JPH0511391A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To provide the silver halide photographic sensitive material which does not generate roller marks even when the material is subjected to rapid processing. CONSTITUTION:This silver halide photographic sensitive material consists of silver halide emulsions which are formed by desorbing the sensitizing dyes adsorbed onto the surfaces of the silver halide particles at >=0.8mol% of silver halide by processing with an adsorbent prior to chemical sensitization to regulate the total amt. of the sensitizing dyes to <=0.75mol% of the silver halide.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a high-speed processable silver halide photographic light-sensitive material. In particular, the present invention relates to a silver halide photographic light-sensitive material which has high sensitivity and produces few roller marks even when subjected to ultra-rapid processing.

[0002]

2. Description of the Related Art In recent years, the processing time of a photographic light-sensitive material has been greatly shortened, and a developing solution giving sufficient sensitivity in a short processing time, excellent in developing progress, and having a sufficient blackening degree in a short time. A sensitive material to be given and a property of being dried in a short time after washing with water are required. As a method commonly used as a method for improving the drying property of a light-sensitive material, a sufficient amount of a hardener is added in advance in the coating step of the light-sensitive material, and the emulsion layer in the developing-fixing-water washing step is added. Alternatively, there is a method of reducing the water content in the photosensitive material before the start of drying by reducing the swelling amount of 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. Even if the development progress could be improved, the delay in the fixing speed due to the high hardness causes problems such as residual silver and residual hypo, and residual color of the sensitizing dye, which is an obstacle to shortening the processing time. On the other hand, a method of 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 0% or less 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-water washing is shortened, not only the photographic sensitivity is lowered but also the fixing silver is deteriorated 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 means for achieving ultra-rapid processing by adjusting the weight ratio (silver / gelatin) of the photosensitive silver halide coated on the emulsion layer to 1.5 or more. Has been done. further,
In JP-A-63-221341, the silver halide grains in the emulsion layer mainly consist of 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 / m ^2. 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 the methylating time to 8 minutes or more and 45 minutes or less is disclosed.

Thus, the total processing time is 60 seconds or less, especially 40 seconds.
When the time was set to less than or equal to 2 seconds, the appropriate amount of time was allocated to the developing-fixing-washing process, resulting in a gelatin coating amount of 2.5 g.
If it is not less than / m ² , the dryness is impaired when the installation environment of the automatic processor is high humidity. As described above, when the amount of gelatin is reduced to 2.5 g / m ² or less, the roller mark is deteriorated and finally reaches an unbearable level. 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.

The present inventor has found that the average iodine content of individual halogen compositions of silver halide grains is 0 to improve the roller mark which is aggravated by the silver iodide contained in the emulsion.
When a silver halide emulsion prepared with less than 6 mol% is coated with a total coating amount of gelatin of 2.5 g / m ² or less, it depends on the amount of the sensitizing dye adsorbed on the silver halide emulsion, It has been found that the elastic modulus decreases and the roller mark deteriorates.

Generally, a sensitizing dye is mainly used to extend the sensitivity of silver halide grains to the longer wavelength side. However, in the silver halide grain forming step, there is a method of adding a dye as a crystal habit controlling agent during grain formation in order to obtain a desired crystal phase or to intentionally introduce defects into crystals. This method can be referred to JP-A No. 61-205929.

Also in the chemical sensitization step, a dye may be added as a chemical sensitization aid for the purpose of controlling the chemical sensitization nuclei, improving the high illuminance failure and suppressing the intrinsic desensitization. Regarding this method, for example, JP-A-58-58
No. 113926, No. 58-113927, No. 58-1
13928, U.S. Pat. Nos. 4,439,520, 4,435,501, Research Disclosure, Item.
17643, Section III, JP-A-62-6251,
58-126526, 62-56949, 6
2-43644, 58-113928, Japanese Patent Application No. 6
No. 2-203635, No. 62-219982, No. 62
-197741, 62-219983, 62-
No. 219994, No. 62-231373, No. 62-2
Reference can be made to the description of No. 51377.

On the other hand, it is possible to remove the chemical sensitizers and chemical sensitization aids that have become unnecessary after chemical sensitization with an adsorption carrier such as an ion exchange resin or an inorganic ion exchanger.
No. 9948, No. 61-219994, No. 62-230.
No. 35 and No. 62-240951. As a result of examining these prior arts, the present inventors have found that the roller mark can be improved by reducing the amount of the sensitizing dye without lowering the spectral sensitization sensitivity.

[0010]

SUMMARY OF THE INVENTION The object of the present invention is to have high sensitivity even when subjected to ultra-rapid processing, to be free from any troubles in various performances such as drying property, fixing property and residual color property, and roller marks. It is to provide a light-sensitive material that has been sufficiently improved to a practical level.

[0011]

The above objects of the present invention have been achieved by the following method. (1) Prior to chemical sensitization, the sensitizing dye adsorbed on the surface of silver halide grains in an amount of 0.8 mol% or more with respect to silver halide is treated with an adsorbent to desorb the adsorbed sensitizing dye and halogenate it. A silver halide photographic material comprising a silver halide photographic emulsion in which the total amount of sensitizing dyes with respect to silver is 0.75 mol% or less. (2) The sensitizing dye adsorbed by 0.8 mol% or more in the above (1) is partially or completely desorbed by an adsorbent, and then the total amount of the sensitizing dye is 0.10 mol or more based on silver halide. A silver halide photographic light-sensitive material characterized by being adsorbed on the surface of a silver halide grain so that the content thereof will be 0.75 mol% or less. (3) On a support after processing a silver halide photographic emulsion having an average iodine content of individual halogen compositions of silver halide grains of less than 0.6 mol% by the method described in (1) or (2) above The total amount of gelatin coated on one side is 1.7 g / m ² or more 2.
A silver halide photographic light-sensitive material characterized by being coated at 5 g / m ² or less. The present invention will be described in detail below.

In the present invention, in the step of producing a silver halide emulsion, a sensitizing dye is adsorbed on the surface of silver halide grains before or simultaneously with chemical sensitization. The amount of dye adsorbed is 0.8 with respect to silver halide.
It is desirable that the amount is at least 1.0 mol% and preferably at least 1.0 mol% and less than 2.0 mol%. At the time of chemical sensitization, it is necessary that 0.8 mol or more of the sensitizing dye is adsorbed on the surface of the silver halide grain. As the sensitizing dye in the present invention, a cyanine dye, a merocyanine dye, a complex cyanine dye,
Complex merocyanine dyes, holopolar cyanine dyes, styryl dyes, hemicyanine dyes, oxonol dyes, hemioxonol dyes and the like can be used.

Useful sensitizing dyes used in the present invention are, for example, US Pat. Nos. 3,522,052 and 3,619,19.
No. 7, No. 3,713, 828, No. 3, 615, 643
Issue No. 3,615,632 Issue 3,617,293
No. 3,628,964, 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 addition amount of the sensitizing dye is 0.8 mol% or more, preferably 1.0 mol% and 2.0 mol% or less with respect to 1 mol of silver halide. Among these sensitizing dyes, cyanine dyes and merocyanine dyes are more preferable, and cyanine dyes are more preferable. An example is shown below.

[0014]

[Chemical 1]

R ₀ represents H, CH ₃ or C ₂ H ₅ ,
R ₁ and R ₂ each represent an alkyl group having a sulfo group, and X ₁ and X ₂ are both halogens, or X ₁ is a halogen and X ₂ is a phenyl group.

In the present invention, the sensitizing dye adsorbed on the surface of the silver halide grains is partially or wholly desorbed with an adsorbent before or after the chemical sensitization of the silver halide emulsion. Let As the adsorbent, it is desirable to mainly use a solid adsorption carrier.

The solid adsorption carrier in the present invention is an inorganic or organic solid which is insoluble in water. In particular,
Examples thereof include activated carbon, ion exchange resin, porous resin, porous organic synthetic resin having no ion exchange group, and inorganic adsorption carrier. The activated carbon referred to in the present invention is, for example, coconut shell activated carbon, and any of those described in "Activated Carbon" edited by the Society of Carbon Science (Kodansha, 1978) can be used. More specifically, the ion exchange resin referred to in the present invention is

Cation exchange resin, for example, Amberlite (trade name, manufactured by Rohm and Haas Co.) IR-120; Diaion (manufactured by Mitsubishi Kasei Co., Ltd.) S
K-1B, SK-102, SK-104, SK-10
6, SK-110, SK-112, SK-116, PK
-206, PK-212, PK-216, PK-22
0, PK-228, WK-10, WK-11, WK-2
0: Powdex (powder resin) PCH. Anion exchange resin For example, trade name (Dow Chemical Co.) Dowex 1x
8; Diaion (manufactured by Mitsubishi Kasei) SA-10A, SA
-11A, SA-12A, SA-20A, SA-21
A, PA-306, PA-308, PA-312, PA
-316, PA-318, PA-416, PA-40
8, PA-412, PA-416, PA-418, WA
-10, WA-11, WA-20, WA-21, WA-
30; Powdex (powder resin) PAO and the like. Chelate resin For example, trade name Diaion (manufactured by Mitsubishi Kasei) CR-1
0, CR-20, etc. These ion exchange resins are
There are many types on the market, and you can easily get the one that suits your purpose. In addition, a resin which is not commercially available can be synthesized according to the method described in "Chelate Resin / Ion Exchange Resin" by Shujo Hojo, which can also be used as a solid adsorbent.

The term "porous resin" as used in the present invention means an organic synthetic resin having macropores having an average pore diameter of 500 nm or less. The porous organic synthetic resin having no ion exchange group in the present invention means 1) having a macropore having an average pore size of 500 nm or less, 2) a quaternary amine group, a carboxyl group, a sulfonic acid group, etc. An organic synthetic resin that does not have a functional group that itself dissociates into positive and negative ions. Specifically, styrene-divinylbenzene copolymer, chloromethylstyrene-divinylbenzene copolymer, methoxymethylol-divinylbenzene copolymer, ethylene-divinylbenzene copolymer, methylmethacrylate-divinylbenzene copolymer, methyl Acrylate-divinylbenzene copolymer and the like. The specific structure is shown below.

[0020]

[Chemical 2]

The method for synthesizing the porous resin is described in "Chelate Resin / Ion Exchange Resin", Chapter 2 (p. 127-) by Shujo Hojo.
Although a linear polymer addition method, a precipitant addition method, etc. are known as described in 1), they may be synthesized by any method. A part of the above-mentioned porous resin is commercially available and can be easily obtained according to the intended use. Specific examples of commercially available resins are shown in the table below. Mitsubishi Kasei resin matrix Specific surface area Pore volume Mode radius m ² / g-HP ml / g-HP (Angstrom) HP10 Styrene 500 0.9 100 ~ 700 20 Styrene 720 1.1 100 ~ 1300 30 Styrene 570 1.0 100 ~ 900 40 Styrene 700 700 100 ~ 600 50 Styrene 600 0.9 900 Brand name Grain size Specific surface area Pore volume (μ) (m ² / g) (ml / g) MCI GEL CHP20P 37 ~ 75 500 ~ 700> 1 〃 75 〜 150 500 〜 700 ＞ 1 〃 150 〜 300 500 〜 700 ＞ 1 Specific surface area Pore volume Mode radius m ² / g-HP ml / g-HP (Angstrom) XAD 1 Styrene 100-205 2 Styrene 300 0.6 90 4 Styrene type 784 1.1 50 7 Styrene type 450 0.8 90 8 Styrene type 140 0.5 235 9 Sulfoxide type 69-366 11 Amide type 69-352 12 N-O Polarity value 22 1300

[0022] Inorganic adsorbent carrier in the present invention, specifically, zeolite, diatomaceous _{earth, MgO · nH 2 O, MgO} · XAl 2 O 3
NH ₂ O (X = 0 to 0.25) (inorganic adsorbent M-511 manufactured by Kunimine Industry Co., Ltd.), smectite, montmorillonite and the like.
The commercially available zeolites are synthetic zeolite A-3, synthetic zeolite A-4, and synthetic zeolite F-.
9 (above, manufactured by Wako Pure Chemical Industries, Ltd.), but not limited thereto. For example, “Zeolite-edited” edited by Nobuyoshi Hara and Hiroshi Takahashi.
All zeolites described in "Basics and Applications" (Kodansha, 1975) can be used as the solid adsorbent. As smectite and montmorillonite, smecton, Kunipia and the like (manufactured by Kunimine Industries Co., Ltd.) can be used.

Among the solid adsorbents listed above, activated carbon, ion exchange resin, porous resin and organic synthetic resin having no ion exchange group are preferable, and activated carbon, porous resin and ion exchange are particularly preferable. It is a porous organic synthetic resin having no base. The most preferable one is a porous organic synthetic resin having no ion exchange group. The solid adsorbents listed above have various forms such as a granular form, a powder form and a film form, but a granular form, a powder form and a film form are preferable.
The size is preferably larger than that of the silver halide grains used in the silver halide emulsion. This is because after the silver halide emulsion is treated with the adsorption carrier of the present invention, these often remain in the emulsion, and there is no harm even if they remain. This is because it is preferable to remove the adsorbent from the emulsion.

Desorption of the dye from the silver halide emulsion in the present invention by the solid adsorption carrier of the present invention means that the solid adsorbent is added to the silver halide emulsion in a batch manner and mixed with stirring, and then the solid adsorbent is added. A step of removing by filtration, or a solid adsorbent is continuously filled in an adsorption bed or adsorption column,
It refers to the process of passing a silver halide emulsion there,
Either step can be used in the present invention. The amount of solid adsorbent used depends on the performance of the adsorbent (for example, ion exchange capacity, total adsorption capacity, pore volume) and shape (grain size, effective surface area), and the content of the target silver halide emulsion (for example,
It can be appropriately selected depending on the chemical sensitization aid and the type of dye). For example, in the case of batch type, it can be used in the range of addition amount of 0.1 g to 1000 g per kg of silver halide emulsion, and in the case of continuous type, the amount of solid adsorbent relative to the total amount of silver halide emulsion to be passed is If considered, it can be used in the same range as the batch type. The processing temperature may be in a temperature range from the temperature at which the silver halide emulsion is liquefied (about 30 ° C) to the durability temperature of the carrier, and the processing time is 1 minute or more for both batch type and continuous type. Time is enough.

As described above, before the chemical sensitization in the step of producing a silver halide emulsion or after the chemical sensitization, the sensitizing dye adsorbed on the surface of the silver halide grains is chemically sensitized,
A part or all of the above solid adsorbent is desorbed, and after desorption, the amount of the sensitizing dye finally coated before the coating step of the emulsion is 0 to silver halide. .
10 mol or more and 0.75 mol% or less, preferably 0.
A sensitizing dye of 3 mol% or more and 0.6 mol% or less can be adsorbed on silver halide grains. The sensitizing dye that can be used at this time may be any of the above-mentioned sensitizing dyes. The temperature for adding the sensitizing dye may be any temperature as long as it is a temperature at which the silver halide emulsion is dissolved. The roller mark is deteriorated depending on the amount of the sensitizing dye adsorbed on the silver halide grains during coating of the silver halide emulsion, so it is desirable to keep the roller mark as small as possible unless the spectral sensitization sensitivity is impaired.

Regarding the amount of silver iodide contained in the silver halide grains, the average iodine content of the halogen composition is less than 0.6 mol% so as not to deteriorate the roller mark. As a method for measuring the halogen composition of the silver halide emulsion grains, for example, a powder X-ray diffraction method as 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 preferable 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. In forming the surface silver iodobromide phase of the silver halide grains, it is preferable to use a silver halide solvent together, and it is particularly preferable to use KSCN. In addition, JP-A-63-
An organic compound containing iodine as described in 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 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 1.70 to 2.50 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 gelatin amount is more preferably in the range of 1.80 to 2.40 g / m ² , particularly 1.90 to ² .
A range of 30 g / m ² is preferred.

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 menting time referred to in this specification means that at least one layer of silver halide constituting the sensitive material when the sensitive material cut into 1 cm x 2 cm is immersed in a 1.5 wt% aqueous solution of sodium hydroxide 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 may have a regular crystal form such as a cube, an octahedron or a tetrahedron, or a spherical,
It may have an irregular crystal shape such as a plate shape or a potato shape. It may consist of a mixture of particles of various crystal forms. As the composition of silver halide, silver iodobromochloride or silver iodobromide or pure silver bromide can be used substantially because it has high sensitivity. 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 of accelerating the addition rate, as described in JP-B-48-36890, JP-A-52-16364, and JP-A-55-142329, the addition rate of the silver salt aqueous solution and the halide aqueous 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 are temperature, pH, pAg, degree of stirring, composition of silver halide grains, solubility, grain size, inter-grain distance, or protection. It changes depending on the type and concentration of 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
Author "The Theory of the Photographic Process" 4th
Edition, published by Macmillan Co. (1977), pp. 38-104, neutral method, acidic method, ammonia method, forward mixing, back mixing, double jet method, controlled double jet method, conversion method. , Core / shell method, etc. can be applied to manufacture.

Further, tabular grains having a grain size of 5 times or more the grain thickness are preferably used in the present invention (for details, RE
SEARCH DISCLOSURE Volume 225 I tem 22534 P.P. Two
0-P. 58, January issue, 1983, and JP-A-58-
No. 127921, 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, "Development of Morphology of Silver Bromide Crystals During Physical Ripening (Evolution of the Morphology of Silver Promide Crystals).・ During / Physical / Liping) Science
E-Industrie Photography, Volume 33, No.
(1962) pp. 121-125, Duffin, "Photographic Emulsion Chemistry (Pho
tographic emulsion Chemistry) "Focal Press
(FocalPress), New York, 1966, p-66-
p. 72, APH Trivelli, WF Smith
th) Photographic Jour
nal), 80, 285 (1940) and the like, but JP-A-58-127,921 and JP-A-58-11.
3, 927, JP-A-58-113,928, and U.S. Pat. No. 4,439,520 can be easily prepared. The projected area diameter of the tabular emulsion of the present invention is 0.3.
.About.2.0 .mu.m, preferably 0.5 to 1.2 .mu.m. The distance between parallel planes (particle thickness) is 0.05μ.
m-0.3 μm, particularly 0.1-0.25 μm,
The aspect ratio is 3 or more and less than 20, especially 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.
The average aspect ratio of the tabular grains is 3 or more, particularly 4 to 8
Is preferred. 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 according to the present invention are described in JP-A-63-151618.

The chemical sensitization method of the silver halide emulsion used in the present invention includes sulfur sensitization method, selenium sensitization method, reduction sensitization method and gold sensitization method in the presence of the above-mentioned sensitizing dye. Known methods can be used, and they can be used 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. Specific examples thereof are described in US Pat. No. 2,448,060 and British Patent 618,061. As the sulfur sensitizer, various sulfur compounds such as thiosulfates, thioureas, thiazoles, rhodanins and the like can be used in addition to the sulfur compounds contained in gelatin. Specific examples are US Pat.
4,944, 2,278,947, 2,41
0,689, 2,728,668, 3,50
Nos. 1,313 and 3,656,955. The combined effect of sulfur sensitization, selenium sensitization, and gold sensitization with thiosulfate can effectively exert the effect of the present invention.

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 Japanese Examined Patent Publication Nos. 41-15748 and 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, the following general formulas (I) and (II) are preferable. General formula (I)

[0034]

[Chemical 3]

In the formula, Z ₁ and Z _{2, which} may be the same or different, each represents an alkyl group (for example, a methyl group,
Ethyl group, t-butyl group, adamantyl group, t-octyl group), alkenyl group (eg vinyl group, propenyl group), aralkyl group (eg benzyl group, phenethyl group), aryl group (eg phenyl group, penta) Fluorophenyl group, 4-chlorophenyl group, 3-nitrophenyl group, 4-octylsulfamoylphenyl group, α-
Naphthyl group), heterocyclic group (for example, pyridyl group, thienyl group, furyl group, imidazolyl group), -NR ₁ (R ₂ ),-
It represents an OR ₃ or -SR _4. R ₁ , R ₂ , R ₃ and R _{4, which} may be the same or different, each represents an alkyl group, an aralkyl group, an aryl group or a heterocyclic group.
Examples of the alkyl group, aralkyl group, aryl group or heterocyclic group are the same as those for Z ₁ . However, R ₁ and R ₂ are a hydrogen atom or an acyl group (eg, acetyl group, propanoyl group, benzoyl group, heptafluorobutanoyl group, difluoroacetyl group, 4-nitrobenzoyl group, α-naphthoyl group, 4-trifluoro group). Methylbenzoyl group). In formula (I), Z ₁ is preferably an alkyl group, an aryl group or —NR ₁ (R ₂ ).
And Z ₂ represents —NR ₅ (R ₆ ). R ₁ , R ₂ , R ₅
R ₆ and R ₆ may be the same or different and each represents a hydrogen atom, an alkyl group, an aryl group, or an acyl group. In the general formula (I), more preferably N, N-dialkylselenourea, N, N, N′-trialkyl-N′-acylselenourea, tetraalkylselenourea, N, N-
Dialkyl-arylselenoamide, N-alkyl-N
Represents an aryl-arylselenoamide. General formula (II)

[0036]

[Chemical 4]

In the formula, Z ₃ , Z ₄ and Z ₅ may be the same or different and each is an aliphatic group, an aromatic group, a heterocyclic group, -OR ₇ , -NR ₈ (R ₉ ), -SR. ₁₀ , -Se
Represents R ₁₁ , X ₁ and a hydrogen atom. R ₇ , R ₁₀ and R ₁₁ represent an aliphatic group, an aromatic group, a heterocyclic group, a hydrogen atom or a cation, and R ₈ and R ₉ represent an aliphatic group, an aromatic group, a heterocyclic group or a hydrogen atom. , X represents a halogen atom.
In the general formula (II), Z ₃ , Z ₄ , Z ₅ , R ₇ ,
The aliphatic group represented by R ₈ , R ₉ , R ₁₀ and R ₁₁ is a linear, branched or cyclic alkyl group, alkenyl group, alkynyl group, aralkyl group (eg, methyl group, ethyl group, n-propyl group). , Isopropyl group, t-butyl group,
n-butyl group, n-octyl group, n-decyl group, n-hexadecyl group, cyclopentyl group, cyclohexyl group,
Allyl group, 2-butenyl group, 3-pentenyl group, propargyl group, 3-pentynyl group, benzyl group, phenethyl group). In the general formula (II), Z ₃ , Z ₄ ,
The aromatic group represented by Z ₅ , R ₇ , R ₈ , R ₉ , R ₁₀ and R ₁₁ is a monocyclic or condensed aryl group (for example, phenyl group, pentafluorophenyl group, 4-chlorophenyl group, 3 -Sulfophenyl group, α-naphthyl group, 4-methylphenyl group). In the general formula (II), Z ₃ ,
The heterocyclic group represented by Z ₄ , Z ₅ , R ₇ , R ₈ , R ₉ , R ₁₀ and R ₁₁ is a saturated 3- to 10-membered ring containing at least one of a nitrogen atom, an oxygen atom or a sulfur atom. Alternatively, it represents an unsaturated unsaturated group (for example, a pyridyl group, a thienyl group, a furyl group, a thiazolyl group, an imidazolyl group, a benzimidazolyl group). In the general formula (II), the cations represented by R ₇ , R ₁₀ and R ₁₁ represent an alkali metal atom or ammonium, and the halogen atom represented by X is, for example, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. Represents In formula (II), preferably Z ₃ , Z ₄ or Z
₅ represents an aliphatic group, an aromatic group or -OR _7, R ₇ represents an aliphatic group or an aromatic group. In formula (II), it is more preferably trialkylphosphine selenide, triarylphosphine selenide, trialkylselenophosphate or triarylselenophosphate. Specific examples of the compounds represented by formulas (I) and (II) are shown below, but the invention is not limited thereto.

[0038]

[Chemical 5]

[0039]

[Chemical 6]

[0040]

[Chemical 7]

[0041]

[Chemical 8]

[0042]

[Chemical 9]

[0043]

[Chemical 10]

[0044]

[Chemical 11]

[0045]

[Chemical 12]

As the reduction sensitizer, there can be used primary tin salts, amines, formamidinesulfinic acid, silane compounds and the like. The photographic emulsion used in the present invention contains a silver halide in the chemical sensitization step of the present invention for the purpose of preventing fog during the production process of the light-sensitive material, storage or photographic processing, or stabilizing photographic performance. Various compounds can be contained in addition to the adsorptive substance. That is, azoles {for example, benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles,
Nitroindazoles, benzotriazoles, aminotriazoles, etc.); Mercapto compounds {eg, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, mercaptotetrazole, mercaptopyrimidines, mercaptotriazines, etc.} Thioketo compounds such as oxadrinethione; azaindenes {eg triazaindenes, tetraazaindenes (especially 4-hydroxy-substituted (1,3,3a, 7) tetraazaindenes), pentaazaindenes, etc. };
Many compounds known as antifoggants or stabilizers can be added, such as benzenethiosulfonic acid, benzenesulfinic acid, benzenesulfonic acid amide, and the like. In particular, JP-A-60-76743 and JP-A-60-8732
Nitron and its derivatives described in Japanese Patent Application Laid-Open No. 2-6, JP-A-60
No. 80839 gazette, the mercapto compound described in JP-A No. 57-164735, and the heterocycle compound-silver complex salt (for example, 1-phenyl-5).
-Mercaptotetrazole silver) and the like 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, coating aids, antistatic agents, slipperiness improvement, emulsion dispersion, adhesion prevention and photographic property improvement (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 alkylphenyl ethers; amphoteric surfactants such as alkyl betaines, alkyl sulfobetaines;
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 Cations such as didium chloride, betaines such as N-dodecyl-N, N-dimethylcarboxybetaine and N-oleyl N, N-dimethylsulfobutylbetaine, poly (average degree of polymerization n = 1
0) oxyethylene cetyl ether, poly (n = 25) oxyethylene p-nonylphenol ether, bis (1
Nonionics such as -poly (n = 15) oxyethylene-oxy-2,4-di-t-pentylphenyl) ethane can be particularly preferably used. As the antistatic agent, perfluorooctanesulfonic acid K salt, N-propyl-N-
Perfluorooctanesulfonyl glycine Na salt, N-
Propyl-N-perfluorooctanesulfonylaminoethyloxypoly (N = 3) oxyethylenebutanesulfonic 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 Particle size is 1.0-10 μm, especially 2-5 μm
Is preferred. In the surface layer of the photographic light-sensitive material of the present invention, as a slip agent, US Pat.
Silicon compounds described in 047958, etc.
In addition to the colloidal silica described in JP-A-6-23139, paraffin wax, higher fatty acid ester, den powder derivative and the like can be used. Polyols such as trimethylolpropane, pentanediol, butanediol, ethylene glycol and glycerin can be used as a plasticizer in the hydrophilic colloid layer of the photographic light-sensitive material of the present invention.

As the binder or protective colloid which 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, mucophenoxycyclo acid etc.) isoxazoles, dialdehyde starch, 2-chloro-6-hydroxytriazine Nilated 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 polymer hardener can be effectively used. Examples of the high-hardening agent 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. Polymers having an epoxy group described in US Pat. No. 3,362,827, polymers having a dichlorotriazine group described in US Pat. No. 3,362,827 and Research Disclosure 17333 (1978), and JP-A-56-66841. Polymers having active ester groups, JP-A-56-142524, US Pat. No. 4,161,407, JP-A-54-65033, Research Disclosure 16725 (1978).
Examples thereof include polymers having an active vinyl group or a group serving as a precursor thereof, and the like, and polymers having an active vinyl group or a group serving as a precursor thereof are preferable, and among them, JP-A-56-142524. Polymers in which the active vinyl groups, or their precursor groups, are attached to the polymer backbone by long spacers, as described, are particularly preferred.

The hydrophilic colloid layer in the photographic light-sensitive material of the present invention is preferably hardened with these hardeners so that the swelling ratio 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 swelling ratio of the hydrophilic colloid layer is measured when the photographic material is aged at 25 ° C. and 60% RH for 7 days. The dry thickness (a) is determined by a scanning electron microscope of the section. The swollen film thickness (b) is determined by observing with a scanning electron microscope after the photographic material is immersed in distilled water at 21 ° C. for 3 minutes, freeze-dried with liquid nitrogen. The swelling ratio is a value (%) obtained by dividing the value of {(b)-(a)} by (a) and multiplying it by 100.

The support is preferably a polyethylene terephthalate film or a cellulose triacetate film. The support is preferably subjected to corona discharge treatment, claw discharge treatment or ultraviolet irradiation treatment on its surface in order to improve the adhesion with the hydrophilic colloid layer, or is made of a styrene butadiene latex, a vinylidene chloride latex or the like. 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. The structural formulas of the dyes I-1 and I-2 used in the examples are as follows.

[0054]

[Chemical 13]

[0055]

【Example】

Example 1 (Preparation of emulsions A-1 to 3) In 1 liter of water, 4.5 g of potassium bromide, 20.6 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 6
37cc silver nitrate aqueous solution while stirring in a container kept at 0 ° 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, 15 cc of 25% aqueous ammonia solution was added and physically aged for 20 minutes at the same temperature, and then 100
14 cc of a% acetic acid solution was added. Followed by silver nitrate 13
An aqueous solution of 3.3 g and an aqueous solution of potassium bromide was added to pAg8.
While maintaining at 5, the control double jet method was added over 35 minutes. Next, 10 cc of 2N potassium thiocyanate solution 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 was 0.26 mol%, the average projected area diameter was 1.10 μm.
m, the thickness was 0.165 μm, and the monodisperse tabular grains having a diameter variation coefficient of 18.5% were obtained.

After that, soluble salts were removed by a precipitation method. The temperature was again raised to 40 ° C., 30 g of gelatin, 2.35 g of phenoxyethanol, and 0.8 g of sodium polystyrene sulfonate as a thickener were added, and pH was adjusted to 5.90 and pAg was adjusted to 8.25 with caustic soda and silver nitrate solution. This emulsion was chemically sensitized while being kept at 56 ° C. with stirring. First, 0.043 mg of thiourea dioxide was added and the mixture was held for 22 minutes as it was for reduction sensitization. Next, 20 mg of 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene and 300 mg of sensitizing dye I-1 were added. Subsequently, 3.3 mg of sodium thiosulfate, 2.6 mg of chloroauric acid and 90 mg of potassium thiocyanate were added,
After 40 minutes it was cooled to 40 ° C. Emulsion A-1 was thus prepared. Emulsions A-2 and A-3 were prepared in the same manner as emulsion A-1, except that the sensitizing dye I-1 was changed to 500 mg and 750 mg, respectively. Emulsion A- prepared as above
1 to 3 were melted at 40 ° C. to desorb the sensitizing dye.
The solid adsorbent used for desorption is a porous organic synthetic resin without ion-exchange groups. MCI GEL CHP manufactured by Mitsubishi Kasei.
The particle size was 75 to 150 μm at 20 P, and 200 g was added to 1 kg of the emulsion and the mixture was stirred. After stirring for 1 hour, the solid adsorbent was separated from the emulsion by filtration using a microfilter. The emulsion of this filtrate was measured for absorption spectrum with a Hitachi Model 307 color analyzer, and sensitizing dye I-
It was confirmed that 1 was completely desorbed.

(Preparation of coating sample) The following chemicals were added to 1 mol of silver halide of A-1 to A-3 to prepare a coating liquid.・ 2,6-bis (hydroxyamino) -4-diethylamino-1,3,5-triazine 72 mg ・ Sensitizing dye I-2 is added in an amount such that the total addition amount is the value shown in Table-1 ・ Gelatin Surface protection described later Add an amount such that the total coating amount of the layer and gelatin used in the undercoat layer is 2.4 g / m ²・ Trimethylolpropane 9 g ・ Dextran (average molecular weight 39,000) 18.5 g ・ Polystyrene sulfonic acid Sodium (average molecular weight 600,000) 1.8 g Hardener 1,2-bis (vinylsulfonylacetamide) ethane 1.6 g

[0058]

[Chemical 14]

Preparation of Coating Solution for Surface Protective Layer The surface protective layer was prepared and prepared so that each component had the following coating amount. Contents of surface protective layer Coating amount-Gelatin 0.966 g / m ² -Sodium polyacrylate (average molecular weight 400,000) 0.023 4-Hydroxy-6-methyl-1,3,3a, 7-tetrazaindene 0 .015

[0060]

[Chemical 15]

Polymethylmethacrylate (average particle size 3.7 μm) 0.087 g / m ² Proxel 0.0005 g / m ² (pH adjusted to 7.4 with NaOH) Preparation of support (1) Dye for undercoat layer Preparation of D-1 The following dye was ball milled by the method described in JP-A-63-197943.

[0062]

[Chemical 16]

434 ml of water and 791 ml of a 6.7% aqueous solution of Triton X-200 surfactant (TX-200) were placed in a 2 liter ball mill. 20 g of dye were added to this solution. Zirconium oxide (ZrO) beads 4
00 ml (2 mm diameter) was added and the contents were crushed for 4 days. After this, 160 g of 12.5% gelatin was added. After defoaming, the ZrO beads were removed by filtration. Observing the obtained dye dispersion, the particle size of the crushed dye has a wide range of diameters from 0.05 to 1.15 μm, and the average particle size was 0.37 μm. Further, centrifugation was performed to remove dye particles having a size of 0.9 μm or more. Thus, Dye Dispersion D-1 was obtained. (2) Preparation of support Corona discharge treatment was performed on a biaxially stretched polyethylene terephthalate film having a thickness of 183 μm, and a first undercoating liquid having the following composition was applied to a coating amount of 5.1 cc / m ^2. It was applied with a wire bar coater and dried at 175 ° C. for 1 minute. The polyethylene terephthalate used was one containing 0.04 wt% of the dye having the following structure.

[0064]

[Chemical 17]

Butadiene-styrene copolymer latex solution (solid content 40% butadiene / styrene weight ratio = 31/69) 79 cc 2,4-dichloro-6-hydroxy-s-triazine sodium salt 4% solution 20.5 cc Distillation Water 900.5 cc * A latex solution contained 0.4 wt% of the following compound as an emulsifying dispersant with respect to the latex solid content.

[0066]

[Chemical 18]

A second undercoat layer having the following composition was coated on one side of the above first undercoat layer at 150 ° C. on one side by a wire bar coater system so that the coating amount was as described below.
It was applied and dried.・ Gelatin 160 mg / m ²・ Dye Dispersion D-1 (26 mg / m ² as dye solid content)

[0068]

[Chemical 19]

Matting agent Polymethylmethacrylate having an average particle size of 2.5 μm 2.5 mg / m ²

Preparation of photographic material On the prepared support, the above emulsion layer and surface protective layer were coated on both sides by the simultaneous extrusion method. The coated silver amount per one side was 1.75 g / m ² . The amount of coated gelatin and the swelling ratio obtained by the freeze-drying method using the liquid nitrogen method are adjusted to 200% to 280% by adjusting the amount of gelatin added to the emulsion layer and the amount of hardener.
I tried to fit in between. Photographic materials 1 to 15 for evaluating photographic performance and roller mark were prepared.

Evaluation of Photographic Performance Each sample of photographic materials 1 to 15 was exposed for 0.05 seconds from both sides using an X-ray orthoscreen HR-4 manufactured by Fuji Photo Film Co., Ltd., and sensitivity was evaluated. Was done.
After the exposure, the following processing was performed. The sensitivity was defined as the reciprocal of the ratio of the amount of exposure which gives a density of 1.0, with the photographic material 5 being 100. [Processing] Automatic processor ... SRX5 manufactured by KONICA
The drive motor and gear of 01 were modified to speed up the transfer speed. <Developer concentrate> Potassium hydroxide 56.6 g Sodium sulfite 200 g Diethylenetriaminepentaacetic acid 6.7 g Potassium carbonate 16.7 g Boric acid 10 g Hydroquinone 83.3 g Diethylene glycol 40 g 4-Hydroxymethyl-4-methyl 1-phenyl-3-pyrazolidone 22.0 g 5-methylbenzotriazole 2 g

[0072]

[Chemical 20]

Make up to 1 liter with water (adjust to pH 10.60). <Fixing solution concentrate> Ammonium thiosulfate 560 g Sodium sulfite 60 g Ethylenediaminetetraacetic acid / disodium dihydrate 0.10 g Sodium hydroxide 24 g Water is adjusted to 1 liter (pH is adjusted to 5.10 with acetic acid). When the development processing was started, each tank of the automatic processor was filled with the following processing solutions. Developing tank: 333 ml of the above developing solution concentrate, 667 ml of water and 10 ml of a starter containing 2 g of potassium bromide and 1.8 g of acetic acid were added to bring the pH to 10.25. Fixing tank: 200 ml of the above fixing solution concentrate and 800 ml of water Processing speed … Dry to Dry 35 seconds Development temperature… 35 ℃ Fixing temperature… 32 ℃ Drying temperature… 55 ℃ Replenishing amount… Developer 22ml / 10 × 12 inches Fixer 30ml / 10 × 12 inches

(Evaluation of roller mark) Photographic materials 1 to 8
Is cut into 30.5 cm x 25.4 cm and the color temperature is 5400 °.
Exposure was performed from one side with a K light source. At this time, by adjusting the exposure time, the density in the roller mark evaluation process was adjusted to be 1.0 uniformly including the pace density. 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. The results, which are largely unacceptable, are summarized in Table 1.

[0075]

[Table 1]

From Table 1, the amount of the sensitizing dye added before or during the chemical sensitization was 0.
When it is 6 mol%, the spectral sensitivity is low and it is not practical regardless of the treatment with a solid adsorbent. The amount of sensitizing dye added before or during chemical sensitization is 1.0 mol% and 1.
The spectral sensitivity is high when the amount of the sensitizing dye added before coating after desorption of the sensitizing dye adsorbed on the 5 mol% emulsion is 0.5 to 0.75 mol% with respect to the silver halide. The roller mark is an allowable level, and the effect of the present invention is clear.

Example 2 (Preparation of Emulsions T-1 to 3) In the process of preparing tabular grains of Emulsion A-1, 2N potassium thiocyanate solution was added, and then AgI fine particles having a diameter of 0.07 μm were added to total silver. 0.2 mol% was added to the amount. After physically aging for 5 minutes at the same temperature, the temperature was lowered to 35 ° C. Thus, the total silver iodide content was 0.46 mol% and the average projected area was 1.10μ.
m, the thickness was 0.165 μm, and the monodisperse tabular grains having a variation coefficient of the diameter of 18.5% were obtained. After this, the soluble salts were removed by the sedimentation method. The temperature was raised to 40 ° C. again, and 30 g of gelatin, 2.35 g of phenoxyethanol and 0.8 g of sodium polystyrene sulfonate as a thickener were added, pH was 5.90 with caustic soda and silver nitrate solution, pAg was 8.25.
Adjusted to. This emulsion was chemically sensitized while being kept at 56 ° C. with stirring. First, thiourea dioxide 0.043
mg was added and the mixture was held for 22 minutes as it was for reduction sensitization. Next, 4-hydroxy-6-methyl-1,3,3
20 mg of a, 7-tetrazaindene and 300 mg, 400 mg and 500 mg of sensitizing dye I-3 were added, respectively. Subsequently, 3.3 mg of sodium thiosulfate, 2.6 mg of chloroauric acid and 90 mg of potassium thiocyanate were added, and 40 minutes later, 40
Cooled to ° C. Thus, the preparation of emulsions T-1 to T-3 was completed.

Emulsions T-1 to 3 prepared as described above were mixed at 40 ° C.
Melted at Mitsubishi Kasei MCI GELCHP 20P particle size 75 ~
200 g of 150 μm and 100 cc of methanol were added to 1 kg of the emulsion, and the mixture was stirred for 2 hours. Then, the mixture was filtered using a microfilter, and the absorption spectrum of the filtered emulsion was measured with a Hitachi Model 307 color analyzer to confirm that desorption was completed. The applied sample is Example-1.
Photographic materials 16 to 29 for photographic performance and roller mark evaluation were prepared in the same manner as in. Photographic performance and roller mark evaluation were performed in the same manner as in Example-1. The results are summarized in Table 2.

[0079]

[Table 2]

From the results shown in Table 2, the dye is desorbed from the emulsion in which the amount of the sensitizing dye present during the chemical sensitization is 0.8 mol% or more based on the silver halide, and the amount of the sensitizing dye added thereafter is the halogen. The sample having 0.75 mol% or less with respect to silver halide has a high spectral sensitivity and has an improved roller mark.
The effect of the present invention is clear.

─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] September 9, 1991

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0004

[Correction method] Change

[Correction content]

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.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0013

[Correction method] Change

[Correction content]

Useful sensitizing dyes used in the present invention are, for example, US Pat. Nos. 3,522,052 and 3,619,1.
No. 97, No. 3,713, 828, No. 3, 615, 64
No. 3, No. 3,615, 632, No. 3,617, 293
No. 3,628,964, 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 the sensitizing dye added is 0.8 mol% or more, preferably 1.0 mol% or more and 2.0 mol, based on 1 mol of silver halide.
It is preferably not more than mol%. Among these sensitizing dyes, cyanine dyes and merocyanine dyes are more preferable, and cyanine dyes are more preferable. An example is shown below.

[Procedure 3]

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The sensitive material of the present invention has a melting time of 8
It is preferable that the time is set to not less than 45 minutes and not more than 45 minutes. The melting time referred to in this specification is 1 cm x 2 cm.
When the cut sensitive material is dipped in a 1.5 wt% aqueous solution of sodium hydroxide at 50 ° C., it means the time until at least one silver halide emulsion layer constituting the sensitive material begins to melt.

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Further, tabular grains having a grain size of 5 times or more the grain thickness are preferably used in the invention (specifically,
RESEARCH DISCROSURE 225 Volume It
em 22534P. 20-P. 58, January issue, 198
3 years, and JP-A-58-127921 and 58-11.
3926). The tabular silver halide grains can be produced by appropriately combining the methods known in the art. Tabular silver halide emulsions include Kunac and Chateau (Cha)
tau) "The evolution of the morphology of silver bromide crystals during physical ripening (Evolution of the Morphology of
Silver Promide Crystals During
Physical Reinforcement) "Science & Industry, Photography, Vol. 33, No. (196
2) pp. 121-125, Duffin
Written "Photographic emulsion chemistry (Photographic emulation Ch
"emission" Focal Press (FocalP)
Less), New York, 1966, P-66-
P. 72, A. P. H. Trivel
i), W. F. Smith Photographic Journal
al), 80, 285 (1940), and the like, but JP-A-58-127,921 and JP-A-58-1.
13, 927, JP-A-58-113,928, and U.S. 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, and particularly 0.1 to 0.25.
The aspect ratio is preferably 3 or more and less than 20, and particularly preferably 4 or more and less than 8. In the tabular silver halide agent of the present invention, the aspect ratio is 2
The above silver halide grains account for 50% of all grains (projected area)
It is preferable that the content of the tabular grains is not less than 70%, and the average aspect ratio of the tabular grains is not less than 3 and particularly 4 to 8.
Among the tabular silver halide grains, monodisperse hexagonal tabular grains are particularly useful grains. Details of the structure and manufacturing method of the monodisperse hexagonal tabular grains referred to in the present invention are described in JP-A-63-151.
618 as described.

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As the reduction sensitizer, a primary tin salt, an amine, formamidinesulfinic acid, a silane compound or the like can be used. The photographic emulsion used in the present invention contains a silver halide in the chemical sensitization step of the present invention for the purpose of preventing fog during the production process of the light-sensitive material, storage or photographic processing, or stabilizing photographic performance. Various compounds can be contained in addition to the adsorptive substance. That is, azoles {for example, benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles,
Nitroindazoles, benzotriazoles, aminotriazoles, etc.); Mercapto compounds {eg, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, mercaptotetrazole, mercaptopyrimidines, mercaptotriazines, etc.} Thioketo compounds such as oxadrinethione; azaindenes {eg triazaindenes, tetraazaindenes (particularly 4-hydroxy-substituted (1,3,3a, 7) tetraazaindenes), pentaazaindenes, etc. };
Many compounds known as antifoggants or stabilizers can be added, such as benzenethiosulfonic acid, benzenesulfinic acid, benzenesulfonic acid amide, and the like. In particular, JP-A-60-76743 and JP-A-60-8732
Nitron and its derivatives described in Japanese Patent Application Laid-Open No. 2-6, JP-A-60
No. 80839 gazette, the mercapto compound described in JP-A No. 57-164735, and the heterocycle compound-silver complex salt (for example, 1-phenyl-5).
-Mercaptotetrazole silver) and the like 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.

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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, glitalaldehyde, etc.), N-methylol compounds (dimethylolurea, methyloldimethylhydantoin, etc.), dioxane derivatives (2,3-dihydroxydioxane, etc.) ), An active vinyl compound (1,3,5-triacryloyl-hexahydro-s-triazine, bis (vinylsulfonyl) methyl ether, N, N′-methylenebis- [β- (vinylsulfonyl) propionamide], an active halogen Compounds (2,4-dichloro-6-hydroxy-s-triazine etc.), mucohalogen acids (mucochloric acid, mucophenoxycycloric acid etc.) isoxazoles, dialdehyde starch, 2-chloro-6-hydroxytriazinylated Keratin, etc. can be used alone or in combination. Among them, JP 53-41
221, the same 53-57257, the same 59-162546,
Active vinyl compounds described in JP-A-60-80846 and active halides described in US Pat. No. 3,325,287 are preferable. As the hardener of the present invention, a polymer hardener can be effectively used. Examples of the polymer 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. Polymers having an epoxy group described in US Pat. No. 3,362,827, polymers having a dichlorotriazine group described in US Pat. No. 3,362,827 and Research Disclosure 17333 (1978), and JP-A-56-66841. Having an active ester group, which is disclosed in JP-A-56-142524,
U.S. Pat. No. 4,161,407, JP-A-54-650
33, Research Disclosure Magazine 16725 (1
978) and the like, and polymers having an active vinyl group or a group that is a precursor thereof.
A polymer having an active vinyl group or a group serving as a precursor thereof is preferable. Among them, as described in JP-A-56-142524, an active vinyl group with a long spacer or a group serving as a precursor thereof is a polymer main chain. Polymers such as those attached to are particularly preferred.

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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. An undercoat layer may be provided, and a gelatin layer may be provided as an upper 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.

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Make up to 1 liter with water (pH 10.60)
Adjusted). <Fixing solution concentrate> Ammonium thiosulfate 560 g Sodium sulfite 60 g Ethylenediaminetetraacetic acid / disodium dihydrate 0.10 g Sodium hydroxide 24 g Water is adjusted to 1 liter (pH is adjusted to 5.10 with acetic acid). When the development processing was started, each tank of the automatic processor was filled with the following processing solutions. Developing tank: 333 ml of the above concentrated developer, water 667 m
1 and 10 ml of a starter containing 2 g of potassium bromide and 1.8 g of acetic acid were added to adjust the pH to 10.25. Fixing tank: 200 ml of the above fixing solution concentrate and 800 water
ml Processing speed ... Dry to Dry 35 seconds Development temperature ... 35 ° C. Fixing temperature ... 32 ° C. Drying temperature ... 55 ° C. Replenishment amount ... Developer 22 ml / 10 × 12 inches Fixer 30 ml / 10 × 12 inches

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(Evaluation of roller mark) Photographic materials 1 to 1
5 was cut into 30.5 cm x 25.4 cm, and the color temperature was 54
Exposure was performed from one side with a light source of 00 ° K. At this time, the exposure time was adjusted so that the density in the roller-mark evaluation process was uniformly 1.0 including the pace density. 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 mark is generated ○… Slightly roller mark is generated, but it is not a concern △… Roller mark is generated, but it is practically acceptable ×. ． ． Table 1 summarizes the results that the number of roller marks frequently occurred and the density unevenness was large and the result was unacceptable.

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Example 2 (Preparation of Emulsions T-1 to 3) In the process of preparing tabular grains of Emulsion A-1, 2N potassium thiocyanate solution was added, and then AgI fine particles having a diameter of 0.07 μm were added to total silver. 0.2 mol% was added to the amount. After physically aging for 5 minutes at the same temperature, the temperature was lowered to 35 ° C. Thus, the total silver iodide content was 0.46 mol% and the average projected area was 1.10μ.
m, the thickness was 0.165 μm, and the monodisperse tabular grains having a variation coefficient of the diameter of 18.5% were obtained. After this, the soluble salts were removed by the sedimentation method. The temperature was raised to 40 ° C. again, and 30 g of gelatin, 2.35 g of phenoxyethanol and 0.8 g of sodium polystyrene sulfonate as a thickener were added, pH was 5.90 with caustic soda and silver nitrate solution, pAg was 8.25.
Adjusted to. This emulsion was chemically sensitized while being kept at 56 ° C. with stirring. First, thiourea dioxide 0.043
mg was added, and the mixture was kept for 22 minutes to carry out reduction sensitization. Next, 4-hydroxy-6-methyl-1,3,3
20 mg of a, 7-tetrazaindene and 300 mg, 400 mg, and 500 mg of sensitizing dye I-2 were added, respectively. Subsequently, 3.3 mg of sodium thiosulfate, 2.6 mg of chloroauric acid and 90 mg of potassium thiocyanate were added, and 40 minutes later, the mixture was cooled to 40 ° C. Emulsion T-1
Preparation of 3 was completed.

Claims (3)

[Claims] 1. Prior to chemical sensitization, a sensitizing dye adsorbed on the surface of silver halide grains in an amount of 0.8 mol% or more based on silver halide is treated with an adsorbent to desorb the adsorbed sensitizing dye and halogenate it. A silver halide photographic light-sensitive material comprising a silver halide photographic emulsion in which the total amount of sensitizing dyes with respect to silver is 0.75 mol% or less. 2. The chemical sensitizing dye adsorbed by 0.8 mol% or more is partially or completely desorbed by an adsorbent, and the total amount of the sensitizing dye is 0.10 mol or more and 0.75 mol% or less with respect to silver halide. 2. The silver halide photographic light-sensitive material according to claim 1, wherein the silver halide photographic light-sensitive material is adsorbed on the surface of the silver halide grain. 3. The average iodine content of individual halogen compositions of silver halide grains is less than 0.6 mol%, and the total amount of gelatin coated on one side of a support is 1.7 g / m ² or more and 2.5 g or less.
/ M ² or less, the silver halide photographic light-sensitive material according to claim 1 or 2.