JPH0562727B2 - - Google Patents

Description

[Detailed description of the invention]

(A) Industrial Application Field The present invention relates to a method for developing silver halide photographic materials. (B) Prior art and its problems There have been many methods to increase the sensitivity of silver halide photographic emulsions, such as gold, platinum,
Noble metal sensitization using compounds of noble metals such as iridium, sulfur sensitization using sulfur-containing compounds such as thiourea and hypo, reduction sensitization using monovalent tin salts, polyamines, hydrazine derivatives, etc., or quaternary ammonium salts, Methods such as development acceleration using polyalkylene glycol and the like are known. Silver halide photographic emulsions with higher sensitivity can also be obtained by applying the above sensitization method to emulsions made of silver halide containing silver bromide as a main component, especially silver halide with increased grain size. well known. However, a photosensitive material having such a highly sensitive silver halide emulsion layer is subjected to pressure when it is bent, tightly wound, or transported through a processing machine. It has the disadvantage that scratches and fogging are likely to occur. It is known that this pressure or abrasion fog can be improved by including oil droplets of a high boiling point organic solvent in certain layers. (For example, JP-A No. 53-13923, JP-A No. 53-85421, JP-A No. 58-147734)
Incidentally, in recent years, silver halide photographic materials have been processed more and more quickly, and desired characteristics can be obtained by short-term development, for example within 1 minute, especially about 10 to about 50 seconds. may be required. However, it has been found that when a silver halide photographic material containing oil droplets as described above is developed for a short period of time, such as 50 seconds or less, a high maximum density cannot be obtained. (C) Object of the Invention The object of the invention is to provide a processing method that can obtain a high maximum density when rapidly processing a silver halide photographic light-sensitive material that prevents pressure or scratch fog. (D) Structure of the Invention The present invention provides a silver halide photographic material containing oil droplets in at least one of a silver halide emulsion layer and a hydrophilic colloid layer provided thereon as necessary. This is a processing method in which development is performed in 50 seconds or less using a developer containing approximately 50 mol % or more of potassium ions. Oil droplets for preventing pressure or scratch fog are contained in at least one of the silver halide emulsion layer and a hydrophilic colloid layer (for example, a surface protective layer, an intermediate layer, etc.) provided thereon if necessary. Preferably used oil droplets are, for example, disclosed in Japanese Patent Application Laid-open No. 1983-
99928 can be arbitrarily selected. For example, boiling point at normal pressure
It can be selected from carboxylic acid esters, phosphoric acid esters, carboxylic acid amides, ethers, and substituted hydrocarbons with a temperature of 150°C or higher. Specific examples include di-n-butylphthalate, di-isooctylphthalate,
Dimethoxyethyl phthalate, di-n
-butyl adipate, diisooctyl azelenate, tri-n-butyl citrate, tricresyl phosphate, tri-n-
Butyl phosphate, triisooctyl phosphate, N・N-diethylcaprylic acid amide, N・
N-dimethylpalmitic acid amide, n-butyl-
m-pentadecyl phenyl ether, ethyl-
Examples include 2,4-tert-butyl phenyl ether and chlorinated paraffin. The amount of oil droplets used is approximately 2
It ranges from about 150% by weight, preferably from about 5 to about 100% by weight. A high boiling point organic solvent can be made into oil droplets by a known method, that is, by dissolving it in a low boiling point solvent such as methyl acetate, ethyl acetate, butyl propionate, or cyclohexanol, and by dissolving anionic solvents such as alkylbenzenesulfonic acid and alkylnaphthalenesulfonic acid. It is mixed with an aqueous solution containing a hydrophilic colloid material such as gelatin containing a surfactant and a nonionic surfactant such as sorbitan sesquioleate and sorbitan monolaurate, and then mixed with a colloid mill, homogenizer, or ultrasonic dispersion device. The dispersion obtained by emulsification and dispersion may be added and applied as a coating solution. Further, additives such as antifoggants, developing agents, and other photographically useful chemicals can be included in the high-boiling organic solvent. Gelatin is mainly used as a hydrophilic colloid substance used in the emulsion layer, surface layer, intermediate layer, undercoat layer, back layer, etc. constituting the silver halide photographic light-sensitive material used in the present invention. Molecular substances (e.g., styrene-maleic anhydride copolymer, condensate of styrene-maleic anhydride and polyvinyl alcohol, copolymer or blend composition of styrene-maleic acid copolymer and acrylamide, acrylic acid copolymer, etc.) ), hydrophilic binders such as natural polymeric substances (e.g. colloidal albumin, casein, cellulose derivatives, agar, sodium alginate, dextran, gum arabic, starch derivatives, etc.), vinyl polymer latex, etc. I can do it. A hardening agent and a surfactant are used in these hydrophilic colloid layers. Hardeners include aldehyde compounds such as formaldehyde and glutaraldehyde, titone compounds such as diacetyl and micropendione, and 2-hydroxy-4,6-
Compounds with reactive halogens such as dichloro-1.3.5 triazine, divinyl sulfone, reactive olefin compounds as described in U.S. Pat. No. 3,635,718, N-methylol compounds as described in U.S. Pat. No. 2,732,316, U.S. Pat. No. 3,103,437. Isocyanates as described in U.S. Pat. No. 3,017,280;
Aziridine compounds as described in US Pat. No. 2983611, carbodiimide compounds as described in US Pat. No. 3,100,704, epoxy compounds as described in US Pat. No. 3,091,537, halogen carboxaldehydes such as mucochromic acid, dioxane derivatives such as dihydroxydioxane, chromium Alum, potash alum,
There are inorganic hardeners such as zirconium sulfate.
These can be used alone or in combination of two or more. Specific examples of surfactants include natural surfactants such as saponin, nonionic surfactants such as alkylene oxide, glycerin, and glycidol, higher alkylamines, quaternary ammonium salts, pyridine, and other complexes. rings,
Cationic surfactants such as sulfoniums, anionic surfactants containing acidic groups such as carboxylic acids, phosphoric acids, sulfuric acid ester groups, and phosphoric ester groups, amphoteric surfactants such as amino acids, aminosulfonic acids, and sulfuric or phosphoric acid esters of amino alcohols. There are surfactants and the like, and these can be used alone or in combination of two or more. The silver halide emulsion used in the practice of the present invention can be prepared by a known or commonly used method, including methods for producing and dispersing silver halide, silver halide composition (for example, silver chloride, silver bromide, iodobromide, etc.). silver, silver chlorobromide, etc.), the size and crystal habit of silver halide grains, the ratio of silver halide to gelatin, and the pH of silver halide emulsions.
Although there are no restrictions on the type and amount of chemical sensitizers, PAg, chemical sensitizers, other additives, gelatin, and other binders, preferably used silver halide has an average particle size of about 0.4. Silver bromide, silver chlorobromide containing approximately 50 mol% or more of silver bromide,
Silver iodobromide and silver chloroiobromide. Supports used for silver halide photographic materials include paper laminated with baryta or polyolefin resin, transparent films made opaque by adding dyes or pigments such as titanium oxide, salesrose acetate films, and polystyrene films. , polyethylene terephthalate film, polycarbonate film, and the like. In the present invention, a silver halide photographic light-sensitive material containing oil droplets is developed for a short time and then subjected to a fixing process. The developer used in the present invention includes alkaline agents (e.g. carbonates, sodium hydroxide, potassium hydroxide, lithium hydroxide, etc.), developing agents (e.g. hydroquinone and its derivatives such as methylhydroquinone, 1-phenyl-3- pyrazolidone and its derivatives such as 4,4-dimethyl-1-phenyl-3-pyrazolidone, metol, etc.), preservatives (e.g. sulfites, bisulfites, etc.), antifoggants (bromides, iodides, mercapto compounds, benzotriazole and its derivatives), and other known additives. The developing solution used in the present invention has a ratio of potassium ions to the total number of moles of alkali metal ions such as sodium, potassium, and lithium from about 50 to
It is in the range of 100 mol%. For example, 20-30 mol%
Although the effect of the present invention can be seen to some extent even with potassium ions up to 100%, when a silver halide photographic light-sensitive material containing oil droplets in an amount sufficient to prevent pressure or abrasion fog is subjected to short-term development, Difficult to obtain maximum concentration. The preferred potassium ion ratio is about 70-100
It is mole%. Also, the amount of potassium ions is approximately
0.5 mol/l, preferably about 0.7 mol/l or more is preferred. The development processing time depends on the processing temperature, but it is 10 to 50 minutes.
seconds. Generally, development processing is performed at 30 to 45°C for 10 to 40 seconds. As the fixer, any known fixer such as a quick fixer can be used. Such development and fixing processing is normally performed using an automatic processing machine in which processing temperature and time are controlled. (E) Examples The present invention will be explained in detail below using Examples, but the present invention is not limited to these embodiments. Example 1 A silver iodobromide emulsion (average grain size 0.5 μm) containing 1.2 mol % of silver iodide was prepared by a conventional ammonia method. This emulsion was chemically ripened at 60° C. for 60 minutes with the addition of 20 mg of sodium thiosulfate per mole of silver halide and 10 mg of chloroauric acid per mole of silver halide. PH
After adjusting to 5.8, add sensitizing dye, hardener, stabilizer,
Samples A and B were prepared by adding a surfactant and coating on polyethylene laminated paper at a silver content of 3.5 g/m ² together with the following protective layer coating solution containing a hardening agent and a surfactant.

[Table] was prepared and added as follows.
65g of dioctyl phthalate and 8g of ethyl acetate
1g of sodium triisopropylnaphthalene sulfonate mixed and dissolved at ℃ and heated this solution to 50℃
was added to 100 c.c. of a 6% aqueous gelatin solution with stirring, and then dispersed with a homogenizer.
A dispersion liquid was prepared. After exposing samples A and B for sensitometry, they were developed with the following developing solutions [] to [] at 35°C for 20 seconds, followed by fixing, washing with water, and drying using a conveyor roller type automatic developing machine.

[Table] Table 1 shows the presence or absence of pressure fog and the maximum reflection density.

[Table] The processing method of the present invention using Sample B and developer [ ] can produce high maximum density without pressure fog. Example 2 Sample C was prepared in which the DOP of Sample B of Example 1 was contained in the silver halide emulsion layer. 35 using the developer solution [] to [] of Example 1.
The test was conducted under the same conditions as in Example 1, except that development was carried out at 35 seconds. The results are shown in Table 2.

[Table] Example 3 Silver iodobromide with an average grain size of 0.8 μm (silver iodide 1.5 mol%)
An emulsion was prepared and coated as in Example 1.
During coating, the protective layer was divided into an upper layer and a lower protective layer, and multilayer coating was performed together with the emulsion layer. Samples D and E each having the following structure as a protective layer were prepared (containing a hardening agent and a surfactant).

[Table] Things.
The results of development processing under the same conditions as Example 2 are shown in the third example.
Shown in the table.

[Table] Example 4 The following developing solutions [] and [] to [] were prepared. (g/l)

【table】

[Table] Developer solutions [], [], and [] contain sodium sulfite and sodium hydroxide in [], and the proportion of potassium ions to the total cations becomes 35 mol%, 70 mol%, and 100 mol% in order. As such, the potassium salt is used. Sample B of Example 1 was developed under the conditions of Example 1. The maximum reflection density is shown in Table 4.

[Table] This result was also confirmed in the maximum transmission density of a silver halide photographic material using a polyester film support. (F) Effects of the Invention According to the present invention, a high maximum density can be obtained even when a high-sensitivity silver halide photographic material that is free from pressure or abrasion fog is subjected to short-time development processing.

Claims (1)

[Claims] 1. A silver halide photographic material containing oil droplets in at least one of the silver halide emulsion layer and a hydrophilic colloid layer provided thereon as necessary,
The ratio of potassium ions to the total cations is approximately 50
A processing method in which development is performed in less than 50 seconds using a developer with a mol% or higher content.