JPS6360371B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a silver halide photographic material with improved developability, and more particularly to a silver halide photographic material with improved developability, which contains a developing agent precursor with good stability over time. be. Generally, the image forming method for silver halide photographic materials is completed through steps such as development and fixing (or bleaching and fixing). This development step typically uses a developing agent well known in the art (e.g., “The Theory of the
Photographic Processes” 4th edition, THJames
The compound described in ed. pp. 298-324) is dissolved in an alkaline aqueous solution and used as a developer. However, the developer is unstable and easily oxidized by dissolved oxygen, etc., so preservatives are added to prevent this, but the composition of the developer does not change during storage. Since this phenomenon is easy to occur and difficult to control, a method of incorporating a developing agent into a silver halide photosensitive material has recently been proposed. Incorporating a developing agent into a photosensitive material not only simplifies the composition of the processing solution, which not only simplifies the management of the aforementioned developer, but also basically allows development to be carried out using only an alkaline bath. There are many advantages in simplifying or speeding up processing. Therefore, attempts have been made to incorporate a developing agent into a light-sensitive material. For example, photographic elements in which a black and white developing agent is incorporated into a light-sensitive material are disclosed in U.S. Pat.
It is described in No. 4209580 etc. However, in general, when a developing agent is incorporated into a photosensitive material as it is, the developing agent is oxidized in a relatively short period of time, which tends to cause desensitization, fogging, or contamination during storage of the photosensitive material. Further, there are drawbacks such as the developing agent loses its effectiveness and the resulting image density is insufficient. One method proposed to overcome these drawbacks is to incorporate a developing agent as a precursor into a photosensitive material. This developing agent precursor has no developing effect during storage and therefore does not undergo oxidation, and only releases the silver halide developing agent when it comes into contact with an appropriate activator (for example, an alkali, a nucleophile, etc.). It is a compound. Such precursors include, for example, metal salts (lead, cadmium, calcium, barium, etc.) of hydroquinone, catechol, etc. in U.S. Pat. No. 3,295,978; acyl halides of hydroquinone in U.S. Pat. No. 3,246,988 U.S. Pat. No. 3,462,266 describes a derivative of hydroquinone such as oxazine, U.S. Pat. No. 3,615,512 describes a lactone type developing agent precursor, and British Patent No. 1,258,924 describes a hydroquinone precursor having a quaternary ammonium group. Are listed. Also UK patent
1023701 describes acyl derivatives of 1-phenyl-3-pyrazolidinone. However, these conventional developing agent precursors gradually liberate the developing agent during storage, and this may be oxidized and lose its effectiveness, or become desensitized, cause fogging, or become colored products. thing,
Or the decomposition rate is very slow during the desired development;
These were not satisfactory, as they did not generate any developing agents. In other words, conventional developing agent precursors satisfy the following two conditions:
(1) It is stable against decomposition, oxidative deterioration, etc. during storage, and does not liberate the developing agent or deteriorate into other compounds. (2) The release rate during desired development is fast compared to the development time. , were not fully satisfied. Therefore, the first object of the present invention is to provide a silver halide photographic material with improved developability and which can be processed easily and rapidly. The third purpose is to provide a silver halide photographic material with extremely good stability over time.The third purpose is to provide a silver halide photographic material with high sensitivity.The fourth purpose is to provide a silver halide photographic material with high image density. An object of the present invention is to provide a silver photosensitive material. As a result of various studies conducted by the present inventors, these objects of the present invention have been achieved by a silver halide photographic material containing at least one layer of a developing agent precursor represented by the general formula (). General formula () [HX] [B] Here, HX represents an organic or inorganic acid, and B represents 1-phenyl-3-pyrazolidinone shown in the following general formula (). General formula () In the formula, R ₁ and R ₂ each independently represent a hydrogen atom or an alkyl group, and R ₃ and R ₄ each independently represent a hydrogen atom, an alkyl group, an alkoxycarbonyl group, or an aryl group. _R5 , _R6 and _R7
each independently represents a hydrogen atom, a halogen atom, a hydroxy group, an alkyl group, an alkoxy group, an aryl group, a carbonamide group or a sulfonamide group. [HX] and [B] in the general formula () represent a complex or an ion pair. Examples of organic acids represented by HX in the general formula () include sulfonic acids (methanesulfonic acid, dodecylsulfonic acid, p-toluenesulfonic acid, etc.), sulfinic acids (benzenesulfonic acid, p-toluenesulfonic acid, etc.), and sulfuric acid. Monoesters (monohexadecyl sulfate, monododecyl phenyl sulfate, etc.), carboxylic acids (trichloroacetic acid,
trimellitic acid, etc.), phosphoric acid esters (diphenyl phosphate, didodecyl phosphate,
phosphoric acid monotolyl ester, etc.), phosphite esters (phosphite diphenyl ester, phosphite dioctyl ester, etc.), phosphonic acids (phenylphosphonic acid, etc.), phenols (pentachlorophenol, 2,4-dinitrophenol, etc.) , pyruvic acid (phenylpyruvic acid, etc.), organic boron compounds (tetraphenylboron, etc.), and other inorganic acids.
Examples include HBF ₄ , HClO ₄ , HPF ₆ , HSbCl ₅ and the like. Preferred embodiments of the general formula () are as follows. R ₁ and R ₂ are each independently a hydrogen atom and a carbon number
It represents up to 15 alkyl groups (methyl group, ethyl group, hydroxymethyl group, acetoxymethyl group, benzoyloxymethyl group, tetradecanoyloxymethyl group, etc.), with hydrogen atom, methyl group or hydroxymethyl group being particularly preferred. R ₃ and R ₄ are each independently a hydrogen atom, an alkyl group with up to 12 carbon atoms (methyl group, ethyl group, etc.), an alkoxycarbonyl group with up to 13 carbon atoms (methoxycarbonyl group, ethoxycarbonyl group, hexyloxycarbonyl group, etc.) ) or an aryl group having up to 18 carbon atoms (phenyl group, 4-methoxyphenyl group, 2-methoxyphenyl group, 4-chlorophenyl group, 2-hydroxyphenyl group, 3-butoxyphenyl group, etc.), especially hydrogen Atom, phenyl group, 4-methoxyphenyl group, 2-methoxyphenyl group, and 2-hydroxyphenyl group are preferable. R ₅ , R ₆ and R ₇ are each independently a hydrogen atom, a halogen atom, a hydroxy group, an alkyl group having up to 12 carbon atoms (methyl group,
ethyl group, dodecyl group, etc.), alkoxy groups with up to 14 carbon atoms (methoxy group, butoxy group, dodecyloxy group, methoxyethoxy group, butoxyethoxy group, etc.), aryl groups with up to 12 carbon atoms (phenyl group,
p-tolyl group, etc.), carbonamide group with up to 13 carbon atoms (acetamido group, etc.) or sulfonamide group with up to 12 carbon atoms (methanesulfonamide group, etc.)
represents a hydrogen atom, a chlorine atom, a methyl group,
Or a methoxy group is preferred. The utility of the present invention is explained as follows. 1-phenyl-3-pyrazolidinone, which is a developing agent, is represented by B, and protonated 1-phenyl-3
When -pyrazolidinone is denoted by HB ⁺ , the proton dissociation equilibrium is expressed by the following formula. BH ⁺ Ka ---→ ←----B+H ⁺ (1) Therefore, if the concentration of each substance is shown in [ ], the dissociation constant Ka is given by the following formula. Ka=[B][H ⁺ ]/[BH ⁺ ] (2) Similarly, for acid HX, the following is true. HXKa ――――→ ←――――X ^- +H ⁺ (3) Ka = [X ^- ] [H ⁺ ] / [HX] (4) Here, 1-phenyl-3-pyrazolidinone B
Considering the acid-base competitive equilibrium between HX and HX, it can be expressed as follows. B+H×Kc ―――→ ←――――BH ⁺ X ^- (5) Kc＝[BH ⁺ ][X ^- ]/[B][HX] (6) Therefore, from equations (2) and (4) logKc＝pKa〓−pKa〓 (7) From equations (6) and (7), when pKa〓＞pKa〓〔BH ⁺ 〓＞
[B]. That is, protonated 1-
If the pKa of acid HX is smaller than the pKa of phenyl-3-pyrazolidinone, it is protonated 1.
-The concentration of phenyl-3-pyrazolidinone becomes higher than the concentration of free 1-phenyl-3-pyrazolidinone. protonated 1-phenyl-
3-pyrazolidinone is a free 1-
Since it is more stable than phenyl-3-pyrazolidone, by increasing the concentration of protonated 1-phenyl-3-pyrazolidinone, it becomes possible to stably incorporate the developing agent 1-phenyl-3-pyrazolidinone. . Since the pKa of protonated 1-phenyl-3-pyrazolidinone is about 4 to 5, the object of the present invention can generally be achieved by selecting an acid with a pKa smaller than this (e.g., sulfonic acid). . On the other hand, once the developing agent precursor of the present invention is developed, the pH of the system increases, so that the developing agent 1-phenyl-3-pyrazolidinone is quickly released by an acid-base reaction. The developing agent precursor represented by the general formula () of the present invention may be dispersed in a photosensitive material as a solid or dissolved in an organic solvent such as water, methanol, ethanol, dimethylformamide, etc. When dissolved and dispersed in an organic phase such as a polymeric solvent, it is separated from the aqueous phase, making it possible to incorporate it more stably. Examples of the 1-phenyl-3-pyrazolidinone compound represented by B preferably used in the present invention are shown below.

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

[Formula] Various types of organic acids can be used as the organic acid represented by HX in the general formula (), but arylsulfonic acids represented by the general formula () are particularly preferably used. General formula () R ₈ , R ₉ , R ₁₀ and R ₁₁ may be the same or different and each represents a hydrogen atom, an alkyl group having 1 to 22 carbon atoms, an alkenyl group having 1 to 22 carbon atoms, or an alkenyl group having 1 to 22 carbon atoms.
represents an alkoxy group, an aryl group having 6 to 24 carbon atoms, a hydroxy group, or a halogen atom. Two substituents among R ₈ to R ₁₁ may be combined to form a condensed ring. Polymeric arylsulfonic acids can also be used. The polymeric arylsulfonic acid may be a homopolymer made of arylsulfonic acid monomers such as styrene sulfonic acid, or other monomers such as acrylic acid, methacrylic acid, ethyl acrylate, butyl acrylate, acrylamide, acrylonitrile, diethyl maleate, A copolymer with styrene, N-vinylpyrrolidone, N-vinylpyridine, etc.) may also be used. Examples of arylsulfonic acid compounds represented by the general formula () are shown below.

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

Specific examples of the compounds of the present invention are shown below. The compound of the present invention can be easily synthesized by reacting 1-phenyl-3-pyrazolidinone with an acid in an organic solvent such as methanol, ethanol, ethyl acetate, or acetonitrile. A synthesis example is shown below. Synthesis Example 1 Synthesis of Compound Example (1) 8.1 g of 1-phenyl-3-pyrazolidinone and 9.5 g of p-toluenesulfonic acid were dissolved in 100 ml of methanol and stirred at 50°C for 1 hour. Methanol was distilled off under reduced pressure, 200 ml of ethyl acetate was added to the residue, and the mixture was stirred at room temperature for 30 minutes. The precipitated crystals were collected by filtration to obtain 16 g of the desired compound example (1). Yield 96%,
White crystal, melting point 160-161.5℃

[Table] Synthesis Example 2 Synthesis of Compound (2) 4.1 g of 1-phenyl-3-pyrazolidinone and 8.2 g of p-dodecylbenzenesulfonic acid were dissolved in 100 ml of methanol and stirred at 50°C for 2 hours. Methanol was distilled off under reduced pressure, and the residue was dissolved in 50 ml of ethyl acetate.
8.4 g of the target compound example (2) was obtained by crystallizing the crystal and filtering it. Yield 69%, white crystals Melting point
108~110℃

[Table] Synthesis Example 3 Synthesis of compound (6) 1,5-diphenyl-3-pyrazolidinone 11.9
9.5 g of g and p-toluenesulfonic acid were dissolved in 10 ml of methanol and stirred at 50°C for 2 hours. Distill the methanol under reduced pressure and add 200ml of ethyl acetate to the residue.
was added and stirred at room temperature for 30 minutes. The precipitated crystals were collected by filtration to obtain 10.7 g of the desired compound example (6). yield
52%, white crystals, melting point 112-114℃

[Table] Two or more developing agent precursors used in the present invention may be used in combination. The developing agent precursor of the present invention includes a silver halide emulsion layer, a coloring material layer, an undercoat layer, a protective layer, an intermediate layer, a filter layer, an antihalation layer, an image receiving layer, a cover sheet layer, a silver halide photographic light-sensitive material, It may be added to any of the other auxiliary layers. In order to add the developing agent precursor used in the present invention to these layers, it is necessary to add the developing agent precursor to the coating solution for forming the layer as it is or to add the developing agent precursor to the coating solution for forming the layer, or to add the developing agent precursor to the coating solution for forming the layer. It can be added by dissolving it at an appropriate concentration in a solvent that does not give any oxidation, such as water or alcohol. Alternatively, the developing agent precursor can be dissolved in a high boiling point organic solvent and/or a low boiling point organic solvent, and added by emulsifying and dispersing the solution in an aqueous solution. Also, JP-A-51-39853, JP-A No. 51-39853,
59942, 54-32552, US Pat. No. 4,199,363, etc., it may be impregnated into a polymer latex and added. In addition, the developing agent 1-phenyl-3-pyrazolidinone is added as a solid or dissolved in a solvent such as water, methanol, or ethanol to a coating solution containing an arylsulfonic acid polymer in advance, and the developing agent precursor is added in the coating solution. to form,
May be dispersed. The developing agent precursor may be added at any time during the manufacturing process, but it is generally preferable to add the developing agent precursor immediately before coating. The amount added is suitably 10 ^-9 mol to 10 -1 mol, preferably ^{10 -7 mol} to 10 ^-2 mol, per 1 m ² of silver halide photographic light-sensitive material. The compounds of the present invention can be used, for example, in coupler type color photographic materials. A common method for forming color images from color photographic materials is to convert silver halide materials into aromatic primary amines in the presence of color couplers that have the ability to form dyes by reacting with oxidized developing agents. This is a method for obtaining azomethine or indoaniline dyes by developing with a developing agent. This color development method was basically developed in 1935 by L.DMannees.
& L. Godowsky, various improvements have been made since then, and it is currently used in the industry worldwide today. In this system, subtractive color reproduction is usually used for color reproduction, with silver halide emulsions selectively sensitive to blue, green, and red, and yellow, magenta, and cyan color image-forming agents, which are complementary colors, respectively. is used. To form a yellow image, for example, an acylacetanilide or dibenzoylmethane coupler is used, and to form a magenta image, a pyrazolone, pyrazolobenzimidazole, cyanoacetophenone or indazolone coupler is mainly used. phenolic couplers, such as phenols and naphthols, are used primarily to form cyan images. Normally, color photographic materials are roughly divided into two types: an external method in which couplers are placed in a developing solution, and an internal method in which couplers are incorporated in each photosensitive layer of the material so as to maintain their independent functions. Ru. In the latter, the dye image-forming coupler is added to the silver halide emulsion. Couplers added to the emulsion must be non-diffusible (diffusion resistant) in the emulsion binder matrix. In the internal mold method, the processing process for color photographic materials basically consists of the following three steps. (1) Color development step (2) Bleaching step (3) Fixing step The bleaching step and the fixing step can be performed simultaneously. That is, the bleach-fixing process (so-called Blix)
Through this step, developed silver and undeveloped silver halide are desilvered. In addition to the two basic steps of color development and desilvering mentioned above, the actual development process involves the following steps in order to maintain the photographic and physical quality of the image.
Alternatively, an auxiliary process is involved, such as to improve the storage stability of the image. For example, a hardening bath is used to prevent excessive softening of the photosensitive film during processing, a stop bath is used to effectively stop the development reaction, an image stabilization bath is used to stabilize the image, and a removal bath is used to remove the backing layer of the support. Examples include processes such as a membrane bath. Conventionally known methods of adding or dispersing couplers to emulsions and methods of adding them to gelatin/silver halide emulsions or hydrophilic colloids are applicable. For example, a method of mixing and dispersing a coupler with a high boiling point organic solvent such as dibutyl phthalate, tricrediphosphate, wax, higher fatty acids and their esters, etc., for example, US Pat.
2322027, etc. Another method is to mix and disperse the coupler with a low boiling point organic solvent or a water-soluble organic solvent. A method of dispersing couplers in combination with a high boiling point organic solvent. For example, US Patent No.
Methods described in No. 2801170, No. 2801171, No. 2949360, etc. When the coupler itself has a sufficiently low melting point (for example, 75°C or lower), a method of dispersing it alone or in combination with other couplers to be used in combination, such as colored couplers or uncolored couplers. For example, the description in German Patent No. 1143707 is applicable. As dispersion aids, commonly used anionic surfactants (e.g. sodium alkylbenzene sulfonate, sodium di-octyl sulfosuccinate, sodium dodecyl sulfate, sodium alkylnaphthalene sulfonate, Fischer type couplers, etc.) and amphoteric type couplers are used. Surfactants (for example, N-tetradecyl/N.N dipolyethylene α betaine, etc.) and nonionic surfactants (for example, sorbitan, monolaurate, etc.) are used. Couplers used in combination with the compound of the present invention include, for example, the following known couplers. A specific example of a magenta coloring coupler is a U.S. patent
No. 2600788, No. 2983608, No. 3062653, No.
No. 3127269, No. 3311476, No. 3419391, No. 3127269, No. 3311476, No. 3419391, No.
No. 3519429, No. 3558319, No. 3582322, No.
No. 3615506, No. 3834908, No. 3891445, West German Patent No. 1810464, West German Patent Application (OLS) No. 2408665,
No. 2417945, No. 2418959, No. 2424467, Japanese Patent Publication No. 1973-6031, Japanese Patent Publication No. 51-20826, No. 52-58922
No. 49-129538, No. 49-74027, No. 50-
No. 159336, No. 52-42121, No. 49-74028, No. 50
-60233, No. 51-26541, No. 53-55122, etc. A specific example of a yellow emitting coupler is U.S. Patent No. 2875057.
No. 3265506, No. 3408194, No. 3551155,
3582322, 3725072, 3891445, West German Patent No. 1547868, West German Patent Application No. 2219917,
No. 2261361, No. 2414006, British Patent No. 1425020,
Special Publication No. 51-10783, Japanese Patent Publication No. 47-26133, No. 48-
No. 73147, No. 51-102636, No. 50-6341, No. 50
−123342, No. 50-130442, No. 51-21827,
These are described in No. 50-87650, No. 52-82424, No. 52-115219, etc. Specific examples of cyan couplers are U.S. Patent No. 2369929,
Same No. 2434272, No. 2474293, No. 2521908, Same No.
No. 2895826, No. 3034892, No. 3311476, No. 3311476, No.
No. 3458315, No. 3476563, No. 3583971, No.
3591383, 3767411, 4004929, West German patent application (OLS) 2414830, 2454329, JP 48-59838, 51-26034, 48-5055,
These are those described in No. 51-146828, No. 52-69624, and No. 52-90932. As a colored coupler, for example, a US patent
No. 3476560, No. 2521908, No. 3034892, Tokko Akira
No. 44-2016, No. 38-22335, No. 42-11304, No. 42-11304, No.
No. 44-32461, JP-A No. 51-26034, No. 52-
Specification No. 42121, West German Patent Application (OLS) 2418959
You can use those listed in the issue. As a DIR coupler, for example, the US patent
No. 3227554, No. 3617291, No. 3701783, No.
No. 3790384, No. 3632345, West German patent application (OLS)
No. 2414006, No. 2454301, No. 2454329, British Patent No. 953454, Japanese Patent Application Publication No. 1983-69624, No. 49-122335
Those described in Japanese Patent Publication No. 51-16141 can be used. Other than the DIR coupler, the light-sensitive material may also contain a compound that releases a development inhibitor upon development; for example, U.S. Pat. No. 3,297,445, U.S. Pat.
West German Patent Application (OLS) No. 2417914, Japanese Unexamined Patent Publication No. 1983-
Those described in No. 15271 and JP-A-53-9116 can be used. High boiling point organic solvents include, for example, US Pat. No. 2,322,027;
No. 2533514, No. 2835579, Special Publication No. 46-232333
No., U.S. Patent No. 3287134, British Patent No. 958441, Japanese Unexamined Patent Publication No. 1987-1031, British Patent No. 1222753, U.S. Patent No.
No. 3936303, Japanese Patent Application Publication No. 1983-26037, Japanese Patent Application Publication No. 1973-
82078, U.S. Patent No. 2353262, U.S. Patent No. 2852383, U.S. Pat.
No. 3554755, No. 3676137, No. 3676142, No. 3676142, No. 3676137, No. 3676142, No.
No. 3700454, No. 3748141, No. 3837863,
OLS2538889, JP-A-51-27921, JP-A No. 51-
No. 27922, No. 51-26035, No. 51-26036, No. 50
-62632, Special Publication No. 49-29461, US Patent
It is described in No. 3936303, No. 3748141, and Japanese Patent Application Laid-open No. 1521/1983. The compounds of the invention can also be used in various types of instant photography. For example, U.S. Patent Nos. 3134764, 3173929, 3929848,
A method using a dye developer disclosed in US Pat. No. 3706557, etc., for example, US Pat.
4013635, etc., which releases a diffusible dye. The compounds of the invention may be used, for example, in The Theory of
the Photographic Process, Chapter 12,
Principles and Chemistry of Color
Photography. Silver Dye Bleaeh Process,
4th ed., THJames ed., Macmillan, New
York, 1977, pp 363-366, may also be used. The compounds of the present invention can also be used in black-and-white photographic materials. Examples of black-and-white photosensitive materials include X-ray film for direct medical use, black-and-white film for general photography, lithographic film, and scanner film. Other constitutions of the silver halide photographic material of the present invention, such as a method for producing a silver halide emulsion, halogen composition, crystal habit, grain size, chemical sensitizer, antifoggant, stabilizer, surfactant, gelatin There are no particular restrictions on hardening agents, hydrophilic colloid binders, matting agents, dyes, sensitizing dyes, anti-fading agents, anti-color mixing agents, polymer latexes, brighteners, antistatic agents, etc. For example, Research
The description in Disclosure Vol. 176, p22-p31 (December 1978) can be referred to. Furthermore, there are no particular limitations on the exposure method, development method, etc. of the silver halide photographic light-sensitive material of the present invention, and known methods and known methods such as those described on pages 28 to 30 of the above-mentioned (Research Disclosure) may be used. Any of the treatment liquids can be applied. This photographic processing may be either photographic processing that forms a silver image (black and white photographic processing) or photographic processing that forms a dye image (color photographic processing), depending on the purpose. The processing temperature is usually chosen between 18°C and 50°C, but temperatures below 18°C or above 50°C may also be used. The developer used in black-and-white photographic processing can contain known developing agents. As the developing agent, dihydroxybenzenes (for example, hydroquinone), 3-pyrazolidinones (for example, 1-phenyl-3-pyrazolidinone), aminophenols (for example, N-methyl-p-aminophenol), etc. may be used alone or in combination. Can be done. The developing solution generally contains other well-known preservatives, alkaline agents, PH buffers, antifoggants, etc., and, if necessary, solubilizing agents, color toners, development accelerators, surfactants, antifoaming agents, etc. It may also contain water softeners, hardeners, viscosity-imparting agents, and the like. The photographic emulsion of the present invention can be subjected to a so-called "lith type" development process. "Lith-type" processing is used for photographic reproduction of line images or halftone dots.
This refers to a development process that uses dihydroxybenzenes as a developing agent and allows the development process to be carried out in a contagious manner under a low sulfite ion concentration (for details, see Mason, "Photographic Processing Chemistry" (1966), 163). ~described on pages 165). When forming a dye image, conventional methods can be applied.
For example, negative-positive method (e.g. “Journal of the
Society of Motion Picture and Television
Engineers, Vol. 61 (1953), pp. 667-701); developed in a developer containing a black and white developing agent to produce a negative silver image, followed by at least one uniform exposure or other A color reversal method in which a dye-positive image is obtained by performing appropriate fogging treatment and subsequent color development; a photographic emulsion layer containing a dye is exposed and developed to form a silver image, and this is used as a bleaching catalyst to bleach the dye. Silver dye bleaching method etc. are used.The color developer generally consists of an alkaline aqueous solution containing a color developing agent.The color developing agent is a known primary aromatic amine developer such as phenylenediamines (e.g. 4-amino-N , N-diethylaniline, 3-methyl-4-amino-N,N-diethylaniline, 4-amino-N-ethyl-N-β
-Hydroxyethylaniline, 3-methyl-4-
Amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfamide ethylaniline,
4-amino-3-methyl-N-ethyl-N-β-
methoxyethylaniline, etc.) can be used. Other Photography by LFAMason
Processing Chemistry (Focal Press, 1966)
pages 226-229, U.S. Patent No. 2193015, U.S. Patent No. 2592364
JP-A No. 48-64933, etc. may be used. After color development, the photographic emulsion layer is usually bleached. The bleaching process may be performed simultaneously with the fixing process, or may be performed separately. Bleach agents include iron (), cobalt (), chromium (), and copper ().
Compounds of polyvalent metals such as, peracids, quinones, nitroso compounds, etc. are used. The present invention will be further explained below with reference to Examples. Example 1 Comparison of compounds of the present invention and their controls for the effectiveness of developing agent precursors in the present invention
In order to evaluate the compound, it was dissolved and emulsified in a high boiling point organic solvent and added to a cellulose triacetate film support provided with an undercoat layer along with the developing agents and their precursors shown in Table 1. Samples 1-10 were prepared by coating emulsion layers. The amount of each substance applied was expressed numerically in the box as g/m ² or mol/m ² . (1) Emulsion layer negative silver iodobromide emulsion (grain size 1.5μ)
(Silver 1.6×10 ^-2 mol/m ² ) Magenta coupler Cp-1
(1.33×10 ^-3 mol/m ² ) Developing agent or its precursor
(1.33×10 ^-3 mol/m ² ) Gelatin (2.50 g/m ² ) (2) Protective layer gelatin (1.30 g/m ² ) 2,4-dichloro-6-hydroxy-s-triazine sodium salt (50 g/m 2 ) ^m2 ) These films were subjected to imagewise exposure for sensitometry and then subjected to the following color development process. Color development process Time Temperature 1 Color development 3'15'' 38℃ 2 Bleaching 6'30'' 〃 3 Water washing 2' 〃 4 Fixing 4' 〃 5 Water washing 4' 〃 6 Stability 1' 〃 Here the color development process The composition of each treatment liquid is as follows. Color developer water 800ml 4-(N-ethyl-N-hydroxyethyl)amino-2-methylaniline sulfate 5g Sodium sulfite 5g Hydroxylamine sulfate 2g Potassium carbonate 30g Potassium bicarbonate 1.2g Potassium bromide 1.5g Sodium chloride 0.2g trisodium nitrotriacetate 1.2g Add water 1 (PH10.1) Bleach solution water 800ml Ferric ammonium salt of ethylenediaminetetraacetic acid
100g Disodium ethylenediaminetetraacetate 10g Potassium bromide 150g Acetic acid 10g Add water 1 (PH6.0) Fixer water 800ml Ammonium thiosulfate 150g Sodium sulfite 10g Sodium hydrogen sulfite 2.5g Add water 1 (PH6.0) Stabilizing liquid water 800 ml Formalin (37%) 5 ml Dry well 3 ml Add water 1. The photographic properties obtained are shown in Table 1.

【table】

[Table] It is clear from Table 1 that in the samples containing the developing agent precursor according to the present invention, gamma, sensitivity, and color density increased with almost no increase in fog. The magenta coupler and developing agent used here are as follows.

【formula】

【formula】

【formula】

[Formula] Example 2 To evaluate the effectiveness of the developing agent precursor in the present invention, compounds of the present invention and their control compounds were prepared as in Example 1 on a paper support double-sided laminated with polyethylene. The developing agent or its precursor shown in Table 2 was applied to Sample 11.
Adjusted ~18. (1) Emulsion layer negative silver chlorobromide emulsion (grain size 0.7μ)
(Silver 5.12×10 ^-3 mol/m ² ) Yellow coupler Cp-2
(8.53×10 ^-4 mol/m ² ) Developing agent or precursor (5.12×10 ^-4 mol/m ² ) Gelatin (1.35 g/m ² ) (2) Protective layer gelatin (1.30 g/m ² ) 2, 4-dichloro-6-hydroxy-s-triazine (50 mg/m ² ) These films were subjected to imagewise exposure for sensitometry and then subjected to the following color development process. Color development processing Time Temperature 1 Color development 3'30'' 33℃ 2 Bleach-fixing 1'30'' 33℃ 3 Water washing 2'30'' 25-30℃ The composition of each processing solution in the color development process is as follows. Color developer Benzyl alcohol 15ml Diethylene glycol 8ml Ethylenediaminetetraacetic acid 5g Sodium sulfite 2g Anhydrous potassium carbonate 30g Hydroxylamine sulfate 3g Potassium bromide 0.6g 4-Amino-N-ethyl-N-(β-methanesulfonamide ethyl )-m-Toluidine 3/2 sulfate monohydrate 5g Add water 1 Adjust pH to 10.20 Bleach-fix solution Ethylenediaminetetraacetic acid 2g Ethylenediaminetetraacetic acid ferric salt 40g Sodium sulfite 5g Ammonium thiosulfate 70g Add water 1 The photographic properties obtained are shown in Table 2.

【table】

[Table] From Table 2, when a developing agent is added, sensitization occurs but fogging occurs, or fogging does not increase but desensitization occurs, but with the compound of the present invention, fogging does not increase. It can be seen that sensitization can be achieved without any The yellow coupler Cp-2 and developing agent used here are as follows. D-2 and D-3 are the same compounds as in Example 1 Example 3 The following photosensitive sheet and image receiving sheet were prepared. Photosensitive Sheet Photosensitive sheets 1 to 7 were prepared by coating the following emulsion layer and protective layer on a polyethylene laminated paper support. The developing agent and its precursors were dissolved in methyl alcohol and added to the emulsion. (1) Emulsion layer Silver iodobromide emulsion containing 4% silver iodide (silver 9.2
×10 ^-3 mol/m ² ) The developing agent or its precursor shown in Table 3 (1.0
×10 ^-6 mol/m ² ) Gelatin (1.50 g/m ² ) (2) Protective layer gelatin (1.0 g/m ² ) 2,4-dichloro-6-hydroxy-s-triazine sodium salt (0.01 g/m ² ) Image-receiving sheet A common diffusion transfer image-receiving sheet was prepared by immersing a polyethylene laminate paper having a 6 μm cellulose triacetate layer in an alkaline hydrolysis solution containing silver deposition nuclei for 1 minute. The alkaline hydrolyzate was prepared as follows. Dissolve 0.1 g of nickel nitrate in 2 ml of water, add to 100 ml of glycerin, and stir vigorously.
1 g of sodium sulfide dissolved in 2 ml of water was further added to prepare a dispersion of silver deposition nuclei of nickel sulfide.
20 ml of this dispersion was added to 1000 ml of water-methyl alcohol (1/1) solution in which 80 g of sodium hydroxide was dissolved.
was added to prepare an alkaline hydrolyzate containing silver deposition nuclei. Forced deterioration conditions for the photosensitive sheets 1 to 7 (60℃3
The samples that were kept for a day and those that were not kept were subjected to imagewise exposure for sensitomerite. Diffusion transfer development was carried out by spreading the following processing solution to a thickness of 0.1 mm between these photosensitive sheets and the image receiving sheet. Treatment liquid Potassium hydroxide (40% aqueous solution) 323ml Titanium dioxide 3g Hydroxyethylcellulose 79g Zinc oxide 9.75g N,N-bismethoxyethylhydroxylamine
75g Triethanolamine 45% aqueous solution 17.14g Tetrahydropyrimidinethione 0.4g 2,4-dimercaptopyrimidine 0.35g Uracil 90g Water 1193ml Measure the optical density of the resulting transferred silver image, and calculate the reciprocal of the exposure amount to obtain an optical density of 0.7. Sensitivity. The sensitivity of the additive-free sample (photosensitive sheet No. 1), which was not subjected to forced deterioration conditions, was set as 100, and the sensitivity is shown in Table 3 as a relative value.

【table】

[Table] Sample exposure is Precursor Transfer silver Transfer silver sheet Body Sensitivity Density Sensitivity Density
6 (4) 130 1.59 125 1.4
7
(This invention)
7 (7) 125 1.59 120 1.4
1
(This invention)
As shown in Table 3, Samples 2 to 7 to which a developing agent or a developing agent precursor was added were all highly sensitive compared to No. 1 to which no developing agent was added. However, in all of the developing agents (Samples 2 to 4) that have not been used as precursors, the transferred silver concentration significantly decreased under forced deterioration conditions.
In contrast, sample 5 to which the compound of the present invention was added
In Sample No. 7, there was only a slight decrease in transferred silver density while maintaining high sensitivity. The developing agents used here were D-1, D-3, D
-4 is the same as in Example 1. Example 4 Comparison of compounds of the present invention and their controls for the effectiveness of developing agent precursors in the present invention
In order to evaluate the compound, the developing agents and their precursors shown in Table 4 were dissolved and emulsified in dibutyl phthalate and ethyl acetate and added to the cellulose triacetate film support provided with an undercoat layer. Samples 20-24 were prepared by applying layers. The coating amount of each substance is shown in the box as g/m ² or mol/m ² . (1) Emulsion layer negative silver iodobromide emulsion (grain size 0.6μ)
(Silver 2.5×10 ^-2 mol/m ² ) Gelatin (2.50 g/m ² ) (2) Protective layer developing agent or its precursor
(1.33×10 ^-3 mol/) Gelatin (1.30 g/m ² ) 2,4-dichloro-6-hydroxy-s-triazine sodium salt (50 mg/m ² ) These films were subjected to imagewise exposure for sensitometry. The following black development process was carried out. Black and white development process Time Temperature 1 Black and white development 4' 20°C 2 Stop 1' 〃 3 Fixation 10' 〃 4 Water washing 10' Here, the composition of each processing solution in the black and white development process is as follows. Black and white developer water 800ml 1-phenyl-3-pyrazolidiline (phenidone) 0.2g Hydroquinone 12.0g Sodium carbonate 79.0g Sodium sulfite 45g Potassium bromide 1.9g Add water 1 Stop solution Acetic acid 1.5% aqueous solution Fixed Water landing 800ml Thiosulfuric acid Add 100 g of sodium and water 1 The photographic results obtained are shown in Table 4.

[Table] * Same as used in Example 1 From Table 4, samples 23 and 24 containing the precursor according to the present invention showed an increase in gamma and sensitivity with almost no increase in fog. It is clear that

Claims (1)

[Scope of Claims] 1. A silver halide photograph characterized in that at least one layer contains a compound of the following general formula () obtained by reacting 1-phenyl-3-pyrazolidinones with an organic or inorganic acid. photosensitive material. General formula () [HX] [B] Here, HX represents an organic or inorganic acid, and B
represents 1-phenyl-3-pyrazolidinone shown in the following general formula (). General formula () In the formula, R ₁ and R ₂ each independently represent a hydrogen atom or an alkyl group, and R ₃ and R ₄ each independently represent a hydrogen atom, an alkyl group, an alkoxycarbonyl group, or an aryl group. R ₅ , R ₆ and
R ₇ is each independently a hydrogen atom, a halogen atom,
Represents a hydroxy group, alkyl group, alkoxy group, aryl group, carbonamide group or sulfonamide group. Here, [HX] [B] in the general formula ()
represents a complex or an ion pair.