JPH08220693A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE: To provide a highly sensitive silver halide photographic sensitive material excellent in rapid processability and not marked with a roller. CONSTITUTION: This silver halide photographic sensitive material has at least one silver halide emulsion layer on a substrate, and >=50% of the silver halide grains contained in the emulsion layer in the total projected area have >=3 average aspect ratio, the emulsion layer contains a silver halide grain contg. >=50 mol% silver chloride, and the substrate is a drawn film consisting of a syndiotactic styrene polymer.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic light-sensitive material having high sensitivity, excellent ultra-rapid processing property, and no roller mark.

[0002]

2. Description of the Related Art In photographic light-sensitive materials, medical X-ray films generally require urgency, and therefore, rapid development processing is strongly desired.

Various methods are known as means for accelerating the developability. For example, as a silver halide emulsion, it is known to use a silver chloride emulsion having excellent developability and fixability. However, silver chloride grains have a drawback that it is difficult to obtain high sensitivity as compared with silver bromide grains and silver iodobromide grains.

In recent years, sensitivity, sharpness, covering,
It is well known that so-called tabular grains having a grain size larger than the grain thickness are preferable as the silver halide grains for enhancing the power. However, the tabular grains are
It has major drawbacks in handleability such as pressure fog and pressure desensitization peculiar to tabular grains. In particular, it has a drawback that black spots (referred to as roller marks) are likely to occur frequently due to the pressure of the conveying roller of the automatic processor. For medical light-sensitive materials, these black spots may lead to serious misdiagnosis, and therefore their improvement has been strongly desired.

On the other hand, polyethylene terephthalate (hereinafter referred to as PET) or cellulose triacetate (hereinafter referred to as TAC) or the like has been mainly used as a support for a silver halide photographic light-sensitive material. Of these, P
ET is suitable as a photosensitive material for medical use and printing, and has been used as a support excellent in strength / rigidity or dimensional stability of the support.

However, according to the study by the present inventor, in the light-sensitive material coated with a conventional PET base as a support and coated with a high-sensitivity silver halide emulsion having good developability, the above-mentioned roller mark is apt to occur. Turned out to be.

It has been desired to develop a silver halide photographic light-sensitive material comprising a support having high sensitivity, rapid processability and pressure resistance, and having good rigidity and dimensional stability.

[0008]

SUMMARY OF THE INVENTION It is, therefore, an object of the present invention to provide a silver halide photographic light-sensitive material which has high sensitivity, is excellent in rapid processability and does not generate roller marks.

[0009]

The objects of the present invention have been achieved by the following.

In a silver halide photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer on a support, 50% or more of the total projected area of silver halide grains in the emulsion layer has an average aspect ratio of 50% or more. A halogen containing a silver halide grain having a ratio of 3 or more and a silver chloride content of 50 mol% or more, and the support is a stretched film made of a styrene polymer having a syndiotactic structure. Silver halide photographic light-sensitive material.

The present invention will be described in detail below.

In the silver halide photographic light-sensitive material of the present invention, at least one silver halide emulsion layer contains silver chloride grains having an average silver chloride content of 50 mol% or more, preferably 70 mol% to 90 mol%. To do.

The layer containing silver halide grains used in the present invention has an average aspect ratio of 3 or more, preferably 5 to 8.

The tabular silver halide grains referred to in the present invention are crystallographically classified as twins. Twins are silver halide crystals that have one or more twin planes in one grain, but the morphology of twins is classified by Klein and Moiser in the article Photographie Correspondents (Photographi
sches Korrespondenz) Vol. 99, p. 99, p. 100, p. 57.

The tabular silver halide grains used in the present invention mainly have an even number of parallel twin planes, and these twin planes may or may not be parallel to each other. Particularly preferably, it has two twin planes.

The outer wall of the crystal of the tabular silver halide grains according to the present invention may be substantially composed of {111} planes or {100} planes. Further, it may have both a {111} plane and a {100} plane. In this case, 50% or more of the grain surface is a {111} plane, more preferably 60% to 90% is a {111} plane, and particularly preferably 70 to 95% is a {111} plane. It is preferable that the planes other than the {111} plane are mainly the {100} plane. This plane ratio is {111} plane and {100} plane in the adsorption of sensitizing dye.
Utilizing the difference in adsorption dependence with the surface [T. Tani, J. Imaging
Sci. 29,165 (1985)].

The tabular silver halide grains according to the present invention are
It may be polydisperse or monodisperse, but is preferably monodisperse. Specifically, (standard deviation of particle size / average particle size) x 100 = width of particle size distribution
When the width of the distribution is defined by the relative standard deviation (coefficient of variation) that can be expressed by (%), it is preferably 25% or less, more preferably 20% or less, and particularly preferably 15% or less.

The tabular silver halide grains of the present invention preferably have a small thickness distribution. Specifically, (standard deviation of thickness / average thickness) x 100 = width of thickness distribution
When the breadth of distribution is defined by (%), it is preferably 25% or less, more preferably 20% or less, and particularly preferably 15% or less.

Further, it is preferable that the distribution of the halogen content of individual grains in the tabular silver halide grain emulsion of the present invention is also small. Specifically, (standard deviation of halogen content / average halogen content) x 10
0 = 25% or less is preferable when the breadth of the halogen content is defined by the breadth (%) of the halogen content, more preferably 20% or less, and particularly preferably 15% or less.

In the present invention, the tabular silver halide grains are preferably hexagonal. Hexagonal tabular grains
(Hereinafter also referred to as hexagonal tabular grains) means its main plane ({111}
The shape of (face) is hexagonal, and the maximum adjacency ratio is 1.0 to 2.
Say it is 0. Here, the maximum adjacent side ratio is the ratio of the length of the side having the maximum length to the length of the side having the minimum length forming a hexagon. In the present invention, it is also preferable that the hexagonal tabular grains have rounded corners if the maximum adjacent side ratio is 1.0 to 2.0. The length of a side when the corner is rounded is represented by the distance between the straight line portion of the side and the intersection with the line obtained by extending the straight line portion of the adjacent side. Further, it is also preferable that the tabular grains are more rounded and have a substantially circular shape.

In the present invention, each side forming the hexagon of the hexagonal tabular grain preferably has a half or more of a substantially straight line. In the present invention, the ratio of adjacent sides is 1.0
More preferably, it is ˜1.5.

The silver halide grains according to the present invention may have dislocations. The dislocation is, for example, JF Hamilton, Phot.Sc
i.Eng, 57 (1967), T.Shiozawa, J.Soc.Phot.Sci.Japa
n, 35, 213 (1972), and can be observed by a direct method using a transmission electron microscope at low temperature. That is, the silver halide grains, which were taken out carefully so as not to apply pressure enough to cause dislocation to the grains from the emulsion, were placed on the mesh for electron microscope observation, and the sample was taken to prevent damage (printout etc.) due to electron beams. In the cooled state, observation is performed by the transmission method. At this time, the thicker the particles, the more difficult it is for the electron beam to penetrate, so it is possible to observe more clearly by using a high-pressure electron microscope (200 KV or more for particles having a thickness of 0.25 μm). .

The position and number of dislocations for each grain can be determined from the photograph of the grain obtained by such a method. The position of dislocation of the silver halide grain according to the present invention is 0.58 L from the center of the halide grain toward the outer surface.
It is desirable that it occurs in a region of up to 1.0 L, but more preferably it occurs in a region of 0.80 L to 0.98 L. The direction of the dislocation line is approximately from the center to the outer surface, but it often meanders.

In the present invention, the center of the silver halide grain means that silver halide microcrystals are dispersed in a methacrylic resin in the same manner as the method described in the summary of Inoue et al. When solidified and made into an ultrathin section with a microtome, and focusing on the section sample with the maximum cross-sectional area and the cross-sectional area of 90% or more than that, when drawing the minimum circumscribed circle to the cross section Is the center of the circle. In the present invention, the distance L from the center to the outer surface is defined as the distance between the center of the circle and the point intersecting the outer circumference of the particle when a straight line is drawn outward from the center of the circle.

With respect to the number of dislocations of the silver halide grain according to the present invention, it is desirable that 50% (number) or more of grains containing one or more dislocations are present, and the ratio of the number of tabular grains having dislocation lines (number) ) Is higher, the more preferable.

In the present invention, the particle size is a diameter when a projected image of particles is converted into a circular image having the same area. The projected area of a grain can be calculated from the sum of the grain areas. All of them can be obtained by observing, with an electron microscope, a silver halide crystal sample distributed on the sample stage to the extent that grains do not overlap.

The average projected area diameter of the tabular silver halide grains in the present invention is represented by the diameter corresponding to the circle of the projected area of the grains, and is preferably 0.30 μm or more, more preferably
It is 0.30 μm to 5 μm, more preferably 0.40 μm to 2 μm.

The particle size can be obtained by enlarging and projecting the particles with an electron microscope at a magnification of 10,000 to 70,000 and measuring the area of the projected image on the print.

The average particle diameter (φi) can be calculated by the following equation, where n is the number of measured particle diameters and ni is the frequency of particles having the particle diameter φi.

Average particle size (φi) = Σnidi / n (The number of measured particles is indiscriminately 1.000 or more.) The particle thickness can be obtained by observing the sample obliquely with an electron microscope. . The preferred thickness of the tabular grains of the present invention is 0.03-1.0 μm, more preferably
It is 0.05 to 0.5 μm.

The longest distance (a) between two or more parallel twin planes of the silver halide grain of the present invention and the grain thickness (b).
The ratio (b / a) is preferably 5 or more, and the ratio is preferably 50% (number) or more.

The twin plane distance (a) can be determined as follows. That is, observation of the section using the above transmission electron microscope, with respect to the main plane, arbitrarily select 100 or more tabular silver halide grains showing a cross section cut substantially perpendicularly, for each grain ( It can be obtained by measuring a) and averaging them.

In the present invention, the average value of (a) is 0.008 μm.
It is preferably not less than 0.010 μm and more preferably not more than 0.05 μm.

Further, in the present invention, it is necessary that (a) is in the above value range and at the same time, its variation coefficient is 35% or less, preferably 30% or less.

Further, in the present invention, tabularity expressed by the following equation: A in consideration of factors of aspect ratio and grain thickness: A
= ECD / b2 is preferably 20 or more.

Here, ECD is the average projected diameter (μm) of tabular grains.
(B) is the thickness of the particles. Here, the average projected diameter represents the number average of diameters of circles having an area equal to the projected area of tabular grains.

In the tabular grains of the present invention, silver chlorobromide or silver chloroiodobromide having an average silver chloride content of 0 mol%, preferably 70 mol% or more may be used as silver halide. The preferable silver halide composition is 2 mol% or less, preferably
An example is a silver iodochlorobromide emulsion containing 0.1 to 1.5 mol% silver iodide.

The tabular halogenated grains have at least two layer structures (core / core) having substantially different halogen compositions in the grains.
It may have a shell structure) or a uniform composition, but preferably has a core / shell structure. In this case, the grain center may have a halogen composition region different from that of the core. In the case of such a layered structure, grains having a high silver iodide phase in the grain and a low silver iodide phase or a silver bromide phase in the surface phase are preferable. In the present invention, halogen conversion type (conversion type) particles may be used.
The halogen conversion type is preferably 0.2 mol% to 2.0 mol% with respect to the amount of silver, and the conversion time may be physical ripening or after completion. As a conversion method, an aqueous halogen solution or a silver halide grain having a smaller solubility product with silver than the halogen composition on the grain surface before the halogen conversion is usually added. At this time, the particle size is preferably 0.2 μm or less, more preferably 0.02 to 0.1 μm.

The silver halide grain of the present invention comprises a water-soluble silver salt solution and a water-soluble halide for obtaining a silver halide emulsion on a seed crystal as described in, for example, JP-A-60-138538. In the method for producing an emulsion by supplying the solution in the presence of a protective colloid, (a) the silver iodide content is 0 to 5 mol%.
From the beginning of the formation of silver halide precipitate in
Provide a particle generation step to keep the pBr of the mother liquor at 2.5 to -0.7,
(B) Subsequent to the grain forming step, a silver halide solvent is contained in the mother liquor to form ^10-5 mol to 2.0 mol of silver halide solvent per mol of silver halide to form substantially monodispersed spherical silver halide seed grains. Or a seed particle step of forming a silver halide twin crystal grain by raising the temperature of the mother liquor to 40 to 80 ° C. subsequent to the particle generation step, and A method is preferably used in which a growing step of adding seed silver particles and a water-soluble halide solution and / or silver halide particles to enlarge seed particles is provided.

Here, the mother liquor refers to a liquid (including a silver halide emulsion) that is used in the preparation stage of a silver halide emulsion up to a completed emulsion.

In the preparation of the emulsion of the present invention, a silver halide solvent such as ammonia, thioether or thiourea can be present during the seed grain forming step and growth.
Conditions for enlarging the seed particles are, for example, JP-A-51-39027.
No. 55, No. 55-142329, No. 58-113928, No. 54-48521, No.
As in 58-49938, a water-soluble silver salt solution and a water-soluble halide solution are added by the double jet method, and the addition rate is within the range where new nucleation does not occur according to particle enlargement and Ostwald ripening does not occur. Can be changed gradually. As another method, it is also possible to use a method in which silver halide grains are added and dissolved and recrystallized to enlarge the size as described in Section 88 of the 1983 Annual Meeting of the Photographic Society of Japan.

The silver halide grains of the present invention can be used in the grain formation process and / or the growth process in a cadmium salt, a zinc salt, a lead salt,
At least one metal ion selected from thallium salt, iridium salt (including complex salt), rhodium salt (including complex salt), and iron salt (including complex salt) is added to the inside of the particle and / or the surface layer of the particle. A metal element can be contained, and a reduction sensitizing nucleus can be imparted to the inside of the grain and / or the grain surface by placing in a suitable reducing atmosphere.

The emulsion layer containing the silver halide grains of the present invention may contain other silver halide grains as long as the effects of the present invention are not impaired. The other particles referred to here may be normal particles such as a cube, a tetrahedron, and an octahedron,
It may consist of spherical particles or twinned particles.

Next, the styrene polymer having a syndiotactic structure according to the present invention will be described in detail.

The support (hereinafter abbreviated as SPS) composed of a stretched film composed of a styrene polymer having a syndiotactic structure or a composition containing the syndiotactic structure in the present invention means that the constitutional unit is a syndiotactic stereo structure. Refers to a homopolymer composed of SPS units having regularity, but also includes a small amount of SPS modified with a second component such as 20 mol% or less, preferably 10 mol% or less, more preferably 5 mol% or less. Be done.

The modified SPS is, for example, an olefin monomer such as ethylene, propylene, butene or hexene,
It is an SPS modified with olefin monomers such as butadiene and isoprene, cyclic olefin monomers, cyclic diene monomers and polar monomers such as methyl methacrylate, maleic anhydride and acrylonitrile.

It is generally produced by polymerizing styrene or a derivative thereof under a suitable reaction condition using an organometallic catalyst. The syndiotactic polystyrene is a racemic diad having a stereoregularity of 75% or more, preferably 80% or more, or a racemic pentad, 30% or more, preferably 50% or more. In that case, a general plastic plasticizer can be added as the second component in a range that does not deteriorate the flexural modulus, and such a thing is performed to obtain an appropriate flexural modulus.

SPS can be synthesized by polymerizing styrene or a derivative thereof in the presence of a catalyst of a condensation product of a titanium compound and a trialkylaluminum at an appropriate reaction temperature. These are disclosed in JP-A-62-187708 and JP-A-1-46912.
The method described in JP-A No. 1-178505 and the like can be referred to. The degree of polymerization of SPS is not particularly limited, but those of 10,000 or more and 5 million or less can be preferably used. In order to increase the flexural modulus of SPS, it is necessary to select the optimum stretching conditions. 30 ° C ± 25 from the glass transition point of unstretched film
At the point of ℃, that is, at 120 ℃ ± 25 ℃, first stretch longitudinally 3.3 ± 0.3 times. Next, it is laterally stretched by 3.6 ± 0.6 times under the same temperature condition. The heat treatment after stretching is performed at 230 ± 18 ° C. Good results can be obtained if the heat treatment is performed not only in the first stage but also in the second stage. Thus, an SPS film having a flexural modulus of 350 kg / mm ² or more is manufactured.

In order to actually apply the SPS film to the X-ray film, an anthraquinone dye can be used as the blue coloring dye of the support. The anthraquinone dye can be substituted with any substituent at the 1st to 8th positions of the anthraquinone. The preferable substituent represents optionally substituted aminobenzene, a hydroxy group, a nitro group, an amino group, or a hydrogen atom. These substituents are represented by R, and the positions of R are represented by R _{1 to} R ₈ in correspondence with supplementary characters.
At least one of R _{1 to} R ₈ is optionally substituted aminobenzene. Substituents on the aminobenzene ring are represented by f, and f corresponds to the positions 1 to 5 of the benzene ring.
It is represented by _{1 to} f ₅ . f ₁ , f ₂ , f ₃ , f ₄ and f ₅ are substituted with a hydrogen atom, a halogen atom, an alkoxy group, an optionally substituted alkyl group, an allyloxy group, an aralkoxy group, a hydroxyalkyl group, a cyclohexylsulfonamide group, etc. It

The specific examples of the anthraquinone dyes are shown below, but the invention is not limited thereto.

Specific compound (1) 1,4-diphenylaminoanthraquinone (2) 1,4-di (2,4,6-trimethylphenyl) anthraquinone (3) 1,4-di (2,4-diethyl- 4-Methylphenyl) anthraquinone (4) 1,4-di (2,4,6-trimethyl-4-cyclohexylsulfonamidophenyl) anthraquinone (5) 1-methoxyphenylamino-4-hydroxy-5-methoxyphenylamino- 8-Hydroxyanthraquinone (6) 1,4-di (2,4,6-tripropylcyclohexylsulfonamidophenyl) anthraquinone (7) 1-Ethoxyphenylamino-4-hydroxy-5-methoxyphenylamino-8-hydroxyanthraquinone (8) 1,4-di (2,4,6-trimethoxyphenylamino) anthraquinone (9) 1,4-di (2,4,6-triethylphenyl) anthraquinone (10) 1,4-di (2 , 4-diisopropoxy-4-methylphenyl)
Anthraquinone (11) 1,4-di (2,4,6-trichloro-4-cyclohexylsulfonamidophenyl) anthraquinone (12) 1- (2,4,6-trimethoxyphenylamino) -4-hydroxy-5- (2,4,6-Trimethoxyphenylamino) -8-hydroxyanthraquinone (13) 1,4-di (2,4,6-tripropylcyclohexylsulfonamidophenyl) anthraquinone (14) 1,5-dimethoxyphenylamino -4,8-Dihydroxyanthraquinone In such a film having a high flexural modulus, it is difficult to apply the photographic layer as it is and firmly bond it. But,
The fact that there are many patents and documents regarding the method is described in pages 3 to 4 of JP-A-3-54551 and is effective.

For example, regarding the surface treatment, it is described that a corona discharge treatment is performed and an undercoat layer is further applied. Examples of the undercoat layer include vinylidene chloride, methacrylic acid, acrylic acid, itaconic acid, maleic anhydride and the like.

The thickness of the support is preferably 50 to 250.
μm, particularly preferably 70 to 200 μm.

The silver halide emulsion used in the practice of the present invention has a Nudel water washing method and a flocculation method in order to remove soluble salts and obtain a pAg ion concentration suitable for chemical sensitization after the completion of the growth of silver halide grains. A sedimentation method or the like may be used, and a preferable washing method is, for example, Japanese Patent Publication
A method using an aromatic hydrocarbon aldehyde resin containing a sulfo group described in 35-16086, or a desalting method using a polymer flocculant such as Exemplified G-3 and G-8 described in JP-A-2-7037. Can be mentioned.

In the silver halide emulsion according to the present invention, various hydrophilic colloids for wrapping silver halide are used as a binder. For this purpose, gelatin and other synthetic polymers such as polyvinyl alcohol and polyacrylamide, colloidal albumin,
Photographic binders such as polysaccharides and cellulose derivatives are used.

In the case of chemical sensitization, ordinary sulfur sensitization,
Reduction sensitization, precious metal sensitization and combinations thereof are used. More specific chemical sensitizers include sulfur sensitizers such as allyl tiocarbamide, thiourea, thiosulfate, thioether and cystine;
Potassium chloroaurate, aura thiosulfate and Potassium chloroparadate
Noble metal sensitizers such as lladates); reduction sensitizers such as tin chloride, phenylhydrazine and retactone.

The photographic emulsions used in the practice of this invention may be spectrally sensitized with cyanine dyes and the like. The sensitizing dyes may be used alone, or a combination thereof may be used, and the combination of the sensitizing dyes is often used particularly for the purpose of supersensitization.

The photographic light-sensitive material using the silver halide photographic emulsion of the present invention can use various photographic additives in the steps before and after physical ripening or chemical ripening of the emulsion. Examples of compounds that can be used in such a step include Research Disclosure (RD) 17643 and (RD) 18716 (1
And various compounds described in (RD) 308119 (December 1989). These three (RD)
The types and locations of the compounds described in are listed below.

Additive RD-17643 RD-18716 RD-308119 Page Classification Page Page Classification Chemical sensitizer 23 648 Upper right 996 Sensitizing dye 23 648-649 996-8 IV A Desensitizing dye 23 998 IV B Dye 25-26 649 to 650 1003 Development accelerator 29 XXI 648 Upper right fog inhibitor / stabilizer 24 649 Upper right 1006 to 7 Whitening agent 24 998 Hardener 26 651 Left 1004 to 5 Surfactant 26 to 27 XI 650 Right 1005 to 6 XI Plasticizer 27 XXI 650 Right 1006 XXI Sliding Agent 27 XXI Matting Agent 28 XVI 650 Right 1008-9 XVI Binder 26 XXII 1003-4 Support 28 XVII
1009 XVII As the hardener which can be used in the silver halide photographic light-sensitive material of the present invention, mucochloric acid, mucobromic acid, mucophenoxycycloric acid, mucophenoxybromic acid, formaldehyde, dimethylolurea, trimethylolmelamine, glyoxal, monomethylglyoxal , 2,3-
Aldehyde compounds such as dihydroxy-1,4-dioxane, 2,3-dihydroxy-5-methyl-1,4-dioxane, succinaldehyde, 2,5-dimethoxytetrahydrofuran, glutaraldehyde; divinyl sulfone, methylene bismaleimide, 5 -Acetyl-1,3-diacryloyl-hexahydro-s-triazine, 1,3,5-triacryloyl-hexahydro-s-triazine, 1,3,5-trivinylsulfonyl-hexahydro-s-triazinebis (vinylsulfonyl) (Methyl)
Active vinyl compounds such as ether, 1,3-bis (vinylsulfonylmethyl) propanol-2, bis (α-vinylphonylacetamido) ethane; 2,4-dichloro-6-hydroxy-
s-Triazine sodium salt, 2,4-dichloro-6-methoxy-s-triazine, 2,4-dichloro-6- (4-sulfoanilino)
active halogen compounds such as -s-triazine sodium acid, 2,4-dichloro-6- (2-sulfoethylamino) -s-triazine and N, N'-bis (2-chloroethylcarbamyl) piperazine; Bis (2,3-epoxypropyl) methylpropylammonium ・ p-toluenesulfonate, 1,4-bis (2 ′,
Epoxy compounds such as 3′-epoxypropyloxy) butane, 1,3,5-triglycidyl isocyanurate, and 1,3-diglycidyl-5- (γ-acetoxy-β-oxypropyl) isocyanurate; 2,4, Ethyleneimine compounds such as 6-triethyleneimino-s-triazine, 1,6-hexamethylene-N, N'-bisethyleneurea and bis-β-ethyleneiminoethylthioether; 1,2-di (methanesulfonoxy) ) Ethane, 1,4-di (methanesulfonoxy) butane, 1,5
-Methanesulfonic acid ester-based compounds such as di (methanesulfonoxy) pentane; carbodiimide-based compounds; isoxazole-based compounds; inorganic compounds such as chrome meiban and U.S. Pat. Nos. 3,057,723 and 3,396,029
Nos. 4,161,407 and the like. The amount of hardener varies depending on the type of hardener and the drying conditions during the production of the light-sensitive material, so it cannot be decided in any way, but the amount of hardener per 100 g of dried gelatin is
It can be appropriately adjusted within the range of 0.05 to 100 mmol, particularly 0.1 to 50 mmol.

The silver halide photographic light-sensitive material of the present invention comprises
In addition, if necessary, an antihalation layer, an intermediate layer, a filter layer, etc. can be provided.

The processing of the light-sensitive material of the present invention is carried out, for example, in RD-17643, XX to XXI, pages 29 to 30 or 308119, XX.
~ XXI, treatments with treatment solutions as described on pages 1011-1012 may be performed.

Developers for black and white photographic processing include dihydroxybenzenes (eg hydroquinone), 3-pyrazolidones (eg 1-phenyl-3-pyrazolidone), aminophenols (eg N-methyl-aminophenol).
Etc. can be used alone or in combination.
It should be noted that the developer may be a known one such as preservative, alkaline agent, p
An H buffer, an antifoggant, a film hardener, a development accelerator, a surfactant, an antifoaming agent, a toning agent, a water softener, a dissolution aid, a viscosity imparting agent and the like may be used as necessary.

A fixing agent such as thiosulfate or thiocyanate is used in the fixing solution, and may further contain a water-soluble aluminum salt such as aluminum sulfate or potassium alum as a hardening agent. Other preservatives, pH adjusters,
It may contain a water softener and the like.

[0064]

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited thereto.

Example 1 (Preparation of Support) Using 200 parts by weight of toluene, 100 parts by weight of styrene, 56 g of triisobutylaluminum, and 234 g of pentamethylcyclopentadienyl titanium trimethoxide were reacted at 96 ° C. for 8 hours. went. The catalyst was decomposed and removed with a methanol solution of sodium hydroxide, and then washed with methanol three times to obtain 34 parts by weight of the desired product.

(Preparation of SPS film) The obtained SPS is 330
The film was melt-extruded from a T-die at a temperature of ° C and rapidly cooled and solidified on a cooling drum to obtain an uncentrifuged film. At this time, the take-up speed of the cooling drum was set in two steps, and the unstretched film having a thickness of 1844 μm was preheated at 135 ° C., longitudinally stretched (3.1 times), and then horizontally stretched at 130 ° C. (3.4 times). ,
Furthermore, heat fixation was performed at 250 ° C. As a result, a biaxially stretched film having a bending elastic modulus of 450 kg / mm ² and a thickness of 175 μm was obtained as a support.

(Application of undercoat layer of SPS film) S obtained
Glycidyl methacrylate 50 wt%, methyl acrylate 10 wt%, butyl methacrylate 4 on PS film
An aqueous dispersion obtained by diluting 0 wt% of a copolymer latex composed of three kinds of monomers with pure water so that the concentration thereof was 10 wt% was applied onto the SPS base of 175 μm and the support of the present invention. (B).

(Coating of undercoat layer of PET film) Copolymer latex consisting of three kinds of monomers of 50% by weight of glycidyl methacrylate, 10% by weight of methyl acrylate and 40% by weight of butyl methacrylate was prepared so as to have a concentration of 10% by weight. A polyethylene terephthalate base having a thickness of 175 μm was prepared by applying an aqueous dispersion obtained by diluting with water as an undercoating liquid to prepare a comparative support (A). (Preparation of Em-1) 1) Preparation of seed emulsion 1 Iodobromide containing 2 mol% of silver iodide having an average grain size of 0.3 μm by the double jet method while controlling at 60 ° C., pAg = 8 and pH = 2.0. Monodisperse cubic grains of silver were prepared.

The emulsion thus obtained was desalted at 40 ° C. using an aqueous solution of demol N (an aldehyde condensate of sodium salt of naphthalene sulfonic acid) manufactured by Kao Atlas [Company] and magnesium sulfate, and then desalted into an aqueous gelatin solution. Redispersion gave a seed emulsion.

2) Grain Growth from Seed Emulsion 1 (Preparation of Em-1) The above seed emulsion was dispersed in a gelatin aqueous solution kept at 40 ° C., and the pH was adjusted to 9.7 with aqueous ammonia and acetic acid. An aqueous ammoniacal silver nitrate solution and an aqueous solution of potassium bromide and potassium iodide were added to this solution by the double jet method.

During the addition, the pH was controlled to be 7.3 and pH = 9.7 to form a layer having a silver iodide content of 35 mol%. Next, an ammoniacal silver nitrate aqueous solution and a potassium bromide aqueous solution were added by the double jet method, and pAg was kept at 9.0 up to 95% of the target particle size,
The pH was continuously changed from 8.0 to 9.0. Then pAg ＝
The grain size was adjusted to 11.0 and the pH was grown to the target grain size while maintaining pH = 8.0. Then, the pH was lowered to 6.0 with acetic acid, and then 5,5'-dichloro-9-ethyl-3,3'-di- (3-sulfopropyl) -oxacarbocyanine sodium salt anhydride was used as a spectral sensitizing dye. Was added to 400 mg / mol AgX, desalted in the same manner as above, and then dispersed in a gelatin aqueous solution.

By this method, the average silver iodide content is 2.0.
In mol%, the average particle size of the tetrahedron with rounded vertices is
Monodisperse silver iodobromide emulsion Em with a coefficient of variation of 0.16 at 1.00 μm
-1 was prepared.

(Preparation of Em-2 [Twin Crystal Emulsion]) A monodispersed twin silver iodobromide emulsion Em-2 containing 1.53 mol% of silver iodide was prepared using the following four kinds of solutions.

[0074] Solution A ossein gelatin _{29.4g HO (CH 2 CH 2 O} ) n [CH (CH 3) CH 2 O] 17 - (CH 2 CH 2 O) m H (n + m = 5.7) (10% methanol solution ) 2.5 ml seed emulsion Em-A 0.588 mol equivalent Make up to 4800 ml with distilled water Solution B AgNO ₃
1404.2g Distilled water to make 2360ml Solution C KBr 968g Kl 20.6g Distilled water to make 2360ml Solution D 1.75N KBr Aqueous solution The following silver potential control amount 60 ° C, as described in JP-B-58-58288 and 58-58299 Using the mixing stirrer of No. 1, the total amount of Solution B and Solution C was added and grown by the simultaneous mixing method at a flow rate of 21.26 ml / min for 111 minutes.

During this period, the silver potential was controlled to be +25 mv using the solution D. After the completion of the addition, the spectral sensitizing dyes (A) and (B) were added in the same manner as Em-1 at 300 mg and 15 mg, respectively, per mol of silver halide, and then desensitized in the same manner as Em-1 to remove excess salts. Salted About 3000 particles of the obtained Em-2 were observed and measured by an electron microscope, and the average diameter was 1.05 μm, the average particle thickness was 0.25 μm, and the equivalent spherical diameter was 0.59 μ.
m, the coefficient of variation was 18%.

(Preparation of Em-3) 6000 distilled water containing 90 g of high methionine gelatin (containing 59.7 micromoles of methionine per 1 g of gelatin) in a reactor equipped with a stirrer.
g, 0.5 M CaCl ₂ .2H ₂ O and 9.3 g NaBr. 40
The pH was adjusted to 5.1 at ℃ and the value of the whole precipitation was maintained by adding NaOH or HNO ₃ . It was added AgNO ₃ solution of 0.5M over 4 minutes at a rate consuming 1.6% of the total Ag used. Next, the addition speed was linearly accelerated over another 55 minutes (9.32 times from the start to the end), during which the remaining Ag
It consumed 98.4%. 4 minutes, 16 minutes and 36 minutes after the start of precipitation
30 cc of 37 mM adenine solution was added. 3M C at the 10th minute
3.78 g of aCl ₂ solution was added to the precipitate. During the addition of the adenine and CaCl ₂ solution, the AgNO ₃ inflow was stopped for 1 minute and the additives were mixed uniformly. A total of 1.44M Ag was precipitated. By this method, the average silver chloride content is 50 mol%, the grain size is 0.4 μm, and the projected area diameter is
A tabular silver chlorobromide emulsion (Em-3) having a coefficient of variation of 0.25 and an aspect ratio of 4 at 1.2 μm was prepared. (Preparation of Em-4) E-4 was grown in the same manner as Em-1 except that the average silver chloride content was adjusted to 10 mol%.
m-4 was obtained.

(Preparation of Em-5) The average silver chloride content was set to 80.
Em-5 was obtained by growing in the same manner as Em-1 except that the concentration was adjusted to be mol%.

Next, after the above-mentioned emulsions Em-1 to Em-5 were heated to 60 ° C., the following spectral sensitizing dye was added as a solid fine particle dispersion, and adenine, ammonium thiocyanate, chloroauric acid and sodium thiosulfate were added. The mixed aqueous solution and the dispersion liquid of triphenylphosphine selenide were added, and the mixture was aged for a total of 2 hours. At the end of aging, a predetermined amount of 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene (TAI) was added as a stabilizer.

Sensitizing dye (A) 5,5′-dichloro-9-ethyl-3,
Anhydrous 3'-di- (3-sulfopropyl) -oxacarbocyanine sodium salt Sensitizing dye (B) 5,5'-di- (butoxycarbonyl) -1,1'-diethyl-3,3'- Anhydrous Di- (4-sulfobutyl) -benzimidazolocarbocyanine-sodium salt The above additives and their addition amounts (per mol of AgX) are shown below.

Sensitizing dye (A) 2.0 g Sensitizing dye (B) 120 mg Adenine 15 mg Potassium thiocyanate 95 mg Chloroauric acid
2.5 mg sodium thiosulfate
2.0 mg triphenylphosphine selenide 0.4 mg 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene (TAI) 500 mg A solid dispersion of a sensitizing dye is described in Japanese Patent Application No. 4-99437. Prepared by a method according to the method. That is, a predetermined amount of dye is added to water whose temperature has been adjusted to 27 ° C in advance, and a high-speed stirrer (dissolver) is added.
Obtained by stirring at 3.500 rpm for 30-120 minutes.

A dispersion liquid of the above selenium sensitizer was prepared as follows. That is, 120 g of triphenylphosphine selenide was added to 30 kg of ethyl acetate at 50 ° C. and completely dissolved by stirring. On the other hand, 3.8 kg of photographic gelatin is used with 38 kg of pure water.
Was dissolved in the solution, and 93 g of a 25 wt% aqueous solution of sodium dodecylbenzenesulfonate was added thereto. Then, these two liquids were mixed and dispersed at 50 ° C. for 30 minutes at a peripheral speed of the dispersing blade of 40 m / sec by a high-speed stirring type disperser having a dissolver having a diameter of 10 cm. After that, rapidly stirring under reduced pressure until the residual concentration of ethyl acetate becomes 0.3 wt% or less,
The ethyl acetate was removed. Then, this dispersion was diluted with pure water to obtain 80 kg. A part of the thus obtained dispersion was collected and used in the above experiment.

Next, the following additives were added to the emulsion thus sensitized to prepare an emulsion layer coating solution. At the same time, a protective layer coating solution was also prepared.

(Preparation of sample) The addition amount is indicated by the addition amount per 1 m ^{2 on} one side of the silver halide photographic light-sensitive material.

First layer (transverse light shielding layer) Solid fine particle dispersion dye (AH) 180 mg Gelatin 0.2 g Sodium dodecylbenzenesulfonate 5 mg Compound (I) 5 mg 2,4-dichloro-6-hydroxy-1,3,5 -Triazine sodium salt 5 mg Colloidal silica (average particle size 0.014 μm) 10 mg Second layer (emulsion layer) The following various additives were added to each emulsion obtained above.

Compound (G) 0.5 mg 2,6-bis (hydroxyamino) -4-diethylamino-1,3,5-triazine 5 mg t-butyl-catechol 130 mg polyvinylpyrrolidone (molecular weight 10,000) 35 mg styrene-maleic anhydride Polymer 80 mg Sodium polystyrene sulfonate 80 mg Trimethylolpropane 350 mg Diethylene glycol 50 mg Nitrophenyl-triphenyl-phosphonium chloride 20 mg 1,3-Dihydroxybenzene-4-ammonium ammonium 500 mg 2-Mercaptobenzimidazole-5-sodium sulfonate 5 mg Compound ( H) 0.5 mg nC ₄ H ₉ OCH ₂ CH (OH) CH ₂ N (CH ₂ COOH) ₂ 350 mg Compound (M) 5 mg Compound (N) 5 mg Colloidal silica 0.5 g Latex (L) 0.2 g Dextrin (average molecular weight 1000) 0.2 g (where the second layer volume with gelatin was coated was adjusted to 1.0 g / m ^2.) the third layer (protective layer) gelatin 0.8g polymethyl Matting agent composed of methacrylate 50 mg (Area average particle size 7.0 μm) Formaldehyde 20 mg 2,4-Dichloro-6-hydroxy-1,3,5-triazine sodium salt 10 mg Bis-vinylsulfonylmethyl ether 36 mg Latex (L) 0.2 g Poly Acrylamide (average molecular weight 10000) 0.1 g Sodium polyacrylate 30 mg Polysiloxane (SI) 20 mg Compound (I) 12 mg Compound (J) 2 mg Compound (S-1) 7 mg Compound (K) 15 mg Compound (O) 50 mg Compound (S- 2) 5mg C ₉ F ₁₉ O (CH ₂ CH ₂ O) ₁₁ H 3mg C ₈ F ₁₇ SO ₂ N (C ₃ H ₇ ) (CH ₂ CH ₂ O) ₁₅ H 2mg C ₈ F ₁₇ SO ₂ N (C ₃ H ₇ ) (CH ₂ CH ₂ O) ₄ (CH ₂ ) ₄ SO ₃ Na 1
mg

[0086]

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[0087]

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[0088]

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The above coating solution was applied to a film (B) consisting of a 175 μm-thick polyethylene terephthalate support (A) colored with an undercoat and a styrene polymer having a syndiotactic structure according to the present invention. Samples Nos. 1 to 10 shown in Table 1 were prepared by simultaneously coating the transverse light-shielding layer, the emulsion layer, and the emulsion protective layer on both sides in this order from the support side and drying. The coated silver amount was adjusted to be 1.6 g / m ² for one side.

<Evaluation of Sensitivity> The obtained sample was sandwiched between intensifying screens XG-S for X-ray photography, irradiated with X-rays through a penetrometer type B, and then SR-developed by using a roller transport type automatic processor SRX-503. -DF
A treatment solution (both manufactured by Konica Corporation) was treated at 35 ° C. for a total treatment time of 45 seconds. At this time, the replenishment rate of the processing solution was 210 ml / m ^{2 for} both the developing solution and the fixing solution.

Sensitivity is a relative value when the reciprocal of the X-ray exposure amount required for sample No. 1 to give the density of base density + fog density + 1.0 is calculated and the sensitivity of sample No. 3 is 100. did.

<Evaluation of ultra-rapid processability (total process time: 25 seconds)>
After each sample was irradiated with X-rays in the same manner as in the sensitivity evaluation, the SRX-503 automatic developing machine was modified so that the processing time was as follows, and then the processing was performed. The replenishment rate of processing solution is 125 ml / m ^{2 for} both developer and fixer.
Processed in. The sensitivity at this time is shown in Table 1 as the ultra-rapid processing sensitivity.

Development time: 8 seconds Fixing time: 6.3 seconds Water washing time: 3.4 seconds Water washing-drying (squeeze): 2 seconds Drying time: 5.3 seconds Total processing time 25 seconds <Evaluation of roller mark> The film developed by the method was visually evaluated.

Evaluation Criteria ⊚: No pressure spots ○: Light spots scattered around the edges of the film when observed carefully, but practically unfavorable Δ: Light spots scattered at the center of the film, but practically unproblematic × : Dark spots are scattered on the edge of the film, which is a problem in practical use. XX: Dark spots are scattered on the central portion of the film and on the edges, which is not practical. The results obtained are shown in Table 1 below.

[0095]

[Table 1]

As is clear from the table, the sample of the present invention can obtain a high sensitivity even in the ultra-rapid processing with the total processing time of 25 seconds,
Also, it can be seen that there is no roller mark and it is excellent.

[0097]

As demonstrated in the examples, according to the present invention, a silver halide photographic light-sensitive material having good processability and high sensitivity even when super-rapidly processed by an automatic developing machine and having no roller mark. Was obtained.

Claims (1)

[Claims] 1. In a silver halide photographic light-sensitive material having at least one photosensitive silver halide emulsion layer on a support, 50% or more of the total projected area of silver halide grains present in the emulsion layer is Contains silver halide grains having an average aspect ratio of 3 or more and a silver chloride content of 50 mol% or more,
A silver halide photographic light-sensitive material, wherein the support is a stretched film made of a styrene polymer having a syndiotactic structure.