JPS63108336A - Direct positive color photosensitive material - Google Patents

Abstract

PURPOSE:To make hard to change the max. image density and the min. image density of cyan coloring from the optimum value, even in case of changing a temp. and pH of a color developing solution by incorporating a specific cyan coupler to the titled material. CONSTITUTION:In the photosensitive material contg. an inner latent image type silver halide particle which is not previously fogged, the emulsion layer comprises one or more kinds of a non-diffusive cyan coupler shown by formula I wherein R1 is an aliphatic group or an aromatic group, etc., R2 is 2-20C an aliphatic group, R3 is H or halogen atom, etc., Y1 is H or a group capable of releasing by coupling reaction with an oxidant of developing agent. A hydroquinone compd. (for example, the compd. shown by formula II) contg. sulfonic group is also incorporated to the titled material, thereby suppressing effectively the increasement of the min. image density of the cyan coloring. In the formula, R4 is alkyl group or H etc., R5 is alkylene or acylamino group, etc.

Description

Detailed Description of the Invention (Industrial Field of Application) The present invention is directed to a method in which a positive silver halide photographic light-sensitive material is subjected to color development treatment after imagewise exposure, after being subjected to fogging treatment, or while being subjected to fogging treatment. The present invention relates to a direct positive color photosensitive material from which a direct positive color image can be obtained.

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

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

One type uses a silver halide emulsion that has been fogged in advance and creates a positive image directly after development by destroying the blurring nuclei (latent image) in the exposed area using solarization or the Burschel effect. It's something you get.

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

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

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

Various techniques are known to date in this technical field. For example, U.S. Patent No. 2. 592゜250, same No. 2.466.957, same No. 2゜497.875,
2.588,982, 3.317.322 (2,497.875), 3.761,266, 3,761.276, 3.796. 577
and British Patent No. 1.151.363, 1. 1
The main ones are those described in No. 50°553 (No. 1,011,062) and various specifications.

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

For details on the direct positive image formation mechanism, see
The Theory of the Photographic Process J by T. H. James.
of The Photographic Proc
ess) 4th edition, Chapter 7, pages 182-193 and US Patent 3
, 761°276, etc.

In other words, capri nuclei are selectively generated only on the surface of silver halide grains in unexposed areas by a surface desensitization effect based on a so-called internal latent image generated inside 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 capri nuclei, a method of applying a second exposure to the entire surface of the photosensitive layer, which is generally called "light fogging method" (for example, British Patent No. 1,151.3
63) and a nucleating agent (nu
creating agent) is known. Regarding this latter method, for example, ``Research Disclosure'' (Research D
isclosure) Magazine Volume 151 No. 15162
(published November 1976), pages 72-87.

To directly form a positive color image, the internal latent image type silver halide photosensitive material is subjected to a fogging process or a surface color development process while being subjected to a fogging process, followed by bleaching and fixing (
or bleach-fixing). After the bleaching and fixing treatments, washing and/or stabilizing treatments are usually performed.

(Problem to be solved by the invention) In the presence of a nucleating agent, the maximum image density is not constant and color reproduction is unstable because it is easily affected by fluctuations in developer temperature and pH that occur during running processing. It has the problem of stability.

On the other hand, in the case of the photofogging method, the chemical fogging method has a high p
Although it is relatively advantageous in practice as it does not require H conditions, it is susceptible to fluctuations in the temperature and pH of the developer.
It is difficult to obtain constant performance.

In particular, the minimum density area in a light-sensitive material using a direct positive emulsion, which corresponds to the "capri area" of a normal negative emulsion, is affected by the temperature and pH of the developer, and changes in the amount of light and wavelength of light fog. It is difficult to obtain a constant low minimum concentration.

In particular, when processing photosensitive materials using an internal latent image type direct positive emulsion in an automatic processor, changes in the liquid composition due to the amount of processed photosensitive material can be calculated to some extent during continuous processing, so the liquid composition of the replenisher is determined based on this. Although it is possible to adjust
For example, air oxidation of the processing solution, which occurs when the solution comes into contact with air while the machine is running, i.e., when the processing solution is left at a high temperature, improves the oxidation resistance of the solution, to some extent. The only option is to design processing solutions and photosensitive materials so that photographic performance does not change even if oxidation occurs. For example, leaving an automatic processing machine like the one mentioned above in overnight operation is a good idea, especially in a laboratory office where the usage of the automatic processing machine is small, in order to save warm-up time when restarting after a shutdown. , is often done.

However, in light-sensitive materials using internal latent image type direct positive emulsions, even if processing solutions and light-sensitive materials are designed based on the knowledge of negative emulsions, photographic performance changes (especially an increase in the minimum density for cyan images). I couldn't hold back.

Therefore, it is an object of the present invention to process an internal latent image type silver halide photosensitive material which has not been previously fogged with a low pH color developing solution to produce a direct positive color image having a high maximum density and a low minimum image density, especially of the cyan color. It is an object of the present invention to provide a photosensitive material that can form quickly and stably.

It also provides a photosensitive material that forms direct positive color images in which the maximum and minimum image densities, especially for cyan color development, are less likely to fluctuate from their optimum values even if the temperature and pH of the color developer vary. It's about doing.

Furthermore, even if the color development time varies with respect to the standard time, the maximum and minimum image densities for cyan color development in particular do not easily vary from their optimum values, and the photosensitive material forms direct positive color images in which the brown color reproducibility does not change easily. Our goal is to provide the following.

Another object of the present invention is to provide a photosensitive material that forms direct positive images in which the maximum image density is less likely to decrease and the minimum image density is less likely to increase when the photosensitive material is stored for a long period of time.

A further object of the present invention is to provide a photosensitive material that directly forms positive color images with less generation of re-inverted negative images during high-intensity exposure.

(Means for Solving the Problems) As a result of conducting various researches to achieve the above object, the present inventors have surprisingly found that the above problems can be achieved by using a specific cyan coupler described in detail below. We have discovered that this can be achieved effectively, and based on this knowledge we have arrived at the present invention.

That is, the present invention relates to a direct positive color light-sensitive material having at least one photographic emulsion layer containing internal latent image type silver halide grains and a color image-forming coupler on a support, which are not pre-fogged. Formula [C-I
] This is a direct positive color photographic material characterized by containing at least one non-diffusible cyan coupler selected from the group of compounds shown below.

fermentation Y.

(In the formula, R represents an aliphatic group, an aromatic group, a heterocyclic group, an aromatic amino group, or a heterocyclic amino group, and R2 has 2 carbon atoms.
~20 aliphatic groups, R5 represents a hydrogen atom, a halogen atom, an aliphatic group, an aliphatic oxy group, or an acylamino group; Represents a leaving group (hereinafter abbreviated as leaving group).

Alternatively, R,, R,, R, or Y may form a multimer of two or more layers. ) The above object of the present invention, particularly suppressing the increase in the minimum image density of cyan coloring due to deterioration of the developer due to air oxidation, etc., can be achieved by further containing a hydroquinone compound having a sulfonic acid group in the photosensitive material, which will be described in detail below. It has been found that this can be achieved even more effectively.

The cyan coupler of the present invention is a coupler represented by the following general formula [C-I] as known from Japanese Patent Application Laid-open No. 60-232550 and US Pat. No. 3,772.002.

Y.

(In the formula, R1 represents an aliphatic group, an aromatic group, a heterocyclic group, an aromatic amino group, or a heterocyclic amino group, and R1 has 2 carbon atoms.
~20 aliphatic groups, R3 represents a hydrogen atom, a halogen atom, an aliphatic group, an aliphatic oxy group, or an acylamino group; Represents a leaving group (hereinafter abbreviated as leaving group).

Furthermore, R1, R2, R1, or Y may form a multimer of two or more members.

The aliphatic group mentioned here represents a linear, branched or cyclic alkyl, alkenyl or alkynyl group, and these groups may be further substituted.

RI to R1 and Y in general formula [C-1] will be explained in detail below.

In general formula [C1], Y is a coupling-off group (
(hereinafter referred to as a leaving group), the leaving group is oxygen,
Aliphatic groups, aromatic groups, heterocyclic groups, aliphatic/aromatic or heterocyclic sulfonyl groups, aliphatic/aromatic or heterocyclic carbonyl groups bonded to the coupling active carbon via nitrogen, sulfur or carbon atoms group; or a halogen atom, an aromatic azo group, etc., and the aliphatic, aromatic, or heterocyclic group contained in these leaving groups is R.

It may be substituted with a substituent as described in (described later), and when there are two or more of these substituents, they may be the same or different, and these substituents may further have a substituent as described in R3. may have.

Specific examples of coupling-off groups include halogen atoms (e.g. fluorine atom, chlorine atom, bromine atom, etc.), alkoxy groups (e.g. ethoxy group, dodecyloxy group, methoxyethylcarbamoylmethoxy group, carboxypropyloxy group, methylsulfonyl group). ethoxy group, etc.), oryloxy group (e.g., 4-chlorophenoxy group, 4-methoxyphenoxy group, 4-carboxyphenoxy group, etc.), acyloxy group (e.g., acetoxy group, tetrazocallyoxy group, benzoyloxy group, etc.) ), aliphatic or aromatic sulfonyloxy groups (e.g. methanesulfonyloxy group, toluenesulfonyloxy group, etc.), acylamino groups (e.g. dichloroacetylamino group, heptafluorobutyrylamino group, etc.), aliphatic or aromatic sulfonamide groups (e.g., methanesulfonamino group, P-toluenesulfonylamino group, etc.), alkoxycarbonyloxy groups (e.g., ethoxycarbonyloxy group, benzyloxycarbonyloxy group, etc.), aryloxycarbonyloxy groups (e.g., phenoxycarbonyloxy group, etc.), Aliphatic, aromatic or heterocyclic thio groups (e.g. ethylthio, phenylthio, tetrazolylthio, etc.), carbamoylamino groups (e.g. N-
methylcarbamoylamino group, N-phenylcarbamoylamino group), 5- or 6-membered nitrogen-containing heterocyclic group (e.g. imidazolyl group, pyrazolyl group, triazolyl group, tetrazolyl group, 1,2-dihydro-2-oxo- 1-pyridyl group, etc.), imide groups (eg, succinimide group, hydantoinyl group, etc.), and aromatic azo groups (eg, phenylazo group, etc.). Furthermore, there are bis-type couplers obtained by condensing a four-equivalent coupler with an aldehyde or a ketone as a leaving group bonded via a carbon atom. The leaving group of the present invention may contain photographically useful groups such as development inhibitors and development accelerators.

In the general formula [C-r), R3 preferably has 1 carbon number
~36 aliphatic groups, preferably aromatic groups having 6 to 36 carbon atoms (e.g., phenyl group, naphthyl group, etc.), heterocyclic groups (e.g., 3-pyridyl group, 2-furyl group, etc.), or
aromatic or heterocyclic amino groups (e.g. anilino group,
naphthylamino group, 2-benzothiazolyl amino group, 2
-pyridylamino group, etc.), and these groups further represent an alkyl group, an aryl group, a heterocyclic group, an alkoxy group (e.g., methoxy group, 2-methoxyethoxy group, etc.), an aryloxy group (e.g., 2゜4 -Geetert
-amylphenoxy group, 2-chlorophenoxy group, 4-
cyanophenoxy group, etc.), alkenyloxy group (e.g., 2-propenyloxy group, etc.), acyl group (e.g., acetyl group, benzoyl group, etc.), ester group (e.g., butoxycarbonyl group, phenoxycarbonyl group,
acetoxy group, benzoyloxy group, butoxysulfonyl group, toluenesulfonyloxy group), amide group (
For example, acetylamino group, ethylcarbamoyl group, dimethylcarbamoyl group, methanesulfonamide group, butylsulfamoyl group, etc.), sulfamide group (e.g.
dipropylsulfamoylamino group, etc.), imide group (
For example, succinimide group, hydantoinyl group, etc.)
Ureido groups (e.g., phenylureido, dimethylureido, etc.), aliphatic or aromatic sulfonyl groups (e.g., methanesulfonyl, phenylsulfonyl, etc.), aliphatic or aromatic groups (e.g., ethylthio, phenylthio, etc.) ), hydroxy group, cyano group,
It may be substituted with a group selected from a carboxy group, a nitro group, a sulfo group, a halogen atom, etc.

Representative examples of aliphatic groups include methyl group, ethyl group, butyl group, dodecyl group, octadecyl group, icosenyl group,
1so-propyl group, tert-butyl group, tert-
Examples include octyl group, tert-dodecyl group, cyclohexyl group, cyclopentyl group, allyl group, vinyl group, 2-hexadecenyl group, and propargyl group. These may be substituted with the substituents mentioned above.

- In formula [C-1], R1 is a hydrogen atom, a halogen atom (e.g., a fluorine atom, a chlorine atom, a bromine atom, etc.)
, preferably an aliphatic group having 1 to 20 carbon atoms, preferably an aliphatic oxy group having 1 to 20 carbon atoms, or an acylamino group having 1 to 20 carbon atoms (e.g., acetamido group, penzamide group, tetradecaneamide group, etc.) , these aliphatic groups, aliphatic oxy groups, and acylamino groups may be substituted with the substituents described for R3.

In general formula [C-I], Rt, R2, R3 or Yl
Any one group may independently or jointly form a dimer or more multimeric coupler. In the case of a dimer, these groups are simple bonds or divalent linking groups (e.g., divalent groups such as alkylene groups, arylene groups, ether groups, ester groups, amide groups, and divalent groups that combine these groups). (e.g., divalent groups) and when forming oligomers or polymers, those groups are preferably in the polymer backbone or are attached to the polymer backbone through divalent groups as mentioned for dimers. .

When forming a polymer, even if it is a homopolymer of coupler derivatives, other non-chromogenic ethylene-like monomers (e.g.
(acrylic acid, methacrylic acid, methyl acrylate n-butylacrylamide, β-hydroxymethacrylate, vinyl acetate, acrylonitrile, styrene, crotonic acid, maleic anhydride, N-vinylpyrrolidone, etc.),
A copolymer may be formed with one or more of them.

In general formula [C-1), R8 is preferably a substituted or unsubstituted alkyl group or aryl group, and as a substituent for the alkyl group, an optionally substituted phenoxy group or a halogen atom is particularly preferable (phenoxy group As the substituent, an alkyl group, an alkoxy group, a halogen atom, a sulfonamide group, and a sulfamide group are more preferable)
The aryl group is particularly preferably a phenyl group substituted with at least one halogen atom, alkyl group, sulfonamido group or acylamino group.

In the general formula [C-1], R2 is preferably an optionally substituted alkyl group having ia 2 to 20 carbon atoms.

The substituent for R2 is preferably an alkyl or aryloxy group, an acylamino group, an alkyl or arylthio group, an imido group, a ureido group, or an alkyl or arylsulfonyl group.

In the general formula [C-1], R3 is preferably a hydrogen atom, a halogen atom (particularly preferably a fluorine atom or a chlorine atom), or an acylamino group, and particularly preferably a halogen atom.

In general formula [C-1], R1 is more preferably an alkyl group having 2 to 4 carbon atoms.

In general formula [C-1], Yl is preferably a halogen atom, more preferably a chlorine atom.

The couplers represented by the general formula [C-I] can be used alone or in a mixture of a plurality of couplers. Furthermore, it can also be used in combination with a cyan coupler other than the cyan coupler represented by the general formula [C-I] of the present invention.

The cyan coupler of the present invention is preferably used in an amount of 0.02 to 0.5 mol per mol of silver.

Specific examples of the non-diffusible cyan coupler represented by the general formula [C-I] of the present invention are listed below, but the present invention is not limited thereto.

[C-1-1) [C-1-2) [C-1-3) [C-1-4] [C-1-5) [C-1-7] [C-1-8) [ C-1-9) [C-1-10) [C-1-11] [C-1-12] [C-1-13) (All ratios of X%y represent weight ratios) Hydroquinone compounds having a sulfonic acid group that can be effectively used in the invention include, for example, U.S. Pat.
The following general formula (HQ-1) as described in No. 227.552
Compounds represented by and (HQ-If) and their ammonium and alkali metal salts are useful.

General formula (HQ-I) General formula (HQ=II) (wherein, R4 represents an alkyl group, an acylamino group, a hydrogen atom, or a sulfonic acid group, R3 represents an alkylene group or an acylamino group, and R4 represents an alkyl The acylamino group in R, , R% and R, may be substituted, for example, the following formula (wherein R? and R1 are aryl groups (e.g. phenyl))
, represents an alkyl group, a hydrogen atom or a sulfonic acid group. )
It can be expressed as

The alkyl groups in R4 and R1 may be substituted and also include aralkyl groups.

The chain length or size of the alkyl, alkylene, and acylamino groups can vary widely depending on the degree of diffusivity desired, and one skilled in the art can easily obtain the amount of "ballast" required depending on the purpose. Can be done. Alkyl groups and alkylene groups having 1 to 22 carbon atoms are suitable, but those having 8 to 22 carbon atoms
An alkyl group having 1 to B carbon atoms and an alkylene group having 1 to B carbon atoms are preferred.

Specific examples of hydroquinone compounds having a sulfonic acid group that can be used in the present invention are listed below.

(HQ-1)2-[β-(3-(3-(4-amyl-X
-sulfophenoxy)benzamide]benzamido)ethyl]hydroquinone (sodium salt) (HQ-2) 2.5-bis[N-(3-(2,4-(cyamylphenoxy)-5- (2-sulfobenzamide) benzamido]phenyl)carbamylmethyl]hydroquinone (sodium salt) (HQ-3) 5-octadecyl-2-(2-sulfo-t
er t,-butyl)hydroquinone (sodium salt) (HQ-4)5-sec,-octadecy)Ll-2-.

(2-sulfo-tert, -butyl) Hydroquinone (sodium salt) (HQ-5) 2.5-bis(β-(3-<p-t e
r t, -amylphenoxy)-X-sulfo]benzamidoethyl) hydroquinone (sodium salt) (HQ-6) 2-(2'-(2',4'-di-tert)
, -amylphenoxy)-5'-(3',5'-disulfobenzamide)benzamiderahydroquinone (sodium salt) (HQ-7) s ec, -lanticyl-hytroquinone-X-potassium sulfonate (HQ- 8) n-hexadecyl-hydroquinone-X-
Potassium sulfonate (HQ-9) n-octadecyl-hydroquinone-X-
Potassium sulfonate (HQ-10) 2-Methyl-5-sec, -octadecyl-hydroquinone-X-potassium sulfonate (HQ-11) 3-benzyl-X-su) Lt-phosphate (HQ-12) Potassium 3-ethylbenzyl-X-sulfonate (HQ-13) 3-(p-benzyl)-benzyl-X
- Potassium sulfonate The sulfonated hydroquinone mentioned above can be inserted directly into the silver halide emulsion layer, interlayer or protective layer. Appropriate concentrations can be determined by those skilled in the art, but are usually about 1 to 1000, preferably 10 to 1000, per rrf of window light material.
It is 200■. However, the amount may be greater or less than the above amount.

The unfogged internal latent image type silver halide emulsion used in the present invention is an emulsion containing silver halide in which the surfaces of silver halide grains are not fogged in advance and latent images are mainly formed inside the grains. However, more specifically, 0.5 to 3 g of silver halide emulsion is deposited on a transparent support.
/rd, 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 is the maximum density obtained when a silver halide emulsion coated in the same amount and exposed in the same manner as above is developed in the following developer B (surface type developer) at 20 ° C. for 6 minutes. Those with a concentration at least 5 times greater are preferred, and more preferably those with a concentration at least 10 times greater.

Internal developer A Metol 2g Sodium sulfite (anhydrous) 90g Hydroquinone 8g Soda carbonate (-hydrate)
52.5gKBr
5 gKI
O, add 5g water 1
a Surface developer B Metol 2.5 g 1-ascorbic acid 10 g NaBOz -4Hz
0 35 gKBr
Add lg water
Specific examples of 11 latent type emulsions include:
U.S. Patent No. 2,592,250, Japanese Patent Publication No. 5B-543
79, 58-3536, 60-5582, JP-A-52-156614, JP-A-57-79940, and JP-A-58-70221; Emulsion with a shell attached thereto, U.S. Pat. No. 3,761.276, U.S. Pat. No. 3,850
, No. 637, No. 3923.513, No. 4,035.
No. 185, No. 4.395.478, No. 4,431,7
No. 30, No. 4,504,570, JP-A-53-602
No. 22, No. 56-22681, No. 59-208540
No. 60-107641, No. 61-3137, Patent Application No. 61-3642, Research Disclosure Magazine No. 23510 (published in November 1983)
P236, No. 18155 (issued in May 1979) P265-268 disclose core/shell type silver halide emulsions doped with a metal inside.

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

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

The average grain size of the silver halide grains is 2μ or less and 0.
It is preferably 1 μ or more, but particularly preferably 1 μ or less and 0.
The particle size distribution of 15 μ or more may be narrow or wide, but in order to improve graininess and sharpness, it should be within ±40% of the average particle size in terms of particle number or weight, preferably within ±20%. It is preferred to use a so-called "monodisperse" silver halide emulsion in the present invention, which has a narrow grain size distribution in which 90% or more of the total grains are contained in the grains. 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. of particles are mixed in the same layer or in a separate layer.
Can be applied. 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 examples, see Research Disclosure Magazine No. 17643-1 (published December 1978)
It is in the patent described on page 23 etc.

The photographic emulsions used in this invention are spectrally enhanced with photographic sensitizing dyes in a conventional manner. Particularly useful dyes are those belonging to cyanine dyes, merocyanine dyes and complex merocyanine dyes, and these dyes can be used alone or in combination. Further, detailed specific examples of the use of the above-mentioned dyes and supersensitizers in combination can be found, for example, in the patents described in Research Disclosure Magazine No. 17643-rV (published December 1978), pages 23-24.

The photographic emulsion used in the present invention may contain an anti-capri agent or a stabilizer for the purpose of preventing capri during the manufacturing process, storage or photographic processing of the light-sensitive material, or for stabilizing the photographic performance. For detailed examples, see Research Disclosure Magazine No. 17643-
Vl (published December 1978) pages 24-25 and
E. J. Birr “5 tabilization of
Photographic 5ilver Hali
de E + aulsions” (FocalPress
), published in 1974, etc.

Various magenta and yellow color couplers can be used with the cyan couplers of the present invention to form positive color images directly in accordance with the zero invention. Useful color couplers are compounds that undergo a coupling reaction with oxidized aromatic primary amine color developers to form or release non-diffusible dyes, which are themselves substantially non-diffusible. It is. Typical types of useful color couplers include:
Specific examples of these magenta and yellow couplers that can be used in the present invention include pyrazolone or pyrazolone azole compounds and open-chain or heterocyclic ketomethylene compounds.
7643 (issued December 1978) P25■-D section,
same! 1hlB717 (issued November 1979) and Japanese Patent Application No. 61-32462 (pages 298 to 373) and the patents cited therein.

Among them, representative examples of yellow couplers that can be used in the present invention include yellow m:equivalent couplers of the oxygen atom elimination type and the nitrogen atom elimination type. Especially α−
Pivaloylacetanilide couplers are preferred because they provide excellent color fastness, particularly light fastness, while α-penzoylacetanilide 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)(1,2,4) 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 preferred in terms of low yellow side absorption and light fastness; The described pyrazolo(1,5-b) (1,2,4) ) riazoles are particularly preferred.

Specific examples of particularly preferred yellow and magenta couplers include Japanese Patent Application No. 16952.3/1981 (Japanese Patent Application No.
Nos. 35 to 46 of Fuji Photo Film Co., Ltd. (filed on April 18th)
In addition to the compounds listed on page 1, the following compounds can also be cited as preferred examples.

o:I: Yellow coupler: el:l nee-U-U ^ 1 1:! : > 0 Colored couplers to correct unnecessary short wavelength absorption of the generated dyes, couplers in which coloring dyes have appropriate diffusivity, non-coloring couplers, DIRs that release development inhibitors along with coupling reactions. Coupler or development accelerator releasing couplers and polymerized couplers can also be used.

Typical usage amounts of color couplers range from o,oot to 1 mole per mole of photosensitive silver halide;
Preferably o, oi to 0.5 for yellow couplers.
moles, for magenta couplers 0.003 moles to 0
．． It is 3.

Furthermore, commonly used cyan couplers other than the cyan coupler of the present invention may be used in combination with the cyan coupler of the present invention.

The light-sensitive materials produced using the present invention contain hydroquinone derivatives, aminophenol derivatives, amines, gallic acid derivatives, catechol derivatives, ascorbic acid derivatives, colorless couplers, and sulfone as a color capri-preventing agent or color-mixing preventive agent. It may also contain amidophenol derivatives and the like. Typical examples of color antifogging agents and color mixing prevention agents are patent applications filed in 1983.
-32.

No. 462, pages 600-630.

Various anti-fading agents can be used in the light-sensitive material of the present invention. Organic anti-fading agents include hydroquinones,
Hindered phenols, mainly 6-hydroxychromans, S-hydroxycoumarans, spirochromans, p-flufuxiphenols, and bisphenols,
Representative examples include 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. 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 caused by light, spiroindanes described in JP-A-56-159644 and hydroquinone diethers or monomers described in JP-A-55-89835 are used. Ether substituted chromans give favorable results.

Representative examples of these anti-fading agents are disclosed in Japanese Patent Application No. 32462/1986.
No. 401-440.

The purpose of these compounds can be achieved by co-emulsifying them with the couplers and adding them to the photosensitive layer, usually in an amount of 5 to 100% by weight based on the respective color couplers. 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. Representative examples of compounds are given in Japanese Patent Application No. 61-32462.
It is described on 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 light-sensitive material of the present invention includes dyes that prevent irradiation and halation, ultraviolet absorbers, plasticizers, fluorescent whitening agents, matting agents, air capping inhibitors, coating aids, hardeners, and antistatic agents. It is possible to add a slip property improver, etc. Representative examples of these additives are [Research Disclosure]
Magazine No. 17643■-x■ (issued December 197B) 925-27, and 18716 (1979
Published in January), 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. A preferred calendar 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 emulsion layers may be composed of two or more emulsion layers having different sensitivities, or two or more emulsion layers having the same sensitivity.
A non-light-sensitive layer may be present between the two or more emulsion layers, with a cyan-forming coupler in the red-sensitive emulsion layer, a magenta-forming coupler in the green-sensitive emulsion layer, and a yellow-forming coupler in the blue-sensitive emulsion layer. Although this is usually included, 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 disclosed in Research Disclosure Magazine No. 17643.
Items listed in Section X (issued December 1978) p. 28 and European patents 0. 182. No. 253 and JP-A-61
-97655. Also, Research Disclosure Magazine No. 17643, Section XV p.
The coating methods described in 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, and color reversal paper. It can also be applied to full-color copying machines and color hard copies for storing images on CRTs. The present invention can also be applied to black-and-white light-sensitive materials using a three-color coupler mixture as described in Research Disclosure, No. 17123 (published July 1978).

After imagewise exposure, the light-sensitive material of the present invention is subjected to fogging treatment with light or a nucleating agent, and then developed with a surface developer containing an aromatic primary amine color developer, and subjected to bleaching and fixing treatment. By doing so, a positive color image can be directly formed.

The fogging treatment in the present invention is carried out as described above (the so-called "light fogging method" in which the entire surface of the photosensitive layer is exposed to light, and the "chemical fogging method" in which a developing treatment is carried out in the presence of a nucleating agent). Either method may be used. Development may be performed in the presence of a nucleating agent and fogging light. Alternatively, a photosensitive material containing a nucleating agent may be exposed to fogging light.

The entire surface exposure, that is, fogging exposure in the "light fogging method" of the present invention is performed after imagewise exposure, before development processing, and/or during development processing. The imagewise exposed photosensitive material is placed in a developer solution.
Alternatively, the film may be exposed to light by immersing it in a pre-bath of a developer, or by taking it out from this solution and exposing it to light before it dries, but it is most preferable to expose it in a developer.

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. may be used.

These specific methods are described, for example, in British Patent No. 1,151.
No. 363, Special Publication No. 45-1.2710, No. 45-12
, No. 709, No. 58-6936, JP-A-48-972
No. 7, No. 56-137350, No. 57-129438
No. 5B=62652, No. 5B-60739, No. 58-70223 (corresponding U.S. Pat. No. 4,440,851),
No. 58-120248 (corresponding European patent 89101A2
) etc. For photosensitive materials that are sensitive to all wavelengths, such as color photosensitive materials, Japanese Patent Application Laid-Open No. 56-137
A light source with high color rendering properties (as close to white as possible) such as those described in No. 350 and No. 58-70223 is preferable. The appropriate illuminance of the light is 0.01N2000 lux, preferably 0.05 to 30 lux, more preferably 0.05 to 5 lux. For light-sensitive materials that use emulsions with higher sensitivity, exposure at lower illuminance is preferable. Adjustment of illuminance can be done by changing the luminous intensity of the light source, attenuating the light using various filters, or adjusting the light-sensitive material. The exposure time can also be shortened by changing the distance between the photosensitive material and the light source, and by changing the angle between the light-sensitive material and the light source, and by using weak light initially and then using stronger light.

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 seconds to 1 minute, more preferably 1 second to 4 minutes
It is 0 seconds.

As the nucleating agent used in the present invention, all compounds conventionally developed for the purpose of nucleating latent silver halide can be used. Nucleating agents may be used in combination of two or more types. To explain in more detail, examples of nucleating agents include "
Research disclosure? -J (Resear
ch Disclosure) Magazine Na22゜534 (
Published January 1983, pp. 50-54) 15.162
(19, published in November 1976, pages 76-77) and the same magazine 11
h23,510 (November 1983 issue 346-35
These include quaternary heterocyclic compounds (compounds represented by the general formula (N-I)), hydrazine compounds (compounds represented by the general formula (N-1I)), and It is roughly divided into three other compounds.

General formula [N-13 9111,,-1,-・-Z,,,,.

(In the formula, 2 represents a nonmetallic atom group necessary to form a 5- to 6-membered heterocycle, 2 may be substituted with a substituent, R1 is an aliphatic group, and R1 is a hydrogen atom. , is an aliphatic group or an aromatic group. R' and R'' may be substituted with a substituent. However, at least one of the groups represented by R', R'' and Z is an alkynyl group. , an acyl group, a hydrazine group, or a hydrazone group, or R1 and ・R2 form a 6-membered ring to form a dihydropyridinium skeleton.Furthermore, one or more of the substituents of R1, Rg, and Z is X'-1: L'
)-II, where xl is a group promoting adsorption to silver halide and Ll is a divalent linking group. Y is a counter ion for charge balance, n is O or 1
and m is 0 or 1. ) To explain in more detail, the heterocycle completed by Z is, for example, quinolinium, benzothiazolium, benzimidazolium, pyridinium, thiazolinium, thiazolium, naphthothiazolium, selenazolium, benzoselenazolium, imidazolium, tetrazolium, Mention may be made of indolenium, pyrrolinium, acridinium, phenanthridinium, isoquinolinium, oxacillium, naphthooxacillium, naphthopyridinium and benzoxacillium nuclei. Substituents for 2 include alkyl groups, alkenyl groups, aralkyl groups, aryl groups, alkynyl groups, hydroxy groups, alkoxy groups, aryloxy groups, halogen atoms, amino groups, alkylthio groups, arylthio groups, acyloxy groups, acylamino groups, Sulfonyl group, sulfonyloxy group, sulfonylamino group, carboxyl group, acyl group, carbamoyl group, sulfamoyl group, sulfo group,
Cyano group, ureido group, urethane group, carbonate ester group,
Examples include hydrazine group, hydrazone group, and imino group. For example, at least one substituent is selected from the above substituents, but if two or more substituents are used, they may be the same or different, and the above substituent may be further substituted with these substituents. Good too.

Furthermore, as a substituent for Z, a heterocyclic quaternary ammonium group completed with Z via a suitable linking group may be included, in which case it takes a so-called dimer structure.

Preferred examples of the heterocycle completed by 2 include quinolinium, benzothiazolium, benzimidazolium, pyridinium, acridinium, phenanthridinium, naphtopyridinium and isoquinolinium nuclei.

More preferred are quinolinium, benzothiazolium, and naphtopyridinium, and most preferred is quinolinium.

The aliphatic groups of R1 and Rt are an unsubstituted alkyl group having 1 to 18 carbon atoms and a substituted alkyl group having 1 to 18 carbon atoms in the alkyl portion. Examples of the substituent include those described as the substituent for Z.

l The aromatic group represented by R1 has 6 to 20 carbon atoms.
For example, phenyl group, naphthyl group, etc. Examples of the substituent include those described as substituent 2. R1 is preferably an aliphatic group, most preferably a methyl group or a substituted methyl group.

At least one of the groups represented by R', R'' and Z has an alkynyl group, an acyl group, a hydrazine group, or a hydrazone group, or R1 and Rg form a 6-membered ring, and dihydrolysinium Forms a bone nucleus, but these may be substituted with the groups mentioned above as substituents for the group represented by Z. Hydrazine groups include, among others, acyl groups and sulfonyl groups as substituents. The hydrazone group is preferably one having an aliphatic group or an aromatic group as a substituent, and the acyl group is preferably, for example, a formyl group, an aliphatic group, or an aromatic ketone.

At least one of the substituents to the group or ring represented by R1, R1 and Z is preferably an alkynyl group or an acyl group, or R1 and Rz are preferably linked to form a dihydropyridinium core, The most preferred case is that it further contains at least one alkynyl group.

Preferred examples of the adsorption promoting group to silver halide represented by XI include a thioamide group, a mercapto group, and a 5- to 6-membered nitrogen-containing heterocyclic group.

These may be substituted with the substituents mentioned in 2. The thioamide group is preferably an acyclic thioamide group (e.g., thiourethane group, thiourido group, etc.)
It is.

As the mercapto group of
3,4-thiadiazole, etc.) are preferred.

The 5- to 6-membered N-containing heterocycle represented by XI is one consisting of a combination of nitrogen, enzyme, sulfur, and carbon,
Preferred examples include those that produce imino silver, such as benzotriazole.

The divalent linking group represented by Ll includes 01NSS,
It is an atom or atomic group containing at least one type of 0.

Specifically, for example, alkylene group, alkenylene group, alkynylene group, arylene group, -〇-1-S-1-NH
-1-N-1-CO-1-3Oz (these groups may have a substituent), alone or in combination.

Counter ions Y for charge balance include, for example, bromide ion, chloride ion, iodide ion, p-toluenesulfonate ion, ethylsulfonate ion, perchlorate ion,
Examples include trifluoromethanesulfonate ion and thiocyanate ion.

Examples of these compounds and their synthesis methods can be found, for example, in Research Disclosure.
Closure) Magazine! 1h22.534 (published January 1983, pages 50-54), and the same! 1h23,213
(Published in January 1983, pp. 267-270), Japanese Patent Publication No. 49-38,164, No. 52-19
No. 452, No. 52-47.326, JP-A No. 52-6
No. 9.613, No. 52-3.426, No. 55-138
, No. 742, No. 60-11.837, U.S. Patent No. 4,
No. 306.016 and No. 4,471.044.

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

(N-1-1), 6-nitoxy 2-methyl-1-propargylquinolinium bromide (N-1-2), 2. 4-dimethyl-1-propargylquinolinium bromide (N-I-3), 2-methyl-1-(3-(2-(
4-methylphenyl)hydrazonocobutyl)quinolinium iosito(N-1-4), 3,4-dimethyl-dihydropyrido(
2,1-b) Benzothiazolylam promide (N-I-5), 6-nitoxythiocarponylamino-2-methyl-1-propargylquinolinium trifluoromethanesulfonate (N-1-6), 2 -Methyl-6-(3-phenylthioureido)-1-propargylquinolinium bromide (N-1-7), 6-(5-benzotriazolecarboxamide)-2-methyl-1-propargylquinolinium trifluoromethane Sulfonate (N-1-8), 6- (3-(2-mercaptoethyl)ureido-2-methyl-1 monopropargylquinolinium trifluoromethanesulfonate (N-1-9), 6- (3-( 3-(5-mercapto-thiadiazol-2-ylthio)propyl]ureido)-2-methyl-1-propargylquinolinium trifluoromethanesulfonate (N-1-10), 6-(5-mercaptotetrazole-1- yl)-2-methyl-1-propargylquinolinyl ram iodide shell formula (N-II) (wherein, R21 represents an aliphatic group, aromatic group, or heterocyclic group; R1 is a hydrogen atom, an alkyl group, an aralkyl group, an aryl group, an alkoxy group, an aryloxy group, or an amino group; G is a carbonyl group, a sulfonyl group,
Sulfoxy group, phosphoryl group, or iminomethylene group (
R1'' and Rz4 are both hydrogen atoms, or one is a hydrogen atom and the other is an alkylsulfonyl group, an arylsulfonyl group, or an acyl group, provided that c, R1!, R24 and hydrazone structure (ゝN-N-c
/,, > may be formed. Furthermore, the groups mentioned above may be substituted with a substituent if possible.) To explain in more detail, R11 may be substituted with a substituent,
Examples of the substituent include the following. These groups may be further substituted, such as alkyl groups, aralkyl groups, alkoxy groups, alkyl or aryl groups, substituted amino groups, acylamino groups, sulfonylamino groups, ureido groups, urethane groups, aryloxy groups, Examples include sulfamoyl group, carbamoyl group, aryl group, alkylthio group, arylthio group, sulfonyl group, sulfinyl group, hydroxy group, halogen atom, cyano group, sulfo group, and carboxyl group.

Among these, ureido groups are particularly preferred.

These groups may be linked to each other to form a ring when possible.

RlI is preferably an aromatic group, an aromatic heterocycle, or an aryl-substituted methyl group, and more preferably an aryl group (eg, phenyl group, naphthyl group, etc.).

Among the groups represented by Rtt, preferred are a hydrogen atom, an alkyl group (e.g. methyl group) or an aralkyl group (
For example, 0-hydroxybenzyl group, etc.), and a hydrogen atom is particularly preferred.

As the substituent for RlI, in addition to the substituents listed for R″′, for example, an acyl group, an acyloxy group,
Alkyl or aryloxycarbonyl groups, alkenyl groups, alkynyl groups and nitro groups are also applicable.

These substituents may be further substituted with these substituents, and if possible, these groups may be linked to each other to form a ring.

RlI or Rlg, especially R11, may contain a diffusion-resistant group such as a coupler, a so-called ballast group (especially preferred when linked with a ureido group), a group X that promotes adsorption on the surface of silver halide grains. ! →L"-)-
m”.

X here! represents the same meaning as XI in general formula (N-1), and is preferably a thioamide group (excluding thiosemicarbazide and its substituted substances), a mercapto group, or a 5 to 6
It is a nitrogen-containing heterocyclic group.

Lz represents a divalent linking group, and Ll in general formula (N-1)
0m2, which has the same meaning as , is 0 or 1.

Even more preferable X! is an acyclic thioamide group (e.g., thioureido group, thiourethane group, etc.), a cyclic thioamide group (i.e., a mercapto-substituted nitrogen-containing heterocycle, e.g., a 2-mercaptothiadiazole group, a 3-mercapto-1
, 2,4-) lyazole group, 5-mercaptotetrazole group, 2-meth)Lth boudo 1. 3. 4-oxadiazole group, 2-mercaptopenzoxazole group, etc.), or a nitrogen-containing heterocyclic group (eg, benzotriazole group, benzimidazole group, indazole group, etc.).

The most preferable X2 varies depending on the photosensitive material used. For example, when using a color material (so-called coupler) that forms a dye through a coupling reaction with an oxidized form of a p-phenylenediamine developer in a color sensitive material, X2 is a mercapto-substituted nitrogen-containing heterocycle or an imino A nitrogen-containing heterocycle that forms silver is preferable, and when a coloring material that generates a diffusible dye (so-called DRR compound) by cross-oxidizing an oxidized developer is used in a color sensitive material, a non-containing heterocycle as x2 is preferable. A cyclic thioamide group or a mercapto-substituted nitrogen-containing heterocycle is preferred.

Furthermore, in terms of black and white photosensitive materials, X! Preferred examples include mercapto-substituted nitrogen-containing heterocycles or nitrogen-containing heterocycles forming iminosilver.

R"% R" is most preferably a hydrogen atom.

G in formula -a (N-f[) is most preferably a carbonyl group.

Further, as the general formula (N-ff), those having an adsorption group to silver halide or those having a ureido group are more preferable.

Examples of these compounds and their synthesis methods are as follows: Examples of hydrazine-based nucleating agents having silver halide adsorption groups include, for example, U.S. Pat. 4.031,127
No. 3,718,470, No. 4.269.92
No. 9, No. 4.276゜364, No. 4.278, 7
No. 48, No. 4゜385,108, No. 4,459,
No. 347, No. 4,478.928, No. 4. 56
0. No. 638, British Patent No. 2.01! , No. 391B,
JP-A-54-74.729, JP-A No. 55-163.533
No. 55-74.536, and No. 60-179.7
It is described in No. 34, etc.

Other hydrazine-based nucleating agents include, for example, JP-A No. 5
No. 7-86,829, U.S. Pat. No. 4,560.638, U.S. Pat. No. 4.478, and U.S. Pat.

Specific examples of the compound represented by the -M formula (N-If) are shown below, however, the present invention is not limited to the following compounds.

(N-II-1), 1-formyl-2-(4-(
3-(2-methoxyphenyl)ureido]-phenyl)hydrazine (N-II-2), 1-formyl-2-(4-(
3-(3-(3-(2,4-di-tert-pentylphenoxy)propylthureido)phenylsulfonylaminogophenyl)hydrazine(N-11-3), I-formyl-2-(4-(3)
-(5-mercaptotetrazol-1-yl)benzamido]phenyl)hydrazine (N-ff-4), 1-formyl-2-(4-(
3-(3-(5-mercaptotetrazol-1-yl)phenyl]ureido)phenyl]hydrazine (N-n-5), 1-formyl-2-(4-(3
-(N-(5-mercapto-4-methyl-1,2,4-)lyazol-3-yl)carbamoyl]propanamido)phenyl]hydrazine (N-II-6), 1-formyl-2-(4 −(
3-(N-(4-(3-mercapto-1,2,4-)lyazol-4-yl)phenylcarbamoyl) monopropanamido]phenyl)hydrazine (N-II-7), 1-formyl-2- (4-(
3-(N-(5-mercapto-1,3゜4-thiadiazol-2-yl) carbamoyl]propanamide) phenyl]hydrazine (N-11-8), 2-(4-(benzotriazole-5-carboxamide) ) phenyl) -1-formylhydrazine (N-n-9), 2- (4-(3-(N-(benzotriazole-5-carboxamido)carbamoyl]propanamido)phenyl]-1-formylhydrazine (N- 11-10), 1-formyl-2-(4-(
1-(N-phenylcarbamoyl)thiosemicarbazide]phenyl)hydrazine (N-11-11), 1-formyl-2-(4-(
3-(3-phenylthioureido)benzamido]phenyl)hydrazine (N-11-12), 1-formyl-2-(4-(
3-Hexylureido)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 in the sensitive 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 bank layer. When adding a nucleating agent to the processing solution, it should be added to the developer solution or a low p
It may be contained in the H pre-bath.

When the nucleating agent is contained in the sensitive material, the amount used is preferably 10-8 to 104 mol per mol of halogenated 1M,
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 10-1 mol, more preferably 10-4 to 10-2 mol per 11.

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 photosensitive material, or speeding up development.

Hydroquinones (e.g. U.S. Pat. No. 3,227.5
No. 52, No. 4,279.987): Chromans (for example, U.S. Patent No. 4,268.621, Japanese Patent Application Laid-Open No. 103031/1983, Research Disclosure Magazine Arashi 18264 (published June 1979) 333-334
Compounds described on page) Quinones (e.g. Research Disclosure Magazine Fish 21206 (December 1981, 433)
- Compounds described on pages 434): Amines (e.g., compounds described in U.S. Pat.
No. 39, Research Disclosure 16936 (
(Published May 1978) Compounds described on pages 10-11):
Catechols (e.g., compounds described in JP-A-55-21013 and JP-A-55-65944): Compounds that release nucleating agents during development (e.g., JP-A-60-107,029)
(Compounds described in No. 1983): Thioureas (e.g., JP-A-60-
Compounds described in No. 95533) Nispirobisindanes (
For example, the compound described in JP-A-55-65944).

Nucleation accelerators that can be used in the present invention include tetrazaindenes, triazaindenes and pentazaindenes, which have at least one mercapto group optionally substituted with an alkali metal atom or an ammonium group. and Japanese Patent Application Publication No. 1983-136948, (pages 2-6 and 16-43), Japanese Patent Application No. 136949-1980,
(pages 12-43) and No. 61-15348 (pages 10-29)
Examples include the compounds described on page 1).

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

(A-1) 3-mercapto-1,2,4-)riazolo(4,5-a)pyridine (A-2) 3-mercapto-1,2,4-)riazolo(4,5-a)pyrimidine (A-3) 5-Mercapto-1,2,4-) Riazolo (1,5-a) Tori Sewing Machine (^-4)? -(2-dimethylaminoethyl)-5-mercapto-1,2,4-)riazolo[1°5-a]pyrimidine (A-5) 3-mercapto-7-methyl-1,2,
4-triazolo(4,5-a)pyrimidine (A-6)
3. 6-Dimerkabuto 1.2.4-) Riazolo (
4,5-b) Pyridazine (^-7) 2-mercapto-5-methylthio-1,3゜4-thiadiazole (A-8) 3-mercapto-4-methyl-1,2,
4-Triazole (A-9) 2-(3-dimethylaminopropylthio)-5-mercapto-1,3,4-thiadiazole hydrochloride (A-10) 2-(2-morpholinoethylthio)-5
-Mercapto-1,3,4-thiadiazole hydrochloride (A-11) 2-Mercapto-5-methylthiomethylthio-1,3,4-thiadiazole sodium salt.

(A-12) 4-(,2-morpholinoethyl)-3
-Mercapto-1,2,4-)lyazole (a-13) 2- (2-(2-dimethylaminoethylthio)ethylthio]-5-mercapto-1゜3.4-
Thiadiazole Hydrochloride The nucleation promoter in this case is preferably added to the silver halide emulsion or to a layer adjacent thereto.

The amount of nucleation accelerator added is 10-' per mole of silver halide.
-10-'' mole is preferred, more preferably 10-S~
It is 104 moles.

In addition, when the nucleation accelerator is added to the processing solution, that is, the developer or its pre-bath, 10-8 to 10-3 per 11.
molar is preferred, more preferably 10-''I to 10-4
It is a mole.

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

The color developer used in the development of the light-sensitive material of the present invention does not substantially contain a silver halide solvent, and is preferably an alkaline solution containing an aromatic primary amine color developing agent as a main component. Aminophenol compounds are also useful as the main drug, but p-phelenediamine compounds are preferred; a typical example is 3-methyl-
4-Amino-N-ethyl-N-(β-methanesulfonamidoethyl)-aniline, 3-methyl-4-amino-N
-ethyl-N-(β-hydroxyethyl)aniline, 3
Examples include -methyl-4-amino-N-ethyl-N-methoxyethylaniline and salts thereof such as sulfates and hydrochlorides. Other color developing agents include: F
, A. Mason, Photographic Processing Chemistry, Focal Press (196
6th year) (L.

F, A, Mason' Photographic
ProcessingChes+1try', F
p. 226-229 of U.S. Patent No. 2,193.015; 592°364,
Those described in JP-A No. 48-64933 and the like may be used, and if necessary, two or more color-producing agents may be used in combination.

The amount of the color developing agent used is 0.1 g to 20 g, more preferably 0.5 g to 15 g, per 11 of the developer.

Furthermore, as a preservative, JP-A-52-49828 and JP-A-52-49828,
No. 6-47038, No. 56-32140, No. 59-1
Aromatic polyhydroxy compounds described in US Pat. No. 60142 and US Pat. No. 3,746,544; US Pat. No. 3,615.503
Hydroxyacetones described in JP-A-52-143020 and British Patent No. 1306.176;
α-Aminocarbonyl compounds described in JP-A No. 89425: Various metals described in JP-A-57-44148 and JP-A-57-53749, etc.: Various Ws described in JP-A-52-102727; described in JP-A-52-27638 Hydroxamic acids: α-α'-dicarbonyl compounds described in No. 59-160141 '15: Salicylic acids described in No. 59-180588: Child lucanolamines of No. 54-3532: No. 56-94349 The poly(alkylene imine)s described; the gluconic acid derivatives described in No. 56-75647, and the like can be mentioned. Two or more of these preservatives may be used in combination if necessary, especially 4,5-di-L-droxy-m-benzenedisulfonic acid and poly(ethyleneimine).
It is preferable to add substituted phenols such as p-ditrophenol, and it is preferable to add substituted phenols such as p-ditrophenol.It is also preferable to use the alkylhydroxylamine compound of JP-A-54-3532, especially for alkylhydroxyl. It is preferable to use the amine compound in combination with the above preservative.

The amount of these preservatives used is from 0.1 g to 20 g, more preferably from 0.5 g to 10 g, per developer solution 11.

The pH of the color developer of the present invention is preferably between 9.5 and 1.
1.3, particularly preferably 10.0 to 10°8. Various buffers can be used to maintain the above pH. As a buffering agent, carbonate such as potassium carbonate,
Patent application for phosphates such as potassium phosphate, etc.
Compounds described on pages 11 to 22 of Specification No. 462 can be used.

Furthermore, various chelating agents can be used in the color developer to prevent precipitation of calcium or magnesium or to improve the stability of the color developer.

As a chelating agent, for example, Japanese Patent Publication No. 48-030496
and aminopolycarboxylic acids described in JP-A No. 44-30232, JP-A No. 56-97347, JP-A No. 56-39
359 and the organic phosphonic acids described in West German Patent No. 2゜227.639, JP-A-52-102726 and JP-A-52-102726;
No. 42730, No. 54-121127, No. 55-12
Phosphonocarboxylic acids described in JP-A-58-195845, JP-A-58-203440 and JP-B-Sho 53-40900
Examples include the compounds described in No. 1, etc. Two or more of these chelating agents may be used in combination if necessary, and the amount of these chelating agents added may be sufficient as long as it is sufficient to sequester metal ions in the color developer. For example, it is about 0.1 g to 10 g per 11.

Any development accelerator can be added to the color developer if necessary.

As a development accelerator, Japanese Patent Publication No. 37-16088 and No. 3
No. 7-5987, No. 38-7826, No. 44-123
No. 80, No. 45-9019 and U.S. Patent No. 381324
Thioether compounds described in No. 7, etc.; JP-A-52-4
p-phenylenediamine compounds described in No. 9829 and No. 50-15554, JP-A-50-137726
No., Special Publication No. 44-30074, Japanese Patent Publication No. 5671568
Quaternary ammonium salts described in U.S. Pat. No. 26 and U.S. Pat. No. 52-43429, etc.; U.S. Pat.
p-aminophenols described in U.S. Pat. No. 119.462; U.S. Pat. No. 2,494,903, U.S. Pat.
Special Publication No. 41-11431, U.S. Patent No. 2,482.54
No. 6, No. 2゜596.926 and No. 3,582,34
Amine compounds described in No. 6, etc.; Japanese Patent Publication No. 37-1608
No. 8, No. 42-25201, U.S. Patent No. 3,128.1
No. 83, Special Publication No. 41-11431, No. 42-2388
No. 3 and U.S. Patent 3. 532. Polyalkylene oxide described in No. 501 etc., others, 1-phenyl-3
- Pyrazolidones, hydrazines, mesoion type compounds, thione type compounds, imidazoles, etc. can be added as necessary. Particularly preferred are thioether compounds and 1-phenyl-3-pyrazolidones.

In the present invention, an arbitrary antifoggant can be added to the color developer, if necessary. As anti-capri agents, alkali metal halides such as potassium bromide, sodium chloride, potassium iodide and organic anti-foggants may be used. Examples of organic antifoggants include benzotriazole, 6-nidropenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chloro-benztriazole, 2-thiazolyl-benzimidazole. , 2-thiazolylmethyl-benzimidazole, hydroxyazaindolizine, and mercapto-substituted heterocyclic compounds such as 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, adenine, and mercapto-substituted heterocyclic compounds such as thiosalicylic acid. aromatic compounds can be used. These anti-capri agents may be eluted from the color photosensitive material during processing and may accumulate in the color developer, but from the viewpoint of reducing the amount of discharge, it is preferable that the amount of these accumulated is small.

The color developer of the present invention preferably contains a fluorescent brightener. As a fluorescent brightener, 4,4-diamino-2
, 2'-disulfostilbene type compounds are preferred. The amount added is 0 to 5 g/l, preferably 0.1 g to 2 g/f.

Furthermore, various surfactants such as alkylphosphonic acids, arylphosphonic acids, aliphatic carboxylic acids, and aromatic carboxylic acids may be added as necessary.

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

The bleaching process may be carried out simultaneously with the fixing process in a single bath bleach-fixing process, or may be carried out separately. Furthermore, in order to speed up the processing, a method may be employed in which bleaching is followed by bleach-fixing, or a method in which fixing is followed by bleach-fixing. An aminopolycarboxylic acid iron complex salt is usually used as a bleaching agent in the bleaching solution or bleach-fixing solution of the present invention. Additives used in the bleaching solution or bleach-fixing solution of the present invention include Japanese Patent Application No. 61-32462, pages 22 to 30.
A variety of compounds described on page can be used. After the desilvering step (bleach-fixing or fixing), treatments such as water washing and/or stabilization are performed. It is preferable to use softened water as the washing water or stabilizing liquid. Examples of the water softening treatment include a method using an ion exchange resin or a reverse osmosis device as described in Japanese Patent Application No. 131632/1982. These specific methods are described in the patent application 1986-
Preferably, the method described in No. 131632 is carried out.

Further, as additives used in the water washing and stabilization steps, various compounds described on pages 30 to 36 of Japanese Patent Application No. 61-32462 can be used.

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

(Example) Example 1 A 1M aqueous solution of potassium bromide and an aqueous solution of silver nitrate were vigorously stirred into an aqueous gelatin solution to which 0.3 g of 3,4-dimethyl-1°3-thiazoline-2-thione was added per mole of Ag. However, they were simultaneously added at 65° C. over about 30 minutes to obtain an octahedral monodisperse silver bromide emulsion with an average grain size of 0.45 μm. To this emulsion were added sodium thiosulfate and chlorauric acid (tetrahydrate) in an amount of 16 μm each per mole of silver, and the mixture was heated to 80°C at 75°C.
Chemical sensitization treatment was performed by heating for minutes.

Using the thus obtained silver bromide grains as cores, they were further grown by further treatment for 40 minutes in the same precipitation environment as the first time, and the final grain size was octahedral monodisperse with an average grain size of 0.8 μm (coefficient of variation 11%). A core/shell silver bromide emulsion was obtained. Add 1.5 g of hydrogen peroxide and 1 mol of Ag to this emulsion and
After heating at 60°C for 8 minutes, washing with water and desalting, sodium thiosulfate and chloroauric acid (tetrahydrate) were added in an amount of 2.2 μ per mole of silver, and heated at 60°C for 60 minutes for chemical amplification. A sensitivity treatment was performed to obtain an internal latent image type silver halide emulsion A.

A full weight color photographic paper having the layer structure shown in Table 1 was prepared using core/shell type internal latent image emulsion A on a paper support laminated on both sides of polyethylene.

The coating solution was prepared as follows.

1st layer coating liquid preparation Add 10 g of nitrogen coupler (shown in Table 2) and 2.3 g of color stabilizer (b) to 1 ml of ethyl acetate.
Qml and solvent (c) 4mj! Add and dissolve this solution and add 5ml of 10% sodium dodecylbenzenesulfonate.
The mixture was emulsified and dispersed in 99 mji of a 10% aqueous gelatin solution. On the other hand, the above-mentioned silver halide emulsion (Ag70g/Kg
A red-sensitive emulsion was prepared by adding 2°oxio-4 mol of the red-sensitive dye shown below per mol of silver halide to the red-sensitive emulsion.
I made g. The emulsified dispersion, the emulsion, and the development accelerator were mixed and dissolved, and the concentration was adjusted with gelatin so that the composition shown in Table 1 was obtained, and the nucleating agent (N-I-9) was added at 4% per mole of Ag.
．． 5X10-' moles and nucleation accelerator (A-15) as
A coating solution for the first layer was prepared by adding 1X10-' mole per mole.

The coating solutions for the second to seventh layers were also prepared in the same manner as the first layer coating solution. 1-oxy-3 as gelatin hardening agent in each layer
, 5-dichloro-5-) riazine sodium salt was used.

The following spectral sensitizers were used in each emulsion.

Table 1 red-sensitive pigment; green angry pigment Blue-sensitive dye; The following dyes were used as anti-irradiation dyes.

The structural formulas of the compounds used in this example, including the irradiation-preventing dye for the green-sensitive emulsion layer and the irradiation-preventing dye coupler for the red-sensitive emulsion layer, are as follows.

(b) Color image stabilizer l:3:3 mixture (molar ratio) It is also possible to take the following structure. The same applies below.

(c) Solvent (e) Color mixing inhibitor (f) Magenta coupler (g) Color image stabilizer (h) 1:2:2 mixture (weight ratio) of solvent (i) Ultraviolet absorber 1: 5:3 mixture (molar ratio) (j) Color mixing inhibitor (k) Solvent (iso C* Htwoh-P = 0 (j) Yellow coupler ti3 The color photographic paper thus prepared was exposed to wedge light. (1/10 seconds, IOCMS), the following processing steps (a) and (b) are carried out, and the minimum color image density of cyan is measured. D
The difference in mtn was shown.

The results obtained are shown in Table 2.

Processing process (a) Time Temperature color development 3 minutes 30 seconds 33℃ bleach fixing
1 minute 30 seconds Stable at 33℃ 0 1 minute Stable at 33℃ ■ 1 minute
The replenishment method for the 33°C stable bath was a so-called countercurrent replenishment method in which the stable bath (1) was replenished, the overflow liquid from the stable bath (2) was led to the stable bath (2), and the overflow liquid from the stable bath (2) was led to the stable bath (2).

[Color developer]

, mother liquor Diethylenetriaminepentaacetic acid 2.0g Benzyl alcohol 12.8g Diethylene glycol 3.4g Sodium sulfite
2.0 g Sodium Bromide 0.2
6g hydroxyamine sulfate 2.60g sodium chloride 3.20g 3-methyl-
4-Amino-N-4,25g Ethyl-N-(β-methanesulfonamidoethyl)-aniline potassium carbonate 30.0g Fluorescent brightener (Stilbeni/based) 1.0g Add water
IO00nlpH10,20 pH was adjusted with potassium hydroxide or hydrochloric acid.

[Bleach-fix solution]

Mother liquor Ammonium thiosulfate 110 g Sodium bisulfite 10 g Diethylenetriamine 5B g Iron (III) acid ammonium monohydrate Ethylenediamine 4-section A2 5 g Sodium dihydrate 2-mercapto-1,3,4-0,5 g Triazole water Add 1000mj! pH6
, 5 pH was adjusted with aqueous ammonia or hydrochloric acid.

[Stabilizing liquid]

Mother, liquid 1-hydroxyethylidene 1.5mm! -1,
1'-Diphosphonic acid (-60%) Bismuth chloride 0.35g Polyvinylpyrrolidone 0.25g Aqueous ammonia
'1.5ml nitrilotriacetic acid/3Na
1.0g 5-chloro-2-methyl-4-isothiazolin-3-one 50 ■2-octyl-4-isothiazolin-3-one 50 ■Fluorescent brightener (4,4'-diaminostilbene type) 1.0g water Add 1000 ml pi (7,5 pH is adjusted with potassium hydroxide or hydrochloric acid.

Processing Step (B) The automatic developing machine was operated overnight without replenishing the processing solution used in the above processing step (A), and then the same processing as in the above processing step (A) was performed.

Table 2 *Cyan coupler for comparison [C-1) [C-2) **) The cyan coupler of the present invention is the example number mentioned above.

It can be seen that in the photosensitive material containing the cyan coupler of the present invention, the increase in minimum image density is clearly suppressed when post-processing is performed with an automatic processor running overnight.

Furthermore, the light-sensitive material containing the cyan coupler of the present invention had good color development in both processing steps (a) and (b). Further, the minimum density in the treatment step (a) was the same regardless of whether the cyan couplers of the present invention or the comparative example were used, and the values were all 0°21.

Example 2 Same as Example 1 except that Emulsion B described below was used, no nucleating agent or nucleation accelerator was added, and the cyan coupler shown in Table 3 was used. Color photographic paper was created.

The thus obtained color photographic paper was subjected to wedge exposure in the same manner as in Example 1, and then subjected to the following processing steps (c) and (d), and evaluated as in Example 1. The results obtained are shown in Table 3.

Emulsion (B) Gelatin 30g 5KBr0.7mol, NaCl0.25
A mixture containing 1.31 to 6 moles and KIo, 002 moles
After adding 1.21 of a solution containing 0.7 mol/1 silver nitrate at 5° C. over 20 minutes, physical ripening was further performed for 20 minutes.

This emulsion is 709mj! Furthermore, at 60°C, a 0.6 mol/l silver nitrate aqueous solution and a 0.8 mol/l mixed aqueous solution of sodium chloride and potassium bromide (molar ratio 1.3:1) were added.
) were added simultaneously to precipitate a silver chloride shell, which was then washed with water. Average particle size 0. A 75 μm silver halide emulsion B was obtained.

Processing steps (c) and (d): Processing steps (a) of Example 1, except that 0.5 lux light (5400K) was continuously applied to the surface of the photosensitive material for 20 seconds from 15 seconds after the start of development.
and (b) are the same.

Table 3 *), **) Same as the footnote in Table 2 The photosensitive material of the present invention has good color development in both processing steps (c) and (d), and the light-sensitive material of the present invention in processing step (c) The Dmin values of the light-sensitive materials of the and comparative examples were both 0.22.

It can be seen that the same results as in Example 1 can be obtained.

Example 3 Example 1 was repeated except that Emulsion C, described below, and the cyan coupler shown in Table 4 were used.

How to make emulsion C: First, an aqueous solution of potassium bromide and an aqueous solution of silver nitrate were vigorously stirred into an aqueous gelatin solution to which 0.56 g of 3.4-dimethyl-1,3-thiazoline-2-thione was added per mole of Ag. However, they were simultaneously added at 75° C. over about 40 minutes to obtain an octahedral monodisperse silver bromide emulsion with an average grain size of 0.5 μm. To this emulsion were added sodium thiosulfate and chloroauric acid (tetrahydrate) in an amount of 30 μg per mole of primate, and the mixture was heated at 75°C to 8 μm.
Chemical sensitization treatment was performed by heating for 0 minutes. Using the thus obtained silver bromide particles as cores, they were further grown by further treatment for 40 minutes in the same precipitation environment as the first time, and finally octahedral monodisperse core/shell silver bromide particles with an average particle diameter of 1°1 μm were obtained. An emulsion was obtained. After washing and desalting, sodium thiosulfate and chloroauric acid (tetrahydrate) were added to the emulsion in an amount of 2.1 molar per mole of silver, and heated at 60°C for 60 minutes to perform chemical sensitization. A latent image type silver halide emulsion C was obtained.

In all cases in Table 4, even when the treatment step (b) was applied in the same manner as in Example 1, it was possible to maintain good color development while suppressing an increase in the minimum image density.

Example 4 In Example 1, color photographic paper was prepared by adding 32 μg of the following compound (h g) per 1 d of the photosensitive material to the 1.3 and 5th layers of the photosensitive material and adding the cyan coupler shown in Table 5. Example 1 was repeated except that the following processing steps (e) and (f) were further performed.

Compound (h g) Processing step (e) Color development 2 minutes 30 seconds 38°C Bleach-fixing 40 seconds 38°C Stable 0 20 seconds'38°C Stable ■ 20 seconds 38°C Each processing solution was used in the processing step (a) of Example 1. It is exactly the same as the one used. (F) In the processing step (E), the film was operated as it was in an automatic processor at 38° C. overnight without replenishing the processing solution, and then processed.

Table 5 When a hydroquinone compound having a sulfonic acid group is combined with the cyan coupler of the present invention, the increase in minimum image density is further suppressed even when the overnight operating temperature of an automatic processor is increased. I understand that.

In addition, good color development was maintained. Furthermore, the Dmin values of the light-sensitive materials of the present invention and comparative examples under processing conditions (e) were both 0.23.

(Effects of the Invention) According to the present invention, by using a specific cyan coupler in the photosensitive material, even if the temperature or pH of the color developer changes,
It is possible to form an excellent direct positive color image in which the maximum image density and minimum image density do not easily vary from the optimum values.

In particular, it has the unexpected effect that the minimum density is less likely to increase when an automatic processor is put into operation without replenishing the processing solution, and therefore is put into a high temperature state.

The above-mentioned effects become particularly noticeable when a hydroquinone compound having a sulfonic acid group is used in combination with the photosensitive material.

Claims (2)

[Claims] (1) A direct positive color light-sensitive material having at least one photographic emulsion layer containing internal latent image type silver halide grains and a color image-forming coupler on a support, which have not been fogged in advance, the light-sensitive material has the following general formula [ A direct positive color light-sensitive material containing at least one non-diffusible cyan coupler selected from the group of compounds represented by C-I]. General formula [C-I] ▲ Numerical formulas, chemical formulas, tables, etc. R_3 represents a hydrogen atom, a halogen atom, an aliphatic group, an aliphatic oxy group, or an acylamino group, and Y_1 represents a hydrogen atom or a coupling reaction with an oxidized form of a developing agent. (Alternatively, R_1, R_2, R_3, or Y_1 may form a dimer or more multimer.) (2) The direct positive color photosensitive material according to claim (1), further containing a hydroquinone compound having a sulfonic acid group.