JPH0659375A - Internal latent image type direct positive silver halide emulstion and color diffusion transfer photosensitive material using same - Google Patents

Abstract

PURPOSE:To provide the internal latent image type direct positive silver halide emulsion high in sensitivity and good in a sound to noise ratio and the color diffusion transfer photosensitive material using this emulsion. CONSTITUTION:The internal latent image type direct positive silver halide emulsion is characterized by executing nucleation of the photosensitive silver halide grains and/or a part or all of the course of crystal growth in the presence of a dispersion medium selected synthetic polymers having a protective colloid action and at least one of metals selected from the transition metals of group 8 of the periodic table, and Re, Pb, Mn, Cr, Cu, Zn, Cd, and Bi, and controlling the content of gelatin to <=10g per mol of silver halide at that time, and the color diffusion transfer photosensitive material is characterized by using this emulsion.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to an internal latent image type direct positive silver halide emulsion and a color diffusion transfer light-sensitive material using the same.

[0002]

2. Description of the Related Art The photographic method using silver halide is superior in sensitivity and gradation characteristics to other photographic methods such as electrophotographic method and diazo photographic method, and has been widely used. . Among them, a method of directly forming a positive image is known. This is described, for example, in US Pat.
No. 6 and Japanese Patent Publication No. 60-55821, an internal latent image type direct positive silver halide emulsion is used to form a silver halide grain having an internal latent image on a surface developing solution (inside the silver halide grain). When developing with a developer which leaves the latent image forming site of (3) substantially undeveloped, a positive image is obtained by giving uniform exposure or by using a nucleating agent.

Examples of internal latent image type silver halide emulsions include US Pat. Nos. 2,456,953 and 2,595.
The conversion type silver halide emulsion as described in US Pat. No. 250 and the silver halide emulsion of the first phase and the second phase as described in US Pat. No. 3,935,014 have different halogen compositions. Examples thereof include a laminated type silver halide emulsion, a core / shell type silver halide emulsion in which a shell is coated on core grains which are doped with metal ions or chemically sensitized. Of these, a core / shell type silver halide emulsion is preferred in order to obtain high sensitivity.

It is possible to sensitize a silver halide emulsion by adding a transition metal compound at several stages of producing the silver halide emulsion in US Pat. No. 2,448,06.
No. 0. It is known that there is a significant difference in the photographic effect of the transition metal compound in the silver halide emulsion between the case where the transition metal compound is added during the formation of the silver halide grains and the case where it is added after the precipitation of the silver halide grains. There is. The former case is called a metal dopant. About these, Research Disclosure, Volume 176, December 1978.
Published Monthly, Item 17643.

In an internal latent image type direct positive silver halide photographic emulsion, it is known that the low density portion on the reversal characteristic curve becomes harder by doping with metal ions. This is described, for example, in U.S. Pat.
No. 367,778, No. 3,447,927, No. 3,5
31,291, 3,761,267, 3,76
1,276, 3,850,637, 3,92
No. 3,513, No. 4,035,185, No. 4,44
4,874, 4,444,865, 4,43
No. 3,047, No. 4,395,478, British Patent Nos. 1,151,782, No. 1,529,011, and JP-A-1-145647. However, it has been known that the effect of doping metal ions is insufficient and the maximum concentration is lowered.

On the other hand, European Patent No. 0,336,425,
U.S. Pat. And a silver halide emulsion excellent in gradation stability over time and having improved low illumination failure. Here, it is recognized that the hexacoordinated transition metal complex is accommodated in the void space of a single halide ion inside the crystal structure,
This is different from the conventional belief that transition metals are incorporated into silver halide grains as single ions or atoms.

Further, JP-A-2-259749 discloses an internal latent image type direct positive silver halide emulsion containing a hexacyanoiron complex among iron complexes, which has a high maximum density and a low minimum density, and has a reversal negative in a high illuminance exposure. Although it is described that a direct positive silver halide photographic light-sensitive material with less image formation can be obtained, no adverse effect of hexacyanoiron complex doping by using gelatin is mentioned, and the amount of gelatin as a protective colloid is not mentioned. Is not specified.

Gelatin has been used for a long time as a dispersion medium having a protective colloid action for a silver halide emulsion for use in image formation. The first is that the protective colloid property is large, and secondly that the sol-gel conversion is easy and easy to handle, and coating is possible. However, gelatin is easily decomposed by bacteria and fungi, and the quality of gelatin varies because it comes from the living body. For these problems, it is already known to use synthetic polymers instead of gelatin as a dispersion medium having a protective colloid effect. For example, U.S. Pat. Nos. 3,615,624 and 3,536,536.
No. 677, No. 3,692,753, No. 3,690,8
No. 88, No. 3,679, 425, No. 3,706, 56
No. 4, No. 3,706,565, No. 3,713,833
No. 3,840,628, 3,690,888
No. 4,400,463, and JP-A-2-
166442, 4-110934, 4-110
No. 935, Research Disclosure, 104
Vol. 44-48 and Journal of Imaging Science, 31.
Vol., Pp. 148-156. Although these patents and references describe examples of chemical sensitization and direct positive emulsions, chemical sensitization is chemical sensitization for negative emulsions and direct positive emulsions are prefogged direct emulsions. It is a positive emulsion and there is no description of an internal latent image type direct positive silver halide emulsion which has not been fogged as in the present invention.

In the field of direct positive silver halide emulsions, a positive image is obtained by means of an earlier prefogged direct positive emulsion, followed by "providing uniform exposure or by using a nucleating agent. It has been developed into an internal latent image type direct positive silver halide emulsion. In this process, a significant improvement in sensitivity and S / N was achieved. With the progress of direct positive image forming methods in recent years, the superiority of internal latent image type direct positive silver halide emulsions is increasing more and more. There has been a long-awaited search for peptizers that can improve performance and development of their use.

By the way, when gelatin is used as a protective colloid, even deionized gelatin is not truly inert and contains impurities regardless of whether it is inorganic or organic, which is not intended for photographic properties. The fact that it has an influence cannot be denied. Further, while recognizing the existence of impurities, it is currently very difficult to further raise the purity of gelatin. As a result of earnest research by the present inventors,
When a metal is doped at the time of grain formation in an internal latent image type direct positive silver halide emulsion, if gelatin is used as a dispersion medium having a protective colloid effect, high internal fogging that is considered to be due to the chemical reactivity inherent in gelatin occurs. It was found that an insufficient S / N was obtained after the occurrence.

[0011]

DISCLOSURE OF THE INVENTION An object of the present invention is to provide an internal latent image type direct positive silver halide emulsion which fully exhibits the effect of metal doping, has high sensitivity and good S / N, and uses it. Another object of the present invention is to provide a color diffusion transfer photosensitive material.

[0012]

The objects of the present invention have been achieved by the following internal latent image type direct positive silver halide emulsions (1) to (6), and a color diffusion transfer light-sensitive material using the same. .

(1) A dispersion medium selected from synthetic polymer compounds having a protective colloid action for part or all of the process of nucleation and / or crystal growth of photosensitive silver halide grains, and Group 8 of the periodic table. Transition metal, Re, Pb, M
An internal latent image formed in the presence of at least one metal selected from n, Cr, Cu, Zn, Cd and Bi, and the gelatin content in that case is 10 g or less per mol of silver halide. Type direct positive silver halide emulsion. (2) Group 8 transition metal as described in (1) above, or R
An internal latent image type direct positive silver halide emulsion characterized in that e, Mn and Cr are present in the form of hexacoordination complex ions. (3) Group 8 transition metal as described in (1) above, or R
An internal latent image type direct positive silver halide emulsion characterized in that e, Mn and Cr are present in the form of hexacoordinated cyano complex ions. (4) An internal latent image type direct positive silver halide emulsion, wherein the metal described in (1) above is Pb. (5) An internal latent image type direct positive silver halide emulsion, wherein the synthetic polymer compound according to any one of the above items (1) to (4) is a polymer having a vinylimidazole group. (6) On a support, at least one photosensitive silver halide emulsion layer combined with a dye image-forming substance is provided, and the dye image-forming substance is represented by the following general formula (I). In a color diffusion transfer light-sensitive material comprising a non-diffusible compound which releases a diffusible dye or a precursor thereof or a compound which changes its own diffusivity, at least one of the silver halide emulsion layers comprises (1) ~
A color diffusion transfer light-sensitive material comprising the internal latent image type direct positive silver halide emulsion described in any one of (5). In formula (I) (DYE-Y) _n -Z, DYE represents a dye group, a temporarily shortened dye group or a dye precursor group, Y represents a simple bond or a linking group, and Z represents A diffusivity of the compound represented by (DYE-Y) _n -Z is changed corresponding to or opposite to a photosensitive silver salt having an image-wise latent image, or DYE is released and released. Represents a group having a property of causing a difference in diffusivity between DYE and (DYE-Y) _n -Z, n represents 1 or 2, and when n is 2, two DYE-Y May be the same or different.

The present invention will be described in more detail below. The metal used as a metal dopant in the present invention is a Group 8 transition metal of the periodic table, Re, Pb, Mn, Cr, Cu,
Zn, Cd, and Bi. Specifically, Fe, Rh, Ru,
Os, Co, Ni, Ir, Pd, Pt, Re, Mn, C
r, Pb, Cu, Zn, Cd, and Bi. Above all, F
e, Ru, Co, Ir, Mn, Cr and Pb are preferable.
The metal used in the present invention can be added in the form of a salt that can be dissolved at the time of grain formation, such as ammonium salt, acetate salt, nitrate salt, sulfate salt, phosphate salt, hydroxide salt or hexacoordinate complex salt, and tetracoordinate complex salt. .

When contained in the silver halide as a hexacoordinated complex ion, a Group 8 transition metal and Re, Mn, C
r is preferred. Among them, Fe, Co, Ir and Ru are more preferable. Examples of the ligand include halogen ion and cyano ion, and among them, cyano ion is preferable.

As the counterion of the hexacoordinated metal complex ion,
Alkali metal ions are preferable, and potassium ions and sodium ions are more preferable.

The amount of the metal used in the present invention is 1.0 × 10 ⁻⁹ mol or more, 1.0 × 1 mol per mol of silver halide.
It is preferably 0 ^-3 mol or less, and more preferably 1.0 x 10 ^-8 mol or more and 1.0 x 10 ^-5 mol or less per mol of silver halide. The hydrogen ion concentration in the reaction solution when this metal is added is preferably pH = 1 or higher, and more preferably pH = 3 or higher.

The metal used in the present invention is added at the time of preparation of silver halide grains, that is, at the time of nucleation, physical ripening and growth, but it may be added at any stage. Further, it may be added additionally during the chemical sensitization. The pAg when these metals are added during the preparation of silver halide grains is preferably 6 or more, more preferably 7 or more.

This metal may be added dividedly over several times. These metals, in the form of salts, are dissolved in water or a suitable solvent and added to the reaction solution. To stabilize the solution, an aqueous solution of hydrogen halide (eg HCl,
HBr etc.) or alkali halide (eg K
Cl, NaCl, KBr, NaBr, etc.) can be used. Moreover, you may add an acid, an alkali etc. as needed.

The metal used in the present invention may be added directly to the reaction solution at the time of forming silver halide grains, or may be added to an aqueous solution of a halide for forming silver halide grains, an aqueous solution of silver salt, or other solution. It is preferable to add the particles by adding them to form particles. It is also possible to use a method in which a twin-free silver halide fine grain emulsion containing a metal is added and dissolved and then deposited on the silver halide grains in the reaction solution by Ostwald ripening. further,
It is also possible to combine various addition methods.

Next, a synthetic polymer compound other than gelatin having a protective colloid action will be described in detail. Typical examples of the synthetic polymer compound having a protective colloid action used in the present invention are shown below. (1) Polyacrylamide Polymer A homopolymer of acrylamide, US Pat. No. 2,541,
No. 474, a copolymer of polyacrylamide and imidized polyacrylamide, West German Patent 1,20
Copolymers of acrylamide and methacrylamide shown in US Pat. No. 2,132, partially aminated acrylamide polymers shown in US Pat. No. 3,284,207,
JP-B-45-14031, US Pat. No. 3,713,83
No. 4, No. 3,746,548, British Patent 788,34
Substituted Acrylamide Polymers Shown in No. 3 (2) Amino Polymers US Pat. Nos. 3,345,346 and 4,350,759
Amino polymers shown in West German Patent 2,138,872, polymers having quaternary amines shown in British Patent 1,413,125 and US Patent 3,425,836, US Patent 3,511,818. Having an amino group and a carboxyl group shown in US Pat.
Polymers shown in 832 and 185, and copolymers with pyridine (3) Polyvinyl alcohol Vinyl alcohol homopolymer, US Pat.
0741 organic acid monoesters of polyvinyl alcohol, maleic acid esters shown in US Pat. No. 3,236,653, and copolymers of polyvinyl alcohol and polyvinylpyrrolidone shown in US Pat. No. 3,479,189. (4) Acrylic acid polymer Acrylic acid homopolymer, US Pat. No. 3,832,185
No. 3,852,073, an acrylic acid ester polymer having an amino group, US Pat. No. 4,131,
Halogenated acrylic acid ester polymer shown in US Pat. No. 471, cyanoalkyl acrylic acid ester shown in US Pat. No. 4,120,727 (5) Polymer having hydroxyquinoline US Pat. Nos. 4,030,929 and 4,152, 161
Having hydroxyquinoline shown in (6) Acetal US Pat. Nos. 2,358,836 and 3,003,879
No. 2,828,204, British Patent 771,155
(7) Polyvinylpyrrolidone Homopolymer of vinylpyrrolidone, French Patent 2,0
Copolymer of acrolein and pyrrolidone shown in 31,396 (8) Polystyrene Polystyrylamine polymer shown in US Pat. No. 4,315,071, halogenated styrene polymer shown in US Pat. No. 3,861,918 ( 9) Imidazole polymer JP-B-43-7561, JP-A-47-25374, JP-A-47-25374
2-16365, German Patent 2,012,095,
No. 2,012,970, U.S. Pat. No. 3,520,857.
Having vinylimidazole group (10) Vinylpyridine polymer Research Disclosure, 105, 10505
(11) Others Vinyl polymer having an azaindene group described in JP-A-59-8604, polyalkylene oxide derivative described in US Pat. No. 2,976,150, US Pat.
Polyvinylamine imide polymers shown in US Pat. No. 022,623, US Pat.
Polymers shown in US Pat. No. 2,688, US Pat.
Polyvinylpyridine shown in 4,456, Japanese Patent Publication No. 6
No. 0-658, a vinyl polymer having a triazole group, polyvinyl-2-methylimidazole and acrylamide-imidazole copolymers, dextran, and zeite shrift bisene shown in Journal of Photographic Society of Japan, Vol. 29, No. 1, page 18. Water-soluble polyalkyleneaminotriazoles shown in Shaftricher Photography, Vol. 45, p. 43 (1950). Among these, polyvinylpyrrolidone of (7),
The imidazole polymer (9) and the vinylpyridine polymer (10) are more preferable. Among the imidazole polymers, the polymers described in JP-B-52-16365 are more preferable.

The molecular weight and molecular weight distribution of the synthetic polymer compound used in the present invention are not particularly limited and can be arbitrarily selected according to the purpose, and it is also possible to use several kinds of these compounds in combination. There is no particular limitation on the amount used.

The dispersion medium having a protective colloid effect of the present invention is used at the time of grain formation. The method used is as follows. A solution in which a dispersion medium having an action is dissolved is added to the reaction vessel, or
It can be added in parallel with the silver salt solution. It is preferable to add it as an aqueous solution to the reaction vessel in advance.

When silver halide emulsion grains are formed by the method of the present invention, gelatin, the above-mentioned synthetic polymer compounds or natural polymer compounds (for example, British Patents 542,704 and 551,659) are formed in the subsequent steps. Nos. 2,127,573, 2,311,086 and 2,322,085), or derivatives of starch) can be added any number of times at any time, The amount used can also be added in a necessary amount according to the purpose.

As the protective colloid used in the preparation of the emulsion in the present invention, gelatin can be used in combination with the above-mentioned synthetic polymer. Examples of gelatin include lime-processed gelatin, acid-processed gelatin, and Bull. Soc. Sci. Photo.
An enzyme-treated gelatin as described in Japan, No. 16, P30 (1966) may be used, and a hydrolyzed product or an enzymatically decomposed product of gelatin may also be used. Although many impurity ions are contained in gelatin, it is also preferable to use gelatin in which the amount of inorganic impurity ions is reduced by ion exchange treatment.

The amount of gelatin used in the present invention for forming silver halide grains is 10 g or less per mol of silver halide. Preferably, gelatin is not used during grain formation.

The present invention is applicable to internal latent image type direct positive silver halide emulsions. An internal latent image type direct positive silver halide emulsion (hereinafter sometimes abbreviated as an internal latent image type silver halide emulsion) means that when imagewise exposed, a latent image is mainly formed inside the silver halide grains. With a silver halide emulsion,
Specifically, a certain amount of a silver halide emulsion is coated on a transparent support and exposed to light for a fixed time of 0.01 to 1 second, and the following developer A (“internal type” developer) is used. Inside,
The maximum density obtained when developed at 20 ° C. for 5 minutes was the same as the above.
It is defined as having a density which is at least 5 times greater than the maximum density obtained when developed in ("surface type" developer) at 20 ° C for 5 minutes. Here, the maximum density is measured by a usual photographic density measuring method. Developer A N-methyl-p-aminophenol sulfite 2g Sodium sulfite (anhydrous) 90g Hydroquinone 8g Sodium carbonate (monohydrate) 52.5g Potassium bromide 5g Potassium iodide 0.5g Water added 1 liter Developer B N-methyl-p-aminophenol sulfite 2.5 g 1-ascorbic acid 10 g potassium metaborate 35 g potassium bromide 1 g Water added 1 liter As an internal latent image type silver halide emulsion, for example, US Pat. 456,953 and 2,592,250 and the like, conversion type silver halide emulsions, and the first phase and the first phase as described in U.S. Pat. No. 3,935,014 and the like. Laminated structure silver halide emulsions having different two-phase halogen composition, doped with metal ions, or Such core / shell type silver halide emulsion coated with shell academic sensitized core particles. Of these, a core / shell type silver halide emulsion is particularly preferable as the internal latent image type silver halide emulsion used in the present invention.
Examples thereof include US Pat.
317,322, 3,761,266, 3,7
61,276, 3,850,637, 3,92
No. 3,513, No. 4,035,185, No. 4,18
4,878, 4,395,478, 4,50
4,570, JP-A-57-136641, JP-A 61-
No. 3137, No. 63-151618, JP-A No. 1-13
Examples thereof include those described in No. 1547.

In order to directly obtain a positive image, a uniform second exposure is applied to the entire surface of the photosensitive layer after the above-mentioned internal latent image type silver halide emulsion is imagewise exposed and before or during the development processing ("light Fogging method ", for example, British Patent 1,151,363
No.) or in the presence of a nucleating agent (“chemical fogging method”, for example, Research Disclosure, Volume 151, No. 151).
62, pp. 76-78), but a method of directly obtaining a positive image by the "chemical fogging method" is preferred in the present invention. The nucleating agent used in the present invention will be described later. As described above, in order to directly obtain a positive image using the internal latent image type silver halide emulsion, after the image exposure, before the development processing or during the development processing, the entire surface is uniformly exposed to the second exposure, or It is obtained by carrying out development processing in the presence of a nucleating agent. As a nucleating agent, US Pat.
3,785, 2,588,982 hydrazines, U.S. Pat. No. 3,227,552 hydrazides, hydrazones, British Patent 1,283,
No. 835, JP-A Nos. 52-69613 and 55-138.
No. 742, No. 60-11837, No. 62-21045.
No. 1, 62-291637, U.S. Pat. No. 3,615,
No. 615, No. 3,719,494, No. 3,734,7
No. 38, No. 4,094,683, No. 4,115,12
No. 2, No. 4,306,016, No. 4,471, 044
Heterocyclic quaternary salt compounds described in U.S. Pat.
No. 4,430,92, a sensitizing dye having a substituent having a nucleating action in a dye molecule, described in US Pat.
No. 5, No. 4,031,127, No. 4,245, 037
No. 4,255,511, 4,266,013
No. 4,276,364, British Patent No. 2,012,4
No. 43, etc., and thiourea-bonded acylhydrazine compounds, and US Pat. Nos. 4,080,270 and 4,
Acylhydrazine compounds having a thioamide ring or a heterocyclic group such as triazole or tetrazole described in British Patent No. 278,748 and British Patent No. 2,011,391B as an adsorption group are used. The amount of the nucleating agent used here is preferably an amount which gives a sufficient maximum density when the internal latent image type emulsion is developed with a surface solid developing solution. In practice, the appropriate content may vary over a wide range since it depends on the characteristics of the silver halide emulsion used, the chemical structure of the nucleating agent and the development conditions, but the silver content in the internal latent silver halide emulsion may vary. About 0.1 mg to 5 per mole
A range of g is practically useful, preferably about 0.5 mg to about 2 g per mole of silver. When it is contained in the hydrophilic colloid layer adjacent to the emulsion layer, the same amount as described above may be contained with respect to the amount of silver contained in the inner latent type emulsion having the same area.

Various shapes of silver halide grains can be used in the present invention. As an example, those having a regular crystal form such as a cube, octahedron, tetradecahedron and rhombic dodecahedron, and those having an irregular crystal form such as a sphere and a plate, Examples thereof include those having the following plane ((hkl) plane), and a mixture of grains of these crystal forms. For particles with higher surfaces, see the Journal of Imaging Science.
247 of the maging Science magazine, Volume 30 (1986)
See pages 254. The silver halide grains used in the present invention, even if they are normal crystals that do not contain twin planes, are edited by The Photographic Society of Japan, Fundamentals of The Photographic Industry, Silver Salt Photography (Corona Publishing Co.), p. 163, for example, single twin containing one twin plane, parallel multiple twin containing two or more parallel twin planes, non-parallel containing two or more non-parallel twin planes. It can be selected and used from multiple twins and the like according to the purpose. An example of mixing particles having different shapes is disclosed in U.S. Pat. No. 4,865,964, but this method can be selected if necessary. In case of normal crystal (10
A cube consisting of (0) faces, an octahedron consisting of (111) faces,
JP-B-55-42737, JP-A-60-222842
The dodecahedral grains composed of (110) planes disclosed in Japanese Patent No. 3,095,049 can be used. Furthermore, Journal of Imaging Science, Vol. 30, p. 247, 198.
(Hll) plane particles typified by (211) and typified by (331) as reported in 2006 (hh1)
The face particles, the (hk0) face particles typified by the (210) face, and the (hk1) face particles typified by the (321) face may be selected and used according to the purpose although some preparation methods are required. Tetrahedral particles in which (110) plane and (111) plane coexist in one grain, particles in which (100) plane and (110) plane coexist, or particles in which (111) plane and (110) plane coexist. For example, particles in which two surfaces or a large number of surfaces coexist can be selected and used according to the purpose.

As the silver halide composition of these grains, any of silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide, silver chloroiodide and silver chloride is used. However, silver bromide and silver iodobromide are preferred. Further, other silver salts such as silver thiocyanate, silver cyanate, silver sulfide,
Silver selenide, silver carbonate, silver phosphate, and organic acid silver may be contained as separate grains or as a part of silver halide grains.

The silver halide grains may have different phases in the inside and the surface layer, or may have a uniform phase.
The silver halide composition in the grain may be uniform, may have a different silver halide composition between the inside and the outside, or may have a layered structure (JP-A-57-154).
No. 232, No. 58-108533, No. 58-2484
69, 59-48755, 59-52237.
U.S. Pat. Nos. 3,505,068 and 4,433.
048, 4,444,877, European Patent No. 10
0,984 and British Patent No. 1,027,146.
issue). Also, particles having dislocation lines may be used.

In the case of silver halide grains in which two or more silver halides exist as a mixed crystal or with a structure, it is important to control the halogen composition distribution between grains. The method for measuring the halogen composition distribution between grains is described in JP-A-60-254032. A uniform halogen distribution between grains is a desirable property. In particular, a highly uniform emulsion having a variation coefficient of 20% or less is preferable.
Another preferred form is an emulsion where there is a correlation between grain size and halogen composition.

It is important to control the halogen composition near the surface of the grain. Increase the content of silver iodide near the surface,
Alternatively, increasing the silver chloride content changes the adsorbability of the dye and the developing rate, and can be selected according to the purpose.
When changing the halogen composition in the vicinity of the surface, it is possible to select either a structure that encloses the entire grain or a structure that attaches only a part of the grain. For example, (100) plane and (11
1) The case where the halogen composition is changed only on one surface of the tetradecahedral grain composed of faces, or the halogen composition is changed on one of the main plane and the side surface of the tabular grain.

The grain size of the emulsion used in the present invention depends on the circle equivalent diameter of the projected area using an electron microscope, the sphere equivalent diameter of the grain volume calculated from the projected area and the grain thickness, or the sphere equivalent diameter of the volume by the Coulter counter method. Can be evaluated. It can be selected from ultrafine particles having a sphere-equivalent diameter of 0.05 μm or less and coarse particles having a diameter of more than 10 μm. Particles of 0.1 μm or more and 3 μm or less are preferable. The grain size distribution of the silver halide grains is arbitrary, but may be monodisperse. Here, monodisperse means
It is defined as a dispersion system in which 95% of the total weight or the total number of silver halide grains contained therein falls within ± 60% of the number average grain size, preferably within 40%.
Here, the number average grain size is the number average diameter of the projected area diameters of silver halide grains. Monodisperse emulsions are described in U.S. Pat. Nos. 3,574,628 and 3,655,394 and British Patent 1,413,748. These monodisperse emulsions are mixed and used. May be.

Two or more kinds of silver halides having different crystal habits, halogen compositions, grain sizes, grain size distributions, etc. can be used in combination, and are used in different emulsion layers and / or the same emulsion layer. It is possible to

In the present invention, more preferable effects can be obtained when tabular silver halide grains are used. Regarding tabular silver halide grains, Cleve, Photography Theory and Practice has already been written by Cleve.
(1930)), 131; Gatov, Photographic Science and Engineering (Gutof
f, Photographic Science and Engineering), 14th
Vol. 248-257 (1970); U.S. Pat. No. 4,
No. 434, 226, No. 4,414, 310, No. 4, 4
33,048, 4,439,520, 4,41
No. 4,306, No. 4,459,353, British Patent No. 2,112,157, Japanese Unexamined Patent Publication Nos. 59-99433, 62-209445, and the like, their manufacturing methods and use techniques are disclosed. In particular, a tabular internal latent image type direct positive silver halide emulsion is described in US Pat. No. 4,395,478.
And 4,504,570, 4,996,137
Japanese Patent Publication No. 64-8327, JP-A-1-131547.
It is described in detail in the issue. These tabular internal latent image type direct positive emulsions are excellent in that they have a good sharpness, a rapid development progress, and a direct positive image having a small development temperature dependency. The shape of tabular grains can be selected from triangles, hexagons, circles, and the like. A regular hexagon with approximately six sides of equal length, as described in U.S. Pat. No. 4,996,137, is a preferred form. In the case of tabular grains, dislocation lines can be observed with a transmission electron microscope. Particles containing no dislocation lines, particles containing several dislocations, or particles containing many dislocations can be selected according to the purpose. It is also possible to select dislocations or curved dislocations that are introduced linearly with respect to a specific direction of the crystal orientation of the particles, or to introduce the dislocations throughout the particles or only at specific sites of the particles, for example, The dislocation can be introduced only in the fringe portion of the grain. Dislocation lines can be introduced not only in the case of tabular grains but also in the case of regular grains or amorphous grains typified by potato grains. For example, JP-A-63-220238 and JP-A-1-201649 disclose tabular silver halide grains in which dislocations are intentionally introduced.

The ratio of the average grain diameter to the average grain thickness (hereinafter referred to as grain diameter / thickness) in the tabular grains is preferably 2 or more, more preferably 3 to 12, and especially 5
It is preferably -8. Here, the average grain diameter of tabular silver halide grains is the average value of the diameters of circles of two opposing parallel or nearly parallel principal planes (the diameter of a circle having the same projected area as the principal plane). The average particle thickness represents the average value of the distances between the main planes. Here, the grain diameter / thickness can be obtained by averaging the grain diameters / thicknesses of all tabular grains. A simple method is to calculate the average diameter of all tabular grains and the average thickness of all tabular grains. It can also be calculated as a ratio.

The tabular grains have a diameter (corresponding to a circle) of 0.3 μm or more, preferably 0.3 to 10 μm, more preferably 0.
5 to 5.0 μm, more preferably 0.5 to 3.0 μm
Is. The grain thickness is less than 1.0 μm, preferably 0.0
It is 5 to 0.5 μm. Furthermore, the coefficient of variation of particle thickness is 3
Emulsions with high thickness uniformity of 0% or less are also preferable. Further, grains described in JP-A-63-163451, in which the grain thickness and the interplanar distance between twin planes are defined, are also preferable. In the present invention, the tabular grains account for 50% or more of the total grain projected area in the emulsion containing the tabular grains. It is preferably 70% or more, more preferably 90% or more. The grain diameter and grain thickness of tabular grains can be measured by US Pat.
It can be determined by electron micrographs of particles as described in the method described in No. 34,226.

Further, in the present invention, the tabular grains are preferably monodisperse. The structure and manufacturing method of monodisperse tabular grains are described in, for example, JP-A-63-151618.

The silver halide emulsion used in the present invention is a treatment for rounding grains as disclosed in European Patent Nos. 96,727B1 and 64,412B1 or West German Patent No. 2,306,447C2. , JP Sho 60
The surface may be modified as disclosed in US Pat. A structure having a flat particle surface is generally used, but intentionally forming irregularities is sometimes preferable. JP-A-58-106532, 60-22132
US Pat.
Raffle particles described in 643,966 are examples.

The silver halide grains used in the present invention are
Research Disclosure (RD) No. 1764
3 (Dec. 1978), pp. 22-23, "I. Emulsion preparation and types", ibid. 1
8716 (November 1979), p. 648, ibid. Three
07105 (November 1989), pages 863-865,
And Graphide, "Physics and Chemistry of Photography," published by Paul Montel (P. Glafkides, Chimie et Pysique Photograph
ique, Paul Montel, 1967), "Photographic emulsion chemistry" by Duffin, published by Focal Press (GF Duffin, Photog
raphic Emulsion Chemistry, Focal Press, 196
6), "Production and Coating of Photographic Emulsions" by Zelikmann et al., Published by Focal Press (VL Zelikman et al, Making and
Coating Photographic Emulsion, Focal Press, 196
It can be prepared using the method described in 4) or the like. That is, any of an acidic method, a neutral method, an ammonia method and the like may be used, and a method of reacting a soluble silver salt and a soluble halogen salt may be a one-sided mixing method, a simultaneous mixing method, a combination thereof or the like. Good. Method of forming grains in the presence of excess silver ion (so-called reverse mixing method)
Can also be used. As one form of the simultaneous mixing method, a method of keeping pAg in a liquid phase where silver halide is formed constant, that is, a so-called controlled double jet method can be used. According to this method, a silver halide emulsion having a regular crystal form and a substantially uniform grain size can be obtained. Also, tabular grains are described in Gatov, Photographic Science and Engineering (Guto
ff, Photographic Science and Engineering), 14th
Vol. 248-257 (1970); U.S. Pat. No. 4,
No. 434, 226, No. 4,414, 310, No. 4, 4
It can be easily prepared by the methods described in 33,048, 4,439,520 and British Patent 2,112,157.

The silver halide emulsion comprising the above regular grains can be obtained by controlling the pAg and pH during grain formation. For more information, for example,
Science and Engineering (Photographic S
cience and Engineering), Volume 6, 159-165 (1962); Journal of Photographic Science, 1
Volume 2, Pages 242-251 (1964), U.S. Pat. No. 3,
655,394 and British Patent 1,413,748.
No. Regarding monodisperse emulsions, JP-A Nos. 48-8600, 51-39027 and 51-
83097, 53-137133, and 54-48.
No. 521, No. 54-99419, No. 58-37635.
No. 58-49938, Japanese Patent Publication No. 47-11386
No. 3,655,394 and British Patent No. 1,413,748.

The method of adding pre-precipitated silver halide grains to a reaction vessel for emulsion preparation is described in US Pat. Is more preferable. These can be used as seed crystals, and are also effective when provided as silver halide for growth. In the latter case, it is preferable to add an emulsion having a small grain size. As an addition method, the whole amount can be added at once, divided into a plurality of times, or added continuously. It is also effective in some cases to add particles having various halogen compositions in order to modify the surface.

A method for converting most or only a part of the halogen composition of silver halide grains by the halogen conversion method is described in US Pat. Nos. 3,477,852 and 4,14.
2,900, European Patents 273,429, 273.
No. 430 and West German Laid-Open Patent No. 3,819,241 and the like, which is an effective particle forming method. A solution of soluble halogen or silver halide grains can be added to convert it to a more sparingly soluble silver salt. It is possible to select from a method such as conversion at once, conversion by dividing into plural times, or continuous conversion.

Besides the method of adding soluble silver salt and halogen salt at a constant concentration and a constant flow rate for grain growth, British Patent No. 1,
469,480, U.S. Pat. No. 3,650,757,
A particle forming method in which the concentration is changed or the flow rate is changed as described in U.S. Pat. No. 4,242,455 is a preferable method. By increasing the concentration or increasing the flow rate, the amount of silver halide supplied can be changed by a linear function, a quadratic function, or a more complicated function of the addition time. It is also preferable in some cases to reduce the amount of silver halide supplied if necessary. Furthermore, when adding a plurality of soluble silver salts having different solution compositions, or when adding a plurality of soluble halogen salts having different solution compositions, an addition method in which one is increased and the other is decreased is also an effective method. Is. A mixer for reacting a solution of a soluble silver salt and a soluble halogen salt is disclosed in US Pat. Nos. 2,996,287, 3,342,605 and 3,3.
The method can be selected from the methods described in 415,650, 3,785,777 and West German Laid-Open Patents 2,556,885, 2,555,364.

A silver halide solvent is useful for the purpose of promoting ripening. For example, it is known to have excess halogen ions present in the reactor to accelerate aging. Other ripening agents can also be used. The total amount of these ripening agents can be compounded in the dispersion medium in the reactor before adding silver and halide salts, and the halide salts, silver salts or peptizers can be added in the reactor as well. Can also be introduced. As another variation, the ripening agent can be introduced independently at the halide salt and silver salt addition stages.

As ripening agents other than halogen ions, ammonia, amine compounds, thiocyanate salts,
For example, alkali metal thiocyanate salts, especially sodium and potassium thiocyanate salts, and ammonium thiocyanate salts can be used. The use of thiocyanate ripening agents is described in US Pat. No. 2,222,264.
Nos. 2,448,534 and 3,320,06
Instructions can be found in No. 9. Organic thioether compounds (for example, US Pat. Nos. 3,271,157 and 3,574,574)
No. 628, No. 3,737,313, No. 3,021,2
No. 15, No. 3,057,724, No. 3,038,80
5, No. 4,276,374, No. 4,297,439
No. 3,704,130, No. 4,782,130
JP-A-57-104926) and thione compounds (for example, JP-A-53-82408).
No. 55-77737, U.S. Pat. No. 4,221,8.
Tetrasubstituted thioureas described in JP-A No. 63-63, compounds described in JP-A-53-144319),
Examples thereof include mercapto compounds described in JP-A-57-202531, which can promote the growth of silver halide grains, and amine compounds (for example, JP-A-54-100717).

During the production of an emulsion containing tabular grains, a silver salt solution (eg AgN) added to accelerate grain growth.
A method of increasing the addition rate, the addition amount, and the addition concentration of the O ₃ aqueous solution) and the halide solution (for example, KBr aqueous solution) is preferably used. Regarding these methods, for example, British Patent No. 1,335,925 and US Pat.
672,900, 3,650,757, 4,2
42,445, JP-A-55-142329 and JP-A-55.
The description of No. 158124 can be referred to.
The above silver halide solvent is effective for promoting the ripening.

The method of adding a chalcogenide compound as described in US Pat. No. 3,772,031 during emulsion preparation may be effective in some cases. In addition to S, Se and Te, cyanate, thiocyanate, selenocyanate, carbonate,
Phosphate and acetate may be present. Regarding these, US Pat. Nos. 2,448,060 and 2,628,
No. 167, No. 3,737,313, No. 3,772,0
No. 31, and Research Disclosure, 134
Vol., June 1975, 13452, etc.

The internal latent image type silver halide grains used in the present invention preferably have a core / shell structure as described above. The shell manufacturing method is disclosed in JP-A-63-151618.
No. 3,206,316, 3,317,322, 3,761,276, 4,269,927, 3,367,778 and the like. Can be In this case, the core / shell molar ratio (weight molar ratio) is preferably 1/30 to 5/1, more preferably 1/20 to 2/1, and further preferably 1/2.
It is 0 to 1/1.

In the silver halide emulsion of the present invention, it is preferable that after chemically sensitized core grains are coated with a shell, the grain surfaces are further chemically sensitized, but the grain surfaces are not chemically sensitized. I don't mind. In general, chemical sensitization on the grain surface shows good reversal performance with high maximum density. When chemical sensitization is applied to the grain surface, Japanese Patent Publication No. 60-558
A polymer as described in No. 21 may coexist. The above chemical sensitization is described by James, The Theory of the Photographic Process, 4th Edition, published by Macmillan, 1977 (TH James, The Theory of
the Photographic Process, 4th ed., Macmillan, 197
7), pp. 67-76, using active gelatin, and Research Disclosure, 120, April 1974, 12008; Research Disclosure, 34, June 1975. ,
13452, U.S. Pat. Nos. 2,642,361 and 3,
297,466, 3,772,031, 3,8
57,711, 3,901,714, 4,26
6,018, and 3,904,415, and British Patent 1,315,755, p.
It can be carried out using Ag, 5 to 10, pH 5 to 8 and a temperature of 30 to 80 ° C., using sulfur, selenium, tellurium, gold, platinum, palladium, iridium, rhodium, osmium, rhenium or a combination of a plurality of these sensitizers.

It is also possible to carry out chemical sensitization in the presence of a chemical sensitization aid. The chemical sensitization aids used include compounds known to control fog and increase sensitivity during the chemical sensitization process, such as azaindene, azapyridazine and azapyrimidine. Examples of chemical sensitization aids are
US Pat. Nos. 2,131,038 and 3,411,91
No. 4, 3,554, 757, JP-A-58-1265.
36, 62-253159, and Duffin, "Photoemulsion Chemistry", pp. 138-143 (Focal Press, 1966).

Japanese Patent Publication No. 58-1410, Mois
ar) et al., Journal of Photographic Science, 25, 1977, pp. 19-27, silver halide emulsions can reduce and sensitize the inside of grains during the precipitation process. . The following reduction sensitization can also be used as the chemical sensitization. U.S. Pat. No. 3,891,
As described in US Pat. No. 2,518,698 and US Pat. No. 2,743, U.S. Pat. No. 2,518,698, and US Pat.
182 and 2,743,183 with reducing agents or low pAg (eg less than 5).
Alternatively, reduction sensitization can be performed by treatment with high pH (for example, greater than 8). Stannous salt as a typical reduction sensitizer,
Ascorbic acid and its derivatives, amines and polyamines, hydrazine derivatives, formamidinesulfinic acid,
Silane compounds and borane compounds are known. For reduction sensitization, these known reduction sensitizers can be selected and used, or two or more kinds of compounds can be used in combination. As reduction sensitizers, stannous chloride, thiourea dioxide, dimethylamine borane, ascorbic acid and its derivatives are preferred compounds. The chemical sensitization methods described in US Pat. Nos. 3,917,485 and 3,966,476 can also be applied.

Further, JP-A-61-3134 and 61-3
The sensitizing method using an oxidizing agent described in JP-A No. 136 can also be applied. The oxidizing agent for silver refers to a compound that acts on metallic silver to convert it into silver ions. In particular, a compound that converts extremely fine silver grains, which are a by-product in the process of forming silver halide grains and the process of chemical sensitization, into silver ions is effective. The silver ions generated here may form a poorly soluble silver salt such as silver halide, silver sulfide and silver selenide, or may form a readily soluble silver salt such as silver nitrate. Good. The oxidizing agent for silver may be an inorganic substance or an organic substance. Inorganic oxidizers include ozone, hydrogen peroxide and its adducts (eg Na
BO ₂ · H ₂ O ₂ · 3H ₂ O, 2NaCO ₃ · 3H ₂ O
₂ , Na ₄ P ₂ O ₇・ 2H ₂ O ₂ , 2Na ₂ SO ₄・ H
₂ O ₂ · 2H ₂ O), peroxy acid salts (eg K ₂ S _{2
O 8, K 2 C 2 O} 6, K 2 P 2 O 8), peroxy complex compounds _{(e.g., K 2 [Ti (O 2} ) C 2 O 4] · 3H
₂ O, 4K ₂ SO ₄ · Ti (O ₂ ) OH · SO ₄ · 2H
₂ O, permanganate (eg, KMnO ₄ ), chromate (eg, K ₂ Cr ₂ O ₇ ) and other oxyacid salts, halogen elements such as iodine and bromine, and perhalogenates (eg, periodic acid). Potassium), high valent metal salts (eg potassium hexacyanoferrate) and thiosulfonates. Examples of the organic oxidizing agent include quinones such as p-quinone, organic peroxides such as peracetic acid and perbenzoic acid, and compounds that release active halogen (for example, N-bromosuccinimide, chloramine T, chloramine B). ) Is mentioned as an example. Preferred oxidizing agents of the present invention are ozone, hydrogen peroxide and its adducts, halogen elements, inorganic oxidizing agents of thiosulfonates and organic oxidizing agents of quinones. It is a preferable embodiment to use the reduction sensitization and the oxidizing agent for silver in combination. It is possible to select and use the method of performing reduction sensitization after using an oxidizing agent, the reverse method thereof, or the method of coexisting both. These methods can be selectively used in the grain forming step and the chemical sensitization step.

The emulsion of the present invention is preferably washed with water for desalting and dispersed in a newly prepared protective colloid. The temperature of washing with water can be selected according to the purpose, but it is preferably selected in the range of 5 to 50 ° C. The pH at the time of washing with water can also be selected according to the purpose, but it is preferably selected between 2 and 10. More preferably, it is in the range of 3-8. The pAg at the time of washing with water can also be selected according to the purpose, but it is preferably selected between 5 and 10. As a method of washing with water, a noodle washing method, a dialysis method using a semipermeable membrane, a centrifugation method, a coagulation sedimentation method, or an ion exchange method can be selected and used. In the case of the coagulation sedimentation method, it can be selected from a method using a sulfate, a method using an organic solvent, a method using a water-soluble polymer, a method using a gelatin derivative and the like.

In the present invention, spectral sensitization can be carried out using a sensitizing dye. Examples of the sensitizing dye used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes. Specifically, U.S. Pat. No. 4,617,257,
JP-A-59-180550 and JP-A-60-140335.
No. 61-160739, RD17029 (197).
8) 12 to 13 pages, RD17643 (1978) 2
The sensitizing dyes described on page 3, etc. may be mentioned.

These sensitizing dyes may be used alone, or a combination thereof may be used, and the combination of sensitizing dyes is often used especially for the purpose of supersensitization. Typical examples thereof are US Pat. Nos. 2,688,545 and 2,9.
77,229, 3,397,060, 3,52
No. 2,052, No. 3,527,641, No. 3,61
7,293, 3,628,964, 3,66
6,480, 3,672,898, 3,67
9,428, 3,703,377 and 3,76
9,301, 3,814,609, 3,83
7,862, 4,026,707, British Patents 1,344,281, 1,507,803, Japanese Patent Publication Nos. 43-4936, 53-12375, and Japanese Patent Laid-Open No. 5-12375.
2-110618 and 52-109925.

Along with the sensitizing dye, a dye having no spectral sensitizing effect itself or a substance which does not substantially absorb visible light and exhibits supersensitization may be contained in the emulsion. (For example, US Pat. Nos. 3,615,613 and 3,3
No. 615, 641, No. 3,617, 295, No. 3, 6
35,721, 2,933,390, 3,74
3,510, those described in JP-A-63-23145, etc.). The sensitizing dye may be added to the emulsion at any stage in the emulsion preparation which has heretofore been known to be useful. Most commonly, it is carried out after the completion of chemical sensitization and before coating, but it is described in US Pat. No. 3,628,969.
JP-A-58-113928 discloses that spectral sensitization can be performed simultaneously with chemical sensitization by adding it at the same time as the chemical sensitizer as described in JP-A No. 58-113928. As described above, the chemical sensitization can be carried out prior to the chemical sensitization, or the spectral sensitization can be started by the addition before the completion of the silver halide grain precipitation formation. Furthermore, US Pat. No. 4,22
Adding these said compounds separately as taught in US Pat. No. 5,666, ie adding some of these compounds prior to chemical sensitization and the rest after chemical sensitization. Is also possible, and US Pat. No. 4,183,7
It may be at any time during the formation of silver halide grains including the method disclosed in No. 56.

The amount of addition is 10 mol per mol of silver halide.
It can be used in an amount of from ^-8 to 10 ^-2 mol, but about 5 x 10 ^-5 to 2 x 10 ^-3 mol is more effective for a more preferable silver halide grain size of 0.2 to 1.2 µm.

The coating amount of the photosensitive silver halide used in the present invention is in the range of 1 mg to 10 g / m ² in terms of silver.

In the present invention, various antifoggants and photographic stabilizers can be used for the purpose of preventing sensitivity deterioration and fogging. For example, RD17643
(1978) 24-25, U.S. Pat. No. 4,629,
No. 678, azoles and azaindenes, nitrogen-containing carboxylic acids and phosphoric acids described in JP-A-59-168442, or mercapto compounds and metal salts thereof described in JP-A-59-111636, JP-A-62. −
The acetylene compounds described in 87957 are used. These additives are described in more detail in Research Disclosure Item 17643 (1978).
Year), the same Item 18716 (November 1979) and the same
It is described in Item 307105 (November 1989), and the relevant portions are summarized in the table below.

Types of Additives RD17643 RD18716 RD307105 (December 1978) (November 1979) (November 1989) 1 Chemical sensitizer 23 pages 648 right column 866 2 Sensitivity enhancer page 648 right column 3 Spectral sensitizer, pages 23 to 24, page 648, right column, page 866 to 868, supersensitizer, page 649, right column 4, whitening agent, page 24, page 647, page 868, 5 antifoggant, pages 24 to 25, page 649, right column 868 to 870 Stabilizer 6 Light absorber, 25 to 26 page 649 Right column, 873 Filter dye, ~ 650 page left column, UV absorber 7 Stain inhibitor 25 page, Right column 650 page, Left column 872 to right column 8 Dye image stabilizer page 25 page 650 left column page 872 9 hardener page 26 page 651 page left column 874 to 875 page 10 binder 26 page same as above 873 to 874 page 11 plasticizer and lubricant page 27 page 650 right column page 876 12 Coating aid, pages 26-27 ibid., 875-876 pages Surfactant 13 Antistatic agent, p. 27 ibid., Pages 876-877, 14 Matting agent, pages 878-879

The constituent elements included in the present invention will be sequentially described below. I. Photosensitive Sheet A) Support The support of the photosensitive sheet used in the present invention may be any smooth transparent support usually used for photographic light-sensitive materials, such as cellulose acetate, polystyrene, polyethylene terephthalate, and polycarbonate. It is preferable to provide an undercoat layer. The support usually contains a slight amount of a dye or a pigment such as titanium oxide in order to prevent light piping. The thickness of the support is 50
˜350 μm, preferably 70 to 210 μm, more preferably 80 to 150 μm. If necessary, a curl-balancing layer is provided on the back side of the support or JP-A No.
An oxygen barrier layer described in 6-78833 can be provided.

B) Image Receiving Layer The dye image receiving layer used in the present invention comprises a hydrophilic colloid containing a mordant. This may be a single layer or may have a multi-layered structure in which mordants having different mordant strengths are applied in layers. Regarding this, JP-A-61-25255
No. 1 is described. As the mordant, a polymer mordant is preferable. The polymer mordant is a polymer having a secondary or tertiary amino group, a polymer having a nitrogen-containing heterocyclic moiety, a polymer having a quaternary cation, or the like and having a molecular weight of 5,000 or more, particularly preferably 10,000 or more. It is a thing. The amount of mordant applied is generally 0.5.
10 to 10 g / m ^2, preferably 1.0 to 5.0 g / m ^{2, and} particularly preferably ² to 4 g / m ² . As the hydrophilic colloid used in the image receiving layer, gelatin, polyvinyl alcohol, polyacrylamide, polyvinylpyrrolidone and the like are used, and gelatin is preferable. In the image receiving layer, the anti-fading agents described in JP-A-62-30620, JP-A-62-30621 and JP-A-62-215272 can be incorporated.

C) White Reflective Layer The white reflective layer forming the white background of the color image usually contains a white pigment and a hydrophilic binder. The white content for the white reflective layer includes barium sulfate, zinc oxide, barium stearate,
Silver flakes, silicates, alumina, zirconium oxide, sodium zirconium sulfate, kaolin, mica, titanium dioxide and the like are used. Further, non-film-forming polymer particles made of styrene or the like are also used. Further, these may be used alone or may be mixed and used within a range capable of obtaining a desired reflectance. A particularly useful white pigment is titanium dioxide. The whiteness of the white reflective layer is
Although it depends on the type of pigment, the mixing ratio of the pigment and the binder, and the coating amount of the pigment, the light reflectance is preferably 70% or more. Generally, the greater the amount of pigment applied, the better the whiteness, but as the imaging dye diffuses through this layer, the pigment resists the diffusion of the dye,
It is desirable to have an appropriate coating amount. Titanium dioxide 5
A white reflective layer having a light reflectance of 78 to 85% with light having a wavelength of 540 nm is preferred, which is applied to -40 g / m ² , preferably 10 to 25 g / m ² . Titanium dioxide can be selected from various commercially available brands and used. Among these, it is particularly preferable to use rutile type titanium dioxide. Most of the commercially available products are surface-treated with alumina, silica, zinc oxide or the like. In order to obtain a high reflectance, the surface treatment amount is preferably 5% or more. Examples of commercially available titanium dioxide include Ti-pure R93 manufactured by DuPont.
In addition to 1, there are those described in Research Disclosure No. 15162. As a binder for the white reflective layer, an alkali-permeable polymer matrix, for example, gelatin, polyvinyl alcohol, or a cellulose derivative such as hydroxyethyl cellulose or carboxymethyl cellulose can be used. A particularly preferred binder for the white reflective layer is gelatin. The ratio of white pigment to gelatin is
1/1 to 20/1 (weight ratio), preferably 5/1 to 10
It is / 1 (weight ratio). In the white reflective layer, Japanese Patent Publication Sho 62
It is preferable to incorporate an anti-fading agent such as -30620 and 62-30621.

D) Light-shielding layer A light-shielding layer containing a light-shielding agent and a hydrophilic binder is provided between the white reflective layer and the photosensitive layer. As the light shielding agent, any material having a light shielding function is used, but carbon black is preferably used. US Pat. No. 4,61
You may use the decomposable dye as described in 5,966.
The binder for coating the light-shielding agent may be any as long as it can disperse carbon black, and gelatin is preferable. Examples of carbon black raw materials include D
onnel Voet "Carbon Black" MarcelDekker, Inc. (1
Any method such as a channel method, a thermal method and a furnace method as described in 976) can be used. The particle size of carbon black is not particularly limited, but is preferably 90 to 1800Å. The addition amount of the black pigment as the light-shielding agent may be adjusted depending on the sensitivity of the light-sensitive material to be shielded, but it is preferably about 5 to 10 in optical density.

E) Photosensitive Layer In the present invention, a photosensitive layer comprising a silver halide emulsion layer combined with a dye image forming substance is provided above the light shielding layer. The constituent elements will be described below. (1) Dye image-forming substance The dye image-forming substance used in the present invention is a non-diffusible compound that releases a diffusible dye (may be a dye precursor) in association with the silver phenomenon, or its own diffusivity. Is changing, and "the theory of photographic process" (The The
ory of the Photographic Process) 4th edition. All of these compounds can be represented by the following general formula (I). In formula (I) (DYE-Y) _n -Z, DYE represents a dye group, a temporarily shortened dye group or a dye precursor group, Y represents a simple bond or a linking group, and Z represents A diffusivity of the compound represented by (DYE-Y) _n -Z is changed corresponding to or opposite to a photosensitive silver salt having an image-wise latent image, or DYE is released and released. Represents a group having a property of causing a difference in diffusivity between DYE and (DYE-Y) _n -Z, n represents 1 or 2, and when n is 2, two DYE-Y May be the same or different. According to the function of Z, it is roughly classified into a negative type compound which becomes diffusive in a silver developed area and a positive type compound which becomes diffusible in an undeveloped area. Specific examples of the negative Z include those that are oxidized and cleaved to release a diffusible dye as a result of development. Specific examples of Z are described in US Pat.
928,312, 3,993,638 and 4,0
76,529, 4,152,153, 4,05
5,428, 4,053,312 and 4,19
8,235, 4,179,291, 4,14
9,892, 3,844,785, 3,44
3,943, 3,751,406, 3,44
No. 3,939, No. 3,443,940, No. 3,62
8,952, 3,980,479 and 4,18
3,753, 4,142,891, 4,27
8,750, 4,139,379, 4,21
8,368, 3,421,964, 4,19
9,355, 4,199,354, 4,13
5,929, 4,336,322, 4,13
9,389, JP-A-53-50736, and JP-A-51-1.
No. 04343, No. 54-130122, No. 53-11.
0827, 56-12642, 56-1613.
No. 1, No. 57-4043, No. 57-650, No. 57.
-20735, 53-69033, 54-13
0927, 56-164342, 57-119.
345 and the like. Among Z of the negative type dye-releasing redox compound, a particularly preferable group is an N-substituted sulfamoyl group (as the N-substituent, a group derived from an aromatic hydrocarbon ring or a hetero ring).
Representative examples of Z are shown below, but the present invention is not limited thereto.

[0068]

[Chemical 1]

As for the positive type compounds, Angevante Hemi International Edition English (Angev. Chem. Inst. Ed. Engl.), 22, 191
(1982). A specific example thereof is a compound (dye developing agent) which is initially diffusible under alkaline conditions but is oxidized by development to become non-diffusible. Effective Z for this type of compound is described in US Pat.
Typical examples are those listed in No. 83,606. Further, as another type, a diffusible dye is released by self-ring closure under an alkaline condition, but the dye is substantially not released when oxidized by development. Specific examples of Z having such a function are described in US Pat. No. 3,980,479 and JP-A-53-69033.
No. 54-130927, U.S. Pat. No. 3,421,9.
64, 4,199,355 and the like. Another type is one that does not itself release a dye but releases a dye when reduced. This type of compound can be used in combination with an electron donor to release the diffusible dye imagewise by reaction with the remaining electron donor which has been imagewise oxidized by silver development. Regarding the atomic group having such a function, for example, U.S. Pat. Nos. 4,183,753, 4,142,891, 4,278,750, 4,139,379, and 4,218 are disclosed. 368, JP-A-53-1108827,
U.S. Pat. Nos. 4,278,750 and 4,356,249.
No. 4,358,525, JP-A-53-11082.
No. 7, No. 54-130927, No. 56-164342
No., Open Technical Report 87-6199, European Patent Publication 220,
746A2 and the like. Specific examples thereof will be illustrated below, but the present invention is not limited thereto.

[0070]

[Chemical 2]

When this type of compound is used, it is preferably used in combination with a diffusion-resistant electron donating compound (known as an ED compound) or its precursor (precursor). Examples of ED compounds include, for example, US Pat.
263,393, 4,278,750, JP-A-5
6-138736 and the like. The following can also be used as specific examples of another type of dye image-forming substance.

[0072]

[Chemical 3]

The details are described in US Pat. Nos. 3,719,489 and 4,098,783. On the other hand, specific examples of the dye represented by the above general formula DYE are described in the following documents. Examples of yellow dyes: US Pat. Nos. 3,597,200, 3,309,199, 4,013,633, 4,245,028, 4,156,609 and 4,139. , 383, 4,195,992, 4,148,641, 4,148,643, 4,336,322: JP-A-51-114930.
56-71072: Research Disclosure 1763.
No. 0 (1978) and No. 16475 (1977). Examples of magenta dyes: U.S. Pat. Nos. 3,453,107, 3,544,545, 3,932,380, 3,931,144, 3,932,308 and 3,954. , 476, 4,233,237, 4,255,509, 4,250,246, 4,142,891, 4,207,104, 4,287,292. No .: JP-A-52-106727,
53-23628, 55-36804, 56
-73057, 56-71060, 55-13
What is described in No. 4. Examples of cyan dyes: US Pat. Nos. 3,482,972, 3,929,760, 4,013,635, 4,268,625, 4,171,220 and 4,242. , 435, 4,142,891, 4,195,994, 4,147,544, 4,148,642; British Patent 1,551,138.
Nos. 54-99431 and 52-8827.
No. 53-47823, No. 53-143323, No. 5
4-99431, 56-71061; European Patents (EP) 53,037, 53,040; Rese
those described in arch Disclosure 17,630 (1978) and 16,475 (1977). These compounds are disclosed in JP-A-62-215272, 144.
It can be dispersed by the method described on page 146. Further, in these dispersions, JP-A-62-215272, 137
The compounds described on pages 144 to 144 may be included.

(2) Silver Halide Emulsion As the silver halide emulsion of the present invention, those described above are used.

(3) Construction of Photosensitive Layer For the reproduction of natural colors by the subtractive color method, the above dye that provides a dye having a selective spectral absorption in the same wavelength range as the emulsion spectrally sensitized by the above spectral sensitizing dye. A photosensitive layer consisting of at least two layers with an image-forming substance is used. The emulsion and the dye image-forming substance may be coated as separate layers,
Alternatively, they may be mixed and coated as a single layer. When the dye image-forming substance is coated and has absorption in the spectral sensitivity region of the emulsion combined with it, another layer is preferable. The emulsion layer may be composed of a plurality of emulsion layers having different sensitivities, and an arbitrary layer may be provided between the emulsion layer and the dye image-forming substance layer. For example, a layer containing a nucleation development accelerator described in JP-A-60-173541, JP-B-60-1
The partition layer described in No. 5267 can be provided to increase the color image density, and a reflective layer can be provided to increase the sensitivity of the photosensitive element. The reflective layer is a layer containing a white pigment and a hydrophilic binder, preferably the white pigment is titanium oxide and the hydrophilic binder is gelatin. The amount of titanium oxide applied is 0.1 g / m ^{2 to} 8 g / m ² , preferably 0.1.
It is a ^{2g / m 2 ~4g / m 2} . Examples of the reflective layer are described in JP-A-60-91354. In a preferable multilayer structure, a combination unit of blue-sensitive emulsion, a combination unit of green-sensitive emulsion and a combination unit of red-sensitive emulsion are sequentially arranged from the exposure side. An arbitrary layer can be provided between each emulsion layer unit as needed. In order to prevent the unfavorable influence of the development effect of one emulsion layer on other emulsion layer units,
It is preferable to install an intermediate layer. When the developer is used in combination with a non-diffusible dye image-forming substance, the intermediate layer preferably contains a non-diffusible reducing agent to prevent diffusion of the oxidized product of the developer. Specific examples thereof include non-diffusible hydroquinone, sulfonamide phenol, sulfonamide naphthol, and the like, and more specifically, JP-A-50-2.
1249, 50-23813, JP-A-49-10.
6329, 49-129535, U.S. Pat.
36,327, 2,360,290, 2,40
3,721, 2,544,640, 2,73
2,300, 2,782,659, 2,93
7,086, 3,637,393, 3,70
0,453, British Patent 557,750, JP-A-57.
No. 24941, No. 58-21249, and the like. Regarding the dispersion method thereof, JP-A-60-23
8831 and Japanese Examined Patent Publication No. 60-18978. When a compound capable of releasing a diffusible dye by silver ion as described in JP-B-55-7576 is used, it is preferable to include a compound for capturing silver ion in the intermediate layer. In the present invention, an irradiation prevention layer, a UV absorber layer, a protective layer and the like are coated as necessary.

F) Peeling Layer In the present invention, a peeling layer may be provided for peeling off the photosensitive sheet in the unit at any place after the treatment, if necessary. Therefore, this peeling layer must be easy to peel off after the treatment. Materials for this purpose include, for example, JP-A-47-8237, JP-A-59-220727 and JP-A-5-220727.
9-229555, 49-4653, U.S. Pat. Nos. 3,220,835, 4,359,518, JP-A-49-4334, 56-65133, 45-.
24075, U.S. Pat. Nos. 3,227,550, 2,759,825, 4,401,746 and 4,366,227 can be used. One of the specific examples is a water-soluble (or alkali-soluble) cellulose derivative. For example, hydroxyethyl cellulose, cellulose acetate phthalate, plasticized methyl cellulose, ethyl cellulose, cellulose nitrate, carboxymethyl cellulose, and the like. Another example is various natural polymers such as alginic acid, pectin, and gum arabic. Also, various modified gelatins such as acetylated gelatin and phthalated gelatin can be used. Yet another example is a water-soluble synthetic polymer. For example, polyvinyl alcohol, polyacrylate, polymethylmethacrylate, polybutylmethacrylate, or a copolymer thereof may be used. The release layer can be a single layer,
Further, for example, JP-A-59-220727 and JP-A-60-6.
It may be composed of a plurality of layers as described in No. 0642.

II. Cover Sheet In the present invention, a layer having a neutralizing function (neutralizing layer and timing of neutralization) is provided in order to uniformly spread the processing liquid on the photosensitive element and neutralize the alkali after processing to stabilize the image. A transparent cover sheet having a layer) is used.

G) Support The support of the cover sheet used in the present invention may be any smooth transparent support usually used for photographic light-sensitive materials, such as cellulose acetate, polystyrene, polyethylene terephthalate and polycarbonate. ,
It is preferable to provide an undercoat layer. The support preferably contains a trace amount of dye in order to prevent light piping.

H) Layer Having Neutralizing Function The layer having a neutralizing function used in the present invention is a layer containing an acidic substance in an amount sufficient to neutralize an alkali carried from the treatment composition, and if necessary, Accordingly, it may have a multi-layered structure including layers such as a neutralization rate adjusting layer (timing layer) and an adhesion enhancing layer. A preferred acidic substance is a substance containing an acidic group having a pKa of 9 or less (or a precursor group which gives such an acidic group by hydrolysis), more preferably oleic acid described in US Pat. No. 2,983,606. Higher fatty acids such as US Pat. No. 3,362,819
Polymers of acrylic acid, methacrylic acid or maleic acid and their partial esters or anhydrides as disclosed in US Pat. No. 2,290,699; acrylic acid and acrylic acid as disclosed in French Patent 2,290,699 Ester isotopes;
No. 4,139,383 or Research Disclosure No. 16102 (19
Mention may be made of latex-type acidic polymers as disclosed in 77). Others, US Patent 4,08
No. 8,493, JP-A Nos. 52-153739 and 53-
No. 1023, No. 53-4540, No. 53-4541
The acidic substances disclosed in JP-A No. 53-4542 and the like can also be mentioned. Specific examples of acidic polymers include ethylene,
Examples thereof include copolymers of vinyl monomers such as vinyl acetate and vinyl methyl ether with maleic anhydride, and n-butyl esters thereof, copolymers of butyl acrylate and acrylic acid, cellulose, and acetate-hydrogenphthalate. The polymer acid can be used as a mixture with a hydrophilic polymer. As such a polymer,
Examples include polyacrylamide, polymethylpyrrolidone, polyvinyl alcohol (including partially saponified products), carboxymethyl cellulose, hydroxymethyl cellulose, hydroxyethyl cellulose, polymethyl vinyl ether and the like. Of these, polyvinyl alcohol is preferable. Further, the polymer acid is a polymer other than a hydrophilic polymer,
For example, cellulose acetate or the like may be mixed. The coating amount of the polymer acid is adjusted by the amount of alkali spread on the photosensitive element. The equivalent ratio of polymer acid and alkali per unit area is preferably 0.9 to 2.0. If the amount of the polymer acid is too small, the hue of the transfer dye is changed or stains are generated on the white background portion, and if it is too large, the hue is changed or the light resistance is deteriorated. A more preferable equivalent ratio is 1.0 to 1.3. If too much or too little hydrophilic polymer is mixed, the quality of the photograph will be degraded. The weight ratio of hydrophilic polymer to polymeric acid is 0.1 to 10, preferably 0.3 to 3.0. Additives can be incorporated into the layer having a neutralizing function of the present invention for various purposes. For example, hardening agents well known to those skilled in the art for hardening this layer, and polyhydric hydroxyl compounds such as polyethylene glycol, polypropylene glycol, glycerin, etc. for improving the brittleness of the film can be added. In addition, if necessary, an antioxidant, a fluorescent brightening agent, a development inhibitor and a precursor thereof may be added.

The timing layer used in combination with the neutralization layer has a low alkali permeability such as gelatin, polyvinyl alcohol, a partial acetalization product of polyvinyl alcohol, cellulose acetate, and partially hydrolyzed polyvinyl acetate. Polymer; made by copolymerizing a small amount of hydrophilic comonomers such as acrylic acid monomer,
Latex polymers which increase the activation energy of alkali permeation; polymers having a lactone ring are useful. Among them, a timing layer using cellulose acetate disclosed in JP-A-54-136328, US Pat. Nos. 4,267,262, 4,009,030, and 4,029,849; Kaisho 54-128335
No. 56-69629, No. 57-6843, U.S. Pat. Nos. 4,056,394, 4,061,496,
A small amount of a hydrophilic comonomer such as acrylic acid disclosed in 4,199,362, 4,250,243, 4,256,827, 4,268,604, etc. is copolymerized. Latex polymer prepared by the method; polymers having a lactone ring disclosed in U.S. Pat. No. 4,229,516;
-97346, 57-6842, European Patent (EP) 31,957A1, 37,724A1,
The polymers disclosed in JP-A-48,412A1 and the like are particularly useful. In addition, those described in the following documents can also be used. US Pat. Nos. 3,421,893 and 3,455
No. 686, No. 3,575, 701, No. 3,778, 2
No. 65, No. 3,785,815, No. 3,847,61
No. 5, No. 4,088,493, No. 4,123,275
No. 4,148,653, 4,201,587
No. 4,288,523, 4,297,431
, West German Patent Applications (OLS) 1,622,936, 2,162,277, Research Disclosure 1516
2, No. 151 (1976). The timing layer using these materials may be used alone or in combination of two or more layers. Further, for the timing layer made of these materials, for example, US Pat. No. 4,009,029, West German Patent Application (OLS) 2,913,164, and 3,014,
672, JP-A-54-155837, and JP-A-55-13.
No. 8745, development inhibitors and / or their precursors disclosed in US Pat.
It is also possible to incorporate the hydroquinone precursor disclosed in Japanese Patent No. 578, and other useful photographic additives or their precursors. Further, as a layer having a neutralizing function, providing an auxiliary neutralizing layer as described in JP-A Nos. 63-168648 and 63-168649 reduces the change in transfer density over time after the treatment. effective.

I) Others In addition to the layer having a neutralizing function, a back layer, a protective layer, a capture mordant layer, a filter dye layer and the like may be provided as a layer having an auxiliary function. The back layer is provided for adjusting curl and imparting slipperiness. Filter dyes may be added to this layer. The protective layer is mainly used to prevent adhesion to the back surface of the cover sheet and adhesion to the protective layer of the photosensitive material when the photosensitive material and the cover sheet are superposed. The capture mordant layer can prevent the delay of the image completion time and the deterioration of the sharpness by capturing the dye diffused to the alkali treatment composition side. Usually, a dye capturing layer is provided on the outermost layer of the cover sheet. The dye-capturing layer contains a polymer mordant in a hydrophilic colloid like the dye image-receiving layer described above, and is disclosed in JP-A-1-198747 and JP-A-2-1987.
No. 82253. The cover sheet may contain a dye to adjust the sensitivity of the photosensitive layer. The filter dye may be added directly to the support of the cover sheet or a layer having a neutralizing function, and further to the back layer, the protective layer, the capture mordant layer, or the like, or a single layer may be provided. .

III. Alkali Processing Composition The processing composition used in the present invention is uniformly spread on the photosensitive element after exposure of the photosensitive element and placed on the back surface of the support or on the side of the photosensitive layer opposite to the processing solution. It forms a pair with a light-shielding layer to completely shield the photosensitive layer from external light, and at the same time, develops the photosensitive layer with the components contained therein. Therefore, in the composition, an alkali, a thickener, a light-shielding agent, a developing agent, and further, a development accelerator for controlling the development, a development inhibitor, and an antioxidant for preventing the deterioration of the developing agent. Contains etc. A sunscreen is always included in the composition. Alkali is sufficient to adjust the pH of the liquid to 12 to 14, and alkali metal hydroxides (eg sodium hydroxide, potassium hydroxide, lithium hydroxide), alkali metal phosphates (eg potassium phosphate). Examples thereof include guanidines and quaternary amine hydroxides (eg, tetramethylammonium hydroxide), but potassium hydroxide and sodium hydroxide are preferred. The thickener is necessary for uniformly developing the processing liquid and for maintaining the close contact between the photosensitive layer and the cover sheet. For example, an alkali metal salt of polyvinyl alcohol, hydroxyethyl cellulose or carboxymethyl cellulose is used, and preferably hydroxyethyl cellulose or sodium carboxymethyl cellulose is used. As the light-shielding agent, any dye or pigment, or a combination thereof, can be used as long as it does not diffuse to the dye image-receiving layer to generate stain. Carbon black is a typical example. As the preferred developing agent, any developing agent can be used as long as it cross-oxidizes the dye image-forming substance and does not substantially cause stain when oxidized. Such developing agents may be used alone or in combination of two or more, and may be used in a precursor type. These developers may be included in the appropriate layers of the light sensitive element or in the alkaline processing liquid. Specific examples of the compound include aminophenols and pyrazolidinones. Of these, pyrazolidinones are particularly preferable because they generate less stain. For example, 1-phenyl-3-pyrazolidinone, 1-p-tolyl-4,4-dihydroxymethyl-3
-Pyrazolidinone, 1- (3'-methyl-phenyl)-
4-methyl-4-hydroxymethyl-3-pyrazolidinone, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidinone, 1-p-tolyl-4-methyl-
4-hydroxymethyl-3-pyrazolidinone, and the like. JP-A-62-215272 7 for either photosensitive sheet, cover sheet or alkaline processing composition
2-91, development accelerators, 146-155, hardeners, 201-210, surfactants 210
Fluorine-containing compounds described on page 222, thickeners described on pages 225 to 227, antistatic agents described on pages 227 to 230, 230
The polymer latex described on page 239 to the matting agent described on page 240 may be included.

[0083]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited thereto. First, a method for preparing a silver halide emulsion will be described.

Preparation of emulsion A for the present invention (octahedral internal latent image type direct positive emulsion, synthetic polymer, lead acetate): 13 g of potassium bromide and 0.05 g of 1,8-dihydrooxy-3,
In 0.5 cc of 0.5 wt% synthetic polymer (P-1) (Note 1) aqueous solution containing 6-dithiaoctane, 0.4 M silver nitrate aqueous solution and 0.4 M silver nitrate solution were added while keeping the temperature at 75 ° C.
300 cc of an aqueous solution of potassium nitrate was added over 40 minutes while controlling the addition rate of the aqueous solution of potassium bromide of M by the control double jet method so that the pBr was 1.30. (Note 1) Synthetic polymer (P-1): Acrylamide /
Acrylic acid / vinyl imidazole / diacetone acrylamide copolymer (60/7/8/25 molar ratio) When addition is complete, the average particle size (equivalent sphere diameter) is about 0.8μ.
Octahedral silver bromide crystals (hereinafter referred to as core grains) with a uniform grain size of m were produced. Next, 0.7 mg of sodium thiosulfate and 0.4 mg of potassium chloroaurate (both were added in an aqueous solution) were added to the silver bromide grains, and the mixture was heated at 75 ° C. for 80 minutes to perform a chemical sensitization treatment. It was The chemical sensitized core particles were treated with 0.8 M silver nitrate aqueous solution and 0.8 M potassium bromide aqueous solution by the control double jet method while maintaining the temperature at 75 ° C. as in the core particle preparation. 740 cc of silver nitrate aqueous solution was added over 60 minutes while adjusting the addition rate of the potassium bromide aqueous solution so that the ratio was 1.30. At that time, 1 minute after the start of addition of the aqueous solution of silver nitrate and potassium bromide, 0.0
5 cc of 01% lead acetate aqueous solution was added. This emulsion was washed with water by a conventional flocculation method, and gelatin was added thereto to form an octahedral silver bromide crystal having an average particle size (sphere equivalent diameter) of about 1.4 μm (hereinafter referred to as internal latent image type). Called core / shell particles). Next, 0.4 mg of sodium thiosulfate and 20 mg of poly (N-vinylpyrrolidone) per mol of silver were added to this internal latent image type core / shell emulsion, and 6
The grain surface was chemically sensitized by heating at 0 ° C. for 60 minutes to prepare an octahedral internal latent image type direct positive emulsion.

Preparation of comparative emulsion B (octahedral internal latent image type direct positive emulsion, gelatin, lead acetate): 0.5% by weight aqueous solution of synthetic polymer (P-1) in emulsion A of the present invention 100
Emulsion B for Comparative Example was prepared by using 1000 cc of 8% by weight aqueous gelatin solution instead of 0 cc.

Preparation of emulsion C for the present invention (octahedral internal latent image type direct positive emulsion, synthetic polymer, potassium iridium hexacyanide): 0.5% by weight of synthetic polymer (P-1 in emulsion A for the present invention) ) Instead of 1000 cc of aqueous solution, use 1000 cc of 0.1 wt% polyvinylpyrrolidone aqueous solution,
Emulsion C for the present invention was prepared by using 50 cc of 0.1% potassium iridium hexacyanide aqueous solution instead of 5 cc of 0.001% lead acetate aqueous solution.

Preparation of emulsion D for the present invention (octahedral internal latent image type direct positive emulsion, synthetic polymer, potassium iridium hexacyanide): Instead of 1000 cc of 0.1% by weight polyvinylpyrrolidone aqueous solution in emulsion C for the present invention. 2.5% by weight
Emulsion D for the present invention was prepared using the aqueous solution of 2-methyl-5-vinyl pyridine / styrene copolymer (9/1 molar ratio).

Preparation of emulsion E for comparative examples (octahedral internal latent image type direct positive emulsion, gelatin, potassium iridium hexacyanide): Instead of 1000 cc of 0.1% by weight aqueous polynylpyrrolidone solution in emulsion C for the present invention. A comparative emulsion E was prepared using 1000 cc of 8% by weight gelatin aqueous solution.

Preparation of emulsion F for the present invention (octahedral internal latent image type direct positive emulsion, synthetic polymer, yellow blood salt): 0.1 in place of 5 cc of 0.001% lead acetate aqueous solution in emulsion A for the present invention
% Emulsion F for use in the present invention was prepared by using 50 cc of an aqueous solution of iron (II) hexacyanide.

Preparation of emulsion G for comparative examples (octahedral internal latent image type direct positive emulsion, gelatin, yellow blood salt): 0.5% by weight of synthetic polymer (P-1) aqueous solution in emulsion F of the present invention 100
Comparative Example Emulsion G was prepared using 1000 cc of 8% by weight aqueous gelatin solution instead of 0 cc.

Preparation of emulsion H for the present invention (octahedral internal latent image type direct positive emulsion, synthetic polymer, gelatin content 10 g / 1 mol silver halide, lead acetate): 13 in emulsion A for the present invention
7 g of gelatin was added to 1000 cc of 0.5% by weight aqueous solution of synthetic polymer (P-1) containing g of potassium bromide and 0.05 g of 1,8-dihydrooxy-3,6-dithiaoctane, and the present invention was added. Emulsion H for the present invention was prepared in the same manner as for Emulsion A.

Preparation of emulsion I for comparative examples (octahedral internal latent image type direct positive emulsion, synthetic polymer, gelatin content 20 g / 1 mol silver halide, lead acetate): 13 in emulsion A for the present invention
14 g of gelatin was added to 1000 cc of 0.5% by weight aqueous solution of the synthetic polymer (P-1) containing g of potassium bromide and 0.05 g of 1,8-dihydrooxy-3,6-dithiaoctane, and the present invention was added. In the same manner as for emulsion A for
Comparative Emulsion I was prepared. The synthetic polymers and metals used in each emulsion are shown in Table-A.

[0093]

[Table 1]

Preparation of emulsion for low-sensitivity layer (octahedral internal latent image type direct positive emulsion): 13 g of potassium bromide and 1.3 g of 1,
In 1000 cc of 8% by weight gelatin aqueous solution containing 8-dihydrooxy-3,6-dithiaoctane, the temperature was adjusted to 7
While keeping the temperature at 5 ° C, 0.4M silver nitrate aqueous solution and 0.4M potassium bromide aqueous solution are controlled by a double jet method while controlling the addition rate of the potassium bromide aqueous solution so that the pBr becomes 1.30. Was added over 5 minutes. When the addition was completed, octahedral silver bromide crystals (hereinafter referred to as core particles) having a uniform particle size with an average particle size (sphere equivalent diameter) of about 0.4 μm were produced. Next, 1.4 mg of sodium thiosulfate and 0.8 mg of potassium chloroaurate (both were added as an aqueous solution) were added to the silver bromide grains, and the mixture was heated at 75 ° C. for 80 minutes to perform a chemical sensitization treatment. It was The chemical sensitized core particles were treated with 0.8 M silver nitrate aqueous solution and 0.8 M potassium bromide aqueous solution by the control double jet method while maintaining the temperature at 75 ° C. as in the core particle preparation. Is 1.30
740 cc of silver nitrate aqueous solution was added over 30 minutes while adjusting the addition rate of the potassium bromide aqueous solution so that This emulsion was washed with water by a conventional flocculation method, and gelatin was added to obtain an average particle diameter (equivalent sphere diameter) of about 0.
An octahedral silver bromide crystal having a uniform grain size of 7 μm (hereinafter referred to as internal latent image type core / shell grain) was obtained. Then, the internal latent image type core / shell emulsion was added with 0.8
Sodium thiosulfate (40 mg) and poly (N-vinylpyrrolidone) (40 mg) were added, and the grain surface was chemically sensitized by heating at 60 ° C. for 60 minutes to prepare an octahedral internal latent image type direct positive emulsion. From these, a photosensitive element of the present invention (Sample 101) having the constitution shown in Table B below was prepared.

[0095]

[Table 2]

[0096]

[Table 3]

[0097]

[Table 4]

[0098]

[Chemical 4]

[0099]

[Chemical 5]

[0100]

[Chemical 6]

[0101]

[Chemical 7]

The cover sheet was prepared as follows. The following layers were coated on a polyethylene terephthalate transparent support containing a gelatin-primed anti-light piping dye. (1) 10.4 g / m ² of acrylic acid-butyl acrylate (molar ratio 8: 2) copolymer having an average molecular weight of 50,000 and 0.1 g of 1,4-bis (2,3-epoxypropoxy) -butane A neutralization layer containing m ² . (2) Acetyl cellulose having an acetylation degree of 51% 4.3 g /
m ^2, poly (methyl vinyl ether - co - monomethyl maleate aid) neutralization timing layer containing 0.2 g / m ^2. (3) Styrene / butyl acrylate / acrylic acid /
N-methylol acrylamide in a weight ratio of 49.7 / 4
A polymer latex emulsion-polymerized at a ratio of 2.3 / 4/4 and a polymer latex emulsion-polymerized at a weight ratio of 93: 3: 4 of methyl methacrylate / acrylic acid / N-methylol acrylamide have a solid fraction of 6 A layer containing 2.5 g / m ^{2 of the} total solid content, blended so as to be 4 pairs. (4) A layer containing 1 g / m ² of gelatin.

The formulation of the alkaline treatment composition is shown below.
A destructible container was filled with 0.8 g of the treatment liquid having the following composition. 1-p-tolyl-4-hydroxymethyl-4-methyl-3-pyrazolidone 10.0 g methylhydroquinone 0.18 g 5-methylbenzotriazole 3.0 g sodium sulfite (anhydrous) 0.2 g benzyl alcohol 1.5 cc carboxymethylcellulose Na Salt 58 g Carbon black 150 g Potassium hydroxide (28% aqueous solution) 200 cc Water 680 cc 0.8 g of the treatment liquid having the above composition was filled in a "pressure rupturable container".

Next, Samples 102 to 109 were prepared by changing Emulsion A of the 7th layer, 13th layer and 19th layer of Sample 101 to Emulsion B to Emulsion I shown in Table-A.

After exposing the light-sensitive elements 101 to 109 from the emulsion layer side through a gray step wedge, they are superposed on the cover sheet, and the above processing solution is placed between both materials.
It was developed using a pressure roller so as to have a thickness of 5 μm. The treatment was carried out at 25 ° C., and after 10 minutes, the transfer density was measured with a color densitometer. The results are shown in Table-C.

[0106]

[Table 5]

However, the midpoint sensitivity shown here is the reciprocal of the exposure amount that gives the density at the midpoint of the maximum density and the minimum density, expressed as a relative value with respect to the reference sample.

[0108]

As shown in Table-C, the internal latent image type direct positive silver halide emulsion of the present invention is superior to conventional emulsions in which gelatin is used as a dispersion medium having a protective colloid property.
It showed good S / N and high reversal sensitivity.

Continuation of the front page (51) Int.Cl. ⁵ Identification code Office reference number FI technical display location G03C 8/10 504 8910-2H

Claims (6)

[Claims] 1. A dispersion medium selected from synthetic polymer compounds having a protective colloid action for a part or all of the process of nucleation and / or crystal growth of photosensitive silver halide grains, and transition of Group 8 of the periodic table. Metal, Re, Pb, M
An internal latent image formed in the presence of at least one metal selected from n, Cr, Cu, Zn, Cd and Bi, and the gelatin content in that case is 10 g or less per mol of silver halide. Type direct positive silver halide emulsion. 2. The Group 8 transition metal according to claim 1, Re,
An internal latent image type direct positive silver halide emulsion characterized in that Mn or Cr is present in the form of a hexacoordinated complex ion. 3. The Group 8 transition metal according to claim 1, Re,
An internal latent image type direct positive silver halide emulsion characterized in that Mn or Cr is present in the form of a hexacoordinated cyano complex ion. 4. An internal latent image type direct positive silver halide emulsion, wherein the metal according to claim 1 is Pb. 5. An internal latent image type direct positive silver halide emulsion, wherein the synthetic polymer compound according to any one of claims 1, 2, 3 and 4 is a polymer having a vinylimidazole group. .. 6. A support having at least one light-sensitive silver halide emulsion layer in combination with a dye image-forming substance, which dye-forming substance is represented by the following general formula (I):
A color diffusion transfer light-sensitive material comprising a non-diffusible compound that releases a diffusible dye or a precursor thereof in association with silver development, or a compound that changes its own diffusivity, wherein at least one silver halide emulsion layer is formed. Is claim 1,
6. A color diffusion transfer light-sensitive material containing the internal latent image type direct positive silver halide emulsion described in any one of 2, 3, 4 and 5. In formula (I) (DYE-Y) _n -Z, DYE represents a dye group, a temporarily shortened dye group or a dye precursor group, Y represents a simple bond or a linking group, and Z represents A diffusivity of the compound represented by (DYE-Y) _n -Z is changed corresponding to or opposite to a photosensitive silver salt having an image-wise latent image, or DYE is released and released. Represents a group having a property of causing a difference in diffusivity between DYE and (DYE-Y) _n -Z, n represents 1 or 2, and when n is 2, two DYE-Y May be the same or different.