JPS5953528B2 - Negative silver halide photographic material - Google Patents

Description

[Detailed description of the invention] I Background of the invention Technical field The present invention relates to negative-working silver halide photographic materials.

Prior art and its problems The supply of metallic silver, which is essential as a raw material for silver halide photographic materials, is decreasing, while the demand in various industries is increasing. Efforts are being made to reduce the number of banks.

Among silver-saving silver halide photographic materials for obtaining negative images, the applicant of this application has proposed a material that can significantly reduce the amount of silver, has high sensitivity, high contrast, and has a high maximum density. First, (1) photosensitive silver halide grains, and (2) metal salt particles that are more easily soluble than the photosensitive silver halide grains of (1) and have substantially no photosensitivity, are made to be less soluble. (3) A product containing physical development nuclei has been published (Japanese Patent Application Laid-Open No. 5448544).
issue).

This negative-tone sensitive material is processed with a developer containing a silver halide reducing agent and a substance that dissolves metal salt particles, so that metals corresponding to the metal salt particles are formed on physical development nuclei in the exposed area. It is deposited to obtain a blackened image.

However, in such sensitive materials, a refractory agent such as a 3-mercapto compound such as 1-phenylene-5-menolecaptotetrazone is used to render the easily soluble metal salt particles refractory. Unless a relatively large amount is used, it is difficult to obtain a good negative image.

For this reason, the refractory agent may have an adverse effect on the photosensitive silver halide grains that coexist or exist adjacent to it, resulting in a loss of sensitivity, a decrease in maximum density and gamma, and an increase in fog. It's inconvenient. Furthermore, due to the influence of the refractory agent, photographic properties deteriorate during storage (raw storage) of the photosensitive material, resulting in decreased sensitivity, gamma, etc., and increased fog.

In this case, it has been found that an unexpected and specific phenomenon occurs in terms of raw storage stability, particularly in that the increase in fog is extremely significant under high temperature and low humidity conditions. In addition, in terms of image quality after development, there are drawbacks such as poor graininess and sharpness.

In response to these, the present inventors have previously developed a negative-tone sensitive material to which a poorly soluble agent was added as a precursor (
JP-A No. 55-16642), or one in which a non-diffusing type refractory agent is added (JP-A No. 56-66840). According to the improvement of the refractory agent in these previous proposals, the desensitization property and the like are improved, and the photographic properties can be satisfied.

However, it was found that raw storage stability, especially increased fog and deterioration of graininess due to storage under high temperature and low humidity conditions, was not improved. 11 Purpose of the Invention The present invention was made in view of the above-mentioned circumstances, and its first purpose is to achieve the above (1) detailed in the preceding paragraph.
An object of the present invention is to improve the shelf life of a silver-saving negative-working silver halide photographic light-sensitive material containing (3).

The second objective is to significantly reduce fogging, especially during storage under high temperature and low humidity conditions.

The third purpose is to obtain a high quality image with good graininess, sharpness, etc.

The fourth objective is to provide a negative-sensitive silver halide photographic material that has good photographic properties immediately after production, provides images with extremely high sensitivity and high contrast, and has a low silver content. It's about doing. The present inventors believe that in order to achieve this purpose, rather than improving the refractory agent,
Based on the idea that it is necessary to improve photosensitive silver halide, the present invention has been completed through intensive research.

That is, in the present invention, in the constituent layers formed on the support,
Photosensitive silver halide grains, metal salt particles whose surfaces are made difficult to solubilize with a refractory agent, which are themselves more easily soluble than the photosensitive silver halide grains, and have substantially no photosensitivity, and physical It contains development nuclei and further has the following general formula [
At least one kind of compound represented by [1] and at least one kind of compound represented by the following general formula [11],
This is a negative-working silver halide photographic light-sensitive material, characterized in that it is contained in combination with the photosensitive silver halide grains.

General formula [1] {In the above general formula [1], Q represents a nonmetallic atomic group necessary to complete 1,3-di-1-hydroxybenzene or 1,3-dihydroxynaphthalene.

R1 is a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl group that may have a substituent, an alkoxy group,
Or it represents an acyl group. R2 is -COOM group,
or -SO3M group (M represents a hydrogen atom, an alkali metal atom, or -NH4 group).
m and n are each an integer of 1 or 2. }
General formula [11) {In the above general formula [11], Z is
Represents the atomic group necessary to form an aromatic ring into a five-membered or six-membered heterocycle that may be fused.

The heterocycle formed by Z and C=N is -C
OOM group, SO3M group (where M represents a hydrogen atom, an alkali metal atom, or -NH4 group), a hydroxyl group, or a substituted or unsubstituted carbamoyl group or sulfamoyl group, or any of these It has at least one substituent.
Furthermore, a halogen atom, an alkyl group, or an ether group may be bonded to the heterocycle or the substituent.
Note that M is the same as above. }111 Specific Configuration of the Invention The specific configuration of the present invention will be described in detail below.

In the compound represented by the above general formula [1], when R1 is a substituted or unsubstituted alkyl group, alkoxy group or acyl group, the number of carbon atoms of these alkyl group, alkoxy group or acyl group is 1 to 3. It is preferable that there be.

In addition, when R1 is an alkyl group, alkoxy group, or acyl group having a substituent, examples of the substituent include the above-mentioned -COOM group, -SO3M (however, M is the same as above).
It is preferable that

Furthermore, when R1 is an alkyl group having a substituent, the substituent of the alkyl group may be .

Note that the number of -COOM groups and -SO3M groups that may be included in R1 and also included as R2 is preferably 1 to 3, more preferably 1 or 2 in total.

Typical specific examples of the compound represented by the above general formula [1] are shown below, but the compound represented by the above general formula [1] is not limited to these specific examples.

As a method for synthesizing the compound represented by the above general formula [1], for example, Gazzetta simica Italiana
) 1972, Vol. 57, pp. 793-802, Chemical abstracts 4
Volume 1, 5495 pages, Henorebetika Siemika Acta (H
elvetica chimica acta) 1960・
Volume 43, page 644, Beilste Utah, IN.
It is easily synthesized by the method described in (inOrganishe Chemie) Vol. 11, p. 304, Vol. 6, p. 978, and US Pat. No. 2,487,586, and the synthesized product can also be easily purchased from the general market.

On the other hand, in the above general formula [11], C=N and Z
Examples of the heterocycle formed by include a tetrazole ring,
Preferred are imidazole ring, oxazole ring, thiazole ring, benzimidazole ring, benzoxazole ring, benzthiazole ring, triazole ring, triazine ring and the like.

In addition, when the substituent bonded to such a heterocycle is or has a substituted carbamoyl or sulfamoyl group, the substituent/group of the carbamoyl or sulfamoyl group has a carbon atom number of 1
-3 alkyl groups are preferred.

Further, the substituent bonded to the above heterocycle is a COOM group,
-SO3M group, hydroxyl group, or substituted or unsubstituted carbamoyl or sulfamoyl group, these groups are bonded to an alkyl group or alkylthio group having 1 to 3 carbon atoms, or a phenyl group, It is preferable to form a substituent! ).

In addition, these COOM groups, etc. that constitute or are included in the substituents bonded to such a heterocycle,
It is preferable that the molecule contains about 1 to 3, usually 1 or 2, in total.

In addition, a halogen atom, an alkyl group, or an ether group (preferably having 1 to 2 carbon atoms) which may be included in the above-mentioned substituents, or which may be directly bonded to the heterocycle in addition to or in place of the substituent. The number is preferably 2 or less in total in the molecule, more preferably 1 at most. Typical specific examples of such compounds represented by the above general formula [IID] include the following, but the compounds represented by the above general formula [11] are not limited thereto. . As a method for synthesizing the compound represented by the above general formula [11], US Pat. No. 3,266,897? British Patent No. 1275
The specification of No. 701 or R. G. DubenkO. ．．
D. Panchenk OKhim. GetevOtsi
kiSOedin. Sb-10Az0ts. 0dev
．． ZhaschieGeter0tsiky199~2
011967K. H0tn1ann:Thechemi
tryOfHet・CyclllccOmpOunds
．． ImidazOleandDerivatives.
Published by Interscience Part-138219
53, etc. may be followed.

The compounds represented by the above general formulas [1] and [11] are respectively contained in combination with state-forming silver halide grains which will be described in detail later.

In this case, both may be added to a constituent layer containing a mixture of photosensitive silver halide grains, metal salt particles, and physical development nuclei; It is preferable to use it by adding it and adsorbing it to shoulder-sensitive silver halide grains.

In such a case, when using it, it is preferable to dissolve it in a hydrophilic organic solvent and then add it to the photosensitive silver halide emulsion. L can also be dissolved and added together.

The amount used is determined by whether one or more of the compounds represented by the general formula [1] are photosensitive halogenated. per mole, 10-3
~1 mol, more preferably 10-0.5 mol, and one or more of the compounds represented by the general formula [11) is 1 mole of photosensitive silver halide, 10-7 to 10-2 mol. , more preferably 10 −5 to] mol. The timing of adding both compounds may be at any time during the photosensitive silver nogenide emulsion production process, but it is advantageous to add them after the chemistry course and before coating. .

On this premise, the photosensitive halogen particles contained as essential components in the negative-tone K of the present invention include silver chloride,
Silver bromide, silver iodide, silver chlorobromide, silver chloroiodobromide, or mixtures thereof are included, but silver iodobromide with high sensitivity is preferably used, especially 50 mol Silver iodobromide containing less than % silver iodide is preferred in the present invention.

Such photosensitive silver halide grains are applied to the present invention in the form of a silver halide emulsion, but the emulsion to be used may be manufactured by various manufacturing methods including the usual manufacturing method, such as Japanese Patent Publication No. 46-J. Methods such as those described in Camo V2, or the so-called convergence emulsion methods described in US Pat. No. 2,592,250, such as the single-jet emulsion method and. It can be prepared by the double jet emulsion method, etc. Further, the photosensitive silver halide grains used in the present invention include those having various crystal habits.

Although the particle size varies depending on the purpose of use of the photographic element, it is usually within the range of 0.1 to 3.0 .mu.m. This photosensitive silver halide emulsion is then chemically sensitized using various chemical sensitizers.

Chemical sensitizers include known sensitizers such as sulfur sensitizers, selenium sensitizers, and noble metal sensitizers, as well as reduction sensitizers,
Polyalkylene oxide-based sensitizers can also be widely used. Furthermore, the photosensitive silver halide emulsion can also be spectrally sensitized using various sensitizing dyes.

If necessary, in addition to the compounds represented by the general formulas [1] and [11), known photographic additives such as tetrazaindenes and tetrazoles may be used to stabilize the emulsion. You can also.

Next, when the surface of the metal salt particles used in the present invention is not coated with the refractory agent,
The metal salt has a higher dissolution rate than the photosensitive silver halide in a substance (described later) that dissolves metal salt particles, and is made of a metal salt that has substantially no photosensitivity.

That is, to explain in more detail, the dissolution rate (
or mass of substance dissolved per unit time), (4)
, (B) When measured under the condition that the total mass of the particles contained in both particle groups is equal to each other, it is necessary that the mass of the particle group is larger than that of the particle group (B). As a measurement method for actually verifying whether or not such conditions are met, the following method is suitable.

First, two types of emulsions containing photosensitive silver halide grains and metal salt grains in hydrophilic colloids were prepared,
Two types of samples are prepared by applying each onto a support and drying.

The amount of coating at this time is such that the amounts of photosensitive silver halide, metal salt, and hydrophilic colloid per unit area are equal between the two types of samples. In the measurement, sodium thiosulfate is used as a standard metal salt dissolving agent, and the obtained sample is immersed in a 5% aqueous sodium thiosulfate solution (temperature 20° C.) without stirring.

The immersion time is set at several levels, for example 2 seconds, 5 seconds and 8 seconds. Next, the sample is immediately transferred to a water tank, washed with water, and then dried. The residual photosensitive silver halide and residual metal salt amounts of the sample treated in this manner are analyzed and measured by a known method, and the residual rate (%) is determined for each. A graph of the residual rate and immersion time is drawn, and the immersion time t1 of the photosensitive silver halide sample and the immersion time T2 of the metal salt particle sample corresponding to a residual rate of 50% are determined, and the value of T2/t1 is determined.
The value of T2/t1 determined in this way needs to be smaller than 1, and preferably smaller than 0.7.

The metal salt particles are readily soluble in the sense described above, but at the same time they are substantially non-photosensitive.

In this case, in the present invention, "not photosensitive" means "non-photosensitive" in relation to the photosensitive silver halide, and specifically, It should be understood that when the light energy necessary to sensitize the photosensitive silver halide is applied to the sensitive material of the present invention, it is "substantially not sensitized" depending on the light energy.

More specifically, the metal salt particles of the present invention are fine particles of a metal salt that generally have at most 1/10 the photosensitivity of the photosensitive silver halide. The metal salt particles used in the present invention may be appropriately selected from those having the above properties.

However, in a preferred embodiment of the present invention, the metal salt grains are silver halide grains that do not have substantial photosensitivity, and compared to the photosensitive silver halide grains, the metal salt grains are made of a substance that dissolves the silver halide grains. Particles are selected that have a high dissolution rate.

More specifically, the metal salt particles preferably applied to the present invention are pure silver bromide, pure silver chloride, or a mixed silver halide thereof that has not been subjected to chemical sensitization treatment, and is It is preferable that the crystals be finer than the above.
The metal salt particles used in the present invention are used in an amount of 0.1 mol to 100 mol per mol of photosensitive silver halide.

In addition, metal ions or metal complex ions generated as a result of dissolving such metal salt particles in the presence of a metal salt dissolving agent described below are reduced to metals on physical development nuclei described below in the presence of a reducing agent. It is something.

The surfaces of the metal salt particles used in the present invention are coated with a refractory agent, which is adsorbed onto the surface of the metal salt particles or forms a part of the particle surface that becomes an active site for the dissolution reaction. This is a compound that slows down the dissolution rate of particles in the presence of the metal salt dissolving agent by adsorbing to the metal salt dissolving agent.This poorly soluble agent also adsorbs to the surface of the easily soluble metal salt particles and dissolves the metal ions of the metal salt. It also includes compounds that form poorly soluble salts or complex salts. According to one preferred embodiment of the present invention, the refractory agent is selected from compounds that adsorb to non-photosensitive silver halide grains, which are easily soluble metal salt grains, to reduce their solubility.

These compounds are preferably mercapto compounds, more specifically cysteine, 1-phenol-5-
Menolecaptotetrazone, Menolecaptobenzthiazole, Mercaptobenzselenazole, Mercaptobenzoxazole, Mercaptobenzimidazole, Benzinolemenolecaptan, 4-ethal-2-thio-
Oxazoline, 2-mercapto-6-azauracinole,
Representative examples include 4-hydroxy-2-menolecapto-6-methynolepyrimidine, 3-menolecapto-4-phenylene-5-methynole-1,2,4-triazole, and the like.

Further, thiourea, intazoles, triazoles, imidazoles and the like are also preferred compounds that can be used in the present invention. Among these, mercaptotetrazole compounds are particularly preferred.

On the other hand, the physical development nucleus used in the present invention is, for example, a noble metal such as gold, silver, or platinum, preferably a colloid thereof, a metal sulfide such as silver, palladium, or zinc, or a metal selenide. be able to.

Among these, metal silver particles obtained by reducing silver compounds (for example, silver nitrate, silver halide, etc.), noble metal colloids,
Alternatively, palladium sulfide and silver sulfide are particularly preferred.

Note that this physical development nucleus is a metal ion produced by dissolving the metal salt, or a substance that has the function of catalytically promoting the process in which the metal ion is reduced to a metal by a reducing agent, or such a substance. They contain chemically active sites that have a function and do not necessarily have to be physical particles.

The content of such physical development nuclei in a sensitive material varies depending on the type thereof, but for example, in the case of silver sulfide, it is 0.001 g/M2 to 1.0 g/M2 as metallic silver, for example, metallic silver ( (produced by reducing fine particles of silver chloride), the appropriate range is 0.01 g to 3.0 g/M2.

The photosensitive material of the present invention may have various configurations depending on its purpose or use. I can do that.

That is, the light-sensitive material of the present invention includes (1) photosensitive silver halide grains, (2) metal salt particles that are more easily soluble than the silver halide and have substantially no photosensitivity, and a refractory agent on the support. and (3) physical development nuclei, but even if the above (1) to (3) are contained in separate layers, or the above (1) to (3) Any two or more may be contained in the same layer. For example, on a support, from the support side, a constituent layer containing physical development nuclei, a constituent layer containing metal salt particles, a constituent layer containing photosensitive silver halide grains, and, if necessary, a halogen Starting from the layer structure in which the constituent layers containing the silver oxide developer are laminated in the order, the order of lamination may be reversed, and further, for example, from the support side, the physical development nuclei and the later-described layers are layered as necessary. Coating a constituent layer containing a silver halide developer,
On top of this, a constituent layer in which photosensitive silver halide grains and metal salt particles are mixed and present in the same layer is laminated, and a two-layer structure may be formed. A constituent layer containing a mixture of metal salt particles and physical development nuclei may be coated on a support to form a single layer structure.

Furthermore, as another method, it is possible to apply the constituent layers on both sides of the support, prepare two supports, and form the constituent layers separately for each support, or even three. Supports may be prepared and the constituent layers may be coated one by one on each support.

The preferable layer structure of the sensitive material of the present invention is as follows:
A layer structure in which photosensitive silver halide grains, metal salt particles, and physical development nuclei are mixed in the same constituent layer and coated on the same support as a single layer, or metal salt particles and physical development nuclei are coated on the same support from the support side. A two-layer structure is preferred, in which a constituent layer containing physical development nuclei is coated, and a constituent layer containing only photosensitive silver halide grains is coated thereon.

The layer structure of the photosensitive material of the present invention is as described above, but the photosensitive material of the present invention may include, if necessary,
For example, auxiliary layers such as a protective layer and an antihalation layer can be provided, and photographic additives other than those mentioned above can also be added to this layer.

In the present invention, the photosensitive silver halide, metal salt particles, and physical development nuclei are each used alone or in a mixture of two or more, dispersed in a suitable binder, and present in a predetermined constituent layer.

Various hydrophilic colloids can be used as the binder, and gelatin is typically preferably used.

Furthermore, for the purpose of improving the physical properties of a coating film containing the above-mentioned hydrophilic colloid as a binder, it is preferable to use various film property improving agents, such as a hardening agent, as necessary. Coating film compositions containing hydrophilic colloid as a binder may contain photographic additives other than the above-mentioned hardeners, such as gelatin plasticizers, surfactants, ultraviolet absorbers, antistain agents, and PH regulators, if necessary. , antioxidants, antistatic agents, thickeners, graininess improvers, dyes, mordants, brighteners, development speed regulators, matting agents, silver halide developers described below, etc. that may impair the effects of the present invention. It can be used within a certain range.

Supports used in the photosensitive material of the present invention include, for example, baryta paper, polyethylene-coated paper, polypropylene synthetic paper, glass plates, cellulose acetate, cellulose nitrate, polyester films such as polyethylene terephthalate, polyamide films, polypropylene films, and polycarbonates. Typical examples include film, polystyrene film, etc., and each of these supports is appropriately selected depending on the intended use of the photographic element.

DETAILED DESCRIPTION OF THE INVENTION After exposure, the sensitive material of the present invention is processed with a developer containing a reducing agent and a substance that dissolves metal salt particles.

As the reducing agent used in the developer, a developing agent is advantageously used.

As the developing agent, well-known in the art, for example,
Polyhydroxybenzenes represented by hydroquinone, toluhydroquinone, 2,5-dimethylhydroquinone, etc., such as 1-phenyl-3-pyrazolidone,
3-pyrazolidones represented by 1-phenyl-4-methyl-3-pyrazolidone, aminophenols represented by 0-aminophenol, P-aminophenol, etc., such as 1-(P-hydroxyphenol); 1-aryl-3-aminopyrazolines such as 1-(P-methylaminophenyl)-3-aminopyrazoline, 1-(P-methylaminophenyl)-3-aminopyrazoline, ascorbic acid, etc., C.I. E. K. M staff member T. H. Co-authored by James “Th
eTheOryOfthePhOtOgraphicP
rOcess” 3rd edition (1966, Maanilla
nCO. ,N. Y. ), Chapter 13 and L. P. A. Mas
"PhOtOgl'AphicPrOcessi" by On
ngChemistry” (1966, ThePO
Compounds described as developing agents in CalPress, LOndOn), pages 16 to 16 can be used alone or in combination. A substance that dissolves metal salt particles used in a developer (metal salt dissolving agent) is a substance that acts on metal salt particles to generate metal ions or soluble metal complex ions, and this is a substance that dissolves metal salt particles in the developer solution itself. , for example, water may be used.

In this case, the metal salt dissolving agent is a substance that does not substantially dissolve the photosensitive silver halide, or it is a substance that does not dissolve the photosensitive silver halide in an amount added that does not substantially dissolve the photosensitive silver halide. The material is preferably a substance that dissolves metal salt particles such as fine particles of silver halide having different ions.

Typical specific examples of such metal salt dissolving agents include sulfites such as sodium sulfite, thiosulfates such as sodium thiosulfate, potassium thiosulfate, and ammonium thiosulfate, cyanates such as potassium cyanide, sodium cyanide, and thiocyanide. Thiocyanate salts such as sodium chloride and potassium chloride, amino acid compounds such as cystine and cysteine, thiourea, phenylthiourea, 3,6-dithia-1
- Thiourea compounds such as 8-octadiol, thioether compounds, etc. can be mentioned.

The metal salt dissolving agent is normally contained in the developer, but in some cases it can also be contained in the sensitive material as described above.

Among the above metal salt dissolving agents, sodium sulfite in particular is generally used as a preservative for developing solutions, so the amount used per 11 is 0.1 g to 100 g, more preferably 1 g to 70 g. Preferably, the range is within the range.

The pH of such a developer is 5 or more, preferably PH5.
．． Approximately 5 to 13.2 is optimal.

Further, the developer may contain various additives such as an alkaline agent, a PH buffer, a development accelerator, and an antifoggant, if necessary. The processing temperature using the above processing liquid is 2.
A range of 0°C to 50°C is suitable. By processing with such a developer, the photosensitive silver halide grains in the exposed area are reduced by the reducing agent, and the resulting halogen ions,
In particular, bromide ions and iodide ions destroy the coating of the refractory agent present on the surface of the metal salt.

As a result, the metal salt particles are dissolved in the presence of the metal salt dissolving agent,
It is deposited on the physical development nucleus and becomes black, forming a negative image.
The processing after development may be carried out in accordance with the commonly used processing for black-and-white photosensitive materials, such as stopping and fixing. V
Specific Effects of the Invention According to the present invention, the compounds represented by the above general formulas [1] and [11) are combined and contained in photosensitive silver halide grains, thereby improving raw storage stability and improving storage stability. There is very little deterioration in sensitivity, gamma, maximum density, and gamma.

In particular, fog caused by raw storage under high temperature and low humidity is significantly reduced.

Furthermore, image quality such as graininess and sharpness of the obtained image is also improved.

In addition, the photographic properties immediately after manufacture are good, with high sensitivity and
High contrast images can be obtained.

As a result, a negative photosensitive material is realized that can stably produce images of excellent overall quality. VI Specific Examples of the Invention The present invention will be explained in more detail with reference to specific examples below.

Example 1 [Preparation of photosensitive silver halide emulsion] High-sensitivity iodobromide containing 4.0 mol% silver iodide that was gold-sensitized and sulfur-sensitized and aged to the highest sensitivity by a conventional method. A photosensitive silver halide grain emulsion was prepared by adding 1.5 g of 4-hydroxy-6-methyl-1.3.3a.1.7-tetrazydene per mole of silver halide as a stabilizer to the silver emulsion.

The average grain size of this emulsion was about 1.3 microns. [Preparation of metal salt grains (substantially non-photosensitive silver halide grains)] A pure silver chloride emulsion consisting of silver nitrate and sodium chloride was prepared by a neutral method.

The average grain size of this emulsion was easily soluble silver chloride grains of about 0.1 μm.

[Preparation of physical development nuclei]

Add 0.2% to 10ml of an aqueous solution of 1% polyvinyl alcohol (a polymer with a degree of saponification of 99% and a degree of polymerization of 1000).
Add 50ml of chloroauric acid of 1% to the stirred mixture at room temperature.
10 ml of sodium borohydride was added to form a physical development nucleus for gold colloid.

First, a silver chloride emulsion with substantially no photosensitivity was taken from among the three types prepared as described above, and 1-phenyl-5-mercaptotetrazole was added to 1-phenyl-5-mercaptotetrazole as an insoluble agent to make silver halide 1
1.2 g per mole was added, and then 120 mg of the above-mentioned physical development nucleus was added as chloroauric acid per mole of silver chloride emulsion, and then an appropriate amount of saponin was added as a coating aid to prepare a coating solution.

At the time of application, it was applied uniformly to both sides of a polyethylene terephthalate base that had been subjected to undercoat processing. Subsequently, the photosensitive emulsion prepared as described above was collected and divided into equal parts, and then the above general formula [1] and general formula [1] in the present invention were obtained.
One was prepared in which each of the compounds represented by 1) was added as shown in Table 1 below, and for comparison, one in which each of these compounds was added singly, and one in which no compound was added.

Next, appropriate amounts of saponin as a coating aid and formalin as a hardening agent were added to each, and then both sides were uniformly coated in multiple layers on the silver chloride emulsion layer to prepare a sample.

As for the amount of coating on both sides of the sample that cannot be obtained, the amount of silver in the silver chloride layer as a non-photosensitive silver halide negative emulsion layer is 1.
0g/In! , the physical development nucleus is 1.0 mg/m as gold amount
The amount of silver in the silver iodobromide layer as a photosensitive silver halide emulsion layer is 3.0 g/m! It was hot.

These samples were stored under high temperature and high humidity conditions and under high temperature and low humidity conditions, and then double-sided wedge exposure with 3.2 CMS light was performed.
Table 1 below shows the results of second development, fixing, washing with water, drying, and sensitometry. Developer formulation Phenidone 1.0g Anhydrous sodium sulfite 70g Hydroquinone 25g Potassium bromide
4g caustic soda
20g 5-methylbenzotriazole 0.1g glutaraldehyde (25%)
Add 5.0cc water
Note that in Table 1, the sensitivity is for sample No. 11. It is expressed as a relative value with the sensitivity of l as 100.

Furthermore, gamma represents the slope of the straight line portion of the characteristic curve.

From the results shown in Table 1, the samples belonging to the present invention. The fee is
In particular, there is very little fogging even when left for long periods of time under high temperature and high humidity conditions, and even after raw storage.
It can be seen that images with high sensitivity, high contrast, and high gamma can be obtained.

Example 2 Using exactly the same emulsion and physical development nuclei as used in Example 1, the compounds of general formulas [1] and [11) in the present invention were each made into single monomers, as shown in Table 2 below. Alternatively, they were added in combination for multilayer coating.

The photographic properties obtained by developing the obtained sample in the same manner as in Example 1 are shown in Table 2 below.

Next, the four kinds of photosensitive materials prepared in this way were irradiated with X-rays under the conditions of a tube voltage of 100K and a tube current of 100mA.
Image sharpness and granularity were measured for a sample obtained by processing in the same manner as in Example 1.

For the sharpness, use 0TF, and place a 0TF measuring chart containing a lead rectangular wave of 0.8 to 10 lines/Mm tightly on the back side of the front side of the intensifying screen, and use the lead rectangular wave on the film surface. The film was developed by irradiating X-rays so that the density of the unshielded area was 1.0 on both sides.

Next, the emulsion layer on the front side with respect to the X-ray generator is peeled off, and the rectangular wave pattern on the other side is
Measurement was performed using Sakura Microdensitometer M-5 type (manufactured by Konishiroku Photo KK). The aperture size at this time was 230 μ in the rectangular wave direction and 25 μ in the perpendicular direction, and the magnification was 100 times.

Sample No. Results obtained for lO, 11.13, 16. is shown in Figure 1.

On the other hand, graininess was measured by placing an acrylic plate with a thickness of 10 cm in front of the photosensitive material sandwiched between intensifying screens, and performing X under the above conditions so that the density after development was 1.0 on both sides. It was irradiated with radiation.

Next, in the same manner as in the 0TF measurement, the emulsion layer on one side was peeled off, and then the RMS value was measured on the other side using a Sakura One Touch type RMS measuring device (manufactured by Konishiroku Photo Industry KK).

Note that the aperture size at this time was 50μ, and the magnification was 5×10 times.

The results obtained are shown in Table 3.

Note that the sensitivity values in the table are relative sensitivities to the blank sample (NO.1O).

As is clear from the results shown in FIG. 1 and Table 3, it can be seen that the photosensitive material of the present invention provides extremely high-quality, high-sensitivity images with little fog.

[Brief explanation of drawings]

FIG. 1 is a diagram showing the relationship between spatial frequency and 0TF value for confirming the sharpness-related effects of the present invention.

Claims (1)

[Scope of Claims] 1. In the constituent layer formed on the support, photosensitive silver halide grains, the surface of which is made difficult to dissolve with an insoluble agent,
It contains metal salt particles which are more easily soluble than the photosensitive silver halide grains and have substantially no photosensitivity, and physical development nuclei, and further contains at least one of the compounds represented by the following general formula [I]. 1 and at least one compound represented by the following general formula [II] in combination with the photosensitive silver halide grains. . General formula [I]▲There are mathematical formulas, chemical formulas, tables, etc.▼ {In the above general formula [I], Q is a nonmetallic atom necessary to complete 1,3-dihydroxybenzene or 1,3-dihydroxynaphthalene. represents a group. R^1 is a hydrogen atom, a halogen atom, a hydroxyl group,
Alternatively, it represents an alkyl group, an alkoxy group, or an acyl group that may have a substituent. R^2 represents a -COOM group or a -SO_3M group (where M represents a hydrogen atom, an alkali metal atom, or a -NH_4 group). m and n are each an integer of 1 or 2. }General formula [II] ▲ Numerical formulas, chemical formulas, tables, etc. Represents the required atomic group. The heterocycle formed by Z and C=N is -C
OOM group, -SO_3M group (where M is a hydrogen atom,
Represents an alkali metal atom or -NH_4 group. ),
It has at least one substituent consisting of, or having one of, a hydroxyl group, a substituted or unsubstituted carbamoyl group, or a sulfamoyl group. Furthermore, a halogen atom, an alkyl group, or an ether group may be bonded to the heterocycle or the substituent. Note that M is the same as above. }