JPH039343A - Production of silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To improve the suitability of rapid processing and the shelf life of a sensitive material at high temp. by incorporating a specified hardening agent and specifying the water content of the sensitive material and the weight ratio of the amt of org. substances after development to that before development. CONSTITUTION:A hardening agent represented by formula I is incorporated into one of the emulsion layer and protective surface layer of a sensitive mate rial and the water content of the sensitive material is requlated to such an equilibrium state as 40-60% at 25 deg.C relative humidity after forming. When the sensitive material is developed with an automatic developing machine, org. substances contained in the emulsion layer and other hydrophilic colloidal layer are removed by >=10% of the total amt. during passing through developing, fixing, washing and drying stages. Thus, the adjusted photosensitive material is obtd. In the formula I, R is H, optionally substd. alkyl, aralkyl or aryl. A high drying rate, high covering power, superior shelf life at high temp. and acceleration of hardening are ensured and satisfactorily high sensitivity is obtd. by short-time processing.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a method for preparing a silver halide photographic material,
In particular, it relates to techniques for improving rapid processing suitability (i.e., high sensitivity with short-term processing and drying in a shorter time) and high-temperature storage stability, and particularly relates to methods for preparing X-ray photosensitive materials. It is.

(Prior Art) In recent years, high-temperature, rapid processing has rapidly become popular in the development process of photographic light-sensitive materials, and the processing time has been greatly shortened even in automatic processing of various light-sensitive materials.

In order to achieve high-temperature, rapid processing, we need a developer that can achieve sufficient sensitivity in a short time, a photosensitive material that has excellent development progress and does not leave any residual color even during short processing times, and dries quickly after washing with water. Sensitive material is required.

Many automatic processors have a built-in drying zone, and if the drying properties of the photosensitive material are poor, the automatic processor will be required to have a higher drying capacity, which means that the automatic processor will be larger. I have no choice but to do it. In addition, as a result of generating a large amount of heat, there are also disadvantages such as an increase in the temperature of the room in which the automatic processor is installed.

To prevent this from happening, efforts are made to make the drying speed of photosensitive materials as fast as possible.

The method used for boat fishing is to add a sufficient amount of hardening agent in advance during the coating process of the photosensitive material, and to reduce the swelling t of the emulsion layer and surface protection layer during the development, fixing and water washing processes. This method reduces the water content in the photosensitive material before drying begins.

In this method, if a large amount of hardening agent is used, the drying process can be accelerated accordingly, but by strengthening the hardening agent, development may be delayed and deterioration may occur, or the covering power may be reduced, and undeveloped halogen This method has the drawbacks of various disadvantages, such as a delay in the fixing speed of silver oxide particles, worsening of residual color, and an increase in residual hypo in the photosensitive material after processing. On the other hand, reducing the water content in the photosensitive material before drying starts by reducing the water content of the photosensitive material by hydrophilic substances such as gelatin, synthetic polymers, etc. that are applied to the photosensitive material.
It can also be done by reducing and drying hydrophilic low-molecular substances, etc. Hydrophilic low-molecular substances are generally added to prevent drying fog of silver halide during the coating process, and if they are removed, the photosensitive material will suffer from fog. On the other hand, if gelatin and synthetic polymer substances used as binders for silver halide grains are removed, the amount of binder to silver halide grains will decrease, resulting in so-called high silver. .

Decreasing the amount of binder has the disadvantage of worsening graininess in terms of photographic performance, and increasing and decreasing sensitivity due to scratches and bends when handling the photosensitive material becomes less than 1-7. Even if an attempt is made to improve drying properties, it is impossible to do so without leaking the amount of binder due to these adverse effects. Under these circumstances, there is a need for a technology that can achieve sufficient sensitivity in a short processing time, has excellent fixing properties and washability, leaves no residual color, and dries in a short time. Kaisho 63-68837 and Kaisho 63-1
No. 49641, at least 11! In the development process using an automatic processor for a photographic light-sensitive material having a silver halide emulsion layer of 10% of the total weight of the material applied before processing (substances, other organic substances) during the development-fixing-washing-drying process.
This can be achieved by designing the sensitive material so that it will wash away.

(RB to be Solved by the Invention) However, there is a problem in that when a sensitive material provided with such a function is processed and packaged and placed in a high temperature environment, fogging is likely to occur and the sensitivity is likely to decrease. Various attempts were made, such as adding anti-capri agents, but side effects such as a decrease in initial sensitivity occurred, and it was difficult to find a solution.

(Objective of the Invention) The object of the present invention is to have a sufficiently fast drying rate, a higher covering power, and a high sensitivity sufficient for short processing times with excellent high-temperature storage stability and dura progression. The object of the present invention is to provide a method for preparing a photographic material that can achieve tπ.

In particular, it is an object of the present invention to provide a method for preparing an X-ray photographic material having the above-mentioned properties.

(Means for Solving the Problems) The above object of the present invention is to provide a support having at least one photosensitive silver halide emulsion layer and at least one surface retaining layer, and represented by the general formula (I). A hardening agent was included in either or both of the emulsion layer and the surface protective layer. It is a photosensitive material, and the moisture content of the photosensitive material is 40% or more and 60% at relative humidity at 25°C in processed form (sealed state).
organic substances (e.g. gelatin, matting agents, The photosensitive material is coated in such a way that more than 10% of the total Mfi applied before processing (plasticizers, synthetic polymeric substances, other organic substances) leaches out during the development, washing, and drying processes. This can be achieved by adjusting the method.

General formula (I) CHχ-CN3(hcH(OCI()-5OtCH2C
LRR In the formula, R is a hydrogen atom, an alkyl group, an aralkyl group,
It represents an aryl group, and these groups may be substituted.

n represents O or 1.

To explain in more detail, R is a hydrogen atom or a carbon number of 1 to
20 alkyl groups (e.g. methyl group, ethyl group, etc.),
Aralkyl groups having 6 to 20 carbon atoms (e.g. benzyl group, phenethyl group, etc.), aryl groups having 5 to 20 carbon atoms (e.g. phenyl group, naphthyl group, pyridyl group, etc.), and these groups may be substituted. Examples of substituents include sulfonic acid groups, hydroxyl groups, and carboxyl groups. Particularly preferred as R is a hydrogen atom. n represents O or 1.

Examples of hardeners represented by general formula (I) used in the present invention are listed below, but the present invention is not limited thereto.

■-1) ■-2) ■-3) ■-4) CHtoCH3(hcflzsOzcH=clhCH2*
CH30□CIh0CIhSOtCH=CHxCHt=
C)ISO2CHSOzCH=CHaCHz=CH5O
zCHSOtCH=CHiC! H5 CHz=CH3OzCHSOtCH=CHt■-7) 1-11) CHz-CH5OtCH5OzCH=CHtCHg=C
H5 (hCH5 (hcIl=cHzSO, Na 5o, Na) The amount of the hardening agent used in the present invention can be arbitrarily selected depending on the purpose. Usually, it is 0% to the dry gelatin.
It can be used in proportions ranging from 401 to 20 times. The hardener of the present invention is particularly preferably used in a proportion ranging from 0.05 to 15 weight percent. In a method of extending the chain length of gelatin by curing, it can also be effectively used as a curing agent for partial curing.

Furthermore, it can also be used to harden such chain-extended gelatin.

As the hardening agent of the present invention, any black-and-white photographic material using gelatin can be used. Examples include black-and-white photosensitive materials such as black-and-white photographic film, X-ray film, plate-making film, black-and-white photographic paper, aviation film, microfilm, facsimile film, and graph film.

In addition, in this case, the hardener of the present invention may be used as a halogenated emulsion layer or a non-photosensitive layer such as an undercoat layer, a backing layer, a filter layer, etc. in addition to the surface protection layer. It can also be used in gelatin-containing photographic layers such as intermediate layers.

The hardener of the present invention may be used alone, or two or more kinds of hardeners of the present invention may be used in combination. It may also be used in combination with other hardening agents known so far. Examples of known hardening agents include aldehyde compounds such as formaldehyde and glutaraldehyde, ketone compounds such as diacetyl and cyclobentanedione, bis(2-chloroethylurea L 2-hydroxy-46-dichlororJ-1, 3,5) Leah Jin, et al. U.S. Patent No. 3,288,775, 2,732°30
No. 3, British Patent No. 974,723, ibid.

Compounds containing reactive halogens such as those described in No. 167.207, divinylsulfone, 5-acetyl-1,3-diacryloyl-, 14+hydro-1,3
, 5') Reazin, etc. US January Patent No. 3.635,
No. 718, No. 3,232.763, British-Russian Patent No. 994
, 869, etc., N-hydroxymethylphthalimide', and other U.S. Pat. Nos. 2.732.316 and 2,586.
N-methylol compounds described in No. 168 etc.
Isocyaners described in U.S. Pat. No. 3,103.437, etc., U.S. Pat. No. 3,017.280,
Aziridine compounds described in U.S. Patent No. 2,983.611, etc., U.S. Pat.
Examples thereof include acid derivatives described in US Pat. No. 25,295, etc., epoxy compounds described in U.S. Pat. Or wA Kikidai compound MI! Examples of metals include chrome light pan, zirconium sulfate, etc. Also, compounds in the form of a precursor instead of a monovalent compound, such as alkali metal vinyl rulphite aldehyde adducts, methylol derivatives of hydantoin, primary aliphatic ditroalcohols, mesyloxyethylsulfonyl compounds , chloroethylsulfonyl compounds, etc. may be used in combination. When the hardening agent of the present invention and other hardening agents are used in combination, the proportion of the hardening agent of the present invention can be selected at any rate depending on the purpose and effect, but the hardener of the present invention! It is preferable that the film agent accounts for 50 mol% or more.

A compound that promotes hardening of gelatin can also be used in combination with the Wll side coating of the present invention. For example, the hardening agent of the present invention and the polymer containing a sulfinic acid group described in JP-A No. 56-4141 are used together as a hardening agent.

The gelatin to which the hardening agent of the present invention is applied is, in its manufacturing process, subjected to so-called alkali-treated (lime-treated) gelatin immersed in an alkaline bath, acid-treated gelatin immersed in an acid bath, or both treatments before gelatin extraction. Double-soaked gelatin or oxygen-treated gelatin may be used. Wood hardeners are made by heating these gelatins in a water bath or exposing them to proteolytic oxygen to partially hydrolyze low-molecular-weight seratin. can also be applied.

The organic substance used in the present invention may be lost by physical elution or by chemical reaction, specifically, in the emulsion amount and/or other hydrophilic colloid layer. It is preferable to contain an organic substance that may flow out during the development process. When the substance to be washed away is gelatin, it is preferable to use a type of gelatin that is not involved in the cross-linking reaction of gelatin with a hardening agent, such as acetylated gelatin or phthalated gelatin, and those with a small molecular weight are preferable. As the polymer substance, polyacrylamide as described in US Pat. I such as pullulan! Types are also valid.

Among them, polyacrylamide and dextran are preferred;
Polyacrylamide is a particularly preferred material.

The average molecular weight of these substances is preferably 20,000 or less, more preferably 10,000 or less. The flow rate during processing is 10% of the total weight of coated organic material other than silver halide grains.
above, 50% or less is effective, preferably 15% or more, 3
Preferably, it disappears by 0% or less.

Processing using a hardening film during development and a hardening film during fixing is common in rapid automatic processing of X-ray sensitive materials, but the present invention uses a type of developer that does not apply a hardening film during development. This is also noticeable in automatic processing using a combination of a fixer solution that does not harden the film during fixing, or only slightly hardens the film during fixing.

The layer containing the effective substance washed away in the process of the present invention may be an emulsion layer or a surface protective layer, but if the total amount of the effective substance coated is the same, the layer containing the effective substance in the surface protective layer is more effective than the layer containing it only in the emulsion layer. It is preferable to include the organic substance in the emulsion layer, and it is even more preferable to include it only in the surface protective layer.In a sensitive material with a multilayer emulsion layer, when the total amount of the organic substance coated is the same, it is more preferable to include it in the surface protective layer. It is preferable that a large amount of the compound be contained in a nearby emulsion layer.

The emulsion layer of the silver halide photographic light-sensitive material of the present invention can contain ordinary silver halide grains (eg, spherical grains). These are P. gelafchides (P, G
``Chimie et Physiqu Photography'' (Lafkides)
e Photographique)J (Ball・
(Published by Paul Monte1, 1967),
G. F. Duffin
) Author: Photographic Emulsion Chemistry
mistry) J (The Focal Press The
Focal Press, 1966), V. L. Zeliks+a
Making and Coating Photographic Emulsions (Making and Coating Photographic Emulsions) by N et al.
and Coating Photographic E
mulsion)” (Focal PressThe Fo
Cal Press, 1964).

The silver halide may be any one such as silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide, and silver chloride.

In the process of silver halide grain formation or physical ripening,
Cadmium salts, zinc salts, lead salts, thallium salts, iridium salts or complex salts thereof, rhodium salts or complex salts thereof, iron salts or iron complex salts, etc. may be present together, and if necessary, chemical sensitization may be performed. .

Chemical sensitization methods include gold sensitization using so-called gold compounds (for example, U.S. Pat. Nos. 2,448,060 and 3,32).
No. 0,069) or sensitization methods using metals such as iridium, platinum, rhodium, palladium (for example, US Pat.
No. 48,060, No. 2.566.245, No. 2,56
6.263) or a sulfur sensitization method using a sulfur-containing compound (for example, U.S. Pat. No. 2,222,264), a reduction sensitization method using tin salts, polyamines, etc., or a combination of two or more of these methods. Can be used.

Tabular grains can also be effectively used as silver halide grains applicable to the present invention.

The tabular silver halide grains can be produced by appropriately combining methods known in the art.

The tabular silver halide emulsion is manufactured by Cugnac.
and Chateau r Evolution of the morphology of silver chloride crystals during physical ripening (Evolution of the morphology of silver bromide crystals)
"Crystals Dueling Physical Living)" Science, Engineering, Indus [Rie Photography, Volume 33, Floor 2 (I962), pp, 121-1
25. Photography Emulsion Chemistry by Duffir+
aphic emulsion) chemist
y) J Focal Pres
s), New York, 1966, 2.66-p, 72
, Δ, P, H.

]・Trivelli, W, F,
Smith Photographic Journal, 80
JP-A-58-127,921, JP-A-58-113,927, which are described in Vol., page 285 (I940), etc.
It can be prepared into a container by referring to the method described in JP-A-5-113-928.

In addition, a seed crystal in which tabular grains are present in an amount of 40% or more by weight is formed in an atmosphere with a relatively low pBr value of pBrl, 3 or less, and silver and halogen solutions are simultaneously added while maintaining the pBr value at the same level. Obtained by growing seed crystals.

During this grain growth process, it is desirable to add a silver and halogen solution to prevent new crystal nuclei from forming.

The size of tabular silver halide grains depends on factors such as humidity, type of solvent and selection of grains, silver salt used during grain growth, and addition rate of halide. - Can be adjusted by rolling.

The photographic emulsion used in the present invention can contain various compounds for the purpose of preventing fogging or stabilizing photographic performance during the manufacturing process, storage, or photographic processing of the light-sensitive material. That is, azoles such as benzothiazolium salts, nitroindazoles, dil-lovenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzitrizoles; mercaptothiadiazoles, aminotriazoles, benzotriazoles, nitrobenzotriazoles, mercaptotetrazoles (especially l
mercaptopyrimidines; mercaptotriazines; thioketo compounds such as oxazolinthione; azaindenes, such as triazaindenes, tetraazaindenes (especially 4-hydroxy substituted (I, ,3a,7
) tetrazaindenes), pentaazaindenes, etc.;
Many compounds known as antifoggants or stabilizers can be added, such as benzenethiosulfonic acid, benzenesulfinic acid, benzenesulfonic acid amide, and the like. For example, U.S. Patent No. 3.954, . No. 474, same 3,
Those described in No. 982,947 and Japanese Patent Publication No. 52-28,660 can be used.

The silver halide grains used in the present invention may be spectrally sensitized with a sensitizing dye.

The dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol 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. That is, pyridine nucleus, oxazoline nucleus, thiazoline nucleus 9, virol 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 A nucleus in which an aromatic hydrocarbon ring is fused to these nuclei, that is, an indolenine nucleus,
Benzindolenine nucleus, indole nucleus, benzoxadole nucleus, naphthoxazole nucleus, benzothiazole nucleus,
A naphthothiazole nucleus, a benzoselenazole nucleus, a benzimidazole nucleus, a quinoline nucleus, etc. are applicable.

These nuclei may be substituted on carbon atoms.

Ketomechi for merocyanine pigments or complex merocyanine pigments! Examples of the nucleus having the /in structure include the virazolin-5-one nucleus, the thiohydantoin nucleus, and the 2-thioxazolidine-
2,4-dione nucleus, thiazolidine-2,4-dione nucleus,
A 5- to 6-membered heterocyclic nucleus such as a rhodanine nucleus or a thiobarbic acid nucleus can be applied.

Specifically, Research Disclosure Volume 176
Those described in RD-17643 (December 1978 issue), page 23, and US Pat. No. 4,425.425 and US Pat. No. 4,425.426 can be used.

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 3,63
5,721), 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 Nos. 3,615°613, 3,615.641, 3,617.295, 3
, 635,721 are particularly useful.

The timing of adding the sensitizing dye used in the present invention to the emulsion is as follows:
This is generally carried out before the emulsion is coated on a suitable support, but it may also be carried out in a chemical ripening step or in a silver halide grain forming step.

The emulsion layer of the photographic material of the present invention may contain a plasticizer such as a polymer or an emulsion in order to improve pressure characteristics.

For example, British Patent No. 738,618 describes heterocyclic compounds, British Patent No. 738,637 describes alkyl phthalates, British Patent No. 738,639 describes alkyl esters, and U.S. Patent No. 2,960,404 describes polyhydric compounds. Algol, same 3.1
No. 21.060 contains carboxyalkylcellulose,
Japanese Patent Publication No. 49-5017 discloses a method using paraffin and a carboxylic acid salt, and Japanese Patent Publication No. 53-28086 discloses a method using an alkyl acrylate and an organic acid.

The photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material prepared using the present invention may include coating aids, antistatic properties, smoothness improvement, emulsification dispersion, adhesion prevention, and photographic property improvement (e.g.,
Various surfactants may be included for various purposes such as development acceleration, high contrast, and sensitization.

For example, saponins (steroids), alkylene oxide derivatives (e.g. polyethylene glycol, polyethylene glycol/polypropylene glycol condensates, polyethylene glycol alkyl ethers or polyethylene glycol alkyl aryl ethers, polyethylene glycol esters, polyethylene glycol sorbitan esters, polyalkylene glycols Nonionic surfactants such as alkylamines or amides, polyethylene oxide adducts of silicone), glycidol derivatives (e.g. alkenylsuccinic acid polyglycerides, alkylphenol polyglycerides), fatty acid esters of polyhydric alcohols, alkyl esters of sugars, etc. Agents; alkyl carboxylates, alkyl sulfonates, alkylbenzene sulfonates, alkylnaphthalene sulfonates, alkyl sulfates, alkyl phosphates, N-acyl-N-alkyl taurines, sulfosuccinates, sulfonate Carboxy groups, such as alkyl polyoxyethylene alkylphenyl esters, polyoxyethylene alkyl phosphate ethers, etc.
Anionic surfactants containing acidic groups such as sulfo groups, phospho groups, sulfate ester groups, phosphate ester groups; amino acids;
Amphoteric surfactants such as aminoalkyl sulfonic acids, aminoalkyl sulfates or phosphates, alkyl betaines, and amine oxides; complexes such as alkyl amine salts, aliphatic or aromatic quaternary ammonium salts, pyridinium, and imidazolium. Cationic surfactants such as ring quaternary ammonium salts and phosphonium or sulfonium salts containing aliphatic or heterocycles can be used.

These are written by Ryohei Oda et al. “Surfactants and their applications” (t
a used bookstore 1964), “New Surfactants” by Hiroshi Horiguchi (
Tool Publishing Co., Ltd., 1975) or [McCation's Detergent and Emulsion Fires] (Matsukation Division, MC Publishing Company, 1985) ('Mc
Cuteheons' Detergent, s&E
ulsifiers J (McCuteheon
Divisions.

MCP Publishing Co., 1985)
), JP-A-6076741, JP-A-62-1723
No. 43, No. 62-173459, No. 62-21527
It is written in No. 2, etc.

As a Wt inhibitor, in particular, JP-A-62-21.0904
4, fluorine-containing surfactant or polymer described in JP-A No. 62-215272, JP-A-60-76742, JP-A-62-215272.
No. 0-80846, No. 60-80848, No. 60-8
No. 0839, No. 6076741, No. 5B-20874
No. 3, JP-A-62-172343, JP-A No. 62-1734
59, No. 62-215272, etc., or JP-A-5720
Conductive polymers or latexes (nonionic, anionic, cationic, amphoteric) described in No. 4540 and JP-A No. 62-215272 can be preferably used. In addition, as inorganic antistatic agents, ammonium, alkali metal, alkaline earth metal halogen salts, nitrates, perchlorates, sulfates, acetates, phosphates, thiocyanates, etc.
Preferably used are 1iit tin oxide, zinc oxide, or composite oxides prepared by doping antimony or the like with these metal oxides, as described in JP-A-57-118242.

In the hydrophilic colloid layer of the photographic material of the present invention, polyols such as trimethylol, propane, bentanediol, butanediol, ethylene glycol, and glycerin are used as pressure fog preventive agents (plasticizers) during drying during the manufacturing process. be able to.

In addition, the photographic material of the present invention may optionally include an intermediate layer,
It can have a filter layer, an antihalation layer, etc.

In the photographic material of the present invention, the photographic emulsion layer and other layers are coated on a flexible support such as a plastic film commonly used in photographic materials. Useful flexible supports include films of semi-synthetic or synthetic polymers such as cellulose nitrate, cellulose acetate, cellulose acetate butyrate, polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate, and the like. The support may be colored using dyes or pigments.

The layer structure of the silver halide photographic light-sensitive material used in the present invention is as follows:
No. 841, No. 58-111934, JP-A-61-20
Preferably, the support has at least one silver halide emulsion layer on each side, as described in No. 1235 and the like.

In the present invention, there are no particular limitations on the method of coating the emulsion layer, surface image t1 layer, etc. on the support, but for example, U.S. Pat. , No. 2,761.791 and the like can be preferably used.

The moisture content of the photosensitive material in the processing state (I!? closed state) is determined by setting the temperature and humidity of the drying air immediately after the drying point to the desired temperature and humidity during coating and drying, and while maintaining the temperature and humidity. It can be controlled by processing or by adjusting temperature and humidity during processing.

The method for preparing the photosensitive material of the present invention is not limited to 25°C, and the water content of the photosensitive material is 4.
This means that the relationship is in equilibrium with a relative humidity of 0% or more and 60% or less.

The developer used in the present invention can contain known developing agents. As the developing agent, dihydroxybenzenes (e.g. hydroquinone), 3-pyrazolidones (e.g. l-phenyl-3-pyrazolidone), aminophenols (e.g. N-methyl-P-aminophenol, etc.) may be used alone or in combination. can.

The developing solution W generally contains other known preservatives, alkaline agents, p
Contains H street slowing agent, antifogging agent, etc., and further contains a melting aid, color toning agent, development accelerator (for example, quaternary salt, hydrazine, benzyl alcohol), surfactant, antifoaming agent, etc.
water softeners, hardeners (e.g. glutaraldehyde),
It may also contain a viscosity-imparting agent.

As the fixer, one having a commonly used composition can be used. As the fixing agent, in addition to thiosulfates and thiocyanates, organic sulfur compounds known to be effective as fixing agents can be used.

The fixing solution may contain a water-soluble aluminum salt as a hardening agent.

The developing method using an automatic developing machine in the present invention includes a roller conveyance type automatic processing method described in U.S. Pat. No. 3,025,779, U.S. Pat. It is desirable to use a developing machine.

The developing temperature is 18°C to 50°C, especially 30°C to 45°C.
℃ is desirable, and the development time is 8 seconds to 40 seconds.
It is preferably 8 seconds to 25 seconds.

The entire development process from the start of development to the end of fixing, water dissolution and drying is preferably from 30 seconds to 200 seconds, particularly from 40 seconds to 100 seconds.

There are no particular restrictions on the various additives, development methods, exposure methods, etc. of the photosensitive material of the present invention, and there are no particular restrictions on the various additives, development methods, exposure methods, etc.
May) and Vol. 184, Item 18431 (August 1979) can be referred to.

(Example) Next, the present invention will be specifically explained.

Example 1 (I) Preparation of sample consisting of potato-shaped silver iodobromide grains Formation of potato-shaped grains of silver iodobromide (3 mol % silver iodide) in the presence of ammonia by the double jet method and average grain size. size 0.98 pm), chemically sensitized with chlorauric acid salts and sodium thiosulfate. After chemical sensitization, an anti-capri agent 4-hydroxy-6-methyl-1,3,3a,7-titrazaindene was added to obtain sensitizing dye (I) with the following structural formula.
Ortho sensitization was carried out by adding 200 mg of per mole of silver halide grains.

This was used as the basic coating solution.

C@F,? Soko K.

C3H? CsF+tSOJnCH*h (Cut-3OsN
(a) Furthermore, trimethylolpropane as a plasticizer, dodecylbenzenesulfonate as a coating aid, and polypotassium p-vinylbenzenesulfonate as a thickener were added to form a basic coating solution for the emulsion layer.

The weight ratio of silver/gelatin at this time was 1.35. On the other hand, as a surface protective layer, in addition to gelatin, molecules i1B, 0
A 7 wt % gelatin aqueous solution containing 0.00 polyacrylamide (0.7 g/per 1 g of surface protective layer gelatin), polymethyl methacrylate fine particles, saponin, sodium polystyrene, and a compound with the following structure as an antistatic material was beaten with Cs H. SelfFrtSOtN+CHtCHgOBlueT]
-(CHt Cut cH!oh-n Immediately before coating, 1°2-(bisvinylsulfonylacetamido)ethane was added to the emulsion layer in an amount of 6.5 wt% of the total amount of gelatin contained in the surface protective layer and the emulsion layer. This was used as a comparison coating solution.As shown in Table 1, using this as the basic formulation, hardener compound !-1 of the present invention and compound 1-
A coating solution was prepared by adding each of 2 in the amounts shown in Table 1 immediately before coating. These coating solutions were coated on both sides of a polyester support and dried to prepare an X-ray photosensitive material. At this time, the humidity of the drying air immediately after the drying point was changed. Subsequently, it was processed while substantially maintaining that state. The amount of silver coated was 2.5 g/rd per side, the amount of gelatin coated for the surface retention layer was 1.3 g/rd per side, and the emulsion layer was 1. 85g
/nl: Conditions were set so that 25°C in processing state
The relative humidity at 30%, 45%, and
They were 0%, 60%, 65%, and 70%.

(2) Evaluation of dura mater progression, sensitivity and Ds+ax (I)
Immediately after the processing described in , the samples were incubated at 25°C for 1, 2, and 3 days.
4th, 5th, 6th, 7th, 10th, 14th, 21st, 2
After the 8th day, I used an optical wedge (
Irradiated with light in the green light range through a light filter, and using a developing solution and a fixing solution with the following composition, a roller conveyance type automatic development 111PPM-4000-1 manufactured by Fuji Photo Film Co., Ltd. was used to perform normal drying. t.

The normal rapid processing was carried out for 90 seconds with drying, and the sensitivity (logarithm of the reciprocal of the exposure interval required to obtain a blackening density of fog + 0.5) and the maximum density (Dmax) were determined (Article A (4)
On the other hand, immediately after the processing described in (I), the sample was heated to 40"C for 24 hours.
After standing for a period of time, the above-mentioned sensitometry was performed. (Condition B), considering B condition as a condition in which dura progression is saturated, the value of the minimum number of stitches at which the performance of condition A, which has been left for a different number of days, almost matches the performance of condition B, is the value of the dural progression of the processed sample. It is shown in Table 1 as a scale. It should be noted that there was virtually no significant difference between the attained sensitivity and Dmax of the sample in which dura mater progression was saturated.

(Developer) 1-phenyl-3-pyrazolidone 1.58 Hydroquinone 30g 5-Nitroindazole 0.25g Potassium bromide
3.0g anhydrous sodium sulfite
50g potassium hydroxide
30e Boric acid 10g Glutaraldehyde j 5g Add water to bring the total volume to 11 (pH adjusted to 10.20 9) (Fixer) Ammonium thiosulfate 200.0g Sodium sulfite (anhydrous) 20.0g Boric acid
8.0g Disodium ethylenediaminetetraacetate 0.1g Aluminum sulfate 15.0g Sulfuric acid
Add 22.0g of 2°Og glacial acetic acid (pH adjusted to 4.20). The following method can be used to measure what percentage (weight ratio) of the organic material coated on the surface has been washed away. The dura progression was saturated (the 2-day sample was first left at 25°C and 10% relative humidity until the water content of the sample reached equilibrium with the atmosphere, and then the weight of the sample was measured. After processing the sample from development to drying using an automatic developing machine, it was left again at 25°C and 10% relative humidity, and when the moisture content reached equilibrium, heavy Q determination was carried out. The weight of the support was measured at L7, and it was determined as %9i'Q that there was no change in weight due to the treatment of only the support.

The developed silver weight ratio was determined by uniform or no 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 was calculated. From these values, the weight of the organic material washed away during the treatment was determined. Although inorganic salts were also contained in the emulsion, their weight was negligible compared to the loss of organic substances. Here, the amount of organic substances washed away was determined by weight measurement, but the value can also be found by measuring the film thickness before and after treatment, and the amount of washed out substances can also be quantified by analyzing the treatment liquid. All wetting amounts determined by the former method were 12.5-13.5%.

(4) Measurement of drying speed After washing with water using the processing agent in (2) and FPM-4000, the film was squeezed and was taken out just before it entered the drying zone, and the following measurements were carried out (at the time of this measurement, FPM-4000
00 drying air was stopped). While blowing hot air onto the taken-out film using a commercially available dryer, the time until the temperature of the film surface reached 30°C was measured using a surface thermometer. The development temperature was 35°C, and the rinsing water temperature was 14°C. All samples used were samples in which dura mater progression was saturated. All samples measured were from 16 seconds to 17 seconds.
It had a value of seconds.

(5) Evaluation of high-temperature storage stability Samples that have been aged for a number of days until it is considered that the dura mater progression in (2) has been saturated are left at 60°C for 3 days, and the same conditions as in (2) are taken. Sensitometry was performed to measure changes in sensitivity and fog to evaluate storage stability.

The results are shown in Table 1.

From Table 1, it is clear that the dura progression of the samples using the hardening agent of the present invention is extremely rapid. It is clear that the samples using the hardener of the present invention at a relative humidity of 40% to 60% are superior to the comparative samples in both high-temperature storage stability and hardening progress. Even at a relative humidity of 30%, as mentioned above, the dura progression is good, but the high temperature storage stability is poor.

Example 2 Preparation of a sample consisting of plate-like silver iodobromide grains and high temperature storage test The thickness of silver iodobromide (silver iodide 3.5 mol%) was measured in the presence of ammonia and potassium thiocyanate by the double jet method. Plate-like twin grains were formed. The average particle size is 0.7 as the average diameter of spheres with the same volume as each particle (sphere equivalent diameter).
It was 8 μm. The particles were chemically sensitized with chloroauric acid salts and sulfur thiosulfate. Thereafter, ortho-sensitization was carried out by adding 400 μm of an enhancing dye (II) having the following structure per mole of silver halide grains.

(n) SOs' SO3Na The rfi/gelatin weight ratio of this emulsion was 1.05.

A binder, a coating aid, a thickener, etc. were added in the same manner as in Example 1 to prepare a basic coating solution for an emulsion layer. This also includes Example 1
The same surface protection N coating solution was prepared as in Example 1, and a hardening agent was added just before coating. Exactly the same samples were prepared except for the following. Using this sample, the same test as in Example 1 was conducted to confirm the effect of improving the storage stability of the sample processed using the hardener of the present invention at a relative humidity of 40% to 60%.

Example 3 (I) Preparation of a sample consisting of a silver iodobromide tabular grain emulsion Potassium bromide, potassium iodide and silver nitrate were added to an aqueous gelatin solution with vigorous stirring to give an average projected area diameter of 0.08 m
Tabular grains having a diameter of 3 μm and an average thickness of 08161 μm were prepared (average iodine content 0.8 mol %).

Thereafter, the mixture was washed with water using a conventional precipitation method, 744 μ/Ag-1 mol of a sensitizing dye represented by the following structural formula was added, and then chemically sensitized using a gold-sulfur sensitization method using chloroauric acid and sodium thiosulfate. The preparation of the emulsion was completed.

The antifoggant 4-hydroxy-6methyl-1 was added to this emulsion.
．． 3.3a, tetrazaindene, coating aid dodecylbenzenesulfone hydrochloric acid, thickener polybotacium p-vinylbenzenesulfonate, etc. were added to prepare a basic coating solution for the emulsion layer. The weight ratio of silver/gelatin at this time is 1.02
It was 6.

On the other hand, keep the surface! For layer 11, a coating solution having exactly the same formulation as in Examples 1 and 2 was prepared. The only difference from Example 1 was the hardening agent added to the emulsion layer immediately before coating, and the coating and drying was carried out in the same manner as in Example 1, but the coating and silver amount was 1.9 g/I per side.

(2) Experiment 1 to confirm the effects of the present invention In an experiment similar to Example 1, samples processed using the hardener I-3 of the present invention at a relative humidity of 40% to 60% showed no hardening progress. It was shown that it has excellent properties and good storage stability at high temperatures.

(3) Experiment 2 to confirm the effects of the present invention 1) Measurement of dry to dry 48 seconds processability and outflow amount An automatic processor capable of implementing the following composition and conditions was prepared.

<Developer: Test solution a> Potassium hydroxide 56.6g Sodium sulfite 200g Diethylenetriaminepentaacetic acid 6.7g Potassium carbide
16.7g boric acid
10g hydroquinone 83
．． 3g diethylene glycol 40g4
-Hydroxymethyl-4 Methyl 1-phenyl-3-virazolidone 11.0g5-Methylbenzotriazole 2g Make up to 11 with water (p
(prepared to H10,60).

<Fixer: A test solution> Ammonium thiosulfate 560g Sodium sulfite 60g Ethylenediaminetetraacetic acid disodium dihydrate 0.10g Sodium hydroxide 24g lj with water! (adjust to pH 5.10 with acetic acid).

Automatic developing machine Second processing developing tank 6.5j! 35@cx12.5 seconds fixing tank
6.5ffi 35℃ x 10 seconds water washing tank 6. !
M! Dry at 20℃ x 7.5 seconds
50℃Dry to Dry processing time
When starting the 48-second development process, each tank was filled with the following processing solution.

Developing tank: 333 nl of the above developer concentrate, 661 m of water
10 ml of a starter containing 2 g of potassium bromide and 1.8 g of acetic acid were added to bring the pH to 10.15.

Fixing tank: above developer - AM liquid 250mf! and water 7
50mj! Among the samples of the present invention, a sample processed using hardener compound 1-3 at a relative humidity of 50% (those with saturated hardening progress) was exposed to the same light as in Example 1, and the above-mentioned A dry-to-dry process for 48 seconds was performed according to the conditions. At the same time, a sample under the same exposure conditions was subjected to a 90-second dry-to-dry self-development process using the same processing materials and processor as in Example 1.The sample of the present invention had almost the same photographic properties in both developments [Capri were the same, and the sensitivity difference between the front and rear (logarithmic difference in n light amount) was within 0.03]. It was also confirmed that the drying properties of the former sample were sufficiently acceptable for practical use. Also, the amount of leakage in both automatic processor development was 11.8% in the former.
, the latter was 12.9%.

Preferred implementations of the present invention are described below.

1. A method for preparing a photosensitive material according to the claims, wherein the photosensitive material is an X-ray photosensitive material having at least one layer of silver halide emulsion on both sides of the support.

2. Polyacrylamide, polyvinyl alcohol, polyvinylpyrrolidone, in the emulsion layer and/or the surface protective layer.
The method of 1 above, comprising a photosensitive material containing dextran or sucrose.

3. The method of 1 above using a photosensitive material containing polyacrylamide and/or dextran with an average molecular weight of 20,000 or less in the emulsion layer and/or surface protective layer, where the average molecular weight of the polyacrylamide and/or dextran is 10,000 or less The above method 1.

4. Methods 1 to 3 above using a roller conveyance type automatic developing machine.

Claims (1)

[Scope of Claims] A support has at least one photosensitive silver halide emulsion layer and a surface protective layer, each or either of which has a hardening layer represented by the following general formula (I). It is a photosensitive material that contains an agent, and the moisture content of the photosensitive material is determined by the processing form (
When the relative humidity is 40% or more at 25℃ (closed condition) 60
% or less, and when the photosensitive material is developed using an automatic processor, the amount of organic substances present in the photosensitive material after the development process is 90% of that before the development process. % by weight or less. General formula (I) ▲ Numerical formulas, chemical formulas, tables, etc. are included▼ In the formula, R represents a hydrogen atom, an alkyl group, an aralkyl group, or an aryl group, and these groups may be substituted. n represents 0 or 1.