JPH0534867A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To maintain high sensitivity even in the case of rapid processing without deteriorating dryability and fixability and to reduce occurrence of roller marks and static electricity. CONSTITUTION:The photosensitive material contains a polyhydroxylated benzene compound, or silver halide emulsion layers contains iodine in an average content of <0.6mol%, and a surface protective layer contains a polyoxyethylene type nonion surfactant represented by formulae I and II and the total gelatin coating amounts on both sides of a support are 2.0-2.8g/m<2>. In the formulae I and II, each of R1, R2, R6, and R8 is II, halogen, sulfamoyl, alkyl, or the like: each of R5 and R7 is halogen, sulfamoyl, alkyl, or the like; the substituents of the phenyl group may be asymmetric to each side; each of R3 and R4 is H, alkyl, or aryl; each of (R3 and R4), (R5 and R6), and (R7 and R8) may combine with each other to form a ring: each of n1, n2, and n3 is an average polymerization degree and 2-50; and m is an average polymerization degree the formula I.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a silver halide photographic light-sensitive material capable of high-speed processing. In particular, the present invention relates to a silver halide photographic light-sensitive material having high sensitivity, low fog even when subjected to ultra-rapid processing, generation of roller marks, excellent pressure resistance, and sufficient antistatic properties.

[0002]

2. Description of the Related Art In recent years, high-temperature rapid processing has rapidly spread in the development process of photographic light-sensitive materials (hereinafter referred to as "light-sensitive materials"), and the processing time for automatic light-processing machines for various light-sensitive materials has been greatly shortened. Came. In order to achieve rapid processing, a developer for achieving sufficient sensitivity in a short time, a photosensitive material that is excellent in development progress and gives a sufficient degree of blackening in a short time, and dried in a short time after washing with water. The characteristics to do are necessary. As a method commonly used to improve the drying property of a light-sensitive material, a sufficient amount of a hardening agent (gelatin cross-linking agent) is added in advance in the step of applying the light-sensitive material, and the development-fixing-water washing step is performed. There is a method of reducing the water content in the light-sensitive material before the start of drying by reducing the swelling amount of the emulsion layer or the hydrophilic colloid layer. In this method, if a large amount of a hardener is used, the drying time can be shortened to that extent, but the decrease in swelling results in delaying development, desensitization and softening, and lowering of covering power. In addition, even if the development progress could be improved, the fixing speed of the high-hardened film is greatly affected by residual silver and residual hypo.
This caused problems such as residual color of the sensitizing dye, which was an obstacle to shortening the processing time. On the other hand, a method for increasing the activity of the processing solution is also known, and a method of increasing the amount of the main agent or auxiliary developing agent in the developing solution, increasing the pH of the developing solution, or raising the processing temperature is effective. However, all of these methods have the drawbacks of impairing the temporal stability of the treatment liquid, softening the tone, and increasing fog.

For the purpose of improving the above-mentioned viewpoint, a technique utilizing tabular grains is disclosed in US Pat. No. 4,43.
9, 520, 4,425, 425 and the like. Also, JP-A-63-305343 and JP-A-1-77
No. 047 discloses a technique for improving the development progress and the sensitivity / fogging ratio by controlling the development start point of a silver halide grain having a (111) plane to the apex and / or lobe of the grain and the vicinity thereof. . Further, JP-A-58-11193
3 uses tabular grains to prevent swelling of the hydrophilic colloid layer.
A radiographic photographic element having a high covering power of less than 00% and requiring no additional dura during processing is disclosed. These known techniques are excellent techniques for improving the development progress of the light-sensitive material and have high utility value. However, if the processing time of each step of development-fixing-washing is shortened, not only the processing sensitivity decreases but also the amount of residual silver and the amount of residual hypo increase due to the deterioration of the fixing property. In addition, the problem of residual color comes to the surface in a light-sensitive material that has been spectrally sensitized with a sensitizing dye. These problems other than photographic properties are limited in improvement by modification of silver halide grains, and ultimately result in problems of film quality. That is, the thickness of the hydrophilic colloid layer regulates fixing and residual color, which is an obstacle to rapid processing.

In this regard, JP-A-64-7333
3, JP-A-64-86133, JP-A-1-10524
4, JP-A-1-158435, JP-A-1-158436
For example, the amount of gelatin on the side having the hydrophilic colloid layer including the silver halide emulsion layer is adjusted to be in the range of 2.00 to 3.50 g / m ² , and the total processing time is 20 by combining with other technical elements. Means for achieving ultra-rapid processing in the range of seconds to less than 60 seconds are disclosed. Further, JP-A-2-68537 discloses a means for achieving ultra-rapid processing by adjusting the weight ratio of silver and gelatin (silver / gelatin) of the photosensitive silver halide coated in the emulsion layer to 1.5 or more. Is disclosed. Further, in JP-A-63-221341, the silver halide grains in the emulsion layer are mainly tabular grains having a grain system of 5 times the grain thickness or more, and the amount of gelatin is 2.00 to 3.20 g /.
There is disclosed a means for achieving an ultra-rapid treatment with a total treatment time of 20 seconds or more and less than 60 seconds by setting m ² to be a melting time of 8 minutes or more and 45 minutes or less. As a result of examining these prior arts, the present inventor has found that when the amount of gelatin is reduced or the ratio of silver / gelatin is increased while keeping the amount of coated silver constant, the blackening of the scratches and the roller mark are remarkably deteriorated. It was confirmed that the product would not be practically acceptable and that would make it impossible to complete the product as a product that could be processed very quickly. Scratch blackening refers to a phenomenon in which, when the film is handled, the films are rubbed with each other, or when the film is rubbed with another substance, scratch-like blackening occurs after the development processing. The roller mark is a phenomenon in which, when the photosensitive material is processed by an automatic developing machine, pressure is applied to the photosensitive material due to fine irregularities on the surface of the transport roller, resulting in black spot-like density unevenness. When the total processing time is set to 70 seconds or less, especially 50 seconds or less,
As a result of proper time allocation in the developing-fixing-washing process, if the gelatin coating amount is not less than 2.8 g / m ² , the dryness is impaired when the environment for installing the automatic processor is high humidity. . On the other hand, when the gelatin coating amount was 2.0 g / m ² or less, the drying property and fixing property were improved by that amount.
By rubbing with the conveying roller of the automatic processor, the surface protective layer and the emulsion layer were peeled off from the support in a circular or elliptical shape with a diameter of about 50 μm to 1 mm, which was not practical.

According to the present inventor, the gelatin coating amount is 2.8 g /
As a result of studying means for improving scratches and roller marks at m ² or less, it was found that the problem was improved by reducing the amount of silver iodide contained in the silver halide emulsion. JP-A-6
In 3-221341, there is an example in which tabular grains having a silver iodide content of 0.57 mol% at the time of silver halide grain formation are used. However, after the subsequent gold / sulfur sensitization, spectral sensitization was performed. 0.1 mol% of potassium iodide was added, and the average silver iodide content was 0.67 mol%. The emulsion of this example was additionally tested and the performance of the roller mark at a gelatin coating amount of 2.0 g / m ² was evaluated. As a result, it was at a practically unsatisfactory level. At the same time, the blackening level of scratches, which was also evaluated, was an unsatisfactory level. On the other hand, JP-A-58-11
In the example of tabular grains described in 1933, the gelatin coating amount of the light-sensitive material was 2.87 g / m ² , and there was no problem in drying property due to sufficient hardening, but the total processing time was 40 seconds or less. It was found that there is a problem in fixability and residual color when set to.

Techniques for adding polyhydroxybenzenes to a light-sensitive material are disclosed in JP-A-54-40629, JP-A-51-1936, JP-A-62-21143, and the like. In particular, JP-A-62-21143 discloses that the presence of a polyhydroxy-substituted benzene compound in a concentration of less than 5 × 10 ^-2 mol per mol of silver can reduce pressure sensitivity. . However, these patents relate to a high-contrast negative developing system using an aryl hydrazide, and the sensitivity of the light-sensitive material is considerably low for the purpose of the present invention. In addition, JP-A-6
4-72141 contains a polyhydroxy-substituted benzene compound in an amount less than 10 ^-1 mol per mol of silver in a system in which tabular silver halide grains having an aspect ratio of 3 or more are color-sensitized. It has been shown that sensitivity can be reduced. However, the grains of Examples of the patent all have an average silver iodide content of 0.77 mol% and 2.6 mol%, and an average silver iodide content of 0.77 mol%.
In the emulsion example, the total coating amount of gelatin exceeded 2.8 g / m ² .

As described above, if the iodine content of silver halide grains is reduced or polyhydroxybenzenes are effectively used, a photographic material having excellent roller marks and pressure resistance and suitable for high speed processing. It has been found that there is a possibility that it can be designed, but as a sensitive material product, it is necessary to prevent failures due to electrostatic charge as well as these physical characteristics. Since the processed light-sensitive material is generally composed of an electrically insulating support and a photographic layer, it is electrostatically affected by contact friction or peeling with the surface of the same kind or different kinds during the manufacturing process of the photographic light-sensitive material and during use. Charge is often accumulated. This accumulated electrostatic charge causes many obstacles, but the most serious obstacle is when the photosensitive emulsion layer is exposed by developing the photographic film by discharging the accumulated electrostatic charge before the development processing. It is the formation of spotted spots or dendritic or feather-like line spots. This is the so-called static mark, which significantly impairs the commercial value of photographic film and in some cases it is completely lost. It will be readily appreciated that this can lead to very dangerous judgments when it appears in eg medical or industrial X-ray films. This phenomenon becomes apparent only after development, and is one of the very troublesome problems. Further, these accumulated electrostatic charges may cause a secondary failure such as dust adhering to the film surface or non-uniform coating. As described above, such electrostatic charges are often accumulated during the manufacture and use of the photographic light-sensitive material. For example, in the manufacturing process, the contact friction between the photographic film and the roller or the winding and rewinding process of the photographic film is performed. It is caused by the peeling of the support surface and the emulsion surface. Or, it is caused by contact peeling between a mechanical portion of the X-ray film in an automatic photographing machine or a fluorescent intensifying screen. Contact with other packaging materials also occurs. The static marks of the photographic light-sensitive material, which are induced by the accumulation of such electrostatic charges, become more noticeable as the sensitivity of the photographic light-sensitive material increases and the processing speed increases. Particularly in recent years, the occurrence of static marks has become more likely to occur due to the increased sensitivity of photographic light-sensitive materials and the increased opportunities for severe handling such as high-speed coating, high-speed photography, and high-speed automatic processing. In order to eliminate these problems due to static electricity, it is preferable to add an antistatic agent to the photographic light-sensitive material. However, as the antistatic agent that can be used in the photographic light-sensitive material, the antistatic agent generally used in other fields cannot be used as it is, and is subject to various restrictions peculiar to the photographic light-sensitive material. That is, an antistatic agent that can be used in a photographic light-sensitive material has excellent antistatic performance, and also does not adversely affect photographic characteristics such as sensitivity, fog, graininess, and sharpness of the photographic light-sensitive material. Do not adversely affect the film strength of the photographic material (that is, not easily scratched by friction or scratching), and do not adversely affect the adhesion resistance (that is, the surface of the photographic light-sensitive material or the surface of another substance) Anti-static agent for photographic light-sensitive materials, such as that they do not easily stick to each other), that the fatigue of the processing liquid for photographic light-sensitive materials is not accelerated, and that the adhesive strength between the constituent layers of photographic light-sensitive materials is not reduced. Applying is subject to numerous constraints.

One method of eliminating the damage caused by static electricity is to increase the electrical conductivity of the surface of the photosensitive material so that the electrostatic charges can be dissipated in a short time before the accumulated charges are discharged. Therefore, conventionally, a method of improving the conductivity of the support of the photographic light-sensitive material and various coated surface layers has been considered, and various hygroscopic substances, water-soluble inorganic salts, certain surfactants, polymers and the like have been tried to be used. Came. For example, U.S. Pat. Nos. 2,882,157, 2,972,535 and 3,306.
No. 2785, No. 3262807, No. 3514291
No. 361553, No. 3753716, No. 393
Polymers such as those described in 8999 and the like, for example, US Pat. Nos. 2,982,651 and 3,428,456.
Issue No. 3457076, No. 3454625, No. 35
Surfactants such as those described in US Pat. Nos. 5,297,3,655,387, etc., such as US Pat. No. 3,062,700.
Nos. 3,245,833, 3,525,621 and the like, metal oxides, colloidal silica and the like are known. However, these materials show specificity depending on the type of film support and photographic composition, giving good results for one particular film support and photographic emulsions and other photographic components, but for other different film supports. The support and photographic constituents have no useful antistatic properties, or have excellent antistatic properties, but adversely affect photographic properties such as sensitivity, fog, graininess, and sharpness of photographic emulsion, or immediately after production. Has a good antistatic property, but the antistatic property deteriorates with time, and it is extremely difficult to apply these substances to a photographic light-sensitive material. British Patent 861
No. 134 and German Patent No. 1422809 1
Nonionic surfactants having one polyoxyethylene chain in the molecule are known to have excellent antistatic properties.

Japanese Patent Publication No. 3-4890, JP-A-60-76
No. 743 and the like describe that these nonionic surfactants having a polyoxyethylene chain have a good antistatic ability, but have adverse effects such as deterioration of photographic performance and screen contamination. In the constitution of the present invention, several compounds having a polyoxyethylene chain were tested, and the result was that the roller mark was deteriorated. JP-A-60-119551 discloses that the compound of the general formula (I) or (II) of the present invention is unlikely to cause roller marks, but the sensitive material of the patent has an emulsion layer having a thickness of 5 μm. The silver halide emulsion has a large iodine content of 1.5 mol% and can withstand the 45-second treatment which has become popular in the treatment of medical X-ray sensitive materials in recent years, and much less, the high-speed treatment. It wasn't something.

[0010]

The object of the present invention is to have a high sensitivity even when subjected to an ultra-rapid processing, to have no problem in the drying property and the fixing property, and the blackness degree by the roller mark and the pressure is at a practical level. Another object of the present invention is to provide a light-sensitive material which has been improved and which is antistatic.

[0011]

The above-mentioned object of the present invention has been solved by the following method. That is, in a silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support, the polyhydroxy-substituted benzene compound is added to the emulsion layer or other hydrophilic colloid layer in an amount of 1 × 10 1 per mol of silver. ^-1 mol or less and at least one nonionic surfactant having a polyoxyethylene chain selected from the compounds represented by formula (I) or (II) in the surface protective layer of the emulsion layer. And the total amount of gelatin coated on one side of the support is 2.
The light-sensitive material was prepared so that the amount was 0 g / m ² or more and 2.8 g / m ² or less. Alternatively, in a silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support,
The average halide content of the individual halogen compositions of the silver halide grains in the emulsion layer is less than 0.6 mol%, and the compound represented by the general formula (I) or (II) is contained in the surface protective layer of the emulsion layer. It contains at least one nonionic surfactant having a polyoxyethylene chain selected from the group, and the total amount of gelatin coated on one side of the support is 2.0 g.
The light-sensitive material was prepared so that it was not less than / m ^{2 and not} more than 2.8 g / m ² . General formula (I)

[0012]

[Chemical 5]

General formula (II)

[0014]

[Chemical 6]

R ₁ , R ₂ , R ₆ and R ₈ represent a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, a halogen atom or a sulfamoyl group. These alkyl group, aryl group and alkoxy group may be further substituted. Further, in the formula, R ₅ and R ₇ represent an alkyl group, an aryl group, an alkoxy group, a halogen atom or a sulfamoyl group. These alkyl group, aryl group and alkoxy group may be further substituted. In the general formula (II), the substituents on the phenyl ring may be left-right asymmetric. R ₃ and R
₄ represents a hydrogen atom, a substituted or unsubstituted alkyl group or an aryl group. R ₃ and R ₄ , R ₅ and R _6, and R ₇ and R ₈ may be linked to each other to form a substituted or unsubstituted ring. n ¹ , n ² and n ³ are average degrees of polymerization of ethylene oxide and are numbers of 2 to 50. Further, m is an average degree of polymerization, and is a number of 2 to 50. Preferred examples of the present invention will be described below. R ₁ , R ₂ , R ₅ , R ₆ , R ₇ and R ₈ are preferably methyl, ethyl, t-propyl, t-butyl, t-amyl, t-hexyl, t-octyl, nonyl, decyl, dodecyl, Substituted or unsubstituted aryl group such as trichloromethyl, tribromomethyl, 1-phenylethyl, 2-phenyl-2-propyl, etc., having 1 to 20 carbon atoms, substituted or unsubstituted alkyl group, phenyl group, p-chlorophenyl group, etc. A group, -OR ₁₀ (wherein R ₁₀ is a carbon number of 1 to
20 represents a substituted or unsubstituted alkyl group or aryl group. The same applies hereinafter), a substituted or unsubstituted alkoxy group represented by the following, a halogen atom such as a chlorine atom or a bromine atom,
Or

[0016]

[Chemical 7]

It may be a sulfamoyl group represented by and R ₁ , R ₂ , R ₆ and R ₈ may be hydrogen atoms. Of these, R ₅ and R ₇ are preferably an alkyl group or a halogen atom, and particularly preferably a tertiary alkyl group such as a bulky t-butyl group, t-amyl group or t-octyl group. R ₆ and R ₈ are particularly preferably hydrogen atoms. That is, the compound of the general formula (II) synthesized from 2,4-disubstituted phenol is particularly preferable.

R ₃ and R ₄ are preferably hydrogen atom, methyl group, ethyl group, n-propyl group, i-propyl group, n-
Heptyl group, 1-ethylamyl group, n-undecyl group,
Substituted or unsubstituted alkyl group such as trichloromethyl group or tribromomethyl group, α-furyl group, enyl group, naphthyl group, p-chlorophenyl group, p-methoxyphenyl group, m-nitrophenyl group or the like It is a substituted aryl group. Also R ₃ and R ₄ , R ₅ and R ₆ and R ₇
And R ₈ may combine with each other to form a substituted or unsubstituted ring, for example, a cyclohexyl ring. Of these, R ₃ and R ₄ are particularly preferably a hydrogen atom or a carbon atom of 1
~ 8 alkyl, phenyl and furyl groups.
n ₁ , n ₂ and n ₃ are particularly preferably numbers of 5 to 30. n ₂ and n ₃ may be the same or different. These compounds are described, for example, in US Pat.
No. 28456, No. 3457076, No. 3454625
No. 3,552,972, No. 3,655,387, Japanese Patent Publication No. 51-9610, Japanese Patent Publication No. 53-29715, Japanese Patent Publication No. 54-89626, Japanese Patent Application No. 57-85764, Japanese Patent Application No. 57-90909, Horiguchi. It is described in Hiroshi "New Surfactant" (Sankyo Publishing, 1975) and the like. Next, specific examples of the nonionic surfactant preferably used in the present invention are shown.

[0019]

[Chemical 8]

[0020]

[Chemical 9]

[0021]

[Chemical 10]

[0022]

[Chemical 11]

[0023]

[Chemical 12]

[0024]

[Chemical 13]

The amount of the nonionic surfactant having a polyoxyethylene chain represented by the general formula (I) or (II) varies depending on the type, form or coating method of the photographic light-sensitive material to be used. The amount used may be 5 to 500 mg, and particularly preferably 20 to 100 mg per 1 m ² of the processed light-sensitive material. The method of applying the nonionic surfactant having a polyoxyethylene chain represented by the general formula (I) or (II) to the layer of the photographic light-sensitive material is water or an organic solvent such as methanol, ethanol, acetone, or water. After being dissolved in a mixed solvent of the above organic solvents, it may be sprayed on the surface of the support, coated, or immersed in the solution and dried. At this time, two or more nonionic surfactants belonging to the general formula (I) or (II) of the present invention may be mixed. Next, typical examples of the polyhydroxy-substituted benzene compound of the present invention will be shown.

[0026]

[Chemical 14]

Preferred substituents for X are --H and --O.
H, -Cl, -Br, -COOH, -CH 2 CH 2 COO
_{H, -CH (CH 3) 2} , -CH 3, -C (C
_{H 3) 3, -OCH 3,} -CHO -, - SO 3 Na, -
COONa, -SO ₃ K, such as -COOK and the like. -SO ₃ Na Among these compounds, --COON
a, -SO ₃ K, preferably in -COOK particularly the present invention.
The polyhydroxy-substituted benzene compound may be added at either the silver halide emulsion layer or another hydrophilic colloid layer. The addition amount is 1 per 1 mol of silver in the light-sensitive material.
The amount is less than 0 ⁻¹ mol, but particularly preferably in the range of 1 × 10 ⁻³ or more and less than 6 × 10 ⁻² mol.

As the method for measuring the halogen composition of the silver halide emulsion grains, for example, the powder X-ray diffraction method described in JP-A-56-110926 may be used.
As the method for forming the surface silver iodobromide phase of the silver halide grains of the present invention, a method of simultaneously adding an aqueous solution of silver nitrate and an aqueous solution of potassium iodide, an aqueous solution of silver nitrate and an aqueous solution of a mixture of potassium iodide and potassium bromide are simultaneously added. A method, a method of adding a silver iodide fine grain emulsion or a silver iodobromide fine grain emulsion is known, and these methods may be used in an appropriate combination. Of these, the method of adding fine silver iodide grains is particularly preferred for the present invention, and the fine grain emulsion preferably has a size of 0.001 μm or more and less than 0.2 μm. When forming the surface silver iodobromide phase of silver halide grains, it is preferable to use a silver halide solvent in combination, and it is particularly preferable to use KSCN. Further, an organic compound containing iodine as described in JP-A-63-220187 may be added to the bulk liquid in the reaction vessel. Representative compounds include, but are not limited to, the following compounds.・ ICH ₂ CH ₂ COOH ・ ICH ₂ COOH ・ ICH ₂ CN

In the light-sensitive material of the present invention, at least one photosensitive silver halide emulsion layer may be provided on one side of the support, or at least one photosensitive silver halide emulsion layer may be provided on both sides of the support. Good. The light-sensitive material of the present invention may have a hydrophilic colloid layer in addition to the light-sensitive silver halide emulsion layer, if desired. For example, a surface protective layer is preferably provided. In the light-sensitive material of the present invention, the amount of gelatin on the side having the hydrophilic colloid layer including the light-sensitive silver halide emulsion layer is preferably in the range of 2.0 to 2.80 g / m ² . If the photosensitive emulsion layer is present only on one side of the support, the amount of gelatin on that side is preferably within the above range, and if the photosensitive emulsion layer is on both sides of the support, the amount of gelatin on both sides is Is preferably within the above range. When there is no hydrophilic colloid layer other than the photosensitive emulsion layer, the amount of gelatin in the photosensitive emulsion layer is within the above range. The amount of gelatin is more preferably in the range of 2.10 to 2.70 g / m ² ,
The range of 2.20 to 2.60 g / m ² is particularly desirable.

The melting time of the light-sensitive material of the present invention is preferably set to 8 minutes or longer and 45 minutes or shorter. The melting time referred to in the present invention means that at least one layer of silver halide constituting the photosensitive material when the photosensitive material cut into 1 cm × 2 cm is immersed in a 1.5 wt% sodium hydroxide aqueous solution at 50 ° C. It is the time until the emulsion layer begins to melt.

Next, the emulsion grains used in the present invention will be described. The diameter of a sphere having the same volume as the emulsion grains (hereinafter referred to as sphere-equivalent average grain size) is preferably 0.4 μm or more and less than 2.0 μm, and particularly preferably 0.5 or more and less than 1.5 μm. The particle size distribution should be narrow. The silver halide grains in the emulsion are cubic, octahedral, 1
It may have a regular crystal form such as a tetrahedron,
It may also have an irregular crystal form such as a sphere, a plate, or a potato. It may consist of a mixture of particles of various crystal forms. When a monodisperse emulsion is used as an emulsion in the practice of the present invention, the rate of addition of the aqueous solution of silver nitrate and the water-soluble halide can be increased with the growth of silver halide grains in the preparation of the monodisperse emulsion. By increasing the addition rate, the particle size distribution can be made more monodisperse, and the addition time can be shortened, which is advantageous for industrial production. Further, it is also preferable in that the chance of structural defects being formed inside the silver halide grain is reduced.

As a method for accelerating the addition rate, as described in JP-B-48-36890, JP-A-52-16364 and JP-A-55-142329, the addition rate of an aqueous silver salt solution and an aqueous halide solution is added. May be increased continuously or stepwise. The upper limit of the addition rate may be a flow rate just before the generation of new grains, and the values thereof are temperature, pH, pAg, degree of stirring, composition of silver halide grains,
It changes depending on the solubility, particle size, distance between particles, or type and concentration of protective colloid. A method for producing a monodisperse emulsion is known, and for example, J. Phot. Sci. 12, 242-251 (19).
63), Japanese Examined Patent Publication No. 48-36890, and No. 52-1636.
No. 4, JP-A-55-142329, and the technique described in JP-A-57-179835 can be employed. The silver halide emulsion used in the present invention may be a core-shell type monodisperse emulsion, and these core-shell emulsions are disclosed in JP-A-54-4852.
No. 1 and the like are known. When a polydisperse emulsion is used as an emulsion in the practice of the present invention, a known method can be used for producing the polydisperse emulsion. For example, TH James's “The Theory of the Photographic Process” 4th edition,
Neutral method, acidic method, ammonia method, forward mixing, back mixing, double jet method, controlled double jet method, conversion method, core described in Macmillan Company (1977) pp. 38-104. It can be manufactured by applying a method such as a shell method.

Further, tabular grains having a grain size of 5 times the grain thickness or more are preferably used in the present invention (for details, RE
SEARCH DISCLOSURE 225 Volume Item 22534P. 20
~ P. 58, January issue, 1983, and JP-A-58-1.
28921 and 58-113926). The tabular silver halide grains can be produced by appropriately combining the methods known in the art. Tabular silver halide emulsions are described by Cugnac and Chateau, "Progress in the morphology of silver bromide crystals during physical ripening (Evolution of the Montforgee of Silver Promide Crystals).・
Dualing Physical Reinforcement) "Science & Industry Photography, Volume 33,
No. (1962) pp. 121-125, Duff
in) "Photographic emulsion Chemistry," Focal Press, New York, 1966,
p-66 to p. 72, A. P. H. Trivel
i), W. F. It is described in Smith Photographic Journal, Volume 80, page 285 (1940) and the like.
7,921, JP-A-58-113,927, JP-A-58
It can be easily prepared by referring to the method described in US Pat. No. 4,439,520. The projected area diameter of the tabular emulsion of the present invention is preferably 0.3 to 2.0 μm, and particularly preferably 0.5 to 1.2 μm. The distance between parallel planes (particle thickness) is 0.05 μm to 0.3.
μm, particularly 0.1 to 0.25 μm is preferable, and the aspect ratio is 3 or more and less than 20, particularly 4 or more and 8
Less than 1 is preferable. In the tabular silver halide emulsion of the present invention, silver halide grains having an aspect ratio of 2 or more are present in an amount of 50% (projected area) or more, particularly 70% or more of all grains, and the average aspect ratio of the tabular grains is 3 or more, especially 4
It is preferably -8. Among the tabular silver halide grains, monodisperse hexagonal tabular grains are particularly useful grains. The details of the structure and manufacturing method of the monodisperse hexagonal tabular grains referred to in the present invention are described in JP-A-63-151618.

In order to effectively use the effects of the present invention,
During chemical sensitization during the emulsion preparation process as in JP-A-2-68539, it is preferable to allow 0.5 mmol or more of a silver halide-adsorbing substance to be present per mol of silver halide. This silver halide-adsorptive substance may be added at any time during grain formation, immediately after grain formation, or before and after the start of post-ripening, but a chemical sensitizer (for example, gold or sulfur sensitizer) is added. It is preferable to be added before or at the same time as the chemical sensitizer, and it must be present at least in the process of progress of chemical sensitization. As a condition for adding the silver halide adsorbing substance, the temperature may be any temperature from 30 ° C. to 80 ° C., but the range of 50 ° C. to 80 ° C. is preferable for the purpose of enhancing the adsorbing property. The pH and pAg may be arbitrary, but at the time of chemical sensitization, it is preferably pH 5 to 10 and pAg 7 to 9.

In the present invention, the silver halide-adsorptive substance means a sensitizing dye or a class of photographic performance stabilizers. That is, azoles {eg, benzothiazolium salt, benzimidazolium salt, imidazoles, benzimidazoles, nitroindazoles, triazoles, benzotriazoles, tetrazoles, triazines, etc.); mercapto compounds {eg mercaptothiazoles, Mercaptobenzothiazoles, mercaptoimidazoles, mercaptobenzimidazoles, mercaptobenzoxazoles, mercaptothiadiazoles, mercaptooxadiazoles, mercaptotetrazoles, mercaptotriazoles, mercaptopyrimidines, mercaptotriazines, etc .; for example, oxadrine Thioketo compounds such as thione; azaindenes {eg triazaindenes, tetraazaindenes (especially 4-hydroxy Conversion (1,3,3a, 7) tetraazaindenes), pentaazaindenes such like);
Many compounds known as antifoggants or stabilizers can be mentioned as the silver halide adsorbing material. Further, purines or nucleic acids, or polymer compounds described in JP-B-61-36213, JP-A-59-90844 and the like are also adsorbable substances that can be used. Of these, azaindenes, purines, and nucleic acids are particularly preferable and can be used in the present invention. The addition amount of these compounds is 10 to 300 per mol of silver halide.
mg, preferably 20-200 mg.

As the silver halide adsorbing material of the present invention,
Sensitizing dyes can achieve favorable effects. As the sensitizing dye, a cyanine dye, a merocyanine dye, a complex cyanine dye, a complex merocyanine dye, a holoholer cyanine dye, a styryl dye, a hemicyanine dye, an oxonol dye, a hemioxonol dye and the like can be used. Useful sensitizing dyes used in the present invention are, for example, U.S. Pat. Nos. 3,522,052 and 3,619,
No. 197, No. 3,713,828, No. 3,615,6
No. 43, No. 3,615, 632, No. 3,617, 29
No. 3, No. 3,628,964, No. 3,703,377
Issue No. 3,666,480 Issue 3,667,960
Nos. 3,679,428 and 3,672,897
Issue No. 3,769,026 Issue No. 3,556,800
Issue No. 3,615,613 Issue No. 3,615,638
Nos. 3,615,635 and 3,705,809
No. 3,312,349, No. 3,677,765
Nos. 3,770,449, 3,770,440
Issue No. 3,769,025 Issue No. 3,745,014
Issue 3, Issue 3,713,828, Issue 3,567,458
Nos. 3,625,698, 2,526,632
No. 2,503,776, JP-A-48-76525.
And Belgian Patent No. 691,807. The amount of sensitizing dye added is 1 per mol of silver halide.
00 mg or more and less than 2000 mg, preferably 200 mg or more 1
Less than 000 mg is good. Specific examples of the sensitizing dye effective in the present invention are shown below.

[0037]

[Chemical 15]

[0038]

[Chemical 16]

The combined use of the sensitizing dye and the above-mentioned stabilizer is a preferred embodiment. The sensitizing dye used in the present invention may be added after chemical sensitization and before coating. The chemical sensitization method of the silver halide emulsion used in the present invention includes sulfur sensitization method, selenium sensitization method, reduction sensitization method, gold sensitization method, etc. in the presence of the above-described silver halide adsorbing substance. Known methods can be used, either alone or in combination.
Among the noble metal sensitizing methods, the gold sensitizing method is a typical one, which uses a gold compound, mainly a gold complex salt. Noble metals other than gold, for example, complex salts of platinum, palladium, iridium, etc. may be contained. A specific example is U.S. Pat. No. 2,448,06.
No. 0, British Patent 618,061 and the like. As the sulfur sensitizer, in addition to the sulfur compound contained in gelatin, various sulfur compounds such as thiosulfate,
Thioureas, thiazoles, rhodanines and the like can be used. Specific examples are US Pat. No. 1,574,944,
Nos. 2,278,947, 2,410,689, 2,728,668, 3,501,313, and 3,656,955. The combined use of sulfur sensitization with thiosulfate and gold sensitization can effectively exert the effect of the present invention. Examples of the reduction sensitizer that can be used include primary tin salts, amines, thioureas, formamidinesulfinic acid, and silane compounds.

As the selenium sensitizer used in the present invention, the selenium compounds disclosed in conventionally known patents can be used. That is, usually, an unstable selenium compound and / or a non-unstable selenium compound is added,
It is used by stirring the emulsion at a high temperature, preferably 40 ° C. or higher for a certain time. Unstable selenium compounds are disclosed in JP-B-44-15748 and JP-B-43-13489.
No. 2, Japanese Patent Application No. 2-130976, Japanese Patent Application No. 2-22930
It is preferable to use the compounds described in No. 0 and the like. Specific examples of unstable selenium sensitizers include isoselenocyanates (for example, aliphatic isoselenocyanates such as allyl isoselenocyanate), selenoureas, selenoketones, selenamides, selenocarboxylic acids (for example,
2-selenopropionic acid, 2-selenobutyric acid), selenoesters, diacyl selenides (for example, bis (3-chloro-2,6-dimethoxybenzoyl) selenide), selenophosphates, phosphine selenides, colloidal metal selenium And so on. The preferred types of labile selenium compounds have been described above, but are not limiting. To those skilled in the art, when it comes to unstable selenium compounds as sensitizers for photographic emulsions, the structure of the compounds is not so important as long as selenium is unstable,
It is generally understood that the organic portion of the selenium sensitizer molecule carries selenium and plays no role other than allowing it to be present in the emulsion in an unstable form. In the present invention, the labile selenium compound having such a broad concept is advantageously used. Examples of the non-labile selenium compound used in the present invention include JP-B-46-4553 and JP-B-52-344.
The compounds described in JP-B No. 92 and JP-B-52-34491 are used. Examples of non-labile selenium compounds include selenious acid, potassium selenocyanide, selenazoles, quaternary salts of selenazoles, diaryl selenides, diaryl diselenides, dialkyl selenides, dialkyl diselenides, 2-selenazolidinediones, Examples include 2-selenooxazolidinethione and derivatives thereof. Of these selenium compounds, preferably the following 2
There are two compounds.

[0041]

[Chemical 17]

[0042]

[Chemical 18]

The photographic emulsion used in the present invention has a chemical sensitization step of the present invention for the purpose of preventing fog during the manufacturing process of the light-sensitive material, storage or photographic processing, or stabilizing photographic performance. Various compounds can be contained in addition to the silver halide adsorbing material. That is, azoles {eg benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, nitroindazoles, benzotriazoles, aminotriazoles, etc.); mercapto compounds {eg mercapto Thiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, mercaptotetrazoles, mercaptopyrimidines, mercaptotriazines, etc .; thioketo compounds such as oxadrinthione; azaindenes {eg triazaindenes, Tetraazaindenes (especially 4-hydroxy-substituted (1,3,3a, 7) tetraazaindenes), pentaazaindenes, etc.}; Benzenethios Acid, benzene sulfinic acid, known as antifoggants or stabilizers such as benzenesulfonic acid amide, can be added to many compounds. Particularly, the nitrones and their derivatives described in JP-A-60-76743 and JP-A-60-87322, and JP-A-60-8083.
The mercapto compound described in JP-A No. 9-58, JP-A-57-16
The heterocyclic compound described in Japanese Patent No. 4735 and a complex salt of a heterocyclic compound and silver (for example, 1-phenyl-5-mercaptotetrazole silver) can be preferably used. Even when a sensitizing dye is used as the silver halide adsorbing substance in the chemical sensitization step, a spectral sensitizing dye in another wavelength range may be added, if necessary.

In the photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material produced by using the present invention, a coating aid, an antistatic agent, an improvement in slipperiness, an emulsion dispersion, an adhesion prevention and an improvement in photographic characteristics (for example, development acceleration). , Hardener, sensitization) and various other surfactants may be included. For example, saponin (steroid form), alkylene oxide derivative (eg polyethylene glycol, polyethylene glycol /
Nonionic surfactants such as polypropylene glycol condensates, polyethylene glycol alkyl ethers or polyethylene glycol alkylaryl ethers, polyethylene oxide adducts of silicones), alkyl esters of sugars; alkyl sulfonates, alkylbenzene sulfonates , Alkylnaphthalene sulfonate, alkyl sulfates, N-acyl-N
Anionic surfactants such as alkyl taurines, sulfosuccinates, sulfoalkyl polyoxyethylene alkyl phenyl ethers; amphoteric surfactants such as alkyl betaines, alkyl sulvebetaines;
Cationic surfactants such as aliphatic or aromatic quaternary ammonium salts, pyridinium salts and imidazolium salts can be used. Among them, saponin, sodium salt of dodecylbenzene sulfonic acid, sodium salt of di-2-ethylhexyl α-sulfosuccinic acid, Na salt of p-octylphenoxyethoxyethanesulfonic acid, Na salt of dodecyl sulfate,
Anion such as sodium salt of triisopropylnaphthalene sulfonic acid, Na salt of N-methyl-oleoyl taurine, dodecyl trimethyl ammonium chloride, N-oleoyl-N ', N', N'-trimethylammoniodiaminopropane bromide, dodecyl pyri Particularly preferred are cations such as dichloride and nonions such as betaine such as N-dodecyl-N, N-dimethylcarboxybetaine and N-oleyl N, N-dimethylsulfobutylbetaine. As the antistatic agent, perfluorooctanesulfonic acid K salt, N-propyl-N-perfluorooctanesulfonylglycine Na salt, N-propyl-N-perfluorooctanesulfonylaminoethyloxypoly (n = 3) oxyethylenebutanesulfone Acid Na salt, N-perfluorooctanesulfonyl-
Fluorine-containing surfactants such as N ', N', N'-trimethylammoniodiaminopropane chloride and N-perfluorodecanoylaminopropyl-N ', N'-dimethyl-N'-carboxybetaine, JP-A-60- -8084
No. 8, No. 61-112144, No. 62-172343.
No. 62-173459 and the like, nonionic surfactants, alkali metal nitrates, conductive tin oxide, zinc oxide, vanadium pentoxide or complex oxides obtained by doping these with antimony or the like can be preferably used. .

In the present invention, as a matting agent, US Pat. Nos. 2,992,101, 2,701,245 and 4,142 are used.
Homopolymers of polymethylmethacrylate or copolymers of methylmethacrylate and methacrylic acid, organic compounds such as starch, and fine particles of inorganic compounds such as silica, titanium dioxide, sulfuric acid, and strontium barium, as described in U.S. Pat. Nos. 894 and 4396706. You can The particle size is 1.0 to 10 μm, especially 2 to 5
It is preferably μm. In the surface layer of the photographic light-sensitive material of the present invention, as a slip agent, US Pat. No. 3,489,576,
In addition to the silicone compounds described in JP-A-4047958 and the colloidal silica described in JP-B-56-23139, paraffin wax, higher fatty acid ester, den powder derivative and the like can be used. The hydrophilic colloid layer of the photographic light-sensitive material of the present invention contains trimethylolpropane,
Polyols such as pentanediol, butanediol, ethylene glycol and glycerin can be used as a plasticizer.

As the binder or protective colloid that can be used in the emulsion layer, intermediate layer and surface protective layer of the light-sensitive material of the present invention, it is advantageous to use gelatin.
Other hydrophilic colloids can also be used. For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, cellulose sulfates, etc., sugar derivatives such as sodium alginate, dextran and starch derivatives; polyvinyl. Use various synthetic hydrophilic polymer substances such as alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, and other single or copolymers. be able to. As the gelatin, acid-treated gelatin or enzyme-treated gelatin may be used in addition to lime-treated gelatin, and a hydrolyzed product or an enzymatically-decomposed product of gelatin may also be used. Among these, gelatin has an average molecular weight of 5
It is preferable to use not more than 10,000 dextran and polyacrylamide in combination. JP-A-63-68837, also 63
The method described in -149641 is also effective in the present invention.

The photographic emulsion and the non-photosensitive hydrophilic colloid of the present invention may contain an inorganic or organic hardener. For example, chromium salts (chromium alum, chromium acetate, etc.), aldehydes (formaldehyde, glyoxal, glital aldehyde, etc.), N-methylol compounds (dimethylol urea, methylol dimethylhydantoin, etc.),
Dioxane derivatives (2,3-dihydroxydioxane etc.), active vinyl compounds (1,3,5-triacryloyl-hexahydro-s-triazine, bis (vinylsulfonyl) methyl ether, N, N'-methylenebis-
[Β- (vinylsulfonyl) propionamide], etc.,
Active halogen compounds (2,4-dichloro-6-hydroxy-s-triazine, etc.), mucohalogen acids (mucochloric acid, mucophenoxycycloric acid, etc.) isonoxazoles, dialdehyde starch, 2-chloro-6-hydroxytriazine Azinylated gelatin and the like can be used alone or in combination. Among them, JP-A-53-4122
1, ibid 53-57257, ibid 59-162546, ibid 6
The active vinyl compounds described in 0-80846 and the active halides described in US Pat. No. 3,325,287 are preferred.

As the hardener of the present invention, a polymeric hardener can be effectively used. Examples of the hardener used in the present invention include dialdehyde starch, polyacrolein, polymers having an aldehyde group such as acrolein copolymers described in US Pat. No. 3,396,029, US Pat.
A polymer having an epoxy group described in 623,878;
Polymers having a dichlorotriazine group described in U.S. Pat. No. 3,362,827, Research Disclosure 17333 (1978), and the like, JP-A No. 6-58242.
6-66841, a polymer having an active ester group, described in JP-A-56-142524, US Pat. No. 4,161,407, JP-A-54-65033, Research Disclosure 16725 (1978) and the like. The polymer having an active vinyl group or a group serving as a precursor thereof is mentioned, and a polymer having an active vinyl group or a group serving as a precursor thereof is preferable, and among them, it is described in JP-A-56-142524. A polymer in which an active vinyl group or a group serving as a precursor thereof is bonded to a polymer main chain by a long spacer is particularly preferable.

The hydrophilic colloid layer in the photographic light-sensitive material of the present invention is preferably hardened by these hardeners so that the swelling rate in water is 280% or less, particularly 200 to 280%. The swelling ratio in water in the present invention is measured by the freeze-drying method. That is, the photographic material is 25 ° C. 60
The swelling rate of the hydrophilic colloid layer is measured after 7 days under the condition of% RH. The dry thickness (a) is determined by a scanning electron microscope of the section. The swelling film layer (b) is made of photographic material 21
It is determined by observing with a scanning electron microscope after freeze-drying with liquid nitrogen a state of being immersed in distilled water at ℃ for 3 minutes. The swelling ratio is a value (%) obtained by dividing the value of {(b)-(a)} by (a) and multiplying the value by 100.

The support is preferably a polyethylene terephthalate film or a cellulose triacetate film. In order to improve the adhesion to the hydrophilic colloid layer, the support is preferably subjected to corona discharge treatment, glow discharge treatment or ultraviolet irradiation treatment on its surface, or is made of styrene butadiene latex, vinylidene chloride latex, etc. A subbing layer may be provided, or a gelatin layer may be provided on the subbing layer. An undercoat layer using an organic solvent containing a polyethylene swelling agent and gelatin may be provided. By applying a surface treatment to these undercoat layers, the adhesion with the hydrophilic colloid layer can be further improved.

The emulsion layer of the photographic light-sensitive 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. 738,61
No. 8 is a heterocyclic compound, Nos. 738,637 is an alkyl phthalate, Nos. 738,639 is an alkyl ester, and US Pat. No. 2,960,404 is a polyhydric alcohol. No. 121,060 discloses carboxyalkyl cellulose, JP-A-49-5017 discloses paraffin and carboxylate, and JP-A-53-28086 discloses method using alkyl acrylate and organic acid. . The other constitution of the emulsion layer of the silver halide photographic light-sensitive material of the present invention is not particularly limited, and various additives can be used if necessary. For example, Rese
archDisclosure 176, 22-28 (1978, 1
The binders, surfactants, other dyes, coating aids, thickeners, etc. described in (February) can be used. Hereinafter, the present invention will be specifically described with reference to examples.

[0052]

【Example】

Example 1 (Preparation of tabular grains T-1) 4.5 g of potassium bromide, 12.0 g of gelatin, and thioether HO (C
_{H 2) 2 S (CH 2} ) 2 S (CH 2) supplemented with 5% aqueous solution 2.5cc of ₂ OH 5
37cc silver nitrate aqueous solution while stirring into a container kept at 5 ° C
33 cc of an aqueous solution containing (3.43 g of silver nitrate), 2.97 g of potassium bromide and 0.363 g of potassium iodide was added in 37 seconds by the double jet method. Next, an aqueous solution of 0.9 g of potassium bromide was added, the temperature was raised to 70 ° C., and 53 cc of an aqueous silver nitrate solution (4.90 g of silver nitrate) was added over 13 minutes. Here, add 8cc of 25% aqueous ammonia solution,
After physically aging for 10 minutes at the same temperature, 7 cc of 100% acetic acid solution was added. Subsequently, 133.3 g of silver nitrate
While maintaining the pAg at 8.5, the aqueous solution of the above and the aqueous solution of potassium bromide were added by the control double jet method over 35 minutes. Next, 10 cc of a 2N potassium thiocyanate solution and AgI fine particles having a diameter of 0.07 μm were added to the total amount of silver.
05 mol% was added. After physically aging for 5 minutes at the same temperature, the temperature was lowered to 35 ° C. Thus, the total silver iodide content is 0.31 mol%, the average projected area diameter is 0.61 μm.
Thus, monodisperse tabular grains having m, thickness of 0.120 μm and variation coefficient of diameter of 16.5% were obtained. After this, the soluble salts were removed by the sedimentation method. The temperature is raised to 40 ° C again and 30 g of gelatin is added.
And 2.35 g of phenoxyethanol and 0.8 g of sodium polystyrene sulfonate as a thickening agent,
The solution was adjusted to pH 5.90 and pAg 7.90 with caustic soda and silver nitrate solution. This emulsion was chemically sensitized while being kept at 56 ° C. with stirring. First, thiourea dioxide 0.043 mg
Was added and held for 22 minutes for reduction sensitization.
Next, 250 mg of Sensitizing Dye III-7 was added. Subsequently, sodium thiosulfate The following selenium sensitizer was added at a molar ratio of 6: 4.

[0053]

[Chemical 19]

Subsequently, chloroauric acid and potassium thiocyanate were added, and 40 minutes later, the mixture was cooled to 35 ° C. In this way, preparation of tabular grains T-1 was completed. (Preparation of emulsion layer coating solution) The following chemicals were added to 1 mole of silver halide of tabular grains T-1 to prepare an emulsion layer coating solution.・ 2,6-bis (hydroxyamino) -4-diethylamino-1,3,5-triazine 72 ・ Gelatin Add an amount such that the total coating amount with gelatin used in the surface protective layer described later becomes the value in Table 1 ・Dextran (average molecular weight 39,000) 18.5 g-Sodium polystyrene sulfonate (average molecular weight 600,000) 1.8 g-Hardener 1,2-bis (vinylsulfonylacetamide) ethane Swelling rate is 230% Adjust the amount added

[0055]

[Chemical 20]

[0056]

[Chemical 21]

Snowtex C (manufactured by Nissan Kagaku Co., Ltd.) Solid content 9.6 g Dextran (average molecular weight 39,000) 5.8 g Polyhydroxybenzene Table 1 Types and amounts (of the emulsion layer surface protective layer) Preparation) The surface protective layer of the emulsion layer was prepared and prepared so that each component had the following coating amount.・ Gelatin 0.97 g / m ²・ Sodium polyacrylate (average molecular weight 400,000) 0.018 g / m ² 4-Hydroxy-6-methyl-1,3,3a, 7-tetrazaindene 0.003 g / m ² · Polymethylmethacrylate (average particle size 2.5 μm) 0.05 g / m ² · Proxel 0.0005 g / m ²

[0058]

[Chemical formula 22]

The prepared emulsion layer coating solution and the surface protective layer coating solution were simultaneously extruded onto a polyethylene terephthalate film having a thickness of 183 μm which had been adjusted to pH 7.2 with NaOH and biaxially stretched and previously coated with an undercoat layer. , Coated on one side. The amount of coated silver is 2.75.
It was adjusted to be g / m ² . The polyethylene terephthalate used was one containing 0.04 wt% of the dye having the following structure.

[0060]

[Chemical formula 23]

(Preparation of Antihalation Layer) An antihalation layer and a surface protection layer of the antihalation layer were coated on the side on which the emulsion layer and the surface protection layer were coated, and on the side opposite to the support. Each layer was prepared so as to have the following coating amount. (Antihalation layer) ・ Gelatin 1.5 g / m ²・ Phosphoric acid 5.2 g / m ²・ Snowtex C (Nissan Chemical Co., Ltd.) Solid content 0.5 g / m ²・ Potassium polystyrene sulfonate (Average molecular weight 600,000) 25 mg / m ² Polymer latex (Poly (ethyl acrylate / methacrylic acid) = 97/3) 0.53 g / m ²

[0062]

[Chemical formula 24]

[0063]

[Chemical 25]

(Surface protection layer of antihalation layer) Gelatin 1.05 g / m ² Polymethylmethacrylate (average particle size 3.5 μm) 65 mg / m ²

[0065]

[Chemical formula 26]

C ₈ F ₁₇ SO ₃ K 1.7 mg / m ² · potassium polystyrene sulfonate (average molecular weight 600,000) 2 mg / m ² · NaOH 2.5 mg / m ² antihalation layer and its surface protection layer It was simultaneously coated and dried by the simultaneous extrusion method. The swelling ratio of the antihalation layer and the surface protection layer was measured by the cryo-SEM method. 2
It was 20%. The constitutional contents of the photographic material thus obtained are summarized in Table 1.

[0067]

[Table 1]

(Determination Method of Antistatic Ability) The antistatic ability was measured by measuring surface resistance and generation of static marks. To measure the surface resistance, the test pieces of each photographic material were sandwiched between brass electrodes with an electrode spacing of 0.14 cm and a length of 10 cm (the part in contact with the test piece was made of stainless steel), and Takeda Riken insulation tester T was used.
The value for 1 minute was measured with R8651 type. The static mark generation test was carried out by a method in which the side of the emulsion layer of the unexposed photographic material was faced down on a rubber sheet, and after pressure bonding from above with a rubber roller, peeling was performed to generate static marks. After the test, each photographic material was subjected to automatic processor processing under the following conditions in order to evaluate the degree of generation of static marks. Automatic processor Fuji Photo Film Co., Ltd. FPM9000 Developer Same RD7 (use starter) Fixer Same FujiJ Development temperature 35 ℃ Fixing temperature 31 ℃ Processing time Dry to Dry 45 seconds Static mark evaluation is based on the following 3 levels. Obeyed. A: Generation of static marks was not found. B: Some static marks are generated. C: Static marks are generated on the entire surface. Each measurement was performed under the conditions of 25 ° C. and a relative humidity of 25%, and the surface resistance was represented by the logarithm of the measured value.

(Evaluation of Sensitivity) Each photographic material is sandwiched between two optical wedges whose density gradients are mirror-symmetrically aligned, and a color temperature of 54 is obtained.
The light source of 00 ° K was used to perform an exposure of 0.1 second at the same time from both sides and with an equivalent amount. Processing is carried out using an automatic processor SRX501 manufactured by KONICA, using the following developer and fixer 30
Second processing was performed. The processing for 30 seconds was performed by modifying the automatic processing machine and increasing the transfer speed to 1.5 times the processing for 45 seconds. <Developer> Potassium sulfite 40 g Hydroxyethylethylenediamine triacetate trisodium 8 g 1,4-Dihydroxybenzene 28 g Boric acid 10 g 5-Methylbenzotriazole 0.04 g 1-Phenyl-5-mercaptotetrazole 0.01 g Metabisulfite Sodium 5 g Acetic acid (90%) 13 g Triethylene glycol 15 g 1-Phenyl-3-pyrazolidone 3.2 g 5-Nitroindazole 0.2 g Glutaraldehyde 4.0 g

[0070]

[Chemical 27]

Ethylenediaminetetraacetic acid disodium 2.0 g Potassium bromide 4.0 g 5-Nitrobenzimidazole 1.0 g The above solution is made into 1 liter aqueous solution and adjusted to pH 10.50 with potassium hydroxide. <Fixer> Sodium thiosulfate-5-hydrate 45 g Ethylenediaminetetraacetic acid disodium 0.5 g Ammonium thiosulfate 150 g Anhydrous sodium sulfite 8 g Potassium acetate 16 g Aluminum sulfate 10-18 hydrate 27 g Sulfuric acid (50 wt%) 6 g citric acid 1 g boric acid 7 g glacial acetic acid 5 g The above solution was made into 1 liter aqueous solution and adjusted to pH 4.0 with glacial acetic acid. From the obtained characteristic curve, base concentration + fog concentration + 1.0
The ratio of the reciprocal of the exposure amount in was evaluated as the relative sensitivity when the photographic material 1 was set to 100. The processing temperatures for development and fixing were as follows. Current image 35 ℃ Settlement 33 ℃ Water wash 25 ℃ Squeeze 40 ℃ Dry 45 ℃

(Evaluation of Roller Mark) The glutaraldehyde in the developer evaluated for photographic properties was halved to 2 g / liter. Photographic materials 1 to 16 were cut into 30.5 cm x 25.4 cm and exposed with a light source having a color temperature of 5400 ° K. At this time, by increasing / decreasing the exposure time, the density in the roller mark evaluation process is made uniform to 1.
It was adjusted to be 0. The black-spotted roller marks observed on the photosensitive material thus treated were evaluated. The evaluation criteria were the following sensory evaluations. ◎ ... Almost no roller marks are generated ....... Slightly roller marks are generated, but I do not care ....... Roller marks are generated, but it is practically acceptable. × ... Roller marks occur frequently and uneven density occurs. Big impossible

(Evaluation of abrasion blackening) Unexposed photographic material 1
.About.16 under a relative humidity condition of 25.degree.
It was scratched at a speed of 1 cm / sec by applying a weight with a 5 mm hemispherical stainless needle. The weight was set to 4 conditions of 25 g, 50 g, 75 g, and 100 g for each photographic material. Then, the same processing as in the evaluation of photographic properties was performed, and the blackening of the portion scratched by the stainless needle was evaluated. The evaluation criteria were the following sensory evaluations. ◎ ... Almost no scratches ○: Slight scratches are not noticeable △… Scratches have been generated but are practically acceptable ×… Scratch blackening occurs severely and unacceptable results Are summarized in Table 2.

[0074]

[Table 2]

From the results shown in Table 2, it can be seen that only the combination of the present invention is uniquely excellent in antistatic ability, photographic sensitivity, roller mark, and blackening of scratches. Photographic material 1 with total gelatin coating on the emulsion side of 1.8g / m ²
No. 4 had a defect in roller marks and blackening of scratches.
On the other hand, the photographic materials 13 to 16 having a total gelatin coating amount of 3.0 g / m ^{2 on} the emulsion side are distinguished from the present invention because of marked decrease in photographic sensitivity and insufficient drying property in continuous processing. there were. That is, under the same conditions as those used for evaluating photographic performance, each photographic material cut into four pieces was set so that the short side of the film was in the transport direction and the interval between the rear end of the film and the front end of the next film was 1 second. It was continuously processed. At this time, the photographic materials 13 to 16 were already the 10th sheet, and the film was already wet, resulting in poor drying.

Example 2 (Preparation of tabular grains T-2) In 1 liter of water, 4.5 g of potassium bromide, 12.0 g of gelatin and thioether HO (C
_{H 2) 2 S (CH 2} ) 2 S (CH 2) supplemented with 5% aqueous solution 2.5cc of ₂ OH 5
37cc silver nitrate aqueous solution while stirring into a container kept at 5 ° C
33 cc of a mixed aqueous solution containing (3.43 g of silver nitrate), 2.97 g of potassium bromide and 0.363 g of potassium iodide was added by the double jet method in 37 seconds. Next, 0.9 g of potassium bromide was added, the temperature was raised to 70 ° C., and 53 cc of an aqueous silver nitrate solution (4.9 g of silver nitrate) was added over 13 minutes. Next, 8 cc of 25% aqueous ammonia solution was added, and after physically aging for 10 minutes at the same temperature, 7 cc of 100% acetic acid solution was added. Subsequently, an aqueous solution of 133.3 g of silver nitrate and a mixed aqueous solution of potassium bromide and potassium iodide were added to pAg.
While maintaining at 8.35, the control double jet method was added over 35 minutes while accelerating the flow rate. At this time, the amount of potassium iodide added by the control double jet method was 0.2 mol% with respect to the total amount of silver. Next 2
N-potassium thiocyanate solution 10cc and diameter 0.07μ
m AgI fine grain emulsion was added in an amount of 0.1 mol% based on the total silver amount. After physical aging for 5 minutes at the same temperature, 35 ℃
I lowered the temperature. Thus, the total silver iodide content is 0.51 mol%, the average projected area diameter is 0.60 μm, and the thickness is 0.122 μm.
Monodisperse tabular grains having a coefficient of variation of m and a diameter of 17% were obtained. Thereafter, desalination and chemical sensitization were performed in the same manner as in the tabular grain T-1 of Example 1 to complete the preparation of T-2.

(Preparation of tabular grains T-3) In 1 liter of water, 4.5 g of potassium bromide, 12.0 g of gelatin, thioether HO (CH ₂ ) ₂ S (CH ₂ ) ₂ S (CH ₂ ) ₂ OH. 5% aqueous solution of 2.5
1. Add cc and stir into a container kept at 55 ° C. while stirring 37 mg of silver nitrate aqueous solution (3.43 g of silver nitrate) and potassium bromide.
Mixed aqueous solution 3 containing 97 g and 0.363 g of potassium iodide 3
3 cc was added by the double jet method in 37 seconds. Next, 0.9 g of potassium bromide was added, the temperature was raised to 70 ° C., and 53 cc of an aqueous silver nitrate solution (4.9 g of silver nitrate) was added over 13 minutes. Next, 8 cc of 25% aqueous ammonia solution was added, and the mixture was physically aged at the same temperature for 10 minutes and then 10
7 cc of 0% acetic acid solution was added. Followed by silver nitrate 13
3.3 g of the aqueous solution and a mixed aqueous solution of potassium bromide and potassium iodide were added by the control double jet method over 35 minutes while accelerating the flow rate while keeping the pAg at 8.5. At this time, the amount of potassium iodide added by the control double jet method was 0.3 mol% with respect to the total amount of silver. Next, 10 ml of a 2N potassium thiocyanate solution and 0.2 mol% of AgI fine grain emulsion having a diameter of 0.07 μm were added to the total amount of silver. After physically aging for 5 minutes at the same temperature, the temperature was lowered to 35 ° C. Thus, monodisperse tabular grains having a total silver iodide content of 0.76 mol%, an average projected area diameter of 0.62 μm, a thickness of 0.121 μm and a variation coefficient of diameter of 17.6% were obtained. Thereafter, desalination and chemical sensitization were performed in the same manner as in the tabular grain T-1 of Example 1 to complete the preparation of T-3.

(Preparation of Photographic Materials) Photographic materials 17 to 30 were prepared in the same manner as in Example 1. The contents are shown in Table 3.

[0079]

[Table 3]

(Performance Evaluation) Each performance was evaluated in the same manner as in Example 1. The results are summarized in Table 4.

[0081]

[Table 4]

From the results shown in Table 4, it is clear that the effect of the present invention is remarkable when the silver iodide content of the silver halide grains is 0.6 mol% or less.

Claims (2)

[Claims] 1. A silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support,
In the emulsion layer or other hydrophilic colloid layer, the polyhydroxy-substituted benzene compound was added in an amount of 1 × per mol of silver.
The content of the nonionic surfactant is less than 10 ^-1 mol and the surface protective layer of the emulsion layer contains at least a nonionic surfactant having a polyoxyethylene chain selected from the compounds represented by formula (I) or (II). 1. The total coating amount of gelatin which is contained in one kind and which is coated on one side of the support is 2.0 g / m ² or more.2.
A silver halide photographic light-sensitive material characterized by being less than 8 g / m ² . General formula (I) General formula (II) R ₁ , R ₂ , R ₆ and R ₈ represent a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, a halogen atom or a sulfamoyl group. Further, in the formula, R ₅ and R ₇ represent an alkyl group, an aryl group, an alkoxy group, a halogen atom, or a sulfamoyl group. In the general formula (II), the substituents on the phenyl ring may be left-right asymmetric. R ₃ and R ₄ represent a hydrogen atom, an alkyl group or an aryl group. R ₃ and R
₄ , R ₅ R ₆ and R ₇ and R ₈ may combine with each other to form a ring. n ₁ , n ₂ and n ₃ are average degrees of polymerization of ethylene oxide and are numbers from 2 to 50. Moreover, m is an average degree of polymerization and is a number of 2 to 50. 2. A silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support,
A compound represented by the general formula (I) or (II) in the surface protective layer of the emulsion layer, wherein the average silver iodide content of silver halide grains in the emulsion layer is less than 0.6 mol%. 1. At least one nonionic surfactant having a polyoxyethylene chain selected from the above, and the total amount of gelatin coated on one side of the support is 2.0 g / m ² or more.2.
A silver halide photographic light-sensitive material characterized by being less than 8 g / m ² . General formula (I): General formula (II): R ₁ , R ₂ , R ₆ and R ₈ represent a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, a halogen atom or a sulfamoyl group. Further, in the formula, R ₅ and R ₇ represent an alkyl group, an aryl group, an alkoxy group, a halogen atom, or a sulfamoyl group. In the general formula (II), the substituents on the phenyl ring may be left-right asymmetric. R ₃ and R ₄ represent a hydrogen atom, an alkyl group or an aryl group. R ₃ and R
₄ , R ₅ R ₆ and R ₇ and R ₈ may combine with each other to form a ring. n ₁ , n ₂ and n ₃ are average degrees of polymerization of ethylene oxide and are numbers from 2 to 50. Moreover, m is an average degree of polymerization and is a number of 2 to 50.