JPH0758390B2 - Direct positive image forming method - Google Patents

Description

The present invention relates to a direct positive color image forming method.

(Prior Art) Photographic methods for obtaining direct positive images without the need for reversal processing steps or negative films are well known.

The conventionally used methods for producing a positive image using a direct positive silver halide photographic light-sensitive material, except for special ones, can be mainly classified into two types in consideration of practical usefulness. it can.

One type uses a fog-fogged silver halide emulsion in advance and directly obtains a positive image after development by destroying fog nuclei (latent image) in the exposed area by utilizing solarization or Herschel effect. is there.

The other type uses an unfogged internal latent image type silver halide emulsion and directly develops a positive image by performing surface development after or after fogging after image exposure.

The above-mentioned internal latent image type silver halide photographic emulsion is a type of silver halide photographic emulsion in which a silver halide grain has a photosensitive nucleus mainly inside and a latent image is mainly formed inside the grain by exposure. Say.

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

Various techniques have been known so far in this technical field. For example, U.S. Patent Nos. 2,592,250 and 2,466,9
No. 57, No. 2,497,875, No. 2,588,982, No. 3,317,
No. 322, No. 3,761,266, No. 3,761,276, No. 3,79
6,577 and British Patents 1,151,363 and 1,150,553
No. (No. 1,011,062) Main items are described in each specification.

By using these known methods, a photographic light-sensitive material having a relatively high sensitivity as a direct positive type can be produced.

Further, for details of the mechanism for forming a direct positive image, for example,
The James of James, The Theory of the Photograph
ic Process) Fourth Edition, Chapter 7, pp. 182-193 and U.S. Pat. No. 3,
761,276, etc.

That is, the fog nuclei are selectively formed only on the surface of the unexposed area of the silver halide grain due to the surface desensitizing effect caused by the so-called internal latent image (positive hole) generated inside the silver halide by the first imagewise exposure. , Then the normal,
It is believed that a photographic image (direct positive image) is formed on the unexposed portion by subjecting it to so-called surface development treatment.

As described above, as a means for selectively generating fog nuclei, a method of giving a second exposure to the entire surface of the photosensitive layer, which is generally called "light fog method" (for example, British Patent 1,151,363)
And a nucleating agent called "chemical fogging"
gent) method is known. This latter method is described, for example, in "Research Disclosure".
(Research Disclosure) Vol. 151, No. 15162 (November 1976)
Monthly issue), pages 76-78.

To directly form a positive color image, the internal latent image type silver halide light-sensitive material is subjected to a fogging process, or a surface color development process is performed while the fogging process is being performed, and then a bleaching and fixing (or bleach-fixing) process is performed. Can be achieved. After the bleaching / fixing treatment, washing and / or stabilizing treatment is usually performed.

(Problems to be Solved by the Invention) In the direct positive image formation using such a light fogging method or a chemical fogging method, the developing speed is slow and the processing time is long as compared with the case of a normal negative type. Therefore, conventionally, a method of shortening the processing time by increasing the pH and / or the liquid temperature of the developer has been used. However, in general, there is a problem that the minimum image density of the direct positive image obtained when the pH is high is increased. Further, under high pH conditions, the developing agent is apt to be deteriorated by air oxidation, resulting in a problem that the developing activity is remarkably lowered.

As a means for increasing the development speed in direct positive image formation, another method using a hydroquinone derivative (US Pat.
No. 552), those using a mercapto compound having a carboxylic acid group or a sulfonic acid group (JP-A-60-170843), and the like, but the effect of using these compounds is small, and a direct positive image is used. No technique has been found that can effectively increase its maximum concentration without increasing its minimum rate. In particular, there is a demand for a technique capable of obtaining a sufficient maximum image density even when processed with a developer having a low pH.

In addition, an instant color photograph (color material diffusion transfer method) can obtain a positive image in a short time, but in such a technique, it is desired to shorten the developing time.

On the other hand, various methods have been conventionally used in this field in order to increase the developing speed and color developing speed of the color developing solution. Benzyl alcohol is now widely used as an almost essential component as an additive for promoting the above.

Benzyl alcohol dissolves in water to some extent but has poor solubility, and it is widely used to use diethylene glycol, triethylene glycol or alkanolamine to increase the solubility, but these compounds and benzyl alcohol themselves are also used as wastewater. Benzyl alcohol is reduced from the viewpoint of wastewater treatment despite the advantages such as high pollution load and high BOD value and COD value in treatment, and improvement in color development or solubility as described above. Or was desired to be removed.

Furthermore, the solubility of benzyl alcohol is still insufficient even when the above-mentioned solvent such as diethylene glycol is used, which causes a burden on labor and time for preparing a developer.

Further, if benzyl alcohol is brought into the bleaching bath or bleach-fixing bath which is the subsequent bath together with the developer and accumulates therein, it may cause formation of a leuco body depending on the type of the cyan dye and may lower the color density. I was waking up. Further, it was also found that the accumulation causes insufficient washing out of the developing solution components, especially the color developing agent in the washing step, thereby causing deterioration of image storability due to the residual thereof.

However, in the current color lab, there is a need to shorten the processing time in the trend of shortening the delivery time of print finish, and if the development time is shortened after removing benzyl alcohol from the color developing solution, Since it is obvious that the color density is remarkably reduced, it is a technology in which high color density and removal of benzyl alcohol are difficult to achieve at the same time, and its solution is strongly desired.

Further, the direct positive emulsion has a peculiar problem that a re-inversion negative image is generated in a high illuminance exposure unlike a general negative emulsion. Therefore, there is also a demand for means capable of effectively preventing the occurrence of such a re-inversion negative image.

Accordingly, an object of the present invention is to form a direct positive color image having a sufficient maximum image density (coloring density) and a low minimum image density even when subjected to a processing for a short time with a color developer containing substantially no benzyl alcohol. To provide a method.

A further object of the present invention is to provide a direct positive color image forming method capable of effectively preventing the occurrence of a re-inverting negative image.

It is a further object of the present invention to provide a method for forming a direct positive color image which is free from the cyan dye recoloring defect and is excellent in image storability.

It is a further object of the present invention to provide a method for forming a direct positive color image which is excellent in the stability of a developing solution and which is remarkably reduced in the increase of fog density and the generation of re-inversion gas image during continuous processing. .

(Means for Solving the Problems) The above object of the present invention is to provide a light-sensitive material containing at least one pre-fogged internal latent image type silver halide emulsion layer and a color image-forming coupler on a support. After imagewise exposure, prior to the development or during the development process, in the presence of fog exposure and / or in the presence of a nucleating agent, development, bleaching / fixing treatment with a surface color developing solution containing an aromatic primary amine type color developing agent. In the method for directly forming a positive color image, the color developer contains substantially no benzyl alcohol, contains hydroxylamine or a salt thereof in a concentration of 1.0 × 10 ^-2 mol or less per developer, and Sulfite ion in developer 1
It was found to be achieved by a direct positive color image forming method characterized by containing at a concentration of 1.0 × 10 ^-2 mol or less per unit.

In the present invention, hydroxylamine (or a salt thereof) and sulfite ion, which have been most commonly used as a preservative in a surface color developing solution containing an aromatic primary amine color developing agent, have been used. Unexpectedly, not only can a sufficient maximum image density be obtained even when color development processing is performed using a developer that does not substantially contain benzyl alcohol, but the minimum image density can be significantly reduced. It was found to be done. Further, according to the present invention, it is possible to effectively prevent the occurrence of a re-inversion negative image peculiar to a direct positive type photosensitive material, and it is possible to obtain a direct positive color image having an extremely good whiteness in a highly exposed portion.

The color developer containing substantially no benzyl alcohol in the present invention means a color developer having a benzyl alcohol content of 2 ml or less per developer, preferably 1 ml or less, and more preferably no developer. Is.

Specific examples of the hydroxylamine or a salt thereof of the present invention include hydroxylamine, hydroxylamine hydrochloride, hydroxylamine sulfate and the like.

Examples of the compound that releases sulfite ion in the present invention include sodium sulfite, potassium sulfite, sodium bisulfite, potassium metabisulfite and the like.

In the present invention, hydroxylamine or a salt thereof is used in an amount of 0 to 1.0 × 10 ⁻² mol, preferably 5 × 10 ⁻³ mol or less, more preferably 0 mol, and sulfite ion to 0 per 1 developer.
Characteristically, it is contained at a very low content of up to 1.0 × 10 ⁻² mol, preferably 5 × 10 ⁻³ mol or less, more preferably 2 × 10 ⁻³ mol or less. If it is more than the above content,
In the developer system of the present invention which does not substantially contain benzyl alcohol, sufficient color density cannot be produced, and a preferable image cannot be obtained.

The pre-fogged internal latent image type silver halide emulsion used in the present invention is an emulsion in which the surface of silver halide grains is not pre-fogged and which contains a silver halide mainly forming a latent image inside the grains. More specifically, a silver halide emulsion is silver-coated on a transparent support in an amount of 0.5 to 3 g / m ² and exposed to light at a fixed time of 0.01 to 10 seconds to give a developer A ( The maximum density obtained by a usual photographic density measuring method when developed at 18 ° C. for 5 minutes in an internal type developer) is the same as the above, and the silver halide emulsion exposed in the same manner is developed with the following developer B. 20 in (surface type developer)
Those having a density at least 5 times higher than the maximum density obtained when developed at 6 ° C. for 6 minutes are preferable, and those having a density at least 10 times higher are more preferable.

Internal developer A Metol 2 g Sodium sulfite (anhydrous) 90 g Hydroquinone 8 g Sodium carbonate (monohydrate) 52.5 g KBr 5 g KI 0.5 g Water is added 1 Surface developer B Metol 2.5 g l-Ascorbic acid 10 g NaBO ₂ .4H ₂ O 35 g KBr 1 g Water is added 1 As a specific example of the internal latent type emulsion, for example, U.S. Pat.
No. 0, Japanese Patent Publication No. 58-54379, No. 58-3536, No. 60-5582
No. 52-156614, No. 57-79940, No. 58-70221
Conversion type silver halide emulsion described in the specification of U.S. Pat.
3,761,276, 3,850,637, 3,923,513, 4,03
5,185, 4,395,478, 4,431,730, 4,504,570
JP-A Nos. 53-60222, 56-22681, and 59-208540.
No. 60-107641, No. 61-3137, Japanese Patent Application No. 61-3642
Issue, Research Disclosure No. 23510 (1983
Issued in November) P236, No. 18155 (issued in May 1979) P265 ~
Mention may be made of internally metal-doped core / shell type silver halide emulsions described in the patents disclosed in US Pat.

The silver halide grains used in the present invention have a regular crystal form such as a cube, an octahedron, a dodecahedron and a tetradecahedron, an irregular crystal form such as a sphere, and a length / length of Tabular grains having a thickness ratio of 5 or more may be used. Further, it may be an emulsion having a composite form of these various crystal forms, or an emulsion composed of a mixture thereof.

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

The average grain size of silver halide grains is 0.1 at 2μ or less.
μ or more is preferable, but 0.1 μ or less is particularly preferable.
That is all. The particle size distribution may be narrow or wide, but within the range of ± 40% of the average particle size in terms of the number of particles or the weight in order to improve graininess, sharpness, etc., preferably ±
So-called "monodisperse" silver halide emulsions having a narrow grain size distribution such that 90% or more of all grains fall within 20% are preferably used in the present invention. In order to satisfy the target gradation of the light-sensitive material, two or more kinds of monodispersed silver halide emulsions having different grain sizes or a plurality of emulsions having the same size but different sensitivities are used in the emulsion layers having substantially the same color sensitivity. The particles can be mixed in the same layer or multi-layered in different layers. Further, two or more kinds of polydisperse silver halide emulsions or a combination of monodisperse emulsions and polydisperse emulsions can be mixed or laminated and used.

The silver halide emulsion used in the present invention can be chemically sensitized inside or on the surface of the grain by sulfur or selenium sensitization, reduction sensitization, noble metal sensitization or the like alone or in combination. Specific examples are described in the patents described in, for example, Research Disclosure No. 17643-III (issued in December 1978) P23.

The photographic emulsion used in the present invention is spectrally sensitized with a photographic sensitizing dye in a conventional manner. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes and complex merocyanine dyes, and these dyes can be used alone or in combination. Further, the above dye and supersensitizer may be used in combination. Detailed specific examples are found in patents described in, for example, Research Disclosure No. 17643-IV (published in December 1978) P23-24.

The photographic emulsion used in the present invention may contain an antifoggant or stabilizer for the purpose of preventing fog during the production process of a light-sensitive material, storage or photographic processing, or stabilizing photographic performance. For more specific examples,
For example, Research Disclosure No.17643-VI
(Published December 1978) Pages 24-24 and "Stab" by EJBirr
ilizationof Photographic Silver Halide Emulsions "
(FocalPress), published in 1974.

Various color couplers can be used to directly form a positive color image. Useful color couplers are
A compound which produces or releases a dye, preferably a non-diffusible dye, by a coupling reaction with an oxidized product of a p-phenylenediamine color developing agent, and is a compound which is substantially non-diffusible in itself. Typical types of useful color couplers are naphthol or phenolic compounds, pyrazolone or pyrazolone azole compounds and open chain or heterocyclic ketomethylene compounds. Specific examples of these cyan, magenta and yellow couplers that can be used in the present invention are No. 1 of "Research Disclosure".
7643 (issued in December 1978) P25 VII-D, No. 18717 (19)
Issued in November 1979) and Japanese Patent Application No. 61-32462 (pp. 298-373)
Page) and the patents cited therein.

Among them, as the yellow coupler which can be used in the present invention, oxygen atom-releasing type and nitrogen atom-releasing type yellow two-equivalent couplers can be exemplified. Especially α
The -pivaloyl acetanilide type couplers are preferable because the fastness, especially the light fastness, of the color forming dye is excellent, while the α-benzoyl acetanilide type couplers can obtain a high color density.

The 5-pyrazolone-based magenta coupler that can be preferably used in the present invention is a 5-pyrazolone-based coupler in which the 3-position is substituted with an arylamino group or an acylamino group (among others, a sulfur atom-eliminating type two-equivalent coupler).

More preferred are pyrazoloazole couplers, and among them, pyrazolo [5,1-c] [1,2,4] triazoles described in US Pat. No. 3,725,067 are preferred,
The imidazo [1,2-b] described in U.S. Pat. No. 4,500,630 in terms of low yellow sub-absorption of a coloring dye and light fastness.
Pyrazoles are even more preferred and are described in US Pat. No. 4,540,65
The pyrazolo [1,5-b] [1,2,4] triazole described in No. 4 is particularly preferable.

Cyan couplers that can be preferably used in the present invention include naphthol-based and phenol-based couplers described in U.S. Pat.Nos. 2,474,293 and 4,052,212, and an ethyl group at the meta position of the phenol nucleus described in U.S. Pat. Phenol cyan couplers having the above alkyl groups, and other 2,5-diacylamine-substituted phenol couplers are also preferable in terms of color image fastness.

Specific examples of particularly preferable yellow, magenta and cyan couplers include Japanese Patent Application No. 61-169523 (July 18, 1986).
The compounds listed on pages 35 to 51 of Nichi Fuji Photo Film Co., Ltd.), and the following compounds can also be mentioned as preferred examples.

A colored coupler for correcting unnecessary absorption in the short wavelength range of the dye to be produced, a coupler in which a coloring dye has an appropriate diffusivity, a non-coloring coupler, a DIR coupler which releases a development inhibitor along with a coupling reaction, or Couplers that release development accelerators and polymerized couplers can also be used.

The standard amount of the color coupler used is in the range of 0.001 to 1 mol per mol of the light-sensitive silver halide, preferably 0.01 to 0.5 mol for the yellow coupler, 0.003 to 0.3 mol for the magenta coupler, and cyan coupler. Is 0.002 to 0.3 mol.

The light-sensitive material produced by using the present invention, as a color antifoggant or color mixing inhibitor, is a hydroquinone derivative, an aminophenol derivative, an amine, a gallic acid derivative, a catechol derivative, an ascorbic acid derivative, a colorless coupler, a sulfonamidephenol. You may contain a derivative etc. Typical examples of color antifoggants and color mixture inhibitors are Japanese Patent Application No. 61
-32462, pp. 600-630.

Various anti-fading agents can be used in the light-sensitive material of the present invention. Hydroquinones as organic anti-fading agents,
6-hydroxychromans, 5-hydroxycoumarans, spirochromans, p-alkoxyphenols,
Typical examples are hindered phenols centered on bisphenols, gallic acid derivatives, methylenedioxybenzenes, aminophenols, hindered amines and ether or ester derivatives obtained by silylating and alkylating the phenolic hydroxyl groups of these compounds. Can be mentioned. Further, a metal complex represented by a (bissalicylaldoximato) nickel complex and a (bis-N, N-dialkyldithiocarbamato) nickel complex can also be used.

To prevent deterioration of the yellow dye image due to heat, humidity and light,
A compound having both a hindered aomine and a hindered phenol partial structure in the same molecule as described in US Pat. No. 4,268,593 gives good results. Further, in order to prevent deterioration of the magenta dye image, particularly deterioration by light, substitution of spiroindanes described in JP-A-56-159644 and hydroquinone diether or monoether described in JP-A-55-89835. The chromans given give favorable results.

Typical examples of these anti-fading agents are Japanese Patent Application No. Sho 61-32462 401-
It is described on page 440. These compounds are usually used in an amount of 5 to 1000% by weight based on the corresponding color coupler.
By co-emulsifying with a coupler and adding to the photosensitive layer,
You can reach your purpose. In order to prevent deterioration of the cyan dye image due to heat and especially light, it is effective to introduce an ultraviolet absorber into both layers adjacent to the cyan color developing layer. An ultraviolet absorber can also be added to the hydrophilic colloid layer such as the protective layer. Representative examples of the compounds are described in Japanese Patent Application No. 61-32462, 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, gelatin is advantageously used, but other hydrophilic colloids can be used.

The light-sensitive material of the present invention includes dyes that prevent irradiation and halation, ultraviolet absorbers, plasticizers, fluorescent brighteners, matting agents, air antifoggants, coating aids, hardeners,
An antistatic agent, a slipperiness improving agent, etc. can be added.
A typical example of these additives is “Research Disclosure No.17643VIII-XIII”.
(Issued in December 1978) p25-27, and 18716 (1979)
Published in November) p647-651.

The present invention is also applicable to multilayer multicolor photographic materials having at least two different spectral sensitivities on the support. Multilayer spot color photographic materials usually have at least one red-sensitive emulsion layer, one green-sensitive emulsion layer and one blue-sensitive emulsion layer on a support.
The order of these layers can be arbitrarily selected as required. The preferred order of layer arrangement is red-sensitive, green-sensitive, blue-sensitive from the support side or green-sensitive, red-sensitive and blue-sensitive from the support side. Further, each of the above emulsion layers may be composed of two or more emulsion layers having different sensitivities, and a non-photosensitive layer may be present between two or more emulsion layers having the same sensitivity. Usually, a cyan-forming coupler is contained in the red-sensitive emulsion layer, a magenta-forming coupler is contained in the green-sensitive emulsion layer, and a yellow-forming coupler is contained in the blue-sensitive emulsion layer, but different combinations can be used depending on circumstances.

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

In the photographic light-sensitive material of the present invention, the photographic emulsion layer and other layers are described in Research Disclosure No. 17643XVII (1978).
Issued December, 2012) and European patents 0,182,2
It is coated on the support described in JP-A No. 53-63655 or JP-A No. 61-97655. Also, Research Disclosure No. 17643XV
The coating method described in p28 to 29 can be used.

When the light-sensitive material of the present invention is used for a color diffusion transfer method, a dye developing agent can be used as a color material,
The coloring material itself is alkaline (in the developing solution) and non-diffusible (non-migrating), but it is advantageous to use a coloring material that releases a diffusible dye (or its precursor) as a result of development. Is. Examples of the diffusible dye-releasing coloring material (DRR compound) include couplers and redox compounds that release diffusible dyes, and these are not only used for the coupler diffusion transfer method (wet method) but also disclosed in, for example, JP-A-58- It is also useful as a color material for a heat-developable photosensitive material (dry method) as described in 58543.

The diffusible dye-releasing redox compound (hereinafter referred to as “DRR compound”) can be represented by the following general formula.

(Ballast redox cleaving atomic group D In the formula, for (Ballast) and the redox cleaving atomic group, compounds described in JP-A No. 58-1639380, pages 12 to 22 can be used. D is a dye (or a precursor thereof). The dye moiety may be bound to the redox-cleaving atomic group via a linking group, and as the dye moiety represented by D, those described in the following documents are effective. .

Examples of yellow dyes: US Pat. Nos. 3,597,200, 3,309,199 and 4,013,633
No. 4,245,028, 4,156,609, 4,139,383,
4,195,992, 4,145,641, 4,148,643, 4,3
36,322; JP-A-51-114930, JP-A-56-71072; Research Disclosure 17630.
(1978) and 16475 (1977).

Examples of magenta dyes: US Pat. Nos. 3,453,107, 3,544,545 and 3,932,380
Issue 3,931,144, Issue 3,932,308, Issue 3,954,476,
4,233,237, 4,255,509, 4,250,246, 4,1
42,891, 4,207,104, 4,287,292; JP-A-52-
106,727, 52-106727, 53-23,628, 55-3
6,804, 56-73,057, 56-71060, 55-134
What is listed in the issue.

Examples of cyan dyes: U.S. Patents 3,482,972, 3,929,760, 4,03,635,
4,268,625, 4,171,220, 4,242,435, 414
2,891, 4,195,995, 4,147,544, 4,148,642
British Patent 1,551,138; Japanese Patent Laid-Open Nos. 54-99431 and 52-
No. 8827, No. 53-47823, No. 53-143323, No. 54-99431
No. 56-71061; European Patent (EPC) 53,037,
No. 53,040; Research Disclosure) 17,630 (1978)
And those described in No. 16,475 (1977).

A suitable coating amount of these compounds is generally about 1 × 10 ⁻⁴ to 1 × 10 ⁻² mol / m ² , preferably 2 × 10 ⁻⁴ to 2 × 10 ⁻² mol / m ² .

In the present invention, the coloring material may be contained in the silver halide emulsion layer associated therewith, or may be contained in the adjacent layer of the emulsion layer on the side to be exposed or on the side opposite thereto.

When the light-sensitive material of the present invention is used in the color diffusion transfer method, the photographic dairy material may be integrally coated on the same support as that on which the image-receiving layer is coated, or another support. It may be coated on. The silver halide photographic emulsion layer (light-sensitive element) and the image-receiving layer (image-receiving element) may be provided in the form of being combined as a film unit, or may be provided as a separate and independent photographic material. Also,
The form of the film unit may be one that is integrated through exposure, development, and viewing of the transferred image all the time, or may be a type that peels after development, but the latter type is more preferable for the present invention. It is effective.

It can be applied to various color light-sensitive materials of the present invention.

Typical examples include color reversal films for slides or televisions, color reversal papers, and instant color films. It can also be applied to full-color copiers and color hard copies for storing CRT images. The present invention also relates to "Research Disclosure" No. 17123 (19
It can also be applied to black-and-white light-sensitive materials that use a mixture of three-color couplers such as those issued in July 1978).

In the present invention, after imagewise exposure of the light-sensitive material, after or while being subjected to fogging treatment with light or a nucleating agent, development with a surface developing solution containing an aromatic primary amine color developing agent,
A positive color image can be directly formed by bleaching / fixing treatment.

As described above, the fogging treatment in the present invention is carried out in the presence of a so-called "light fogging method" which gives a second exposure to the entire surface of the photosensitive layer and a "chemical fogging method" in the presence of a nucleating agent. Either of the methods may be used. You may develop in the presence of a nucleating agent and fog light. Further, a light-sensitive material containing a nucleating agent may be fog-exposed.

The whole surface exposure, that is, the fog exposure in the "light fog method" of the present invention is performed after imagewise exposure and before and / or during the development processing. Imagewise exposed photosensitive material in developer,
Alternatively, the exposure is carried out before being dipped in a pre-bath of the developing solution or taken out of these solutions and not dried, but exposure in the developing solution is most preferable.

As the light source for fogging exposure, a light source within the photosensitive wavelength of the light-sensitive material may be used, and generally, a fluorescent lamp, a tungsten lamp, a xenon lamp, sunlight, etc. can be used.
These specific methods are described in, for example, British Patent 1,151,363.
No. 45, No. 45-12710, No. 45-12709, No. 58-6936
No. 48-9727, No. 56-137350, No. 57-129438.
No. 58-62652, No. 58-60739, No. 58-70223 (corresponding US Pat. No. 4440851), No. 58-120248 (corresponding European patent 89101A2) and the like. For a light-sensitive material having photosensitivity in all wavelength regions, for example, color light-sensitive material
A light source having a high color rendering property (as close as possible to white) as described in Nos. 56-137350 and 58-70223 is preferable. The illuminance of light is suitably 0.01 to 2000 lux, preferably 0.05 to 30 lux, and more preferably 0.05 to 5 lux. Light-sensitive materials using higher sensitivity emulsions are preferred to have low illuminance. The illuminance may be adjusted by changing the luminous intensity of the light source, dimming by various filters, changing the distance between the photosensitive material and the light source, or changing the angle between the photosensitive material and the light source. It is also possible to shorten the exposure time by using weak light at the beginning of exposure and then using stronger light.

It is preferable to immerse the light-sensitive material in a developing solution or a solution of its pre-bath so that the solution sufficiently penetrates into the emulsion layer of the light-sensitive material before irradiation with light. The time from the penetration into the liquid to the light fog exposure is generally 2 seconds to 2 minutes, preferably 5 seconds to 1 minute, and more preferably 10 seconds to 30 seconds.

The exposure time for fogging is generally 0.01 second to 2 minutes, preferably 0.1 second to 1 minute, more preferably 1 second to 40 seconds.

As the nucleating agent that can be used in the present invention, all compounds conventionally developed for the purpose of nucleating an internal latent silver halide can be applied. Two or more nucleating agents may be used in combination. More specifically, examples of the nucleating agent include "Research Disclosure".
ure) No.22,534 (issued January 1983, 50-54 pages) No.15,
162 (76-77 pages issued in November 1976) and No. 23,510 (19)
There are items described in November 1983, pages 346-352),
These are roughly classified into quaternary heterocyclic compounds (compounds represented by the general formula [NI]), hydrazine compounds (compounds represented by the general formula [N-II]) and other compounds.

General formula [N-1] (In the formula, Z represents a non-metal atom group necessary for forming a 5- to 6-membered heterocycle, Z is optionally substituted with a substituent, R ¹ is an aliphatic group, and R ² is A hydrogen atom, an aliphatic group or an aromatic group, R ¹ and R ² may be substituted with a substituent, provided that, among the groups represented by R ¹ , R ² and Z,
At least one contains an alkynyl group, an acyl group, a hydrazine group, or a hydrazine group, or R ¹ and R ² are 6
It forms a member ring and forms a dihydropyridinium skeleton.
Further, at least one of the substituents of R ¹ , R ² and Z is X ¹
It may have L ¹ _m . Here, X ¹ is an adsorption promoting group to silver halide, and L ¹ is a divalent linking group. Y is a counter ion for charge balance, n is 0 or 1, and m is 0 or 1. ) More specifically, the heterocycle completed by Z is, for example, quinolinium, benzothiazolium, benzimidazolium, pyridinium, thiazolinium, thiazolium, naphthothiazolium, selenazolium, benzoselenazolium, imidazolium, tetrazolium, And indolenium, pyrrolinium, acridinium, phenanthridinium, isoquinolinium, oxazolium, naphthoxazolium and benzoxazolium nuclei. As the substituent of Z, an alkyl group, an alkenyl group, an aralkyl group, an aryl group, an alkynyl group, a hydroxy group, an alkoxy group, an aryloxy group, a halogen atom, an amino group, an alkylthio group, an arylthio group, an acyloxy group, an acylamino group, Sulfonyl group, sulfonyloxy group, sulfonylamino group, carboxyl group, acyl group, carbamoyl group, suifamoyl group, sulfo group, cyano group, ureido group, urethane group, carbonic acid ester group, hydrazine group, hydrazone group, imino group, etc. can give. As the substituent of Z, for example, at least one is selected from the above-mentioned substituents, but when there are two or more, they may be the same or different. Further, the above substituents may be further substituted with these substituents.

Further, as a substituent of Z, a heterocyclic quaternary ammonium group completed with Z via an appropriate linking group L may be included. In this case, a so-called dimer structure is adopted.

Heterocycles completed with Z preferably include quinolinium, benzothiazolium, benzimidazolium, pyridinium, acridinium, phenanthridinium, and inquinolinium nuclei. Quinolinium and benzothiazolium are more preferable, and quinolinium is most preferable.

The aliphatic groups represented by R ¹ and R ² 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 moiety. As the substituent, those mentioned as the substituent of Z can be mentioned.

The aromatic group represented by R ² has 6 to 20 carbon atoms, and examples thereof include a phenyl group and a naphthyl group. As the substituent, those mentioned as the substituent of Z can be mentioned. R ²
Is preferably an aliphatic group, and most preferably a methyl group and a substituted methyl group.

At least one of the groups represented by R ¹ , R ² and Z has an alkynyl group, an acyl group, a hydrazine group, or a hydrazine group, or R ¹ and R ² form a 6-membered ring,
The dihydropyridinium skeleton is formed, and these may be substituted with the groups described above as the substituents for the group represented by Z. As the hydrazine group, those having an acyl group or a sulfonyl group are preferable as the substituent. As the hydrazone group, those having an aliphatic group or an aromatic group as a substituent are preferable. As the acyl group, for example, a formyl group, an aliphatic group or an aromatic ketone is preferable.

At least one of the groups represented by R ¹ , R ² and Z or the substituent on the ring is an alkynyl group or an acyl group, or R ¹ and R ² are linked to form a dihydropyridinium skeleton. The case is preferable, and the case where at least one alkynyl group is further contained is most preferable.

Preferred examples of the adsorption promoting group for silver halide represented by X ¹ include a thioamide group, a mercapto group and a 5- or 6-membered nitrogen-containing heterocyclic group.

These may be substituted with those mentioned as the substituent of Z. The thioamide group is preferably an acyclic thioamide group (eg, thiourethane group, thioureido group, etc.)
Is.

The mercapto group for X ¹ is particularly a heterocyclic mercapto group (for example, 5-mercaptotetrazole, 3-mercapto-1,2,4-triazole, 2-mercapto-1,
3,4-thiadiazole) are preferred.

The 5- or 6-membered nitrogen-containing heterocycle represented by X ¹ is
It is composed of a combination of nitrogen, enzyme, sulfur and carbon, and preferably forms imino silver, and examples thereof include benzotriazole.

Examples of the divalent linking group represented by L ¹ include C, N, S and O.
An atom or atomic group containing at least one of the above. Specifically, for example, an alkylene group, an alkenylene group, an alkynylene group, an arylene group, -O-, -S-, -NH-,
-N -, - CO -, - SO 2 - ( may have these groups the substituents), is made of a single or a combination thereof and the like.

Examples of the counter ion Y for charge balance include bromine ion, chlorine ion, iodine ion, p-toluenesulfonate ion, ethylsulfonate ion, perchlorate ion,
Examples thereof include trifluoromethanesulfonate ion and thiocyanate ion.

Examples of these compounds and their synthetic methods are described, for example, in Research Disclosure No. 2
2,534 (issued January 1983, pages 50-54), and No. 23,213
(Patents issued on August 1983, pages 267 to 270), Japanese Patent Publication Nos. 49-38,164, 52-19,452, 52-47,326, JP-A-52-69,613, 52-3,426, No. 55-138,742,
60-11,837, U.S. Pat.Nos. 4,306,016, and 4,47.
No. 1,044.

Specific examples of the compound represented by formula [N-1] are shown below, but the invention is not limited thereto.

(N-I-1), 6-ethoxy-2-methyl-1-propargylquinolinium bromide (N-I-2), 2,4-dimethyl-1-propargylquinolinium bromide (N-I-3) ), 2-Methyl-1- {3- [2- (4-methylphenyl) hydrazono] butyl} quinolinium iodide (NI-4), 3,4-dimethyl-dihydropyrido [2,1
-B] Benzothiazolium bromide (N-1-5), 6-ethoxythiocarbonylamino-2
-Methyl-1-propargylquinolinium trifluoromethanesulfonate (N-I-6), 2-methyl-6- (3-phenylthioureido) -1-propargylquinolinium bromide (N-I-7), 6- (5-benzotriazolecarboxamido) -2-methyl-1-propargylquinolinium trifluoromethanesulfonate (N-I-8), 6- [3- (2-mercaptoethyl) ureido] -2-methyl- 1-Propargylquinolinium trifluoromethanesulfonate (N-I-9), 6- {3- [3- (5-mercapto-thiazazol-2-ylthio) propyl] ureido}-
2-Methyl-1-propargylquinolinium trifluoromethanesulfonate (NI-10), 6- (5-mercaptotetrazole-1
-Yl) -2-methyl-1-propargylquinolinium iodide General formula (N-II) (In the formula, R ²¹ represents an aliphatic group, an aromatic group, or a heterocyclic group; R ²² represents 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, a sulfoxy group, a phosphoryl group, or an iminomethylene group (HN = C
R ²³ and R ²⁴ are both hydrogen atoms, or one is a hydrogen atom and the other is an alkylsulfonyl group, an arylsulfonyl group or an acyl group.
However, a hydrazone structure (NN = C) may be formed in a form including G, R ²³ , R ²⁴ and hydrazine nitrogen.
Further, the above-mentioned groups may be substituted with a substituent, if possible. ) More specifically, R ²¹ may be substituted with a substituent, and examples of the substituent include the following. These groups may be further substituted. For example, alkyl group, aralkyl group, alkoxy group, alkyl or aryl group, substituted amino group, acylamino group, sulfonylamino group, ureido group, urethane group, aryloxy group, sulfamoyl group, carbamoyl group, aryl group, alkylthio group, arylthio group. , A sulfonyl group,
Examples include sulfinyl group, hydroxy group, halogen atom, cyano group, sulfo group and carboxyl group. Of these, the ureido group is particularly preferable.

When possible, these groups may be linked to each other to form a ring.

R ²¹ is preferably an aromatic group, an aromatic heterocycle or an aryl-substituted methyl group, and more preferably an aryl group (eg, a phenyl group, a naphthyl group, etc.).

R ²² is preferably a hydrogen atom,
Examples thereof include an alkyl group (for example, a methyl group) and an aralkyl group (for example, a 0-hydroxybenzyl group), and a hydrogen atom is particularly preferable.

As the substituent for R ^22, the substituents enumerated for R ²¹ can be applied, and for example, an acyl group, an acyloxy group, an alkyl or aryloxycarbonyl group, an alkenyl group, an alkynyl group, a nitro group and the like can also be applied.

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

R ²¹ or R ²² , and especially R ²¹ may contain a diffusion resistant group such as a coupler, a so-called ballast group (particularly preferable when linked by an ureido group), and is adsorbed on the surface of the silver halide grain. Promoting group X ²
It may have L ² m ² .

Here, X ² has the same meaning as X ¹ in the general formula [NI],
Preferred are a thioamide group (excluding thiosemicarbazide and its substitution product), a mercapto group, or a 5- to 6-membered nitrogen-containing heterocyclic group. L ² represents a divalent linking group,
It has the same meaning as L ^{1 in} formula [N-1]. m ² is 0 or 1.

More preferred X ² is an acyclic thioamide group (eg, thioureido group, thiourethane group, etc.), a cyclic thioamide group (ie, a mercapto-substituted nitrogen-containing heterocycle, for example, 2
-Methylcaptothiadiazole group, 3-mercapto-1,
2,4-triazole group, 5-mercaptotetrazole group, 2-mercapto-1,3,4-oxadiazole group, 2
-Mercaptobenzoxazole group) or a nitrogen-containing heterocyclic group (eg, benzotriazole group, benzimidazole group, indazole group, etc.).

The most preferable X ² depends on the photosensitive material used. For example, when a color material (so-called coupler) which forms a dye by a coupling reaction with an oxidized product of a p-phenylenediamine-based developer is used in a color light-sensitive material, X ² is a mercapto-substituted nitrogen-containing heterocycle or imino. Nitrogen-containing heterocycles that form silver are preferred. Further, in a color light-sensitive material, when a coloring material that produces a diffusible dye by cross-oxidizing an oxidized product of a developer (a so-called DRR compound) is used, X ² is an acyclic thioamide group, or a mercapto-substituted nitrogen-containing heterocycle. preferable.

Further, in the black-and-white light-sensitive material, X ² is preferably a mercapto-substituted nitrogen-containing heterocycle or a nitrogen-containing heterocycle forming imino silver.

A hydrogen atom is most preferable as R ²³ and R ²⁴ .

A carbonyl group is most preferable as G in the general formula (N-II).

Further, as the general formula (N-II), one having an adsorption group to silver halide or one having an ureido group is more preferable.

Examples of these compounds and the synthesis method thereof, as an example of a hydrazine-based nucleating agent having a silver halide adsorptive group, for example, U.S. Patent Nos. 4,030,925, 4,080,207, and 4,
031,127, coaxial 3,718,470, same 4,269,929, same
4,276,364, 4,278,748, 4,385,108, 4,459,347, 4,478,928, 4,560,638,
British Patent No. 2,011,391B, JP 54-74,729, 55-
Nos. 163,533, 55-74,536, and 60-179,734.

Other hydrazine-based nucleating agents include, for example, JP-A-57
-86,829, U.S. Pat. Nos. 4,560,638, 4,487, and further 2,563,785 and 2,588,982.

Specific examples of the compound represented by formula (N-II) 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) proyl] ureido} phenylsulfonylamino] -phenyl} hydrazine (N-II-3), 1-formyl-2- {4- [3- (5-
Mercaptotetrazol-1-yl) benzamido] phenyl} hydrazine (N-II-4), 1-formyl-2- [4- {3- [3-
(5-mercaptotetrazol-1-yl] phenyl]
Ureido} phenyl] hydrazine (N-II-5), 1-formyl-2- [4- {3- [N-
(5-Mercapto-4-methyl-1,2,4-triazol-3-yl] carbamoyl] propanamide} phenyl] hydrazine (N-II-6), 1-formyl-2- [4- {3- [ N-
[4- (3-mercapto-1,2,4-triazole-4-
Yield] phenyl] carbamoyl} -propanamide] phenyl} hydrazine (N-II-7), I-formyl-2- [4- {3- [N-
(5-Mercapto-1,3,4-thiazoazol-2-yl) carbamoyl] propanamide) phenyl] hydrazine (N-II-8), 2- [4- (benzotriazole-5-
Carboxamido) phenyl] -1-formylhydrazine (N-II-9), 2- [4- {3- [N- (benzotriazole-5-carboxamido) carbamoyl] propanamide} phenyl] -1-formylhydrazine (N -II-10), 1-formyl-2- {4- [1- (N-
Phenylcarbamoyl) thiosemicarbazide] phenyl} hydrazine (N-II-11), 1-formyl-2- {4- [3- (3-
Phenylthioureido) benzamido] phenyl} hydrazine (N-II-12), 1-formyl-2- [4- (3-hexylureido) phenyl] hydrazine The nucleating agent used in the present invention is a sensitive material or a sensitive material. It can be contained in the processing solution, and preferably in the photosensitive material.

When it is contained in the light-sensitive material, it is preferably added to the inner latent type silver halide emulsion layer, but as long as it is diffused during coating or during processing and the nucleating agent is adsorbed on the silver halide, it is added to other layers. For example, it may be added to the intermediate layer, the undercoat layer or the back layer. When the nucleating agent is added to the processing solution, it may be contained in a developing solution or a low pH pre-bath as described in JP-A-58-178350.

When the nucleating agent is contained in the light-sensitive material, the amount used is preferably 10 ^-8 to 10 ^-2 mol, and more preferably 10 ^-7 to 10 ^-3 mol, per mol of silver halide.

When the nucleating agent is added to the treatment liquid, the amount used is
It is preferably 10 ^-5 to 10 ^-1 mol, more preferably 10 ^-5
-4 to 10 ^-2 mol.

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 the development.

Hydroquinones, (eg US Pat. No. 3,227,552,
Compounds described in 4,279,987: Chromans (for example, U.S. Pat. No. 4,268,621, Japanese Patent Laid-Open No. 54-103031, Research Disclosure Magazine No. 18264 (issued in June 1979) 333-3.
Compounds described on page 34) Quinones (for example, Research Disclosure Magazine No. 21206 (compounds described on pages 433 to 434, December 1981)): Amines (for example, described in U.S. Pat. No. 4150993 and JP-A-58-174757). Compounds: Oxidizing agents (for example, JP-A-60-260039, Research Disclosure No. 1)
6936 (published in May, 1978), pages 10 to 11): catechols (for example, JP-A-55-21013 and JP-A-55-65944)
No., described)): a compound that releases a nucleating agent during development (for example, a compound described in JP-A-60-1007029): thioureas (for example, a compound described in JP-A-60-95533): spirobisindane Class (for example, compounds described in JP-A-55-69544).

Examples of the nucleation accelerator that can be used in the present invention include tetrazaindenes, triazaindenes, and pentazaindenes having at least one mercapto group optionally substituted with an alkali metal atom or an ammonium group. And JP-A-61-136948 (pages 2 to 6 and 16
~ 43), Japanese Patent Application No. 61-136949, (Pages 12-43) and 61-
The compounds described in No. 15348 (pages 10 to 29) can be mentioned.

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

(A-1) 3-mercapto-1,2,4-triazolo [4,5-
a] Pyridine (A-2) 3-mercapto-1,2,4-triazolo [4,5-
a] Pyrimidine (A-3) 5-mercapto-1,2,4-triazolo [1,5-
a] pyrimidine (A-4) 7- (2-dimethylaminoethyl) -5-mercapto-1,2,4-triazolo [1,5-a] pyrimidine (A-5) 3-mercapto-7-methyl- 1,2,4-triazolo [4,5-a] pyrimidine (A-6) 3,6-dimercapto-1,2,4-triazolo [4,
5-b] pyridazine (A-7) 2-mercapto-5-methylthio-1,3,4-
Thiazoazole (A-8) 3-Mercapto-4-Tityl-1,2,4-triazole (A-9) 2- (3-Dimethylaminopropylthio)-
5-Mercapto-1,3,4-thiazoazole hydrochloride (A-10) 2- (2-morpholinoethylthio) -5-mercapto-1,3,4-thiazoazole hydrochloride (A-11) 2-mercapto- 5-Methylthiomethylthio-1,3,4-thiadiazole sodium salt.

(A-12) 4- (2-morpholinoethyl) -3-mercapto-1,2,4-triazole (A-13) 2- [2- (2-dimethylaminoethylthio) ethylthio] -5-mercapto- 1,3,4-thiazoazole hydrochloride In this case, the nucleation accelerator is preferably added in the silver halide emulsion or in the layer adjacent thereto.

The amount of nucleation accelerator added is 10 ^-6 to 10 per mol of silver halide.
^It is preferably ^-2 mol, more preferably 10 ^-5 to 10 ^-2 mol.

When the nucleation accelerator is added to the processing solution, that is, the developing solution or its pre-bath, the amount is preferably 10 ^-8 to 10 ^-3 mol, and more preferably 10 ^-7 to 10 ^-4 mol. .

Also, two or more nucleation accelerators can be used in combination.

The color developing solution used for the development processing of the light-sensitive material of the present invention is an alkaline solution containing substantially no silver halide solvent and preferably containing an aromatic primary amine color developing agent as a main component. Although aminophenol compounds are also useful as color developing agents, p-phenenediamine 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 thereof include -methyl-4-amino-N-ethyl-N-methoxyethylaniline and salts thereof such as sulfate and hydrochloride. Other color-developing agents include LFA Mason's "Photographic Processing Chemistry", Focal Press (1966) (LFA
Mason “Photographic Processing Chemistry”, FocalPre
ss), pages 226-229, U.S. Pat.Nos. 2,193,015 and 2,592,364.
Nos. 48-64933, and the like. If desired, two or more color developing agents can be used in combination.

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

Further, as preservatives, JP-A-52-49828 and JP-A-56-47038
No. 56-32140, No. 59-160142 and U.S. Pat. No. 37465.
Aromatic polyhydroxy compounds described in US Pat.
Hydroxyacetones described in 5,503 and British Patent 1,306,176; α-aminocarbonyl compounds described in JP-A-52-143020 and 53-89425; described in JP-A-57-44148 and 57-53749 Various metals of JP-A-52-10272
Various saccharides described in No. 7; hydroxamic acids described in No. 52-27638; α-α'-dicarbonyl compounds described in No. 59-160141; salicylic acids described in No. 59-180588; 54-3532
And the gluconic acid derivatives described in JP-A-56-75647 and the like. Two or more kinds of these preservatives may be used in combination, if necessary. 4,5-
Addition of dihydroxy-m-benzenesulfonic acid, poly (ethyleneimine), triethanolamine and the like is preferable. Further, it is preferable to add a substituted phenol such as p-nitrophenol. Further, it is also preferable to use the alkylhydroxylamine compound described in JP-A-54-3532. In particular, the alkylhydroxylamine compound is preferably used in combination with the above preservative.

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

The pH of the color developer of the present invention can be applied in the range of 9 to 14, preferably 9.5 to 12.0, particularly preferably 10 to 11.
Is 2. Various buffers can be used to maintain the above pH. Examples of buffering agents include carbonates such as potassium carbonate and phosphates such as potassium phosphate.
The compounds described on pages 11 to 22 of 61-32462 can be used.

Further, various chelating agents can be used in the color developing solution as a precipitation preventing agent for calcium or magnesium or for improving the stability of the color developing solution.

Examples of chelating agents include aminopolycarboxylic acids described in JP-B-48-030496 and 44-30232, and JP
6-97347, Japanese Patent Publication No. 56-39359 and West German Patent 2,227,639
Organic phosphonic acids described in JP-A Nos. 52-102726 and 53
-42730, 54-121127, 55-126241 and 55
No. 65956, Phosphorcarboxylic Acids Equivalently, Others JP-A-58-195845, JP-A-58-203440 and JP-B-53-40
Examples thereof include compounds described in No. 900 and the like. Two or more of these chelating agents may be used in combination, if necessary.
The amount of these chelating agents added may be an amount sufficient to block the metal ions in the color developing solution. Eg 1
It is about 0.1g to 10g.

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

As the development accelerator, Japanese Patent Publication Nos. 37-16088 and 37-5987.
No. 38-7826, No. 44-12380, No. 45-9019 and U.S. Pat. No. 3813247, and other thioether compounds;
P-phenylenediamine compounds described in JP-A-52-49829 and JP-A-50-15554, JP-A-50-137726, JP-B-44-30074, JP-A-56-156826 and JP-A-56-156826. -43429 and other quaternary ammonium salts; US Pat. No. 2,610,122
And p-aminophenols described in U.S. Pat. No. 4,119,462; U.S. Pat. Nos. 2,494,903, 3,128,182 and 4,230,79.
No. 6, No. 3,253,919, Japanese Patent Publication No. 41-11431, U.S. Pat.
82,564, 2,596,926 and 3,582,346 and the like amine compounds; JP-B-37-16088, JP-A-42-25201,
U.S. Pat.Nos. 3,128,183, Japanese Patent Publication Nos. 41-11431, 42-2388
No. 3, polyalkylene oxides described in U.S. Pat. it can. Especially thioether compounds and 1-phenyl-
The 3-pyrazolidones are preferred.

In the present invention, an optional antifoggant can be added to the color developer, if necessary. As the antifoggant, alkali metal halides such as potassium bromide, sodium chloride and potassium iodide and organic antifoggants may be used. Examples of the organic antifoggants include benzotriazole, 6-nitrobenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chloro-benzotriazole, 2-thiazolyl-benzimidazole, 2 -Nitrogen-containing heterocyclic compounds such as thiazolylmethyl-benzimidazole and hydroxyazaindolizine, mercapto-substituted heterocyclic compounds such as 2-mercaptobenzimidazole and 2-mercaptobenzothiazole, adenine and mercapto-substituted aromatic compounds such as thiosalicylic acid Can be used. These antifoggants are
Although it may be eluted from the color light-sensitive material during the processing and accumulated in the color developing solution, it is preferable that the accumulated amount thereof is small from the viewpoint of reducing the discharge amount.

The color developer of the present invention preferably contains a fluorescent whitening agent. As a fluorescent whitening agent, 4,4-diamino-2,2 '
-Disulfostilbene compounds are preferred. Addition amount is 0
-5g / preferably 0.1g-2g /.

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

The photographic emulsion layer after color development is usually bleached. The bleaching treatment may be carried out simultaneously with the fixing treatment by one-bath bleach-fixing, or may be conducted individually. Further, in order to speed up the processing, a processing method of performing bleach-fixing processing after bleaching processing or a method of performing bleach-fixing processing after fixing processing may be used. Aminopolycarboxylic acid iron complex salt is usually used as a bleaching agent in the bleaching solution or the bleach-fixing solution of the present invention. As the additive used in the bleaching solution or the bleach-fixing solution of the present invention,
Various compounds described on pages 22 to 30 of Japanese Patent Application No. 61-32462 can be used. After the desilvering process (bleach-fixing or fixing), a treatment such as washing with water and / or stabilization is performed. It is preferable to use softened water as the washing water or the stabilizing solution. Examples of the water softening treatment and the method include a method using an ion exchange resin or a reverse osmosis device described in Japanese Patent Application No. 61-131632. As a concrete method for these, it is preferable to carry out the method described in Japanese Patent Application No. 61-131632.

Further, various compounds described in Japanese Patent Application No. 61-32462, pp. 30-36 can be used as additives used in the washing and stabilizing steps.

It is preferable that the amount of replenisher in each processing step is small. The amount of the replenisher is preferably 0.1 to 50 times, more preferably 3 to 30 times the carry-in amount of the pre-bath per unit area of the light-sensitive material.
Double.

When the DRR compound is used in the present invention, any silver halide developing agent (or electron donor) can be used as long as it can be cross-oxidized.

Such developers may be included in the alkaline developer (processing element) or in the appropriate layers of the photographic element. Examples of the developing agent that can be used in the present invention are as follows.

Hydroquinone, aminophenols such as N-methylaminophenol, 1-phenyl-3-pyrazolidinone, 1-phenyl-4,4-dimethyl-3-pyrazolidinone, 1-phenyl-4-methyl-4-oxymethyl-3
-Pyrazolidinone, N, N-diethyl-p-phenylenediamine, 3-methyl-N, N-diethyl-p-phenylenediamine, 3-methoxy-N-ethoxy-p-phenylenediamine and the like.

Among the materials listed here, a black-and-white developer, which has the property of generally reducing the stain type of the image receiving layer (mordanting layer) as in the case of the above-mentioned alkaline developing solution, is particularly preferable.

When the light-sensitive material of the present invention is used for a diffusion transfer film unit, it is preferably treated with a viscous developer.
This viscous developer is a liquid composition containing processing components necessary for development of a silver halide emulsion (and formation of a diffusion transfer dye image), the main solvent being water, and methanol,
It may also contain a hydrophilic solvent such as methyl cellosolve.
Preferably the treatment composition contains a hydrophilic polymer such as high molecular weight polyvinyl alcohol, hydroxyethyl cellulose, sodium carboxymethyl cellulose.
These polymers are added to the treatment composition at room temperature for one or more voices,
It is preferable to use it so as to give a viscosity of about 500 to 1000 voices.

The above-mentioned treatment composition is described in U.S. Patent Nos. 2,543,181 and 2,643,8.
86, 2,653,732, 2,723,051, 3,056,491
No. 3,056,492, No. 3,152,515, etc., it is preferable to use by filling a container that can be ruptured by pressure.

(Example) Next, the present invention will be described in detail with reference to examples, but the present invention is not limited to the following examples.

Example 1. Emulsions A, B, C and D were prepared according to the method shown below.

Emulsion A An aqueous solution of potassium bromide and an aqueous solution of silver nitrate were added to an aqueous gelatin solution to which 0.3 g of 3,4-dimethyl-1,3-thiazoline-2-thione was added per 1 mol of Ag at 75 ° C with vigorous stirring.
It takes about 20 minutes to add them at the same time, and the average particle size is 0.4 μm.
An octahedral monodisperse silver bromide emulsion was obtained. Chemical sensitization treatment was carried out by adding 6 mg of sodium thiosulfate and potassium chloroaurate (tetrahydrate) per mol of silver to this emulsion and heating at 75 ° C. for 80 minutes. The silver bromide grains thus obtained were used as cores for further growth for 40 minutes in the same precipitation environment as in the first time, and finally the average grain size was determined.
A 0.7 μm octahedral monodisperse core / shell silver bromide emulsion was obtained. After washing and desalting, each emulsion contained 1.5m of silver.
Sodium thiosulfate and chloroauric acid (tetrahydrate) in an amount of g were added, and the mixture was heated at 60 ° C. for 60 minutes for chemical sensitization to obtain an internal latent image type silver halide emulsion A.

Emulsion B 30 g of gelatin was added to the mixed solution 1 having a concentration of 0.5 mol of KBr, 0.2 mol of NaCl and 0.015 mol of KI, and dissolved at 700C, and 700 cc of 1 mol of silver nitrate was mixed. It was added to the liquid over 20 minutes, and physical ripening was performed for 20 minutes.

Then, the mixture was washed with water to remove the water-soluble halide, 20 g of gelatin was added, and the total amount was adjusted to 1200 cc with water. A silver halide emulsion having an average grain size of 0.4 μm was obtained.

To 300 cc of this emulsion, 1 mol / silver nitrate aqueous solution at 60 ° C 5
00 cc and 500 cc of 2 mol / sodium chloride aqueous solution were simultaneously added to precipitate silver chloride shell, followed by washing with water. A silver halide emulsion B having an average grain size of 0.7 μm was obtained.

Emulsion C An aqueous solution of potassium bromide and an aqueous solution of silver nitrate were simultaneously added to an aqueous solution of gelatin with vigorous stirring at 75 ° C for about 90 minutes to give an octahedral silver bromide emulsion having an average grain size of about 0.8μ. Obtained (core particles). However, before precipitation of silver halide grains in this emulsion, 0.65 g of 3,4-dimethyl-1,3-
Thiazoline-2-thione was added and the pH was about 6 during the precipitation process.
And pAg was kept at about 8.7. In this silver bromide grain,
Chemical sensitization was performed by adding 3.4 mg of sodium thiosulfate and 3.4 mg of potassium chloroaurate (tetrahydrate) per mol of silver. The chemically sensitized grains were further grown in the same precipitation environment to form core grains, and finally the octahedron core / 1.2 μ /
Ciel silver bromide grains were formed. In addition to this Iodokari 9.
Emulsion C was obtained by adding 6 × 10 ⁻⁴ mol / silver mol and 4.2 × 10 ⁻² g / Ag mol of N-vinylpyrrolidone polymer (weight average molecular weight 38,000).

Emulsion D An aqueous solution of potassium bromide and an aqueous solution of silver nitrate were stirred vigorously in an aqueous gelatin solution containing potassium bromide at about 75 ° C.
A silver bromide emulsion was obtained by mixing at the same time for 60 minutes. Before precipitation (simultaneous mixing), as a silver halide emulsion in a gelatin aqueous solution, 150 m per mol of silver was used.
g 3,4-Dimethyl-1,3-thiazoline-2-thione and 15 g benzimidazole were added. When the precipitation is complete,
Octahedral silver bromide crystals were formed with an average grain size of about 0.8 microns. Next, 4.8 mg of sodium thiosulfate per mol of silver and 2.4 mg of potassium chloroaurate per mol of silver were added to the silver bromide grains, and the mixture was heated at 75 ° C. for 80 minutes for chemical sensitization. The inner core (core) silver bromide emulsion thus chemically sensitized was mixed for the first time, and similarly, each aqueous solution of potassium bromide and silver nitrate was simultaneously mixed for 45 minutes to simultaneously form an internal latent image type core. / Ciel silver bromide emulsion was precipitated, and hydrogen peroxide was used as an oxidizer at 2.5 g / mol A
After adding g and heating at 75 ℃ for 8 minutes, wash with water and average particle size
A 1.0 micron emulsion was obtained.

Next, to this internal latent image type core / shell silver bromide emulsion, 0.75 mm of sodium thiosulfate per 1 mol of silver and 20 mg of poly (N-vinylpyrrolidone) per 1 mol of silver were added, and the mixture was heated at 60 ° C. for 60 minutes to chemically analyze the grain surface. An image (ripening) was performed to obtain an emulsion D.

Full-layer color photographic papers 101 to 104 having the layer constitution shown in Table 1 were prepared on a paper support laminated on both sides of polyethylene using each of the core / shell type internal latent image emulsions A, B, C and D. The coating liquid was prepared as follows.

Preparation of coating liquid for the first layer: 10 g of cyan coupler (a) and 2.3 g of color image stabilizer (b), 10 ml of ethyl acetate and 4 ml of solvent (c)
Was dissolved, and this solution was emulsified and dispersed in 90 ml of a 10% gelatin aqueous solution containing 5 ml of 10% sodium dodecylbenzenesulfonate. On the other hand, the above silver halide emulsion (Ag70g / Kg
To the content, the following red-sensitive dye was added in an amount of 2.0 × 10 ^-4 mol per mol of silver halide to prepare a red-sensitive emulsion (90 g). The emulsified dispersion, the emulsion, and the development accelerator are mixed and dissolved.
The concentration was adjusted with gelatin so that the composition shown in the table was obtained, and the nucleating agent (n) was 2 × 10 ^-6 mol per 1 mol of Ag and the nucleation accelerator (o) was 6 × 10 ^-4 mol per 1 mol of Ag. In addition, a coating liquid for the first layer was prepared.

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

The following were used as the spectral sensitizer for each emulsion.

The following dyes were used as anti-irradiation dyes.

Structural formulas of compounds such as couplers used in this example are as follows.

(K) Solvent (isoC ₉ H ₁₉ O ₃ P = O After the color printing papers 101 to 104 produced in this manner and wedges (1/10 seconds, 10 CMS) are applied, the following processing step A is performed.
Then, the color image density was measured.

The results obtained are shown in Table 2. Processing Step A Time Temperature Color Development 3 minutes 30 seconds 33 ° C Bleach-fixing 1 minute 30 seconds 33 ° C Stabilizer 2 minutes 33 ° C Here, the benzyl alcohol concentration and diethylene glycol concentration in the color developing solution are as shown in Table 2. It changed and processed.

The pH was adjusted with aqueous ammonia or hydrochloric acid.

Adjust the pH with potassium hydroxide or hydrochloric acid.

As is clear from Table 2, in the developer having the sulfite ion concentration and the hydroxyamine concentration according to the present invention, the maximum concentration was relatively high when the color developer containing substantially no benzyl alcohol was used. It can be seen that not only is the color developed equally, but the minimum density is also clearly reduced, and a preferable white background is obtained.

In the examples, only the yellow density was shown, but similar results were obtained for the maximum and minimum densities of magenta and cyan.

Example 2. Full-layer color photographic paper 105 as in Example 1, except that the compound and its addition amount were changed as shown in Table 4 below.
.About.108 (emulsion A to D, respectively) were prepared.

The following compounds were used as a nucleating agent and a nucleation accelerator.

The color printing papers 101 to 108 thus prepared were processed in the same manner as in Example 1 except that the color developing and bleach-fixing solutions were changed as follows.

Table 5 shows the results of the above processing.

As is clear from Table 5, the minimum density of each color photographic paper is clearly reduced in the case of being treated with the color developer containing substantially no benzyl alcohol, as compared with the case of containing the benzyl alcohol. However, the maximum concentration is not sufficient. On the other hand, when treated with a color developing solution containing neither hydroxylamine sulfate nor sodium sulfite (color developing solutions C and D), good whiteness was maintained and the maximum density was further increased. did. Although only the yellow image is shown in this example, the same results as the yellow image were obtained for the magenta and cyan images.

Example 3 The color photographic paper 101 prepared in Example 1 was imagewise exposed and then continuously processed at 10 m ² per day for 30 days by a sheet-conveying type automatic developing machine which is continuously processed in the following processing steps. After continuous processing, the sample subjected to wedge exposure (1/10 second, 10 CMS) was processed, and the color image density was measured. The results are shown in Table 7.

Continuous processing was carried out using the following color developing solution (e) or (e).

Rinsing water Both the tank liquid and the replenishing liquid are well water of the following water quality, and H type strong acidic cation exchange resin (Mitsubishi Kasei Co., Ltd., Diaion SK-1)
B) and OH type strong acid group anion exchange resin (Mitsubishi Kasei Co., Ltd., Diaion SA-10A) are passed through a column to soften the water, and then 20 mg of sodium 2-chlorinated isocyanurate per wash water is added. And used as washing water.

As is clear from Table 8, in the case of continuous processing with the color developing solution of the present invention, a preferable image having a lower minimum density than that of the comparative example was obtained as in the above-mentioned Examples.

Example 4 The color photographic light-sensitive material 101 prepared in Example 1 was processed in the same manner as in Example 1 except that the following color developing solution was used and the composition of other processing solutions and the processing steps were the same.

The results obtained are shown in Table 8.

As is clear from Table 8, when the color developing solution having the sulfite ion concentration and the hydroxylamine concentration according to the present invention was processed, the minimum density (stain) was low and a preferable image having a high maximum density was obtained.

(Effects of the Invention) From the above results, according to the present invention, a sufficient maximum image density (coloring density) and a low minimum image density can be obtained even if a short time processing is carried out with a color developer containing substantially no benzyl alcohol. It is possible to form a positive color image directly.

Further, according to the present invention, it is possible to effectively prevent the occurrence of a re-inverting negative image.

Further, it is possible to form a direct positive color image having no color restoration failure of the cyan dye and having excellent image storability, excellent stability of the developer, and an increase in fog density and a reversal negative image during continuous processing. It is possible to form a direct positive color image in which the occurrence of is significantly reduced.

Claims (2)

[Claims] 1. A light-sensitive material containing at least one prefogged internal latent image type silver halide emulsion layer and a color image-forming coupler on a support after imagewise exposure, prior to or before development. In the method of directly forming a positive color image by developing, bleaching and fixing with a surface color developing solution containing an aromatic primary amine color developing agent in the presence of fog exposure and / or nucleating agent. The developer contains substantially no benzyl alcohol, contains hydroxylamine or a salt thereof at a concentration of 1.0 × 10 ^-2 mol or less per developer, and contains sulfite ion at 1.0 × 1 per developer.
A direct positive color image forming method characterized by containing at a concentration of 0 ^-2 mol or less. 2. The method according to claim 1, wherein the color developing solution contains sulfite ions at a concentration of 2 × 10 ⁻³ mol or less per developing solution.