JPH0229644A - Direct positive image forming method - Google Patents

Abstract

PURPOSE:To provide the high max. image density and the low min. image density by executing development processing in the presence of a specific compd. in case of forming a direct positive image by executing the development processing while executing a fogging processing. CONSTITUTION:The photographic sensitive material having at least 1 layer of photographic emulsion layers contg. internal latent image type silver halide particles which are not previously fogged on a base is subjected to imagewise exposing, then to the fogging processing or to the development processing while subjecting the material to the fogging processing, by which the direct positive image is formed. The development processing is executed in the presence of the compd. expressed by the formula I in this case. In the formula, A denotes a block group which can release a nucleation accelerating agent at the time of the processing; B denotes a nucleation accelerating agent bonded to A via a hetero atom. The direct positive photographic sensitive material which provides both the high max. image density and the low min. image density in combination is obtd. in this way and this characteristic is not impaired even if the material is preserved at a high temp.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a method for forming photographic images, and more particularly to a method for forming direct positive images.

[Conventional technology]

A well-known method is to directly obtain a positive image by using an internal latent image type silver halide emulsion that has not been fogged in advance, and performing capri processing after image exposure, or surface development while performing fogging processing.

Here, the internal latent image type silver halide photographic emulsion is a type of silver halide that has photosensitive nuclei mainly inside the silver halide grains, and a latent image is mainly formed inside the grains by the n-tip. Photographic emulsion.

Various techniques are heretofore known in this technical field; examples include U.S. Pat.
, No. 588,982, No. 3゜317.322, No. 3,
761.266, 3.761.276, 3.7
The main ones are those described in British Patent No. 96,577 and the specifications of British Patent Nos. 1,151.363, 1.150.553, and 1.011,062.

By using these known methods, it is possible to produce direct positive type photographic materials with relatively high sensitivity.

For details of the above direct positive image formation mechanism, see, for example, T.
, H. James, The Theory of the Photographic Process J.
of the Photographic Proc
ess), 4th edition, Chapter 7, pages 182 to 193, and US Pat. No. 3,761,276.

In other words, fog nuclei are selectively generated only on the surface of the silver halide grains in unexposed areas due to the surface desensitization effect caused by the so-called internal latent image generated inside the silver halide by the initial imagewise exposure. A photographic image (direct positive image) is then created in the unexposed area by subjecting it to a conventional so-called surface development process.

As mentioned above, as a means for selectively generating fog nuclei, a method of applying a second exposure to the entire surface of the photosensitive layer, which is generally called a "photofogging method" (for example, British Patent No. 1,151,
363) and a nucleating agent (n
A method using a nucleating agent is known. Regarding this latter method, an example is ``Research Disclosure J''.
Disclosure) Magazine, No. 151 JJ, &1516
2 (issued November 1976), 76-78.

In order to directly form a positive (color) image, after fogging the internal latent image type silver halide photosensitive material, or surface development treatment while performing fogging treatment, then (bleaching), fixing (or ( This can be achieved by bleaching) fixing) processing. (
Bleaching) After the fixing process, washing with water and/or stabilizing process are usually performed.

[Problem that the invention seeks to solve]

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

The above hydrazine nucleating agent generally has a maximum image density (Dma
x) and the minimum image density (Dmtn), and is the best in terms of discrimination, but requires a high pH (p) (>12) for processing.

Heterocyclic quaternary ammonium salts are known as nucleating agents that act even at low processing pH (pH≦12); for example, U.S. Pat.
No. 4, No. 3,734,738, No. 3,759.901
No. 3. 854. No. 956, 4,094,68
No. 3, No. 4,306°016, British Patent No. 1,283,
No. 835, JP-A-52-3.426 and JP-A No. 52-6
No. 9,613. Especially US Patent 4,11
The propargyl- or butynyl-substituted heterocyclic quaternary ammonium salt compounds described in No. 5゜122 are:
It is a nucleating agent with excellent discrimination in direct positive silver halide emulsions.

(Problem to be Solved by the Invention) However, when a nucleating agent and a sensitizing dye are added to the silver halide emulsion for the purpose of spectral sensitization, for example, there is a gap between the sensitizing dye and the nucleating agent. In this case, competitive adsorption to silver halide occurs, so it is necessary to add a large amount of a nucleating agent with weak adsorptive properties.Especially in the case of multilayer color sensitive materials, density unevenness and color balance may occur. It could not be said that it showed good performance.

Note that this tendency tends to increase even more under high temperature and high humidity conditions.

For the purpose of solving the above problem, U.S. Patent No. 4,471.04
Examples of nucleating agents having a group capable of adsorbing silver halide are reported in No. 4, No. 4459357, and JP-A-62948. Here, the introduction of adsorption groups is sufficient.
*The amount of addition required to obtain ax decreases, and D
Although it is said that the reduction in +sax is improved, this effect was not at a fully satisfactory level.

Further, US Pat. No. 3,227,552 describes the use of hydroquinone derivatives to increase the development rate of medium densities. However, even with this, the development speed was not sufficient, and in particular, an insufficient development speed was obtained with a developer having a pH of 12 or less.

Further, JP-A-60-170843 describes adding a mercapto compound having a carboxylic acid group or a sulfonic acid group to increase the maximum image density. However, the effect of adding these compounds is still not sufficient, and furthermore, the phi of the developer is 12.0, and the stability of the developer is insufficient.

JP-A-55-134848 discloses a treatment solution containing a tetrazaindene compound (pH 12.0) in the presence of a nucleating agent.
) to reduce the minimum image density and prevent the formation of re-inverted negative images. However, this method does not increase the maximum image density or increase the development speed.

Furthermore, Japanese Patent Publication No. 12709/1983 describes the addition of triazoline-thione and tetrazoline-thione type compounds as antifogging agents to sensitive materials on which positive images are directly formed by the photofogging method. However, even with these methods, high maximum image density and fast development speed could not be achieved.

Japanese Patent Publication No. 63-8740, Patent Application No. 136°948, 1987
When using the nucleation accelerator described in No. 61-136,949, No. 61252846, and No. 62-310029, direct positive images with high maximum image density and low minimum image density can be quickly produced. However, it is highly dependent on the amount of addition, and in order to obtain a sufficient maximum image density, there are some that increase the minimum image density when the amount of addition is increased.

On the other hand, these nucleation accelerators themselves adsorb to silver halide, so if the amount added is increased to obtain a sufficient maximum image density, the sensitivity and maximum image density will decrease due to long-term storage. However, there was no level of satisfaction, and a solution to this problem was desired.

Therefore, it is an object of the present invention to first provide a direct positive photographic material having a high maximum image density and a low minimum image density.

A second object of the present invention is to provide a direct positive photographic light-sensitive material in which the maximum image density does not decrease and the minimum image density does not easily increase when the material is stored at high temperatures or at room temperature for a long period of time.

(Problems to be Solved by the Invention) The above object of the present invention is to provide a photographic light-sensitive material having at least one photographic emulsion layer on a support containing internal latent image type silver halide grains which are not fogged in advance. In the method of directly forming a positive image by performing fogging treatment after exposure or developing treatment while performing fogging treatment, the developing treatment is performed in the presence of at least one compound represented by the following general formula (I). This is achieved by a direct positive image forming method characterized by:

General formula (1) A represents a blocking group capable of releasing a nucleation promoter during treatment, and B represents a nucleation promoter bonded to A via a heteroatom.

Here, the nucleation accelerator refers to a compound that does not itself have a fogging effect, but has an action of promoting the fogging effect.

The compound represented by the general formula (I) will be explained in detail below.

Blocking groups A are already known (a few examples can be mentioned; for example,
No. 8, JP-A-52-8,828, JP-A No. 57-82,83
No. 4, U.S. Patent No. 3,311゜476, Special Publication No. 47-4
No. 4,805 (U.S. Pat. No. 3,615.617) that utilizes blocking groups such as acyl groups and sulfonyl groups;
No. 888.677), No. 55-9,696 (US Patent No. 3,791,830), No. 55-34°927 (US Pat.
U.S. Pat.
No. 842 (U.S. Pat. No. 4,307°175), No. 59-
Block group utilizing the so-called reverse Michael reaction described in No. 105.642 and No. 59105.640;
No. 4-39°727, U.S. Patent No. 3,674,478, U.S. Patent No. 3,932.480, U.S. Patent No. 3,993,661
No., JP-A-57-135,944, JP-A No. 57135.9
45, block group utilizing the production of quinone methide or quinone methide compounds by intramolecular electron transfer as described in JP-A No. 55-53.330, JP-A No. 59-218゜439 JP-A-57-76.541 (U.S. Pat. No. 4.335.200), U.S. Pat.
No. 57-179.842, No. 59-137.945, No. 59-140.445, No. 59-219.741
No. 60-41.034, which utilizes 5- or 6-membered ring cleavage; or JP-A-59-201.0
No. 57, No. 61-43゜739, No. 61-95, 34
Blocking groups that utilize the addition of a nucleophile to an unsaturated bond as described in No. 7 can be mentioned.

General formula (1) can be more specifically represented by general formula (II).

General formula (n) A + It represents a divalent linking group bonded to A, and ml represents 0 or 1.

- The nucleation accelerator represented by D in formula (II) is as follows -
It is represented by the formula (III) and (rV).

- Formula (III) General formula (IV) In the formula, Q represents an atomic group necessary to form a 5- or 6-membered heterocycle, and this heterocycle is fused with a carbon aromatic ring or a heteroaromatic ring. Good too. -In formula (Ill), W
represents a nitrogen atom, a carbon atom, - a sulfur atom in the case of the formula (Ill), - a nitrogen atom in the case of the formula (IV), even if it is directly bonded to A (m+ = O) % or Xl (m, = 1), and can be separated from A by photographic processing (development, fixing, bleaching, etc.).

Xl represented by general formula (II) represents a divalent linking group, which is bonded to A through the heteroatom of Xl, and after being cleaved as X and -D during treatment, D is immediately released. represents a group.

Examples of such linking groups include JP-A-54-145135 (British Patent Publication No. 2.010.818A), U.S. Pat. 2.096°783, which releases D by an intramolecular ring-closing reaction, and British Patent No. 2.072.
No. 363, JP-A-57-154,234, etc. which release D by intramolecular electron transfer, and JP-A-57-179,842, which releases D by desorption of carbon dioxide gas. or JP-A-59-9342
The structural formulas of the representative XI- mentioned above are shown below together with D, which can include linking groups such as those which release D upon elimination of formalin as described in No. 2.

10CR1-D -O-C-OCH! -D supply Js Ox position 0 +CHz+sN CD What kind of material is used as X is selected depending on the type of D, timing of release, speed, etc.

Preferable A of the blocked nucleation accelerator represented by the general formula (II) used in the present invention is; C=C
group, >C=O group, >c=N' group, >C=S group, and >
It has at least one C=N group and releases a nucleation accelerator by attack of a nucleophile (typically OH0 ion) on the carbon atom of the functional group and the subsequent reaction. Among these compounds, particularly preferred compounds include those represented by the following formula (V).

In the general formula (V) (Rl), R1, xRl and R2 represent a hydrogen atom or a substitutable group, and R2 and R8 and R8 and R1 are bonded to form a carbocyclic ring, or It may form a heterocycle.

In the case of l nt -〇, /\ represents a cyano group, or /\ represents a nitro group (here, R4, Rs, R4, Ry and R1 represent a hydrogen atom or a substitutable group), and Xl and ml represent the above-mentioned - It has the same meaning as that in formula (II).

The compound represented by the general formula (V) can be used for photographic processing (development,
During bleaching, fixing, bleach-fixing, etc.), the nucleation accelerator represented by D is added to the unsaturated bond of a nucleophile (e.g. OH- ion, 5Off"-ion, hydroxylamine, etc.) in the processing solution. It is possible to remove the

As a method of blocking active groups using the addition of a nucleophile to such an unsaturated bond, JP-A-59-201.057, JP-A-61-43.739, JP-A-61-95. 3
No. 47 can be used.

Next, general formula (V) will be explained in detail.

R1 represents a hydrogen atom or a substitutable group, and examples of the substitutable group include an alkyl group (preferably having 1 to 20 carbon atoms);
alkenyl group (preferably 2 to 20 carbon atoms), aryl group (preferably 6 to 20 carbon atoms), alkoxy group (preferably 1 to 20 carbon atoms), aryloxy group (preferably 6 to 20 carbon atoms), ), alkylthio group (preferably having 1 to 20 carbon atoms), arylthio group (preferably having 6 to 20 carbon atoms),
20), amino group (unsubstituted amino, preferably 1 carbon number
It represents a secondary or tertiary amino substituted with an alkyl group of ~20 or an alkyl group having 6 to 20 carbon atoms, a hydroxy group, etc., and these substituents have one or more of the following substituents. and when there are two or more substituents, they may be the same or different.

Here, specific substituents include halogen atoms (fluorine, chlorine, bromine), alkyl groups (preferably 1 to 2 carbon atoms),
0), aryl group (preferably 6 to 20 carbon atoms), alkoxy group (preferably 1 to 20 carbon atoms), aryloxy group (preferably 6 to 20 carbon atoms), alkylthio group (
(preferably carbon atoms 1 to 20), arylthio groups (preferably carbon atoms 6 to 20), acyl groups (preferably carbon atoms 2
~20), acylamino group (preferably 1 to 20 carbon atoms)
alkanoylamino, benzoylamino having 6 to 20 carbon atoms), nitro group, cyano group, oxycarbonyl group (preferably alkoxycarbonyl having 1 to 20 carbon atoms, aryloxycarbonyl having 6 to 20 carbon atoms), hydroxy group, carboxy group, sulfo group, ureido group (preferably alkylureido having 1 to 20 carbon atoms, arylureido having 6 to 2 carbon atoms), sulfonamide group (preferably alkylsulfonamide having 1 to 20 carbon atoms, 6 to 2 carbon atoms)
0 arylsulfonamide), sulfamoyl group (preferably alkylsulfamoyl having 1 to 20 carbon atoms, arylsulfamoyl having 6 to 20 carbon atoms), carbamoyl group (preferably alkylcarbamoyl having 1 to 20 carbon atoms, carbon arylcarbamoyl having 6 to 20 carbon atoms), acyloxy group (preferably having 1 to 20 carbon atoms), amino group (unsubstituted amino, preferably alkyl group having 1 to 20 carbon atoms,
or secondary or tertiary amino substituted with an aryl group having 6 to 20 carbon atoms), carbonate group (preferably alkyl carbonate ester having 1 to 20 carbon atoms, aryl nysteryl carbonate having 6 to 20 carbon atoms), sulfone group (preferably alkyl sulfone having 1 to 20 carbon atoms, alkyl sulfone having 6 to 20 carbon atoms), sulfinyl group (preferably 1 to 20 carbon atoms),
to 20 alkylsulfinyl, and arylsulfinyl having 6 to 20 carbon atoms).

Furthermore, R3 may be combined with R2 or R3 to form a carbocycle or a heterocycle (eg, a 5- to 7-membered ring). R1, R
2 may be the same or different and each represents a hydrogen atom or a substitutable group, and substitutable groups include a halogen atom (fluorine, chlorine, bromine), an alkyl group (preferably having 1 to 20 carbon atoms), and an aryl group. (preferably carbon number 6-2o
), alkoxy group (preferably having 1 to 20 carbon atoms), aryloxy group (preferably having 6 to 2 carbon atoms), alkylthio group (preferably having 1 to 2 carbon atoms), arylthio group (preferably having 6 to 2 carbon atoms), 20), an acyloxy group (preferably having 2 to 20 carbon atoms), an amino group (unsubstituted amino, preferably an alkyl group having 1 to 20 carbon atoms, or a secondary substituted with an alkyl group having 6 to 2 carbon atoms) or tertiary amino), carbonamide group (preferably 1 to 2 carbon atoms)
0 alkylcarbonamide, arylcarbonamide having 6 to 2 carbon atoms), ureido group (preferably 1 carbon atom)
~20 alkylureido, arylureido having 6 to 20 carbon atoms), carboxy group, carbonate group (preferably alkyl carbonate ester having 1 to 20 carbon atoms, 6 to 20 carbon atoms)
20 aryl carbonate), oxycarbonyl group (
(preferably alkyloxycarbonyl having 1 to 20 carbon atoms, aryloxycarbonyl having 6 to 20 carbon atoms), carbamoyl group (preferably alkylcarbamoyl having 1 to 20 carbon atoms, orcarbamoyl having 6 to 20 carbon atoms),
Acyl group (preferably alkylcarbonyl having 1 to 20 carbon atoms, arylcarbonyl having 6 to 20 carbon atoms), sulfone group, sulfonyl group (preferably alkylsulfonyl having 1 to 20 carbon atoms, arylsulfonyl having 6 to 20 carbon atoms) , sulfinyl group (preferably alkylsulfinyl having 1 to 20 carbon atoms, arylsulfinyl having 6 to 20 carbon atoms), sulfamoyl group (preferably 1 to 20 carbon atoms)
alkylsulfamoyl, arylsulfamoyl having 6 to 20 carbon atoms), a cyano group, and a nitro group.

These substituents represented by Rz and R3 may have one or more substituents, and when there are two or more substituents, they may be the same or different. Specific substituents include the above R7. The same substituents can be mentioned.

Represents a nitro group, R4, Rs, R1, R7 and R1
They may be the same or different and each represents a hydrogen atom or a substitutable group, and specific substituents include an alkyl group (preferably having 1 to 20 carbon atoms) and an alkenyl group (preferably having 2 to 20 carbon atoms). , oryl group (preferably having 6 to 20 carbon atoms), alkoxy group (preferably having 1 to 20 carbon atoms),
20), ori-ruoxy group (preferably 6 to 20 carbon atoms)
), an acyloxy group (preferably having 2 to 20 carbon atoms), an amino group (an unsubstituted amino group, preferably an alkyl group having 1 to 20 carbon atoms, or a secondary substituted with an alkyl group having 6 to 20 carbon atoms) or tertiary amino), carbonamide, do group (preferably alkylcarbonamide having 1 to 20 carbon atoms, arylcarbonamide having 6 to 20 carbon atoms), ureido group (preferably alkylureido having 1 to 20 carbon atoms, carbon number 6-20 aryl ureido), oxycarbonyl group (preferably C1-C20 furkyloxycarbonyl, C6-20 aryloxycarbonyl), carbamoyl group (preferably C1-20 furkylcarbamoyl, Arylcarbamoyl having 6 to 20 carbon atoms)
, acyl group (preferably alkylcarbonyl having 1 to 20 carbon atoms, arylcarbonyl having 6 to 20 carbon atoms), sulfonyl group (preferably alkylsulfonyl having 1 to 20 carbon atoms, orylsulfonyl having 6 to 20 carbon atoms) ), sulfinyl group (preferably alkylsulfinyl having 1 to 20 carbon atoms, carbon 5J [arylsulfinyl having 6 to 20 carbon atoms),
It represents a sulfamoyl group (preferably an alkylsulfamoyl having 1 to 20 carbon atoms, an arylsulfamoyl having 6 to 20 carbon atoms), a cyano group, or a nitro group. Of these, Rq
, Rs include an oxycarbonyl group, a carbamoyl group, an acyl group, a sulfonyl group, a sulfamoyl group, a sulfinyl group, a cyano group, and a nitro group. These substituents may have one or more substituents, and when there are two or more substituents, they may be the same or different (specific substituents are the same as the substituent for R1 above). I can list things.

Next, the nucleation promoter represented by the general formula (1[[), -(TV)] will be described in detail.

In the general formula (III), Q is preferably a carbon atom, a nitrogen atom, an oxygen atom, a sulfur atom, and a selenium atom (both of which are necessary to form a 5- or 6-membered heterocycle composed of one type of atom). Represents a group of atoms.

The heterocycle may also be fused with a carbon aromatic ring or a heteroaromatic ring. W represents a nitrogen atom or a carbon atom.

Examples of the heterocycles include tetrazoles, triazoles, imidazoles, thiadiazoles, oxadiazoles, selenadiazoles, oxane/s, thiane/J, penzoxasols, benzthiazoles, Examples include benzimidazo, -ru, pyrimidines, tetraazaindene, triazaindene, pentaazaindene, and the like.

These heterocycles include nitro groups, halogen atoms (e.g. chlorine, bromine), mercapto groups, cyano groups, substituted or unsubstituted alkyl groups (e.g. methyl, ethyl, propyl, t-butyl, methoxyethyl, methylthioethyl, dimethylaminoethyl, morpholinoethyl, dimethylaminoethylthioethyl, diethylaminoethyl, dimethylaminopropyl, dipropylaminoethyl, dimethylaminohexyl, methylthioethyl, methoxyethoxyethoxyethyl, trimethylammonioethyl, cyanoethyl), 7-aryl groups (e.g. Phenyl, 4-methanesulfonamidophenyl, 4methylphenyl, 3-methoxyphenyl, 4-dimethylaminophenyl, 3.4
-dichlorophenyl, naphthyl), fulkenyl groups (e.g. allyl), aralkyl groups (e.g. benzyl, 4-methylbenzyl, phenethyl, 4-methoxybenzyl), alkoxy groups (e.g. methoxy, ethoxy, methoxyethoxy, methylthioethoxy, dimethyl aminoethoxy), aryloxy groups (e.g. phenoxy, 4-methoxyphenoxy), furkylthio groups (e.g. methylthio,
Ethylthio, propylthio, methylthioethyl, dimethylaminoethylthio, methoxyethylthio, morpholinoethylthio, dimethylaminopropylthio, piperidinoethylthio, pyrrolidinoethylthio, morpholinoethylthioethylthio, imidazolylethylthio, 2-pyridylmethylthio, diethylamino ethylthio), arylthio groups (e.g. phenylthio, 4-dimethylaminophenylthio), heterocyclic oxy groups (e.g. 2-pyridyloxy, 2-imidazolyloxy), heterocyclic thio groups (e.g. 2-benzthiazolylthio, 4- virazolylthio)
, sulfonyl group (e.g. evamethanesulfonyl, ethanesulfonyl, p-toluenesulfonyl, methoxyethylsulfonyl, dimethylaminoethylsulfonyl), carbamoyl group (e.g. unsubstituted carbamoyl, methylcarbamoyl, dimethylaminoethylcarbamoyl, methoxyethylcarbamoyl, morpholinoethylcarbamoyl) , methylthioethylcarbamoyl, phenylcarbamoyl),
Sulfamoyl groups (e.g. unsubstituted sulfamoyl, methylsulfamoyl, imidazolylethylsulfamoyl, phenylsulfamoyl), carbonamide groups (e.g. acetamide, henzamide, methoxypropionamide, dimethylaminopropionamide), sulfonamide groups (e.g. methane sulfonamide, benzenesulfonamide, p-toluenesulfonamide), acyloxy groups (e.g. acetyloxy, benzoyloxy), sulfonyloxy groups (e.g. methanesulfonyloxy),
Ureido groups (e.g. unsubstituted ureido, methylureido, ethylureido, methoxyethylureido, dimethylaminopropylureido, methylthioethylureido,
morpholinoethylureido, phenylureido), thioureido groups (e.g. unsubstituted thioureido, methylthioureido, methoxyethylthioureido), acyl groups (
(e.g. acetyl, benzoyl, 4-methoxybenzoyl), heterocyclic groups (e.g. 1-morpholino, 1-piperidino, 2-hyridyl, 4-pyridyl, 2-thienyl, l-
pyrazolyl, ■-imidazolyl, 2-tetrahydrofuryl, tetrahydrothienyl), oxycarbonyl groups (e.g. methoxycarbonyl, phenoxycarbonyl, methoxyethoxycarbonyl, methylthioethoxycarbonyl, methoxyethoxyethoxyethoxycarbonyl, dimethylaminoethoxycarbonyl, morpholinoethoxycarbonyl), Oxycarbonylamino groups (e.g. methoxycarbonylamino, phenoxycarbonylamino,
2-ethylhexyloxycarbonylamino), amino groups (e.g., unsubstituted amino, dimethylamino, methoxyethylamino, anilino), carboxylic acids or their salts, sulfonic acids or their salts, hydroxyl groups, etc. Good and preferred heterocycles include pyrimidines,
Pyridazines, triazaindenes, tetraazaindenes, pentaazaindenes, and the following formula (Vl
), thiadiazoles, oxadiazoles, and selenadiazoles are mentioned.

General formula (VT) X represents an oxygen atom, a sulfur atom or a selenium atom.

ts or -N-, R%, R16, Ro, R1! ,
R1& R13, R14, Rts and R1& each represent a hydrogen atom, a substituted or unsubstituted alkyl group (for example, methyl,
ethyl, propyl, 2-dimethylaminoethyl), substituted or unsubstituted aryl groups (e.g. phenyl, 2-dimethylaminoethyl);
methylphenyl), substituted or unsubstituted alkenyl groups (e.g. propenyl, 1-methylvinyl), or substituted or unsubstituted aralkyl groups (e.g. benzyl,
R represents a straight-chain or branched alkylene group (e.g., methylene, ethylene, propylene, butylene, hexylene, 1-methylethylene), a straight-chain or branched alkenylene group (e.g., vinylene, 1-methylvinylene) ), straight-chain or branched aralkylene groups (eg benzylidene), arylene groups (eg phenylene, naphthylene), the above-mentioned groups represented by R may be further substituted.

M is a hydrogen atom, a halogen atom (e.g. chlorine, bromine),
Nitro group, cyano group, each substituted or unsubstituted amino group (including salt form, for example, amino, hydrochloride of amino group, methylamino, dimethylamino, hydrochloride of dimethylamino group, dibutylamino, dipropylamino) , N-
dimethylaminoethyl-N-methylamino, etc.), quaternary ammonio groups (e.g. trimethylammonio, dimethylbenzylammonio), alkoxy groups (e.g. methoxy group, ethoxy group, 2-methoxyethoxy group, etc.),
Aryloxy groups (e.g. phenoxy), alkylthio groups (e.g. methylthio, butylthio, 3-dimethylaminopropylthio), arylthio groups (e.g. phenylthio), heterocyclic oxy groups (e.g. 2-pyridyloxy, 2-imidazolyloxy) ), peterocyclic thio group (
For example, 2-benzthiazolylthio, 4-virazolylthio), sulfonyl group (e.g. methanesulfonyl, ethanesulfonyl aS, p-)luenesulfonyl), carbamoyl group (e.g. unsubstituted carbamoyl, methylcarbamoyl), sulfamoyl group (e.g. unsubstituted sulfamoyl, methylsulfamoyl), carbonamide group (
For example, acetamide, benzamide), sulfonamide groups (for example, methanesulfonamide, benzenesulfonamide), acyloxy groups (for example, acetyloxy, benzoyloxy), ureido groups (for example, unsubstituted ureido, methylureido, ethylureido), Acyl groups (e.g., acetyl, benzoyl), thiourido groups (e.g., unsubstituted thioureido, methylthioureido)
, sulfonyloxy groups (e.g. methanesulfonyloxy, p-1-luenesulfonyloxy), heterocyclic groups (
Examples include 1-morpholino, 1-piperidino, 2-pyridyl, 4-pyridyl, 2-thienyl, 1-pyrazolyl, 1
-imidazolyl, 2-tetrahydrofuryl, 2-tetrahydrothienyl), oxycarbonyl group (e.g. methoxycarbonyl, methylthiomethoxycarbonyl, phenoxycarbonyl), oxysulfonyl group (e.g. methoxysulfonyl, phenoxysulfonyl, ethoxysulfonyl), oxycarbonylamino group (For example, ethoxycarbonylamino, phenoxycarbonylamino, 4
-dimethylaminophenoxycarbonylamino) or mercapto group.

n represents 0 or 1.

In terms of the nucleation promoting effect, in the compound of general formula (Vl), preferably X is a sulfur atom and Y is -3-. Further, R is preferably linear or branched alkylene.

Next, the compound represented by general formula (IV) will be explained.

In the formula, Q has the same meaning as those in general formula (III),
Examples of the heterocycle formed by Q include indazoles, benzimidazoles, benzotriazoles, benzoxazoles, benzthiazoles, imidazoles, thiazoles, oxazoles, triazoles, tetrazoles, tetraazaindenes, Examples include triazaindenes, diazaindenes, pyrazoles, and indoles.

These heterocycles may be substituted with a substituent applicable to the heterocycle of formula (DI) above, or may be substituted with a hydroxyl group, a carboxyl group, or a salt thereof, or a sulfonic acid group, or a salt thereof. good.

Moreover, the -formula (IV) also includes a tautomer (Via), which is a case in which W in the -formula (III) is a nitrogen atom and is connected through the nitrogen atom.

-Math (Via) 'Q　,, Q in the formula has the same meaning as Q in the formula (I[I).

The nucleation accelerator used in the present invention is Berichte der Deutschen Hemitzen Gesellschaft (Berichte der Deutschen Hemitzen Gesellschaft).
Richte der Deutschen Chem
ischenGesellschaft) 28,?
? (1895), JP-A-50-37436, JP-A No. 51-
No. 3231, U.S. Patent No. 3,295,976, U.S. Patent No. 3,376°310,
der Deutschen Chemischen G
e5ellschaft), i! , 56B (188
9), I Eng., 2483 (1896), Journal of the Chemical Society (J.

Chew, Soc,) 1 ■ Yu I, 1806, Journal of the American Chemical Society (J, Am, Ches+, Soc,)? soil, 40
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Organic Chemistry), , i-Sat,
779-801 (1959L same magazine ■, 361-36
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Heterocyclic Chemistry
)i, 165 (196B), Organic Synthesis N, 56
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oc,) 45.2390 (1923), Hemische
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．． No. 066, No. 3,511.663, No. 3,060,
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No. 91, No. 3.598,599, No. 3,148,06
6, Japanese Patent Publication No. 43-4135, U.S. Pat.
No. 65, No. 2,444,605, No. 2゜444.60
No. 6, No. 2,444,607, No. 2.935,404
No. 2,152,406, No. 2,713.541, No. 2,743,181, No. 2,743,180,
2,887,378, 2,935.404, 2. 444゜609, 2,933.388, 2,891.862, 2,861,076, 2
It can be easily synthesized by the method described in No. 735.769.

Next, examples of compounds represented by general formula (1) will be shown, but the present invention is not limited thereto.

HI HI ut OOH CI! 3 H3 C11゜L (to) S ・C0OH oon ・HCJ Synthesis example 1 Synthesis of exemplified compound +11 6-chloro-1,3-dimethyluracil was added to Ltebig
sAnn, Chem, Bd, 612. 161 (1
It was synthesized by the following method described in 958).

1. 276 g (3,14 mol) of 3-dimethylurea and 376 g (3,62 mol) of malonic acid are dissolved in glacial acetic acid 600°C at 60-70°C, followed by acetic anhydride 125°C.
0d and gradually raise the temperature to 90°C. After stirring for 6 hours, the mixture was allowed to stand overnight at room temperature, and glacial acetic acid and acetic anhydride were distilled off under reduced pressure.

The residue was poured into 500 sd of ethanol while still hot, and the precipitated crystals were filtered off, heated under reflux with 380 M of concentrated hydrochloric acid and 400 M of water for 2 hours, and then allowed to stand for 6 hours under water cooling. The precipitated crystals were filtered and washed with a small amount of ethanol.1.
360 g of 3-dimethylbarbic acid was synthesized.

To 110 g of this 1,3-dimethylbarbylic acid, 32 g of water
M1 is added, and 800 m of phosphorus oxychloride is gradually added dropwise. After heating under reflux for 1.5 hours, phosphorus oxychloride was distilled off under normal pressure, and the residue was poured into ice while hot. The precipitated crystals were filtered off, and the filtrate was extracted with chloroform (X3) L, anhydrous sodium sulfate. Next, chloroform was distilled off, the resulting residue was combined with the previous crystals, and recrystallized from water to obtain 6-chloro-1,3-dimethyluracil 80
g was synthesized.

To a solution of 21 g of 6-chloro-1,3-dimethyluracil in 7°C of acetonitrile was added 16 g of N-chlorosuccinimide under ice cooling (internal temperature: 5°C).

After the internal temperature gradually increased and reached 35°C, 70°C of water was added to the reaction solution which was stirred for an additional hour, and the precipitated crystals were collected by filtration and washed with a mixed solvent of 18ml of cold acetonitrile and 18ml of water. When dried, 5,6-dichloro-1,3-dimethyluracil was obtained.Next, 1,8-
Diazabicyclo(5,4,O)uradecene-? (D
BU) 6 g of acetonitrile solution 20- was added dropwise and stirred for 1 minute at room temperature, then 5.6-dichloro-1,3-dimethyluracil 6.8 g acetonitrile solution 15 ml was added dropwise and stirred at room temperature for 2 hours. did. The acetonitrile was removed under reduced pressure, 2Ni concentrated hydrochloric acid and 100% of water were added, and the mixture was extracted twice with 100% of ethyl acetate. The organic layer was collected and dried over anhydrous magnesium sulfate, and then the ethyl acetate was removed under reduced pressure. A mixed solvent of n-hexane and ethyl acetate was added to the residue and recrystallized to give the target exemplary compound +11 to 12.
3g was obtained.

Synthesis Example 2 (Synthesis method of Exemplary Compound 14) 2.1 g of 5.6-dichloro-1,3-dimethyluracil
30-acetonitrile was added to 361 g of 2-(6-dimethylaminohexylthio)-5-mercapto-1,3,4-thiadiazole hydrochloride, and 1,8-diazabicyclo(5,4,0)-7-undecene was added at room temperature. 3.3- was added dropwise. After reacting at room temperature for 1 hour, 4.1 g of the oil obtained by drying under reduced pressure was dissolved in 20 d of acetone.
A solution of 1 g of oxalic acid dissolved in 20+d of acetone was added, and the precipitated crystals were collected by filtration. The obtained crystals were recrystallized from 50d of a mixed solvent of acetone and methyl alcohol (5/1) to obtain 2.3 g of the desired product.

Synthesis Example 3 Synthesis method for Exemplified Compound (5) Into a 300mm reaction vessel equipped with distillation equipment, 50g of 2-ethylhexylamine, 29g of methyl carbamate, and 100+d of toluene were added, and a catalytic amount of 0.1g of dibutyltin oxide was added, followed by heating. The reflux temperature was 110°C (boiling point of toluene) except for the methanol produced during the stirred reaction.
The Nawatara distillation equipment was removed, a reflux equipment was attached in its place, and after stirring for another 30 minutes, the mixture was allowed to cool. Toluene was removed under reduced pressure, the residue was washed with n-hexane, filtered, and N-
61 g of (2-ethylhexyl)urea was obtained.

A solution of 50 g of the obtained N-(2-ethylhexyl)urea, 36 g of malonic acid, and 100 d of acetic acid was heated to 80° C. and stirred for 4 hours. After cooling, remove acetic acid under reduced pressure and add 100 d of water.
, chloroform 500- was added and extracted.

The organic layer was washed with saturated sodium bicarbonate solution and then with saturated brine, dried over anhydrous magnesium sulfate, chloroform was removed under reduced pressure, the residue was washed with n-hexane, and filtered to give N-(2-ethylhexyl) barbyl. acid 6
Obtained 4g'lc.

Obtained N-(2-ethylhexyl)barbylic acid 4
120 g of phosphorus oxychloride was added to 0 g, and 3 g of water was gradually added dropwise. After heating under reflux for 2 hours, phosphorus oxychloride is distilled off under normal pressure, and the residue is poured onto ice while hot. It is further extracted three times with 200 ml of chloroform, and the organic layer is collected and dried over anhydrous magnesium sulfate.

Next, chloroform was removed under reduced pressure, n-hexane was added to the resulting residue, and the precipitated crystals were collected by filtration. Recrystallization from ethyl acetate gave 32 g of 6-chloro-3-(2-ethylhexyl)uracil as yellow crystals.

To a solution of 20 g of the obtained 6-chloro-3-(2-ethylhexyl)uracil in dimethylformamide, tt
After adding 12.1 g of potassium carbonate and further adding 12.1 g of iodomethyl, the reaction solution was stirred at room temperature for 1.5 hours. The filtrate was poured into water and extracted twice with 100% chloroform. After washing the organic layer with saturated brine and drying over anhydrous magnesium sulfate, chloroform was removed under reduced pressure to obtain 21 g of 6-chloro-3-(2-ethylhexyl)-1-methyl-uracil as an oil.

Obtained 6-chloro-3-(2-ethylhexyl)-1
-Methyl-uracil 20g solution in acetonitrile 50-
8.6 g of N-chlorosuccinimide was added to the mixture, heated to 40°C, and stirred for 2 hours. After cooling, acetonitrile was removed under reduced pressure, water was added to the residue, and the mixture was extracted with 100% chloroform. After washing the organic layer with saturated brine and drying over anhydrous magnesium sulfate, chloroform was removed under reduced pressure, and the residue was purified by silica gel chromatography to form an oil.
22 g of 6-dichloro-3-(2-ethylhexyl)-1-methyluracil was obtained.

Next, 6-methyl-4-mercapto-1,3,3a,7-
7 Setonitrile solution of 9 g of tetraazaindene 50H1
A solution of 8.3 g of 1,8-diazabicyclo[5°4.0]undecene-7 (DBU) in acetonitrile was added dropwise to the mixture, and the mixture was stirred at room temperature.

After 10 minutes, a solution of 16.7 g of 5.6-dichloro-3-(2-ethylhexyl)l-methyluracil in acetonitrile (30°) was added dropwise, and the mixture was stirred at room temperature for 2 hours. Acetonitrile was removed under reduced pressure, 3 d of concentrated hydrochloric acid and 50 d of water were added, and the mixture was extracted twice with 100 d of chloroform. The organic layer was collected, dried over anhydrous magnesium sulfate, chloroform was removed under reduced pressure, n-hexane was added to the residue, and the precipitated crystals were collected by filtration, yielding the desired exemplary compound (5) with 23.7
g was obtained.

Synthesis Example 4 Synthesis of Exemplified Compound (7) Dimedone 100g (0.71 mol) Chloroform 2
Add phosphorus trichloride 21- to the solution and heat under reflux for 3 hours. Ice water is added to the reaction solution to stop the reaction, chloroform is distilled off under reduced pressure, and the aqueous layer is extracted with ethyl acetate. After drying the organic layer over anhydrous sodium sulfate, it was concentrated under reduced pressure, and the residue was purified by distillation under reduced pressure to obtain 3-chloro-5,5
-Dimethyl-2-cyclohexen-1-one (45 g) was synthesized.

Yield 40%, boiling point 95°C/18 Tsuru Hg 1,8-diazabicyclo(5,4,0)undecene-7( DBU)6
．． Add dropwise 4 g of acetonitrile solution 10-
After stirring for 0 min, 3-chloro-5,5-dimethyl-2
15 d of an acetonitrile solution containing 6.1 g of -cyclohexene-1one was added dropwise, and the mixture was stirred at room temperature for 2 hours. Acetonitrile was removed under reduced pressure, 50 ad of concentrated hydrochloric acid 3-1 water was added, and the mixture was extracted with 100 mf of chloroform. The organic layer was dried over anhydrous magnesium sulfate, chloroform was removed under reduced pressure, diethyl ether was added to the residue, the precipitated crystals were collected by filtration, and recrystallized from n-hexane to give the desired exemplary compound (Katana 10. 8g was obtained.

Synthesis Example 5 Synthesis of Exemplary Compound Head 20 g (0.2 moles) of cyclohexanone and 16 g (0.2 moles) of formic acid ethyl ester were mixed with 400 g of dry ether.
16 g (0.4 mol) of NaH (60% content) are added over 1 hour while cooling in a water bath. After the addition is complete, stir the reaction mixture at room temperature for 6 hours (
B precipitates) is cooled again in a water bath while PCl52
150 d of a solution of 7 g (0.2 mol) in ether are added dropwise. After the dropwise addition is completed, the precipitate formed is filtered off under reduced pressure at room temperature for 3 hours. When the mother liquor is concentrated, 31 g of oily substance is obtained.
The resulting oil was dissolved in 100 d of acetonitrile without purification, and 6-methyl-4-
Mercapto-1,3,3a,7 = pentaazaindene 3
into a system in which 3 g is dissolved in 300 - of acetonitrile,
It was added dropwise at room temperature.

After stirring the reaction mixture for 6 hours, the acetonitrile was removed under reduced pressure. Add 5 d of hydrochloric acid and 200 ml of water to the residue,
Extracted twice with 00-chloroform.

After drying the organic layer over anhydrous magnesium sulfate, chloroform was distilled off under reduced pressure to obtain 55 g of crude crystals. When this is recrystallized with acetonitrile, the desired exemplary compound 0
35g of 0 was obtained.

The amount of the compound represented by general formula (1) of the present invention is:
Preferably IX 10-' per mole of silver halide
-10-'' mole, more preferably lXl0-'~
10-" moles.

In the present invention, when the compound represented by general formula (I) is contained in a photographic light-sensitive material, it is preferably contained in a silver halide emulsion layer, but it is preferably contained in a non-photosensitive hydrophilic colloid layer (for example, a protective layer, intermediate layer, filter layer, halation soil barrier layer, etc.). Specifically, if the compound to be used is water-soluble, it can be prepared as an aqueous solution, or if it is poorly water-soluble, it can be prepared using water-miscible organic solvents such as alcohols, esters, ketones, THF, or gelatin surfactants. It may be dissolved, dispersed, and added to a hydrophilic colloid solution. Also, like the couplers described below, it can be dissolved in a high boiling point organic solvent and emulsified and dispersed using a homogenizer. When added to the silver halide emulsion layer, it may be added at any time from the start of chemical ripening to before coating, but it is preferably added between the end of chemical ripening and before coating, especially when prepared for coating. It is best to add it to the applied coating solution.

Moreover, two or more kinds of compounds represented by the general formula (1) can also be used.

Here, the compound of general formula (I) is JP-A No. 63-8740, Japanese Patent Application No. 61-136948, No. 61136949, No. 61-252846, No. 62-310029,
It may be used in combination with the nucleation accelerator described in .

The unfogged internal latent image type silver halide emulsion used in the present invention is an emulsion containing silver halide in which the surfaces of silver halide grains are not fogged in advance and latent images are mainly formed inside the grains. But, more specifically,
A certain amount (0.5 to 3
g/rrr), 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. Normal photographic density measurement. The maximum density measured by the method is the following development WI of a silver halide emulsion coated in the same amount and exposed in the same manner as above.
Preferably, those having a density at least 5 times greater, more preferably at least 10 times greater, than the maximum density obtained when developed for 6 minutes at 20° C. in B (surface developer).

Internal developer A Metol 2g Sodium sulfite (anhydrous) 90g Hydroquinone
8g Soda carbonate (-water salt)
52.5gKBr
5gKI Q,
Add 5g water 11 Internal developer B Metol 2.5g L-ascorbic acid 10g NaBOz' 4HzO
35 g KBr 1 g water is added to form a IIl intraclinical emulsion.Examples include the conversion type silver halide emulsion described in U.S. Pat. '276, 3,850
．． No. 637, No. 3,923.513, No. 4,035,
No. 185, No. 4,395,478, No. 4.504.5
No. 70, JP-A-52-156614, JP-A No. 551275
No. 49, No. 53-60222, No. 5622681,
No. 59-208540, No. 60-107641, No. 61-3137, Japanese Patent Application No. 61-32462, Research Disclosure Magazine No. 23510 (1983
The core/shell type silver halide emulsion described in the patent disclosed on page 236 (published in January) can be mentioned.

The shapes of the silver halide grains used in the present invention include regular crystal shapes such as cubes, octahedrons, dodecahedrons, and tetradecahedrons, irregular crystal shapes such as spherical shapes, and length/ Tabular particles having a thickness ratio of 5 or more may be used. Further, an emulsion having a composite form of these various crystal forms or a mixture thereof may be used.

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

The average grain size of silver halide grains is 2 μm or less.
．． The particle size distribution is preferably 1 μm or more, and particularly preferably 1 μm or less and 0.15 μm or more.The particle size distribution may be narrow or wide, but it may be necessary to increase the particle size or weight to improve graininess and sharpness. 140% of average particle size
So-called "monodisperse" particle size distribution with a narrow particle size distribution in which 90% or more of all particles fall within ±20%, preferably within ±20%.
Preferably, silver halide emulsions are used in the present invention.

In addition, in order to satisfy the target gradation of a light-sensitive material, two or more types of monodisperse silver halide emulsions with different grain sizes or multiple types of monodisperse silver halide emulsions with the same size but different sensitivities are used in an emulsion layer having substantially the same color sensitivity. The particles can be mixed in the same layer or coated in separate layers. Furthermore, two or more types of polydisperse silver halide emulsions or a combination of a monodisperse emulsion and a polydisperse emulsion may be mixed or layered for use.

The silver halide emulsion used in the present invention can be chemically sensitized inside or on the grains by sulfur or selenium sensitization, reduction aggravation, noble metal sensitization, etc. alone or in combination. For detailed specific examples, see Research Disclosure magazine m17643 [[(Published December 1978) P2
This is in the patents described in 3.

The photographic emulsions used in the present invention are spectrally sensitized with photographic sensitizing dyes in a conventional manner. Particularly useful dyes are those belonging to cyanine dyes, merocyanine dyes and complex merocyanine dyes, and these dyes can be used alone or in combination. Further, detailed specific examples of the above-mentioned dyes and supersensitizers may be used in combination can be found in patents such as Research Disclosure Magazine No. 1'7643-IV (published December 1978), pages 23-24. .

The photographic emulsion used in the present invention may contain an antifoggant or a stabilizer for the purpose of preventing capri during the manufacturing process, storage, or photographic processing of the light-sensitive material, or for stabilizing photographic performance. For detailed examples, see Research Disclosure Magazine No. 17643-Vl.
(Published December 19'78) and E, J, Btrr
Author: 5tabilizationofPhotogr
aphtc 5ilver 1laflde E@ul
sion (Focal Press), published in 1974.

The fogging treatment of the present invention is carried out by the "photofogging method" and/or the "chemical fogging method" described below.

The entire surface exposure, that is, the fogging exposure in the "light fogging method" of the present invention is carried out after the imagewise exposure and/or during the development process. The imagewise exposed light-sensitive material is immersed in a developer solution or a pre-bath of the developer solution, or is taken out from the solution and exposed before it dries; most preferably, it is exposed in a developer solution.

As a light source for fogging exposure, a light source within the wavelength range to which the photosensitive material is sensitive may be used, and generally any of fluorescent lamps, tungsten lamps, xenon lamps, Taiyosho, etc. can be used.

These specific methods are described, for example, in British Patent No. 1,151,
No. 363, Special Publication No. 45-12710, No. 45-127
No. 09, No. 5B-6936, JP-A No. 48-9727, No. 56-137350, No. 57-129438,
No. 58-62652, No. 5B-60739, No. 58
-70223 (corresponding U.S. Patent No. 4,440°851)
, No. 58-120240 (corresponding European patent 89101A
2) etc.

Photosensitive materials sensitive to all wavelength ranges, such as color photosensitive materials, are disclosed in Japanese Patent Application Laid-open No. 56-137350 and No. 58-702.
A light source with high color rendering properties (as close to white as possible) as described in No. 23 is preferable, and the illuminance of the light should be 0. O1~200
0 lux, preferably 0.05 to 30 lux, more preferably 0.05 to 5 lux is suitable. For light-sensitive materials that use emulsions with higher sensitivity, exposure at lower illuminance is preferable. The illuminance may be adjusted by changing the luminous intensity of the light source, by reducing the light using various filters, by changing the distance between the photosensitive material and the light source, or by changing the angle between the photosensitive material and the light source. Further, the illuminance of the fogging light can be increased continuously or stepwise from low illuminance to high illuminance.

It is best to immerse the light-sensitive material in the developer solution or its pre-bath solution and irradiate it with light after the solution has sufficiently penetrated into the emulsion layer of the light-sensitive material. The time is generally 2 seconds to 2 minutes, preferably 5 seconds to 1 minute, more preferably 10 seconds to 30 seconds.

The exposure time for fogging is generally 0.01 seconds to 2 minutes.
Preferably 0.1 seconds to 1 minute, more preferably 1 second to 4 minutes
It is 0 seconds.

In the present invention, the nucleating agent used when carrying out the so-called "chemical fogging method" can be contained in the light-sensitive material or in the processing solution for the light-sensitive material. Preferably, it can be incorporated into the photosensitive material.

Here, the "nucleating agent" is a substance that acts to directly form a positive image during surface development of an internal latent image type silver halide emulsion that has not been fogged in advance. In particular, in the present invention, it is preferable to perform fogging treatment using a nucleating agent.

The nucleating agent, a compound represented by general formula (1), may be contained in the same layer or in different layers in the photographic light-sensitive material.

The nucleating agent preferably used in the present invention has the following general formula (
■) and (■).

- Formula (■) (In the formula, Z represents a nonmetallic atomic group necessary to form a 5- to 6-membered heterocycle, Z may be substituted with a substituent, R37 is an aliphatic group, , R18 is a hydrogen atom, an aliphatic group or an aromatic group.

R1? and R11 may be substituted with a substituent.

Furthermore, R2 may be further combined with the heterocycle completed by Z to form a ring, provided that at least one of the groups represented by Ro, RIS, and Z is an alkynyl group, an acyl group, It contains a hydrazine group or a hydrazone group, or R1 and R1 form a 6-membered ring to form a dihydropyridinium skeleton.

More R1? , R1, and at least one of the substituents of Z may have a group that promotes adsorption to silver halide.

X is a counterion for charge balance, and m is O or 1.

More specifically, the heterocycle completed by Z includes, for example, quinolinium, benzothiazolium, benzimidazolium, pyridinium, thiazolinium, thiazolium, naphthothiazolium, selenazolium, benzoselenazolium, imidazolium, tetrazolium, indo Mention may be made of rhenium, pyrrolinium, acridinium, phenanthridinium, isoquinolinium, oxacillium, naphthooxacillium and benzoxacillium nuclei. Substituents for Z include alkyl groups, alkenyl groups,
Aralkyl group, aryl group, alkynyl group, hydroxy group, alkoxy group, aryoloxy 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, urethane group, Examples include carbonate ester group, hydrazine group, hydrazone group, and imino group. As the substituent for Z, for example, at least one substituent is selected from the above substituents, but in the case of two or more substituents, they may be the same or different. Moreover, the above-mentioned substituents may be further substituted with these substituents.

Further, as the Z unit m group, a heterocyclic quaternary ammonium group may be used to complete Z via a suitable linking group. In this case, it takes a so-called dimer structure.

The heterocycle completed by Z preferably includes quinolinium, benzothiazolium, benzimidazolium, pyridinium, acridinium, phenanthridinium, and isoquinolinium nuclei. More preferred are quinolinium and benzothiazolium.

R1? The aliphatic group of R11 is an unsubstituted alkyl group having 1 to 18 carbon atoms and an alkyl moiety having 1 to 18 carbon atoms.
substituted alkyl groups. Examples of the substituent include those described as the substituent for Z.

The aromatic group represented by R11+ has 6 to 20 carbon atoms, and includes, for example, a phenyl group and a naphthyl group. Examples of the substituent include those described as the substituent for Z.

At least one of the groups represented by Rtt, R1, and Z has an alkynyl group, an acyl group, a hydrazine group, or a hydrazine group, or Rtt and R1 have 6
A membered ring is formed to form a dihydropyridinium core, which may be substituted with the group described above as a substituent for the group represented by Z.

At least one of the groups or substituents on the ring represented by Rtt, Rtt and Z is preferably an alkynyl group or an acyl group, or Rtt and Rtt are preferably linked to form a dihydropyridinium core.

These compounds and their synthesis methods are described, for example, in Research Disclo
sure) Magazine 11m22.534 (published January 1983, pages 50-54), and Na23,213 (19
Patent cited in (August 1983, pp. 267-270), Japanese Patent Publication No. 49-38,164, No. 52-19.452
No. 52-47,326, JP-A-52-69.61
No. 3, No. 52-3,426, No. 55138.742, No. 60-11,837, U.S. Patent No. 4,306,0
No. 16, and No. 4.471.044.

Specific examples of the compound represented by the -C formula (■) are listed below.

(■-1) CH, C=CH (■-2) CI(.

(■-3) (■-7) (■-4) CH, C: CI (■-8) H cnzc=cn (■-5) cthcmiCH (■-9) co, c=c■ 1゛C1I□C=CU (■-10) CB, C=CH C1hC=CH CI, CmiCI (■-15) CH,C=CI( (■-16) 1゛CHtC=Ct1 C1(2CmiCH C )l, C=C)l cn, c=C)l General formula (■) R? -N-N-G, -R Treasure I Az In the ceremony, R? represents an aliphatic group or an aromatic group, [represents a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an amino group, a carbamoyl group, or an oxycarbonyl group; group, P- group, or iminomethylene group, and A1, R? Both A2's represent a hydrogen atom, one of which is a hydrogen atom, and the other of which is a substituted or unsubstituted alkylsulfonyl group, a substituted or unsubstituted arylsulfonyl group, or a substituted or unsubstituted acyl group.

In the general formula (■), R? The aliphatic group represented by preferably has 1 to 30 carbon atoms, particularly 1 to 30 carbon atoms.
~20 straight chain, branched or cyclic alkyl groups. The branched alkyl group herein may be cyclized to form a saturated heterocycle containing one or more heteroatoms therein. Further, this alkyl group may have a substituent such as an aryl group, an alkoxy group, a sulfoxy group, a sulfonamide group, or a carbonamide group.

-R in formula (■)? The aromatic group represented by is a monocyclic or bicyclic heptaryl group or an unsaturated heterocyclic group.

Here, the unsaturated heterocyclic group may be condensed with a monocyclic or bicyclic aryl group to form a heteroaryl group.

For example, benzene ring, naphthalene ring, pyridine ring, pyrimidine ring, imidazole ring, pyrazole ring, quinoline ring,
Examples include isoquinoline ring, benzimidazole ring, thiazole ring, and benzothiazole ring, among which those containing a benzene ring are preferred.

R? The aryl group or unsaturated heterocyclic group may be substituted, and typical substituents include a linear, branched or cyclic alkyl group (preferably having 1 to 20 carbon atoms), an aralkyl group (preferably The number of carbon atoms in the alkyl part is 1 to 3
monocyclic or bicyclic), alkoxy groups (preferably carbon atoms 1 to 20), substituted amino groups (preferably carbon atoms 1 to 20)
(amino substituted with an alkyl group), acylamino group (
Preferably, there are 2 to 30 carbon atoms), a sulfonamide group (preferably 1 to 30 carbon atoms), and a ureido group (preferably 1 to 30 carbon atoms).

-R in formula (■)? The alkyl group represented by is preferably an alkyl group having 1 to 4 carbon atoms,
It may have a substituent such as a halogen atom, cyano group, carboxy group, sulfo group, alkoxy group, or phenyl group.

The aryl group is preferably a monocyclic or bicyclic aryl group, such as one containing a benzene ring. This aryl group is, for example, a halogen atom, an alkyl group, a cyano group,
It may be substituted with a carboxyl group, a sulfo group, etc.

The alkoxy group is preferably an alkoxy group having 1 to 8 carbon atoms, and may be substituted with a halogen atom, an aryl group, or the like.

The aryloxy group is preferably monocyclic, and the substituent includes a halogen atom.

As the amino group, unsubstituted amino group and carbon number 1-10
An alkylamino group or an arylamino group is preferred, and may be substituted with an alkyl group, a halogen atom, a cyano group, a nitro group, a carboxy group, or the like.

The carbamoyl group is preferably an unsubstituted carbamoyl group, an alkylcarbamoyl group having 1 to 10 carbon atoms, or an arylcarbamoyl group, and may be substituted with an alkyl group, a halogen atom, a cyano group, a carboxy group, or the like.

At and Ax are hydrogen atoms, alkylsulfonyl groups and arylsulfonyl groups having 20 or less carbon atoms (preferably phenylsulfonyl groups, or a group where the sum of Hammett's substituent constants is -0
, 5 or more), an acyl group having 20 or less carbon atoms (preferably a benzoyl group, or a benzoyl group substituted so that the sum of Hammett's substituent constants is -0.5 or more) group, or linear, branched, or cyclic unsubstituted and substituted aliphatic acyl groups (substituents include, for example, halogen atoms, ether groups, sulfonamide groups, carbonamide groups, hydroxyl groups, carboxy groups, and sulfonic acid groups) )) - Specific examples of the compound represented by formula (■) are shown below.

(■-1) (■-6) (■-2) (■-7) (■-4) (■-8) H (■-5) (■-9) cHzcHzcHzsH (■-10) (■- 11) (■-12) (■-13) (■-18) (■-21) (■-14) (■-16) (■-17) LLs11++ H1 to 5lhNH (■-22) (■-23 ) In addition to the above-mentioned hydrazine derivatives used in the present invention, RESEARCfl DISCLO5UR
E l tea23516 (November 1983 issue, P
, 346) and the documents cited therein, as well as U.S. Pat.
．． No. 276.364, No. 4,278,748, No. 4,
385.108, 4,459.347, 4,5
No. 60,638, No. 4,478,928, British Patent 2
, 011,391B, JP 60-179734, JP 62-270.948, JP 63-29.751, JP 61-170,733, JP 61-270,744
No. 62-948, Ep21? , No. 310, etc. can be used.

The nucleating agent used in the present invention can be contained in the sensitive material or in the processing solution for the sensitive material, preferably in the sensitive material. Moreover, two or more types of nucleating agents may be used in combination.

When it is added to the sensitive material, it is preferably added to the inner silver halide emulsion layer, but as long as the nucleating agent is adsorbed to the silver halide by diffusion during coating or processing, it may be added to other layers, e.g. , an intermediate layer, an undercoat layer or a back layer. When adding a nucleating agent to the processing solution, it should be added to the developer solution or a low p
It may be contained in the H pre-bath.

When a nucleating agent is included in the sensitive material, the amount used is preferably 10-1' to 10-2 mol, more preferably 10-7 to 10-3 mol, per 1 mol of Im halide.

In addition, when adding a nucleating agent to the processing solution, the amount used is:
As a nucleating agent in combination with the nucleation accelerator precursor represented by the general formula (1) of the present invention, the amount is preferably 10-S to 10-1 mol, more preferably 10-' to 10-8 mol per ltl. is represented by the above-mentioned formula (■). Heterocyclic quaternary ammonium salts for low pH treatment (pH<12)
It is particularly preferred in terms of promoting nucleation.

In order to further enhance the nucleation promoting effect according to the present invention, the following compounds can be used in combination with a wooden nucleation promoter.

Hydroquinones (e.g., U.S. Pat. No. 3,227.55)
No. 2, No. 4,279,987); chromans (e.g., U.S. Pat. No. 4,268,621, JP-A No.
-No. 103031, Research Disclosure 182
64 (1979)) ; quinone is (
For example, Research Disclosure No. 21206 (1
981); amines (e.g., compounds described in U.S. Pat. No. 4,150,993 and JP-A-58-174,757);
No. 39, Research Disclosure, Year 16936 (
(1978); catechols (for example, JP-A-55-21013 and JP-A-55-65944;
Compounds that release nucleating agents during development (e.g. compounds described in JP-A-60-107029);
Thiourea [(e.g., the compound described in JP-A-60-95533); spirobisindanes (e.g., JP-A-55-9553);
-65944).

A variety of color couplers can be used to form direct positive color images in the present invention. A color coupler is a compound that generates or releases a substantially non-diffusible dye through a coupling reaction with an oxidized form of an aromatic primary amine color developer, and is itself a substantially non-diffusible dye. Preferably, it is a compound. Typical examples of useful color couplers are naphthol or phenolic 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 given in "Research Disclosure", No. 17643 (published December 1978), p. 25;
■-D section, turning magnet 18717 (published in November 1979)
and the compounds described in Japanese Patent Application No. 61-32462 and the patents cited therein.

Among them, representative examples of yellow couplers that can be used in the present invention include oxygen atom elimination type and nitrogen atom elimination type yellow m:equivalent couplers. Especially α
-Pivaloylacetanilide couplers are preferred because they provide excellent color fastness, particularly light fastness, while α-benzoylacetanilide couplers provide high color density.

Further, as the 5-pyrazolone magenta coupler that can be preferably used in the present invention, a 5-pyrazolone coupler in which the 3-position is substituted with an arylamino group or an acylamino group (especially a sulfur atom-eliminated two-equivalent coupler) is used.

More preferred are pyrazoloazole couplers, particularly pyrazolo(5,1-c)(1,2,4) triazoles described in U.S. Pat. No. 3,725,067, but coloring dyes The imidazo[1°2-b]pyrazoles described in U.S. Pat. No. 4,500,630 are more preferred in terms of low yellow side absorption and light fastness; The described pyrazolo(1,5-b)(1,2,4))riazoles are particularly preferred.

Cyan couplers that can be preferably used in the present invention include:
U.S. Patent No. 2,474,293, 4°502.21
naphthol-based and phenol-based couplers described in US Pat. .5
-Diacylamino-substituted phenolic couplers are also preferred from the viewpoint of color image fastness.

Colored couplers to correct unnecessary absorption in the short wavelength range of the generated dyes, couplers in which coloring dyes have appropriate diffusivity, non-coloring couplers, DIR couplers that release development inhibitors along with the campling reaction, and Polymerized couplers can also be used.

Typical amounts of color couplers used range from 0.001 to 1 mole per mole of photosensitive silver halide;
Preferably from 0.01 to 0.5 for yellow couplers.
moles, for magenta couplers, from 0.03 moles to 0.03 moles.
5 mol, and for cyan couplers 0.002 to 0
．． It is 5 moles.

The coupler of the present invention is dissolved in an organic solvent with a high boiling point and/or a low boiling point, and is added to an aqueous solution of gelatin or other hydrophilic colloid by high-speed stirring using a homogenizer, mechanical pulverization using a colloid mill, or using ultrasonic waves. Emulsification and dispersion is performed using the technology described above, and this is added to the emulsion layer. In this case, it is not necessary to use a high boiling point organic solvent, but
Preferably, the compounds described on page 67 are used.

The coupler of the present invention is disclosed in JP-A-62-215272 No. 468.
It can be dispersed in a hydrophilic colloid by the method described on pages 1 to 475.

As the binder or protective colloid L7 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 photosensitive material of the present invention includes dyes that prevent irradiation and halation, ultraviolet absorbers, plasticizers, optical brighteners, matting agents, air fog preventers, coating aids, hardeners, and antistatic agents. It is possible to add a slip property improver, etc. Typical examples of these additives are found in Research Disclosure Magazine No. 17643 VX-Xlff (published December 1978), pages 25-27, and Research Disclosure No. 18716 (1979).
Published in November 2013) on pages 647-651.

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

In the photographic light-sensitive material of the present invention, the photographic emulsion layer and other layers are described in Research Disclosure Magazine N117643 (
Published in December 1978) on page 28, European Patent No. 0,182,253, and JP-A-61-97655.
It is coated on the support described in No. Further, the coating method described in Research Disclosure Magazine No. 17643XI Section 1 pzs-29 can be used.

The present invention can be applied to various color photosensitive materials.

For example, typical examples include color reversal film for slides or television, color reversal paper, and instant color film. It can also be applied to full-color copying machines and color hard copies for storing images on CRTs. The present invention also applies to [Research Disclosure Magazine 17123 (
It can also be applied to black-and-white light-sensitive materials using a mixture of three-color couplers, such as those described in J.D., published in July 1978).

Furthermore, the present invention can also be applied to black and white photographic materials.

As a black-and-white (B/W) photographic material to which the present invention can be applied, Japanese Patent Application Laid-Open No. 59-208540. Japanese Patent Application Publication No. 60-2600
B/W direct positive photographic material described in 39 (
For example, there are X-ray sensitive materials, duplex sensitive materials, micro sensitive materials, photographic sensitive materials, printing materials), etc.

The color developing solution used in the development 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. Aminophenol compounds are also useful as color developing agents, but p-phenylenediamine compounds are preferably used, representative examples of which include 3-methyl-4-amino-N, N-diethylaniline, 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
-β-methoxyethylaniline and their sulfates, hydrochlorides or p-)luenesulfonates.

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.

After color development, the photographic emulsion layer is usually bleached.

The bleaching process may be carried out simultaneously with the fixing process (bleach-fixing process) or separately. Furthermore, in order to speed up the processing, it is possible to use a processing method in which bleaching is followed by bleach-fixing, furthermore, processing in two consecutive bleach-fixing baths, fixing before bleach-fixing, or bleach-fixing. A post-bleaching treatment can also be optionally carried out depending on the purpose. Examples of bleaching agents include iron (■) and cobalt (1).
, chromium (Vl), and polyvalent metal compounds such as w4(u), peracids, quinones, nitro compounds, etc. are used.

Typical bleaching agents include ferricyanide; dichromate; organic complex salts of iron (I) or cobalt (I), such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1 .Using aminopolycarboxylic acids such as 3-diaminopropanetetraacetic acid, glycol etheramine tetraacetic acid, or complex salts of citric acid, tartaric acid, malic acid, etc.; persulfates; bromates; permanganates; nitrobenzenes, etc. be able to. Of these, iron ethylenediaminetetraacetate (I[[)! Aminopolycarboxylic acid iron(III) complex salts and persulfates, including 1 salt, are preferable from the viewpoint of rapid processing and prevention of environmental pollution. Furthermore, aminopolycarboxylic acid iron (I[l) complex salts are particularly useful in both bleaching solutions and bleach-fixing solutions. The pH of bleaching solutions or bleach-fixing solutions using these aminopolycarboxylic acid iron(III) complexes is usually 5.5 to 8, but in order to speed up the processing, the pH can be lowered. .

Examples of fixing agents include thiosulfates, thiocyanates, 1,000-onythyl compounds, thioureas, and large amounts of iodide salts, but thiosulfates are commonly used, with ammonium thiosulfate being the most commonly used. Can be used widely. As the preservative for the bleach-fix solution, sulfites, bisulfites, or carbonyl bisulfite adducts are preferred.

The silver halide color photographic light-sensitive material of the present invention is generally subjected to water washing and/or stabilization steps after desilvering treatment.

The amount of water used in the washing process depends on the characteristics of the photosensitive material (e.g., depending on the materials used, such as couplers), the application, the temperature of the washing water, the number of washing tanks (stage 31), the replenishment method such as countercurrent, forward flow, etc. It can be set over a wide range depending on various conditions. Among these, the relationship between the number of flushing tanks and the amount of water in the multi-stage countercurrent method is described in the Journal of the 5ociety.
f Motion Picture and Tele
vision Engineers Volume 64, P, 24B
-253 (May 1955 issue).

The pH of the washing water in the processing of the photosensitive material of the present invention is 4 to 4.
9, preferably 5-8. The washing water temperature and washing time can also be set variously depending on the characteristics of the photosensitive material, its use, etc., but generally it is 20 seconds to 10 minutes at 15 to 45°C, preferably 2
A range of 30 seconds to 5 minutes is selected at 5 to 40°C. Furthermore,
The light-sensitive material of the present invention can also be directly processed with a stabilizing solution instead of washing with water. In such stabilization treatment, Japanese Patent Application Laid-Open Nos. 57-8543 and 5B-14834
All known methods described in No. 60-220345 can be used. Various chelating agents and antifungal agents can also be added to this stabilizing bath.

On the other hand, various known developing agents can be used to develop the black and white light-sensitive material in the present invention. namely polyhydroxybenzenes, such as hydroquinone, 2-chlorohydroquinone, 2-methylhydroquinone, catechol, birogal, etc.; aminophenols, such as p-aminophenol, N-methylnylulaminophenol, 2,4-diaminophenol, etc.;
3-pyrazolidones, such as l-phenyl-3-virazolidones, 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. Further, the developer described in JP-A No. 58-55928 can also be used.

For detailed examples of developers, preservatives, buffers, and development methods for black and white photosensitive materials, and how to use them, see
Research Disclosure” magazine 17643 (19
Published in December 1978) Violet ~ is written in the section etc.

(Example) The present invention will be explained below based on examples.

Example-1 The following emulsion was prepared.

Emulsion A An aqueous solution of potassium bromide and an aqueous solution of silver nitrate were added to an aqueous gelatin solution containing 0.3 g of 3.4-dimethyl-1,3-thiazolidine-2-thione per mole of Ag at 75°C with vigorous stirring. They were added simultaneously over a period of about 20 minutes to obtain an octahedral monodisperse silver bromide emulsion with an average grain size of 0.4 μm. A chemical sensitization treatment was carried out by adding sodium thiosulfate and gold chloride M (tetrahydrate) in an amount of 6 μm per mole of silver to this emulsion and heating at 75° C. for 80 minutes. Using the thus obtained silver bromide grains as a core, they were further grown by further treatment for 40 minutes in the same precipitation environment as the first time, resulting in a final octahedral monodisperse/shell silver bromide emulsion with an average grain size of 0.7 μm. I got it. After washing with water and desalting, this emulsion was mixed with 1.0% each mole of silver. Chemical sensitization was carried out by adding 5 μm of sodium thiosulfate and gold chloride #I (tetrahydrate) and heating at 60° C. for 60 minutes to obtain internal latent image type silver halide emulsion A.

Example 1 Color photographic paper Na
1-28 were created.

[Preparation of coating solution]

Add ethyl acetate and solvent (C1 to a container containing magenta coupler (al) and color image stability (bl) to dissolve the magenta coupler.
It was emulsified and dispersed in a 0% aqueous gelatin solution.

This emulsified dispersion and the core/shell type internal latent image silver halide emulsion A (containing a green-sensitive dye and an irradiation dye) were mixed and dissolved, and the concentration was adjusted with gelatin to obtain the composition shown in Table 1. The compound of the present invention (
+) and a comparative compound were added to prepare a coating solution.

This coating liquid was applied onto polyethylene laminate paper. At the same time, an ultraviolet absorbing layer having the composition shown below was coated on this layer, and a protective layer having the composition shown below was further applied thereon.

Ultraviolet absorbing layer gelatin 1.60 g/rr (colloidal silver 0.10 g/rr + protective layer gelatin 133 g/acrylic modified copolymer of iborivinyl alcohol (denaturation degree 17%)' 0.17 g/rrl Table 1 Green-sensing layer Composition of 1 Dotomo bottom 1 - Sashiho 1 = Emulsion A
II40, 39g/n (gelatin magenta coupler ial 4.6 x 10-'
s+ol/n (color image stabilizer fake 1 0.1
4g/solvent resistant (010,42g/nf Nucleating agent (■-27) Compound (1) of the present invention and comparative compounds (Table 2) Development accelerator tX1 32■/d Green-translucent dye Illustrator for green-sensitive emulsion layer 03K in SO3 (C) t:x:t,s mixture (weight ratio) (n) LCa\/CJ* (n) L:2:2 mixture (weight ratio) (x) 0■ H A green filter is applied to the color photographic paper created in this way.
After applying wedge exposure (1/10 second IQCMS) through (Fuji Photo Film ■ 5P-2), the following processing step A was performed and the magenta color image density was measured (Photographic characteristics-1).

Processing step A Color development 1 minute 30 seconds 33℃ Bleach-fixing 40 seconds 33℃ Stable ■ 20 seconds 33℃ 0 20 seconds 33℃ ■ 20 seconds 33℃ A so-called countercurrent replenishment system was adopted in which the overflow liquid of bath (1) was led to stable bath (2), and the overflow liquid of stable bath (2) was led to stable bath (2).

[Color developer]

Diethylenetriamine Pentaacetic acid Hensyl alcohol Diethylene glycol Sodium sulfite Sodium bromide Hydroxylamine Sodium chloride 3-Methyl-4-amino-N Ethyl-N-(β-methanesulfonamidoethyl) 2.0g 12.8g 3,4g 2.0g 0.26g 2.60g 3.20g Aniline 4.25g Potassium carbonate
Add 30.0g fluorescent brightener (stilbene type) 1.0g water
1ooo-pH 11,20 pH was adjusted with potassium hydroxide or hydrochloric acid.

[Bleach-fix solution]

Mother liquor Ammonium thiosulfate 110g Sodium bisulfite lOg Diethylenetriaminepentaacetic acid iron (I[I) ammonium monohydrate 56g Ethylenediaminetetraacetic acid disodium dihydrate 5g Add water
1000adpH6.5 The pH was adjusted with aqueous ammonia or hydrochloric acid.

[Stabilizing liquid]

l-hydroxyethylidene 1.1'-diphosphonic acid (60%) Bismuth chloride polyvinylpyrrolidone ammonia water nitrilotriacetic acid/3Na 5-chloro-2-methyl-4 isothiapurin-3-o mother liquor 1,6- 0.35g 0. 25g 2,5-1,0g
50 ■ 2-octyl-4-isothiazolin-3-one 50 ■ Fluorescent brightener (
Add 1.0 g of 4,4'-diaminostilbene-based water to pH 7.5. Adjust the pH with potassium hydroxide or hydrochloric acid.

Comparative Compound A Comparative Compound B Comparative Compound C As is clear from Table 2, the comparative compound sample OI~α that does not use the compound of General 2N) has a sufficient maximum image density (
When increasing the amount of the comparative compound added to obtain Dmax),
Photographic characteristics showing an increase in minimum image density (Dmin)-1
), and even with a good addition amount, high temperature aging (45℃,
Exposure and development test after 80%RH (17 days) (Photographic characteristics-2)
), the maximum image density decreased significantly. In contrast, samples treated with the compound represented by the general formula (1) of the present invention +
11 to (9), even if the amount added was increased, the minimum image density did not increase, and even in the above-mentioned high-temperature aging test (photographic characteristics-2) with a good amount added, the maximum image density did not decrease and was good. A great image was obtained.

Example-2 Paper support laminated on both sides with polyethylene (thickness 10
A color photographic light-sensitive material was prepared in which the front side of the photosensitive material was coated with four layers starting from the next layer, and the back side was layered with five layers to six layers. The polyethylene on the coating side of the first layer contains titanium oxide as a white pigment and a trace amount of ultramarine as a bluish dye (the chromaticity of the surface of the support is Ll), a*
, 88.0 for be system. -0.20, -0.75. ).

(Photosensitive layer composition) The components and coating amount (g/rrf unit) are shown below. For silver halide, the coating amount is shown in terms of silver.

The emulsions used in each layer were prepared according to the manufacturing method for emulsion B. However, a Lippmann emulsion with no surface chemical sensitization was used for the Deshi four-layer emulsion.

1st layer (antihalation layer) Black colloidal silver 0.10 Gelatin 0.70 2nd layer (intermediate layer) Gelatin 0.70 3rd layer (low sensitivity red sensitive layer) Red sensitizing dye (ExS-1, 2, 3) Bromide 1 spectrally sensitized! (Average particle size 0.25μ, size distribution [8
%, octahedral) 0.04 red sensitizing dye (ExS-1
, 2, 3) spectrally sensitized chlorobromide! ! (115 mol% chloride, average particle size 0.40μ, size distribution 10%,
Octahedron) 0.08 gelatin 1.00 cyan coupler (
ExS-1, 2, 3 equivalents) 0.30 Anti-fading agent (Cpd-1, 2, 3, 4 equivalents) 0.18 Anti-stinting agent (Cpd-5) 0.003 Force puller dispersion medium (Cpd- 6) o, 03 coupler solvent (
sotv-1 + 2 + 3 + equivalent) 0.12 4th layer (high sensitivity red-sensitive layer) Silver bromide spectrally sensitized with red sensitizing dye (ExS-1, 2, 3) (average grain size 0.60μ, size Distribution 15%
, octahedron) 0.14 gelatin
1.00 Cyan coupler (ExC-12, 3 equivalents) 0.30 Antifading agent (Cpd-1, 2, 3, 4 equivalents) 0.18 Coupler dispersion medium (Cpd-6) 0.03 Coupler solvent ( Solv-1, 2, 3 equivalent) 0.12 5th layer (middle layer) Gelatin 1.00 Color mixing inhibitor (Cpd-7) 0.08 Color mixing inhibitor solvent (S
olv-4,5 equivalent) 0.16 Polymer latex (Cpd-8>0, lO 6th layer (low sensitivity green sensitive layer) Silver bromide (
Average particle size 0.25μ, size distribution 8%, octahedral)
0.04 green color enhancer (ExS-4)
Silver chlorobromide (1.5 mol% chloride, average grain size 0.40μ, size distribution 10%, octahedral) spectrally sensitized with 0.
06 Gelatin 0.80 Magenta coupler (ExM-L2 equivalent) 0.11 Anti-fade agent (Cpd-9) 0.10 Anti-stain agent (Cpd-10, 11, 12, 13 in a 10 near:7:1 ratio >0.025 force puller dispersion medium (Cp
d-6) 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 (Ex ,
Octahedron) 0.10 gelatin
0.80 magenta coupler (ExM-1,
2 equivalents) 0°0°11. 0゜0゜6 equivalents) 0.15 Anti-fade agent (Cpd-9) Anti-stinting agent (Cpd-10, 13 in 10N:7:l ratio) Coupler dispersion medium (Cpd-6) Coupler solvent (Solv -4, 12, 8th layer (intermediate layer) 9th layer (yellow filter layer) same as 5th layer Yellow colloidal silver gelatin Color mixing inhibitor (Cpd-7) Color mixing inhibitor solvent (Solv-4, 0, 12 0 , 07 0, 03 5 etc. 0, 10 Polymer latex (Cpd-8) 0, 07 10th layer (intermediate layer) 11th layer (low sensitivity blue sensitive layer) same as 5th layer Blue sensitizing dye (ExS- Silver bromide (average grain size 0.40 μ, size distribution 8%, octahedral) spectrally sensitized with 0.07 blue color multiplying dye (Ex
-5,6) spectrally sensitized silver chlorobromide (silver chloride 8 mol%
, average particle size 0.60 μ, size distribution 11%, octahedral) 0.14 Gelatin 0.80 Yellow coupler (ExY-1) 0.35
d-14) 0.10 stain inhibitor (Cpd
-5,15 in 1:5 ratio)
O, OQ7 coupler dispersion medium (Cpd-6) 0
．． 05 coupler? Container (Solv-2) 0.1
0 12th layer (high-frequency blue light layer) Silver bromide spectrally sensitized with blue sensitizing dye (ExS-5, 6) (average grain size 0.85μ, size distribution 18%, octahedron) 0. 15 gelatin
0.600, 30 0, 10 15 to 1=5 ratio 0, QO7 0, 05 0, l 0 Yellow coupler (ExY-1) Anti-fading agent (Cpd-14) Anti-stinting agent (cpa-5, at) Coupler Dispersion medium (Cpd-6) Coupler solvent (Sol・v-2) 13th layer (ultraviolet absorption layer) Gelatin ultraviolet absorber (Cpd 1,00 2.4.16 equivalent) 0,50 Color mixing inhibitor (Cpd- 7,17, etc. 1t) 0,03 Dispersion medium (Cpd-6) 0.02 Ultraviolet absorbing autopsy solvent (Solv-2, 7 equivalent) 0.08 Anti-irradiation dye (Cpd-18, 19, 20
, 21 in lQ:10=13:15 ratio)
0.04 14th layer (protective layer) Fine particle chloride bromide (chloride t!97 mol%, average size 0
．． 2 μ > 0.03 Acrylic modified copolymer of polyvinyl alcohol 0.01 Polymethyl methacrylate particles (average particle size 2.4
μ) and silicon oxide (average particle size 5μ) equivalent amount
0.05 gelatin
1.80 Gelatin hardening agent (H-1, H-2 equivalent) 0
．． 18 15th layer (back layer) Gelatin 2.50 16th layer (
Back protective layer) Polymethyl methacrylate particles (average particle size 2.4
μ) and silicon oxide (average particle size 5μ) equivalent amount
0.05 gelatin
2. OO gelatin hardener (H-1, H-2 equivalent) 0.1
4. How to make emulsion B: Add an aqueous solution of potassium bromide and silver nitrate to an aqueous gelatin solution at the same time with vigorous stirring over a period of 15 minutes at 75°C.
Octahedral silver bromide grains with an average grain size of 0.40 μm were obtained. To this emulsion was added 0.3 g of 3.4-dimethyl-1 per mole of silver.
, 3-thiazoline-2-thione, 6μ1g of sodium thiosulfate, and 700ml of chloroauric acid (tetrahydrate) were added in sequence at 75°C.
Chemical sensitization treatment was carried out by heating for 80 minutes. Using the thus obtained grains as cores, they were further grown in the same precipitation environment as the first time, and finally an octahedral monodisperse core/shell silver bromide emulsion with an average grain size of 0.7μ was obtained. The coefficient of variation was approximately 10%. To this emulsion, 1.5 μ of sodium thiosulfate and 1.5 μ of chloroauric acid (tetrahydrate) were added per mole of silver and heated at 60°C for 60 minutes to perform chemical sensitization treatment. Silver compound emulsion B was obtained.

In each photosensitive layer, ■-8 was added as a nucleating agent at 3.6 x 10-h mol/Ag mol based on the coating amount of silver halide, and the general formula (
The compound of I) and the comparative compound were added. Furthermore, each layer contains Alkanol XC (Dupon) as an emulsification and dispersion aid.
Company T) and sodium hyalkylbenzenesulfonate, succinate ester and Magefac as coating aids.
F-120 (manufactured by Dainippon Ink Co., Ltd.) was used. Silver halide and colloidal silver containing layers contain (Cpd) as a stabilizer.
-23, 24, 25) were used. Add this sample to the sample number (
1) to t1.

The compounds used in the examples are shown below.

xS-3 xS xS (CHz)s O3 O3H ・N(Czlls)s (CHz) x O3H xS-5 5OJ-N(CJs)+ O3H ExS-6 Cpd ■0 Cpd Cpd Cpd-IQ Cpd-11 Cpd-12 Cpd-13 0■ pct Cpd pti-6 H Cpd-7 Cpd 0■ Cpd Cpd-14 Cpd-15 H Cpd-17 H pd pd 03K pd-20 S (hK XC XC XC-3 03K SO, H pd- 21 pd-23 pd pd XM-1 CeH+t(t) XM-2 CsH+,(t) Di(2-ethylhexyl)separate trinonylphosphate di(3-methylhexyl)phthalate tricresyl phosphate dibutyl phthalate trioctyl phosphate di(2-ethylhexyl) phthalate 1.2-bis(vinylsulfonylacetamido)ethane 4.6- Dichloro-2-hydroxy-1,3,5-) riazine Na salt? -(3-(5-mercaptotetrazol-1-yl)benzatridine)-10-propargyl-1,2,3,4-tetrahydroacridinium perflora- A photographic property test was carried out in the same manner as in Example 1 except that the processing step B was changed. The cyan density of the obtained color image was measured.

Processing step B Color development 90 seconds 38℃ Bleach-fixing 40〃 33〃 Water washing Tll 40” 33〃 Water washing (2) 40#33〃 Water washing (3115〃33〃 Drying 30-80〃Washing water replenishment method is a washing bath (3), the overflow liquid from the washing bath (3) is led to the washing bath (2), and the overflow liquid from the washing bath (2) is led to the washing bath Tl), a so-called countercurrent replenishment method.At this time, The amount of bleach-fix solution brought into the washing bath (1) from the bleach-fix bath for photosensitive materials is 35 d/n (
The ratio of the amount of washing water replenished to the amount of bleach-fix solution brought in was 9.1 times.

The composition of each treatment liquid was as follows.

Optical brightener (diaminostilbene type) 1.0g Ethylenediaminetetrakismethylenephosphonic aciddiethyleneglycolbenzylalcoholPotassium bromideSodium sulfite N,N-diethylhydroxylamineTriethylenediamine (1゜4-diazabicyclo[2゜2.2]octane) N -Ethyl-N-(β-methanonylphonamidoethyl) -3-methylaniline sulfate Potassium carbonate 0.5 g 10- 12, (ld O, 65 g 2.4 g 4゜0g 4゜g 5゜g 27゜g pH (25°C) 10.50 Ethylene dithymine tetraacetic acid, 2 Sodium dihydrate, Ethylenediamine tetra acetic acid, Fe (III), Ammonium, Dihydrate ammonium thiosulfate (700 g/1) p-) Sodium luenesulfinate Sodium bisulfite Ammonium bromide Ammonium nitrate 4.0g 46.0g 20゜12゜50゜30゜pH (25°C) 6,20 Comparative compound treatment step C As is clear from Table 4, the present invention Samples (11 to (8)) treated with the compound represented by the general formula (1) of Example 1
Similarly, even if the amount added was increased, the minimum image density did not increase, and even in the high-temperature aging test (Photographic Properties-2), the maximum image density did not decrease and good images were obtained.

Example 3 A color photosensitive material was produced in the same manner as in Example 2 except that the nucleating agent was removed. The same photographic properties test as in Example 2 was carried out except that the processing step C was changed. Example-2
I got results that were equivalent to or inferior to.

Time Temperature color development 135 seconds 36℃ Bleach fixing 40 seconds 36℃ Stable 0 40 seconds 36℃ Stable ■ 40 seconds 36℃ Drying 40 seconds 70℃ rate l) After immersing in color developer for 15 seconds, 11ux white light Color development processing was carried out while performing light fogging for 15 seconds.

[Color developer]

Mother liquor Hydroxyethyliminodiacetic acid β-cyclodextrin Monoethylene glycol Benzyl alcohol Monoethanolamine Sodium bromide Sodium chloride 0,5 g 1,5 g 9,0 g 9.0 g 2,5 g 2,3 g 5,5 g N,N-diethylhydroxyl Amine 5,9g3-Methyl-4-amino-N-ethyl-N-(β-methanesulfonamidoethyl) monoaniline sulfate 2.7g3-methyl-
4-Amino-N-ethyl-N-(β-hydroxyethyl)-aniline sulfate 4.5g Potassium carbonate 30.0g Optical brightener (Stilbene type) 1.0g Add pure water
1000mff100O10,30 pti was adjusted with potassium hydroxide or hydrochloric acid.

[Bleach-fix solution]

Ammonium thiosulfate 110g Sodium bisulfite 12g Diethylenetriaminepentaacetic acid Iron (Il[) ammonium 80g Diethylenetriaminepentaacetic acid 5g 2-Mercapto-5
-Amino1.3.4-thiadiazole Add 0.3g of pure water
100 (ldpH6.80 ptt was adjusted with aqueous ammonia or hydrochloric acid.

[Stabilizing liquid]

Mother liquor 1-hydroxyethylidene 1.1-diphosphonic acid O-phenylphenol potassium chloride bismuth chloride zinc chloride sodium sulfite ammonium sulfate Fluorescent brightener (stilbene type) Add pure water 2.7g 0.2g 2.5g 1.0g 0.25g 0.3g 4.5g 0.5g 000d pH7.2 pH was adjusted with potassium hydroxide or hydrochloric acid.

Example 4 Example 2 was repeated to obtain the same results, except that the nucleating agent was changed to -13 and the treatment steps were as follows.

Processing process Color development 70 seconds 38℃ Bleach fixing 30 seconds 38℃ Wash with water ■ 30 seconds 38℃ Washing with water 0 30 seconds 38℃ At this time, the replenishment ratio of the washing liquid was 8.6 times.

[Color development]

Diethylenetriaminepentaacetic acid 1-hydroxyethylidene-1,1-diphosphonic acid diethylene glycol 0,5g 0,5g 8,0g Benzyl alcohol 9.0g Sodium bromide 0.7g Sodium chloride
0.5g sodium sulfite
2.0g Hydroxylamine sulfate 2.8
g3-methyl-4-amino-N ethyl-N-(β-methanesulfonamidoethyl) -aniline sulfate 2.0g3-methyl-
4-Amino-N ethyl-N-(β-hydroxyethyl)-aniline sulfate 4.0g Potassium carbonate 30.0g Optical brightener (Stilbene type) 1.0g Add pure water
100 (1+ff1pH10.50 pH was adjusted with potassium hydroxide or hydrochloric acid.

[Bleach-fix solution]

Ammonium thiosulfate? ? .

Sodium bisulfite 14.0g Ethylenediaminetetraacetic acid (DI) ammonium dihydrate 40.0g Ethylenediaminetetraacetic acid M2 sodium dihydrate 4.0g 2-mercapto-1,3,4 Add pure water 1000adpH7,
O pH was adjusted with aqueous ammonia or hydrochloric acid.

[Washing water]

Using pure water (mother solution - replenisher) Example-5 1 x 1 ΩU silver nitrate aqueous solution and potassium bromide aqueous solution were simultaneously mixed at a constant rate while keeping the silver electrode potential constant. , 8-dihydroxy-3,6-cythiaoctane) at 75°C (pH-
1/8 mol of silver nitrate was added to 5,5) with thorough stirring for 5 minutes to obtain a spherical AgBr monodisperse emulsion with an average grain size of about 0.14 μm. To this emulsion, 20 μ of sodium thiosulfate and 20 μ of chloroauric acid (tetrahydrate) were respectively added per mole of silver halide to adjust the concentration of I)H to 7.5, and the mixture was heated at 75° C. with thorough stirring. The core emulsion was chemically sensitized for 80 minutes at While maintaining the silver electrode potential at which the hedral grains grow, they were simultaneously added over a period of 40 minutes to allow the shell to grow, thereby obtaining a monodisperse cubic core/shell type emulsion with an average grain size of about 0.3 μm. The pH of this emulsion
was adjusted to 6.5, and 5 μ of sodium thiosulfate and 5 μ of chloroauric acid (tetrahydrate) were added per mole of silver halide, and the mixture was aged at 75°C for 60 minutes. A chemical sensitization treatment was performed to finally obtain an internal latent image type monodisperse octahedral core/shell type emulsion (emulsion X). As a result of measuring the grain size distribution of this emulsion from electron micrographs, the average grain size was 0.30μ, and the coefficient of variation (percentage of the value obtained by dividing the statistical standard deviation by the above-mentioned average grain size) was 10%. Ta.

Panchromatic sensitizing dye 3.3'-diethyl-9 was added to the above emulsion
- After adding methylthiacarbocyanine in an amount of 5 μm per mole of silver halide, 1-formyl-2-
(4-(3-(5-mercaptotetrazol-1-yl)benzamide]fenyl)hydrazine (■-10),
Halogenation of 3.5XlO-' mol per mol of silver halide and those listed in Table 5 as a nucleation accelerator! 11
1.8 x 10-' moles per mole were coated on a polyethylene terephthalate support at a silver content of 2.8 g/d, on which a protective layer consisting of gelatin and a hardener was simultaneously applied. Direct positive photographic materials-1 to Na1O, which are sensitive to red light, were prepared by coating.

The above photosensitive material was heated using an IKW tungsten lamp (color temperature 285).
4 (b)) With a photosensitive needle, through a step wedge,
．． Exposure was made for 1 second. Next, an automatic processor (Kodak P
Roster I Processor) by Kodak
ProsterPlus processing solution (developer pH 10.7
) for 18 seconds at 38° C., followed by washing with water, fixing, washing with water, and drying using the same developing machine. The maximum density (D+5ax) of the direct positive image of each sample obtained in this way,
The minimum concentration (Dmin) was measured.

Table 5 Comparative Compound E Comparative Compound F As is clear from Table 5, D+may is higher and the mouth sin Dmax did not decrease even in the high-temperature aging test (photographic characteristics-2), and good results were obtained.

(Effects of the Invention) According to the present invention, a direct positive photographic light-sensitive material can be obtained which provides both a high maximum image density and a low minimum image density. Furthermore, the above properties are not impaired even when stored at high temperatures, which is a great practical advantage.

Claims (1)

[Scope of Claims] A photographic light-sensitive material having on a support at least one photographic emulsion layer containing internal latent image type silver halide grains which has not been fogged in advance is fogged or subjected to fogging treatment after imagewise exposure. 1. A direct positive image forming method in which a direct positive image is formed by developing while developing the image, the developing being carried out in the presence of at least one compound represented by the following general formula (I). General formula [I] A-B In the formula, A represents a blocking group capable of releasing a nucleation accelerator during treatment, and B represents a nucleation accelerator bonded to A via a heteroatom. .