JPH0782224B2 - Direct positive photographic material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a direct positive photographic light-sensitive material, and more particularly to a direct positive photographic light-sensitive material excellent in image discrimination.

[Conventional technology]

Photographic methods for obtaining direct positive images without the need for reversal processing steps or negative films are well known.

The method used to create a positive image using a conventionally known direct positive silver halide emulsion photographic material is
Except for special ones, in consideration of practical usefulness, they can be mainly divided into two types.

The first type uses a pre-fogged silver halide emulsion and directly develops a positive image after development by destroying the fog nuclei (latent image) in the exposed area by utilizing solarization or the Herschel effect. Is what you get.

The second type uses an internal latent image type silver halide emulsion which has not been fogged in advance, and directly after the image exposure is subjected to a fogging treatment or is subjected to surface development to directly obtain a poly image. .

Further, the above-mentioned internal latent image type silver halide photographic emulsion is a type of silver halide in which a silver halide grain has a photosensitive nucleus mainly inside and a latent image is mainly formed inside the grain upon exposure. A photographic emulsion.

As described above, as a means for selectively generating fog nuclei, a method of giving a second exposure to the entire surface of the photosensitive layer, which is generally called "light fog method" (for example, British Patent 1,151,363)
And a nucleating agent called "chemical fogging"
gent) method is known. This method is described, for example, in "Research Disclosure" (Rese
Arch Disclosure) Vol. 151 No. 15162 (issued in November 1976), pages 76-78.

The second type method is generally more sensitive than the first type method, and is suitable for applications requiring high sensitivity, and the present invention relates to the latter type. .

Various techniques have been known so far in this technical field. For example, U.S. Patent Nos. 2,592,250 and 2,466,9
No. 57, No. 2,497,875, No. 2,588,982, No. 3,317,
No. 322, No. 3,761,266, No. 3,761,276, No. 3,79
6,577 and British Patents 1,151,363 and 1,150,553
No. (No. 1,011,062) Main items are described in each specification.

By using these known methods, a photographic light-sensitive material having a relatively high sensitivity as a direct positive type can be produced.

Further, for details of the mechanism for forming a direct positive image, for example,
The Theory of the Photograph, TH Themes, The Theory of the Photograph
ic Process) Fourth Edition, Chapter 7, pp. 182-193 and U.S. Pat. No. 3,
761,276, etc.

That is, the fog nuclei are selectively generated only on the surface of the unexposed silver halide grains due to the surface desensitizing effect caused by the so-called internal latent image generated inside the silver halide by the first imagewise exposure. Then, a normal, so-called surface development treatment is applied to the photographic image (direct positive image) on the unexposed area.
Is believed to be formed.

[Problems to be Solved by the Invention]

In the direct positive image formation using such a light fogging method or a chemical fogging method, the developing speed is slower and the processing time is longer than that in the case of a normal negative type. Alternatively, a method of increasing the liquid temperature to shorten the processing time has been taken. However, in general, when the pH or the liquid temperature is high, the minimum image density of the direct positive image obtained increases. Further, under high pH conditions, the developing agent is apt to deteriorate due to air oxidation, resulting in a marked decrease in developing activity.

As a means for increasing the maximum density while keeping the minimum density of a direct positive image small, a method using a hydroquinone derivative (US Pat. No. 3,227,552) using a mercapto compound having a carboxylic acid group or a sulfonic acid group 60-1
70843) are known, but the effect of using these compounds is small. Therefore, no technique has been found that can effectively increase the maximum density of the direct positive image without increasing the minimum density. In particular, there is a demand for a technique capable of obtaining a sufficient maximum image density even when processed with a developer having a low pH.

Next, in the direct positive image formation using such a light fogging method or a chemical fogging method, there is a problem that the gradation is soft. In particular, this is remarkable in the highlight portion, and the image formed by this method has a drawback that tone reproduction tends to be insufficient.

In order to solve this problem, as means for obtaining a hard-tone photosensitive material for direct positive image formation, a method of monodispersing silver halide grains and a method of doping polyvalent metal ions into silver halide grains ( US3,367,778,3,387,136), or a method of adjusting the sensitization method of the core part in a so-called core / shell emulsion (US4035185), etc. are known, but the effect by these methods is still insufficient.

Therefore, a first object of the present invention is to provide a direct positive photographic light-sensitive material which gives a direct positive image having a low minimum image density while maintaining a high maximum image density.

A second object of the present invention is to provide a direct positive photographic light-sensitive material which gives a hard direct image.

[Means for Solving the Problems]

The above object of the present invention is a direct positive photographic light-sensitive material having at least one photographic emulsion layer containing internal latent image type silver halide grains which have not been fogged in advance, wherein the photographic emulsion layer is represented by the following general formula [A], A direct positive photographic light-sensitive material characterized by containing at least one selected from the compounds represented by [B] and [C].

Formula (A) Z-SO ₂ -S-M Formula (B) General formula [C] However, Z: an alkyl group (having 1 to 18 carbon atoms), an aryl group (having 6 to 18 carbon atoms), or a heterocyclic group, Y ₁ , Y ₂ : an aromatic ring (having 6 to 18 carbon atoms), or forming a heterocycle Atoms required for M: metal atom or organic cation n: integer of 2 to 10 Z, Y _{1 in the} general formula [A], [B] or [C]
And the alkyl group, aryl group, heterocyclic group, aromatic ring and heterocycle represented by Y ₂ may be substituted.

The internal latent image type silver halide grains which have not been fogged in advance in the present invention will be described. The particles preferably have a so-called core / shell structure.

The core particles may be formed by a conversion type, and one or more kinds of ordinary chemical sensitization such as gold sensitization, sulfur sensitization and reduction sensitization may be used, or they may not be chemically sensitized. good. Alternatively, a metal such as iridium, palladium, or rhodium may be used for doving.

The shell does not have to be chemically sensitized, but the above-mentioned chemical sensitization is preferable.

The pre-fogged internal latent image type silver halide emulsion used in the present invention is an emulsion in which the surface of silver halide grains is not pre-fogged and which contains a silver halide mainly forming a latent image inside the grains. More specifically, a silver halide emulsion is silver-coated on a transparent support in an amount of 0.5 to 3 g / m ² and exposed to light at a fixed time of 0.01 to 10 seconds to give a developer A ( The maximum density measured by an ordinary photographic density measuring method when developed at 18 ° C. for 5 minutes in an internal developing solution is the same as the above coating, and the silver halide emulsion exposed similarly is developed as follows. 20 in solution B (surface type developer)
Those having a density at least 5 times higher than the maximum density obtained when developed at 6 ° C. for 6 minutes are preferable, and those having a density at least 10 times higher are more preferable.

Surface developer B Metol 2.5 g l-ascorbic acid _{10g NaBO 2 · 4H 2 O 35g} KBr 1g Water to make 1 Internal Developer A Metol 2g sodium sulfite (anhydrous) 90 g Hydroquinone 8g sodium carbonate (monohydrate) 52.5 g KBr 5g KI 0.5g Water is added 1 Specific examples of the latent latent emulsion include, for example, British Patent No. 1,011,
Examples thereof include the convergence type silver halide emulsions and core / shell type silver halide emulsions described in the specifications of No. 062, US Pat. Nos. 2,592,250, and 2,456,943. As silver halide emulsions, JP-A-47-32813, 47-32814, 52-134721 and 53-60
No. 222, No. 53-66218, No. 53-66727, No. 57-136641,
58-70221, 59-208540, 59-216136, 60-1
07641, 60-247237, 61-2148, 61-3137,
Japanese Patent Publications Sho 56-18939, No. 58-1412, No. 58-1415, No. 58-6
No. 935, No. 58-108528, Japanese Patent Application No. 61-36424, U.S. Pat.
No. 206,313, No. 3,317,322, No. 3,761,266, No. 3
No. 3,761,276, No. 3,850,637, No. 3,923,513, No. 4,035,185, No. 4,395,478, No. 4,431,730,
No. 4,504,570 European Patent No. 0017148, Research Disclosure Magazine RD16345 (November 1977) No.
18155 (May 1979), No. 23510 (November 1983) and the like.

The composition of silver halide is not particularly limited. Silver bromide, silver iodobromide, silver chloride, silver chlorobromide, silver chloroiodobromide and the like can be used. The halogen compositions of the core and the shell may be the same or different.

The silver halide preferably used in the present invention does not contain silver iodide, but the content thereof is 10 mol% or less.

The average grain size of silver halide grains (represented by the diameter of spheres of the same species as the grains) is preferably 2.0 μ or less and 0.2 μ or more, more preferably 1.2 μ or less and 0.4 μ or more. The grain size distribution may be narrow or wide, but it is preferable to use a so-called "monodisperse" silver halide emulsion having a narrow grain size distribution for the purpose of improving graininess, sharpness and the like. .

The monodisperse silver halide grains in the present invention have a grain size distribution as defined by the following formula. That is, when the standard deviation S of the particle size distribution is divided by the average particle size, the value is 0.20 or less.

The average grain size referred to here is the average value of the diameter of spherical silver halide grains, and the projected image is converted to a circular image of the same area in the case of cubic grains or grains having a shape other than spherical. When the particle diameter is ri and the number thereof is ni, the average value of the diameters when defined is defined by the following formula.

The above-mentioned particle diameter can be measured by various methods generally used in the technical field for the above purpose. A representative method is Loveland's “Particle Size Analysis” ASTM Symposium on Ride Microscopy, 1955, 94-
122 pages or "Theory of Photographic Processes", co-authored by Mies and James, 3rd edition, Chapter 2 published by Macmillan, Inc. (1966). This particle diameter can be measured using the projected area of the particle or an approximate diameter value. In order to satisfy the target gradation of the light-sensitive material, two or more kinds of monodispersed silver halide emulsions having different grain sizes or a plurality of emulsions having the same size but different sensitivities are used in the emulsion layers having substantially the same color sensitivity. The particles can be mixed in the same layer or multi-layered in different layers. Further, two or more kinds of polydisperse silver halide emulsions or a combination of monodisperse emulsions and polydisperse emulsions can be mixed or laminated and used.

The silver halide grain of the present invention may have a regular crystal form such as an octahedron and a tetradecahedron, or an irregular crystal form such as a sphere. It may be one.

Further, tabular grains may be used, and an emulsion having a length / thickness ratio of 5 or more, particularly 8 or more and occupying 50% or more of the total projected area of tabular grains may be used. Further, it may be an emulsion having a composite form of these crystal forms, or an emulsion comprising a mixture thereof.

The silver halide emulsion used in the present invention can be chemically sensitized inside or on the surface of the grain by sulfur or selenium sensitization, reduction sensitization, noble metal sensitization or the like alone or in combination.

Specific examples are described in the patents described in, for example, Research Disclosure No. 17643-II (issued in December 1978) P23.

The photographic emulsion used in the present invention is spectrally sensitized with a photographic sensitizing dye in a conventional manner. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes and complex merocyanine dyes, and these dyes can be used alone or in combination. Further, the above dye and supersensitizer may be used in combination. Detailed specific examples are found in patents described in, for example, Research Disclosure No. 17643-IV (published in December 1978) P23 to 24.

The above emulsion of the present invention can be spectrally sensitized to the infrared region. In that case, JP-A-60-80841, U.S. Pat.
The method described in No. 6,473 can be used. The infrared light source used may be one described in the above patent.

Next, the compounds represented by the general formulas [A], [B] and [C] will be described in more detail.

Formula (A) Z-SO ₂ -S-M Formula (B) General formula [C] However, Z: an alkyl group (having 1 to 18 carbon atoms), an aryl group (having 6 to 18 carbon atoms), or a heterocyclic group, Y ₁ , Y ₂ : an aromatic ring (having 6 to 18 carbon atoms), or forming a heterocycle Atoms required for M: metal atom or organic cation n: integer of 2 to 10 Z, Y _{1 in the} general formula [A], [B] or [C]
And the alkyl group, aryl group, heterocyclic group, aromatic ring and heterocycle represented by Y ₂ may be substituted.

Examples of the substituent include a lower alkyl group such as a methyl group and an ethyl group, an aryl group such as a phenyl group, an alkoxyl group having 1 to 8 carbon atoms, a halogen atom such as chlorine, a nitro group, an amino group and a carboxyl group. You can

Examples of the heterocycle represented by Z, Y ₁ and Y ₂ include thiazole, benzthiazole, imidazole, benzimidazole, oxazole, benzoxazole and azole rings.

The metal atom represented by M is sodium ion,
An alkali metal atom such as potassium ion and an organic cation are preferably ammonium ion, guanidine group and the like.

Specific examples of the compounds represented by the general formulas [A], [B], and [C] include the following.

1-3 H ₃ C ・ SO ₂・ SNa 1-4 H ₅ C ₂・ SO ₂・ SNa 1-5 nH ₇ C ₃・ SO ₂・ SNa 1-6 nH ₉ C ₄・ SO ₂・ SNa 1-7 nH ₁₇ C ₈ · SO ₂ · SNa 1-8 nH ₂₅ C ₁₂ · SO ₂ · SNa 1-9 nH ₃₃ C ₁₆ · SO ₂ · SNa 1-18 1-cystine-disulfooxide The compounds represented by the general formulas [A], [B] and [C] can be generally synthesized by a well-known method.

For example, it can be synthesized by reacting a corresponding sulfonyl fluoride with sodium sulfide or by reacting a corresponding sodium sulfinate with sulfur. On the other hand, these compounds can also be easily obtained as commercial products.

Among the compounds represented by the general formula [A], [B] or [C], the preferable one is [A].

The compounds represented by the above general formulas [A], [B] and [C] of the present invention are contained in the photographic emulsion layer containing the internal latent image type silver halide grains of the present invention.

As a method of containing the emulsion, it may be added to the coating solution containing the emulsion particles immediately before coating, but it is preferably added to the emulsion of the present invention in advance. General formula [A] of the present invention,
The compounds represented by [B] and [C] are more preferably added during grain formation of the internal latent image type silver halide grains of the present invention. The most preferable method is to add the compounds represented by the general formulas [A], [B] and [C] of the present invention during the core grain formation, the chemical sensitization of the core grain or the conversion.

The amount used is generally from 10 ⁻⁶ to 10 ⁻² mol, preferably from 10 ⁻⁵ to 1 mol, per mol of the internal latent image type silver halide of the present invention.
It is in the range of 10 ^-2 mol.

The compounds represented by the general formulas [A], [B] and [C] of the present invention may be used alone or in combination of two or more kinds.

The amount of the compound of the present invention present in the silver halide grain is determined by immersing the grain in a dilute solution of a silver halide solvent to dissolve the vicinity of the surface of the grain, then separating the grain and analyzing. Thus, the amount present inside the particle can be determined. At that time, by determining the degree of dissolution, it is also determined whether the compounds represented by the general formulas [A], [B] and [C] are present near the surface or deep inside the particle. You can

The photographic emulsion used in the present invention contains a benzenesulfinic acid compound, a thiocarbonyl compound, etc. for the purpose of preventing fog during the production process of the light-sensitive material, storage or photographic processing, or stabilizing photographic performance. be able to.

For more detailed examples of antifoggants or stabilizers and their use, see, for example, US Pat. No. 3,954,474.
No. 3,982,947, Japanese Patent Publication No. 52-28660, Research
Dice Closure (RD) Magazine 17643 (December 1978) VI A
~ VII M and EJ Birr, "Stabilization of Photographic Silv"
er Halide Emulsions) Focal Pre
ss), 1974, etc.

Various color couplers can be used in the present invention to directly form a positive color image. The color coupler is a compound that produces or releases a substantially non-diffusible dye by a coupling reaction with an oxidized product of an aromatic primary amine color developing agent, and is a substantially non-diffusible compound itself. Is preferred. Typical examples of useful color couplers are naphthol or phenol compounds, pyrazolone or pyrazoloazole compounds and open chain or heterocyclic ketomethylene compounds. Specific examples of these cyan, magenta and yellow couplers that can be used in the present invention are No. 17643 (published in December 1978), P25.VII-D, N, "Research Disclosure" magazine.
No. 18717 (issued in November, 1979) and Japanese Patent Application No. 61-32462 and the patents cited therein.

Colored couplers for correcting unnecessary absorption in the short wavelength range of the dyes formed, couplers with a suitable diffusibility of color forming dyes, colorless couplers, DIR couplers and polymers that release development inhibitors with the coupling reaction. Modified couplers can also be used.

As the binder or protective colloid that can be used in the emulsion layer or intermediate layer of the light-sensitive material of the present invention, it is advantageous to use gelatin, but other hydrophilic colloids can also be used.

Color fog inhibitors or color mixture inhibitors can be used in the light-sensitive material of the present invention.

Representative examples of these are described in JP-A-62-215272, pages 600 to 63.

Various anti-fading agents can be used in the light-sensitive material of the present invention.

Typical examples of these anti-fading agents are JP-A-62-215272 400-
It is described on page 440.

The light-sensitive material of the present invention includes a dyeing agent for preventing irradiation or halation, an ultraviolet absorber, a reversible agent, a fluorescent whitening agent, a matting agent, an air fog preventing agent, a coating aid, a hardener,
An antistatic agent, a slipperiness improving agent, etc. can be added.
Typical examples of these additives are Research Disclosure No. 17643 VIII to XIIII (published in December 1978) p25
~ 27, and 18716 (issued in November 1979) p647-651.

The light-sensitive material according to the present invention, in addition to the silver halide emulsion layer,
Protective layer, intermediate layer, filter layer, anti-halation agent,
It is preferable to appropriately provide an auxiliary layer such as a back layer and a white reflective layer.

In the photographic light-sensitive material of the present invention, the photographic emulsion layer and other layers are No. 17643XV, Research Disclosure No. 11 (197).
Issued in Dec. 8) P28 and European patents 0,182,
It is coated on the support described in JP-A No. 253 or JP-A-61-97655. Also Research Disclosure Magazine No.17643 XV
The coating method described in Items P28 to 29 can be used.

The present invention can be applied to various color photographic light-sensitive materials.

Representative examples include color reversal films for slides or televisions, color reversal papers, and instant color films. It can also be applied to full-color copiers and color hard copies for storing CRT images. The present invention also provides
It can also be applied to a black and white light-sensitive material using a three-color coupler mixture described in "Research Disclosure" magazine No. 17123 (issued in July 1978).

The light-sensitive material of the present invention can also be applied to a color diffusion transfer material. In that case, "Research Disclosure" magazine No. 15162 (1976), Japanese Patent Application No. 61-259326, 6
Compounds and methods described in 3-23491 and the like can be used in combination.

Furthermore, the present invention can be applied to black and white photographic light-sensitive materials.

The black and white (B / W) photographic light-sensitive materials to which the present invention can be applied include B / W direct positive photographic light-sensitive materials described in JP-A-59-208540 and JP-A-60-260039 (for example, X-ray photographic materials). Material,
(Dyeup sensitive material, micro sensitive material, photosetting sensitive material, printing sensitive material)
and so on.

The direct positive photographic light-sensitive material of the present invention is subjected to fog treatment as described below after imagewise exposure.

The fogging in the fog is either a method of exposing the entire surface of the photosensitive layer so-called "light fogging method" as described above or a method of developing in the presence of a nucleating agent called "chemical fogging method". May be used. You may develop in the presence of a nucleating agent and fog light. Further, a light-sensitive material containing a nucleating agent may be fog-exposed.

In the present invention, it is particularly preferable to perform fogging treatment with a nucleating agent.

The overall exposure in the "light fog method" of the present invention, that is, the fog exposure is carried out after the imagewise exposure and during the developing treatment and / or the developing treatment. Exposure is carried out before the imagewise exposed light-sensitive material is dipped in a developing solution or in a pre-bath of the developing solution, or taken out from these solutions and not dried, but exposure in the developing solution is most preferred.

As the light source for the fogging exposure, a light source within the light-sensitive wavelength of the light-sensitive material may be used, and generally, a fluorescent lamp, a tungsten lamp, a xenon lamp, sunlight or the like can be used.
These specific methods are described in, for example, British Patent 1,151,363.
No. 45, Japanese Patent Publication No. 45-12710, No. 45-12709, No. 58-6936,
JP-A-48-9727, 56-137350, 57-129438, 5
8-62652, 58-60739, 58-70223 (corresponding US Pat. No. 4,440,851), 58-120248, and the like.

As the nucleating agent used in the present invention, all compounds developed for the purpose of nucleating internal latent type silver halide can be applied. Two or more nucleating agents may be used in combination. More specifically, examples of the nucleating agent include, for example, “Research Disclosure”, N.
o.22534 (issued January 1983), pages 50-54, same magazine, No.15162
(Published November 1976) Pages 76-77, and the same magazine, No.23510 (19
(November 1983) There are items listed on pages 346-352,
These are roughly classified into three types: quaternary heterocyclic compounds, hydrazine compounds and other compounds.

Other hydrazine-based nucleating agents include, for example, JP-A-57
-86829, U.S. Pat.Nos. 4,560,638, 4,478,928,
Further, they are described in Nos. 2,563,785 and 2,588,982.

In the present invention, in order to further promote the action of the nucleating agent, the following nucleating accelerator can be used.

As the nucleation accelerator, tetrazaindenes, triazaindenes and pentazaindenes having at least one mercapto group optionally substituted with an alkali metal atom or an ammonium group and Japanese Patent Application No. 62- 145932
Nos. (Pages 15 to 50) and Japanese Patent Application No. 62-145933 (pages 19 to 55) can be added.

As the exposure light source for the light-sensitive material of the present invention, a wavelength conversion element made of a non-linear optical material can be used in addition to the light source usually used in a photographic light-sensitive material.

A wavelength conversion element made of a non-linear optical material used in the present invention will be described. The non-linear optical material is a material capable of exhibiting a non-linearity between the polarization and the electric field, which appears when a strong optical electric field such as laser light is applied-a non-linear optical effect, and includes lithium niobate and diphosphoric acid. Inorganic compounds represented by potassium hydrogen (KDP) lithium iodate, BaB ₂ O _{4 and the} like, urea derivatives and nitroaniline derivatives (for example, 2-methyl-4-nitroaniline (MNA), 2-N, N-).
Dimethylamino-5-nitroacetanilide (DAN),
Metanitroaniline, L-N- (4-nitphenyl)-
2- (Hydroxymethyl) pyrrolidine and Japanese Patent Application No. 61
-53462, Japanese Patent Application No. 61-53884, Japanese Patent Application No. 61-29999, etc.), nitropyridine-N-oxide derivatives (for example, 3-methyl-4-nitropyridine-1-).
Oxides (POM), diacetylene derivatives (for example, compounds described in JP-A-56-43220), and JP-A-61
-60638, JP 61-78748, JP 61-152647, JP 61-137136, JP 61-147238, JP 61-14843.
3, compounds described in JP-A No. 61-167930, "Nonlin
er Optical Properties of Organic and Polymeric Mat
erials "ACS SYMPOSIUM SERIES 233, David J. Williams
Ed. (American Chemical Society, 1983), "Organic Nonlinear Optical Materials", supervised by Masao Kato, Hachiro Nakanishi (CM.
C, Inc., 1985). Organic compounds such as the compounds described in 1. are known.

Regarding the present invention, among these, those having a high blue light transmittance, for example, KDP, lithium iodate, lithium niobate, BaB ₂ O ₄ , urea, POM, Japanese Patent Application No. 61-53462 and Japanese Patent Application No. The compounds described in JP-A-61-53884 are preferable, and further, POM and the organic compounds described in JP-A-61-53462 and JP-A-61-53884 are particularly preferable.

Non-linear optical effects include second-harmonic generation, optical mixing, parametric oscillation, optical rectification, and Pockels effect as second-order effects, and third-harmonic generation, Kerr effect, optical bistable as third-order effects. , Light mixing, etc., and also has higher effects. In the present invention, the purpose of using a nonlinear optical material is to convert the light of a semiconductor laser having a wavelength in the infrared range into a wavelength in the visible range, and therefore, the second harmonic wave related to wavelength conversion among the above effects. Generation, light mixing, parametric oscillation, and third harmonic generation are important.

The form of the wavelength conversion element using the semiconductor laser and the nonlinear optical material used in the present invention is a single crystal optical waveguide type,
Fiber type and the like are known. As the optical waveguide type, JP-A-51-142,284, JP-A-52-108,779 and JP-A-52-12
A flat plate waveguide described in 5,286, JP-A-60-14,222
, JP-A-60-57,825 and JP-A-60-112,023, and embedded waveguide-shaped ones described in JP-A-60-250,334. As the fiber type, there is one that satisfies the phase matching condition of the incident laser wave and the converted laser wave described in JP-A-57-211,125. The developing solution is preferably an alkaline aqueous solution containing an aromatic primary amine type color developing agent as a main component. As the color developing agent, an aminophenol compound is also useful, but a p-phenylenediamine compound is preferably used, and a typical example thereof is 3-methyl-4-amino-N-.
N, diethylaniline, 3-methyl-4-amino-N-
Ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-
Mention may be made of ethyl-N-β-methoxyethylaniline and their sulphates, hydrochlorides or p-toluenesulphonates. Two or more of these compounds can be used in combination depending on the purpose.

The pH of these color developing solutions is 9 to 12, preferably 9.
5 to 11.5.

The photographic emulsion layer after color development is usually bleached. The bleaching process may be performed simultaneously with the fixing process (bleach-fixing process), or may be performed individually. Further, in order to speed up the processing, a processing method of bleach-fixing processing after bleaching processing may be used.

The silver halide color photographic light-sensitive material of the present invention is generally washed with water and / or stabilized after the desilvering process.
The amount of rinsing water in the rinsing process depends on the characteristics of the photosensitive material (for example, depending on the materials used such as couplers), application, and further, the rinsing water temperature, the number of rinsing tanks (the number of stages), the replenishment system such as countercurrent and forward flow, and various other conditions. Therefore, it can be set in a wide range.

The silver halide color light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and accelerating the processing. For incorporation, it is preferable to use various precursors of color developing agents.

On the other hand, various known developing agents can be used for developing the black-and-white light-sensitive material of the present invention. That is, polyhydroxybenzenes such as hydroquinone, 2
-Chlorohydroquinone, 2-methylhydroquinone,
Catechol, pyrogallol, etc .; aminophenols,
For example, p-aminophenol, N-methyl-p-aminophenol, 2,4-diaminophenol, etc .; 3-pyrazolindones such as 1-phenyl-3-pyrazolidones, 1-phenyl-4,4'-dimethyl-3. -Pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, 5,5-dimethyl-1-phenyl-
3-pyrazolidone and the like; ascorbic acids and the like, alone or in combination. Further, the developer described in JP-A-58-55928 can also be used.

For detailed examples of developing agents, preservatives, buffers, and developing methods for black and white light-sensitive materials and their usage, see "Research Disclosure," No. 17643 (1978).
Published in December) XIX to XXI, etc.

〔Example〕

The present invention will be described in detail below with reference to examples. However, the present invention is not limited thereto.

Example 1 Preparation of Emulsion 1 An aqueous solution of potassium bromide and silver nitrate was added in an amount of 0.3 g per mol of Ag.
Approximately 20 ° C at 75 ° C with vigorous stirring in an aqueous gelatin solution containing 3,4-dimethyl-1,3-thiazoline-2-thione.
The addition was carried out at the same time, and a monodisperse silver bromide core emulsion having an average grain size of about 0.40 μm octahedron was obtained. A core chemical sensitization treatment was carried out by adding 6 mg of sodium thiosulfate and 7 mg of chloroauric acid (tetrahydrate) to 1 mol of silver and heating the emulsion at 75 ° C. for 80 minutes. The silver bromide grain core thus obtained was
Further shell formation was carried out in the same precipitation environment as the first time, and finally a monodisperse core / shell silver bromide emulsion having an average grain size of about 0.7 μm octahedron was obtained. The variation coefficient of particle size was about 10%.

1.5 mg sodium thiosulfate per mole silver was added to this emulsion.
1.5 mg of chloroauric acid (tetrahydrate) was added, and the mixture was heated at 60 ° C. for 60 minutes to carry out chemical sensitization treatment of Ciel to obtain an internal latent image type halogenated emulsion 1.

Emulsion 1 was prepared in the same manner as Emulsion 1 except that the compounds shown in Table 1 were added immediately after obtaining the core emulsion.
Emulsions 2-7 were obtained.

The following photographic light-sensitive material was prepared using Emulsion 1. The support is a paper support (thickness: 100 microns) laminated on both sides with polyethylene, and the coating side contains titanium white as a white pigment.

(Photosensitive layer composition) The components and the coating amounts shown in g / m ² are shown below. For silver halide, the coating amount in terms of silver is shown.

First layer (high-sensitivity red-sensitive layer) Emulsion 1 spectrally sensitized with a red sensitizing dye (ExS-1,2,3) ...
0.28 Gelatin 2.00 Cyan coupler (Exc-1) 0.30 Cyan coupler (Exc-2) 0.30 Anti-fading agent (Cpd-2,3,4,13 equivalent) 0.30 Coupler dispersion medium (Cpd-5) 0.06 Second layer (protective layer) Acrylic modified copolymer of polyvinyl alcohol (Modification degree
17%)… 0.04 Polymethylmethacrylate particles (average particle size 2.4 micron), silicon oxide (average particle size 5 micron) Equivalent… 0.10 Gelatin… 3.00 Gelatin hardener (H-1)… 0.34 First layer is nucleating As an agent, ExZK-1 was used in an amount of 10 ^-3 % by weight based on the coated amount of silver halide, and as a nucleation accelerator, Cpd-24 was used in an amount of 10 ^-2 % by weight. In each layer, alkanol XC (Dupont) and sodium alkylbenzene sulfonate were used as emulsification / dispersion aids, and succinate and Ma were used as coating aids.
gefac F-120 (manufactured by Dainippon Ink and Chemicals, Inc.) was used. (Cpd-19, 20, 21) was used as a stabilizer in the first layer. This sample was designated as sample number 101.

Samples except that Emulsions 2 to 7 were used instead of Emulsion 1
Samples 102 to 107 were prepared in the same manner as 101.

Pass a red filter through the above sample and perform wet exposure (1/10
20 CMS), the following development processing was performed.

The replenishing method of the washing water was a so-called countercurrent replenishing method in which the washing bath was replenished and the overflow solution of the washing bath was introduced into the washing bath and the overflow solution of the washing bath was introduced into the washing bath.
At this time, the carry-in ratio of the photosensitive material from the prebath was 35 ml / m ² , and the replenishment ratio was 9.1. [Color developer] Mother liquor Ethylenediaminetetrakismethylenephosphonic acid 0.5g Diethylene glycol 8.0g Benzyl alcohol 12.0g Sodium bromide 0.6g Sodium chloride 0.5g Sodium sulfite 2.0g N, N-diethylhydroxyamine 3.5g Triethylenediamine (1,4-diazabicyclo 〔2,2,2〕
Octane) 3.5 g 3-Methyl-4-amino-N-ethyl-N- (B-methanesulfonamidoethyl) -aniline sulfate 5.5 g Potassium carbonate 30.0 g Optical brightener (stilbene type) 1.0 g Pure water is added 1000 ml pH 10.50 pH was adjusted with potassium hydroxide or hydrochloric acid. [Bleaching fixer] Mother liquor Ammonium thiosulfate 100g Sodium bisulfite 21.0g Ethylenediaminetetraacetic acid iron (III) ammonium dihydrate 50.0g Ethylenediaminetetraacetic acid disodium dihydrate 5.0g Pure water added 1000ml pH 6.3 It was adjusted with water or hydrochloric acid.

[Wash water]

Pure water was used (mother liquor = replenisher) Here, pure water was obtained by ion exchange treatment to remove all cations other than hydrogen ions and all anions other than hydroxide ions in tap water to 1 ppm or less. Is.

The cyan color density of the obtained direct positive image was measured, and the results are shown in Table 2.

Dmax Dmin gamma shown in the table is determined as follows. That is, the abscissa is the logarithm of the exposure amount,
When the cyan color density is displayed on the vertical axis, a characteristic curve as shown in FIG. 1 is obtained. Dm is the cyan color density in the unexposed area
ax, the cyan color density in the area with sufficient exposure Dmi
When a tangent line is drawn on the characteristic curve at a point where n and the cyan color density are Dmin + (Dmax-Dmin) / 3, gamma is obtained by reversing the positive and negative signs of the slope of the tangent line.

This gamma is an index representing the degree of hard and soft gradation.

In Samples 102 to 107 containing the compound of the present invention, the minimum image density (Dmin) can be reduced while keeping the maximum image density (Dmax) high, and the gamma is large and hard and favorable results are obtained. Was given.

Example 2 Emulsions 21 to 25 were prepared by changing the time of addition of Compound I-1 in Emulsion 2 as shown in Table 3.

Samples except that Emulsions 21-25 were used instead of Emulsion 1
Samples 221-225 were prepared in the same manner as 101.

Further, in the sample 101, after preparing the coating liquid for the first layer, the compound I-1 was added so as to have a ^{concentration} of 2.5 × 10 ⁻⁴ mol / mol Ag to prepare a sample 231.

These samples were exposed and treated in the same manner as in Example 1, the cyan color density of the obtained direct positive image was measured, and the results are shown in Table 4.

As can be seen from Table 4, the materials using the compound of the present invention have a large gamma, a high contrast, and a small Dmin and favorable results as compared with those not using the compound. Further, when the compound of the present invention is used, it is preferable to add the compound after forming the coating solution and then during the emulsion formation, and most preferably during the core formation or before the chemical sensitization of the core. I understand.

Example 3 Emulsion 1 was used to prepare the following photographic light-sensitive material.

The support is a paper support (thickness: 100 μm) laminated on both sides with polyethylene, and contains titanium white as a white pigment on the coating side.

(Photosensitive layer composition) The components and the coating amounts shown in g / m ² are shown below. For silver halide, the coating amount in terms of silver is shown.

First layer (high-sensitivity red-sensitive layer) Emulsion 1 spectrally sensitized with a red sensitizing dye (ExS-1,2,3) ...
0.28 Gelatin ... 2.00 Cyan coupler (ExC-1) ... 0.30 Cyan coupler (ExC-2) ... 0.30 Anti-fading agent (Cpd-2,3,4,13 equivalent) ... 0.30 Coupler dispersion medium (Cpd-5) ... 0.06 Coupler solvent (Solv-7,2,3 equivalent) 0.20 Second layer (protective layer) Acrylic modified copolymer of polyvinyl alcohol (Degree of modification
17%)… 0.04 Polymethylmethacrylate particles (average particle size 2.4 micron), silicon oxide (average particle size 5 micron) Equivalent… 0.10 Gelatin… 3.00 Gelatin hardener (H-1)… 0.34 Emulsion dispersion aid for each layer As Alkanol XCC (Dupont
And sodium alkylbenzene sulfonate, and succinic acid ester and Magefac F-120 (manufactured by Dainippon Ink and Chemicals, Inc.) were used as coating aids. The first layer used (Cpd-19,20,21) as a stabilizer. This sample was designated as sample number 301.

Samples 302 to 304 were prepared by using the emulsions 2, 3, and 5 in place of the emulsion 1 in Samples 301 to 304, respectively.

A red filter is passed through these samples to obtain a wet exposure (1 /
After applying 20 CMS for 10 seconds, the same treatment as in Example 1 was performed. At that time, light of 0.5 lux (color temperature 5400K) was applied on the light-sensitive material film for 15 seconds from 15 seconds after the start of color development.

The cyan color density of the obtained direct positive image was measured, and the results are shown in Table 5.

It has been found that in the sample using the compound of the present invention, Dmin can be reduced while keeping Dmax large, and the contrast is high, and favorable results can be obtained.

Example 4 The following photographic light-sensitive material was prepared using the emulsion 1.

Paper support laminated on both sides with polyethylene (thickness 100
Micron) was coated on the front side with the following first to fourteenth layers, and on the back side with a multi-layer coating of the fifteenth to sixteenth layers to prepare a color photographic light-sensitive material. Titanium white is contained as a white pigment, and a slight amount of ultramarine is contained as a bluish dye on the coating side of the first layer of polyethylene.

(Photosensitive layer composition) The components and the coating amounts shown in g / m ² are shown below. For silver halide, the coating amount in terms of silver is shown. The emulsion used for each layer was prepared according to the method for preparing emulsion 1. However, the 14th
The layer emulsion used was a Lipman emulsion which was not surface-sensitized.

1st layer (anti-halation layer) Black colloidal silver 0.10 Gelatin 1.30 Second layer (intermediate layer) Gelatin 0.70 3rd layer (low-sensitivity red-sensitive layer) Red sensitizing dye (ExS-1,2,3) Silver bromide spectrally sensitized with (average grain size 0.3μ, size distribution [variation coefficient] 8
%, Octahedron) 0.06 Silver bromide spectrally sensitized with red sensitizing dye (ExS-1,2,3) (average grain size 0.45μ, size distribution 10%, octahedron)
0.10 Gelatin 1.00 Cyan coupler (ExC-1) 0.11 Cyan coupler (ExC-2) 0.10 Anti-fading agent (Cpd-2,3,4,13 equivalent) 0.12 Coupler dispersion medium (Cpd-5) 0.03 Coupler solvent (Solv-7,2,3 equivalent) 0.06 4th layer (high-sensitivity red-sensitive layer) Silver bromide spectrally sensitized with red sensitizing dye (ExS-1,2,3) (average grain size) Size 0.60μ, size distribution 15%, octahedron) ...
0.14 Gelatin 1.00 Cyan coupler (ExC-1) 0.15 Cyan coupler (ExC-2) 0.15 Anti-fading agent (Cpd-2,3,4,13 equivalent) 0.15 Coupler dispersion medium (Cpd-5) 0.03 Coupler solvent (Solv-7,2,3 equivalents) ... 0.10 Fifth layer (intermediate layer) Gelatin ... 1.00 Color mixing inhibitor (Cpd-7) ... 0.08 Color mixing inhibitor solvent (Solv-4,5 equivalents) ... 0.16 Polymer Latex (Cpd-8) ... 0.10 6th layer (low-sensitivity green-sensitive layer) Silver bromide spectrally sensitized with a green sensitizing dye (ExS-3) (average grain size 0.25μ, grain size distribution 8%) , Octahedron) ...
0.04 Silver bromide spectrally sensitized with a green sensitizing dye (ExS-3,4) (average grain size 0.45μ, grain size distribution 11%, octahedron) ...
0.06 Gelatin 0.80 Magenta coupler (ExM-1,2 equivalent) 0.11 Anti-fading agent (Cpd-9) 0.10 Anti-stain agent (Cpd-10,22 equivalent) 0.014 Anti-stain agent (Cpd-23) ... 0.001 Anti-stain agent (Cpd-12)… 0.01 Coupler dispersion medium (Cpd-5)… 0.05 Coupler solvent (Solv-4,6 equivalent)… 0.15 7th layer (high sensitivity green sensitive layer) Green sensitizing dye (ExS Emulsion 1 spectrally sensitized with −3, 4) (average grain size 0.6μ, grain size distribution 16%, octahedron) ...
0.10 Gelatin ... 0.80 Magenta coupler (ExM-1,2) ... 0.10 Anti-fading agent (Cpd-9) ... 0.10 Anti-staining agent (Cpd-10,22 equivalent) ... 0.013 Anti-staining agent (Cpd-23) ... 0.001 Stain Inhibitor (Cpd-12) ... 0.01 Coupler dispersion medium (Cpd-5) ... 0.05 Coupler solvent (Solv-4,6 equivalents) ... 0.15 8th layer (intermediate layer) Same as 5th layer 9th layer (yellow filter) Layer) Yellow colloidal silver… 0.20 Gelatin… 1.00 Color mixing inhibitor (Cpd-7)… 0.06 Color mixing inhibitor solvent (Solv-4,5 equivalent)… 0.15 Polymer latex (Cpd-8)… 0.10 Layer 10 (intermediate) Layer) Same as the fifth layer Eleventh layer (low-sensitivity blue sensitive layer) Silver bromide spectrally sensitized with a blue sensitizing dye (ExS-5, 6) (average grain size 0.45μ, grain size distribution 8%, Octahedron) ...
0.07 Silver bromide spectrally sensitized with blue sensitizing dye (ExS-5,6) (average grain size 0.60μ, grain size distribution 14%, octahedron) ...
0.10 Gelatin ... 0.50 Yellow coupler (ExY-1) ... 0.22 Anti-staining agent (Cpd-11) ... 0.00 Anti-fading agent (Cpd-6) ... 0.10 Coupler dispersion medium (Cpd-5) ... 0.05 Coupler solvent (Solv-2) ... 0.05 12th layer (high-sensitivity blue-sensitive layer) Silver bromide spectrally sensitized with a blue sensitizing dye (ExS-5,6) (average grain size 1.2μ, grain size distribution 21%, octahedron).
0.25 Gelatin ... 1.00 Yellow coupler (ExY-1) ... 0.41 Anti-staining agent (Cpd-11) ... 0.00 Anti-fading agent (Cpd-6) ... 0.10 Coupler dispersion medium (Cpd-5) ... 0.05 Coupler solvent (Solv-2) 0.10 13th layer (UV absorbing layer) Gelatin 0.15 UV absorber (Cpd-1,3,13 equivalents) 1.00 Color mixing inhibitor (Cpd-6,14 equivalents) 0.06 Dispersion medium (Cpd-5) … 0.05 UV absorber solvent (Solv-1,2 equivalent)… 0.15 Irradiation prevention dye… 0.02 (Cpd-15,16 grade) Irradiation prevention dye… 0.02 (Cpd-17,18 equivalent) 14th layer (protective layer) ) Fine grain silver chlorobromide (97% silver chloride, average grain size 0.2μ)
... 0.05 Acrylic modified copolymer of polyvinyl alcohol (Modification degree
17%) 0.02 Polymethylmethacrylate particles (average particle size 2.4 microns), Silicon oxide (average particle size 5 microns) Equivalents ... 0.05 Gelatin ... 1.50 Gelatin hardening agent (H-1) ... 0.17 15th layer (back layer) Gelatin: 2.50 16th layer (back surface protective layer) Polymethylmethacrylate particles (average particle size: 2.4 microns), silicon oxide (average particle size: 5 microns) Equivalents: 0.05 Gelatin: 2.00 Gelatin hardening agent (H-1): 0.11 each In the photosensitive layer, ExZK-1 as a nucleating agent is 10 ^-3 % by weight based on the coated amount of silver halide, and Cpd-24 is 10 ^-2 % as a nucleating accelerator.
Used by weight%. Furthermore, in each layer, alkanol XC (Dupont) and sodium alkylbenzene sulfonate as an emulsification dispersion aid, and succinate and
Magefac F-120 (manufactured by Dainippon Ink and Chemicals, Inc.) was used. For the layer containing silver halide and colloidal silver, (Cpd-
19,20,21) was used. This sample was designated as sample number 401.
Here, the structural formulas of the compounds used in the examples are shown.

Cpd-8 Polyethyl acrylate Solv-1 Di (2-ethylhexyl) phthalate Solv-2 Trinonylphosphate Solv-3 Di (3-methylhexyl) phthalate Solv-4 Tricresylphosphate Solv-5 Dibutylphthalate Solv-6 Trioctylphosphate Solv- 7 Di (2-ethylhexyl) sebacate H-1 1,2-bis (vinylsulfonylacetamido) ethane EXZK-1 7- [3- (5-mercaptotetrazole-
1-yl) benzamido] -10-propargyl-1,2,3,
4-Tetrahydroacridinium Perchlorate Samples 402 to 404 were prepared by using Emulsions 2, 3, and 5 in place of Emulsion 1 in the seventh layer.

After subjecting these samples to wet exposure (1/10 second 300 CMS), the same treatment as in Example 1 was performed.

The magenta color density of the obtained direct positive image was measured, and the results are shown in Table 6.

As shown in Table 6, in the sample of the present invention, it is possible to keep Dmax high while lowering Dmin, and it is hard to obtain favorable results.

[Effect of the present invention]

By forming an image using the direct positive photographic light-sensitive material of the present invention, a direct positive image having both a high maximum image density and a low minimum image density, high contrast and suitable for practical use can be obtained.

[Brief description of drawings]

FIG. 1 is a diagram showing a characteristic curve of a direct positive image obtained in the embodiment of the present invention.

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Claims (1)

[Claims] 1. A direct positive photographic light-sensitive material having at least one photographic emulsion layer containing an internal latent image type silver halide grain which has not been previously fogged, wherein the photographic emulsion layer has the following general formulas [A] and [B]. ], And at least one selected from the compounds represented by [C], a direct positive photographic light-sensitive material. Formula (A) Z-SO ₂ -S-M Formula (B) General formula [C] However, Z: an alkyl group (having 1 to 18 carbon atoms), an aryl group (having 6 to 18 carbon atoms), or a heterocyclic group, Y ₁ , Y ₂ : an aromatic ring (having 6 to 18 carbon atoms), or forming a heterocycle Atoms required for M: metal atom or organic cation n: integer of 2 to 10 Z, Y _{1 in the} general formula [A], [B] or [C]
And the alkyl group, aryl group, heterocyclic group, aromatic ring and heterocycle represented by Y ₂ may be substituted.