JPH0652386B2 - Direct positive color image forming method - Google Patents

Description

The present invention relates to a photographic image forming method, and more particularly to a direct positive image forming method.

[Conventional technology]

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 forming a positive image using a direct positive silver halide photographic light-sensitive material, except for special ones, are 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 develops a positive image after development by destroying fog nuclei (latent image) in the exposed area by utilizing solarization or the Herschel effect. I will get it.

The other type is one in which an internal latent image type silver halide emulsion which is not fogged is used and surface development is carried out either after image exposure and after fog treatment or while fog treatment is carried out to directly obtain a positive image.

Further, the above-mentioned internal latent image type silver halide photographic emulsion is a type of silver halide photographic in which a silver halide grain has a photosensitive nucleus mainly inside and a latent image is mainly formed inside the grain upon exposure. An emulsion.

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, US Pat. Nos. 2,592,250, 2,466,957, 2,497,875, 2,588,982, 3,371,322, and 3,761,266. No. 3,761,276, No. 3,796,577 and British Patent No. 1,151,3.
No. 63, No. 1,150,533, No. 1,011,06
No. 2 The items described in each specification are the main ones.

According to the above method, the surface desensitizing effect caused by the so-called internal latent image generated inside the silver halide by the first imagewise exposure selectively causes only the surface of the silver halide grains in the unexposed area. A photographic image (direct positive image) is formed on the unexposed portion by generating fog nuclei and then subjecting to a usual 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 "photofogging method" (for example, British Patent No. 1,151,
363) and a nucleating agent called "chemical fogging method" (nuc
It is known to use a "leating agent)".

To directly form a positive color image, after performing fog processing on the internal latent image type silver halide light-sensitive material, or performing surface color development processing while performing fog processing, bleaching,
It can be achieved by fixing (or bleach-fixing) processing. 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 the optical fogging method or the chemical fogging method, the developing speed is slower and the processing time is longer than in the case of obtaining a normal negative image. The method of reducing the processing time by increasing the pH and / or the liquid temperature of the developing solution has been used. However, there is generally 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, and the carbon dioxide gas in the air is absorbed to lower the pH. As a result, there is a problem that the developing activity is significantly reduced.

Further, the optical fogging method is practically advantageous without being affected by the above-mentioned conditions, but it still has a problem in providing it for various purposes in a wide range of photographic fields. That is, the "photofogging method" is, as described in JP-A-56-51734, appropriate exposure depending on the type and characteristics of silver halide used for forming fog nuclei by photolysis of silver halide. Illuminance and exposure amount are different.

For example, Japanese Patent Publication No. 54-12709 describes a method of uniformly exposing the entire surface with light of low illuminance. However, in order to obtain good direct positive image characteristics, it is necessary to expose with light of relatively low illuminance within a certain limited range, and sufficient maximum density cannot be obtained at lower illuminance,
Further, at higher illuminance, not only the maximum density is lowered, but also the minimum density is significantly increased, so that the image quality of the direct positive image in the highlight region is significantly deteriorated.

Further, since exposure with a relatively low illuminance requires a long time, it is practically disadvantageous from the viewpoint of speeding up the processing.

In order to keep the developing activity high, it is preferable to use a benzoyl type coupler as the yellow coupler, but when the above benzoyl type coupler is used, the photobleaching property is inferior.

On the other hand, when using a pivaloyl type as a yellow coupler in order to maintain good photobleachability, it is difficult to obtain a sufficient maximum image density because of low developing activity, and a high maximum image density is required. If a long-term development is attempted to obtain the image, the minimum image density is also increased, and it has been desired to solve this problem.

Accordingly, it is a first object of the present invention to provide a direct positive image forming method having good photobleaching resistance and providing high maximum image density.

Further, a second object of the present invention is to provide a method for forming a direct positive image having excellent photobleaching resistance and having a sufficient maximum density by rapid development processing.

[Means for Solving the Problems]

The above object of the present invention is to develop a photographic 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 and development. In the method of directly forming a positive image by subjecting the entire surface to exposure before or during development, the photographic light-sensitive material contains at least one compound represented by the following general formula (I), The silver halide grains contained in the light-sensitive material are silver chlorobromide grains having a silver bromide content in the range of 80 mol% to 45 mol%, and the illuminance is continuously or stepwise during the whole surface exposure. And a direct positive color image forming method characterized by irradiating while increasing or decreasing the amount.

General formula (I) In the formula, Z represents a group capable of splitting off during a coupling reaction with an oxidized product of a developing agent, G ₁ represents a halogen atom or an alkoxy group, and G ₂ represents a hydrogen atom, a halogen atom or a substituent. Represents a good alkoxy group. R represents an alkyl group which may have a substituent.

The yellow coupler used in the present invention is represented by the above general formula (I).

In the formula (I), Z represents a group capable of splitting off during a coupling reaction with an oxidized product of a developing agent, G ₁ represents a halogen atom or an alkoxy group, and G ₂ represents a hydrogen atom, a halogen atom or a substituent. Represents an optionally substituted alkoxy group.
R represents an alkyl group which may have a substituent.

More specifically, when Z represents a coupling-off group (hereinafter referred to as a leaving group), the leaving group is a coupling-active carbon, an aliphatic group, an aromatic group or a heterocyclic group via an oxygen, nitrogen, sulfur or carbon atom. Group, a group capable of bonding with an aliphatic / aromatic or heterocyclic sulfonyl group, an aliphatic / aromatic or heterocyclic carbonyl group, a halogen atom, an aromatic azo group, etc., and a fat contained in these leaving groups Tribe,
The aromatic or heterocyclic group may be substituted with a substituent, and when the number of these substituents is two or more, they may be the same or different, and these substituents further have a substituent. Good.

Specific examples of the coupling-off group include a halogen atom (eg, fluorine atom, chlorine atom, bromine atom), an alkoxy group (eg, ethoxy group, dodecyloxy group, methoxyethylcarbamoylmethoxy group, carboxypropyloxy group, methylsulfonyl group). Ethoxy group), aryloxy group (eg 4-chlorophenoxy group, 4-methoxyphenoxy group, 4-carboxyphenoxy group etc.), acyloxy group (eg acetoxy group, tetradecanoyloxy group, benzoyloxy) Group), an aliphatic or aromatic sulfonyloxy group (eg, methanesulfonyloxy group, toluenesulfonyloxy group, etc.),
Acylamino group (eg, dichloroacetylamino group, heptafluorobutyrylamino group, etc.), aliphatic or aromatic sulfonamide group (eg, methanesulfonamino group, p-toluenesulfonylamino group, etc.), alkoxycarbonyloxy group (eg, ethoxy) Carbonyloxy group, benzyloxycarbonyloxy group etc.), aryloxycarbonyloxy group (eg phenoxycarbonyloxy group etc.), aliphatic / aromatic or heterocyclic thio group (eg ethylthio group, phenylthio group, tetrazolylthio group etc.) A carbamoylamino group (eg N
-Methylcarbamoylamino group, N-phenylcarbamoylamino group, etc.) 5- or 6-membered nitrogen-containing heterocyclic group (for example, imidazolyl group, pyrazolyl group, triazolyl group, tetrazolyl group, 1,2-dihydro-2-oxo) -1-pyridyl group, etc.), imide group (eg, succinimide group, hydantoinyl group, etc.), aromatic azo group (eg, phenylazo group, etc.), and the like, as a leaving group bonded via a carbon atom, aldehydes or There is a bis-type coupler obtained by condensing a 4-equivalent coupler with a ketone. The leaving group of the present invention may contain a photographically useful group such as a development inhibitor and a development accelerator.

Preferably, a group having a coupling activated carbon bond through an oxygen or nitrogen atom is desirable.

Particularly preferable leaving groups Z are the following (IA) to (I-
The groups represented by the general formulas leading to D) are included.

R ₂₀ represents an optionally substituted aryl group or heterocyclic group.

R ₂₁ and R ₂₂ are each a hydrogen atom, a halogen atom, a carboxylic acid ester group, an amino group, an alkyl group, an alkylthio group, an alkoxy group, an alkylsulfonyl group, an alkylsulfinyl group, a carboxylic acid group, a sulfonic acid group, and an unsubstituted group. Or, it represents a substituted phenyl group or a heterocycle, and these groups may be the same or different.

W ₁ is in the formula Represents a non-metal atom required to form a 4-membered ring, 5-membered ring or 6-membered ring.

Of the general formula (ID), (IE) to (I) are preferable.
-G).

In the formula, R ₂₃ and R ₂₄ each represent a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group or a hydroxy group, and R ₂₅ , R ₂₆ and R ₂₇ each represent a hydrogen atom,
It represents an alkyl group, an aryl group, an aralkyl group, or an acyl group, and W ₂ represents an oxygen or sulfur atom.

The compound of the general formula (I) is disclosed in JP-A-54-48541.
Japanese Patent Publication No. 58-10739, U.S. Patent No. 4,326.
No. 024 and Research Disclosure Magazine No. 1
It can be synthesized by the method described in 8053 or the like.

Specific compounds represented by formula (I) are shown below, but the invention is not limited thereto.

In the present invention, the overall exposure that is performed after the imagewise exposure, that is, the fog exposure is performed by the overall exposure after the imagewise exposure and before and / or during the development processing. Immersing the imagewise exposed light-sensitive material in a developer or in a pre-bath of the developer,
Alternatively, exposure is carried out before taking out from these solutions and not drying, but exposure in a developing solution is most preferred.

As the light source for fog 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 or the like can be used.
These specific methods are described in, for example, British Patent 1,151,
No. 363, Japanese Patent Publications No. 45-12710, No. 45-127
09, 58-6936, JP-A-48-9727.
No. 56-137350, No. 57-129438.
No. 58-62652, No. 58-60739, No. 58-70223 (corresponding U.S. Pat. No. 4,440,851).
No. 58-120248 (corresponding European Patent 89,1)
01A2) and the like. For a light-sensitive material having photosensitivity in the entire wavelength range, for example, a color light-sensitive material, Japanese Patent Laid-Open Publication No.
A light source having a high color rendering property (as close as possible to white) as described in 6-137350 or 58-70223 is preferable. The illuminance of light is 0.01 to 2000 lux, preferably 0.05 to 30 lux, more preferably 0.0.
5 to 5 lux is suitable. The light-sensitive material using a higher-sensitivity emulsion is preferred to have low illuminance.

As a method of applying the illuminance continuously or in a stepwise manner, as shown in FIG. 1, (a), (b), (d),
As shown in (e) and (f), not only a continuous increase in illuminance or a gradual increase in illuminance but also an exposure method using a pattern in which the illuminance increases or decreases from the start of exposure to the point of maximum exposure (first Figures (C), (G), (C), (R), and) are also included. The present invention also includes the continuous exposure described above, for example, the intermittent exposure pattern as shown in FIGS. 1 (n), (l), and (e). 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 use weak light at the beginning of the exposure and then stronger light, which is preferred in the present invention.

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 of the liquid to the light fog exposure 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 second to 2 minutes, preferably 0.1 second to 1 minute, more preferably 1 second to 40.
Seconds.

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 silver halide mainly forming a latent image inside the grains. But more specifically,
A certain amount of silver halide emulsion (0.5 to 3) on a transparent support.
g / m ² ) and exposed to light for a fixed time of 0.01 to 10 seconds to give the following developer A (internal type developer).
The maximum density measured by the usual photographic density measuring method when developed at 18 ° C. for 5 minutes was the same as the above, and the silver halide emulsion exposed in the same manner was developed with the following developing solution B.
It is preferable to have a concentration of at least 5 times higher than the maximum concentration obtained when developed in a (surface type developer) at 20 ° C. for 6 minutes, and more preferable to have a concentration of at least 10 times higher.

Internal developer A 2 g of sodium sulfite (anhydrous) 90 g Hydroquinone 8 g Sodium carbonate (monohydrate) 52.5 g KBr 5 g KI 0.5 g Water was added 1 Surface developer B metol 25 g L-ascorbic acid 10 g NaBO ₂ / 4H ₂ O 35 g KBr 1 g Water is added 1 Specific examples of the internal latent type emulsion include, for example, US Pat.
92,250, a convergence type silver halide emulsion described in US Pat. No. 3,761,276.
Nos. 3,850,637 and 3,923,513
No. 4,035,185, 4,395,478
No. 4,504,570, JP-A-52-15661
No. 4, No. 55-127549, No. 53-60222.
No. 56-22681, No. 59-208540,
No. 60-107641, No. 61-3137, Japanese Patent Application No. 61-32462, Research Journal
No. 23510 (issued in November 1983), P236, may be mentioned core / shell type silver halide emulsions described in the patent.

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 silver halide preferably used in the present invention does not contain silver iodide or contains silver iodide in an amount of 3 mol% or less so as not to affect the present invention.

The average grain size of the silver halide grains is 2 μm or less, preferably 0.1 μm or more, and particularly preferably 1 μm or less and 0.15 μm or more. The grain size distribution may be narrow or wide, but it is preferable to use a so-called "monodisperse" silver halide emulsion having a narrow grain size distribution for the purpose of improving the graininess and sharpness in the present invention. .

The monodisperse silver halide grains in the present invention have a grain size distribution as defined by the following formula. That is, when the standard deviation S of the particle size distribution is divided by the average particle size, the value is 0.20 or less, preferably 0.15 or less.

In the case of spherical silver halide grains, the average grain size referred to here is the average value of its diameter, and in the case of cubic or grains having a shape other than spherical, the projected image is converted into a circular image of the same area. The average value of the diameters when the particle size is r _i , and the particle size is r _i and the number is n _i, it is defined by the following formula.

The above-mentioned particle diameter can be measured by various methods generally used in the technical field for the above purpose. A typical method is Loveland's "particle size analysis method" A. S. T. M.
Symposium on Ride Microscopy, 19
55, pp. 94-122, or "Theory of Photographic Processes", co-authored by Mies and James, 3rd edition, Chapter 2 published by Macmillan, Inc. (1966). This particle diameter can be measured using the projected area of the particle or an approximate diameter value.

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. For specific examples, see Research Disclosure Magazine No. 17643-III (published in December 1978) P
23, etc.

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. For specific examples, see Research Disclosure Magazine No. 17643-IV (published in December 1978).
P23 to 24 and the like.

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. Specific examples are, for example, Research Disclosure No. 17643-V.
I (issued in December 1978) and E.I. J. Birr "S
tabiliaution of Photographic Silver Hailde Emulsio
n "(Focal Press), 1974.

In the present invention, in order to directly form a positive color image, various color couplers can be used in addition to the above yellow coupler. The color coupler is a compound that produces or releases a substantially non-diffusible dye by a coupling reaction with an oxidized product of an aromatic primary amine color developing agent, and is a substantially non-diffusible compound itself. Is preferred. Typical examples of useful color couplers are naphthol or phenol compounds, pyrazolone or pyrazoloazole compounds and open chain or heterocyclic ketomethylene compounds. Specific examples of these cyan and magenta couplers that can be used in the present invention are described in "Research
Dice closure "magazine No. 17643 (1978 1
Issued in February) P25, Item VII-D, No. 18717 (19)
(Published in November 1979) and Japanese Patent Application No. 61-32462 and the patents cited therein.

Colored couplers for correcting unnecessary absorption in the short wavelength range of the dyes produced, couplers in which the coloring dyes have an appropriate diffusibility, non-color couplers, DIR couplers that release a development inhibitor along with the coupling reaction, Polymerized couplers can also be used.

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

Color fog inhibitors or color mixture inhibitors can be used in the light-sensitive material of the present invention.

Typical examples of these are JP-A-62-215272, 600-
Pp. 663.

In the present invention, a color-enhancing agent can be used for the purpose of improving the color-forming property of the coupler. Representative examples of compounds are JP-A-6
2-215272, pages 374-391 are mentioned.

The light-sensitive material of the present invention includes dyes for preventing irradiation and halation, ultraviolet absorbers, plasticizers, fluorescent brighteners, matting agents, air fog preventing agents, coating aids, hardeners,
An antistatic agent, a slipperiness improving agent, etc. can be added.
Typical examples of these additives are Research Disclosure magazine Nos. 17643 VIII to XIII pages (published in December 1978), p25 to 27, and 18716 (1979 1).
Issued in January) p647-651.

The present 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 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 color 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, anti-halation agent,
It is preferable to appropriately provide an auxiliary layer 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 Research Disclosure Magazine No. 17643VVII.
(Issued in December 1978) p28, European Patent No. 0,102,253, and Japanese Patent Laid-Open No. 61-9765.
It is coated on the support described in No. 5. Further, the coating method described in Research Disclosure Magazine No. 17643XV, paragraphs p28 to 29 can be used.

The present invention can be applied to various color light-sensitive materials.

Representative examples include color reversal films for slides or televisions, color reversal papers, and instant color films. It can also be applied to a full-color copying machine or a color hard copy for storing an image of a CRT. The present invention also relates to "Research Disclosure" magazine No. 1712.
No. 3 (issued in July 1978) and the like, and can also be applied to a black-and-white light-sensitive material utilizing a mixture of three-color couplers.

The color developing solution used for the development processing of the light-sensitive material of the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine type color developing agent as a main component. Although aminophenol compounds are also useful as the color developing agent, p-phenylenediamine compounds are preferably used, and typical examples thereof include 3-methyl-4-amino-N, N-diethylaniline and 3 -Methyl-4-amino-N-ethyl-N
-Β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-N
-Β-methoxyethylaniline and their sulfates, hydrochlorides or p-toluenesulfonates.
Two or more of these compounds can be used in combination depending on the purpose.

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

The photographic emulsion layer after color development is usually bleached. The bleaching process may be performed at the same time as the fixing process (bleach-fixing process) or may be performed individually. Further, in order to speed up the processing, a processing method of bleach-fixing processing after bleaching processing may be used. Further processing with two continuous bleach-fix baths,
The fixing treatment before the bleach-fixing treatment or the bleaching treatment after the bleach-fixing treatment can be optionally carried out according to the purpose.

The silver halide color photographic light-sensitive material of the present invention is generally washed with water and / or stabilized after the desilvering process.
The amount of rinsing water in the rinsing process depends on the characteristics of the photosensitive material (for example, depending on the materials used such as couplers), application, and further, the rinsing water temperature, the number of rinsing tanks (the number of stages), the replenishment system such as countercurrent and forward flow, and various other conditions Therefore, it can be set in a wide range. Of these, the relationship between the number of washing tanks and the water volume in the multi-stage countercurrent system is described in the Journal of the Society of Motion Picture and Telev.
ision Engineers Engineers Volume 64, p248-25
3 (May 1955 issue).

The silver halide coupler light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and accelerating the processing.
For incorporation, it is preferable to use various precursors of color developing agents.

〔Example〕

Hereinafter, the present invention will be described in more detail with reference to Examples.
However, the present invention is not limited thereto.

(Reference example) Paper support laminated on both sides with polyethylene (thickness 100
Micron) was coated on the front side with the following first to fourteenth layers, and on the back side with a multi-layer coating of the fifteenth to sixteenth layers to prepare a color photographic light-sensitive material. Titanium white is contained as a white pigment, and a trace amount of ultramarine is contained as a bluish dye on the coating side of the first layer of polyethylene.

(Composition of Photosensitive Layer) The components and the coating amounts shown in g / m ² are shown below.

For silver halide, the coating amount in terms of silver is shown. The emulsion used for each layer was produced according to the production method of Emulsion EM1.
However, as the 14th layer emulsion, a Lipman emulsion which was not surface-sensitized was used.

First layer (anti-halation layer) Black colloidal silver 0.10 Gelatin 1.30 Second layer (intermediate layer) Gelatin 0.70 Third layer (low-sensitivity red sensitive layer) Red sensitizing dye (ExS-1, 2) , 3) spectrally sensitized with silver bromide (average grain size 0.3 μ, size distribution [variation coefficient] 8%, octahedron) spectrally sensitized with red sensitizing dye (ExS-1, 2, 3) Silver bromide (average grain size 0.45μ, size distribution 10%, octahedron) 0.10 gelatin 1.00 cyan coupler (ExC-1) 0.11 cyan coupler (ExC-2) 0.10 anti-fading agent (Cpd-2, 3, 4, 13 equivalents) 0.12 Coupler dispersion medium (Cpd-5) 0.03 Coupler solvent (Solv-7, 2,3 equivalents) 0.06 Fourth layer (high sensitivity red) Sensitive layer) Spectral sensitization with red sensitizing dye (ExS-1, 2, 3) Silver bromide (average grain size 0.60μ, size distribution 12%, octahedron) 0.14 gelatin 1.00 cyan coupler (ExC-1) 0.15 cyan coupler (ExC-2) 0.15 anti-fading agent (Cpd-2,3,4,13 equivalents) 0.15 Coupler dispersion medium (Cpd-5) 0.03 Coupler solvent (Solv-7,2,3 equivalents) 0.10 Fifth layer (intermediate layer) Gelatin 1.00 Color mixture inhibitor (Cpd-7) 0.08 Color mixture inhibitor solvent (Solv-4,5 equivalent) 0.16 Polymer latex (Cpd-8) 0.10 6th layer (low sensitivity green feeling) Layer) Silver bromide spectrally sensitized with a green sensitizing dye (ExS-3) (average grain size 0.25 μ, grain size distribution 8%, octahedron) 0.04 Green sensitizing dye (ExS-3, 4) ) Spectrally sensitized silver bromide (average grain size 0 .45μ, particle size distribution 11%, octahedron) 0.06 gelatin 0.80 magenta coupler (ExM-1,2 equivalent) 0.11 anti-fading agent (Cpd-9) 0.10 anti-staining agent (Cpd-) 10,22 equivalent) 0.014 Anti-staining agent (Cpd-23) 0.001 Anti-staining agent (Cpd-12) 0.01 Coupler dispersion medium (Cpd-5) 0.05 Coupler solvent (Solv-4,6 0.15 Seventh layer (high-sensitivity green-sensitive layer) Silver bromide spectrally sensitized with a green sensitizing dye (ExS-3, 4) (average grain size 0.8 μ, grain size distribution 14%) , Octahedron) 0.10 gelatin 0.80 magenta coupler (ExM-1,2) 0.11 anti-fading agent (Cpd-9) 0.10 anti-staining agent (Cpd-10,22 equivalent) 0.013 stain Inhibitor (C d-23) 0.001 anti-staining agent (Cpd-12) 0.01 coupler dispersion medium (Cpd-5) 0.05 coupler solvent (Solv-4, 6 equivalents) 0.15 eighth layer (intermediate layer) Same as the 5th layer 9th layer (yellow filter layer) Yellow colloidal silver) 0.20 Gelatin 1.00 Color mixture inhibitor (Cpd-7) 0.06 Color mixture inhibitor solvent (Solv-4,5 equivalent) 15 Polymer Latex (Cpd-8) 0.10 10th Layer (Intermediate Layer) Same as 5th Layer 11th Layer (Low Sensitivity Blue Sensitive Layer) Spectral sensitized with a blue sensitizing dye (ExS-5, 6) Silver bromide (average grain size 0.45μ, grain size distribution 8%, octahedron) 0.07 Silver bromide spectrally sensitized with blue sensitizing dye (ExS-5, 6) (average grain size 0.60μ, particle size distribution 12%, octahedron) 0.1 Gelatin 0.50 Yellow coupler (listed in Table-1) Anti-staining agent (Cpd-11) 0.001 Anti-fading agent (Cpd-6) 0.10 Coupler dispersion medium (Cpd-5) 0.05 Coupler solvent (Solv -2) 0.05 12th layer (high-sensitivity blue-sensitive layer) Silver bromide spectrally sensitized with a blue sensitizing dye (ExS-5, 6) (average grain size: 1.2 µ, grain size distribution: 15%). , Octahedron) 0.25 gelatin 1.00 yellow coupler (listed in Table-1) anti-staining agent (Cpd-11) 0.002 anti-fading agent (Cpd-6) 0.10 coupler dispersion medium (Cpd-5) 0.05 Coupler solvent (Solv-2) 0.10 13th layer (ultraviolet absorbing layer) Gelatin 1.50 Ultraviolet absorber (Cpd-1,3,13 equivalent) 1.00 Color mixing inhibitor (Cpd-6,6) 14 equivalents 0.06 Dispersion medium (Cpd-5) 0.05 UV absorber solvent (Solv-1, 2 equivalents) 0.15 Anti-irradiation dye (Cpd-15, 16 equivalents) 0.02 Anti-irradiation dye (Cpd-) 17,18 equivalents) 0.02 14th layer (protective layer) Fine silver bromide (97 mol% silver chloride, average size 0.2 μ) 0.05 Acrylic modified copolymer of polyvinyl alcohol (Modification degree 17%) 0.02 polymethylmethacrylate particles (average particle size 2.4 microns), silicon oxide (average particle size 5 microns) equivalent 0.05 gelatin 0.50 gelatin hardener (H-1) 0.17 Fifteenth layer (back layer) Gelatin 2.50 Sixteenth layer (back surface protection layer) Polymethylmethacrylate particles (average particle size 2.4 microns), Silicon oxide (average particle size) Micron) Equivalent 0.05 gelatin 2.00 Gelatin hardening agent (H-1) 0.11 How to make emulsion EM1 It takes 15 minutes at 75 ° C while vigorously stirring an aqueous solution of potassium bromide and silver nitrate into the gelatin aqueous solution. At the same time,
Octahedral silver bromide grains having an average grain size of 0.40 micron were obtained. 0.3 g of 3,4-dimethyl-1,3-thiazoline-2-thione per mole of silver, 6 mg of sodium thiosulfate and 7 mg of chloroauric acid (tetrahydrate) were sequentially added to this emulsion.
The chemical sensitization treatment was performed by heating at 5 ° C. for 80 minutes. The grains thus obtained were used as cores and further grown in the same precipitation environment as in the first time, to finally obtain an octahedral monodisperse core / shell silver bromide emulsion having an average grain size of 0.7 micron. The coefficient of variation of particle size was about 10%. To this emulsion, 1.5 mg of sodium thiosulfate and 1.5 mg of chloroauric acid (tetrahydrate) were added per mol of silver, and the mixture was heated at 60 ° C. for 60 minutes for chemical sensitization to perform internal latent image type silver halide. An emulsion was obtained.

Alkanol XC (Dupont
And sodium alkylbenzenesulfonate as coating aids and succinate and Magefac F-12.
0 (manufactured by Dainippon Ink and Chemicals, Inc.) was used. For the layer containing silver halide and colloidal silver, (Cpd-19, 2
0, 21) was used. 11th layer (low sensitivity blue sensitive layer) and 1st layer
The yellow coupler of the present invention shown in Table 2 was applied to the two layers (high-sensitivity blue-sensitive layer) to prepare sample numbers 101 to 104. A comparative sample was prepared in the same manner as in Samples 101 to 104 except that the comparative yellow coupler B was applied to the 11th layer (low sensitivity blue sensitive layer) and the 12th layer (high sensitivity blue sensitive layer). Was designated as Sample No. 105. The compounds used in Reference Examples are shown below.

Solv-1 di (2-ethylhexyl) phthalate Solv-2 trinonyl phosphate Solv-3 di (3-methylhexyl) phthalate Solv-4 tricresyl phosphate Solv-5 dibutyl phthalate Solv-6 trioctyl phosphate Solv- 7 Di (2-ethylhexyl) sebacate H-1 1,2-bis (vinylsulfonylacetamido) ethane Comparative yellow coupler B The direct positive color light-sensitive material thus prepared was subjected to a wet exposure (1/10 second, 10 CMS), and then development processing was carried out by the following processing steps to obtain a color image.

The processing steps and processing solutions used here are shown below.

Light exposure condition a: 30 seconds exposure with an illuminance of 0.6 Lux b: 9 seconds exposure with an illuminance of 2 Lux c: Exposure of 3.7 Lux immediately after 5 seconds with an illuminance of 0.6 Lux
4 seconds exposure with 5 Lux d: 9 seconds after the start of exposure, the illuminance is increased linearly so that the illuminance becomes 4 Lux e: 9 seconds exposure e: After 2 seconds exposure with 2 Lux illumination, 0.4 Lu immediately
x exposure for 5 seconds, and then exposure at 6 Lux for 2 seconds f: exposure at 3.75 Lux for 4 seconds and immediately 0.
6-lux exposure for 5 seconds g: 1-second interval illuminance of 2 Lux for 1-second exposure, then immediately repeat for 1-second exposure for 2 Lux, h: Repeat 1-second exposure for 1-second at an illuminance of 0.6 Lux, then Immediately at 1 second intervals with an illuminance of 3.75 Lux 1
Illuminance 3.75Lux immediately after repeating second exposure 3 times
Exposure for 1 second i: Immediately after exposure for 4.5 seconds, increase the illuminance linearly so that the illuminance 4.5 seconds after the start of exposure becomes 4 Lux.
Exposure is performed for 4.5 seconds while linearly decreasing the illuminance so that the illuminance becomes zero after 5 seconds.

[Color developer]

The pH was adjusted with potassium hydroxide or hydrochloric acid.

[Bleaching fixer]

The pH was adjusted with aqueous ammonia or hydrochloric acid.

[Stabilizer]

The pH was adjusted with potassium hydroxide or hydrochloric acid.

The maximum image density (Dmax) and the minimum image density (Dmin) of the yellow image obtained by the development process were measured. Further, the same developed sample was subjected to a photobleaching test under the following conditions, and the maximum image density of the yellow image was measured again.

(Photobleaching test conditions) 100,000 Lux of xenon light was irradiated for 12 hours in an environment of 30 ° C. and 70% RH for 12 hours, stopped for 12 hours, and then irradiated for 120 hours.

The obtained results are shown in Table-1.

From Table 1, Samples 101 to 104 using the yellow coupler of the present invention in the blue-sensitive layer showed less photobleaching of the yellow image than Comparative Sample 105, and the light fog conditions c to i according to the method of the present invention. Then, it can be seen that the positive image forming efficiency is higher than the exposure conditions a and b other than the present invention, and Dmin is small, and the exposure time can be significantly shortened as compared with the conventional uniform low illuminance exposure condition a.

Example-1 The silver bromide emulsions used in the 11th layer (low-sensitivity blue-sensitive layer) and the 12th layer (high-sensitivity blue-sensitive layer) of Reference Example were prepared according to the method for preparing emulsion EM2 described below. Samples 201 to 205 were prepared in the same manner as Samples 101 to 105 of Reference Example, except that the silver chlorobromide emulsion was used.

Eleventh layer (low-sensitivity blue sensitive layer) Silver chlorobromide spectrally sensitized with a blue sensitizing dye (ExS-5, 6) (average grain size 0.45 μ, grain size distribution 8)
%, Silver bromide content 70 mol%) Silver chlorobromide spectrally sensitized with a blue sensitizing dye (ExS-5, 6) (average grain size 0.60 μ, grain size distribution 10)
%, Silver bromide content 60 mol%) 12th layer (high-sensitivity blue-sensitive layer) Silver chlorobromide spectrally sensitized with a blue sensitizing dye (ExS-5, 6) (average grain size 1.2 μ, grain Size distribution 12
%, Silver bromide content 45 mol%) Method for preparing emulsion EM2 0.07 g of 3,4-dimethyl-1,3-thiazoline-2-thione per mol of AgI is used as a mixed aqueous solution of potassium bromide and potassium chloride and an aqueous solution of silver nitrate. Was added simultaneously to the aqueous gelatin solution with vigorous stirring at 62 ° C. for about 14 minutes to obtain a monodispersed silver chlorobromide emulsion having an average particle size of about 0.21 μm (silver bromide content 80 mol%). Obtained. To this emulsion 61 mg sodium thiosulfate and 42 mg per mol silver
Chloroauric acid (4 hydrate) was added and the mixture was heated at 65 ° C. for 60 minutes for chemical sensitization. The silver chlorobromide particles thus obtained were used as cores for further growth in the same precipitation environment as the first time, and finally a monodispersed core / average particle size of about 0.60 μm (silver bromide content 60 mol%) / A shell silver chlorobromide emulsion was obtained. The coefficient of variation of particle size was about 10%. To this emulsion, 1.5 mg of sodium thiosulfate and 1.5 mg of chloroauric acid (tetrahydrate) were added per mol of silver, and the mixture was heated at 60 ° C. for 60 minutes for chemical sensitization, and internal latent image type halogenation was carried out. A silver emulsion EM2 was obtained.

These samples were exposed and developed in the same manner as in Reference Example 1 to obtain color images. Next, with respect to these samples, the same density measurement and photobleaching test as in the reference example were performed.

The obtained results are shown in Table-2.

From Table-2, Samples 201 to 204 using the yellow coupler of the present invention in the blue-sensitive layer showed less photobleaching of the yellow image than Comparative Sample 205, and the light fog conditions c to i according to the method of the present invention. Then, it can be seen that the positive image forming efficiency is higher than the exposure conditions a and b other than the present invention, and Dmin is small, and the exposure time can be significantly shortened as compared with the conventional uniform low illuminance exposure condition a.

Example-2 The undercoated cellulose triacetate film support used in the examples was a support prepared by a conventional solution casting method. This support was treated with a cellulose triacetate solution at a surface temperature of 10 ° C. or lower as described in JP-A-62-11503 (November 14, 1985, Fuji Photo Film, Patent Application No. 60-253788). A light-sensitive material was produced in exactly the same manner except that the cellulose triacetate film support was replaced by a cellulose triacetate film support which was produced by casting the film on a support, peeling the film off, peeling the film, and transporting the film while applying tension to the film.

When the light-sensitive materials differing only in the support were developed in the same manner as in Example 1, the same results as in Example 1 were obtained.

〔The invention's effect〕

According to the present invention, a direct positive color image having both a high maximum density and a low minimum density is formed by rapid processing. The yellow image formed here is excellent in photobleaching property, and has a great merit in practical use. Further, as can be seen from the comparison between Reference Example and Example 1, the silver chlorobromide grains have a higher Dmax and are superior to the case where the halogen composition of the silver halide grains is pure silver bromide.

[Brief description of drawings]

FIG. 1 is a diagram showing various relationships between the exposure time and the exposure illuminance at the time of whole surface exposure.

Claims (1)

[Claims] 1. A photographic 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 is subjected to image-wise exposure, followed by development processing. In the method for directly forming a positive image by subjecting the entire surface to exposure before or during development, the photographic light-sensitive material contains at least one compound represented by the following general formula (I). The silver halide grains contained therein have a silver bromide content of 80 mol% to 45%.
A direct positive color image forming method, characterized in that the silver chlorobromide grains are in the range of mol%, and the whole surface is exposed by irradiating continuously or stepwise while increasing or decreasing the illuminance. General formula (I) In the formula, Z represents a group capable of splitting off during a coupling reaction with an oxidized product of a developing agent, G ₁ represents a halogen atom or an alkoxy group, and G ₂ represents a hydrogen atom, a halogen atom or a substituent. Represents a good alkoxy group. R represents an alkyl group which may have a substituent.