains having a length / thickness ratio value of 5 or more, particularly 8 or more account for 50% or more of the total projected area of the grains may be used. It may be an emulsion composed of a mixture of these various crystal forms.

The silver halide emulsion used in the present invention is a so-called core /
It is a shell type particle, and the shell portion is gold sensitized. Further, chemical sensitization can be carried out in the grain by sensitizing sulfur or selenium, reduction sensitizing, sensitizing noble metal or the like alone or in combination. Specific examples of these are described in detail, for example, in the patents described in "Research Disclosure", RD magazine, 17643II, page 23.

The photographic emulsion used in the present invention is spectrally sensitized with a photographic sensitizing dye in a conventional manner. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes and complex merocyanine dyes, and these dyes can be used alone or in combination. Further, the above dye and supersensitizer may be used in combination. For more detailed examples and their usage,
For example, it is described in RD17643 (December 1978) IV and the like.

The photographic emulsions used in the present invention include benzenethiosulfonic acids, benzenesulfinic acids, and thiocarbonyl for the purpose of preventing fog during the production process, storage or photographic processing of the light-sensitive material or stabilizing the photographic performance. A compound etc. can be contained.

For more detailed examples of antifoggants or stabilizers and their use, see, eg, US Pat.
No. 3,982,947, Japanese Patent Publication No. 52-28660, RD17643 (1978
December) VIA-VIM and EJBirr "Stabilizution of
Photographic Silver Halide Emulsions "(Focal Pres
s, published in 1974).

In order to directly form a positive color image, various cyan and yellow color couplers can be used in the light-sensitive material together with the pyrazoloazole type magenta coupler of the formula [I]. Further, a magenta coupler other than the pyrazoloazole-based magenta coupler used in the present invention can be used in combination.

Useful color couplers are compounds which undergo a coupling reaction with an oxidized form of a p-phenylenediamine color developing agent to produce or release a dye which is substantially non-diffusible, and which are themselves substantially non-diffusible. It is a compound. Typical examples of useful color couplers are naphthol or phenolic compounds and closed or heterocyclic ketomethylene compounds. Specific examples of these cyan, magenta and yellow couplers that can be used in the present invention are "Research Disclosure", No. 17643 (December 1978), Item VII-D and No. 18717 (November 1979, And Japanese Patent Application No. 61-32462
No. 298-372).

Among them, as the yellow coupler which can be used in the present invention, oxygen atom-releasing type and nitrogen atom-releasing type yellow two-equivalent couplers can be exemplified. Especially α
The -pivaloyl acetanilide type couplers are preferable because the fastness, especially the light fastness, of the color forming dye is excellent, while the α-benzoyl acetanilide type couplers can obtain a high color density.

The cyan coupler that can be preferably used in the present invention,
Naphthol-based or phenol-based couplers described in U.S. Pat.Nos. 2,474,293 and 4,052,212, etc., or phenol-based cyan couplers having an alkyl group of ethyl group or more at the meta position of the phenol nucleus described in U.S. Pat. In addition, 2,5-diacylamino-substituted phenol couplers are also preferable in terms of color image fastness.

The standard amount of the color coupler used is in the range of 0.001 to 1 mol per mol of the light-sensitive silver halide, preferably 0.01 to 0.5 mol for the yellow coupler, 0.003 to 0.5 mol for the magenta coupler, and 0.003 to 0.5 mol for the cyan coupler. It is 0.002 to 0.5 mol.

A colored coupler for correcting unnecessary absorption in the short wavelength region of the dye produced by the coupler, a coupler in which the coloring dye has an appropriate diffusibility, a DIR coupler which releases a development inhibitor along with the coupling reaction, and a polymer. A modified coupler can also be used.

In the present invention, a color forming enhancer can be used for the purpose of improving the color forming property of the coupler. A representative example of the compound is Japanese Patent Application No. 61
No. 32462, pages 374 to 391.

The coupler of the present invention is dissolved in an organic solvent having a high boiling point and / or a low boiling point, and is rapidly stirred in a gelatin or other hydrophilic colloid aqueous solution by a homogenizer or the like, by mechanical micronization such as a colloid mill, or by using ultrasonic waves. It is emulsified and dispersed by the technique described above and added to the emulsion layer. In this case, the high boiling point organic solvent is not necessarily used, but it is preferable to use the compounds described in Japanese Patent Application No. 61-32462, pages 440 to 467.

The coupler of the present invention can be dispersed in a hydrophilic colloid by the method described in Japanese Patent Application No. 61-32462, 468 to 475.

The light-sensitive material produced by using the present invention is used as an antifoggant or a mixing inhibitor as a hydroquinone derivative, an aminophenol derivative, an amine, a gallic acid derivative, a catechol derivative, an ascorbic acid derivative, a colorless coupler, a sulfonamidephenol. You may contain a derivative etc.

Various anti-fading agents can be used in the light-sensitive material of the present invention. Hydroquinones as organic anti-fading agents,
6-hydroxychromans, 5-hydroxycoumarans, spirochromans, p-alkoxyphenols,
Typical are hindered phenols centered on bisphenols, gallic acid derivatives, methylenedioxybenzenes, aminophenols, hindered amines and ether or ester derivatives obtained by silylating or alkylating the phenolic hydroxyl groups of these compounds. Take as an example. Further, a metal complex represented by a (bissalicylaldoximato) nickel complex and a (bis-N, N-dialkyldithiocarbamato) nickel complex can also be used.

To prevent deterioration of the yellow dye image due to heat, humidity and light,
Compounds having both hindered amine and hindered phenol substructures in the same molecule, as described in US Pat. No. 4,268,593, give good results. In order to prevent deterioration of the magenta dye image, especially deterioration due to light,
The spiroindanes described in JP-A-56-159644 and the hydroquinone diether- or monoether-substituted chromanes described in JP-A-55-89835 give preferable results. These compounds can achieve the object by usually coemulsifying 5 to 100% by weight of the corresponding color coupler with the coupler and adding them to the photosensitive layer. In order to prevent deterioration of the cyan dye image due to heat and especially light, it is effective to introduce an ultraviolet absorber into both layers adjacent to the cyan color developing layer. An ultraviolet absorber can also be added to the hydrophilic colloid layer such as the protective layer.

As the binder or protective colloid that can be used in the emulsion layer or intermediate layer of the light-sensitive material of the present invention, it is advantageous to use gelatin, but other hydrophilic colloids can also be used.

To the light-sensitive material of the present invention, it is possible to add a dyeing agent for preventing irradiation or halation, an antistatic agent, a slipperiness improving agent and the like.

Representative examples of these additives are described in "Research Disclosure No. 17643 (December 1978) and 18716 (November 1979).

The present invention is also applicable to multilayer multicolor photographic materials having at least two different spectral sensitivities on the support. Multilayer natural color photographic materials usually have at least one red-sensitive emulsion layer, one green-sensitive emulsion layer and one blue-sensitive emulsion layer on a support.
The order of these layers can be arbitrarily selected as required. The preferred order of layer arrangement is red-sensitive, green-sensitive, blue-sensitive from the support side or blue-sensitive, red-sensitive and green-sensitive from the support side.
Each of the above emulsion layers may be composed of two or more emulsion layers having different sensitivities, and a non-photosensitive layer may be present between two or more emulsion layers having the same sensitivity. Usually, a cyan-forming coupler is contained in the red-sensitive emulsion layer, a magenta-forming coupler is contained in the green-sensitive emulsion layer, and a yellow-forming coupler is contained in the blue-sensitive emulsion layer, but different combinations can be used depending on circumstances.

The light-sensitive material according to the present invention, in addition to the silver halide emulsion layer,
Protective layer, intermediate layer, filter layer, antihalation layer,
It is preferable to appropriately provide auxiliary layers such as a back layer and a white reflective layer.

In the photographic light-sensitive material of the present invention, the photographic emulsion layer and other layers are coated on a flexible support usually used for photographic light-sensitive materials such as a plastic film, paper, cloth or a rigid support such as glass, ceramics or metal. To be done. Useful as the flexible support is a film made of a semi-synthetic or synthetic polymer such as cellulose nitrate, cellulose acetate, cellulose acetate butyrate, polystyrene, polyvinyl chloride, polyethylene terephthalate, or polycarbonate, a variator layer or an α-olefin polymer. Examples include paper coated or laminated with (eg, polyethylene, polypropylene, ethylene / butene copolymer). The support may be colored with a dye or pigment. It may be black for the purpose of shading. The surface of these supports is generally subbed to improve adhesion with photographic emulsion layers and the like. The surface of the support may be subjected to glow discharge, corona discharge, ultraviolet irradiation, flame treatment or the like before or after the undercoat treatment.

For coating the silver halide photographic emulsion layer and other hydrophilic colloid layers, various known coating methods such as dip coating method, roller coating method, curtain coating method and extrusion coating method can be used.

The present invention can be applied to various color light-sensitive materials. Typical examples are color reversal films for slides or televisions, color reversal papers, and the like. It can also be applied to full-color copiers and color hard copies for storing CRT images. The present invention can also be applied to a black-and-white light-sensitive material utilizing a three-color coupler mixture described in "Research Disclosure No. 17123 (issued in July 1978).

The light-sensitive material of the present invention is developed, bleached and fixed with a surface developing solution containing a p-phenylenediamine color developing agent, after imagewise exposure, after or while being subjected to fogging with light or a nucleating agent. Thus, a positive color image can be directly formed.

In particular, the light-sensitive material of the present invention is advantageous in that a good direct positive color image can be obtained even when a low pH color developing solution having a pH of 10.0 to 11.0 is used.

As described above, the fogging treatment in the present invention is carried out in the presence of a so-called "light fogging method" which gives a second exposure to the entire surface of the photosensitive layer and a "chemical fogging method" in the presence of a nucleating agent. Either of the methods may be used.

The overall exposure or fog exposure (for example, British Patent 1,151,363) in the present invention is carried out after imagewise exposure and before and / or during development processing. Exposure is carried out before the imagewise exposed light-sensitive material is dipped in a developing solution or in a pre-bath of the developing solution, or taken out from these solutions and not dried, but exposure in the developing solution is most preferred.

As the light source for fogging exposure, a light source within the light-sensitive wavelength of the light-sensitive material may be used, and generally, a fluorescent lamp, a tungsten lamp, a xenon lamp, sunlight or the like can be used.
These specific methods include, for example, British Patent 1,151,363,
Japanese Patent Publications No.45-12709, No.45-12710, No.46-22515, No.58-6
No. 936, 58-120248, etc. Particularly in the case of photosensitive materials having sensitivity in the entire wavelength range, for example, color photosensitive materials, JP-A-56-137350, 57-129438 and 58-62652.
No. 58-60739 and No. 58-70223, light with a high pickling property (as close to white as possible) is good. The illuminance of light is suitably 0.01 to 2000 lux, preferably 0.05 to 30 lux, and more preferably 0.05 to 5 lux. The light-sensitive material using a higher sensitivity emulsion is more preferable for low-illuminance exposure. The illuminance may be adjusted by changing the luminous intensity of the light source, dimming by various filters, changing the distance between the photosensitive material and the light source, or changing the angle between the photosensitive material and the light source. It is also possible to shorten the exposure time by using weak light at the beginning of exposure and then using stronger light.

It is preferable to immerse the light-sensitive material in a developing solution or a solution of its pre-bath so that the solution sufficiently penetrates into the emulsion layer of the light-sensitive material before irradiation with light. The time from the immersion in the liquid to the light fog exposure is generally 2 seconds to 2 minutes, preferably 5 seconds to 1 minute, more preferably 10 seconds to 30 seconds.

The exposure time for fogging is generally 0.01 second to 2 minutes, preferably 0.1 second to 1 minute, more preferably 1 second to 40 seconds.

In the present invention, the nucleating agent used when performing the so-called "chemical fogging method" can be contained in the photosensitive material or in the processing liquid of the photosensitive material. It can be preferably contained in the light-sensitive material.

Here, the "nucleating agent" is a substance which acts when the surface of an internal latent image type silver halide emulsion which has not been fogged in advance is subjected to a surface development treatment to directly form a positive image.

When it is contained in the light-sensitive material, it is preferably added to the inner latent type silver halide emulsion layer, but as long as it diffuses during coating or during processing and the nucleating agent is adsorbed on the silver halide, it is added to other layers. For example, it may be added to the intermediate layer, the undercoat layer or the back layer.

When a nucleating agent is added to the processing liquid, it may
It may be contained in a low pH pre-bath as described in 58-178350.

When the nucleating agent is contained in the light-sensitive material, the amount used is preferably 10 ^-8 to 10 ^-2 mol, and more preferably 10 ^-6 to 10 ^-3 mol, per mol of silver halide.

When a nucleating agent is added to the treatment liquid, the amount used is
It is preferably 10 ^-5 to 10 ^-1 mol, more preferably 10 ^-5
-4 to 10 ^-2 mol. Moreover, you may use together 2 or more types of nucleating agents.

As the nucleating agent used in the present invention, all compounds conventionally developed for the purpose of nucleating an internal latent silver halide can be applied. An example of this is Research Disclosure No. 22534 (issued January 1983).
There are compounds described on pages 50-54. Moreover, you may use these compounds in combination of 2 or more types.

The nucleating agent useful in the present invention preferably has the general formula [N
-I] and [N-II].

General formula [NI] (In the formula, Z represents a non-metal atom group necessary for forming a 5- to 6-membered heterocycle, Z may be substituted with a substituent, R ¹ is an aliphatic group, and R ² is A hydrogen atom, an aliphatic group or an aromatic group, R ¹ and R ² are substituents and may be substituted, provided that at least one of the groups represented by R ¹ , R ² and Z is , An alkynyl group, an acyl group, a hydrazine group, or a hydrazone group, or R ¹ and
A 6-membered ring is formed with R ² to form a dihydropyridinium skeleton. Further, at least one of the substituents of R ¹ , R ² and Z may have X ¹ L ¹ _m . Here, X ¹ is an adsorption promoting group to silver halide, and L ¹ is a divalent linking group. Y is a counter ion for charge balance, and n is 0
Or 1, and m is 0 or 1. ) More specifically, the heterocyclic ring completed by Z is, for example, quinolinium, benzothiazolium, benzimiguzolium, pyridinium, thiazolinium, thiazolium, naphthothiazolium, selenazolium, benzoselenazolium, imidazolium, Examples include tetrazolium, indolenium, pyrrolinium, acridinium, phenanthridinium, isoquinolinium, oxazolium, naphthoxazolium and benzoxazolium nuclei.

Z is a substituent, an alkyl group, an alkenyl group, an aralkyl group, an aryl group, an alkynyl group, a hydroxy group,
Alkoxy group, aryloxy group, halogen atom, amino group, alkylthio group, arylthio group, acyloxy group, acylamino group, sulfonyl group, sulfonyloxy group, sulfonylamino group, carboxyl group, acyl group,
Examples thereof include a carbamoyl group, a sulfamoyl group, a sulfo group, a cyano group, a ureido group, a urethane group, a carbonic acid ester group, a hydrazine group, a hydrazone group, and an imino group. As the substituent of Z, for example, at least one is selected from the above-mentioned substituents, but when there are two or more, they may be the same or different. Further, the above substituents may be further substituted with these substituents.

Further, it may have a heterocyclic quaternary ammonium group completed with Z via a suitable linking group L as a substituent of Z. In this case, a so-called dimer structure is adopted.

Heterocycles completed with Z preferably include quinolinium, benzothiazolium, benzimidazolium, pyridinium, acridinium, phenanthridinium, and isoquinolinium nuclei.

More preferably, quinolinium, benzothiazolium,
Benzimidazolium, most preferably quinolinium and benzothiazolium.

The aliphatic group of R ¹ and R ² is an unsubstituted alkyl group having 1 to 18 carbon atoms and a substituted alkyl group having 1 to 18 carbon atoms in the alkyl moiety. As the substituent, those mentioned as the substituent of Z can be mentioned.

The aromatic group represented by R ² has 6 to 20 carbon atoms, and examples thereof include a phenyl group and a naphthyl group. As the substituent, those mentioned as the substituent of Z can be mentioned.

At least one of the groups represented by R ¹ , R ² and Z has an alkynyl group, an acyl group, a hydrazine group, or a hydrazone group, or R ¹ and R ² form a 6-membered ring,
They form dihydropyridinium bone nuclei, which may be substituted with the groups mentioned above as substituents for the groups represented by Z.

As the hydrazine group, those having an acyl group sulfonyl group as a substituent are preferable.

As the hydrazone group, those having an aliphatic group or an aromatic group as a substituent are preferable.

The acyl group is preferably, for example, a formyl group or an aliphatic or aromatic ketone.

Some of the alkynyl substituents represented by R ¹ , R ² or Z have already been described, but more detailed explanations preferably include those having 2 to 18 carbon atoms, such as ethynyl. Group, propargyl group, 2-butynyl group, 1-methylpropargyl group, 1.1-dimethylpropargyl group, 3-butynyl group, 4-pentynyl group and the like.

Further, these may be substituted with the groups described as the substituent of Z. Examples thereof include a 3-phenylpropargyl group, a 3-methoxycarbonylpropargyl group, a 4-methoxy-2-butynyl group, and the like.

At least one of the groups represented by R ¹ , R ² and Z or the substituent on the ring is an alkynyl group or an acyl group, or R ¹ and R ² are linked to form a dihydropyridinium skeleton. The case is preferred, and the case where at least one alkynyl group is further contained as a substituent on the group or ring represented by R ¹ , R ² and Z is most preferred.

Preferred examples of the adsorption promoting group for silver halide represented by X ¹ include a thioamide group, a mercapto group and a 5- or 6-membered nitrogen-containing heterocyclic group.

The thioamide adsorption promoting group represented by X ¹ is Is a divalent group represented by and may be a part of the ring structure, or may be an acyclic thioamide group. Useful thioamide adsorption promoting groups are described, for example, in U.S. Pat.
No. 4,031,127, 4,080,207, 4,245,037,
No. 4,255,511, No. 4,266,013, and No. 4,276,364,
And Research Disclosure
Losure) Vol. 151 No. 15162 (November 1976), and No. 1
Volume 76, No. 17626 (December 1978) can be selected from those disclosed.

Specific examples of the acyclic thioamide group include, for example, thioureido group, thiourethane group, dithiocarbamic acid ester group and the like, and specific examples of the cyclic thioamide group include, for example, 4-thiazoline-2-thione, 4-imidazoline- group.
2-thione, 2-thiohydantoin, rhodanine, thiobarbituric acid, tetrazoline-5-thione, 1,2,4-
Triazoline-3-thione, 1,3,4-thiadiazoline-2
-Thion, 1,3,4-oxadiazoline-2-thione, benzimidazoline-2-thione, benzoxazoline-
Examples thereof include 2-thione and benzothiazoline-2-thione, which may be further substituted.

The mercapto group of X ^{1 is} a group represented by R ¹ , R ² or Z to which a —SH group is directly bonded, and a substituent to the group represented by R ¹ and R ² or Z is a —SH group. In the end, the mercapto group is an aliphatic mercapto group, an aromatic mercapto group or a heterocyclic mercapto group (when the carbon atom to which the --SH group is bonded is a nitrogen atom, a tautomerism Synonymous with a cyclic thioamide group having a body relationship, and specific examples of this group are the same as those listed above).

Examples of the 5- to 6-membered nitrogen-containing heterocyclic group represented by X ¹ include 5- to 6-membered nitrogen-containing heterocycles consisting of a combination of nitrogen, oxygen, sulfur and carbon. Among these, preferred are benzotriazole, triazole, tetrazole, indazole, benzimidazole, imidazole, benzothiazole, thiazole, benzoxazole, oxazole, thiadiazole, oxadiazole, triazine and the like.
These may be further substituted with appropriate substituents. As the substituent, those mentioned as the substituent of Z can be mentioned. The nitrogen-containing heterocycle is more preferably benzotriazole, triazole, tetrazole or indazole, and most preferably benzotriazole.

The divalent linking group represented by L ¹ is an atom or atomic group containing at least one of C, N, S and O. Specifically, for example, an alkylene group, an alkenylene group, an alkynylene group, an arylene group. Group, -O-, -S-, -NH-, -N
=, - CO -, - SO 2 - is made of a single or combination of such (which may have an substituent on these groups).

The counterion Y for charge balance is any anion capable of offsetting the positive charge generated by the quaternary ammonium salt in the heterocycle, such as bromide, chloride,
Examples thereof include iodine ion, p-toluene sulfonate ion, ethyl sulfonate ion, perchlorate ion, trifluoromethane sulfonate ion, and thiocyanate ion. In this case, n is 1. When the heterocyclic quaternary ammonium salt contains an anionic substituent such as a sulfoalkyl substituent,
The salt may take the form of betaine, in which case no counterion is needed and n is 0. When the heterocyclic quaternary ammonium salt has two anionic substituents, for example two sulfoalkyl groups, Y is a cationic counterion, for example an alkali metal ion (sodium ion,
Potassium ion), ammonium salt (triethylammonium, etc.) and the like.

Specific examples of the compound represented by the general formula [NI] are shown below, but the invention is not limited thereto.

The compounds described above are, for example, patents cited in Research Disclosure No. 22,534 (issued in January 1983, pages 50 to 54) and US Pat. No. 4,47.
It can be synthesized by the method described in 1,044 or the like and a method similar thereto.

General formula (N-II) (In the formula, RR ²¹ represents an aliphatic group, an aromatic group, or a heterocyclic group, R ²² represents a hydrogen atom, an alkyl group, an aralkyl group, an aryl group, an alkoxy group, an aryloxy group, or an amino group; Is a carbonyl group, a sulfonyl group, a sulfoxy group, a phosphoryl group, or an iminomethylene group (HN =
C ²³ ) and R ²³ and R ²⁴ both represent a hydrogen atom or one represents a hydrogen atom and the other represents an alkylsulfonyl group, an arylsulfonyl group or an acyl group.
However, a hydrazone structure (NN = C) may be formed in a form including G, R ²³ , R ²⁴ and hydrazine nitrogen. The above-mentioned groups may be substituted with a substituent, if possible. In the general formula [N-II], the aliphatic group represented by R ²¹ is a linear, branched or cyclic alkyl group, alkenyl group or alkynyl group.

The R ²¹ heterocycle is a 3- to 10-membered saturated or unsaturated heterocycle containing at least one of N, O, and S atoms, which may be a single ring or may be another ring. An integrated ring may be formed with an aromatic ring or a heterocycle.
The heterocycle is preferably a 5- or 6-membered aromatic heterocyclic group, and examples thereof include a pyridyl group, a quinolinyl group, an imidazolyl group, and a benzimidazolyl group.

It may be substituted with an R ²¹ substituent. As a substituent,
For example: These groups may be further substituted.

The aromatic group represented by R ²¹ is a monocyclic or bicyclic aryl group, and examples thereof include a phenyl group and a naphthyl group.

Preferred among the groups represented by R ²² are hydrogen atom, alkyl group (eg, methyl group, trifluoromethyl group, 3-hydroxypropyl group, 3-methanesulfonamidopropyl group, etc.) when G is carbonyl group. ), An aralkyl group (for example, 0-hydroxybenzyl group, etc.), an aryl group (for example, phenyl group, 3,5-dichlorophenyl group, 0-methanesulfonamidophenyl group, 4-methanesulfonylphenyl group, etc.), and particularly hydrogen. Atoms are preferred. When G is a sulfonyl group, R ²² is an alkyl group (eg, methyl group), an aralkyl group (eg, 0-hydroxyphenylmethyl group), an aryl group (eg, phenyl group) or a substituted amino group (eg, dimethyl group). Amino group, etc.) and the like are preferable.

As the substituent for R ^22, the substituents listed for R ²¹ can be applied, and for example, an amyl group, an amyloxy group, an alkyl or aryloxycarbonyl group, an alkenyl group, an alkynyl group, a nitro group, and the like can also be applied.

These substituents may be further substituted with these substituents. If possible, these groups may form a ring in which these groups are connected to each other.

R ²¹ or R ²² , and especially R ²¹ preferably contains a diffusion resistant group such as a coupler, a so-called ballast group. This ballast group has 8 or more carbon atoms and is an alkyl group, phenyl group, ether group, amide group, ureido group, urethane group,
It is composed of one or more combinations of sulfonamide groups, thioether groups and the like.

R ²¹ or R ²² is a group X ² L ² that promotes adsorption of the compound represented by the general formula [N-II] on the surface of the silver halide grain.
_It may have _m2 . Where X ² is a general formula [NI]
X ¹ has the same meaning as X ^1, and is preferably a thioamide group (excluding thiosemicarbazide and its substituted product), a mercapto group, or a 5- to 6-membered nitrogen-containing heterocyclic group. L ²
Represents a divalent linking group and has the same meaning as L ^{1 in} formula [NI]. m ² is 0 or 1.

More preferable X ² is a cyclic thioamide group (that is, a mercapto-substituted nitrogen-containing heterocycle, for example, 2-mercaptothiadiazole group, 3-mercapto-1,2,4-triazole group, 5-mercaptotetrazole group, 2-mercapto-
1,3,4-oxadiazole group, 2-mercaptobenzoxazole group, etc.), or nitrogen-containing heterocyclic group (for example,
Benzotriazole group, benzimidazole group, indazole group, etc.).

R ²³ and R ²⁴ are a hydrogen atom, an alkylsulfonyl group having 20 or less carbon atoms and an arylsulfonyl group (preferably a phenylsulfonyl group or a phenylsulfonyl group substituted such that the sum of Hammett's substituent constants is −0.5 or more). An acyl group having 20 or less carbon atoms (preferably a benzoyl group, or a benzoyl group substituted so that the sum of Hammett's substituent constants is −0.5 or more, or a linear or branched or cyclic unsubstituted or substituted fat Group acyl groups (substituents include, for example, halogen atoms, ether groups, sulfonamide groups, carbonamide groups, hydroxyl groups, carboxy groups, and sulfonic acid groups) are preferable.

Most preferably, R ²³ and R ²⁴ are hydrogen atoms.

A carbonyl group is most preferable as G in the general formula [N-II].

Specific examples of the compound represented by the general formula [N-II] are shown below. However, the present invention is not limited to the following compounds.

(75) ⁽ⁿ⁾ C ₁₂ H ₂₅ NHNHCHO The method for synthesizing the compound represented by the general formula [N-II] used in the present invention is described in, for example, Research Disclosure (Re
sarch Disclosure) No. 15, 162 (November 1976 76-77)
Pp.), No. 22534 (January 1983, pages 50-54) and N.
o.23510 (November 1983, pages 346 to 352) and U.S. Pat. Nos. 4080207, 4269924, and 427636.
No. 4, No. 4278748, No. 4385108, No. 4459347,
No. 4478928, No. 4560638, British Patent No. 20113918
And Japanese Patent Application Laid-Open No. 60-179734.

The following compounds can be added for the purpose of increasing the maximum image density, decreasing the minimum image density, improving the storage stability of the light-sensitive material, or speeding up the development.

Hydroquinones, such as U.S. Pat. No. 3,227,552, 4,
Compounds described in 279,987; Chromans (for example, compounds described in U.S. Pat. No. 4,268,621, JP-A-54-103031, Research Disclosure No. 18264 (published in June 1979) pages 333 to 334), quinones Disclosure magazine No. 21206 (compounds described on pages 433 to 434, December 1981); amines (for example, US Pat.
8-174757 compounds); oxidizing agents (eg
60-260039, Research Disclosure No. 16936 (1
(Published May 978) Compounds described on pages 10 to 11): Catechols (for example, compounds described in JP-A Nos. 55-21013 and 55-65944): compounds that release a nucleating agent during development (for example, Compounds described in JP-A-60-107029): Thioureas (for example, compounds described in JP-A-60-95533): Spirobisindanes (for example, compounds described in JP-A-55-65944).

Compounds of tetrazaindenes, triazaindenes and pentazaindenes having at least one mercapto group optionally substituted with an alkali metal atom or an ammonium group as a nucleation accelerator, and the following general formula: The compounds represented by [AI] and [A-II] can be added in the light-sensitive material or in the nucleating bath or the developing bath.

General formula [AI] General formula (A-II) In the general formulas [AI] and [A-II], Z preferably represents a substituted or unsubstituted amino group, quaternary ammonium group, alkoxy group, alkylthio group or heterocyclic group.

Typical nucleation accelerators are shown below.

The color developing solution used for the development processing of the light-sensitive material of the present invention is a so-called surface developing solution which does not substantially contain a silver halide solvent, and is an alkaline aqueous solution containing a p-phenylenediamine type color developing agent as a main component. . The phrase "substantially free of silver halide solvent" means that some silver halide solvent may be included as long as the object of the invention is not impaired. The pH of the color developer used in the present invention is in the range of 10.0 to 11.0, and in the present invention, the above object can be rapidly achieved even if a color developer stable to air oxidation having such a low pH value is used. You can Typical examples of p-phenylenediamine compounds include 3-methyl-4-amino-N, N-diethylaniline, 3-methyl-4-amino-N-ethyl-N- (β-hydroxylethyl) aniline, 3 -Methyl-4-amino-N-ethyl-Nβ-methanesulfonamidoethylaniline, 3-methyl-4-amino-N
-Ethyl-N-β-methoxyethylaniline and their sulfates, hydrochlorides, phosphates or p-toluenesulfonates, tetraphenylborate, p- (t-octyl) benzenesulfonate and the like. To be Salts of these diamines are generally more stable than free. Color developing agent is generally about 1 per color developing solution.
0.1 g to a concentration of about 30 g, more preferably color developer 1
Use at a concentration of about 1 g to about 15 g per unit. Further, the replenishing amount can be reduced by using a replenishing solution in which the concentration of a halide, a color developing agent or the like is adjusted as the color developing solution.

The color development processing time of the present invention is usually 5 minutes or less, but it is preferable to perform the color development processing at a processing time of 2 minutes and 30 seconds or less because of a rapid processing compound. Further, it is preferably 10 seconds to 2 minutes, and shorter is preferable if a sufficient color density is obtained.

It is preferable that the color developing solution contains substantially no benzyl alcohol in order to prevent pollution, improve the preparation of the developing solution, and improve storage stability. With substantially no
The concentration of benzyl alcohol is 2 ml / l or less, preferably 0.5 ml / l or less, and most preferably, no benzyl alcohol is contained.

The silver halide color light-sensitive material of the present invention may contain a color developing agent or a precursor thereof for the purpose of simplifying and accelerating the processing. For incorporation, a precursor is preferable because it improves the stability of the photosensitive material. Specific examples of the developer precursor include, for example, indoaniline type compounds, Schiff base type compounds, aldol compounds and urethane type compounds.

The silver halide color light-sensitive material of the present invention may contain various 1-phenyl-3-pyrazolidones in order to accelerate color development.

The color developer of the present invention includes Japanese Patent Application No. 61-23462, No. 14
A pH buffering agent, a preservative, and a metal chelate compound described on pages 22 to 22 can be contained. Bromide ion,
Halide ions such as iodide ions, and competing couplers such as citrazinic acid can be included.

The photographic emulsion layer after color development is usually bleached. The bleaching treatment may be carried out at the same time as the fixing treatment by one-bath bleach-fixing (Brix) or separately. Further, in order to speed up the processing, a processing method of performing bleach-fixing processing after bleaching processing or a method of performing bleach-fixing processing after fixing processing may be used.

As the bleaching agent used in the bleaching process or the bleach-fixing process,
Iron (III) organic complex salts and persulfates are preferable from the viewpoint of rapid treatment and environmental pollution.

Among the organic complex salts of iron (III), ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, 1,2-diaminopropanetetraacetic acid, methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid, glycol ether diaminotetraacetic acid. The iron (III) complex salt of is preferable because of its high bleaching power.

The persulfate is preferably an alkali metal persulfate such as potassium persulfate or sodium persulfate or ammonium persulfate.

A suitable amount of the bleaching agent per bleaching solution is 0.1 to 2 mol, and a preferable pH range of the bleaching solution is 0.5 to 8.0 in the case of ferric ion complex salt, especially aminopolycarboxylic acid, aminopolyphosphonic acid, In the case of a ferric ion complex salt of phosphonocarboxylic acid or organic phosphonic acid, it is 4.0 to 7.0. In the case of persulfate, the concentration is preferably 0.1 to 2 mol / l and the pH is preferably in the range of 1 to 5.

The fixing agents used for fixing or bleach-fixing are known fixing agents, that is, thiosulfates such as sodium thiosulfate and ammonium thiosulfate; thiocyanates such as sodium thiocyanate and ammonium thiocyanate; ethylenebisthioglycolic acid, 3 It is a thioether compound such as 1,6-dithia-1,8-octanediol and a water-soluble silver halide decomposing agent such as thioureas.
A mixture of two or more species can be used.

In the case of fixing or bleach-fixing processing, the concentration of the fixing agent is 0.2 to 4
Mol / l is preferred. In the bleach-fixing treatment, the ferric ion complex salt is 0.1 to 2 mol per 1 bleach-fixing solution,
The fixing agent is preferably in the range of 0.2 to 4 mol. Also, fixing
The pH of the bleach-fixing solution is usually preferably 4.0 to 9.0, and particularly preferably 5.0 to 8.0.

In the fixer or the bleach-fixer, sulfites (for example, sodium sulfite, potassium sulfite, ammonium sulfite), bisulfite, hydroxylamine, hydrazine, as a preservative, in addition to the above-mentioned additives that can be added to the bleaching solution, A bisulfite adduct of an aldehyde compound (for example, acetaldehyde sodium bisulfite) can be contained. Furthermore, various fluorescent whitening agents, antifoaming agents or surfactants, polyvinylpyrrolidone, organic solvents such as methanol and the like can be contained.

If necessary, a bleaching accelerator can be used in the bleaching solution, the bleach-fixing solution and their pre-bath. Specific examples of useful bleaching accelerators include compounds having a mercapto group or a disulfide group, thiazolidine derivatives, thiourea derivatives, iodides, polyethylene oxides, polyamines, and the like. -42434
No. 49, 59-644, 53-94927, 54-35727, 55
The compounds described in -26506 and 58-163940 and iodine and bromine ions can also be used. Among them, compounds having a mercapto group or a disulfide group are preferable from the viewpoint of a large accelerating effect, and the compounds described in U.S. Pat. No. 3,893,858, West German Patent 1,290,812 and JP-A-53-95630 are particularly preferable. Further, the compounds described in US Pat. No. 4,552,834 are also preferable. These bleaching accelerators may be added to the light-sensitive material.

After the fixing step or the bleach-fixing step, it is common to carry out processing steps such as washing with water and stabilization.

Various known compounds may be added to the washing process and the stabilizing process for the purpose of preventing precipitation and stabilizing the washing water. For example, chelating agents such as inorganic phosphoric acid, aminopolycarboxylic acid, and organic phosphonic acid, bactericides and antifungal agents that prevent the generation of various bacteria, algae, and molds (for example, "Journal of Antibacterial・ Anti-Fungal Agents (J.Antibact.Antifung.Agent
s) ”vol.11, No.5, compounds described in p207-223 (1983) and compounds described in Hiroshi Horiguchi's" Chemistry of antibacterial and antifungal "), magnesium salts, aluminum salts, bismuth salts, etc. If necessary, a metal salt, an alkali metal and an ammonium salt to be used, or a surfactant for preventing drying load and unevenness can be added. Alternatively, compounds described in “Photographic Science and Engineering Magazine (Phot.Sci.Eng.)” By West, Vol. 6, pp. 344-359 (1965), etc. may be added. It is particularly effective to add a chelating agent, a bactericidal agent or a fungicide.

The water washing step is performed by multi-stage countercurrent water washing of two or more tanks (for example, 2-9
It is common to use a tank) to save the washing water. Further, instead of the washing step, a multistage countercurrent stabilization treatment step as described in JP-A-57-8543 may be carried out. In addition to the above-mentioned additives, various compounds are added to the stabilizing bath for the purpose of stabilizing an image. For example, adjust the membrane pH (eg pH
3 to 9) various buffers (for example, borate, metaborate, borax, phosphate, carbonate, potassium hydroxide, sodium hydroxide, aqueous ammonia, monocarboxylic acid, dicarboxylic acid, polycarboxylic acid) Typical examples include aldehydes such as formalin). Other chelating agents (inorganic phosphoric acid, aminopolycarboxylic acid, organic phosphonic acid, aminopolyphosphonic acid,
(Phosphonocarboxylic acid, etc.), bactericide, antifungal agent (thiazole-based, isothiazole-based, halogenated phenol, sulfanilamide, benzotriazole, etc.), surfactant, fluorescent brightening agent, hardener metal salt, etc. Various additives may be used, and two or more kinds of the same or different target compounds may be used in combination.

Further, it is preferable to add various ammonium salts such as ammonium chloride, ammonium nitrate, ammonium sulfate, ammonium phosphate, ammonium sulfite, and ammonium thiosulfate as a film pH adjuster after the treatment in order to improve the image storability.

The washing and stabilizing treatment time of the present invention is usually 20 seconds to 10 minutes, preferably 20 seconds to 5 minutes, although it varies depending on the type of the photosensitive material and the processing conditions.

The various treatment liquids in the present invention are used at 10 ° C to 50 ° C. A temperature of 33 ° C to 38 ° C is standard, but it is possible to raise the temperature to accelerate the treatment and shorten the treatment time, and conversely to lower the temperature to improve the image quality and improve the stability of the treatment liquid. it can.

In addition, each processing time can be shortened from the standard time within a range that does not cause any trouble in order to accelerate the processing.

Further, in the case of continuous processing, a constant finish can be obtained by using a replenisher for each processing solution to prevent fluctuations in the liquid composition.

If necessary, a heater, a temperature sensor, a liquid level sensor, a circulation pump, various types of filters such as floating pigs, various types of squeegees, etc. may be provided in each treatment bath.

The preferred embodiments of the nucleating agents of the general formulas [NI] and [N-II] that can be effectively used in the present invention are as follows.

(1) In the nucleating agent of the formula (N-I), the heterocycle completed by Z is a quinolium, benzothiazolium, benzimidazolium, pyridinium, acridinium, phenanthridinium, or isoquinolinium nucleus. If it is.

(2) In the nucleating agent of the formula (N-I), when the adsorption promoting group represented by X ¹ on the silver halide is a thioamide group, a heterocyclic mercapto group or a nitrogen-containing heterocycle forming iminosilver. .

(3) In the nucleating agent of the formula (N-I), the heterocycle for which Z is completed is quinolinium, benzothiasolium or benzimidazolium.

(4) In the nucleating agent of formula (NI), the heterocycle completed by Z is quinolinium or benzothiazolium.

(5) In the nucleating agent of formula (NI), the heterocycle completed by Z is quinolinium.

(6) The case where the nucleating agent of the formula (NI) has an alkynyl group as a substituent of R ¹ , R ² or Z.

(7) In the nucleating agent of (6), the heterocycle completed by Z is quinolinium.

(8) In the case of the nucleating agent of (7), having an adsorption promoting group for silver halide represented by X ¹ .

(9) In the case where the adsorption promoting group of (8) onto silver halide is composed of a thioamide group, a heterocyclic mercapto group, or a nitrogen-containing heterocycle that produces imino silver.

(10) In the nucleating agent of the formula (NI), the group represented by GR ²² is a formyl group.

(11) In the nucleating agent of the formula (N-II), R ²³ and R ²⁴ are hydrogen atoms and the group represented by G R ²² is a formyl group.

(12) In the nucleating agent of the formula (N-II), R ²¹ is an aromatic group and has a ureido group as a substituent.

(13) In the nucleating agent of the formula (N-II), R ²¹ is an aromatic group, and a heterocyclic mercapto group, an aryl mercapto group, an aliphatic mercapto group or a nitrogen-containing heterocyclic ring that produces imino silver as a substituent. When it has a group that promotes adsorption to silver halide.

(14) In the nucleating agent of (11), R ²¹ is an aromatic group, and as a substituent, a heterocyclic mercapto group or an adsorption promoting group to a silver halide consisting of a nitrogen-containing heterocycle that produces imino silver. , Or having an ureido group.

(Examples) The present invention is illustrated by the following examples, but the present invention is not limited to these examples.

Example 1 1) Production of emulsions Emulsions A to H are produced as follows.

Emulsion A An octahedral monodisperse silver bromide emulsion with an average particle size of 0.4 μm was prepared by simultaneously adding an aqueous solution of potassium bromide and an aqueous solution of silver nitrate to an aqueous solution of gelatin with vigorous stirring at 75 ° C. for about 40 minutes. Got To this emulsion, add 4 mg of sodium thiosulfate and chloroauric acid (tetrahydrate) per mol of silver, and add at 75 ° C
The chemical sensitization treatment was performed by heating for 80 minutes. The silver bromide grains thus obtained are used as cores for further growth by treating for 40 minutes in the same precipitation environment as the first time, and finally, octahedral monodisperse cores with an average grain size of 0.6 μm (variation coefficient 14%). / Ciel silver bromide emulsion was obtained. After washing with water and desalting, 0.9 mg of sodium thiosulfate was added to this emulsion and the mixture was heated at 65 ° C. for 60 minutes for chemical sensitization to obtain an internal latent image type silver halide emulsion A.

Emulsion B KBr 0.5 mol NaCl 0.2 mol KI 0.0015 mol / l of mixed solution 1 was added with 30 g of gelatin and dissolved, and then at 60 ° C., a silver nitrate 1 mol / l solution was added to 700 c.
c was added over 20 minutes, and physical ripening was further performed for 20 minutes. Then, the mixture was washed with water to remove the water-soluble halide, gelatin 20 ° C was added, and the total amount was adjusted to 1200 cc with water.

An emulsion having an average grain size of 0.4 μm was obtained.

This emulsion was washed with water and desalted to obtain an internal latent image type emulsion B.

Emulsion C KBr 0.5 mol NaCl 0.2 mol KI 0.0015 mol / l of mixed solution 1 was added with 30 g of gelatin and dissolved, and then at 60 ° C., a solution of silver nitrate 1 mol / l was added to 700c.
c was added over 20 minutes, and physical ripening was further performed for 20 minutes. Then, the mixture was washed with water to remove the water-soluble halide, 20 g of gelatin was added, and the total amount was adjusted to 1200 cc with water.

 An emulsion having a uniform grain size of 0.4 μm was obtained.

To 300 cc of this emulsion, 1 mol of silver nitrate aqueous solution (500 cc) and 2 mol of sodium chloride aqueous solution (500 cc) were simultaneously added at 60 ° C. to precipitate a silver chloride shell, followed by washing with water.

Emulsion C having an average particle size of 0.7 μm was obtained.

Emulsion D An aqueous solution of potassium bromide and an aqueous solution of silver nitrate were simultaneously added to an aqueous solution of gelatin with vigorous stirring at 75 ° C for about 40 minutes, and an octahedral monodisperse silver bromide emulsion having an average particle size of 0.4 µm was added. Got To this emulsion, add 4 mg of sodium thiosulfate and chloroauric acid (tetrahydrate) per mol of silver, and add at 75 ° C
The chemical sensitization treatment was performed by heating for 80 minutes. Using the silver bromide particles thus obtained as a core, a 2 mol sodium chloride aqueous solution and 1 mol silver nitrate aqueous solution were added at 75 ° C. for 40 minutes to grow, and a cubic silver chlorobromide core of 0.6 μm (variation coefficient 15%) / Shell emulsion was obtained. After washing with water and desalting, the amount of this emulsion was 0.
Emulsion D was obtained by adding 5 mg of sodium thiosulfate and heating at 55 ° C. for 60 minutes for chemical sensitization.

Emulsion E An aqueous solution of potassium bromide and an aqueous solution of silver nitrate were simultaneously added to an aqueous solution of gelatin with vigorous stirring at 75 ° C for about 90 minutes to give a regular octahedral silver bromide emulsion having an average grain size of about 0.8μ. Obtained (core particles). However, before the precipitation of silver halide grains in this emulsion, 0.65 g of 3,4-dimethyl-1,
3-Thiazoline-2-thione was added, the pH was kept at about 6 during the precipitation step and the pAg was kept at about 8.7. The silver bromide grains were chemically sensitized by adding 3.4 mg of sodium thiosulfate and 3.4 mg of potassium chloroaurate per mol of silver. The chemically sensitized grains were further grown in the same precipitation environment as the core grains were formed, and finally 1.2 μ octahedral core /
Shell silver bromide grains were formed. In addition to this Iodokari 9.
Emulsion E was obtained by adding 6 × 10 ⁻⁴ mol / silver mol and 4.2 × 10 ⁻² g / Ag mol of N-vinylpyrrolidone polymer (weight average molecular weight 38,000).

Emulsion F A silver bromide emulsion was obtained by simultaneously mixing an aqueous solution of potassium bromide and an aqueous solution of silver nitrate in an aqueous gelatin solution at 75 ° C. for about 60 minutes while stirring vigorously. Prior to precipitation, 100 mg of 3,4-dimethyl-mole per mol of silver was placed in the precipitation tank.
1,3-thiazoline-2-thione and 15 per mole of silver
g of benzimidazole was added. When the precipitation was completed, crystals with an average particle size of about 1.1 microns were produced. Next to the silver bromide grains, 5.4 m of sodium thiosulfate per mol of silver
g and 3.9 mg of potassium chloroaurate per 1 mol of silver, 75
The chemical sensitization treatment was performed by heating at 80 ° C. for 80 minutes. A core / shell emulsion was prepared by simultaneously mixing the thus chemically sensitized core emulsion with aqueous solutions of potassium bromide and silver nitrate for 40 minutes in the same manner as the first time.
The final average particle size was 1.5 microns.

This core / shell emulsion was then charged with 0.32 mg of sodium thiosulfate per mol of silver and a weight average molecular weight of 3 per mol of silver.
Add 8,000 of poly (N-vinylpyrrolidone) 57mg at 6 ℃
The grain surface was chemically sensitized by heating for 0 minutes to obtain an emulsion F.

Emulsion G A silver bromide emulsion was obtained by mixing an aqueous solution of potassium bromide and an aqueous solution of silver nitrate in an aqueous gelatin solution containing potassium bromide with vigorous stirring at 75 ° C. for about 60 minutes at the same time. Prior to precipitation (simultaneous mixing), 15 mol per mol silver as a silver halide solvent in gelatin aqueous solution.
0 mg of 3,4-dimethyl-1,3-thiazoline-2-thione and 15 g of benzimidazole were added. Upon completion of the precipitation, octahedral silver bromide crystals having a uniform grain size and an average grain size of about 0.8 micron were formed. Next, to the silver bromide grains, 4.8 mg of sodium thiosulfate per mol of silver and 2.4 mg of potassium chloroaurate per mol of silver were added, and the mixture was heated at 75 ° C. for 80 minutes for chemical sensitization. The internal core (core) bromide emulsion thus chemically sensitized was mixed with the aqueous solution of potassium bromide and silver nitrate for 45 minutes at the same time as the first time, and the internal latent image type core / Precipitate the shell emulsion and add 2.5 g / mol A of hydrogen peroxide as an oxidant.
After adding g and heating at 75 ℃ for 8 minutes, wash with water and average particle size
An emulsion of 1.0 μm (variation coefficient 12%) was obtained.

Next, to this internal latent image type core / shell silver bromide emulsion, 0.75 mg of sodium thiosulfate per 1 mol of silver and 20 mg of poly (N-vinylpyrrolidone) per 1 mol of silver were added, and the mixture was heated at 60 ° C. for 60 minutes to chemistry of the grain surface. Sensitization (ripening) was performed to obtain Emulsion G.

Emulsion H To an aqueous solution of potassium bromide and an aqueous solution of silver nitrate, 0.3 g of 3,4-dimethyl-1,3-thiazoline-2-thione was added per mol of Ag, and the mixture was vigorously stirred at 75 ° C. in an aqueous gelatin solution.
It takes about 20 minutes to add them at the same time, and the average particle size is 0.4 μm.
An octahedral monodisperse silver bromide emulsion was obtained. Chemical sensitization was carried out by adding 6 mg of sodium thiosulfate and chloroauric acid (tetrahydrate) per mol of silver to this emulsion and heating at 75 ° C. for 80 minutes. The silver bromide grains thus obtained were used as cores for further growth for 40 minutes in the same precipitation environment as in the first time, and finally the average grain size was 0.7 μm.
An m octahedral monodisperse core / shell silver bromide emulsion was obtained. After washing with water and desalting, 1.5 mg each of sodium thiosulfate and chloroauric acid (tetrahydrate) were added to this emulsion at 60 ° C.
The mixture was heated for 60 minutes for chemical sensitization to obtain an internal latent image type silver halide emulsion H.

2) Production of color photographic paper On the paper support laminated on both sides with polyethylene using core / shell type autopositive emulsions A to H, a multi-layer color photographic paper having the layer constitution shown in Table 1 was prepared. The coating liquid was prepared as follows.

Preparation of coating solution for the first layer: 6.4 g of cyan coupler (a) and 2.3 g of color image stabilizer (b), 10 ml of ethyl acetate and 4 ml of solvent (c)
Was dissolved, and this solution was emulsified and dispersed in 90 ml of a 10% gelatin aqueous solution containing 5 ml of 10% sodium dodecylbenzenesulfonate. On the other hand, the above silver halide emulsion (Ag70g / kg
To the content, the following red-sensitive dye was added in an amount of 2.0 × 10 ^-4 mol per mol of silver halide to prepare a red-sensitive emulsion (90 g). The emulsified dispersion and emulsion were mixed and dissolved, and the concentration was adjusted with gelatin so that the composition shown in Table 1 was obtained, and the nucleating agent (n) was further added.
Was added in an amount of 30 mg per 1 mol of Ag (and 5 × 10 ⁻⁴ mol of a nucleation accelerator (O) was added per 1 mol of Ag to prepare a coating solution for the first layer.

The coating solutions for the second to seventh layers were also prepared in the same manner as the coating solution for the first layer. 1-oxy- as a gelatin hardening agent for each layer
The 3,5-dichloro-s-triazine sodium salt was used.

The following were used as the spectral sensitizer for each emulsion.

Blue sensitive emulsion layer; Green-sensitive emulsion layer; Red-sensitive emulsion layer; The following dyes were used as the anti-irradiation dye in each emulsion layer.

Green-sensitive emulsion layer; Red-sensitive emulsion layer; Structural formulas of compounds such as couplers used in this example are as follows.

(M) Solvent (isoC ₉ H ₁₉ O ₃ P = O Development regulator (x) Nucleating agent (n) Nucleation accelerator (o) (J) Solvent (isoC ₉ H ₁₉ O ₃ P = O Multilayer silver halide color photographic light-sensitive materials A to H can be prepared by simultaneously coating the coating solutions for the first to seventh layers after adjusting the balance of surface tension and viscosity.

3) Development processing The light-sensitive materials A to H thus obtained were processed at a color temperature of 4800.
After imagewise exposure for 1/10 seconds at K and a light amount of 100 CMS, the following processing step A (pH 10.2) and processing step B in which only the pH was adjusted to 11.0 were carried out to directly obtain a positive image.

The stabilizing bath was replenished into the stabilizing bath, the overflow liquid of the stabilizing bath was introduced into the stabilizing bath, and the overflow liquid of the stabilizing bath was introduced into the stabilizing bath, that is, a so-called countercurrent replenishing system.

The pH was adjusted with potassium hydroxide or hydrochloric acid.

The pH was adjusted with aqueous ammonia or hydrochloric acid.

Adjust the pH with potassium hydroxide or hydrochloric acid.

The minimum density of magenta in the obtained direct positive image is measured. The results are shown in Table 3.

Comparative Example 1 Using the emulsions A to H produced in Example 1, the same color photographic papers A'to H'as the layer structure (additives and amount used) of Table 1 except for the third layer shown in Table 2 are used. Was obtained and developed.

The magenta minimum density of the obtained direct positive image was measured, and the results are shown in Table 3 together with the results of Example 1.

The compound used for the third layer is shown below (e ′),
Except for (f ') and (g'), all are the same as in the first embodiment.

Magenta images obtained with the pyrazoloazole-based magenta couplers according to the present invention have a clearly smaller minimum density. Further, the maximum concentration was a sufficient value with no particular difference between the example and the comparative example.

Example 2 and Comparative Example 2 In Example 1 and Comparative Example 1, the color photographic paper was prepared without using the nucleating agent (n) and the nucleation accelerator (o), and after the start of development in the development processing step A. Direct positive images for the present invention and for comparison were respectively obtained in the same manner as in Example 1 and Comparative Example 1 except that light of 0.5 lux (5400K) was applied to the surface of the light-sensitive material for 15 seconds. The magenta minimum density was measured. The results are shown in Table 4.

According to the present invention, it is found that the minimum density is reduced by using the pyrazoloazole-based magenta coupler even when the light fogging method is used.

Example 3 Exactly the same as Example 1 except that the emulsions B, C, F and H were used and the magenta couplers (shown by the exemplified compound numbers) as shown in Table 5 were used. A color light-sensitive material was prepared and developed (the same processes A and B as in Example 1). The results are shown in Table 5.

For comparison, the results of Emulsions B, C, F and H conducted in Comparative Example 1 are also shown together.

Magenta images obtained with the pyrazoloazole-based magenta couplers of the present invention have significantly smaller minimum densities.

Example 4 Preparation of Emulsion I An aqueous solution of potassium bromide and silver nitrate was added at 0.27 g of 3, per mol of Ag.
It was added simultaneously to the aqueous gelatin solution containing 4-dimethyl-1,3-thiazoline-2-thione at 45 ° C for about 30 minutes with vigorous stirring, and the average particle size was about 0.19 µm. A silver bromide emulsion was obtained. 40 moles per mole of silver in this emulsion
Add mg sodium thiosulfate and chloroauric acid (tetrahydrate) 75
The chemical sensitization treatment was performed by heating at 80 ° C. for 80 minutes.
Using the silver bromide grains thus obtained as a core, they were further grown in the same precipitation environment as the first time, and finally the average grain size was 0.34 μm.
An m octahedral monodisperse core / shell silver bromide emulsion was obtained. The coefficient of variation of particle size was about 12%.

30 mg of sodium thiosulfate was added to this emulsion per mol of silver.
Chloroauric acid (tetrahydrate) (mg) was added and the mixture was heated at 60 ° C. for 60 minutes for chemical sensitization to obtain an internal latent image type halogenated emulsion I.

Preparation of Emulsion J An aqueous solution of potassium bromide and silver nitrate was added in an amount of 0.12 g per mol of Ag 3.
Simultaneously added to an aqueous gelatin solution containing 4-dimethyl-1,3-thiazoline-2-thione at 75 ° C for about 20 minutes with vigorous stirring, and the average particle size was about 0.36 µm. A silver bromide emulsion was obtained. 20 moles per mole of silver in this emulsion
Add mg sodium thiosulfate and chloroauric acid (tetrahydrate) 75
The chemical sensitization treatment was performed by heating at 80 ° C. for 80 minutes.
The silver bromide grains thus obtained were used as cores for further growth in the same precipitation environment as the first time, and finally the average grain size was about 0.6.
A μm octahedral monodisperse core / shell silver bromide emulsion was obtained.
The coefficient of variation of particle size was about 9%.

7 mg of sodium thiosulfate and 7 mg per mole of silver in this emulsion
Chloroauric acid (tetrahydrate) was added and heated at 60 ° C. for 60 minutes for chemical sensitization to obtain an internal latent image type halogenated emulsion J.

Preparation of Emulsion K An aqueous solution of potassium bromide and silver nitrate was added to 15 g of 3,6 per mol of Ag.
-A monodisperse silver bromide emulsion of octahedron with an average grain size of about 0.40 μm, which was added simultaneously to an aqueous gelatin solution containing dithia-1,8-octanediol with vigorous stirring at 75 ° C for about 20 minutes. Got To this emulsion were added 6 mg of sodium thiosulfate and 7 mg of chloroauric acid (tetrahydrate) per mol of silver, and the temperature was 75 ° C.
Chemical sensitization was performed by heating at 80 ° C. for 80 minutes. The silver bromide grains thus obtained were used as cores for further growth in the same precipitation environment as the first time, and finally the average grain size was about 1.0 μm.
An m octahedral monodisperse core / shell silver bromide emulsion was obtained. The coefficient of variation of particle size was about 7%.

2.0 mg sodium thiosulfate per mole silver was added to this emulsion.
2.0 mg of chloroauric acid (tetrahydrate) was added and the mixture was heated at 60 ° C. for 60 minutes for chemical sensitization to obtain an internal latent image type halogenated emulsion K.

On a paper support laminated on both sides with polyethylene, a multi-layer color light-sensitive material 4-1 having the following layer constitution was prepared.

(Layer constitution) The composition of each layer is shown below. The number is the amount applied per m ² in g
Express with. For silver halide emulsions and colloidal silver, the coating amount in terms of silver is expressed in g, and for the spectral sensitizing dye, the addition amount is expressed in mol per mol of silver halide.

Support Polyethylene laminated paper (thickness 105 μm) [White pigment (TiO ₂ ) and bluish dye (ulter blue) on polyethylene on the E1 layer side]
E1 layer Silver halide emulsion I 0.07 Spectral sensitizing dye (ExSS-1) 2.0 × 10 ^-4 Spectral sensitizing dye (ExSS-2) 1.2 × 10 ^-4 Gelatin 0.30 Cyan coupler (ExCC-1) 0.057 Cyan coupler (ExCC-2) 0.07 UV absorber (ExUV-1) 0.046 Solvent (ExS-1) 0.062 Development modifier (ExGC-1) 0.005 Stabilizer (ExA-1) 0.0016 Nucleation accelerator (ExZS-1) 8 × 10 ^-5 Nucleating agent (ExZK-1) 2.2 × 10 ^-6 Layer E2 Silver halide emulsion J 0.07 Spectral sensitizing dye (ExSS-1) 1.5 × 10 ^-4 Spectral sensitizing dye (ExSS-2) 9.0 × 10 ^-5 Gelatin 0.30 Cyan coupler (ExCC-1) 0.057 Cyan coupler (ExCC-2) 0.07 UV absorber (ExUV-1) 0.046 Solvent (ExS-1) 0.062 Development modifier (ExGC-1) 0.005 Stabilizer (ExA-1) 0.0016 Nucleation accelerator (ExZS-1) 8 × 10 ^-5 Nucleating agent (ExZK-1) 2.2 × 10 ^-6 E3 layer Silver halide emulsion K 0.12 Spectral sensitizing dye (ExSS-1) ) 1.0 × 10 ^-4 spectral sensitization dye (ExSS-2) 6.1 × 10 -5 gelatin 0.51 Shi Coupler (ExCC-1) 0.097 Cyan coupler (ExCC-2) 0.12 UV absorber (ExUV-1) 0.078 Solvent (ExS-1) 0.11 Development regulator (ExGC-1) 0.009 Stabilizer (ExA-1) 0.0028 Nucleation Accelerator (Ex ¹ ZS-1) 1.4 × 10 ^-4 Nucleating agent (ExZK-1) 3.7 × 10 ^-4 Layer E4 Gelatin 1.41 Color mixture inhibitor (ExKB-1) 0.09 Solvent (ExS-1) 0.10 Solvent ( ExS-2) 0.10 E5 layer Silver halide emulsion I 0.06 Spectral sensitizing dye (ExSS-3) 6.0 × 10 ^-4 Gelatin 0.27 Magenta coupler (ExMC-1) 0.042 Color image stabilizer (ExSA-1) 0.052 Solvent ( ExS-3) 0.065 Development modifier (ExGC-1) 0.005 Stabilizer (ExA-1) 0.0016 Nucleation accelerator (ExZS-1) 7.0 × 10 ^-5 Nucleating agent (ExZK-1) 3.7 × 10 ^-6 E6 layer Silver halide emulsion J 0.06 Spectral sensitizing dye (ExSS-3) 4.5 × 10 ^-4 Gelatin 0.27 Magenta coupler (ExMC-1) 0.042 Color image stabilizer (ExSA-1) 0.052 Solvent (ExS-3) 0.065 Development Regulator (ExGC-1) 0.005 Stabilizer (ExA-1) 0.0016 Nucleating accelerator (ExZS-1) 7.0 × 10 -5 nucleating agent (ExZK-1) 3.7 × 10 -6 second E7 layer silver halide emulsion K 0.11 spectral sensitizing dye (ExSS-3) 3.0 × 10 -4 Gelatin 0.48 Magenta coupler (ExMC-1) 0.074 Color image stabilizer (ExSA-1) 0.092 Solvent (ExS-3) 0.11 Development regulator (ExGC-1) 0.0092 Stabilizer (ExA-1) 0.0028 Nucleation accelerator (ExZS- 1) 1.2 × 10 ^-4 Nucleating agent (ExZK-1) 6.5 × 10 ^-6 Layer E8 Gelatin 0.47 Color mixing inhibitor (ExKB-1) 0.03 Irradiation prevention dye (ExIS-1) 0.012 Irradiation prevention dye (ExIS -2) 0.018 Solvent (ExS-1) 0.03 Solvent (ExS-2) 0.03 Layer E9 Colloidal silver 0.18 Gelatin 0.49 Color mixture inhibitor (ExKB-1) 0.03 Solvent (ExS-1) 0.03 Solvent (ExS-2) 0.03 E10 layer Same as E8 layer E11 layer Silver halide emulsion I 0.114 Spectral sensitizing dye (ExSS-3) 4.2 × 10 ^-4 Gelatin 0.62 Yellow coupler (ExYC-1) 0.14 Solvent (ExS-2) 0.057 Solvent (ExS -4) 0.057 Development modifier (ExGC-1) 0.017 Stabilizer (ExA-1) 0.0003 Nucleation accelerator (ExZS-1) 1.4 × 10 ^-4 Nucleating agent (ExZK-1) 3.4 × 10 ^-7 E12 layer Silver halide emulsion J 0.114 Spectral sensitizing dye (ExSS-3) 4.2 × 10 ^-4 Gelatin 0.62 Yellow coupler (ExYC-1) 0.14 Solvent (ExS-2) 0.057 Solvent (ExS-4) 0.057 Development modifier (ExGC-1) 0.017 Stabilizer ( ExA-1) 0.0003 Nucleation accelerator (ExZS-1) 1.4 × 10 ^-4 Nucleating agent (ExZK-1) 3.4 × 10 ^-7 Layer E13 Silver halide emulsion K 0.172 Spectral sensitizing dye (ExSS-3) 4.2 × 10 ^-4 Gelatin 0.93 Yellow coupler (ExYC-1) 0.22 Solvent (ExS-2) 0.086 Solvent (ExS-4) 0.086 Development modifier (ExGC-1) 0.026 Stabilizer (ExA-1) 0.0004 Nucleation accelerator (ExZS-1) 2.2 × 10 ^-4 Nucleating agent (ExZK-1) 5.2 × 10 ^-7 Layer E14 gelatin 0.54 UV absorber (ExUV-2) 0.21 Solvent (ExS-4) 0.08 Layer E15 gelatin 1.28 Polyvinyl Acrylic modified copolymer of alcohol (Degree of modification 17%) 0.17 Fin 0.03 Latex particles of polymethylmethacrylate (average particle size 2.8 μm) 0.05 Layer B1 gelatin 6.2 Layer B2 Same as layer E9 Each layer contains gelatin hardener ExGK-1 and surfactant in addition to the above composition. Was added.

Compound used to make the sample (ExS-4) solvent O = PO-C ₉ H ₁₉ (iso)) ₃ (ExUV-2) UV absorber 2: 9: 8 mixture of (1) :( 2) :( 3) above (weight ratio) (ExA-1) Stabilizer 4-Hydroxy-5,6-trimethylene-1,3,3a, 7-tetrazaindene (ExZS-1) Nucleation accelerator 2- (3-Dimethylaminopropylthio) -5- Mercapto-1,3,4-thiadiazole hydrochloride (ExZK-1) Nucleating agent 6-ethoxythiocarbonylamino-2-methyl-1-
Propargyl quinolinium trifluoromethane sulfonate (ExGK-1) Gelatin hardener 1-oxy-3,5-dichloro-S-triazine sodium salt Same as Photosensitive Material 4-1, but magenta coupler ExMC of layers E5 to E7 For Comparative Photosensitive Material 4
-2-4 and photographic materials 4-5-9 of the present invention were prepared.

The magenta couplers of the present invention are indicated by the exemplified compound numbers.

The color temperatures of the light-sensitive materials 4-1 to 9 thus obtained are 32
After imagewise exposure at 00K and light intensity of 300 CMS for 1/10 seconds, the following processing steps C and D were performed to directly obtain a positive image.

The replenishing method of the washing water was a so-called countercurrent replenishing method in which the washing bath was replenished and the overflow solution of the washing bath was introduced into the washing bath and the overflow solution of the washing bath was introduced into the washing bath.
At this time, the replenishment ratio was 9.1 times because the carry-in of the light-sensitive material from the previous bath was 35 ml / m ² .

The pH was adjusted with potassium hydroxide or hydrochloric acid.

The pH was adjusted with aqueous ammonia or hydrochloric acid.

[Wash water]

Pure water was used (mother liquor = replenisher) Pure water here means that all cations other than hydrogen ions and all anions other than hydroxide ions in tap water have been removed to 1 ppm or less by ion exchange treatment. Is.

The replenishment method of the washing bath was a so-called countercurrent replenishment method in which the washing bath was replenished, and the overflow solution of the washing bath was introduced into the washing bath and the overflow solution of the washing bath was introduced into the washing bath.
At this time, the replenishment ratio for the wash water was 8.6.

The pH was adjusted with potassium hydroxide or hydrochloric acid.

The pH was adjusted with aqueous ammonia or hydrochloric acid.

[Wash water]

Tap water for H type strong acid cation exchange resin (Mitsubishi Kasei)
(Diaion SK-1B manufactured by Co., Ltd.) and OH type strongly basic anion exchange resin (Diaion SA-10A) are passed through a mixed bed column to make the following water quality, and then as a bactericide 20 mg / l sodium isocyanurate dichloride was added. Calcium ion 1.1 mg / l Magnesium ion 0.5 mg / l pH 6.9 The minimum magenta density of the obtained direct positive image was measured, and the results are shown in Table 7.

Processing step C using the magenta coupler of the present invention,
The image density is obviously small in any of D, and the effect is remarkable in the processing step C which is a quicker processing.

In addition, the maximum concentration is not particularly different between Examples and Comparative Examples,
Both were sufficient values.

Example 5 Preparation of Emulsion L KBr 0.5 mol NaCl 0.2 mol KI 0.001 mol / l Mixture 1
Add 30 g of gelatin to and melt it, then add silver nitrate 1 at 60 ℃.
700 cc of the mol / l solution was added over 20 minutes, and physical ripening was performed for 20 minutes. Then, the mixture was washed with water to remove the water-soluble halide, 20 g of gelatin was added, and the total amount was adjusted to 1200 cc with water.

An emulsion having an average grain size of 0.35 μm was obtained.

To 300 cc of this emulsion, 1 mol of silver nitrate aqueous solution (500 cc) and 2 mol of sodium chloride aqueous solution (500 cc) were simultaneously added at 60 ° C. to precipitate a silver chloride shell, followed by washing with water.

Emulsion L having an average particle size of 0.5 μm was obtained.

Preparation of Emulsion M A mixture aqueous solution of potassium bromide and sodium chloride and an aqueous solution of silver nitrate were vigorously stirred into a gelatin aqueous solution to which 0.14 g of 3,4-dimethyl-1,3-thiazoline-2-thione was added per mol of Ag. Simultaneously adding at 21 ° C. for about 21 minutes, a monodisperse silver chlorobromide emulsion having an average grain size of about 0.24 μm (silver bromide content 80 mol%) was obtained. 61 mg per mole of silver in this emulsion
Chemical sensitization treatment was carried out by adding sodium thiosulfate of 4 and 42 mg of chloroauric acid (tetrahydrate) and heating at 65 ° C. for 60 minutes. The silver chlorobromide grains thus obtained were used as cores for further growth in the same precipitation environment as the first time, and finally a monodisperse core / shell with an average grain size of about 0.74 μm (silver bromide content 70 mol%). A silver chlorobromide emulsion was obtained. Coefficient of variation of particle size is about 12
%Met. To this emulsion were added 1.8 mg of sodium thiosulfate and 2.0 mg of chloroauric acid (tetrahydrate) per mol of silver, and the mixture was added at 60 ° C for 6 times.
A chemical sensitization treatment was performed by heating for 0 minutes to obtain an internal latent image type halogenated emulsion M.

A multi-layer color light-sensitive material 5-1 having the following layer structure was prepared on a polyethylene terephthalate support having a thickness of 100 [mu] which was undercoated with gelatin.

(Layer constitution) The composition of each layer is shown below. The number is the amount applied per m ² in g
Express with. The silver halide emulsion and colloidal silver are expressed in terms of silver, and the spectral sensitizing dye is expressed in terms of mol per mol of silver halide. The compound used is the same as in Example 4.

However, 1,4-bis (vinylsulfonylacetamide) ethane was used as a gelatin hardener.

Layer E1 Silver halide emulsion L 0.26 Spectral sensitizing dye (ExSS-1) 1.0 × 10 ^-4 Spectral sensitizing dye (ExSS-2) 6.1 × 10 ^-5 Gelatin 0.7 Cyan coupler (ExCC-1) 0.21 Cyan coupler ( ExCC-2) 0.26 UV absorber (ExUV-1) 0.17 Solvent (ExS-1) 0.23 Development regulator (ExGC-1) 0.02 Stabilizer (ExA-1) 0.006 Nucleation accelerator (ExZS-1) 3.0 × 10 ^-4 Nucleating agent (ExZK-1) 8.0 × 10 ^-6 Layer E2 Silver halide emulsion M 0.26 Spectral sensitizing dye (ExSS-1) 1.0 × 10 ^-4 Spectral sensitizing dye (ExSS-2) 6.1 × 10 ^-5 Gelatin 0.7 Cyan coupler (ExCC-1) 0.21 Cyan coupler (ExCC-2) 0.26 UV absorber (ExUV-1) 0.17 Solvent (ExS-1) 0.23 Development modifier (ExGC-1) 0.02 Stabilizer (ExA- 1) 0.006 Nucleation accelerator (Ex ¹ ZS-1) 3.0 × 10 ^-4 Nucleating agent (ExZK-1) 8.0 × 10 ^-6 Layer E3 Gelatin 1.41 Color mixing inhibitor (ExKB-1) 0.18 Solvent (ExS- 1) 0.20 Solvent (ExS-2) 0.20 Layer E4 Silver halide emulsion L 0.23 Spectral sensitization Containing (ExSS-3) 3.0 × 10 -4 Gelatin 1.05 Magenta Coupler (ExMC-1) 0.16 Color Image Stabilizer (ExSA-1) 0.20 solvent (ExS-3) 0.25 development modifiers (ExGC-1) 0.02 Stabilizer ( ExA-1) 0.006 Nucleation accelerator (ExZS-1) 2.7 × 10 ^-4 Nucleating agent (ExZK-1) 1.4 × 10 ^-5 Layer E5 Silver halide emulsion M 0.23 Spectral sensitizing dye (ExSS-3) 3.0 × 10 ^-4 Gelatin 1.05 Magenta coupler (ExMC-1) 0.16 Color image stabilizer (ExSA-1) 0.20 Solvent (ExS-3) 0.25 Development modifier (ExGC-1) 0.02 Stabilizer (ExA-1) 0.006 Nuclear accelerator (ExZS-1) 2.7 × 10 ^-4 Nucleating agent (ExZK-1) 1.4 × 10 ^-5 Layer E6 Gelatin 0.47 Color mixing inhibitor (ExKB-1) 0.06 Irradiation prevention dye (ExIS-1) 0.012 Anti-irradiation dye (ExIS-2) 0.018 Solvent (ExS-1) 0.06 Solvent (ExS-2) 0.06 E7 layer Colloidal silver 0.18 Gelatin 0.49 Color mixing inhibitor (ExKB-1) 0.03 Solvent (ExS-1) 0.03 Solvent ( ExS-2) 0.03 E8 layer Same as E6 layer E9 layer Silver halide emulsion 0.40 Spectral sensitizing dye (ExSS-3) 4.2 × 10 ^-4 Gelatin 1.5 Yellow coupler (ExYC-1) 0.51 Solvent (ExS-2) 0.20 Solvent (ExS-4) 0.20 Development modifier (ExGC-1) ) 0.06 Stabilizer (ExA-1) 0.001 Nucleation accelerator (ExZS-1) 5.0 × 10 ^-4 Nucleating agent (ExZK-1) 1.2 × 10 ^-6 Layer E10 Silver halide emulsion 0.40 Spectral sensitizing dye ( ExSS-3) 4.2 × 10 ^-4 Gelatin 1.5 Yellow coupler (ExYC-1) 0.51 Solvent (ExS-2) 0.20 Solvent (ExS-4) 0.20 Development modifier (ExGC-1) 0.06 Stabilizer (ExA-1) 0.001 Nucleation accelerator (ExZS-1) 5.0 × 10 ^-4 Nucleation agent (ExZK-1) 1.2 × 10 ^-6 Layer E11 Gelatin 0.54 UV absorber (ExUV-2) 0.21 Solvent (ExS-4) 0.08 E12 Layer Gelatin 1.28 Polyvinyl alcohol acrylic modified copolymer (Degree of modification 17%) 0.17 Liquid paraffin 0.03 Polymethylmethacrylate latex particles (Average particle size 2.8 μm) 0.05 Layer B1 Gelatin 7.2 Dye (ExIS-1 0.02 Dye (ExIS-2) 0.02 Layer B2 Gelatin 1.28 Polyvinyl alcohol acrylic modified copolymer (modification degree 17%) 0.17 Liquid paraffin 0.03 Polymethylmethacrylate latex particles (average particle size 2.8 μm) 0.05 Charge control agent ( ExEL-1) 1.0 In addition to the above composition, a gelatin hardening agent ExGK2 and a surfactant were added to each layer.

Same as Photosensitive Material 5-1, except that magenta coupler ExMC of E4 to E5 layers was changed as shown in Table 8 and Comparative Photosensitive Material 5 was used.
-2-4 and photographic materials 5-5-9 of the present invention were prepared.

ExMC-2 to 4 are the same as the compound of Example 4.

The magenta coupler of the present invention is represented by the above-mentioned exemplary compound numbers.

The color temperature of the light-sensitive materials 5-1 to 9 thus obtained is 32
Each image was exposed for 1/10 seconds at a light intensity of 1000 CMS at 00K and then subjected to processing steps C'and D'to directly obtain a positive image. Process steps C'and D'are 1.3 times longer than the color development times of process steps C and D of Example 4, respectively.

The magenta minimum density of the obtained direct positive image was measured, and the results are shown in Table 9.

The treatment step C ′ using the magenta coupler of the present invention is
The image density is obviously small in any of D ',
Further, the effect is remarkable in the processing step C which is a more rapid processing.

In addition, the maximum concentration is not particularly different between Examples and Comparative Examples,
Both were sufficient values.

Example 6 Similar to Example 5, except that E1 layer, E2 layer, E4 layer, E5 layer
A light-sensitive material 6-1 was prepared by removing the nucleation accelerator (ExZS-1) and the nucleating agent (ExZK-1) from the layers, E9 layer and E10 layer, and using 180 μm thick polyethylene terephthalate as a support. .

Further, as in Example 5, only the magenta coupler was changed to prepare photosensitive materials 6-2 to 6-4 of comparative examples and photosensitive materials 6-5 to 9 of the invention.

After exposing these light-sensitive materials 6-1 to 9 in the same manner as in Example 5, the subsequent processing step E and the pH of the color developing solution were 10.3.
Process step F was changed from 1 to 11.0.

The pH was adjusted with potassium hydroxide or hydrochloric acid.

The pH was adjusted with aqueous ammonia or hydrochloric acid.

The pH was adjusted with potassium hydroxide or hydrochloric acid.

Similar to Example 5, the light-sensitive materials 6-5 to 9 of the present invention had lower minimum densities in both the processing steps E and F as compared with Comparative Examples 6-1 to 4.

Examples 7 and 8 As in Example 4, except that the latex particles of polymethylmethacrylate were removed from the E15 layer, and the B1 layer was added.
And photographic materials having no B2 layer at all were prepared on the supports shown in Table 10 to produce photographic materials 7-1 to 9 and 8-1 respectively.
9 to 9-1 to 9. These were exposed and processed in the same manner as in Example 4.

Similar to Example 4, the light-sensitive materials 7-5 to 9 and 8-5 to 9 of the present invention had low minimum image density in both the processing steps C and D.

(Effect of the invention) When the light-sensitive material of the present invention is used, an internal latent image type silver halide light-sensitive material which has not been fogged in advance is rapidly processed in the presence of a nucleating agent or under light-fog processing, resulting in a very low level. A direct positive color image having the minimum image density can be stably obtained.

Further, the light-sensitive material of the present invention can be developed even with a color developing solution having a low pH value. Therefore, when a low pH developing solution is used, the developing solution is less susceptible to air oxidation and the performance is stable.

 ─────────────────────────────────────────────────── ─── Continuation of front page (56) Reference JP-A-60-112034 (JP, A) JP-A-58-178345 (JP, A) JP-A-59-77436 (JP, A) JP-A-58- 120248 (JP, A) JP 60-197688 (JP, A) JP 61-141447 (JP, A) JP 61-50136 (JP, A) JP 60-11837 (JP, A) Japanese Patent Sho 58-14665 (JP, B1)

Claims (2)

[Claims] 1. A core / shell type silver halide grain which is not previously fogged and which has an internal latent image type and whose shell portion is gold-sensitized, and a compound group represented by the following general formula [I]. After imagewise exposure of a light-sensitive material having at least one photographic emulsion layer containing at least one pyrazoloazole-based magenta coupler on a support, after fog treatment with light and / or a nucleating agent, and And / or a direct positive color image forming method characterized by performing development treatment with a surface color developing solution having a pH of 10.0 to 11.0 while applying. General formula [I] (In the formula, R ₁ represents a hydrogen atom or a substituent, and X represents a hydrogen atom or a group capable of splitting off by a coupling reaction with an oxidized product of an aromatic primary amine developer. Za, Zb and Zc.
Represents methine, substituted methine, = N- or -NH-,
One of the Za-Zb bond and the Zb-Zc bond is a double bond, and the other is a single bond. When Zb-Zc is a carbon-carbon double bond, it includes the case where it is part of an aromatic ring. Furthermore, the case where R ₁ or X forms a dimer or higher multimer is also included. Also, Za, Zb or Zc
Is a substituted methine, it also includes the case where the substituted methine forms a dimer or higher multimer. ) 2. The nucleating agent is at least one compound selected from the group of compounds represented by the following general formulas [NI] and [N-II]. The direct positive color image forming method described. General formula [NI] (In the formula, Z represents a non-metal atom group necessary for forming a 5- to 6-membered heterocycle, Z may be substituted with a substituent, R ¹ is an aliphatic group, and R ² is A hydrogen atom, an aliphatic group or an aromatic group, R ¹ and R ² may be substituted with a substituent, provided that, among the groups represented by R ¹ , R ² and Z,
At least one contains an alkynyl group, an acyl group, a hydrazine group or a hydrazone group, or R ¹ and R ² are 6
It forms a member ring and forms a dihydropyridinium skeleton.
Further, at least one of the substituents of R ¹ , R ² and Z is X ¹
It may have L ¹ _m . Here, X ¹ is an adsorption promoting group to silver halide, and L ¹ is a divalent linking group. Y is a counter ion for charge balance, n is 0 or 1, and m is 0 or 1. ) General formula [N-II] (In the formula, R ²¹ represents an aliphatic group, an aromatic group, or a heterocyclic group, and R ²² represents a hydrogen atom, an alkyl group, an aralkyl group,
Represents an aryl group, an alkoxy group, an aryloxy group, or an amino group, and G represents a carbonyl group, a sulfonyl group, a sulfoxy group, a phosphoryl group, or an iminomethylene group (HN
= C), and R ²³ and R ²⁴ are both hydrogen atoms, or one is a hydrogen atom and the other is an alkylsulfonyl group, an arylsulfonyl group or an acyl group. However, a hydrazone structure (NN = C) may be formed in a form including G, R ²³ , R ²⁴ and hydrazine nitrogen. Further, the above-mentioned groups may be substituted with a substituent, if possible. )