JPH01155335A - Direct positive type silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To improve the stability of a development processing of the title material against the changes of a developing time and a fog illumination by incorporating two kinds of inner latent image type silver halide particles which have the different sensitivities but almost the same mean particle size in the sensitive material. CONSTITUTION:The photographic sensitive material comprises a silver halide emulsion layer contg. at least two kinds of the inner latent image type silver halide particles which are not previously fogged. At least two kinds of the inner latent image type silver halide particles as mentioned above have the different sensitivities but almost the same average particle size. The mean average particle size of the silver halide particle is a range of 0.18-0.95mum, preferably, a range of 0.20-0.80mum. And the silver halide particle may be obtained by an acidic, a neutral or an ammonia method. The silver halide photographic sensitive material is imagewisely exposed according to an ordinary method, and then the direct positive image is easily obtained by a surface development, thus improving the development processing of the sensitive material.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a direct positive type silver halide photographic light-sensitive material. In particular, the present invention relates to a direct positive type silver halide photographic light-sensitive material that has good development processing stability even with changes in development time and fogging illuminance, in a light-sensitive material that directly produces a positive image through full-surface exposure processing. It is something.

[Background of the invention]

Techniques used to create positive images using conventionally known direct positive photosensitive materials can be divided into two main types.

One type uses an emulsion containing silver halide grains that have been fogged in advance, and uses solarization or the Burschel effect to destroy fog nuclei (latent images) in exposed areas to obtain a positive image after development. It is.

The other type uses an emulsion containing internal latent image type silver halide grains that have not been fogged in advance, and performs surface development after image exposure and fogging treatment, or while performing fogging treatment, to create a positive image. It's something you get.

The above-mentioned internal latent image type silver halide grains refer to silver halide grains which mainly have photosensitive nuclei inside the grains and form latent images inside the grains upon exposure.

Compared to the former type of technology, this latter type of technology is more sensitive for boat fishing and is suitable for applications requiring high sensitivity, and the present invention relates to this latter type of technology.

Various techniques are known to date in this technical field. For example, U.S. Patent Nos. 2.592.250, 2.466.957, 2.497.875,
Same No. 2,588.982, Same No. 3.76L266,
The main ones are those described in British Patent No. 3.761,276, British Patent No. 3.796,577 and British Patent No. 1.151.363.

By using these known techniques, it is possible to produce a relatively highly sensitive photographic material as a direct positive type.

Although the details of the direct positive image formation mechanism are not necessarily clear, unexposed silver halide It is thought that fog nuclei are selectively generated only on the surface of the particles, and then a photographic image is formed in the unexposed areas by normal development.

As means for selectively generating fogging nuclei, two methods are generally known: photofogging, in which the entire surface of the photosensitive layer is exposed to light, and chemical fogging, in which fogging is performed using a chemical such as a fogging agent. It is being

However, chemical fogging treatment has a high pH of 12 or more.
Since there are severe conditions in which the effect of the fogging agent is obtained for the first time in H, the fogging agent tends to deteriorate due to air oxidation, which has the disadvantage that the fogging effect is significantly reduced.

On the other hand, in the case of photofogging treatment, there are no harsh conditions such as those mentioned above, and it is convenient for practical use. However, technical problems still remain in order to serve various purposes in a wide range of photographic fields.

That is, since the photofogging treatment is based on the formation of fog nuclei by photodecomposition of silver halide, the appropriate fogging illuminance and exposure amount for fogging exposure vary depending on the type and characteristics of the silver halide.

For example, Japanese Patent Publication No. Sho 45-12709 describes a method of uniformly exposing the entire surface to light with low fogging illuminance. According to this document, it is possible to obtain a good positive image having a high maximum density and a low minimum density by exposing the entire surface with low fogging illuminance.

In addition, as a result of studies conducted by the present inventors, in order to obtain a relatively good positive image, it is necessary to perform fog exposure at a relatively low illuminance within a certain limited range; Even with sufficient exposure, a sufficient maximum image density cannot be obtained, and at higher fogging illuminances, the maximum density decreases and the minimum density increases in proportion to the fogging illuminance. It turns out that there is a phenomenon called failure.

Therefore, the fogging illuminance and time of uniform exposure over the entire surface must be adjusted depending on the internal latent image type photosensitive material, the processing conditions, the type of light source used, etc., so as to obtain the best positive image.

However, it is extremely troublesome to adjust the fogging illuminance and development processing time in accordance with various conditions.

Therefore, even if the fogging illuminance changes or the development time changes, the resulting direct positive photosensitive material always produces good images.
In other words, there is a need for a direct positive photosensitive material with good development processing stability, which has a wide tolerance range for fogging illuminance and development time in order to obtain good images, and which can provide stable images even under these fluctuations. There is.

On the other hand, a soft positive image can be formed using an internal latent image type direct positive photosensitive material. In this case, it is well known to mix silver halide grains with different sensitivities or to layer silver halide emulsion layers with different sensitivities in order to adjust the gradation.

For example, Research Disclosure (hereinafter referred to as R)
D), Tao 15162, U.S. Patent No. 4.035.1
In addition to mixing silver halide grains with different average grain sizes, No. 85 also mixes silver halide grains with approximately the same average grain size but with different sensitivities and gradations. It says that it can be adjusted. (However, what is described here is for adjusting the gradation due to chemical fogging.) However, silver halide grains with different sensitivities affect not only the sensitivity during photography but also the gradation during light fogging. Since the sensitivity to full-face exposure is also different, the optimal conditions (or optimal exposure range) for each full-face exposure are different.
will also be different. Therefore, it has been found that in combinations of different sensitivities, the optimal exposure range is the range where the respective exposure ranges coincide with each other, so the optimal exposure range becomes even narrower depending on the combination. Therefore, such a combination of particles generally tends to further narrow the permissible range of fluctuations in fogging illuminance and development time. Regarding this point, there is nothing described in the above-mentioned RD or the US patent.

In other words, an internal latent image type photosensitive material containing silver halide grains having two or more different sensitivities has poor development processing stability of -11 ffl, and when such a photosensitive material is fully exposed and subjected to photofogging processing for development processing. ,If there is a change in fogging illuminance on the photosensitive surface during light fogging, sensitivity fluctuations tend to occur, and the gradation also changes in response to fluctuations in development processing time, making it difficult to obtain good images. It turns out.

Also, as a technique for adjusting the gradation, it is known that the average grain size of silver halide grains is changed to differentiate the sensitivity, but when light fogging is applied, it is possible to desensitize and achieve good results. Development processing stability is difficult to obtain.

[Purpose of the invention]

The present invention was made in order to solve the above problems, and an object of the present invention is to obtain a direct positive silver halide photographic light-sensitive material that has good development processing stability against changes in development time and fogging illuminance. .

[Structure and operation of the invention]

The above object of the present invention is to have at least one silver halide emulsion layer containing at least two types of internal latent image type silver halide grains that are not fogged in advance, and to provide a method for forming a silver halide emulsion layer while carrying out full-surface exposure after image exposure, and/or Alternatively, in a photographic light-sensitive material in which a positive image is obtained directly by surface development after application, the at least two types of internal latent image type silver halide grains have different sensitivities but have approximately the same average grain size. This is achieved using direct positive silver halide photographic materials.

The present invention will be explained in detail below.

In the present invention, the photographic light-sensitive material has at least IN a silver halide emulsion layer containing at least two types of internal latent image type silver halide grains that have not been fogged in advance.

The at least two types of internal latent image type silver halide grains have different sensitivities, but have approximately the same average grain size. Sensitivity here means sensitivity to fogging exposure.

When we say that the average grain sizes are approximately equal, if there are two types of silver halide grains with different sensitivities and the average grain size of grain A is a and the average grain size of grain B is b, then The average particle size of particles B is within the range of aXo, 90≦b≦aX1.10, that is, within ±10% of the average particle size a; conversely, the average particle size a is within the range of Including cases within ±10%. Preferably, the above relationship is in the range of 0.95≦b 5 a Xl,05, that is, the average particle size a is within ±5% of the average particle size ±5% of
This includes cases within the range. When there are three or more types of silver halide grains having different sensitivities, it is sufficient that there are at least two types of silver halide grains having the above relationship (within ±10% or within 5%).

Further, when there are three or more types of silver halide grains having different sensitivities, it is sufficient that the average grain diameters of at least two types of grains among them are approximately equal as described above.

Here, the average particle size means the particle size ri at which the product ni x ri3 of the frequency ni of particles having the particle size ri and ri'' is the maximum (3 significant figures, the minimum number of digits is rounded off).

In addition, the grain size here refers to the diameter in the case of spherical silver halide grains, and in the case of grains with shapes other than spherical, the diameter when the projected image is converted into a circular image with the same area. It is.

The particle size can be obtained, for example, by magnifying the particle 10,000 to 50,000 times with an electron microscope and projecting it, and actually measuring the particle diameter or area at the time of projection on the print (the number of particles measured is (Assume there are more than 1000 items indiscriminately.)

The shape of the internal latent image type silver halide grains according to the present invention may be any shape, for example, cubic, regular octahedral, 12
The particles may be in the shape of a hedron, a tetradecahedron, or a mixture thereof, or may be particles of a spherical, tabular, irregular shape, or a mixture of these as appropriate.

The average grain size of the internal latent image type silver halide grains according to the present invention is preferably in the range of 0.18 .mu.m to 0.95 .mu.m, more preferably in the range of 0.20 .mu.m to 0.80 .mu.m.

The internal latent image type silver halide grains according to the present invention can be produced by an acid method,
It may be obtained by either the neutral method or the ammonia method. The particles may be grown during processing, or may be grown after seed particles are produced. The method of creating and growing the seed particles may be the same or different. A silver halide emulsion containing the silver halide grains may be prepared by simultaneously mixing halide ions and silver ions, or by mixing one of them in a solution in which the other is present. In addition, while considering the critical growth rate of silver halide crystals, the pH and p
It may be produced by controlling and sequentially adding Ag.

By this method, silver halide grains having a regular crystal shape and a nearly uniform grain size can be obtained. Conversion methods can also be used to change the halogen composition of the particles after growth.

Such an emulsion containing internal latent image type silver halide grains is
Any particle size distribution may be used. Therefore, an emulsion with a wide grain size distribution (referred to as a polydisperse emulsion) may be used, or an emulsion with a narrow grain size distribution (referred to as a polydisperse emulsion) may be used.
Monodisperse emulsions (referred to as monodisperse emulsions) may be used alone or in combination, or polydisperse emulsions and monodisperse emulsions may be mixed.

Preferably, a monodisperse emulsion is used. Monodispersity in a monodisperse emulsion means that the coefficient of variation in the grain size distribution of silver halide grains contained in the emulsion is 22% or less;
It refers to an emulsion having preferably 15% or less.

The internal latent image type silver halide grains according to the present invention may consist of at least two types of layers, that is, at least two types of layers having mutually different halogen compositions (in this case, the outermost shell layer is , it may just cover at least a part of the inner core layer.

It is preferable to adopt a so-called core/shell structure in which the inner core layer forms a core and the outer shell layer covers the core as a shell, and a structure in which the first layer covers a part of the second layer may be adopted.

Next, the case where core/shell structure grains are used as internal latent image type silver halide grains according to the present invention will be explained.

The outermost shell layer can completely cover the surface of the silver halide grain, or can selectively cover a part of the surface.

Silver halide of any halogen composition can be used for the shell. Examples include silver chloride, silver chlorobromide, silver chloroiodobromide, silver chloroiodide, and the like. Silver chlorobromide is preferred.

The shell may be a single layer having a silver halide composition, or may be a multilayer shell having a silver halide composition of 2N or more.

In the case of a multi-layer shell, it may have a structure in which a small number of layers (consisting of an outermost layer and an adjacent layer, but having different silver halide compositions) are laminated.

Further, the multilayer shell layer may have a structure in which the silver halide composition changes continuously in the radial direction of the silver halide grains.

In the case of forming the above-mentioned multilayer shell, silver halide having any halide composition can be used for the outermost shell of the multilayer shell (the surface thereof may be used), and the entire grain or the inner layer may be Any silver halide composition may be used. Examples include silver iodobromide, silver bromide, silver chlorobromide, silver chloroiodide, and silver chlorobromide.

It is preferable that the shell covers 50% or more of the surface area of the core, and it is particularly preferable that the shell completely covers the core.

The core preferably consists primarily of silver bromide and may also contain silver chloride and/or silver iodobromide. The silver halide grains forming the core may have any shape (for example, cubic, octahedral, dodecahedral, tetradecahedral, or a mixture thereof, spherical,
The particles may be tabular particles, irregularly shaped particles, or an appropriate mixture of these particles. In the present invention, the core preferably has a cubic shape. In carrying out the present invention, the average particle size and particle size distribution of the silver halide grains constituting the core can be varied over a wide range depending on the desired photographic performance, but a narrower particle size distribution is more preferable.

That is, the silver halide grains constituting the core are preferably substantially monodisperse.

Silver halide grains with a monodisperse core are defined as silver halide grains that have a monodisperse core with an average grain diameter of ±
The weight of silver halide grains within the 20% grain size range is 60% or more of the total silver halide weight, preferably 70% or more, particularly preferably 80% or more.

Examples of the method for producing the monodisperse core emulsion include, for example, Japanese Patent Publication No. 4B-36890, Japanese Patent Application Laid-open No. 48520/1986,
The double jet method disclosed in various publications such as No. 54-65521 can be used. In addition, JP-A-54-15
A premix method described in Japanese Patent No. 8220 and the like can also be used.

The core may be chemically sensitized and/or doped with metal ions, or both, or not at all.

As the chemical sensitization, sulfur sensitization, gold sensitization, reduction sensitization, noble metal sensitization, and a combination of these sensitization methods can be employed. As the sulfur aggravating agent, thiosulfates, thioureas, thiazoles, rhodanines, and other compounds can be used.

Such methods are described, for example, in U.S. Pat. No. 1,574,944.
No. 1.623.499, No. 2.410,689, No. 3, No. 656.955, etc.

The core is described, for example, in U.S. Pat. No. 2,399,083;
As described in No. 597.856, No. 2.642.361, etc., sensitization can be carried out with a water-soluble gold compound or with a reduction sensitizer. Such methods are described, for example, in U.S. Pat.
No. 50, No. 2,518,698, No. 2.983.61
You can refer to the description of No. 0 etc.

Furthermore, noble metal sensitization can also be carried out using noble metal compounds such as platinum, iridium, palladium, and the like. Such methods are described, for example, in U.S. Pat.
8,060 and British Patent No. 618,061.

The core can also be doped with metal ions. The core can be doped with metal ions, for example, by adding the metal ions as a water-soluble salt during any process of forming the core particle. Preferred specific examples of metal ions include metal ions such as iridium, lead, antimony, bismuth, gold, osmium, and rhodium.

These metal ions are preferably used in an amount of 1 per mole of silver.
Xl0-' to IXl0-' molar concentrations are used.

However, the core may not be subjected to the above-mentioned chemical sensitization treatment or metal ion doping. In this case, it is thought that the photosensitive center is generated by forming crystal strain at the interface between the core and shell during the process of covering the core particle with the shell, and in this regard, US Pat. No. 3,935. No. 014, No. 3,957,
Reference may be made to the description in No. 488.

A double jet method or a premix method can be used to form the shell on the core described above. It is also possible to form the core emulsion by mixing fine grains of silver halide and performing Ostwald ripening.

The internal latent image type silver halide grains according to the present invention are grains whose surfaces are not fogged in advance. Here, the meaning that the surface of the internal latent image type silver halide grains is not fogged in advance means that 35 mg of such an emulsion is deposited on a transparent film support.
When a test piece coated to give A g /aa is developed with the following surface developer A at 20°C for 10 minutes without exposure, the density obtained does not exceed 0.6, preferably 0.4. say.

Surface developer A Metol 2.5g-Ascorbic acid 10g NaBOz ・
4To0 35 gKB,
Add 1g water
11 Furthermore, the emulsion containing the internal latent image type silver halide grains according to the present invention has a sufficient density when the test piece prepared as described above is exposed and then developed with internal developer B having the following formulation. It is preferable to use what is given.

Internal developer A Metol 2g Sodium sulfite
90 g hydroquinone
8g Soda carbonate (-water salt)
52.5 gKB,
5 gKI
O, add 5g water 1
1. More specifically, when a portion of each specimen is exposed to a light intensity scale for a defined period of time up to about 1 second and developed in internal developer B for 10 minutes at 20°C, Use one that exhibits a maximum density that is at least 5 times, preferably at least 10 times, that obtained when a separate portion of each specimen exposed under the same conditions is developed in surface developer A for 10 minutes at 20°C. It is preferable.

Silver halide emulsions can be optically enhanced by commonly used enhancement dyes. Combinations of sensitizing dyes used for supersensitization of internal latent image type silver halide emulsions, negative type silver halide emulsions, etc. are also useful for the silver halide emulsions used in the present invention. Regarding sensitizing dyes, see Research Disclosure.
closure) 11h15162 and Na 1764
3 can be referred to.

The direct positive type silver halide photographic light-sensitive material of the present invention can directly obtain a positive image by performing surface development after image exposure and/or while performing full-surface exposure.

That is, the silver halide photographic material of the present invention is subjected to image exposure (so-called photographing, in which light is applied to a photosensitive material to form an image) in a conventional manner, and then surface-developed. A positive image can be easily obtained directly. Surface development here means developing latent image nuclei formed on the surface of silver halide grains. The main process of directly forming a positive image is to process a photographic material having an emulsion layer containing internal latent image type silver halide grains by photochemical action to generate fog nuclei after image exposure. It consists of performing surface development while and/or after exposure.

For example, full-surface exposure is performed by immersing or moistening the image-exposed photosensitive material in a developer or other aqueous solution, and then exposing the entire surface uniformly to light. The light source used here may be any light within the sensitive wavelength range of the photographic light-sensitive material, and it may be a short-term exposure to high-intensity light such as a flash light, or a long-term exposure to weak light. . In addition, the total exposure time can be varied over a wide range depending on the photographic material, processing conditions, type of light source used, etc. in order to obtain the best final positive image, and the exposure amount for the full surface exposure depends on the photosensitive material. It is most preferable to apply an exposure amount within a certain range in combination of Therefore, the permissible range is wide, which is advantageous in obtaining stable and good images.

The light-sensitive material of the present invention can be applied as a black-and-white and color light-sensitive material. It can also be preferably implemented as a full-color photographic material, in which case it usually comprises a green-sensitive silver halide emulsion layer containing a magenta coupler, a blue-sensitive silver halide emulsion layer containing a yellow coupler, and a cyan coupler. A photographic light-sensitive material is formed having a red-sensitive silver halide emulsion layer containing the red color-sensitive silver halide emulsion layer.

As the yellow coupler, known acylacetanilide couplers can be preferably used, and among these, benzoylacetanilide and pivaloylacetanilide compounds are preferred.

As the magenta coupler, a pyrazoloazole type magenta coupler, a 5-pyrazolone type coupler, a pyrazolobenzimidazole type coupler, or an open chain acylacetonitrile type coupler can be arbitrarily used.

As the cyan coupler, naphthol couplers and phenol couplers can be preferably used.

In addition, the above photographic light-sensitive material has a small number of photosensitive silver halide emulsion layers on the support, as well as a filter layer, an intermediate layer, a protective layer, a subbing layer, a backing layer, an antihalation layer, etc. It is possible to provide a large number of various photographic constituent layers.As these coating methods, date coating method, air doctor coating method, extrusion coating method, slide hopper coating method, curtain flow coating method, etc. can be applied. Can be done.

The support may be opaque or transparent,
It can be selected depending on the intended photosensitive material.

Examples of the support include polyethylene terephthalate film, polycarbonate film, polystyrene film, polypropylene film, cellulose acetate film, glass, baryta paper, polyethylene laminate paper, etc., which have been subbed as necessary.

In carrying out the present invention, various photographic additives such as wetting agents, film property improvers, coating aids, etc. may be added to the silver halide emulsion of the light-sensitive material depending on the purpose. Furthermore, other photographic additives include gelatin plasticizers, surfactants, ultraviolet absorbers, pH adjusters, antioxidants, antistatic agents, thickeners, graininess improvers, dyes, mordants, brighteners, A development speed regulator, matting agent, etc. may also be used.

Furthermore, it is useful to use ultraviolet absorbers, such as thiazolidone, benzotriazole, acrylonitrile, and benzophenone compounds, to prevent fading of dye images due to short-wavelength actinic rays.

In addition to gelatin, suitable gelatin derivatives can be used as protective colloids or binders in the silver halide emulsion layer used in the above-mentioned light-sensitive materials. A binder may be included. The above-mentioned photographic light-sensitive material can be added to photographic constituent layers such as an emulsion layer, an intermediate layer, a protective layer, a filter layer, and a backing layer depending on the purpose.
Furthermore, the hydrophilic binder may contain a suitable plasticizer, wetting agent, etc. depending on the purpose.

Further, the constituent layers of the above photographic light-sensitive material can be effected with any suitable hardening agent.

When carrying out the present invention, an AS agent (antistine agent) can be used. Further, in the development process, an inhibitor can be used.

[Examples] Specific examples of the present invention will be described below, but the embodiments of the present invention are not limited thereto.

Example 1 Preparation of emulsion> Equimolar aqueous silver nitrate solution and aqueous potassium bromide solution were simultaneously added to an aqueous gelatin solution at 50°C for about 50 minutes by the double jet method to obtain cubic bromide with an average particle size of 0.28 μm. An emulsion consisting of silver particles was obtained. To this emulsion, a silver nitrate aqueous solution and a sodium chloride/potassium bromide mixed aqueous solution (molar ratio 1:1) were added simultaneously, and the average grain size was 0.50 μm.
A cubic core consisting of a silver bromide core and a silver chlorobromide shell/
A shell emulsion (a) was prepared.

A cubic core/shell type emulsion (bl) was prepared in the same manner. That is, silver bromide particles with an average grain size of 0.18 μm obtained by simultaneous addition of an aqueous silver nitrate solution and an aqueous potassium bromide solution were further added with an aqueous silver nitrate solution and an aqueous potassium bromide solution. Silver chlorobromide was grown by simultaneously adding an aqueous solution of sodium and potassium bromide (molar ratio 1:1) to obtain an emulsion consisting of core/shell type grains with an average grain size of 0.31 μm.

Next, in emulsion (a), emulsion ( An emulsion (C) consisting of core/shell type grains having an average grain size of 0.48 μm, which is approximately the same as that of a), was prepared.

After adding a commonly used spreading agent and hardening agent to the emulsions (a), (b), and (c) obtained above, they were coated on a resin-coated paper support to give a silver content of 35 mg/100 ad. , and dried directly to create a positive photosensitive material.

The obtained sample was exposed to light through a sensitometric wedge using a photosensitive needle, and a developer having the following formulation was used.

(Developer) Sodium sulfite (anhydrous) 75g Hydroquinone 12g Sodium carbonate (monohydrate) 40g Sodium hydroxide 4g Potassium bromide 4g 5-methylbenzotriazole 10mg Add water
IJ The entire surface was uniformly exposed to white light of 1 lux for 4 minutes and 30 seconds at 20° C. for 10 seconds starting 20 seconds after the start of development using the developer described above. As a result, emulsion (a)
and (C1 had different sensitivities; (al showed high sensitivity, (C) showed low sensitivity; emulsion peak) and (C) showed almost the same sensitivity.

Single layer coating conditions) The obtained emulsions (a) and (C) were mixed in a molar ratio of 1:1 and the same (emulsions (al and C) were mixed in a molar ratio of 1:
: After adding a commonly used spreading agent and a hardening agent to the mixture in the following proportions, it was coated on a resin-coated paper support to give a silver content of 35 mg/10Qcd, and dried to form two types of direct positives. Photosensitive material samples A and B were prepared.

Since emulsions (a) and (medium) have different sensitivities and average grain sizes, the light-sensitive material of the present invention cannot be obtained even if these mixed emulsions are used, and therefore Sample A is outside the scope of the present invention.

On the other hand, emulsions (al and (C) have different sensitivities, but
The average grain size is the same, and when these mixed emulsions are used,
A photosensitive material of the present invention is obtained. Therefore, sample B using this is a sample according to the present invention.

Processing solution and processing conditions> The obtained samples A and B were exposed to light through a sensitometry wedge using a photosensitive needle, and then exposed to light using a developing solution with the following formulation.
Development was carried out at a temperature of 1 minute and 50 seconds, 2 minutes and 1 seconds, 2 minutes and 30 seconds, and 2 minutes and 50 seconds.

l-phenyl-3-pyrazolidone 0.4 g Sodium sulfite (anhydrous) 75 g Hydroquinone 12 g Sodium carbonate (l hydrate) 40 g Sodium hydroxide 4 g Potassium bromide 4 g 5-methylbenzotriazole 10 mg Add water
1β However, from 20 seconds after the start of development, 1
The entire surface was uniformly exposed to white light at 1 lux for 0 seconds. Next, ring C was fixed, washed with water, and dried.

Development processing time was 1 minute 50 seconds, 2 minutes 10 seconds, and 2 minutes 30 seconds.

Table 1 shows the gradation results when changing the time to 2 minutes and 50 seconds.Table 1 * γ1 value is the density point of minimum density (D in) +0.3 and minimum density (Dmin) +0.8 It shows the slope of the straight line connecting the concentration points of , and each T value is γ1 at 2 minutes 50 seconds
The relative value is shown when the value is set to 100.

As is clear from the results in Table 1, Sample B according to the present invention exhibits small variations in gradation with respect to changes in development time and is excellent in development processing stability.

1. On the other hand, Comparative Sample A, which is not of the present invention, shows large gradation fluctuations with respect to changes in development time, and cannot obtain as good development processing stability as the sample according to the present invention. a Example 2 Trials A and B were prepared in the same manner as in Example 1 using the same emulsions (a) to (C).

This sample A, Fl was heated for 10 seconds from 20 seconds after the start of development.
As shown in Table 2, the fogging illuminance (indicated by exposure amount) was set to 8.
Change in 4 stages to uniformly cover the entire surface with white light 7
All except for exposure and development time fixed at 2 minutes 30 seconds.
It was treated in the same manner as in Example 1. 1 The obtained sensitivity results are shown in Table 2. [Table 2 Sensitivity 1 indicates the relative value of the reciprocal of the light saving amount required to provide a density of Dmin + 0.3, and the sensitivity S for each capri illuminance
1 indicates a relative value when the value when the Capri illuminance is 0.45- is taken as 100.

As is clear from the results in Table 2, Sample B according to the present invention exhibits an 11% change in sensitivity with respect to changes in Capri illuminance, and is excellent in development processing stability.

On the other hand, Comparative Sample A other than the one according to the present invention has a large variation in sensitivity with respect to changes in the illumination intensity, and cannot provide better development processing stability than the sample according to the present invention.

Example 3 Single-layer coating and processing conditions for magenta> Emulsions (a), (b), and (C1) used in Example 1 each contain a round sensitizing dye anhydro-9-ethyl-3,3'
-Di(3-sulfobutyl)-5,5'-diphenyloquinolupocyanine hydroxide was added for spectral sensitization.

As a magenta coupler, 1-(2,4,6-dolichlorophenyl)-3-(2-chloro-5-octadecylsuccinimidoanilino)-5-pyrazolone was dissolved in a mixed solvent of dibutyl phthalate and ethyl acetate. , an emulsion dispersed in an aqueous gelatin solution was prepared, and using the above spectrally sensitized emulsions (a), (b), (C1), 1
One is a mixture of emulsions (a) and (b) in a molar ratio of 1:1, and the other is a mixture of emulsions (a) and (C) in a molar ratio of 1:1.
A mixture was prepared and added and mixed to each. After adding a hardener to these two emulsions, they were coated on a resin-coated paper support at a silver content of 5 mg/100 cn and dried to prepare samples C and D.

These samples were wedge-exposed through a yellow filter, and developed at 38°C using a developing solution with the following formulation for varying development times of 1 minute 50 seconds, 2 minutes 10 seconds, 2 minutes 30 seconds, and 2 minutes 50 seconds. did.

4-Amino-3-methyl-N-ethyl-N-(β-methanesulfonamidoethyl)aniline sulfate 5g Sodium sulfite (anhydrous) 2g Sodium carbonate (
Monohydrate) 15g Sodium Bromide 1g Benzyl Alcohol 10mj! add water
II! (with potassium hydroxide p
(Adjusted to H10.2) However, from 20 seconds after the start of development,
The entire surface was uniformly exposed to white light for 0 seconds. Next, the film was bleach-fixed, washed with water, and dried in a conventional manner.

Table 3 shows the gradation results of the obtained magenta positive image.

Table 3 As is clear from the results in Table 3, it can be seen that the samples according to the present invention have small gradation fluctuations with respect to changes in development time, and are excellent in development processing stability.

In addition, the entire surface of Samples C and D was uniformly exposed to white light for 10 seconds from 20 seconds after the start of development, with fogging illuminance (indicated by exposure amount) being varied in four stages as shown in Table 4, and Processing was carried out in exactly the same manner except that the development time was fixed at 2 minutes and 30 seconds.

Table 4 shows the sensitivity results of the obtained magenta positive image.

Table 4 As is clear from the results in Table 4, it can be seen that the sample plate according to the present invention has small sensitivity fluctuations with respect to changes in fogging illuminance and is excellent in development processing stability.

Example 4 (Single layer coating and processing conditions for cyan) The sensitizing dye anhydro-9-ethyl-3,3 was added to each of the emulsions (at, (b), (cl) used in Example 1).
'-Di(3-sulfopropyl)-5,5'-dichlorothiacarbocyanine hydroxide was added to perform spectral sensitization.

Separately, as a cyan coupler, 2,4-dichloro-3-methyl-6-(2-(2,4-di-t-amylphenoxy)
Butylamido]phenol was dissolved in a mixed solvent of dibutyl phthalate and ethyl acetate, and an emulsion was prepared by dispersing it in an aqueous gelatin solution, and the above spectrally sensitized emulsion (a) was prepared.
(bl, using (C), one with emulsion (a) and inside)
One is a mixture of 1=1 in molar ratio, and the other is an emulsion (
A mixture of a) and (C) at a molar ratio of 1:1 was prepared, and added and mixed to each. After adding a hardener to the two emulsions, 4 m of silver was deposited on a resin-coated paper support.
Samples E and F were prepared by coating and drying to give a weight of 100 g/100 aJ.

These samples were wedge-exposed through a red filter, and developed at 38° C. with a developing solution having the following formulation, while changing the development time to 1 minute 50 seconds, 2 minutes 10 seconds, 2 minutes 30 seconds, and 2 minutes 50 seconds.

4-Amino-3-methyl-N-ethyl-N-(β-methanesulfonamidoethyl)aniline sulfate 5 g Sodium sulfite (anhydrous) 0.3 g Sodium carbonate (monohydrate) 15 g Potassium bromide 0.3 g Water 11 (adjusted to pH 10.2 with sodium hydroxide) However, the entire surface was uniformly exposed to white light for 10 seconds starting 20 seconds after the start of development. Then, it was bleach-fixed, washed with water, and dried in a conventional manner.

Table 5 shows the sensitivity results of the obtained cyan positive images.

Table 5 As is clear from the results in Table 5, Sample F according to the present invention has small gradation fluctuations with respect to changes in development time, and is found to have excellent development processing stability.

In addition, the entire surface of Samples E and F was uniformly exposed to white light for 10 seconds after 20 seconds after the start of development, with the fogging illuminance (indicated by exposure amount) being varied in four stages as shown in Table 6, and then developed. The treatment was carried out in exactly the same manner as above, except that the time was fixed at 2 minutes and 30 seconds.

Table 6 shows the sensitivity results of the obtained cyan positive images.

Table 6 As is clear from the results in Table 6, Sample F according to the present invention has small sensitivity fluctuations with respect to changes in fogging illuminance and is excellent in development processing stability.

Example 5 Monolayer coating and processing conditions for yellow Yellow coupler α-(4-(1-benzyl-2- Phenyl-3,5-dioxo-1,2,4
-Triaziridinyl)]-]α-pivalyl-2-chloro-5-γ-(2,4-di-t-amylphenoxy)butyramide] Add and mix an emulsion of oil-protected dispersed acetanilide, and then add a hardening agent. Emulsions (al, (b), (C) prepared using
One was made by mixing a) and (b) in a molar ratio of 1:1, and the other was made by mixing emulsions (a) and (C) in a molar ratio of 1:1, and then coated with resin. Samples G and H were prepared by coating these emulsions on a paper support so that the amount of silver was 5 mg/100cj.

These samples were wedge-exposed with white light, and the developer used in Example 3 was used at 38°C for development times of 1 minute 50 seconds and 2 minutes 1.
Developing was performed at different times: 0 seconds, 2 minutes 30 seconds, and 2 minutes 50 seconds. However, the entire surface was uniformly exposed to white light for 10 seconds from 20 seconds after the start of development. Then, it was bleach-fixed, washed with water, and dried in a conventional manner.

Table 7 shows the sensitivity results of the yellow positive image obtained.

Table 7 As is clear from the results in Table 7, sample H according to the present invention
It can be seen that the variation in gradation is small with respect to changes in development time, and the stability of the development process is excellent.

In addition, the entire surface of Samples G and H was uniformly exposed to white light for 10 seconds after 20 seconds after the start of development, with the fogging illuminance (indicated by exposure amount) being varied in four stages as shown in Table 8, and then developed. The treatment was carried out in exactly the same manner as above, except that the time was fixed at 2 minutes and 30 seconds.

Table 8 shows the sensitivity results of the yellow positive image obtained.

Table 8 As is clear from the results in Table 8, Sample H according to the present invention has small sensitivity fluctuations with respect to changes in fogging illuminance, and is found to have excellent development processing stability.

Example 6 Multilayer coating and processing conditions> The emulsion obtained by mixing emulsions (a) and (b) in a ratio of 1:1 used in Example 1 was divided into three parts, and a part of the emulsion was mixed with anhydro-sensitizing dye.
9-ethyl-3,3”-di(3-sulfopropyl)-5
, 5'-dichlorothiacarbocyanine hydroxide to give a red-sensitive emulsion. Another part was spectrally sensitized using the sensitizing dye anhydro-9-ethyl-3,31-di(3-sulfopropyl)-5,5''-diphenyloxacarbocyanine hydroxide to make a green-sensitive emulsion. Another portion was spectrally sensitized using the enhancing dye anhydro-3-sulfopropyl)-3'-carboxymethyl-5,51-dichlorothiacarbocyanine hydroxide to form a blue-sensitive emulsion.

Sample r was prepared by sequentially applying the following layers onto a resin-coated paper support from the support side. Next, emulsion (a) and (
Sample J was prepared in exactly the same manner except that the emulsion was changed using an emulsion in which C) was mixed at a ratio of 1:1.

(1) Red-sensitive emulsion layer The above-mentioned red-sensitive emulsion (5 mg/100 cal in terms of silver)
) and an oil-protected dispersed cyan coupler (same as the cyan coupler used in Example 4, 0.45 mol per mol of silver halide).

(2) Intermediate layer oil protection Contains dispersed 2,5-di-t-octylhydroquinone.

(3) Green-sensitive emulsion layer The above-mentioned green-sensitive emulsion (5 mg/100cn in terms of silver)
Contains a magenta coupler (same as the magenta coupler used in the example, 0.25 mole per mole of halogenated i) dispersed in oil protection.

(4) Yellow filter layer yellow colloidal silver and oil protection dispersed 2
, 5-di-t-octylhydroquinone.

(5) Front window emulsion layer The above blue-sensitive emulsion (6 mg/100 cff in terms of silver)
l) and oil-protected dispersed yellow coupler (
It contains 0.45 mol per mol of silver halide, which is the same as the yellow coupler used in Example.

(6) Protective layer gelatin layer.

Table 9 shows the results of the gradation and sensitivity of the obtained positive image.

Table 9 Table 9 As is clear from the results in Table 9, sample J according to the present invention has small gradation fluctuations with respect to changes in development time, and small sensitivity fluctuations with respect to changes in fogging illuminance. It can be seen that it has excellent stability.

Example 7 Emulsion of Example 1 (average grain size 0 using the preparation method of C1)
．． An emulsion (dl) consisting of core/shell type grains was prepared so as to have a particle size of 54 μm. When the sensitivity of the emulsion (dl) was evaluated, it was found to have a sensitivity equivalent to that of the emulsion (bl) used in Example 1.

Single layer coating and processing conditions for magenta > This emulsion (dl) and the emulsion (a) used in Example 1, (
C) as in Example 3, namely emulsion (at, (cl
, (d) were spectrally sensitized by adding the sensitizing dye anhydro-9-ethyl-3,3°-di(3-sulfobutyl)-5,5'-diphenyloxacarbocyanine hydroxide. Separately, 1-(2,4
゜6-Dolichlorophenyl)-3-(2-chloro-5-
The spectrally sensitized emulsion (a) was prepared by dissolving octadecylsuccinimideanilino)-5-pyrazolone in a mixed solvent of dibutyl phthalate and ethyl acetate and dispersing it in an aqueous gelatin solution.

(Using C1, (dl), one is a mixture of emulsions (al and +d) in a molar ratio of 1=1, and the other is an emulsion (a
) and (C) in a molar ratio of 1=1,
They were added to each and mixed. After adding a hardener to these two emulsions, a silver content of 5 mg/g was deposited on a resin-coated paper support.
It was applied to a thickness of 100 cd and dried to create a sample L.

These samples were wedge-exposed to L through a yellow filter, and the developer of Example 3 was used to perform the same two types of processing as in Example 3. The resulting magenta positive image gradation results and sensitivity The results are shown in Table 10.

Table 10 Table 10 As is clear from the results in Table 10, compared to sample K, sample K had smaller gradation fluctuations with respect to changes in development time, and also had smaller sensitivity fluctuations with respect to changes in fogging illuminance. Excellent processing stability.

From a practical point of view, the sample is superior to comparative samples outside the present invention and has no problems.

〔Effect of the invention〕

As described above, according to the present invention, there is an effect that good development processing stability can be obtained against changes in development time and fogging illuminance.

Claims (1)

[Scope of Claims] 1. Having at least one silver halide emulsion layer containing at least two types of internal latent image type silver halide grains that are not fogged in advance, and after image exposure, while performing full-surface exposure, and/or in a photographic light-sensitive material in which a positive image is directly obtained by surface development after application, the at least two types of internal latent image type silver halide grains have different sensitivities, but have approximately the same average grain size. Direct positive silver halide photographic material with special features.