JPH10142723A - Silver halide photographic sensitive material and composition and processing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To enhance sensitive and to reduce fog and the like. SOLUTION: Silver is applied to one side in an amount of <=2.0g/m<2> and flat silver halide grains occupying >=60% of the projection areas of the total silver halide grains have principal faces [100] and an aspect ratio (diameter/ thickness) of >=2.0 and anisotropic growth defects and a length to breadth (longer side to shorter side) ratio of 1∼6 in a rectangular tetragon surrounded by the faces (100) of the edges or that formed by extending the faces (100) of the edges and this silver halide emulsion is prepared ion the presence of a compound A<0> and/or compound B<0> , and the compound A<0> is an organic compound having 2 or more adsorbent groups in one molecule, for accelerating formation of the (100) faces of silver bromide grains, covalently combined with the compound and the compound B<0> is an organic compound having 2 or more alcohol groups in one molecule, and both compounds are organic compounds except gelatins and proteins.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION An object of the present invention is to provide a high sensitivity,
A silver halide photographic light-sensitive material that reduces processing load, reduces replenishment of developer and fixer, is suitable for rapid processing, and provides X-ray images with improved image quality, and has excellent characteristics in balance between sensitivity and image quality The present invention relates to a novel assembly of the silver halide photographic material and a radiation intensifying screen as described above, and a method of processing the silver halide photographic material.

[0002]

2. Description of the Related Art When tabular AgX emulsion grains are used in a photographic light-sensitive material, the ratio of incident light passing through the photosensitive layer is reduced and the light trapping efficiency is increased as compared with non-tabular AgX grains. And image quality (covering power, sharpness,
(Granularity), development progress, spectral sensitization characteristics and the like are improved.
For this reason, they have twin planes parallel to each other and the main plane is # 11.
Tabular grains having a 1｝ plane have been frequently used. However, the {111} plane is usually a plane mostly composed of halogen ions (hereinafter referred to as X ⁻ ), whereas the {100} plane is a plane in which Ag ⁺ and X ⁻ are alternately arranged. Better photographic properties. Therefore, tabular grains having a {100} plane as the main plane are attracting attention. Regarding the {100} tabular grains, JP-A-51-88017, JP-B-64
-8323, JP-A-5-281640 and 5-31
No. 3273, No. 6-59360, No. 6-324446
No. 5,534,395 A1, US Pat.
632, 5314798 and 5264337. The present invention provides a better {100} tabular grain emulsion than conventional {100} tabular grains. The {100} tabular grains become tabular because of having crystal defects that allow preferential growth in the edge direction, but the shape characteristics of the grains generated by the defect forming method,
Photographic characteristics are significantly different. Further, the shape characteristics and photographic characteristics of the produced grains also differ greatly depending on the growth method of the tabular grains. Therefore, improvement of the method of forming the defect and improvement of the growth method have attracted attention. EP 0 534 395 A1 describes forming the tabular grains in the presence of an adsorbent which promotes {100} plane formation, but the method gives unsatisfactory results in grain shape and photographic properties. Absent.

[0003]

SUMMARY OF THE INVENTION The present invention provides a silver halide photographic light-sensitive material which has a small processing load, that is, is environmentally friendly and has specific photographic characteristics, and has an excellent balance between image quality and sensitivity. Another object of the present invention is to provide a novel X-ray photographing system, that is, a combination of a silver halide photographic light-sensitive material and a radiographic intensifying screen, and a processing method therefor.

[0004]

The object of the present invention has been attained by the following items. (1) In a silver halide photographic material having at least one silver halide emulsion layer on a support, the silver halide emulsion has a coated silver amount per side of 2.0 g / m ² or less, and The silver halide emulsion has at least a dispersion medium and silver halide grains, and at least 60% of the total projected area of the silver halide grains has a {100} plane as a main plane,
A tabular grain having anisotropically grown crystal defects having an aspect ratio (diameter / thickness) of 2.0 or more, and a right-angled parallelogram surrounded by {100} planes of edges of the tabular grain; Alternatively, the aspect ratio (length of the long side / length of the short side) of the right-angled parallelogram formed by extending the {100} plane of the edge is 1 to 6, and the silver halide emulsion is compound A ⁰ and / or silver halide photographic material, characterized in that is produced in the presence of a compound B ^0. Here, compound A ⁰ represents an organic compound in which at least two adsorbents for promoting the formation of {100} planes of AgBr particles are covalently bonded in one molecule, and compound B ⁰ has two alcohol groups in one molecule. Represents an organic compound other than gelatin having the above, and,
Both represent organic compounds other than gelatin and protein.

(2) Compound A ⁰ or Compound B
⁰ is characterized by a defect formed by addition of Ag ⁺ and halide ions in a state adsorbed to the silver halide grains (1) a silver halide photographic material as claimed.

(3) The silver halide photographic material as described in (1), wherein the defects are not substantially formed during the growth of the tabular grains.

[0007] (4) the defect is, at the time of nucleation, is formed by forming at least one of the halogen composition gap interface, the halogen composition gap interface is Cl ^-, or Br ^- content: or I, ^- in content: (1) The silver halide photographic material as described in (1), having a halogen composition difference of 10 mol% or more.

(5) The silver halide photographic material as described in any one of (1) to (4) above, wherein the silver halide tabular grains have silver halide projections having an epitaxial junction. .

(6) The silver halide grains correspond to 4, 5 in the periodic table.
The silver halide photograph according to any one of (1) to (5), wherein the crystal lattice contains a coordination metal complex or a metal ion containing a metal of an element belonging to Group 3 to 14 of 6 periods. Photosensitive material.

(7) The tabular silver halide emulsion contains a compound represented by the following formula (1) and a compound represented by the following formula (2): ) The silver halide photographic material according to any one of the above.

[0011]

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In the formula, R ₁ represents a sulfoalkyl group or a carboxyalkyl group, and R ₂ represents an alkyl group, an alkenyl group or an aryl group. R ₃ represents an alkyl group. X
Represents the counter ion required to neutralize the charge on the molecule,
n represents the number required for neutralization. However, when an inner salt is formed, n is 0. Z ₁ and Z ₂ each represent a group of nonmetallic atoms necessary to complete a benzene ring or a naphtho ring.

[0013]

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In the formula, R ₁₁ to R ₁₄ each represent an alkyl group, X ₁ represents a counter ion necessary for neutralizing the molecular charge, and n ₁ represents a number required for neutralization. However, when an inner salt is formed, n ₁ is 0. Z ₁₁ and Z ₁₂ each represent a group of nonmetallic atoms necessary to complete a benzene ring or a naphtho ring.

(8) When the silver iodide content of the tabular silver halide grains is 1 mol% or less, the silver iodide content is maximum near the surface of the tabular silver halide grains and the maximum value is such that Any one of (1) to (7), wherein the content is at least 6 times the minimum silver iodide content in the tabular silver halide grains.
The silver halide photographic light-sensitive material according to the above item.

(9) The silver halide photographic material as described in any one of (1) to (8) above, which contains a compound represented by the general formula (3).

[0017]

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[0018] In the formula, Z _a represents an atomic group necessary for forming a 5- or 6-membered heterocyclic nucleus. R _1a represents an aliphatic group, R _2a
Represents a hydrogen atom or an aliphatic group, and R _3a and R _4a each represent a hydrogen atom, a halogen atom, an aliphatic group, an alkoxy group, a hydroxy group or an aromatic group, and R _1a , R _2a , R _3a and R _4a At least one of them represents a substituent having a propargyl group, a butynyl group, or a propargyl group.
X _a ^- represents an anion. n _a represents 1 or 2, n _a when the compound forms an intramolecular salt represent 1.

(10) The silver halide photographic material as described in any one of (1) to (9), further comprising a compound represented by formula (4).

[0020]

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In the formula, Z is -SO ₃ M, -COOR _1b ,-
Represents a heterocyclic ring having at least one directly or indirectly in OH and -NHR _2b, M represents a hydrogen atom, an alkali metal atom or a quaternary ammonium group or a quaternary phosphonium group, R _1b is a hydrogen atom, an alkali metal An atom or an alkyl group having 1 to 6 carbon atoms, R _2b is a hydrogen atom,
An alkyl group of -COR _3b , -COOR _3b or -SO ₂
Represents R _3b, R _3b represents a hydrogen atom, an aliphatic group or an aromatic group.

(11) The silver halide photographic material as described in any one of (1) to (10) above, wherein the tabular silver halide grain emulsion is chemically sensitized with a selenium compound.

(12) It is characterized by containing a compound represented by the general formula (5), (6) or (7) (1)
(11) The silver halide photographic light-sensitive material according to any one of (1) to (11). (5) _{R-SO 2 S-M (} 6) R-SO 2 S-R 1 (7) R-SO 2 S-Lm-SSO 2 -R 2 Formula, R, R ^1, also R ² is the same It may be different and represents an aliphatic group, an aromatic group, or a heterocyclic group, and M represents a cation. L represents a divalent linking group, and m is 0 or 1. The compounds of the general formulas (5) to (7) may be polymers containing a divalent group derived from the structure represented by any of the formulas (5) to (7) as a repeating unit.

(13) The silver halide photographic light-sensitive material according to any one of (1) to (12), further comprising a compound represented by formula (8).

[0025]

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In the formula, R _2c , R _3c , R _5c , and R _6c may be the same or different and are a hydrogen atom or a group that can be substituted on a benzene ring, and R _1c and R _4c are a hydrogen atom or an alkaline condition. Is a protecting group that can be deprotected. R _2c to R _6c , O
R _1c and OR _4c may form a ring together.

(14) The silver halide photographic material as described in any one of (1) to (13), further comprising an infrared absorbing dye.

(15) The silver halide photographic material as described in any one of (1) to (14), further comprising a polymer latex.

(16) The silver halide photographic material as described in any one of (1) to (15) above, which comprises colloidal silica.

(17) The silver halide photographic material as described in any one of (1) to (16), further comprising a surfactant containing a polyalkylene oxide and / or fluorine.

(18) The protective layer contains a matting agent comprising a polymer having a hydrophilic group in the protective layer.
(17) The silver halide photographic material as described in any one of the above items.

(19) The silver halide photographic material as described in any one of (1) to (18), wherein the swelling ratio is 20% or more and less than 200%.

(20) The photographic material according to any one of (1) to (19), wherein the photographic material has a photosensitive silver halide emulsion layer on both sides of a support. Exposure with monochromatic light having the same wavelength as the main emission peak wavelength of the radiation intensifying screen and having a half width of 15 ± 5 nm,
After the development processing, the photosensitive silver halide emulsion layer on the side opposite to the exposed surface was peeled off and the density was measured. When the density was measured, the density obtained in the photosensitive silver halide emulsion layer on the exposed side was reduced to 0%. The amount of exposure required to reach the value obtained by adding .5 is 0.01.
A silver halide photographic material having a sensitivity of 0 lux seconds to 0.035 lux seconds.

(21) When a silver halide photographic light-sensitive material is provided between a support and at least one photosensitive silver halide emulsion layer, a hydrophilic colloid layer containing a dye which is decolorized in a developing treatment or a fixing treatment is provided. The silver halide photographic material according to any one of (1) to (20), which is provided.

(22) The silver halide photographic material as described in (21), wherein the dye is contained as microcrystalline particles.

(23) The silver halide photographic light-sensitive material as described in any one of (20) to (22), wherein the emulsion layers on both sides each have the characteristics specified in (20).

(24) From the silver halide photographic light-sensitive material according to any one of (20) to (23) and two radiation intensifying screens respectively disposed on the front side and the rear side of the photographic material. A combination of a silver halide photographic material and a radiation intensifying screen, wherein at least one of the radiation intensifying screens satisfies the following requirements. (I) When viewed from the side facing the silver halide photographic material, the protective layer, the phosphor layer, and the support layer are arranged in this order. (II) The protective layer is a transparent synthetic resin layer having a thickness of 1 μm or more and 10 μm or less formed by coating on the phosphor layer. (III) Contrast transfer coefficient (CTF) is spatial frequency 1
Lines / mm is 0.79 or more, and spatial frequency 3 lines / mm
It is 0.36 or more in mm. (IV) 30% for X-ray of 80KVp through 7cm of water
The above absorption amount is shown.

(25) The radiation intensifying screen according to (24), wherein the thickness of the radiation intensifying screen specified in (24) is not less than 95 μm and not more than 300 μm. Assembly.

(26) The crossover radiated to the emulsion layer on the back surface of the silver halide photographic light-sensitive material is 15% or less with respect to the light emitted from the radiation intensifying screen disposed in front of the silver halide photographic light-sensitive material. An assembly of the silver halide photographic light-sensitive material according to (24) or (25) and a radiographic intensifying screen, characterized in that:

(27) The silver halide according to any one of (24) to (26), wherein each of the front and rear radiographic intensifying screens has the characteristics specified in (24). An assembly of a photographic material and a radiation intensifying screen.

(28) Regarding the method of processing the silver halide photographic light-sensitive material according to any one of (1) to (23) and (26) with a developer, the developer has the following general formula (9) A method for processing a silver halide photographic material, comprising at least one compound represented by the formula (1): General formula (9)

[0042]

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In the formula, X represents an oxygen atom or a sulfur atom, Y represents a hydrogen atom or a substituent, and M represents a hydrogen atom, an alkali metal ion, a quaternary ammonium ion or a quaternary phosphonium ion.

(29) In the method for processing the silver halide photographic light-sensitive material according to any one of (1) to (23) and (26) with a developer, the developer comprises an ascorbic acid compound. A method for processing a silver halide photographic light-sensitive material, comprising a 3-pyrazolidone compound as a developing agent, wherein development processing is completed in 5 seconds to 30 seconds.

(30) The silver halide photographic material as described in (29), wherein the developer contains at least one compound represented by the general formula (9) as described in (28). Processing method.

(31) The replenishment amount of development and / or fixation per square meter of silver halide photographic material is 25 ml or more.
(28)-(30) characterized by being less than 200 ml
A method for processing a silver halide photographic material as described in any one of the above.

(32) development of a silver halide photographic light-sensitive material,
Any one of (28) to (31), wherein the total processing time of fixing, washing and drying is 25 seconds or more and 200 seconds or less.
The method for processing a silver halide photographic light-sensitive material described in the above item.

(33) The silver halide according to any one of (28) to (32), wherein the silver halide photographic material is subjected to a non-hardening treatment in the developing and / or fixing step. Processing method of photographic photosensitive material.

Other preferred embodiments of the present invention are as follows. (34) The formation of the defect first is substantially free of the defect.
gX ₀ nuclei, then the compounds A ₀ and / or B
Was added ^0, adsorbed, followed by addition of Ag ⁺ and halide ions, wherein, characterized in that the defect is formed by laminating on the AgX ₀ supranuclear (1) to (23), ( 26)
A silver halide photographic material according to any one of the preceding claims.

(35) The compound A ⁰ is a polymer of one or more ethylenically unsaturated monomers, and contains two or more imidazole groups or benzimidazole groups in one molecule. (1) to (23), (26),
(34) The silver halide photographic light-sensitive material according to any one of (1) to (11).

(36) When the compound B ⁰ has a molecular weight of 300 or more, the X ₁ value in one molecule (the number of alcohol groups / the total number of functional groups)
Is a polyvinyl alcohol of 0.2 to 1.0, wherein the silver halide photographic light-sensitive material according to any one of the above (1) to (23), (26) and (34).

(37) The above-mentioned (1) to (23), wherein the concentration of the compound A ⁰ and / or the compound B ⁰ is such that the equilibrium crystal habit potential shift amount is 10 mV or more.
(26) The silver halide photographic light-sensitive material according to any one of (34) to (36).

Next, the present invention will be described in more detail. The compound A ⁰ is represented by the general formula (10), and the compound B ⁰ is represented by the general formula (11) and the general formula (11-1). ad
Represents the weight percentage of each component. Therefore, a + b = 10
0, d + e = 100. These compounds will be described in order. General formula (10)-(A) _a- (B) _b -General formula (11)-(D) _d- (E) _e -General formula (11-1)-(D) _d -S-(E) _e −

(I) Compound A ^{0 The} compound A ⁰ contains 2 or more, preferably 4 to 10 ³ , more preferably 4 or more molecules in one molecule of the adsorbent C ⁰ for promoting the formation of the {100} plane of AgBr particles. Represents an organic compound covalently bonded to 8 to 100 molecules, more preferably 20 to 100 molecules. Here, the compound A ⁰ refers to a compound having the following characteristics. First, normal crystal AgBr emulsion grains having an average diameter of about 0.2 μm are formed in the presence of conventional photographic gelatin. From the emulsion, N ⁰ equal amounts of sample emulsion are taken as seed crystals. One of them was placed in a conventional aqueous solution of gelatin dispersion medium for photographic use, and at ⁺ 60 ° C., Ag ⁺ and Br ⁻ were added by a double jet while keeping the silver potential at a constant value. Grow to 1.0 μm. A similar experiment was performed at various silver potentials, and silver potential, pair, particle shape,
Ask for a relationship. On the other hand, a compound A ^{0 in} which C ⁰ is covalently bonded in the above-described manner is added in an amount of 30% by weight of the weight of gelatin in the aqueous solution, and the same experiment is performed to determine the relationship between the silver potential and the particle shape. The gelatin amount of the aqueous solution at the start of the particle growth is 18 g / liter. Ag ⁺ is added
It is 70g in NO _3. The pH is a constant value equal to or higher than the pKa value of A ⁰ , preferably (pKa + 0.5). Here, the pKa value indicates an acid dissociation constant value. The silver potential indicates the potential of the silver bar with respect to the room temperature saturated calomel electrode. The silver potential was calculated using an AgBr electrode, an AgI electrode, an Ag ₂ electrode instead of a silver rod.
An S electrode or a mixed crystal electrode of two or more of them can be used. However, the comparison experiment between the two showed that compound A ₀ was present,
Except for nothing, the same conditions are used.

When the two are compared, the silver potential at which the tetrahedral particles of the same shape can be obtained is 10 mV or more, preferably 20 to 150 mV, more preferably 30 to 120 mV, and most preferably the silver potential as compared with the gelatin system. 50-100mV
Only the relationship shifted to the lower potential side is given. When such a low potential shift occurs due to the presence of a certain amount of a certain compound, the potential shift amount is referred to as an equilibrium habit potential shift amount in the present invention. The tetradecahedral particle is preferably a tetrahedral particle in which each corner of the cubic particle is missing on average 30% of a side length, and a top view of the particle shape is shown in FIG. Regarding other details of the silver potential measurement, see Ion Selective Electrode, Kyoritsu Shuppan, translated by Shin Munemori et al.
7), Electrochemical Handbook, Chapter 5, Maruzen (1985).

Here, the adsorbent C ⁰ is an organic compound having at least one nitrogen atom N having a π-pair of electrons which is resonance-stabilized. First, 1) a heterocyclic compound containing N in the ring can be mentioned. . A substitutable saturated or unsaturated heterocyclic ring containing only one N as a hetero atom in the ring (for example, pyridine, indole, pyrrolidine, quinoline, etc.);
And a substitutable saturated or unsaturated heterocyclic ring containing one or more heteroatoms selected from N and O in the ring (eg, imidazoline, imidazole, pyrazole, oxazole, piperazine, triazole, tetrazole, oxa Diazole, oxatriazole, dioxazole, pyrimidine, pyrimidazole, pyrazine, triazine, tetrazine, benzimidazole, etc.).

Other examples include 2) an organic compound represented by the formula (12) having an N atom group group substituted on an aromatic ring. Here, Ar is an aromatic ring having 5 to 14 carbon atoms, preferably an aromatic ring having a carbon ring. R ¹ and R ² are each H, Ar, an aliphatic group,
Or aniline, α-naphthylamine, carbazole, 1,8-naphthyridin, nicotine, benzoxazole, etc. which together form a 5- or 6-membered ring. For further details see EP05343
95A1 and JP-A-6-19029 can be referred to. Among these compounds, more preferred are imidazole and benzimidazole.

The compound A ⁰ can be prepared by polymerizing two or more molecules of the polymerizable ethylenically unsaturated monomer represented by the formula (13), or by polymerizing the ethylenically unsaturated monomer represented by the formula (14). It is formed by copolymerization with a monomer. (1
3) The monomer represented by the formula may be only one kind or a mixture of two or more kinds. What is necessary is just to copolymerize in the ratio satisfying the said aspect. (13) C ¹ in the formula represents a residue when compound C ⁰ is bonded to the monomer. (14) In the formula, d ¹ represents a functional group. The compound of the formula (14) is copolymerized to form a B or E moiety.

[0059]

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Here, R ³ and R ⁴ represent a hydrogen atom or an alkyl group having 1 to 10, preferably 1 to 5 carbon atoms.

The following compounds can be mentioned as specific examples of the compound of the formula (13). Vinylimidazole, 2-methyl-1-vinylimidazole, 4-vinylpyridine, 2
-Vinylpyridine, N-vinylcarbazole, 4-acrylamidopyridine, N-acryloylimidazole,
N-2-acryloyloxyethylimidazole, 4-
N- (2-acryloyloxyethyl) aminopyridine, 1-vinylbenzimidazole, N-vinylbenzylimidazole, N-methacryloyloxyethylpyrrolidine, N-acryloylpiperazine, 1-vinyltriazole, 3,5-dimethyl-1-vinyl Pyrazole,
Monomers having a heterocyclic group containing a basic nitrogen atom, such as N-methacryloyloxyethylmorpholine, N-vinylbenzylpiperidine, and N-vinylbenzylmorpholine.

Preferred copolymerizable ethylenically unsaturated monomers capable of forming B are those whose homopolymers are soluble in any of acidic, neutral and alkaline aqueous solutions. Specific examples of compounds include acrylamide, methacrylamide, N-methylacrylamide, N, N-
Non-ionic monomers such as dimethylacrylamide, N-acryloylmorpholine, N-ethylacrylamide, diacetoneacrylamide, N-vinylpyrrolidone, N-vinylacetamide, acrylic acid, methacrylic acid, itaconic acid, vinylbenzoic acid, styrene Monomers having an anionic group such as sulfonic acid, styrene sulfinic acid, phosphonoxyethyl acrylate, phosphonoxyethyl methacrylate, 2-acrylamido-2-methylpropanesulfonic acid, and 3-acrylamidopropionic acid, or salts thereof Or N, N, N-trimethyl-N-vinylbenzylammonium chloride,
Monomers having a cationic group such as N, N, N-trimethyl-N-3-acrylamidopropylammonium chloride can be mentioned.

B is one or more of these copolymers. In B, other hydrophobic ethylenically unsaturated monomers can be copolymerized within a range that does not impair the water solubility of the entire molecule of the formula (10). For example, ethylene, propylene, 1-butene, styrene, α-methylstyrene, methyl vinyl ketone, monoethylenically unsaturated esters of aliphatic acids (eg, vinyl acetate, allyl acetate), ethylenically unsaturated monocarboxylic acids or dicarboxylic acids Acid esters (eg, methacrylic acid esters), ethylenically unsaturated monocarboxylic amides (eg, t-butylallylamide), monoethylenically unsaturated compounds (eg, acrylonitrile, methacrylonitrile), dienes ( For example, butadiene, isoprene). In the equation (10), a is (0.00
2 to 1.0) × 100, preferably (0.01 to 0.1).
8) × 100, more preferably (0.05 to 0.7) ×
100, more preferably (0.15 to 0.6) × 100
It is. The molecular weight of the compound A ⁰ is 150-10 ^6, preferably 300-3 × 10 ^5, more preferably 10 ³ to 3 ×
10 ⁵ . In the formula (13), the chemical bond between C ¹ and the ethylenically unsaturated monomer may be directly bonded as shown in the following formula (14), or as H ₂ C = C (H) -LC ¹ . It can also be bonded via a divalent linking group L. For example, H ₂ C = C (H) -C
It can be mentioned aspects of the ONH-C ¹ and _{H 2 C = C (H)} COO-C 1.
The details of the divalent linking group and the bonding mode can be referred to the descriptions in JP-A-3-109439 and JP-A-4-226449. More generally, compound A ⁰ has two or more molecules of a polymerizable monomer having a C ¹ group,
Preferably 4 to 10 ³ molecules, more preferably 8 to 100
It is a polymer of an embodiment in which molecules, more preferably 20 to 100 molecules are polymerized. It can be formed by polymerizing a polymerizable monomer having a C ¹ group, or by bonding the C ¹ group to a polymer that exists immediately. Examples of the polymerization method include addition polymerization, polycondensation, polyaddition polymerization, ring-opening polymerization, and addition condensation, and are preferably addition polymerization of a vinyl compound, a vinylidene compound, and a diene compound, and more preferably, addition of a vinyl compound. It is polymerization. The details can be referred to the descriptions of New Experimental Chemistry Course 19, Polymer Chemistry [I], Maruzen (1978), 4th Edition Experimental Chemistry Courses 28 and 29, Maruzen (1992). The monomer has at least one C ¹ group, preferably 1 to 3, more preferably 1 group. The C ¹ group is not on the main chain of the polymer but is attached as a branch. Compound A ⁰ is preferably
A polymer of one or more ethylenically unsaturated monomers,
2 or more molecules in the molecule, preferably 4 to 10 ³ molecules, more preferably 8 to 100 molecules, more preferably 20 to 10
It has zero imidazole groups or benzimidazole groups.

(II) Compound B ⁰ Compound B ⁰ has a molecular weight of preferably 90 or more, more preferably 300 to 10 ⁶ , still more preferably 10 ³ to 10 ⁵ ,
Most are preferably the 3000-10 ^5, the alcohol group 2 group in one molecule, preferably 4 to 10 ⁵ groups, more preferably 10 to 10 ^four, most preferably 30 to 10
It is a compound other than gelatin and proteins with ³ groups or 100 to ³ group. Furthermore in one molecule (alcohol groups / total number of functional groups) = x ₁ is preferably 0.05
Above, more preferably 0.2 to 1.0, still more preferably 0.4 to 1.0, most preferably 0.6 to 1.0.
It is. Here, the functional group refers to a residue that is more reactive than a hydrocarbon residue such as a methyl group, and refers to a heteroatom group or an atomic group containing a heteroatom. In one molecule, (total mass of all alcohol groups / total mass of one molecule) = x ₂
Is preferably 0.01 to 0.6, more preferably 0.05 to 0.55, and most preferably 0.1 to 0.5.

As specific examples of the compounds, 1) carbohydrates can be mentioned. Carbohydrate is a polysaccharide satisfying the above-mentioned molecular weight specification, and examples thereof include a homopolysaccharide composed of one kind of constituent saccharide and a heteropolysaccharide composed of two or more kinds of saccharides. The constituent sugars with (CH ₂ O) _n molecular formula, n = 5 to 7 monosaccharide, sugar alcohol, aldonic acid having a -COOH group instead of a -CHO group, -CH ₂ OH group is -COOH group Uronic acid and amino sugars. Others
Sugar derivatives (viscose, methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose, soluble starch, carboxymethyl starch, dialdehyde starch, glycosides, etc.) can be mentioned. Carbohydrates excluding nucleic acids are preferred, and carbohydrates excluding glycosides are more preferred. Specific examples of carbohydrates include starchy substances (potato starch, potato starch, tapioca starch, wheat starch, corn starch), konjac, seaweed, agar, sodium alginate, troloioi, tragacanth, gum, gum arabic, dextran, dextrin, dextrin, And galactose (agar or the like) is preferred.

2) Polyhydric alcohol. Also referred to as alkane polyol, as specific examples glycerin, glycitol,
Ethylene glycol can be mentioned. 3) A polymer represented by the formulas (11) and (11-1), wherein D represents a repeating unit formed from an ethylenically unsaturated monomer having at least one alcohol group. E represents a repeating unit other than D formed from an ethylenically unsaturated monomer. d and e represent the weight percentage of each component, d is 5 to 100, preferably 20 to 100, more preferably 40 to 100, and e is 0 to 95, preferably 0 to 80, more preferably 0 to 60. is there. Examples of the ethylenically unsaturated monomer capable of forming E include the aforementioned ethylenically unsaturated monomer capable of forming B and the monomer represented by the formula (13).

A more preferred specific example of the compound 3) is a copolymer of vinyl acetate and a vinyl alcohol, and the copolymerization ratio can be selected by adjusting the saponification rate of polyvinyl acetate. Further, a copolymer with acrylic acid is preferred. The polymerization ratio is such that the ratio (a2 / a1) of the number of carboxyl groups (a2) to the number of hydroxyl groups (a1) is 0.0
01-0.6 is preferred, 0.01-0.4 is more preferred, and 0.03-0.3 is even more preferred. The ratio (a3 / a1) of the number of acetate groups (a3) to a1 is 0.1.
001 to 0.3 are preferred. 0.01 to 0.1 is more preferable. Examples of the compound represented by (11-1) include a compound in which polyvinyl alcohol and polyacrylic acid are linked by a thioether bond. When thioacetic acid is reacted with polyvinyl alcohol as a chain transfer agent, -S
Polyvinyl alcohol having an H group is produced. The copolymer is obtained by polymerizing an acrylic acid monomer with the monomer.

Regarding the other details of the compounds represented by the formulas (10), (11) and (11-1), and their polymerization methods, see, for example, revised version of Teiji Tsuruta “Polymer Synthesis Reaction”, Nikkan Kogyo Shimbunsha (1971), written by Takatsu Otsu et al.
Reference can be made to "Experimental method for polymer synthesis", Kagaku Doujin, pp. 124-154 (1972), JP-A-6-19029, and the description of water-soluble polymers described below.

The compounds 1) to 3) may be used in combination of two or more kinds at a suitable ratio. These compounds may be added as they are to the reaction solution in the form of a powder or a solution, or may be added after dissolving in acidic, neutral or alkaline water. For other details of the compounds 1) to 3), see Shinji Nagatomo, Application and Market of New Water-Soluble Polymer, CMC (1988), Business Development Center Publishing Division, Water-Soluble Polymer / Water-dispersible Resin Comprehensive technical data, Management Development Center Publishing Division (1981), Tadanori Misawa, Ed.
A. Finch, polyvinyl alcohol, John Wiley & So
ns (1992).

(III) Physical Properties of AgX Emulsion In the above (1) and (2), the projected area means that the AgX emulsion grains do not overlap each other, and the tabular grains have a main plane parallel to the substrate surface. It refers to the projected area of particles when placed on a substrate in a state. The AgX emulsion of the present invention is an AgX emulsion having at least a dispersion medium and AgX particles.
60% or more of the total projected area of the grains, preferably 70 to
100%, more preferably 90 to 100%, are tabular grains having a {100} major plane and an aspect ratio (diameter / thickness) of 2 or more, preferably 3 to 25, more preferably 4 to 20. . The diameter of the tabular grains refers to the diameter of a circle having an area equal to the projected area of the grains when the grains are observed with an electron microscope. The thickness refers to the distance between the main planes of the tabular grains. The thickness is preferably 0.5 μm or less, more preferably 0.03 to 0.3 μm, and 0.05 μm or less.
０．２0.2 μm is more preferable. The projected particle diameter of the tabular grains equivalent to a circle is preferably 10 μm or less, more preferably 0.2 to 5 μm. The halogen composition of the tabular grains is not particularly limited, and any composition is possible, but the I ^- content is preferably 20 mol% or less, more preferably 0 to 10 mol%.
The diameter distribution of the particles is preferably monodisperse, and the coefficient of variation (standard deviation / average diameter) of the distribution is preferably from 0 to 0.4, more preferably from 0 to 0.3, further preferably from 0 to 0.2. preferable.

The principal plane refers to the largest outer surface of a tabular grain and another large outer surface parallel to the largest outer surface. The projected outline shape of the tabular grains (the outline shape of the edge surface in the top view when the main plane of the tabular grains is placed parallel to the substrate surface) is as follows.
One of the four corners of a right-angled parallelogram, right-angled parallelogram
One or more are unequally missing (for details, refer to Japanese Patent Application No.
No. 5031, No. 5-264059), a mode in which at least two opposite sides of the four sides of the right-angled parallelogram are outwardly convex curves, An embodiment in which four corners are equivalently missing [1
(Maximum missing area / minimum missing area) <2 aspect] of the main plane within one particle.

In addition, there can be mentioned an embodiment having a {n10} plane between the principal plane and the {100} plane of the edge. Here, n is an integer of 1 to 5, preferably 1, and the area ratio of the {n10} plane to the entire surface of the tabular grains is preferably 0.1 to 30%, more preferably 1 to 15%. In the case of the above, the edge surface of the missing portion is # 11
A case having a {1} plane, a {n10} plane, or both sides can be given. n complies with the above-mentioned rules. Preferably,
It is an aspect of. Right-angled parallelogram surrounded by {100} planes of edges of the tabular grains, or {1} of edges
The aspect ratio of the right-angled parallelogram formed by extending the 00 ° plane is 1 to 6, preferably 1 to 4, more preferably 1 to 3, and most preferably 1 to 2. The former right-angled parallelogram corresponds to the projected outline shape of the tabular grains, and the latter right-angled parallelogram corresponds to the {10} of the tabular grains.
This corresponds to a 0 ° circumscribed right-angled parallelogram.

In the present invention, the particles having the (aspect ratio ≧ 7) and / or the crystal particles formed by joining at least two of the particles having such a shape at right angles or in parallel are 18 wt% of the total AgX. %, Preferably 0 to 15%, more preferably 0 to 10%, and most preferably 0 to 2%. The halogen composition of the whole tabular grains is AgCl, AgB
r, AgBrI, AgClI and mixed crystals thereof, and the I ⁻ content is preferably 0 to 20 mol%, more preferably 0 to 10 mol%. The AgCl content is preferably from 50 to 100 mol%, more preferably from 75 to 99.9 mol%.

With respect to the distribution of the halogen composition in the grains of the tabular grains, JP-A-6-59360 and JP-A-5-31327 can be used.
3, Japanese Patent Application Nos. 6-47991 and 5-27411 can be referred to. In the drawing of the particle structure in the specification, the Br ^- content or the Cl ^- content differs from 1 to 70 mol%, preferably from 5 to 50 mol% between the white background portion and the hatched portion, or the I ^- content. Is 0.3 to 30 mol%,
Preferably, embodiments differing by 1 to 20 mol% can be given. The hatched portion of the particle structure indicates a thickness of at least three atomic layers. It is preferable that the halogen content and the thickness distribution of the hatched portion are substantially uniformly distributed within the grains and between the grains. Other, the particle surface layer SCN ^- or I ^-
An embodiment having a content of 0.1 mol% or more, preferably 0.5 to 50 mol% can be mentioned. In addition, B of the particle surface layer
An embodiment having an r ^- content of 1 to 100 mol%, preferably 5 to 80 mol% can be mentioned. Here, the particle surface layer means a portion of 1 to 1000 atomic layers, preferably 1 to 3 atomic layers from the surface. More preferably, these contents and the thickness of the surface layer are substantially uniformly distributed on the surface of the particles and between the particles. The term “substantially uniform” means that the coefficient of variation of the content (standard deviation / average content) is preferably 0 to 0.4, more preferably 0 to 0.2, and still more preferably 0 to 0. .1. In addition, there can be mentioned a mode in which the particles are unevenly distributed on the particle surface (the coefficient of variation> 0.4). In particular, there can be cited a mode in which the edges and corners of the particles and the vicinity thereof are raised. For example, US Pat.
The description in No. 30 can be referred to.

(IV) Formation of Tabular Grains (IV) -1. Seeding Step The tabular grains are tabular because they have crystal defects that allow preferential growth in the edge direction. The defects are formed during seeding of tabular grains. The following method can be mentioned as the defect forming method. 1) Compound A ⁰ and / or
Alternatively, Ag ⁺ and X ⁻ are added to an aqueous solution containing B ⁰ . In this case, the compound is adsorbed on the generated AgX nucleus,
Further, when Ag ⁺ and X ^- are stacked on the nucleus, the defect occurs. In addition, the compound may form a complex with the added Ag ⁺ or X ⁻ and the defect may occur when the complex is incorporated into the AgX nucleus. 2) First, an AgX ₀ nucleus substantially free of the defect is formed in an aqueous dispersion medium solution, and then the compound is added, and the compound is adsorbed on the AgX ₀ nucleus. Next, Ag ⁺ and X ^- are added, and the defect is formed by laminating on the AgX nucleus. Here, “substantially” means that the amount of defects contained in the AgX ₀ nucleus is preferably 0 to 0
20%, more preferably 0-5%, most preferably 0
Refers to 1%. The addition of the compound, Ag ⁺ and X ^- can either be added while adding, Ag ⁺ and X ^- can be added after stopping the addition of. After the addition of the compound, the following Ag ⁺ and X ⁻ can be further added at the same temperature, or the temperature is raised by 3 ° C. or more, preferably 5 to 70 ° C., more preferably 10 to 60 ° C. Later, Ag ⁺ and X ^- can be added to form the defect. The latter is more preferred. The most preferable conditions can be selected and added.

3) When forming an AgX species, a halogen composition gap interface is formed in the nucleus, crystal lattice strain is formed,
The defect is formed. For example, Ag ⁺ and Xa ^- are added to first form an AgXa nucleus, and then Ag ⁺ and Xb ^- are added to form (AgXa | AgXb) species. in this case,
Xa ^- and Xb ^- have a Cl ^- content, a Br ^- content, or an I ^- content of 10 to 100 mol%, preferably 30 to 1 mol%.
It differs by 00 mol%, more preferably by 50-100 mol%. Here, Xa ⁻ and Xb ⁻ indicate the halogen composition of the added halogen salt solution. One or more, preferably 1 to 5, more preferably 2 to 4 gap surfaces are formed in the seed. As a method for forming | (AgXa AgXb) other, after forming the AgXa nucleus, Xc ^- alone or in a molar amount ^(Xc -> Agc ^+), preferably ^(Xc -> 2Agc
^+), More preferably ^(Xc -> Xc at a rate of 5Agc ^{+) -} there is a Agc ⁺ method of adding a more preferred. Here ^(Xc -> 2Agc ⁺⁾ is Xc ^- indicates that the addition molar amount of is more than twice the Agc ⁺ addition molar amount of.
The solubility of AgXc was 1 / 1.1 of the solubility of AgXa.
5 or less is preferable, 1/3 or less is more preferable, and 1/8
The following are more preferred. In this case, the added Xc and AgX
a, a halogen conversion reaction takes place, and (AgX
a | AgXc) is formed.

[0077] The X ^- include a method of adding, Cl _2, B
A method in which one or more of r ₂ and I ₂ are added, and then a reducing agent is added to generate X ⁻ can be used. They can be added in any form of gas, aqueous solution, solid or clathrate. Further, it can be added in the form of X ₂ + X ⁻ → (X ₃ ) ⁻ . For example, (I ₃₎ ^- it can be exemplified an aqueous solution of. As the reducing agent, a reducing agent that gives a standard electrode potential more negative than the standard electrode potential of X ₂ +2 electrons 2X ⁻ may be added. A photographically inert reducing agent is preferred, with H ₂ SO ₃ being preferred. It can also be added as a mixed aqueous solution with the carbohydrate. Other, Br
^- or I ^- after the release agent was added to the reaction solution, Br
^- or I ^- can be used a method of releasing. The method is described in JP-A-6-19029, European Patent 05
No. 61415A and U.S. Pat. No. 5,061,615 can be referred to. In addition, first, an AgXa nucleus is formed, and then AgXb fine particles are added, the mixture is aged, and (AgXa
| AgXb) A method of forming a halogen composition gap. Here, Xa and Xb comply with the above-mentioned rules. AgXb fine particles have a particle diameter of 0.15 μm or less, preferably 0.003 μm or less.
０．０0.07 μm, more preferably 0.005 to 0.05
μm particles.

4) In addition, before the nucleation, a method of putting I ⁻ in an aqueous dispersion medium solution and / or, of Ag ⁺ and X ⁻ added during nucleation, X ⁻ is replaced with I ⁻ and Cl ^{− -} it can be exemplified the way to a solution containing. In the former case, I
^- the amount of 10 ^-5 to 10 ^-1 mol / liter, preferably from 10 ^-4 to 10 ^-2 mol / liter. In the latter case,
The I ^- content is preferably 30 mol% or less, more preferably 0.1 to 10 mol%. The Cl ^- content: preferably at least 30 mol%, more preferably more than 50 mol%. In these cases, it is preferable to determine the optimum amount of the defect formation amount by observing the shape of the finally generated AgX particles. When the defect formation amount is too small, the number ratio of the tabular grains in the AgX becomes small. If it is too large, many defects will be contained in one particle, and the number ratio of low aspect ratio particles will increase. Therefore, it is preferable to select the defect formation amount at which the projected area ratio of the tabular grains becomes a preferable ratio. In the cases of 1) and 2), the larger the amount of the compound added, the lower the concentration of gelatin, and the higher the adsorptivity of the compound, the larger the amount of the defects formed. In the case of 3), the larger the gap difference, the larger the conversion amount, and the larger the amount of AgXa or AgXb added, the larger the defect formation amount. In the case of 4), as the I ^- amount increases, the defect formation amount increases. In these cases, the amount of the defects formed also depends on the pH and the X ^- concentration of the reaction solution. Therefore, preferred pH value, X ^-
You can choose the concentration. In the case of 3), the halogen conversion reaction occurs preferentially at the edge or corner of the AgXa nucleus, where the defect is preferentially formed. 1)
Of the methods 4) to 4), 1) to 3) are preferable, and 1) and 2).
Is more preferable, and 2) is most preferable. The reason 2) works effectively even under low pH conditions (pH = 1 to 6), and is therefore more advantageous for thinning. In the present application, the nucleus is a fine A
gX particles.

(IV) -2. Aging, growth process, particle formation aspect of the present invention After the seeds containing the crystal defects are formed in this way, preferably, the ripening process is next started. Specifically, 5 ° C or more,
Preferably 10-70 ° C, more preferably 20-70 ° C
Only the temperature is raised, Ostwald ripening is performed, non-tabular grains disappear, and tabular grains grow. The ripening can be carried out while adding Ag ⁺ and X ^- at a low rate. Others, X ^-
The aging may be performed by increasing the concentration or adding an AgX solvent to increase the AgX solubility. At this time, the pH of the reaction solution can be selected from a preferable value of 1 to 11, preferably 1.7 to 9. Regarding the AgX solvent, the description in the following literature can be referred to. The addition amount of the AgX solvent is 0
10 ^-1 mol / l, preferably 0-10 ^-3 mol / l
Liter, and the AgX solvent can be deactivated after the aging. For example, in the case of NH ₃ , instead of NH ₄ ⁺ , in the case of a thioether compound, it can be deactivated by oxidizing the thioether group. By the aging, the number ratio of tabular grains is preferably increased to 1.5 times or more, more preferably 3 to 500 times, and further preferably 6 to 200 times. After increasing the tabular grain ratio, the process then proceeds to the growth process.
The mode of forming the tabular grains of the present invention is classified as follows.

(1) Seed formation (→ treatment to reduce the adsorbing power of the adsorbent → ripening) → growth according to the mode (1) or 2) of (IV) -1. However, one or more steps in parentheses may be omitted as appropriate. (2) Speciation of the embodiments (3) and (4) of (IV) -1 →
Aging → growing. The adsorbent A ⁰ and / or B ⁰ having an appropriate adsorbing power is applied during a period from before ripening to 5 minutes before the end of growth,
Preferably, it can be added after ripening and before growth. Here, a measure for weakening the adsorbing power of the adsorbent will be described.
When the adsorbent is A ⁰ , the pH is adjusted to (pKa +
0.5) or less, preferably (pKa + 0.2) or less, more preferably pKa to (pKa-4.0).
When the adsorbent is B ⁰ , the adsorbing power can be reduced by selecting the pH and the X ^- concentration of the reaction solution. In many cases, the lower the pH value of the reaction solution and the higher the X ^- concentration, the weaker the adsorption power becomes. By lowering the pH value,
The change of the alcohol group to —OH ₂ ⁺ , the alcohol group reacts with hydrogen halide, and R—OH + HX → R−X +
It is considered that change to H ₂ O is effective. In addition, a method of adding an oxidizing agent such as H ₂ O ₂ or KMnO ₄ to oxidize an alcohol group to an aldehyde or a carboxylic acid,
There are a method of esterifying an alcohol group, a method of performing a dehydration reaction, a method of reacting with a phosphorus trihalide, and the like. For more information on these, see Morrison Boyd Organic Chemistry, 6th Edition, Chapter 6, Tokyo Kagaku Dojin (1994);
Patai ed., The Chemistry of the hydroxyl group, Int
erscience Publishers (1971).

In addition, although this is an effective treatment for both the adsorbents A ⁰ and B ^0, a dispersion medium for suppressing the formation of defects is added. For example, gelatin is added. In this case, the ratio of (gelatin weight / adsorbent weight) is 0.1 or more,
Preferably 0.3 to 300 times, more preferably 1 to 10
Increase to 0 times. Raise the temperature. As the temperature rises, the (adsorption / desorption) equilibrium generally shifts to the right. Preferably, the temperature is raised by 5 to 60C, more preferably by 10 to 50C. Part or all (preferably 10 to 100%, more preferably 20 to 90%) of the adsorbent is removed out of the system. Examples thereof include a centrifugal separation method and a filtration method using an ultrafiltration membrane.
In this case, a method of removing the compound after adding the compound, for example, gelatin, is more preferable. As the dispersion medium and gelatin, preferred ones can be selected from conventionally known photographic dispersion mediums, and the description in the following literature can be referred to. By these measures, the formation of the defect during growth can be substantially eliminated. In the present invention, it is preferable that the formation of the defect during the growth is not substantially performed even in the embodiment (2). Here, “substantially” means that the amount of the defect generated during the growth is 3 times the amount of the defect existing immediately before the growth.
0% or less, preferably 0 to 10%, more preferably 0 to
Refers to 2%. In this case, it is preferable to leave the shape control ability during grain growth. When the adsorbing force of the adsorbent is weakened, the ability to form the defects is first lost, and when it is further weakened, the shape controlling ability is also weakened, and the shape controlling ability is equivalent to that of ordinary gelatin. Therefore, this mode can be obtained by appropriately weakening the adsorption force. Here, the shape controllability means that the relationship between the silver potential and the shape of the AgBr particles is 10 mV or more, preferably 20 to 150 mV, more preferably 30 to 120 mV, most preferably 50 to 50 mV, as compared with the gelatin system. 100
It refers to the ability to give a relationship shifted to the lower potential side by mV.

In the case of (2), the added adsorbent acts not as the defect forming agent but as a shape controlling agent. The shape control ability will be described more directly as follows. When the tabular grains are grown under the same conditions as the presence of the control agent except for the following, the thickness increase during growth is 80% or less, preferably 0 to 60%, as compared with the case where the tabular grains are not present. More preferably, it indicates an aspect of 0 to 30%. However, it is assumed that the pH of the reaction solution can be independently selected from 1 to 11 under the optimum condition (the condition under which the increase in thickness is most suppressed). If the X ^- concentration can be freely selected,
The X ^- concentration condition for producing tabular grains having the same thickness is 1.5 times or more, preferably 2 to
It becomes 100 times.

The formation of the tabular grains in the presence of compound C ⁰ is described in EP 0 534 395 A1. However, the effect of compound A ⁰ in which two or more molecules of compound C ⁰ are covalently bonded in one molecule is more excellent.
It is assumed that the adsorption energy when compound C ⁰ is adsorbed on the {100} surface of AgX particles is EC ⁰ , that of compound A ⁰ in which n molecules of compound C ⁰ are bonded in one molecule is about nxEC ⁰ It is thought to be. That is, EC ⁰
It is considered that even if is small, the attraction force can be almost freely selected by selecting the value of n. Therefore, at the time of forming the crystal defect, a strong attraction force mode can be realized. on the other hand,
At the time of growth, the adsorptive power can be weakened by adjusting the pH to, for example, a pKa value of A ⁰ or less. (PKa-
If the pH is lowered to 1.0) or less, the adsorptive power can be almost eliminated. Therefore, there is an advantage that the attraction force can be freely adjusted in a wider range, and more excellent effects can be obtained. When A ⁰ is present at the time of growth as in the embodiment (2), C ⁰ having a weak adsorption force is selected from the beginning and n
By selecting a large value, it is possible to realize an aspect in which no new defects are formed, growth suppression is small, and the particle shape is controlled. As shown in FIG. 2, these molecules have a large number of adsorption sites as one molecule, the adsorption mode is maintained, and the particle shape control ability is maintained. Frequent adsorption and desorption are repeated. The desorption during Ag ⁺ and X ^- is because allowing the laminate.

On the other hand, the compound B ⁰ also strongly adsorbs on the AgX particles, and can form the crystal defects.
The growth characteristics can be controlled without substantially forming the defect. The action of forming the defect by the polyhydric alcohol compound and the action of controlling the shape of the tabular grains at the time of growth are not known so far, and the compound A ⁰
The effect is better than that. In this case, enough to increase the number of alcohol groups in one molecule (thus molecular weight increased), also, as the x ₁ value increases, the suction force is increased. Therefore, by adjusting these values, the attraction force can be adjusted. In one molecule both cases adsorbents A ^0, B ^0, higher the ratio of the non-adsorbed water-soluble functional group is increased, it weakens the suction force. The non-adsorbing, water-soluble functional groups help the adsorbent to freely swim in a non-adsorbing state in the reaction solution. The adsorbents A ⁰ and B ⁰ can be used in combination at a preferable ratio.

The manner of adsorption of the polyhydric alcohol compound on the surface of the AgX particles is complicated. PH at which C ⁰ is equal to or higher than pKa
When added under conditions, the C ⁰ is the A on the surface of the AgX particles.
adsorbed on the g ⁺ site to lower the ionic conductivity (σ _i ) of the AgX particles, but when the compound B ⁰ was adsorbed on the AgX particles, cubic AgBr particles, octahedral AgBr particles,
The σ _i of each of the cubic AgCl particles was increased. Such an adsorbent (an adsorbent that promotes the formation of {100} planes and increases the σ _i of the particles) is not known and is a new phenomenon. In particular, the increase in σ _i of the cubic AgBr particles was more than twice. Therefore, X on the particle surface
^- and by that interact strongly, it is considered to exhibit a strong shape controllability. However, the dielectric loss method was used for measuring σ _i . In the present invention, it is preferable that the defect formation is substantially completed before the start of grain growth. The amount of silver salt added before the start of grain growth is preferably 以下 or less, more preferably １ ／ or less, of the total amount of silver salt added during the entire grain formation. At the time of seeding, forming, and growing, it is more preferable to use gelatin in combination than to use the adsorbent alone. As the gelatin, known gelatin can be used, preferably 0.05 to 10 g / liter, more preferably 0.2 to 5 g / liter, and the ratio of (the weight of the adsorbent / the weight of gelatin) is preferably 0.01 to 0. 0.9, more preferably 0.03 to 0.5, and still more preferably 0.06 to 0.5.
0.3. The temperature at the time of forming the seed crystal can be 10 to 90 ° C., but the temperature at the time of forming the defects in 1) and 2) is 30 ° C.
-90 ° C is preferred, and 40-85 ° C is more preferred. Defect formation ability to AgCl particles of the compound B ₀ is 50
In the 85 ° C. region, the pH is maximum near pH 4, and decreases as the distance from the pH increases.

(V) Others In the present invention, the seed formation period refers to a period from the start of AgX nucleation to the start of temperature rise, and the ripening period refers to a period from the start of temperature rise to the start of growth. Indicates the period from the start of growth to the end of growth. The pH during the seeding, ripening and growth periods is 1 to 11, preferably 1.7 to 9, X ⁻
The concentration is 10 ^−0.9 mol / liter or less, preferably 10 ^−4.
The most preferable combination condition can be selected from the combinations of ^-10 to ^-1.2 . The oxidizing agent and the reducing agent are described in Chemical Dictionary, "Oxidizing Agents" and "Reducing Agents" by Tokyo Chemical Dojin (1994), Japanese Patent Application No. 6-102485, edited by The Chemical Society of Japan, New Experimental Chemistry, Volume 15, Oxidation and Reduction,
Maruzen (1976), Minoru Imoto, Lecture on Organic Reaction Mechanisms, Vol. 10, Tokyo Kagaku Doujin (1965), Yoshiro Ogata, Ed., Oxidation and Reduction of Organic Compounds, Nankodo (1963), No. 3134, Dictionary of Chemistry, Kyoritsu Publishing (1963)
Year), the description of “oxidizing agent” and “reducing agent” can be referred to.

The characteristics of the defect will be described below. Most of the defects are considered to be surface defects in a plane parallel to the main plane. It makes the tabular grains themselves below -100 ° C,
When photographed with a transmission electron microscope, as shown in FIG.
It is based on a line determined to be a dislocation line and a corresponding step on the edge surface. FIG. 3 is a typical example thereof. In the case of FIG. 3A, an edge surface between two dislocation lines has a step line 32 and has a growth promoting effect.
(B) In the case of the figure, the step line 33 on the edge surface has a growth promoting action. When the dislocation line grows at a high temperature, it is observed that the dislocation line moves little by little in the grain, for example, as shown in FIG. In the present invention, as shown in FIG.
20% or more, preferably 30 to 100%, or more of the total projected area of all tabular grains in the tabular grains having the extended dislocation lines.
%, More preferably 40 to 80%. The species corresponds to the species generated during seed formation. (IV)
In -1 3) (AgCl | AgI | and AgCl) gap species, AgCl nuclei I ^- For conversions reacted with the formed tabular grains, the step line 33 in FIG. 3 is a long trend. After forming the tabular grains, the entire grain surface can be covered with an AgX layer having a halogen composition different from the halogen composition on the grain surface. Its thickness is at least one atomic layer, preferably 5 to 10 ³ atomic layers. After forming the tabular grains, a rhodane salt or a halogen salt solution may be added to cause a halogen conversion reaction on the grain surface. The number of moles added is 0.1 to 10 of the number of moles of surface halogen atoms of all grains.
³ times. Examples of the halogen salts I ^-, Br ^- or I ^-, Br ^-, Cl ^- of refers to a mixture of two or more salt (mixing ratio can be selected any mixing ratio).

As a dispersion medium at the time of forming the particles, gelatin having a methionine content of 0 to 40 μmol / g;
The modified gelatin described in No. 4128 (for example, phthalated gelatin) can be preferably used. 20 to 1 of all dispersion media
It can be used in an amount of 00% by weight, preferably 50 to 100% by weight, more preferably 80 to 100% by weight. In addition, after the formation of the AgX ₀ nucleus, a treatment for reducing the ability of the dispersion medium to form a complex with Ag ⁺ to ¹ to 90% within 5 minutes before the completion of the growth, preferably the pH of the dispersion medium is 2 to 90%. 4, the complex forming ability of the 1.0% by weight aqueous solution is 3 to 70% of the original value.
It is preferable to carry out a treatment for reducing the temperature. Specifically, it is preferable to add an oxidizing agent, and it is preferable to add H ₂ O ₂ . These details are described in Japanese Patent Application Laid-Open No. 7-31142.
The description in No. 8 can be referred to. In the present invention, when producing the tabular grains, compound A ⁰ and / or compound B ⁰ are present, and the presence concentration thereof is such that the equilibrium crystal habit potential shift amount is 10 mV or more, preferably 20 to 150 mV, more preferably 30-120 mV, most preferably 50-10
Add at a concentration of 0 mV. In (IV) -1-2), the AgX ₀ nucleus does not substantially have the defect, but this can be confirmed by the following method. Cool the nuclei to low temperature (25-4
0 ° C.), without AgX solvent, at an addition rate that does not cause Ostwald ripening and also does not cause new nucleation.
Add g ⁺ and X ^- and grow all nuclei to about 0.3 μm diameter. The transmission electron micrograph image (TEM image) of the replica film of the formed particles is observed, and the ratio of the tabular particles is counted. When the gelatin of the above embodiment is used and grown under a lower degree of supersaturation, tabular grains having a higher aspect ratio can be obtained.

The obtained particles may be used as host particles to form epitaxial particles. Further, particles having dislocation lines therein may be formed using the particles as a core.
Alternatively, the particles may be used as a substrate, and AgX layers having a different halogen composition from the substrate may be laminated to produce various known particles having various particle structures. Regarding these, the description in the following literature can be referred to. Further, a shallow inner latent emulsion may be formed using the tabular grains as a core. Also, core / shell type particles can be formed. This is disclosed in JP-A-59-133.
Nos. 542 and 63-151618, U.S. Pat.
06,313, 3,317,322, 3,76
Nos. 1,276, 4,269,927 and 3,36
No. 7,778 can be referred to.

The silver halide tabular grains of the present invention are grains containing a large amount of silver iodide near the surface. As a method for measuring the silver iodide content distribution of silver halide grains, Japanese Patent Application No.
127328, WO92 / 10785, the ISS method (slow ion scattering spectroscopy) is used. In this measurement method, the silver halide grains of the present invention have a maximum silver iodide content near the grain surface, and this maximum value is at least 6 times, preferably at least 8 times the minimum silver iodide content inside the grains. , More preferably 10 times or more. Here, the silver iodide content is the ratio of the measured value of iodine atoms to the sum of the measured values of all halogen atoms.
Refers to the area within the atomic layer. The timing of adding iodine to the surface of the silver halide tabular grains of the present invention is not limited. Examples of the method of adding iodine include a method of adding an aqueous solution of an iodide salt (for example, KI) and a method of adding silver iodide-containing silver halide fine particles. It is preferred to add.

The term “silver halide fine grains containing silver iodide” as used in the present invention refers to those having a silver iodide content of 10 mol% to 100 mol%, preferably 20 mol% to 1 mol%.
00 mol% or less, most preferably 100 mol%
It is composed of silver iodide. In addition, the size refers to a particle having an average equivalent sphere diameter of 0.1 μm or less because it is necessary to grow the layer on the surface of the substrate particle by dissolution.
Preferably, the thickness is 0.05 μm or less. The average equivalent sphere diameter mentioned here is an average diameter when the particles are viewed as a sphere.

The silver halide grains used in the present invention preferably contain a coordination metal complex or a metal ion containing a metal of an element of Groups 3 to 14 of the periodic table 4, 5 and 6 in the crystal lattice. . The coordination metal complex or metal ion can be selected from the elements of Groups 3 to 14 of the Periodic Tables 4, 5, and 6 in which the group numbers are described from 1 to 18 from the left.
These metals can also be used as metal ions by using them as metal salts such as ammonium salts, acetates, nitrates, sulfates, phosphates, and hydroxides. By using a mononuclear coordination metal complex, or a dinuclear metal complex, or a polynuclear metal complex,
It is also possible to derive performance depending on the structure of the ligand or complex salt.

When a coordination metal complex is used, the ligand may be halo (X), aquo (H ₂ O), azide (N ₃ ), cyano (CN), cyanate (OCN), thiocyanate (SCN), Selenocyanate (SeCN), tellurocyanate (TeCN), nitrosyl (NO), thionitrosyl (NS), oxo (O), or carbonyl (C
O) and the like are preferably used. Also, U.S. Pat.
4,4′-, disclosed in the specification of JP-A-360,712.
Carbon such as bipyridine, pyrazine, thiazole, etc.
Organic ligands containing one or more carbon, carbon-hydrogen, or carbon-nitrogen-hydrogen bonds may be included.

The coordination metal complex or metal ion of the present invention may be mixed with water or a suitable water-miscible organic solvent (eg, alcohols, ethers, glycols, ketones, esters, amides, etc.). Can be added by dissolving in a mixed solvent of

The silver halide emulsion used in the present invention is:
It is preferred that a coordinating metal complex or metal ion be present during emulsion preparation, for example, during grain formation, desalting, chemical sensitization, and before coating. In the case of doping the grains, it is preferable to add them at the time of grain formation, when modifying the grain surface or when using as a chemical sensitizer, after grain formation and before the end of chemical sensitization. When doping the whole grain and only the core of the grain,
Alternatively, a method of doping only the shell portion, only the epitaxial portion, or only the base particle can be selected.

When the coordinating metal complex or metal ion of the present invention is doped into silver halide grains, they may be added directly to the reaction solution during silver halide grain formation, or may be added to form silver halide grains. It is preferable to add the compound to a solution containing halide ions or to a solution other than the above, and then to the solution for forming particles. Further, various addition methods may be combined. When doping the silver halide grains with the coordination metal complex or metal ion of the present invention,
It may be uniformly present inside the particles.
8936, JP-A-2-125245, JP-A-3-1
As disclosed in U.S. Pat. No. 8,884,37, a higher concentration of doping may be achieved by the grain surface phase. Also, U.S. Pat.
As disclosed in US Pat. Nos. 252,451 and 5,256,530, the grain surface phase may be modified by physical ripening with doped fine particles. Thus, a method of preparing doped fine particles, adding the fine particles and subjecting them to physical ripening to dope the silver halide particles is also preferable. Further, the above doping methods may be used in combination.

The coordination metal complex or metal ion satisfying the requirements of the present invention can be used in transition metal doping at the same concentration per mol of silver as conventionally used.
It can be contained in silver halide grains. In this connection, a very wide range of concentrations is known,
No. 1 per mole of silver disclosed in JP-A-1-1107129
0 ^-10 molar low concentrations, U.S. Patent 3,687,676
No. 3,690,891 in the high concentration range of ^10.sup.-3 mol per mol of silver disclosed in each of the specifications. The effective concentration will vary greatly depending on the halide content of the grains, the selected coordination metal complex or metal ion, its oxidation state, the type of ligand, if any, and the desired photographic effect.

The hydrogen ion concentration in the reaction solution when the coordination metal complex or metal ion used in the present invention is added is not particularly limited, but is preferably pH 3 or more.

The doping amount and doping ratio of the coordinating metal complex or metal ion in the silver halide grains in this study were determined by the atomic absorption method and the ICP method (inductively coupled method) for the doped coordinating metal complex or metal ion. Pl
asma Spectrometry; ICPMS (Inductively Coupled Plasma)
Mass spectrometry (inductively coupled plasma mass spectrometry) or the like can be used.

Specific examples of the coordinating metal complex or metal ion of the present invention include “Comprehensive Coordination Chemistry (Comprehensive Coordination Chemistry)”.
Chemistry ")" (Pergamon Press (1987)).

Next, the compounds represented by formulas (1) and (2) will be described in detail.

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In the formula, R ₁ represents a sulfoalkyl group or a carboxyalkyl group, and R ₂ represents an alkyl group, an alkenyl group or an aryl group. R ₃ represents an alkyl group. X represents a counter ion necessary for neutralizing the molecular charge, and n represents a number required for neutralization. However, when an inner salt is formed, n is 0. Z ₁ and Z ₂ each represent a nonmetallic atomic group which may have a substituent and is necessary for completing a benzene ring or a naphtho ring.

In the above formula, R ₂ is an alkyl group having 1 to 4 carbon atoms (for example, methyl group, ethyl group, propyl group, butyl group, etc.), a substituted alkyl group (for example, halogen atom, sulfo group, carboxy group, hydroxy group). Substituted carbon number 1
Alkenyl group having 2 to 4 carbon atoms (e.g., allyl group, 2-butenyl group, etc.) or 6 to 10 carbon atoms
(For example, phenyl). R ₁ represents a sulfoalkyl group or a carboxyalkyl group. The sulfoalkyl group preferably has 2 to 4 carbon atoms, for example, 2-sulfoethyl group, 3-sulfopropyl group,
Sulfobutyl, 4-sulfobutyl, 2- [3-sulfopropoxy] ethyl, 2-hydroxy-3-sulfopropyl, 3-sulfopropoxyethoxyethyl and the like.

As the carboxyalkyl group, one having 2 carbon atoms
To 5 are preferable, and examples thereof include a 2-carboxyethyl group, a 3-carboxypropyl group, a 4-carboxybutyl group, and a carboxymethyl group. R ₃ has 1 carbon atom
Of the alkyl groups 2 to 2, a methyl group and an ethyl group are preferred.
X is an anion, for example, a halogen atom (I, Br, Cl, etc.). Z ₁ and Z ₂ each represent a nonmetallic atom group necessary for forming a benzene ring or a naphthalene ring which may have a substituent in a condensed ring, and the substituent (for example, a halogen atom, a cyano group, an alkyl group, an alkoxy group) Group, aryl group, trifluoromethyl group, alkoxycarbonyl group, acyl group, etc.) may be substituted.

N represents 1 or 2, and when the dye forms an internal salt, n is 1. Incidentally, the sulfoalkyl group or carboxyalkyl group of R ₁ may form a salt with an alkali metal atom (for example, Na, K or the like) or ammonium, respectively.

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In the formula, R ₁₁ to R ₁₄ each represent an alkyl group, X ₁ represents an ion necessary for neutralizing the charge of the molecule, and n ₁ represents a number required for neutralization. However, when an inner salt is formed, n ₁ is 0. Z ₁₁ and Z ₁₂ each represent a group of nonmetallic atoms necessary to complete a benzene ring or a naphtho ring. R ₁₁ to R ₁₄ in the above formula have 1 to 1 carbon atoms.
4 alkyl groups (eg, methyl, ethyl, propyl, butyl), substituted alkyl groups having 1 to 5 carbon atoms (eg, hydroxyalkyl, alkoxyalkyl, halogenated alkyl, alkoxycarbonylalkyl, acyloxyalkyl, carboxyalkyl, sulfoalkyl, Alkoxyalkyl, etc. Specifically, hydroxyethyl, 2
-Methoxyethyl, 2-ethoxyethyl, 2-chloroethyl, 2,2,2-trifluoroethyl, 2,2,3
3-tetrafluoropropyl, methoxycarbonylmethyl, 2-methoxycarbonylethyl, 2-acetyloxyethyl, 3-acetyloxyethyl, carboxyethyl, carboxypropyl, sulfoethyl, sulfopropyl, sulfobutyl, etc.). In addition, the sulfoalkyl group and the carboxyalkyl group are alkali metals (for example, N
a, K) Salts and salts in the form of ammonium salts may be formed.

Z ₁₁ and Z ₁₂ represent a group of nonmetallic atoms necessary for forming a benzene ring or a naphthalene ring, and may have a substituent. As the substituent, for example, a halogen atom (Cl, Br, F), a trifluoromethyl group, or-
COOR group (R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms such as a methyl group, an ethyl group, a propyl group, a butyl group,
A pentyl group), an aryl group (for example, a phenyl group), and a cyano group.

X ₁ and n ₁ each represent X in the general formula (1)
And n are synonymous. The preferable addition amount of the compound of the general formula (1) is 10 ^-4 mol to 10 mol per 1 mol of silver halide.
^-2 mol, preferably 3 × 10 ^{−4 to} 3 × 10 ⁻³ mol.

The amount of the compound of the general formula (2) to be used is 1/2000 to 1/20 of the amount of the compound of the general formula (1).
Mol is preferable, and 1/1000 to 1/50 mol is particularly preferable. This is because if the amount is too large, desensitization due to a dye called intrinsic desensitization occurs, and fog under safelight tends to increase when used for, for example, a medical X-ray sensitive material. .

These dyes may be added at any time during the grain formation, the chemical sensitization step, and during coating, or may be added separately. In particular, as a method of adding a sensitizing dye during the formation of silver halide emulsion grains, US Pat. Nos. 4,225,666 and 4,82
No. 8,972 and JP-A-61-103,149 can be referred to. A method of adding a sensitizing dye in a desalting step of a silver halide emulsion is disclosed in European Patent 29
No. 1,339-A and JP-A-64-52,137 can be referred to. The method of adding a sensitizing dye in the chemical sensitization step can be referred to JP-A-59-48,756. In the present invention, the sensitizing dye of the present invention is most preferably added to an emulsion before a chemical sensitizer such as a selenium sensitizer, a sulfur sensitizer, or a gold sensitizer is added. It is particularly preferred that it is added before. It is also preferable to divide and add at various positions.

As a mode of adding the sensitizing dye, the sensitizing dye may be dissolved in a solvent such as water or methanol. A sensitizing dye dispersion which is mechanically pulverized and dispersed into fine particles having a size of 1 μm or less in an aqueous system under non-existent conditions may be used.

In the present invention, the compound of the general formula (1) and the compound of the general formula (2) are preferably added to the emulsion at the same time, and particularly preferably before the start of chemical sensitization. The term "before the start of chemical sensitization" means before the addition of a chemical sensitizer such as a selenium sensitizer, a sulfur sensitizer, or a gold sensitizer. Therefore, it may be added during the desalting, washing and dispersion steps during the formation of the particles. The molecular weight of the compound of the general formula (1) is preferably 680 or less, and particularly preferably 650 or less.
Hereinafter, specific examples of the general formulas (1) and (2) of the present invention are shown, but the present invention is not limited thereto.

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[0116]

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[0117]

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[0118]

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[0119]

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The compound of the formula (3) is described in detail in, for example, JP-A-52-69613.

Specific examples of the compound represented by the general formula (3) are shown below, but it should not be construed that the invention is limited thereto. 3-1 3-propargyl benzothiazolium bromide 3-2 5,6-dimethyl-3-propargyl benzothiazolium bromide 3-3 5-methoxy-6-methyl-3-propargyl benzothiazolium bromide 3-4 2-methyl-3-propargylbenzothiazolium bromide 3-5 5-chloro-2-methyl-3-propargylbenzothiazolium bromide 3-6 2-methyl-6-methoxy-3-propargylbenzothiazolium bromide 3-7 2-methyl-3-propargyl naphtho [1,2
-D] thiazolium bromide 3-8 2-methylthio-3-propargylbenzothiazolium bromide 3-9 2-methyl-3-propargyl-5-propargyloxybenzothiazolium bromide 3-10 1,4-bis (3-propargylbenzothiazolium-2) butane dibromide 3-11 2-ethyl-3-propargylbenzothiazolium bromide 3-12 3-methyl-2-propargyloxymethylbenzothiazolium iodide 3-13 3-propyl-2-propargyloxymethylbenzothiazolium chloride 3-14 2,3-dimethyl-5-propargyloxybenzothiazolium iodide 3-15 anhydro-2-methyl-5-propargyloxy-3-sulfo Propylbenzothiialium bromide 3-16 2-methyl 5-propargyloxy-3-propyl benzothiazolium potassium chloride 3-17 2-methyl -6-alpha-naphthylmethoxy -1-
Propargylquinolinium bromide 3-18 2,6-dimethyl-3-propargylbenzothiazolium bromide 3-19 5,6-dichloro-1-ethyl-2-methyl-
3-propargylbenzimidazolium bromide 3-20 2-propyl-3-propargylbenzothiazolium bromide 3-21 3- (3-butynyl) benzothiazolium thiocyanate 3-22 2,4-dimethyl-3-propargyltia Zolium bromide 3-23 2-methoxy-4-methyl-3-propargylthiazolium bromide 3-24 2-methyl-3-propargylthiazolinium iodide 3-25 2,4-dimethyl-3-propargyloxazo Lium iodide 3-26 2,5-methyl-4-carbomethoxy-3-propargyloxazolium iodide 3-27 2-methyl-4-phenyl-3-propargyloxazolium iodide 3-28 2-methyl -4,5-diphenyl-3-propargyloxazolium iodide 3-29 2-methyl-5-phenyl-3-propargylbenzoxazolium bromide 3-30 2-methyl-5-trifluoromethyl-3-propargylbenzoxazolium bromide 3-31 2-methyl-5-chloro-3- Propargyl benzoxazolium bromide 3-32 2,3,3-trimethyl-1-propargyl indolenium chloride 3-33 2-methyl-1-propargyl pyridinium chloride 3-34 2-methyl-3-propargyl benzoselenazolium Bromide 3-35 2-propargyloxymethyl-3-methylbenzoselenazolium bromide 3-36 2-methyl-3-propargyl-5-propargyloxybenzoselenazolium bromide 3-37 5-methyl-1-propargyltetrazolium bromide 3-38 N Le benzothiazolium iodide

The timing of adding these compounds is not particularly limited, but they are generally added in the chemical sensitization step and thereafter. Further, it may be added to another layer at the time of coating. The preferable addition amount is 1 × 10 ⁻⁶ mol or more, more preferably 1 × 10 ⁻⁵ mol or more and 1 × 10 ⁻² mol or less per 1 mol of silver halide.

The method of using the water-soluble mercapto compound represented by the general formula (4) and examples of the compound described in the present invention are described in, for example, JP-A-57-14836 and JP-A-59-7.
1047, 60-101530. Preferred examples of the compound are described below, but the present invention is not limited thereto.

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[0125]

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[0126]

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[0127]

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[0128]

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[0129]

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The preferable method of adding these compounds is not particularly limited, but there is a method of adding these compounds at the time of preparing a coating solution. This may be added to another layer. Or
The preferred addition amount is 1 × per mole of silver halide.
It is 10 ^-6 mol or more, more preferably 1 × 10 ^-5 mol or more and 1 × 10 ^-2 mol or less.

The photographic emulsion used in the present invention contains a water-soluble emulsion represented by the general formula (4) for the purpose of preventing fogging during the production process, storage or photographic processing of the photographic material or stabilizing photographic performance. Various compounds can be contained in addition to the mercapto compound. Azoles such as benzothiazolium salts, nitroindazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles , Benzotriazoles,
Nitrobenztriazoles, mercaptotetrazoles (especially 1-phenyl-5-mercaptotetrazole)
Azaindenes such as triazaindenes, tetraazaindenes (especially 4-hydroxy-substituted (1,3,3a, 7) tetraazaindenes), pentaazaindenes, etc .; benzenethiosulfonic acid Many compounds known as antifoggants or stabilizers can be added, such as benzenesulfinic acid, benzenesulfonamide, and the like. For example, U.S. Patent Nos. 3,954,474 and 3,982,947
And JP-B No. 52-28,660 can be used.

Regarding the preferred use examples of the thiosulfonic acid compound described in the present invention, see, for example,
191938 and the like.
General formulas (5), (6) preferably used in the present invention,
Specific examples of the thiosulfonic acid compound (7) are shown below. Preferred compound examples

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These compounds may be added during grain formation or during chemical sensitization. Further, it may be added to the coating solution at the time of coating, or may be added to the next layer. The addition amount of these compounds is preferably from 1 × 10 ⁻⁶ mol to 1 × 10 ⁻¹ mol, more preferably from 1 × 10 ⁻⁵ mol to 1 × 10 ⁻³ mol, per 1 mol of silver halide. It is.

The hydroquinone represented by the general formula (8) described in the present invention is described in, for example,
No.-72141 and JP-A-4-155330. Specific examples of the compound preferably used in the present invention are shown below, but the present invention is not limited thereto.

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[0140]

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[0141]

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[0142]

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[0143]

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The preferred timing of adding these compounds is not particularly limited, but they may be added to the coating solution during normal coating. Further, it may be added to the coating solution for the protective layer. The preferred addition amount is 1 × 10 ^-4 mol or more per mol of silver halide.

The emulsion of the present invention is preferably selenium-sensitized. Here, selenium sensitization is performed by a conventionally known method. That is, usually, an unstable selenium compound and / or a non-unstable selenium compound is added,
It is preferably carried out by stirring the emulsion at 40 ° C. or higher for a certain period of time. Selenium sensitization using an unstable selenium sensitizer described in JP-B-44-15748 is preferably used. Specific unstable selenium sensitizers include aliphatic isoselenocyanates such as allyl isoselenocyanate, selenoureas, selenoketones, selenoamides,
There are selenocarboxylic acids and esters, selenophosphates. Particularly preferred unstable selenium compounds are shown below.

I. Colloidal metal selenium II. Organic selenium compounds (a selenium atom is double-bonded to a carbon atom of an organic compound by a covalent bond) a isoselenocyanates, for example, aliphatic isoselenocyanates such as allyl isoselenocyanate b selenoureas (enol type For example, methyl, ethyl, propyl, isopropyl, butyl, hexyl octyl, dioctyl, tetramethyl, N- (β-carboxyethyl) -N ′, N′-dimethyl, N, N-dimethyl, diethyl, dimethyl, etc. Aliphatic selenoureas having one or more aromatic groups such as phenyl and tolyl; heterocyclic selenoureas having heterocyclic groups such as pyridyl and benzothiazolyl c selenoketones such as selenoacetone; Selenoacetophenone, selenoketo with alkyl group bonded to> C = Se Selenoamides such as selenoacetamide e selenocarboxylic acids and esters such as 2-selenopropionic acid, 3-selenobutyric acid, methyl-3-selenobutyrate and the like III. Others a selenides such as diethyl selena Id, diethyl diselenide,
B Selenophosphates, for example, tri-p-tolylselenophosphate, tri-n-butylselenophosphate, etc.

The preferred types of unstable selenium compounds have been described above, but these are not limiting. Those skilled in the art will note that an unstable selenium compound as a sensitizer of a photographic emulsion is not so important as long as selenium is unstable, and the structure of the selenium sensitizer molecule is not important. It is generally understood that the moieties carry selenium and have no role other than to cause them to be present in the emulsion in an unstable manner. In the present invention, an unstable selenium compound having such a broad concept is advantageously used. Tokiko Sho 46-
No. 4553, Japanese Patent Publication No. 52-34492 and Japanese Patent Publication No. 5
Selenium sensitization using the non-labile selenium sensitizer described in 2-34491 is also used. Non-labile selenium compounds include, for example, selenous acid, potassium selenocyanide, selenazoles, quaternary ammonium salts of selenazoles, diaryl selenide, diaryl diselenide, 2-thioselenazolidinedione, 2-selenooxolidine And thione and derivatives thereof. Japanese Patent Publication No. 52-38408
The non-labile selenium sensitizer and thioselenazolidinedione compound described in the above item are also effective.

Specific examples of preferred selenium sensitizers are shown below, but the present invention is not limited thereto.

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[0150]

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These selenium sensitizers are dissolved in water or an organic solvent such as methanol or ethanol alone or in a mixed solvent, and added during chemical sensitization. Preferably, it is added before the start of chemical sensitization. The selenium sensitizer used is not limited to one, and two or more of the above-described selenium sensitizers can be used in combination. It is preferable to use a combination of an unstable selenium compound and a non-unstable selenium compound. The addition amount of the selenium sensitizer used in the present invention varies depending on the activity of the selenium sensitizer used, the type and size of silver halide, the ripening temperature and time, but preferably 1 mol of silver halide. 1 × 10 ^-8 per
More than mole. More preferably, 1 × 10 ⁻⁷ mol or more 1
× 10 ^-5 mol or less. The temperature for chemical ripening when using a selenium sensitizer is preferably 45 ° C. or higher. More preferably, it is 50 ° C. or more and 80 ° C. or less. pAg and p
H is optional. For example, the effects of the present invention can be obtained in a wide range of pH from 4 to 9.

The chemical sensitization is more effective when carried out in the presence of a silver halide solvent. Examples of the silver halide solvent that can be used in the present invention include U.S. Pat.
Nos. 271,157, 3,531,289, 3,574,628, JP-A-54-1019, and 5
(A) Organic thioethers described in JP-A-4-158917, JP-A-53-82408 and JP-A-55-7773.
(B) thiourea derivatives described in JP-A Nos. 7-55-2982, etc .; and (c) thiocarbonyl groups sandwiched between an oxygen or sulfur atom and a nitrogen atom described in JP-A-53-144319. Silver halide solvent having
(D) imidazoles described in -100717,
(E) sulfite, (f) thiocyanate and the like. Particularly preferred solvents include thiocyanate and tetramethylthiourea. The amount of the solvent used varies depending on the kind. For example, in the case of thiocyanate, the preferred amount is 1 × 10 ⁻⁴ mol to 1 × 10 ⁻² mol per mol of silver halide.

The silver halide photographic emulsion of the present invention can provide a higher sensitivity by using gold sensitization in chemical sensitization.
Low fog can be achieved. It is preferable to further use sulfur sensitization if necessary. Sulfur sensitization is usually carried out at a high temperature, preferably at 40 ° C, by adding a sulfur sensitizer.
The above is carried out by stirring the emulsion for a certain time.
The gold sensitization is usually carried out by adding a gold sensitizer and stirring the emulsion at a high temperature, preferably at 40 ° C. or higher for a certain period of time.

For the above-mentioned sulfur sensitization, known sulfur sensitizers can be used. Examples include thiosulfate, allyl thiocarbamide thiourea, allyl isothiocyanate, cystine, p-toluene thiosulfonate, rhodanine and the like. Other US Patent No. 1,574
No. 944, No. 2,410,689, No. 2,27
No. 8,947, No. 2,728,668, No. 3,5
Nos. 01,313 and 3,656,955,
German Patent 1,422,869, JP-B-56-249
No. 37, JP-A-55-45016 and the like can also be used. The sulfur sensitizer may be added in an amount sufficient to effectively increase the sensitivity of the emulsion. This amount varies over a considerable range under various conditions such as pH, temperature, silver halide grain size, etc., but is not less than 1 × 10 ⁻⁷ mol per mol of silver halide.
It is preferably at most 5 × 10 ⁻⁵ mol.

As the gold sensitizer for the gold sensitization, the oxidation number of gold may be +1 or +3, and gold compounds usually used as gold sensitizers can be used. Representative examples include chloroaurate, potassium chloroaurate, auric trichloride, potassium auric thiocyanate, potassium iodooleate, tetracyano auric acidide, ammonium aurothiocyanate, pyridyl trichlorogold, and the like. Although the amount of the gold sensitizer to be added varies depending on various conditions, the standard is preferably 1 × 10 ⁻⁷ mol or more and 5 × 10 ⁻⁵ mol or less per mol of silver halide.

At the time of chemical ripening, there is no particular limitation on the timing and order of addition of a silver halide solvent and a gold sensitizer used in combination with a selenium sensitizer or tellurium sensitizer. The compounds can be added simultaneously (preferably) or during the course of chemical ripening, or at different times. In addition, the above compound may be added by dissolving the above compound in water or an organic solvent miscible with water, for example, a single solution or a mixed solution of methanol, ethanol, acetone or the like.

The method of reduction sensitization used in the present invention may be, for example, as a so-called reduction sensitizer, in addition to ascorbic acid, thiourea dioxide, stannous chloride, aminoiminomethanesulfinic acid, hydrazine derivatives, borane compounds, Reduction sensitization can be performed using a silane compound or a polyamine compound. Further, the pH of the emulsion was 7 or more or the pAg was 8.3.
Reduction sensitization can be achieved by holding and aging the following. Further, reduction sensitization can be achieved by introducing a single addition portion of silver ions during grain formation. However, from the viewpoint of reducing the influence on grain formation and crystal growth and performing controlled reduction sensitization, reduction sensitization using ascorbic acid and its derivatives or thiourea dioxide is preferred. Used amount of the reduction sensitizer may vary depending reducing agent species 10 ^-7 mol to 10 ^-2
A mol / mol Ag amount is preferably used. Reduction sensitization is
It may be carried out at any point during grain formation, and may be carried out at any time after grain formation but before chemical sensitization.

In the present invention, tellurium sensitization can also be preferably used. As tellurium sensitizers, U.S. Pat.
623,499, 3,320,069, 3,7
72,031; British Patent No. 235,211;
121,496, 1,295,462, 1,3
96,696; Canadian Patent No. 800,958; Journal of Chemical Society Chemicals.
Communication (J.Chem.Soc.Chem.Commun.) 635 (1
980), ibid 1102 (1979), ibid 645 (1979), and the compounds described in Journal of Chemical Society Parkin Transaction (J. Chem. Soc. Perkin Trans.) 1, 2191 (198). Is preferred.

Specific tellurium sensitizers include colloidal tellurium and telluroureas (for example, allyl tellurourea,
N, N-dimethyltellurourea, tetramethyltellurourea, N-carboxyethyl-N ′, N′-dimethyltellurourea, N, N′-dimethylethylenetellurourea, N,
N'-diphenylethylene tellurourea), isotellurocyanates (e.g. allyl isotellurocyanate), telluro ketones (e.g. telluroacetone, telluroacetophenone), telluroamides (e.g. telluroacetamide, N, N-dimethyltellurobenzamide), tellurohydrazide (Eg, N, N ′, N′-trimethyltellurobenzhydrazide), telluroester (eg, t-butyl-t-hexyltelluroester), phosphine tellurides (eg, tributylphosphine telluride, tricyclohexylphosphine telluride, triisopropyl) Phosphine telluride, butyl-diisopropylphosphine telluride, dibutylphenylphosphine telluride) and other tellurium compounds (for example, the negatively charged tellurium described in GB 1,295,462). Doion containing gelatin, Potassium nitrosium telluride, Potassium nitrosium tellurocyanate diisocyanate, tellurocarbonyl penta isethionate, sodium salt, allyl tellurocyanate)
And the like.

The amount of the tellurium sensitizer used in the present invention varies depending on the silver halide grains to be used, the conditions of chemical ripening and the like, but is generally from 10 ^-8 to 1 mol per mol of silver halide.
It is used in an amount of 10 ⁻² mol, preferably about 10 ^{−7 to} 5 × 10 ⁻³ mol.

The conditions for chemical sensitization in the present invention include:
Although there is no particular limitation, the pAg is 6 to 11, preferably 7 to 10, and the temperature is 40 to 95 ° C, preferably 45 to 85 ° C.

In the present invention, it is preferable to use a noble metal sensitizer such as gold, platinum, palladium or iridium in combination. In particular, it is preferable to also perform gold sensitization agent include chloroauric acid, potassium chloroaurate, potassium aurithiocyanate, gold sulfide, gold selenide, and the like, per mol of silver halide, 10 ^{- About 7} to 10 ^-2 mol can be used.

In the present invention, it is preferable to further use a sulfur sensitizer in combination. Specific examples thereof include known unstable sulfur compounds such as thiosulfates (eg, hypo), thioureas (eg, diphenylthiourea, triethylurea, allylthiourea), rhodanines and the like. About 10 ^-7 to 10 ^-2 mol per mol can be used.

The emulsion layer of the silver halide photographic light-sensitive material of the present invention may contain ordinary silver halide grains in addition to tabular silver halide grains. In this case, the silver halide may be any of silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide and silver chloride. They are,
P. Glafkides Chimie et Physique Photographique (
Paul Montel 1967), GFDuffin Photo
graphic Emulsion Chemistry (The Focal Press 19
66), Making and Coating P by VLZelikman et al
hotographic Emulsion (The Focal Press 1964
Year)). That is, any of an acidic method, a neutral method, an ammonium method and the like may be used, and a method of reacting a soluble silver salt and a soluble halide may be any of a one-side mixing method, a double-mixing method, a combination thereof and the like. . Method of forming grains in excess of silver ions (so-called reverse mixing method)
Can also be used. As one type of the double jet method, a method in which pAg in a liquid phase in which silver halide is formed is kept constant, that is, a so-called controlled double jet method can be used.

In the course of silver halide grain formation or physical ripening, cadmium salts, zinc salts, lead salts, thallium salts, iridium salts or complex salts thereof, rhodium salts or complex salts thereof, iron salts or complex salts thereof, etc. may be used. Good.

In the emulsion layer of the present invention, the emulsion layer contains 1 mol per mol of silver.
0 × 10 ⁻³ mol or more and less than 2.0 × 10 ⁻² mol may be contained. The thiocyanic acid compound may be added in any process of grain formation, physical ripening, grain growth, chemical sensitization and coating, but is preferably added before chemical sensitization. As the thiocyanate compound used during the preparation of the silver halide emulsion in the present invention, a water-soluble salt such as a metal thiocyanate or an ammonium salt can be generally used. Care should be taken to use a metal element that does not affect, and potassium and sodium salts are preferred. Further, a sparingly soluble salt such as AgSCN may be added in the form of fine particles.

In the present invention, it is also preferable to carry out chemical sensitization in the presence of a nucleic acid or a decomposition product thereof before completion of chemical sensitization. Regarding nucleic acids or their degradation products,
No. 67541 can be used. The nucleic acid used in the present invention includes deoxyribonucleic acid (DN)
A) and ribonucleic acid (RNA), and examples of the nucleic acid degradation products include those undergoing degradation and simple substances such as adenine, guanine, uracil, cytosine, and thymine.
In particular, adenine is a preferred nucleolytic product. These can be used alone or in combination. In this case, it goes without saying that the nucleic acid and the nucleic acid degradation product may be used in combination. The amount of the nucleic acid or the decomposition product thereof varies depending on the type of the nucleic acid decomposition product, but is in the range of 20 mg or more, preferably 100 mg to 1 g per mol of silver halide. As described above, when these nucleic acids or nucleic acid degradation products are used alone or in combination of two or more, the total amount of additions described above is sufficient.

The coated silver amount of the light-sensitive material of the present invention is 2.0 g / m ² or less per one side. Preferably, it is 0.8 g / m ² or more and 1.7 g / m ² or less. More preferably, 1.
0 g / m ² or more and 1.5 g / m ² or less.

In the light-sensitive material of the present invention, an infrared-absorbing dye is used in order to provide a sensor provided for detecting that the light-sensitive material has been inserted and carried into an automatic developing machine or the like to have detectability. It is preferable to include them. The infrared absorbing dye preferably used in the present invention will be described below. The infrared absorbing dye for sensor detection needs to satisfy the following conditions. (1) To have appropriate spectral absorption according to the infrared sensor. (2) Photochemically inert. That is, sensitivity, latent image regression, fogging and the like should not be adversely affected on the performance of the halogenated photographic emulsion. (3) No harmful coloring is left on the processed photographic light-sensitive material. (4) Excellent stability over time in a solution or a photographic material.

In particular, decolorizable dyes have been used to satisfy the condition (3). However, if the decolorizable dyes are used, the needs such as rapid processing and reduction of replenishment of the processing solution cannot be met, and decolorization is also required. Under the present circumstances, the dyes do not satisfy the condition (2) because they often diffuse into other layers. Further, the dye diffused to other layers or the dye added to the surface protective layer in advance is used for the rollers of the automatic transporting machine to which the photographic material contacts,
There is also a problem that transfer to a fluorescent intensifying screen causes contamination. Preferred examples of the compound are shown in formula (15). General formula (15)

[0172]

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In the formula, R ¹⁰ and R ¹¹ each represent an alkyl group, an aralkyl group or an alkenyl group, and R ¹² and R ¹⁴ each represent a hydrogen atom or an atom necessary for forming a 5- or 6-membered ring by bonding to each other. R ¹³ represents an aryl group, —N
^{(R 19) (R 20)} , - represents SR ²¹ or -OR ^22, R
¹⁹ represents a hydrogen atom, an alkyl group or an aryl group,
R ²⁰ represents an aryl group, a sulfonyl group or an acyl group. R ¹⁹ and R ²⁰ may be linked to each other to form a ring. R ²¹ and R ²² each represent an aryl group. R ¹⁵ , R
¹⁶ , R ¹⁷ and R ¹⁸ each represent an alkyl group, and R ¹⁵ and R ¹⁶ and R ¹⁷ and R ¹⁸ may be linked to form a ring. The general formula (15) will be described in detail. R ¹⁰ , R ¹¹ , R ¹⁵ , R ¹⁶ ,
The alkyl group represented by R ¹⁷ , R ¹⁸ and R ¹⁹ has 1 carbon atom.
To 10, more preferably 1 to 6 unsubstituted alkyl groups (eg, methyl, ethyl, propyl, butyl, isobutyl, pentyl, hexyl). R ¹⁵ and R ¹⁶ , R
¹⁷ and R ¹⁸ may be linked to each other to form a ring (for example, cyclohexane or the like). The alkenyl group and aralkyl group represented by R ¹⁰ and R ¹¹ are preferably aralkyl groups having 7 to 12 carbon atoms (eg, benzyl, phenylethyl), and substituents (eg, methyl, carboxy, alkoxy, chloro atoms) ) May be included. R ¹³ ,
The aryl group represented by R ¹⁹ , R ²⁰ , R ²¹ and R ²² is-
N (R ⁶ ) (R ⁷ ), SR ⁸ or —OR ⁹ is preferable,
N (R ⁶ ) (R ⁷ ) is particularly preferred. R ⁶ is preferably an alkyl group or an aryl group, particularly preferably an aryl group. In —N (R ⁶ ) (R ⁷ ), one of R ⁶ and R ⁷ is preferably an aryl group, and more preferably, both R ⁶ and R ⁷ are an aryl group. R ⁶ ,
R ⁷ is most preferably a phenyl group.

The aryl group represented by R ⁶ and R ⁷ is 6 to
Those having 12 carbon atoms are preferred, and include a phenyl group or naphthyl. The aryl group may be substituted, and any substituent may be used as long as it does not dissolve the dye during development. For example, a methyl group, an ethyl group,
Examples thereof include a chlorine atom, a methoxy group, and a methoxycarbonyl group.

The sulfonyl group represented by R ⁷ is 1 to 10
An alkyl or aryl sulfonyl group having the number of carbon atoms of, for example, a mesyl group, a tosyl group, a benzenesulfonyl group, and an ethanesulfonyl group can be given. The acyl group represented by R ⁷ is preferably an alkyl or aryl acyl group having 2 to 10 carbon atoms, and examples thereof include an acetyl group, a propionyl group, and a benzoyl group.

R ⁶ and R ⁷ may be linked to each other to form a 5- or 6-membered ring. Examples of such a ring include piperidine, morpholine, piperazine and the like, and these rings have substituents (for example, methyl, phenyl,
Ethoxycarbonyl).

The sulfonyl group or acyl group represented by R ²⁰ has the same meaning as the sulfonyl group or acyl group for R ⁷ .

Examples of the halogen atom for R ¹³ include F, Cl and Br. Ring formation by R ¹⁹ and R ²⁰ is synonymous with ring formation by R ⁶ and R ⁷ .

R ¹⁰ and R ¹¹ are preferably an alkyl group. Preferably, R ¹² and R ¹⁴ are linked to form a 5- or 6-membered ring. R ¹³ is ^{-N (R 19) (R 20} ), - SR 21
Or preferably ^{-OR 22, -N (R 19)} (R 20) is particularly preferred. R ¹⁹ is preferably an alkyl group or an aryl group. R ¹⁹ of -N in ^{R 13 (R 19) (R} 20), R
²⁰ preferably may either have an aryl group, R ¹⁹
And more preferably R ²⁰ are both an aryl group. Most preferably, R ¹⁹ and R ²⁰ are phenyl groups.

Preferably, R ¹⁰ and R ¹¹ are alkyl groups, and R ¹³ is —N (R ¹⁹ ) (R ²⁰ ), —S
The case for R ²¹ or -OR ^22. More preferably, R ¹² and R ¹⁴ are linked to form a 5- or 6-membered ring, and R ¹³ is —N (R ¹⁹ ) (R ²⁰ ). Among them particularly preferred a case R ^19, R ²⁰ is either one of the aryl group, most preferably R ¹⁹ and R ²⁰ are both an aryl group.

Specific examples of the infrared absorbing dye are shown below, but the present invention is not limited thereto.

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[0183]

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[0184]

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[0185]

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[0186]

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[0187]

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[0188]

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[0189]

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[0190]

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The dyes represented by the general formula (15) of the present invention (hereinafter referred to as dyes of the present invention) are described in US Pat. No. 3,671,648, US Pat. No. 2,095,854, JP-A-6-43583 and the like. Can be synthesized with reference to the synthesis example of

(Synthesis of Compound 1) 9.8 g of 1,2,3,3-tetramethyl-5-carboxyindolenium p-toluenesulfonate, 1- [2,5-bis (anilinomethylene) cyclopentylidene ] -Diphenylanilinium tetrafluoroborate (6 g), ethyl alcohol (100 ml), acetic anhydride (5 ml) and triethylamine (10 ml) were stirred at an external temperature of 100 ° C for 1 hour, and the precipitated crystals were separated by filtration. Recrystallization was performed with 100 ml of methyl alcohol to obtain 7.3 g of compound 1. Melting point: 270 ° C. or higher, λmax: 809.1 nm ε:
1.57 × 10 ⁵ (dimethyl sulfoxide) Other compounds can be similarly synthesized.

The infrared absorbing dye is a non-eluting dye, that is, a dye having substantially no change in spectrum before and after development processing. Further, the above-mentioned infrared absorbing dye has a λm
ax is about 700 to 1100 nm, more preferably 800
１０００1000 nm, more preferably 850 nm〜950 nm
And there is little absorption in the visible region, or even if there is, it is harmless to photographic properties.

In the present invention, the infrared absorbing dye is preferably used in the form of solid fine particles dispersed therein. In order to make the solid fine particles dispersed, JP-A-52-92716, International Publication 88
The method can be performed using a dispersing machine such as a ball mill, a vibration ball mill, a planetary ball mill, a sand mill, a colloid mill, a jet mill, and a roller mill described in US Pat.

In each case, a solvent (eg, water, alcohol, etc.) may be allowed to coexist, and it is preferable to use a surfactant for dispersion. As the dispersing surfactant, anionic surfactants described in JP-A-52-92716 and WO 88/04794 are mainly used. In addition, an anionic polymer, a nonionic or cationic surfactant can be used as necessary. Preferably, it is an anionic surfactant. Also,
After dissolving the infrared absorbing dye in a suitable solvent, a poor solvent for the dye may be added to obtain a fine particle powder. Also in this case, the above-mentioned surfactant for dispersion may be used. Or pH
May be dissolved first by controlling the pH, followed by changing the pH for microcrystallization.

The fine particles of the infrared absorbing dye dispersed in the dispersion have an average particle size of 0.005 to 10 μm, preferably 0.01 to 10 μm.
To 1 μm, more preferably 0.01 to 0.5 μm, and in some cases, preferably 0.01 to 0.1 μm. Solid fine particle dispersion of the infrared absorbing dyes in the present invention is used is applied in the range of ^{0.001g / m 2 ~1g / m 2} , preferably, 0.005 g / m ² to 0.5 g
/ M ² , particularly in the range of 0.005 g / m ^{2 to} 0.1 g / m ² .

In the present invention, the hydrophilic colloid layer to which the fine particles of the infrared absorbing dye are added must not be a surface protective layer (top layer) or an emulsion layer. When a dye is added to the surface protective layer (uppermost layer), there is a problem in that transfer of the dye is caused between a roller of an automatic transporter, a roller of an automatic developing machine, and adjacent photographic materials.

On the other hand, when the dye is added to the silver halide emulsion layer, the partially dissolved dye is adsorbed on the silver halide and sensitizes the color, thereby deteriorating the safelight property and causing desensitization in the exposure wavelength range. It often happened. In the present invention, as an additional layer of the infrared absorbing dye, an intermediate layer between the surface protective layer and the emulsion layer, or an intermediate layer provided between a plurality of emulsion layers, an undercoat layer of the emulsion layer and the support. A hydrophilic colloid layer such as an undercoat layer provided between the layers or a subbing layer itself of a support can be considered. The coating amount of gelatin in the infrared-absorbing dye-containing layer is preferably from 0.02 g / m ^{2 to} 1 g / m ² , and more preferably from 0.1 g / m ^{2 to} 0.6 g / m ^2.
m ² or less.

An optical sensor uses a light emitting diode or a semiconductor laser emitting light at a wavelength of 700 nm or more as a light source.
It has a light receiving sensitivity peak near 900 nm, and
It is used in combination with a light receiving element having a sensitivity range of 200 nm. As light emitting diodes, GL-514 (manufactured by Sharp Corporation) and TLN108 (manufactured by Toshiba Corporation)
For example, PT501 (made by Sharp Corporation) and TPS601A (made by Toshiba Corporation)
And the like. Automatic devices using such an optical sensor system are sold by various companies.

For the light-sensitive material of the present invention, a polymer latex obtained by polymerizing the following hardly soluble monomers can be preferably used. The monomer according to the present invention will be described.

The above-mentioned monomer is preferably an acrylate compound, particularly preferably when both an acrylate compound and a methacrylate compound are used. The particle size of the polymer latex is preferably 300 nm or less.

Further, the polymer latex is preferably polymerized in the presence of a water-soluble polymer and / or a surfactant.

As the surfactant used in the polymerization of the polymer latex, any of anionic surfactants, nonionic surfactants, cationic surfactants and amphoteric surfactants can be used. Anionic surfactants and / or nonionic surfactants. As the anionic surfactant and the nonionic surfactant, various compounds known in the art can be used, and an anionic surfactant is particularly preferably used.

The water-soluble polymer used in the polymerization of the polymer latex includes, for example, a synthetic polymer and a natural water-soluble polymer. In the present invention, any of them can be preferably used. Among them, synthetic water-soluble polymers include those having a nonionic group in the molecular structure, those having an anionic group, those having a cationic group, those having a nonionic group and an anionic group, those having a nonionic Examples include those having a group and a cationic group, those having an anionic group and a cationic group, and the like. Examples of the nonionic group include an ether group, an alkylene oxide group, a hydroxy group, an amide group, and an amino group. Examples of the anionic group include a carboxylic acid group or a salt thereof, a phosphoric acid group or a salt thereof, a sulfonic acid group or a salt thereof, and the like. Examples of the cationic group include a quaternary ammonium base and a tertiary amino group.

Also, natural water-soluble polymers include those having a nonionic group, those having an anionic group, those having a cationic group, those having a nonionic group and an anionic group, Examples include those having a nonionic group and a cationic group, those having an anionic group and a cationic group, and the like.

The water-soluble polymer used in the polymerization of the polymer latex may be any of a synthetic water-soluble polymer and a natural water-soluble polymer having an anionic group and those having a nonionic group and an anionic group. Can be preferably used.

The water-soluble polymer is water at 20 ° C.
It is sufficient to dissolve 0.05 g or more per 0 g, and preferably 0.1 g or more.

As a natural water-soluble polymer, a comprehensive technical data collection of water-soluble polymer water-dispersed resin (Management Development Center)
Preferred are lignin, starch, pullulan, cellulose, dextran, dextrin, glycogen, alginic acid, gelatin, collagen, guar gum, gum arabic, laminaran, lichenin, nigran and the like and derivatives thereof. is there. As the derivative of the natural water-soluble polymer, sulfonated, carboxylated, phosphorylated, sulfoalkylated, carboxyalkylated, alkylphosphorylated, and salts thereof are preferably used. Particularly preferred are glucose, gelatin, dextran, cellulose and derivatives thereof.

The polymer latex can be easily produced by various methods. For example, there is a method of redispersing a polymer obtained by an emulsion polymerization method, a solution polymerization, a bulk polymerization, or the like.

In the emulsion polymerization method, water is used as a dispersing medium, and 10 to 50% by weight of the monomer and 0.0
Using 5 to 5% by weight of a polymerization initiator and 0.1 to 20% by weight of a dispersant, about 30 to 100 ° C, preferably 60 to 90 ° C.
For 3 to 8 hours with stirring.
The concentration of the monomer, the amount of the initiator, the reaction temperature, the time and the like can be widely and easily changed.

Examples of the initiator include water-soluble peroxides (eg, potassium persulfate, ammonium persulfate, etc.) and water-soluble azo compounds (eg, 2,2′-azobis- (2-aminodipropane) -hydrochloride, etc.) Can be mentioned.

Examples of the dispersant include an anionic surfactant, a nonionic surfactant, a cationic surfactant, and an amphoteric surfactant in addition to the water-soluble polymer. These may be used alone or in combination. Preferably, a combination of a water-soluble polymer and a nonionic or anionic surfactant is used. In the solution polymerization, a mixture of monomers (usually 40% by weight or less, preferably 10 to 25% by weight, based on the solvent) is mixed with an appropriate concentration of a monomer in an appropriate solvent (eg, ethanol, methanol, water, etc.). Polymerization initiator (for example,
Benzoyl peroxide, azobisisobutyronitrile, ammonium persulfate, etc.) at an appropriate temperature (eg, 40
To 120 ° C, preferably 50 to 100 ° C) to carry out the copolymerization reaction. Thereafter, the reaction mixture is poured into a medium that does not dissolve the formed copolymer, the product is allowed to settle, and then the unreacted mixture is separated and removed by drying.

Next, the copolymer is dissolved in a solvent that dissolves but is not soluble in water (eg, ethyl acetate, butanol, etc.), and is vigorously dispersed in the presence of a dispersant (eg, a surfactant, a water-soluble polymer, etc.). Is distilled off to obtain a polymer latex.

Regarding the method of synthesizing the polymer latex,
U.S. Pat. Nos. 2,852,386 and 2,853,457
Nos. 3,411,911 and 3,411,912
No. 4,197,127, Belgian Patent 688,8
Nos. 82, 691, 360, 712, 823, JP-B-45-5331, JP-A-60-18540, JP-A-5130-21717, JP-A-58-137831, and JP-A-5
No. 5,50,240.

The average particle size of the polymer latex is 0.5
Any one having a thickness of from 300 to 300 nm can be preferably used, and a thickness of from 30 to 250 nm is particularly preferred.

The particle size of the polymer latex can be measured by an electron micrograph, a soap titration method, a light scattering method, or a centrifugal sedimentation method described in Chemistry of Polymer Latex (Polymer Publishing Association, 1973). The light scattering method is preferably used. As an apparatus for the light scattering method, DLS700 is used.
(Manufactured by Otsuka Electronics Co., Ltd.).

The molecular weight is not particularly limited, but is preferably from 1,000 to 1,000,000, more preferably from 2,000 to 500,000 in total molecular weight.

In the present invention, the polymer latex can be contained in the photographic component layer as it is or after being dispersed in water.

Specific examples of the polymer latex and the dispersant used for its synthesis are shown below. The suffix of the monomer unit indicates the content percentage of each.

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[0221]

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[0222]

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[0223]

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[0224]

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A polymer latex may be added to any layer of the silver halide photographic light-sensitive material of the present invention. It may be added to only one of the silver halide emulsion layer and the other hydrophilic colloid layer, but preferably added to both. More preferably, it is added to both the silver halide emulsion layer and the hydrophilic colloid layer furthest from the support. In order to further exert the effects of the present invention, it is most preferable to add it to the emulsion layer and the protective layer on the uppermost layer thereof.

The amount of the polymer latex added is preferably in the range of 5 to 70% by weight based on the amount of the binder in the photographic constituent layer. When the amount is less than this range, the effect of the present invention is poor, and when it is too large, photographic performance is degraded. When the polymer latex is added to both the emulsion layer and the protective layer, the ratio of the added amount of the protective layer / the added amount of the emulsion layer is preferably in the range of 0.3 to 0.4. The photosensitive material of the present invention preferably contains colloidal silica,
An embodiment in which colloidal silica is contained in a photosensitive silver halide emulsion layer is preferred.

The colloidal silica preferably has an average particle size of 0.1 μm or less, and preferably has a mean particle size of 0.005 to 0.08 μm.
Is particularly preferred.

The main component of the colloidal silica is composed of silicon dioxide, and may contain an aluminate as a minor component. Examples of the aluminate include sodium aluminate and potassium aluminate.

These colloidal silicas may contain, as a stabilizer, inorganic salts such as sodium hydroxide, potassium hydroxide, lithium hydroxide and ammonium hydroxide, and organic salts such as tetramethylammonium ion.

Specific examples of colloidal silica include, for example,
Ludox AM, from EIDu Pont de Nemouvs & Co (USA)
Ludox AS, Ludox LS, Ludox TM, Ludox HS, etc., Snowtex 20 and Snowtex 3 from Nissan Chemical Industries, Ltd.
Syton C-30, SytonZOO from Mons anto Co (USA) with trade names such as 0, Snowtex C and Snowtex O
Nalco Chem Co from Nalcoag-1060
, Nalcoag-ID 21-64 and the like, which are easily available.

The use amount of the above-mentioned colloidal silica to be added to the light-sensitive material of the present invention may be 0.05 to 1.5 g / m ² ,
More preferably, it is 0.1% to 1.0 g / m ² . At the time of addition, those appropriately diluted with water or a hydrophilic solvent may be added, and the timing of addition to the emulsion is not particularly limited, but it is preferably added to any step after the completion of chemical ripening and before coating. .

Although the amount of silver relative to the gelatin binder is not particularly limited, it is preferable to use silver in a ratio of (weight) / gelatin (weight) in the range of 0.01 to 5.0 depending on the purpose. .

When the silver halide photographic material has a plurality of silver halide emulsion layers, the plurality of silver halide emulsion layers may be provided on one side of the support. It may be provided. Colloidal silica may be contained in all of the plurality of silver halide emulsion layers, or may be contained in some of the silver halide emulsion layers. When colloidal silica is contained in a part of the silver halide emulsion layer, it is preferred that the silver halide emulsion layer farthest from the support contains colloidal silica.

The light-sensitive material of the present invention has the following general formula (I-
It is preferable to include any of the compounds represented by 1), (I-2) and (I-3). General formula (I-1)

[0235]

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Formula (I-2)

[0237]

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Formula (I-3)

[0239]

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In the formula, R ₁ represents a substituted or unsubstituted alkyl group, alkenyl group or aryl group having 1 to 30 carbon atoms,
Is -O- group, -S- group, -COO- group, -N (R ₁₀₎ -
A —CO—N (R ₁₀ ) — group or a —SO ₂ N (R ₁₀ ) — group (where R ₁₀ represents a hydrogen atom or a substituted or unsubstituted alkyl group). R ₂ , R ₃ , R ₇ and R _{9 each} represent a hydrogen atom, a substituted or unsubstituted alkyl group, an aryl group,
Represents an alkoxy group, a halogen atom, an acyl group, an amide group, a sulfonamide group, a carbamoyl group or a sulfamoyl group. In the formula, R ₆ and R ₈ represent a substituted or unsubstituted alkyl group, aryl group, alkoxy group, halogen group, acyl group, amide group, sulfonamide group, carbamoyl group or sulfamoyl group. Formula (I-
In 3), the substituent on the phenyl ring may be left-right asymmetric. R ₄
And R ₅ represent a hydrogen atom, a substituted or unsubstituted alkyl group, or an aryl group. R ₄ and R ₅ , R ₆ and R ₇
And R ₈ and R ₉ may be linked to each other to form a substituted or unsubstituted ring. n ₁ , n ₂ , n ₃ and n ₄ are average degrees of polymerization of ethylene oxide and are 2 to 50 numbers.
M is an average degree of polymerization, and is a number of 2 to 50.

Formulas (I-1), (I-2) and (I-
3) will be described in detail. R ₁ is preferably an alkyl group, alkenyl group, or alkylaryl group having 4 to 24 carbon atoms, and particularly preferably a hexyl group, a dodecyl group,
Isostearyl group, oleyl group, t-butylphenyl group, 2,4-di-t-butylphenyl group, 2,4-di-
t-pentylphenyl group, p-dodecylphenyl group, m
-Pentadecaphenyl group, t-octylphenyl group,
2,4-dinonylphenyl group, octylnaphthyl group and the like. R ₂ , R ₃ , R ₆ , R ₇ , R ₈ and R ₉ are preferably methyl, ethyl, i-propyl, t-butyl, t-
Amyl, t-hexyl, t-octyl, nonyl, decyl, dodecyl, trichloromethyl, tribromomethyl,
1-phenylethyl, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms such as 2-phenyl-2-propyl, phenyl group, a substituted or unsubstituted aryl group such as a p- chlorophenyl group, -OR ₁₁ (wherein R ₁₁ represents a substituted or unsubstituted alkyl group or aryl group having 1 to 20 carbon atoms; the same applies hereinafter), a substituted or unsubstituted alkoxy group represented by COR ₁₁
An acyl group represented by —NR ₁₂ COR ₁₁ (where R ₁₂
Represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms.
The same applies hereinafter), an amide group represented by —NR ₁₂ SO ₂ R ₁₁
In represented by a sulfonamido group, a sulfamoyl group represented by -CON (R ₁₂₎ a carbamoyl group represented by _2, or _{-SO 2 N (R 12) 2} , also R _2, R _3, R
₇ , R ₉ may be a hydrogen atom. Of these, R ₆ and R ₈ are preferably an alkyl group or a halogen atom, and particularly preferably a tertiary alkyl group such as a bulky t-butyl group, t-amyl group, or t-octyl group.
R ₇ and R ₉ are particularly preferably a hydrogen atom. That is, a compound of the general formula (I-3) synthesized from a 2,4-disubstituted phenol is particularly preferred.

R ₄ and R ₅ are preferably a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an i-propyl group,
A substituted or unsubstituted alkyl group such as a heptyl group, a 1-ethylamyl group, an n-undecyl group, a trichloromethyl group, a tribromomethyl group, an α-furyl group, a phenyl group, a naphthyl group, a p-chlorophenyl group, p- A substituted or unsubstituted aryl group such as a methoxyphenyl group and an m-nitrophenyl group. R ₄ and R ₅ , R ₆ and R _7, and R ₈ and R ₉ may be linked to each other to form a substituted or unsubstituted ring, for example, a cyclohexyl ring. Among them, R ₄ and R ₅ are particularly preferably a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a phenyl group or a furyl group. n ₁ , n ₂ , n ₃ and n ₄ are particularly preferably 5 to 3
Number of 0. n ₃ and n ₄ may be the same or different.
Specific examples of the polyalkylene oxide compound described in the present invention are shown below.

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[0244]

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[0245]

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[0246]

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[0247]

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The protective layer of the present invention preferably contains a matting agent having hydrophilicity. The hydrophilic group in the present invention is a group that facilitates dissolution of the polymer in water by being introduced into the polymer, and is a carboxyl group, a phosphate group, a sulfonic acid group, or a sulfate group, and is preferably a carboxyl group. It is. As a monomer having a carboxyl group as a hydrophilic group, specifically, acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, itaconic acid, monoalkyl maleic acid, monoalkyl citraconic acid, styrene carboxylic acid, and the like No. Examples of the monomer having a phosphate group as a hydrophilic group include a phosphate ester of hydroxyethyl acrylate. Examples of the monomer having a sulfonic acid group as a hydrophilic group include styrene sulfonic acid, methacryloyloxypropyl sulfonic acid, and 2-acrylamido-2-methylpropane sulfonic acid. Examples of the monomer having a sulfuric acid group as a hydrophilic group include a sulfuric acid ester of hydroxyethyl acrylate.

Other monomers for forming a copolymer in combination with the above-mentioned monomers include, for example, monomers having at least one ethylenic double bond. These may be used in combination of two or more. Specific examples include the following. As acrylic acid esters, methyl acrylate, ethyl acrylate, n-
Propyl acrylate, isopropyl acrylate, n
-Butyl acrylate, isobutyl acrylate, sec
-Butyl acrylate, tert-butyl acrylate, amyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, tert-
Octyl acrylate, 2-chloroethyl acrylate, 2-bromoethyl acrylate, 4-chlorobutyl acrylate, cyanoethyl acrylate, 2-acetoxyethyl acrylate, dimethylaminoethyl acrylate, benzyl acrylate, methoxybenzyl acrylate, 2-chlorocyclohexyl acrylate, cyclohexyl acrylate , Furfuryl acrylate,
Tetrahydrofurfuryl acrylate, phenyl acrylate, 2-hydroxyethyl acrylate, 5-hydroxypentyl acrylate, 2,2-dimethyl-3-
Hydroxypropyl acrylate, 2-methoxyethyl acrylate, 3-methoxybutyl acrylate, 2-
Ethoxyethyl acrylate, 2-iso-propoxy acrylate, 2-butoxyethyl acrylate, 2-
(2-methoxyethoxy) ethyl acrylate, 2-
(2-butoxyethoxy) ethyl acrylate, ω-methoxy polyethylene glycol acrylate (additional mole number n = 9), 1-bromo-2-methoxyethyl acrylate, 1,1-dichloro-2-ethoxyethyl acrylate, and the like.

Examples of methacrylates include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate,
-Butyl methacrylate, isobutyl methacrylate,
sec-butyl methacrylate, tert-butyl methacrylate, amyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, chlorobenzyl methacrylate, octyl methacrylate, sulfopropyl methacrylate, N-ethyl-N-phenylaminoethyl methacrylate, 2-
(3-phenylpropyloxy) ethyl methacrylate, dimethylaminophenoxyethyl methacrylate,
Furfuryl methacrylate, tetrahydrofurfuryl methacrylate, phenyl methacrylate, cresyl methacrylate, naphthyl methacrylate, 2-hydroxyethyl methacrylate, 4-hydroxybutyl methacrylate, triethylene glycol monomethacrylate,
Dipropylene glycol monomethacrylate, 2-methoxyethyl methacrylate, 3-methoxybutyl methacrylate, 2-acetoxyethyl methacrylate, 2-
Acetoacetoxyethyl methacrylate, 2-ethoxyethyl methacrylate, 2-iso-propoxyethyl methacrylate, 2-butoxyethyl methacrylate, 2
-(2-methoxyethoxy) ethyl methacrylate, 2
-(2-ethoxyethoxy) ethyl methacrylate, 2
-(2-butoxyethoxy) ethyl methacrylate, ω
-Methoxypolyethylene glycol methacrylate (addition mole number n = 6), allyl methacrylate, dimethylaminoethyl methyl methacrylate chloride salt and the like.

Examples of vinyl esters include vinyl acetate, vinyl propionate, vinyl butyrate,
Examples thereof include vinyl isobutyrate, vinyl caproate, vinyl chloroacetate, vinyl methoxy acetate, vinyl phenyl acetate, vinyl benzoate, and vinyl salicylate.

Examples of olefins include dicyclopentadiene, ethylene, propylene, 1-butene and 1-butene.
Penten, vinyl chloride, vinylidene chloride, isoprene,
Chloroprene, butadiene, 2,3-dimethylbutadiene and the like can be mentioned.

Examples of styrenes include styrene,
Examples include methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, isopropylstyrene, chloromethylstyrene, methoxystyrene, acetoxystyrene, chlorostyrene, dichlorostyrene, bromostyrene, trifluoromethylstyrene, and methyl vinyl benzoate.

Examples of crotonates include butyl crotonate and hexyl crotonate.

Examples of itaconic acid diesters include dimethyl itaconate, diethyl itaconate and dibutyl itaconate.

Examples of maleic acid diesters include diethyl maleate, dimethyl maleate, dibutyl maleate and the like.

As the fumaric acid diesters, for example,
Examples thereof include diethyl fumarate, dimethyl fumarate, and dibutyl fumarate.

Examples of the acrylamides include acrylamide, methyl acrylamide, ethyl acrylamide, propyl acrylamide, butyl acrylamide, tert-
Butylacrylamide, cyclohexylacrylamide, benzylacrylamide, hydroxymethylacrylamide, methoxyethylacrylamide, dimethylaminoethylacrylamide, phenylacrylamide,
Dimethyl acrylamide, diethyl acrylamide, β
-Cyanoethylacrylamide, N- (2-acetoacetoxyethyl) acrylamide and the like;

Methacrylamides such as methacrylamide, methyl methacrylamide, ethyl methacrylamide, propyl methacrylamide, butyl methacrylamide, tert-butyl methacrylamide, cyclohexyl methacrylamide, benzyl methacrylamide, hydroxymethyl methacrylamide, methoxyethyl methacryl Amide, dimethylaminoethyl methacrylamide, phenyl methacrylamide, dimethyl methacrylamide,
Diethyl methacrylamide, β-cyanoethyl methacrylamide, N- (2-acetoacetoxyethyl) methacrylamide and the like;

Allyl compounds, for example, allyl acetate, allyl caproate, allyl laurate, allyl benzoate and the like;

Vinyl ethers, for example, methyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, methoxyethyl vinyl ether, dimethylaminoethyl vinyl ether and the like;

Vinyl ketones, for example, methyl vinyl ketone, phenyl vinyl ketone, methoxyethyl vinyl ketone and the like; vinyl heterocyclic compounds, for example, vinyl pyridine, N-vinyl imidazole, N-vinyl oxazolidone, N-vinyl triazole, N-vinyl triazole Vinylpyrrolidone and the like;

Glycidyl esters such as glycidyl acrylate and glycidyl methacrylate; unsaturated nitriles such as acrylonitrile and methacrylonitrile;

[0264] Polyfunctional monomers such as divinylbenzene, methylenebisacrylamide, ethylene glycol dimethacrylate and the like can be mentioned.

Examples of such a polymer having a hydrophilic group include a methyl methacrylate / methacrylic acid mole described in US Pat. No. 2,992,102 and US Pat. No. 3,767,448. A copolymer having a ratio of 1/1, a copolymer having a molar ratio of methyl methacrylate / methacrylic acid of 6/4 to 9/1 described in JP-A-53-7231, and a copolymer having a molar ratio of 6/4 to 9/1; And the copolymer of ethyl methacrylate / methyl methacrylate / methacrylic acid described in JP-A-60-126644. JP-A-62-14647 and JP-A-62-15543 describe copolymers comprising a fluorine atom and an alkali solubilizing group. Particles composed of these polymers can be preferably used as the matting agent of the present invention, but are not limited thereto.

In the present invention, the polymer forming the matting agent preferably has a monomer having a hydrophilic group in which the mol% of the monomer is 2 to 70 mol%, more preferably 3 to 50 mol%, and particularly preferably. Is 5 to 20 mol%.

The coating amount of the matting agent contained in the protective layer is from 0.001 to 0.3 g / m ² , preferably from 0.01 to 0.1 g / m ² .
The average particle size of the matting agent is preferably ² to 15 μm, particularly preferably ² to 8 μm. In this case, if the matting agent of the present invention accounts for 30% by weight or more, preferably 50% by weight or more of the total coating amount, the present effect can be exhibited. Further, the matting agent other than the present invention used in this case is not particularly limited, and may be an organic compound such as polymethyl methacrylate or polystyrene or an inorganic compound such as silicon dioxide. Further, in the present invention, even when two or more kinds of the matting agents of the present invention are used in combination, the effect is sufficiently exhibited.

In the present invention, it is preferred that 70% by weight or more, preferably 80% by weight, particularly preferably 90% by weight or more of the whole matting agent used in the light-sensitive material is present in the protective layer. As a more preferable example of the matting agent, a mixing ratio of methyl methacrylate and methacrylic acid is 70/3.
0-95 / 5 or in a mixed system of methyl methacrylate / methyl acrylate / methacrylic acid, the mixing ratio of methyl methacrylate and methacrylic acid is 60 / 40-95.
When / 5, methyl acrylate is preferably 0 to 50% of methyl methacrylate.

The average particle size of the matting agent of the present invention is preferably 2 μm or more. In particular, those having a maximum of the particle size distribution at 3 μm or more and less than 3 μm are preferable. This is because a matting agent of 3 μm or more controls the exfoliation of the photosensitive material, while
This is because the matting agent having a particle size of less than m mainly controls the slipperiness and gloss of the light-sensitive material. It is these 3 μm or more particles that usually cause sedimentation in the coating solution and peeling during processing. The present invention is particularly effective for the component having a size of 3 μm or more.

The swelling ratio and the amount of gelatin applied to the light-sensitive material of the present invention are described below. The total coated amount of gelatin of the light-sensitive material of the present invention is preferably 0.5 g / m ² or more and 3.5 g / m ² or less per one surface. Particularly preferably, 1.0 g or more and 2.5 g /
m ² or less. In this case, the gelatin coating amount of the protective layer is
The amount is preferably from 0.2 g to 1.0 g / m ² . The swelling ratio of the light-sensitive material is defined as a value obtained by subtracting the dry film thickness from the film thickness after immersing the light-sensitive material in distilled water at 25 ° C. for 1 minute,
The value can be defined and obtained as a value (%) obtained by multiplying the value obtained by dividing the value by the film thickness value in a dry state by 100. The preferred range of the swelling ratio is 30% to 200%, more preferably 50% or more and 180% or less.

The light-sensitive material of the present invention preferably contains a water-soluble polymer. Examples of the water-soluble polymer used in the light-sensitive material of the present invention include a synthetic water-soluble polymer and a natural water-soluble polymer, and any of them can be preferably used in the present invention. Among them, examples of the synthetic water-soluble polymer include those having a nonionic group in the molecular structure, those having an anionic group, and those having a nonionic group and an anionic group. Examples of the nonionic group include an ether group, an ethylene oxide group,
Examples of the hydroxy group include anionic groups such as a sulfonic acid group or a salt thereof, a carboxylic acid group or a salt thereof, and a phosphoric acid group or a salt thereof.
Examples of the natural water-soluble polymer include those having a nonionic group, those having an anionic group, and those having a nonionic group and an anionic group in the molecular structure.

As the water-soluble polymer, any of a synthetic water-soluble polymer and a natural water-soluble polymer, those having an anionic group and those having a nonionic group and an anionic group can be preferably used. In the present invention, the water-soluble polymer refers to 100 g of water at 20 ° C.
May be dissolved in an amount of 0.05 g or more.
1 g or more. Furthermore, the solubility of the water-soluble polymer of the present invention in a developing solution or a fixing solution is preferably as high as possible, and the solubility is preferably 0.05 g or more, more preferably 0.5 g or more, with respect to 100 g of the developing solution. Preferred is 1 g or more.

As the synthetic water-soluble polymer, a repeating unit represented by the following general formula [P] may be used in an amount of 10 to 100 per molecule of the polymer.
Molar% is included. General formula [P]

[0274]

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In the formula, R ₁ is a hydrogen atom, an alkyl group, preferably an alkyl group having 1 to 4 carbon atoms (including those having a substituent. Examples thereof include a methyl group, an ethyl group, a propyl group and a butyl group. ), Halogen atom (for example, chlorine atom)
Or represents -CH ₂ COOM, L is -CONH-,
J represents -NHCO-, -COO-, -OCO-, -CO- or -O-, and J represents an alkylene group, preferably an alkylene group having 1 to 10 carbon atoms (including those having a substituent. Group, ethylene group, propylene group, trimethylene group, butylene group, hexylene group, etc.),
An arylene group (including those having a substituent, such as a phenylene group), or

[0276]

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[0277]

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Represents the following. M represents a hydrogen atom or a cation; R ₂ represents an alkyl group having 1 to 4 carbon atoms (eg, a methyl group, an ethyl group, a propyl group, a butyl group, etc.), and R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ are an alkyl group having 1 to 20 carbon atoms (eg, a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, a decyl group, a hexadecyl group, etc.), an alkenyl group (eg, a vinyl group, an aryl group) Etc.), a phenyl group (eg, a phenyl group, a methoxyphenyl group, a chlorophenyl group, etc.) and an aralkyl group (eg, a benzyl group), X represents an anion, and p and q each represent 0 or 1. Particularly, a polymer containing acrylamide or methacrylamide is preferable. Next, specific examples of the synthetic water-soluble polymer represented by the general formula [P] will be described.

[0279]

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[0280]

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The synthetic water-soluble polymer of the present invention has a molecular weight of
1,000-100,000, preferably 2,000-
50,000.

As the natural water-soluble polymer, glucose polymers and derivatives thereof are preferable. Among the glucose polymers and derivatives thereof, starch, glycogen, cellulose, lichenin, dextran, nigeran and the like are preferable, and dextran and its derivatives are particularly preferable. Derivatives are preferred.
The molecular weight of these natural water-soluble polymers is 1000-10
Although it is preferably 10,000, particularly preferred is 2000 to 50,000.

The synthetic or natural water-soluble polymer used in the present invention can be used in a photographic light-sensitive material in an amount of 1% of the total gelatin coating amount.
The content is 0% or more, preferably 10% or more and 30% or less.

The silver halide photographic light-sensitive material of the present invention has a crossover radiated to the rear light-sensitive layer of the light-sensitive material of 15% or less with respect to the light emitted from the radiation intensifying screen disposed on the front side. It is preferably prepared as such, more preferably at most 10%, particularly preferably at most 5%.

The crossover was measured by using a single intensifying screen, placing a photographic light-sensitive material having an emulsion layer on both sides in contact with the front of the intensifying screen, and then placing black paper on the front of the light-sensitive material. In the state where the X-rays are in contact with each other, exposure is performed by changing the X-ray irradiation amount by changing the distance between the focal spot of the X-ray generator and the intensifying screen. The exposed light-sensitive material is developed and divided into two parts. From one side, the emulsion layer on the side in contact with the intensifying screen (back side emulsion layer) is peeled off, and from the other side, the opposite side is removed. The emulsion layer (front side photosensitive layer) is peeled off. Then
The density for each exposure amount in each photosensitive layer is plotted on a graph, and a characteristic curve of each photosensitive layer is created. Then, the average value of the difference ΔlogE between the two is obtained in the linear portion of each characteristic curve, and the crossover is calculated according to the following equation. Crossover (%) = 100 / (antilog (Δlog
E) +1)

In the method for measuring the sensitivity of a silver halide photographic light-sensitive material, the exposure light source to be used must match or almost match the wavelength of the main emission peak of the radiation intensifying screen used in combination. For example, when the phosphor of the radiation intensifying screen is terbium-activated gadolinium oxysulfide, since the peak wavelength of the main emission is 545 nm, the light source for measuring the sensitivity of the silver halide photographic light-sensitive material has a wavelength of 545 nm. And light centered at As a method for obtaining monochromatic light, a method using a filter system combining an interference filter can be used. According to this method, although it depends on the combination of interference filters, it usually has a required exposure amount and a half width of 15 ± 5.
nm monochromatic light can be easily obtained. It should be noted that the silver halide photographic material has a continuous spectral sensitivity spectrum irrespective of whether or not the spectral sensitization processing has been performed, and the sensitivity does not substantially change in a wavelength range of 15 ± 5 nm. be able to.

As a typical constitution of the silver halide photographic light-sensitive material used in the present invention, an undercoat layer and a cloth, if necessary, are provided on both sides (front and rear sides) of a transparent support colored blue. A dye layer for reducing over, or a layer containing a dye which is decolored by development or fixing for reducing crossover, a dye layer for position detection, at least one photosensitive silver halide emulsion layer, and a protective layer are sequentially formed. Examples of the structure formed include: It is desirable that each of the front and rear layers be substantially the same layer.

The support is made of a transparent material such as polyethylene terephthalate and is colored with a blue dye. As the blue dye, various dyes such as anthraquinone dyes known for coloring an X-ray photographic film can be used. Support thickness is 16
It can be appropriately selected from the range of 0 to 200 μm. An undercoat layer made of a water-soluble polymer substance such as gelatin is provided on the support in the same manner as a normal X-ray photographic film.

On the undercoat layer, if necessary, a dye layer for reducing crossover is provided. This dye layer is usually formed as a colloid layer containing a dye, and is desirably a dye layer that is decolorized in a development process. In the dye layer, it is desirable that the dye is fixed at the lower part of the layer so as not to diffuse into the upper photosensitive silver halide emulsion layer or the protective layer. Further, as another example, a dye capable of decoloring upon development or fixing is adsorbed on the surface of silver halide fine particles or synthetic mineral microcrystals.
A mode in which the color is erased by a change in environment such as H is also preferable.

Various methods are known for improving and fixing the decolorization of the dye in the colloid layer containing the dye as described above. For example, a combination of a cationic mordant and an anionic dye described in EP Patent Publication No. 211273B1, and an ethylenically unsaturated monomer having an anionic functional group described in JP-A-2-207242 added to a cationic mordant. A method of using a polymer dispersion obtained by polymerization as a mordant and combining it with an anionic dye, and a method of using a solid microcrystalline dye (microcrystalline dye particles) described in US Pat. No. 4,803,150. is there.
Among these methods, a method using a solid microcrystalline dye is preferable. The above dye layer and dye layer are effective for reducing the crossover to 15% or less.

Examples of the anionic dye used when the above dye layer is formed by a combination of a cationic mordant and an anionic dye include the following.

[0292]

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[0293]

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[0294]

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[0295]

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[0296]

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Examples of solid microcrystals used when the dye layer is formed from solid microcrystals include the following.

[0298]

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[0299]

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[0300]

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[0301]

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[0302]

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Other methods for lowering the sensitivity of the silver halide emulsion include a method of adding a dye and a method of reducing the degree of spectral sensitization or chemical sensitization.

As described above, the silver halide photographic light-sensitive material of the present invention is preferably provided with a dye layer which is decolorized by a development process. It is preferable to keep the amount of the binder used low. That is, the amount of the binder used in the photosensitive layer is 0.5 g.
/ M ² or more and 5 g / m ² or less, more preferably 0.5 g / m ² or less.
preferably with g / m ² or more 3 g / m ² or less.

The silver halide photographic light-sensitive material used in the assembly of the present invention is exposed stepwise by X-rays, and an exposure image obtained under the above-mentioned development processing conditions has an optical density (D) and an exposure amount (log E). In the characteristic curve on the orthogonal coordinates having the same coordinate axis unit length, the minimum density (Dmin) + the density 0.
The average gamma (γ) formed by the point 1 and the point of minimum density (Dmin) + density 0.5 is 0.5 to 0.9, and the point of minimum density (Dmin) + density 1.2 and minimum Concentration (Dmin)
+ The average gamma (γ) made with the point of density 1.6 is 3.2 to
Preferably, it is prepared to have a characteristic curve of 4.0. When a silver halide photographic light-sensitive material having such a characteristic curve is used in the X-ray imaging system of the present invention, X-rays having excellent photographic characteristics such as a very long leg and a high gamma in a medium density portion are obtained. A line image is obtained.
Due to this photographic characteristic, the mediastinum part with a small amount of X-ray transmission, the depiction of low-density areas such as cardiac shadows are good, and the density is easily visible even in an image of a lung field part with a large amount of X-ray transmission,
Also, there is an advantage that the contrast is improved.

The silver halide photographic light-sensitive material having the preferable characteristic curve as described above has, for example, a structure in which each of the light-sensitive layers on both sides is composed of two or more silver halide emulsion layers having mutually different sensitivities. It can be easily manufactured by the method. In particular, use a high-sensitivity emulsion for the upper layer,
For the lower layer, it is preferable to form a photosensitive layer using an emulsion having low sensitivity and high photographic characteristics. When such a two-layered photosensitive layer is used, the emulsion sensitivity difference between the layers is 1.5 times or more and 20 times or less, preferably 2 times or more and 15 times or less.
Less than twice. The ratio of the amount of the emulsion used for forming each layer differs depending on the sensitivity difference between the emulsions used and the covering power. In general, the larger the difference in sensitivity, the lower the proportion of emulsion used on the high sensitivity side. For example, when the sensitivity difference is twice, the preferred ratio of each emulsion used is:
If the covering powers are almost equal,
It is adjusted so that the value of the high-speed emulsion to the low-speed emulsion is in the range of 1:20 or more and 1:50 or less.

There are no particular restrictions on the emulsion sensitization method, various additives, constituent materials, and the like used in the production of the silver halide photographic light-sensitive material of the present invention.
No. 9, JP-A-2-103037 and JP-A-2-115837 can use various techniques described in the following relevant portions.

Items Related places 1. From the lower right column on page 8, lower right column of JP-A-2-68539, from line 6 to the upper right column on page 10, JP-A-2-68539. 2. Chemical sensitization method: From page 10, upper right column, line 13 to lower left column, line 16 of the same. 3. Antifoggant / stable page 10, lower left column, line 17 to page 11, upper left column 7 agent line and 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. Surfactant / Electrostatic Protection Line 11 on page 11, upper left column to line 9, Stopper on page 12, upper left column. 6. Matting agent, slip agent, page 12, top left column, line 10 to top right column, line 10. Plasticizer Same as page 14, lower left column, line 10 to lower right column, line 1. 7. Hydrophilic colloid, page 12, line 11, upper right column to line 16, lower left column. 8. Hardener From page 12, lower left column, line 17 to page 13, upper right column, line 6; 9. Supporting substance: From page 7, line 7 to line 20 in the upper right column. 10. Dyes and mordants From page 13, lower left column, line 1 to page 14, lower left column, line 9.

Next, the radiation intensifying screen of the present invention will be described. The radiographic intensifying screen has, as a basic structure, a support and a phosphor layer formed on one surface thereof. The phosphor layer is a layer in which the phosphor is dispersed in a binder (binder). In general, a transparent protective film is provided on the surface of the phosphor layer opposite to the support (the surface not facing the support) so that the phosphor layer is chemically altered or Protects against physical shock.

There are many known phosphors for a radiographic intensifying screen. The phosphor preferably used in the present invention is represented by the following general formula. M ₂ O ₂ X: Tb (M is at least one of metal yttrium, cadmium and lutetium, and X is a chalcogen (S,
Se or Te). )

Specific examples of the radiation intensifying phosphor preferably used in the radiation intensifying screen of the present invention include the following phosphors. Terbium-activated rare earth oxysulfide phosphor: Y ₂ O ₂ S:
Tb, Gd ₂ O ₂ S: Tb, La ₂ O ₂ S: Tb,
(Y, Gd) ₂ O ₂ S: Tb, (Y, Gd) ₂ O ₂ S:
Tb, Tm The terbium-activated cadolinium oxysulfide phosphor is described in detail in US Pat. No. 3,725,704. Particularly preferably used in the present invention is a phosphor represented by a composition formula of Gd ₂ O ₂ S: Tb.

[0312] The phosphor layer is provided on the support generally using a coating method under normal pressure as described below. That is, a coating solution is prepared by mixing and dispersing a particulate phosphor and a binder in an appropriate solvent, and this coating solution is irradiated with radiation under normal pressure using a coating means such as a doctor blade, a roll coater, or a knife coater. After directly applying on the support of the sensitive screen, the solvent is removed from the coating film, or the coating solution is applied in advance on a temporary support such as a glass plate under normal pressure, and then the solvent is removed from the coating film. By removing the phosphor-containing resin thin film and peeling it off from the temporary support and joining it to the support of the radiation intensifying screen, the phosphor layer is provided on the support. .

The radiographic intensifying screen of the present invention uses a thermoplastic elastomer as described below as a binder, and performs a compression treatment to increase the packing ratio of the phosphor (that is, to reduce the porosity in the phosphor layer). (Reduced). By employing such a method, a radiographic intensifying screen having a phosphor volume filling ratio of 68% or more can be easily obtained. Furthermore, by optimizing the particle size distribution of the phosphor, it is possible to obtain a screen having a phosphor volume filling ratio of 72% or more.

The sensitivity of the radiation intensifying screen basically depends on the total luminescence of the phosphor contained in the panel.
The total amount of light emission depends not only on the emission luminance of the phosphor itself but also on the content of the phosphor in the phosphor layer. A high content of the phosphor also means that absorption of radiation such as X-rays is large, so that higher sensitivity can be obtained and at the same time, image quality (particularly, granularity) is improved.
On the other hand, when the phosphor content in the phosphor layer is constant, the layer thickness can be reduced as the phosphor particles are more densely packed, so that the spread of emitted light due to scattering is reduced. And a relatively high sharpness can be obtained.

To produce the above-described radiographic intensifying screen, there are a) a step of forming a phosphor sheet comprising a binder and a phosphor, and b) placing the phosphor sheet on a support, And bonding the phosphor sheet on a support while compressing at a temperature equal to or higher than the softening temperature or the melting point of the phosphor sheet.

First, the step a) will be described. The phosphor sheet serving as the phosphor layer of the radiation intensifying screen is prepared by applying a coating solution in which the phosphor is uniformly dispersed in a binder solution onto a temporary support for forming the phosphor sheet, drying, and temporarily supporting the phosphor sheet. It can be manufactured by removing it from the body. That is, first, in a suitable organic solvent, a binder and phosphor particles are added,
Stir and mix to prepare a coating solution in which the phosphor is uniformly dispersed in the binder solution.

The binder has a softening temperature or melting point of 3
A thermoplastic elastomer at 0 ° C to 150 ° C is used alone or together with another binder polymer. Since the thermoplastic elastomer has elasticity at normal temperature and becomes fluid when heated, it is possible to prevent the phosphor from being damaged by the pressure at the time of compression. Examples of the thermoplastic elastomer include polystyrene, polyolefin, polyurethane, polyester, polyamide, polybutadiene, ethylene vinyl acetate, polyvinyl chloride, natural rubber, fluoro rubber, polyisoprene, chlorinated polyethylene, and styrene.
Butadiene rubber, silicon rubber and the like can be mentioned. The component ratio of the thermoplastic elastomer in the binder,
The binder may be 10% by weight or more and 100% by weight or less.
Preferably, it consists of 0% by weight of a thermoplastic elastomer.

Examples of solvents for preparing the coating solution include lower alcohols such as methanol, ethanol, n-propanol and n-butanol; hydrocarbons containing chlorine atoms such as methylene chloride and ethylene chloride; acetone, methyl ethyl ketone and methyl isobutyl ketone. Ketones such as methyl acetate, ethyl acetate, and butyl acetate; esters of lower alcohols with lower alcohols; ethers such as dioxane, ethylene glycol monoethyl ether, and ethylene glycol monomethyl ether; and mixtures thereof. The mixing ratio between the binder and the phosphor in the coating solution varies depending on the characteristics of the intended radiographic intensifying screen, the type of the phosphor, and the like. In general, the mixing ratio between the binder and the phosphor is from 1: 1 to 1: 1. 1: 100
(Weight ratio), and particularly preferably in the range of 1: 8 to 1:40 (weight ratio). It is more preferably in the range of 1:15 to 1:40 (weight ratio).

[0319] The coating solution contains a dispersant for improving the dispersibility of the phosphor in the coating solution, and a binding force between the binder and the phosphor in the formed phosphor layer. Various additives such as a plasticizer for improvement may be mixed. Examples of dispersants used for such purposes include phthalic acid, stearic acid, caproic acid, and lipophilic surfactants. Examples of the plasticizer include triphenyl phosphate, tricresyl phosphate,
Phosphoric acid esters such as diphenyl phosphate; phthalic acid esters such as diethyl phthalate and dimethoxyethyl phthalate; glycolic acid esters such as ethyl phthalyl ethyl glycolate and butyl phthalyl butyl glycolate; and a mixture of triethylene glycol and adipic acid Examples include polyesters, polyesters of polyethylene glycol and aliphatic dibasic acids such as polyesters of diethylene glycol and succinic acid, and the like. Next, the coating solution containing the phosphor and the binder prepared as described above is uniformly applied to the surface of the temporary support for forming a sheet to form a coating film of the coating solution. This coating operation can be performed by using ordinary coating means, for example, a doctor blade, a roll coater, a knife coater, or the like.

The temporary support is, for example, glass, a metal plate,
Alternatively, it can be arbitrarily selected from known materials as a support for the radiation intensifying screen. Examples of such materials include films of plastic substances such as cellulose acetate, polyester, polyethylene terephthalate, polyamide, and triacetate; metal sheets such as aluminum foil and aluminum alloy foil; and ceramic plates such as alumina, zirconia, magnesia, and titania. Alternatively, a sheet or the like can be used. A coating solution for forming a phosphor layer is applied on the temporary support, dried, and then peeled off from the temporary support to form a phosphor sheet to be a phosphor layer of the radiographic intensifying screen. Therefore, it is preferable to apply a release agent on the surface of the temporary support in advance so that the formed phosphor sheet can be easily peeled off from the temporary support.

Next, step b) will be described. First, a support for a phosphor sheet formed as described above is prepared.
This support can be arbitrarily selected from the same materials as the temporary support used when forming the phosphor sheet. Particularly preferred is TiO ₂ kneaded polyethylene terephthalate, and the thickness is preferably 150 μm to 400 μm.

In known radiographic intensifying screens, in order to strengthen the bond between the support and the phosphor layer, or to improve the sensitivity or image quality (sharpness, granularity) of the radiographic intensifying screen, the phosphor layer is used. It is known that a polymer material such as gelatin is applied to the surface of the support on which the is provided, to form an adhesion-imparting layer, or a light-reflecting layer made of a light-reflecting material such as titanium dioxide is provided. The support used in the present invention can also be provided with these various layers, and the configuration thereof can be arbitrarily selected according to the desired purpose and application of the radiographic intensifying screen. In the case of the light reflecting layer, it is particularly preferable that the layer is densely filled with TiO ₂ having a particle size of 0.1 μm to 0.3 μm. Volume filling rate is 30-50%, thickness is 40
Those having a size of about μm are preferably used. By forming such a reflective layer, a diffuse reflectance of 90% or more, more preferably 95% or more, can be obtained, and it greatly contributes to improvement of screen performance. The phosphor sheet obtained in step a) is placed on a support, and then the phosphor sheet is bonded to the support while compressing at a temperature equal to or higher than the softening temperature or the melting point of the binder.

In this manner, by utilizing the method of compressing the phosphor sheet without previously fixing it on the support, the sheet can be spread thinly, and not only can the phosphor be prevented from being damaged, but also the sheet can be compressed. As compared with the case where the pressure is fixed and pressurized, a high phosphor filling rate can be obtained even with the same pressure. Examples of the compression apparatus used for the compression processing of the present invention include generally known apparatuses such as a calender roll and a hot press. For example,
The compression treatment by a calender roll is performed by placing the phosphor sheet obtained in step a) on a support and passing the phosphor sheet at a constant speed between rollers heated to a temperature higher than the softening temperature or melting point of the binder. However, the compression device used in the present invention is not limited to these devices, and may be any device capable of compressing the above-mentioned sheet while heating it. The pressure at the time of compression is preferably 50 kgw / cm ² or more.

[0324] The thickness of the phosphor layer thus formed can be set to any thickness between 90 µm and 400 µm. More preferably, the thickness is from 95 μm to 300 μm.

In the case where the radiation screen is a direct medical X-ray screen used in pairs, the front screen and the back screen can have different film thicknesses.

The front screen has a thickness of 90 μm.
m to 140 μm, particularly preferably 95 μm to 120 μm. The back screen has a thickness of 95 μm to 300 μm, particularly 10 μm, depending on the required system sensitivity.
0 μm to 200 μm is preferably used.

[0327] A transparent protective film is formed on the phosphor layer obtained as described above. The transparent protective film is made of a transparent material such as a cellulose derivative such as cellulose acetate or nitrocellulose; or a synthetic polymer such as polymethyl methacrylate, polyvinyl butyral, polyvinyl formal, polycarbonate, polyvinyl acetate, vinyl chloride, or vinyl acetate copolymer. It can be formed by a method in which a solution prepared by dissolving a polymer substance in an appropriate solvent is applied to the surface of the phosphor layer. Or polyethylene terephthalate, polyethylene naphthalate,
A transparent thin film separately formed from polyethylene, vinylidene chloride, polyamide, or the like can also be formed by a method such as bonding to the surface of the phosphor layer using a suitable adhesive. The thickness of the transparent protective film thus formed is
Preferably, it is about 3 to 20 microns.

[0327] Among these, two of the thicknesses of 10 μm or less
Axial stretched polyethylene terephthalate or 5μm thick
The following stretched polyethylene naphthalate is particularly preferred.
By using such a thin protective layer, the distance from the phosphor of the radiation intensifying screen to the silver halide photosensitive material is shortened, which contributes to the improvement of the sharpness of the obtained X-ray image.

As the protective film, an organic solvent-soluble fluororesin can be used. In the case of fluororesin,
It is particularly preferable in terms of performance that the thickness is 2 μm to 5 μm.
The film formed by the coating film of the fluororesin may be crosslinked. Protective film made of fluororesin removes dirt such as plasticizer that leaks out of the film when it comes into contact with other materials or X-ray film, etc. It is advantageous because it has the advantage of being able to do so. As this fluororesin, Lumiflon manufactured by Asahi Glass Co., Ltd. is particularly preferred.

The protective film of the intensifying screen of the present invention is preferably formed from a coating film further containing one or both of a polysiloxane skeleton-containing oligomer and a perfluoroalkyl group-containing oligomer. . The polysiloxane skeleton-containing oligomer has, for example, a dimethylpolysiloxane skeleton, preferably has at least one functional group (eg, a hydroxyl group), and has a molecular weight (weight average) of 500 to 10
It is preferably in the range of 0000. In particular, the molecular weight is preferably in the range of 1000 to 100,000,
It is more preferably in the range of 3,000 to 10,000. The oligomer containing a perfluoroalkyl group (eg, tetrafluoroethylene group) preferably has at least one functional group (eg, hydroxyl group: -OH) in the molecule, and has a molecular weight (weight average) of 500 to 100.
000 is preferable. In particular, the molecular weight is 1
It is preferably in the range of 000 to 100,000, and more preferably in the range of 10,000 to 100,000. If an oligomer containing a functional group is used, a crosslinking reaction occurs between the oligomer and the protective film-forming resin during the formation of the protective film, and the oligomer is incorporated into the molecular structure of the film-forming resin. Even if the conversion panel is used repeatedly for a long time or the operation such as cleaning the surface of the protective film, the oligomer is not removed from the protective film, and the effect of adding the oligomer is effective for a long time. Use is useful. The oligomer is contained in the protective film in an amount of 0.01 to 10
% By weight, especially 0.1% by weight.
Preferably, it is contained at about 2% by weight.

Further, it is preferable that any one of the layers contains a conductive material functioning as an antistatic agent. Examples of the conductive material used as the antistatic agent include Zn, T
oxides of at least one metal selected from i, Sn, In, Si, Mo and W, metal composite oxides composed of two or more of these metal oxides, or Al, Particles (eg, spherical particles), whisker-like (fibrous) made of, for example, those doped with different atoms such as In, Nb, Ta, Sn, and halogen atoms.
And the like, and a solid conductive material having an arbitrary shape. Among these conductive materials, C, ZnO, SnO
_2, InO _2, SnO ₂ and InO ₂ K ₂ has been surface treated with one or more substances of such a mixed crystal of O · nTiO ₂ (where, n is an integer ranging from 1 to 8) of the single crystal Fibers (whiskers) are preferred because of their excellent antistatic properties. Further, a conductive zinc oxide whisker that is three-dimensionally expanded in a tetrapot shape is a particularly preferred conductive material because it has excellent antistatic properties and little deterioration in film strength after coating.

This conductive material can be introduced at any place. In particular, it is preferable to introduce a conductive material into a surface protective layer or the like. The conductive material is used in a weight ratio of 4/1 to 1 to the binder (binder) forming the layers.
It is preferred to add in an amount in the range of / 3. It is also preferable to introduce a conductive material on the back surface of the support layer, between the support layer and the phosphor layer, or between the phosphor layer and the protective layer. Also in these cases, the conductive material is mixed into the binder (binder) in a weight ratio of 4/1 to 1/3 and applied to a support or a protective layer to form a layer. Is preferred. In particular, it is preferable that a conductive material is mixed with a binder to form an independent undercoat layer (antistatic layer) between the support layer and the phosphor layer. In this case, it is preferable to introduce the conductive material in such an amount that the surface electric resistivity of the undercoat layer becomes 10 ¹² Ω or less. It is particularly preferable to introduce an organic antistatic agent such as a polyethylene oxide-based surfactant into the surface protective layer, if desired, independently or in combination with the above-described metal oxide-based conductive material.

It is also preferable to add a matting agent such as silica or PMMA to the surface protective layer. Their particle size is 4
It is not less than μm and not more than 20 μm.

The radiographic intensifying screen used in the present invention is:
It preferably has an absorptivity of 30% or more, more preferably an absorptivity of 35% or more, and particularly preferably an absorptivity of 40% or more with respect to X-rays of 80 KVp passing through 7 cm of water. The radiographic intensifying screen used in the present invention has a high sensitivity as described above, and as a characteristic thereof, the contrast transfer function (CTF) has a spatial frequency of 1
It is prepared so as to show 0.79 or more at the number of lines / mm and 0.36 or more at the spatial frequency of 3 lines / mm.

The radiation intensifying screen used in the present invention has a spatial frequency (lp / mm or book / mm) on the horizontal axis as a characteristic, and a contrast transfer function (CTF).
Is plotted on the vertical axis, the following lp / mm value and C
Lp / mm value represented by a curve created by sequentially connecting points represented by TF values so as to form a smooth curve, and CTF
As compared with the relationship with the value, it is preferable that the CTF value shows a higher CTF value than the curve in all the spatial frequency regions. lp / mm CTF 0.00 1.00 0.25 0.950 0.50 0.905 0.75 0.840 1.00 0.790 1.25 0.720 1.50 0.655 1.75 0 .595 2.00 0.535 2.50 0.430 3.00 0.360 3.50 0.300 4.00 0.255 5.00 0.180 6.00 0.130

The measurement and calculation of the contrast transfer function from the radiation intensifying screen to the photosensitive material can be performed using a sample in which a rectangular chart is printed on a one-sided material of MINP manufactured by Fuji Photo Film Co., Ltd.

A curve formed by connecting the points expressed by the lp / mm value and the CTF value so as to form a smooth curve is shown in FIG. 4 in the accompanying drawings. A preferable radiographic intensifying screen having such characteristics can be easily obtained by a method in which a thermoplastic layer is used as a binder as described above and the filling rate of the phosphor layer is increased by a compression treatment.

Next, the assembly of the present invention will be described. According to the study of the present inventor, in a combination of a silver halide photographic light-sensitive material and a radiographic intensifying screen, the optimum distribution of the sensitivity between the intensifying screen and the light-sensitive material is determined by the sensitivity level of the assembly,
It was found to change depending on the size of the subject. However, as a result of further research, a photosensitive material having an appropriate sensitivity was used, and as an intensifying screen, the amount of the phosphor was increased to an extent that an acceptable sharpness level could be maintained, and the X-ray absorption amount was increased. It has been found that a high-sensitivity, high-quality X-ray image can be obtained by using an increased and high contrast transfer function (CTF).

In the assembly of the present invention, the radiation intensifying screen and the silver halide photographic light-sensitive material have a high sensitivity radiation intensifying screen exhibiting a specific range of spatial frequency values and exhibiting X-ray absorption, and a specific range. And any combination with a silver halide photographic light-sensitive material exhibiting the sensitivity described above. However, as a preferable combination, a radiation intensifying screen showing an absorption of 30 to 60% with respect to X-rays of 80 KVp passing through 7 cm of water, and a sensitivity value defined above of 0.012 to 0.015 lux And a combination with a silver halide photographic light-sensitive material. According to the combination of the ranges, a high-quality X-ray image with standard sensitivity can be obtained. Also,
30-50% for X-ray of 80KVp through 7cm of water
The combination of a radiation intensifying screen showing the absorption amount of the above and a silver halide photographic light-sensitive material having a sensitivity of 0.02 to 0.03 lux seconds as defined above is also a preferable combination. An X-ray image with even better image quality can be obtained at a sensitivity without any problem (that is, a range in which the X-ray exposure dose is acceptable).

In the assembly of the present invention, a silver halide photographic light-sensitive material in which the front and rear light-sensitive layers satisfy the above-mentioned sensitivity requirements and have substantially the same characteristics as each other is used. And the rear side), it is preferable to use a combination of radiation intensifying screens having the above-mentioned characteristics so as to have substantially the same characteristics. However, in order to improve the balance between image sharpness and sensitivity, the front intensifying screen and the rear intensifying screen are replaced by a fluorescent screen of the front intensifying screen as described in US Pat. No. 4,710,637. By reducing the body coating amount from the phosphor coating amount of the post-sensitizing screen, the balance between image quality and sensitivity can be improved.

The assembly of the present invention has a sensitivity which does not cause a problem in practical use, and an X obtained by photographing.
To ensure that the image quality of the line image is at a high level, the sensitivity of the assembly is set to 80 KVp, and the exposure is 0.5 to 1.5 mR when a three-phase X-ray source is used. It is preferable to use a silver halide photographic material in combination with two radiographic intensifying screens so that a density of 1.0 can be obtained when developed under development conditions.

Next, the processing method of the present invention will be described.
Hereinafter, the general formula (9) will be described in detail. Where X
Represents an oxygen atom or a sulfur atom, Y represents a hydrogen atom or a substituent, and examples of the substituent include a straight-chain, branched or cyclic alkyl group having 1 to 10 carbon atoms, and 6 to 10 carbon atoms.
Aryl group, mercapto group, linear or branched alkylthio group having 1 to 10 carbon atoms, arylthio group having 6 to 10 carbon atoms, acyloxy group having 1 to 10 carbon atoms, amino group, alkyl having 1 to 10 carbon atoms Amino group, carbon number 2-1
0 carbonamide group, C1-10 sulfonamide group, C2-10 oxycarbonylamino group, C1-10 ureido group, C2-10 acyl group, C2-10 An oxycarbonyl group having 1 to 1 carbon atoms
A carbamoyl group having 10 carbon atoms, a sulfonyl group having 1 to 10 carbon atoms, a sulfinyl group having 1 to 10 carbon atoms, a sulfamoyl group, a carboxyl group (including salts), and a sulfo group (including salts). These groups may have a substituent, and examples of the substituent include an alkyl group, an aryl group, a heterocyclic group, a hydroxy group, an alkoxy group, an alkylthio group, an amino group, an alkylamino group, a carbonamide group, and a sulfonyl group. Groups, carboxylic acids (including salts), and sulfonic acids (including salts).

The substituent of Y is shown in more detail. The alkyl group is a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms, and these groups may have a substituent. The groups mentioned as substituents for Y can be applied, and examples thereof include methyl, ethyl, propyl, isopropyl, butyl, t-butyl, and hydroxymethyl. The aryl group is an aryl group having 6 to 10 carbon atoms, and these groups may have a substituent. As the substituent, the groups exemplified as the substituent of Y can be applied, and phenyl, o
-Carboxyphenyl, o-sulfophenyl and the like. The heterocyclic group includes 5 to 6 carbon atoms, nitrogen atoms, oxygen atoms, or sulfur atoms.
Examples of the membered heterocyclic group include furyl, benzofuryl, pyrrolyl, imidazolyl, pyrazolyl, pyridyl, thienyl, isothiazolyl, pyrrolidinyl, pyrazinyl, and morpholinyl. These groups may have a substituent, and as the substituent,
The groups mentioned as substituents for Y can be applied, and preferably, for example, imidazolyl, pyrrolidinyl, piperazinyl, morpholinyl and the like.

The alkoxy group is an alkoxy group having 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms, and these groups may have a substituent. Examples of the substituent include the substituents for Y. And methoxy, ethoxy, propoxy, butoxy, pentyloxy, 2-hydroxyethoxy and the like. The alkylthio group has 1 to 10 carbon atoms, preferably 1 to 10 carbon atoms.
In the alkylthio group of 5, these groups may have a substituent, and as the substituent, the groups mentioned as the substituent of Y can be applied, for example, methylthio, carboxymethylthio, 2-dimethylaminoethylthio , 2-sulfoethylthio and the like. The alkylamino group has 1 to 1 carbon atoms.
10, preferably an alkylamino group having 1 to 6 carbon atoms,
These groups may have a substituent, and as the substituent, the groups exemplified as the substituent of Y can be applied, and for example, monomethylamino, dimethylamino, diethylamino, diisopropylamino, dibutylamino, dicarboxymethyl Amino, dicarboxyethylamino and the like. The carbonamido group is a carbonamido group having 1 to 6 carbon atoms, and these groups may have a substituent. As the substituent, the groups exemplified as the substituent of Y can be applied. , Propionamide. The sulfonyl group is a sulfonyl group having 1 to 5 carbon atoms, such as methanesulfonyl. These substituents may be further substituted, if possible.

The alkyl group represented by Y in the above general formula (9) is preferably an alkyl group having 1 to 5 carbon atoms.
And more preferably an alkyl group substituted with a hydroxy group, an amino group, an alkylamino group, a carboxyl group (including a salt), or a sulfo group (including a salt). And, for example,
Methyl, ethyl, butyl, i-propyl, hydroxymethyl, carboxymethyl, sulfomethyl, hydroxyethyl, carboxyethyl, 1,2-dicarboxyethyl, sulfoethyl, carboxypropyl, sulfopropyl, carboxybutyl, aminomethyl, dimethylaminomethyl, Examples thereof include diethylaminomethyl, dimethylaminoethyl, diethylaminoethyl and the like.
The aryl group represented by Y in the above general formula (9) is preferably a phenyl group, including those substituted by the groups mentioned as substituents of Y, such as phenyl, p-methylphenyl, and anisyl. , P-carboxyphenyl, p
-Sulfonylphenyl, p-acetamidophenyl and the like. These substituents may be further substituted, if possible.

The alkylthio group represented by Y in the general formula (9) is preferably an alkylthio group having 1 to 6 carbon atoms, including those substituted by the groups mentioned as the substituent of Y. Preferred is an alkylthio group substituted with a heterocyclic group, a hydroxy group, an alkoxy group, an alkylthio group, an amino group, an alkylamino group, a sulfonyl group, a carboxyl group (including a salt), and a sulfo group (including a salt); For example, methylthio, ethylthio, benzylthio, hydroxyethylthio, carboxymethylthio,
Sulfomethylthio, carboxyethylthio, 1,2-dicarboxyethylthio, sulfoethylthio, 1-carboxypropylthio, sulfopropylthio, sulfobutylthio, ethoxyethylthio, aminomethylthio, dimethylaminomethylthio, diethylaminomethylthio, aminoethyl Thio, monomethylaminoethylthio, dimethylaminoethylthio, diethylaminoethylthio, diisopropylaminoethylthio, dimethylaminopropylthio, dimethylaminobutylthio, dimethylaminohexylthio, 2-imidazolylethylthio, 2-pyrrolidinylethylthio, Examples thereof include 2-pirazinylethylthio, 2-morpholinylethylthio, and methanesulfonylethylthio. These substituents may be further substituted, if possible.

The arylthio group represented by Y in the general formula (9) is preferably a phenylthio group, including those substituted by the groups mentioned as substituents of Y. For example, phenylthio, p-carboxy Phenylthio, p-
And sulfonylphenylthio. The acyloxy group is preferably an acyloxy group having 1 to 5 carbon atoms,
For example, acetoxy. The alkylamino group is preferably an alkylamino group having 1 to 5 carbon atoms,
For example, methylamino, dimethylamino, diethylamino and the like. The carbonamido group is preferably a carbonamido group having 2 to 7 carbon atoms, such as acetamido and benzamido. The sulfonamide group is preferably a sulfonamide group having 1 to 6 carbon atoms,
For example, methanesulfonamide, benzenesulfonamide, etc. As the oxycarbonylamino group, preferably an oxycarbonylamino group having 1 to 7 carbon atoms,
For example, methoxycarbonylamino, phenoxycarbonylamino and the like. The ureide group is preferably a ureide group having 1 to 7 carbon atoms, such as ureide, methylureide, and phenylureide. The acyl group is preferably an acyl group having 1 to 6 carbon atoms, such as acetyl and benzoyl. The oxycarbonyl group is preferably an oxycarbonyl group having 1 to 7 carbon atoms, such as methoxycarbonyl and phenoxycarbonyl. The carbamoyl group is preferably a carbamoyl group having 1 to 6 carbon atoms, such as carbamoyl. The sulfonyl group is preferably a sulfonyl group having 1 to 6 carbon atoms, such as methanesulfonyl. The sulfinyl group is preferably a sulfinyl group having 1 to 6 carbon atoms, such as methanesulfinyl. The sulfamoyl group is preferably a sulfamoyl group having 1 to 6 carbon atoms, such as sulfamoyl and diethylsulfamoyl. These substituents may be further substituted, if possible.

In the formula, examples of the alkali metal represented by M include lithium, sodium and potassium, and examples of the quaternary ammonium include
Ammonium, trimethylammonium and the like can be mentioned.

Among the compounds represented by the general formula (9), the compound represented by the following general formula (16) is more preferable. General formula (16)

[0350]

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In the formula, Y ′ has the same meaning as Y in the general formula (9), and M ′ has the same meaning as M in the general formula (9). In the formula, Y ′ is particularly preferably an alkyl group, a mercapto group, an alkylthio group, an amino group, or an alkylamino group, and most preferably an alkylthio group. These groups include those substituted with other substituents, such as heterocyclic groups, hydroxy groups, alkoxy groups, alkylthio groups, amino groups, alkylamino groups, carboxyl groups (including salts), Sulfo groups (including salts);
More preferred are an amino group, an alkylamino group and a carboxyl group. These substituents may be further substituted, if possible, and the substituents described above as the substituents for Y can be applied.

Examples of the specific compounds of the present invention include, but are not limited to, the following compounds.

[0353]

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[0354]

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[0355]

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[0356]

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[0357]

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[0358]

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[0359]

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[0360]

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[0361]

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[0362]

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[0363]

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[0364]

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[0365]

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[0366]

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The compound represented by the general formula (9) is
es in Heterocyclic Chemistry, vol. 9,165-20
9. J. Am. Chem. Soc., Vol. 44, 1502-1510.
JP-A-55-59463, JP-B-49-8334.
Gazette, U.S. Pat.
No. 0169, West German Patent No. 2716707, etc. can be used for synthesis. The concentration of the compound represented by the general formula (9) in the developer (solution used) is 0.1.
The range is from 0.01 mmol to 50 mmol / L, more preferably from 0.05 mmol to 10 mmol / L, and particularly preferably from 0.1 mmol to 5 mmol / L.

The ascorbic acid-based developing agent preferably used in the present invention is preferably a compound represented by the following formula (17).

[0369]

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In the formula, R ¹ and R ² each represent a hydroxy group, an amino group, an acylamino group, a sulfonylamino group,
Represents an alkoxycarbonylamino group, a mercapto group or an alkylthio group. P and Q each represent a hydroxy group, a carboxy group, an alkoxy group, an alkyl group, a sulfo group, an amino group or an aryl group, or P and Q are bonded to each other and substituted by R ¹ and R ² . It represents an atomic group forming a 5- to 8-membered ring together with a vinyl carbon atom and a carbon atom substituted by Y ¹ . Y ¹ represents ＯO or ＮN—R ³ . Here, R ³ represents a hydrogen atom, a hydroxy group, an alkyl group, or an acyl group.

The general formula (17) will be described in detail.

In (17), R ¹ and R ² each represent a hydroxy group, amino group, acylamino group, sulfonylamino group, alkoxycarbonylamino group, mercapto group or alkylthio group (for example, methylthio, ethylthio). The amino group may have a substituent, and examples of the substituted amino group include an alkyl-substituted amino group having 1 to 10 carbon atoms (eg, methylamino, ethylamino, n-butylamino, hydroxyethylamino). The acylamino group may be substituted, for example, acetylamino, benzoylamino. The alkylsulfonylamino group may be substituted, for example, methanesulfonylamino. The arylsulfonylamino group may be substituted, and examples thereof include benzenesulfonylamino and p-toluenesulfonylamino. The alkoxycarbonylamino group may be substituted, for example, methoxycarbonylamino.
Preferred examples of R ¹ and R ² include a hydroxy group, an amino group, an alkylsulfonylamino group, and an arylsulfonylamino group.

P and Q are each a hydroxy group, a carboxy group, an alkoxy group, an alkyl group, a sulfo group, an amino group,
Represents an aryl group, or P and Q are linked together to form R
^1, R ² represents an atomic group forming a 5- to 8-membered ring together with the carbon atom to which the two vinyl carbon atoms and Y ¹ which is substituted is substituted. An alkoxy group, an alkyl group, an amino group, and an aryl group may be substituted. Specific examples of the ring structure ^{-O -, - C (R 9} ) (R 10) -, - C (R 11) =,
-C (= O) -, - N (R 12) -, - formed by combining the N = like. Where R ⁹ , R ¹⁰ , R ¹¹ and R ¹²
Each represents a hydrogen atom, an alkyl group (preferably having 1 to 10 carbon atoms, which may have a substituent; examples of the substituent include a hydroxy group, a carboxy group, and a sulfo group), a hydroxy group, and a carboxy group Represents a group. Further, a saturated or unsaturated condensed ring may be formed on the 5- to 8-membered ring.

Examples of the 5- to 8-membered ring include a dihydrofuranone ring, a dihydropyrroline ring, a pyranone ring, a cyclopentenone ring, a cyclohexanone ring, a pyrrolinone ring, a pyrazolinone ring, a pyridone ring, an azacyclohexenone ring, a uracil ring and the like. Preferred examples of the 5- to 8-membered ring include a dihydrofuranone ring, a cyclopentenone ring, a cyclohexenone ring, a pyrazolinone ring, an azacyclohexenone ring, and a uracil ring.

Y ¹ represents ＯO or ＮN—R ³ . R
³ represents a hydrogen atom, a hydroxy group, an alkyl group (eg, methyl, ethyl) or an acyl group (eg, acetyl). The alkyl group and the acyl group may be substituted. Examples of the substituted alkyl group include a hydroxyalkyl group (eg, hydroxymethyl, hydroxyethyl), a sulfoalkyl group (eg, sulfomethyl, sulfoethyl), and a carboxyalkyl group (eg, carboxymethyl, carboxyethyl).

The specific examples of the ascorbic acid-based developing agent of the present invention are shown below, but the present invention is not limited to these.

[0377]

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[0378]

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[0379]

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[0380]

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Of these, ascorbic acid or erythorbic acid (diastereomer of ascorbic acid) represented by C-1 and alkali metal salts such as lithium salt, sodium salt and potassium salt thereof are preferable. The ascorbic acid compound is used in an amount of 1 to 10 per liter of developer.
It is preferable to use 0 g, preferably 5 to 80 g.

The developer or developer of the present invention preferably does not substantially contain a polyhydroxybenzene compound represented by dihydroxybenzene such as hydroquinone. That is, the content of the polyhydroxybenzene compound in the developer is desirably 0.0001 mol / liter or less, and most preferably, it is not contained at all.

In the present invention, a 3-pyrazolidone compound is used as an auxiliary developing agent. 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-
And tolyl-4-methyl-4-hydroxymethyl-3-pyrazolidone. These auxiliary developing agents are 10 ^-4 ~
It is preferably used at 10 ^-1 mol / l, more preferably 5 × 10 ^{-4 to} 5 × 10 ^-2 mol / l.

The pH of the developer is preferably 8.5 or more and 12 or less, more preferably 9.3 or more and 11 or less. As an alkaline agent, sodium hydroxide, potassium hydroxide, or the like is used.
As the H buffer, sodium phosphate monobasic, sodium phosphate dibasic, potassium phosphate monobasic, potassium phosphate dibasic and the like can be used. As the carbonate, sodium hydrogen carbonate, sodium carbonate, potassium hydrogen carbonate, potassium carbonate and the like can be used. These pH buffers are at least 0.2 mol / l, more preferably at least 0.30 mol / l, in the developer solution. Among them, carbonate is particularly preferable as the pH buffer. In particular, it is preferable to use a carbonate of 0.5 mol / liter or more.

Development inhibitors such as potassium bromide and potassium iodide; organic solvents such as dimethylformamide, methyl cellosolve, hexylene glycol, ethanol and methanol; 5-methylbenztriazole and 5-bromobenztriazole as benzotriazole derivatives , 5
-Chlorobenztriazole, 5-butylbenztriazole, benztriazole and the like, but particularly preferred is benztriazole. Further, the developer of the present invention may be used as a silver stain inhibitor in JP-B-56-46585 and JP-B-62-47.
02, JP-B-62-4703, U.S. Pat.
Nos. 4,215 and 3,318,701;
No. 203439, No. 62-56959, No. 62-17
No. 8247, Japanese Patent Application Laid-Open No. 1-2209, Hei.
No. 4955, No. 3-112275, No. 3-23371
The compound described in No. 8 can be used. These silver antifouling agents are used in an amount of 0.01 to 5 mmol per liter of developer.
It is more preferably 0 mmol to 10 mmol, particularly preferably 0.1 mmol to 5 mmol. Examples of the sulfite preservative that can be used in the developer of the present invention include sodium sulfite, potassium sulfite, lithium sulfite, ammonium sulfite, sodium bisulfite, potassium metabisulfite, and the like. The sulfite is preferably at least 0.01 mol / l, particularly preferably at least 0.02 mol / l. The upper limit is preferably up to 1.0 mol / liter. In addition, LFA Mason
Processing Chemistry ", Focal Press (1966), pp. 226-229, U.S. Pat.
Nos. 93,015 and 2,592,364;
-64933 may be used. Further, if necessary, it may contain a surfactant, a water softener, a hardener and the like.

As the chelating agent in the developing solution, ethylenediamine diorthohydroxyphenylacetic acid, diaminopropanetetraacetic acid, nitrilotriacetic acid, hydroxyethylethylenediaminetriacetic acid, dihydroxyethylglycine, ethylenediaminediacetic acid, ethylenediaminedipropionic acid, iminodiacetic acid, Diethylenetriaminepentaacetic acid, hydroxyethyliminodiacetic acid, 1,3-diaminopropanoltetraacetic acid, triethylenetetraminehexaacetic acid, transcyclohexanediaminetetraacetic acid, ethylenediaminetetraacetic acid, glycol etherdiaminetetraacetic acid, ethylenediaminetetrakismethylenephosphonic acid, diethylenetriaminepentane Methylenephosphonic acid, nitrilotrimethylenephosphonic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, 1,1- Hosuhon'etan-2-carboxylic acid, 1,2,4-tricarboxylic acid, 1-hydroxy-1-phosphono-1,3,
Examples thereof include 3-tricarboxylic acid, catechol-3,4-disulfonic acid, sodium pyrophosphate, sodium tetrapolyphosphate, and sodium hexametaphosphate, and particularly preferably, for example, diethylenetriaminepentaacetic acid, triethylenetetraminehexaacetic acid, and 1,3-diaminopropanol. Tetraacetic acid, glycol etherdiaminetetraacetic acid, hydroxyethylethylenediaminetriacetic acid, 2-phosphonobutane-
1,2,4-tricarboxylic acid, 1,1-diphosphonoethane-2-carboxylic acid, nitrilotrimethylenephosphonic acid, ethylenediaminetetraphosphonic acid, diethylenetriaminepentaphosphonic acid, 1-hydroxypropylidene-1,1-diphosphonic acid, 1- Aminoethylidene-
1,1-diphosphonic acid, 1-hydroxyethylidene-
There are 1,1-diphosphonic acids and salts thereof. These chelating agents are used in an amount of 0.5 g / liter or more, preferably 1.0 g / liter or more, per 1 liter of the used liquid.

In the present invention, the replenishment amounts of the developing and fixing are preferably 25 ml or more and 200 ml or less, and most preferably 40 ml or more and 150 ml or less per square meter of the photographic material. In the present invention, it is preferable that the development processing by the developer is completed in 5 seconds or more and 30 seconds or less. Further, in the present invention, the total processing time of development, fixing, washing and drying is preferably from 25 seconds to 200 seconds, and most preferably from 25 seconds to 120 seconds.

In the present invention, the photographic light-sensitive material can exhibit excellent performance in that it is subjected to automatic development processing through general development, fixing, washing and drying steps. The treatment is preferably carried out with a non-hardening treatment solution substantially free of a film agent or a so-called treated hardening agent represented by aluminum ions in the fixing solution.

In the processing method of the present invention, the method for drying a silver halide photographic light-sensitive material by an automatic developing machine is described below.
The method of blowing hot air onto the photosensitive material is generally used.In particular, a heat roller method in which a heat conductor roller with a temperature of 70 ° C or more is brought into direct contact with the photosensitive material at the pre-drying stage of an automatic processor, or infrared radiation heat by a heater It is preferable to use the radiant heat method for drying the photosensitive material together with the hot air drying as appropriate.

As the automatic machine used in the present invention, various types such as a roller transport type and a belt transport type can be used, but a roller transport type automatic machine is preferable. In addition, by using a developing machine having a small opening ratio as disclosed in JP-A-1-166040 and JP-A-1-193853, air oxidation and evaporation are reduced, and washing water is squeezed out, that is, through a squeeze roller. Dried. The washing water used in the present invention may be more preferably subjected to a filter member or a filter of activated carbon to remove dust and organic substances present in the water as a pretreatment before being supplied to the washing tank.

[0391] Japanese Unexamined Patent Publication No.
Ultraviolet irradiation method described in No. 0-263939, ibid.
No. 263940, using a magnetic field;
No. 131632, a method of making pure water using an ion exchange resin, Japanese Patent Application Nos. 2-2088638 and 2-3.
No. 03055, a method of circulating through a filter and an adsorbent column while blowing ozone, Japanese Patent Application No. Hei.
No. 4138, a method based on microbial degradation.
2-115154, 62-153952, 62
-220951 and 62-209532 can be used in combination.

Further, MW Beach, “Microbiologica
l Growths in Motion-picture Processing "SMPTE Jour
nal Vol. 85 (1976), RO Deegan, “Photo Processing
Wash Water Biocides "J. Imaging Tech. Vol.10, No.
6 (1984) and JP-A Nos. 57-8542 and 57-58.
No. 143, No. 58-105145, No. 57-1321
No. 46, No. 58-18631, No. 57-97530
If necessary, antibacterial agents, antibacterial agents, surfactants, and the like described in JP-A Nos. 57-257244 can be used.

Further, a washing bath (or a stabilizing bath) may be used, if necessary, by RT Kreiman, J. Image. Tec.
h. Vol. 10, No. 6, pp. 242 (1984), isothiazoline compounds, bromochlorodimethylhydantoin, Research Disclosure Vol. 205, No.
20526 (May 1981), Vol. 228, N
An isothiazoline compound described in O. 22845 (April 1983), a compound described in JP-A-62-209532, and the like can be used in combination as a microbiocide, if necessary. .

In addition, "The Chemistry of Bacterial Prevention and Prevention", Hiroshi Horiguchi,
Compounds such as those described in Mitsui Shuppan (Showa 57), “Handbook of Bacterial Prevention and Deterrence Technology”, Japan Society of Bacterial Prevention and Deterrence, Hakuhodo (Showa 61) may be included.

As the automatic developing device, it is preferable to use an automatic developing machine provided with a rinsing tank and a rinsing roller (crossover roller) between the developing tank and the fixing tank and between the fixing tank and the washing tank. Further, it is preferable that a stock tank for water to be supplied with various water rust preventive agents (antibacterial agents) is installed in the washing tank and the rinsing tank. Further, it is preferable that an electromagnetic valve is installed at the drain of the washing tank.

Further, it is preferable that the washing tank of the automatic developing apparatus is a multi-chamber tank or that a multi-stage countercurrent washing system is adopted.

[0397]

Next, the present invention will be described in more detail by way of examples, but embodiments of the present invention are not limited thereto. Example 1 Emulsion A Aqueous gelatin solution-1 [1200 ml of H ₂ O,
It contains 25 g of gelatin and 1.0 g of NaCl, and has a pH of 4.0.
2], stirring and maintaining at 40 ° C., Ag-1 solution [AgNO ₃ 200 g / liter solution] and X-1 solution [N
aCl 70 g / liter solution] at 60 ml / min for 15 seconds. Next, 2 minutes later, solution X-2 [KBr
14.4 g / liter solution] at 60 ml / min for 20 seconds. Two minutes later, 55 ml of the Ag-1 solution and the X-1 solution were added simultaneously at 60 ml / min. After 2 minutes, X-1 solution was added to 23
ml and then a 1N solution of NaOH was added to adjust the pH to 5.
Adjusted to 2. The temperature was raised to 75 ° C. in 12 minutes, followed by aging for 20 minutes. HNO ₃ 1N solution and aqueous solution of polyvinyl alcohol [Including 5 g of polyvinyl alcohol (hereinafter referred to as PV-1) having an average degree of polymerization of vinyl acetate of 500 and an average saponification rate of 98% to alcohol, and containing 0.1 liter of H ₂ O] Was added to adjust the pH of the reaction solution to 3.8. At this time, the silver potential (vs. room temperature saturated calomel electrode) is about 100 m.
V. Next, using the Ag-1 solution and the X-1 solution, while maintaining the silver potential at 100 mV, the Ag-1 solution was supplied at an initial speed of 7 ml /
And a double jet was added for 35 minutes at a linear flow rate acceleration of 0.05 ml / min.

After 2 minutes, Ag-1 solution and X-3 solution [100
7 g of NaCl and 2.1 g of KBr in ml)
Simultaneous addition was performed at 5 ml / min for 5 minutes. A precipitant was added, the temperature was lowered to 30 ° C., pH was brought to 4.0 and the emulsion was sedimented. The precipitated emulsion was washed with water, and a gelatin solution was added at 38 ° C.
The emulsion was redispersed to pH 6.2, pCl 2.8. A part of the emulsion was sampled, and a TEM image [transmission electron micrograph image] of a replica of the emulsion particle was observed. According to this, the total projected area of all AgX particles (hereinafter, TP
94% of A) are tabular grains having a principal plane of {100} plane, a projected outline shape of a rectangular parallelogram, and an aspect ratio of 3 or more, and the average diameter of the tabular grains is 1.3 μm.
m, the average aspect ratio was 7.6, the average aspect ratio was 1.3, and the variation coefficient of the diameter distribution (standard deviation of distribution / average diameter) (hereinafter, CV) was 0.17. Emulsion A is as described in (IV) above.
-1) The defect is formed by the method of 3), and the defect is grown under the condition of high X ^- concentration and low pH in the presence of the compound B ⁰ , and the high AgCl
This shows an embodiment in which tabular grains having a content are formed.

Emulsion B In a reaction vessel 21, an aqueous solution of gelatin-2 [containing 1.2 liters of H ₂ O, 25 g of gelatin, and 0.3 g of NaCl,
pH 3.0], kept at 30 ° C., and
g-21 solution (AgNO ₃ 20 in 1 liter of H ₂ O)
0 g, gelatin 8 g, HNO ₃ 1N 2.0 ml) and X-21 solution (NaCl in 1 liter H ₂ O)
70 g and 8 g of gelatin) at 120 ml / min for 1 minute. After 3 minutes, a portion of the emulsion (24
0 ml), and the reaction vessel 22 (960 ml of H ₂ O,
It contains 0.3 g of NaCl and 15 g of PV-1, and has a pH of 3.
0, temperature 40 ° C). While stirring, Ag-1
Solution and Solution X-1 were added at 25 ml / min for 10 minutes. Then gelatin solution -21 (gelatin 20g, H ₂ O 120ml
) And X-1 solution, pH 3.8, silver potential 100
mV, and the temperature was raised to 75 ° C. for 12 minutes. After aging for 12 minutes, the silver potential was adjusted to 100 using Ag-1 solution and X-1 solution.
While maintaining the voltage at mV, the Ag-1 solution was double jet-added at an initial speed of 10 ml / min and a linear flow rate acceleration of 0.07 ml / min for 35 minutes. After 2 minutes, Ag-1 solution and X-3 solution were added at a rate of 7 ml / min.
Co-mix addition for minutes. After the addition of the following sedimentation agent, it was the same as Emulsion A. A part of the obtained emulsion was sampled, and a TEM image of a replica of the emulsion grains was observed. 95% of TPA has a main plane of {100}
The surface and projected outline are tabular grains having a right-angled parallelogram and an aspect ratio of 3 or more. The tabular grains have an average diameter of about 1.3 μm, an average aspect ratio of 7.0, and an average aspect ratio of 1. 5, C.I. V. Was 0.16. Emulsion B
Adsorbs compound B ⁰ on defect-free AgCl nuclei,
In this embodiment, the defects are formed by laminating g ⁺ and Cl ⁻ and then gelatin is added to weaken the adsorptive power, and the temperature is increased, ripened, and grown.

Emulsion C The aqueous gelatin solution-1 was placed in a reaction vessel, and while keeping the temperature at 35 ° C., the Ag-1 solution and the X-1 solution were simultaneously mixed and added at 60 ml / min for 25 seconds. Next, 2 minutes later, solution X-2 was added at 60 ml / min for 27 seconds. After the temperature was raised to 40 ° C. and 5 minutes had passed, the Ag-1 solution and the X-1 solution were added at 60 ml / min at 60 ml / min.
Was added simultaneously. After 2 minutes, 23 mL of the X-1 solution was added, and the polyvinyl imidazole copolymer 1 [average copolymerization ratio was 50 molecules of acrylamide, 9 molecules of acrylic acid, N-
Vinyl imidazole 10 molecules, weight average molecular weight 1.5 ×
10 ⁵ ] and an aqueous solution containing 100 ml of H ₂ O were added to adjust the pH to 5.5. The temperature was raised to 75 ° C. in 12 minutes, followed by aging for 20 minutes. Ag-1 solution was added to adjust the silver potential to 120 mV, and using the Ag-1 solution and the X-1 solution, while maintaining the silver potential, the Ag-1 solution was 7 ml / min, and the linear flow rate acceleration was 0.05 ml / min. For 35 minutes. Two minutes later, the Ag-1 solution and the X-3 solution were simultaneously added at 6 ml / min for 5 minutes. After the addition of the next settling agent, the procedure was the same as in Example 1. TEM of replica of obtained emulsion grains
When the image was observed, it was as follows. 93% of TPA are tabular grains having a principal plane of {100} plane, a projected outline shape of a right-angled parallelogram, and an aspect ratio of 3 or more, and the tabular grains have an average diameter of 1.33 μm and an average aspect ratio of 7.4, average aspect ratio 1.6, C.I. V. Is 0.1
It was 7. Next, a sedimentation agent was added, and the remainder was the same as Emulsion A. Emulsion C formed the defect by the method described in 3) of (IV) -1 above, and the high AgCl grown in the presence of compound A ⁰ was used.
Represents tabular grain content.

Comparative Emulsion D The same as Emulsion A except that water was added instead of the aqueous polyvinyl alcohol solution. A part of the obtained emulsion was sampled, and a TEM image of a replica of the emulsion grains was observed. There were no tabular grains having an aspect ratio ≧ 3, the average aspect ratio was 2.0, the average diameter was about 0.83 μm, and C.I. V. = 0.15.

Comparative Emulsion E The tabular grains were formed in the presence of 3-amino-1H-1,2,4-triazole as described in Example 11B of EP 0534395A1. 65% of the TPA had a {100} major plane, an average diameter of 1.28 μm, and an average aspect ratio of 9.8. Emulsion A after addition of sedimentation agent
Same as.

<Chemical sensitization> Emulsions A to A prepared as described above
E was chemically sensitized while being kept at 45 ° C. with stirring. First, immediately after the addition of 10 ^-4 mol of thiosulfonic acid compound-1 per mol of silver halide, the thiosulfonic acid compound-1 has a diameter of 0.1 mol.
Fine AgI particles of 0.3 μm were added in an amount of 0.15 mol% based on the total silver. Three minutes later, 1 × 10 ⁻⁶ mol / mol Ag of thiourea dioxide was added, and the mixture was kept for 22 minutes to perform reduction sensitization. Next, 4-hydroxy-6-methyl-1,
3,3a, 7-tetraazaindene was added in an amount of 3 × 10 ^-4 mol per mol of silver halide, and the dispersion of sensitizing dye-1 was used as the amount of sensitizing dye-1 to obtain 1 mol of silver halide. Sensitizing dye-2 equivalent to 1 × 10 ^-3 mole per mole of silver halide, and sensitizing dye-3 equivalent to 1.2 × 10 ^-5 mole per mole of silver halide.
Was added at the same time as 2.4 × 10 ^-4 mol per mol of silver halide, and calcium chloride was further added.

Thereafter, a silver nitrate solution and a sodium chloride solution were added by a double jet method in an amount of 6 mol% with respect to the silver amount of the host tabular grains to form silver chloride epitaxy. At this time, potassium hexacyanoruthenate was added to the aqueous sodium chloride solution to dope the silver cyanide epitaxy with an amount of 5 × 10 ⁻⁵ mol of hexacyanoruthenate ion per mol of silver of the host tabular grains. I let it.

Subsequently, sodium thiosulfate was added in an amount of 6 × 10 ⁻⁶ mol per mol of silver halide and selenium compound-1.
After the addition corresponding 4 × 10 ^-6 mol per mol of silver halide, of chloroauric acid per mol of silver halide 1 × 10 ^-5 mol equivalent and potassium thiocyanate per mol of silver halide per 2 × 10 ^{- 3} moles were added. Further, azolium compound-1 was added in an amount of 1 × 10 ^-4 mol per mol of silver halide. Furthermore, 67 mg of nucleic acid (manufactured by Sanyo Kokusaku Pulp Co., Ltd .: trade name: RNA-F) per mole of silver halide
Equivalent to 5 × 10 ^-5 mol of mercapto compound-1 per mol of silver halide. Thereafter, the temperature was raised to 60 ° C. and the mixture was ripened for 10 minutes. Then, sodium sulfite was added in an amount of 3.2 × 10 ^-4 mol per mol of silver halide, and the mixture was ripened for another 5 minutes to convert the water-soluble mercapto compound-1 into silver halide 1. It was added in an amount of 1 × 10 ⁻⁴ mol per mol and cooled to 35 ° C. Thus, the preparation of the emulsion (chemical ripening) was completed.

[0406]

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<Preparation of Dispersion of Sensitizing Dye-1> 50 m of water
1 g of sensitizing dye-1 to pH 7.0 ± 0.5,
At 50-65 ° C, 2000-2 using a dissolver.
The particles were mechanically dispersed at 500 rpm in solid fine particles of 1 μm or less, 50 g of 10% gelatin was added, and the mixture was cooled after mixing.

(Measurement of Iodine Surface Ratio) When the host tabular emulsion immediately before epitaxial formation was measured by an ISS apparatus, the iodine surface ratio (a value obtained by dividing the maximum value of I / total halogen amount by the minimum value) was 18%. there were.

(Preparation of Coating Solution for Emulsion Layer) A coating solution for the emulsion layer was prepared such that the components to be added to the emulsion layer T1 had the following coating amounts per one side of the support. 2,6-bis (hydroxyamino) -4-diethylamino-1,3,5-triazine 1.7 mg / m ² dextran 0.45 g / m ² sodium polystyrene sulfonate (average molecular weight 600,000) 33 mg / m ² (including the emulsion added content) gelatin 1.1 g / m ² (including the emulsion added content) compound a-1 0.1g / m ² · Snowtex C 200 mg / m ² · polymer latex Lx-17 0. 50 g / m ² · Compound A-3 0.11 g / m ² · Dye emulsion b (as dye solids) 6.8 mg / m ² · Dye emulsion m (as dye solids) 0.4 mg / m ²

[0410]

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• 1,2-bis (vinylsulfonylacetamido) ethane The amount was adjusted so that the swelling ratio was 130%, and added.

(Preparation of Dye Emulsion b) 60 g of Dye-1
62.8 g of 2,4-diamylphenol, 62.8 g of dicyclohexyl phthalate and ethyl acetate 3
33 g were melted at 60 ° C. Next, 65 ml of a 5% aqueous solution of sodium dodecylbenzenesulfonate and gelatin 94
g and water (581 ml) were added, and the mixture was treated at 60 ° C. with a dissolver at 3 ° C.
Emulsified and dispersed for 0 minutes. Next, 2 g of methyl p-hydroxybenzoate and 6 liters of water were added, and the temperature was lowered to 40 ° C. Next, Asahi Kasei ultrafiltration lab module ACP105
Using 0, the mixture was concentrated to a total amount of 2 kg, and 1 g of methyl p-hydroxybenzoate was added to obtain a dye emulsion b.

[0413]

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(Preparation of Dye Emulsion m) 10 g of Dye-2
After weighing and dissolving in a solvent consisting of 10 ml of tricresyl phosphate and 20 ml of ethyl acetate, a 15% aqueous gelatin solution containing 750 mg of anionic surfactant-1 is added.
A dye emulsion m was prepared by emulsification and dispersion in ml.

[0415]

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(Preparation of Dye Dispersion i) Dye-3 was handled as a wet cake without drying, and weighed to a dry solid content of 6.3 g. The dispersing aid V was treated as a 25% by weight aqueous solution, and was added so that the dry solid content was 30% by weight based on the solid content of the dye. Add water and add 6
3.3 g, and mixed well to form a slurry. 100 cc of beads made of zirconia having an average diameter of 0.5 mm are prepared, put into a vessel together with the slurry, and dispersed with a dispersing machine (1 / 16G sand grinder mill: manufactured by Imex Co., Ltd.) for 6 hours to give a dye concentration of 8% by weight. Water was added to obtain a dye dispersion. The resulting dispersant was mixed so that the solid content of the dye was 5% by weight and the photographic gelatin was equal to the solid content of the dye by weight.
An aqueous solution was added to a concentration of 000 ppm, refrigerated, and stored in a jelly form. Thus, a dye dispersion i was obtained as a non-elutable solid fine particle dispersion dye having a light absorption maximum at 915 nanometers. The average particle diameter of the solid fine particles of the dye dispersion i was 0.4 μm.

[0417]

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[0418]

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(Preparation of Coating Solution for Surface Protective Layer) A coating solution for the surface protective layer was prepared so that each component of the surface protective layer would have the following coating amount per one side of the support.・ Gelatin 780 mg / m ²・ Additive D 1.4 mg / m ²・ Sodium polyacrylate (average molecular weight 41,000) 34 mg / m ²・ Additive-1 40 mg / m ²・ Additive-2 5.4 mg / M ² · additive-3 22.5 mg / m ² · additive-4 0.5 mg / m ² · matt agent-1 (average particle size 3.7 microns) 72.5 mg / m ²

[0420]

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Compound A-4 4.4 mg / m ² Compound A-5 1.3 mg / m ² Compound A-6 0.5 mg / m ²

[0422]

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(Preparation of Dye Layer Coating Solution) A coating solution was prepared so that each component of the dye layer had the following coating amount. Gelatin 0.25 g / m ² Additive D 1.4 mg / m ² Sodium polystyrene sulfonate (average molecular weight 600,000) 5.9 mg / m ² Dye dispersion i (as dye solids) 20 mg / m ²

(Preparation of Support) Biaxially stretched thickness 17
Corona discharge treatment was performed on a 5 μm blue-dyed polyethylene terephthalate film, and both surfaces were coated using a wire bar coater so that the hydrophobic polymer layer had the following coating amount, and dried at 185 ° C. for 1 minute.

[0425] (hydrophobic polymer layer) Butadiene - Styrene copolymer latex of butadiene / styrene weight ratio ^{= 31/69 0.32g / m 2} · 2,4- dichloro-6-hydroxy -s- triazine sodium salt 8. 4 mg / m ² * The latex solution contains 0.4 wt% of emulsifying dispersant-A based on the solid content of the latex.

[0426]

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Next, the hydrophilic colloid layer was coated on both sides with a wire bar coater so that the following coating amount was obtained.
Dry at 55 ° C. for 1 minute.

(Hydrophilic colloid layer) ・ Gelatin 80 mg / m ²・ Polyethyl acrylate 20 mg / m ²・ Coating aid-B 1.8 mg / m ²・ Dye-C 2-60 mg / m ²・ Dye-D 2 to 60 mg / m ² · additives -D 0.27 mg / m ²

[0429]

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Method for Preparing Dye-C 20 g of dye and 1% aqueous solution of carboxymethyl cellulose 2
200 g, by mixing H ₂ O 287 g, and 8 hours at Eiger mill (Eiger Japan Co., Ltd.) at 5,000rpm conditions with beads of zirconium oxide having a diameter of 2 mm (ZrO _2). The resulting mixture is filtered and ZrO
_Two beads were removed. Preparation of Dye-D Prepared in the same manner as for Dye-C.

(Preparation of photographic material) On the support prepared as described above, the emulsion layer consisting of the above emulsions A to E, the dye intermediate layer for infrared position detection, and the surface protective layer were combined and simultaneously extruded to form both surfaces. Applied. The dye interlayer for infrared position detection was coated by being disposed between the emulsion layer and the support. The amount of silver applied per side was 1.3 g / m ² . At this time, the coating amounts of the undercoat upper layer dye dispersions C and D were adjusted within the above range so that the crossover light of the photographic materials became the same. At this time, the gradation of the light-sensitive material is the same as that of a commercially available UR-film manufactured by Fuji Photo Film Co., Ltd.
It was almost the same as 2. In this way, silver halide photographic materials A to E were prepared.

(Preparation of a developing replenisher) A developing replenisher having the following formulation and using sodium erythorbate as a developing agent was prepared. Diethylenetriaminepentaacetic acid 8.0 g Sodium sulfite 19.6 g Sodium bisulfite 2.8 g Sodium carbonate monohydrate 52.0 g Potassium carbonate 55.0 g Sodium erythorbate (C-1) 60.0 g 4-hydroxymethyl-4-methyl -1-phenyl-3-pyrazolidone 13.2 g 3,3'-diphenyl-3,3'-dithiopropionic acid 1.44 g diethylene glycol 50.0 g Compound A-1 of the present invention 0.15 g Compound A-15 of the present invention Add 0.15 g water to make 2 liters. Adjust the pH to 10.1 with sodium hydroxide or acetic acid. The above developer was used as a developer replenisher as it was. (Preparation of new developing solution)
55 ml of a starter solution having the following composition was added per 1 liter of each developing replenisher and adjusted to pH 9.5 to obtain a new developing solution. Starter solution Potassium bromide 11.1 g Acetic acid 10.8 g Add water to make up to 55 ml

(Preparation of Fixing Replenisher) A fixing replenisher having the following formulation was prepared. Water 0.5 L Ethylenediaminetetraacetic acid dihydrate 0.05 g Sodium thiosulfate pentahydrate 400 g Sodium bisulfite 98.0 g Sodium hydroxide 2.91 g Adjust pH to 5.4 with NaOH, add water, and add 1 L And

(Preparation of New Fixing Solution) 3 L of the above fixing replenisher was diluted with water to 6 L. pH was 5.6. The developing system was used to improve the drive system and tank of the automatic processing machine Sepros S manufactured by Fuji Photo Film Co., Ltd., and the following processing steps and the replenishment amount (almost the same amount was the waste liquid amount) were set. Process temperature Processing time Tank capacity Current image 35 ° C 13 seconds 6 liters Fixed 32 ° C 10 seconds 6 liters First rinsing 20 ° C 6 seconds 4 liters Second rinsing 20 ° C 6 seconds 4 liters Drying 10 seconds (total 45 seconds) ) per developer replenishment rate 100ml / sensitive material 1 m ² per fixing replenishing amount 100ml / sensitive material 1 m ² per washing replenishing amount 100ml / sensitive material 1 m ² Note that the water washing set a two-stage water washing system, washing water replenished from the second washing A two-stage countercurrent system was used. The overflow of the first washing water was used as a fixing diluent. Also, this automatic developing machine
A tank having a capacity of 10 liters for collecting the developing and fixing waste liquid was provided inside the automatic developing machine to collect the waste liquid. Further, in the drying section, a heat roller similar to the automatic developing machine SEPROS M2 manufactured by Fuji Photo Film Co., Ltd. was used. The temperature of the roller was set at 85 ° C. Also, the waste duct was removed. In the first washing tank of the automatic processor, 1-bromo-3-chloro-
5,5-Dimethylhydantoin was set in the form of a tablet in the middle of the water supply pipe so that the disinfectant was dissolved in the washing water.

Further, a silver collecting device for the fixing solution is attached to the automatic developing machine externally to the automatic developing machine, silver in the fixing solution is removed by electrolysis and a fine particle filter, and the purified fixing solution is returned to the fixing tank. Returned and circulated.

(4) Measurement of characteristics of silver halide photographic light-sensitive material 1) Measurement of sensitivity Using a filter having the filter characteristics shown in FIG. 5 of the accompanying drawings, a tungsten light source having a color temperature of 2856 K ° (545 nm by the filter, and Light with a half width of 14 nm
(Corresponding to the main emission wavelength of a radiation intensifying screen used together later)-lights centered at the center were selected and used) as the irradiation light, and the photographic materials A to E were exposed, and the sensitivity was measured. That is, exposure was performed by irradiating the photosensitive material with the above-mentioned irradiation light through a neutral step wedge for 1/20 second. After the exposure, the photographic photosensitive materials A to E are subjected to the above-described developing treatment, and after the photosensitive layer on the side opposite to the exposed surface is peeled off, the density is measured, and a characteristic curve is obtained. From the characteristic curve, the minimum density (Dmin) is obtained. The exposure amount required to obtain a density obtained by adding 0.5 was calculated, and this was defined as the sensitivity. In calculating the exposure amount, the illuminance of light emitted from a tungsten light source and transmitted through a filter was measured using a PI-3F illuminometer (corrected). Table 1 shows the results. The superiority of the photographic light-sensitive material of the present invention was confirmed.

2) Measurement of crossover The silver halide photographic material was sandwiched between a HG-M screen (using a terbium-activated gadolinium oxysulfide phosphor (main emission wavelength: 545 nm, green light)) and black paper. X-rays were irradiated from the black paper side. The same X-ray source as that used in the evaluation of the intensifying screen was used. The X-ray irradiation was performed while changing the X-ray irradiation amount by the distance method. After irradiation, the light-sensitive material was developed by the same method as that used in the above-described sensitivity measurement. The developed photosensitive material was divided into two parts, and the respective photosensitive layers were peeled off. The density of the photosensitive layer on the side in contact with the intensifying screen was higher than the density of the photosensitive layer on the opposite side.
A characteristic curve is obtained for each photosensitive layer, and an average value of the sensitivity difference (ΔlogE) in a linear portion (from 0.5 to 1.0) of the characteristic curve is obtained. Was calculated. Crossover (%) = 100 / (antilog (Δlog
E) +1) Even when the intensifying screen was changed to another one, almost the same value was obtained. Table 1 shows the calculated crossover (%) of the present invention.

[0438]

[Table 1]

The following radiographic intensifying screens were prepared in pairs. HG-M (commercially available from Fuji Photo Film Co., Ltd.)

(2) Measurement of characteristics of radiographic intensifying screen 1) Measurement of X-ray absorption X-rays generated from a tungsten target tube operated at 80 KVp with three-phase power supply were converted to an aluminum plate having a thickness of 3 mm. Through a 7 cm water filter to reach a sample radiation intensifying screen fixed at 200 cm from the tungsten anode of the target tube. Then, the amount of X-rays transmitted through the intensifying screen is measured by the intensifying screen. Was measured using an ionizing dosimeter at a position 50 cm after the phosphor layer of Example 2 to determine the amount of X-ray absorption. Note that, as a reference, the X-ray dose at the above measurement position measured without passing through the intensifying screen was used. Table 2 shows the measured values of the X-ray absorption of the intensifying screen.

2) Measurement of Contrast Transfer Function (CTF) A single-sided photosensitive material of MINP30 manufactured by Fuji Photo Film Co., Ltd. was placed in contact with an intensifying screen to be measured.
Rectangular chart for TF measurement (made of molybdenum, thickness: 80μ)
m, spatial frequency: 0 lines / mm to 10 lines / mm).
The chart was placed at a position 2 m from the X-ray tube, a photosensitive material was placed in front of the X-ray source, and then an intensifying screen was placed. The X-ray tube used was DRX-3 manufactured by Toshiba Corporation.
724HD, which uses a tungsten target, has a focal spot size of 0.6 mm × 0.6 mm, passes through a 3 mm aluminum equivalent material including an aperture, and generates X-rays. A voltage of 80 KV was applied to the three phases by a pulse generator, and X-rays passed through a 7 cm water filter having absorption substantially equivalent to a human body were used as a light source. The photosensitive material after shooting,
Development processing was performed using CEPROS-30 manufactured by Fuji Photo Film Co., Ltd. to prepare a measurement sample. Note that the exposure amount at the time of the X-ray photography was adjusted so that the average value of the maximum density and the minimum density after the development processing was 1.0.

Next, the measurement sample was operated with a microdensitometer. At this time, the aperture direction is 30μ.
The concentration profile was measured at a sampling interval of 30 μm using a slit having a length of 500 μm and a direction perpendicular to the same. Repeat this operation 20 times to calculate the average value,
It was used as the concentration profile for calculating the CTF.
Thereafter, the density contrast at each frequency was normalized by the density contrast at 0 frequency. Spatial frequency 1 / mm and 3
Table 2 shows the values measured for the book / mm.

[0443]

[Table 2]

(5) Evaluation of the characteristics of the assembly of the silver halide photographic material and the radiation intensifying screen

2) Visual Evaluation (1). Sharpness The degree of blurring was sensory evaluated. Here, the degree of blur obtained by the combination of commercially available HR-4 / SUPER HRS30 manufactured by Fuji Photo Film Co., Ltd. is denoted by Δ, and the combination of HG-M / UR-2 is denoted by Δ, and the degree of blur is smaller than that. ◎ (2). Grain The degree of roughness was sensory evaluated. Where HR-4 / SUPE
The degree of roughness obtained by the combination of R HRS30 was marked with 〇, those with less roughness were marked with ◎, and those with more roughness were marked with △. In addition, each intermediate product was evaluated as, for example, 〜 to 粒 in the case of a particle between ◎ and ○. (3). Visual evaluation Chest phantom manufactured by Kyoto Chemical Co., Ltd., three-phase 12-pulse 1
00KVp (with 3mm thick aluminum equivalent filter), X-ray source with focal spot size 0.6mm x 0.6mm, place phantom at 140cm distance, and then scattered ray prevention with grid ratio 8: 1 A grid, and then an assembly of a light-sensitive material and an intensifying screen were placed and photographing was performed. The development was performed in the same manner as in the measurement of the photographic characteristics.

A certain point in the lung field was determined, and the amount of X-ray exposure was adjusted by changing the exposure time so that the density was 1.6. The finished chest phantom photographs were arranged in a shakasten and visually evaluated. Evaluate mainly the visibility of blood vessel shadows in the lung field,
B was good, C was somehow diagnosable, and D was not diagnosable.

The results of the above evaluation are shown in Table 3.

[0448]

[Table 3]

The following facts were found from the above data.
The assembly of the present invention is much better than expected in terms of sharpness and granularity, and the results are sufficiently reflected in the visual evaluation.

Example 2 Emulsion F Aqueous gelatin solution-4 [containing 1.2 liters of H ₂ O, 25 g of gelatin, and 0.11 g of NaCl in a reaction vessel.
Adjusted to pH 3.9 with NO ₃ solution] and kept at 40 ° C.
AgNO ₃ -1 solution (AgNO ₃ 10 g /
Liter) in 2 seconds. X- after 5 minutes
Solution 41 (KBr 140 g / liter solution) and Ag-41
The solution (AgNO ₃ 200 g / liter solution) was added almost simultaneously at 50 ml / min for 1 minute. However, the start of the addition of the X-41 solution was made earlier by one second than the start of the addition of the Ag-41 solution. One minute after the completion of the addition, a NaOH solution was added,
The pH was adjusted to 5.5. Further, an aqueous polyvinyl alcohol solution [PV-1 5 g, H ₂ O 50 ml] was added, and the silver potential was lowered to 5%.
0 mV and the temperature was raised to 75 ° C. After the temperature was raised, the silver potential was readjusted to 50 mV. After aging for 30 minutes, Ag-4
Using two liquids (AgNO ₃ 100 g / L) and X-42 liquid (KBr 71 g / L), the silver potential was 50 m.
While maintaining V, the Ag-42 solution was added for 30 minutes at an initial speed of 5 ml / min and a linear flow rate acceleration of 0.05 ml / min. After 3 minutes, a precipitant was added, the temperature was lowered to 30 ° C., the pH was adjusted to 4.0, and the emulsion was sedimented. The precipitated emulsion is washed with water and heated to 38 ° C.
A gelatin solution was added and the emulsion was redispersed. Observation of a TEM image of a replica of the obtained emulsion particles showed the following. 92% of the TPA has a {100} plane as its principal plane, and the projected outline shape is a shape in which one or two of the four corners of a right-angled parallelogram are missing, and the average corner loss rate is about 10% of the edge length. there were. Edge surface with missing corner is $ 1
It was 10 mm. Average diameter 1.4 μm, average aspect ratio 6.0, C.I. V. 0.21. Emulsion F formed the defect by the method (3) of (IV) -1 to obtain Compound B ⁰
2 shows tabular grains of high AgBr content grown under high X ^- concentration conditions in the presence of.

Emulsion G Emulsion F was the same as Emulsion F except that no aqueous polyvinyl alcohol solution was added. Observation of a TEM image of a replica of the obtained emulsion particles showed the following. No tabular grains having an aspect ratio of ≧ 3, and the average aspect ratio was 1.8.
With an average diameter of 0.93 μm and C.I. V. = 0.25.

Emulsion H A gelatin solution-1 was placed in a reaction vessel and kept at 30 ° C.
While stirring, the Ag-21 solution and the X-21 solution were simultaneously mixed and added at 36 ml / min for 3 minutes. One minute later, the PV-1 solution (H ₂
O 50 ml, a solution containing 5 g of PV-1), and 15
The temperature was raised to 75 ° C. for 10 minutes and aged for 10 minutes.
5. The silver potential was adjusted to 100 mV. While maintaining the potential, the Ag-1 solution and the X-1 solution were simultaneously mixed and added for 15 minutes.
The Ag-1 solution was added at a starting flow rate of 10 ml / min at a flow rate of 0.1 ml / min. Two minutes later, the Ag-1 solution and the X-3 solution were added simultaneously at 14 ml / min for 1 minute. After the addition of the following sedimentation agent, it was the same as Emulsion A. A part of the obtained emulsion was sampled, and a TEM image of a replica of the emulsion grains was observed. 96% of the TPA is tabular grains having a {100} major plane and an aspect ratio of 3 or more, having an average diameter of about 0.55 μm, an average aspect ratio of 7.5, an average aspect ratio of 1.4, . V. Was 0.14.

Emulsion I A gelatin solution-1 and a PV-1 solution were placed in a reaction vessel, and p
Adjusted to H3.5. Ag at 70 ° C with stirring
Solution -21 and solution X-21 were added simultaneously for 25 minutes while maintaining the silver potential at 100 mV. Ag-21 and X-2
The starting flow rate of 1 was 12 ml / min. Next, the pH was adjusted to 3.0, and the mixture was added simultaneously for 15 minutes under the same conditions. After further aging for 15 minutes, the Ag-1 solution and the X-3 solution were added simultaneously at 16 ml / min for 1 minute. After the addition of the following sedimentation agent, it was the same as Emulsion A. A part of the obtained emulsion was sampled, and a TEM image of a replica of the emulsion grains was observed. 96% of TPA is tabular grains having a {100} major plane and an aspect ratio of 3 or more, having an average diameter of 0.7 μm and an average aspect ratio of 6.
0, average aspect ratio 1.7, C.I. V. Was 0.19.

Emulsion J Aqueous gelatin-7 (1.2 liters of H ₂ O, 25 g of gelatin, 0.3 g of KBr, pH 6.
0) was added, and while maintaining the temperature at 32 ° C., the Ag-41 solution and the X-41 solution were simultaneously mixed and added at 30 ml / min for 5 minutes. Next, a polyvinyl imidazole copolymer 2 is represented by the formula (5). Weight average molecular weight 1.5 × 10 ⁵ , x: y:
z: w = 60: 7: 13: 30] and H ₂ O 1
An aqueous solution containing 00 ml was added, and the pH was adjusted with 1N NaOH solution.
9.0. Then, the temperature was raised to 60 ° C., the pH was readjusted to 9.0, the silver potential was adjusted to 25 mV using a KBr solution (KBr 0.1 g / ml), and then the Ag-41 solution and the X-41 solution were adjusted to the potential. And added simultaneously for 20 minutes. Ag-
The addition flow rate of Liquid 41 was 25 ml / min. After stirring for 3 minutes after the addition, a precipitant was added, the temperature was lowered to 30 ° C, and the pH was lowered.
4.0 and the emulsion was allowed to settle. Wash the sedimented emulsion with water, 3
The temperature was raised to 8 ° C, a gelatin solution was added, and pBr 2.8, p
Adjusted to H6.4.

[0455]

Embedded image

A TEM image of a replica of the obtained emulsion particles was observed, and the result was as follows. 95% of the TPA has a {100} plane as its main plane, a right-angled parallelogram, an average diameter of 0.55 μm, and an average aspect ratio of 4.
0, and the average aspect ratio was 1.8. Emulsion H was formed by the method (2) of (IV) -1, Emulsion I was formed by the method of 1), and Emulsion J was formed by the method of 2).

Emulsions F to H were subjected to chemical sensitization in exactly the same manner as in Example 1, and the gradation was changed to a medical film HR-S30, HR-HA30, HR-A30, manufactured by Fuji Photo Film Co., Ltd.
A light-sensitive material was prepared in exactly the same manner as in Example 1 except that the gradation was substantially the same as HR-C30, UR-1, and UR-3, and the same evaluation as in Example 1 was carried out. The light-sensitive material prepared in Example 1 had excellent photographic characteristics.

[0458]

According to the present invention, the performance required in X-ray diagnosis, such as sensitivity, sharpness, and balance between sensitivity and image quality, is improved.

[Brief description of the drawings]

FIG. 1 shows a top view of a tetrahedral AgBr particle.

FIG. 2 shows an adsorption mode of an adsorbent having a large number of weak adsorbing groups in one molecule.

FIG. 3 shows an example of dislocation lines and plane defects of tabular grains.

FIG. 4 shows a spatial frequency (lp / mm) and a contrast transfer function (CTF) for explaining characteristics of a radiographic intensifying screen used in a combination of the silver halide photographic light-sensitive material of the present invention and a radiographic intensifying screen. The graph which shows the relationship.

FIG. 5 is a spectrum showing characteristics of a green light filter used in combination with a tungsten light source for sensitivity measurement of a silver halide photographic light-sensitive material.

[Explanation of symbols]

21 ... adsorbent C ⁰ of the main chain 23 ... covalently attached to the backbone of the adsorbent A ⁰ of AgX grain surface 22 ... adsorbents A ⁰
30 ... a portion corresponding to the nucleus 31 ... dislocation lines 32, 33, 35 ... step lines on the edge surface 34 ... dislocation lines moved

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI G03C 1/04 501 G03C 1/04 501 1/043 1/043 1/09 1/09 1/18 1/18 1/34 1 / 34 1/38 1/38 1/46 1/46 1/74 1/74 1/83 1/83 1/95 1/95 5/17 5/17 5/26 5/26 5/30 5/30 5/305 5/305 5/31 5/31 5/395 5/395 G21K 4/00 G21K 4/00 A

Claims (33)

[Claims] 1. A silver halide photographic material having at least one silver halide emulsion layer on a support,
When the coated silver amount per one side of the silver halide emulsion is 2.0
g / m ² or less, and the silver halide emulsion has at least a dispersing medium and silver halide grains, and at least 60% of the total projected area of the silver halide grains has a main plane of {10
Tabular grains having anisotropically grown crystal defects having an aspect ratio (diameter / thickness) of 2.0 or more on a 0 ° plane, and
Aspect ratio (long side length / short side) of a rectangular parallelogram surrounded by the {100} plane of the edge of the tabular grains or a rectangular parallelogram formed by extending the {100} plane of the edge (Length of side) is 1 to 6, and the silver halide emulsion is produced in the presence of compound A ⁰ and / or compound B ⁰ . Here, compound A ⁰ represents an organic compound in which two or more molecules of an adsorbent for promoting the formation of {100} planes of AgBr particles are covalently bonded in one molecule, and compound B ⁰ has two alcohol groups in one molecule. It represents an organic compound other than gelatin having the above, and both represent organic compounds other than gelatin and protein. 2. The defect according to claim 1, wherein said defect is a defect formed by adding Ag ⁺ and a halogen ion while compound A ⁰ or compound B ⁰ is adsorbed on silver halide grains. Silver halide photographic material. 3. A silver halide photographic light-sensitive material according to claim 1, wherein said defects are not substantially formed during the growth of said tabular grains. 4. The defect is formed by forming at least one halogen composition gap interface during nucleation, wherein the halogen composition gap interface is Cl ⁻ or Br.
^{2. The} silver halide photographic light-sensitive material according to claim 1, wherein the silver halide photographic material has a halogen composition difference of not less than 10 mol% in -content or I ^- content. 5. The silver halide photographic material according to claim 1, wherein the silver halide tabular grains have silver halide projections having an epitaxial junction. 6. A silver halide grain comprising a coordination metal complex or a metal ion containing a metal of a Group 3 to 14 element of the Periodic Tables 4, 5 and 6 in a crystal lattice. Item 6. The silver halide photographic material according to any one of Items 1 to 5. 7. The method according to claim 1, wherein the tabular silver halide emulsion contains a compound represented by the following general formula (1) and a compound represented by the following general formula (2). 2. The silver halide photographic material according to claim 1. Embedded image In the formula, R ₁ represents a sulfoalkyl group or a carboxyalkyl group, and R ₂ represents an alkyl group, an alkenyl group, or an aryl group. R ₃ represents an alkyl group. X represents a counter ion necessary for neutralizing the molecular charge, and n represents a number required for neutralization. However, when an inner salt is formed, n is 0.
It is. Z ₁ and Z ₂ each represent a group of nonmetallic atoms necessary to complete a benzene ring or a naphtho ring. Embedded image Wherein to no R ₁₁ R ₁₄ each represents an alkyl group, X ₁
Represents a counter ion necessary to neutralize the charge of the molecule, and n
₁ represents the number required for neutralization. However, when an inner salt is formed, n ₁ is 0. Z ₁₁ and Z ₁₂ each represent a group of nonmetallic atoms necessary to complete a benzene ring or a naphtho ring. 8. The tabular silver halide grains have a silver iodide content of 1 mol% or less, and the silver iodide content is maximum near the surface of the tabular silver halide grains and the maximum value is at least The silver halide photographic light-sensitive material according to any one of claims 1 to 7, wherein the content is at least 6 times the minimum silver iodide content inside the silver halide grains. 9. The silver halide photographic material according to claim 1, comprising a compound represented by the general formula (3). Embedded image Wherein, Z _a represents an atomic group necessary for forming a 5- or 6-membered heterocyclic nucleus. The R _1a represents an aliphatic group, R _2a is a hydrogen atom or an aliphatic group, R _3a and R _4a are each a hydrogen atom, a halogen atom, an aliphatic group, an alkoxy group, hydroxy group or an aromatic group, R _1a , R _2a , R _3a and R _{4a represent} at least one substituent having a propargyl group, a butynyl group or a propargyl group. X _a ^- represents an anion. n _a represents 1 or 2, n _a when the compound forms an intramolecular salt represent 1. 10. The silver halide photographic light-sensitive material according to claim 1, comprising a compound represented by the general formula (4). Embedded image Wherein Z is —SO ₃ M, —COOR _1b , —OH and —N
Represents a heterocyclic ring having at least one directly or indirectly of the HR _2b, M represents a hydrogen atom, an alkali metal atom or a quaternary ammonium group or a quaternary phosphonium group, R _1b
Represents a hydrogen atom, an alkali metal atom or an alkyl group having 1 to 6 carbon atoms, R _2b represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, —COR _3b , —COOR _3b or —SO ₂ R _3b ; _3b represents a hydrogen atom, an aliphatic group or an aromatic group. 11. The silver halide photographic material according to claim 1, wherein said tabular silver halide grain emulsion is chemically sensitized with a selenium compound. 12. The general formula (5), (6) or (7)
A compound represented by the formula:
A silver halide photographic light-sensitive material according to any one of the preceding claims. (5) _{R-SO 2 S-M (} 6) R-SO 2 S-R 1 (7) R-SO 2 S-Lm-SSO 2 -R 2 Formula, R, R ^1, also R ² is the same It may be different and represents an aliphatic group, an aromatic group, or a heterocyclic group, and M represents a cation. L represents a divalent linking group, and m is 0 or 1. The compounds of the general formulas (5) to (7) may be polymers containing a divalent group derived from the structure represented by any of the formulas (5) to (7) as a repeating unit. 13. The silver halide photographic material according to claim 1, comprising a compound represented by the general formula (8). Embedded image In the formula, R _2c , R _3c , R _5c and R _6c may be the same or different and each is a hydrogen atom or a group which can be substituted on a benzene ring, and R _1c and R _4c are hydrogen atoms or deprotected under alkaline conditions. A possible protecting group. R _2c to R _6c , OR _1c and OR _4c may form a ring together. 14. The silver halide photographic material according to claim 1, further comprising an infrared absorbing dye. 15. The silver halide photographic material according to claim 1, further comprising a polymer latex. 16. The silver halide photographic light-sensitive material according to claim 1, which contains colloidal silica. 17. The silver halide photographic material according to claim 1, further comprising a surfactant containing a polyalkylene oxide and / or fluorine. 18. The protective layer contains a matting agent comprising a polymer having a hydrophilic group in the protective layer.
17. The silver halide photographic material according to any one of 17. 19. The silver halide photographic light-sensitive material according to claim 1, wherein the swelling ratio is 20% or more and less than 200%. 20. The photographic material according to claim 1, wherein the photographic material has a photosensitive silver halide emulsion layer on both sides of a support, and the photographic material is subjected to radiation sensitization. Exposure to monochromatic light having the same wavelength as the main emission peak wavelength of the screen and a half width of 15 ± 5 nm, development processing, and then peeling off the photosensitive silver halide emulsion layer on the side opposite to the exposed surface When the density was measured after the exposure, the exposure required for the density obtained in the photosensitive silver halide emulsion layer on the exposed surface side to reach a value obtained by adding 0.5 to the minimum density was 0.010.
A silver halide photographic light-sensitive material having a sensitivity of from lux seconds to 0.035 lux seconds. 21. A method wherein a silver halide photographic material is provided between a support and at least one photosensitive silver halide emulsion layer.
The silver halide photographic light-sensitive material according to any one of claims 1 to 20, further comprising a hydrophilic colloid layer containing a dye that is decolorized in a developing process or a fixing process. 22. The silver halide photographic material according to claim 21, wherein the dye is contained as microcrystalline particles. 23. The method according to claim 20, wherein the emulsion layers on both sides have the characteristics defined in claim 20.
2. The silver halide photographic light-sensitive material according to any one of 2. 24. A radiographic image comprising the silver halide photographic light-sensitive material according to claim 20, and two radiographic intensifying screens respectively disposed on the front and rear sides of the light-sensitive material. Wherein at least one of the radiation intensifying screens satisfies the following requirements: a combination of a silver halide photographic material and a radiation intensifying screen. (I) When viewed from the side facing the silver halide photographic material, the protective layer, the phosphor layer, and the support layer are arranged in this order. (II) The protective layer is a transparent synthetic resin layer having a thickness of 1 μm or more and 10 μm or less formed by coating on the phosphor layer. (III) Contrast transfer coefficient (CTF) is spatial frequency 1
Lines / mm is 0.79 or more, and spatial frequency 3 lines / mm
It is 0.36 or more in mm. (IV) 30% for X-ray of 80KVp through 7cm of water
The above absorption amount is shown. 25. The combination of a silver halide photographic material and a radiation intensifying screen according to claim 23, wherein the thickness of the radiation intensifying screen defined in claim 24 is 95 μm or more and 300 μm or less. body. 26. Light emitted from a radiation intensifying screen disposed in front of a silver halide photographic light-sensitive material,
26. The combination of a silver halide photographic light-sensitive material and a radiation intensifying screen according to claim 24 or 25, wherein the crossover radiated to the emulsion layer on the back surface of the silver halide photographic light-sensitive material is 15% or less. body. 27. The silver halide photographic light-sensitive material according to claim 24, wherein each of the front and rear radiation intensifying screens has the characteristics defined in claim 24. And radiation intensifying screen. 28. The method for processing the silver halide photographic material according to claim 1 with a developer, wherein the developer is represented by the following general formula (9). A method for processing a silver halide photographic light-sensitive material, comprising at least one compound. General formula (9) In the formula, X represents an oxygen atom or a sulfur atom, Y represents a hydrogen atom or a substituent, and M represents a hydrogen atom, an alkali metal ion, a quaternary ammonium ion or a quaternary phosphonium ion. 29. The method for processing the silver halide photographic material according to claim 1 with a developer, wherein the developer is an ascorbic acid-based compound and a 3-pyrazolidone-based compound. As a developing agent, and 5
A processing method for a silver halide photographic light-sensitive material, wherein the development processing is completed in at least 30 seconds and at most 30 seconds. 30. The silver halide photographic material according to claim 29, wherein the developer contains at least one compound represented by the general formula (9) according to claim 28. Processing method. 31. A replenishing amount of development and / or fixing per square meter of silver halide photographic light-sensitive material is 25 ml or more.
31. The method according to claim 28, wherein the amount is not more than 0 milliliter.
A method for processing a silver halide photographic material as described in any one of the above. 32. The process according to claim 28, wherein the total processing time of development, fixing, washing and drying of the silver halide photographic material is from 25 seconds to 200 seconds.
The method for processing a silver halide photographic light-sensitive material described in the above item. 33. A silver halide photographic light-sensitive material according to claim 28, wherein the silver halide photographic light-sensitive material is subjected to a non-hardening treatment in the developing and / or fixing step. Processing method.