JP2881471B2 - Direct positive silver halide photographic material - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to a direct positive silver halide photographic light-sensitive material, and more particularly, to a straight line of a characteristic curve which gives good copyability (duplicate characteristics) in ultra-rapid processing. The present invention relates to a direct positive silver halide photographic material having adjusted properties and gamma (γ).

[Background of the Invention]

When a silver halide photographic light-sensitive material is exposed to light in the photosensitive wavelength range and developed, the blackening density increases with an increase in the amount of exposure, reaches a maximum value with a certain amount of fog, but reaches a portion where the amount of exposure is higher. Shows a phenomenon in which the blackening density decreases. This phenomenon is called solarization.

Therefore, in the case of a photosensitive material in which an appropriate development nucleus for which the blackening concentration reaches a maximum value is previously optically or chemically applied to a silver halide emulsion, solarization occurs immediately upon exposure, and a positive image is directly obtained. Can be. A photosensitive material utilizing such an inversion phenomenon is called a development nucleus destruction type direct positive silver halide photographic material (hereinafter, referred to as a direct positive photosensitive material).

This type of direct positive photosensitive material is used for copying various photographs, and is particularly useful as a duplicator film.

Essentially, duplicator film must faithfully reproduce the image of the original film. For that purpose, the characteristic curve must be gamma ≒ 1.0 and have excellent linearity. However, conventionally, since the exposure conditions have been adjusted according to the exposure characteristics of each duplicator, the sensitometric characteristics have greatly changed depending on the type of the duplicator.

The cause is that light that has once passed through the film is irregularly reflected due to the high illuminance of the duplicator, and is incident on the film again, resulting in uneven exposure.
Eliminating this variation can improve the linearity of the characteristic curve. However, it is very difficult to obtain a constant characteristic curve because the exposure conditions, the type of light source, and the like differ depending on the type of the duplicator.

Furthermore, in recent years, the consumption of silver halide photographic light-sensitive materials has been steadily increasing, so that the number of processed light-sensitive materials has been increased. There is a strong demand for increased throughput.

This tendency is no exception in the field of X-ray sensitive materials.
This is because, for example, the number of diagnoses is rapidly increasing due to the enforcement of periodic medical examinations, and the number of examination items is increasing in order to make the diagnosis more accurate, and as a result, the number of X-ray photographs is increasing.

There is also a strong demand for speedup in direct positive materials,
To meet this requirement, it is necessary to provide quick processing suitability directly to the positive photosensitive material as well as to automate diagnosis (photographing, transporting, etc.).

However, when a direct processing is performed directly on the positive photosensitive material, for example, when the total processing time is less than 20 seconds to 60 seconds, there is a problem that the sensitivity is reduced.

Although this sensitivity decrease can be dealt with by increasing the amount of silver halide emulsion, the film cost is naturally increased, but (a) the fixing becomes insufficient in the developing process, and (b) the film is washed with water. Becomes insufficient,
(C) Serious troubles such as insufficient drying of the film occur.

Therefore, in order to directly provide a positive processing material with rapid processing suitability, it is necessary to develop a technique which does not reduce the sensitivity and the maximum density even if the amount of silver halide is reduced. As a method of achieving high sensitivity and saving silver, for example, US Pat. No. 2,996,382 or US Pat.
No. 2,178,382 is known, and this technique has high sensitivity, high contrast by allowing surface latent image type silver halide grains and silver halide grains having fog nuclei inside grains to be adjacent to each other, and It is said that a photosensitive material with high covering power can be obtained.

However, when the photosensitive material is subjected to high-speed processing by an automatic developing machine in which the entire processing time (including the transition portion) is less than 20 seconds to 60 seconds, the minimum density (fog) is high and the graininess is poor.

As a means for improving the minimum density (fogging), various additives are known to be used in an emulsion or a developing solution. However, all of them are not preferable because they cause reduction in sensitivity, contrast and maximum density. As a means of improving the graininess, it is also known to increase the amount of gelatin in the binder, but this also has the disadvantage of causing a decrease in sensitivity, gamma and maximum density.

A direct positive photosensitive material having good photographic characteristics and good rapid processing properties has not yet been obtained.

[Object of the invention]

Accordingly, an object of the present invention is to provide a direct-positive silver halide photographic light-sensitive material which can obtain similar sensitometric characteristics by any duplicator and is suitable for ultra-rapid use.

[Configuration of the invention]

The inventor of the present invention has achieved the following objects as a result of intensive studies for the above purpose.

That is, in a silver halide photographic light-sensitive material having at least one layer comprising a silver halide photographic emulsion on one side of the support, a layer closest to the support having the silver halide photographic emulsion, or a support. The following general formulas [a], [b],
At least one dye selected from the compounds represented by [c] and at least one ultraviolet absorption selected from the compounds represented by the following general formulas [U ₁ ], [U ₂ ], and [U ₃ ] In the characteristic curve when processed under the following processing conditions, the characteristic curve on a rectangular coordinate system having the same optical axis unit length of the optical density (D) and the amount of exposure (logE) has a point having an optical density of 0.03. The gamma (γ) connecting points of 1.50 and 0.95 is 0.9 to 1.1, and the characteristic curve connecting the points of optical density of 0.03 to 1.50 has linearity, and the linearity of the characteristic curve is a characteristic on a rectangular coordinate system. The difference (ΔlogE) between the logarithm of the light exposure and the point on the characteristic curve having the same density as an arbitrary point on the plot connecting the two optical densities defining gamma (γ) with the curve is
This is achieved by a direct positive silver halide photographic material characterized by being 0.02 or less.

[Processing conditions] Using a developing solution and a fixing solution described below, processing is performed by a roller transport type automatic developing machine according to the following steps.

 Processing Step Processing temperature (° C) Processing time (seconds) Insertion-1.2 Development + migration 35 14.6 Fixation + migration 33 8.2 Washing + migration 25 7.2 Squeeze 40 5.7 Drying 45 8.1 Total-45.0 Developer Potassium sulfite 55.0 g Hydroquinone 25.0 g 1-phenyl-3-pyrazolidone 1.2 g boric acid 10.0 g sodium hydroxide 21.0 g triethylene glycol 17.5 g 5-nitrobenzimidazole 0.10 g glutaraldehyde bisulfite 15.0 g glacial acetic acid 16.0 g potassium bromide 4.0 g triethylenetetramine hexaacetic acid Add 2.5 g water to make 1

Fixing solution Ammonium thiosulfate 130.9 g Anhydrous sodium sulfite 7.3 g Boric acid 7.0 g Acetic acid (90 wt%) 5.5 g Disodium ethylenediaminetetraacetate 3.0 g Sodium acetate trihydrate 25.8 g Aluminum sulfate 18 hydrate 14.6 g Sulfuric acid (50 wt%) 6.77 g Water To make 1

The gamma (γ) in the present invention is obtained based on a characteristic curve drawn on a rectangular coordinate system in which the coordinate length of the optical axis (D) and the logarithm of the exposure amount (logE) are made equal.

The γ is a point of the density of base (support) density + fog density + 0.03 on the characteristic curve, and the density of base density + fog density +
It means the slope of the straight line connecting the points with a density of 1.50. In numerical terms, if the angle at which this straight line intersects the exposure axis (horizontal axis) is θ, γ is given by tan θ.

The linearity in the present invention is defined as a point on a characteristic curve having the same density as an arbitrary point on a straight line on the plot connecting the two optical densities defining the above-mentioned gamma on the rectangular coordinate system. Is a curve in which the difference (ΔlogE) of the logarithm of the amount of exposure is within 0.02 at most.

As the silver halide emulsion for obtaining the characteristic curve of the present invention, conventionally developed emulsions are optionally used.

That is, the silver halide emulsion used in the present invention is a neutral method,
Either the acid method or the ammonia method may be used. In addition, a mixing method such as a single jet method, a double jet method, and a control double jet method can be used. In particular, a controlled double jet method in which particles are grown while controlling pH, pAg, and the like is preferable.

When core / shell emulsion grains are used, the silver halide composition may be any of silver chloride, silver chlorobromide, silver bromide, silver iodobromide, and silver chloroiodobromide. Silver chlorobromide, silver bromide and silver chloroiodobromide are preferred, and silver chlorobromide containing 0 to 80 mol% of silver bromide is particularly preferred. The silver halide grains may be monodispersed or polydispersed.

The silver halide composition of the shell may be any as long as it has a lower solubility product than the silver halide of the core, but is preferably silver bromide or silver iodobromide. (In the case of silver iodobromide, silver iodide is preferably at most 6 mol%.) The molar ratio of the shell to the core is from 1:10 to 10: 1, preferably from 1:10 to 5: 1. is there.

The crystal phase after shell formation may be any of cubic, tetradecahedral, octahedral, and other irregular crystal forms.
It is 0.1 to 2.0 μm, preferably 0.15 to 1.0 μm.

In the present invention, an appropriate electron trap can be used to obtain a good positive image. This is effective in preventing a reaction of forming and growing silver nuclei between photoelectrons and silver ions. As a specific means, a noble metal atom or the like can be put as an inorganic desensitizer in the crystal of the silver halide grains, or an electron capture type desensitizing dye adsorbed on the crystal surface can be used.

When an inorganic desensitizer is used, a soluble metal salt of Group VIII is contained in the silver halide grains to contain the inorganic desensitizer.
For example, a soluble rhodium salt, a soluble iridium salt and the like may be added. These soluble salts are preferably 10 ^-8 to 10 ^-2 mol, more preferably 10 ^-5 to 10 mol per mol of silver halide.
It is preferable to add ^-3 mol, which is preferably added to the emulsion as an aqueous solution during the preparation of silver halide grains.

Regarding the technology in the case of using an electron capture type desensitizing dye, British Patent Nos. 1,186,717, 1,186,714 and 1,186,71
No. 6, No. 1,520,817, U.S. Pat.No. 3,501,306, No. 3,501,3
No. 07, 3,501,310, 3,531,288 and the like.

The silver halide emulsion used in the present invention is provided with an appropriate fog, using a reducing agent and a gold compound for the silver halide emulsion. At least one compound selected from thiosulfate and / or thiocyanate is allowed to coexist and fogged, or is fogged with a reducing agent and a gold compound, and then thiosulfate and / or thiocyanate is added. By including at least one or more compounds selected from the above, even better fogging is provided.

In the present invention, fog is imparted by the above-mentioned method, and good "missing" can be obtained by adding a water-soluble iodide to a silver halide emulsion before imparting fog. Examples of the water-soluble iodide include iodides of ammonium, potassium, lithium, and sodium, and the addition amount is 1 to 10 mMol of a water-soluble iodide per 1 mol of silver halide. If the addition amount is less than this, the omission is poor. If the amount is larger than this, a sufficient maximum concentration cannot be obtained, and the concentration decreases during storage.

The conditions for fogging silver halide can vary widely, but the pH is generally in the range of 5.5 to 9, preferably
H6-7. Also, the pAg is generally in the range of 6.5 to 8.5, and the temperature is generally in the range of 40C to 100C, preferably 50C to 70C.

A hydrophilic protective colloid such as gelatin for suspending silver halide grains during fogging is preferably used at a rate of 30 to 200 g per mol of silver halide.

Examples of the reducing agent used in the present invention include aldehyde compounds such as formalin, organic reducing agents such as hydrazine, organic amine compounds such as triethylenetetramine, thiourea dioxide, and imino-amino-methanesulfinic acid, and stannous chloride. An inorganic reducing agent or a reducing agent such as amine borane is preferably used.

And the concentration of the reducing agent used is silver halide grains,
It is variously changed depending on the purpose of application and the like, and further varies depending on the type of reducing agent.
It is in the range of 1.00 mMol.

The gold compound used in the present invention is a monovalent or trivalent soluble gold salt, such as chloroauric acid, gold thiocyanate, sodium chloroaurate, potassium chloroaurate, potassium bromoaurate, or potassium iodoaurate. , Potassium gold cyanide, potassium gold thiocyanate, sodium gold thiomaleate,
Gold thioglucose or the like is used.

The amount of the gold compound used varies depending on the size composition of silver halide grains or the purpose of application, but is generally in the range of 0.0001 to 0.1 mMol, preferably in the range of 0.005 to 0.05 mMol, per mol of silver halide. And good results are obtained when used at low concentrations.

Specific examples of the thiosulfate and thiocyanate used in the present invention include sodium thiosulfate, ammonium thiosulfate, potassium thiocyanate, ammonium thiocyanate, and complexes thereof, and the like. Is generally 0.0003 to 10.0 mM per mol of silver halide.
ol, preferably 0.005 to 0.5 mMol.

Then, these thiosulfates and thiocyanate salts may be used before fogging with a reducing agent and gold, or during fogging, or after fogging,
The required amount varies depending on the time of use, and it is necessary to increase the amount particularly when adding after fog formation.

The gamma of the direct positive photosensitive material of the present invention can be adjusted by utilizing conventional techniques by adjusting the conditions of emulsion composition, grain size distribution and chemical sensitization, and additives.

Further, the adjustment of the linearity can be obtained by mixing the emulsions having the predetermined and substantially equal gamma given by the above-mentioned method by adjusting the mixing ratio of at least two kinds.

The direct positive photosensitive material of the present invention has the following general formula [a],
At least one dye selected from the compounds represented by [b] and [c] and the following general formulas [U ₁ ], [U ₂ ],
A layer containing at least one or more ultraviolet absorbers selected from the compounds represented by [U ₃ ] is provided close to or in contact with the surface of the support.

Specific exemplary compounds of the dyes represented by the general formulas [a], [b] and [c] are as follows. Incidentally, dyes other than these may be used.

Wherein R ₁ is -OX or Wherein X and Y are a hydrogen atom, an alkyl group, a cyanoalkyl group, a carboxyalkyl group, a sulfoalkyl group, a hydroxyalkyl group, a halogenated alkyl group, an alkyl group which may be substituted or R ₂ and R ₃ represent a hydrogen atom, a halogen atom, an alkyl group, a hydroxyl group, an alkoxy group,
Represents an alkylthio group, or a group similar to the aforementioned -OX group,
Q represents at least one halogen atom, a carboxy group, a sulfo group, or a phenyl or sulfoalkyl group, a sulfoalkoxyalkyl group, or a sulfoalkylthioalkyl group substituted with a sulfoalkyl group or a sodium or potassium salt thereof; Represents an optionally substituted methine group. R ₄ represents an alkyl group, a carboxy group, an alkyloxycarbonyl group or an acyl-substituted, sulfo-substituted or unsubstituted amino group. m ₁ represents an integer 0, 1 or 2, and m ₂ represents an integer 0 or 1.

In the formula, R ₅ , R ₆ , R ₈ , R ₉ and R ₁₀ are a hydrogen atom, a halogen atom, an alkyl group, a hydroxyl group, an alkoxy group, an amino group, an acylamino group, a carboxyl group or a sulfone group or a sodium or potassium salt thereof. Represents salt. R ₇ represents an alkyl group or a carboxyl group.

In the formula, R ₁₁ and R ₁₂ represent an alkyl group, a substituted alkyl group, an aryl group, an alkoxycarbonyl group or a carboxyl group, and R ₁₃ and R ₁₄ represent an alkyl group or a sulfonic acid group substituted with a sulfonic acid group or a carboxyl group. Alternatively, it represents an aryl group substituted with a carboxyl group or a sulfonic acid group or a sodium or potassium salt thereof, and L represents a substituted or unsubstituted methine chain. M represents a sodium, potassium or hydrogen atom, and m ₃ represents 0 or 1.

Hereinafter, typical specific examples of the compounds according to the general formulas [a], [b] and [c] are shown.

Further, specific exemplary compounds of the ultraviolet absorbent represented by the general formulas [U ₁ ], [U ₂ ], and [U ₃ ] are as follows. In addition, you may use ultraviolet absorbers other than these.

In the formula, R ₁ is a hydrogen atom, an alkyl group, a substituted alkyl group,
R ₂ represents an alkyl group, a halogen-substituted alkyl group, and R ₃ represents a hydrogen atom, a halogen atom or an alkyl group.

In the formula, R ₄ represents an alkyl, hydroxyalkyl, cyanoalkyl, or sulfoalkyl group, and Z represents oxazole,
Thiazole, benzoxazole, benzothiazole,
A represents an atom group necessary for forming an imidazole or benzimidazole ring, and A represents a pyrrole ring or a pyrrolidine ring.

In the formula, R ₅ , R ₆ , R ₇ , and R ₈ represent an alkyl group, a hydroxyalkyl group, a cyano group, an alkylcyano group, an alkoxy group, or a sulfoalkyl group. R ₉ and R ₁₀ are sulfonic acid groups,
Represents an alkylsulfonic acid group. Next, specific compound examples are shown.

The direct-positive light-sensitive material of the present invention has a form having at least one silver halide emulsion layer on one side of a support and a backing layer of a non-photosensitive hydrophilic colloid layer on the other side. Can be. In addition, a matting agent can be contained on both sides. That is, at least one of the layers on the side of the silver halide emulsion layer and at least one of the layers on the side of the backing layer can contain a matting agent.

When one or more layers are provided on both sides of the support, the matting agent is preferably contained in the uppermost layer.

The matting agent used in the present invention is preferably an organic matting agent, particularly a polymer matting agent, but may be an inorganic matting agent.

Specific examples of the polymer matting agent used in the present invention include a water-dispersible vinyl polymer such as polymethyl methacrylate, cellulose acetate propionate, and starch. In particular, water-dispersible vinyl such as acrylate homopolymer such as methyl methacrylate, cricidyl acrylate, cricidyl acrylate and cricidyl methacrylate, or copolymers of these acrylates or other vinyl monomers. Polymeric spherical matting agents are preferred.

As the inorganic compound matting agent, silver halide, strontium barium sulfate, calcium carbonate, silicon dioxide, magnesium oxide, titanium oxide and the like are preferably used.

More specifically, in the present invention, British Patent 1,055,713
Nos., U.S. Pat.Nos. 1,939,213, 2,992,101, 3,767,44
Organic matting agent described in No. 8, etc., West German Patent 2,529,3
No. 21, UK Patent Nos. 760,775, 1,260,772, U.S. Patent 1,
201,905, 2,192,241, 3,053,662, 3,769,0
Inorganic matting agents and the like described in No. 20, No. 4,029, 504 and the like can be preferably used.

In a direct positive light-sensitive material of the present invention, is preferably the thickness of the backing layer is 0.1 to 10 [mu] m, the amount of matting agent contained in the side having the backing layer is preferably 0.005~1g / m ^2, 0.01~ 0.1 g / m ² is more preferred.

On the side of the direct positive photosensitive material of the present invention having the silver halide emulsion layer, a protective layer is preferably provided on the silver halide emulsion layer, and a matting agent is preferably contained in the protective layer or the uppermost layer. . The content of the side of the matting agent having a silver halide emulsion layer is preferably from 0.005~1g / m ^2, more preferably 0.01 to 0.1 g / m ^2.

In the present invention, the average particle size of the matting agent contained on the side having the silver halide emulsion layer is smaller than the average particle size of the matting agent contained on the side having the backing layer, and the ratio of the average particle size is It is preferably 1: 1.5 or less. Further
It is better to be 1: 2 or less. The ratio of the amount of the matting agent on the emulsion layer side to the amount of the matting agent on the backing layer side may be arbitrary, but it is more preferable that the amount of the matting agent on the backing layer side is larger than the amount of the matting agent on the emulsion layer side.

The shape of the matting agent used in the present invention may be arbitrary, but the matting agent on the emulsion layer side is preferably flat.
The average particle size of the matting agent on the emulsion layer side is the thickness of the emulsion layer +
The thickness is preferably 1.5 times or less the protective film thickness.

It is preferable that the particle size distribution of the matting agent used in the present invention is narrow. Particularly, in the matting agent used on the emulsion surface side, it is desirable that the particle size distribution is narrow and the content of coarse matting agent particles is small.

As for the narrowness of the particle size distribution of the matting agent, when the average particle size is σ and the standard deviation of the particle size is σ, a higher effect is obtained when (σ /) <2, and 0.5 <(σ /) <1. Sometimes, a higher effect is obtained.

The average particle size of the matting agent can be measured by a usual coal tar counter. Also, it can be measured directly from electron microscopes. In the latter case, if not spherical, the projected area is converted to a circle, and the diameter at that time is defined as the particle size.

The direct positive silver halide emulsion according to the present invention may contain other photographic additives. As stabilizers, for example, JP-B-49-16053, JP-B-49-12651, JP-A-48-66828
Or triazoles, azaindenes, benzothiazolium compounds, mercapto compounds, or water-soluble inorganic salts such as cadmium, cobalt, nickel, manganese, and zinc.

Hardening agents such as formalin, glyoxal,
Aldehydes such as mucochloric acid, S-triazines, epoxies, aziridines, vinylsulfonic acid and the like, and sensitizers such as those described in JP-B-42-25203, JP-B-43-10245,
43-13822, 43-17926, 43-17927, 46-2
Polyalkylene oxides and derivatives thereof selected from those described in Nos. 1186, 49-8102, 49-8332 and the like can also be contained. Further, for example, Japanese Patent Publication No. 45-24910,
It is also possible to incorporate a color coupler selected from those described in JP-A-45-29878 and the like. In addition, if necessary, a whitening agent, a thickening agent, a preservative, and the like can be added.

The silver halide emulsion according to the present invention is grafted with protective colloids such as gelatin, gelatin derivatives, polyvinyl alcohol, polyvinyl acrylate, polyvinyl pyrrolidone, cellulose ethers, partially hydrolyzed cellulose acetate, and ethylene oxide described in JP-B-49-20530. And a hydrophilic polymer such as a modified poly- (N-hydroxyalkyl) -β-alanine derivative.

Further, a dispersion-polymerized vinyl compound may be contained as a binder for the emulsion. For example, using a polymer latex of an unsaturated ethylenic monomer emulsion-polymerized in the presence of an activator described in JP-B-49-32344 and a cerium salt described in JP-B-49-20964 to form hydroxyl groups Inclusion of a polymer latex or the like obtained by grafting a polymer compound having the same with an unsaturated ethylenic monomer is preferable from the viewpoint of improving the physical properties of the film.

Also from the top of emulsion technology, Japanese Patent Publication No. 44-2523, 44-9499
Protecting and containing a developing agent as described in No. 2, or protecting and incorporating a higher fatty acid such as liquid paraffin or a higher unsaturated fatty acid such as stearyl acetoglyceride for improving film physical properties, and furthermore, a color coupler according to the purpose, and a stable color coupler. Agents and the like can be protected and contained.

The direct positive silver halide emulsion thus obtained can be prepared on any suitable photographic support such as glass, wood, metal,
Film, for example, cellulose acetate, cellulose acetate butyrate, cellulose nitrate, polyester, polyamide, polystyrene, etc., paper, baryta coated paper, polyolefin coated paper such as polyethylene or polypropylene coated paper, etc. By the treatment, the adhesion of the emulsion can be improved.

Known photographic additives can be added to the direct positive silver halide emulsion according to the present invention.

Known photographic additives include, for example, Research Disclosure RD-17643 (1978) and RD
-18716 (1979).

The support used in the direct positive photosensitive material of the present invention includes all known materials, such as a polyester film such as polyethylene terephthalate, a polyamide film, a polycarbonate film, a styrene film, a baryta paper, and a paper coated with a synthetic polymer. It is.

〔Example〕

Hereinafter, embodiments of the present invention will be described in detail. The present invention is not limited to the embodiments described below.

Example 1 Preparation of Seed Crystal A Cubic silver iodobromide grains containing 2 mol% of silver iodide having an average grain size of 0.20 μm were prepared by a double jet method while controlling pAg at 8.0 and pH = 2.0 at 60 ° C. Prepared. Gelatin obtained by condensing a phenylcarbonyl group to 90% of amino groups was added to the mixed solution, and the mixture was stirred for 3 minutes. Then, potassium hydroxide 0.13 g / AgX
1Mol was added to bring the pH to 4.0. After standing and decantation, pure water 2.1 / AgX at 40 ° C., 1 mol potassium hydroxide 0.25 g / AgX 1Mol were added to adjust the pH to 5.8, and the mixture was stirred for 5 minutes. Then add 1.5 ml / AgX 1Mol nitric acid (1.7N) and pH = 4.3
And leave it still. Decanted. Further, gelatin and potassium hydroxide 0.2g / AgX 1Mol were added to adjust the pH to 5.8 and redispersed to obtain a seed crystal A.

Growth from Seed Crystal A-1 Dissolve the above seed crystals in a gelatin solution maintained at 40 ° C.
Further, ammonia was added to adjust the pH to 8.0.

Rhodium trichloride and potassium hexachloroiridate were added to this solution as shown in Table 1, and after 2 minutes, a 1N aqueous ammonia nitric acid solution and a 1N aqueous potassium bromide solution were added by a double jet method. During the mixing, the pH was controlled to 8.0, and the EAg was controlled to the value shown in Table 1.

After the mixing was completed, the pH was lowered to 6.0 with acetic acid. Thereafter, desalting was carried out in the same manner as for the seed crystal to obtain emulsions E-1 to E-7.

Preparation of Seed Crystals B, C, and D B (particle size: 0.30 μm) was obtained in exactly the same manner except that the temperature and the mixing time of the seed crystal A were changed.

Growth from Seed Crystal B Growth was carried out in the same manner as in Growth 1 from Seed Crystal A, and Emulsions E-8 and E-9 having finished grain sizes of 0.30 and 0.50 μm were obtained.

Emulsion E-10,11 in exactly the same manner except that a mixed aqueous solution of 1N potassium iodide and potassium bromide was used in place of the 1N aqueous potassium bromide solution in growth-1 from seed crystal-1. I got The silver iodide content after the formation of the shell is as shown in Table 1.

First, the solution (b) was added to the solution (a) at 40 ° C., and the solution (c) was further added over 20 minutes while stirring.

Next, after aging for 30 minutes, the solution (d) was added to neutralize the solution to pH 6.5.

Emulsion E-12 was also desalted in the same manner as for seed crystal A.

Each emulsion obtained as described above is adjusted to pH 6.8 at 60 ° C.
Then, 0.3 mg of thiourea dioxide and 1.2 mg of sodium thiosulfate and 1.5 mg of chloroauric acid per 1 mol of AgX were added thereto, and the mixture was aged until an appropriate fog was obtained.

Using the above particles, an emulsion coating solution containing an additive was prepared according to the following composition.

A coating solution for a backing layer was prepared by adding the following additives. Further, a protective layer solution having the composition described below was prepared.

A silver halide emulsion layer is formed on one side of the support by the emulsion coating solution and the protective layer solution, and a protective layer is formed thereon, and a backing layer solution is formed on the side opposite to the emulsion layer side by a backing layer solution. Was formed to prepare a sample. That is, emulsion coating solution per surface 3.2 g / m ² as silver, a protective layer solution at 140 m / min speed so that the per side 0.98 g / m ² as the amount of gelatin, and on the opposite side to the emulsion layer The backing layer solution was applied simultaneously in a multilayer at a speed of 140 m / min so that the amount of gelatin became 3 g / m ² per unit area, dried, and dried.
No. 1 to Sample No. 10 were obtained.

Table 2 shows Comparative Samples A and B in which the dye of the present invention was not added to the backing layer.

Exposure conditions The samples thus obtained were each exposed with a duplicator. The duplicator was exposed using a flat printer II manufactured by Konica Medical and a duplicator manufactured by Konica, using a wedge for sensitometry, and subjected to the above-described development using a Konica SRX501 automatic developing machine and development processing with a fixing solution for 45 seconds. The evaluation of the exposure latitude at this time was represented by an exposure amount difference (logarithmic display) between the optical density of the base density + the fog density + 0.03 and 1.5. Table 2 shows the values.

Evaluation of linearity The evaluation of the linearity of the characteristic curve of each sample described above is performed by using a characteristic curve having the same density as an arbitrary point on a straight line connecting the two optical densities defining the above-mentioned gamma on a rectangular coordinate system. It was expressed by the maximum value of the difference (ΔlogE) of the logarithm of the exposure at the above point. This value
When it is 0.02 or less, the linearity is excellent.

Example 2 To the emulsion prepared in Example 1, the following dye was added to the backing layer in the same manner as in Example 1, and otherwise the same emulsion additives, the same protective layer, Prepare a sample as the same backing layer except for the dye, apply in the same way,
Dried. This was tested and evaluated in the same manner as in Example-1.

The results were the same as in Example 1 as shown in Table-3.

[Effects of the Invention] According to the configuration of the present invention, a direct positive photosensitive material having good copyability and suitable for ultra-rapid processing can be obtained.

Claims (1)

(57) [Claims] 1. A silver halide photographic light-sensitive material having at least one layer comprising a silver halide photographic emulsion on one side of a support, a layer closest to the support having the silver halide photographic emulsion, Alternatively, at least one or more dyes selected from the compounds represented by the following general formulas [a], [b] and [c] may be contained in at least one of the layers on the opposite side of the support, and Equation [U ₁ ],
It contains at least one or more ultraviolet absorbers selected from the compounds represented by [U ₂ ] and [U ₃ ]. In the characteristic curve when processed under the following processing conditions, the optical density (D) and the In a characteristic curve on a rectangular coordinate system having the same coordinate unit length of the exposure amount (logE), the same as the point having an optical density of 0.03.
The gamma (γ) connecting the points of 50 is 0.9 to 1.1, and the characteristic curve connecting the points of the optical density of 0.03 to 1.50 has linearity,
Exposure at a point on the characteristic curve in which the linearity of the characteristic curve is the same as an arbitrary point on a drawing line connecting two optical densities defining gamma (γ) in a characteristic curve on a rectangular coordinate system. A direct positive silver halide photographic material characterized in that the difference in logarithm (ΔlogE) is 0.02 or less. (Wherein R ₁ is -OX or Wherein X and Y are a hydrogen atom, an alkyl group, a cyanoalkyl group, a carboxyalkyl group, a sulfoalkyl group, a hydroxyalkyl group, a halogenated alkyl group, an alkyl group which may be substituted or The sodium and potassium salts are represented by R ₂ and R ₃ are a hydrogen atom, a halogen atom, an alkyl group, a hydroxyl group, an alkoxy group,
Represents an alkylthio group, or a group similar to the aforementioned -OX group,
Q is at least one halogen atom, a carboxy group, a sulfo group, or a sulfoalkyl group or a phenyl or sulfoalkyl group, a sulfoalkoxyalkyl group, a sulfoalkylthioalkyl group substituted with a sodium or potassium salt thereof; Represents an optionally substituted methine chain. R ₄ represents an alkyl group, a carboxy group, an alkyloxycarbonyl group or an acyl-substituted, sulfo-substituted or unsubstituted amino group. m ₁ represents an integer 0, 1 or 2, and m ₂ represents an integer 0 or 1. ) (Wherein R ₅ , R ₆ , R ₈ , R ₉ and R ₁₀ are a hydrogen atom, a halogen atom, an alkyl group, a hydroxyl group, an alkoxy group, an amino group, an acylamino group, a carboxyl group or a sulfone group or a sodium thereof, Represents a potassium salt, and R ₇ represents an alkyl group or a carboxyl group.) (Wherein, R ₁₁ and R ₁₂ represent an alkyl group, a substituted alkyl group, an aryl group, an alkoxycarbonyl group or a carboxyl group, and R ₁₃ and R ₁₄ represent an alkyl group or a sulfonic acid substituted with a sulfonic acid group or a carboxyl group. L represents a substituted or unsubstituted methine chain, L represents a substituted or unsubstituted methine chain, M represents a sodium, potassium or hydrogen atom, and m ₃ represents a substituted or unsubstituted aryl group substituted with a carboxyl group or a sulfonic acid group. Represents 0 or 1.) (Wherein R ₁ is a hydrogen atom, an alkyl group, a substituted alkyl group,
R ₂ represents an alkyl group, a halogen-substituted alkyl group, and R ₃ represents a hydrogen atom, a halogen atom or an alkyl group. ) (Wherein, R ₄ represents an alkyl, hydroxyalkyl, cyanoalkyl, or sulfoalkyl group; Z represents oxazole;
Thiazole, benzoxazole, benzothiazole,
A represents an atom group necessary for forming an imidazole or benzimidazole ring, and A represents a pyrrole ring or a pyrrolidine ring. ) (Wherein, R ₅ , R ₆ , R ₇ and R ₈ represent an alkyl group, a hydroxyalkyl group, a cyano group, an alkylcyano group, an alkoxy group or a sulfoalkyl group. R ₉ and R ₁₀ represent a sulfonic acid group,
Represents an alkylsulfonic acid group. [Processing conditions] Using a developing solution and a fixing solution described below, processing is carried out by a roller transport type automatic developing machine according to the following steps. Processing Step Processing temperature (° C) Processing time (seconds) Insertion-1.2 Development + migration 35 14.6 Fixation + migration 33 8.2 Washing + migration 25 7.2 Squeeze 40 5.7 Drying 45 8.1 Total-45.0 Developer Potassium sulfite 55.0 g Hydroquinone 25.0 g 1-phenyl-3-pyrazolidone 1.2 g boric acid 10.0 g sodium hydroxide 21.0 g triethylene glycol 17.5 g 5-nitrobenzimidazole 0.10 g glutaraldehyde bisulfite 15.0 g glacial acetic acid 16.0 g potassium bromide 4.0 g triethylenetetramine hexaacetic acid Add 2.5 g water to make 1 liter. Fixing solution Ammonium thiosulfate 130.9 g Anhydrous sodium sulfite 7.3 g Boric acid 7.0 g Acetic acid (90 wt%) 5.5 g Disodium ethylenediaminetetraacetate 3.0 g Sodium acetate trihydrate 25.8 g Aluminum sulfate 18 hydrate 14.6 g Sulfuric acid (50 wt%) 6.77 g Water To make 1l.