JPH01150133A - Direct positive image forming method - Google Patents

Abstract

PURPOSE:To increase the max. image density of a direct positive image and to lower the min. image density by using specific nucleation accelerators. CONSTITUTION:This photosensitive material is provided with an emulsion layer contg. internal latent image type silver halide particles which are not previously fogged. Said material is formed by adding >=1 kinds among the nucleation accelerators expressed by formula I-IV to, for example, the above-mentioned emulsion layer or the adjacent layer thereof. In formulas, M denotes H, alkali metal, etc.; R denotes H, group which can substitute H; (n) denotes 1-4; R1-R9 denote H, mercapto group, etc. After this photosensitive material is subjected to imagewise exposing, the material is subjected to fogging processing or development processing under the fogging processing to form the direct positive image. The compd. expressed by formula V is usable for the nucleating agent.

Description

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

[Prior Art] There is a method of directly obtaining a positive image by using an internal latent image type silver halide emulsion that has not been fogged in advance, and performing surface development after image exposure and after fogging treatment, or while performing fogging treatment. Are known.

Here, the 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. Refers to emulsion.

Various techniques are known in this technical field. For example, U.S. Pat. No. 2,592.250, U.S. Pat.
, No. 588.982, No. 3゜317.322, No. 3,
761,266, 3.761,276, 3.7
The main ones are those described in British Patent No. 96,577 and the specifications of British Patent Nos. 1,151,363, 1.150.553, and 1.011,062.

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

For details of the above direct positive image formation mechanism, see, for example, T.
``The Theory of the Photographic Process'' by James H.
f the Photographic Processes
s), 4th edition, Chapter 7, pages 182 to 193, and US Pat. No. 3,761,276.

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

As mentioned above, as a means for selectively generating fog nuclei, a method of applying a second exposure to the entire surface of the photosensitive layer, which is generally referred to as "optical power pre-method" (for example, British Patent No. 1,151), is used.
363) and a nucleating agent (n
A method using a nucleating agent is known. Regarding this latter method, for example, ``Research Disclosure J''
Disclosure) Magazine, Volume 151, Arashi 15162
(published November 1976), pages 76-78.

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

[Problems to be Solved by the Invention] Hydrazine compounds are well known as nucleating agents used in the above-mentioned "chemical fogging method."

The above hydrazine nucleating agent generally has a maximum image density (Dn+
ax ) and the minimum image density (Dn+in ), and is the best in terms of discrimination, but has the disadvantage of requiring high pH (pH>12) for processing.

Heterocyclic quaternary ammonium salts are known as nucleating agents that act even at low processing pH (pH≦12); for example, U.S. Pat. Nos. 3,615,615 and 3,719,49
No. 4, No. 3,734,738, No. 3,759,901
No. 3.854. No. 956, 4,094,683
No. 4,306°016, British Patent No. 1,283.8
No. 35, JP-A No. 52-3,426 and JP-A No. 52-69
, No. 613. Specifically, U.S. Patent 4,115
The propargyl- or butynyl-substituted heterocyclic quaternary ammonium salt compounds described in No. 122 are excellent nucleating agents in terms of discrimination in direct positive silver halide emulsions.

However, when a sensitizing dye is added to the silver halide emulsion for the purpose of spectral sensitization, for example, between the sensitizing dye and the heterocyclic quaternary ammonium nucleating agent, the silver halide emulsion Because competitive adsorption occurs in It could not be said that it showed performance.

It should be noted that this tendency tends to increase even more when exposed to high temperatures.

For the purpose of solving the above problem, U.S. Patent No. 4,471.04
No. 4 reports an example of a quaternary base nucleating agent having a thioamide AgX adsorption promoting group. Here, the introduction of adsorption groups reduces the amount of addition required to obtain a sufficient ma.
Although it is said that the reduction in Dmax over time at high temperatures is improved, this effect was not at a fully satisfactory level.

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

[Means for Solving the Problems] The above object of the present invention is to provide a photographic light-sensitive material having a small number of photographic emulsion layers containing internal latent image type silver halide grains which are not fogged in advance on a support. In the method of directly forming a positive image by fogging after imagewise exposure, or by developing while performing fogging, the developing treatment is carried out using the following general formula (I), (n), (■) or This is achieved by a direct positive image forming method characterized in that it is carried out in the presence of at least one type of compound represented by (TV).

General formula ('I') General formula (II
) General formula (III) General formula (IV)
p.

In the formula, M represents a hydrogen atom, an alkali metal atom, an ammonium group, or a group that cleaves under alkaline conditions, R represents a hydrogen atom or a group capable of substituting it, and n is 1 to 4.
represents.

Rn, Rz, Rz, Rn, Rs, Rh, Rt, R11 and R1 are hydrogen atoms, mercapto groups, substituted or unsubstituted alkyl groups, aryol groups, alkenyl groups, aralkyl groups, alkylthio groups, carbonamide group, a sulfonamide group, a ureido group, a thioureido group, an oxycarbonylamino group, or an amino group.

Also - the heterocycle at maximum (II), (Iff) or (TV) may be fused with a carbon aromatic ring.

The present inventors have discovered that when forming a positive image directly on a photographic light-sensitive material containing a smooth emulsion that has not been fogged in advance in the presence of a nucleating agent, the general formulas (I), (n), (■), Or (
It was surprisingly discovered that a direct positive image having both sufficiently high maximum image density and low minimum image density can be obtained by coexisting at least one compound represented by (TV), leading to the present invention.

The compounds represented by the general formulas (I), CI+), (■), and (IV) do not themselves act as nucleating agents, but they act as so-called "nucleating agents" that promote the action of nucleating agents. It has the function of "promoting agent".

The compounds represented by the general formulas (I), (II), (■), and (IV) will be explained in detail.

In each formula, M is a hydrogen atom, an alkali metal atom (e.g., sodium atom, potassium atom, etc.), an ammonium group (e.g., trimethylammonium group, dimethylbenzylammonium group, etc.), M=H under alkaline conditions, or an alkali metal atom Represents a group that can be an atom (eg, acetyl group, cyanoethyl group, methanesulfonylethyl group, etc.).

R represents a hydrogen atom or a group capable of substituting it. Examples of substitutable groups include nitro groups, halogen atoms (e.g., chlorine atoms, bromine atoms, etc.), mercapto groups, cyano groups, and substituted or unsubstituted alkyl groups (e.g.,
methyl group, ethyl group, propyl group, t-butyl group, dimethylaminoethyl group, cyanoethyl group, etc.), aryl group (e.g. phenyl group, 4-methanehydrophenyl group, 4-methylphenyl group, 3-4 7-chlorophenyl group, naphthyl group, etc.), alkenyl group (e.g. allyl group, etc.), aralkyl group (e.g. benzyl group, 4-methylbenzyl group, phenethyl group, etc.), sulfonyl group (
For example, methanesulfonyl group, ethanesulfonyl group, p-
toluenesulfonyl group, etc.), carbamoyl group (e.g. unsubstituted carbamoyl group, methylcarbamoyl group, phenylcarbamoyl group, etc.), sulfamoyl group (e.g. unsubstituted sulfamoyl group, methylsulfamoyl group, phenylsulfamoyl group, etc.) , carbonamide group (e.g. acetamide group, benzamide group, etc.), sulfonamide group (e.g. methanesulfonamide group, benzenesulfonamide group, p-toluenesulfonamide group, etc.),
Acyloxy group (e.g. acetyloxy group, benzoyloxy group, etc.), sulfonyloxy group (e.g. methanesulfonyloxy group, etc.), ureido group (e.g. unsubstituted ureido group, methylureido group, ethylureido group, phenylureido group, etc.), thioureido groups (e.g., unsubstituted thioureido groups, methylthioureido groups, etc.), acyl groups (e.g., acetyl groups, benzoyl groups, etc.), oxycarbonyl groups (e.g., methoxycarbonyl groups, phenoxycarbonyl groups, etc.), oxy Carbonylamino group (
For example, methoxycarbonylamino group, phenoxyoxycarbonylamino group, 2-ethylhexyloxycarbonylamino group, etc.), alkoxy group (e.g. methoxy group, ethoxy group, methoxyethoxy group, etc.), aryloxy group (e.g. phenoxy group) , 4-methylphenoxy group, etc.), alkylthio group (e.g. methylthio group, ethylthio group, etc.), arylthio group (e.g. phenylthio group, etc.), amino group (e.g. unsubstituted amino group, dimethylamino group, methoxyethylamino group) group, anilino group, etc.), carboxylic acid or its salt, sulfonic acid or its salt, hydroxyl group, etc. n represents 1-4.

R+, Rs, Rs, R4, Rs, R&1Rq, R6 and R9 are hydrogen atoms, mercapto groups, substituted or unsubstituted alkyl groups (e.g., methyl group, ethyl group, propyl group, t-butyl group, methoxyethyl group) group, methylthioethyl group, dimethylamineethyl group, morpholinoethyl group, dimethylaminoethylthioethyl group, diethylaminoethyl group, diethylaminoethyl group, dipropylaminoethyl group, dimethylaminohexyl group, methylthiomethyl group, methoxyethoxyethoxyethyl group , trimethylammonioethyl group, cyano:Lti)LIJ,
etc.), aryl groups (e.g. phenyl group, 4-methanesulfonamidophenyl group, 4-methylphenyl group, 3-methoxyphenyl group, 4-dimethylaminophenyl group, 3
．． 4-dichlorophenyl group, naphthyl group, etc.), alkenyl group (e.g. allyl group, etc.), aralkyl group (e.g. benzyl group, 4-methylbenzyl group, phenethyl group, 4-dichlorophenyl group, naphthyl group, etc.)
-methoxybenzylthio group, etc.), alkylthio groups (e.g. methylthio group, ethylthio group, propylthio group, methylthioethylthio group, dimethylaminoethylthio group, methoxyethylthio group, morpholinoethylthio group, dimethylaminopropylthio group, piperidine noethylthio group, pyrrolidinoethylthio group, morpholinoethylthioethylthio group, imidazolylethylthio group, 2-pyridylmethylthio group, diethylaminoethylthio group, etc.), carbonamide group (e.g. acetamide group, benzamide group, methoxypropion) amide group, dimethylaminopropionamide group, etc.), sulfonamide group (e.g. methanesulfonamide group, benzenesulfonamide group, p-toluenesulfonamide group, etc.), ureido group (e.g. unsubstituted ureido group, methylureido group) , ethylureido group, methoxyethylureido group, dimethylaminopropylureido group, methylthioethylureido group, morpholinoethylureido group, phenylureido group, etc.), thioureido group (e.g. unsubstituted thioureido group, methylthioureido group, methoxyethylthio ureido group, etc.), oxycarbonylamino group (e.g. methoxycarbonylamino group, phenoxycarbonylamino group, 2-ethylhexyloxycarbonylamino group, etc.), amino group (e.g. unsubstituted amino group, dimethylamino group, methoxyethyl (amino group, anilino group, etc.).

Further, the heterocycle represented by the general formula (II), (III) or (IV) may be fused with a carbon aromatic ring. Furthermore, the condensed carbon aromatic ring is preferably a hydrogen atom or a substituted or unsubstituted alkyl group in the general formula (R to (rV)), and R and -R9 are a hydrogen atom, a mercapto group, and a substituted or unsubstituted alkyl group, respectively. Represents a substituted alkyl group, alkylthio group, or benzo-fused ring.

-i Among formulas (I) to (TV), more preferred is general formula (I) or the following general formula (V).

In the general formula, M, R, R1 and n have the same meanings as in the general formulas (I) and (■), respectively.

Specific compounds represented by the general formula (I), (II), (III) or (IV) of the present invention are shown below, but the compounds of the present invention are not limited thereto.

(I) 5H>rt

:bh(IB)
(I9) General formulas (I), (U), (
Compounds represented by I[I] and (IV) are described in, for example, Atopansis in Heterocyclic Chemistry (Advances in Heterocyclic Chemistry).
ic Chemistry) 9, 280
(I96B), Indian Journal Chemistry (Indian J, Chem,) 5ect B
16 B(8), 689 (I978), Journal of Chemical Society (J, Chem,
Soc, ) 242 (I960), 108 (I9
5B), 1004 (I951), Journal of Org Chemistry (J, Org,
Chem, ) Earthworks, 349 (I946), Journal
of the American Chemical Society (J.
Am, Chem, Soc, ) 1 engineering, 2423 (I94
B) It can be easily synthesized by the method described in French Patent No. 1,192,194 and the like.

In the present invention, the nucleation accelerator is contained in the light-sensitive material, especially in internal latent image type silver halide emulsions and other hydrophilic colloid layers (intermediate layer, protective layer, etc.).
Preferably, it is contained in the silver halide emulsion or in a layer adjacent thereto.

The amount of nucleation accelerator added is 10-' per mole of silver halide.
-10-'' mole is preferred, more preferably 10-5~
It is 1O-2 mole.

Moreover, two or more kinds of nucleation accelerators can also be used together.

The unfogged internal latent image type silver halide emulsion used in the present invention is an emulsion containing silver halide in which the surfaces of silver halide grains are not fogged in advance and latent images are mainly formed inside the grains. But, more specifically,
A certain amount (0.5 to 3
g/n? ), and then exposed to light for a fixed time of 0.0 to 10 seconds, using the following developer A (internal type developer).
The maximum density measured by a normal photographic density measurement method when developed at 18°C for 5 minutes was determined by applying the same amount of silver halide emulsion and exposing it in the same manner as above using developer B (described below).
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-type developer.

Internal developer A Metol 2g Sodium sulfite (
anhydrous) 90g hydroquinone
8g Soda carbonate (-water salt)
52.5 gKBr 5
gK I 0.5 g Add water 1e Internal developer B Metol 2.58 L-ascorbic acid 10 g NaBOt 4Hz
0 35g KBr
Add 1 g of water to form an Iz internal type emulsion.For example, US Pat.
No. 2,250, a conversion silver halide emulsion, U.S. Pat. No. 3,761,276;
3,850.637, 3,923,513, 4,035,185, 4,395.478, 4
．． 504. 570, JP 52-156614, JP 55-127549, JP 53-60222, JP 56-22681, JP 59-208540, JP 60
-No. 107641, No. 61-3137, Patent Application No. 1983-
No. 32462, Research Disclosure Magazine Na23
Mention may be made of the core/shell type silver halide emulsion described in the patent disclosed in No. 510 (published in November 1983), p. 236.

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

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

The average grain size of silver halide grains is 2 μm or less.
．． The 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 grains by sulfur or selenium sensitization, reduction aggravation, noble metal sensitization, etc. alone or in combination. For detailed examples, see Research Disclosure Magazine & 17643-III (published in December 1978)
223 and other patents.

The photographic emulsions used in the present invention are spectrally sensitized with photographic sensitizing dyes in a conventional manner. Particularly useful dyes are those belonging to cyanine dyes, merocyanine dyes and complex merocyanine dyes, and these dyes can be used alone or in combination. Further, the above dyes and supersensitizers may be used in combination. For detailed specific examples, see Research Disclosure Magazine Yo 17643-■ (published December 1978) P.
23-24, etc.

The photographic emulsion used in the present invention may contain an anti-capri agent 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 Nα17643-V.
l (published December 1978) and E, J, B
Written by irr”5 tabilization of Photo
graphic 5ilver Hailde Em
ulsion” (Focal Press), 197
It is written in the 4th annual issue.

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

The entire surface exposure, that is, the fogging exposure in the "light fogging method" of the present invention is carried out after the imagewise exposure and/or during the development process. The imagewise exposed light-sensitive material is immersed in a developer solution or a pre-bath of the developer solution, or is taken out from the solution and exposed before 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. 58-6936, JP-A No. 4L-9727, No. 56-137350, No. 57-129438,
No. 58-62652, No. 5B-60739, No. 58
-70223 (corresponding U.S. Patent No. 4,440°851)
, No. 58-120240 (corresponding European patent 89101A
2) etc.

Photosensitive materials sensitive to all wavelength ranges, such as color photosensitive materials, are disclosed in Japanese Patent Application Laid-open No. 56-137350 and No. 58-702.
A light source with high color rendering properties (as close to white as possible) as described in No. 23 is preferable. 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 reducing the light using various filters, by changing the distance between the photosensitive material and the light source, or by changing the angle between the photosensitive material and the light source. Further, the illuminance of the fogging light can be increased continuously or stepwise from low illuminance to high illuminance.

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

The exposure time for fogging is generally 0.01 seconds to 2 minutes.
Preferably 0. 1 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 particular, in the present invention, it is preferable to perform fogging treatment using a nucleating agent.

When incorporated into a light-sensitive material, it is preferably added to the inner silver halide emulsion layer, but as long as the nucleating agent is adsorbed to the silver halide by diffusion during coating or processing, it may be added to other layers, e.g. , an intermediate layer, an undercoat layer or a back layer.

When 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.

Nucleating agents used in the present invention are described on page 50, line 1 to page 53 of the same specification, and in particular compounds represented by general formulas (N-1) and (N-11) in the same specification. It is preferable to use

Specific examples of the compound represented by general formula (N-1) are listed below, but the invention is not limited thereto.

(N-I-1) 5-ethoxy-2-methyl-1-
7” lobargylquinolinium bromide (N-1-2) 2.4-dimethyl-1-propargylquinolinium bromide (N-1-3) 2-methyl-1-(3-C2-(
4-Methylphenyl)hydrazono]butyl)quinolinium iosito(N-1-4) 3.4-dimethyl-dihydropyrido(2,1-b)benzothiazolium bromide(N-1-5) 6-nitoxythiocarponyl Amino-2-methyl-1-propargylquinolinium trifluoromethanesulfonate (N-1-6) 2-Methyl-6-(3-phenylthioureido)-1-propargylquinolinium promide (N-I-7 ) 6-(5-benzotriazolecarboxamide)-21-methyl-1-propargylquinolinium trifluoromethanesulfonate (N-1-8) 6-(3-(2-mercaptoethyl)ureido-2-methyl-1- Propargylquinolinium trifluoromethanesulfonate (N-r-936-(3-(3-(5-mercapto-1)
,3,4-thiadiazol-2-ylthio)propylthureido) -2-methyl-1-propargylquinolinium trifluoromethanesulfonate (N-1-10) 6-(5-mercaptotetrazole-nyyl)- 2-Methyl-1-propargylquinolinium iosito (N-1-11) 1-propargyl-2-(I-
(propenyl) quinolinium trifluoromethanesulfonate (N-1-12) 6-nitoxythiocarbonylamino-2-(2-methyl-1-propenyl)-1-propargylquinolinium trifluoromethanesulfonate (N-1-13 ) 10-propargyl-1,2,
3,4-tetrahydroacridinium trifluoromethanesulfonate (N-1-14) 7-nitoxythiocarponylamino-10-propargyl, 2゜3.4-tetrahydroacridinium trifluoromethanesulfonate (N-1 -15) 6-nitoxythiocarponylamino-1-propargyl-2,3 1-pentamethylene quinolinium trifluoromethanesulfonate (N-1-16) 7- (3-(5-mercaptotetrazol-1-yl) Henzamide 10-propargyl-1゜2.3.4-tetrahydroacridinium perchlorate (If-■-17) 6- (3-(5-mercaptotetrazol-1-yl)henzamide 1-propargyl-2゜3-penta Methylenequinolinium bromide (N-1-18) 7-(5-mercaptotetrazol-1-yl)-9-methyl-10-propargyl-1,2,3゜4-tetrahydroacridinium bromide (N -1-19) 7- (3-N-(2-(5-
Mercapto-1,3,4-thiariazol-2-yl)thioethyl] carbamoyl)propanamide] -10-propargyl-1,2゜3.4-tetrahydroacridinilam tetrafluoroborate (N-1-20) 6 -(5-Mercaptotetrazol-1-yl)-4-methyl-1-propargyl-2,3-pentamethylenequinolinium Bromide (N-1-21) 7-nitoxythiocarponylamino-10-propargyl-1゜2-dihydroacridinium trifluoromethanesulfonate (Nl-22) 7-(5-mercaptotetrazol-1-yl)-9-methyl-10-propargyl-1,2-dihydroacridinium hexafluorophospha -t(N-1-23) 7-(3-(5-mercaptotetrazol-1-yl)benzamide-10-propargyl-1°2-dihydroacridinium bromide of the compound represented by the general formula (N-111) Specific examples are shown below, but the invention is not limited thereto.

(N-4-1) 1-formyl-2-(4-(3-
(2-methoxyphenyl)ureido]phenyl)hydrazine (N-It-2) 1-formyl-2-(4-(3
-(3-(3-(2,4-di-tert-pentylphenoxy)propylthureido)phenylsulfonylamino]phenyl)hydromethane(N-11-3) 1-formyl-2-(4-(3
-(5-mercaptotetrazol-1-yl)benzamido]phenyl)hydrazine (N-I[-4) 1-formyl-2-(4-(3
-(3-(5-mercaptotetrazol-1-yl)phenyl]ureido)phenyl]hydrazine (N-11-5) 1-formyl-2-(4-[3
-(N-(5-mercapto-4-methyl-1,2,4-)lyazol-3-yl)carbamoyl)propanamido)phenyl]hydrazine (N-n-6) 1-formyl-2-(4- (3-
(N-(4-(3-mercapto-1,2,4-triazol-4-yl)phenyl]carbamoyl)propanamido]phenyl)hydrazine[N-■-7) l-formyl-2-(4-[ 3-
(N-(5-mercapto-1゜3.4-thiadiazol-2-yl)carbamoyl)propanamido)phenylgohydrazine (N-n-8) 2-(4-benzotriazole-5
-carboxamide) phenyl-1-formylhydrazine (N-1-9) 2-(4-(3-(N-(benzotriazole-5-carboxamide)carbamoyl]propanamide) phenyl-1-formylhydrazine (N-11 -10) 1-formyl-2-[4-(
I-(N-phenylcarbamoyl) thiosemicarbamido]phenyl) hydrazine (N-It-11) 1-formyl-2-(4-(
3-[3-phenylthioureido]benzamido]phenyl)-hydrazine[N-■-12) 1-formyl-2-(4-(3
-hexylureido)phenyl]hydrazine(N-It-1331-formyl-2-(4-(3-(
5-mercaptotetrazol-1-yl)benzenesulfonamido]phenyl)hydrazine (N-n-14)1-formyl-2-(4-(3-(3
-(3-(5-Mercaptotetrazol-1-yl)phenyl]ureido)benzenesulfonamide]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. , preferably contained in the photosensitive material. Moreover, two or more types of nucleating agents may be used in combination.

When a nucleating agent is contained in the sensitive material, the amount used is preferably 10-'' to 10-2 mol, more preferably 10-'' to 10-'' mol, per 111 mol of halogenide.

In addition, when adding a nucleating agent to the processing solution, the amount used is:
The amount is preferably 10-'' to 10-3 mol, more preferably 10-7 to 10-4 mol per 11.

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. Typical examples of useful color couplers, which are preferably compounds, include naphthol or phenolic compounds, pyrazolones or pyrazoloazole compounds, and open-chain or heterocyclic ketomethylene compounds. , magenta and yellow couplers are given in "Research Disclosure" magazine Na17643 (published in December 1978) P25
．． It is described in the compounds described in Section 2-D, Kaimagai 18717 (published in November 1979) and Japanese Patent Application No. 32462/1983, and the patents cited therein.

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

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

More preferred are pyrazoloazole couplers, and among them, pyrazolo(5,1-c) (I,2,4) triazoles described in U.S. Pat. No. 3,725.067 are preferred; The imidazo[1°2-b]pyrazoles described in U.S. Pat. No. 4,500,630 are more preferable in terms of low yellow absorption and light fastness; The described pyrazolo(I,5-b)(I,2,4))riazoles are particularly preferred.

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

Colored couplers to correct unnecessary absorption in the short wavelength range of the dyes produced, couplers in which the coloring dye has appropriate diffusivity, non-coloring couplers, DIR couplers that release a development inhibitor upon coupling reaction, and Polymerized couplers can also be used.

The standard usage amount of color couplers is in the range of 0.001 to 1 mole per mole of photosensitive halogenated coupler, preferably 0.01 to 0.1 mole for yellow couplers.
5 mol, for magenta couplers 0.03 mol to 0
．． 5 mol, and for cyan couplers 0.002 to 0
．． It is 5 moles.

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 374-391.

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

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

The light-sensitive material produced using the present invention includes hydroquinone mW1, aminophenol derivatives, amines, gallic acid derivatives, catechol derivatives, ascorbin fi2-diAs, colorless couplers, It may also contain sulfonamide phenol derivatives and the like. Representative examples of color antifogging agents and color mixing inhibitors are described in JP-A-62-215272, pages 600-63.

Various anti-fading agents can be used in the light-sensitive material of the present invention. Organic anti-fading agents include hydroquinones,
6-hydroxychroman li, 5-hydroxycoumarans, spirochroman R1p-alkoxyphenols,
Typical examples include hindered phenols, mainly bisphenols, gallic acid derivatives, methylenedioxybenzenes, aminophenols, hindered amines, and ether or ester derivatives obtained by silylating or alkylating the phenolic hydroxyl group of each of these compounds. Can be mentioned. Further, metal complexes such as (bissalicylaldoximado)nickel complex and (bis-N,N-dialkyldithiocarbamado)nickel complex can also be used.

To prevent yellow dye images from deteriorating due to heat, humidity and light.
As described in U.S. Pat. No. 4,268,593,
Compounds having a hindered amine and a hindered phenol structure in the same molecule give good results. In addition, in order to prevent deterioration of magenta dye images, especially deterioration due to light, spiroindanes described in JP-A-56-159644 and hydroquinone diether or monoether substituted as described in JP-A-55-89835 are used. Chromans give favorable results.

A representative example of these anti-fading agents is disclosed in Japanese Patent Application Laid-Open No. 62-21527.
No. 2, pages 401-440.

The purpose of these compounds can be achieved by co-emulsifying them with the respective color couplers, usually in an amount of 5 to 100% by weight, and adding them to the photosensitive layer.

In order to prevent the cyan dye image from deteriorating due to heat and especially light, it is effective to introduce an ultraviolet absorber into the layers on both sides adjacent to the cyan coloring layer.

Further, an ultraviolet absorber can also be added to a hydrophilic colloid layer such as a protective layer. A representative example of the compound is JP-A-62
-215272, pages 391-400.

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

The photosensitive material of the present invention includes a dye that prevents irradiation and halation, an ultraviolet absorber, a plasticizer, an optical brightener, a matting agent, an air anti-capri agent, a coating aid, a hardening agent, and an antistatic agent. It is possible to add a slip property improver, etc. Representative examples of these additives can be found in Research Disclosure Journal N1117643VX-XI
February issue) p25-27, and 1B716 (I9
Published in November 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. Further, each of the above emulsion layers may be made up of two or more emulsion layers having different sensitivities, and a non-photosensitive layer may exist 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 following compounds can be added for the purpose of increasing the maximum image density, decreasing the minimum image density, improving the storage stability of the light-sensitive material, or speeding up development.

Hydroquinone IN (e.g. U.S. Pat. No. 3,227.5)
No. 52, No. 4,279.987); chromans (e.g., U.S. Pat. No. 4,268.621, JP-A No. 103031/1983, Research Disclosure Magazine, N118264 (published June 1979) 333 ~
Compounds described on page 334; quinones (e.g. research
Disclosure magazine, N121206 (I981
Compounds described on pages 433 to 434 (December 2012); Amines (for example, U.S. Pat. No. 4,150,993 and JP
- Compounds described in No. 174757); Oxidizing agents (for example, JP-A-60-260039, Research Disclosure, No. 16936 (published in May 1978) 10
Catechols (for example, the compounds described in JP-A-55-21013 and JP-A-55-65944); Compounds that release nucleating agents during development (for example, the compounds described in JP-A-60-107,029); compounds); thioureas (for example, compounds described in JP-A-60-95533);
spirobisindans (e.g. JP-A-55-6594)
Compound described in No. 4).

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

In the photographic light-sensitive material of the present invention, the photographic emulsion layer and other layers are published in Research Disclosure Magazine 11m17643X■
(published in December 1978), p. 28, European Patent No. 0,182,253, and Japanese Patent Application Laid-open No. 1983-976.
No. 55. Also, Research Disclosure Magazine Na17643 Section XV p.28-29
The coating method described in 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 anti-eaves 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 Yang 17123 (
It can also be applied to black-and-white light-sensitive materials using a mixture of three color couplers, such as those described in J. I., published in July 1978.

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

Black and white (B/W) photographic materials to which the present invention can be applied include JP-A-59-208540 and JP-A-60-2600.
B/W direct positive photographic material described in 39 (
Examples include X-ray photosensitive materials, duplex photosensitive materials, micro photosensitive materials, photographic photosensitive materials, and printing photosensitive materials.

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 to 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-toluenesulfonates.

Two or more of these compounds can be used in combination depending on the purpose.

The pH of these color developing solutions is 9 to 12, preferably 9.5 to 11.5.

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 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. Examples of bleaching agents include iron (■),
Compounds of polyvalent metals such as cobalt (I), chromium (■), and copper (n), peracids, quinones, nitro compounds, and the like are used.

Typical bleaching agents include ferricyanide; dichromate; organic complex salts of iron (III) or cobalt (III), such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, and 1,3-diaminoacetic acid. Aminopolycarboxylic acids such as propanetetraacetic acid, glycol ether diamine tetraacetic acid, or complex salts of citric acid, tartaric acid, malic acid, etc.;
Persulfates; bromates; permanganates; nitrobenzenes and the like can be used. Among these, aminopolycarboxylic acid iron (III) complexes and persulfates, including ethylenediaminetetraacetic acid iron (I[I) complex salts, are preferable from the viewpoint of rapid processing and environmental pollution prevention. [[) Complex salts are particularly useful in both bleach and bleach-fix solutions.

The pH of bleaching solutions or bleach-fixing solutions using these aminopolycarboxylic acid iron(III) complexes is usually 5.5 to 8, but in order to speed up the processing, the pH can be lowered. .

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

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

The amount of water used in the washing process depends on the characteristics of the photosensitive material (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 5ociety of M
tion Picture and Televisi
on Engineers Volume 64, p, 24B-
253 (May 1955 issue).

According to the multi-stage countercurrent method described in the above-mentioned literature, the amount of water used for washing can be significantly reduced, but due to the increase in the residence time of water in the tank, bacteria will breed, and the generated suspended matter will adhere to the photosensitive material. This causes problems. In the processing of the color photosensitive material of the present invention, as a solution to such problems,
The method for reducing calcium ions and magnesium ions described in Japanese Patent Application No. 131632/1988 can be used very effectively. In addition, isothiazolone compounds and thiabendazoles described in JP-A No. 57-8542,
Chlorine-based disinfectants such as chlorinated sodium isocyanurate,
Others, such as benzotriazole, are included in ``Chemistry of Antibacterial and Antifungal Agents'' by Hiroshi Horiguchi, ``Sterilization of Microorganisms, Disinfection, and Antifungal Technology'' edited by the Sanitation Technology Society, and ``Encyclopedia of Antibacterial and Antifungal Agents'' edited by the Japan Society of Antibacterial and Mildew Prevention. The fungicides mentioned can also be used.

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

The overflow liquid from water washing and/or replenishment of the stabilizing liquid can be reused in other processes such as the desilvering process.

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 a color developing agent, it is preferable to use various precursors of the color developing agent. For example, U.S. Patent No. 3,342.59
Indoaniline compound described in No. 7, No. 3,342,
No. 599, Schiff base-type compounds described in Research Disclosure No. 14850 and Research Disclosure No. 15159, Research Disclosure No. 13
Aldol compounds described in No. 924, U.S. Pat. No. 3.71
Metal salt complex described in No. 9.492, JP-A-5313562
The urethane compounds described in No. 8 can be mentioned.

The silver halide color light-sensitive material of the present invention may optionally contain various 1-phenyl-3
- Pyrazolidones may be incorporated. Typical compounds are JP-A-56-64339, JP-A-57-144547,
and No. 58-115438.

Various treatment liquids in the present invention are used at 10°C to 50°C. Normally, the standard temperature is 33°C to 38°C, but higher temperatures can be used to accelerate processing and shorten processing time, or lower temperatures can be used to improve image quality and stability of the processing solution. be able to. In addition, in order to save silver on photosensitive materials, West German Patent No. 2.226,770 or U.S. Patent No. 3
, 674.499 may be carried out using cobalt intensification or hydrogen peroxide intensification.

The smaller the amount of replenishment in each treatment step, the better. The amount of replenisher is preferably 0.1 to 50 times, more preferably 3 to 50 times, the amount of prebath brought in per unit area of the photosensitive material.
It is 30 times more.

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, birogal, 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. Further, the developer described in JP-A No. 58-55928 can also be used.

For detailed examples of developers, preservatives, buffers, and development methods for black and white photosensitive materials, and how to use them, see
Research Disclosure” magazine floor 17643 (I9
Published in December 1978) Section XIX-XX1 etc.

[Examples] The present invention will be explained in more detail with reference to Examples below, 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 next four layers from the second layer on the front side of the tube (0 micron) and the fifth layer through the sixth layer on the back side. The polyethylene coating side of the first layer contains titanium white as a white pigment and a trace amount of ultramarine as a bluish dye.

(Photosensitive layer composition) The ingredients and the coating amount in g/11 (unit) are shown below.

Regarding 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, as the emulsion for the 14th layer, a Lippmann emulsion without surface chemical sensitization was used.

11th (Antihalation layer) Black colloidal silver...0.10 Gelatin...1.30 Second layer (intermediate layer) Gelatin...0.70 Third layer (low sensitivity red sensitive layer) Red sensitization Silver bromide spectrally sensitized with dyes (ExS-1, 2, 3) (average grain size 0°3μ, size distribution [coefficient of variation 8%, octahedral)...0.06 Red enhancing dye (ExS-1, 2, 3) -1,2,3) spectrally sensitized with silver chloride (silver chloride 5 mol%, average grain size 0.45μ)
, size distribution 10%, octahedron)
...0.10 gelatin...
・1.00 cyan coupler (ExC-1) -0,
11 cyan coupler (ExC-2) = -0,10
Antifading agent (Cpd-2, 3, 4, 13 equivalent)...0
．． 12 Coupler dispersion medium (Cpd-5)...0.03 Coupler solvent (Solv-7, 2, 3 equivalent)...0.06 4th N (high sensitivity red sensitivity N) Red sensitizing dye (ExS- Silver bromide (average grain size 0.60μ, size distribution 15%) spectrally sensitized with
, octahedron) ...0.14 gelatin
...1.00 cyan coupler (ExC-1)
-0,15 cyan coupler (ExC-2) -0,
15 Anti-fading agent (Cpd-2, 3, 4, 13 equivalent)...
・0.15 Coupler dispersion medium (Cpd-5) ...0.03 Coupler solvent (Solv-7, 2, 3 equivalent) ...0.10 5th layer (intermediate layer) Gelatin ...1, 00 Color mixing prevention agent (Cpd-7) ・0.08 Color mixing prevention agent solvent (Solv-4, 5 etc.ff1) ・0. 16 polymer latex (Cpd-8)...0.10 61st (low sensitivity green sensitive layer) Silver bromide (spectral sensitized with green sensitizing dye (ExS-3)
Average particle size 0.25 μ, particle size distribution 8%, octahedral) ...0.04 green sensitizing dye (ExS-3,
4) spectrally sensitized silver bromide (average grain size 0.45
μ, particle size distribution 11%, octahedral)...0.06 Gelatin...0.80 Magenta coupler (ExM-1,2 equivalent)...0.11 Antifading agent (Cpd-9) 0.10 Stain inhibitor (Cpd-10,22 equivalent)...0.014 Stain inhibitor (Cpd-23)...0.0
01 Stain inhibitor (Cpd-12) -0,01
Power puller dispersion medium (Cpd-5) -0,05 coupler solvent (Solv-4,6 equivalent)...0.15 7th layer (high sensitivity green sensitive layer) Green sensitizing dye (ExS-3,4 ) spectrally sensitized silver bromide (average grain size 0.8μ, grain size distribution 16%,
Octahedron) ...0.10 gelatin
...0.80 magenta coupler (ExM-1,2
)...0.11 Anti-fading agent (Cpd-9)...0.10 Anti-staining agent (Cpd-10, 22 equivalent)...0.01
3 Anti-staining agent (Cp d-23)...0.0
01 Stain inhibitor (Cpd-12)...0.0
Single force puller dispersion medium (Cpd-5)...0.05 Coupler solvent (Solv-4, 5 equivalent)...0.15 8th layer (intermediate layer) 9th layer (yellow) same as the 5th layer Filter N) Yellow Colloy Fffl ・0.20 Gelatin ・・1.00 Color mixing prevention agent (Cpd-7) ・・0.06 Color mixing prevention agent solvent (Solv-C5 equivalent) ・・o, is Polymer latex (Cpd-8)...0.10 1st
0 layer (intermediate layer) 11th layer (low sensitivity blue sensitive layer) same as 5N M bromide (average particle size 0.45μ, particle size Distribution 8%,
Octahedron) ...0.07 blue sensitizing dye (F, xS-5
, 6) spectrally sensitized silver bromide (average grain size 0.6
0μ, particle size distribution 14%, octahedron)...0. lO
Gelatin...0.50 Yellow coupler (ExY-1)...0.22 Stain inhibitor (Cpd-11)...0.001 Anti-fading agent (Cp
d-6) ...0.10 coupler dispersion medium (Cp
d-5)...0.05 coupler solvent (Solv-
2) -0,05 12th layer (high sensitivity blue sensitive layer) Silver bromide spectrally sensitized with blue sensitizing dye (ExS-5,6) (average grain size 1.2μ, grain size distribution 21%,
Octahedron) ...0.25 gelatin
...1.00 yellow coupler (ExY-1) =
J, 41 stain inhibitor (Cpd-11)...0.0
02 Anti-fading agent (Cpd-6)...0.10
Coupler dispersion medium (Cpd-5) ・・・0.05 Coupler solvent (Solv-2) =・0.10 13th layer (
Ultraviolet absorbing layer) Gelatin...1.50 Ultraviolet absorber (Cpd-1, 3, 13 equivalent)...1.00 Color mixing prevention agent (Cpd-6, 14 equivalent)...0.06 Dispersion Medium (Cpd-5)...0.05 Ultraviolet absorber solvent (Solv-1, 2 equivalents)...0.15 Anti-irradiation dye (cpa-ts, 16 equivalents)...0. 02 Anti-irradiation dye (Cpd-17, 18 equivalent) ...0.02 14th layer (protective layer) Fine grain silver chlorobromide (chloride 897 mol%, average size 0.2
μ) ...0.05 Acrylic modified copolymer of polyvinyl alcohol (degree of modification 17%)
... 0.02 polymethyl methacrylate particles (average particle size 2.4 microns), silicon oxide (average particle size 5 microns) equivalent amount ... 0.05 gelatin
...1.50 gelatin hardening agent (
H-1) ...0.17 15th layer (back layer) Gelatin ...2.50 16th layer
Layer (back protective layer) Polymethyl methacrylate particles (average particle size 2.4
micron), silicon oxide (average particle size 5 micron) equivalent amount...0.05 gelatin
...2.00 Gelatin hardening agent (H-1)
...How to make 0.11 emulsion EMI An aqueous solution of potassium bromide and silver nitrate was simultaneously added to an aqueous gelatin solution at 70°C over 20 minutes with vigorous stirring.
Octahedral silver bromide grains with an average grain size of 0.40 microns were obtained. To this emulsion were sequentially added 0.3 g of 3,4-dimethyl-1,3-thiazoline-2,000 ion per mole of silver, 6 days of sodium thiosulfate, and 7 fflr of chloroauric acid (tetrahydrate) at 75°C. Chemical sensitization treatment was performed by heating for 80 minutes. The particles obtained in this way are used as cores and further grown in the same precipitation environment as the first time, until the average particle size is 0.
A 7 micron octahedral monodisperse core/shell silver bromide emulsion was obtained. The coefficient of variation in particle size was approximately 10%. To this emulsion, 1.5 mg of sodium thiosulfate and 1.5 mg of chloroauric acid (tetrahydrate) were added per mole of SR, and the mixture was heated at 60°C.
Chemical sensitization was carried out by heating for a minute to obtain an internal latent image type silver halide emulsion.

In each photosensitive layer, ExZK-1 was used as a nucleating agent at 3.6×10 −' mol/Ag mol based on the coating amount of silver halide, and the nucleating accelerator listed in Table 1 was used. Furthermore, each layer contains alkano-/l/X C (Dup
ont) and sodium hyalkylhenzenesulfonate, succinate ester and Mager as coating aids.
ac F-120 (manufactured by Dainippon Ink Co., Ltd.) was used. Silver halide and colloidal silver containing layers contain (
Cpd-19, 20, 21) was used. This sample was designated as the sample number.

The compounds used in the examples are shown below.

xS-1 tHs xS-2 t Hs xS-3 tH5 xS-4 0ffH xS-6 (CL)4 (CHJ4 SOi 5O3H・N (C2Hs)3Cpd
-I Cpd-2 and 4
11wLLノ
411q(L)Cpd-5 CONHC,Hw(t) JI-1 Cpd-9 Cpd-12 pa-13 Cpd-15 Cpd-16 (CHt)3SCh K (CHz) So,
Kpd-17 Cpd-18 Cpd-19 Cpd-20 Cpd-21 N-N Cpd-22 Cpd-23 OH OHC,H.

xC-2 xM-1 xM-2 51147(L) xY-1 rρ 5olv-1 di(2-ethylhexyl) phthalate 5o
lv-2) Linonyl phosphate 5olv-3 di(3-methylhexyl) tuclate 5o
lv-4 tricresyl phosphate 5 olv-5 dibutyl phthalate 5 olv-6) lioctyl phosphate 5 OIV-7 di(2-ethylhexyl) sebacate H-11,2-bis(vinylsulfonylmacetamide) ethane ExZK-1
7-[3-(5-mercaptotetrazol-1-yl)
benzamide]-10-propargyl-1,2,3,4
- Tetrahydroacridinium Velchlorate Wedge exposure (32
00K, 0.1 seconds, 100 CMS), and then treatment step A was performed. The magenta density of the obtained color image was measured.

Treatment process A 几工 V日、IJ
Product-1111 Color development 90 seconds 38℃ bleach fixing
40〃 33〃Washing fi+ 4
0' 33 〃Washing (2) 40
〃 33〃 Washing (3115〃33 ll Drying 30〃 801/ - The method of replenishing the washing water is to replenish the washing bath (3) and pour the overflow liquid from the washing bath (3) into the washing bath (2) in a thick layer of water. Washing bath (2)
A so-called countercurrent replenishment system was adopted in which the overflow liquid 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 by the photosensitive material is 3°5.
m 1 /rd, 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 of each treatment liquid was as follows.

Ethylenediaminetetrakis 0.5g methylenephosphonate diethylene glycol l 9ml Hensyl alcohol l 2. Oml Potassium Bromide 0.65g Sodium Sulfite
2.4g N,N-diethylhydroxyl 4.0g amine triethylenediamine (I, 44,0g-diazabicyclo[2,2,21 octane) N-ethyl-N-(β-methane 5.6g sulfonamidoethyl)-3 - Methylaniline sulfate Potassium carbonate 27.0g Fluorescent brightener (diaminostilhene type) 1.0g pH (25°C) 10.50 Ethylenediaminetetraacetic acid.2 4.0g Sodium.
Dihydrate ethylenediaminetetraacetic acid/Fe 46. Og(II
+) ・Ammonium dihydrate ammonium thiosulfate 155ml (700
g/1) p-Toluenesulfinic acid 20.0g Sodium thorium bisulfite 12.0g Ammonium bromide 50.0g Ammonium nitrate
Lose 30.0g 1
000m/pH (25℃) 6.2
0 water permeable tap water was passed through a hotbed column filled with an H-type strongly acidic cation exchange resin (Amberlite IR-120B, manufactured by Rohm and Haas) and an OH-type anion exchange resin (Amberlite IR-400, manufactured by Rohm and Haas). The concentration of calcium and magnesium ions was reduced to 3/l or less, and then 20 qr/1 of sodium isocyanurate dichloride and 1.5 g/It of sodium sulfate were added. The pH of this solution is 6.5
It was in the range of ~7°5.

Table 1 Samples N111 to 7 using the nucleation accelerator of the present invention had a higher D saw and a lower 0 m1n than Comparative Example No. 8.

Similar results were obtained for cyan and yellow image densities.

Example 2 Example 1 was repeated to obtain the same results, except that the following nucleating agent was used in each emulsion layer at 2.6×10 −S mol/Ag mol.

Processing step B Time #I d Two-color development"' 135 seconds 36℃ bleach fixing 40 seconds 36℃ stability 0 40
Seconds Stable at 36℃ ■ 40 seconds
Dry at 36°C, 40 small, 7Q°C bottle)
After immersing in color developer for 15 seconds, 15 seconds with 1lux white light.
Color development processing was performed while performing light fogging for a second.

[Color developing solution 8 hydroxyethylimino vinegar 0.5 g β-cyclodextrin 1.5 g monoethylene glycol 9.0 g benzyl alcohol
9.0g monoethanolamine
2.5g sodium bromide
2.3g Sodium chloride 5.5g
N,N-diethylhydroxyl 5.9g amine 3-methyl-4-amino-N-2,7g ethyl-N=(
β-methanesulfonamidoethyl)-aniline sulfate 3-methyl-4-amino-N-4,5g ethyl-N-(
β-Hydroxydiethyl)-aniline sulfate Potassium carbonate 30.0 g Fluorescent brightener (Stilhen type) 1.0 g Pure water gold added 1000 rn 1 pH 10.30 pH was adjusted with potassium hydroxide or hydrochloric acid.

[e: White fixer] Mother liquor Ammonium thiosulfate 110g Sodium bisulfite 12g Diethylenetriaminepentaacetic acid 80 [Iron ([[l) Ammonium diethylenetriaminepentaacetic acid 5g 2-Mercapto-5-amino-0,3g 1.3.4-Thiadiazole Pure water Plus 1000mj! pH6
, 80 pH was adjusted with aqueous ammonia or hydrochloric acid.

[Stabilizer] 1-hydroxyethylidene-1,2,7g 1-diphosphonic acid O-phenylphenol 0.2g Potassium chloride 2.5g Bismuth chloride
1.0g zinc chloride
0.25 g sodium sulfite
0.3g ammonium sulfate
4.5g1゛whitening agent (stilbene type)
Add 0.5g pure water to 1000ml
pH 7.2 pH was adjusted with potassium hydroxide or hydrochloric acid.

Example 3 A color photosensitive material was produced in the same manner as in Example 1 except that the nucleating agent was removed. After performing the same imagewise exposure as in Example-1, processing step B was performed.

The same results as in Example-1 were obtained.

Example-4 Example-I was repeated except that the treatment step was changed to C, and the same results were obtained.

Processing step C Time - Finishing - Color development 70 seconds 38°C bleach fixing
30 seconds 38℃ water washing ■ 30 seconds 38℃ ■ 30 seconds
3 ()℃ At this time, the replenishment ratio of the washing liquid is 8
．． It was 6 times more.

[Color development] Mother L Diethylenetriaminepentaacetic acid 0.5g 1-hydroxyethylidene-1,0,5g 1-diphosphonic acid diethylene glycol 8.0g Hensyl alcohol 9.0g Sodium bromide 0.78 Sodium chloride
0.5g sodium sulfite
2.0g hydroxylamine sulfate
2.8 g 3-methyl-4-amino-N-2,0 g ethyl-N-(β-methanesulfonamidoethyl)-aniline sulfate 3-methyl-4-amino-N-4,0 g ethyl-N-(
β-Hydroxydiethyl)-aniline sulfate B salt Potassium carbonate 30.0 g Fluorescent brightener (stilbene type) 1.0 g' Water was added to 1000 ml pH 10.50 The pH was adjusted with potassium hydroxide or hydrochloric acid.

[Bleach-fix solution] Mother: Ammonium thiosulfate 77g Sodium bisulfite 14.0g Iron ethylenedilenetetraacetate 40.0g (III) ammonium.
Dihydrate ethylenediaminetetraacetic acid 2s 4.0g Thorium dihydrate 2-mercapto-1,3,4-0.5g Add triazole pure water 1000ml pH 7,
0 p)l was adjusted with aqueous ammonia or hydrochloric acid.

[Washing water] Pure water was used (mother liquor = replenisher) Example 5 Panchromatic sensitizing dye 3.3'-diethyl-9 was added to the above emulsion X.
- Methylthiacarbocyanine was added in an amount of 5 mg per mole of silver halide, and 1-formyl-2 was added as a nucleating agent.
-(4-(3-(5-mercaptotetrazol-1-yl)benzamido]phenyl)hydrazine, 3.5 x 10-' mol per mol of silver halide and halogenated substances listed in Table 2 as nucleation accelerators. 1 per mole of silver
．． 8XIO-' mole added was coated on a polyethylene terephthalate support so that the silver amount was 2.8 g/nr, and at the same time, a protective layer consisting of gelatin and a hardening agent was simultaneously coated thereon. Samples 1 to 5 of a direct positive photographic light-sensitive material sensitive to red light were prepared.

The above photosensitive material was heated using an IKW tungsten lamp (color temperature 285).
4 (b)) Using a sensitometer, measure 0.0 through a step wedge.
Exposure was made for 1 second. Next, an automatic developing machine (Kodak Pr
Kodak (OSTER T Processor)
Proster Plus processing solution (developer pH 10,
7) for 18 seconds at 38°C, and
1, followed by washing with water, fixing, washing with water, and drying. The maximum density (Dmax) of both direct and positive images of each sample obtained in this way
), the Q-low concentration (Dmin) was measured.

Table 2 ml-4 using the nucleation accelerator of the invention had a higher Dmax and a lower Dn+in than the Comparative Example grade 5.

[Effects of the Invention] According to the image forming method of the present invention, a direct positive image having sufficiently high maximum image density and low minimum image density can be obtained, and it is found that the method is practically useful.

Patent Applicant Fuji Photo Film Co., Ltd. Procedural Amendment 1. Indication of the case: 1932, Japanese Patent Application No. 31002, Title of the invention: Direct positive image forming method 3, Person making the amendment Relationship with the case Patent applicant: Address: 210 Nakanuma, Minamiashigara City, Kanagawa Prefecture Name: (520) Fuji Photographic Film Co., Ltd. Contact information 2 Nishi-Azabu, Minato-ku, Tokyo 106
Chome 26-30 No. 4, M Correct Subject: Column 5 of "Detailed Description of the Invention" of the Description, Contents of Amendment All entries in the "Detailed Description of the Invention" section of the description are amended as follows.

1) Line of page 1j of the specification "-yakushiki" "General formula (V)" and correct it.

2) Circular 33rd melon/ri line "Pentylphenoxy" "Pentylphenoxy" and correct it.

3) P. 71 of the same book, “Structural formula of cpd-1/J” and correct it.

"Methylaniline sulfate" Correct it to "methyl-≠-aminoaniline sulfate".

Claims (1)

[Scope of Claims] A photographic light-sensitive material having on a support at least one photographic emulsion layer containing internal latent image type silver halide grains which has not been fogged in advance is fogged or subjected to fogging treatment after imagewise exposure. In the method of directly forming a positive image by performing development processing while applying, the development processing is performed using the following general formulas (I) and (II
), (III) or (IV) in the presence of at least one kind of compound. General formula (I) General formula (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲Mathematical formulas, chemical formulas,
There are tables, etc. ▼ General formula (IV) General formula (III) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas, chemical formulas,
Tables are available.▼ In the formula, M represents a hydrogen atom, an alkali metal atom, an ammonium group, or a group that cleaves under alkaline conditions, and R represents a hydrogen atom or a group that can substitute this. n is 1 to 4
represents. R_1, R_2, R_3, R_4, R_5, R_6, R
_7, R_8, and R_9 are hydrogen atoms, mercapto groups,
Each represents a substituted or unsubstituted alkyl group, aryl group, alkenyl group, aralkyl group, alkylthio group, carbonamide group, sulfonamide group, ureido group, thioureido group, oxycarbonylamino group, or amino group. Further, the heterocycle in general formula (II), (III) or (IV) may be fused with a carbon aromatic ring.