JPH0395546A - Direct positive photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain a direct positive photographic sensitive material high in maximum image density and low in minimum image density by incorporating a specified sensitizing dye and a specified compound in a photographic emulsion layer. CONSTITUTION:The photographic emulsion layer contains at least one of the sensitizing dyes represented by general formula I and at least one of the compounds represented by general formula II. In these formulae I and II, each of Z1 and Z2 is an atomic group necessary to form a thiazole or thiazoline ring or the like; each of R1 and R2 is optionally substituted alkyl, and at least one of both has sulfo or carboxy; each of L1 and L2 is optionally substituted methine; (n) is 0, 1, or 2; R3 is H, halogen, alkyl, or the like; Y is alkylene, arylene, or the like; X1 is an anion; and each of m1 and m2 are integers of 1 - 19, thus permitting the obtained direct positive photographic sensitive material to be high in the maximum image density and low in minimum image density.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a direct positive photographic light-sensitive material having at least one photographic emulsion layer containing internal latent image type silver halide grains which have not been previously fogged.

[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 carrying out surface development after image exposure and fogging treatment, or while performing fogging treatment.

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 upon exposure. Photographic emulsion.

Various techniques are known to date in this technical field. For example, U.S. Pat. No. 2,592,250, U.S. Pat. No. 2.46'6,957, U.S. Pat.
, No. 761,266, No. 3,761,276, No. 3,
No. 796,577 and U.S. Patent No. 1,151.363
No. 1,150,553, OIL No. 1, OIL No. 062 The main ones are those described in each specification etc.

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

For details on the shape and mechanism of the above direct positive image, see
T”.Ir.James Chopsticks] - The Theory of the Four 1 ~ Graphic Process J (TheTh
theory of the Photographic
Process), 4th edition, Chapter 7, pp. 182-19
3, US Pat. No. 3,761,276, etc.

On the other hand, as one of the manufacturing technologies for photographic materials, there is a technology that extends the sensitive wavelength range to longer wavelengths by adding a certain type of cyanine dye to a silver halide photographic emulsion, that is, spectral sensitization technology. It is well known that this applies.

In this case, the sensitivity obtained by spectral sensitization, that is, the spectral sensitivity, is affected by the chemical structure of the sensitizing dye, various properties of the emulsion, such as the halogen composition of silver halide, crystal habit, crystal system, silver ion concentration, hydrogen ion concentration, etc. It is also known that Furthermore, the spectral sensitivity is also influenced by photographic additives such as stabilizers, antifoggants, coating aids, precipitants, color couplers, and hardeners coexisting in the emulsion.

Generally, in light-sensitive materials, one sensitizing dye is used to sensitize a predetermined spectral wavelength range.

However, in addition to this dye, it is known that the presence of a second type of specifically selected dye or other organic substance can significantly increase the efficiency of spectral sensitization; It is known as feeling.

In general, if there is no addition of a second dye or if an organic substance is added, the sensitivity often does not increase or even decreases, so it can be said that supersensitization is a unique phenomenon, Extremely strict selectivity is required for the organic compound used and the second sensitizing dye.

[Problem to be solved by the invention]

In order for a direct positive photographic light-sensitive material to be put to practical use, it must have a high maximum image density, a low minimum image density, and high contrast.

U.S. Pat. No. 4,306,016 describes that the maximum image density increases by using a specific cyanine-based sensitizing dye in an internal latent image type silver halide emulsion, but the degree of increase is still satisfactory. Not a thing, but
It has never been satisfactory in terms of obtaining low minimum image density.

On the other hand, when spectral sensitizing a silver halide photographic emulsion, the sensitizing dye is required to first of all provide high spectral sensitivity. It is desirable to strongly sensitize a specific narrow wavelength range.

The present invention is intended to solve the above problems.

Therefore, a first object of the present invention is to provide a direct positive photographic light-sensitive material that has 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 material that provides high spectral sensitivity without expanding the wavelength range of spectral sensitivity.

[Means to solve the problem]

The present invention provides a direct positive photographic light-sensitive material having at least one photographic emulsion layer containing internal latent image type silver halide grains which have not been fogged in advance, in which the photographic emulsion layer contains (1) the following general formula [1] This has been achieved by a direct positive photographic light-sensitive material characterized by containing at least one sensitizing dye represented by (2) at least one compound represented by the following general formula (II).

General formula (1) R R2 In the formula, Zl and Z2 are a thiazole nucleus, a thiazoline nucleus, a penzthiazole nucleus, a naphthothiazole nucleus, an oxazole nucleus, a penzoxazole nucleus, an oxazoline nucleus, a naph I/oxazole nucleus, an imidazole nucleus, and a penzimidazole. nucleus, imidazoline nucleus, selenazole nucleus, selenazoline nucleus,
Represents the atomic group necessary to form a penzoselenazole nucleus or a naphthoselenazole nucleus.

R- and R2 represent an alkyl group or a substituted alkyl group.

However, at least one of R+ and Rz has a sulfo group or a carboxy group.

L+ and L2 represent a substituted or unsubstituted methine group.

n represents an integer from 0 to 2.

2,,2. As is well known in the field of cyanine dyes, substituents may be introduced into the nucleus formed by . Examples of the substituent include an alkyl group, an alkoxy group, an alkoxycarbonyl group, an aryl group, an aralkyl group, and a halogen atom.

R and R2 may be the same or different.

The alkyl of Rl and R2 preferably has a carbon atom number of I.
~8, such as methyl group, ethyl group, proyl group,
These include butyl group, bentyl group, heptyl group, etc. Examples of substituents for substituted alkyl groups include carboxy groups, sulfo groups, cyano groups, halogen atoms (e.g. fluorine atoms, chlorine atoms, bromine atoms, etc.), hydroxy groups, alkoxycarbonyl groups (carbon atoms of 8 or less, e.g. methoxy groups). carbonyl group, carbonyl group, penzyloxycarbonyl group, etc.), alkoxy group (7 or less carbon atoms, e.g. methoxy group, ethoxy group, propoxy group, butoxy group, penzyloxy group, etc.), aryloxy group (e.g. phenoxy group, p-}lyloxy group, etc.), acyloxy group (up to 3 carbon atoms, e.g. acetyloxy group, propionyloxy group, etc.), acyl group (up to 8 carbon atoms, e.g. acetyl group, propionyl group, benzoyl group, mesyl group, etc.), carbamoyl group (e.g. carbamoyl group, N,N-dimethyl-rubamoyl group, morpholino-rubamoyl group, piberidinocarbamoyl group, etc.), sulfamoyl group (e.g. flufamoyl group, N,N-dimethylsulfamoyl group) , morpholinosulfonyl group, etc.)
, aryl groups (eg, phenyl group, p-hydroxyphenyl group, p-carpoxyphenyl group, p-sulfophenyl group, α-naphthyl group, etc.). The number of carbon atoms in the substituted alkyl group is preferably 6 or less.

The substituted methine group of ILI, L2 is a lower alkyl group (
Examples include methyl group, ethyl group, probyl group, etc.), phenyl group, and benzyl group.

Examples of cyanine dyes suitable for use in the present invention are listed below.

(1) (4) SO3G (5> (2) (3> (6) 13 14 (7) (8) (9) C 2 H s ?Cll■) 4 S (he 1 5 <1 3) (CII2 )3 (CH2)3 SOJa SO:l0 (1 4) ■ 7 (1 0) (Ctlz)4 ?Cll■)4 SO30 SO,lII・N(Czll5)3 (1 1) (1 2) SO:+tl -N(CZII5)3 SO3e 1 6 (1 6) (1 7) SO3e (1 8) C21),, (CH2)3 (CHz)a so. e SO3H・N (C21) 5) 3 1 8 (1 9) C z H 5 (20> C 2 II , (21) C z II s C2H, ?C1) ■) 3 S030 (25) CJs (26) C2HS (27> 21 (22) (23> CZHS (24) CJs (28) (29) (30> C 2 I1 5 CzHs (CHz) a SO3e C.H5 (CHz) y so.e (3 l) ( 34) C 2I1 , C 21) 5 (CHz): + C 2II , n-CsHz (CHz) *SOs e so3e <3 5> C21), C21{S (3 2) SO3e SO3Na C.t15 C 2I1 5 ( 33) C2H, C21)5 C2H5? Il■CHzCItCH3 SO30 (40) C 2 1) , ? II2CIl2CONI+■? C1)■)3 (CH2)3 (Ctlz)3 so3e SO3e SO3H・N (CzHs) z (41) C21)5 C21)5 (CII2)4SO30? CI+■)3? C! 1■)3 SO. K SO3e (39) (:2II S (4 2) C 2H , ?GO■)3 (CI+2) 3SO31)・N(CJs)3SO3e 25 26 (43) C 2II 5 (44) C 2 I+ , (45) CzHs CH3 (CHz) 3S03 ” 27 (50) (Cl12)3 (CHZ) 3 (5 1) 〈52) (CI!')3 (CHz) 3 SQ.,Na SO3e 29 (4 6) (48) ( 49) SO3e SO3H・N(C2Hs)+ 28 (54) C2HS (CHz) 4 SO3e (55) 30 (5 6) Call,, ?CI1■)3 SO3e (5 7) (58) SO.○ 3031)・N(C21)5)3 31 (6 3) (64) SO30 S03l1・N(Cztls)3 33 (5 9) (60) C. H5 (6l) (:2 I+, C21),, ?CI■) 3S03e 32 (65> (Ctlz)3 (CtlzL+ SO3e SO3tl-N (Cztls) 3 (66) 34 All of these cyanine dyes are known compounds and can be easily obtained or synthesized.

The content of the sensitizing dye of the present invention represented by general formula (I) is:
IXIO-6 to IXIO-2 mol, preferably IXIO-5 to IXIO-3 mol, more preferably 5X10-5 to 1x1o-3 mol per mole of silver.

The sensitizing dyes of the general formula (I) of the present invention may be used in combination of two or more types, or may be used in combination with other cyanine, merocyanine, vorimethine dyes, etc.

General formula (If) 2 (X, ) In the formula, R3 represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxycarbonyl group, an acyloxy group, an alkoxy group, an amino group, a substituted amino group, an acylatando group, or a carbamoyl group. represent. Y is alkylene, arylene, aralkylene, -COO-coo-y. -oco-. However, Y represents alkylene, arylene, or aralkylene having 1 to 18 carbon atoms. X1 represents an anion. m1 and m2 each represent an integer from 1 to 19.

In general formula (]I), the following substituents are preferably used. That is, R3 is a hydrogen atom, a halogen atom (e.g., a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc.), an alkyl group (having 1 to 18 carbon atoms, e.g., a methyl group, an ethyl group, a probyl group, etc.), an alkoxycarbonyl group. (The number of carbon atoms is 2
~18, such as methoxycarbonyl group, ethoxycarbonyl group, butoxycarbonyl group, penzyloxycarbonyl group, etc.), acyloxy group (having 1 to 18 carbon atoms)
, for example, acetyloxy group, propionyloxy group, penzoyloxy group, cyclohexyl group, alkoxy group (having 1 to 18 carbon atoms, such as methoxy group, ethoxy group, propoxy group, butoxy group, etc.), adanno group , a substituted adanino group (e.g. methylamino group,
Ethylamino group, propylamino group, dimethylamino group, dodecylamino group, cyclohexylamino group, β-hydroxyethylamino group, anilino group, p-anisylamino group, o-1-luidino group, 2-penzothiazoli lylamino group, etc.), acylado groups (e.g. acetylamide, probionylamide, penzoylado, methanesulfonyl ado), carbamoyl groups (e.g. carbamoyl group, N, N-dimethylcarbamoyl group, morpholinocarbonyl group) , piperidinocarbonyl group, etc.).

Y is alkylene having 1 to 18 carbon atoms, arylene having 6 to 18 carbon atoms, aralkylene having 7 to 1B carbon atoms, 1CO·o- -cooY, 10C01. Here, Y1 is alkylene having 1 to 18 carbon atoms, arylene having 6 to 18 carbon atoms, or aralkylene having 7 to 18 carbon atoms. Y is preferably -CO・〇1 -C○
Oy, -oco one.

Typical examples of the compound represented by the general formula [■] are listed below, but the invention is not limited thereto.

(n-1) (n-2) (II-3) (■-4) 0 0 2C1e -39 (■ 9) (■ 10) (■ 1 1) (■ 1 2) 0 2Bre 40 Used in the present invention The compound represented by the general formula (If) is about 0.0% per mole of silver halide in the emulsion. Amounts of from 1 gram to 5 grams, particularly preferably from 0.1 to 2.5 grams are advantageously used.

The ratio (weight ratio) of the sensitizing dye represented by general formula (I) to the compound represented by general formula (n) is: dye represented by general formula (I)/compound represented by general formula (II) -
A range from 100/1 to 1/100 is advantageously used, particularly a range from 40/1 to 1/40.

The compound represented by the general formula (II) used in the present invention can be directly dispersed in an emulsion, or can be dispersed in a suitable solvent (for example, methyl alcohol, ethyl alcohol, methyl cellosolve, water, etc.) or a mixed solvent thereof. It can also be dissolved in and added to the emulsion. In addition, it can be added to the emulsion in the form of a solution or a dispersion in a colloid according to the method of adding sensitizing dyes.

They can also be dispersed and added into the emulsion by the method described in JP-A-50-801)9.

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 the latent image is mainly formed inside the grains. However, more specifically, a silver halide emulsion is deposited on a transparent support in a certain amount (0.5 to
3 g/nf), exposed to light for a fixed time of 0.01 to 10 seconds, and developed in the following developer A (internal type developer) at 18°C for 5 minutes. The maximum density measured by the density measurement method is obtained when a silver halide emulsion coated in the same amount as above and exposed in the same manner is developed in the following developer B (surface type developer) at 20°C for 6 minutes. preferred are those having a concentration at least 5 times greater, more preferably at least 10 times greater than the maximum concentration
It has twice the concentration.

Internal developer A Metol 2g Sodium sulfite (anhydrous) 90g Hydroquinone
8g soda carbonate (monohydrate)
52.5gKBr
5gKI
O. Add 5g water
1l surface developer B metol 2.5g L-ascorbic acid 10g NaBO2-4H2
0 35g KBr
Add Ig water
Specific examples of the latent type emulsion include the conversion type silver halide emulsion described in US Pat. No. 2,592,250, and US Pat. No. 3,76.
No. 1,276, No. 3,850,637, No. 3,923
, No. 513, No. 4,035,185, No. 4,395,
No. 478, No. 4,504,570, JP-A-51-15
No. 6614, No. 55127549, No. 53-6022
No. 2, No. 5622681, No. 59-208540,
No. 60-107641, No. 61-3137, Japanese Patent Application No. 61-32462, Research Disclosure Magazine No. 23510 (Issued in II, 1983) P236
Mention may be made of the core/shell type silver halide emulsions described in the patent disclosed in .

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, it may be a composite of these various crystal forms, or an emulsion made from a mixture thereof.

Silver halide. The composition includes silver chloride and silver bromide mixed silver halide, and the silver halide preferably used in the present invention is silver salt (iod)bromide that does not contain silver iodide or contains less than 3 mol% of silver iodide. , (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 1 μm or less and 0.15 μm or more. 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 grain by sulfur or selenium sensitization, reduction sensitization, noble metal sensitization, etc. alone or in combination. For detailed specific examples, see Research Disclosure Magazine No. 1 7 6 4 31 [[(Published December 1978) Patent described on page 23 etc.

The photographic emulsion used in the present invention is spectrally sensitized by the above-mentioned photographic sensitizing dyes in a conventional manner. Dyes that can be used in combination with the above dyes include those belonging to merocyanine dyes and complex merocyanine dyes. The above dye and (If)
Other supersensitizers may also be used in combination. For detailed specific examples, see Research Disclosure No. 1
7 6 4 3-IV (issued December 1978) P2
Patent Nos. 3 to 24, etc.

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 specific examples, see Research Disclosure Magazine No. 17643-
VI (published December 1978) and E. J, B
by irr “Stabiliation of Photo
graphic Silver llailde E
mulsion (Focal Press), 1 9
7 It is written in the 4th edition, etc.

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, pyrazolone or virazoloazole 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 J Magazine No. 17643 (December 1978 issue) P25
, ■ Section 1D, same No. 1 8717 (1979
) and Japanese Patent Application No. 61-32462 and the patents cited therein.

Colored couplers to correct unnecessary absorption in the short wavelength region of raw dyes, couplers in which coloring dyes have appropriate diffusivity, colorless couplers DIR couplers that release development inhibitors along with the coupling reaction. 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 prevention agent can be used in the photosensitive material of the wood 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. Representative examples of the compounds include those described in JP-A-62-215272, pages 121-125.

The photosensitive material of the present invention includes dyes that prevent irradiation and halation, ultraviolet absorbers, plasticizers, fluorescent whitening agents, matting agents, aerodynamic anti-blur agents, coating aids, hardeners, Antistatic agents, slippery improvers, etc. can be added. Representative examples of these additives are listed in Research Disclosure magazine no. l 7 643■~X1) 1 (published December 1978) p25~27, and 18716 (1
Published in January 1979), 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 has two or more layers with different sensitivities.
It may be composed of two emulsion layers, or a non-light-sensitive layer may be present between two or more emulsion layers having the same color sensitivity. Usually, the red-sensitive emulsion layer contains a cyan-forming coupler, the green-sensitive emulsion layer contains a Mazenk-forming coupler, and the blue-sensitive 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 as described in Research Disclosure Magazine No. 17643V■
(published in December 1978) p. 28, European Patent No. 0,102,253, and Japanese Patent Application Laid-Open No. 1983-976.
No. 55. Also, Research Disclosure Magazine No. 1 7 6 4 3 X
The coating method described in Section V, pages 28 to 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 is also described in "Research Disclosure" magazine No. 1712
It can also be applied to black-and-white photosensitive materials using the three-color coupler mixture described in No. 3 (published July 1978).

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. 5B-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. The more sensitive a light-sensitive material uses an emulsion, the more preferable it is to be exposed to light at a lower illuminance. 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 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 exposure to light fog 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. Ol 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 term "nucleating agent" refers to a substance that acts during surface development of an internal latent image type silver halide emulsion that has not been fogged in advance to directly form a positive image. In the present invention, it is particularly preferable to carry out fogging treatment using a nucleating agent.

When incorporated into a light-sensitive material, it is preferably added to the latent type 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. 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-I
] and [N-It) are preferably used.

General formula (N-1) Z R4 (wherein, Z represents a nonmetallic atom group necessary to form a 5- to 6-membered heterocycle, and Z may be substituted with a substituent. R4 is It 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.In addition, R5 is further bonded to a heterocycle which is completed with Z. may be used to form a ring.However, R', R
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 6-membered ring and form a dihydropyridinium skeleton. do. Furthermore, R4, R5
At least one of the substituents of and Z may have a group that promotes adsorption to silver halide.

Y is a counter ion for charge balance, and n is 0 or 1.

Specific examples of the compound represented by formula (N-1) of the present invention are shown below.

(N-1-1) 5-ethoxy 2-medyl-1 probargylquinolinium bromide (N-I-2) 2,4-dimethyl-2-probargylquinolinium bromide (N-1-3) 3.4-dimethyl-dihydropyride (2
．． 1-b) Henzothiazolium bromide (N-I-4) 6-ethoxythiocarbonyl urea draft No. 2
-Methyl-1-propargylquinolinium trifluoromethane (N-I (N-1 (N-1 (N-1 (N-1) Luphonar 1, 5) 6-(5-penzotriazole carpokiza 5-do) -2-Methyl-1 Propargylquinolinium trifluoromethanesulfonate 6) 6-(5-Mercaptotetradu-1-yl)-2-Methyl-1 Propargylquinolinium iodide 7) 6-Ethoxythioluponylamino 2-(2-Methyl-1-probenyl)-1-propargylquinolinium 1-lifluoromethanesulfoner I. 8) 10-propargyl-1 2 3 4-tetrahydride acridinium 1-lifluoromethanesulfonate 9) 7-ethoxythiocarbonylamino-10-propargyl-12,3,4-tetrahydroacridinium trifluoromethanesulfonate (N-■ (N-I (N-I (N-I (N-1 10)7- ( 3-(5-Merkab 1 Tetrazole-
1-yl)penzamide] 10-propargyl-1,2,3,4-tetrahydride acridinium perchlorate 1)) 7-(5-mercabutotetrazol-1-yl)-9-methyl-10 probargyl- ( 1,2,3.4-Diatriazole-5-ylamino)benzado] 1, 2. 3. 4-tetrahydroacridinium perchlorate 14) 7-(3-cyclohexylmethoxythiocarbonyl-benzagodo)-10-propargyl-1,2 3,4-tetrahydroacridinium trifluoromethanesulfonate (N-1 -15) 7-(3-ethoxythiocarbonylaminobenzamide)-10-propargyl-1.2.34-tetrahydroacridinium trifluoromethanesulfonate (N-I-16)7-[3-(3-ethoxythio 10-propargyl-1.2, . 3.4-Tetrahydroacridinium trifluoromethanesulfonate (N-1-17) 7-(3-ethoxythioluponylaminobenzenesulfonate) 10-propargyl-1.2,3. 4-Tetrahydroacridinium trifluoromethanesulfonate (N-1-18) 7-(1- {3- (3- (5-
mercaptotetrazol-1-yl) phenyl]ureido}benzatate] 10-propargyl-1.2,3. 4-Tetrahydroacridinium trifluoromethanesulfonate (N-1-19)7-(3-(5-mercapto-
1.3,4-thiadiazol-1-ylacuno)penzamide]-10-probargyl-1.2,3.4-tetrahydroacridinium trifluoromethanesulfonate (N-I-20) 7-(3- ( 3-butylthioureido)benzaacido)-10-propargyl-1.2,3.4-tetrahydroacridinium trifluoromethanesulfonate general formula (N-II) (wherein, R21 is an aliphatic group, an aromatic group 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, or a phosphoryl group , or an iminomethylene group (HN=C); Rtz and Rza are both hydrogen atoms, or one is a hydrogen atom and the other is an alkylsulfonyl group, an arylsulfonyl group, or an acyl group. However, a hydrazone structure (CAN-N=C) may be formed by including 0,, Rtt, R24 and hydrazine nitrogen. Further, the groups described above may be substituted with a substituent if possible. ) Next, specific examples of the compound represented by the general formula (N-I1) will be shown.

(N-II-1)1-formyl-2- (4- (3(
(2-methoxyphenyl)ureido) phenyl}hydrazine (N-U-2)1-phor5-2- (4-(3-{3
- [3- (2.4-ditertpentylphenoxy)probyl]ureido}phenylsulfonylua] phenyl}hydrazine (N-I[-3)1-fork-1{4- (3(5-
mercaptotetrazol-1yl)penzamide]phenyl} hydrazine (N-If-4)1-forcaru2- (4- (3-
(3-(5-mercaptotetrazol-1-yl)phenyl)ureido} phenyl]hydrazine (N-II-5) 1-formyl-2- [4- (3(
N-(5-Mercapto-4-methyl-1.2.4-triazol-3yl)carbamoyl)propananeξd}phenyl]hydrazine(N-n-6)1-fork2- {4- (3( N
- (4- (3-Mercapto-1,2.4-triazol-4-yl) phenyl]carhamoyl]1propane-a-trilliondophenyl}hydrazine (N-II-7) 1-formyl-2- (4- {31
:N-(5-mercapto-1.3,4-thiadiazol-2-yl)carpamoyl]brobanagodo}phenyl]hydrazine(N-1)-8)l-C4-(penzotriazole5-carboxamide)phenyl ] 1-phorylhydrazine (N-H-9) 2- (4-(3- [N- (henzotriazole-5-carboxamide) carpamoyl) propane hydrazine phenyl]-1-vormyl hydrazine (If- II-10) I-formyl-1- (1-
(1(N-phenylcarbamoyl)thioseξcarbazide]phenyl}hydrazine (N-II-1)) I-formyl-2- (4- [
3(3-Phenylthioureido)benzamido]phenyl}hydrazine (N-IT-12) 1-Forgoru2- C4- (
3-hexylureido)phenyl]hydrazine (N-II-13) 1-formyl-2- {1- C
3(5-Mercaptotetrazol-1yl)henzensulfonadphenyl}hydrazine(N-II-14) I-formyl-2-(4-(3
(:3- (3- (5-mercaptotetrazole-1
-yl)phenyl]ureido}benzenesulfonamide] phenyl}hydrazine (N-IT-15) 1-Holku1- (4- {
3(1(2.4-ditert-pendylphenoxy)probyl)ureido}phenylhydrazine 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 processing solution for the sensitive material. It can be included in the photosensitive material.

When incorporated into a sensitive material, it is preferably added to the latent type 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. For example, it may be added to an intermediate layer, undercoat layer or back layer. When adding a nucleating agent to the processing solution, add it 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 10-8 to 10-2 mol per 1 mol of silver halide.
More preferably, it is 10-7 to 10-3 mol.

In addition, when adding a nucleating agent to the processing solution, the amount used is:
The amount is preferably 10-5 to 10-' mol, more preferably 10-' to 104 mol per 1°C.

In the present invention, in order to further promote the action of the nucleating agent, the following nucleating promoters can be used.

Nucleation accelerators include tetrazaindenes, triazaindenes, and pentazaindenes having at least one merkabuto group optionally substituted with an alkali metal atom or an ammonium group, and JP-A-63-Sho. 10
Compounds described in Publication No. 6656 (pages 6 to 16) can be added.

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

(A-1) 3-merkab l--12.4-triazolo(
4.5-a) Pyridine (A-2) 3-mercabuto-1.2.4-1-riazolo(4,5-a)pyridine (A-3) 5-mercabuto-1.2.4- Triazolo (
1. 5-a) Virimidine (A-4) 7- (2-dimethylaminoethyl) = 5-
Mercapto-1.2.4-}riazolo (1, 5-a)
Pyricudine (A-5) 3-mercabuto-7-methyl-1,2.4-
Triazolo(4,5-a)pyrimidine (A-6) 3,6-dimercap I--1.2.4triazolo(4,5-b)pyridazine (A-7) 2-mercapto-5-methylthio-1 ,3,
4-thiadiazole (A-8) 3-mercapto-4-methyl-1,2,4-
Triazole (A-9) 2- (3-dimethylahonopropylthio)
-5-mercapto-1.3.4-thiadiazole hydrochloride (A-10) l- (2-morpholinoethylthio)5-
The mercapto-1.3.4-thiadiazole hydrochloride nucleation accelerator can be contained in the light-sensitive material or in the processing solution, but it can also be used in internal latent image type silver halide emulsion layers and other hydrophilic materials. It is preferable to include it in a sex colloid layer (such as an intermediate layer or a protective layer). Particularly preferred is a layer in or adjacent to a silver halide emulsion layer.

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 alkyl color developing agent as a main component. Aminophenol compounds are also useful as color developing agents, but p-phenylenediane compounds are preferably used, representative examples of which are 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-1-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 1). 5 or less, more preferably 9.5 to 1).
It is 5.

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

The bleaching process may be performed simultaneously with the fixing process (bleach-fixing process), or may be performed 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 in two continuous 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 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 (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 countercurrent or forward flow, and various other conditions. Can be set over a wide range. Among these, the relationship between the number of washing tanks and the amount of water in the multistage countercurrent method is
Urnal of the Society of M
tion Picture and Televisi
on Engineers Volume 64, P24B-2
53 (May 1955 issue).

The silver halide color 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.

〔Example〕

EXAMPLES The present invention will be explained in detail below using Examples, but the present invention is not limited thereto.

Example 1 Paper support laminated on both sides with polyethylene (thickness 10
A color photographic light-sensitive material was prepared by coating the following first to fourteenth layers on the front side and the fifteenth to sixteenth layers on the back side. The polyethylene on the first layer coating side contains titanium oxide (4 g/bo) as a white pigment, and a trace amount (0
．． Contains ultramarine blue (O O 3 g/e) as a blue-tinting dye.

(Photosensitive layer assembly precepts) The precepts and coating amount (g/rrf unit) are shown below. Regarding 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 EMI described below. However, the emulsion for the 14th layer was a Lippmann emulsion that was not surface chemically sensitized.

1st layer (anti-halation layer) Black colloidal silver ...0.10
Gelatin ・・・・・・0.70
2nd layer (middle layer) Gelatin...0.70
Third layer (low sensitivity red-sensitive layer) Silver bromide spectrally sensitized with the red sensitizing dye (50) of the present invention (average particle size 0.25μ, size distribution [coefficient of variation])
8%, octahedral) ・・・・・・0.04 Silver bromide spectrally sensitized with the red sensitizing dye (50) of the present invention (average grain size 0.40 μ, size distribution 10%, octahedral)
...0.08 gelatin
...1.00 cyan coupler (ExC-
1, 2, 3 as 1=1=0.2)
・・・・・・0.30 Anti-fading agent (Cpd-1, 2
, 3, 4 equivalents)...0.18 Stain inhibitor (Cpd-5)...0.0
03 Coupler dispersion medium (Cpd-6) ・・・・・・0
．． 03 coupler solvent (Solv-1, 2, 3 equivalents)...
...0.12 Fourth layer (high sensitivity red-sensitive layer) Silver bromide spectrally sensitized with the red sensitizing dye (50) of the present invention (average grain size 0.60μ, size distribution 15%, gelatin cyan coupler (ExC O.2) anti-fading agent (Cpd-1, 1, 2, coupler dispersion medium (Cpd-6) coupler solvent (Solv-1, ...0.14 ... ...1.00 1:1 of 2 and 3: ...0.30 3 and 4 equivalents) ...0.1 8 ...0.0 3 2 , 3 equivalents) ...0. 1 2 5th layer (intermediate layer) Gelatin color mixture prevention agent (Cpd-7) Color mixture prevention agent solvent (Solv Polymer latex (Cpd 1.00 0.08 4, 5 Equivalent amount) ・・・・・・0. 1 6 8) ・・・・・・0. 1 0 6th layer (low sensitivity green sensitive layer) Silver bromide spectrally sensitized with the green sensitizing dye (14) of the present invention (average grain size 0.25μ, size distribution 8%, octahedron)... ...0.04 Silver bromide spectrally sensitized with the green sensitizing dye (14) of the present invention (average grain size 0.40μ, size distribution 10%, octahedron)
・・・・・・0.06 gelatin
...0.80 magenta coupler (E
xM-1, 2, 3 equivalents)...0.1) Antifading agent (equal amounts of Cpd-9, 26)...0
．． 15 Stain inhibitor (Cpcl-10, 1), ■2, 13 in a 10:7:7:1 ratio) ...0.025
Coupler dispersion medium (Cpd-6) ...0.0
5 coupler solvent (So1v-4, 6 equivalents)...
0.15 7th layer (high sensitivity green sensitive layer) Green sensitizing dye of the present invention (14) Silver bromide (average grain size 0.6, cloth 16%, octahedral) Gelatin magenta coupler (spectral enhancement with ExM) 5μ, size...0,10...0.80 1,2,3 equivalent)...0.1) Anti-fading agent (Cpcl-9, 26 equivalents)...0
．． 1 5 Stain inhibitor (Cpd-10, 1), 12, 13 in 1
(0:7:7:1 ratio) ・・・・・・0. 02
5 coupler dispersion medium (Cpd-6)...0.05
Coupler solvent (Solv-4, 6 equivalents)...0
．． 15 8th layer (intermediate layer) 9th layer (yellow filter layer) same as 5th layer Yellow colloidal silver (particle size 100)...
・0.12 Gelatin ・・・・・・0.70
Color mixing prevention agent (Cpd-7) ・・・・・・0,0
3 Color mixing inhibitor solvent (3o1v4, 5 equivalents)...
0. 10 Polymer latex (Cpd-8) ...0.07 10th layer (intermediate layer) 1st layer (low sensitivity blue-sensitive layer) same as 5th layer) Blue sensitizing dye of the present invention ( 12) Silver bromide (average particle size 0.4, 8% cloth, octahedron) Blue sensitizing dye of the present invention (12) Silver bromide (average particle size 0.6, 11% cloth, octahedron) Gelatin yellow Coupler (ExY-1, spectrally sensitized with 0 μ, size...0.07 Spectral sensitized with 0 μ, size...0.14...0. 80 2 equivalent) ...0.35 ...0.10 15 to 5 ratio ...0.007 ...0.05 ... ...0.10 Anti-fade agent (Cpd-14) Anti-stain agent (CPd-5, ) Coupler dispersion medium (CPD-6) Coupler solvent (Solv-2) 12th layer (high sensitivity blue sensitive layer) Book Blue sensitizing dye of the invention (12) Silver bromide (average particle size 0.8, cloth 18%, octahedral) Spectrally sensitized with gelatin, 5μ, size...0.15... ...0.60 Yellow coupler (ExY 1, 2 equivalent) ...0. ...0. 15 to 1...0. ...0. ...0. 30 lO:5 ratio 007 05 10 Anti-fade agent (Cpd-14) Anti-stain agent (Cpd-5, with) Coupler dispersion medium (Cpd-6) Coupler solvent (Solv-2) 13th layer (ultraviolet absorbing layer) Gelatin Ultraviolet absorber (Cpd...1.00 2, 4, 16 equivalents)...0. 50 Color mixing prevention agent (Cpd-7, 17 equivalent) ...0.03 Dispersion medium (Cpd-6) ...0.0
2 UV absorber solvent (Solv-2, 7 equivalents)...
・・0. 08 Anti-irradiation dye (Cpd-18, l9, 20
, 21, 27 in a 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 (molecules!50,0
00) ...0.01 polymethyl methacrylate particles (average particle size 2.4μ) and silicon oxide (average particle size 5μ) equivalent amount
...0.05 gelatin
・・・・・・1.80 Gelatin hardening agent (I{-
L H-2 equivalent)...0.18 15th layer (back layer) Gelatin...2.50
Ultraviolet absorber (Cpd-2, 4, 16 equivalent)...
・0.50 dye (equal amounts of Cpd-18, 19, 20, 21, 27)
・・・・・・0.06 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
...2.00 Gelatin hardener (H-1, H-2 equivalent) ...0.14 How to make emulsion EMI Vigorously stir an aqueous solution of potassium bromide and silver nitrate into an aqueous gelatin solution. They were added simultaneously over a period of 15 minutes at 75°C to obtain octahedral silver bromide particles with an average particle size of 0.35μ. In this case, 0.3 g of 3,4-dimethyl-1.
3-thiazoline-2thione was added. 1 silver in this emulsion
per mole of sodium thiosulfate and 7μ of chloroauric acid (
Chemical sensitization treatment was carried out by sequentially adding tetrahydrate salt and heating at 75°C for 80 minutes. The thus obtained grains were used as cores and further precipitated in the same precipitation environment as the first time, to finally obtain an octahedral monodisperse core/shell silver bromide emulsion with an average grain size of 0.7 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 μg of chloroauric acid (tetrahydrate) per mole of silver.
Chemical sensitization was carried out by heating at 0°C for 60 minutes to obtain an internal latent image type silver halide emulsion.

Each photosensitive layer contains ExZK-1 and ExZK- as nucleating agents.
2 to silver halide, respectively 1010-2 heavy weight%,
CP d-2 2 was used as a nucleation accelerator at 10-2 weight. Furthermore, alkanol XC is added to each layer as an emulsification aid.
(Dupon) and sodium alkyl hanzene sulfonate 1
・Rium, succinate ester and Ma as coating aids
gefac F-120 (manufactured by Dainippon Ink Co., Ltd.) was used. (cpa23, 24, 25) was used as a stabilizer in the silver halide and colloidal silver containing layers. This sample was designated as sample number 101. The compounds used in the examples are shown below.

Cpd Cpd Cpd Cpd 4 Cpd Cpd Cpd 5 ICH2-CI1)-. OH COOCztl+s Ul1 Cpd Cpd 6 CONHC4Hq(t) 8 1 Cpd-1) CJs 0 1) Cpd-12 -83= Cpd-16 Cpd 17 0H Cpd 18 SO3K SO3K Cpd 13 0■ Cpd -14 Cpd 15 OH -18 41 Cpd-19 SO3K S03K Cpd 20 SOkK SO3K Cpd 21 SO. K S03K Cpd 22 Cpd 23 0H Cpd 24 Oil Cpd 25 87 EXC 2 EXC-3 EXM 1 89 Cpd 26 C p d -27 EXC 1 EXM 2 EXM-3 88 C1), 90 EXY EXY 1 2 Cl CI So lv 1 Solv 2 Solv 3 lv-4 lv-5 lv-6 lv-7 H 1 H 2 Ex ZK 1 Di(2-ethylhexyl) sebacate trinonyl phosphate di(3-methylhexyl) phthalate tricresyl phosphate dibutyl fuku Trioctyl phosphate di(2-ethylhexyl) phthalate 1.2-bis(vinylsulfonylacetoagodo)ethane 4.6-dichloro-2-hydroxy-1.3.5-triazine Na salt 7-(3-ethoxy thiocarbonylaminobenzad)-9 methyl-10-prohagiru 1,2,3.4-tetrahydroacridinium trifluoromethanesulfonateExZK-2 2 - (4-{3 - (3 -
(3(5- (3- (2-chloro5 (1-dodecyloxycarbonylethoxycarbonyl)phenylcarbamoyl)-4-hydroxy-1-naphthylthio}tetrazol-1-yl]phenyl}ureido)benzenesulfonamide} Phenyl]-1-formanhydrazine Next, the spectral sensitizing dye (50) added to the third and fourth layers
Spectral sensitizing dyes shown in Table 1 and general formula (If) instead of
Samples 102 to 13 containing the compound of the present invention shown in
2 was produced.

The obtained sample was exposed to wedge light (1/10 second, 300
After giving 0MS), the following treatment was performed.

Processing process Time Temperature Mother liquor tank capacity Replenishment amount Color development 135 seconds 38°C 1 1 42
300mR/rd bleach fixing 40〃33〃3〃30
0〃Washing (1) 40 // 33N 3 //
Washing (2) 40〃33〃3〃320〃 Drying 30〃80〃 The method of replenishing the washing water is to replenish it to the washing bath (2) and
A so-called countercurrent replenishment system was adopted in which the overflow liquid of 2) was led to the washing bath (1). At this time, the amount of bleach-fix solution brought into the washing bath (1) from the bleach-fix bath for photosensitive materials is 3
5 d/of, and the ratio of the amount of washing water replenishment to the amount of bleach-fix solution brought in was 9.1 times.

The composition strength of each treatment solution was as follows.

Color Development Lishuho Mother Solution Replenisher D-Sorvit 0.15 g 0.
20 g Sodium naphthalene sulfonate 0.15 g
0.20 g formalin condensate ethylene dianetetrakis 1.5 g 1.5 g
Methylene phosphonic acid diethylene glycol benzyl alcohol potassium bromide penzotriazole sodium sulfite N,N-bis(carboxymethyl)hydrazine D-glucose triethanolamine N-ethyl-N-(β-methanesulfonamidoethyl) 3-methyl-4-aminoaniline Sulfate potassium carbonate optical brightener (diaminostilbene type) 12.0ml 16. Om℃ 13.5m 18.0m℃ 0.70 g 0.003g 0.004g 2.4g 3.2g 4.0g 5.3g 2.0g 2.4g 6.0g 8.0H 6.4g 8.5g 30.0 g 25,Q g 1.0g 1.2g Liaoshu0ReAuthentic Mother Solution Replenisher Ethylenediaminetetraacetic acid 2 2.0g Mother liquor contains the same sodium dihydrate ethylenediaminetetraacetic acid 70.0gFe (Iff
) ・Ammonium・Ammonium thiosulfate dihydrate (70 180 dO g/
IV. ) Sodium p-}luenesulfinic acid 45. Og thorium sodium bisulfite 35.0g 5-mercapto-1.3,4 0.5g triazole ammonium nitrate 10.0g Add water 1000m゜pH (25゜c)
6. Wash 10 bottles with tap water for both mother liquor and replenisher and add H-type strongly acidic cation exchange resin (Amberlite IR-120B manufactured by Rohm and Haas)
and OH type anion exchange resin (Amberlite IR-
400) to reduce the concentration of calcium and magnesium ions to 3 mg/l or less, followed by 20 mg of sodium isocyanurate dichloride.
/I! ．． and 0.15 gel of sodium sulfate were added. The pH of this liquid was in the range of 6.5 to 7.5.

The cyan color density of the obtained direct positive image was measured. Further, the sensitivity was determined from the reciprocal of the exposure amount required to obtain a constant cyan density (D=0.7).

The results obtained are shown in Table 1.

Table 1 shows that the samples using the sensitizing dye of the present invention and the compound of the present invention have high sensitivity and maximum image density (D
It can be seen that the minimum image density (Dmin) can be lowered while keeping the minimum image density (Dmin) high.

Example 2 Instead of the spectral sensitizing dye (■4) added to the 6th and 7th layers of sample 101 of Example 1, the spectral sensitizing dye shown in Table 2 and the compound represented by the general formula (n) were used. Samples 201 to 219 to which the compound of the invention was added were prepared.

These samples were exposed and processed in the same manner as in Example 1, and the magenta color density of the resulting direct positive images was measured. The results are shown in Table 2.

Table 2 shows that the samples using the sensitizing dye of the present invention and the compound of the present invention have high sensitivity and maximum image density (D
It can be seen that the minimum image density (Dmin) can be lowered while keeping the minimum image density (Dmin) high.

Example 3 Instead of the spectral sensitizing dye (12) added to the 1st) layer and the 12th layer of sample 101 of Example 1, the spectral sensitizing dye shown in Table 2 and the book represented by general formula (II) were used. Samples 301 to 319 to which the compound of the invention was added were prepared.

These samples were exposed and processed in the same manner as in Example I, and the yellow color density of the resulting direct positive images was measured. The results are shown in Table 3.

Table 3 shows that the samples using the sensitizing dye of the present invention and the compound of the present invention have high sensitivity and maximum image density (D
It can be seen that the minimum image density (Dmin) can be lowered while keeping the minimum image density (Dmin) high.

Example 4 Preparation of Emulsion EM2 A mixed aqueous solution of potassium bromide and sodium chloride and an aqueous solution of silver nitrate were vigorously stirred into an aqueous gelatin solution containing 0.07 g of 3,4-dimethyl-1,3-thiazoline-2-thione per mole of Ag. They were simultaneously added at 65° C. over a period of about 14 minutes to obtain a monodisperse silver chlorobromide emulsion with an average grain size of about 0.23 μm (silver bromide content: 80 mol %). This emulsion contains 61 μm of sodium thiosulfate per mole of silver and 4
A chemical sensitization treatment was carried out by adding 2 parts of chloroauric acid (tetrahydrate) and heating at 65°C for 60 minutes. Using the silver chlorobromide particles obtained in this way as a core, they were further precipitated in the same precipitation environment as the first time, and the final average particle size was approximately 0.65 μm (
A monodisperse core/shell silver chlorobromide emulsion with a silver bromide content of 70 mol % was obtained. The coefficient of variation in particle size was approximately 12%. To this emulsion were added 1.5 μ 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 EM2.

Next, instead of the internal latent image type silver bromide emulsion used in Sample 101 of Example 1, an internal latent image type silver chlorobromide emulsion prepared according to the manufacturing method of emulsion EM2 described above was used to prepare a sample. 401 was produced.

The average grain size, grain size distribution, and silver chloride content of the emulsion used in each layer are shown below.

Next, instead of the spectral sensitizing dye (50) added to the third and fourth layers of sample 401, the spectral sensitizing dye shown in Table 4 and the compound of the present invention represented by general formula (II) were added. Samples 402 to 418 were prepared.

These samples were exposed and processed in the same manner as in Example 1, and the cyan color density of the resulting direct positive images was measured. The results are shown in Table 4.

Table 4 shows that the samples using the sensitizing dye of the present invention and the compound of the present invention have high sensitivity and maximum image density (D
It can be seen that the minimum image density (Dmin) can be lowered while keeping the minimum image density (Dmin) high.

Example 5 Samples 401 to 418 prepared in Example 4 were prepared in the same manner as in Samples 401 to 418, except that the nucleating agents ExZK-1 and EXZK-2 and the nucleating promoter Cpd-22 were removed from each photosensitive layer of Samples 401 to 418. Samples 501 to 51B were prepared.

These samples were exposed to light in the same manner as in Example 1, and then processed in the same manner as in Example 1.

At that time, the sample was immersed in a color developing solution for 15 seconds, and then light of 0.5 lux (color temperature 5400°K) was continuously applied to the sensitive material film for 15 seconds.

The cyan coloring density of the obtained direct positive image was measured, and the results are shown in Table 5.

Table 5 shows that the samples using the sensitizing dye of the present invention and the compound of the present invention have high sensitivity and maximum image density (D
It can be seen that the minimum image density (Dmin) can be lowered while keeping maχ) high.

(Effects of the Invention) The structure of the present invention, in particular, a photosensitive material made of an internal latent image type silver halide containing a sensitizing dye (T) and a compound (If) is fogged to produce a direct positive image (color). By applying this, it is possible not only to increase the sensitivity but also to lower the minimum density (Dmin) while keeping the maximum density (Dmax) high. This effect is remarkable when the nucleating agent (N-1) and/or (N-2) is used for Kafuri treatment.

Claims (1)

[Scope of Claims] [1] A direct positive photographic light-sensitive material having at least one photographic emulsion layer containing internal latent image type silver halide grains not previously fogged on a support, in which Direct positive photography characterized by containing (1) at least one sensitizing dye represented by the following general formula (I) and (2) at least one compound represented by the following general formula (II) photosensitive material. General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, Z_1 and Z_2 are thiazole nucleus, thiazoline nucleus,
Forms a benzthiazole nucleus, naphthothiazole nucleus, oxazole nucleus, benzoxazole nucleus, oxazoline nucleus, naphthoxazole nucleus, imidazole nucleus, benzimidazole nucleus, imidazoline nucleus, selenazole nucleus, selenazoline nucleus, benzoselenazole nucleus or naphthoselenazole nucleus represents the atomic group necessary for R_1 and R_2 represent an alkyl group or a substituted alkyl group. However, at least one of R_1 and R_2 shall have a sulfo group or a carboxy group. L_1 and L_2 represent a substituted or unsubstituted methine group. n represents an integer from 0 to 2. General formula (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R_3 is a hydrogen atom, a halogen atom, an alkyl group, an alkoxycarbonyl group, an acyloxy group, an alkoxy group, an amino group, a substituted amino group, an acylamido group, or represents a carbamoyl group. Y is alkylene, arylene, aralkylene, -COO-, -COO-Y_1-OC
Represents O-. However, Y_1 represents alkylene, arylene, or aralkylene having 1 to 18 carbon atoms. X_
1 represents an anion. m_1 and m_2 are each 1
Represents an integer between ~19. ) [2] The direct positive image forming method in which the direct positive photographic light-sensitive material is developed after imagewise exposure, after fogging treatment, and/or while being subjected to fogging treatment, characterized in that the fogging treatment is a fogging method. Direct positive image formation method. [3] At least one of the photographic emulsion layers has the following general formula [N
-1] and/or [N-2]. The direct positive photographic light-sensitive material according to claim 1, which contains a nucleating agent represented by [N-1] and/or [N-2]. General formula [N-1] ▲ Numerical formulas, chemical formulas, tables, etc. R^4 is an aliphatic group, and R^5 is a hydrogen atom, an aliphatic group, or an aromatic group. R^4 and R^5 may be substituted with a substituent. Furthermore, R^5 may be further combined with the heterocycle completed by Z to form a ring. However,
At least one of the groups represented by R^4, R^5 and Z contains an alkynyl group, an acyl group, a hydrazine group or a hydrazone group, or R^4 and R^5 combine to form 6
Forms a membered ring and forms a dihydropyridinium skeleton. Furthermore, at least one of the substituents R^4, R^5 and Z may have a group that promotes adsorption to silver halide. Y is a counter ion for charge balance, and n is 0 or 1. General formula [N-II] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R^2^1 is an aliphatic group, an aromatic group, or a small number of heterocyclic groups; R^2^2 is hydrogen represents an atom, alkyl group, aralkyl group, aryl group, alkoxy group, aryloxy group, or amino group; G represents a carbonyl group, sulfonyl group, sulfoxy group, phosphoryl group, or iminomethylene group (▲ mathematical formula, chemical formula, table, etc.) R^2^3 and R^2^4 are both hydrogen atoms, or one is a hydrogen atom and the other is an alkylsulfonyl group, an arylsulfonyl group, or an acyl group.However, A hydrazone structure (▲numerical formula, chemical formula, table, etc. available▼) may be formed by including G, R^2^2, R^2^4, and hydrazine nitrogen.Also, the above-mentioned groups are possible may be substituted with a substituent.)