JPS6389844A - Silver halide photographic sensitive material having improved resistance to roller mark - Google Patents

Abstract

PURPOSE:To improve the pressure resistance during development by incorporating photosensitive silver halide particles, internally fogged silver halide particles and a specified compd. CONSTITUTION:Photosensitive silver halide particles, silver halide particles contg. fogging nuclei and a compd. represented by the formula are incorporated into a photographic emulsion layer. In the formula, each of A and A' is H or an alkali hydrolyzable group, each of R1-R3 is H, alkyl, aryl, alkylthio, arylthio, halogen, hydroxyl alkoxyl, aryloxy, acyl, alkoxycarbonyl, amido, sulfonamido, a heterocyclic group or the like, R2 and R3, R2 and A, or R3 and A' may bond to each other to form a ring, and X is -S-R4 (R4 is a hetero ring contg. N), benzotriazole or tetrazole as a development retarder group. A sensitive material having the photographic emulsion layer shows superior pressure resistance during development and the covering power of developed silver can be increased.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a silver halide photographic material (hereinafter referred to as "photographic material"), and in particular has improved pressure resistance or pressure resistance during development. This invention relates to a photographic material with high covering power (high covering power).

[Background of the Invention] While the supply of metallic silver, which is essential as a raw material for silver halide photographic light-sensitive materials, is decreasing, the demand in various industries is increasing. Efforts are being made to reduce the number of banks.

Furthermore, various demands have been placed on the subject matter of silver halide photographic materials, and in particular, silver halide photographic materials with stable photographic performance and high sensitivity are required.

Especially x&! In order to reduce the amount of X-ray exposure to the human body, photosensitive materials for use in photosensitive materials are required to have higher sensitivity.
Moreover, there is a demand for photographic materials with high image quality.

In silver halide photographic materials, generally by increasing the size of silver halide emulsion grains.

High sensitivity can be achieved. However, according to this method, the blackening density per unit of developed silver decreases, and the gamma (the slope of the linear portion of the characteristic curve) decreases.

In order to improve these problems, lI per unit area of the photosensitive material must be
It was necessary to increase the amount of i.

As a method of high sensitivity and silver saving, US Patent 2,9
No. 96,382 and No. 3,178,2112 use silver halide photographic materials in which surface latent image type silver halide grains and fine silver halide grains having fog nuclei inside the grains are present adjacent to each other. A method for obtaining photographic images with high sensitivity, high contrast, and high covering power is described.

However, this method has the disadvantage that when processed using a roller-type automatic processor, it is susceptible to roller pressure blackening (hereinafter referred to as roller marks).

[Object of the invention] The object of the present invention is to solve the problems of the prior art described above,
Improved pressure resistance during development. An object of the present invention is to provide a silver halide photographic material having a high covering power with developed silver.

[Structure and operation of the invention] A silver halide photographic light-sensitive material according to the present invention that achieves the above object is a silver halide photographic light-sensitive material having at least one silver halide photographic emulsion layer on a support. The photosensitive material is characterized in that it contains photosensitive silver halide grains and silver halide grains 4 whose interiors are covered, and also contains a compound represented by the following general formula (I).

General formula (I) In the formula, A and A' represent a hydrogen atom or a group that can be hydrolyzed in the presence of an alkali, Rt, Rz, and R3 may be the same or different, and each represents a hydrogen atom, an alkyl group, or an aryl group. group, alkylthio group, arylthio group,
Represents a halogen atom, hydroxyl group, alkoxy group, aryloxy group, acyl group, alkoxycarbonyl group, amide group, sulfonamide group, carbamoyl group, sulfamoyl group, heterocyclic residue, or X, R2 and R3,
R2 and A, R3 and A' may be bonded to each other to form a non-aromatic ring, and X is released from the compound of general formula (I) in the development process and is substantially removed by the developer. A group of development inhibitors that is not subject to change in activity, -
3-R, (wherein R4 represents a nitrogen-containing heterocycle) represents one of a substituted or unsubstituted benzotriazole residue or a substituted or unsubstituted tetrazole residue.

In a preferred embodiment of the present invention, a polyalkylene oxide compound having a molecular weight of 300 or more is used in the photographic material of the present invention in an amount of 1 to 10 wt % or more based on the total binder. This provides a good antistatic effect. In addition, the photographic light-sensitive material of the present invention can easily obtain good photographic properties and antistatic effects even when various layers are coated at high speed during manufacture or when coated layers are rapidly dried. Good results are likely to be obtained even when high-speed coating is performed at a speed of 100 m/s or more and when rapid drying is performed for 4 minutes or less.

Next, the compound represented by the general formula (I) used in the present invention will be described.

In general formula (I), A and A' may be the same or different, and each is a hydrogen atom or a group that can be hydrolyzed in the presence of an alkali (for example, an acyl group, a chloroacetyl group, or a dichloroacetyl group). halogen-substituted acyl groups, ethoxycarbonyl groups, alkoxycarbonyl groups,
There are aryloxycarbonyl groups such as phenoxycarbonyl groups, alkylthiocarbonyl groups, arylthiocarbonyl groups, alkylaminocarbonyl groups, and arylaminocarbonyl groups.5 Furthermore, JP-A-59-197037
The preferred one among these is a hydrogen atom.

X is a group of a development inhibitor that is released after the compound of general formula (I) is oxidized in the development process and does not substantially undergo any change in activity even when it comes into contact with a developer, Specifically, -3-R, represents a substituted or unsubstituted benzotriazole residue (e.g., 1-benzotriazolyl group) or a substituted or unsubstituted tetrazole residue (e.g., l-tetrazolyl group), and the above-mentioned R4 represents a substituted or unsubstituted 5-membered, 6-membered or fused heterocyclic group, which may be fused with a benzene nucleus or a naphthalene nucleus.

Specific examples of X are listed below (expressed in the form after release).

1-phenyl-5-mercaptotetrazole.

1-(4-hydroxyphenyl)-5-mercaptotetrazole, 1-(cohydroxyphenyl)-5-mercaptotetrazole, ]-(]4-carboxyphenyl-5-mercaptotetrazole, I-(3-carboxyphenyl)- 5-mercaptotetrazole, 1-(4
-sulfophenyl)-5-mercaptotetrazole, 1
-(4-sulfamoylphenyl)-5-mercaptotetrazole, 1-(3-hexanoylamidophenyl)
-5-mercaptotetrazole, 1-(3-(3-methylureido)phenyl)-5-mercaptotetrazole.

Ni(2-diethylaminoethyl)-5-mercaptotetrazole, 1-(2-dimethylaminoethyl)-5-
Mercaptotetrazole, 1-ethyl-5-mercaptotetrazole, 1-(2-carboxyethyl)-5-mercaptotetrazole, 1-(2-hydroxyethyl)
-5-mercaptotetrazole, 2-methylthio-5-
Mercapto-1,3,4-thiadiazole, 2-(2-
carboxyethyl)-5-mercapto-1,3,4-thiadiazole, 2-(4-sulfobutyl)-5-mercapto-1,3,4-thiadiazole, 2-mercapto-1,3-penzoxazole, 2- Mercapto-1,
3-penzimidazole, 2-mercapto-1,3-benzothiazole, 3-mercapto-4-phenyl-1,
2,4-)-Riazole, 2-mercapto-1-phenylimidazole, 2-methyl-5-mercapto-1,3
, 4-thiadiazole, benzotriazole, 5-methylbenzotriazole, 5,6-dimethylbenzotriazole.

5-chlorobenzotriazole, 5-bromobenzotriazole, 5-nitrobenzotriazole, 5-carboxybenzotriazole, 4,5.6-)-lichloropenzotriazole, 4. S, 6.7-titrachloropenzotriazole, 5-octyloxybenzotriazole, 5-acetamidobenzotriazole, 5-(2,2
, 2-)dichloroethoxycarbonyl)benzotriazole, and 1-phenyl-2-tetrazoline-5-thione, among these, preferred are those having a nitro group, a cyano group, or a halogen atom as a substituent. It is.

In general formula (1), R1, R2 and R□ may be the same or different, and each represents a hydrogen atom, a halogen atom, a hydroxyl group, an argyl group (preferably a carbon number of 1 to 30
), aryl group, alkylthio group (preferably having 1 to 30 carbon atoms), arylthio group, alkoxy group (preferably having 1 to 30 carbon atoms), aryloxy group, alkoxycarbonyl group (preferably having 2 to 30 carbon atoms), acyl group (preferably having an alkyl group having up to 30 carbon atoms), amide group (preferably having an alkyl group having up to 30 carbon atoms), Sulfonamide group (preferably having an alkyl group or phenyl group having up to 30 carbon atoms), carbamoyl group (preferably having an alkyl group having up to 30 carbon atoms), sulfamoyl group (preferably an alkyl group having up to 30 carbon atoms) (having a group)
, a heterocyclic residue (a saturated or unsaturated ring containing at least one of N, S or 0 as a heteroatom, preferably having a ring member number of 5 or 6 members), and the same meanings as above. Among these, hydrogen atom, alkyl group, aryl group, alkylthio group, halogen atom, alkoxy group, carbamoyl group and X are particularly preferable, and R2 and R1 are bonded to each other to form a saturated or unsaturated ring. Furthermore, this ring may have as a substituent the groups described above for Rz and R3.

Preferably, Rt and R3 may be the same or different, and each has a Hammett's σp of 0.
3 or less substituents, examples include hydrogen or alkyl groups (preferably those with up to 18 carbon atoms), aryl groups,
Alkoxy group (preferably one with up to 18 carbon atoms),
Aryloxy group, alkylthio group (preferably up to 18 carbon atoms), arylthio group, acylamido group (preferably up to 17 carbon atoms), sulfonamide group (preferably up to carbon fi 17), ureido a group (preferably one having up to 30 carbon atoms),
Rt and Ryu, R2 and ^, and R3 and A' may be bonded to each other to form a non-aromatic ring.

Examples of compounds that combine R2 and Ra to form a non-aromatic ring include the following.

HH R2 and A or R3 and A' combine to form a non-aromatic ring, including the following. (
(■ combines with phenolic oxygen) Also, these R2
and R3 is further a halogen atom, an alkyl group, an aryl group, an alkoxy group, a cyano group, a carboxy group, a formyl group, an amide group, a carbamoyl group, a sulfonamide group,
Sulfamoyl group, acyloxy group, nitro group, alkoxycarbonyl group, aryloxycarbonyl group, acyl group, amino group, imino group, nitroso group, alkenyl group, alkynyl group, heterocycle, alkylthio group, arylthio group, ureido group, sulfonyl group , a sulfo group, etc., may be substituted with one or more arbitrary substituents.

Preferred Rt and R3 other than hydrogen atoms are as follows.

When R2 and R3 do not form a ring, they are preferably an alkyl group, an alkylthio group, an alkoxy group, an acylamido group, or a sulfonamide group, and more preferably an alkyl group, an alkylthio group, or an alkoxy group.

Preferably, R1 and R3 are bonded to each other to form a non-aromatic ring.

HII R8 is preferably an electron-withdrawing one with a Hammett's σρ value of more than 1. Examples of R1 include a trifluoromethyl group, a diano group, a formyl group, an acyl group, an alkoxycarbonyl group, and an aryl group. oxycarbonyl group,
These include a carbamoyl group, a sulfonyl group, a sulfamoyl group, a sulfinyl group, and particularly preferably an alkoxycarbonyl group and an aryloxycarbonyl group (-COO-
R"4), where R"4. R8 and Rg are a hydrogen atom, an alkyl group (preferably one having 1 to 30 carbon atoms), or an aryl group, and RS and R may be the same or different; may be combined to form a nitrogen-containing heterocycle, and R4. R5 and R6 may further be substituted with one or more arbitrary substituents as in the case of nt and Rx.

Specific examples of the compound represented by general formula (I) are listed below.

[Exemplary compounds (I-1) H (r-2) H (I-4) H U-7) H OH OH 0)I OH OH OH OOH 0■ (I-20) (I-21) OH CQ NO.

(1-23) (t
)C6)1. .

5OJa (I-26) 0■ (I-35) OH (I-36) The compound of the present invention represented by general formula (I) is disclosed in, for example, U.S. Patent No. 3,379.529, Japanese Patent Publication No. 59-52817 .

JP-A-56-1533:16, JP-A-61-1560
No. 43 and E, C, Δr strong et al.
J, Am, Chem, Soc,, 82.1928-1
935 (1960), D.E. Koalens,
J-Am, CI+em, Soc.

2478-2481 (1934), Pharmaceutical Journal 56.81
4-828 (193B) and the like.

The compound of the present invention can be added to the silver halide emulsion layer, to the hydrophilic colloid layer provided above or below the emulsion layer, or to both layers to achieve one object of the present invention.

The amount added varies depending on the type of photographic light-sensitive material, but is generally lx 10-' mol to I per 1 mol of halogenated iR.
A range of X 10-' moles is preferred.

Conventional methods can be used for addition to the silver halide emulsion layer and/or other hydrophilic colloid layers. For example, U.S. Pat.
The method described in No. 43 can be adopted.

As the photosensitive silver halide (grain) emulsion used in the present invention, a conventional silver halide emulsion such as a surface latent image type silver halide emulsion is used.

The surface latent image type silver halide emulsion used in the present invention is a surface latent image type silver halide emulsion that undergoes the following surface development (^
) and internal development method (B),
It is an emulsion in which the sensitivity obtained by surface development (A) is greater than the sensitivity obtained by internal development (R), preferably an emulsion in which the sensitivity of the former is at least twice that of the latter. Here, sensitivity is defined as follows.

0O 8=-Eh S is the sensitivity, Eh is the maximum concentration (1,,,) and the minimum concentration (D
, i,) at a density of 34 (D~800,...
) is the amount of exposure required to obtain

(Surface development (A)) Develop in a developer having the following formulation at a temperature of 20° C. for 10 minutes.

Tomethyl-p-aminophenol (hemisulfate) z, s g Ascorbic acid 10 g Meta am
Sodium salt 35 g Potassium bromide
Add 1g water
1 sentence (internal development (B)) Red blood salt 3g/n and phenosafranin 0.0126g/
4 for 10 minutes at 20"C, then washed with water for 10 minutes, and subjected to ItM imaging for 10 minutes at zo'c in a developer having the following formulation.

N-methyl-p-aminophenol (hemisulfate) 2.5 g
Ascorbic acid 10 g Sodium metaborate/quaternate salt 35 g Potassium bromide
1g sodium thiosulfate
Add 3g water
As the surface latent image type silver halide emulsion, silver iodobromide or silver chloroiodobromide is preferable.The content of silver iodide is preferably 0.1 to 30 mol%, particularly 0.5 ~l
The silver iodide content is preferably O mol%, and the silver iodide is preferably formed inside the grains.

The average particle diameter of the surface latent image type silver halide grains is preferably larger than that of the internal silver halide grains, for example 0.1 to 5 pLm, preferably 0.5 to 3 pLm, giving good results. .

In this specification, the average particle diameter refers to the particle diameter in the case of particles that are spherical or approximately spherical, and in the case of particles with a shape other than spherical, the average particle diameter based on the diameter when the projected image is converted into a circular image of the same area. This is the expressed value.

The average particle size is measured by direct measurement using an electronic mirror, by a Coulter counter, by using a centrifugal particle size distribution measuring device based on the liquid phase sedimentation method, or the like.

The surface latent image type silver halide emulsion grains used in the present invention have regular (r
The particles may have a regular crystal shape, or may have an irregular crystal shape such as spherical, potato-shaped, tabular, etc.), or may even be composed of a mixture of particles of various crystal shapes).

Further, an emulsion may be used in which ultratabular silver halide grains having a grain diameter of three times or more the grain thickness occupy 50 or more of the total projected area.

The silver halide grains may have different layers inside and on the surface, and may be grains in which a latent image is mainly formed on the surface, or grains in which a latent image is mainly formed inside the grain.

The surface latent image type silver halide emulsion may be a monodisperse emulsion. Here, a monodisperse emulsion is defined as: where r is the average grain size of silver halide grains and σ is its standard deviation. σ 1≦0.20.

When using 8gBrl as silver halide grains in a surface latent image type silver halide emulsion, the distribution of silver iodide inside the grains may be uniform, the concentration may be higher as the inner part approaches, or it may be localized inside the grains. , when localizing Agl inside the particle, the inside means all the #IN contained in the particle from the center of the particle.
%.

The intragrain silver oxide distribution of silver halide grains can be determined by a method combining ion etching and X-ray photoelectric spectroscopy.

The photographic emulsion of the present invention can be prepared by an acidic method or a neutral method.

Any method such as the ammonia method may be used, and the reaction between the soluble silver salt and the soluble halogen salt may be carried out by any method such as a one-sided mixing method, a simultaneous mixing method, or a combination thereof.Also, particles may be formed under silver ion overburden. A method of controlling PAg and pH in the liquid phase in which silver halide is produced may also be used as a type of simultaneous mixing method, the so-called Chondrald double jet method. .

Various silver halide solvents can be used to control silver halide grain growth. 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 complex salts thereof, etc. may be present.

Surface latent image type silver halide emulsions can be chemically sensitized by various methods.

Photographic emulsions may be spectrally sensitized with methine dyes and others.

Next, in the present invention, the silver halide emulsion that suppresses fog nuclei inside the grains is prepared using D-19 (developer specified by Eastman Kodak Company) at 35°C without exposing a test piece with a coated silver amount of 2 g/d. The transmission fog density when developed for minutes was 0.5 or less, and the same specimen was not exposed to light at 35°C using a developer containing D-19 with 0.5 g/m of potassium iodide added.
The transmission fog density when developed for 2 minutes is at least 1.
0 is used.

Emulsions having fog nuclei inside the grains can be prepared by various known methods. For example, US Pat. No. 3,206,31
It is obtained by preparing a core emulsion having fog nuclei according to the core-shell emulsion preparation method described in No. 3, and then coating the core emulsion grains with a shell emulsion.

The method of covering the core emulsion is to irradiate it with light;
Methods include chemically fogging with a reducing agent, unstable sulfur compound, or gold compound, and aging at low pAg and high pH. Among these, methods using a reducing agent and methods using a reducing agent and a gold compound in combination are preferred.

The silver halide emulsion having fog nuclei inside the grains may be any of silver chloride, silver chlorobromide, silver chloroiodobromide, silver bromide, and silver iodobromide. , regular (re
It may have a gular crystal shape, or it may have an irregular crystal shape such as a spherical shape, a potato shape, a tabular shape, etc.

Halogenated IR particle size (average particle size) is 0.1 to 0
．． 77LI is preferable, and the thickness of the shell portion is 0.77LI.
It is preferable that it is 01-0.3 gm.

In the present invention, the mixing ratio (ffi amount ratio) of the silver halide emulsion having fog nuclei inside the grains and the surface latent image type emulsion is 1:100 to 1 (preferably 10:1, more preferably 1:20 to 20). :l.

As the binder or protective colloid for the photographic emulsion, gelatin such as 1-lime gelatin, acid-treated gelatin, derivative gelatin, or gelatin graft polymer may be used, or hydrophilic colloid such as hydroxyethyl cellulose, polyvinyl alcohol, or polyvinylimidazole may be used. Can be used.

In the photographic light-sensitive material, a dispersion of a water-insoluble or sparingly soluble synthetic polymer can be contained in the photographic emulsion layer and other wood-philic colloid layers to improve dimensional stability.

In the present invention, various compounds can be included in order to prevent fogging during the manufacturing process, storage, or photographic processing of the photographic material and to stabilize the photographic material.

In the light-sensitive material of the present invention, the silver halide emulsion layer and other wood-philic colloid layers can be hardened with a suitable hardener.

The photographic emulsion layer of the photographic light-sensitive material of the present invention contains, for example, polyalkylene oxide or its derivatives such as ethers, esters, and amines, thioether compounds, thiomorpholines, and class ammonium salt compounds, urethane derivatives,
It may contain urea derivatives, imidazole derivatives, 3-pyrazolidones, etc.

In addition, the photographic emulsion layer or other wood-loving colloid layer of the photographic light-sensitive material may contain coating aids, antistatic properties, slipperiness, emulsion dispersion, prevention of young attachment, and improvement of photographic properties (e.g., development acceleration,
A surfactant may be included for the purpose of increasing contrast, sensitization, etc.

Regarding the layer structure of the silver halide emulsion layer of the light-sensitive material of the present invention, there are several problems, but the typical ones are as follows: 1) A surface latent image type silver halide emulsion, a A structure in which a silver halide emulsion having fog nuclei inside is mixed and coated, 2) A silver halide emulsion layer having fog nuclei inside the grains is coated on a support, and further surface latent image type halogenation is applied on this layer. A structure in which a layer containing a silver emulsion is coated; 3) A layer containing a surface N3 image type silver halide emulsion and a silver halide emulsion having fog nuclei inside the grains is coated on a support; A structure in which an emulsion layer containing a surface latent image type silver halide emulsion is coated.

4) A layer containing a surface latent image type silver halide emulsion and a silver halide emulsion having fog nuclei inside the grains is coated on the support, and a layer containing a surface latent image type silver halide emulsion and a silver halide emulsion having fog nuclei inside the grains is further coated on the support. A structure in which a layer containing a silver halide emulsion having fogging nuclei in a ratio different from that of the lower layer is coated.

etc. can be mentioned.

The compound of the present invention represented by general formula (1) may be added to any of the above layers.

In the light-sensitive material of the present invention, the silver halide emulsion layer may be provided not only on one side but also on both sides of the support. In this case, it is sufficient that the conditions of the present invention are satisfied on at least one side. It is preferable that the conditions of the present invention are satisfied on both sides.

The protective layer of the photosensitive material of the present invention is a layer consisting of a hydrophilic colloid, and the wood-philic colloid used is the one described above. Further, the protective MR may be used alone or in a multilayer structure, and the protective layer may contain an antistatic agent.

The emulsion layer or the MN contains at least one selected from matting agents and smoothing agents. Although Ws may be included, it is preferable to include them in the retaining W.

The silver halide photographic material of the present invention may optionally contain:
An antihalation layer, an intermediate layer, a filter layer, etc. can be provided.

The silver halide photographic material of the present invention can be applied to X-ray light-sensitive materials, lithographic light-sensitive materials, black-and-white photographic light-sensitive materials, color negative light-sensitive materials, color vapor light-sensitive materials, and the like.

The silver halide photographic material of the present invention may contain dyes, optical brighteners, color fog inhibitors, ultraviolet absorbers, and the like, if necessary.

And photographic emulsion is a plastic film.

It is applied to a flexible support such as paper or cloth or a rigid support such as glass, ceramic, or metal by a dip coating method, a roller @ cloth method, a curtain coating method, an extrusion coating method, or the like.

Photographic emulsions may contain color image-forming couplers (even those in which the product of the coupling reaction is colorless), colored couplers, and DIR couplers.

The photographic processing of the silver halide photographic material of the present invention can be carried out using various processing solutions and various methods. As for photographic processing, either black and white photographic processing or color photographic processing can be applied depending on the purpose.

The silver halide photographic light-sensitive material of the present invention includes a processing solution (for example, a developing bath, a prebath thereof, etc.) containing a dialkyl aldehyde hardener (for example, glutaraldehyde, β-methylglutaraldehyde, succinic dialdehyde, etc.). In one preferred embodiment, the amount of addition is about 91 to 20 g per liter). It can also be processed with an automatic roller developing machine.

[Effect of application] According to the present invention, a silver halide photographic material having improved pressure resistance during development and high covering power for developed silver can be provided.

[Example] Hereinafter, the present invention will be explained in detail by referring to an example. However, the present invention is not limited to the examples.

Example 1 Preparation of surface latent image type emulsion (emulsion A) 1.6 g containing 4.0 g of potassium iodide and 80 g of potassium bromide
% aqueous gelatin solution at 56°C and 15H! 100
The ammoniacal silver ion solution containing g was divided into three equal parts, and these were added by a single jet method and a regular mixing method, respectively. Note that the average particle size was controlled by changing the interval time between addition of the ammoniacal silver ions divided into three equal parts.

Note that when adding the ammoniacal silver ion solution, the second and third additions were partially neutralized with acetic acid. After the third addition, Ostwald ripening is carried out.
The pH was adjusted to 6 and desalted using the usual flocculation method to reduce the silver iodide content to 4.
．． An emulsion of 0 mol % silver iodobromide grains having irregular potato-like shapes was obtained. This emulsion has an average grain size (r) of 1
．． 1 舊■, σ/r was 0.26.

To this emulsion, gold and sulfur sensitization was carried out by adding helium, chloroauric acid and ammonium thiocyanate, and 4-hydroxy-
Emulsion A was obtained by adding 6-methyl-1,3,3a, 7-chitrazaindene and l.limethylolbroban.

Preparation of a silver halide emulsion having fog nuclei inside the grains A 2% gelatin solution was kept at 60° C., and an aqueous silver nitrate solution and an aqueous halide solution containing potassium bromide and sodium chloride were simultaneously added thereto. After the addition, the temperature of the emulsion was lowered to 40°C and desalted to reduce the average grain size to 0.22p.
A silver chlorobromide emulsion of Otori (ratio of Br and 0% was 25 near 5) was obtained.

The obtained emulsion was maintained at 60° C., and an aqueous thiourea dioxide solution and an aqueous chloroauric acid solution were added thereto and aged for 50 minutes to form fog nuclei.

p) I was adjusted to 6.0 and pAg to 7.3, and further desalted by a normal coagulation method in which an aqueous silver nitrate solution and an aqueous solution containing potassium bromide and potassium iodide were simultaneously added over 70 minutes, Emulsion B is redispersed in an aqueous gelatin solution and subsequently adsorbed with the mercapto compound shown below to form an emulsion B having fogging nuclei inside the grains with an average particle size (r) of 0.35 μm and σ/r of 0.12. I got it.

[Mercapto Compound] Sample Preparation and Test Results After mixing 4 parts of emulsion A and 1 part of emulsion B, a coating aid dodecylbenzenesulfonate and a thickener p-vinylbenzenesulfonate were added. Table 1 shows the nate compounds and the compounds of general formula (I) according to the present invention.
The amount of silver cloth was added to both sides of the undercoated polyethylene terephthalate support by 2.5% per side.
g/rr+'' and gelatin amount was the same on both sides <2.5 g/m''.

Further, on these emulsion layers, gelatin, thickener polystyrene sulfonate sodium, matting agent polymethyl methacrylate fine particles (average particle size 3.0mm layer), and hardening agent 2 are added.
-hydroxy-4,6-dichloro-1,3,5-triazine sodium salt, coating aid t-octylphenoxyethoxysulfone antistatic agent dinonylphenol ether, polyethylene oxide and substantially non-photosensitive chlorobromide a A liquid mixed with fine particles was applied to form a retained MW:. The amount of gelatin per side is 1
．． It was applied to both sides at a concentration of 2 g/nt'.

Sensitometry While keeping these samples at a temperature and humidity of 25°C and 50% R11, samples were measured 7 days after coating IT1 and under forced deterioration conditions (50% R11).
0'C, 80% RI+, 3 F717JI) After exposing each of the ni&vrib(1)(1)u materials to blue light of 360-480nm with an intensity peak at 414nm through a continuous wedge. 35℃ with the following treatment solution, 2
Developing and fixing was performed for 5 seconds, followed by washing with water and drying.

Developer solution potassium hydroxide 29. 14g ice vinegar @ 10.96g potassium sulfite 44.20g sodium bicarbonate 7.50g boric acid
1.0 parts g diethylene glycol 28.95 g ethylenediaminetetraacetic acid 1.67 g 5-methylbenzotriazole 0.06 g 5-nitroindazole
0.25g hydroquinone
30.00g1-7enyl-3-pyrazolidone 1.50g glutaraldehyde
4.93g Sodium Metabisulfite
12. 50g potassium bromide
7. Add 0g of water to make it 1M and adjust the pH to 10.2.
Adjust to 5.

Fixer ammonium thio'iitate 2QrJ.
0g Sodium sulfite (anhydrous) 20.0
g Boric acid 8.0 g Ammonium sulfate 15.0 g Sulfuric acid
2.0g glacial acetic acid
Add 22.0g water and 1! J.
Finish and adjust the pH to 4.2! :I do it.

Sensitometry of the processed photographic materials was carried out and the results are shown in Table 1.

In Table 1, the sensitivity value is determined as the reciprocal of the exposure amount required to obtain a transmitted light blackening density of fog + 0.3, and
It is expressed as a relative value with the sensitivity of 01 as 100. Also, for the gamma value, the density value of the characteristic curve is fogging +2.5 and fogging +2.
．． It is expressed as a slope between 0 and 0.

Evaluation of roller marks: Pressure resistance during development (pressure marks caused by the roller of an automatic developing machine=roller marks) was evaluated as follows.

That is, without exposing the sample to light, it was developed for 25 seconds at 38°C using the above-mentioned developer as the developer using an X-ray automatic developing machine equipped with a special highly uneven roller with opposed rollers. went. The roller marks that occurred in the poem were classified into five grades according to their severity and evaluated.

5: No roller marks, 4: Slight occurrence, 3: Slight occurrence (within practical tolerance), 2: Many occurrences (outside practical tolerance), 1: Very much occurrence.

Note that sample No. 1 uses only emulsion A. Moreover, when the compound of this invention is used together.

Each was used by one staff member.

The following compounds were used for comparison.

(Comparative Compounds) (a) (b) The amount added was sx io-' mole per mole of silver halide, as in the case of the compounds of the present invention.

As is clear from Table 1, one sample according to the present invention has a sensitivity,
It can be seen that the gamma and maximum density values are good, the fog is low, and the #roller mark property is excellent.

Furthermore, it can be seen that even when stored at high temperature and high humidity, there is little performance deterioration such as desensitization.

Example 2 When preparing an emulsion coating solution, a sensitizing dye having an absorption peak in the green light region was used, and an ethylene oxide addition polymer of 4-nonyl-phenol formalin resin (molecular weight 402G) was used as an antistatic agent in the protective layer coating solution. ) was carried out in exactly the same manner as in Example-1, except that . Along with this, sensitometry is 55
As a result of using green light having an intensity peak at 0 nll, the same results as in Example 1 were demonstrated.

Claims (1)

[Scope of Claims] A silver halide photographic light-sensitive material having at least one silver halide photographic emulsion layer on a support, the photographic light-sensitive material comprising a silver halide whose interior is covered with light-sensitive silver halide grains. A silver halide photographic material comprising grains and a compound represented by the following general formula (I). General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, A and A' represent a hydrogen atom or a group that can be hydrolyzed in the presence of an alkali, and R_1, R_2, and R_3 may be the same or different. Often hydrogen atoms, alkyl groups, aryl groups, alkylthio groups, arylthio groups,
Represents a halogen atom, hydroxyl group, alkoxy group, aryloxy group, acyl group, alkoxycarbonyl group, amide group, sulfonamide group, carbamoyl group, sulfamoyl group, heterocyclic residue, or X, and R_2 and R_
3. R_2 and A, and R_3 and A' may be bonded to each other to form a non-aromatic ring. X is a group of a development inhibitor that is released from the compound of general formula (I) in the development process and whose activity is not substantially changed by the developer, and -S-R_4 (where R_4 is a nitrogen-containing (represents a heterocycle), represents one of substituted or unsubstituted benzotriazole residues, or substituted or unsubstituted tetrazole residues.