JPH0690428B2 - Photographic material for direct positive - Google Patents

Description

The present invention relates to a direct positive photographic light-sensitive material,
In particular, the present invention relates to a direct positive photographic light-sensitive material having good graininess and soft tone, and providing high-quality photographic characteristics.

(Prior Art) Conventionally, a silver halide inner core that has been doped with a metal ion, chemically sensitized, or both, and a halogenation that covers at least a photosensitive site of the inner core. Is it composed of an outer shell of silver, the surface of which is chemically sensitized to develop internal latent image type silver halide grains (hereinafter referred to as core / shell type grains) in the presence of a fogging agent? Alternatively, it is known that a reversal image can be obtained by a direct reversal method of the type in which the entire surface is exposed during development. For more details, see U.S. Pat.
It is described in specifications such as 3,761,276.

Since such a core / shell type silver halide emulsion has monodisperse grains, it has a drawback that the gradation becomes hard and a soft and high quality photosensitive material cannot be prepared. For such a defect, emulsions having the same color sensitivity but different sensitivities are mixed and coated, or by coating in two layers as described in JP-A-56-142531. It is known that it can be solved to some extent.

(Problems to be Solved by the Invention) 2 comprising such core / shell type silver halide grains
When a silver halide photographic light-sensitive material having layers is used, good reversal photographic characteristics can be obtained with respect to gradation, but other photographic performances such as graininess, black spots or spots are poor. There is a problem that it has the drawback.

That is, in order to soften the gradation, it is considered that the development of the emulsion of the high-sensitivity layer when using two types of emulsion layers induces the development of the emulsion layer of the low-sensitivity layer, and the graininess is remarkably deteriorated. To be

Also, when various emulsions are manufactured with the same manufacturing equipment,
The negative emulsion mixed with the direct positive emulsion on the high sensitivity side is affected by the emulsion on the low sensitivity side, which should have been carefully manufactured so as to eliminate the mixing of the negative emulsion, resulting in black spots or spots, and May be significantly worse.

In the present invention, a black spot is a black spot that occurs at a position where a uniform density should be obtained, and is also called a black pepper. Further, in the color light-sensitive material, it is generated as spots having colors such as yellow, magenta and cyan due to the emulsion layer generated.

In order to solve these drawbacks, the developability of the emulsion on the high-sensitivity side can be changed, or the emulsion on the high-sensitivity side can be carefully prepared so as not to mix the negative emulsion, but the former can be solved. The photographic performance is remarkably changed, and the latter causes a problem that the manufacturing cost is increased accordingly.

An object of the present invention is to provide a photographic light-sensitive material for direct positive use which does not have such a problem and has photographic characteristics with good image quality.

Another object of the present invention is to provide a direct positive photographic light-sensitive material having good graininess and a soft tone (wide exposure latitude).

(Means for Solving the Problems) The above-mentioned object of the present invention comprises at least two internal latent image type direct positive emulsion layers having the same color sensitivity, and a fog-inducing agent in the emulsion layer or its adjacent layer ( In a photographic light-sensitive material containing a nucleating agent), at least one hydrophilic colloid layer having a binder amount of 0.05 to 2.0 g / m ² is present between the two emulsion layers. Can be achieved by using a photographic light-sensitive material.

The present invention will be described in detail below.

Known direct positive emulsions are used in the present invention. For details, see RESEARCH DISCLOSURE No. 176.
Volume Item 17643 Page I, p.22 (December 1978 issue), Volume 192 Item1
9227 p.155-156 (April 1980 issue) can be used.

In the present invention, a direct positive emulsion is a core / shell emulsion or a convergence emulsion (for example, US Pat. No. 2,592,250).
, Etc.), but core / shell type silver halide emulsions having an internal latent image are preferred.

The individual core / shell silver halide grains used in the present invention are preferably monodisperse, and their average grain diameter is preferably from about 0.1 to 4 μm, more preferably from about 0.2 to 3 μm.
A μm core / shell silver halide grain gives valid results. The term monodisperse grains refers to those consisting of silver halide grains having a substantially uniform diameter.
Preferred silver halide grains for the present invention are those in which up to 95% of the grains are contained within 40% of the average grain size, preferably within 30%. In order to have a better exposure latitude, an emulsion layer containing a core / shell type silver halide grain having a smaller average grain size is provided as a layer closer to the support (lowermost layer), and a core having a larger average grain size / It is desirable to locate the emulsion layer containing shell type silver halide grains in a layer farther from the support. At this time, the average particle diameter is preferably 0.1 to 0.5 micron for the small size and 0.5 to 1.7 micron for the large size. The difference in sensitivity between the upper and lower emulsion layers is preferably 0.2 or more (the upper limit is 0.5) in logE unit. Further, two or more kinds of core / shell type silver halide grains having different average grain diameters may be used in the same layer.

Next, the hydrophilic colloid layer (intermediate layer) used between the direct positive emulsion layers of the light-sensitive material of the present invention will be described.

The binder used in the hydrophilic colloid layer (intermediate layer) between the two layers of the present invention is preferably gelatin or another water-soluble polymer. Details will be described later. The coating amount is 0.05 g / m ² to ² g / m ² , but more preferably 0.1 g / m ^2.
m ^{2 to} 0.5 g / m ² is good.

The intermediate layer may or may not contain silver halide grains, but it is preferable to include silver halide grains in an amount of 0.1
~ 2.0g-Ag / m ² is good.

The emulsion contained in the intermediate layer may be either a negative type emulsion or a positive type emulsion. Any of the positive type emulsions is preferable. A positive type emulsion is preferred. The negative emulsion here is
It may or may not be chemically sensitized. The appropriate sensitivity range of each emulsion is different, but the sensitivity range can be appropriately selected by those skilled in the art.

When the emulsion contained in the intermediate layer is a negative type, it is preferable that the sensitivity is 2.0 or more lower as ΔlogE than that of a small size direct positive emulsion having a lower sensitivity (for example, core / shell type silver halide grains). Such negative emulsions have a grain size of 0.05μ
It can be prepared by the following procedure or by substantially not performing chemical sensitization.

In the present invention, the intermediate layer may be a single layer or two or more layers.

When the emulsion contained in the intermediate layer is a positive type emulsion, the sensitivity is 2.0 or more higher than ΔlogE and the average grain size is smaller than that of a large size direct positive emulsion having a higher sensitivity (for example, a core / shell type silver halide grain). It is preferable to have a sensitivity between the direct positive emulsion (for example, core / shell type silver halide grains) and the large two layers. The latter case is more preferable, that is, an emulsion having an intermediate sensitivity.

The direct positive emulsion, particularly the core / shell type silver halide emulsion, which constitutes the emulsion of the direct positive photographic light-sensitive material of the present invention will be described below.

The core / shell type silver halide grains are prepared by first preparing an inner core of silver halide which is doped with a metal ion, chemically sensitized, or both, and then the surface thereof is coated with an outer shell of silver halide. It is obtained by chemically sensitizing the outer shell, if necessary. It is not necessary to coat the entire surface of the grain of the inner core with the outer shell, but it is sufficient to coat at least the photosensitive site of the inner nucleus (the site that produces photolytic silver upon exposure). To dope the inner nucleus with a metal ion, for example, in the process of silver halide grain formation or physical ripening of the inner nucleus, cadmium salt, zinc salt, lead salt, thallium salt, iridium salt or its complex salt, rhodium salt or its complex salt is used. A method of coexisting a metal ion source such as iron salt or its complex salt can be adopted.

The metal ion is usually used in a ratio of 10 ^-8 mol or more with ^respect to 1 mol of silver halide. The silver halide in the inner nucleus is a noble metal sensitizer in place of or together with the above-mentioned metal ion dope,
Chemical sensitization may be carried out using at least one of a sulfur sensitizer and a reduction sensitizer. In particular, the sensitivity increases when gold sensitization and sulfur sensitization are performed. A method for treating the silver halide of the inner nucleus and a method of coating the grain surface of the silver halide constituting the inner nucleus with a silver halide serving as an outer shell is known, for example, US Pat.
No.3,206,316, No.3,317,322, No.3,367,778 (however, except for the fogging process on the particle surface), No.3,761,276
The methods described in each specification and the like can be advantageously applied.

The ratio of the silver halide in the inner nucleus to the silver halide in the outer shell is arbitrary, but the latter is usually used in an amount of 2 to 8 mol per mol of the former.

The silver halides of the inner core and the outer shell preferably have the same composition, but may have different compositions. In the present invention, as each silver halide, for example, silver bromide, silver iodide, silver chloride, silver chlorobromide, silver bromoiodide, silver chlorobromoiodide, etc. can be used. Preferred silver halides are odors. It is silver oxide.

Further, the core / shell type silver halide grains may have a regular crystal body such as a cube, an octahedron, a tetrahedron or a rhombodecahedron, or may have an irregular shape such as a sphere or a plate. It may have an (irregular) crystal form, a composite form of these crystal forms, or a mixture of grains of various crystal forms.

The core / shell type silver halide grain surface prepared as described above may be chemically sensitized if necessary.

Glaf is the chemical sensitization of the core / shell type silver halide grain surface.
Kides "Chimie et Physique Photograhique" (Paul
Montel, 1967), VL Zelikman et al, "Making a
nd Coating Photographic Emulsion "(The Focal Pres
s, 1964) or edited by H. Frieser "Die Grundlagen de
r Photograhischen Prozesse mit Silderhalogeniden ''
(Akademische Verlagsgesellschaft, 1968) and the like, and known methods are used.

That is, a sulfur sensitization method using a compound containing sulfur capable of reacting with silver ions or active gelatin, a reduction sensitization method using a reducing substance, a noble metal sensitization method using gold or other noble metal compounds, etc. are used alone or in combination. . Of these, the combination of the gold sensitization method and the sulfur sensitization method gives the best result, but the reduction sensitization method may be used in combination therewith depending on the case.
As the sulfur sensitizer, thiosulfates, thioureas, thiazoles, rhodanines and other compounds can be used, and specific examples thereof are U.S. Pat. No. 1,574,944, 2,41.
0,689, 2,278,947, 2,728,668, 3,656,955. Examples of the reduction sensitizer include a primary tin salt, amines, a hydrazine derivative, fobumusamidine sulfinic acid,
Silane compounds and the like can be used, and specific examples thereof are U.S. Patents 2,487,850, 2,419,974, 2,518,698,
2,983,609, 2,983,610, 2,694,637. For sensitizing a noble metal, a complex salt of a metal of Group VIII of the periodic table such as platinum, iridium and palladium can be used in addition to a gold complex salt. Specific examples thereof are U.S. Pat. No. 2,399,083.
No. 2,448,060, British Patent 618,061 and the like.

When carrying out such a chemical sensitization step, various conditions can be set arbitrarily, and generally pH 8 or less. It is preferable to carry out at a pAg of 10 or less and a temperature of 40 ° C or more.
However, in some cases, conditions outside this range may be set. It goes without saying that the surface / chemical sensitization of the core / shell silver halide grains is carried out to such an extent that the core / shell silver halide grains do not impair the characteristics of the internal latent image type.
The term "characteristics as an internal latent image type" as used herein means that a silver halide emulsion is coated on a transparent support, exposed to light for a fixed time of 0.01 to 10 seconds, and then developed in developer A (internal type developer) described below. When developed at 20 ° C. for 3 minutes, the maximum density measured by the usual photographic density measuring method was 20 ° C. in the following developing solution B (surface type developing solution) for the silver halide emulsion exposed in the same manner as above. It has a density which is at least 5 times higher than the maximum density obtained when developed at 4 ° C. for 4 minutes.

The core / shell silver halide grains are dispersed in a binder as is well known.

As a binder for the direct positive silver halide emulsion and the intermediate layer, it is advantageous to use gelatin, but other hydrophilic colloids can also be used.

For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein: cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, cellulose sulfates, sugar derivatives such as sodium alginate, starch derivatives, etc. be able to.

As the gelatin, in addition to lime-processed gelatin, acid-processed gelatin and enzyme-processed gelatin as described in Bull. Soc. Sci. Phot. Japan. No. 16, page 30 (1966) may be used. Degradation products and enzymatic degradation products can also be used. Gelatin derivatives can be obtained by reacting gelatin with various compounds such as acid halides, isocyanates, bromoacetic acid, alkane sultones, vinyl sulfonamides, maleimide compounds, polyalkylene oxides and epoxy compounds. Things are used.

The internal latent image type silver halide photographic emulsion used in the present invention may be spectrally sensitized with methine dyes or the like.
Dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes, and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes and complex merocyanine dyes. Any of the nuclei normally used for cyanine dyes as a basic heterocyclic nucleus can be applied to these dyes. That is, a pyrroline nucleus, an oxazoline nucleus, a thiazoline nucleus, a pyrrole nucleus, an oxazole nucleus, a thiazole nucleus, a selenazole nucleus, an imidazole nucleus, a tetrazole nucleus, a pyridine nucleus and the like; a nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei; and these Nucleus of fused aromatic hydrocarbon ring, namely, indolenine nucleus, benzindolenine nucleus, indole nucleus, benzoxazole nucleus, naphthoxazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, benzoselenazole nucleus, benzimidazole nucleus A nucleus, a quinoline nucleus, etc. can be applied. These nuclei may be substituted on carbon atoms.

In the merocyanine dye or the complex merocyanine dye, as a nucleus having a ketomethylene structure, a pyrazolin-5-one nucleus, a thiohydantoin nucleus, 2-thiooxazolidine-2,
5- to 6-membered heterocyclic nuclei such as 4-dione nucleus, thiazolidine-2,4-dione nucleus, rhodanine nucleus and thiobarbituric acid nucleus can be applied.

A dye that does not have a spectral sensitizing effect by itself, or a substance that does not substantially absorb visible light, together with a sensitizing dye,
A substance exhibiting supersensitization may be included in the emulsion. For example, aminostilbene compounds substituted with a titanium-containing heterocyclic ring group (for example, those described in U.S. Patents 2,933,390 and 3,635,721), aromatic organic acid formaldehyde condensates (for example, those described in U.S. Patent 3,743,510), It may contain a cadmium salt, an azaindene compound or the like. US Patent
3,615,613, 3,615,641, 3,617,295, 3,63
The combination described in 5,721 is particularly useful.

Support is Research Disclosure vol./76 (1978, XII) RD
-17643 [XVII] can be used.

The internal latent image type silver halide photographic emulsion of the present invention has, for example, a polyalkylene oxide or a derivative thereof such as an ether, an ester or an amine, a thioether compound, a thiomorpholine or a quaternary compound for the purpose of increasing sensitivity, increasing contrast or promoting development. It may contain an ammonium salt compound, a urethane derivative, a urea derivative, an imidazole derivative, 3-pyrazolidones and the like. For example, U.S. Patent 2,400,532
No., No. 2,423,549, No. 2,716,062, No. 3,617,280,
Those described in No. 3,772,021 and No. 3,808,003 can be used.

The internal latent image type silver halide photographic emulsion of the present invention may contain an antifoggant (Antifoggant) and a stabilizer (Stabilizer). As a compound, Reseach Disclosure vol.176 (19
78, XII) RD-17643 [VI] can be used.

The internal latent image type silver halide photographic emulsion of the present invention may contain a developing agent. Reseach Disclosure vo as a developing agent
Those described in the section of l.176 (1978, XII) RD-17643 [XX] can be used.

The internal latent image type silver halide photographic emulsion of the present invention can be dispersed in a colloid which can be hardened by various organic or inorganic hardeners. As a hardener, Reseach Disclosure vol.1
Those described in the section of 76 (1978, XII) RD-17643 [X] can be used.

The internal latent image type silver halide photographic emulsion of the present invention may contain a coating aid. As a coating aid, Reseach Disclosure vo
Those described in the section of l.176 (1978, XII) RD-17643 [XI] can be used.

The internal latent image type silver halide photographic emulsion of the present invention contains a so-called color coupler and can be directly used for a positive color photographic material. As a color coupler, Reseach Disc
Losure vol.176 (1978, XII) RD-17643 [VII] can be used.

The internal latent image type silver halide photographic emulsion of the present invention may also contain an antistatic agent, a plasticizer, a matting agent, a lubricant, an ultraviolet absorber, a fluorescent brightening agent, an air fog inhibitor and the like.

The light-sensitive material produced by using the internal latent image type silver halide photographic emulsion of the present invention may contain a dye in the photographic emulsion layer or other hydrophilic colloid layer as a filter dye or for various purposes such as prevention of irradiation. . As such a dye, Reseach Disclosure vol.176 (197
8, XII) RD-17643 [VII] is used.

The internal latent image type silver halide photographic emulsion of the present invention produces a reversal image by developing in the presence of a fog-inhibiting agent (nucleating agent) or under whole exposure. Examples of the fog-reducing agent that can be used are U.S. Patents 2,588,982 and 2,56
Hydrazines described in 3,785; Hydrazides and hydrazines described in 3,227,552; British Patent 1,283,
No. 835, Japanese Patent Publication No. 49-38464, U.S. Patent No. 3,615,615,
3,719,494, 3,734,738, 3,719,494, 3,73
4,738, 4,094,683, 4,115,122 and the like, quaternary salt compounds, sensitizing dyes having a fogging action (nucleating) substituent described in U.S. Pat. Representative examples are the acylhydrazinophenylthiourea compounds described in JP-A Nos. 4,030,925 and 4,031,127, and the acylhydrazinophenylenyl urea compounds described in JP-A-57-86829. Others, for example, U.S. Pat.No. 4,139,387, JP-A Nos. 54-133126, 54
The compounds described in -74729 can also be mentioned.

The amount of the fog-providing agent used here is preferably an amount which gives a sufficient maximum density when the internal latent image type silver halide photographic emulsion of the present invention is developed with a surface developing solution.
The fogging agent is added to the photographic emulsion layer or its adjacent layer.

The negative emulsion used in the present invention is described in detail in RESEARCH DISCLOSURE Vol. 176, Item 17643, Item I p.22.
(December, 1978 issue) can be used.

A photographic light-sensitive material to which the present invention can be applied is disclosed in JP-A-59-
208540, B / W direct positive photographic light-sensitive materials described in JP-A-60-260039 (for example, X-ray light-sensitive material, dupe light-sensitive material, micro light-sensitive material, photographic light-sensitive material, printing light-sensitive material) and JP Photographic light-sensitive materials for color direct positive (for example, color papers, color photographic light-sensitive materials) and research disks No. 15 using couplers described in JP-A-58-70233.
There is a photographic light-sensitive material for color diffusion transfer direct positive described in Volume 1, No. 15162p75-87 (November 1976).

To develop the light-sensitive material of the present invention, various known developing agents can be used. That is, polyhydroxybenzenes such as hydroquinone, 2-chlorohydroquinone, 2-methylhandoquinone, catechol, pyrogallol and the like; aminophenols such as p-aminophenol, N-methyl-p-aminophenol, 2,4-diaminophenol. 3-pyrazolidones, such as 1-phenyl-3-pyrazolidones, 1-phenyl-4,4'-dimethyl-3-pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, 5 5,5-Dimethyl-1-phenyl-3-pyrazolidone, etc .; ascorbic acids, etc., alone or in combination. Further, the developing solution described in Japanese Patent Application No. 56-154116 can also be used. To obtain a dye image in the presence of a dye-forming coupler, an aromatic primary amine developing agent,
Preferably, a p-phenylenediamine type developing agent can be used. Specific examples thereof include 4-amino-3-methyl-N, N-diethylaniline hydrochloride, N, N-
Diethyl-p-phenylenediamine, 3-methyl-4-
Amino-N-ethyl-N-β- (methane-sulfoamido) ethylaniline, 3-methyl-4-amino-N-ethyl-N- (β-sulfoethyl) aniline, 3-ethoxy-4-amino-N-ethyl These are -N- (β-sulfoethyl) aniline and 4-amino-N-ethyl-N- (β-hydroxyethyl) aniline. Such developers may be included in the alkaline processing composition (processing element) or in the appropriate layers of the photosensitive element.

The developer may contain, as a preservative, sodium sulfite, potassium sulfite, ascorbic acid, reductones (eg piperidinohexose reductone) and the like.

The light-sensitive material of the present invention can directly obtain a positive image by developing with a surface developing solution. A surface developer is one in which the development process thereby is substantially induced by latent images or fog nuclei on the surface of the silver halide grains. Although it is preferable not to include a silver halide dissolving agent in the developing solution, a silver halide dissolving agent (for example, sulfurous acid) may be used as long as the internal latent image does not substantially contribute until development by the surface development center of the silver halide grain is completed. Salt).

The developer contains an alkali agent and a buffering agent such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate,
It may include trisodium phosphate, sodium metaborate and the like. The content of these agents depends on the pH of the developer.
Is 10 to 13, preferably pH 11 to 12.5.

Developers also include direct additions of benzimidazoles, such as 5-, to reduce the minimum density of positive images.
Nitrobenzimidazole; It is advantageous to include benzotriazoles such as benzotriazole, 5-methyl-benzotriazole, and other compounds normally used as antifoggants.

(Example) Next, the present invention will be specifically described based on Examples.

Example 1 Core / shell emulsions A and B were prepared by the following method.

Emulsion A An aqueous solution of potassium bromide and an aqueous solution of silver nitrate were simultaneously added to the aqueous gelatin solution at 40 ° C. for about 20 minutes with vigorous stirring.
A cubic monodisperse silver bromide emulsion having an average grain size of 0.08 μm was obtained.
580 mg of sodium thiosulfate chloroauric acid (tetrahydrate) per mol of silver was added to this emulsion, and the mixture was heated at 75 ° C. for 80 minutes for chemical sensitization. Using the silver bromide grain emulsion thus obtained as the core, grow the grains in the same manner as in the first precipitation environment, but controlling the pAg of the solution to be 7.90, and finally grow the core with an average grain size of 0.18 μm. /
A shell-type monodisperse cubic silver bromide emulsion was obtained. After washing with water and desalting, 6.2 mg of sodium thiosulfate and chloroauric acid (tetrahydrate) per mol of silver were added to the emulsion, and the mixture was heated at 65 ° C. for 60 minutes for chemical sensitization to obtain emulsion A.

Emulsion B An aqueous solution of potassium bromide and an aqueous solution of silver nitrate were simultaneously added to an aqueous solution of gelatin with vigorous stirring at 75 ° C for about 40 minutes, and an octahedral monodisperse silver bromide emulsion having an average particle size of 0.4 µm was added. Got To this emulsion, add 4 mg of sodium thiosulfate and chloroauric acid (tetrahydrate) per mol of silver, and add at 75 ° C.
Chemical sensitization was performed by heating for 80 minutes. Using the silver bromide grains thus obtained as a core, the grains were grown by further treating for 40 minutes in the same precipitation environment as in the first time, and finally an octahedral monodisperse core / shell silver bromide emulsion having an average grain size of 0.6 μm was obtained. Obtained. After washing with water and desalting, 0.9 mg of sodium thiosulfate per mol of silver was added to this emulsion and the mixture was heated at 65 ° C. for 60 minutes for chemical sensitization to obtain an internal latent image type silver halide emulsion B.

Emulsion C An aqueous solution of potassium bromide and an aqueous solution of silver nitrate were vigorously stirred into an aqueous gelatin solution, and the pAg was maintained at about 7.9 by the control double jet method at 40 ° C.
A cubic silver bromide emulsion having an average grain size of 0.05 μm was obtained by simultaneously adding the components in a timely manner. The emulsion was washed with water and desalted to obtain a negative emulsion C without chemical sensitization.

Next, sensitizing dye I was added to core / shell type emulsions A and B in an amount of 140 mg and 220 mg, respectively, per mol of silver, and anhydro-2- [3- (phenylhydrazolo) butyl] was added as a fogging agent. 257 mg of 3- (3-sulfopropyl) benzothiazolium hydroxide was added to 1 mol of silver, and emulsion A was coated on the lower layer and emulsion B was coated on the upper layer. Ag amounts were 1.0 g / m ² and 1.5 g, respectively. / m ² to become so, also the coating amount of gelatin, respectively 1.3 g / m ^2, and multilayer coating so as to be 2.4 g / m ^2, further coated amount of gelatin thereon was coated a gelatin protective layer made of 1.7 g. At this time, sodium dodecylbenzenesulfonate was added as a coating aid to the emulsion layer and the gelatin protective layer to prepare No. 1 sample.

Sample No. 2 was prepared in the same manner as Sample No. 1, except that an intermediate layer having a coated gelatin amount of 1.5 g / m ² was provided between the lower layer containing Emulsion A and the upper layer containing Emulsion B.

In addition, Sample No. 3 was prepared in the same manner as Sample No. 2, except that the emulsion C which had not been subjected to chemical sensitization was added to the intermediate layer so that the coated Ag amount was 0.1 g / m ² .

Sensitizing dye I These samples were exposed to 1kW of tungsten light at a color temperature of 2854 ° K for 1 second through a step wedge. One set of each sample was stirred at 36 ° C. for 1 minute using the following developing solution, stopped, fixed and washed in a conventional manner to obtain a positive image.

Developer Hydroquinone 45g Sodium sulfite 100g Potassium carbonate 20g Sodium bromide 3g 1-phenyl-4-methyl-4hydroxymethyl-3-
Pyrazolidone 3g 5-Methylbenzotriazole 40mg Water was added to adjust the pH to 11.8 with potassium hydroxide. Measure the area in the area with a microdensitometer with an aperture diameter of 24μ, and calculate the root mean square value (RM
S) was calculated and the value was used as a measure of graininess. That is, the larger this value, the coarser the grain. The RMS value was evaluated as 0.04 or more, 1, 0.036 or more and less than 0.04 as 2, 0.032 or more and less than 0.036 as 3, 0.028 or more and less than 0.032 as 4, and less than 0.028 as 5.

The black spots were evaluated on a scale of 5 by observing with a microscope of 50 times. That is, "5" represents the best quality and "1" represents the worst quality. "5" or "4" is practical, "3" is poor but practically usable, and "2" or "1" is not practical.

The results are shown in Table 1.

It can be seen from Table 1 that black spots and graininess are remarkably improved by adding a gelatin layer or a layer containing silver halide grains and a gelatin layer as an intermediate layer as in the present invention.

Example 2 Emulsion D was prepared by the following method.

Emulsion D An aqueous solution of potassium bromide and an aqueous solution of silver nitrate were simultaneously added to an aqueous solution of gelatin with vigorous stirring at 45 ° C. for about 40 minutes to obtain an octahedral silver bromide emulsion having an average particle size of 0.2 μm. . Chemical sensitization treatment was carried out by adding 5 mg of sodium thiosulfate and chloroauric acid (tetrahydrate) per mol of silver to this emulsion and heating at 75 ° C. for 80 minutes.

The silver bromide grains thus obtained are used as cores for further growth by treating for 40 minutes in the same precipitation environment as the first time, and finally an octahedral monodisperse core / shell silver bromide emulsion having an average grain size of 0.35 μm. Got In this emulsion 4.
Add 5 mg of sodium thiosulfate and chloroauric acid (tetrahydrate) 6
The mixture was heated at 5 ° C. for 60 minutes for chemical sensitization to obtain an internal latent image type silver halide photographic emulsion D.

An undercoating support made of polyethylene terephthalate having a thickness of 100 μ is added with anti-halation dyes A, B, C at 65 mg / m ² , 80 mg / m ² , 40 mg / m ² , and 5-methylbenzotriazole at 10 mg. / m ² and 5 g / m ^{2 of} gelatin applied to the antihalation layer, and as a matting agent barium strontium sulfate having an average particle size of 1.0 μ and polymethylmethacrylate having an average particle size of 1.3 μ Of 30 mg / m ^{2, a} charge control agent E of 1 mg / m ² , a hardener F of 100 mg / m ² , and a gelatin 1 g / m ² of a protective layer (upper layer) is applied to form a two-layer back layer. completed.

An Em layer was coated on the opposite side of the backing layer with the support interposed therebetween as described below.

Emulsion D was used in the same manner as in sample No. 3 except that emulsion C was used. However, 200 mg of sensitizing dye I was added to Emulsion D per 1 mol of silver, and anhydro-2- [3- (phenylhydrazolo) butyl] -3- was added as a foggant.
257 mg of (3-sulfopropyl) benzothiazolium hydroxide was added to 1 mol of silver, and the coating Ag amount was 0.8 g / m ² and the coating gelatin amount was 1.3 g between the lower layer containing Emulsion A and the upper layer containing Emulsion B. Sample No. 4 having a layer made of Emulsion D so as to be / m ² was prepared.

The performance of Sample No. 4 is shown in Table 2.

Positive gradation, black spots, and grain were all good.

Example 3 Using the core / shell type autopositive emulsions A, B and D of Examples 1 and 2, a multilayer color photographic paper having the layer constitution shown in Table 3 was prepared on a paper support laminated on both sides with polyethylene. The coating liquid was prepared as follows.

Preparation of coating solution for the first layer: 10 g of yellow coupler (a), 2.3 g of color image stabilizer (b), 10 ml of ethyl acetate and 4 m of solvent (c)
l was added and dissolved, and this solution was emulsified and dispersed in 90 ml of a 10% gelatin aqueous solution containing 5 ml of 10% sodium dodecylbenzenesulfonate. On the other hand, to a silver bromide emulsion B (containing 70 g / kg of Ag), a blue-sensitive dye shown below was added at 2.0 × 10 ^-4 mol per mol of silver bromide to prepare a blue-sensitive emulsion (90 g). The emulsified dispersion and emulsion were mixed and dissolved, and the concentration was adjusted with gelatin so that the composition shown in Table I was obtained. Further, a nucleating agent was added in an amount of 2 × 1 per 1 mol of Ag.
0 ^-4 mol was added to prepare a coating solution for the first layer.

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

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

Blue sensitive emulsion layer; Green-sensitive emulsion layer; Red-sensitive emulsion layer; The following dyes were used as the anti-radiation dye in each emulsion layer.

Green-sensitive emulsion layer; Red-sensitive emulsion layer; Structural formulas of compounds such as couplers used in this example are as follows.

(C) solvent (isoC ₉ H ₁₉ O ₃ P = O (J) Solvent (isoC ₉ H ₁₉ O ₃ P = O A multilayer silver halide color photographic light-sensitive material can be prepared by simultaneously coating the coating solutions for the first to seventh layers after adjusting the balance of surface tension and viscosity.

This photosensitive material was used as Sample 101.

Next, photosensitive samples 102 and 103 were prepared in exactly the same manner except that they were changed as shown in Tables 4 and 5. Further, instead of the silver bromide emulsion B of the red-sensitive layer, the green-sensitive layer and the blue-sensitive layer of Sample 101, an emulsion in which silver bromide emulsions B and A were mixed at a silver weight ratio of 2: 1 was used. Sample 104 was prepared in the same manner except for the above.
These samples were subjected to gradation exposure for sensitometry with a stretcher (Fuji Color Head 609 manufactured by Fuji Photo Film Co., Ltd.), and then developed by the following processing steps.

Processing time Temperature Developer 33 ° C 3.5 minutes Bleach-fixer 33 ° C 1.5 minutes Washing with water 28-35 ° C 3.0 minutes Developer nitrilotriacetic acid ・ 3Na 2.0g Benzyl alcohol 15ml Diethylene glycol 10ml Na ₂ SO ₃ 2.0g KBr 0.5g Hydroxylamine sulfate 3.0 g 4-amino-3-methyl-N-ethyl-N- [β- (methanesulfonamido) ethyl] -p-phenylenediamine / sulfate 5.0 g Na ₃ SO ₃ (monohydrate) 30 g Water Add to 1 (pH 10.1) Bleach and fixer Ammonium thiosulfate (70wt%) 150ml Na ₂ SO ₃ 15g NH ₄ [Fe (EDTA)] 55g EDTA ・ 2Na 4g Add water to set to 1 (pH 6.9) The performance of the treated samples is shown in Table 6.

In this example, different from the black spots of the black-and-white sensitive material, the emulsion layers generated were spots of cyan, magenta, and yellow, and were evaluated by the same evaluation criteria as in Example-1.

From Table 6, it is seen that the sample 102, in which the emulsion layer is made into two layers and the gradation is adjusted, is worse than the sample 101, and the spot is deteriorated even when the sample 104 is used. However, sample 103 of the present invention
Could be solved by the layer structure of.

Example 4 Preparation of core / shell type direct positive emulsion Emulsion E An aqueous solution of potassium bromide and an aqueous solution of silver nitrate were vigorously stirred in an aqueous gelatin solution at 75 ° C. for about 60 minutes,
A silver bromide emulsion was obtained by mixing at the same time. Prior to precipitation, 100 mg of 3,4-dimethyl-1,3-
Thiazoline-2-thione and 15 g of benzimidazole were added per mole of silver. When the precipitation was completed, crystals with an average particle size of about 1.1 microns were produced. Next, 5.4 mg of sodium thiosulfate per mol of silver and 3.9 mg of potassium chloroaurate per mol of silver were added to the silver bromide grains, and the mixture was heated to 80 ° C. at 75 ° C.
The chemical sensitization treatment was performed by heating for a minute. A core / shell emulsion was prepared by simultaneously mixing the chemically sensitized core emulsion with aqueous solutions of potassium bromide and silver nitrate for 40 minutes in the same manner as the first time. The final average particle size was 1.5 microns.

Next, 0.32 mg of sodium thiosulfate per mole of silver and 57 mg of poly (N-vinylpyrrolidone) per mole of silver were added to this core / shell emulsion, and the grains were chemically sensitized by heating at 60 ° C. for 60 minutes. It was (Emulsion E) Emulsion F An equimolar aqueous solution of potassium bromide and an aqueous solution of silver nitrate were added at 75 ° C.
The mixture was mixed for about 30 minutes to obtain a silver bromide emulsion having an average grain size of about 0.5 micron. Next, sodium thiosulfate was added to the silver bromide grains at 3.5 m per mol of silver.
Chemical sensitization treatment was carried out by adding g, potassium chloroaurate (5.4 mg) per mol of silver, and lead nitrate (0.8 mg per mol of silver) and heating at 75 ° C. for 60 minutes. The chemically sensitized grains were further mixed with each other in the same precipitation environment as in the first time for 50 minutes to further grow silver halide. The final average grain size of the obtained silver halide was 0.8 micron. (Core / shell type direct positive Agbr emulsion, emulsion (B)) Next, in this core / shell type emulsion, 0.64 mg of sodium thiosulfate, 0.20 mg of potassium chloroaurate, and 30 mg of poly (N-vinylpyrrolidone) were added per mol of silver. In addition, the surface of the grains was chemically sensitized by heating at 60 ° C for 60 minutes. (Emulsion F) Emulsion G Equimolar potassium bromide aqueous solution and silver nitrate aqueous solution at 75 ° C
The mixture was mixed for about 40 minutes to obtain a silver bromide emulsion having an average grain size of about 0.6 micron. Next, to the silver bromide grains, sodium thiosulfate was added to 2.7 m per mol of silver.
Chemical sensitization was performed by adding g, sodium chloride chloroaurate (3.6 mg) per mol of silver, and lead nitrate (0.8 mg per mol of silver) and heating at 75 ° C. for 60 minutes. The chemically sensitized grains were further mixed with each other in the same precipitation environment as in the first time for 50 minutes to further grow silver halide. The final average grain size of the obtained silver halide was 1.0 micron. (Core / shell type direct positive Agbr emulsion, emulsion (B)) Next, in this core / shell type emulsion, 0.36 mg of sodium thiosulfate, 0.18 mg of potassium chloroaurate, and 42 mg of poly (N-vinylpyrrolidone) per mol of silver were added. In addition, the surface of the grains was chemically sensitized by heating at 60 ° C for 60 minutes. (Emulsion G) Layers (1) to (21) were coated on a polyethylene terephthalate transparent support according to the layer structure shown below to prepare a photosensitive sheet 201.

Layer (1): a copolymer described in US Pat. No. 3,898,088, containing a polymer (3.0 g / m ² ) containing the following repeating units in the following ratio and gelatin (3.0 mg / m ² ). Mordant layer.

Layer (2): white reflective layer containing titanium oxide 20 g / m ² and gelatin 2.0 g / m ^2.

Layer (3): Carbon black 2.0 g / m ² and gelatin 1.5
Light-shielding layer containing g / m ² .

Layer (4): A layer containing the following cyan DRR compound (0.44 g / m ² ), tricyclohexyl phosphate (0.09 g / m ² ), and gelatin (0.8 g / m ² ).

Layer (5): White light reflecting layer containing titanium oxide 2.8 g / m ² and gelatin 1.0 g / m ² Layer (6): Emulsion E (silver amount 1.0 g / m ² ), red sensitizing dye, As the nucleating agent, 0.018 mg / m ² , 4 of the compound of the following structural formula was used.
-Hydroxy-6-methyl-1,3,3a-tetrazaindene 5.3 mg / m ² and 5-pentadecyl-hydroquinone-
Red-sensitive core containing sodium 2-sulfonate 0.12 g / m ²
Shell type direct positive silver bromide emulsion layer Red-sensitive sensitizing dye Nucleating agent Layer (7): Emulsion F (silver amount at 0.27 g / m ²⁾ layer (7) The same red-sensitive sensitizing dye and 0.04 mg / m ² nucleating agent 0.005 mg / m ² 4-hydroxy-6-methyl - 1,3,3a-Tetrazaindene 1.4 mg / m ²
And 5-pentadecyl-hydroquinone sodium 2-sulfonate 0.03 g / m ² of red-sensitive core / shell type direct positive silver bromide emulsion layer Layer (8): 2,5-di-t-pentadecyl hydroquinone
1.0 g / m ^2, color mixing prevention layer containing gelatin 0.8 g / m ^2.

Layer (9): Intermediate layer containing 0.18 g / m ^{2 of} gelatin.

Layer (10): Magenta DRR compound of structural formula I (0.21 g / m
² ), a layer containing the magenta DRR compound of structural formula II (0.11 g / m ² ), tricyclohexyl phosphate (0.08 g / m ² ) and gelatin (0.9 g / m ² ).

Layer (11): Titanium oxide 1.0 g / m ² and gelatin 0.36 g / m ²
A white light reflecting layer containing.

Layer (12): Emulsion E (0.55 g / m ^{2 in} terms of silver), the following green-sensitive sensitizing dye, 0.12 mg / m ² , the compound of Example 1 as 0.008 as the same nucleating agent as in Layer (6). g / m ² , 4-hydroxy-6-methyl-1,3,3a-tetrazaindene 3.2 mg / m ² and 5-
Green-sensitive core / shell type direct positive silver bromide emulsion layer containing sodium pentadecyl hydroquinone-2-sulfonate (0.07 g / m ² ).

Green sensitizing dye Layer (13): Emulsion F (0.15 g / m ^{2 in} amount of silver) The same green-sensitizing sensitizing dye as layer (12) 0.03 mg / m ² , nucleating agent 0.002 g / m ² , 4-hydroxy-6- Methyl-1,3,3a-tetrazaindene 0.21
A green sensitive core / shell type direct positive silver bromide emulsion layer containing mg / m ² and sodium 5-pentadecylhydroquinone-2-sulfonate 0.02 g / m ² .

Layer (14): The same layer as the above layer (7 ').

Layer (15): The same layer as the above layer (8 ').

Layer (16): Yellow DRR compound of the following (0.53 g / m ^2), tri-cyclohexyl phosphine ate (0.13 g / m ^2), and a layer containing gelatin (0.7 g / m ^2).

Layer (17): Titanium oxide 0.6g / m ² and gelatin 0.21g / m ²
Light-reflecting layer including.

Layer (18): Emulsion E (1.00 g / m ^{2 in} the amount of silver), 0.020 mg / m ² , the same compound as layer (6) as a nucleating agent, 4-hydroxy-
Blue-sensitive core / shell type direct positive bromide containing 6-methyl-1,3,3a-tetrazaindene 4.1 mg / m ² and sodium 5-pentadecylhydroquinone-2-sulfonate (0.06 g / m ² ). Silver emulsion layer.

Layer (19): Emulsion F (0.27 g / m ^{2 in} the amount of silver) 0.005 mg / m ² , the same compound as in Layer (6) as a nucleating agent, 4-hydroxy-6.
-Sensitive core / shell type direct positive silver bromide containing -methyl-1,3,3a-tetrazaindene at 1.1 mg / m ² and sodium 5-pentadecylhydroquinone-2-sulfonate (0.015 g / m ² ). Emulsion layer.

Layer (20): 4 × 10 ⁻⁴ each of the UV absorbers having the following structure
An ultraviolet absorbing layer containing mol / m ² and gelatin 0.50 g / m ² .

Layer (21): Polymethyl methacrylate Latte try (average particle size 4 [mu]) protective layer containing a tri-acryloyl-triazine 0.02 g / m ² to 0.10 g / m ^2, gelatin 0.8 g / m ^2, and as a hardening agent.

Cover Sheet The following layers (1) to (3) were sequentially coated on a polyethylene terephthalate transparent support to prepare a cover sheet.

Layer (1): 80:20 (weight ratio) copolymer of acrylic acid and butyl acrylate (22 g / m ² ) and 1,4-bis (2,3-epoxypropoxy) -butane (0.44 g / m ² ). ² ) A neutralization layer containing.

Layer (2): 3.8 acetyl cellulose (hydrolyzing 100 g acetyl cellulose to generate 39.4 g acetyl groups)
g / m ² , 60:40 (weight ratio) copolymer of styrene and maleic anhydride (molecular weight about 50,000) was added to 0.2 g / m ² and 5- (β-
Cyanoethylthio) -1-phenyltetrazole 0.11
Layer containing 5 g / m ² .

Layer (3): 85: 12: 3 (weight ratio) copolymer vinylidene chloride / methyl acrylate / acrylic acid copolymer latex (2.5 g / m ² ) and polymethylmethacrylate latex (particle size 1-3 μm) (0.05) g / m ² ) containing layer.

Processing liquid A container that can be ruptured under pressure by 0.8 g each of the treatment liquid of the above composition
Filled.

Exposure and Development Treatment Each of the above-mentioned cover sheets and the above-mentioned photosensitive sheets were superposed, and image exposure was performed from the cover sheet side through a continuous tone wedge. After that, the above treatment liquid was spread between both sheets so as to have a thickness of 75 μ (spreading was performed with the help of a pressure roller). The treatment was carried out at 25 ° C.

Next, a photosensitive sheet was prepared in the same manner as the photosensitive sheet 201.
However, by adding the following emulsion layers 6a, 12a, 18a, the photosensitive sheet
202 was produced.

Layer (6a): additional emulsion G (0.10 g / m ^{2 in} silver amount) between the light-sensitive sheets (6) and (7), the same red-sensitizing dye 0.015 mg / m ² as in layer (7), Nucleating agent 0.002 mg / m ² 4-hydroxy-
Red-sensitive core / shell type direct positive silver bromide emulsion layer containing 6-methyl-1,3,3a-tetrazaindene 0.5 mg / m ² and 5-pentadecyl-hydroquinone sodium 2-sulfonate 0.01 g / m ² (12a): Additional between the light-sensitive sheets (12) and (13) Emulsion G (0.10 g / m ^{2 in} the amount of silver) The same green sensitizing dye as the layer (12) 0.015 mg / m ² , a nucleating agent 0.001 mg / m ² , 4-hydroxy-
Green-sensitive core / shell type direct positive silver bromide emulsion containing 0.4 mg / m ^{2 of} 6-methyl-1,3,3a-tetrazaindene and 0.01 g / m ² of sodium 5-pentadecylhydroquinone-2-sulfonate layer.

Layer (18a): Emulsion G (0.10 g / m ^{2 in} terms of silver) added between photosensitive sheets (18) and (19), 0.003 mg / m ^{2 of} the same compound as layer (6) as a nucleating agent, Blue-sensitive core / shell type containing 0.5 mg / m ^{2 of} 4-hydroxy-6-methyl-1,3,3a-tetrazaindene and sodium 5-pentadecylhydroquinone-2-sulfonate (0.07 g / m ² ). Direct positive silver bromide emulsion layer.

The experimental results are shown in Table 7. The granularity was visually evaluated by the following ranking.

Rank A: Granularity does not look like a flicker B: Granularity appears, but there is no problem in practice C: Grainy is bad and practically impossible It can be seen that the photosensitive material sheet 202 of the present invention has improved graininess.

Example 5 Sample Nos. 1a, 1b, 1c were prepared in the same manner as in Sample No. 1 of Example 1, except that the types and amounts shown in Table 8 were added as rash agents.
In the same manner, Sample Nos. 2a, 2b, 2c and Nos. 3a, 3b, 3c were prepared from Samples No. 2 and No. 3, respectively, the same treatment as in Example 1 was performed, and then the same evaluation was performed. Did. Results 9th
Shown in the table.

It can be seen that the effect of the present invention does not change even if the kind of the rash agent is changed.

Example 6 Emulsions A, B and D were used to apply a backing layer similar to that in Example 2 to a support similar to that in Example 2. For this back layer,
Samples 4a, 4b, and 4c were prepared in the same manner as in Example 2 except that the kind and amount of the rash agent added were the same as in Example 5 except that the type was changed with the support sandwiched between them. .

The results are shown in Table 11.

Similar to Example 2, all had good performance.

Claims (1)

[Claims] 1. A photographic light-sensitive material comprising at least two internal latent image type direct positive emulsion layers having the same color sensitivity and containing a fog-preventing agent (nucleating agent) in the emulsion layers or adjacent layers thereof.
Between the two emulsion layers, the amount of one or more binders is 0.05 to
A direct-positive photographic light-sensitive material having a hydrophilic colloid layer of ² g / m ² .