JPH03271733A - Method for processing silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To prevent discoloration of a photographic image at the time of storage after development by incorporating organic materials in hydrophilic colloidal layers before development processing and reducing their content to <=90 wt.% after development processing and executing the development processing in the presence of a specified compound. CONSTITUTION:The hydrophilic colloidal layer of the silver halide photographic sensitive material contains the organic materials, after the development processing, decreased to <= 90 wt.% of those before it, and the development processing is carried out in the presence of the compound represented by formula I in which R<1> is alkyl or cycloalkyl; R<2> is H or cycloalkyl; and L is 1 - 8 C saturated or unsaturated bonding group, thus permitting even a photographic image formed by raid processing to prevent discoloration during long storage.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a method for processing silver halide photographic materials. More specifically, the present invention can be suitably used as a processing method suitable for rapid processing, and in particular, it provides a processing method for silver halide photographic materials that does not cause discoloration of photographic images during storage after processing even if rapid processing is performed. This is what we provide.

[Conventional technology]

It is desired that silver halide photographic materials be processed even more rapidly depending on their respective uses.

For example, by introducing an automatic processor for processing silver halide photographic light-sensitive materials, the processing time can be greatly shortened, and in particular, by high-temperature and rapid processing, dry light-sensitive materials can be processed and made dry again. The so-called dry-to-dry time has now become 90 seconds, but more than 20 years have passed since such 90-second processing was realized, and recently,
Furthermore, there is a movement to shorten processing time.

For example, at the 1987 Radiological Society of North America meeting, the applicant presented on the 45 second process. In addition, European Patent No. 0238271A, Japanese Patent Application Laid-Open No. 62-286037, etc.
Several related patent applications have also been filed. The former discloses a technique for achieving faster processing by improving developability and drying properties, and the latter discloses a technique for achieving faster processing by improving drying properties.

This move to speed up processing is being pursued in all areas of photosensitive materials, but especially in the medical field, such as the field of medical X-ray photographic photosensitive materials, there are emergency, surgery, etc.)
There is a desire to obtain images as quickly as possible; - patients do not have to wait; and - it is desirable to save space by making the processing machine more compact. , it is expected that the acceleration will increase.

Speeding up processing largely depends on the automatic processor and processing agent used, but the photosensitive material itself has better performance than conventional photosensitive materials, such as developability (progressivity) and drying properties. It needs to be improved.

[Problem that the invention seeks to solve]

Against the background of the above-mentioned request for speedy processing,
Publication No. 837 and the like disclose techniques that attempt to further improve drying properties. However, it has been found that this technique poses a new problem, particularly when ultra-rapid processing is performed, in that photographic images discolor during storage after development. In the medical field, when confirming a patient's condition, diagnosis is made by comparing it with a previously taken photograph, so discoloration of stored photographs over time is extremely undesirable as it can interfere with diagnosis. .

As described above, in order to meet the demand for ultra-quick processing, it is necessary to develop a processing method that does not cause problems such as discoloration of photographic images, and this is particularly desired, for example, in the field of medical photography mentioned above. It is.

[Object of the Invention] An object of the present invention is to provide a method for processing a silver halide photographic light-sensitive material that does not cause discoloration during storage, even for photographic images obtained by extremely rapid processing.

[Structure of the invention]

The above object of the present invention is to automatically develop a silver halide photographic light-sensitive material having a hydrophilic colloid layer including at least one light-sensitive silver halide emulsion layer and at least one light-insensitive protective layer on a support. A method for developing a silver halide photographic light-sensitive material using a machine, wherein the amount of organic substance present in the hydrophilic colloid layer of the silver halide photographic light-sensitive material after the completion of the development process is reduced before the development process. 90% by weight or less of the amount of the organic substance present, and the development treatment is carried out in the presence of a compound represented by the following general formula (I) (hereinafter sometimes referred to as the "compound of the present invention"). This was achieved by a method for processing silver halide photographic materials.

General formula (1) %Formula% However, in general formula (1), R1 represents an alkyl group or a cycloalkyl group. R2 represents a hydrogen atom or a cycloalkyl group. L represents a saturated or unsaturated linking group having 1 to 8 carbon atoms.

In the present invention, "development processing" includes all processing of processing a photosensitive material to be processed to form a photographic image, and in addition to processing with a developer, fixing processing, washing with water, etc. are employed in each embodiment. It includes various types of processing. Therefore,
In terms of processing using an automatic developing machine, it includes each process from when the leading edge of the photosensitive material to be processed enters the automatic developing machine until the trailing edge comes out.

Furthermore, in this specification, the term "development processing step" means all steps related to the above-mentioned development processing. Moreover, "development processing time" is the time required for the above-mentioned development processing.

The processing method of the present invention can be suitably used as an extremely high-speed processing, and can be preferably implemented as a so-called ultra-rapid processing in which the development time, that is, the total processing time is 60 seconds or less, and even 45 seconds or less.

The present invention will be explained in detail below.

The development processing method of the present invention comprises a silver halide photographic light-sensitive material (hereinafter referred to as The photosensitive material (sometimes also referred to as the "photosensitive material according to the present invention") is used as the photosensitive material to be processed.

Any support can be appropriately selected and used as the support for constructing the photosensitive material according to the present invention. for example,
Transparent or opaque supports used for photography can be used as appropriate, and the supports may or may not be flexible.

The photosensitive material according to the present invention has a hydrophilic colloid layer,
This may include at least one light-sensitive silver halide emulsion layer and at least one light-insensitive protective layer, and the hydrophilic colloid layer may contain one or more light-sensitive silver halide emulsion layers and one or more light-sensitive silver halide emulsion layers. It may consist only of one or more non-photosensitive protective layers, or may have other layers, such as a non-photosensitive intermediate layer.

As the hydrophilic colloid for constituting the hydrophilic colloid layer, gelatin is preferably used, but other substances can also be used.

In the light-sensitive material according to the present invention, the silver halide for constituting the light-sensitive silver halide emulsion layer can be of any silver halide composition, such as silver bromide, silver iodobromide, silver iodobromide, Any of those used in conventional silver halide emulsions can be used, such as silver iodochloride, silver chlorobromide, and silver chloride.

It may be a positive emulsion or a negative emulsion.

The method for producing silver halide grains, grain shape, crystal morphology, average grain size, and grain size distribution are also not particularly limited and may be arbitrary.

The silver halide grains in the light-sensitive silver halide emulsion layer of the photographic material according to the invention may be spectrally sensitized with a sensitizing dye.

Dyes that can be used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes,
Included are holopolar cyanine dyes, hexocyanine dyes, styryl dyes and hexioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes, and complex merocyanine dyes. Any of the nuclei commonly used for cyanine dyes can be used as the basic heterocyclic nucleus for these dyes. Namely, viroline nucleus, oxazoline nucleus, thiazoline nucleus, pyrrole nucleus, oxazole nucleus, thiazole nucleus, selenazole nucleus, imidazole nucleus, tetrazole nucleus, pyridine nucleus, etc.; a nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei; and these A nucleus in which an aromatic hydrocarbon ring is fused to the nucleus of Imidazole nuclei, quinoline nuclei, etc. can be applied.

These nuclei may be substituted on carbon atoms.

Merocyanine dyes or composite merocyanine dyes include a pyrazolin-5-one nucleus, a thiohydantoin nucleus, and a 2-thioxazolidine-2 nucleus having a ketomethylene structure.
, 4-dione nucleus, thiazolidine-2,4-dione nucleus, rhodanine nucleus, thiobarbic acid nucleus, and the like can be applied.

Specifically, Research Disclosure Volume 176R
D-17643 (December 1978 issue), page 23, and those described in U.S. Pat.

These sensitizing dyes may be used alone or in combination, and combinations of sensitizing dyes are often used particularly for the purpose of supersensitization.

Along with the sensitizing dye, it is a dye that itself does not have a spectral sensitizing effect or a substance that does not substantially absorb visible light,
A substance exhibiting supersensitization may also be included in the emulsion. For example, aminostilbene compounds substituted with nitrogen-containing heterocyclic groups (e.g., U.S. Pat. Nos. 2,933°390 and 3,635,7
21), aromatic organic acid formaldehyde condensates (such as those described in US Pat. No. 3,743,510), cadmium salts, azaindene compounds, and the like. U.S. Patent No. 3.615,613, U.S. Patent No. 3.61
No. 5.641, No. 3,617,295, No. 3,635
, 721 are particularly useful.

When a sensitizing dye is used, it is generally added to the silver halide emulsion as a solution in an aqueous solution or a water-miscible organic solvent, such as methanol 1, ethanol, propyl alcohol, methyl cellosolve, pildine, etc. .

Sensitizing dyes may also be dissolved using ultrasonic vibrations as described in US Pat. No. 3,485,634.

Other methods of dissolving or dispersing sensitizing dyes and adding them to emulsions include US Pat. No. 3,482,981;
3,585.195, 3,469,987, 3,425°835, 3,342,605, British Patent 1,271.329, 1,038,029,
No. 1,121,174, U.S. Patent No. 3,660, 101
No. 3,658,546 can be used.

The sensitizing dye is generally added to the emulsion before the emulsion is coated on a suitable support, but it may also be added during the chemical ripening step or the silver halide grain formation step.

In addition, the emulsion used in the light-sensitive material according to the present invention, and other materials other than the emulsion, may also contain appropriate additives.

Regarding these additives, see Research Disclosure Vol. 176, Nα17643 (December 1978) and Research Disclosure Vol. 187, Nα18716 (November 1976).
The relevant sections are summarized in the table below.

The development processing method of the present invention is one in which development processing is performed using an automatic developing machine.

The specifications of the automatic processor used in the present invention are arbitrary.

The development method of the present invention is such that the amount of organic substance present in the hydrophilic colloid layer of the silver halide photographic light-sensitive material after completion of the development process is 90% by weight or less of the amount of the organic substance before the development process. It is. Here, after the development process is completed,
As mentioned above, it refers to the point in time after development and other processes such as fixing, washing with water, and drying, which are adopted as necessary, are completed.

For example, if we focus on (any layer of) a photosensitive silver halide emulsion layer, this process will reduce the amount of organic substances present in the layer after development to 90% by weight or less of the amount before development. It is sufficient if it is processed as follows. Such a change in the amount of organic substance may be made for the entire hydrophilic colloid layer, or may be made for at least one layer.

Preferably, the amount of the organic substance after development is 50% by weight or more and 90% by weight or less of the amount before development, more preferably 70% by weight or more and 85% by weight or less. . The organic substance may be washed away in the development process by physical elution, for example, or by chemical reaction.

Examples of organic substances in the hydrophilic colloid layer include gelatin used as a binder, various organic sensitizers,
Examples include organic spectral sensitizing dyes, silver halide developers such as hydroquinone compounds and 3-pyrazolidone compounds which are incorporated into the light-sensitive material as needed, and precursors thereof.

The organic substance may also include organic polymeric substances other than gelatin, such as polyacrylamide as described in US Pat. No. 3,271.158, or hydrophilic polymers such as polyvinyl alcohol and polyvinylpyrrolidone. In addition, dextran, sucrose,
There are Class Ii such as pullulan.

In the processing method of the present invention, the organic substance to be washed away may be one that is contained as a component of the photosensitive material, or it may be one that is contained in the photosensitive material particularly in order to realize the processing method of the present invention.

Specifically, it is preferred that the emulsion layer and/or other hydrophilic colloid layers contain organic substances that would flow out during the development process. Such polymers may include, for example, water-soluble synthetic or natural polymers. When the substance to be washed away is gelatin, it is preferable to use gelatin types that are not involved in the crosslinking reaction of gelatin with hardeners, such as acetylated gelatin, phthalated gelatin, alkyl (such as methyl, ethyl, propyl,
This includes benzyl) esterified gelatin.

The molecular weight is preferably small, preferably 20,000 or less, more preferably 10,000 or less.

In addition, examples of water-soluble polymers that can be used include synthetic water-soluble polymers and natural water-soluble polymers, both of which can be preferably used in the present invention. Among these, synthetic water-soluble polymers include those having, for example, nonionic groups, anionic groups, and both nonionic and anionic groups in their molecular structures. Nonionic groups include, for example, ether groups, ethylene oxide groups, hydroxy groups, etc., and anionic groups include, for example, sulfonic acid groups or salts thereof, carboxylic acid groups or salts thereof, phosphoric acid groups or salts thereof, and the like. Furthermore, examples of natural water-soluble polymers include those having, for example, nonionic groups, anionic groups, and nonionic and anionic groups in their molecular structures.

As the water-soluble polymer, those having an anionic group, and those having a nonionic group and an anionic group can be preferably used in both synthetic water-soluble polymers and natural water-soluble polymers. The water-soluble polymer referred to here is 0.05% per 100g of water at 20°C.
Any material that dissolves at least 0.1 g is sufficient, preferably 0.1 g or more.
g or more.

Further, when using a water-soluble polymer, it is preferable that the solubility in the developer or fixer is high, and the solubility is preferably 0.05 g or more per 100 g of the copying liquid, more preferably 0.05 g or more. The amount is 5 g or more, particularly preferably 1 g or more.

Examples of synthetic water-soluble polymers include those containing, for example, 10 to 100 mol % of repeating units represented by the following general formula (ff) in one polymer molecule.

General formula (If) In the formula, R1 and R2 may be the same or different and each represents a hydrogen atom, an alkyl group, a halogen atom, or -CHl
Represents CooM. Here, the alkyl group refers to an alkyl group having 1 to 4 carbon atoms (including those having a substituent).
For example, methyl group, ethyl group, propyl group, butyl group, etc.)
is preferred, and the halogen atom is preferably a chlorine atom.

L is -CONH-1-N1(CO-1-coo--oc
.

? 100-1-SO, -1-NH3O2-1-5O2NH
- or -〇-.

J is an alkylene group, preferably an alkylene group having 1 to 10 carbon atoms (including those having a W substituent; for example, a methylene group, an ethylene group, a propylene group, a trimethylene group, a butylene group, a hexylene group, etc.), an arylene group (Includes those with substituents, such as phenylene group),
or +CI(2CH20+V-f-CH2+-→CH
zCHCHZOtenT-suCH, dimension.

H (m is an integer of 0 to 40, n is an integer of 0 to 4).

Also, Q is Represents a hydrogen atom or R3.

M represents a hydrogen atom or a cation, R9 represents an alkyl group having 1 to 4 carbon atoms (e.g. methyl group, ethyl group, propyl group, butyl group, etc.), R3R', R5, R'
, R' and R8 are alkyl groups having 1 to 20 carbon atoms (
For example, methyl group, ethyl group, propyl group, butyl group, hexyl group, decyl group, hexane group, etc.), alkenyl group (for example, vinyl group, aryl group, etc.), phenyl group (for example, phenyl group, methoxyphenyl group, chlorophenyl group, etc.) ), represents an aralkyl group (e.g. benzyl group, etc.),
X represents an anion.

Furthermore, in the general formula (■), p and q each represent O or 1.

As the synthetic water-soluble polymer represented by the general formula (If), a polymer containing acrylamide or methacrylamide is particularly preferable.

Next, specific exemplary compounds of the synthetic water-soluble polymer of general formula (II) will be shown. However, the compounds that can be used in the present invention are not limited to the following examples.

P-1 number average molecular weight M.

-2 15,000 -3 P -5 7- 3 4 5 9 , 000 9,000 12,000 -8 -9 -10 -11 H3 H 10,000 6 000 -17 10,500 (However, 1,: nz Number average molecular weight (Mn) - 50 mol% = 50 mol%, - about 10,000) P-19 (However, n,: n2 = 75 mol% = 25 mol%, Mn =
(approximately 20,000) The exemplified compound and other synthetic water-soluble polymers represented by general formula (I[) can be easily synthesized by various methods such as solution polymerization, bulk polymerization, and suspension polymerization.

For example, in solution polymerization, a mixture of monomers is generally prepared in a suitable solvent (e.g., ethanol, methanol, water, etc.) at an appropriate concentration (usually, preferably 40% by weight or less, more preferably 10 to 25% by weight based on the solvent). mixture) in the presence of a polymerization initiator (e.g., benzoyl peroxide, azobisisobutyronitrile, ammonium persulfate, etc.) at an appropriate temperature (e.g., 40 to 120°C, preferably 50 to 100°C).
The copolymerization reaction is carried out by heating to (°C). Thereafter, the reaction mixture is poured into a medium that does not dissolve the produced water-soluble polymer, the product is precipitated, and then the unreacted mixture is separated and removed by drying. When a synthetic water-soluble polymer is used in the present invention, its molecular weight is 1,0
00 to 100,000 is preferable, more preferably 2.
000 to 50,000.

Natural water-soluble polymers are described in detail in the Water-Soluble Polymer Water-Dispersed Resin Comprehensive Technical Data Collection (Management Development Center Publishing Department), but include lignin, starch, pullulan, cellulose, alginic acid, dextran, dextrin,
Guar gum, gum arabic, glycogen, laminaran, lichenin, nigeran, etc., and derivatives thereof are preferred.

In addition, as m8 bodies of natural water-soluble polymers, sulfonated, carboxylated, phosphorylated, sulfoalkylenated, carboxyalkylenated, alkyl phosphorylated ones, salts thereof, polyoxyalkylene (e.g. ethylene, glycerin, propylene etc.) and alkylated (methyl, ethyl, benzylation, etc.) are preferred.

In the present invention, when using a natural water-soluble polymer, 2
More than one species may be used in combination.

Furthermore, among natural water-soluble polymers, glycose polymers and derivatives thereof are preferable, and among glucose polymers and derivatives thereof, starch, glycogen, cellulose, lichenin, dextran, nigeran, etc. are preferable, and in particular dextran and its derivatives are preferable. Derivatives are preferred.

Dextran is a polymer of α-1,6-linked D-glucose, and is generally obtained by culturing dextran-producing bacteria in the presence of saccharides. It can be obtained by reacting isolated dextran sucrase with saccharides. In addition, these native dextrans are reduced to a desired molecular weight by a partial decomposition polymerization method using acid or alkaline enzymes, and the intrinsic viscosity is reduced to 0.0.
3 to 2.5 can be obtained.

Examples of modified dextran include dextran sulfate, carboxyalkyldextran, and hydroxyalkyldextran.

The molecular weight of these natural water-soluble polymers is 1000-10
10,000 is preferred, and 2,000 to 50,000 is particularly preferred.

Methods for producing these dextrans and their derivatives are described in Japanese Patent Publication No. 35-11989 and U.S. Patent No. 3.76.
No. 2,924, Special Publication No. 45-12820, No. 45-1
No. 8418, No. 45-40149, No. 46-3119
It is described in detail in issue 2.

When a synthetic or natural water-soluble polymer is used in carrying out the present invention, it is preferably contained in the photosensitive material in an amount of 10% or more, more preferably 10% or more and 30% or less of the total weight of the polymer. .

The layer containing the organic substance washed away in the process of the present invention may be an emulsion layer or a protective layer, but when the total amount of the organic substance coated is the same, the layer containing the organic substance in the protective layer and the emulsion layer is more It is more preferable to contain it in the protective layer, and it is even more preferable to contain it only in the protective layer. In a light-sensitive material having a multilayer emulsion layer structure, when the total amount of the organic substance coated is the same, it is preferable that the emulsion layer closer to the protective layer contains the organic substance in a larger amount.

In the present invention, the development treatment is performed in the presence of the compound represented by the general formula (1) described above.

In the general formula (1), R' represents an alkyl group or a cycloalkyl group, and R2 represents a hydrogen atom, an alkyl group, or a cycloalkyl group, and the cycloalkyl group is, for example, a cyclohexyl group. At least one of R1 and RZ is preferably a group having at least 3 carbon atoms, and the total number of carbon atoms in the compound represented by formula (1) is preferably 6 to 20. , 8
It is more preferable that it is -16, and it is especially preferable that it is 9-16.

In general formula (I), L represents a saturated or unsaturated linking group having 1 to 8 carbon atoms (which may be substituted with W), and this linking group is preferably an alkylene group, particularly -
Preferably, it is GHzGHz- or -CHzCHzCHz-.

The compound represented by general formula (I) can also function as a bleach inhibitor.

-a Preferred examples of the compound represented by formula (I) include the following. However, it goes without saying that the compounds that can be used in the present invention are not limited to those exemplified below.

(1) 2-(n-octylamino)ethanethiol (2) 2-(n-butylamino)ethanethiol (3) 2-(cyclohexylamino)ethanethiol (4) 2-(n-decylamino)ethanethiol In the processing method of the present invention, the development process is carried out in the presence of the compound of the present invention represented by general formula (1), and this compound is present in the processing solution, for example, in the developer and/or in the fixer. It may be present during processing by being contained in the medium and/or washing water (particularly in the case of washing with standing water), or may be made to be present during development by being contained in the photosensitive material to be processed. It is preferably contained in a developer and/or a fixer, and more preferably in a fixer.

When the compound of the present invention is contained in the treatment liquid, the preferable addition amount is the treatment liquid II! , per 1X10-6~1
X10-' mole, and further 1X10-' to 1X10-
"Molar is more preferable, and 1X10-' to 5X
More preferably, it is 10-3.

The development processing method of the present invention is preferably carried out under the conditions expressed by the following formula (A).

Formula (A) io・”XT=50~130 0.7<f<4.0 where l is the processing length when processing the photosensitive material (single, l is the time required to pass through the photosensitive material (unit: 2 seconds).

Further, it is preferable to perform the processing using a roller conveyance type automatic developing machine under conditions corresponding to the following.

Formula (A) 2°・”XT=50~130 0.7 <e< 4.Q However, l is the 10th -
It is the length (unit: m) from the core of the roller to the core of the final roller at the drying outlet, and T is the time (unit: 2 seconds) used to pass through 2 above.

The above l can be determined, for example, based on a photosensitive material having a photographic constituent layer on a polyethylene terephthalate support having a thickness of 175 μm.

In addition, the above T indicates that after inserting the leading edge of the film into the core part of the 10th roller in the insertion opening of the automatic processor, proceed to the developing tank, transition area, fixing tank, transition area, washing tank, transition area, and drying area. The total time it takes for the leading edge of the film to emerge from the final roller at the drying outlet [in other words, the total length of the processing line (m) divided by the line conveyance speed (m/sec) (see , ) ) can be said.

The reason why the time for the transition part should be included here is that, as is well known in the industry, even in the transition part, the liquid from the previous process swells in the gelatin film, so it is virtually the processing time. This is because it can be seen as progressing.

The total number of transport rollers in the automatic processor used in the processing method of the present invention is such that the value obtained by dividing l, which is the processing section of the automatic processor, by the number of rollers is in the range of 0.01 to 0.04. is preferred. Further, it is preferable that the time for each treatment site is as follows.

Further, the time for each treatment site is preferably within the following range.

Insertion + Waves during development Waves during fixing Waves during washing Squeeze + Drying 25-40% 12-25% 10-25% 25-45% The rollers used have a conveying section diameter of 12 mm to 60 mm.
The length is preferably between 300 and 110 cm+, and various materials can be used. For example, Bakelite-based materials (which may contain glass powder, metal powder, and plastic powder) are used for the developing, fixing, washing, and drying parts. Rubber-based materials (neoprene, isoprene, silicone rubber, etc.) can be used. For the transition part and the squeeze part, it is preferable to use water-repellent and elastic silicone rubber or the like, or highly water-absorbent synthetic leather "Talarino" (manufactured by Kuraray ■). 3 In the present invention, preferably, The above l exceeds 0.7 and 4
．． The range is less than 0, which gives preferable results. When l is smaller than 0.7, each processing step becomes smaller and the number of rollers used becomes smaller, resulting in decreased sensitivity and poor conveyance. On the other hand, if l is larger than 4.0, the transport speed becomes too high, the film is likely to be scratched, and the durability of the automatic developing machine is deteriorated.

Furthermore, if the product of 10.75 and T is less than 50, the sensitivity of the processed film will decrease, and color retention may be a problem in films where 10 mg/rrf or more of sensitizing dye is used per side of the support. becomes. This problem was discovered through study by the present inventor. Preferably 10.75 and T
The product is 76 or more.

In the processing method of the present invention, various developing processing agents such as black and white, color, and reversal processing agents can be used to develop the photosensitive material, depending on the photosensitive material.

Other additives used in the fixing treatment liquid and the development treatment liquid are optional, and the processing conditions, such as the pH and temperature of the liquid, are also optional.

The processing method of the present invention can be applied to the processing of various photosensitive materials, such as those for printing, X-ray, general negative, general reversal, general positive, direct positive, and the like.

〔Example〕

Examples of the present invention will be described in detail below. Note that, as a matter of course, the present invention is not limited to the embodiments described below.

Prior to specific description of each example, the preparation of silver halide emulsions used on each side will be described.

amount of. 11-1 Monodisperse grains of silver iodobromide containing 280 mol% of silver iodide with an average grain size of 0.22 μm as cores, and a layer of silver iodobromide containing 35 mol% of silver iodide at pH = 9 .3, pAg=7.5
After that, equimolar amounts of potassium bromide and silver nitrate were added at pH=7.8 and pAg=8.9 to obtain silver iodobromide grains with an average silver iodide content of 2.1 mol%. Three types of emulsions were prepared from monodispersed grains with average grain sizes of 1.46 μm (emulsion A), 1.18 μm (emulsion B), and 0.73 μm (emulsion C), respectively. Excess salt was removed from each emulsion using a conventional flocculation method. That is, a formalin condensate of sodium naphthalene sulfonate and an aqueous solution of magnesium sulfate were added to cause coagulation. After removing the supernatant, heat at 40"C.
of pure water was added thereto, and an aqueous magnesium sulfate solution was added again to cause coagulation, and the supernatant liquid was removed. Next, lime-treated gelatin 5
After adding g and making the total volume to 200cc with water, boil at 50″C.
The mixture was stirred and dispersed for 30 minutes.

[Similar to (2), the average silver iodide content is 2.3 mol, and the average grain size is 1.20 μm (emulsion D), 0.65 μm (emulsion E)
, 0.41 μm (emulsion F) monodispersed silver iodobromide grains were prepared. However, excess salt was removed as follows.

That is, (a): After the completion of particle formation, 50 g of the following compound was added to the reaction solution at 40°C, and then 10 g of 56 wt% acetic acid was added.
After adding 5 cc and adjusting the pH to 5.0, the solution was allowed to stand and was decanted.

(b) Second, after adding 1.91% of pure water at 40°C, K
After adding 6.5 g of OH to bring the pH to 6.1 and stirring for 5 minutes, 65 cc of 56-t% acetic acid was added to bring the pH to 4.
3, and then left to stand and decanted. Also,(
b) was repeated one more time. Furthermore, gelatin was added and stirred and dispersed in the same manner as in the preparation of the emulsion.

Example 1 Each of the above-mentioned emulsions A, B, and C was subjected to chemical ripening by adding 2.4 x 10-'' mol of ammonium thiocyanate per mol of silver and optimum amounts of chloroauric acid and hypo. , then 4-hydroxy-6methyl-1.3,
2XIO-'' moles of 3a,7-tetrazaindene were added for stabilization.

Next, each emulsion was mixed at a mixing ratio of A:B:C=15.
:55:30, and an emulsion additive and lime-treated gelatin, which will be described later, were added to prepare an emulsion coating solution.

Furthermore, a protective film coating solution having the composition shown below was prepared.

Each of the obtained coating solutions was simultaneously coated on both sides of a 175 μm thick undercoated polyethylene terephthalate base using two slide hopper type coaters, and dried for 2 minutes and 45 seconds to form samples Nα1-1 to Nα1-N.

1-16 was obtained.

The protective colloid in both the emulsion layer and the protective layer is gelatin.
The configuration shown in 1 was adopted. Further, Samples 1-5 to 1 to 16 were made into photosensitive materials according to the present invention by containing organic substances (water-soluble polymers) of the type and amount shown in Table 1. The amount of silver coated is 3゜0g/rd (per side)
Met.

(Emulsion Additive) The following compound was used as an emulsion layer additive. That is, 400 mg of t-butyl-catechol, 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene per mole of halogenated
3g, polyvinylpyrrolidone (molecular weight 10,000) 1.0
g, styrene/maleic anhydride copolymer 2.5 g, trimethylolpropane 10 g, diethylene glycol 5 g.

Nitrophenyl-triphenylphosphonium chloride 50 mg, ammonium 1,3-dihydroxybenzene-4-sulfonate 4 g.

Sodium 2-mercaptobenzimidazole-5-sulfonate 15 mg, H 11-dimethylol-1-bromo-1-nitromethane
An emulsion layer coating solution was prepared by adding 1 Omg, etc.

(Protective layer additive) In addition, the following compound was added as a protective layer additive to prepare a protective film N coating solution. That is, 3 mg of c, F9so, per 1 g of gelatin.

CqF + qO (CHzCHzO÷77CHzCHzOH
5mg.

Sodium chloride 3mg, 03Na Formalin 20mg.

Glyoxal 301mg.

7 mg of a matting agent made of polymethyl methacrylate with an average particle size of 5 μm, 70 mg of colloidal silica with an average particle size of 0.013 μm, etc. were added.

Each of the above samples was developed as follows. That is, the compound of the present invention was added to the treatment solution as shown in Table 1, and the treatment was performed under the following conditions.

Developer: XD-3R (development temperature = 35°C) Fixer: XF-3R (fixer temperature: 33°C) Processing time: 45 seconds Automatic developing machine used: 5RX-501 (Developer, fixer, (All automatic processors are manufactured by Konica ■) ■ Sensitivity measurement a) A sample was sandwiched between two fluorescent intensifying screens (NR-160: manufactured by Konica ■), and a tube voltage of 8 was applied via an aluminum lamination edge.
After exposure was performed for 0.06 seconds at 0 kvp and a tube current of 100 mA, the development process was performed. For the obtained sample, the logarithm of the reciprocal of the exposure amount required to obtain a density of 10 Capri density plus 1.0 was determined and used as a sensitivity value.

■Evaluation of image discoloration (forced deterioration) The sample used for sensitivity measurement (developed sample) was divided into two parts, one at a temperature of 25'C and a humidity of 50%RH, and the other at a temperature of 40'C, Each sample was stored for 3 days under conditions of humidity 80% RH.
The degree of discoloration of the image was evaluated and indicated on a five-point scale. 5-3
A value of 2 to 1 is not a problem, but a value of 2 to 1 is not practical.

Evaluation of dryness Conditions around the automatic processor Temperature: 25°C 1 Relative humidity = 8
0% and under the development processing conditions described above (however, the drying temperature was 45%).
°C, and washing water was regular tap water flowing at a flow rate of 3 liters per minute), each sample was exposed to light so that the density after development was D = 1.7, and the insertion interval was 7 seconds. 100 sheets were processed, and the dryness of the sample was defined as the point where the dry state did not change among the 100 sheets.

-Completely dry and warm. 5. Completely dry and cold. 4. Slightly damp (however, woodpeckers 3 will not grow).

・Moist (2/3 or less). 2. It’s damp (
2/3 or more). 1 The results obtained are summarized in Table 1.

In this example, the difference in organic substance in the hydrophilic colloid layer before and after the development process, that is, the amount of organic substance lost by the process, was measured as follows.

That is, the sample was allowed to stand at 25° C. and 10% relative humidity until the moisture content of the sample reached equilibrium with the atmosphere, and then the weight of the sample was measured. Next, the sample is processed from development to drying using an automatic developing machine (manufactured by Konica ■, 5RX-501 is used). Then again at 25℃ and relative humidity 1
The sample is left under 0% conditions, and the weight is measured when the moisture content reaches equilibrium.

(Note that the weight of the support should be measured in advance to confirm that there is no change in weight when only the support is treated). The amount of developed silver is determined by exposing the sample uniformly or without any exposure, and from this value and the specific gravity of the silver halide, the weight loss of the silver halide grains themselves due to development and fixing is calculated. From these values, it is possible to know what percentage by weight of the organic substance that was present in the hydrophilic colloid layer before the treatment has flowed out during the development, washing, and drying processes.

In this example, although inorganic salts were also included in the emulsion, the amount of change in these salts was negligible in terms of weight compared to the amount of organic substances flowing out.

In addition, in this example, the amount of organic substances flowing out was determined by weight measurement as described above, but the value can also be obtained by measuring the film thickness before and after treatment. It can also be quantified by analysis.

As is clear from the margins and Table 1 below, it can be seen that when processed using the processing method according to the present invention, good processing without the occurrence of image discoloration during storage can be achieved.

Example 2 Using the above-mentioned emulsions E and F, the total amount of spectral sensitizing dyes (A) and (B) to be described later was added to each mole of silver halide at a weight ratio of 200:1. After addition of 750 μm, ammonium thiocyanate was added at 3.6×10 −3 mol per mol of silver, and chemical ripening was performed with optimal amounts of chloroauric acid and hypo, and 15 minutes before the end, potassium iodide was added to silver halide. 200 μm per mole was added, and then 1.8XIO-" moles of 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene were added for stabilization.

Using the three types of emulsions obtained, each ratio was D:E:
The mixture was mixed so that F=30:40:30, and the same emulsion additives and lime-treated gelatin as in Example 1 were added to prepare an emulsion coating solution. The same protective film coating liquid as in Example-1 was used.

The obtained coating liquid was applied onto a support in the same manner as in Example-1,
Drying was performed to obtain samples No. 2-1 to No. 2-18. (The protective colloid had the structure shown in Table 2.

Further, the amount of coated silver was 22 .mu./bore. ) Sensitivity measurements and image discoloration evaluations were performed on the obtained samples in the same manner as in Example 1, and the results are shown in Table 2. (However, the sensitivity measurement was carried out using a fluorescent intensifying screen made by 0250: Konica ■, and the exposure conditions were changed to tube voltage: 70 kpv, tube current: 120 mA, and exposure time: 0.10 seconds.) Obtained Results are shown in Table-2.

The following amount 1. ], Spectral sensitizing dye (a) Spectral sensitizing dye (b) As is clear from Table 2, the system ortho-sensitized using the above spectral sensitizing dye also had the same effect as Example 1. The effects of the invention are likewise obvious.

Example-3 35 g of gelatin, 5 g of KBr, KI in 1 liter of water
5% A was added to the solution and kept at 65°C.
gN0. 100 cc of aqueous solution and 1 ml of 0.73% KBr aqueous solution
00 cc were added simultaneously over 1 minute. Then, Ag
AgNO. containing 140 g as NOs. Aqueous solution and X
A Br aqueous solution (containing 2.7 g of Kl) was added at the same time. The addition flow rate at this time was gradually accelerated so that it was 7 times as high at the end of the addition as it was at the beginning of the addition.

After the addition, the pH was set to 7.5 and the temperature was set to 50°C, and the sensitizing dyes (A) and (B) were added at a weight ratio of 200:1 in a total amount of 1000 μm per mole of silver halide for 30 minutes. Stirring was performed. After that, the above-mentioned "Preparation of emulsion to be used - ■"
Excess salt was removed using the method shown in .

The resulting emulsion had tabular grains with a projected area diameter of 0.90 μm, an average grain thickness of 0.19 μm, and an average silver iodide content of 2.2 mol %.

Add 200% of the sensitizing dyes (A) and (B) to this emulsion.
:1 weight ratio and the total amount is 2 per mole of silver halide.
After stirring for 10 minutes, ammonium thiocyanate was added at a concentration of 3.6×10 per mole of silver.
Chemical ripening is carried out with -3 moles of chloroauric acid and hypo-chloroauric acid in an optimal amount, and 15 minutes before completion, potassium iodide is added at a concentration of 200 μm per mole of silver halide, and then 4-hydroxy-6
-Methyl-1,3゜3a,7-tetrazaindene 1.8
Stabilization was achieved by adding X10-'' moles.

The same emulsion additives and lime-treated gelatin as in Example 1 were added to the obtained emulsion to prepare an emulsion coating solution. The coating liquid for the protective film was the same as in Examples 1 and 2.

In addition, a backing layer coating solution having the following composition was prepared.

<Hasoking layer> (Banking lower layer coating liquid) (Backing upper layer coating liquid) Backing dye A Backing dye B The obtained emulsion coating liquid and protective layer coating liquid, as well as the backing upper layer coating liquid and the same lower layer coating liquid, are applied to polyethylene that has been subbed. Samples Nα3-1~
Nα3-20 was obtained. The amount of silver coated was 30 µ/bore in all cases.

Regarding the obtained sample, Konica Imaging Camera M0M
(P-45 phosphor), a gray scale was exposed for 1 second, the same treatment as in Example 1 was carried out, and the sensitivity was measured in the same manner.

Furthermore, image discoloration was evaluated in the same manner as in the above-mentioned Examples. The results are shown in Table-3.

(Samples Nα3-15 to Nα3-20 contain 20% of the emulsion of this example and 80% of the emulsion (E) used in Example-2.
% and used as an emulsion. ) As is clear from Table 3, the effects of the present invention were confirmed in this example as well.

[Effects of the Invention] As described above, the method for processing silver halide photographic materials of the present invention has good drying properties and is suitable for rapid processing. Photographic images have the advantage of being prevented from discoloring during storage.

Claims (1)

[Claims] 1. Automatic production of a silver halide photographic light-sensitive material having a hydrophilic colloid layer including at least one light-sensitive silver halide emulsion layer and at least one light-insensitive protective layer on a support. A method for developing a silver halide photographic light-sensitive material using a developing machine, wherein the amount of organic substance present in the hydrophilic colloid layer of the silver halide photographic light-sensitive material after the completion of the development process is lower than that before the development process. 90% by weight or less of the amount of the organic substance present in the silver halide photographic light-sensitive material, wherein the developing treatment is carried out in the presence of a compound represented by the following general formula (I). Processing method. General formula (I) ▲There are numerical formulas, chemical formulas, tables, etc.▼ However, in the general formula (I), R^1 represents an alkyl group or a cycloalkyl group. R^2 represents a hydrogen atom, a cycloalkyl group, or an alkyl group. L represents a saturated or unsaturated linking group having 1 to 8 carbon atoms. Each of the above groups includes those having a substituent. 2. The method for processing a silver halide photographic material according to claim 1, wherein the development treatment is carried out under conditions represented by the following formula (A). Formula (A) l^0^. ^7^5×T=50~130 0.7<l<4.0 where l is the processing length when processing the photosensitive material (unit: m)
, and T is the time required to pass l (unit: seconds)
represents. 3. The silver halide photographic light-sensitive material according to claim 1, wherein the automatic developing machine is a roller conveyance type automatic developing machine and satisfies the condition expressed by the following formula (A). Processing method. Formula (A) l^0^. T represents the time (unit: seconds) required to pass through l.