JPH04333839A - Direct positive color photographic sensitive material - Google Patents

Abstract

PURPOSE:To provide the direct positive silver halide photographic sensitive material which is low in the min. density of images and is improved in whiteness. CONSTITUTION:This direct positive color photographic sensitive material is constituted by providing blue, green and red photosensitive layers contg. internal latent image type silver halide emulsions which are not previously fogged and couplers on a base. The nonphotosensitive layer provided on the side furthest from the base than the above-mentioned red photosensitive layers and green photosensitive layers consists of a layer substantially allowing the transmission of blue light. The ratio (rB/rG) of the average particle size (rB) of the silver halide particles incorporated into the blue photosensitive layers to the average particle size (rG) of the silver halide particles incorporated into the green photosensitive layers and the ratio (rG/rR) of the average particle size (rG) of the silver halide particles incorporated into the green photosensitive layer to the average particle size (rR) of the silver halide particles incorporated into the red photosensitive layers are respectively in 1.3<=rB/rG<=3.0, 1.3<=rG/rR<=3.0 ranges.

Description

[Detailed description of the invention]

0001

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a direct positive color photographic light-sensitive material from which a positive image can be directly obtained using an internal latent image type silver halide emulsion. In particular, the present invention relates to a direct positive color photographic material suitable for creating color proofs used for plate inspection and adjustment in color plate making and printing processes.

0002

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

As a method for producing a positive image using a conventionally known direct positive color silver halide photographic light-sensitive material, there is a method using an internal latent image type silver halide emulsion which has not been fogged in advance. This method is a method in which a photographic light-sensitive material is subjected to surface development after image exposure, after being subjected to fogging treatment, or while being subjected to fogging treatment, to directly obtain a positive color image.

The above-mentioned internal latent image type silver halide photographic emulsion which is not fogged in advance is a type in which photosensitive nuclei are mainly inside the silver halide grains, and a latent image is mainly formed inside the grains upon exposure. A silver halide photographic emulsion.

[0005] Various techniques are known to date in this field. For example, US Patent Nos. 2,592,250, 2,466,957, 2,497,875, and 258
No. 8982, No. 3317322, No. 3761266, No. 3761276, No. 3796577 and British Patent No. 1151363, No. 1150553, No. 10
The main ones are those described in each specification of No. 11062.

The mechanism for forming a direct positive image is explained as follows. That is, when imagewise exposed, a so-called internal latent image is generated on the silver halide, and then by performing a fogging treatment, a surface desensitization effect due to this internal latent image is activated (i.e., the silver halide in the exposed area is development nuclei (fogging nuclei) are not generated on the surface of the silver halide), but development nuclei are selectively generated only on the surface of the silver halide in the unexposed areas, and then by performing normal surface development processing, the unexposed areas become photographic. An image (positive image) is formed. The above-mentioned fogging treatment methods include a method called "photofogging method" in which the entire photosensitive layer is exposed to light, and a method called "chemical fogging method" using a nucleating agent.

In recent years, direct positive color silver halide photographic materials using internal latent image type silver halide emulsions that have not been fogged in advance have been accepted for the simplicity of the processing process and have been used for copying purposes. ing.

[0008] The process of producing color printed matter includes the steps of color-separating a color original and converting it into a halftone image to create a transmission halftone image. A printing plate is made from the obtained transmission halftone image, but prior to this, the final printed matter (actual printing)
There is a process of inspecting the condition, characteristics, etc., and performing necessary calibration (color calibration). Conventionally, the color proofing method has been to create a printing plate and make a trial print. However, in recent years, various color proofs have been created in order to speed up the proofreading process and reduce costs.

Known methods for producing color proofs include photopolymers, diazo methods, surprint methods and overlay methods using photo-adhesive polymers (for example, US Pat. No. 3,582,327, Japanese Unexamined Patent Publication No. 56-
501217, 59-97140). However, all of these methods require overlapping and transferring images, and the process is complicated, requiring a lot of time and cost, as it is necessary to overlay and transfer multiple images. .

[0010] JP-A-56-104335 discloses a method for producing a color proof using a color photosensitive material, and this method has great advantages in terms of simple process and low cost. Moreover, it has features such as excellent tone reproducibility.

The method for producing a color proof using the above-mentioned color photographic light-sensitive material uses a silver halide color photographic light-sensitive material of a color development method having continuous gradations, and a magenta (M) color photographic material is used.
The color, cyan (C), yellow (Y), and ink (B) color plates are sequentially exposed in close contact like printing a color negative onto color paper, and then subjected to specified color development processing to obtain a color proof. It's a method. This method has features that the process is simpler and easier to automate than the various methods mentioned above.

There are several possible silver halide color photographic materials that can be used for such color proofs. Among these, the transmission black-and-white dot images used in the production process of color printed matter mentioned above are often positive, especially in Japan and Europe, so they are not suitable for use as silver halide color photographic materials for color proofing. Positive-positive photosensitive materials are often used. Among them, the above-mentioned direct positive type color photographic materials, whose practical technology has been rapidly progressing in recent years, are attracting attention as being most suitable for color proofing applications because of their ease of processing.

The above-mentioned direct positive color photographic light-sensitive material generally has a red-sensitive layer containing a cyan coupler and an internal latent image type silver halide emulsion that is not pre-fogged, a magenta coupler and an internal latent image that is not pre-fogged on a support. A green-sensitive layer containing a type silver halide emulsion and a blue-sensitive layer containing a yellow coupler and an internal latent image type silver halide emulsion which have not been fogged in advance are provided in this order. Usually, as the photosensitive layer and the non-photosensitive layer, there is an antihalation layer on the support, an intermediate layer between each photosensitive layer, and a yellow filter layer between the blue sensitive layer and the green sensitive layer. , and a protective layer is provided on the top layer, respectively.

[0014]

[Problems to be Solved by the Invention] As mentioned above, with the diversification of uses for direct positive color photographic materials, the requirements for the images (image quality) obtained are becoming increasingly strict.
It is desired that the image has a high maximum image density and a low minimum image density, that is, a large ratio between the maximum image density and the minimum image density. Particularly in color proof applications, it is important to achieve high whiteness by reducing the minimum image density in order to obtain good color reproducibility.

Various methods have been proposed to increase the degree of whiteness (ie, lower the minimum image density). For example, there is a method of incorporating metals such as manganese, copper, zinc, cadmium, etc. into internal latent image type silver halide grains that have not been fogged in advance (Japanese Patent Application Laid-open No. 1-145647), or a method of incorporating highly active hydroquinone into an emulsion layer. There is a method of adding (Japanese Unexamined Patent Publication No. 2-220049).

However, even if these methods are used, the above requirements have not yet been fully satisfied.

[0017] Accordingly, an object of the present invention is to provide a direct positive silver halide photographic light-sensitive material having a low minimum image density and improved whiteness.

[0018]

[Means for Solving the Problems] The present inventor aims to realize an image that has a high maximum density and a low minimum density, in particular, a low minimum image density and further improved whiteness. I considered it carefully. As a result, the yellow filter layer normally provided in light-sensitive materials (generally silver halide emulsions have inherent sensitivity to blue light, and the yellow filter layer has a green-sensitive layer and a red-sensitive layer that are sensitive to blue light) It was found that yellow colloidal silver or yellow dye is included to prevent this from occurring. That is, it was found that the colloidal silver or dye contained in the yellow filter layer increases the minimum image density by covering the emulsion or partially remaining in the image area without being bleached. Therefore, the inventors of the present invention achieved the above object by constructing a light-sensitive material without a yellow filter layer and setting the sensitivity of the blue-sensitive layer to be relatively higher than the sensitivity of the other green-sensitive layers and red-sensitive layer. The inventors have discovered that this can be achieved, and have completed the present invention.

The present invention provides a red light-sensitive layer containing a cyan coupler and an internal latent image type silver halide emulsion that has not been fogged in advance, a magenta coupler and an internal latent image type silver halide emulsion that has not been fogged in advance, on a support. and a blue light-sensitive layer containing a yellow coupler and an internal latent image type silver halide emulsion that has not been fogged in advance, the direct positive color photographic material is provided with a green light-sensitive layer containing: The non-photosensitive layer provided on the side far from the support substantially consists of a layer that transmits blue light, and is included in the blue-sensitive layer with respect to the average grain size (rG) of the silver halide grains contained in the green-sensitive layer. Ratio of average grain size (rB) of silver halide grains (rB/
rG ), and the ratio of the average grain size (rG ) of the silver halide grains contained in the green light-sensitive layer to the average grain size (rR ) of the silver halide grains contained in the red light-sensitive layer (
rG /rR ) are 1.3≦rB /rG ≦3.0, 1, respectively.
．． The present invention provides a direct positive color photographic material characterized in that 3≦rG /rR≦3.0.

Conventionally, it has been considered that the smaller the difference in sensitivity between the photosensitive layers, the better (for example, Japanese Patent Laid-Open No. 2-170159). For this reason, the average grain size of the silver halide grains contained in each photosensitive layer is set to be approximately the same size. Therefore, conventional photosensitive materials, like the photosensitive material of the present invention, cover the sensitivity of the blue-sensitive layer, the sensitivity of the green-sensitive layer and the red-sensitive layer, and the function of the yellow filter layer (a function that does not cause spectral color mixture). It was not set as high as possible.

[0021] In the present invention, "a layer that substantially transmits blue light" means that the absorbance for light with a wavelength of 450 nm is less than 0.1. In addition, the average grain size of silver halide grains (rB, rG and r
R) means weight average particle size. moreover,"
"Coupler" means that the coupler itself is non-diffusible, and the dye produced by coupling with the oxidized form of a developing agent is also non-diffusible.

[0022] Preferred embodiments of the present invention will be described below. (1) Each photosensitive layer is provided on a support in the order of a red-sensitive layer, a green-sensitive layer, and a blue-sensitive layer, and the layer that substantially transmits blue light is the green-sensitive layer and the blue-sensitive layer. Exists between the sensitive layers. (2) The value of (rB /rG) is 1.5≦rB
/rG ≦2.5, and the above (rG /r
The value of R ) is in the range of 1.5≦rG /rR ≦2.5.

(3) In the case of (1) above, an intermediate layer is provided between the support and the red-sensitive layer and between each photosensitive layer. (4) An antihalation layer is provided on the support.

(5) A protective layer is provided on the uppermost layer of the support on the side having the emulsion layer. (6) The layers (photosensitive layer and non-photosensitive layer) provided on the support are formed using a simultaneous multilayer coating method. (7) The compound represented by the above formula (I) or (II) is contained in all the photosensitive layers.

[0025]

[Effects of the Invention] The photographic material of the present invention has a structure in which the yellow filter layer attached to a conventional photographic material is omitted. For this reason, as mentioned above, the disadvantageous effects of colloidal silver or dyes on image areas (emulsion fog,
Alternatively, stains due to insufficient decolorization can be avoided. Therefore, the minimum image density is further lowered (whiteness is increased).
can do. Further, in the photographic light-sensitive material of the present invention, the sensitivity of the blue-sensitive layer is set higher than the sensitivity of the green-sensitive layer and the red-sensitive layer to such an extent that spectral color mixture does not occur. Therefore, since exposure to blue light can be performed at a reduced amount compared to the normal exposure amount, the sensitization effect of the green-sensitive layer and the red-sensitive layer to blue light can be minimized. Therefore, spectral color mixing due to removal of the yellow filter layer is unlikely to occur, and color mixing will not occur due to this. Furthermore, the minimum image density can be further lowered by using a compound represented by formula (I) or (II). By using the direct positive color photographic material having the structure of the present invention as described above, images with high whiteness (minimum image density) can be obtained.
Good color reproducibility is achieved, and therefore,
It is particularly suitable for color proofing purposes.

The direct positive color photographic material of the present invention will be explained in detail below. The direct positive color photographic light-sensitive material of the present invention comprises a support, a red-sensitive layer containing a cyan coupler and an internal latent image type silver halide emulsion that has not been fogged in advance, a magenta coupler and an internal latent image type halogen emulsion that has not been fogged in advance. A green sensitive layer containing a silver halide emulsion and a blue sensitive layer containing a yellow coupler and an internal latent image type silver halide emulsion which had not been previously fogged were provided. Although the order in which the photosensitive layers described above are arranged on the support is not particularly limited, in the present invention, each photosensitive layer is placed on the support,
It is particularly preferable that the red-sensitive layer, green-sensitive layer, and blue-sensitive layer are arranged in this order.

Further, each photosensitive layer may be composed of a single layer or a plurality of layers. When each photosensitive layer is composed of a plurality of layers, these plurality of layers are arranged as one unit (a unit of the same color sensitivity). For example, in the case of an embodiment in which each photosensitive layer (each photosensitive layer is composed of a plurality of layers) is arranged on a support in the order of red-sensitive layer, green-sensitive layer, and blue-sensitive layer as described above. In this method, all of the plurality of layers constituting the red-sensitive layer are arranged closer to the support than any of the plurality of layers constituting the green-sensitive layer, and the plurality of layers constituting the blue-sensitive layer are All of the layers are arranged farther from the support than any of the plurality of layers constituting the green-sensitive layer.

In the photosensitive material of the present invention, it is preferable that an intermediate layer, which is a non-photosensitive layer, is provided between each photosensitive layer. When the photosensitive layer is composed of a plurality of layers, the intermediate layer may be present between these layers.

In the present invention, the non-photosensitive layer provided on the red-sensitive layer and the green-sensitive layer consists of a layer that substantially transmits blue light. That is, the so-called yellow filter layer that cuts blue light, which is attached to ordinary photosensitive materials, is not present in the photosensitive material of the present invention. As mentioned above, "a layer that substantially transmits blue light" means 4.
This means that the absorbance for light with a wavelength of 50 nm is less than 0.10.

In the photosensitive material of the present invention, it is preferable that an antihalation layer is provided on the support as the non-photosensitive layer, and a protective layer is provided on the uppermost layer of the support on the side having the photosensitive layer. Preferably.

The average grain size (rG) of the silver halide grains contained in the blue-sensitive layer relative to the average grain size (rG) of the silver halide grains contained in the green-sensitive layer of the photographic light-sensitive material of the present invention.
The ratio of rB ) (rB /rG ) is 1.3≦rB /
rG ≦3.0, and the average grain size (r
The ratio of G) (rG/rR) is 1.3≦rG/r
It is in the range of R≦3.0.

In the present invention, the above (rB /rG)
The value of is in the range of 1.5≦rB /rG ≦2.5, and the value of (rG /rR) is in the range of 1.5≦rG
It is preferable that /rR≦2.5.

Note that the average grain size (rB, rG and rR) of the silver halide grains above represents the weight average grain size. The average grain size of silver halide grains is determined by conventional electron microscopy.

When the photosensitive layer is composed of a plurality of layers as one unit (unit of the same color sensitivity) as described above, the average grain size of the silver halide grains (rB, rG
and rR ), the weight average grain size of the silver halide grains contained in the plurality of layers is within the average grain size range defined above.

Examples of preferred layer constitutions of the direct positive color photographic material of the present invention are listed below. (1) Support 1st layer: Antihalation layer 2nd layer: Intermediate layer 3rd layer: Red-sensitive layer 4th layer: Intermediate layer 5th layer: Green-sensitive layer 6th layer: Intermediate layer 7th layer: Blue-sensitive layer Layer 8: Protective layer

(2) support 1st layer: middle layer 2nd layer: anti-halation layer Third layer: middle layer 4th layer: low sensitivity red sensitivity layer 5th layer: Medium sensitivity red sensitivity layer 6th layer: High sensitivity red sensitivity layer 7th layer: middle layer 8th layer: low sensitivity green sensing layer 9th layer: Medium sensitivity green sensing layer 10th layer: High sensitivity green sensing layer Layer 11: Middle layer 12th layer: low sensitivity blue sensitivity layer Layer 13: Mid-sensitivity blue-sensing layer 14th layer: High sensitivity blue sensing layer Layer 15: Middle layer Layer 16: Protective layer

In the case of the above layer configurations (1) and (2), the layers provided on the support are preferably formed using a simultaneous multilayer coating method.

The unfogged internal latent image type silver halide emulsion used in the present invention contains silver halide grains whose surfaces are not fogged and which forms latent images mainly inside the grains. More specifically, a silver halide emulsion is deposited on a transparent support in a certain amount (
0.5 to 3 g/m2), exposed to light for a fixed time of 0.01 to 10 seconds, and developed in the following developer (internal type developer) at 20°C for 5 minutes. The maximum density measured by the photographic density measurement method is obtained when a silver halide emulsion coated in the same amount as above and exposed in the same manner is developed in the following developer (surface type developer) at 18°C for 6 minutes. preferably at least 5 times greater, more preferably at least 1
It has a concentration 0 times greater.

Internal type developer Metol

2.0g Sodium sulfite (anhydrous)
90.0g
hydroquinone
8.0g
Sodium carbonate (monohydrate)
52.8g KB
r
5.0g
KI

Add 0.5g water

1000cc surface type developer Metol

2.5g L-ascorbic acid
10.
0g NaBO2 ・4H2 O
35.0
g KBr

Add 1.0g water

1000cc

Specific examples of internal latent image type emulsions include conversion type silver halide emulsions described in US Pat. No. 2,592,250, or US Pat. Nos. 3,761,276 and 3,850,637;
No. 3923513, No. 4035185, No. 4395
Specifications of No. 478 and No. 4504570, Japanese Unexamined Patent Publication No. 1983
-156614, 55-127549, 53-
No. 50222, No. 56-22681, No. 59-208
No. 540, No. 60-107641, No. 61-3137
No. 62-215272, Research Disclosure Magazine No. No. 23510 (issued in November 1983) on page 236, as well as U.S. Pat.
-47766, Japanese Patent Application No. 1-2467, JP-A-63-191145 concerning emulsion doped with metal ions,
Examples include core/shell type silver halide emulsions described in JP-A-1-52146. The molar ratio of silver halide between the core and the shell of the internal latent image type core-shell silver halide emulsion is particularly preferably 20/1 or less and 1/100 or more.

The internal latent image type silver halide grains that have not been fogged in advance include Mn, Cu, Zn, Cd, Pd, and Bi.
Alternatively, at least one metal selected from the group consisting of metals belonging to Group VIII of the periodic table may be incorporated.

Mn, Cu, Zn, Cd, Pd, which are contained in the internal latent image type silver halide grains that are not fogged in advance,
The amount of Bi or metal belonging to Group VIII of the periodic table is preferably 10-9 to 10-2 mol, more preferably 10-7 to 10-3 mol, per mol of silver halide.

Among the metals mentioned above, particular preference is given to using lead, iridium and bismuth and rhodium.

When these metals are mixed with a silver ion solution and an aqueous halogen solution to form silver halide grains, the metal ions can be made to coexist in the form of an aqueous solution or an organic solvent solution and incorporated into the grains. Alternatively, after forming the grains, metal ions may be added in the form of an aqueous or organic solvent solution and then further coated with silver halide.

Methods for incorporating these metals are described in US Pat. No. 3,761,276, US Pat.

The shapes of the silver halide grains used in the present invention are cubic, octahedral, dodecahedral, and dodecahedral (Japanese Patent Laid-Open No. 2-22
3948), irregular crystal forms such as spherical, and the length/thickness ratio value described in JP-A-1-131547 and JP-A-1-158429 is 5 or more. In particular, an emulsion may be used in which 8 or more tabular grains account for 50% or more of the total projected area of the grains. Further, emulsions having composite forms of these various crystal systems or mixtures thereof may be used.

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

The average grain size of silver halide grains (in the case of spherical or nearly spherical grains, the grain diameter is taken as the grain size, and in the case of cubic grains, the vertical length is taken as the grain size, respectively, and expressed as an average based on the projected surface). , 1.5 μm or less, 0.1 μm
It is preferably at least m, but particularly preferably at most 1.2 μm and at least 0.2 μm. The particle size distribution may be narrow or wide, but in order to improve granularity and sharpness, the particle number or weight should be within ±40% of the average particle size, preferably within 30%, most preferably ± It is preferable to use in the present invention a so-called "monodisperse" silver halide emulsion having a narrow grain size distribution in which 90% or more, especially 95% or more of all grains fall within 20%.

In addition, in order for the light-sensitive material to satisfy the target gradation, two or more types of monodispersed silver halide emulsions with different grain sizes or two or more types of monodisperse silver halide emulsions with different grain sizes are used in the emulsion layer having substantially the same color sensitivity, or two or more types of monodisperse silver halide emulsions with the same size and sensitivity are used. A plurality of particles having different properties can be mixed in the same layer or coated in separate layers. Furthermore, two or more types of polydisperse silver halide emulsions or a combination of monodisperse emulsions and polydisperse emulsions may be mixed or layered for use.

The silver halide emulsion used in the present invention can be chemically sensitized inside or on the grains by sulfur or selenium sensitization, reduction sensitization, noble metal sensitization, etc. alone or in combination. As a chemical sensitization method for core particles, methods described in JP-A-2-199450 and JP-A-2-199449 can be used. In the presence of a mercapto compound as described in JP-A No. 1-197742, JP-A No. 1-254946, JP-A No. 2-69738, JP-A No. 2-
Thiosulfinic acid, sulfinic acid, and sulfite may be added as described in Japanese Patent No. 273735. For detailed examples, see Research Disclosure Magazine No. 176
43-III (published in December 1978), page 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 cyanine dyes, merocyanine dyes and complex merocyanine dyes, which may be used alone or in combination. Further, the above dyes and supersensitizers may be used in combination. For detailed specific examples, please refer to research
Disclosure magazine No. 17643-IV (197
(Published in December 1998) on pages 23-24.

The photographic emulsion used in the present invention may contain an antifoggant or a stabilizer for the purpose of preventing fog during the manufacturing process, storage, or photographic processing of the light-sensitive material, or for stabilizing photographic performance. Can be done. For detailed specific examples, see Research Disclosure Magazine No.
17643-VI (issued December 1978) and E
．． J. “Stabilization o” by Birr
f Photographic Silver Hai
'lde Emulsion' (Focal Pres.
s), published in 1974.

In the present invention, various color couplers can be used in combination. Typical examples of useful color couplers include naphthol or phenolic compounds, pyrazolone or virazoloazole compounds, and open chain or heterocyclic ketomethylene compounds. Specific examples of these cyan, magenta and yellow couplers that can be used in combination in the present invention are given in "Research Disclosure" magazine No.
17643 (published December 1978) 25 pages, VII-
Section D, same No. No. 18717 (published in November 1979) and JP-A-62-215272 and the patents cited therein.

Among them, 5 preferably used in the present invention
The -prazolone type magenta coupler is a 5-pyrazolone type coupler in which the 3-position is substituted with an arylamino group or an acylamino group (particularly a sulfur atom separation type two-equivalent coupler).

More preferred are pyrazoloazole couplers, and among them are pyrazolo[5,1-c][1,2,4]triazoles described in US Pat. No. 3,725,067. U.S. Patent No. 45006 in terms of low yellow side absorption of the dye and light fastness.
Even more preferred are the imidazo[1,2-b]pyrazoles described in US Pat. No. 30, and particularly preferred are the pyrazolo[1,5-b][1,2,4]triazoles described in US Pat.

As a cyan coupler, US Pat. No. 24
Naphthol-based and phenol-based couplers described in US Pat. No. 74293, US Pat. Other 2,5-diacylamino-substituted phenolic couplers are also preferred from the viewpoint of color fastness.

Examples of the yellow coupler include US Pat. No. 3,933,501, US Pat. No. 4,022,620, US Pat.
No. 1,476,760 and the like are preferred.

Colored couplers for correcting unnecessary absorption in the short wavelength range of the generated dyes, couplers in which coloring dyes have appropriate diffusivity, colorless couplers, and release of development inhibitors along with coupling reactions. DIR couplers and polymerized couplers can also be used.

Couplers that release photographically useful residues upon coupling are also preferably used in the present invention. DIR couplers that release development inhibitors are described in Research Disclosure no. 17643, patents described in sections VII to F, JP-A-57-151944, JP-A-57-
154234, 60-184248, U.S. Pat. No. 42,8962, and JP-A-63-146035 are preferred.

As a coupler that releases a nucleating agent or a development accelerator in an image form during development, British Patent No. 2097
No. 140, Specifications of No. 2131188, JP-A-59
Preferred are those described in WO 88/01402 and WO 88/01402.

Typical amounts of color couplers used range from 0.001 to 1 mole per mole of photosensitive silver halide, preferably from 0.01 to 0.5 mole for yellow couplers, and for magenta couplers. 0.03 mole to 0.5 mole, and 0.002 mole for cyan couplers
The amount is between 1.0 mol and 1.0 mol.

Next, the above-mentioned compound represented by formula (I) or (II) (hydroquinone compound) will be explained. The hydroquinone compound is disclosed in JP-A-2-220049 as mentioned above. Formula (I):

[In the above formula (I), R31 to R34 are a hydrogen atom, a halogen atom, a sulfo group, a carboxyl group, a cyano group, an alkyl group, an alkenyl group, an aryl group, an acylamino group, a sulfonamide group, an alkoxy group , represents an aryloxy group, an alkylthio group, an arylthio group, an acyl group, an acyloxy group, a sulfonyl group, a carbamoyl group, an alkoxycarbonyl group, or a sulfamoyl group, and the above R31 and R32 and R33 and R34 jointly represent a carbocycle or a heterocycle. may be formed, provided that the above R3
At least one of 1 to R34 is not a hydrogen atom, and when the above R31 to R34 consists of only a hydrogen atom and an alkyl group, at least one of the alkyl groups has 6 or more carbon atoms, and R31 to R34 The total number of carbon atoms is 15 or less. ]

In the above formula (I), the halogen atoms represented by R31 to R34 are:
For example, chlorine can be mentioned.

The alkyl group represented by R31 to R34 includes an alkyl group having 1 to 15 carbon atoms, such as methyl, sec-butyl, t-butyl, t-pentyl, t-hexyl, cyclohexyl, t-octyl, benzyl. Examples include groups such as.

[0065] As the alkenyl group represented by R31 to R34, an allyl group can be mentioned.

Examples of the aryl group represented by R31 to R34 include aryl groups having 6 to 15 carbon atoms, such as phenyl and p-tolyl.

Examples of the acylamide group represented by R31 to R34 include acylamide groups having a substituent having 2 to 15 carbon atoms, such as acetylamino and benzoylamino groups.

Examples of the sulfonamide group represented by R31 to R34 include sulfonamide groups having a substituent having 1 to 15 carbon atoms, such as methanesulfonamide and benzenesulfonamide.

Examples of the alkoxy group represented by R31 to R34 include alkoxy groups having 1 to 15 carbon atoms, such as methoxy, butoxy, benzyloxy, and dodecyloxy.

Examples of the aryloxy group represented by R31 to R34 include aryloxy groups having 6 to 15 carbon atoms, such as phenoxy and p-methoxyphenoxy.

Examples of the alkylthio group represented by R31 to R34 include alkylthio groups having 1 to 15 carbon atoms, such as butylthio and decylthio.

Examples of the arylthio group represented by R31 to R34 include arylthio groups having 6 to 15 carbon atoms, such as phenylthio and p-hexyloxyphenylthio.

The acyl group represented by R31 to R34 is an acyl group having 2 to 15 carbon atoms, such as acetyl,
Mention may be made of groups such as benzoyl and hexanoyl.

Examples of the acyloxy group represented by R31 to R34 include acyloxy groups having 1 to 15 carbon atoms, such as acetyloxy and benzoyloxy.

The sulfonyl group represented by R31 to R34 includes a sulfonyl group having a substituent having 1 to 15 carbon atoms, such as methanesulfonyl and benzenesulfonyl.

The carbamoyl group represented by R31 to R34 includes a carbamoyl group having a substituent having 1 to 15 carbon atoms, such as N,N-diethylcarbamoyl, N-
It can include groups such as phenylcarbamoyl.

Examples of the alkoxycarbonyl group represented by R31 to R34 include alkoxycarbonyl groups having 2 to 15 carbon atoms, such as methoxycarbonyl and butoxycarbonyl.

The sulfamoyl group represented by R31 to R34 includes a sulfamoyl group having a substituent having 0 to 15 carbon atoms, such as N,N-dipropylsulfamoyl, N-phenylsufamoyl, etc. Can be done.

Further, R31 and R32 and R33 and R34 may jointly form a carbocycle or a heterocycle.

Furthermore, the above R31 to R34 may have a substituent or a substituent atom. Examples of the substituent or substituent atom include an alkyl group, an aryl group, an alkoxy group, an aryloxy group, a sulfo group, a carboxyl group, an amide group, a carbamoyl group, and a halogen atom.

[0081] However, at least one of the above R31 to R34 is not a hydrogen atom, and the above R31 to R3
When 4 consists of only a hydrogen atom and an alkyl group, at least one of the alkyl groups has 6 or more carbon atoms, and R
The total number of carbon atoms in 31 to R34 is 15 or less (preferably 4
-13), more preferably 7-13).

In the above formula (I), the above R31 to R3
4 is preferably a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an acylamino group, or an alkylthio group, and more preferably a hydrogen atom, an alkyl group, or an acylamino group.

Specific examples of the compound represented by formula (I) are shown below.

(I-1)

[C4]

(I-2)

[C5]

(I-3)

[C6]

(I-4)

[C7]

(I-5)

[Chemical formula 8]

(I-6)

[Chemical formula 9]

(I-7)

[Chemical formula 10]

(I-8)

[Chemical formula 11]

(I-9)

[Chemical formula 12]

(I-10)

[Chemical formula 13]

(I-11)

[Chemical formula 14]

(I-12)

[Chemical formula 15]

(I-13)

[Chemical formula 16]

(I-14)

[Chemical formula 17]

(I-15)

[Chemical formula 18]

(I-16)

[Chemical formula 19]

(I-17)

[C20]

(I-18)

[C21]

(I-19)

[C22]

(I-20)

[C23]

(I-21)

[C24]

(I-22)

[C25]

(I-23)

[C26]

(I-24)

[C27]

(I-25)

[C28]

(I-26)

[C29]

(I-27)

[C30]

(I-28)

[Chemical formula 31]

(I-29)

[C32]

Formula (II):

[Chemical formula 33]

[In the above formula (II), R41 to R
46 is a hydrogen atom, a halogen atom, a sulfo group, a carboxyl group, a cyano group, an alkyl group, an alkenyl group, an aryl group, an acylamino group, a sulfonamido group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an acyl group, represents an acyloxy group, sulfonyl group, carbamoyl group, alkoxycarbonyl group or sulfamoyl group, and the above R41 and R42 and R44 and R
45 may jointly form a carbocycle or a heterocycle, R47 and R48 above represent a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group, and R47 and R48 may jointly form a carbocycle, Alternatively, it may form a heterocycle. ]

In the above formula (II), R41 to R4
The groups represented by 6 are the above-mentioned R31 to R31, respectively.
It is the same as the group represented by 34. Also, R41 and R4
2 and R44 and R45 may jointly form a carbocycle or a heterocycle, and R41 to R46 may be substituted with the substituents listed above as substituents for R31 to R34.

Examples of the alkyl group represented by R47 and R48 include alkyl groups having 1 to 40 carbon atoms, such as methyl, i-bropyl, undecyl, and benzyl.

[0117] As the alkenyl group represented by R31 to R34, an allyl group can be mentioned.

Examples of the aryl group represented by R47 and R48 include aryl groups having 6 to 40 carbon atoms, such as phenyl and p-tolyl.

[0119] Examples of the heterocyclic group represented by R47 and R48 include a heterocyclic group having 1 to 40 carbon atoms, such as a pyridin-2-yl group.

Further, R47 and R48 may jointly form a carbocycle or a heterocycle. Above R47, R48
may be further substituted with an alkyl group, aryl group, alkoxy group, aryloxy group, sulfo group, carboxyl group, amide group, carbamoyl group, or halogen atom. Furthermore, the compound of formula (II) has this R47 and/
Alternatively, R48 may form a bis form (a tetrakis form as the hydroquinone moiety).

In the above formula (II), R41 to R46
is preferably a hydrogen atom, a halogen atom, an alkyl group,
It is an aryl group, an acylamino group or an alkylthio group. More preferably a hydrogen atom, an alkyl group or an acylamino group.

Further, R47 and R48 are preferably a hydrogen atom or an alkyl group, and it is also preferable that R47 and R48 jointly form a carbocyclic ring. More preferably R47
is a hydrogen atom, and R48 is a hydrogen atom or an alkyl group.

[0123] The total number of carbon atoms in R41 to R48 is 6.
0 or less, preferably 5 to 45, more preferably 1
It is 0-30.

Specific examples of the compound represented by formula (II) are shown below.

(II-1)

[C34]

(II-2)

[C35]

(II-3)

[C36]

(II-4)

[C37]

(II-5)

[C38]

(II-6)

[C39]

(II-7)

[C40]

(II-8)

[C41]

(II-9)

[C42]

(II-10)

[C43]

(II-11)

[C44]

(II-12)

[C45]

(II-13)

[C46]

(II-14)

[C47]

(II-15)

[C48]

(II-16)

[C49]

(II-17)

[C50]

(II-18)

[C51]

(II-19)

[C52]

(II-20)

[C53]

(II-21)

[C54]

(II-22)

[C55]

(II-23)

[C56]

(II-24)

[C57]

(II-25)

[C58]

The above compounds may be used alone or in combination of two or more. The above formula (I) or (
The compound represented by II) is generally 1 x 10-8 mol/m2 to 1 x 10-2 mol/m2, preferably 1
×10-7 mol/m2 to 1×10-3 mol/m2,
More preferably 1 x 10-6 mol/m2 to 1 x 10
-4 mol/m2.

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.

[0152] In the light-sensitive material of the present invention, a color antifogging agent or a color mixing preventive agent can be used. Representative examples of these are described in JP-A-62-215272, pages 185-193.

Compounds that release photographically useful groups include:
JP 63-153540, JP 63-259555, JP 2-61636, JP 2-244041
No. 2-308240.

A color enhancer can be used in the present invention for the purpose of improving the color development of the coupler. Representative examples of compounds are JP-A-62-215272, 121-125.
Examples include those listed on page.

The photosensitive material of the present invention contains dyes that prevent irradiation and halation (for example, JP-A-2-85
Compounds described in Publications No. 850 and No. 2-89047 may also be used. Further, as a dye dispersion method, a solid microcrystal dispersion method may be used. ), ultraviolet absorbers, plasticizers, optical brighteners, matting agents, air antifogging agents, coating aids, hardeners, antistatic agents, slipperiness improvers, etc. can be added. Representative examples of these additives are listed in Research Disclosure magazine no. 17643 VII-XIII (19
Published in December 1978) pages 25-27, and 18716
(published November 1979), pages 647-651.

[0156] As mentioned above, the photographic material of the present invention has the following characteristics:
The support has a red-sensitive layer (red-sensitive emulsion layer), a green-sensitive layer (green-sensitive emulsion layer), and a blue-sensitive layer (blue-sensitive emulsion layer). The order of these layers can be arbitrarily selected as necessary. The preferred order of layer arrangement is red sensitivity, green sensitivity, and blue sensitivity from the support side, or green sensitivity, red sensitivity, and blue sensitivity from the support side. In particular, in the present invention, it is preferable to configure in the former order. Furthermore, each emulsion layer described above may be made up of two or more emulsion layers having different sensitivities, or two or more emulsion layers having the same color sensitivity.
A non-light sensitive layer may be present between the two or more emulsion layers. Usually, the red-sensitive emulsion layer contains a cyan-forming coupler, the green-sensitive emulsion layer contains a magenta-forming coupler, and the blue-sensitive emulsion layer contains a yellow-forming coupler, but in some cases, the green-sensitive layer contains a yellow coupler and a magenta coupler. It is also possible to use different combinations, such as mixing them.

In addition to the silver halide emulsion layer, the light-sensitive material according to the present invention is preferably provided with auxiliary layers such as a protective layer, an intermediate layer, an antihalation layer, 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 as described in Research Disclosure Magazine No.
．． Section 17643VVII (issued December 1978) 2
The one described on page 8 and European Patent No. 01202253
and JP-A-61-97655. Also, Research Disclosure Magazine No. 17
The coating method described in Section 643XV, pages 28-29 can be used.

The fogging treatment of the present invention is carried out by the following "photofogging method" and/or "chemical fogging method". The entire surface exposure in the "light fogging method", that is, the fogging exposure, is
This is carried out after imagewise exposure, after or during color development. That is, the imagewise exposed photosensitive material is immersed in a color developer or a pre-bath of a color developer, or is taken out from these solutions and exposed before drying. is most preferred.

[0160] As a light source for fogging exposure, a light source with high color rendering properties (as close to white as possible) as described in, for example, Japanese Patent Laid-Open Nos. 56-137350 and 58-70223 is preferable. The appropriate illuminance of the light is 0.01 to 2000 lux, preferably 0.05 to 30 lux, more preferably 0.05 to 5 lux. The more sensitive a light-sensitive material uses an emulsion, the more preferable it is to be exposed to light at a lower illuminance. The illuminance may be adjusted by changing the altitude of the light source, exposure using various filters, the distance between the photosensitive material and the light source, or the angle between the photosensitive material and the light source. Further, the illuminance of the fogging light can be increased continuously or stepwise from low illuminance to high illuminance.

It is preferable that the light-sensitive material is immersed in a color developing solution or its pre-bath solution, and that the solution is sufficiently permeated into the emulsion layer of the light-sensitive material before irradiation with light. The time from when the liquid penetrates to when the light fog exposure is carried out is generally 2 seconds to 2 minutes, preferably 5 seconds to 1 minute, and more preferably 10 seconds to 30 seconds. The exposure time for fogging is generally 0.01 seconds to 2 minutes, preferably 0.1 seconds to 1 minute, and more preferably 1 second to 40 seconds.

In the present invention, the nucleating agent used in the so-called "chemical fogging method" can be contained in the light-sensitive material or in the processing solution for the light-sensitive material. Preferably, it is used by incorporating it into a photosensitive material.

Here, the nucleating agent is a substance that acts to directly form a positive image during surface development of an internal latent image type silver halide emulsion that has not been fogged in advance. In the present invention, the fogging treatment is preferably performed using a nucleating agent. When incorporated into a light-sensitive material, it is preferably added to the internal latent image type silver halide emulsion layer, but as long as the nucleating agent is adsorbed to the silver halide by diffusion during coating or processing, other additives may be used. For example, it may be added to an intermediate layer, an undercoat layer or a back layer.

[0164] Furthermore, two or more types of nucleating agents may be used in combination. Nucleating agents that can be used in the present invention include, for example, Research Disclosure Magazine, No. 2253
4 (January 1983) pp. 50-54, same magazine, No. 15
162 (November 1976) pp. 76-77, same magazine No.
23510 (November 1983), pages 346-352, quaternary heterocyclic compounds, hydrazine compounds, and the like.

Examples of quaternary heterocyclic nucleating agents include US Pat. No. 3,615,615, US Pat.
No. 4738, No. 3759901, No. 3854956, No. 4094683, No. 4306016, British Patent No. 1283835, Japanese Patent Publication No. 49-38164, No. 52
-No. 19452, No. 52-47326, JP-A-52-
No. 69613, No. 52-3426, No. 55-1387
42, No. 60-11837, and the aforementioned Research Disclosure magazine, No. 22534, Comrade No.
．． 23213 (Published August 1983, pages 267-270)
Examples include those listed in . Furthermore, as highly active quaternary salt compounds, JP-A Nos. 63-121042 and 63-3
No. 01942, Japanese Unexamined Patent Publication No. 191132, Japanese Patent Application No. 1983
-255360, 63-230589, 63-
The one described in No. 255361 can be used.

In the present invention, a nucleating agent represented by the following general formula [Fa] is preferably used. Hereinafter, the nucleating agent represented by the general formula [Fa] will be explained in detail.

General formula [Fa]:

[C59]

In the general formula [Fa], the heterocycle completed by Z is, for example, quinolinium, benzothiazolium,
Benzimidazolium, pyridinium, thiazolinium, thiazolium, naphthothiazolium, selenazolium, benzoselenazolium, imidazolium, tetrazolium, indolenium, pyrrolinium, acridinium, phenanthridinium, isoquinolinium, oxazolium, naphthooxazolium and benzoxa Examples include zolium nuclei.

Substituents for Z include alkyl groups, alkenyl groups, aralkyl groups, aryl groups, alkynyl groups, hydroxy groups, alkoxy groups, aryloxy groups, halogen atoms, amino groups, alkylthio groups, arylthio groups,
Acyloxy group, acylamino group, sulfonyl group, sulfonyloxy group, sulfonylamino group, carbonylamino group, carboxyl group, acyl group, carbamoyl group, sulfamoyl group, sulfo group, cyano group, ureido group, urethane group, carbonate ester group, hydrazine group, hydrazone group, or imino group. As the substituent for Z, for example, at least one substituent is selected from the above substituents, but in the case of two or more substituents, they may be the same or different. Moreover, the above-mentioned substituents may be further substituted with these substituents. Further, as a substituent for Z, a heterocyclic quaternary ammonium group completed with Z via a suitable linking group L may be included. In this case, it takes a so-called dimer structure.

Preferred examples of the heterocycle completed by Z include quinolinium, benzothiazolium, benzimidazolium, pyridinium, acridinium, phenanthridinium, and isoquinolinium nuclei. More preferred are quinolinium and benzothiazolium, most preferred is quinolinium.

[0171] The aliphatic group of R11 and R12 has 1 carbon number.
~18 unsubstituted alkyl groups and substituted alkyl groups in which the alkyl moiety has 1 to 18 carbon atoms. Examples of the substituent include those described as the substituent for Z.

[0172] The aromatic group represented by R12 has 6 to 6 carbon atoms.
Examples of the 20 groups include phenyl group and naphthyl group. Examples of the substituent include those described as the substituent for Z. R12 is preferably an aliphatic group, most preferably a methyl group, a substituted methyl group, or a case in which it is bonded to a heterocycle further completed by Z to form a ring.

At least one of the groups represented by R11, R12 and Z has an alkynyl group, an acyl group, a hydrazine group, or a hydrazone group, or R11
and R12 form a 6-membered ring to form a dihydropyridinium skeleton, which may be substituted with the group described above as a substituent for the group represented by Z.

[0174] At least one of the groups or substituents on the ring represented by R11, R12 and Z may be an alkynyl group or an acyl group, or R11 and R12 may be linked to form a dihydropyridinium skeleton. Preferably, it further contains at least one alkynyl group, most preferably a propargyl group.

[0175] At least one of the substituents R11, R12 and Z preferably has a group represented by the following formula. Formula: X12-(L11)m - Here, X12 represents an adsorption promoting group to silver halide, L11 represents a divalent linking group, and m represents 0 or 1.

Preferred examples of the adsorption-promoting group to silver halide represented by X12 include a thioamide group, a mercapto group, and a 5- to 6-membered nitrogen-containing heterocyclic group. These may be substituted with the substituents listed as substituents for Z. The thioamide group is preferably an acyclic thioamide group (eg, thiourethane group, thiourido group, etc.).

[0177] The mercapto group represented by
-mercapto-1,3,4-thiadiazole, 2-mercapto-1,3,4-oxadiazole, etc.) are preferred.

The 5- or 6-membered nitrogen-containing heterocycle represented by can give.

The divalent linking group represented by L11 is an atom or atomic group containing at least one of C, N, S, and O. Specifically, for example, alkylene group, alkenylene group, alkynylene group, arylene group, -O-,
-S-, -NH-, -CO-, -SO2- (these groups may have a substituent), etc. alone or in combination.

Examples of combinations include -COO-, -CONH-, -SO2NH-, -OC
ONH-, -NHCONH-, -NHSO2 NH-, -alkylene-CONH-, -arylene-SO2 NH-, -arylene-NHC
ONH-, -arylene-CONH-, etc. are preferred. In the present invention, the divalent linking group represented by L11 is -arylene-SO2 NH-, -arylene-NHC
ONH-, -arylene-CONH-, and the like are more preferred.

Counter ions Y for charge balance include, for example, bromide ion, chloride ion, iodide ion, p-toluenesulfonate ion, ethylsulfonate ion, perchlorate ion, trifluoromethanesulfonate ion,
Examples include thiocyanine ion, boron tetrafluoride ion, and phosphorus hexafluoride ion. Among these, bromide ion, iodide ion, perchlorate ion or trifluoromethanesulfonate ion are preferred, and more preferably,
These are iodide ion, perchlorate ion, or trifluoromethanesulfonate ion.

[0182] These compounds and their synthesis methods are described in, for example, Research Disclosure (Research D).
isclosure) magazine, No. 22,534 (19
Published in January 1983, pp. 50-54), and No. 23,
Patent cited in 213 (Published August 1983, pp. 267-270), Japanese Patent Publication No. 49-38164, No. 5
No. 2-19452, No. 52-47326, Japanese Unexamined Patent Publication No. 1973
-69163 Publication, Publication No. 52-3426, Publication No. 55-1
No. 38742, No. 60-11837, U.S. Patent No. 43
It is described in the 06016 specification and the 4471044 specification.

Specific examples of the nucleating agent represented by the general formula [Fa] are listed below, but the invention is not limited thereto.

[Fa-1]

[C60]

[Fa-2]

[C61]

[Fa-3]

[C62]

[Fa-4]

[C63]

[Fa-5]

[C64]

[Fa-6]

[C65]

[Fa-7]

[C66]

[Fa-8]

[C67]

[Fa-9]

[C68]

[Fa-10]

[C69]

[Fa-11]

[C70]

[Fa-12]

[C71]

[Fa-13]

[C72]

[Fa-14]

[C73]

[Fa-15]

[C74]

[Fa-16]

[C75]

[Fa-17]

[C76]

[Fa-18]

[C77]

[Fa-19]

[C78]

[Fa-20]

[C79]

[0204] As the hydrazine compound, for example, the above-mentioned Research Disclosure Magazine No. 15,162
(Published in November 1976) Pages 76-77 and magazine No.
．． 23,510 (issued November 1983) 346-35
Examples include those listed on page 2. More specifically, those described in the following patent specifications can be mentioned. First, examples of hydrazine-based nucleating agents having silver halide adsorption groups include, for example, US Pat. No. 4,030,925;
Same No. 4080207, Same No. 4031127, Same No. 3
No. 718470, No. 4269929, No. 4276
No. 364, No. 4278748, No. 4385108
No. 4459347, British Patent No. 2011391
No. B, JP-A-54-74729, JP-A No. 55-16353
No. 3, No. 55-74536, and No. 60-1797
Examples include those described in No. 34 and No. 63-231441.

[0205] Other hydrazine-based nucleating agents include, for example, JP-A-57-86829, US Pat.
No. 8, No. 4478928, and No. 256378
Examples include the compounds described in No. 5 and No. 2588982.

As highly active hydrazine compounds, JP-A Nos. 63-231441, 63-234244, 63-234245, 63-234246, 6
3-204256, JP-A No. 2-18558, JP-A No. 1-
Examples include compounds described in each publication of No. 131557.

Representative hydrazine-based nucleating agents are shown below. (B-1) 1-formyl-2-{4-[3-(2-
methoxyphenyl)ureido]phenyl}hydrazine,
(B-2) 1-formyl-2-{4-[3-(5-
Mercaptotetrazol-1-yl)benzamido]phenyl}hydrazine, (B-3) 1-formyl-2-[4-{3-[3-
(5-mercaptotetrazol-1-yl)phenyl]
ureido}phenyl]hydrazine,

[0208] As the nucleating agent, quaternary heterocyclic compounds are preferable, as described above, since they greatly exhibit the effects of the present invention. Note that a quaternary heterocyclic compound and a hydrazine compound may be used together. When a nucleating agent is added to the processing solution, the nucleating agent may be contained in the developer or a low pH pre-bath as described in JP-A-58-178350. When the nucleating agent is added to the treatment liquid, the amount used is preferably 10-8 to 10-1 mol, more preferably 10-7 to 10-3 mol per liter.

In the present invention, the nucleating agent may be contained in the hydrophilic colloid layer adjacent to the silver halide emulsion layer, but it is preferably contained in the silver halide emulsion layer. The amount added varies depending on the characteristics of the silver halide emulsion used in practice, the chemical structure of the nucleating agent, and the development conditions, so it can vary over a wide range, but it is approximately 1x per mole of silver in the silver halide emulsion. 10-8 mol to about 1×1
A range of 0-2 moles is useful in practice, with a preferred range of about 1.times.10@-7 moles to about 1.times.10@-3 moles per mole of silver.

[0210] When using a nucleating agent, it is preferable to use a nucleating promoter to promote the action of the nucleating agent. A nucleation accelerator is a substance that has virtually no function as a nucleation agent, but
A substance that acts to enhance the action of a nucleating agent to increase the maximum density of a direct positive image and/or to speed up the development time required to obtain a given maximum density of a direct positive image.

Such nucleation accelerators include tetrazaindenes, triazaindenes and pentazaindenes having at least one mercapto group optionally substituted with an alkali metal atom or an ammonium group. and JP-A No. 63-106656, Nos. 5-1
Examples include the compounds described on page 6. Also, JP-A No. 63-226652, No. 63-106656, No. 6
Examples include the compounds described in No. 3-8740.

Specific examples of the nucleation accelerator are listed below. S-1

[C80] S-2

[Chemical formula 81] S-3

[C82]

[0213]S-4

[Chemical formula 83] S-5

[Chemical formula 84] S-6

[Chemical formula 85]

[0214]S-7

[C86] S-8

[Chemical formula 87] S-9

[Chemical formula 88]

The nucleation accelerator can be contained in the photosensitive material or in the processing solution, but it can also be included in the internal latent image type silver halide emulsion and other hydrophilic colloid layers (
It is preferable to include it in an intermediate layer, a protective layer, etc.). Particularly preferred is a layer in or adjacent to a silver halide emulsion.

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

[0217] When adding the nucleation accelerator to the processing solution, that is, the developer or its pre-bath, add 1 liter per liter of the nucleation accelerator.
Preferably 0-8 to 10-3 mol, more preferably 1
It is 0-7 to 10-4 mol.

[0218] Two or more types of nucleation accelerators can also be used in combination.

[0219] Known photographic additives that can be used in the present invention are those listed in the aforementioned Research Disclosure No. 17643
(December 1978) and the same No. 18716 (19
(November 1979), and the relevant sections are summarized in the table below.

[0220] Additive type RD
17643 RD18716 ─
──────────────────────────
─── 1 Chemical sensitizer
Page 23 Page 648 Right column
2 Sensitivity enhancer
Same as above
3 Spectral sensitizer, 23-2
Page 4 Page 648 Right column ~
supersensitizer
Page 649 right column 4 increase
Whitening agent page 24
5 Antifoggant
Pages 24-25 Page 649 Right column ~
stabilizer
Page 650 right column
6 Light absorbers, page 25, right column, page 649, right column ~
filter dye,
Page 650 left column Ultraviolet absorber 7 Stain inhibitor Page 25 right column 8 Dye image stabilizer 2
Page 5 9 Hardener
Page 26 Page 651 Left column
10 Binder 2
Page 6 Same as above
────────────────────────
──────

[0221] In the photographic light-sensitive material of the present invention, the photographic emulsion layer and other layers are formed of a flexible support such as plastic film, paper, or cloth, or a rigid support such as glass, ceramic, or metal, which is commonly used in photographic light-sensitive materials. applied to the body. Useful as flexible supports are films of semi-synthetic or synthetic polymers such as cellulose nitrate, cellulose acetate, cellulose acetate, polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate, baryta layers or alpha-olefin polymers. (For example, paper coated with or laminated with polyethylene, polypropylene, ethylene/butene copolymer), etc. The support may be colored using dyes or pigments.

For coating the silver halide photographic emulsion layer and other hydrophilic colloid layers, various known methods can be used, such as dip coating, roller coating, curtain coating, and extrusion coating. . In the present invention, as described above, it is preferable that the emulsion layer etc. be formed using the simultaneous multilayer coating method, and in this case, U.S. Pat. , No. 3508947, etc. may be used.

Next, the color development processing method will be explained. The internal latent image type silver halide emulsion-containing light-sensitive material of the present invention can be developed directly into a positive image by using a surface developer. A surface developer is one in which the development process is substantially induced by latent images or fog nuclei on the surface of silver halide grains.

[0224] The color developer used in the present invention contains:
Contains a known aromatic primary amine color developing agent. Preferred examples are p-phenylenediamine derivatives, representative examples of which are shown below, but are not limited thereto. (1) N,N-diethyl-p-phenylenediamine, (
2) 2-amino-5-diethylaminotoluene, (3)
2-amino-5-(N-ethyl-N-laurylamino)
Toluene, (4) 4-[N-ethyl-N-(β-hydroxyethyl)amino]aniline, (5) 2-methyl-4
-[N-ethyl-N-(β-hydroxyethyl)amino]aniline, (6) 4-amino-3-methyl-N-ethyl-N-[β-(methanesulfonamido)ethyl]-aniline, Among these, compounds represented by (2), (4), (5) and (6) are preferred.

[0225] These p-phenylenediamine derivatives may also be salts such as sulfates, hydrochlorides, sulfites, and p-toluenesulfonates. The amount of the aromatic primary amine developing agent used is preferably about 0.1 g to about 20 g, more preferably about 0.5 g per liter of developer.
g to about 10 g.

[0226] Color developers also require sulfites such as sodium sulfite, potassium sulfite, sodium bisulfite, potassium bisulfite, sodium metasulfite, potassium metasulfite, and carbonyl compound sulfite adducts as preservatives. It can be added accordingly. The preferred amount added is 0.5g to 10g per liter of color developer.
More preferably, it is 1 g to 5 g.

[0227] As compounds that directly preserve the developing agent, various hydroxylamines, JP-A-63-4
Hydroxamic acids described in Publication No. 3138, No. 63-17
Hydrazines described in Publication No. 0642 and JP-A-2-64
Hydrazine derivatives and hydroxylamine derivatives described in JP-A No. 632, phenols described in JP-A-63-44657 and JP-A-63-58443, JP-A No. 63-58443;
α-Hydroxyketones and α described in Publication No.-44656
-aminoketones and/or 63-3624
It is preferable to add various saccharides described in Publication No. 4. In addition, in combination with the above compounds, JP-A-63-4235, JP-A-63-24254, JP-A-63-21647, JP-A-63-
No. 146040, No. 63-27841, and No. 63
Monoamines described in various publications such as No.-25654, JP-A-63-30845, JP-A-63-146040, and JP-A-6
Diamines described in various publications such as No. 3-43439, polyamines described in JP-A-63-21647 and JP-A-63-26655, polyamines described in JP-A-63-44655, Nitroxy radicals described in JP-A-63-53551, JP-A-63-43
140 and 63-53549, oximes described in JP-A-63-56654, and tertiary amines described in JP-A-63-239447. is preferable.

[0228] Other preservatives include JP-A-57-441
48 and 57-53749, salicylic acids described in JP-A-59-180588, alkanolamines as described in JP-A-54-3532, JP-A-56-94349. Polyethyleneimines described in the above publication, aromatic polyhydroxy compounds described in US Pat. No. 3,746,544, and the like may be contained as necessary.

[0229] The content of these compounds in the color developer is preferably as follows per liter of color developer:
o. 5g to 50g, more preferably 1.0 to 30g,
Particularly preferably, it is 1.5 g to 20 g.

[0230] These compounds may be present in the photosensitive material. In addition, color developing agents present in each solution (for example, due to being brought in from the color developer), not only in color developers, but also in bleach and bleach-fix solutions, water washes, or water wash substitute stabilizers, Acting on the oxidant,
It can give good performance.

[0231] The color developer used in the present invention preferably has a pH of 9 to 12, more preferably 9 to 11.0, and the color developer may contain compounds of other known developer components. be able to.

[0232] In order to maintain the above pH, it is preferable to use various buffers. Carbonates, phosphates, tetraborates, and hydroxybenzoates are especially soluble as buffering agents.
Excellent buffering ability in the high pH range of pH 9.0 or higher.

Specific examples of buffering agents include sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate,
Trisodium phosphate, tripotassium phosphate, dipotassium phosphate, sodium borate, potassium borate, sodium tetraborate (borax), potassium tetraborate, sodium o-hydroxybenzoate (sodium salicylate), o-
Examples include potassium hydroxybenzoate, sodium 5-sulfo-2-hydroxybenzoate (sodium 5-sulfosalicylate), potassium 5-sulfo-2-hydroxybenzoate (potassium 5-sulfosalicylate), and the like. However, the present invention is not limited to these compounds.

[0234] The amount of the buffer added to the color developer is 0.
．． It is preferably 1 mol/liter or more, especially 0
．． It is preferably 1 mol/liter to 0.4 mol/liter.

[0235] In addition, various chelating agents can be used in the color developer as an agent for preventing precipitation of calcium or magnesium, or to improve the stability of the color developer.

[0236] The chelating agent is preferably an organic acid compound, such as aminopolycarboxylic acids, organic phosphonic acids, and phosphonocarboxylic acids. Specific examples are shown below, but the invention is not limited to these. Nitrilotriacetic acid, diethylenetriaminepentaacetic acid, ethylenediaminetetraacetic acid, N,N,N-trimethylenephosphonic acid, ethylenediamine-N,N,N',N'-tetramethylenephosphonic acid, transcyclohexanediaminetetraacetic acid, 1,2- diaminopropanetetraacetic acid, hydroxyethyliminodiacetic acid, glycol ether diaminetetraacetic acid,
Ethylenediamine orthohydroxyphenylacetic acid, 2
-phosphonobutane-1,2,4-tricarboxylic acid, 1-
Hydroxyethylidene-1,1-diphosphonic acid, N,N
'-Bis(2-hydroxybenzyl)ethylenediamine-N,N'-diacetic acid, 1,2-hydroxybenzene-
3,5-disulfonic acid and these chelating agents may be used in combination of two or more types, if necessary.

[0237] These chelating agents may be added in an amount sufficient to sequester metal ions in the color developer. For example, it is about 0.1 g to 10 g per liter.

[0238] Any development accelerator can be added to the color developer if necessary. However, the color developer used in the present invention preferably does not substantially contain benzyl alcohol from the viewpoints of formulation properties and prevention of color staining. Here, "substantially" means that the developer contains less than 2 milliliters per liter of developer, preferably not at all.

Other development accelerators include:
No. 16088, No. 37-5987, No. 38-7826
No. 44-12380, No. 45-9019, and U.S. Pat. No. 3,813,247, etc.;
p-phenylenediamine compounds represented by No. 0-15554, JP-A-50-137726, and JP-B No. 44-
30074, JP-A-56-156826 and JP-A-56-156826
Quaternary ammonium salts represented by No. 2-43429, etc., U.S. Patent Nos. 2,494,903 and 3,128,18
No. 2, No. 4,230,796, No. 3,253,919
No. 41-11431, U.S. Patent No. 2,482
, No. 546, No. 2,596,926 and No. 3,58
Amine compounds described in No. 2,346, etc., Japanese Patent Publication No. 37-Sho.
No. 16088, No. 42-25201, U.S. Patent No. 3,
No. 128,183, Special Publication No. 41-11431, No. 42
Polyalkylene oxides shown in -23883 and U.S. Patent No. 3,532,501, etc., and others 1-
Phenyl-3-pyrazolidones, imidazoles, etc. can be added as necessary.

[0240] In the present invention, any antifoggant can be added if necessary. As antifoggants, alkali metal halides such as sodium chloride, potassium bromide, potassium iodide, and organic antifoggants can be used. Examples of organic antifoggants include benzotriazole, 6-nitrobenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole, 5-
Nitrobenzotriazole, 5-chloro-benzotriazole, 2-thiazolyl-benzimidazole, 2-thiazolylmethyl-benzimidazole, indazole,
Representative examples include nitrogen-containing heterocyclic compounds such as hydroxyazaindolizine and adenine.

[0241] The color developer used in the present invention may contain a fluorescent brightener. As the fluorescent whitening agent, 4,4'-diamino-2,2'-disulfostilbene compounds are preferred. The amount added is 0 to 5 g/liter, preferably 0.1 g to 4 g/liter.

[0242] Also, if necessary, alkyl sulfonic acid,
Various surfactants such as aryphosphonic acid, aliphatic carboxylic acid, and aromatic carboxylic acid may be added.

[0243] The processing temperature of the color developer of the present invention is 20~
The temperature is 50°C, preferably 30-40°C. Processing time is 2
The time is 0 seconds to 5 minutes, preferably 30 seconds to 2 minutes. The smaller the amount of replenishment, the better, but 100 per m2 of photosensitive material.
~1500 ml, preferably 100-800 ml. More preferably, it is 100 ml to 400 ml.

Next, the desilvering process will be explained. The desilvering process generally involves any process such as bleaching-fixing process, fixing process-bleach-fixing process, bleaching process-bleach-fixing process, bleach-fixing process, etc. Good too. The process period of the desilvering process is 1 minute 30 seconds or less, more preferably 15 seconds to 60 seconds.

(Desilvering step) The bleaching solution, bleach-fixing solution and fixing solution used in the desilvering step will be explained. As the bleaching agent used in the bleaching solution or bleach-fixing solution, any bleaching agent can be used, but in particular organic complex salts of iron(III) (e.g., aminopolycarboxylic acids such as ethylenediaminetetraacetic acid and diethylenetriaminepentaacetic acid, aminopolycarboxylic acids such as ethylenediaminetetraacetic acid and diethylenetriaminepentaacetic acid) Complex salts of phosphonic acid, phosphonocarboxylic acid and organic phosphonic acid) or organic acids such as ecunic acid, tartaric acid and malic acid; sulfates; hydrogen peroxide and the like are particularly preferred from the viewpoint of bleaching power and prevention of environmental pollution.

Aminopolycarboxylic acids, aminopolyphosphonic acids useful for forming organic complex salts of iron(III),
Or, to list organic phosphonic acids or their salts, ethylenediaminetetraacetic acid, diethyleneditriaminepentaacetic acid, 1,3-diaminopropanetetraacetic acid, propylenediaminetetraacetic acid, nitrilotriacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, imino Examples include diacetic acid, glycol ether diamine tetraacetic acid, and the like.

These compounds include sodium, potassium,
Either lithium or ammonium salt may be used. Among these compounds, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid,
, 3-diaminopropanetetraacetic acid, and methyliminodiacetic acid are preferred because of their high bleaching power.

Among these, organic complex salts of iron (III) can be prepared using ferric phosphate or the like and a chelating agent such as aminopolycarboxylic acid, aminopolyphosphonic acid, or phosphonocarboxylic acid from the viewpoint of rapid processing. A ferric ion complex salt may be formed in solution. Further, the chelating agent may be used in excess of the amount required to form the ferric ion complex. Among the iron complexes, aminopolycarboxylic acid iron complexes are preferred, and the amount added is 0.01 to 1.0 mol/liter, preferably 0.05 to 0.50 mol/liter.

Various compounds can be used as bleach accelerators in the bleach solution, bleach-fix solution and/or their pre-bath. For example, US Pat. No. 3,893,858,
German Patent No. 1290812, JP-A-53-9
Publication No. 5630, Research Disclosure No. 171
No. 29 (July 1978 issue), compounds having a mercapto group or disulfide bond, and
No. 506, JP-A-52-20832, JP-A No. 53-327
Thiourea compounds described in No. 35, US Pat. No. 3,706,561, and halides such as iodine and bromide ions are preferred because they have excellent bleaching power.

In addition, the bleach or bleach-fix solution used in the present invention may contain bromides (for example, potassium bromide, sodium bromide, ammonium bromide) or chlorides (for example,
Rehalogenating agents such as potassium chloride, sodium chloride, ammonium chloride) or iodides (eg, ammonium iodide) can be included. Boric acid, borax, if necessary
One or more inorganic acids and organic acids having pH buffering capacity such as sodium metaborate, acetic acid, sodium acetate, sodium carbonate, potassium carbonate, phosphorous acid, phosphoric acid, sodium phosphate, citric acid, sodium citrate, tartaric acid, and these Alkali metal or ammonium salts or corrosion inhibitors such as ammonium nitrate and guanidine can be added.

The fixing agent used in the bleach-fixing solution or fixing solution according to the present invention is a known fixing agent, namely, a thiosulfate such as sodium thiosulfate or ammonium thiosulfate; or a thiocyanic acid such as sodium thiocyanate or ammonium thiocyanate. Salt; ethylene bisthioglycolic acid, 3,6-
These are water-soluble silver halide dissolving agents such as thioether compounds such as dithia-1,8-octanediol and thioureas, and these can be used alone or in combination of two or more. Also, JP-A-55-155354
A special bleach-fixing solution consisting of a combination of the fixing agent described in the above publication and a large amount of a halide such as potassium iodide may also be used.

In the present invention, thiosulfates, particularly ammonium thiosulfates, are preferably used. The amount of fixing agent per liter is preferably from 0.3 to 2 mol, more preferably from 0.5 to 1.0 mol. The pH range of the bleach-fixing solution or fixing solution is preferably 3 to 10, more preferably 5 to 10.
-9 is particularly preferred.

The bleach-fix solution may also contain various other fluorescent brighteners, antifoaming agents, surfactants, and organic solvents such as polyvinylpyrrolidone and methanol.

[0254] The bleach-fixing solution and fixing solution in the present invention contain sulfites (for example, sodium sulfite, potassium sulfite, ammonium sulfite, etc.) and bisulfites (such as sodium sulfite, potassium sulfite, ammonium sulfite, etc.) as preservatives.
For example, ammonium bisulfite, sodium bisulfite,
It is preferred to contain a sulfite ion releasing compound such as potassium bisulfite, etc.), metabisulfite (eg, potassium metabisulfite, sodium metabisulfite, ammonium metabisulfite, etc.). The content of these compounds is preferably about 0.02 to 0.0.50 mol/liter in terms of sulfite ion, and more preferably 0.0 mol/liter.
It is 4 to 0.40 mol/liter.

As a preservative, sulfite is generally added, but ascorbic acid, carbonyl bisulfite adducts, carbonyl compounds, etc. may also be added.

[0256] Furthermore, buffering agents, optical brighteners, chelating agents,
Antifoaming agents, antifungal agents, etc. may be added as necessary.

Aqueous Solution and/or Stabilization [0257] In the treatment of the present invention, an aqueous solution and/or stabilization treatment is generally carried out after desilvering treatment such as fixing or bleach-fixing.

The amount of washing water in the washing process depends on the characteristics of the photosensitive material (for example, depending on the materials used such as couplers), the purpose, the washing water temperature, the number of washing tanks (number of stages), the replenishment method such as countercurrent or forward flow, etc.
It can be set in a wide range depending on various other conditions. Among these, the relationship between the number of flushing tanks and the amount of water in the multistage countercurrent method is described in the Journal of the Society of Motion Picture and Television Engineers.
of Motion Picture and Tel
(evision Engineers) Volume 64, P2
48-253 (May 1955 issue), the number of stages in the normal multi-stage countercurrent system is 2.
-6 is preferable, and 2-4 is especially preferable.

According to the multi-stage countercurrent method, the amount of washing water can be greatly reduced, for example, from 0.5 liters to 1 liter or less per 1 m 2 of photosensitive material. The increased residence time of water in the tank causes problems such as bacteria propagation and the resulting floating matter adhering to the photosensitive material. In the processing of the color light-sensitive material of the present invention, the method for reducing calcium and magnesium described in JP-A-62-288838 can be used very effectively as a solution to such problems. In addition, isothiazolone compounds and thiabendazoles described in JP-A-57-8542;
Chlorine-based disinfectants such as chlorinated sodium isocyanurate described in No. 1-120145, JP-A-61-26776
Benzotriazole, copper ion, etc. described in No. 1, "Chemistry of antibacterial and antifungal agents" by Hiroshi Horiguchi, "Sterilization, sterilization, and antifungal technology of microorganisms", edited by the Society of Hygiene Technology, "Edited by the Japan Antibacterial and Antifungal Society" It is also possible to use disinfectants listed in the Antibacterial and Antifungal Dictionary.

Furthermore, in the washing water, a surfactant as a draining agent and a chelating agent typified by EDTA as a water softener can be used.

[0261] The above-mentioned water washing step can be followed or the stabilizing solution can be directly treated without going through the water washing step. A compound having an image stabilizing function is added to the stabilizing solution, such as an aldehyde compound typified by formalin, a buffer for adjusting the membrane pH suitable for dye stabilization, and an ammonium compound. In addition, in order to prevent bacterial growth in the liquid and to provide anti-mold properties to photosensitive materials after processing,
The various fungicides and antifungal agents mentioned above can be used.

[0262] Furthermore, surfactants, optical brighteners, and hardeners can also be added. In the processing of the photosensitive material of the present invention, when stabilization is carried out directly without passing through a water washing process,
All known methods described in Japanese Patent No.-220345 and the like can be used.

Others: 1-hydroxyethylidene-1,
It is also a preferred embodiment to use a chelating agent such as 1-diphosphonic acid or ethylene diamino tetramethylene phosphonic acid, or a magnesium or bismuth compound.

[0264] In the present invention, a so-called rinsing solution can also be used as a washing solution or a stabilizing solution used after the desilvering treatment.

[0265] The pH of the water washing step or stabilization step is 4 to 1.
0, preferably 5-8. The temperature can be set variously depending on the use and characteristics of the photosensitive material, but generally it is between 15 and 45
℃, preferably 20 to 40℃. The time can be set arbitrarily, but a shorter time is preferable. Preferably it is 30 seconds to 3 minutes, more preferably 30 seconds to 2 minutes. The smaller the amount of replenishment, the better from the viewpoints of running costs, reduced emissions, ease of handling, etc., and the effects of the present invention are also greater.

A specific preferred amount of replenishment is 0.5 to 50 times, preferably 3 to 40 times, the amount brought in from the prebath per unit area of the photosensitive material. Or it is 1 liter or less, preferably 500 ml or less per m2 of photosensitive material. Further, replenishment may be performed continuously or intermittently.

[0267] The liquid used in the water washing and/or stabilization step was
Furthermore, it can also be used in a pre-process. An example of this is to flow the overfloat of washing water reduced by a multi-stage countercurrent system into a bleach-fixing bath, which is a pre-bath, and replenishing the bleach-stabilizing bath with concentrated liquid to reduce the amount of waste liquid.

[0268] The direct positive color photographic material of the present invention is
Although it has various uses, it is particularly suitable for creating color proofs.

[0269] Various exposure means can be used to expose the photosensitive material of the present invention. Any light source that emits radiation corresponding to the sensitivity wavelength of the photosensitive material can be used as the illumination or writing light source. Natural light (sunlight)
, incandescent lamps, halogen-filled lamps, mercury vapor lamps, fluorescent lamps, and flash light sources such as strobes or metal-fired flashbulbs are common. Gaseous, dye solution or semiconductor lasers, light emitting diodes and plasma light sources emitting light in the wavelength range from ultraviolet to infrared can also be used as recording light sources. In addition, fluorescent screens (such as CRT) and liquid crystals (such as CRTs) emitted from fluorescent substances excited by electron beams, etc.
An exposure means that combines a linear or planar light source with a micro-shutter array using lanthanum-doped lead titanium zirconate (PLZT) or the like can also be used. If necessary, the spectral distribution used for exposure can be adjusted using color filters. In addition, Fuji Photo Film (
The scanning exposure method used in the color copier AP-5000 manufactured by Co., Ltd. can be used.

0270]

[Examples] The present invention will be explained in more detail below with reference to Examples. However, the present invention is not limited to these examples.

[Example 1] (Preparation of Sample 101) The following 1st to 11th layers were placed on the front side of a paper support (thickness 100 μm) laminated on both sides with polyethylene, and the 12th to 13th layers were placed on the back side. A color photographic material was prepared by applying multiple layers (comparative sample). Titanium oxide (4 g/m
2) as a white pigment, and a trace amount (0.003 g/m
2) contains ultramarine blue as a blue-tinged dye (the chromaticity of the surface of the support is 88.0, -0.20 for L*, a*, b* systems,
-0.75).

(Photosensitive layer composition) The components and coating amount (g/
m2). However, the amount of sensitizing dye added is expressed in moles per mole of silver. Regarding silver halide, the coating amount is shown in terms of silver. The emulsions used in each layer were prepared by changing the grain size by changing the grain formation temperature in accordance with the manufacturing method for emulsion EM-1 described below. However, as the emulsion for the 11th layer, a Lippmann emulsion whose surface was not chemically sensitized was used.

0273 First layer (antihalation layer) Black colloidal silver

0.07 Gelatin

0.70

0274 Second layer (middle layer) Gelatin

0.70

3rd layer (red sensitive layer) Red sensitizing dye (ExS-1, 2, 3, equal amounts of each,
Silver bromide spectrally sensitized with a total of 5.4 x 10-4 (average grain size (rR): 0.2
8 μm, particle size distribution: 10%, octahedral)
0.25 Gelatin

1.00
Cyan coupler (ExC-1, 2, 3)
0.30 1
:1:0.2 ratio)

Antifading agent (Cpd-1, 2, 3, 4
each equivalent amount) 0.18 Hydroquinone compound (I-27)
0.014 Coupler dispersion medium (Cpd-6)
0.03 coupler solvent (
Equal amounts of Solv-1, 2, and 3)
0.12

0276 Fourth layer (middle layer) Gelatin

1.00 Color mixing prevention agent (Cpd-7)

0.08 Color mixing inhibitor solvent (Solv-
4, 5 each equal amount) 0.16
Polymer latex (Cpd-8)
0.10

027
7] 5th layer (green sensitive layer) Green sensitizing dye (ExS-4, 2.6 x 10-4)
Silver bromide (average grain size (rG): 0.45 μm, grain size distribution 10%, octahedral) spectrally sensitized with 0.25
gelatin

0.80 Magenta coupler (ExM-1, 2,
3 each equivalent amount) 0.11 Yellow coupler (ExY-1)
0.03 Anti-fading agent (equal amounts of Cpd-9 and 26)
0.15 Stain inhibitor (Cpd-
10, 11, 12 in a 10:7:7 ratio)

0.025 Hydroquinone compound (I-27)
0.014 Coupler dispersion medium (Cpd-
6)
0.05 coupler solvent (Solv-4,
6 each equal amount) 0.15

0278] 6th layer (middle layer) Same as 4th layer

7th layer (yellow filter layer) Yellow colloidal silver (particle size 100 Å)
0.12 Gelatin
0.70
Color mixing inhibitor (Cpd-7)
0.03
Color mixing inhibitor solvent (Equivalent amounts of Solv-4 and 5)
0.10 Polymer latex (Cpd-8)
0.07

0280] 8th layer (middle layer) Same as 4th layer

9th layer (blue sensitive layer) Blue sensitizing dye (Equivalent amounts of ExS-5 and 6,
Spectrally sensitized with a total of 3.5 x 10-4)
Silver bromide (average particle size (rB): 0.72 μm,
Particle size distribution 11%, octahedral)
0.40
gelatin

0.80 Yellow coupler (ExY-1, 2
, 3 in equal amounts) 0.35 Antifading agent (Cpd-14)
0.10 Hydroquinone compound (I-27)
0.014 Coupler dispersion medium (Cpd-6)
0.05 Coupler solvent (So
lv-2)
0.10

0282 Layer 10 (ultraviolet absorbing layer) Gelatin

1.00 Ultraviolet absorber (Cpd-2,
Equal amounts of 4 and 16) 0.50
Color mixing inhibitor (Equivalent amounts of Cpd-7 and 17)
0.03 Dispersion medium (C
pd-6)
0.02 Ultraviolet absorber solvent (equal amounts of Solv-2 and Solv-7)
0.08 Anti-irradiation dye (
Cpd-18, 19, 20, 21, 27 in the ratio of 10:10: 13:15:20)

0.05

11th layer (protective layer) Fine grain silver chlorobromide (silver chloride 97 mol%,
average size 0.1μm)
0.03
Acrylic modified copolymer of polyvinyl alcohol
0.01 (molecular weight: 5
0000) Equal amounts of polymethyl methacrylate particles (average particle size: 2.4 μm) and silicon oxide (average particle size: 5 μm)

0.05 gelatin

1.80
Gelatin hardening agent (equal amounts of H-1 and H-2)
0.18

0284 12th layer (back layer) Gelatin

2.50 Ultraviolet absorber (Cpd-2,
Equal amounts of 4 and 16) 0.50
Dye (equal amounts of Cpd-18, 19, 20, 21, 27) 0.06

13th layer (back layer protective layer) Polymethyl methacrylate particles (
average particle size 2.4μm) and silicon oxide
(average particle size 5 μm) in equal amounts of each
0.05 gelatin

2.00
Gelatin hardening agent (equal amounts of H-1 and H-2)
0.14

(Emulsion E
How to make M-1) Add an aqueous solution of potassium bromide and silver nitrate simultaneously to an aqueous gelatin solution over 15 minutes at 65°C with vigorous stirring to obtain octahedral silver bromide particles with an average particle size of 0.23 μm. Ta. At this time, 0.3 per mole of silver
g of 3,4-dimethyl-1,3-thiazoline-2-thione were added. A chemical sensitization treatment was performed by sequentially adding 6 mg of sodium thiosulfate and 7 mg of chloroauric acid (tetrahydrate) per mole of silver to this emulsion and heating at 75° C. for 80 minutes. The thus obtained grains were used as cores and further grown in the same precipitation environment as in the first precipitation to finally obtain an octahedral monodispersed core/shell silver bromide emulsion with an average grain size of 0.4 μm. To this emulsion were added 1.5 mg of sodium thiosulfate and 1.5 mg of chloroauric acid (tetrahydrate) per mole of silver.
A chemical sensitization treatment was performed by heating at 0° C. for 60 minutes to obtain an internal latent image type silver halide emulsion.

Each photosensitive layer contains (ExZK-
1) and (ExZK-2) at 10-3% by weight and 10-2% by weight, respectively, based on silver halide, and C as a nucleation accelerator.
PD-22, 28, and 29 were each used in an amount of 10-2% by weight. Additionally, each layer contains alkanol XC (
Du Pont) and sodium alkylbenzene sulfonate, succinate ester and M
agefac F-120 (Dainippon Ink and Chemicals)
Co., Ltd.) was used. (Equivalent amounts of Cpd-23, 24, and 25) were used as stabilizers in the silver halide and colloidal silver containing layers.

[0288] The compounds used in the above sample preparation are shown below.

0289 ExS-1

[Chemical formula 89]

0290 ExS-2

[C90]

0291 ExS-3

[Chemical formula 91]

0292 ExS-4

[C92]

0293 ExS-5

[C93]

0294 ExS-6

[C94]

Cpd-1

[C95]

[0296]Cpd-2

[C96]

Cpd-3

[C97]

Cpd-4

[C98]

Cpd-6

[C99]

0300 Cpd-7

[Chemical formula 100]

0301 Cpd-8

[Chemical formula 101]

0302 Cpd-9

[Chemical formula 102]

0303] Cpd-10

[Chemical formula 103]

0304 Cpd-11

[Chemical formula 104]

0305] Cpd-12

[Chemical formula 105]

0306] Cpd-14

[Chemical formula 106]

0307] Cpd-16

[Chemical formula 107]

0308 Cpd-17

[Chemical formula 108]

0309] Cpd-18

[Chemical formula 109]

0310]Cpd-19

[Chemical formula 110]

0311] Cpd-20

[Chemical formula 111]

[0312]Cpd-21

[Chemical formula 112]

[0313]Cpd-22

[Chemical formula 113]

[0314]Cpd-23

[Chemical formula 114]

[0315]Cpd-24

[Chemical formula 115]

[0316]Cpd-25

[Chemical formula 116]

[0317]Cpd-26

[Chemical formula 117]

0318 Cpd-27

[Chemical formula 118]

0319 Cpd-28

[Chemical formula 119]

0320] Cpd-29

[Chemical formula 120]

0321 ExC-1

[Chemical formula 121]

0322 ExC-2

[Chemical formula 122]

0323 ExC-3

[Chemical formula 123]

0324 ExM-1

[Chemical formula 124]

0325 ExM-2

[Chemical formula 125]

0326 ExM-3

[Chemical formula 126]

0327 ExY-1

[Chemical formula 127]

0328 ExY-2

[Chemical formula 128]

0329 ExY-3

[Chemical formula 129]

0330 I-27

[Chemical formula 130]

[0331]Solv-1 Di(2-ethylhexyl) sebacate

0332 Solv-2 trinonyl phosphate

0333 Solv-3 Di(3-methylhexyl) phthalate

0334 Solv-4 tricresyl phosphate

0335 Solv-5 dibutyl phthalate

0336 Solv-6 trioctyl phosphate

0337 Solv-7 Di(2-ethylhexyl) phthalate

H-1 1,2-bis(vinylsulfonylacetamido)ethane

H-2 4,6-dichloro-2-hydroxy-1,3,5-triazine/Na salt

ExZK-1 7-(3-ethoxythiocarbonylaminobenzamide)-9-methyl-10propargyl-1,2,3,4-
Tetrahydroacridinium trifluoromethanesulfonate

ExZK-2 2-[4-{3-[3-{3-[5-{3-[2-chloro-5-(1-dodecyloxycarbonylethoxycarbonyl)phenylcarbamoyl]-4-hydroxy- 1
-naphthylthio}tetrazol-1-yl]phenyl}
ureido]benzenesulfonamide}phenyl]-1-
Formylhydrazine

(Preparation of Sample 102) In the preparation of Sample 101, the amount of yellow colloidal silver used in the seventh layer (yellow filter layer) was changed to 0.06 g/m
Sample 102 was prepared in the same manner as Sample 101 (comparative sample) except that the sample was changed to 2.

(Preparation of Sample 201) In the preparation of Sample 101, the following yellow dye (Cpd-31) was added at 0.25 g/m2 instead of the yellow colloidal silver used in the seventh layer (yellow filter layer). Sample 201 was prepared in the same manner as Sample 101 (comparative sample) except that the sample 201 was used.

(Cpd-31)

[Chemical formula 131]

(Preparation of Sample 103) Sample 103 was prepared in the same manner as Sample 101 (invention sample) except that yellow colloidal silver was not added to the seventh layer.

(Preparation of Sample 111) Sample 101 was prepared in the same manner as Sample 101, except that the following hydroquinone compound (II-4) was used instead of hydroquinone compound (I-27). Sample 111
was created (comparison sample).

Compound (II-4)

[Chemical formula 132]

(Preparation of Sample 113) Sample 103 was prepared in the same manner as Sample 103, except that the hydroquinone compound (II-4) was used instead of the hydroquinone compound (I-27). Sample 113
(sample of the present invention).

(Creation of samples 104 to 109) Sample 1 above
03, the red-sensitive layer (3rd layer) and blue-sensitive layer (9th layer)
Samples 104 to 1 were prepared in the same manner as sample 103, except that the grain size of the emulsion in layer) was changed as shown in Table 1 below.
09 (present invention samples: 104 and 108, comparative samples: 105 to 107, 109)

(Preparation of Samples 121 and 123) In the preparation of Samples 101 and 103, a hydroquinone compound was added to the red-sensitive layer (third layer), green-sensitive layer (fifth layer), and blue-sensitive layer (ninth layer). Corresponding samples 121 (comparative sample) and 123 (invention sample) were prepared in the same manner as samples 101 and 103, respectively, except that (I-27) was not added.

[0351] The characteristics of each sample prepared above are summarized in Tables 1 and 2. Note that in Tables 1 and 2, "absorbance" represents the absorbance for light with a wavelength of 450 nm. In addition to the 7th layer in all samples, the non-photosensitive layers above the green sensitive layer (6th layer, 8th layer, 10th layer, and 11th layer)
The absorbance of all layers) was 0.01 or less.

0352]

[Table 1]

0353]

[Table 2]

[Evaluation as a positive color photographic material]
After storing each sample prepared as above for 10 days at a temperature of 30° C. and a relative humidity of 63%, the following tests were conducted.

[0355] Exposure conditions (r): The sample was exposed to a red filter (
Ratten No. 26) When exposing white light through an ND filter, adjust the ND filter density and expose for 0.1 seconds at the minimum exposure amount that minimizes the cyan density after development. Exposure conditions (g): The sample was exposed to a green filter (Wratten No.
．． 58) and when exposing white light through an ND filter, adjust the ND filter density and expose for 0.1 seconds at the minimum exposure amount that minimizes the magenta density after development. Exposure condition (b): The sample was exposed to a blue filter (Wratten No.
．． 47B) and when exposing white light through an ND filter, the ND filter density is adjusted and exposure is performed for 0.1 seconds at the minimum exposure amount that minimizes the yellow density after development.

(1) Measurement of maximum image density (Dmax) Exposure was performed under the above exposure condition (r), and then the exposure condition (g
), and then processed under the development conditions described below to obtain a yellow colored sample. Let Dmax (Y) be the reflection density of the sample measured using a blue filter. After exposure under the above exposure condition (g) and subsequent exposure under exposure condition (b), processing was performed under the development conditions described below to obtain a cyan colored sample. Let Dmax (C) be the reflection density of the sample measured using a red filter. After exposure under the above exposure condition (r) and subsequently under exposure condition (b), processing was performed under the development conditions described below to obtain a sample colored magenta. Let Dmax (M) be the reflection density of the sample measured using a green filter.

(2) Measurement of minimum image density (Dmin) After exposure under the above exposure conditions (r), (g) and (b), processing was performed under the development conditions described below. Let Dmin (R) be the reflection density of the sample measured using a red filter. Let Dmin (G) be the reflection density of the sample measured using a green filter. Let Dmin (B) be the reflection density of the sample measured using a blue filter.

[Color development processing] Using the method described below using an automatic developing machine, the cumulative replenishment amount of the solution is 3 of the tank capacity.
Continued processing until doubled.

0359] ────────────────────────
──────────── Treatment process Time Temperature Tank capacity
Replenishment amount ──────────
──────────────────────────
─ Color development 135 seconds 38℃
30 liters 240ml/m2 Bleach fixing 60 seconds 35℃
15 liters 300ml/m2 Water washing (1
) 40 seconds 35℃ 10 liters --- Water washing (2
) 40 seconds 35℃ 3 liters 320ml/m2 drying
30 seconds 75℃────────
──────────────────────────
───

0360 The method of replenishing the washing water is the washing bath (2).
The overflow liquid from the washing bath (2) is refilled to the washing bath (2).
A so-called countercurrent replenishment method was adopted, which leads to 1). At this time, the amount of bleach-fix solution brought into the washing bath (1) from the bleach-fixing of the photosensitive material was 35 ml/m2, and the ratio of the amount of washing replenishment to the amount of bleach-fix solution brought in was 9.1 times.

[0361] The composition of each treatment liquid was as follows. ──────────────────────────
──────────── Color developer
Mother liquor
Refill fluid────────────
────────────────────────
D-Sorvit
0.15g 0.20g
Sodium naphthalene sulfonate 0
．． 15g 0.20g Formalin condensate Ethylenediaminetetrakismethylene 1.
5g 1.5g Phosphonic acid diethylene glycol
12.0ml 16.0ml Benzyl alcohol
13.5ml 18.0ml Potassium bromide
0.80g --- Benzotriazole 0
．． 003g 0.004g Sodium sulfite 2
．． 4g 3.2g N,N-bis(carboxymethyl) 6.0g
8.0g hydrazine D-glucose
2.0g 2.4
g Triethanolamine
6.0g 8.0g
N-ethyl-N-hydroxyethyl 4.
2g 5.6g -4-Aminoaniline sulfate Potassium carbonate
30.0g 25.0g
Fluorescent brightener (diaminostilbene type) 1.
0g 1.2g Add water
1000m
l 1000ml────────────
────────────────────────
pH (25℃)
10.50 11.00──
──────────────────────────
─────────

0362] ────────────────────────
──────────── Bleach-fix solution

Mother liquid Replenisher──────
──────────────────────────
────── Ethylenediaminetetraacetic acid, disodium, dihydrate 4.0g Same as mother liquor Ethylenediaminetetraacetic acid, Fe(III), 70
．． 0g ammonium dihydrate ammonium thiosulfate (700g/l)
180ml Sodium p-toluenesulfinate 20.0g Sodium bisulfite
20.0g 5-mercapto-1,3,4-triazole 0.5g Ammonium sulfate

Add 10.0g water
1000ml
──────────────────────────
──────────── pH (25℃)

6.20────────────────────
──────────────────

"Washing water" Both the mother liquor and the replenisher were washed with tap water using H-type strongly acidic cation exchange resin (Amberlite IR-120 manufactured by Rohm and Haas).
B) and OH type anion exchange resin (Amberlite I)
Water was passed through a mixed bed column packed with R-400) to reduce the concentration of calcium and magnesium ions to 3 mg/l or less, followed by 20 m of sodium isocyanurate dichloride.
g/l and 1.5 g/l of sodium sulfate were added. The pH of this liquid was in the range of 6.5 to 7.5. The results are shown in Tables 3 and 4 below.

0364

[Table 3]

0365]

[Table 4]

As is clear from the results shown in Tables 3 and 4, the direct positive color photographic material of the present invention provides a sufficient maximum image density (Dmax) and a low minimum image density (Dmin) (especially , which is noticeable for yellow and magenta). Further, when a hydroquinone compound is further used in the composition of the light-sensitive material of the present invention, an even lower minimum image density can be obtained.

Claims (2)

[Claims] Claim 1: A red-sensitive layer comprising a cyan coupler and an internal latent image type silver halide emulsion that is not prefogged, and a magenta coupler and an internal latent image type silver halide emulsion that is not prefogged on a support. In a direct positive color photographic material comprising a green light-sensitive layer and a blue light-sensitive layer containing a yellow coupler and an internal latent image type silver halide emulsion that has not been fogged in advance, the support is preferable to the red light-sensitive layer and the green light-sensitive layer. The non-photosensitive layer provided on the side farthest from the blue light-sensitive layer is made of a layer that substantially transmits blue light, and the halogenation contained in the blue light-sensitive layer is relative to the average grain size (rG) of the silver halide grains contained in the green light-sensitive layer. Ratio of average particle size (rB) of silver particles (rB/rG
), and the ratio (rG
/rR ) are 1.3≦rB /rG ≦3.0, 1, respectively.
．． A direct positive color photographic material characterized in that 3≦rG /rR≦3.0. 2. At least one layer of the photosensitive layer has the following formula (I): [In the above formula (I), R31 to R34 are each independently,
Hydrogen atom, halogen atom, sulfo group, carboxyl group,
Cyano group, alkyl group, alkenyl group, aryl group, acylamino group, sulfonamido group, alkoxy group, aryloxy group, alkylthio group, arylthio group, acyl group, acyloxy group, sulfonyl group, carbamoyl group, alkoxycarbonyl group or sulfamoyl group and R31 and R32 or R33 and R34 may jointly form a carbocycle or a heterocycle, provided that at least one of R31 to R34 is not a hydrogen atom, and R31 When ~R34 consists of only a hydrogen atom and an alkyl group, at least one of the alkyl groups has 6 or more carbon atoms, and the total number of carbon atoms of R31 to R34 is 15 or less. ] or the following formula (II): [In the above formula (II), R41 to R46 each independently represent a hydrogen atom, a halogen atom, a sulfo group, a carboxyl group, a cyano group, an alkyl group, an alkynyl group, aryl group,
represents an acylamino group, a sulfonamido group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an acyl group, an acyloxy group, a sulfonyl group, a carbamoyl group, an alkoxycarbonyl group, or a sulfamoyl group, and the above R41 and R42 or R44 and R45 are May jointly form a carbocycle or a heterocycle; R
47 and R48 each independently represent a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group, and the above R47 and R48 may jointly form a carbocycle or a heterocycle. 2. The direct positive color photographic material according to claim 1, which contains a compound represented by the following.