JPH0876305A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE: To provide a photosensitive material enhanced in visual sharpness by exhibiting high-contrast photographic response even in the case of rapid processing. CONSTITUTION: This photosensitive material has >=2 silver halide emulsion layers on at least one side of a support, and optical 2 of the emulsion layers satisfy the relations of (1) and (2): (1) each layer comprises at least one following emulsion containing flat silver halide grains having a silver chloride content of >=10mol% and an aspect ratio of >=2 and occupying >=50% of the projection areas of the total silver halide, and (2) one of the 2 emulsion layers near to the support contains the emulsion higher in sensitivity than the emulsion contained in the layer farther from the support.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a silver halide photographic light-sensitive material excellent in sharpness. Further, the present invention relates to a photographic light-sensitive material which is excellent in development progress and fixing property in rapid processing.

[0002]

BACKGROUND OF THE INVENTION There are numerous prior art techniques relating to tabular grains having a high silver chloride content. Examples of tabular grains having a {111} plane as a main plane include, for example, Japanese Examined Patent Publication No.
No. 8326, No. 64-8325, No. 64-8324
No. 2, JP-A 1-250943, Japanese Patent Publication No. 3-14328
No. 4, JP-B 4-81782, JP-B 5-40298
No. 5,39,459, No. 5-12696, and JP-A Nos. 63-213836, 63-218938 and 6
3-281149 and JP-A-62-218959 are mentioned. Prior art of tabular grains having a {100} plane as the principal plane includes JP-A-5-204073, JP-A-51-88017 and JP-A-63-24238. In particular, JP-A-6-059360 describes a silver chloride-containing {100} flat plate, but these documents do not disclose any means for improving sharpness. These prior arts include rapid processability of silver chloride plates,
Although there is a description of excellent fixability, etc., when exposed to UV light at the same time, the absorption coefficient increases, so the light absorption by the particles in the upper layer increases and the amount of light absorbed by the particles in the lower layer decreases. In addition, the characteristics of the light-sensitive material become relatively soft. When the light-sensitive material becomes softer, the formed image has a lower contrast and the visual sharpness is lowered.
This problem is more prominent in a system of silver bromide whose light absorption has a long wave. For example, in International Publication (WO) 93/01521, silver bromide is flattened against ultraviolet (UV) light,
A method for increasing light transmittance by using silver chloride is described. However, these methods are not sufficient because a sufficiently high gradation cannot be obtained.

Therefore, it has not been possible to realize a light-sensitive material having a high gradation characteristic curve with high visual sharpness in combination with a fluorescent intensifying screen that emits UV light. On the other hand, as a result of diligent studies, the present inventors have found that the silver chloride content is increased, and the tabular grains are formed to increase the transmittance of silver halide, whereby UV light is sufficiently distributed to the lower layer. It has been found that not only the tone becomes higher, but also a higher-sensitivity light-sensitive material can be constituted by forming a multi-layer structure and further making the highest-sensitivity emulsion a lower layer. Moreover, surprisingly, in the ultra-rapid processing in which the total processing time of Dry to Dry is less than 60 seconds, the diffusion of the developing solution is usually slow and the original performance of the high-sensitivity emulsion is maintained even if the high sensitivity is the lower layer. Although it was not possible to draw it out, the image was not sensitized, and a sufficiently high-contrast image could not be formed.However, when tabular grains having a high silver chloride content as in the present invention were used, this problem was solved and a high-sensitivity emulsion was obtained even in the lower layer. It was found that the original photographic performance was exhibited, and as a result, a high contrast image can be formed. Furthermore, it has been found that such a phenomenon is particularly effective for X-ray image formation using a UV-emitting phosphor.

[0004]

SUMMARY OF THE INVENTION It is an object of the present invention to produce a light-sensitive material having high visual sharpness by exhibiting a hard photographic response even in rapid processing.

[0005]

As a result of earnest studies, the present inventors have solved the problem by the following method. (I) In a silver halide photographic light-sensitive material having two or more silver halide emulsion layers on at least one side of a support, any two of the two or more silver halide emulsion layers can be used. A silver halide photographic light-sensitive material characterized in that the emulsion layer satisfies the following relationships 1) and 2). 1) Each layer contains at least one of the following emulsions. 50% or more of the projected area of all silver halide grains contained in the emulsion are tabular silver halide grains having a silver chloride content of 10 mol% or more and an aspect ratio of 2 or more. 2) Of the two emulsion layers, the emulsion of 1) contained in the emulsion layer closer to the support is higher in sensitivity than the emulsion of 1) contained in the emulsion layer farther from the support. Is. (II) The silver halide photographic light-sensitive material described in (I) above, which is used in combination with an X-ray absorption fluorescent intensifying screen having an emission peak at 400 nm or less.

The present invention will be described in detail below. The photographic light-sensitive material of the present invention has two or more emulsion layers on the support, and each layer may contain one or more emulsions.
1 type or more and 5 types or less, more preferably 1 type or more and 3 types or less are preferable. Each emulsion layer preferably has a silver amount of 10% to 90%, and more preferably 20% to 80% of the silver coating amount of all emulsion layers contained on the same surface. . It is preferable that the sensitivity of the layer farther from the support than any two of the layers included in the same plane is lower than the sensitivity of the layer closer to the support. The sensitivity difference between the two layers is 20
% Or more, more preferably 30% or more, still more preferably 60% or more and less than 500%. The evaluation of the sensitivity is obtained from the reciprocal of the light amount which gives a point giving an optical density of fog + 0.1 on the basis of the sensitometric characteristics of each layer.

The photographic light-sensitive material of the present invention preferably contains the highest sensitivity emulsion in a layer other than the layer farthest from the support. The total silver content of the highest-sensitivity emulsion contained in the light-sensitive material of the present invention is 20% to 80% of the total silver content in the light-sensitive material. Also, preferably 30
% To 70%. When the highest sensitivity emulsion is used in both the layer farthest from the support and the other layers, if the ratio of the highest sensitivity emulsion contained in the farthest layer to the total highest sensitivity emulsion is less than 50%, It may be an aspect of the invention.

The light-sensitive material of the present invention is provided on one side of the support with 2
In the case of having multiple emulsion layers, it is preferable to use the highest sensitivity emulsion in the emulsion layer closer to the support and to make the sensitivity of the layer higher than that of the emulsion layer farther from the support than the layer. . Further, when the first emulsion layer, the second emulsion layer and the third emulsion layer are provided on the support in the order close to the support, the first emulsion layer has higher sensitivity than the second and / or third emulsion layers. The second emulsion layer may have higher sensitivity than the third emulsion layer.
Of course, such a layer structure may be provided on both sides of the support.

The tabular grains containing silver chloride of the present invention will be described. In a silver halide emulsion containing at least a dispersion medium and silver halide grains, Cl ^- content is 50% or more, preferably 60% to 100%, more preferably 70 to 100% of the total projected area of the silver halide grains. 10 mol% or more, preferably 20 mol% to 100%, more preferably 30 to 100 mol%, further preferably 40 to 100 mol%, and a flat plane having a {100} plane and / or a {111} plane It is a particle. Here, the tabular grains are grains having an aspect ratio (diameter / thickness) of 2 or more. The principal plane refers to the maximum outer surface of tabular grains. The tabular grains have a thickness of 0.35 μm or less, more preferably 0.05 to 0.3 μm, still more preferably 0.05 to 0.25 μm. The average aspect ratio is 2 or more, preferably 2 to 25, more preferably 5 to 20. Here, the diameter refers to the diameter of a circle having an area equal to the projected area of the tabular grains, and the thickness refers to the distance between two principal planes. The average aspect ratio is the average aspect ratio of all tabular grains.

Among the emulsions of the present invention, the nucleation of the emulsion having the {111} plane as the main plane is described in JP-B-64-8326.
No. 64-8325, No. 64-8324, JP-A No. 1-250943, Japanese Patent Publication No. 3-14328, Japanese Patent Publication No. 4-81782, Japanese Patent Publication No. 5-40298, 5-3.
No. 9459, No. 5-12696 and JP-A-63-213.
No. 836, No. 63-218938, No. 63-2811
No. 49, JP-A-62-218959 and the like, and as the prior art of tabular grains having a {100} plane as a main plane, JP-A-5-204073 and 51- 88017, JP-A-63-24238,
It is described in Japanese Patent Application No. 5-264059.

In the present invention, any of the nucleation methods described in these prior arts can be used.
The method of crystal growth of the present invention by physical ripening in the presence of fine silver halide grains (fine grains are dissolved and substrate grains grow) is described below. In the fine grain emulsion addition method, it is 0.
AgX fine grain emulsion having a diameter of 15 μm or less, preferably 0.1 μm or less, more preferably 0.06 to 0.006 μm is added, and the tabular grains are grown by Ostwald ripening. The fine grain emulsion can be added continuously or continuously. Fine grain emulsion is AgNO in mixer provided in the vicinity of the reaction vessel ₃ solution and X ^-
The salt solution may be supplied and continuously prepared, and then immediately added continuously to the reaction vessel, or may be previously prepared in a batch manner in another vessel and then continuously or continuously added. The fine grain emulsion can be added in a liquid form or as a dry powder. It is also possible to mix the dry powder with water immediately before addition to liquefy it and add it. The added fine particles are preferably added in such a manner that they disappear within 20 minutes, more preferably 10 seconds to 10 minutes. If the disappearance time becomes long, ripening occurs between the fine particles and the particle size becomes large, which is not preferable. Therefore, it is preferable not to add the entire amount at once. It is preferable that the fine particles are substantially free of twinned grains. Here, the multi-twin grain means a grain having two or more twin planes per grain. The term "substantially free" means that the number ratio of multiple twinned grains is 5% or less, preferably 1% or less, more preferably 0.1% or less. Further, it is preferable that substantially no single twin crystal grains are contained. Furthermore, it is preferable that the screw dislocation is not substantially contained. Here, the term "substantially free" is in accordance with the above-mentioned rules.

The halogen composition of the fine particles is AgCl, Ag
Br and AgBrI (I ^- content is preferably 10 mol% or less, more preferably 5 mol% or less) and a mixed crystal of two or more thereof. For other details, see Japanese Patent Application No. 4-2141.
The description of No. 09 can be referred to. The total amount of fine grains added should be 20% or more of the total amount of silver halide.
Preferably 40% or more, more preferably 50% or more 9
It is 8% or less. The Cl content of the fine particles is preferably 10% or more, more preferably 50% or more and 100% or less.

As the dispersion medium for nucleation, ripening and growth, a conventionally known dispersion medium for an AgX emulsion can be used, but the methionine content is preferably 0 to 50 μmol / g, more preferably 0. -30 μmol / g gelatin can be preferably used. When the gelatin is used during ripening and growth, thinner tabular grains having a uniform diameter size distribution are formed, which is preferable. In addition, Japanese Patent Publication Sho 52
-16365, Journal of the Photographic Society of Japan, Volume 29 (1), 17,
22 (1966), Volume 30 (1), 10, 19 (19
67), Vol. 30 (2), 17 (1967), 33.
The synthetic polymer described in Volume (3), 24 (1967) can be preferably used as a dispersion medium. The pH during growth due to addition of fine particles needs to be 2.0 or higher, but 6 or higher, 1
It is preferably 0 or less. The pH is more preferably 6 or more and 9 or less. Also, pCl needs to be 1.0 or more, but 1.
6 or more is preferable. More preferably 2.0 or more and 3.0
The following are preferred. These growth conditions are especially {100}
It is particularly preferable for tabular grains having a plane as the main plane. Here pCl and the activity of Cl ions in the solution ^- to pCl = -log [Cl] ^- defined by [Cl]. THJames THE THEORY OF THE RHOTO
It is described in detail in Chapter 1 of the GRAPHIC PROCESS, 4th Edition.

When the pH is 2.0 or less, for example, in the case of tabular grains having a {100} plane as a main plane, lateral growth is suppressed, the aspect ratio is lowered, and the emulsion covering power is reduced. Tends to be low, and the sensitivity becomes low. When the pH is 2.0 or more, the growth rate in the lateral direction becomes high, an emulsion having a high aspect ratio and a high covering power can be obtained, but fog is high and desensitization is likely to occur. p
When Cl is 1.0 or less, growth in the vertical direction is promoted, the aspect ratio is lowered, the covering power of the emulsion is low, and the sensitivity is lowered. When pCl is 1.6 or more, the aspect ratio is increased and the covering power is increased, but fog is high and the sensitivity is easily lowered. At this time, when the substrate particles are grown with silver halide fine particles, the fog is low even if the pH is 6 or more and / or the pCl is 1.6 or more, and the feeling is high and the aspect ratio is high and the covering power is high.

The monodispersity of the emulsion of the present invention is preferably 30% or less, and preferably 5% or more, when considering the monodispersity based on the coefficient of variation defined by the method described in JP-A-59-745481. It is preferably 25% or less. Particularly when used for a sensitive material having a high contrast, it is preferably 5% or more and 15% or less.

In the present invention, the above-described silver chloride tabular silver halide emulsion is contained in at least two emulsion layers. 50 to 1 of the emulsion layer containing the silver chloride tabular emulsion
It is preferable to occupy 00%, particularly 90 to 100%. The present invention is characterized in that a high-sensitivity emulsion is contained in an emulsion layer close to the support, but the sensitivity of the emulsion layer as a whole is higher in the emulsion layer closer to the support than in the emulsion layer farther from the support. It is preferably sensitivity.

Selenium, which is the preferred sensitization method for the present invention,
Tellurium sensitization is described. These may be used alone or in combination. Particularly preferable examples of these and compounds are disclosed in, for example, JP-A-3-116132,
No. 5-113635, No. 5-165136, No. 5-
165137, 5-134345 and the like. Particularly preferred selenium sensitizers include, for example, compounds represented by formula (I) or (II) of JP-A-5-165137 and compound examples I-1 to I-20, II- described therein. 1-II-19
Can be mentioned. Regarding the tellurium sensitizer, it is disclosed in Japanese Patent Laid-Open No. Hei 5
-134345 Compounds represented by general formulas (IV) and (V) and compound examples IV-1 to IV-2 described therein
2 and V-1 to V-16 can be mentioned.

For the formation of tabular grains containing silver chloride of the present invention, JP-A-4-139439 and JP-A-4-13 have been used.
9440, Japanese Patent Laid-Open No. 4-139441 and US Pat. No. 5,104,786, and the like, by using an apparatus such as a multi-coaxial nozzle, by adding the halogen aqueous solution and the silver nitrate aqueous solution to the reaction vessel immediately before mixing. Nucleation and growth can be preferably performed.

In the most preferred embodiment of the present invention, at least one side of the support has two silver chloride emulsion layers according to the present invention, and of the two layers, the emulsion layer closer to the support is the support. This is a mode in which the sensitivity is 20 to 500% higher than that of the emulsion layers farther from the body, and in particular, the two emulsion layers are present on both sides of the support.

PEN can be preferably used as the support. However, it is not limited to this.
PEN is preferably polyethylene-2,6-naphthalate. The polyethylene-2,6-naphthalate referred to in the present invention means that its repeating structural unit is substantially ethylene-
As long as it is composed of 2,6-naphthalene dicarboxylate units, polyethylene that is not copolymerized
Not only 2,6-naphthalenedicarboxylate, but also copolymers in which 10% or less, preferably 5% or less of the number of repeating structural units are modified with other components, and a mixture or composition with other polymers Is included. Polyethylene
2,6-naphthalate is synthesized by combining naphthalene-2,6-dicarboxylic acid, or a functional derivative thereof, and ethylene glycol or a functional derivative thereof in the presence of a catalyst under appropriate reaction conditions. However, the polyethylene-2,6-naphthalate referred to in the present invention includes one or more suitable third component (modifying agent) before the completion of the polymerization of the polyethylene-2,6-naphthalate.
Added

It may be a copolymerized or mixed polyester. Suitable third component is a compound having a divalent ester-forming functional group such as oxalic acid, adipic acid, phthalic acid, isophthalic acid, terephthalic acid, naphthalene-2,7-dicarboxylic acid, succinic acid, diphenyl ether dicarboxylic acid. Such as dicarboxylic acids, or lower alkyl esters thereof, oxycarboxylic acids such as p-oxybenzoic acid, p-oxyethoxybenzoic acid, or lower alkyl esters thereof, or dihydric alcohols such as propylene glycol and trimethylene glycol. Compounds. Polyethylene-2,6-naphthalate or a modified polymer thereof is obtained by blocking the terminal hydroxyl group and / or carboxyl group with a monofunctional compound such as benzoic acid, benzoylbenzoic acid, benzyloxybenzoic acid or methoxypolyalkylene glycol. Or a compound modified with a trifunctional or tetrafunctional ester-forming compound such as glycerin or pentaerythritol in an extremely small amount within a range where a substantially linear copolymer is obtained.

The light-sensitive material of the present invention is particularly effective when it has at least one silver halide emulsion layer on each side of the support. When the present invention is applied to a light-sensitive material having an emulsion on both sides of such a support, in addition to the effects described above, it is characterized in that an image having high image quality and high sharpness can be obtained. It also has the unexpected effect of not contaminating the tank or rollers. As the chemical sensitization method, a gold sensitization method using a so-called gold compound, a sensitization method using a metal such as iridium, platinum, rhodium or palladium, a sulfur sensitization method using a sulfur-containing compound, or a reduction sensitization method using a tin salt, polyamine or the like is used. Method, a sensitization method with a selenium compound, a sensitization method with a tellurium compound, or a combination of two or more thereof. The tabular silver halide grains can be produced by appropriately combining methods known in the art. The silver amount of the light-sensitive material of the present invention is preferably 0.5 g / m ^{2 to} 5 g / m ² (on one side), more preferably 1 g / m ^{2 to} 3.4 g / m ² (on one side).
For proper rapid processing, it is preferable not to exceed 5 g / m ² .

There are no particular restrictions on the various additives used in the light-sensitive material of the present invention, for example, JP-A-2-6853.
It is possible to use those described in the following relevant portions of Japanese Patent Publication No. Item This section 1. Silver halide emulsions and JP-A-2-68539, page 8, lower right column, line 6 from the bottom or from its manufacturing process, page 10 upper right column, line 12 2. Chemical sensitization method, page 10, upper right column, line 13 to lower left column, line 16 3. Antifoggant / stability Page 10, left lower column, line 17 to page 11, upper left column, line 7 and agent, page 3, lower left column, line 2 to page 4, lower left column 4. Spectral sensitizing dyes, page 4, lower right column, line 4 to page 8, lower right column, 5. Surfactants / antistatics Page 11, upper left column, line 14 to page 12, upper left column, line 9 Antistatic agent 6. Matting agent, slip agent, page 12, upper left column, line 10 to upper right column, line 10 14th plasticizer, page lower left column, line 10 to right lower column, line 1 7. Hydrophilic colloid, page 12, upper right column, line 11 to left lower column, line 16 8. Hardener, page 12, lower left column, line 17 to page 13, upper right column, line 6 9. Support, page 13, upper right column, lines 7 to 20 10. Dyes / mordanting agents, page 13, lower left column, line 1 to page 14, lower left column, line 9

As a method of forming an image using the light-sensitive material of the present invention, a method of forming an image in combination with a phosphor having a main peak at 400 nm or less is preferable. More preferably, a method of forming an image by combining with a phosphor having a main peak at 380 nm or less is preferable. A screen having a main emission peak at 400 nm or less is disclosed in JP-A-6-11804, WO9.
The screen described in 3/01521 is used, but the screen is not limited to this.

The replenishment amount of the processing liquid is preferably 10 cc / 4 cuts or less, more preferably 5 cc / 4 cuts or less, and the effect is greatly exhibited. Ascorbic acid or its derivative used in the developing solution of the present invention is described in JP-A-5-165.
No. 161, the compound represented by formula (I) and the compound examples I-1 to I-8 and II-9 to II- described therein.
12 is particularly preferred. Ascorbic acids used in the developer used in the present invention are endiol type (Endiol),
Enaminol type (Endamino type)
in), thiol-enol type (Thiol-Enol) and enamine-thiol type (Enamin-Thiol) are generally known as compounds. Examples of these compounds are given in US Pat.
88,549, JP-A-62-237443 and the like. Methods for synthesizing these ascorbic acids are also well known, and are described in, for example, Tsujio Nomura and Hirohisa Omura, "The Chemistry of Reductones" (Uchida Lao Tsukuba Shinsha 1969). The ascorbic acid used in the present invention can also be used in the form of an alkali metal salt such as lithium salt, sodium salt and potassium salt. These ascorbic acids are used in an amount of 1 to 100 g, preferably 5 to 80 g, per liter of the developing solution.

In the present invention, it is particularly preferable to use 1-phenyl-3-pyrazolidones or p-aminophenols together with ascorbic acids. 3 used in the present invention
-Pyrazolidone-based developing agents include 1-phenyl-3
-Pyrazolidone, 1-phenyl-4,4-dimethyl-3
-Pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, 1-phenyl-4,
4-dihydroxymethyl-3-pyrazolidone, 1-phenyl-5-methyl-3-pyrazolidone, 1-p-aminophenyl-4,4-dimethyl-3-pyrazolidone, 1-
p-tolyl-4,4-dimethyl-3-pyrazolidone, 1
-P-tolyl-4-methyl-4-hydroxymethyl-3
-Such as pyrazolidone. Developing agent is usually 0.001
It is preferably used in an amount of mol / liter to 1.2 mol / liter. Examples of the p-aminophenol-based developing agent used in the present invention include N-methyl-p-aminophenol, p-aminophenol, N- (β-hydroxyethyl) -p-aminophenol and N- (4-hydroxyphenyl). Glycine, 2-methyl-p-aminophenol, p-benzylaminophenol and the like are available, but N-methyl-p-aminophenol is preferred.

Alkaline agents used to set the pH include sodium hydroxide, potassium hydroxide, sodium carbonate,
Includes pH adjusting agents such as potassium carbonate, sodium triphosphate, potassium triphosphate. Examples of the sulfite preservative used in the developer of the present invention include sodium sulfite, potassium sulfite, lithium sulfite, ammonium sulfite, sodium bisulfite and potassium metabisulfite. The sulfite content is preferably 0.01 mol / liter or more, particularly preferably 0.02 mol / liter or more. Further, the upper limit is preferably up to 2.5 mol / liter. In addition, 22 of "Photographic Processing Chemistry" by LFA Mason, published by Focal Press (1966).
Those described in pages 6 to 229, U.S. Pat. Nos. 2,193,015, 2,592,364, and JP-A-48-64933 may be used.

In general, a boric acid compound (for example, boric acid, borax) is often used as a pH buffering agent in the developing solution, but the boric acid compound is used in the developing solution containing ascorbic acid of the present invention. It is preferable not to contain substantially.
When the ascorbic acid-containing developer contains a boric acid compound, the effect of the present invention cannot be obtained even in combination with the packaging material of the present invention having a low oxygen transmission rate. The relationship between the presence or absence of the boric acid compound and the effect in the system of the present invention was completely unexpected.

A method for preparing the treating agent used in the present invention is described in JP-A-61-177132 and JP-A-3-134666.
The method described in JP-A-3-67258 can be used. As the method of replenishing the developing solution as the processing method of the present invention, the method described in Japanese Patent Application No. 54131/1992 can be used. When performing dry to dry development processing for 100 seconds or less, a roller made of a rubber material as described in JP-A-63-151943 is used to prevent development unevenness peculiar to rapid processing. It is applied to a roller, and as described in JP-A-63-151944, the discharge flow rate for stirring the developing solution in the developing solution tank is set to 10 m / min or more. As described in JP-A-63-264758, it is more preferable to stir more strongly than during standby at least during the development processing.

The light-sensitive material of the present invention is not particularly limited as a photographic light-sensitive material. In particular, photographic materials for laser light sources, printing sensitizers, and direct medical X-ray sensitizers, indirect medical X-ray sensitizers, CRT image recording sensitizers, microfilm, general photographing color negative, color reversal sensation. Although it can be used as a material, a color photographic paper sensitive material, etc., it is particularly preferably used as a medical direct photographing X-ray sensitive material.
The present invention will be specifically described below with reference to examples.

[0031]

【Example】

 Example 1 Preparation of {111} Tabular Emulsion A (Low Sensitive Emulsion) Silver chloride tabular grains were prepared as follows. Solution (1) Inert gelatin 30 g Crystal habit control agent A 0.8 g

[0032]

Embedded image

NaCl 4g H ₂ O 1750cc solution (2) AgNO ₃ 7.6g H ₂ O added 30cc solution (3) NaCl 2.8g H ₂ O added 30cc solution (4) AgNO ₃ 24.5g H ₂ O was added and 96 cc solution (5) NaCl 0.3 g H ₂ O was added and 65 cc solution (6) AgNO ₃ 101.9 g H ₂ O was added and 400 cc solution (7) NaCl 37.6 g H ₂ O was added. 400cc

The solution (2) and the solution (3) were simultaneously added to the solution (1) kept at 35 ° C. with stirring over 1 minute, and the temperature of the solution was raised to 50 ° C. over 15 minutes. At this point, grains corresponding to about 5.7% of total silver were formed. Then add solution (4) and solution (5) simultaneously over 24 minutes,
Further, the solution (6) and the solution (7) were simultaneously added over 40 minutes to obtain a silver chloride tabular emulsion. After the emulsion was washed with water and desalted by a precipitation method, 30 g of gelatin and H ₂ O were added, 2.0 g of phenoxyethanol and 0.8 g of sodium polystyrene sulfonate as a thickener were added, and the pH was adjusted to 6.0 with caustic soda. Redistributed into In the emulsion thus obtained, the ratio a ₁ = 90% of the total projected area of grains having an aspect ratio of 2 or more. Average circle equivalent diameter a ₃ = 1.
55 μm, average thickness a ₄ = 0.18 μm, average aspect ratio a ₂ = 8.6, variation coefficient a ₅ =
It is a silver chloride tabular emulsion having 19% of {111} plane as the main plane.

Preparation of {111} Tabular Emulsion B (High Sensitive Emulsion) Exactly the same as Emulsion A, except that 30 g of the inactive gelatin in Solution (1) was changed to 20 g, and crystal habit controlling agent A was added from 0.8 g to 1.0 g. Emulsion B was prepared in exactly the same manner except that The characteristic values of this emulsion were a ₁ = 95% a ₂ = 9.3 a ₃ = 1.92 μm a ₄ = 0.206 μm a ₅ = 17%.

Preparation of {100} Tabular Emulsion C (Low Sensitive Emulsion) 1582 ml of gelatin aqueous solution (gelatin-1) in a reaction vessel.
(Deionized alkali-treated bone gelatin having a methionine content of about 40 μmol / g) 19.5 g, HNO ₃ 1N liquid 7.
Containing 8 ml, pH 4.3, NaCl-1 solution (100 ml)
13 ml of NaCl (containing 10 g) was added and the temperature was adjusted to 4
While keeping the temperature at 0 ° C, Ag-1 solution (100 mL of AgNO
₃ including 20 g) and X-1 solution (NaCl in 100ml
(Including 7.05 g) was simultaneously mixed and added at 62.4 ml / min in 15.6 ml portions. After stirring for 3 minutes, Ag-2 solution (1
AgNO ₃ containing 2g) and X-2 solution in 100 ml (100
1.4g of KBr in ml) 80.6ml / min 2
Simultaneous mixing of 8.2 ml each. After stirring for 3 minutes, Ag-
Solution 1 and solution X-1 were simultaneously mixed and added at a rate of 62.4 ml / minute and 46.8 ml each. After stirring for 2 minutes, gelatin aqueous solution 20
3 ml (gelatin-113 g, NaCl 1.3 g, Table 1
NaOH 1N solution) to obtain the pH of
After setting Cl to 1.8, the temperature is raised to 75 ° C. and pCl
And then aged for 42 minutes. An AgCl fine grain emulsion (average grain diameter 0.1 μm) was added for 20 minutes at an addition rate of 2.68 × 10 ⁻² mol / min AgCl. After addition 1
After aging for 0 minutes, a precipitating agent was added, the temperature was lowered to 35 ° C., and the precipitate was washed with water. Add gelatin aqueous solution and p at 60 ℃
Adjusted to H6.0. A transmission electron micrograph image (hereinafter referred to as TEM) of the particle replica was observed. The resulting emulsion was high silver chloride {100} tabular grains containing 0.44 mol% of AgBr based on silver. The shape characteristic values of the particles were as follows. (Total projected area of {100} tabular grains having an aspect ratio of 2 or more / sum of projected areas of all AgX grains) × 100 = a ₁ = 9
0% (average aspect ratio (average diameter / average thickness) of {100} tabular grains having an aspect ratio of 2 or more) = a ₂ = 9.3 (average diameter of {100} tabular grains having an aspect ratio of 2 or more) = A ₃ = 1.67 μm, (average thickness) = a ₄ = 0.
18 μm Average diameter variation coefficient = a ₅ = 19%

Preparation of {100} Tabular Emulsion D (High Sensitive Emulsion) Exactly the same as in the preparation of Emulsion C, except that the nucleation temperature was changed from 40 ° C. to 50 ° C. and the KBr amount of the X-2 solution was 1. Emulsion B was prepared in exactly the same manner except that the amount was changed from 0.4 g to 1.0 g. The shape characteristic values of the particles are as follows. a ₁ = 93% a ₂ = 8.0 a ₃ = 1.93 μm a ₄ = 0.24 μm a ₅ = 22%

Preparation of Silver Halide Emulsion E (Low Sensitive Emulsion) 32 g of gelatin was dissolved in 1 liter of water, and 0.3 g of potassium bromide and 5 g of sodium chloride were placed in a container heated at 53 ° C.
g and compound [I]

[0039]

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After adding 46 mg, 444 ml of an aqueous solution containing 80 g of silver nitrate and 452 ml of an aqueous solution containing 27.6 g of potassium bromide were added over about 20 minutes by the double jet method, and then 400 ml of an aqueous solution containing 80 g of silver nitrate and odor were added. 28.5 g of potassium iodide and hexachloroiridium (II
I) Aqueous solution 4 containing potassium acidate (10 ^-7 mol / mol silver)
15 ml and the double jet method were added over about 25 minutes to give an average particle size (projected area diameter) of 0.45 μm.
Cubic monodisperse silver chloride particles (Coefficient of variation of projected area diameter 1
0%) was prepared. This emulsion was desalted by a coagulation method, and then 62 g of gelatin and 1.75 g of phenoxyethanol.
Was added to adjust the pH to 6.5 and pAg 8.5.

Preparation of Silver Halide Emulsion F (High Sensitive Emulsion) Cubic monodisperse silver chloride grains having an average grain size of 0.65 μm (varied) were prepared in exactly the same manner as Emulsion E, but the temperature was raised from 53 ° C. to 60 ° C. A coefficient of 9%) was produced.

Chemical Sensitization Particles A and F prepared as described above were subjected to chemical sensitization while being kept at 60 ° C. with stirring. First, thiosulfonic acid compound-I was added in an amount of 10 ^-4 mol per mol of silver halide, and then AgBr fine particles having a diameter of 0.10 μm was added in an amount of 1.0 mol% based on the total amount of silver, and thiourea dioxide was added. 1 × 10 ⁻⁶ mol / mol Ag was added, and the mixture was kept for 22 minutes for reduction sensitization. Next, 4-hydroxy-6-
Methyl-1,3,3a, 7-tetraazaindene 3 ×
10 ⁻⁴ mol / mol Ag and sensitizing dyes-1 and 2 were added respectively. Further calcium chloride was added. Successively, sodium thiosulfate, selenium compound-I and potassium thiocyanate were added in optimum amounts, and each emulsion was ripened for an optimum time and then cooled to 35 ° C. Emulsions A to F chemically sensitized in this manner were prepared.

[0043]

[Chemical 3]

(Preparation of emulsion coating layer) An emulsion coating solution was prepared by adding the following chemicals to 1 mole of silver halide to the chemically sensitized emulsion.・ Gelatin (including gelatin in emulsion) 111 g ・ Dextran (average molecular weight 39,000) 21.5 g ・ Sodium polyacrylate (average molecular weight 400,000) 5.1 g ・ Sodium polystyrene sulfonate (average molecular weight 600,000) 1.2 g-Hardener 1,2-bis (vinylsulfonylacetamido) ethane Addition amount was adjusted so that the swelling ratio would be 230% -Compound I 42.1 mg-Compound II 10.3 g-Compound III 0. 11 g-Compound IV 8.5 mg-Compound V 0.43 g-Compound VI 0.004 g-Compound VII 0.1 g-Compound VIII 0.1 g pH adjusted to 6.1 with NaOH

[0045]

[Chemical 4]

[0046]

[Chemical 5]

Dye Emulsion A was added to the above coating solution so that the amount of Dye-I was 10 mg / m ² per side.

[0048]

[Chemical 6]

(Preparation of Dye Emulsion A)
0g and 62.8 g of the following high boiling point organic solvent-I, -II
Of 62.8 g and 333 g of ethyl acetate were dissolved at 60 ° C. Next, 65 cc of a 5% aqueous solution of sodium dodecyl sulfonate, 94 g of gelatin and 581 cc of water were added, and the mixture was emulsified and dispersed by a dissolver at 60 ° C. for 30 minutes. Next, 2 g of the following compound-VI and 6 liters of water were added, and the temperature was lowered to 40 ° C. Next, Asahi Kasei Ultrafiltration Laboratory Module AC
Using P1050, the mixture was concentrated to a total amount of 2 kg, and 1 g of the compound-VI was added to obtain a dye emulsion A.

[0050]

[Chemical 7]

(Preparation of Coating Solution for Surface Protective Layer) A coating solution for surface protective layer was prepared so that each component had the following coating amount.・ Gelatin 0.780 g / m ²・ Sodium polyacrylate (average molecular weight 400,000) 0.035 ・ Sodium polystyrene sulfonate (average molecular weight 600,000) 0.0012 ・ Polymethyl methacrylate (average particle size 3.7 μm) 072-Coating aid-I 0.020-Coating aid-II 0.037-Coating aid-III 0.0080-Coating aid-IV 0.0032-Coating aid-V 0.0025-Compound-VII 0.0022 ・ Proxel 0.0010 (pH adjusted to 6.8 with NaOH)

[0052]

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(1) Preparation of Support) Corona discharge was performed on a biaxially stretched polyethylene terephthalate film having a thickness of 175 μm, and a first undercoat liquid having the following composition was applied at an amount of 4.9 cc / m ² . The coating was applied by a wire converter so that it was dried, and dried at 185 ° C. for 1 minute. Next, a first undercoat layer was similarly provided on the opposite surface. The polyethylene terephthalate used is a dye-
I containing 0.04 wt% was used. * Butadiene-styrene copolymer latex solution (solid content 40% butadiene / styrene weight ratio = 31/69) 158cc * 2,4-dichloro-6-hydroxy-s-triazine sodium salt 4% solution 41cc * Distilled water 801cc * The latex solution contains the following compounds as emulsifying dispersants in an amount of 0.4 wt% based on the latex solids.

[0054]

[Chemical 9]

(2) Coating of undercoat layer A second undercoat layer having the following composition is coated on the above-mentioned first undercoat layers on both sides, one side at a time so that the coating amount is as described below. To the wire bar coder method,
It was dried at 155 ° C.・ Gelatin 80 mg / m ²・ Dye Dispersion B (as dye solid content) 8 ・ Coating Aid-VI 1.8 ・ Compound-VIII 0.27 ・ Mat Agent Polymethylmethacrylate 2.5 with an average particle diameter of 2.5 μm

[0056]

[Chemical 10]

(Preparation of Photographic Material) The above emulsion layers were coated on both sides of the support prepared as described above, and a combined sample was prepared so that the coated silver amount was as shown in Table 1. The emulsion first layer is the layer closest to the support and the emulsion third layer is the layer furthest from the support.

[0058]

[Table 1]

X-ray sensitometry was carried out by using Ultra Vision First Detail (UV) manufactured by Du Pont Co., Ltd., making both sides adhere to each other and exposing from both sides for 0.05 seconds. The exposure amount was adjusted by changing the distance between the X-ray tube and the cassette. After the exposure, automatic developing machine processing was performed with the following developing solution and fixing solution.

(Processing) Automatic processor: CEPROS-M manufactured by FUJIFILM Corporation
Was modified to incorporate a heat roller into the drying zone to accelerate the transport speed and set Dry to Dry for 30 seconds. Preparation of Concentrated Solution <Developer> Part Agent A Potassium hydroxide 330 g Potassium sulfite 630 g Sodium sulfite 255 g Potassium carbonate 90 g Boric acid 45 g Diethylene glycol 180 g Diethylenetriaminepentaacetic acid 30 g 1- (N, N-diethylamine) ethyl-5-mercaptotetrazole 0. 75 g Hydroquinone 450 g 4-Hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone 60 g Water was added to 4125 ml.

Part Agent B Diethylene glycol 525 g 3,3 ′ Dithiobishydrocinnamic acid 3 g Glacial acetic acid 102.6 g 2-Nitroindazole 3.75 g 1-Phenyl-3-pyrazolidone 34.5 g Water 750 ml

Parts agent C Glutaraldehyde (50 wt / wt%) 150 g Potassium bromide 15 g Potassium metabisulfite 105 g Water added 750 ml

<Fixer> Ammonium thiosulfate (70 wt / vol%) 3000 ml Ethylenediaminetetraacetic acid / disodium dihydrate 0.45 g Sodium sulfite 225 g Boric acid 60 g 1- (N, N-diethylamine) -ethyl-5-mercapto Tetrazole 15 g Tartaric acid 48 g Glacial acetic acid 675 g Sodium hydroxide 225 g Sulfuric acid (36 N) 58.5 g Aluminum sulfate 150 g Water was added to it 6000 ml pH 4.68

(Preparation of Treatment Solution) The developer solution was filled in the following container for each parts agent. In this container, the partial containers of the parts agents A, B and C are connected together by the container itself. Further, the above fixing solution concentration was filled in the same kind of container. First, as a starter in the developing tank,
Aqueous solution 30 containing 54 g of acetic acid and 55.5 g of potassium bromide
0 ml was added. Insert the above treatment agent container upside down and insert it into the perforation blade of the treatment solution stock tank mounted on the side of the automatic processing machine to break the sealing film of the cap and transfer each treatment agent in the container to the stock tank. Filled. These processing agents were filled in the developing tank and fixing tank of the developing machine at the following ratios by operating the pumps installed in the developing machine. Also,
Every time 8 sheets of photosensitive material were processed in terms of four-cut size, the processing agent stock solution and water were mixed at this ratio and replenished in the processing tank of the developing machine.

Developer solution Parts solution A 51 ml Parts solution B 10 ml Parts solution C 10 ml Water 125 ml pH 10.50 Fixer concentrate 80 ml water 120 ml pH 4.62 The washing tank was filled with tap water.

As a water stain inhibitor, 0.4 g of actinomycetes supported on perlite having an average particle size of 100 μm and an average pore size of 3 μm was covered with a polyethylene bottle (the bottle opening was covered with a 300-mesh nylon cloth. Prepare three pieces filled with water and fungi from the cloth), two of them at the bottom of the washing tank, and one at the bottom of the stock tank for washing water (liquid volume 0.2 liters). I sunk each. Processing speed and processing temperature Current image 35 ° C 8.8 seconds Settling 32 ° C 7.7 Water washing 17 ° C 3.8 Squeeze 4.4 Dry 58 ° C 5.3 Total 30 Replenishing amount Developer 25ml / 10 × 12 inches Fixing solution 25 ml / 10 × 12 inches The results are shown in Table 2.

[0067]

[Table 2]

The sensitivity was shown as a relative sensitivity when the sensitivity of Sample 5 was set to 100 using the reciprocal of the exposure amount that gives an optical density of fog + 0.2. Gradation G is the slope of the straight line connecting the points of density 0.2 and 2.0 (density (2.0-0.2) / light quantity)
Indicates. As shown in Table 2, the sensitive material of the present invention has high gradation (G
Value) indicating that the material has high contrast and is excellent in sharpness.

Example 2 In the same manner as the photosensitive material prepared in Example 1, except that the support was changed to a PEN (polyethylene naphthalate support) prepared as follows, and after the coating, it was aged in a roll state. It was also possible to prepare a light-sensitive material having a small curl and a small blur of an image due to crossover light when an emulsion layer is coated on both sides.Support A: Commercial polyethylene-2,6-naphthalate at 300 ° C. Extruded from T die after melting at 140 ℃
Was longitudinally stretched 3.3 times, and then laterally stretched 3.3 times, and further heat-set at 250 ° C. for 6 seconds to obtain a 140 μm film. Support B: 150 pellets of polyethylene terephthalate and polyethylene-2,6-naphthalate were previously prepared.
After vacuum drying at 4 ° C for 4 hours, the mixture was kneaded and extruded at 280 ° C using a biaxial kneading extruder, and then pelletized. This pellet was formed into a film in the same manner as the support B. Corona discharge was applied to each support. For the corona discharge treatment, a solid state corona treatment machine 6KVA model manufactured by Pillar Co. is used, and a 30 cm wide support is treated at 20 m / min. At this time, the object to be processed was 0.37 from the readings of current and voltage.
Processing of 5 KV · A · min / m ² was performed. The discharge frequency during the treatment was 9.6 KHz, and the gap clearance between the electrode and the dielectric roll was 1.6 mm. The undercoat is Example 1
The same procedure as for the support of

Example 3 The photographic light-sensitive materials prepared in Examples 1 and 2 were processed with the following developing solutions. [Automatic processor processing] The automatic processor is "Fuji X Ray Processor CEPROS-M" manufactured by Fuji Photo Film Co., Ltd.
The drive shaft was modified so that the total processing time was 30 seconds. The dry blowing temperature was set to 55 ° C. Developer formulation PartA Potassium hydroxide 18.0 g Potassium sulfite 30.0 g Sodium carbonate 30.0 g Diethylene glycol 10.0 g Diethylenetriaminepentaacetic acid 2.0 g 1- (N, N-diethylamine) ethyl-5-mercaptotetrazole 0.1 g L- Ascorbic acid 43.2 g 4-Hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone 2.0 g Water was added to 300 ml.

Part B triethylene glycol 45.0 g 3,3′-dithiobishydrocinnamic acid 0.2 g glacial acetic acid 5.0 g 5-nitroindazole 0.3 g 1-phenyl-3-pyrazolidone 3.5 g Water added 60 ml

PartC Glutaraldehyde (50%) 10.0 g Potassium bromide 4.0 g Potassium metabisulfite 10.0 g Water was added to 50 ml PartA 300 ml, PartB 60 ml and PartC 50 ml Water was added to 1 liter to pH 10. Set to 90. Part
A 4.50 liters, PartB 0.90 liters, PartC 0.75
The CE-DF1 bottle manufactured by FUJIFILM Corporation was filled with 1 liter for use in 1.5 liters of the working solution. Development Starter Solution Acetic acid was added to the development replenisher solution to adjust the pH to 10.20, which was used as a development starter solution.

As the fixing solution, CE-F1 manufactured by Fuji Photo Film Co., Ltd. was used. Development temperature: 35 ° C Fixing temperature: 35 ° C Drying temperature: 55 ° C Replenishment amount (both developer and fixer) 25 ml / 10 x 21 inches (325 ml / m ² ) Each sample 10 x 600 pieces of 12-inch size film were subjected to running processing, and good performance was obtained. It was found that the combination of the light-sensitive material of the present invention and the developing solution was good with no change in sensitivity at the start and in the running solution.

Example 4 The light-sensitive materials of the present invention obtained in Examples 1 to 3 were used in Japanese Patent Laid-Open No. 6-11.
When an image was formed by X-ray exposure using the phosphor screen described in No. 804, it was confirmed that a good X-ray image was formed.

Claims (2)

[Claims] 1. A silver halide photographic light-sensitive material having two or more silver halide emulsion layers on at least one side of a support, wherein any two of the two or more silver halide emulsion layers are included. A silver halide photographic light-sensitive material, wherein the emulsion layers of the layers satisfy the relationships 1) and 2) below. 1) Each layer contains at least one of the following emulsions. 50% or more of the projected area of all silver halide grains contained in the emulsion are tabular silver halide grains having a silver chloride content of 10 mol% or more and an aspect ratio of 2 or more. 2) Of the two emulsion layers, the emulsion of 1) contained in the emulsion layer closer to the support is higher in sensitivity than the emulsion of 1) contained in the emulsion layer farther from the support. Is. 2. The silver halide photographic light-sensitive material according to claim 1, which is used in combination with an X-ray absorption fluorescent intensifying screen having an emission peak at 400 nm or less.