JPH0690434B2 - Direct positive image forming method - Google Patents

Description

The present invention relates to a photographic image forming method, and more particularly to a direct positive image forming method.

[Conventional technology]

It is well known that a direct positive image is obtained by using an internal latent image type silver halide emulsion which has not been fogged in advance, and then performing surface development after performing fog processing after image exposure or while performing fog processing.

Here, the internal latent image type silver halide photographic emulsion layer is
A silver halide photographic emulsion of a type having a photosensitive nucleus mainly inside the silver halide grain and a latent image being mainly formed inside the grain upon exposure.

Various techniques have been known so far in this technical field. For example, U.S. Patent Nos. 2,592,250 and 2,466,957.
No., No. 2,497,875, No. 2,588,982, No. 3,317,322,
3,761,266, 3,761,276, 3,796,577, and British Patents 1,151,363, 1,150,553, 1,011,06
No. 2 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.

For details of the direct positive type forming mechanism, see T.
The Theory of the Photograph by H. Giems (The Theory of the Photograph)
ic Process), 4th edition, Chapter 7, pp. 182-193 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.
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 "photofogging method" (for example, British Patent No. 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", Volume 151, No. 15162.
(Published November 1976), pages 76-78.

In order to directly form a positive (color) image, the internal latent image type silver halide light-sensitive material is subjected to fog treatment or surface development treatment while performing fog treatment, and then (bleaching) and fixing (or ( It can be achieved by bleaching) fixing) processing.
After the (bleaching) fixing treatment, washing and / or stabilizing treatment is usually performed.

[Problems to be solved by the invention]

A hydrazine compound is well known as a nucleating agent used in the "chemical fogging method".

The hydrazine-based nucleating agent generally has a large difference between the maximum concentration (Dmax) and the minimum concentration (Dmin), and is the best in terms of disinfection, but has a high pH (pH> 12) for treatment.
Has the drawback of requiring.

Heterocyclic quaternary ammonium salts are known as nucleating agents that act even when the treatment pH is low (pH ≦ 12). For example, U.S. Pat. Nos. 3,615,615, 3,719,494, 3,734,738, and
3,759,901, 3,854,956, 4,094,683, 4,30
6,016, British Patent 1,283,835, and Japanese Patent Laid-Open Nos. 52-3,426 and 52-69,613. Especially US Patent 4,
The propargyl- or butynyl-substituted heterocyclic quaternary ammonium salt compounds described in No. 115,122 are excellent nucleating agents in the point of dispersion in direct positive silver halide emulsions. However, when a sensitizing dye is added to the silver halide emulsion for the purpose of spectral sensitization, a silver halide emulsion is added between the sensitizing dye and the heterocyclic quaternary ammonium-based nucleating agent. As a result, competitive adsorption of quaternary salt nucleating agents with weak adsorptivity needs to be added in large amounts, especially in the case of multi-layer color light-sensitive materials, uneven density or loss of color balance may occur, resulting in sufficient performance. That was not the case. Note that this tends to increase further due to running treatment and storage under high temperature and high humidity.

For the purpose of solving the above problems, US Pat. No. 4,471,044 reports an example of a quaternary salt-based nucleating agent having a thioamide AgX adsorption promoting group. Here, the amount of addition necessary to obtain a sufficient Dmax is reduced by the introduction of adsorption groups, and
The reduction of ax is said to be improved, but this effect was not sufficiently satisfactory.

Therefore, a first object of the present invention is to provide a method for forming a direct positive image having a high maximum image density and a low minimum image density even by treatment with a developer having a relatively low pH. Especially.

A second object of the present invention is to provide a method for forming a direct positive image which maintains the above-mentioned high maximum image density and low minimum image density even when running processing is performed.

A third object of the present invention is a direct positive image having a small degree of change in photographic performance such as a decrease in maximum image density and an increase in minimum image density even when the photographic light-sensitive material is stored under high temperature and / or high humidity conditions. It is to provide a method of forming.

[Means for solving problems]

The above object of the present invention is to provide a photographic light-sensitive material having at least one pre-fogged internal latent image type silver halide emulsion layer on a support, after imagewise exposure in the presence of a nucleating agent. In the method of forming a positive image directly by developing, the nucleating agent is represented by the following general formula [NI], and the developing treatment is carried out at pH 12.0 or less. And a positive image forming method.

General formula [NI] In the formula, Z ¹ represents a nonmetallic atom group necessary for forming a 5- or 6-membered heterocycle. An aromatic ring or a heterocycle may be further condensed with this heterocycle. R ¹ is an aliphatic group and X 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 on silver halide, Y is a counter ion for charge balance, and n is for charge balance. It is the required number.

The nucleating agent represented by the general formula [N-I] will be described in more detail. Examples of the heterocycle completed by Z ¹ include quinolinium, benzimidazolium, pyridinium, thiazolium, selenazolium, imidazolium, tetrazolium and indolenium. , Pyrrolinium, acridinium, phenanthridinium, isoquinolium, and naphthopyridinium nuclei. Z ¹ may be substituted with a substituent, 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,
Halogen atom, amino group, alkylthio group, 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, Examples thereof include urethane group, carbonic acid ester group, hydrazine group, hydrazone group, and 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 2 - ( may be these groups having a substituent), is made of a single or a combination thereof and the like.

As an example of the combination, The counterion Y for charge balance, for example, a bromine ion, a chlorine ion, an iodine ion, p- toluenesulfonate ion, ethyl sulfonate ion, perchlorate ion, trifluoromethanesulfonate ion, thiocyanate ion BF ₄ ^- ion, PF ₆ ^- such as an ion, and the like.

Among 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 the general formula [N-I] are shown below, but the present invention is not limited thereto.

In the present invention, when the compound represented by the general formula [N-1] 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) 52.5g KBr 5g Kl 0.5g Water to make 1 internal developer B Metol 2.5 g L-ascorbic acid 10g NaBO ₂ · 4H ₂ O 35g KBr 1g Water 1 is added. 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 details are, for example, in the patents described in Research Disclosure Magazine No. 17643-VI (published in December 1978) P23-24.

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 December 1978) and "Stabilization of" by EJBirr
Photographic Silver Halide Emulsion "(Focal Pres
s), 1974, etc.

Various color couplers can be used to directly form a positive color image. The color coupler is a compound that produces or releases a substantially non-diffusible dye by a coupling reaction with an oxidized product of an aromatic primary amine color developing agent, and is a substantially non-diffusible compound itself. Is preferred. Typical examples of useful color couplers include:
There are naphthol or phenol type compounds, pyrazolone or pyrazoloazole type compounds and open chain or heterocyclic ketomethylene compounds. Specific examples of these cyan, magenta and yellow couplers which can be used in the present invention are described in "Research Disclosure", No. 17643.
(Published December 1978) P25, VII-D, same No.18717 (1979)
(Published in November 1999) 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.

The cyan coupler that can be preferably used in the present invention,
US Pat. Nos. 2,474,293, 4,502,212 and other naphthol-based and phenol-based couplers, US Pat.
No. 772,002, a phenol type cyan coupler having an ethyl group or higher alkyl group at the meta position of the phenol nucleus, and other 2,5-diacylamino-substituted phenol type couplers are also preferable in terms of color image fastness.

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 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 mechanically refining 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 JP-A No. 62-215272, pp. 440-467.

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.

To prevent deterioration of the yellow dye image due to heat, humidity and light,
Compounds having both hindered amine and hindered phenol partial structures in the same molecule, as described in US Pat. No. 4,268,593, give 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 a dyeing agent for preventing irradiation and halation, an ultraviolet absorber, a plasticizer, a fluorescent whitening agent, a matting agent, an air fog preventing agent, a coating aid, a hardener,
An antistatic agent, a slipperiness improving agent, etc. can be added.
Typical examples of these additives are Research Disclosure No. 17643 VIII to XIII (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 up the development.

Hydroquinones (eg US Pat. Nos. 3,227,552 and 4)
Compounds described in Japanese Patent No. 279,987); Chromans (for example, U.S. Pat. No. 4,268,621, Japanese Patent Laid-Open No. 54-103031, Research Disclosure Magazine, No. 18264 (issued in June 1979) 333.
~ Compounds described on pages 334; quinones (for example, 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)
No. 3, 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). ); Spirobisindanes (for example, JP-A-55-
65944).

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. 17643XV11 (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 relates to "Research Disclosure" magazine No. 17123 (19
It can also be applied to black-and-white light-sensitive materials that use a mixture of three-color couplers as published in July 1978).

Further, the present invention can be applied to a black and white photographic light-sensitive material.

The black and white (B / W) photographic light-sensitive materials to which the present invention can be applied include B / W direct positive photographic light-sensitive materials described in JP-A-59-208540 and JP-A-60-260039 (for example, X-ray photographic light-sensitive materials). Materials, Dyupu sensitive materials, micro sensitive materials, typesetting sensitive materials, printing sensitive materials) and the like.

In the present invention, in order to promote the action of the nucleating agent represented by the above [NI], the following nucleating accelerator can be used. Examples of the nucleation accelerator include tetrazaindenes, triazaindenes, pentazaindenes, and Japanese Patent Application No. Sho 61, which have at least one mercapto group optionally substituted with an alkali metal atom or an ammonium group.
-136948 (pp. 2-6 and p. 16-43), Japanese Patent Application No. 61-13
The compounds described in No. 6949 (pages 12 to 43) can be added.

Specific examples of the nucleation accelerator are shown below, but the invention is not limited thereto.

(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 color developing solution used in the development processing of the light-sensitive material of the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine 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 these color developing solutions is 9 to 12, preferably 9.
5 to 11.5.

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.

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 the Journal of the Society of Motion Picture and Telev.
ision Engineers Volume 64, p.248-253 (May 1955 issue)
It can be determined by the method described in.

According to the multi-stage countercurrent method described in the above-mentioned document, the amount of washing water can be greatly reduced, but due to the increase in the residence time of water in the tank, bacteria propagate, and the suspended matter produced adheres to the photosensitive material, etc. Cause problems. In the processing of the color light-sensitive material of the present invention, as a solution to such a problem,
The method of reducing calcium ion and magnesium ion described in Japanese Patent Application No. 61-131632 can be used very effectively. Further, isothiazolone compounds and siabendazoles described in JP-A-57-8542, chlorinated germicides such as chlorinated sodium isocyanurate, and other benzotriazoles, etc., Hiroshi Horiguchi "Chemistry of antifungal agents" It is also possible to use the bactericides described in "Microbial Sterilization, Sterilization, and Antifungal Technology" edited by the Society of Hygiene Technology and "Encyclopedia of Antibacterial and Antifungal Agents" edited by the Society for Antibacterial and Antifungal Society of Japan.

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, 58-14843, and 60-220345 can be used. Various chelating agents and antifungal agents can also be added to this stabilizing bath.

The overflow solution accompanying the above washing with water and / or supplementation of the stabilizing solution can be reused in other steps such as the desilvering step.

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.

On the other hand, in the present invention, various known developing agents can be used for developing the black-and-white light-sensitive material. That is, polyhydroxybenzenes such as hydroquinone, 2-chlorohydroquinone, 2-methylhydroquinone, catechol and pyrogallol; aminophenols such as p-aminophenol and N-methyl-p.
-Aminophenol, 2,4-diaminophenol, etc .; 3
-Pyrazolidones, for example 1-phenyl-3-pyrazolidones, 1-phenyl-4,4'-dimethyl-3-pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, 5,5- Dimethyl-1-phenyl-3-pyrazolidone and the like; ascorbic acids and the like can be used alone or in combination. In addition, JP-A-58-55
The developing solution described in No. 928 can also be used. For detailed examples of developing agents, preservatives, buffers, and developing methods for black and white light-sensitive materials and their usage, see "Research Disclosure" magazine No. 17643 (December 1978) XI.
It is described in items X to XXI.

〔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 spectrally sensitized with red sensitizing dye (ExS-1,2,3) (average silver 5 mol%, average particle size 0.45μ, size distribution)
10%, octahedron) …… 0.10 Gelatin …… 1.00 Cyan coupler (ExC-1) …… 0.11 Cyan coupler (ExC-2) ・ ・ ・ 0.10 Anti-fading agent (Cpd-2,3,4,13 equivalents) …… … 0.12 Coupler dispersion medium (Cpd-5) …… 0.03 Coupler solvent (Solv-7,2,3 equivalent) …… 0.06 4th layer (high sensitivity red sensitive layer) Red sensitizing dye (ExS-1,2, Silver bromide spectrally sensitized by 3) (average grain size 0.60μ, size distribution 15%, octahedron) ...
… 0.14 Gelatin …… 1.00 Cyan coupler (ExC-1) …… 0.15 Cyan coupler (ExC-2) …… 0.15 Anti-fading agent (Cpd-2,3,4,13 equivalent) …… 0.15 Coupler dispersion medium (Cpd) -5) ...... 0.03 Coupler solvent (Solv-7,2,3 equivalent) ...... 0.10 Fifth layer (intermediate layer) Gelatin ...... 1.00 Anti-fading agent (Cpd-7) ...... 0.08 Anti-fading solvent (Solv -4,5 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 green sensitizing dye (ExS-3,4) (average grain size 0.45μ, grain size distribution 11%, octahedron) …… 0.06 Gelatin …… 0.80 Magenta coupler (ExM- 0.12 Anti-fading agent (Cpd-9) 0.10 Anti-stain agent (Cpd-10,22 equivalent) ... 0.014 Anti-stain agent (Cpd-23) ... 0.001 Anti-stain agent ( Cpd-12) …… 0.01 Coupler dispersion medium (Cpd-5) …… 0.05 Coupler solvent (Solv-4,6 equivalent) …… 0.15 7th layer (high sensitivity green sensitive layer) Green sensitizing dye (ExS-3) , 4) spectrally sensitized silver bromide (average grain size 0.8μ, 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-staining agent (Cpd-10,22 equivalent) ... 0.013 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 8th layer (intermediate layer) Same as 5th layer 9th layer (yellow filter layer) Yellow colloidal silver …… 0.20 Gelatin: 1.00 Anti-fading agent (Cpd-7): 0.06 Anti-fading solvent (Solv-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) Silver bromide spectrally sensitized with blue sensitizing dye (ExS-5, 6) (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 12th layer (high-sensitivity blue sensitive layer) Silver bromide spectrally sensitized with 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 (Cpd- 6,14 equivalents) …… 0.06 Dispersion medium (Cpd-5) …… 0.05 UV absorber solvent (Solv-1,2 equivalents) …… 0.15 Anti-indication dye (Cpd-15, 16 equivalents) …… 0.02 Anti-indication dye (Cpd-17, 18 equivalents) ...... 0.02 14th layer (protective layer) Fine silver chlorobromide (97 mol% silver chloride, average size 0.2μ)
0.05 Acrylic modified copolymer of polyvinyl alcohol (Modification degree
17%) 0.02 Polymethylmethacrylate particles (average particle size 2.4 microns), Silicon oxide (average particle size 5 microns) Equivalent …… 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) Equivalent: 0.05 Gelatin: 2.00 Gelatin hardening agent (H- 1) …… 0.11 How to make Emulsion EM1 An aqueous solution of potassium bromide and silver nitrate was added to an aqueous gelatin solution with vigorous stirring at 75 ° C for 15 minutes at the same time. Got 0.3 g of 3,4-dimethyl-1,3-thiazoline-2-thione per mol of silver, 6 mg of sodium thiosulfate and 7 mg of chloroauric acid (tetrahydrate) were sequentially added to this emulsion, and the mixture was added at 75 ° C for 80 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 an octahedral monodisperse core / average particle size of 0.7 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 1.5 mg of chloroauric acid (tetrahydrate) per mol of silver were added, and the temperature was 60 ° C.
The mixture was heated for 60 minutes for chemical sensitization to obtain an internal latent image type silver halide emulsion.

The nucleating agent was used in each photosensitive layer as described in Table 1. Furthermore,
Alkanol XC (Dupont
And sodium alkylbenzene sulfonate, and succinic acid ester and Magefac F-120 (manufactured by Dainippon Ink and Chemicals, Inc.) were used as coating aids. (Cpd-19, 20, 21) was used as a stabilizer for the silver halide and colloidal silver-containing layers.

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 (vinylsulfonylacetamide)
Ethane Wet exposure (32
00 ° K, 0.1 second, 10 CMS) and then processed using process step A. The resulting magenta color image densities (maximum image density; Dmax and minimum image density; Dmin) were measured and are shown in Table 1.

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 carry-in ratio of the photosensitive material from the prebath was 35 ml / m ² , and the replenishment ratio was 9.1.

The pH was adjusted with potassium hydroxide or hydrochloric acid.

[Bleaching fixer] Mother liquor = Replenisher Ammonium thiosulfate 100g Sodium bisulfite 21.0g Ethylenediaminetetraacetic acid iron (III) 50.0g Ammonium dihydrate Ethylenediaminetetraacetic acid 2 5.0g Sodium dihydrate Pure water 1000ml pH 6.3 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.

Samples Nos. 1 to 11 using the nucleating agent of the present invention had lower Dmin than No. 12 of the comparative example, higher Dmax than No. 13, and low Dmin.

Similar results were obtained with cyan and yellow color image densities.

Example-2 8 l of color developing tank, 4 l of each tank for bleach-fixing and washing
Development rate of the samples of Examples 1 to 13 using the automatic processor of
After exposure to 60%, it was treated with 20 m ² . B was used for the treatment step. The samples Nos. 1 to 13 of Example-1 were used as Example-1.
Exposure was carried out in the same manner as above, and after the running processing, processing step B was performed. The cyan color image density was measured and the results are shown in Table 2.

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) Samples Nos. 1 to 11 of the present invention have a lower Dmin than those of Comparative Sample No. 12 even when treated with the treatment liquid after running,
Compared to o.13, Dmax was high and Dmin was low, which was preferable.

Similar results were obtained with magenta and cyan color image densities.

Example-3 Example-2 was repeated except that the pH of the color developing solution was set to 11.2 and the developing time was set to 45 seconds, and the same result was obtained.

Example 4 A color photographic paper was prepared in the same manner as in Example 1 except that the magenta coupler was changed to the one described below and the emulsion EM ₂ and the emulsion having the changed size were used. However, the sample
No. 14 contained no nucleating agent.

This sample was stored in an atmosphere of 45 ° C. and 80% KH for 3 days (kinky basin), and then subjected to the same post-treatment step C as the same exposure as in Example-1.

The magenta color image density was measured and is shown in Table 3.

Magenta coupler Emulsion B A mixed aqueous solution of potassium bromide and sodium chloride and an aqueous solution of silver nitrate were added to an aqueous gelatin solution containing 0.07 g of 3,4-dimethyl-1,3-thiazoline-2-thione added per mol of Ag at 65 ° C. with vigorous stirring. About 21 minutes were required for simultaneous addition to obtain a monodispersed silver chlorobromide emulsion having an average grain size of about 0.23 μm (silver bromide content: 30 mol%). 45 mg per mole of silver in this emulsion
Chemical sensitization treatment was carried out by adding sodium thiosulfate (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 having an average grain size of about 0.58 μm (silver bromide content 20 mol%). A silver chlorobromide emulsion was obtained. Coefficient of variation of particle size is about 15
It was in%. To this emulsion were added 1.5 mg of sodium thiosulfate and 0.8 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 B.

The pH was adjusted with potassium hydroxide or hydrochloric acid.

[Bleach-fixing solution] Mother liquor = replenisher Ammonium thiosulfate 110g sodium bisulfite 12g diethylenetriaminepentaacetic acid 80g of iron (III) ammonium diethylenetriamine pentaacetic acid 5 g 2-mercapto-5-amino-0.3 g-1,3,4 thiadiazole - Le pure water 1000 ml pH 6.80 pH was adjusted with aqueous ammonia or hydrochloric acid.

[Stabilizer] Mother liquor = replenisher 1-hydroxyethylidene-2.7g 1,1-diphosphonic acid o-phenylphenol 0.2g potassium chloride 2.5g bismuth chloride 1.0g zinc chloride 0.25g sodium sulfite 0.3g ammonium sulfate 4.5g fluorescence brightening Agent (stilbene type) 0.5 g Pure water was added and 1000 ml pH 7.2 pH was adjusted with potassium hydroxide or hydrochloric acid.

Sample Nos. 1 to 11 containing the nucleating agent of the present invention have a lower Dmin than the comparative sample No. 12, a high Dmax and a low Dmin as compared to No. 13, and compared to No. 14. Has a high Dmax and is preferred. Moreover, this effect was remarkable after the ink incubation.

Similar results were obtained with cyan and yellow color image densities.

Example-4 Emulsion X 20 mg of thioether (1,8-dihydroxy-3,6-dithiaoctane) was contained in each of an aqueous silver nitrate solution and an aqueous potassium bromide solution at the same time while keeping the silver electrode potential constant at a constant rate. 1/8 mol of silver nitrate corresponding to 1/8 mole of silver nitrate was added over 5 minutes to a gelatin aqueous solution (pH = 5.5) at 75 ° C., to obtain a spherical AgBr monodisperse emulsion having an average grain size of about 0.14 μm. To this emulsion were added 20 mg of sodium thiosulfate and 20 mg of chloroauric acid (tetrahydrate) per mol of silver halide, the pH was adjusted to 7.5, and the mixture was chemically stirred at 75 ° C for 80 minutes. The sensitized product was used as the core emulsion. Next, at the same temperature, an aqueous solution of silver nitrate (containing 7/8 mol of silver nitrate) and an aqueous solution of potassium bromide were stirred well for 40 minutes while maintaining the silver electrode potential at which the octahedral grains grow. Then, at the same time, let the shell grow, and the average particle size is about 0.
A 3 μm monodisperse cubic core / shell emulsion was obtained. Adjusting the pH of this emulsion to 6.5, 5 mol / mol of silver halide
Sodium thiosulfate (5 mg) and chloroauric acid (tetrahydrate) (5 mg) were added respectively, and the mixture was aged at 75 ° C for 60 minutes, chemically sensitized the shell surface, and finally subjected to internal latent image type monodispersion. An octahedral core / shell emulsion (Emulsion X) was obtained. As a result of measuring the grain size distribution of this emulsion from an electron micrograph, the average grain size was 0.30 μm, and the coefficient of variation (percentage of the value obtained by dividing the statistical standard deviation by the average grain size) was 10%. .

The above emulsion X was mixed with panchromatic sensitizing dye 3,3'-diethyl-9-
5m of methyl thiacarbocyanine per mol of silver halide
After adding g, the nucleating agent shown in Table 1 was added in an amount of 1.4 × 10 ^-5 mol per mol of silver halide, and the amount of silver was 2.8 g / m ² on the polyethylene terephthalate support. And a protective layer composed of gelatin and a hardener at the same time, to prepare direct positive photographic light sensitive material samples No. 1 to No. 5 which are sensitive to red light. .

1kw tungsten lamp (color temperature 2854
(B)) It was exposed for 0.1 seconds through a step wedge with a sensitometer. Next, an automatic processor (Kodak Proster I Proc
essor) Kodak Proster Plus processing solution (developer pH / 0.7)
Was developed at 38 ° C. for 18 seconds, followed by subsequent washing with water, fixing, washing with water and drying. The maximum density (Dmax) and minimum density (Dm) of the direct positive image of each sample obtained in this way
in) was measured.

Sample Nos. 1 to 4 containing the nucleating agent of the present invention are comparative No. 5
Compared to, Dmax was high and Dmin was low, which was preferable.

〔The invention's effect〕

The method of the present invention produces a direct positive image having a high maximum density and a low minimum density. The above image quality is maintained well even after the running process and when the photographic light-sensitive material is stored under high temperature and high humidity.

The method of the present invention is extremely suitable for practical use.

 ─────────────────────────────────────────────────── ─── Continuation of front page (56) Reference JP-A-60-11837 (JP, A) JP-A-62-210451 (JP, A) JP-A-62-291637 (JP, A) JP-A-63- 301942 (JP, A) JP 58-14665 (JP, B2) JP 5-84889 (JP, B2)

Claims (1)

[Claims] 1. A photographic light-sensitive material having at least one pre-fogged internal latent image type silver halide emulsion layer on a support is subjected to image-wise exposure and development treatment in the presence of a nucleating agent. In the method for directly forming a positive image, the nucleating agent is represented by the following general formula [NI], and the developing treatment is carried out at pH 12.0 or less. Forming method. General formula [NI] In the formula, Z ¹ represents a nonmetallic atom group necessary for forming a 5- or 6-membered heterocycle. An aromatic ring or a heterocycle may be further condensed with this heterocycle. R ¹ is an aliphatic group and X 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 on silver halide, Y is a counter ion for charge balance, and n is for charge balance. It is the required number.