JPH0667369A - Image forming method, and silver halide photographic sensitive material and developer to be used for the same - Google Patents

Abstract

PURPOSE:To form a practicable image on a silver halide photographic sensitive material imagewise exposed in advance by using an enzimatic reaction and an extremely stable developer or an activator processing agent and a development processing method same as usual development processing. CONSTITUTION:This image-forming method is that for development processing the silver halide photographic sensitive material imagewise exposed in advance by using a developing agent precursor and an enzyme, and the photographic sensitive material and the developer are used for this method.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an image forming method for obtaining an image by causing a developing agent precursor and an enzyme to act on a silver halide photographic light-sensitive material which has been imagewise exposed in advance, and a silver halide photographic light-sensitive material used therefor. It relates to materials and processing agents.

[0002]

2. Description of the Related Art There are various well-known methods for forming an image by exposing a silver halide photographic light-sensitive material to an image and causing a developing agent or a developing agent precursor to act thereon. Has been. However, it has not been known that an enzyme reaction can be used as one of the image forming methods. For example, it has been known that the enzyme concentration and the silver image concentration can be made to have a proportional relationship as proposed in JP-A-58-10344, but image formation using a normal silver halide photographic light-sensitive material. It has not yet been known that a light-sensitive material that has been imagewise exposed in advance can be subjected to imagewise image formation by utilizing an enzymatic reaction in the same manner as the method.

[0003]

SUMMARY OF THE INVENTION Therefore, the problem to be solved by the present invention is to develop a developing agent in a silver halide photographic light-sensitive material which has been imagewise exposed in advance, by developing a developing agent precursor with an enzyme. Print, medical,
An object of the present invention is to provide an image forming method capable of forming an image usable in fields such as amateur photography, a silver halide photographic light-sensitive material and a developing agent used therefor.

[0004]

DISCLOSURE OF THE INVENTION The above-mentioned problems of the present invention include a halogen precursor which has been imagewise exposed in advance in the presence of a developing agent precursor and an enzyme capable of hydrolyzing the developing agent precursor in an alkaline aqueous solution to generate a developing agent. This can be achieved by developing the silver halide photographic light-sensitive material.

The enzyme used in the present invention has a pH of 7.0.
The alkaline hydrolase which can act on a substrate (in the present invention, a developing agent precursor) in the above alkaline aqueous solution to hydrolyze the substrate to produce a developing agent can be mentioned. Further, the alkaline hydrolases used in the present invention have specific substrates that act on them, and it is necessary to select and use a developing agent precursor as a substrate. Examples of such a combination of a developing agent precursor and an alkaline hydrolase include a carboxyl ester of a developing agent and an alkaline acylhydrolase such as lipase, acetylcholinesterase, cholinesterase, or the like. Phosphoric acid monoester and alkaline phosphatase, developing agent phosphoric acid diester and alkaline phosphodiesterase, developing agent sulfate ester and alkaline sulfatase, developing agent O-glycoside and alkaline glycoside hydrolase ( Amylase, glucosidase, galactosidase, mannosidase, fructofuranosidase, etc.), developing agent N-glucoside and alkaline N-glucoside hydrolase, developing agent ether and alkaline Ether hydrolase can be mentioned

The enzyme used in the present invention can be purchased as a commercial product (for example, Sigma Co.), or as described in Hiroki Horikoshi, Journal of Japanese Society of Agricultural Chemistry, Vol. 63, No. 8, 1343 (1989). Produced using alkaline microorganisms, Zephren, P.P. L. It can also be used after being extracted and purified from tissue cells or cells according to the method described by Holle, translated by Iwao Tabushi, "Enzyme Reaction Mechanism", Society Publishing Center (1977), pp. 15 et seq.

The enzyme used in the present invention is used as an enzyme which is purified and then dried and solidified, or an aqueous solution which is stabilized by a buffering agent, a stabilizing agent or the like, but is preferably stabilized by a pH buffer solution and salts. Used as a prepared aqueous solution. pH
As the buffer used in the buffer solution, edited by the Japanese Biochemical Society,
The biochemical data book, (I), 5th edition, Tokyo Kagaku Dojinsha, (1989), pages 17 to 24 can be selected and used, preferably ammonium sulfate and citric acid. A buffering agent that does not inhibit an ordinary enzyme activity such as sodium, sodium phosphate, and triethanolamine can be used, and salts for stabilizing are sodium chloride, sodium sulfate, magnesium chloride, magnesium acetate, zinc chloride, zinc acetate, Zinc sulfate or the like is preferably used.

To add the enzyme to the silver halide emulsion layer or other hydrophilic colloid layer, a necessary amount of the enzyme buffer solution may be added directly to the silver halide emulsion or the hydrophilic colloid solution. Also, as another method of adding an enzyme to a silver halide emulsion or a hydrophilic colloid solution, Ichiro Chibata, "Immobilized Biocatalyst", Kodansha (1986), 15
According to the method described in detail on the following pages, a so-called immobilized enzyme is prepared by preliminarily immobilizing the enzyme by a carrier binding method, a cross-linking method or an encapsulation method, and then added and dispersed in a desired silver halide emulsion or hydrophilic colloid solution. There is also a way to do it. At this time, the enzyme may be immobilized on gelatin forming a silver halide emulsion or a hydrophilic colloid solution.

The enzyme of the present invention may be added to a silver halide emulsion or other hydrophilic colloid solution at any time during the process for producing a silver halide photographic light-sensitive material, but it is preferably halogenated. This is the period after the chemical ripening of the silver emulsion and immediately before the coating. The enzyme-added silver halide emulsion or hydrophilic colloid solution as described above is coated on a suitable support and dried to be used as a silver halide photographic light-sensitive material.

The enzyme thus added to the silver halide emulsion or hydrophilic colloid solution is stable,
The enzyme in the silver halide photographic light-sensitive material obtained by drying under a drying condition of 5 ° C. or lower hydrolyzes the developing agent precursor, and has sufficient activity to generate a developing agent sufficient to obtain a negative image from a photo image. keeping.

The enzyme can be used by adding it to either the silver halide emulsion layer or the hydrophilic colloid layer, but is preferably used by adding it to the hydrophilic colloid layer other than the silver halide emulsion layer.

The enzyme of the present invention may be added to the silver halide emulsion layer or the hydrophilic colloid layer in an amount of from 2 × 10 ² units to 1 × 10 ¹⁰ units per mol of silver halide, but is preferably used. From 1 × 10 ⁴ units to 2 × 10 ⁸ units.

The unit referred to here is 1 micromol of the developing agent precursor as a substrate at the optimum pH of the enzyme.
It means the amount of enzyme that can be hydrolyzed in 1 minute at ° C.

The enzyme can also be used by adding it to the development processing agent. To add the enzyme to the processing agent,
This can be achieved by adding a necessary amount of the enzyme buffer solution to the development processing agent whose pH is adjusted to a pH at which the enzyme can stably exist. When the enzyme is immobilized on the water-soluble polymer, a necessary amount of the immobilized enzyme prepared in advance may be directly added to the developing agent.

When the enzyme of the present invention is added to the development processing agent, the addition amount is from 20 units to 1 × 10 ¹⁰ units, preferably 1 × 10 ⁵ units per liter of the development processing agent.
³ units to 1 × 10 ⁷ units.

The developing agent precursors used in the present invention are typically derived from developing agents used in the art. The developing agent used as the starting material for the developing agent precursor is described by James (THJAMES), Theory of the Photographic Pro
cess), 4th revised edition, pages 298 to 326, Macmillan Publishing C
o., Inc.) 1977, Basics of Photographic Engineering, Silver Salt Photography, Photographic Society of Japan, pp. 323 and after (Corona Publishing, 19
1979) and Akira Sasai, Chemistry of Photography, 161 to 1
Page 65 (published by Photo Kogyo Publishing, 1982), hydroquinone, catechol, pyrogallo.
And dihydroxybenzenes such as chlorohydroquinone, aminophenols such as methyl, para-aminophenol, amidole, glycine, atom, and iconogen, phenyl such as phenidone, methylphenidone, dimezone and dimezone S. Pyrazolidones, paramine, orthomine, diethylparamine, CD-2, CD-3, C
Diaminophenylenes such as D-4, reductones such as ascorbic acid, alicyclic developing agents such as 4-amino-5-pyrazolones, 1,3-diazines and pyrimidine derivatives can be used.

Carboxyl ester compounds, phosphoric acid monoester compounds, phosphoric acid diester compounds, sulfuric acid ester compounds, o-glycoside compounds, n-glucoside compounds, ether compounds used in the present invention using these developing agents as starting materials. In order to obtain a developing agent precursor such as a chain amide compound, it is possible to synthesize by using a well-known organic synthesis method.
Detailed synthesis conditions are already well known. Also, some compounds can be purchased as commercial products.

The developing agent precursor used in the present invention can be used by adding it to a silver halide emulsion layer or other hydrophilic colloid layer. At this time, the developing agent precursor is preferably added to a silver halide emulsion layer or a hydrophilic colloid layer different from the above-mentioned enzyme-added layer.

To add the developing agent precursor to the silver halide emulsion layer or other hydrophilic colloid layer, water or a water-miscible organic solvent such as alcohols, ketones, esters, amides is used. It may be added to the silver halide emulsion or the hydrophilic colloid solution used in the present invention after being dissolved in.

The developing agent precursor used in the present invention may be added to the silver halide photographic light-sensitive material at any time during the process for producing the photographic light-sensitive material. For example, when it is added to a silver halide emulsion, it can be added at any time from the start of chemical ripening to before coating, but it is preferably added at any time after the end of chemical ripening and immediately before coating. .

The amount of the developing agent precursor of the present invention added to the silver halide photographic light-sensitive material is 0.
The amount is preferably 001 to 10 mol, more preferably 0.1 to 2 mol.

Further, the developing agent precursor of the present invention can be used by adding it to a developing treatment agent. The developing agent precursor is added to the developer by dissolving it in water or an organic solvent miscible with water, for example, alcohols, ketones, esters, amides, etc. and adding it to the developer of the present invention. Good.
The amount of the developing agent precursor used in the present invention added to the developer is 0.001 to 10 mol, preferably 0.01 to 1 mol, per liter of the developer.

When the developing agent precursor and the enzyme of the present invention are simultaneously present in the developing agent for the developing treatment, the developing agent precursor and the enzyme are separately prepared in advance and immediately before the developing treatment. It is preferable to use them as a mixture. That is,
A method of obtaining an image by developing an alkaline aqueous solution of a developing agent precursor and an alkaline aqueous solution of an enzyme just before performing the developing treatment to form a uniform alkaline developing agent and then developing the previously exposed silver halide photographic light-sensitive material. Immediately before performing the developing treatment to the alkaline aqueous solution of the developing agent precursor, a necessary amount of the enzyme buffer solution is added to form a uniform alkaline developing treatment agent, and the pre-exposed silver halide photographic light-sensitive material is subjected to the developing treatment to form an image In order to obtain a uniform alkaline developing agent by adding a necessary amount of a developing agent precursor immediately before performing the developing treatment to a stable alkaline aqueous solution of an enzyme, the silver halide photographic light-sensitive material previously exposed is developed. To obtain an image. By adopting such a method, the developing agent precursor and the enzyme can be stably stored until immediately before the development processing.

As another method of image formation, a silver halide photographic light-sensitive material containing no substrate and enzyme of the present invention is coated with an aqueous solution of an enzyme, dried, and exposed to an image to contain a developing agent precursor. A method of developing treatment with an alkaline developer, exposing an image to a silver halide photographic light-sensitive material containing no substrate and enzyme of the present invention, applying an aqueous solution of the enzyme and then drying, and using an alkaline developer containing a developing agent precursor. Method of developing treatment, an alkaline activator treating agent containing an enzyme after applying an aqueous solution of a developing agent precursor to a silver halide photographic light-sensitive material containing no substrate and enzyme of the present invention, followed by drying and exposing the image. Development method, the substrate of the present invention and an enzyme-free silver halide photographic light-sensitive material are exposed to an image, and then an aqueous solution of a developing agent precursor is applied and dried to contain an enzyme. A method of developing with a alkaline activator processing agent, exposing the image to a silver halide photographic light-sensitive material containing no substrate and enzyme of the present invention, and then developing the image with an alkaline developer containing a developing agent precursor. There is a method of performing development processing separately from an alkaline activator processing agent containing an enzyme.

Furthermore, the silver halide photographic light-sensitive material containing the developing agent precursor of the present invention can be subjected to development processing with an alkaline activator processing agent containing the enzyme of the present invention after image exposure to obtain an image. it can.

Further, the halogenated photographic light-sensitive material containing the enzyme of the present invention can be subjected to image development to develop an image with a developer containing the developing agent precursor of the present invention to obtain an image.

Further, the silver halide photographic light-sensitive material containing the enzyme and the developing agent precursor of the present invention can be subjected to development processing with an alkaline activator processing agent after image exposure to obtain an image.

Specific examples of the substrate (developing agent precursor) and enzyme which can be used in the image forming method according to the present invention are shown below, but the present invention is not limited to these specific examples.

Specific Example Developing Agent Precursor and Enzyme 1. Ascorbic acid 2-acetate and alkaline lipase [EC 3.1.1.3] 2. Ascorbic acid 2-phosphate and alkaline phosphatase magnesium salt [EC 3.1.3.1] 3. 3. Ascorbic acid 2-diphosphate and alkaline phosphodiesterase [EC 3.1.4.1] 4. Ascorbic acid 2-sulfate and alkaline sulfatase magnesium salt [EC 3.1.6] 5. Ascorbic acid 2-O-α- and alkaline α-glucosidase glucoside [EC 3.2.1] 6.2-Aminoascorbic acid 2-N- and alkaline α-glucosidase glucoside [EC 3.2.2] 7. 2-Butyl ether ascorbate and alkaline etherase [EC 3.3.2] In addition, the EC number of the enzyme is shown in [].

In the image forming method using the developing agent precursor and the enzyme of the present invention, it is preferable to add a developing agent as an auxiliary developing agent to the extent that the enzymatic reaction is not inhibited. The developing agent is added to the silver halide photographic light-sensitive material or the developer so that the activity of the enzyme is not lost. For example, when the enzyme is added to the silver halide emulsion layer or the hydrophilic colloid layer of the silver halide photographic light-sensitive material,
The developing agent is added by selecting a silver halide emulsion layer other than the enzyme-added layer or a hydrophilic colloid layer, or by adding it to the developing treatment agent. When the enzyme is added to the developer, the developing agent is added to the silver halide photographic light-sensitive material. However, this does not apply when the developing agent does not affect the activity of the enzyme.

Next, the silver halide photographic light-sensitive material of the present invention will be described. The silver halide photographic light-sensitive material used in the present invention has at least one emulsion layer composed of a negative type silver halide emulsion. There is no particular limitation on the halogen composition of the silver halide emulsion used, and any composition such as silver chloride, silver chlorobromide, silver iodobromide, silver iodobromochloride can be used.

The grain size distribution of the silver halide grains used in the present invention is not particularly limited, it can have a relatively broad grain size distribution, and 90% of all grains can be used.
It may have a narrow grain size distribution, such as a monodisperse emulsion having a grain size occupying within ± 40% of the average grain size.

There is no particular limitation on the size of the silver halide grains used in the present invention, and the shape may be a regular crystal form such as a cube or octahedron.
It may have an irregular crystal form such as spherical, plate-like, clam-like, or epitaxial.

The silver halide grains used in the present invention can be prepared by any known method. That is, any of an acidic method, a neutral method, an ammonia method and the like may be used. As a reaction mode of the soluble silver salt and the soluble halogen salt, any one of a forward mixing method, a back mixing method, a simultaneous mixing method, a combination thereof and the like may be used. Good. As one of the simultaneous mixing methods, the silver ion concentration (pA
g) is kept constant, that is, the pAg controlled double jet method (CDJ method) is used to obtain monodispersed silver halide grains having a uniform crystal form and a substantially uniform grain size. . In the process of silver halide grain formation or physical ripening, a cadmium salt, an iridium salt or a rhodium salt may coexist in order to increase the contrast of the silver halide emulsion.

The binder contained in the silver halide photographic emulsion layer used in the present invention is 250 g per mol of silver halide.
It is preferable not to exceed. Gelatin is most preferable as the binder, but a hydrophilic colloid other than gelatin can be used. For example, albumin, casein,
Graft polymers of gelatin and other polymers, hydrophilic polymers such as polyvinyl alcohol and polyacrylamide can be used.

The silver halide emulsion used in the present invention does not need to be chemically sensitized, but it is usually chemically sensitized. Sulfur sensitization, reduction sensitization, noble metal sensitization and combinations thereof are used as the chemical sensitization method, and particularly preferred chemical sensitization for the practice of the present invention is sulfur sensitization method or sulfur sensitization,
This is a method that combines gold sensitization, which is one of the noble metal sensitizations.

As the sulfur sensitizer, active gelatin, thiosulfate, thioureas, allylthiocarbamide, etc. can be used. HAuCl ₄ , Au as gold sensitizer
(SCN) ₂ ^-salt , Au (S ₂ O ₃ ) ₂ ^{3 -salt and the} like can be used.

The silver halide emulsion used in the present invention may be spectrally sensitized with one type or two or more types of sensitizing dyes in order to impart photosensitivity to a desired wavelength range of light.

As the sensitizing dye, cyanine dye, merocyanine dye, styryl dye, hemicyanine dye, holopolar cyanine dye, oxonol dye, hemioxonol dye and the like can be used. Particularly useful dyes are cyanine dyes and merocyanine dyes. Any of the nuclei normally used for cyanine dyes as the basic heterocyclic nuclei of dyes can be applied. That is, pyrroline nucleus, oxazole nucleus, oxazoline nucleus, thiazole nucleus, thiazoline nucleus, pyrrole nucleus, selenazole nucleus, imidazole nucleus, tetrazole nucleus, pyridine nucleus, indole nucleus, benzoxazole nucleus, benzothiazole nucleus, benzoselenazole nucleus, benzimidazole nucleus. A nucleus, a quinoline nucleus, etc. can be applied.

The silver halide photographic light-sensitive material according to the present invention comprises a support and at least one hydrophilic colloid layer containing a negative type silver halide emulsion coated on the support. It may be composed of a plurality of hydrophilic colloid layers such as a developing agent precursor containing layer and / or a developing agent containing layer. Further, a non-photosensitive hydrophilic colloid layer other than the silver halide emulsion layer, for example, a protective layer,
An intermediate layer, an anti-halation layer, a filter layer, an enzyme-containing layer, a developing agent precursor-containing layer, a developing agent-containing layer and the like may be coated. These hydrophilic colloid layers may contain an inorganic or organic hardener. Hardeners include chromium salts (chromium alum, etc.), aldehydes (formaldehyde, glyoxal, etc.), N-methylol compounds (dimethylol urea, methylol dimethylhydantoin, etc.), active halogen compounds (2,4-dichloro-6).
-Hydroxy-s-triazine, mucochloric acid, etc.), active vinyl compounds (1,3,5-triacryloyluluhexahydro-s-triazine, divinyl sulfone, etc.), epoxy and aziridine type hardeners can be used.

In the hydrophilic colloid layer used in the present invention, various photographic additives, such as emulsion stabilizers (hydroxytetratetramethylindene such as 6-hydroxy-4-methyl-1,3,3a, 7-tetrazaindene) may be added, if desired. Zaindene compounds), extenders (such as saponins), gelatin plasticizers (such as acrylic ester copolymers), antistatic agents, coating aids, and photographic property improvement (for example, development acceleration and contrast enhancement).
Various surfactants (cationic,
Anionic, nonionic, amphoteric surfactants), antifoggants (hydroquinone, 5-methylbenzotriazole, 1-phenyl-5-mercaptotetrazole, etc.), matting agents, purposes for improving dimensional stability of photographic light-sensitive materials A water-insoluble or sparingly-soluble polymer latex (homo or copolymer of alkyl acrylate, alkyl methacrylate, acrylic acid, glycidyl acrylate, etc.) can be used within a range that does not impair the effects of the present invention.

The support which can be used in the above photographic light-sensitive material is
Polyolefin such as polyethylene, polypropylene and polystyrene, cellulose ester film such as cellulose acetate and cellulose nitrate, polyester film such as polyethylene terephthalate, paper, synthetic paper, or a combination thereof, for example, polyolefin on both sides or one side of paper or film. Any known support such as a glass plate or a glass plate coated with can be used.

As the development processing agent used in the present invention, different development processing agents are used depending on the type of silver halide photographic light-sensitive material used for image formation. That is, when a silver halide photographic light-sensitive material containing both the substrate (developing agent precursor) of the present invention and an enzyme is subjected to development processing, an activator processing agent for alkaline aqueous solution, the substrate of the present invention (developing agent precursor) In the case of developing a silver halide photographic light-sensitive material containing an enzyme, in the case of developing a silver halide photographic light-sensitive material containing an enzyme of the present invention, an activator processing agent for an alkaline aqueous solution containing an enzyme. Is a developer of an alkaline aqueous solution containing a developing agent precursor, a substrate (developing agent precursor) of the present invention, and a developing agent precursor and an enzyme when developing a silver halide photographic light-sensitive material containing no enzyme. There are four types of development processing agents: an alkaline aqueous solution developer contained therein.

All of these four types of developing agents are alkaline aqueous solutions, and alkaline agents are used to make them alkaline at pH 7.0 or higher.

Examples of the alkaline agent used in the present invention include inorganic alkaline agents such as sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium phosphate, ammonium phosphate, sodium bicarbonate, sodium borate, ammonium borate and ammonia. And monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, n-butylamine, monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, ethyleneimine, ethylenediamine, Organic primary amines such as pyridine, secondary
There are primary amines and tertiary amine compounds, and these can be used alone or in combination as long as they do not inhibit the enzyme activity.

In any of the developing treatment agents, it is desirable to set the pH of the developing treatment agent to the optimum pH of the enzyme to be used in order to efficiently carry out the enzymatic reaction between the substrate and the enzyme. Agents are used.

As the buffer used in the present invention, an enzyme reaction such as an inorganic buffer such as sodium phosphate, sodium carbonate, sodium bicarbonate, ammonium sulfate, sodium metaborate or an organic buffer such as sodium citrate or triethanolamine can be used. A buffering agent that does not inhibit is preferably used.

Further, in any of the developing treatment agents, a water-soluble acid (eg, acetic acid, malic acid), a preservative (eg, sodium sulfite) may be added, if necessary, in addition to the above components, as long as the enzyme reaction is not hindered. , Potassium sulfite, lithium sulfite, ammonium sulfite, sodium bisulfite, potassium bisulfite, potassium metabisulfite), inorganic fog inhibitors (eg sodium bromide, potassium bromide), organic fog inhibitors (eg 1-phenyl-5) -Mercaptotetrazole, 5-nitroindazole etc.), organic solvents (eg ethylene glycol, diethylene glycol, methyl cellosolve etc.), inorganic and organic salts (sodium chloride, sodium sulfate, magnesium chloride, magnesium acetate), toning agents, surface active agents Agents, defoamers, water softeners It can be used.

A small amount of the developing agent is preferably used in the alkaline aqueous solution activator-treating agent or the developing agent of the alkaline aqueous solution containing the developing agent precursor used in the present invention, if necessary, as long as the enzyme reaction is not hindered. Is added.

It should be noted that the developing agent containing an enzyme is an enzyme, the developing agent containing a developing agent precursor is a developing agent precursor, and the developing agent containing an enzyme and a developing agent precursor is an enzyme. The developing agent precursor is added according to the method described above.

The development processing temperature of the development processing agent of the present invention is selected in the range of 18 to 50 degrees Celsius, and more preferably in the range of 20 to 40 degrees Celsius.

The silver halide photographic light-sensitive material of the present invention processed by the developing method utilizing the enzymatic reaction of the present invention can stabilize the image by a usual fixing method.

As the fixing agent used in the present invention, those having a generally used composition can be used. For example, “The Basics of Photographic Engineering: Silver Salt Photography” edited by the Photographic Society of Japan 3
Page 30 onwards (Corona Publishing Co., Ltd. in 1979), Akira Sasai "Chemistry of Photography" page 320 onwards (Photo Industry Publishing Co. Ltd., 1982)
And "SP-Handbook of Photographic Science and Engineering (SPSEHANDBOOK OF PHOT
OGRAPHIC SCIENCE ANDENGIN
EERING) "Thomas (W. THOMAS, J
r. ), John Willie and Sons (JOHN
Published by WILEY & SONS (1973) 52
Reference can be made to page 8 and the like. As the fixing agent base, thiosulfates, thiocyanates, and organic sulfur compounds known to be effective as a fixing agent can be used. Further, as fixing aids, acid agents (eg, acetic acid, citric acid, etc.), preservatives (eg, sodium sulfite, etc.), buffer agents (eg, boric acid, etc.) and hardeners (eg, potassium alum, alum, sulfuric acid). Aluminum, etc.) can be used.

[0054]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to the following examples as long as the gist thereof is not exceeded.

Example 1 In a gelatin aqueous solution kept at 60 ° C., an aqueous silver nitrate solution and 3.0 × 10 ⁻⁷ mol of rhodium hexabromide (II) were ^added per mol of silver.
I) An aqueous potassium bromide solution containing sodium was added to pAg7.
A cubic crystal monodisperse silver bromide emulsion having an average grain size of 0.22 μm was prepared by simultaneously adding over 60 minutes while keeping at 0. After removing soluble salts by a conventional method,
25 × 10 ⁻⁵ mol of sodium thiosulfate and 5 × 10 ⁻⁵ mol of potassium (III) chloroaurate were added to 1 mol of silver halide, and the mixture was chemically ripened at 60 ° C. for 70 minutes. This emulsion contains 80 g of gelatin per mol of silver halide. The emulsion thus prepared contained 12 × 10 ^-3 mol of 6-hydroxy-4-methyl-per mol of silver halide.
A silver bromide emulsion was prepared by adding 1,3,3a, 7-tetrazaindene and 0.01 mol of 5-methylbenzotriazole. The prepared silver bromide emulsion was divided into small portions, and one divided silver bromide emulsion contained 0.06 mole of methyl ester and 0.30 mole of ascorbic acid-2-phosphate magnesium ester per 1 mole of silver bromide. Add salt (Film sample 1
For other divided silver bromide emulsions, 0.06 mol of meth- ol, 0.30 mol of ascorbic acid-2-phosphate magnesium salt and 1.6 x 1 are used per mol of silver bromide.
0 ⁵ units of alkaline phosphatase - added peptidase (film sample 2), respectively polyethylene terephthalate -
It was coated on a base so that the amount of silver was 40 mg per 100 cm ² .

Onto these emulsion layers, a gelatin protective layer containing formalin and dimethylolurea as a hardening agent was applied and dried to obtain film samples 1 and 2. Samples obtained by allowing these samples to stand naturally at room temperature for one month were designated as film sample 3 (sample 1 left in the natural state) and film sample 4 (sample 2 left in the natural state).

LB-200 filters were used for these film samples and exposed for 5 seconds through a step wedge having a step of 0.15 with a tungsten light source of 2666K, and then an alkaline activator (1) having the following composition was used. It was developed at 30 ° C. for 5 minutes, stopped, fixed, washed with water and dried.

Composition of alkaline activator (1) Water 800 g Potassium bromide 1 g Sodium carbonate 2.8 g Sodium hydrogencarbonate 14.6 g Water in addition 1 l pH 9.0

The photographic characteristics obtained are shown in Table 1.

[0060]

[Table 1]

In Table 1, fog represents the density of the non-exposed area, gamma represents the average gradient between the blackened densities of 0.5 and 2.0 excluding the fog, and Dmax represents the maximum density of the image area excluding the fog.

As can be seen from Table 1, the image forming method of the present invention can provide an image having a sufficient optical density. Further, it is found that a sufficient density can be obtained even with the film left naturally for one month. On the other hand, in Comparative Examples that do not satisfy the requirements of the present invention, practical density cannot be obtained and gamma cannot be displayed.

Example 2 Subdivided silver bromide emulsion obtained by operating in the same manner as in Example 1 (film sample 5), and silver bromide emulsion with silver bromide 1
An emulsion (for film sample 6) to which 1.6 × 10 ⁵ units of alkali phosphatase per mole was added was coated on a polyethylene terephthalate base so that the amount of silver was 40 mg per 100 cm ² . .

Onto these emulsion layers, a gelatin protective layer containing formalin and dimethylolurea as a hardener was coated and dried to obtain film samples 5 and 6. In addition, these samples were allowed to stand at room temperature for one month and were designated as film sample 7 (sample 5 allowed to stand) and film sample 8 (sample 6 allowed to stand), respectively.

These film samples were exposed for 5 seconds using a LB-200 filter with a tungsten light source of 2666K through a step wedge having a step of 0.15, and then a developer (1) having the following composition was used at 30 ° C. Development for 5 minutes, stopped, fixed, washed with water and dried.

Composition of Developer (1) Water 750 g Potassium bromide 1.0 g Sodium carbonate 2.8 g Sodium hydrogen carbonate 14.6 g Methol 20.6 g Ascorbic acid-2-phosphate ester 122.0 g Magnesium salt Add water 1 l pH 9.0

The photographic characteristics obtained are shown in Table 2.

[0068]

[Table 2]

As is clear from Table 2, the image forming method of the present invention can provide an image having a sufficient optical density. Further, it is found that a sufficient density can be obtained even with the film left naturally for one month. On the other hand, in the comparative examples that do not satisfy the requirements of the present invention, practical concentrations cannot be obtained.

Example 3 The film sample 1 produced in Example 1 was exposed in a tungsten light source of 2666K through a step wedge having a step of 0.15 for 5 seconds, and then produced in Example 1. Alkaline activator
1 in (1) and this alkaline activator (1)
Alkaline activator (2) with 2.4 × 10 ⁵ units of alkaline phosphatase added per liter.
And this alkaline activator (2) stored at room temperature for 2 weeks in a closed container.
Development was carried out using (3) at 30 ° C. for 5 minutes, stopping, fixing, washing with water and drying.

Table 3 shows the obtained photographic characteristics.

[0072]

[Table 3]

As is clear from Table 3, the image forming method of the present invention can provide an image having sufficient optical density. It is also found that a sufficient concentration can be obtained even with the enzyme-containing alkaline activator that has been sealed and stored for 2 weeks. On the other hand, in the comparative examples that do not satisfy the requirements of the present invention, practical concentrations cannot be obtained.

Example 4 The film sample 5 produced in Example 2 was exposed in a tungsten light source of 2666K through a step wedge having a step of 0.15 for 5 seconds, and then produced in Example 2. A closed container for the developer (1) and the developer (2) in which 2.4 × 10 ⁵ units of alkaline phosphatase per liter was added to the developer (1) and stirred for 1 hour and the developer (2) Development was carried out for 5 minutes at 30 ° C. with the developer (3) stored at room temperature for 1 day, and stopped, fixed, washed with water and dried.

The photographic characteristics obtained are shown in Table 4.

[0076]

[Table 4]

As can be seen from Table 4, the image forming method of the present invention can provide an image having a sufficient optical density. It is also found that a sufficient concentration can be obtained even with the enzyme-containing developer that has been sealed and stored for 1 day. On the other hand, in the comparative examples that do not satisfy the requirements of the present invention, practical concentrations cannot be obtained.

[0078]

INDUSTRIAL APPLICABILITY According to the present invention, an extremely stable developer or activator processing agent is used, and it is practically applied to a silver halide photographic light-sensitive material which has been imagewise exposed in advance by a development processing method similar to a normal development processing. Possible images can be formed.

Claims (11)

[Claims] 1. A method for forming an image by developing a silver halide photographic light-sensitive material with a developing agent, wherein the developing agent is released from a developing agent precursor by an enzyme during development, and the image is developed. Image forming method. 2. An image forming method, which comprises developing a silver halide photographic light-sensitive material with an alkaline developer containing a developing agent precursor and an enzyme. 3. An alkaline developer containing a developing agent precursor and an enzyme. 4. An image forming method comprising developing a silver halide photographic light-sensitive material containing a developing agent precursor with an alkaline activator processing agent containing an enzyme. 5. A silver halide photographic light-sensitive material containing a developing agent precursor. 6. An alkaline activator treating agent containing an enzyme. 7. An image forming method comprising developing a silver halide photographic light-sensitive material containing an enzyme with an alkaline developer containing a developing agent precursor. 8. A silver halide photographic light-sensitive material containing an enzyme. 9. A developer containing a developing agent precursor. 10. A silver halide photographic light-sensitive material containing a developing agent precursor and an enzyme is treated with an alkaline activator.
An image forming method comprising developing with a processing agent. 11. A silver halide photographic light-sensitive material containing a developing agent precursor and an enzyme.