JPH0690439B2 - Direct positive color photographic light-sensitive material - Google Patents

Description

The present invention relates to a silver halide photographic light-sensitive material, and more particularly to a photographic light-sensitive material that directly forms a positive color image.

[Conventional technology]

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 fog-fogged silver halide emulsion in advance, and directly develops a positive image after development by destroying fog nuclei (latent image) in the exposed area by utilizing solarization or the Herschel effect. I will get it.

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

Further, the above-mentioned internal latent image type silver halide photographic emulsion is a type of silver halide photographic in which a silver halide grain has a photosensitive nucleus mainly inside and a latent image is mainly formed inside the grain upon exposure. An emulsion.

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

Various techniques have been known so far in this technical field. For example, U.S. Patent Nos. 2,592,250 and 2,466,9
No. 57, No. 2,497,875, No. 2,588,982, No. 3,317,
No. 322 (No. 2,497,875), No. 3,761,266, No. 3,761,2
No. 76, No. 3,796,577 and British Patent No. 1,151,363,
The main ones are those described in No. 1,150,553 (No. 1,011,062) and 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 Theory of The Photogra, TH Themes, The Theory of the Photograph Process
phic Process), 4th edition, Chapter 7, pages 182 to 193, and US Pat. No. 3,761,276.

That is, the fog nuclei are selectively generated only on the surface of the unexposed silver halide grains 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.
Are considered 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
No.) and a nucleating agent called "chemical fogging" (nucleati
ng agent) is known. This latter method is described, for example, in Research Disclosure, Vol. 151, No. 15162 (1976).
(Published in November, 2002), pages 72-87.

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 the presence of the nucleating agent, there is a problem that the maximum image density is not constant and the color reproduction is unstable because it is easily affected by changes in the temperature and pH of the developing solution that occur during running processing.

On the other hand, in the case of the optical fogging method, the pH is higher than that of the chemical fogging method.
Although conditions are not required and it is relatively advantageous in practice, it is still susceptible to temperature and pH fluctuations in the developer, and it is difficult to obtain a certain level of performance.

In particular, the minimum density portion in the light-sensitive material using a direct positive emulsion, which corresponds to the "fog portion" of a normal negative emulsion, is affected by the temperature and pH of the developer and the fluctuation of the light amount of fog, wavelength, etc. It is easy and difficult to obtain a constant low minimum concentration.

Therefore, it is an object of the present invention to process an internal latent image type silver halide light-sensitive material which has not been previously fogged, with a color developing solution having a low pH so as to obtain a high maximum density and a low minimum image density especially for cyan color development. Another object of the present invention is to provide a photographic light-sensitive material capable of directly and positively forming a positive color image.

Another object of the present invention is to provide a photographic light-sensitive material which forms a direct positive color image having low re-reversal negative sensitivity even when the light-sensitive material is stored under high temperature and high humidity.

[Means for solving problems]

The above-mentioned object of the present invention is a direct positive color photographic light-sensitive material having at least one pre-fogged internal latent image type silver halide emulsion layer on a support, wherein the photographic light-sensitive material has the following general formula (C -I) containing at least one cyan coupler and having the following general formula (N-
A direct positive color photographic light-sensitive material characterized by containing at least one nucleating agent represented by I).

General formula (C-I) (In the formula, R ₁ represents an aliphatic group, an aromatic group, a heterocyclic group, an aromatic amino group or a heterocyclic amino group, and R ₂ has 2 to 20 carbon atoms.
Represents an aliphatic group, R ₃ represents a hydrogen atom, a halogen atom, an aliphatic group, an aliphatic oxy group, or an acylamino group, and Y ₁ represents a hydrogen atom or is removable during a coupling reaction with an oxidized product of a developing agent. Represents a group.

Alternatively, R ₁ , R ₂ , R ₃ or Y ₁ may form a dimer or higher multimer. ) General formula (NI) (In the formula, Z ¹ represents a non-metal atom group necessary for forming a 5- or 6-membered heterocycle. This heterocycle may be further condensed with an aromatic ring or a heterocycle. R ¹ is a fat X is a group group
Is Is. Q represents a 4- to 12-membered non-aromatic hydrocarbon ring or a non-metal atom group necessary for forming a non-aromatic heterocycle. However, at least one of the substituents of R ¹ and Z ^{1 and} the substituent of Q includes an alkynyl group. Further, at least one of R ¹ , Z ¹ and Q may have an adsorption promoting group for silver halide. Y is a counter ion for charge balance, and n is the number required for charge balance. The cyan coupler represented by formula (CI) of the present invention is known from JP-A-60-232550 and U.S. Pat. No. 3,772,002.

In the above formula, R ₁ represents an aliphatic group, an aromatic group, a heterocyclic group, an aromatic amino group or a heterocyclic amino group, and R ₂ has 2 to 2 carbon atoms.
Represents an aliphatic group of 20, R ₃ is a hydrogen atom, a halogen atom,
It represents an aliphatic group, an aliphatic oxy group, or an acylamino group, and Y ₁ represents a hydrogen atom or a group capable of splitting off during a coupling reaction with an oxidized product of a developing agent (hereinafter abbreviated as splitting group).

Further, R ₁ , R ₂ , R ₃ or Y ₁ may form a dimer or higher multimer.

The aliphatic group mentioned here represents a linear, branched or cyclic alkyl, alkenyl or alkynyl group, and these groups may be further substituted.

R _{1 to} R ₃ and Y ₁ in formula (CI) will be described in detail below.

In the general formula (CI), when Y ₁ represents a coupling-off group (hereinafter referred to as a leaving group), the leaving group is an aliphatic group which is bonded to the activated carbon for coupling via oxygen, nitrogen, sulfur or carbon atom. Group, aromatic group, heterocyclic group,
An aliphatic / aromatic or heterocyclic sulfonyl group, an aliphatic / aromatic or heterocyclic carbonyl group; or a halogen atom, an aromatic azo group, etc., and an aliphatic, aromatic or heterocyclic group contained in these leaving groups. The ring group is R ₁ (described later)
May be substituted with a substituent such as those described above under, and when these substituents are two or more, they may be the same or different, and these substituents may further have a substituent as described for R _1. You may have.

Specific examples of the coupling-off group include a halogen atom (eg, fluorine atom, chlorine atom, bromine atom), an alkoxy group (eg, ethoxy group, dodecyloxy group, methoxyethylcarbamoylmethoxy group, carboxypropyloxy group, methylsulfonyl group). Ethoxy group), aryloxy group (eg 4-chlorophenoxy group, 4-methoxyphenoxy group, 4-carboxyphenoxy group etc.), acyloxy group (eg acetoxy group, tetradecanoyloxy group, benzoyloxy) Group), an aliphatic or aromatic sulfonyloxy group (eg, methanesulfonyloxy group, toluenesulfonyloxy group, etc.),
Acylamino group (eg, dichloroacetylamino group, heptafluorobutyrylamino group, etc.), aliphatic or aromatic sulfonamide group (eg, methanesulfonamino group, P-toluenesulfonylamino group, etc.), alkoxycarbonyloxy group (eg, ethoxy) Carbonyloxy group, benzyloxycarbonyloxy group etc.), aryloxycarbonyloxy group (eg phenoxycarbonyloxy group etc.), aliphatic, aromatic or heterocyclic thio group (eg ethylthio group, phenylthio group, tetrazolylthio group etc.) A carbamoylamino group (eg N
-Methylcarbamoylamino group, N-phenylcarbamoylamino group, etc.) 5-membered or 6-membered nitrogen-containing heterocyclic group (for example, imidazolyl group, pyrazolyl group, triazolyl group, tetrazolyl group, 1,2-dihydro-2-oxo) -1-pyridyl group etc.), imide group (eg succinimide group, hydantoinyl group etc.), aromatic azo group (eg phenylazo group etc.) and the like. Further, there is a bis-type coupler obtained by condensing a 4-equivalent coupler with an aldehyde or a ketone as a leaving group bonded via a carbon atom. The leaving group of the present invention may contain a photographically useful group such as a development inhibitor and a development accelerator.

In the general formula (CI), R ₁ preferably has 1 to 1 carbon atoms.
36 aliphatic groups, preferably aromatic groups having 6 to 36 carbon atoms,
(For example, phenyl group, naphthyl group, etc.), heterocyclic group (for example, 3-pyridyl group, 2-furyl group, etc.), or
Aromatic or heterocyclic amino groups (eg, anilino groups,
Naphthylamino group, 2-benzothiazolylamino group, 2
-Pyridylamino group), and these groups further include an alkyl group, an aryl group, a heterocyclic group, an alkoxy group (for example, a methoxy group, a 2-methoxyethoxy group, etc.), an aryloxy group (for example, 2,4). -Di-tert-amylphenoxy group, 2-chlorophenoxy group, 4-cyanophenoxy group, etc.), alkenyloxy group (for example,
2-propenyloxy group etc.), acyl group (eg acetyl group, benzoyl group etc.), ester group (eg
Butoxycarbonyl group, phenoxycarbonyl group, acetoxy group, benzoyloxy group, butoxysulfonyl group, toluenesulfonyloxy group, etc.), amide group (for example, acetylamino group, ethylcarbamoyl group, dimethylcarbamoyl group, methanesulfonamide group, Butylsulfamoyl group), sulfamide group (eg, dipropylsulfamoylamino group), imide group (eg, succinimide group, hydantoinyl group, etc.), ureido group (eg, phenylureido group, dimethylureido group, etc.), fat Group or aromatic sulfonyl group (eg, methanesulfonyl group, phenylsulfonyl group, etc.), aliphatic or aromatic thio group (eg, ethylthio group, phenylthio group, etc.), hydroxy group, cyano group, carboxy group, nitro , A sulfo group, may be substituted with a group selected from a halogen atom.

Typical examples of the aliphatic group include methyl group, ethyl group, butyl group, dodecyl group, octadecyl group, eicosenyl group,
iso-propyl group, tert-butyl group, tert-octyl group, tert-dodecyl group, cyclohexyl group, cyclopentyl group, allyl group, vinyl group, 2-hexadecenyl group,
There are propargyl groups, etc. These may be substituted with the substituents described above.

In the general formula (CI), R ₃ is a hydrogen atom, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, etc.),
It preferably represents an aliphatic group having 1 to 20 carbon atoms, preferably an aliphatic oxy group having 1 to 20 carbon atoms, or an acylamino group having 1 to 20 carbon atoms (for example, acetamide group, benzamide group, tetradecanamide group, etc.). , These aliphatic groups,
The aliphatic oxy group and the acylamino group may be substituted with the substituents described for R ₁ .

In the general formula (CI), a dimer or higher multimeric coupler may be formed independently or jointly by any one group of R ₁ , R ₂ , R _{3 and} Y ₁ . Good. When it is a dimer,
These groups are simple bonds or divalent linking groups (for example, divalent groups such as alkylene groups, arylene groups, ether groups, ester groups, amide groups, etc., and divalent groups combining these). When forming an oligomer or polymer, it is preferred that those groups are the polymer backbone or are attached to the polymer backbone through divalent groups such as those mentioned for dimers. When forming a polymer, even if it is a homopolymer of a coupler derivative, another non-color-forming ethylene-like monomer (for example, acrylic acid, methacrylic acid, methyl acrylate n-butyl acrylamide, β-
Hydroxymethacrylate, vinyl acetate, acrylonitrile, styrene, crotonic acid, maleic anhydride,
(N-vinylpyrrolidone, etc.), and one or more of them may form a copolymer.

In formula (C-I), preferred R ₁ is a substituted or unsubstituted alkyl group or aryl group, and the substituent of the alkyl group is preferably an optionally substituted phenoxy group or a halogen atom (phenoxy). As the substituent of the group, an alkyl group, an alkoxy group, a halogen atom,
A sulfonamide group and a sulfamide group are more preferable),
The aryl group is particularly preferably a phenyl group substituted with at least one halogen atom, an alkyl group, a sulfonamide group or an acylamino group.

In the general formula (CI), preferred R ₂ is an optionally substituted alkyl group having 2 to 20 carbon atoms. The substituent of R ₂ is preferably an alkyl or aryloxy group, an acylamino group, an alkyl or arylthio group, an imide group, a ureido group, an alkyl or arylsulfonyl group.

In formula (CI), R ₃ is preferably a hydrogen atom, a halogen atom (particularly a fluorine atom or a chlorine atom) or an acylamino group, and particularly preferably a halogen atom.

In formula (CI), R ₂ is more preferably an alkyl group having 2 to 4 carbon atoms.

In formula (CI), Y ₁ is preferably a halogen atom, more preferably a chlorine atom.

The couplers represented by the general formula (CI) can be used alone or as a mixture of a plurality of couplers. Further, it can be used in combination with a cyan coupler other than the cyan coupler represented by the general formula (CI) of the present invention.

The cyan coupler of the present invention is preferably based on 1 mol of silver.
Used in an amount of 0.02 to 0.5 mol.

Specific examples of the non-diffusing cyan coupler represented by formula (CI) of the present invention are shown below, but the present invention is not limited thereto.

Next, the nucleating agent represented by the general formula (NI) will be described in more detail. The heterocycle completed with Z ¹ is, for example, quinolinium, benzimidazolium, pyridinium,
Examples include thiazolium, selenazolium, imidazolium, tetrazolium, indolenium, pyrrolinium, acridinium, phenanthridinium, isoquinolinium, and naphthopyridinium nuclei. Z ¹ may be substituted, and as the substituent, an alkyl group, an alkenyl group, an aralkyl group, an aryl group, an alkynyl group, a hydroxy group, an alkoxy group, an aryloxy group, a halogen atom, an amino group, an alkylthio group, An arylthio group,
Acyloxy group, acylamino group, sulfonyl group, sulfonyloxy group, sulfonylamino group, carboxyl group, acyl group, carbamoyl group, sulfamoyl group, sulfo group, cyano group, ureido group, urethane group, carbonic acid ester group, hydrazine group, hydrazone group , Or imino group. As the substituent of Z ¹ , 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 ¹ via a suitable linking group L ¹ as a substituent of Z ¹ . In this case, a so-called dimer structure is adopted.

The heterocyclic bone nucleus completed with Z ¹ is preferably a quinolinium, benzimidazolium, pyridinium, acridinium, phenanthridinium, naphthopyridinium or isoquinolinium nucleus. More preferably,
It is a quinolinium, naphthopyridinium or benzimidazolium nucleus, most preferably a quinolinium nucleus.

The aliphatic group represented by R ¹ is preferably 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. Examples of the substituent include those described as the substituent for Z ¹ .

R ¹ is preferably an alkynyl group, and most preferably a propargyl group.

Q is a group of atoms necessary for forming a 4- to 12-membered non-aromatic hydrocarbon ring or non-aromatic heterocycle. These rings are Z ¹
It may be further substituted with the group described for the substituent.

As the non-aromatic hydrocarbon ring, when X is a carbon atom, examples thereof include rings such as cyclopentane, cyclohexane, cyclohexene, cycloheptane, indane and tetralin.

The non-aromatic heterocycle includes nitrogen, oxygen, sulfur, selenium and the like as a hetero atom, and is, for example, X
When is a carbon atom, examples thereof include rings such as tetrahydrofuran, tetrahydropyran, butyrolactone, pyrrolidone, and tetrahydrothiophene. When X is a nitrogen atom, examples thereof include rings such as pyrrolidine, piperidine, pyridone, piperazine, perhydrothiazine, tetrahydroquinoline and indoline.

Preferred as the ring nucleus formed by Q is when X is a carbon atom, particularly cyclopentane, cyclohexane,
Cycloheptane, cyclohexene, indane, tetrahydropyran, tetrahydrothiophene and the like.

As the alkynyl group to which at least one of the substituents of R ¹ and Z ^{1 and} the substituent of Q corresponds, some have already been described so far, but when explained in more detail, preferably, the number of carbon atoms is 2 to There are 18 groups such as ethynyl group, propargyl group, 2-butynyl group, 1-methylpropargyl group, 1,1-dimethylpropargyl group, 3-butynyl group and 4-pentynyl group.

Further, these may be substituted with the groups described as the substituent for Z ¹ .

The alkynyl group is preferably a propargyl group, and most preferably R ¹ is a propargyl group.

As the adsorption promoting group to silver halide which the substituents of R ¹ , Q and Z ¹ may have, those represented by X ¹ L ¹ _m are preferable.

Here, X ¹ is an adsorption promoting group to silver halide, and L ¹ is a divalent linking group. m is 0 or 1. Preferred examples of the adsorption promoting group for silver halide represented by X ¹ include
Examples thereof include a thioamide group, a mercapto group and a 5- or 6-membered nitrogen-containing heterocyclic group.

These may be substituted with those mentioned as the substituent of Z ¹ . The thioamide group is preferably an acyclic thioamide group (eg, thiourethane group, thioureido group, etc.)
Is.

As the mercapto group of X ¹ , particularly a heterocyclic mercapto group (for example, 5-mercaptotetrazole, 3-mercapto-1,2,4-triazole), 2-mercapto 1,3,4-thiadiazole, 2-mercapto-1, 3,4-oxadiazole) is preferred.

The 5- or 6-membered nitrogen-containing heterocycle represented by X ¹ is
It is composed of a combination of nitrogen, oxygen, sulfur and carbon, and preferably forms imino silver, and examples thereof include benzotriazole and aminothiatriazole.

Examples of the divalent linking group represented by L ¹ include C, N, S and O.
An atom or atomic group containing at least one of the above. Specifically, for example, an alkylene group, an alkenylene group, an alkynylene group, an arylene group —O—, —S—, —NH—, —
N =, —CO—, —SO ₁ — (these groups may have a substituent), etc., or a combination thereof.

Are preferred.

Examples of the counter ion Y for charge balance include, for example, bromine ion, chlorine ion, iodoodor ion, p-toluenesulfonate ion, ethylsulfonate ion, perchlorate ion, trifluoromethanesulfonate ion, thiocyanate BF ₇ ^- ion, PF ₆ ^- such as an ion, and the like.

Of the compounds represented by the general formula (N-I), those having an adsorption promoting group on silver halide are preferable, and particularly, the adsorption promoting group X ¹ is a thioamide group, an azole group or a heterocyclic mercapto group. The case is more preferable.

Examples of these compounds and their synthesis methods are described in, for example, Japanese Patent Application No.
-17,984 and the patents or documents cited therein.

Specific examples of the compound represented by formula (N-I) are shown below, but the invention is not limited thereto.

In the present invention, when the compound represented by the general formula (N-I) is contained in the photographic light-sensitive material, alcohols (eg methanol, ethanol), esters (eg ethyl acetate), ketones (eg acetone) are included. It may be added to the hydrophilic colloid solution as a solution of an organic solvent miscible with water, or when the compound is water-soluble, as an aqueous solution.

When it is added to the photographic emulsion, it may be added at any time from the start of chemical ripening to before coating, but it is preferably added after the completion of chemical ripening.

In the present invention, the nucleating agent represented by the general formula (N-I) may be contained in the hydrophilic colloid layer adjacent to the silver halide emulsion layer, but is contained in the silver halide emulsion layer. preferable. The amount added varies depending on the characteristics of the silver halide emulsion actually used, the chemical structure of the nucleating agent and the developing conditions, and therefore can vary over a wide range. About 1 × 10 ^-8 mol to about 1
A range of x10 ^-2 moles is practically useful, with about 1 x 10 ^-7 moles to about 1 x 10 ^-3 moles per mole silver being preferred.

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 silver halide mainly forming a latent image inside the grains. But more specifically,
A certain amount of silver halide emulsion (0.5-3 g /
m ² ) applied, exposed to light for a fixed time of 0.01 to 10 seconds, and developed in the following developer A (internal type developer) at 18 ° C. for 5 minutes. The maximum density measured in this manner was the same as the above, and the silver halide emulsion exposed in the same manner was developed with the following developing solution B (surface type developing solution).
The maximum density obtained when developed at 20 ° C for 6 minutes in
Those having a concentration of at least 5 times greater are preferred, and more preferably those having a concentration of at least 10 times greater.

Internal developer A Metol 2g sodium sulfite (anhydrous) 90 g Hydroquinone 8g sodium carbonate (monohydrate) 52.5 g KBr 5 g KI 0.5 g Water to make 1 internal developer B Metol 2.5 g L-ascorbic acid 10g NaBO ₂ · 4H ₂ O 35g KBr 1g Water is added 1 Specific examples of the latent latent emulsion include US Pat. No. 2,592,
Convergence type silver halide emulsions described in the specification of No. 250, U.S. Pat.Nos. 3,761,276 and 3,850,637,
3,923,513, 4,035,185, 4,395,478, 4,5
04,570, JP-A-52-156614, 55-127549, 53
-60222, 56-22681, 59-208540, 60-10
7641, 61-3137, Japanese Patent Application No. 61-32462, Research Disclosure Magazine No. 23510 (issued in November 1983) P236
The core / shell type silver halide emulsions described in the patents disclosed in US Pat.

The silver halide grains used in the present invention have a regular crystal form such as a cube, an octahedron, a dodecahedron and a tetradecahedron, an irregular crystal form such as a sphere, and a length / length of Tabular grains having a thickness ratio of 5 or more may be used. Further, it may be an emulsion having a composite form of these various crystal forms, or an emulsion composed of a mixture thereof.

The composition of silver halide includes silver chloride and silver bromide mixed silver halide. The silver halide preferably used in the present invention does not contain silver iodide or contains 3 mol% or less of salt (iodine). It is silver bromide, (iodo) silver chloride or (iodo) silver bromide.

The average grain size of silver halide grains is less than 2 μm.
1 μm or more is preferable, but 1 μm or less is particularly preferable.
It is 0.15 μm or more. The particle size distribution may be narrow or wide, but within the range of ± 40% of the average particle size, preferably ± 20% or less of the average particle size in terms of number of particles or weight in order to improve graininess and sharpness. So-called "monodisperse" silver halide emulsions with a narrow grain size distribution of 90% or more are preferably used in the present invention. In order to satisfy the target gradation of the light-sensitive material, two or more kinds of monodispersed silver halide emulsions having different grain sizes or a plurality of emulsions having the same size but different sensitivities are used in the emulsion layers having substantially the same color sensitivity. The particles 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 emulsion used in the present invention can be chemically sensitized inside or on the surface of the grain by sulfur or selenium sensitization, reduction sensitization, noble metal sensitization or the like alone or in combination. Specific examples are described in the patents described in Research Disclosure Magazine No. 17643-III (published in December 1978) P23 and the like.

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. Specific examples are described in the patents described in, for example, Research Disclosure magazine No. 17643-IV (published in December 1978) P23 to 24.

The photographic emulsion used in the present invention may contain an antifoggant or stabilizer for the purpose of preventing fog during the production process of a light-sensitive material, storage or photographic processing, or stabilizing photographic performance. For more detailed examples, see Research Disclosure No. 17643-VI (19
Published in December 1978) and "Stabiilzation of EJB Jirr"
Photographic Silver Halaide Emulsion "(Focal Pres
s), 1974, etc.

In the present invention, various color couplers can be used in addition to the cyan coupler to form a positive color image directly. A color coupler is a compound that produces or releases a substantially non-diffusible dye by a coupling reaction with an oxidation product of an aromatic primary amine color developing agent,
It is preferably a compound which is itself substantially non-diffusible. Typical examples of useful color couplers are naphthol or phenol compounds, pyrazolone or pyrazoloazole compounds and open chain or heterocyclic ketomethylene compounds. Specific examples of these cyan, magenta and yellow couplers that can be used in the present invention are No.17643 (published in December 1978), P25, VII-D, No. 18717 (1979) of "Research Disclosure". Published in November) and Japanese Patent Application No. 61-32462 and the patents cited therein.

Among them, as the yellow coupler which can be used in the present invention, the oxygen atom-releasing type and nitrogen atom-releasing type yellow two-equivalent couplers can be mentioned as typical examples. In particular, the α-pivaloylacetanilide type coupler is excellent in the fastness, especially the light fastness, of the color forming dye, while the α-benzoylacetanilide type coupler is preferable because a high coloring density can be obtained.

The 5-pyrazolone-based magenta coupler that can be preferably used in the present invention is a 5-pyrazolone-based coupler in which the 3-position is substituted with an arylamino group or an acylamino group (among others, a sulfur atom-eliminating type two-equivalent coupler).

More preferable are pyrazoloazole couplers, and among them, pyrazolo [5,1-c] [1,2,4] triazoles described in U.S. Pat.No. 3,725,067 are preferable,
The imidazo [1,2-b] described in U.S. Pat. No. 4,500,630 in terms of low yellow sub-absorption of a coloring dye and light fastness.
Pyrazoles have always been so preferred, U.S. Pat. No. 4,540,65
The pyrazolo [1,5-b] [1,2,4] triazole described in No. 4 is particularly preferable.

Colored couplers for correcting unnecessary absorption in the short wavelength range of the dyes formed, couplers with a suitable diffusibility of color forming dyes, colorless couplers, DIR couplers and polymers that release development inhibitors with the coupling reaction. Modified couplers can also be used.

The standard amount of color coupler used is in the range of 0.001 to 1 mol per mol of light-sensitive silver halide, preferably 0.01 to 0.5 mol for yellow coupler, 0.03 to 0.5 mol for magenta coupler, and cyan coupler. Is 0.002 to 0.5 mol.

In the present invention, a color forming enhancer can be used for the purpose of improving the color forming property of the coupler. Typical examples of compounds are JP-A-62-62.
No. 215272, pp. 374-391.

The coupler used in 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 ultrasonic wave. Is emulsified and dispersed by a technique utilizing, and this is added to the emulsion layer. In this case, the high-boiling organic solvent is not necessarily used, but JP-A-62-215272, 440-4
It is preferable to use the compounds described on page 67.

The coupler of the present invention can be dispersed in a hydrophilic colloid by the method described in JP-A-62-215272, pages 468 to 475.

The light-sensitive material produced by using the present invention, as a color antifoggant or color mixing inhibitor, is a hydroquinone derivative, an aminophenol derivative, an amine, a gallic acid derivative, a catechol derivative, an ascorbic acid derivative, a colorless coupler, a sulfonamide phenol. You may contain a derivative etc. Representative examples of color fog preventing agents and color mixing preventing agents are JP-A-62-62.
-215272, pp. 600-63.

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 examples 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. As. Further, a metal complex represented by (bissalicylaldoximato) nickel complex and (bis-N, N-dialkyldithiocarbamato) nickel complex can also be used.

In order to prevent the deterioration of the yellow dye image due to heat, temperature and light, a compound having both a hindered amine and a hindered phenol partial structure in the same molecule as described in US Pat. No. 4,268,593 gives good results. Further, in order to prevent the deterioration of the magenta dye image, especially the deterioration by light, a spiroindane described in JP-A-56-159644 and a hydroquinone diether or a monoether described in JP-A-55-89835 are substituted. Chromans give favorable results.

Typical examples of these anti-fading agents are JP-A-62-215272, 401.
~ Page 440. 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. Representative examples of the compounds are described in JP-A No. 62-215272, pp. 391-400.

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.

The light-sensitive material of the present invention includes dyes for preventing irradiation and halation, ultraviolet absorbers, plasticizers, fluorescent brighteners, matting agents, air fog preventing agents, coating aids, hardeners,
An antistatic agent, a slipperiness improving agent, etc. can be added.
Typical examples of these additives are Research Disclosure No. 17643 VII to XIII pages (published in December 1978) P25 to 2
7 and 18716 (issued in November 1979) p647-651.

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 green-sensitive, red-sensitive and blue-sensitive from the support side.
Further, 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 color 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 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 the development.

Hydroquinones (eg US Pat. No. 3,227,552,
Compounds described in 4,279,987); chromanes (for example, U.S. Pat. No. 4,268,621, JP-A-54-103031, Research
Dice Closure Magazine, No.18264 (Published June 1979) 33
Compounds described on pages 3-334; quinones (eg, research
Dice Closure Magazine, No.21206 (December 1981) 433-4
Compounds described on page 34); amines (eg, US Pat. No. 4,15)
0,993 and compounds described in JP-A-58-174757); oxidants (for example, JP-A-60-260039, Research Disclosure Magazine, No. 16936 (issued in May 1978), pages 10 to 11) Compound); catechols (for example, JP-A-55-2101)
Nos. 3 and 55-65944); compounds that release nucleating agents during development (for example, compounds described in JP-A-60-1007029); thioureas (for example, compounds described in JP-A-60-95533). Compound); spirobisindanes (for example, JP-A-55)
-65944 described compound).

The light-sensitive material according to the present invention, in addition to the silver halide emulsion layer,
Protective layer, intermediate layer, filter layer, anti-halation agent,
It is preferable to appropriately provide an auxiliary layer 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 Research Disclosure No. 17643XVII (1978).
Issued December, 2012) Those described in p28 and European patents 0,182,2
It is coated on a support described in JP-A No. 53-63655 / 1986. Research Disclosure Magazine No. 17643XV
The coating method described in p28 to 29 can be used.

The present invention can be applied to various color light-sensitive materials.

Representative examples include color reversal films for slides or televisions, color reversal papers, and instant color films. It can also be applied to full-color copiers and color hard copies for storing CRT images. The present invention also provides
It can also be applied to a black and white light-sensitive material using a three-color coupler mixture described in "Research Disclosure" magazine No. 17123 (issued in July 1978).

The nucleation accelerator for promoting the action of the nucleating agent has at least one mercapto group optionally substituted with an alkali metal atom or an ammonium group, tetrazaindenes, triazaindenes Further, pentazaindenes and the compounds described in Japanese Patent Application No. 61-136948 (pages 2 to 6 and 16 to 43) and Japanese Patent Application No. 61-136949 (pages 12 to 43) can be added.

Specific examples of the nucleating agent will be given below.

(A-1) 3-mercapto-1,2,4-triazolo [4,5-
a] Pyridine (A-2) 3-mercapto-1,2,4-triazolo [4,5-
a] Pyrimidine (A-3) 5-mercapto-1,2,4-triazolo [1,5-
a] pyrimidine (A-4) 7- (2-dimethylaminoethyl) -5-mercapto-1,2,4-triazolo [1,5-a] pyrimidine (A-5) 3-mercapto-7-methyl- 1,2,4-triazolo [4,5-a] pyrimidine (A-6) 3,6-dimercapto-1,2,4-triazolo [4,
5-b] pyridazine (A-7) 2-mercapto-5-methylthio-1,3,4-
Thiadiazole (A-8) 3-Mercapto-4-methyl-1,2,4-triazole (A-9) 2- (3-Dimethylaminopropylthio)-
5-Mercapto-1,3,4-thiadiazole hydrochloride (A-10) 2- (2-morpholinoethylthio) -5-mercapto-1,3,4-thiadiazole hydrochloride (A-11) 2-mercapto- 5-Methylthiomethylthio-1,3,4-thiadiazole sodium salt (A-12) 4- (2-morpholinoethyl) -3-mercapto-1,2,4-triazole (A-13) 2- [2- ( 2-Dimethylaminoethylthio) ethylthio] -5-mercapto-1,3,4-thiadiazole hydrochloride (A-14) 2- (6-dimethylaminohexylthio)-
5-Mercapto-1,3,4-thiadiazole hydrochloride (A-15) 2- {3- [2-methyl-1- (1,4,5,6-
Tetrahydropyrimidinyl)] propylthio} -5-mercapto-1,3,4-thiadiazole hydrochloride A nucleation accelerator can be contained in a light-sensitive material or a processing solution. It is preferably contained in a silver halide emulsion or other hydrophilic colloid layer (intermediate layer, protective layer, etc.). Particularly preferred is in a silver halide emulsion or a layer adjacent thereto.

The amount of nucleation accelerator added is 10 ^-6 to 10 per mol of silver halide.
^It is preferably ^-2 mol, more preferably 10 ^-5 to 10 ^-2 mol.

When the nucleation accelerator is added to the processing solution, that is, the developing solution or its pre-bath, the amount is preferably 10 ^-8 to 10 ^-3 mol, and more preferably 10 ^-7 to 10 ^-4 mol. .

Further, two or more nucleation accelerators can be used in combination.

The color developing solution used for the development processing of the light-sensitive material of the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine type color developing agent as a main component. Although aminophenol compounds are also useful as the color developing agent, p-phenylenediamine compounds are preferably used, and typical examples thereof include 3-methyl-4-amino-N, N-diethylaniline and 3 -Methyl-4-amino-N-ethyl-N-
β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-N-
Examples include β-methoxyethylaniline and their sulfates, hydrochlorides or p-toluenesulfonates. Two or more of these compounds can be used in combination depending on the purpose.

The pH of the color developing solution must be 11.5 or less, preferably 9.5 to 11.2.

The photographic emulsion layer after color development is usually bleached. The bleaching process may be performed simultaneously with the fixing process (bleach-fixing process), or may be performed individually. Further, in order to speed up the processing, a processing method of bleach-fixing processing after bleaching processing may be used. Further processing with two continuous bleach-fix baths,
The fixing treatment before the bleach-fixing treatment or the bleaching treatment after the bleach-fixing treatment can be optionally carried out according to the purpose.
Examples of bleaching agents include iron (III), cobalt (III),
Compounds of polyvalent metals such as chromium (VI) and copper (II), peracids, quinones, nitro compounds and the like are used. Typical bleaching agents include ferricyanide; dichromate; iron (II
I) or cobalt (III) organic complex salts such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3
-Aminopolycarboxylic acids such as diaminopropane tetraacetic acid and glycol ether diamine tetraacetic acid, or complex salts such as citric acid, tartaric acid and malic acid; persulfates; bromates; permanganates; nitrobenzenes and the like can be used. it can. Of these, aminopolycarboxylic acid iron (II) including ethylenediaminetetraacetic acid iron (III) complex salts
I) Complex salts and persulfates are preferable from the viewpoint of rapid processing and prevention of environmental pollution. Furthermore, iron (III) aminopolycarboxylate
Complex salts are particularly useful in both bleaching solutions and bleach-fixing solutions. The pH of the bleaching solution or bleach-fixing solution using these aminopolycarboxylic acid iron (III) complex salts is usually 5.5 to 8, but a lower pH can be used for speeding up the processing.

If necessary, a bleaching accelerator can be used in the bleaching solution, the bleach-fixing solution and their pre-bath. Specific examples of useful bleach accelerators are described in the following specifications: U.S. Pat. No. 3,893,858, West German Patent 1,290,812, JP-A-53-95.
630, Research Disclosure No. 17129 (197
Compounds having a mercapto group or a disulfide bond described in JP-A-58-16235; thiourea derivatives described in US Pat. No. 3,706,561; An iodide salt described in 1.
Polyoxyethylene compounds described in West German Patent No. 2,748,430; polyamine compounds described in JP-B-45-8836; bromide ion and the like can be used. Among them, a compound having a mercapto group or a disulfide group is preferable from the viewpoint of a large accelerating effect, and particularly, U.S. Patent 3,893,858, West German Patent No.
The compounds described in 1,290,812 and JP-A-53-95630 are preferred. 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. These bleaching accelerators are particularly effective when bleach-fixing a color light-sensitive material for photography.

Examples of the fixing agent include thiosulfates, thiocyanates, thioether compounds, thioureas, and large amounts of iodide salts, but thiosulfates are generally used, and ammonium thiosulfate is the most widely used. Can be used for As a preservative for the bleach-fix solution, sulfite, bisulfite or carbonyl bisulfite adduct is preferable.

The silver halide color photographic light-sensitive material of the present invention is generally washed with water and / or stabilized after the desilvering process.
The amount of rinsing water in the rinsing process depends on the characteristics of the photosensitive material (for example, depending on the materials used such as couplers), application, and further, the rinsing water temperature, the number of rinsing tanks (the number of stages), the replenishment system such as countercurrent and forward flow, and various other conditions Therefore, it can be set in a wide range. Of these, the relationship between the number of washing tanks and the water volume in the multi-stage countercurrent system is described in Jour.
nal of the Society of Motion Picture and Televisio
n Engineers Volume 64, P.248-253 (May 1955 issue).

The pH of washing water in the processing of the light-sensitive material of the present invention is 4 to 9
And preferably 5-8. The washing water temperature and washing time can be variously set depending on the characteristics of the light-sensitive material, application, etc., but generally 15 to 45 ° C. for 20 seconds to 10 minutes, preferably 25 to 40 ° C.
A range of seconds to 5 minutes is selected. Further, the light-sensitive material of the present invention can be directly processed with a stabilizing solution instead of the above washing with water. In such stabilization treatment, Japanese Patent Laid-Open No.
All known methods described in Nos. -8543, 58-14834, and 60-220345 can be used. Various chelating agents and antifungal agents can also be added to this stabilizing bath.

The silver halide color light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and accelerating the processing. For incorporation, it is preferable to use various precursors of color developing agents. For example, indaniline compounds described in U.S. Pat.No. 3,342,597, No. 3,342,599, Schiff base type compounds described in Research Disclosure 14850 and No. 15159, aldol compounds described in No. 13924, described in U.S. Pat. Metal salt complex of
The urethane type compounds described in 3-135628 can be mentioned.

The silver halide color light-sensitive material of the present invention contains various 1-phenyl-type light-sensitive materials for the purpose of promoting color development, if necessary.
You may incorporate 3-pyrazolidones. Typical compounds are JP-A-56-64339, JP-A-57-144547, and JP-A-58-1.
No. 15438 is listed.

The various treatment liquids in the present invention are used at 10 ° C to 50 ° C. Normally, a temperature of 33 ° C to 38 ° C is standard, but a higher temperature accelerates the processing to shorten the processing time, and a lower temperature lowers the image quality to improve the stability of the processing liquid. be able to. Further, in order to save silver in the light-sensitive material, processing using cobalt intensification or hydrogen peroxide intensification described in West German Patent No. 2,226,770 or US Pat. No. 3,674,499 may be performed.

It is preferable that the amount of replenishment in each processing step is small. The amount of the replenisher is preferably 0.1 to 50 times, more preferably 3 to 30 times the carry-in amount of the pre-bath per unit area of the light-sensitive material.

〔Example〕

Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited thereto.

Example 1 Paper support laminated on both sides with polyethylene (thickness 100
Micron) was coated on the front side with the following first to fourteenth layers, and on the back side with a multi-layer coating of the fifteenth to sixteenth layers to prepare a color photographic light-sensitive material. Titanium white is contained as a white pigment, and a trace amount of ultramarine is contained as a bluish dye on the coating side of the first layer of polyethylene.

(Photosensitive layer composition) The components and the coating amounts shown in g / m ² are shown below. For silver halide, the coating amount in terms of silver is shown. The emulsion used for each layer was produced according to the production method of Emulsion EM1. However, the first
As the four-layer emulsion, a Lipman emulsion without surface chemical sensitization was used.

1st layer (anti-halation layer) Black colloidal silver …… .0.10 Gelatin ………… 1.30 2nd layer (intermediate layer) Gelatin ・ ・ ・ 0.70 3rd layer (low sensitivity red sensitive layer) Red sensitizing dye (ExS- 1,2,3) spectrally sensitized silver bromide (average grain size 0.3μ, size distribution [variation coefficient] 8
%, Octahedron) ...... 0.06 Silver chlorobromide (5 mol% silver chloride, average grain size 0.45μ, size distribution) spectrally sensitized with red sensitizing dye (ExS-1,2,3)
10%, octahedron) …… 0.10 Gelatin …… 1.00 Cyan coupler (ExC-1) …… 0.23 Anti-fading agent (Cpd-2,3,4,13 equivalent) …… 0.12 Coupler dispersion medium ( Cpd-5) ……… 0.03 Coupler solvent (Solv-7,2,3 equivalent) ……… 0.04 4th layer (high-sensitivity red-sensitive layer) Spectral with red sensitizing dye (ExS-1,2,3) Sensitized silver bromide (average grain size 0.60μ, size distribution 15%, octahedron) ...
…… 0.14 Gelatin ………… 1.00 Cyan coupler (ExC-1) …… 0.32 Anti-fading agent (Cpd-2,3,4,13 equivalent) …… 0.15 Coupler dispersion medium (Cpd-5) ………… 0.03 Coupler solvent (Solv-7,2,3 equivalents) …… 0.10 Fifth layer (intermediate layer) Gelatin ………… 1.00 Color mixing inhibitor (Cpd-7)… 0.08 Color mixing inhibitor solvent (Solv-4) , 6 equivalent) ……… 0.16 Polymer latex (Cpd-8) ……… 0.10 6th layer (low-sensitivity green-sensitive layer) Silver bromide spectrally sensitized with a green sensitizing dye (ExS-3) ( Average particle size 0.25μ, particle size distribution 8%, octahedron) ...
...... 0.04 Silver bromide spectrally sensitized with a green sensitizing dye (ExS-3,4) (average grain size 0.45μ, grain size distribution 11%, octahedron) ...
…… 0.06 Gelatin ………… 0.80 Magenta coupler (ExM-1,2 equivalent) …… 0.11 Anti-fading agent (Cpd-9) …… 0.10 Anti-staining agent (Cpd-10,22 equivalent) ………… 0.014 Anti-staining agent (Cpd-23) ……… 0.001 Anti-staining agent (Cpd-12)… 0.01 Coupler dispersion medium (Cpd-5) ……… 0.05 Coupler solvent (Solv-4,6 equivalents) ……… 0.15 7th layer (high-sensitivity green-sensitive layer) Silver bromide spectrally sensitized with a green sensitizing dye (ExS-3, 4) (average grain size 0.8 µ, grain size distribution 16%, octahedron).
…… 0.10 Gelatin ………… 0.80 Magenta coupler (ExM-1,2) …… 0.11 Anti-fading agent (Cpd-9) …… 0.10 Anti-stain agent (Cpd-10,22 equivalent) …… 0.013 Stain Inhibitor (Cpd-23) ………… 0.001 Stain inhibitor (Cpd-12) …… 0.01 Coupler dispersion medium (Cpd-5) ………… 0.05 Coupler solvent (Solv-4,6 equivalents) …… 0.15 8th layer (Intermediate layer) Same as 5th layer 9th layer (Yellow filter layer) Yellow colloidal silver …… .0.20 Gelatin ………… 1.00 Color mixing inhibitor (Cpd-7) …… 0.06 Color mixing inhibitor Solvent (4,5 equivalents) ………… 0.15 Polymer latex (Cpd-8) ……… 0.10 10th layer (intermediate layer) Same as 5th layer 11th layer (low sensitivity blue sensitive layer) Blue sensitizing dye (ExS -5,6) silver bromide spectrally sensitized (average grain size 0.45μ, grain size distribution 8%, octahedron) ...
…… 0.07 Silver bromide spectrally sensitized with blue sensitizing dye (ExS-5, 6) (average grain size 0.60μ, grain size distribution 14%, octahedron) …… 0.10 Gelatin ………… 0.50 Yellow coupler (ExY-1) ... 0.22 Anti-staining agent (Cpd-11) ... ... 0.001 Anti-fading agent (Cpd-6) ... ... 0.10 Coupler dispersion medium (Cpd-5) ... ... 0.05 Coupler solvent (Solv-2) ) …… 0.05 Layer 12 (high-sensitivity blue-sensitive layer) Silver bromide spectrally sensitized with a blue sensitizing dye (ExS-5,6) (average grain size 1.2μ, grain size distribution 21%, octahedron) …
…… 0.25 Gelatin ………… 1.00 Yellow coupler (ExY-1) …… 0.41 Anti-staining agent (Cpd-11) ……… 0.002 Anti-fading agent (Cpd-6) …… 0.10 Coupler dispersion medium (Cpd-5) ………… 0.05 Coupler solvent (Solv-2) …… .0.10 13th layer (UV absorbing layer) Gelatin …… .1.50 UV absorber (Cpd-1,3,13 equivalent) …… 1.00 Color mixing inhibitor ( 0.06 Dispersion medium (Cpd-5) …… 0.05 UV absorber solvent (Solv-1,2 equivalent) …… 0.15 Irradiation prevention dye (Cpd-15,16 etc.) Amount) ………… 0.
02 Irradiation prevention dye (Cpd-17,18 equivalent) ………… 0.
02 14th layer (protective layer) Fine grain silver chlorobromide (97 mol% silver chloride, average size 0.2μ)
… 0.05 Acrylic modified copolymer of polyvinyl alcohol (degree of modification
17%) ……… 0.02 Polymethylmethacrylate particles (average particle size 2.4 microns), Silicon oxide (average particle size 5 microns) Equivalents ………… 0.05 Gelatin ………… 1.50 Gelatin hardening agent (H-1) ………… 0.17 15th layer (back layer) gelatin ………… 2.50 16th layer (back surface protection layer) Polymethylmethacrylate particles (average particle size 2.4 microns), silicon oxide (average particle size 5 microns) Equivalents ………… 0.05 gelatin… 2.00 Gelatin hardening agent (H-1) 0.11 Preparation of emulsion EM1 An aqueous solution of potassium bromide and silver nitrate was simultaneously added to an aqueous gelatin solution at 75 ° C for 15 minutes with vigorous stirring, and the average particle size was calculated. To obtain 0.40 micron octahedral silver bromide grains. To this emulsion, 0.1 g of 3,4-dimethyl-1,3-thiazoline-2-thione per mol of silver, 4 mg of sodium thiosulfate and 7 mg of chloroauric acid (tetrahydrate) were sequentially added, and the mixture was added at 75 ° C for 25 minutes. The chemical sensitization treatment was performed by heating. The particles thus obtained are used as cores for further growth in the same precipitation environment as in the first time, and finally the octahedral monodisperse core / average particle size of 0.58 micron /
A shell silver bromide emulsion was obtained. Coefficient of variation of particle size is about 10
It was in%. To this emulsion, 1.5 mg of sodium thiosulfate and 1.0 mg of chloroauric acid (tetrahydrate) per mol of silver were added, and the temperature was 60 ° C.
The mixture was heated at 45 ° C. for 45 minutes for chemical sensitization to obtain an internal latent image type silver halide emulsion.

ExZK-1 is used as a nucleating agent in each light-sensitive layer.
2.0 × 10 ^-5 mol per mol, Cpd-24 as a nucleation accelerator 4.
5 × 10 ⁻⁴ mol was added. Further, in each layer, alkanol XC (Dupont) and sodium alkylbenzenesulfonate were used as emulsification / dispersion aids, and succinate and Magefac F-120 (manufactured by Dainippon Ink and Chemicals) were used as coating aids. (Cpd-19, 20, 21) was used as a stabilizer for the silver halide and colloidal silver-containing layers. This sample is sample number 1
It was 01. The compounds used in the examples are shown below.

Cpd-8 Polyethyl acrylate Solv-1 Di (2-ethylhexyl) phthalate Solv-2 Trinonylphosphate Solv-3 Di (3-methylhexyl) phthalate Solv-4 Tricresylphosphate Solv-5 Dibutylphthalate Solv-6 Trioctylphosphate Solv- 7 Di (2-ethylhexyl) sebacate H-1 1,2-bis (vinylsulfonylacetamido) ethane ExZK-1 1-formyl-2- {4- [3- {3- [3
-(5-Mercaptotetrazol-1-yl) phenyl] ureido} benzenesulfonamide] phenyl} hydrazine Next, the cyan couplers added to the third and fourth layers and the nucleating agent added to each layer are shown in Table- Samples 102 to 107 modified to those shown in No. 1 were prepared.

The sample thus obtained was subjected to a wedge exposure (3200 ° K,
1/10 seconds, 10CMS), and after performing the following processing A,
The cyan color image density was measured. The results are shown in Table-2.

It is clear that the samples 103 to 107 using the cyan coupler according to the present invention and the nucleating agent according to the present invention are excellent ones having a high maximum color density (Dmax) and a low minimum color density (Dmin). is there.

Example 2 Example 1 was repeated except that the process of Example 1 was changed to the following processing step B, and similar results were obtained.

The replenishing method of washing water is such that the washing bath (3) is replenished, the overflow solution of the washing bath (3) is introduced into the washing bath (2), and the overflow solution of the washing bath (2) is introduced into the washing bath (1). The so-called countercurrent replenishment method was adopted. At this time, the carry-in amount of the bleach-fixing solution from the bleach-fixing bath to the washing bath (1) by the light-sensitive material was 35 ml / m ² , and the ratio of the replenishing amount of washing water to the carry-in amount of the bleach-fixing solution was 9.1 times.

The composition of each treatment liquid was as follows.

Washing water Both mother liquor and replenisher are tap water filled with H-type strongly acidic cation exchange resin (Amberlite IR-120B manufactured by Rohm and Haas Co.) and OH type anion exchange resin (Amberlite IR-400). Water was passed through the column to adjust the concentration of calcium and magnesium ions to 3 mg / l or less, and subsequently 20 mg / l of sodium isocyanurate dichloride and 1.5 g / l of sodium sulfate were added. The pH of this solution was in the range of 6.5-7.5.

At this time, the replenishment ratio of the washing solution 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]

Pure water was used (mother liquor = replenisher) Example 3 The sample obtained in Example 1 was stored at 45 ° C. and 80% RH for 3 days, and then subjected to wet exposure (3200 ° K, 1/10 second, 10 CMS). The same procedure as in Example 1 was performed, and then the cyan color image density was measured. The same was carried out for those stored at room temperature, and the sensitivities of the re-inversion negative images were compared. The results are shown in Table-3.

It is apparent that the samples 103 to 107 according to the present invention are excellent in that the negative image of re-inversion hardly occurs even when stored under high temperature and high humidity.

Example 4 Sample 401 was prepared by using the following emulsion EM-2 and an emulsion prepared according to the same instead of the emulsion EM-1 and the emulsion prepared according to Examples 101 to 107 of Example 1.
Example 1 was repeated for ~ 407 and similar results were obtained.

Preparation of emulsion EM-2 A mixed aqueous solution of potassium bromide and sodium chloride and an aqueous solution of silver nitrate were vigorously stirred into an aqueous gelatin solution containing 0.3 g of 3,4-dimethyl-1,3-thiazoline-2-thione added per 1 mol of Ag. However, they were added simultaneously at 65 ° C. over about 30 minutes to obtain a monodispersed silver chlorobromide emulsion having an average grain size of about 0.23 μm (silver bromide content 30 mol%). 25 mg per mole of silver in this emulsion
Chemical sensitization treatment was carried out by adding sodium thiosulfate in Example 1 and 15 mg of chloroauric acid (tetrahydrate) and heating at 65 ° C. for 25 minutes. Using the silver chlorobromide grains thus obtained as a core, the core / shell salt was further grown in the same precipitation environment as the first time, and finally the average particle size was about 0.65 μm (silver bromide content 25 mol%) monodispersed. A silver bromide emulsion was obtained. Coefficient of variation of particle size is about 12%
It was. To this emulsion were added 1.5 mg of sodium thiosulfate and 1.5 mg of chloroauric acid (tetrahydrate) per mol of silver, and the mixture was heated at 60 ° C. to 70%.
It was heated for a minute for chemical sensitization to obtain an internal latent image type halogenated emulsion EM-2.

Example 5 Example 2 was repeated with respect to the samples 401 to 407 obtained in Example 4, and similar results were obtained.

Example 6 Example 3 was repeated with respect to the samples 401 to 407 obtained in Example 4, and similar results were obtained.

〔The invention's effect〕

It can be seen that the direct positive color photographic light-sensitive material of the present invention gives a sufficiently high maximum color density, low minimum color density and low re-reversal negative sensitivity. The above-mentioned effects can be obtained stably when the light-sensitive material is stored under high temperature and high humidity, and also with respect to fluctuations in processing steps, which is a great advantage in practical use.

Claims (1)

[Claims] 1. A direct positive color photographic light-sensitive material having at least one pre-fogged internal latent image type silver halide emulsion layer on a support, said photographic light-sensitive material having the following general formula (CI) ) At least one cyan coupler represented by the formula (1) and at least one nucleating agent represented by the following general formula (N-I) are contained in the direct positive color photographic light-sensitive material. General formula (C-I) (In the formula, R ₁ represents an aliphatic group, an aromatic group, a heterocyclic group, an aromatic amino group or a heterocyclic amino group, and R ₂ has 2 to 20 carbon atoms.
Represents an aliphatic group, R ₃ represents a hydrogen atom, a halogen atom, an aliphatic group, an aliphatic oxy group, or an acylamino group, and Y ₁ represents a hydrogen atom or is removable during a coupling reaction with an oxidized product of a developing agent. Represents a group. Alternatively, R ₁ , R ₂ , R ₃ or Y ₁ may form a dimer or higher multimer. ) General formula (NI) (In the formula, Z ¹ represents a non-metal atom group necessary for forming a 5- or 6-membered heterocycle. This heterocycle may be further condensed with an aromatic ring or a heterocycle. R ¹ is a fat X is a group group
Is Is. Q represents a 4- to 12-membered non-aromatic hydrocarbon ring or a non-metal atom group necessary for forming a non-aromatic heterocycle. However, at least one of the substituents of R ¹ and Z ^{1 and} the substituent of Q includes an alkynyl group. Further, at least one of R ¹ , Z ¹ and Q may have an adsorption promoting group for silver halide. Y is a counter ion for charge balance, and n is the number required for charge balance. )