JPH02278253A - Direct positive photographic sensitive material - Google Patents

Abstract

PURPOSE:To form a direct positive image high in the maximum image density and low in the minimum image density by chemically sensitizing the surfaces of grains in the presence of a specified compound. CONSTITUTION:The surfaces of the grains are chemically sensitized in the presence of the compound represented by formula I in which A is a group to be adsorbed to silver halide grains; Y is a divalent combining group selected from H, C, N, O, and S atoms or atomic groups of them; R is an organic group having at least one of thioether, amino, ammonium, ether, and heterocyclic groups; n is 0 or 1; and m is 1 or 2, thus permitting a direct positive image high in the maximum image density and low in the minimum image density to be formed.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a direct positive photographic light-sensitive material having an emulsion layer containing chemically sensitized internal latent image type silver halide grains.

BACKGROUND OF THE INVENTION Photographic methods that provide direct positive images without the need for reversal processing steps or negative film are well known.

Excluding special methods, the methods used to create positive images using conventionally known direct positive silver halide photographic materials can be mainly divided into two types, considering their practical usefulness. can.

One type uses a silver halide emulsion that has been fogged in advance and uses solarization or the Burschel effect to destroy fog nuclei (latent images) in exposed areas, thereby obtaining a positive image directly after development. be.

The other type uses an unfogged internal latent image type silver halide emulsion and directly obtains a positive image by carrying out surface development after or while carrying out fogging treatment after image exposure.

The above-mentioned internal latent image type silver halide photographic emulsion is a type of silver halide photographic emulsion that has photosensitive nuclei mainly inside the silver halide grains and a latent image is mainly formed inside the grains upon exposure. means.

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

Various techniques are known to date in this technical field. For example, U.S. Patent Nos. 2,592.250, 2,466.957, 2.497.875,
No. 2,588,982, No. 3,317,322 (No. 2.497.875), No. 3,761,266
No. 3,761.276, No. 3,796,57
7 and British Patent No. 1,151,363, British Patent No. 1,
The main ones are those described in the specifications of No. 150.553 (No. 1,011,062).

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

For details on the direct positive image formation mechanism, see
The Theory of the Photographic Process, by T. H. James.
The Photographic Process
) 4th edition, Chapter 7, pages 182-193 and U.S. Patent No. 3,
It is described in No. 761,276, etc.

In other words, a so-called internal latent image (positive hole) formed inside the silver halide by the initial imagewise exposure.
), fog nuclei are selectively generated only on the surface of silver halide grains in unexposed areas, and then a photographic image ( It is believed that a direct positive image) is formed.

As mentioned above, as a means for selectively generating fog nuclei, there is generally a method called "light fogging method J" in which the entire surface of the photosensitive layer is exposed to a second light (for example, British Patent No. 1.151,
No. 363) and a nucleating agent (U
A method using a creating agent) is known. Regarding this latter method, for example, ``Research Disclosure J (Re5earch
Disclosure) Magazine Volume 151 Nα15162
(published in November 1976), 72-87.

Direct positive color images can be formed by fogging an internal latent image type silver halide sensitive material, or by performing surface color development processing while performing fogging, and then bleaching and fixing (or bleach-fixing). It can be achieved. After the bleaching and fixing treatments, washing and/or stabilizing treatments are usually performed.

(Problem to be solved by the invention!!i) Among these methods, the conventional chemical fogging method
A nucleating agent that only becomes effective at a high pH of 12 or higher is used, and therefore, under this high pH condition, the developing agent tends to deteriorate due to air oxidation, resulting in a significant decrease in developing activity. . Furthermore, since the developing speed is slow, processing time is long, and in particular, when a low pH developer is used, processing time is further increased. Also p
Even if H is 12 or more, there is a drawback that the development time is long.

On the other hand, the photofogging method does not require high pH conditions and is relatively advantageous in practice. However, there are various technical problems in using it for various purposes in the wide field of photography. That is, since the photofogging method is based on the formation of fog nuclei by photodecomposition of silver halide, the appropriate exposure illuminance and amount vary depending on the type and characteristics of the silver halide used. Therefore, it is difficult to obtain constant performance. To solve this problem, Japanese Patent Application Laid-Open No. 64-5
A number of proposals have been made, such as 0042 and JP-A-64-59348, but none of them have achieved sufficient stability.Furthermore, the developing device is complicated and expensive. Furthermore, there is a drawback that the development time is long.

As described above, with the conventional fogging method, it is difficult to obtain a stable and good direct positive image. As a means to solve this problem, compounds that exhibit a nucleating effect even at a pH of 12 or lower have been proposed in Japanese Patent Application Laid-open No. 52-69613 and U.S. Patent No. 3.615.
, No. 615 and No. 3 850.638, these nucleating agents act on the silver halide during storage of the sensitive material before processing, or the nucleating agent itself decomposes. However, there is a drawback that the maximum image density after processing is the final price.

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 small.

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.

As described above, there has never been a technique to obtain a direct positive image having a high maximum image density and a low minimum image density in a short period of time.

Instant color photography (color material diffusion transfer method) allows images to be obtained in a short time, but there is a need for even faster processing.

Furthermore, direct positive emulsions with high sensitivity generally have the problem of frequently generating re-inversion negative images upon high-intensity exposure.

, in order to improve these problems,
No. 506 discloses a method for forming a direct positive image in which development is carried out in the presence of a nucleation accelerator. According to this method, the problems of the conventional technology, including the method using a nucleating agent, have been dramatically improved. This was insufficient to resolve the issue. Furthermore, when adding a nucleation accelerator to the sensitive material using this method,
It has been found that when the above-mentioned nucleation accelerator is added to a particularly effective silver halide emulsion layer, the photographic properties obtained may vary greatly depending on the aging of the coating solution.

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

It is also an object of the present invention to ensure that the maximum image density and minimum image density do not easily vary from their optimum values, regardless of the storage period of the photosensitive material, even if the coating solution used in the production of the photographic material changes over time. The object of the present invention is to provide a direct positive photographic material capable of forming a direct positive image without variation in gradation.

[Means to solve the problem]

The above object is to provide a direct positive photographic light-sensitive material having at least one emulsion layer containing internal latent image type silver halide grains which are not pre-fogged on a support, the grain surfaces of which are represented by the following general formula (T). This was achieved using a direct positive photographic light-sensitive material characterized by being chemically sensitized in the presence of a chemical compound.

General formula (I) %Formula%) The compound represented by general formula (I) used in the present invention will be explained in detail.

A in the formula represents a group that adsorbs to silver halide.

Examples of the group adsorbed on silver halide include compounds having a mercapto group bonded to a heterocycle, heterocyclic compounds capable of producing iminosilver, or hydrocarbon compounds having a mercapto group.

Examples of mercapto compounds bonded to heterocycles include substituted or unsubstituted mercaptoazoles (e.g. 5-
Mercaptotetrazole, 3-mercapto-1,2,4
-) Riazole, 2-mercaptoimidazole, 2-mercapto-1,3゜4-thiadiazole, 5-mercapto-1,2゜4-thiadiazole, 2-mercapto-1
, 3°4-oxadiazole, 2. Mercapto-1,3
゜4-Selenadiazole, 2-mercaptooxazole, 2-mercaptothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 2-
mercaptobenzthiazole), substituted or unsubstituted mercaptopyrimidines (eg, 2-mercaptopyrimidine), and the like.

Examples of heterocyclic compounds capable of forming iminosilver include substituted or unsubstituted indazoles, benzimidazoles, benzotriazoles, benzoxazoles, benzthiazoles, imidazoles, thiazoles, oxazoles, triazoles, and tetrazoles. Examples include azaindenes, pyrazoles, and indoles.

Examples of the hydrocarbon compound having a mercapto group include alkylmercaptans, arylmercaptans, alkenylmercaptans, and alkylmercaptans.

Y represents a divalent linking group consisting of an atom or atom group selected from hydrogen, carbon, nitrogen, oxygen, and sulfur atoms. Examples of the divalent linking group include -3--0-
-N- It's broken.

These linking groups are connected to A or the heterocycle described below, and are either linear or branched alkylene groups (e.g., methylene, ethylene, propylene, butylene, hexylene, 1-ethylethylene), or substituted or unsubstituted arylene groups (phenylene, etc.). , naphthylene).

The above R+, Rx, Rs, Ra, Rs, R1
, Ry , Ra , R9 and R1 are each a hydrogen atom, a substituted or unsubstituted alkyl group (e.g. methyl, ethyl, propyl, n-butyl), a substituted or unsubstituted aryl group (e.g. phenyl, 2-methyl phenyl), substituted or unsubstituted alkenyl groups (e.g. propenyl, l-methylvinyl), or substituted or unsubstituted aralkyl groups (e.g. benzyl, phenethyl)
represents.

R in general formula (I) represents an organic group containing at least one thioether, amino group (including salt form), ammonium group, ether group, or heterocyclic group (including salt form). Examples of such organic groups include groups selected from substituted or unsubstituted alkyl groups, alkenyl groups, aralkyl groups, or aryl groups combined with the above groups; Good too. For example, hydrochloride of dimethylaminoethyl group, aminoethyl group, diethylaminoethyl group, dibutylaminoethyl group, dimethylaminopropyl group, dimethylaminoethylthioethyl group, 4-dimethylaminophenyl group, 4-dimethylaminobenzyl group, methylthioethyl group. group, ethylthiopropyl group, 4-methylthio-3-cyanophenyl group, methylthiomethyl group, trimethylammonioethyl group, methoxyethyl group, methoxyethoxyethoxyethyl group,
Methoxyethylthioethyl group, 3.4-dimethoxyphenyl group, 3-chloro-4-methoxyphenyl group, morpholinoethyl group, 1-imidazolylethyl group, morpholinoethylthioethyl group, pyrrolidinoethyl group, piperidinoprovil group, 2-pyridylmethyl group, 2-(I-imidazolyl)ethylthioethyl group, pyrazolylethyl group, triazolylethyl group, methoxyethoxyethoxyethoxyethoxycarbonylaminoethyl group, and the like.

In general formula (I), n represents 0 or l, and m represents 1 or 2.

Among the compounds represented by the general formula (I), preferred are the compounds represented by the following general formulas (n) to (■).

General formula (■) In general formula (II), Q preferably forms a 5- or 6-membered heterocyclic ring composed of at least one of carbon atom, nitrogen atom, oxygen atom, sulfur atom, and selenium atom. represents the atomic group necessary for

The heterocycle may also be fused with a carbon aromatic ring or a heteroaromatic ring.

Examples of the heterocycle include tetrazoles, triazoles, imidazoles, thiadiazoles, oxadiazoles, selenadiazoles, oxazoles, thiazoles, benzoxazoles, benzthiazoles, benzimidazoles, and pyrimidines. It will be done.

M is a hydrogen atom, an alkali metal atom (e.g. sodium,
potassium), ammonium groups (e.g. trimethylammonium, dimethylbenzylammonium), groups that can become M-H or alkali metal atoms under alkaline conditions (
For example, acetyl, cyanoethyl, methanesulfonylethyl).

In addition, these heterocycles include a nitro group, a halogen atom (e.g., chlorine, bromine), a mercapto group, a cyano group, a substituted or unsubstituted alkyl group (e.g., methyl, ethyl, propyl, L-butyl, cyanoethyl), and an aryl group. groups (e.g. phenyl, 4-methanesulfonamidophenyl, 4-methylphenyl, 3,4-dichlorophenyl,
naphthyl), alkenyl groups (e.g. allyl), aralkyl groups (e.g. benzyl, 4-methylbenzyl, phenethyl), sulfonyl groups (e.g. methanesulfonyl, ethanesulfonyl, p-toluenesulfonyl), carbamoyl groups (e.g. unsubstituted carbamoyl, methylcarbamoyl). ,
phenylcarbamoyl), sulfamoyl groups (e.g. unsubstituted sulfamoyl, methylsulfamoyl, phenylsulfamoyl), carbonamide groups (e.g. acetamide, benzamide), sulfonamide groups (e.g. methanesulfonamide, benzenesulfonamide, p-)luene sulfonamide), acyloxy groups (e.g. acetyloxy, benzoyloxy), sulfonyloxy groups (
(e.g., methanesulfonyloxy), ureido groups (e.g., unsubstituted ureido, methylureido, ethylureido,
phenylureido), thiourido groups (e.g. unsubstituted thioureido, methylthioureido), acyl groups (e.g. acetyl, benzoyl), oxycarbonyl groups (e.g. methoxycarbonyl, phenoxycarbonyl), oxycarbonylamino groups (e.g. methoxycarbonylamino, phenoxycarbonyl) amino, 2-ethylhexyloxycarbonylamino), carboxylic acid or its salt,
Although it may be substituted with a sulfonic acid or a salt thereof, a hydroxyl group, etc., it is preferable that it is not substituted with a carboxylic acid or a salt thereof, a sulfonic acid or a salt thereof, or a hydroxyl group.

Preferred examples of the heterocycle represented by Q include tetrazoles, triazoles, imidazoles, thiadiazoles, and oxydiazoles.

Y, R, m, and n each have the same meaning as in general formula (I).

General formula (III) Examples include soles, tetraazaindenes, triazaindenes, cyazaindenes, pyrazoles, and indoles.

General formula (IV) In the formula, YSR, m, and nSM have the same meanings as those in general formula CI), and Q' is an atomic group necessary to form a 5- or 6-membered heterocycle that can be formed with iminosilver. represents. 5 or 6 preferably selected from carbon, nitrogen, oxygen, sulfur, and selenium
Represents a group of atoms necessary to form a member heterocycle. Also,
The heterocycle may be fused as a carbon aromatic ring or a heteroaromatic ring. Examples of the heterocycle formed by Q' include indazoles, benzimidazoles, benzotriazoles, benzoxazoles, benzthiazoles, imidazoles, thiazoles, oxazoles, triazoles, tetra, M, R , Y, and n have the same meanings as those in general formula (II). X represents an oxygen atom, a sulfur atom or a selenium atom, with a sulfur atom being preferred.

General formula (V) In the formula, R' is a hydrogen atom, a halogen atom (for example, chlorine,
bromine), nitro group, mercapto group, unsubstituted amino group, substituted or unsubstituted alkyl group (e.g. methyl, ethyl), alkenyl group (e.g. propenyl, 1-
methylvinyl), an aralkyl group (eg benzyl, phenethyl), an aryl group (eg phenyl, 2-methylphenyl), or +Y)-r-R.

R" is a hydrogen atom, an unsubstituted amino group, or 1←Y)i-R
When R' and R' represent 1←Y)-i-R, they may be the same or different.

However, at least one of R' and R' is -(-Y)
-Represents R.

M, R, Y, and n each have the same meaning as in the above general formula (formerly).

General formula (Vl) R#' In the formula, RIP/ represents -←Y)-ii-R, where MSR, Y, and n have the same meanings as in the general formula (■), respectively.

General formula (■) In the formula, R11 and RI2 are hydrogen atoms, halogen atoms (e.g. chlorine, bromine), substituted or unsubstituted amino groups (
For example, unsubstituted amino, methylamino), nitro groups, substituted or unsubstituted alkyl 1 & (e.g. methyl, ethyl), alkenyl groups (e.g. eva, flobenyl, 1
-methylvinyl), aralkyl groups (e.g. benzyl,
phenethyl) or aryl groups (e.g. phenyl, 2-
methylphenyl group).

M and R'' each have the same meaning as each of the above general formula (Vl).

Specific compounds represented by formulas (I) to (■) of the present invention are shown below, but the compounds of the present invention are not limited thereto.

C2 The photographic emulsion containing internal latent image type silver halide grains that has not been fogged in advance and is used to form the light-sensitive material of the present invention has sulfur or selenium sensitization or reduction sensitization inside or on the silver halide grains. Chemical sensitization can be carried out for 3 days using noble metal enhancement alone or in combination.

The compound represented by the general formula (I) used in the present invention is added to the photographic emulsion at any point in the emulsion preparation process in which the surface is chemically sensitized. The amount of the compound added is
It is preferably 10-- to 1 O-ffi mole, more preferably IQ-5 to 10-'' mole per mole of silver halide.

The above-mentioned compound also acts as a so-called nucleation accelerator during the formation of a positive image in a direct positive photographic light-sensitive material. Apart from being used as a nucleation accelerator, the compound can be added to the photosensitive material or to the processing solution as a nucleation accelerator. In that case, it is added to the photosensitive material,
Among these, it is preferable to incorporate it into an internal latent image type silver halide emulsion or other hydrophilic colloid layers (intermediate layer, protective layer, etc.). Particularly preferable is a silver halide emulsion layer or a layer adjacent thereto.

In this case as well, the amount added is 10 - per 111 moles of halogenide.
-~10-! molar is preferred, more preferably 10-'
~104 moles.

When the compound is added to a processing solution, that is, a developer or a pre-bath thereof, the amount is preferably 1 to 10@-3 mol, more preferably 10@-7 to 10@-4 mol per 11 mols.

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. However, more specifically, a silver halide emulsion is deposited on a transparent support in a certain amount (0.5~
3g/po)! ! When exposed to light for a fixed time of 0.01 to 10 seconds and developed at 18°C for 5 minutes in the following developer A (internal type developer), the photographic density was measured using a normal photographic density measurement method. The maximum density was obtained by applying the same amount of silver halide emulsion as above and exposing it in the same manner using the following developer B.
Preferred are those having a density that is 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 a surface developer.

Internal developer A Metol 2g Sodium sulfite (anhydrous) 90g Hydroquinone
8g Soda carbonate (-water salt)
52.5gKBr
5gKIO
, Add 5g water 11 Surface type image solution Metol 2.5g L-ascorbic acid 10g NaBOz' 4H
z0 35gKBr
Add 1g water
Examples of IIl intraclinical emulsions include:
The conversion silver halide emulsion described in U.S. Pat. No. 2,592,250, U.S. Pat.
No. 761.276, No. 3,850,637, No. 3,9
23.513, 4,035,185, 4,39
No. 5,478, 4. 504. No. 570, Japanese Patent Publication No. 5
No. 2-156614, No. 55-127549, No. 53
-60222, 56-22681, 59-20
No. 8540, No. 60-107641, No. 61-313
No. 7, Japanese Patent Application No. 61-32462, and Research Disclosure Magazine NQ23510 (published in November 1983) P2S5.

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 grains having a thickness ratio of 5 or more may be used, or emulsions having composite forms of these various crystal forms or mixtures 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 thickness is preferably 1 μm or more, and particularly preferably 0.15 μm or more below lum. The particle size distribution may be narrow or wide, but in order to improve granularity and sharpness, the particle number or weight should be ±40% of the 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 sensitization, noble metal sensitization, etc. alone or in combination. For detailed specific examples, see Research Disclosure Magazine No. 17643-III (December 1978).
It is in the patent described on page 23 (issued in May).

The photographic emulsions used in this invention are: spectrally sensitized with photographic enhancing dyes in 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, the above dyes and supersensitizers may be used in combination. For detailed specific examples, see Research Disclosure Magazine No. 17643-IV (December 1978).
It is in the patent described on pages 23-24 (published in May).

The photographic emulsion used in the present invention may contain an antifoggant or a stabilizer for the purpose of preventing fog 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 1978) and E, J,
“5tabiliauttonof Pho” written by Birr
tographic 5ilver l1ailde
Emulsion (Focal Press), 19
It is written in the 1974 edition.

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 include naphthol or phenolic compounds, pyrazolones 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" magazine Nα17643 (published December 1978) P25
, ■ = D section, No. 18717 (issued in November 1979), and the compounds described in Japanese Patent Application No. 6132462 and the patents cited therein.

Card couplers for correcting unnecessary absorption in the short wavelength range of the generated dyes, couplers whose coloring dyes have appropriate diffusivity, colorless couplers, and DIR couplers that release a development inhibitor upon coupling reaction. or polymerized couplers can also be used.

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

A color antifogging agent or a color mixing inhibitor can be used in the light-sensitive material of the present invention.

Representative examples of these are JP-A-62-215272 No. 185~
It is described on page 193.

A color enhancer can be used in the present invention for the purpose of improving the color development of the coupler. A typical example of a compound is JP-A No. 6
Examples include those described in No. 2-215272, pages 121 to 125.

The photosensitive material of the present invention includes a dye that prevents irradiation and halation, an ultraviolet absorber, a plasticizer, a fluorescent brightener, a matting agent, an air fog preventer, a coating aid, a hardening agent, and an antistatic agent. It is possible to add additives, shearability improvers, etc. Typical examples of these additives are Research Disclosure LiNNo., Sections 17643
18716 (I97), 225-27, and 18716
Published in November 1999), pages 647-651.

The invention is also applicable to multilayer, multicolor photographic materials having at least two different spectral sensitivities on the support.

Multilayer natural color photographic materials usually have a red-sensitive emulsion layer on a support,
It has at least one green-sensitive emulsion layer and at least one blue-sensitive emulsion layer. The order of these layers can be arbitrarily selected as necessary. The preferred order of layer arrangement is red sensitivity, green sensitivity, and blue sensitivity from the support side, or green sensitivity, red sensitivity, and blue sensitivity from the support side. Furthermore, each of the above-mentioned emulsion layers may be made up of two or more emulsion layers having different sensitivities, and a non-light-sensitive layer may be present between two or more emulsion layers having the same color sensitivity. good. Usually, the red-sensitive emulsion layer contains a cyan-forming coupler, the green-sensitive emulsion layer contains a magenta-forming coupler, and the pre-malignant emulsion layer contains a yellow-forming coupler, but different combinations may be used depending on the case.

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 agent,
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 Nα17643VVI.
(Published in December 1978) p2B, European Patent No. 0,102,253, and Japanese Patent Application Laid-open No. 61-976.
No. 55. Also, Research Disclosure Magazine N (L17643XV section p28-2
The coating method described in 9 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 Nα17123
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.

Examples of black-and-white (B/W) photographic materials to which the present invention can be applied include JP-A-59-208540 and JP-A-60-260.
B/W direct positive photographic materials described in No. 039 (for example, X-ray photosensitive materials, duplex photosensitive materials, micro photosensitive materials,
photosensitive materials, printing photosensitive materials), etc.

The fogging treatment of the present invention is carried out by the following "photofogging method" and/or "chemical fogging method". 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 drying, but it is most preferable to expose the material in the 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, sunlight, 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. 58-60739, No. 58
-70223 (corresponding U.S. Patent No. 4,440°851)
, No. 58-120248 (corresponding European Patent No. 89101A
2) etc.

For photosensitive materials sensitive to all wavelength ranges, such as color photosensitive materials, Japanese Patent Application Laid-open Nos. 56-137350 and 5B-702
A light source with high color rendering properties (as close to white as possible) as described in No. 23 is preferable. The illuminance of the light is 0.01~200
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 changing the exposure 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 preferable to immerse the light-sensitive material in a developer solution or a pre-bath solution, and to irradiate the light-sensitive material after the solution has sufficiently penetrated into the emulsion layer of the light-sensitive material. The time from penetration into the liquid to photofogging exposure is generally 2 seconds to 2 minutes, preferably 5 seconds to 1 minute, and more preferably 10 seconds to 30 seconds.

The exposure time for fogging is generally 0.01 seconds to 2 minutes.
Preferably 0. 1 second to 1 minute, more preferably 1 second to
It is 40 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 the present invention, fogging using a nucleating agent is particularly preferred.

When incorporated into a light-sensitive material, it is preferably added to the latent type 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. For example, it may be added to an intermediate layer, undercoat layer or back layer.

When the nucleating agent is added to the processing solution, it may be contained in the developer solution or a low pH prebath as described in JP-A-58-178350.

Furthermore, two or more types of nucleating agents may be used in combination.

Regarding the nucleating agent used in the present invention, the general formula (N-1
) and (N-If) are preferably used.

General formula (N-I)...Z-- (wherein, Z represents a group of nonmetallic atoms necessary to form a 5- to 6-membered heterocycle, and Z may be substituted with a substituent. R4 is an aliphatic group, and R5 is a hydrogen atom, an aliphatic group, or an aromatic group. R4 and R5 may be substituted with a substituent. Furthermore, R5 is a heterocycle completed with Z. May be combined to form a ring.However, R4, R5
At least one of the groups represented by and Z contains an alkynyl group, an acyl group, a hydrazine group, or a hydrazone group, or R4 and R5 form a 6R ring to form a dihydropyridinium skeleton. Furthermore, at least one of the substituents R4, R5 and Z may have a group promoting adsorption to silver halide. Y is a counter ion for charge balance, and n is 0 or l.

General formula (N- is shown below.

(N-■-1) (N-1-2) (N-1-3) (N-1-4) (N-1-5) (N-1-6) ■] Example 5 - Ethoxy-2-methyl-1 propargylquinolinium promide 2,4-dimethyl-1-propargylquinolinium promide 34-dimethyl-dihydropyrido (2,1-b)penzothiadurium promide 6-nitoxy Thiocarponylamino-2-methyl-1-propargylquinolinium trifluoromethanesulfonate 6-(5-benzotriazolecarboxamide)-2-methyl-1-propargylquinolinium trifluoromethanesulfonate 6-(5-mercaptotetrazole- 1-yl)-2-methyl- 1-propargylquinolinium iosito 6-ethoxythiocarponylamino-2-(2-methyl-1-propenyl)-1-propargylquinolinium trifluoromethanesulfonate 10-propargyl- 1,2 3,4,-Tetrahydroacridinium trifluoromethanesulfonate 7-nitoxythiocarponylamino-IO-propargyl-1 2,3,4-tetrahydroacridinium trifluoromethanesulfonate (N-I-10) 7-(3-(5-mercaptotetrazol-1-yl)benzamide]-10-propargyl-1°(Ni-7) (N-1-8) (N-1-9) 2.3.4-tetrahydro acridinium velchlorate (N-1-11) 7-(5-mercaptotetrazol-1-yl)-9-methyl-10-propargyl-1,2°3.4-tetrahydroacridinilam bromide (N -I-12) 7-nitoxythiocarponylamino-10-propargyl-I.

2-dihydroacridinium trifluoromethanesulfonate (N-J-13) I O-propargyl-7-[3
-(I,2,3,4-thiatriazol-5-ylamino)benzamide)-1,2,3,4-tetodihydroacridinium perchlorate (N-I-14) 7- (3-cyclo,hexylmethoxy thiocarbonylaminobenzamide)-10-propargyl-1,2,3,4-tetrahydroacridinium trifluoromethanesulfonate (N-1-15)? -(3-Ethoxythiocarbonylaminobenzamide)-10-1propargyl~1. 2. 3. 4゜-Tetrahydroacridinium trifluoromethanesulfonate (N-1-16)? -(3-(3-ethoxythiocarbonylaminophenyl)ureido-10-propargyl-1゜2.3,4.Tetrahydroacridinium trifluoromethanesulfonate (N-1-17)7-(3-ethoxythiocarbonylamino benzenesulfonamide)-1O-propargyl-1゜2.3.4-tetrahydroacridinium trifluoromethanesulfonate (Nl-18) 7-[3-[3-[3-(5mercaptotetrazol-1-yl) phenyl]ureido)benzamide go 10-propargyl 1, 2. 3. 4-tetrahydroacridinium
Trifluoromethanesulfonate (N-1-19) 7- (3-(5-mercapto-1,
3,4-thiadiazole-1-ylamino)benzamide] -10-propargyl-1,2゜3.4-tetrahydroacridinilam trifluoromethanesulfonate (N-1-20) 7- (3-(3-butylthio) ureido)benzamide]-IO propargyl-1,2,3,4-tetrahydroacridinium trifluoromethanesulfonate general formula (N-113 (wherein, R21 represents an aliphatic group, an aromatic group, or a heterocyclic group; ; R22 represents a hydrogen atom, an alkyl group, an aralkyl group, an aryl group, an alkoxy group, an aryloxy group, or an amino group; G represents a carbonyl group, a sulfonyl group, a sulfoxy group, a phosphoryl group, or an iminomethylene group (HN=C R13 and R24 are both hydrogen atoms, or one is a hydrogen atom and the other is an alkylsulfonyl group, an arylsulfonyl group, or an acyl group.However, G, R2!, R24 and hydrazine nitrogen The hydrazone structure (N-N=C
) may be formed. Further, the groups described above may be substituted with a substituent if possible. ) Next, the general formula (N-
Specific examples of the compound represented by n) are shown below.

(N-11-1) 1-formyl-2-(4,-(
3-(2-methoxyphenyl)ureido]-phenyl)hydrazine (N-n-2) 1-formyl-2-(4-(3-(
3-(3-(2,4-di-tert-pentylphenoxy)propyl)ureido)phenylsulfonylaminoco-phenyl)hydrazine 1-formyl-2-(4-(3-(5-mercaptotetrazol-1-yl) )benzamido]phenyl)hydrazine■-formyl-2-(4-(3-C3-(5-mercaptotetrazol-1-yl)phenyl]ureido)phenyl]hydrazine1-formyl-2-(4-[3-(N -(5-mercapto-4-methyl-1,2,4-1-riazol-3-yl)carbamoyl]propanamido)phenyl]hydra(N-■-4) (N-n-3) (N-11 -5) Zin 1-formyl-2-(4-(3-[N-[4-(3-mercapto-1,2,4-1 lyazole-4 monoyl)phenyl]carbamoyl]propanamido]phenyl)hydrazine 1-Formyl-2-(4-(3-(N-(5-mercapto-1゜3.4-thiadiazol-2-yl)carbamoyl]propanamido)phenyl]hydrazine (N-11-8) 2-( 4-(benzotriazole-5-carboxamido)phenyl]-1-formylhydrazine2-(4-(3-(N-(benzotriazole-5-carboxamido)carbamoyl]propanamido)phenyl)-1-formylhydrazine(N -11-9) (N-11-6) (N-[[-7) (N-11-10)1-formyl-2-(4-[1-(
N-phenylcarbamoyl) thiosemicarbazide] phenyl) hydrazine (N-n-1],)]1-formyl-2-(4-(3-
(3-phenylthiouredo)benzamido)phenyl)hydrazine (N-II-12) 1-formyl-2-(4-(3-hexylureido)phenyl) hydrazine (N-n-13) 1-formyl-2 -(4-[3-(5
-Mercaptotetrazol-1-yl)benzenesulfonamido]phenyl)hydrazine (N-I[-14)1-formyl-2-(4-C3-(
3-(3-(5-mercaptotetrazol-1-yl)phenyl)ureido)benzenesulfonamide]phenyl)hydrazine (N-n-15) 1-formyl-2-(4-+3(3-
(2,4-di-tert-pentylphenoxy)propyl]ureido)phenyl]hydrazine The nucleating agent used in the present invention can be contained in the sensitive material or in the processing solution for the sensitive material, and is preferably contained in the sensitive material. I can do it.

When contained in a sensitive material, it is preferably added to the Uchinuma-type 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 bank 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 the nucleating agent is contained in the sensitive material, the amount used is preferably from lo-8 to 10-2 mol, more preferably from 10-' to 10-1 mol per 1 mol of halokene (tJ).

In addition, when adding a nucleating agent to the processing solution, the amount used is 1
i! , is preferably 10-'-10-' mole, more preferably 10-4 to 104.

In the present invention, a nucleation accelerator can be used to further promote the action of the nucleation agent.

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, typical examples of which include 3-methyl-4-amino-N, N-diethylaniline, 3-diethylaniline, and 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,
Examples include hydrochloride and P-toluenesulfonate. 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, a processing method may be used in which bleaching is followed by bleach-fixing. Furthermore, treatment with two consecutive bleach-fixing baths, fixing treatment before bleach-fixing treatment, or bleaching treatment after bleach-fixing treatment can be carried out as desired depending on the purpose.

The silver halide photographic material of the present invention is generally subjected to a water washing and/or stabilization process after desilvering treatment. The amount of water used in the washing process varies widely depending on the characteristics of the photosensitive material (for example, depending on the materials used such as couplers), the application, the temperature of the washing water, the number of washing tanks (number of stages), the replenishment method such as free flow or down flow, and various other conditions. Can be set. Among these, the relationship between the number of washing tanks and the amount of water in the multistage countercurrent method is
l of theSociety of Motion
Picture and TelevisionEn
Gineers Volume 64, p24B-253 (I9
It can be determined using the method described in the May 1955 issue).

The silver halide light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and speeding up processing. In order to incorporate the color developing agent, it is preferable to use various precursors of the color developing agent.

On the other hand, various known developing agents can be used to develop the black and white light-sensitive material in the present invention. i.e. polyhydroxybenzenes, such as hydroquinone, 2-chlorohydroquinone, 2-methylhydroquinone, catechol, pyroga, roll, etc.; aminophenols, such as p-aminophenol, N-methyl-
p-aminophenol, 2,4-diaminophenol, etc.; 3-pyrazolidones, such as 1-phenyl-3-pyrazolidones, l-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. or,
The developer described in JP-A No. 58-55928 can also be used.

〔Example〕

The present invention will be explained in detail below using examples.

However, the present invention is not limited thereto.

Example 1 Paper support laminated on both sides with polyethylene (thickness 10
A color photographic material was prepared in which the following 1st to 14th layers were coated on the front side of the film (0 micron), and 15th to 16th layers were coated on the back side. The polyethylene on the first layer coating side contains titanium oxide (4 g/n) as a white pigment, and ultramarine blue (10.003 g/n) as a bluish pigment (
The chromaticity of the surface of the support is 88.0 in Lll, a*, and bs systems.
, −〇.

20, -0.75. ).

(Photosensitive layer composition) Ingredients and application below! (in units of g/rrf). In addition,
For silver halide, the coating amount is shown in terms of silver. The emulsion used in each layer was prepared according to the manufacturing method of emulsion EMI. However, emulsion No. 1411 was a Lippmann emulsion that was not surface chemically sensitized.

1st M (antihalation N) Black colloidal silver...0.10 Gelatin...0.70 2nd layer (middle N
) Gelatin...0.70 3rd layer (
Low sensitivity red sensitive layer) Silver bromide spectrally sensitized with red sensitizing dyes (ExS-1, 2, 3) (average grain size 0.25 μ, size distribution [coefficient of variation] 8%, octahedral)...・0.04 Silver chlorobromide spectrally sensitized with red sensitizing dye (ExS-1, 2, 3) (silver chloride 5 mol%, average particle size 0.40μ
, size distribution 10%, octahedron)
...0.08 gelatin ...
1.00 cyan coupler (ExC-1, 2, 3 1:1
:0.2)...0.30 Anti-fading agent (Cpd-1, 2, 3, 4 equivalent)...0.18 Anti-staining agent (Cpd-5)...0.003 Force puller dispersion Medium (Cpd~6)...0.03 coupler solvent (
Solv-1, 2, 3 equivalent)...0.12 4th layer (high sensitivity red-sensitive layer) Brominated spectrally sensitized with red sensitizing dye (ExS-1, 2, 3)! m (average particle size 0.60μ, size distribution 15
%, octahedron)...0.14 Gelatin...1.00 Cyan coupler (ExC-1, 2, 3 1:1:0.2)
...0.30 anti-fading agent (Cpd-1
, 2, 3, 4 equivalents)...0.18 Coupler dispersion medium (Cpd-6)...0.03 Coupler solvent (Solv-1, 2, 3 equivalents)...0.12 5th Layer (middle layer) Zenlatin...1. 00 Color mixing inhibitor (Cpd-7)...0.08 Color mixing inhibitor solvent (Solv-4, 5 equivalent)...0.16 Polymer latex (Cpd-8)...0.10 6th layer (Low-sensitivity green-sensitive layer) Silver bromide (
Average particle size 0.25μ, size distribution 8%, octahedral)
...0.04 green enhancing dye (ExS-4
) spectrally sensitized silver chlorobromide (silver chloride 5 mol%, average grain size 0.40μ, size distribution lO%, octahedral)...
・0.06 Gelatin...0.80 Magenta coupler (ExM-1, 2, 3 equivalent)...0.11 Antifading agent (Cpd-9, 26, etc.)...0.1
5 Anti-staining agent (Cpd-10, 11, 12, 13)
o near: 7:1 ratio)...0.025 force puller dispersion medium (Cpd-6)...0.05 coupler solvent (Solv
-4,6 equivalent)...0.15 7th layer (high sensitivity green sensitive layer) Silver bromide (
Average particle size 0.65μ, size distribution 16%, octahedral) (EM-1)...0.10 Gelatin...0.80 Magenta coupler (ExM-1, 2, 3 equivalents)...0 .11 Anti-fading agent (Cpd-9,26 equivalent)...0.15 Anti-staining agent (Cpd-10,ii, 12.13 equivalent to 1
0 near:7:1 ratio)...0.025 force puller dispersion medium (Cpd-6)...0.05 coupler solvent (Solv
-4,6 equivalent)...0.15 8th layer (middle layer) 9th layer (yellow filter layer) same as the 5th layer Yellow colloidal silver (particle size 100)...0.
12 Gelatin...0.70 Antifading agent (Cpd-7)...0.03 Color mixing inhibitor Solvent (Solv-4, 5 equivalent)...o, i.

Polymer latex (Cpd-8) ...0.07 10th layer (intermediate layer) 11th layer same as 5th layer (low sensitivity blue sensitivity N) Spectral sensitization with blue sensitizing dye (ExS-5, 6) Silver bromide (average particle size 0.40μ, size distribution 8%, octahedron) ...0.07 blue sensitizing dye (ExS-5
, 6) spectrally sensitized silver chlorobromide (silver chloride 8 mol%, average grain size 0.60μ, size distribution 11%, octahedral)
...0.14 Gelatin ...0.80 Yellow coupler (ExY-1, 2 equivalent) ...0.35 Anti-fading agent (Cpd-14) ...0.10 Anti-stain agent (Cpd- 5,15 at a ratio of 1=5)...0.007 force puller dispersion medium (Cpd-6)...0.05 coupler solvent (Sol v-2) -0,10 12th layer (high Silver bromide spectrally sensitized with blue sensitizing dye (ExS-5, 6) (average grain size 0.85μ, size distribution 18%, octahedron) ...0.15 gelatin
...0.60 Yellow coupler (ExY-12 equivalent) ...0.30 Antifading agent (Cpd-14) ...0. lO stain inhibitor (Cpd-5,15 in a 1:5 ratio)...0.007 force puller dispersion medium (CPd-6)...0.05 Kabrane medium (Sol v-2) - 0,10 13th layer (ultraviolet absorbing layer) Gelatin...1.00 Ultraviolet absorber (Cpd-2, 4, 16 equivalent)...0.50 Anti-fading agent (Cpd-7, 17 equivalent) ...0.03 Dispersion medium (Cpd-6) ...0.02 Ultraviolet absorber solvent (Solv-2, 7 equivalent) ...0.08 Anti-irradiation dye (Cpd-18, Engineering 9) .20.21.27 at 10:10
:13:15:20 ratio)...0.05 14th layer (protective layer) Fine grain silver chlorobromide (silver chloride 97 mol%, average size 0.1
μ) ...0.03 Acrylic modified copolymer of polyvinyl alcohol (molecular weight 50,000) ...0.01 (average particle size 2.4μ) and silicon oxide (average particle size 5μ) equivalent amount...・0.05 gelatin
...1.80 gelatin hardening agent (H-1,
I]-2 equivalent)...0.18 15th layer (back layer) Gelatin...2.50 Ultraviolet absorber (Cpd-21,4,16 equivalent)...0.50 Dye (cpa -ts, 19.20.2 and 1.27 in equal amounts) ...0.06 16th layer (back protective layer) Polymethyl methacrylate particles (average particle size 2.4μ) and silicon oxide (average particle size 5μ) Equivalent amount...0.05 gelatin
...2.00 gelatin hardening agent (H-1, H
-2 equivalents)...0.14 Polymethyl methacrylate grains How to make silver bromide emulsion (EM-1) used in a high-sensitivity green-sensitive layer emulsion. Vigorously stir an aqueous solution of potassium bromide and silver nitrate into an aqueous gelatin solution. and 75° C. over a period of 15 minutes to obtain octahedral silver bromide particles with an average particle size of 0.32 μm. In this case, 0.3 g of 3,4-dimethyl-1 per mole of
3-thiazoline-2thione was added. 1 silver in this emulsion
6.6 mg sodium thiosulfate and 7.7 mg per mole
A chemical sensitization treatment was performed by sequentially adding chloroauric acid (tetrahydrate) and heating at 75°C for 50 minutes. The thus obtained grains were used as cores and further grown in the same precipitation environment as in the first time, to finally obtain an octahedral monodisperse core/shell silver bromide emulsion with an average grain size of 0.65 μm. The coefficient of variation in particle size was approximately 10%.

To this emulsion were added 1.5 mg of sodium thiosulfate and 1.5 mg of chloroauric acid (tetrahydrate) per mole of silver at 60°C.
A chemical sensitization treatment was carried out by heating for 60 minutes to obtain an internal latent image type silver halide emulsion.

Emulsions of various sizes used in other layers were also prepared according to this method.

Each photosensitive layer contains ExZK-1 and ExZK- as nucleating agents.
2 and Cpd-22 were used in an amount of 10-310-2% by weight based on silver halide, respectively, and 10-2% by weight of Cpd-22 as a nucleation accelerator when preparing a coating solution. Further, in each layer, Alkanol X C (Dupon) and sodium alkylbenzenesulfonate were used as emulsification and dispersion aids, and succinate ester and Magefac F-120 (manufactured by Dainippon Ink Co., Ltd.) were used as coating aids. (Cpd-23, 24, 25) was used as a stabilizer in the silver halide and colloidal silver containing layers. This sample was designated as sample number (I-1). The compounds used in the examples are shown below.

xS-1 xS-3 xS-4 xS-2 xS-5 ExS-6 Cpd-1 Cpd-2 Cpd-6 -SoCH, -CH7- CON　HC4H9(t) n-100~1000 Cpd-7 Cpd-8 1+cHz-CH+- C00CxHs Cpd-3 Pd-4 p d-5 Cpd-9 \ C, H++(t) Cpd-11 Cpd-12 Cpd-13 Cpd-17 Cpd-18 Cpd-19 S(JsK )U18 Cpd-14 Cp d-15 Cpd-16 cp d-20 Cpd-21 Cpd-22 cp d-23 Cpd cp d-25 cp d-26 XC xu-t pct XC-1 XC-2 'C1 death! XM-2 XM-3 CH.

IH1? LCJ 5olv-1 di(2-ethylhexyl) sebacate 5olv-2) linonyl phosphate 5olv-3 di(3-methylhexyl) phthalate 5olv-4 tricresyl phosphate 5olv-5 dibutyl phthalate 5olv-6) lioctyl phosphate 5olv -7 di(2-ethylhexyl) phthalate H-11,2-bis(vinylsulfonylacetamide)
Ethane H-24,6-dichloro-2-hydroxy-1,3,5
-) Lyazine Na salt ExZK-17-(3-ethoxythiocarbonylaminobenzamide)-9-methyl-10-propargyl-1,2 3,4-tetrahydroacridinylam trifluoromethanesulfonateExZK-22-(4-( 3-(3-(3-(5-(3)
-(2-chloro-5- (I-dodecyloxycarbonylethoxycarbonyl)phenylrubamoyl]-4-hydroxy-1-naphthylthio)tetrazol-1-yl]phenyl)ureido]benzenesulfonamido)phenyl]-1-formyl High-sensitivity green emulsion (EM-1) used in hydrazine sample (I-1)
), the following emulsions (EM-2) to (EM-6) were prepared as emulsions for high-sensitivity green-sensitive layers. For these emulsions, the steps from core grain formation to core chemical sensitization to shell grain formation are carried out in exactly the same manner as (EM-1), and the surface chemical ripening process (
Only the second chemical sensitization treatment was changed as follows. Only the chemical ripening process for each surface is described below.

(EM-2) 1.5 mg of sodium thiosulfate per mole of silver and 1.
Chemical sensitization treatment was performed by adding 5 mg of chloroauric acid (tetrahydrate) and heating at 60°C for 60 minutes, and then adding Cpd-22 at 10-2% by weight based on silver halide while maintaining the temperature at 60°C. , and further heated at 60°C for 20 minutes to obtain an internal latent image type silver halide emulsion EM-2.

(EM-3) 3.2 mg of sodium thiosulfate per mole of silver and 3.
Chemical sensitization treatment was performed by adding 2 mg of chloroauric acid (tetrahydrate) and heating at 45°C for 80 minutes, and while maintaining the temperature at 45°C, Cpd-22 was added to 10-2% by weight of silver halide. The mixture was further heated at 45°C for 25 minutes to obtain internal latent image type silver halide emulsion EM-3.

(EM-4) 1.5 mg of sodium thiosulfate per mole of silver and 1.
Chemical sensitization was performed by adding 5 mg of chloroauric acid (tetrahydrate) and heating at 60°C for 60 minutes. After cooling rapidly to 40°C, Cpd-22 was
- was added in an amount by weight, and the mixture was further heated at 40°C for 20 minutes to obtain an internal latent image type silver halide emulsion EM-4.

(EM-5) 1.3 mg of sodium thiosulfate per mole of silver and 1,
Chemical sensitization treatment was performed by adding 3 mg of chloroauric acid (tetrahydrate) and heating at 80°C for 35 minutes, and while maintaining the temperature at 80°C, Cpd-22 was added to 10-2% by weight of silver halide. The mixture was further heated at 80° C. for 5 minutes to obtain internal latent image type silver halide emulsion EM-5.

(EM-6) cpd-22 versus silver halide at 60°C! 1.5% by weight per mole of silver after heating for 5 minutes.
mg of sodium thiosulfate and 1. 5 mg chloroauric acid (
tetrahydrate salt) and further heated at 60'C for 65 minutes to perform chemical sensitization treatment to form internal latent image type silver halide emulsion EM-6.
I got it.

Using the emulsions (EM-1) to (EM-6) thus obtained, only the high-sensitivity green-sensitive layer of sample (I-1) was changed as shown in Table 1-1, and sample (I-2) was prepared. (I-7) was obtained.

Color photographic paper samples (I-1) to (I-7) prepared as shown in Table 1 were subjected to wedge exposure (I/10 seconds 300 C).
MS), the following processing was performed, and the magenta color image density was measured.

(Fresh performance, Fr performance) Samples (I-1) to (I-7) were stored in an incubator at a temperature of 55°C and a humidity of 5% for 3 days, and then exposed in the same manner, resulting in a magenta image color. The concentrations were measured and the results are shown in Table 1-2.

Processing steps used in this example After the silver halide color photographic light-sensitive material is imagewise exposed, the method described below is carried out using an automatic processor until the cumulative replenishment amount of the solution becomes three times the tank capacity. Processed continuously.

Bleach-fixing 40〃 33〃 Water washing (I) 40〃 33-Water washing (2) 40# 33# The method of replenishing the washing water is to refill the washing bath (2),
A so-called countercurrent replenishment system was used in which the overflow liquid of 2) was introduced into the washing bath (I). At this time, the amount of bleach-fix solution brought into the washing bath (I) from the bleach-fix bath for 300 〃 20 l photosensitive material is 35 mj! /rrf, and the ratio of the amount of washing water replenishment to the amount of bleach-fix solution brought in is 9.1.
It was double that.

The composition of each treatment liquid was as follows.

Color developer mother solution Replenisher D-Sorvit 0.15g 0.20
g Naphthalene sulfonic acid 0. 15g 0.
20 g Sodium formalin metal condensate ethylene diamine tetate 1.5 g 1.5 g Lachismethylene phosphonate diethylene glycol 12.0 ml 16.0 m
j! Benzyl alcohol 13.5mj! 18
．． 0mf Potassium bromide 0.70g Benzotriazole 0.003g 0.004g Sodium sulfite 2.4g 3.2g N, N-bis(carboxy) 4.0g 5.3g Methyl)hydrazine D-glucose 2.0g 2.4g Triethanolamine 6.0g 8.0g N-ethyl-N-(β-methane 6.4g8.5g tansulfonamidoethyl)-3-methyl-4-amineaniline sulfate potassium carbonate 30. 0 g 25.
0g optical brightener (diaminosti 1.0g 1.
2g Rubene type) pH (25°C) 10°11.00 Ethylenediaminetetraacetic acid, 2.0g Mother liquor contains the same disodium dihydrate ethylenediaminetetraacetic acid, 70.0g Fe(III)
・Ammonium dihydrate ammonium thiosulfate 180mj! (700g/
/ p-Toluenesulfinic acid 45.0g Sodium Sodium bisulfite 5-mercapto-1,3゜4-triazole Ammonium nitrate 35.0g 0.5g 10.0g pH (25°C) 6.10 Washing water mother liquor, replenisher Tomo tap water is passed through a hotbed column filled with H-type strongly acidic cation exchange resin (Amberlite IR-120B manufactured by Rohm & Bath Co., Ltd.) and OH-type anion exchange resin (Amberlite IR-400 manufactured by Rohm & Bath Co., Ltd.) to remove calcium. and magnesium ion concentration below 3 mg/i, followed by 20 mg of sodium isocyanurate dichloride.
/ It and sodium sulfate 1.5g/j! was added.

The pH of this liquid was in the range of 6.5 to 7.5.

Table 1-2 According to Table 1-2, samples of the present invention (I-3) to (I-
It can be seen that Samples 7) are both superior in Dmin to lower and Dmax to higher than Comparative Samples (I-1) and (I-2). Furthermore, samples (I-1) (I-2)i of comparative examples
' Dmin increases significantly after 50°C 55% 34, Dmax decreases greatly and the photographic performance is greatly impaired, whereas samples (I-3) to (I-7) according to the present invention
It can be seen that fluctuations in both Dmin and Dmax are small, and the difference in superiority and inferiority with the comparative example is even larger.

Example 2 Sample (2-2-
1) was produced. In addition, a sample was prepared in which the high-sensitivity green-sensing emulsion layer coating solution of sample (I-1) was coated after completion of the coating by waiting 10 hours while keeping the solution state at 40°C.
2).

Furthermore, emulsion EM-1 was changed to EM-2 of Example 1, and a sample exactly the same as sample (I-3) was prepared and designated as sample (2-3). Further, samples were prepared in which the high-sensitivity green sensitive layer coating solution of sample (2-3) was coated after completion of the coating by waiting for 10 hours while keeping the solution state at 40"C. Sample (:)-4) and did.

Samples (2-1) to (2-4) were exposed and developed in the same manner as in Example 1, and the magenta image color density was measured. The results are shown in Table 2.

Table 2 Samples (32, 40, 41) were made with different emulsions and used in the high-sensitivity green-sensitive layer in the same manner as sample (I-3) in Example 1.
3-11) and (3-20) were produced.

Exposure processing was carried out in the same manner as in Example 1, and the color density of the magenta image was measured, and the results are listed in Table 3.

According to Table 2, samples (2-3) and (2-4) of the present invention are less susceptible to changes in coating liquid over time than comparative examples (2-1 and 2-2). Dmin value and high Dmax
It can be seen that a window material with excellent stability during manufacturing can be obtained.

Example 3 The nucleation accelerator for the high-sensitivity green sensitive layer of sample (I-1) of Example 1 was replaced with Compound 1. 13. 15. 21.
25.29, 31, 32, 40.41 and sample (3
1) and (3-10) were produced. In addition, the nucleation accelerator added in exactly the same manner as in the preparation of emulsion EM-2 shown in Example 1 was added in 13. 15. 21. 25. 29. 31
゜Table-3 As is clear from Table 3, samples (3-11) to (3-20) according to the present invention all have low Dmin and high Dmax.
This shows that excellent photographic properties can be obtained.

(Effects of the Invention) According to the present invention, a direct positive image having a high maximum image density and a low minimum image density can be formed. In addition, even if the coating liquid used in the production of photographic materials changes over time, the maximum and minimum image densities do not easily fluctuate from their optimum values, and the gradation does not easily fluctuate, regardless of the storage period of the photosensitive materials. A positive image can be formed. Furthermore, in the present invention, the maximum image density is higher and the minimum image density is lower than that of a direct positive photographic light-sensitive material produced by adding the same compound as a nucleation promoter to the emulsion coating solution, and the photographic properties are improved. Excellent, and there is little change in photographic properties due to changes in coating liquid over time. (In the above-mentioned direct positive photographic material produced by adding the same compound as used in the present invention to an emulsion coating solution as a nucleation accelerator, the photographic properties obtained change depending on the aging of the coating solution, but the present invention Even when the above-mentioned nucleation accelerator is added in the production, there is an effect that the above-mentioned photographic characteristics change little.

Claims (1)

[Scope of Claims] A direct positive photographic light-sensitive material having at least one emulsion layer containing internal latent image type silver halide grains that are not covered in advance on a support, wherein the grain surface has the following general formula (
A direct positive photographic light-sensitive material characterized by being chemically sensitized in the presence of the compound represented by I). General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, A represents a group that adsorbs to silver halide, and Y is selected from hydrogen atom, carbon atom, nitrogen atom, oxygen atom, and sulfur atom. Represents a divalent linking group consisting of an atom or a group of atoms, R is a thioether group, an amino group, an ammonium group,
Represents an organic group containing at least one ether group or heterocyclic group. n represents 0 or 1, and m represents 1 or 2.