JPH09146207A - Silver halide photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain high sensitivity, high covering power and excellent pressure resistance. SOLUTION: On each surface of a supporting body, all layers of photosensitive silver halide emulsion layers for respective surface, a layer containing an oil agent by 0.2-1.0 weight ratio to gelatin, and a nonphotosensitive layer are formed in this order. Or, the silver halide photographic sensitive material has photosensitive silver halide emulsion layers and nonphotosensitive hydrophilic colloid layers on both surfaces of a supporting body in such a manner that at least one layer selected from emulsion layers and hydrophilic colloid layers on both surfaces contains a complex latex by 0.3-1.5 weight ratio to gelatin.

Description

Detailed Description of the Invention

[0001]

[0001] The present invention relates to a silver halide photographic material.

[0002]

2. Description of the Related Art Conventionally, various proposals have been made to improve the pressure fog of a silver halide photographic light-sensitive material (hereinafter also referred to as a light-sensitive material), including a method of increasing the amount of binder in a silver halide emulsion layer. .

For example, JP-A-50-56227 discloses a method of adding a polymer latex to an emulsion layer.
The method of adding a high boiling point organic solvent to the emulsion layer is disclosed in JP-B-47-507.
No. 23 and JP-A-61-140939 describe the use of colloidal silica, and JP-A No. 1-177033 describes the use of a composite latex containing an acrylic ester and colloidal silica as components.

However, the above-mentioned technique is applied to a light-sensitive material having a thin film structure having a gelatin content per surface of 1.7 g / m ² or less, which corresponds to the recent trend of low replenishment and ultra-rapid processing. In addition to not being able to obtain sufficient withstand voltage performance, there is the problem that the sensitivity and covering power deteriorate.

[0005]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and an object thereof is to provide a silver halide photographic light-sensitive material having high sensitivity, high covering power and excellent pressure resistance. is there.

[0006]

The above-mentioned object of the present invention is to provide at least one side of a support having all of the light-sensitive silver halide emulsion layers on that side, and an oil solution to gelatin in an amount of 0.
2 to 1.0 containing a layer and a non-photosensitive layer in this order with respect to the support, and at least one layer on this side has a composite latex of 0.3 to 1.5 with respect to gelatin. A silver halide photographic light-sensitive material contained in a weight ratio of 1., and a gelatin content per one surface of 1.7 g / m ² or less, and at least one side of the support has a light-sensitive silver halide on that side. All the emulsion layers, the oil was added to gelatin to 0.
A silver halide photographic light-sensitive material having a layer containing a weight ratio of 2 to 1.0 and a non-photosensitive layer in this order from the support, and having a gelatin content per surface of 1.7 g / m ² or less. The material has a light-sensitive silver halide emulsion layer and a non-light-sensitive hydrophilic colloid layer on a support, and at least one layer selected from the emulsion layer and the hydrophilic colloid layer is a composite latex for gelatin. A silver halide photographic light-sensitive material containing a weight ratio of 3 to 1.5 and having a gelatin content per surface of 1.7 g / m ² or less; All layers of silver halide emulsion layer, oil to 0.2 to gelatin
A silver halide photographic light-sensitive material having a layer containing 1.0 weight ratio and a non-light-sensitive layer in this order, a light-sensitive silver halide emulsion layer and a non-light-sensitive hydrophilic colloid layer on both sides of a support. And at least one layer selected from an emulsion layer and a hydrophilic colloid layer on each side is provided by a silver halide photographic light-sensitive material containing a composite latex in a weight ratio of 0.3 to 1.5 with respect to gelatin. It

That is, the present inventor has optimized the relationship between the dispersed amount of the oil agent added to the hydrophilic colloid layer, the added layer, the content of the composite latex and the added layer and the amount of gelatin as the binder. Therefore, the inventors have found that not only the improvement of pressure fog but also the covering power and sensitivity can be improved, and the present invention has been completed.

Hereinafter, the present invention will be described in detail.

In the present invention, at least one surface of the support is the entire layer of the light-sensitive silver halide emulsion layer, a layer containing an oil agent in a weight ratio of 0.2 to 1.0 with respect to gelatin, and a non-light-sensitive layer. Is one of the characteristics.

Of course, having in this order means that a part of the layer constitution on the support may be the constitution, for example, having a non-photosensitive layer such as a crossover cut layer under the silver halide emulsion layer. May be.

The oil agent of the present invention has a boiling point of 165 ° C. under normal pressure.
With the above, the solubility in water at 25 ° C is 10% by weight.
The following liquids are preferably dispersed as oil droplets in the hydrophilic colloid layer. Regarding the particle size of the oil droplets, the number of particles with a size of 0.1-0.4μ is 7
It is preferably dispersed so as to occupy 5% or more.

When dispersing, various surfactants can be used. For example, in US Pat. Nos. 2,332,027, 2,801,170 and 2,801,171, an anionic surfactant is used. JP-B-48-9979 describes a method of adding an anionic and nonionic surfactant.

Specific oil agents include diethyl adipate, dibutyl adipate, diisobutyl adipate, di-n-hexyl adipate, dioctyl adipate, dicyclohexyl acetate, di-z-ethylhexyl acetate, dioctyl sebacate, diisooctyl sebacate, dibutyl. Succinate, octyl stearate, dibenzyl phthalate, tricresyl phosphate, diphenyl-mono-p-tert-butylphenyl phosphate, monophenyl-di-no-chlorophenyl phosphate, monobutyl-dioctyl phosphate, 2,4-di -N-amylphenol, 2,4-di-
tert-amylphenol, 4-n-nonylphenol, 2-methyl-4-n-octylphenol, N, N
-Diethylcaprylamide, N, N-diethyllaurylamide, glycerol triallopionate, glycerol tributyrate, glycerol monolactate acetate, tributyl citrate, acetyl triethyl citrate, di-2-ethylhexyl adipate, dioctyl sebacate, di -Isooctyl azelate, diethylene glycol dibenzoate, dipropylene glycol dibenzoate, triethyl citrate, tri (2-ethylhexyl) citrate, acetyl tri-n-butyl citrate, di (isodecyl) -4,5-epoxy tetrahydrophthalate, Oligovinyl ethyl ether, dibutyl fumarate, polyethylene oxide (n> 1)
6), glycerol tributyrate, ethylene glycol dipropionate, di (2-ethylhexyl) isophthalate, butyl laurate, tri- (2-ethylhexyl) phosphate, triphenyl phosphate, tricresyl phosphate, silicone oil, dimethyl phthalate , Diethyl phthalate, dipropyl phthalate,
Dibutyl phthalate, diisooctyl phthalate, diamyl phthalate, di-n-octyl phthalate, diamyl naphthalene, triamyl naphthalene, monocaprin,
Monolaurin, monomyristin, monopalmitin, monostearin, monoolein, dicaprin, dilaurin,
Dimyristin, dipalmitin, distearin, diolein, 1-stearo-2-palmitin, 1-palmito-3
-Stearin, 1-palmito-2-stearin, triacetin, tricaprin, trilaurin, trimyristin, tripalmitin, tristearin, triolein,
Tripetroserin, trielsin, triricinolein,
Linoleorestearin, linoleozielinolenin, oleozieresin, linoleozieresin, palmitooleolinolenin, paraffin, linseed oil, soybean oil, eno oil, drill oil, asami oil, kayak oil, walnut oil, soy sauce, poppy Dry oils such as oil, sunflower oil, azusa oil, kwai oil, safflower oil; semi-dry oils such as cottonseed oil, corn oil, sesame oil, rapeseed oil, rice bran oil, lotus oil, mustard oil, pumpkin oil, dehydrated castor oil, etc. Peanut oil, olive oil, camellia oil, sasanqua oil, tea oil, castor oil, hydrogenated castor oil, almont oil,
Examples include bundling oil, ben oil, and large-scale oil.

In addition,

[0015]

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A compound represented by the formula (wherein R is a carbon atom 1
Represents an alkyl group having ８8. ) And JP-A-50-
No. 23823, No. 50-62632, No. 51-260
Compounds other than those described in Nos. 35, 51-26036, 51-26037 and the like can also be used as the oil agent of the present invention.

Among these, adipic acid, phthalic acid,
Ester such as sebacic acid, succinic acid, fumaric acid, maleic acid, isophthalic acid, phosphoric acid, glycerin ester, paraffin, etc. have no adverse effect on photosensitive materials, and are easily available, chemically stable and easy to handle. Although it can be conveniently used from the viewpoint, tricresyl phosphate, dibutyl phthalate, di-n-octyl phthalate, tri-
Cresyl phosphate, glycerol tributyrate,
Glycerol tripropionate, dioctyl sebacate, paraffin and silicone oil are particularly preferred.

When forming oil droplets, an organic low-boiling compound that evaporates after coating and drying and hardly remains can be used in combination if necessary. Specifically, methanol, ethanol, propyl alcohol, fluoroalcohol, acetonitrile, Dimethylformamide, dioxane, methyl isobutyl ketone,
Diethylene glycol monoacetate, chloroform,
There are methyl acetate, ethyl acetate, propyl acetate, butyl acetate, cyclohexynol, cyclohexane tetrahydrofuran and the like.

The oil agent of the present invention may contain a lipophilic photographic coupler, an ultraviolet absorber, a development inhibitor releasing compound, a hydroquinone derivative, an image fading inhibitor and the like.
The proportion thereof is preferably 200% by weight or less. Further, two or more kinds of oil agents may be simultaneously dispersed, or two or more kinds of oil agents dispersed individually may be mixed and used.

The average particle diameter when the oil agent of the present invention is dispersed will be illustrated below, but the present invention is not limited thereto.

O-1: tris (isopropylphenyl) phosphate 0.20 μm O-2: trixylyl phosphate 0.25 μm O-3: tributyl phosphate 0.15 μm O-4: dioctyl phthalate 0.15 μm O-5: dibutyl Phthalate 0.20 μm O-6: dihexyl phthalate 0.15 μm O-7: tricresyl phosphate 0.20 μm O-8: o-acetyltriethyl citrate 0.15 μm O-9: N, N-dimethyllaurylamide 0. In the present invention, the composite latex is added to gelatin in an amount of 0.
Another feature is to have the layer contained in a weight ratio of 3 to 1.1.

In the present invention, the composite latex is formed by polymerizing a dispersion of composite polymer particles composed of inorganic particles and a hydrophobic polymer compound, or a composition having a hydrophobic monomer in the presence of the inorganic particles. A dispersion of fine composite polymer particles.

Examples of the inorganic fine particles used in the composite latex according to the present invention include inorganic oxides, nitrides, sulfides, etc., among which oxides are preferable. In particular,
Si, Na, K, Ca, Ba, Al, Zn, Fe, C
u, Sn, In, W, Y, Sb, Mn, Ga, V, N
b, Tu, Ag, Bi, B, Mo, Ce, Cd, Mg,
Single or complex oxides such as Be and Pb are preferable, and particularly Si, Y, Sn, Ti, Al, V, Sb, In, Mn,
A single or complex oxide of Ce and B is preferable from the viewpoint of miscibility with the emulsion.

These may be crystalline or amorphous, but are preferably amorphous.

The average particle size of the inorganic fine particles is 0.5 to 300.
It is about 0 nm, preferably 3 to 500 nm. The inorganic fine particles are preferably used by dispersing in water and / or a solvent soluble in water.

The amount of the inorganic fine particles added is about 1 to 2000% by weight, preferably 30 to 1% by weight based on the hydrophobic polymer compound.
It is 000% by weight.

Examples of preferable oxides are shown below.

SO-1 SiO ₂ SO-11 ZrSiO ₄ SO-2 TiO ₂ SO-12 CaWO ₄ SO-3 ZnO SO-13 CaSiO ₃ SO-4 SnO ₂ SO-14 InO ₂ SO-5 MnO ₂ SO-15 _{SnSbO 2 SO-6 Fe 2 O} 3 SO-16 Sb 2 O 5 SO-7 ZnSiO 4 SO-17 Nb 2 O 5 SO-8 Al 2 O 3 SO-18 Y 2 O 3 SO-9 BeSiO 4 SO-29 CeO ₂ SO-10 Al ₂ SiO ₅ SO-20 Sb ₂ O ₃ Among these, particularly preferable are Si oxides and colloidal silica.

In the present invention, the hydrophobic polymer compound is
It refers to a substance that does not substantially elute in an aqueous solution such as a developing solution. Hydrophobic monomers forming the hydrophobic polymer compound include vinyl esters, acrylic acid esters, methacrylic acid esters, olefins, styrenes, crotonic acid esters, itaconic acid diesters, maleic acid diesters. , Fumaric acid diesters, allyl compounds,
Vinyl ethers, vinyl ketones, vinyl heterocyclic compounds, glycidyl esters, unsaturated nitriles, various unsaturated acids and the like can be mentioned, but preferably vinyl esters as those forming the composite latex used in the present invention, It is at least one selected from acrylic acid esters and methacrylic acid esters, or styrene, and the former is particularly preferable because the ester group has 6 carbon atoms.
That's all. Further, it is preferable to use a hydrophobic monomer having a glycidyl group in combination with these hydrophobic monomers,
It is used in combination of at least 1% by weight, more preferably 20% by weight or more.

Examples of the polymerization method of the composite latex include emulsion polymerization method, solution polymerization method, bulk polymerization method, suspension polymerization method and radiation polymerization method.

(Solution polymerization) A monomer composition having a suitable concentration in a solvent (usually not more than 40% by weight, preferably about 10 to 25% by weight based on the solvent) is added in the presence of an initiator to about 10% by weight.
It is obtained by conducting the polymerization at a temperature of from 200 to 200 ° C, preferably from 30 to 120 ° C, for about 0.5 to 48 hours, preferably for 2 to 20 hours.

Any initiator may be used as long as it is soluble in the polymerization solvent, and an organic solvent-based initiator such as benzoyl peroxide, azobisisobutyronitrile (AIBN) and ditertiary butyl peroxide, ammonium persulfate ( APS), potassium peroxide, 2,2'-azobis- (2-amidinopropane)-
Water-soluble initiators such as hydrochloride,
Redox-based polymerization initiators in which a reducing agent such as a ²⁺ salt or sodium bisulfite is combined can be used.

Any solvent can be used as long as it dissolves the monomer composition, and water, methanol, ethanol, dimethylsulfoxide, dimethylformamide, dioxane, or a mixed solvent of two or more of these can be used. . After completion of the polymerization, the reaction mixture is poured into a solvent that does not dissolve the produced polymer compound, and the product is precipitated.
Then, by drying, the unreacted composition can be separated and removed.

(Emulsion Polymerization) Using water as a dispersion medium, 1 to 50% by weight of the monomer with respect to water and 0.05 to 50% with respect to the monomer.
Using 5% by weight of a polymerization initiator and 0.1 to 20% by weight of a dispersant, a temperature of about 30 to 100 ° C, preferably 60 to 90 ° C,
Obtained by polymerizing under stirring for ~ 8 hours.

As the initiator, water-soluble peroxides (potassium persulfate, ammonium persulfate, etc.), water-soluble azo compounds (2,2'-azobis- (2-amidinopropane) -hydrochloride, etc.), and ^Examples thereof include a redox type polymerization initiator in which a reducing agent such as Fe ²⁺ salt or sodium hydrogen sulfite is combined.

As the dispersant, any of anionic surfactants, nonionic surfactants, cationic surfactants and amphoteric surfactants can be used, but preferably anionic surfactants and nonionic surfactants. It is an agent.

When the composite polymer fine particles of the present invention are contained in an image recording material, the average particle size is 0.005 on a weight average basis.
To about 3.0 μm is preferable, and further 0.01 to 0.8
μm.

<Production Example 1-Production of composite latex L-1> A 1000 ml four-necked flask was equipped with a stirrer, a thermometer,
A dropping funnel, a nitrogen introducing pipe, and a reflux condenser are attached, while nitrogen gas is introduced to perform deoxidation, 360 cc of distilled water,
Add 126 g of 30 wt% colloidal silica dispersion,
It heated until the internal temperature became 80 degreeC. 1.3 g of the following surfactant was added, 0.023 g of ammonium persulfate was added as an initiator, and then vinyl pivalate 1 was added.
2.6 g was added and reacted for 4 hours. Then, the mixture was cooled and the pH was adjusted to 6 with a sodium hydroxide solution to obtain a composite latex L-1.

[0039]

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<Production Example 2—Production of composite latex L-2> A 1000 ml four-necked flask was equipped with a stirrer, a thermometer,
A dropping funnel, a nitrogen introducing pipe, and a reflux condenser are attached, while nitrogen gas is introduced to perform deoxidation, 360 cc of distilled water,
Add 126 g of 30 wt% colloidal silica dispersion,
The mixture was heated until the internal temperature reached 80 ° C., and 4.5 g of hydroxypropyl cellulose and 1 g of dodecylbenzenesulfonic acid were added. Ammonium persulfate as an initiator
023 g was added, and then 12.6 g of vinyl acetate was added and the reaction was carried out for 4 hours. Thereafter, the mixture was cooled and adjusted to pH 6 with a sodium hydroxide solution to obtain a composite latex L-2.

<< Production Example 3--Production of Composite Latex L-3 >> In Production Example 1, in place of vinyl pivalate, 6.3 g of ethyl acrylate and 6. g of glycidyl acrylate were used.
Composite latex L-3 was similarly prepared except that 3 g was added.
I got

In addition, as the commercially available composite latex, the acrylic ester resin composite polymer VONCOAT DV series manufactured by Dainippon Ink Co., Ltd. may be preferably used.

The silver halide emulsion preferably used in the light-sensitive material of the present invention is an emulsion composed of silver chloride tabular grains having a (100) plane as a principal plane, and preferably (a) chloride 30.
A step of introducing nuclei by introducing a silver salt and a halide salt into a dispersion medium under the condition of not less than mol%, and (b) following the nucleation, Ostwald under the condition of maintaining the (100) major plane of the tabular grains. It is prepared by a step of ripening and (c) a step of growing grains so as to have a desired particle size and silver chloride content.

The double jet method is preferably used as the form in which the silver salt and the halide salt are reacted during nucleation.

The double jet method is preferably used also during grain growth, and pAg in the liquid phase in which silver halide is produced is used.
Can be used, that is, a so-called controlled double jet method can be used.

The silver halide emulsion may be formed by supplying fine silver halide grains for a part or all of the steps of grain formation. Since the particle size of the fine particles controls the supply rate of halide ions, it depends on the size and composition of the silver halide grains to be formed, but the preferable size is generally 0.3 μm or less in terms of mean sphere equivalent diameter, and further 0 .1 μm or less. In order for the fine particles to be laminated on the grown particles by recrystallization, it is desirable that the size of the fine particles is smaller than the equivalent spherical diameter of the grown particles,
More preferably, it is 1/10 or less of the equivalent spherical diameter of the grown particles.

The silver halide emulsion used in the present invention is subjected to a noodle washing method, a flocculation sedimentation method or the like in order to remove soluble salts after the growth of silver halide grains to obtain a pAg ion concentration suitable for chemical sensitization. As a preferred washing method, a method using an aromatic hydrocarbon-based aldehyde resin containing a sulfo group described in JP-B-35-16086 or a polymer flocculant described in JP-A-2-7037 can be used. A desalting method using certain exemplified compounds G-3, G-8 and the like can be mentioned. Also, Research Disclosure (RD) Vol. 102 (1972) Oc
t. Item 10208 and Vol. 131 (197
5) Mar. Desalting may be performed using the ultrafiltration method described in Item 13122.

The silver halide emulsion may be spectrally sensitized with cyanine dyes and the like.

The binder used in the silver halide emulsion includes gelatin, polyvinyl alcohol,
Synthetic polymers such as polyacrylamide, and hydrophilic colloids such as colloidal albumin, polysaccharides, and cellulose derivatives can be used. According to the present invention, the effect can be satisfactorily exhibited in a light-sensitive material which is advantageous for ultra-rapid processing with a thin film having a gelatin content of 1.7 g / m ² or less per side.

For the light-sensitive material of the present invention, RD No. was used in the steps before and after physical ripening or chemical ripening of the silver halide emulsion. 17
643, no. 18716 (November 1979), N
o. 308119 (December 1989) and the like can be used.

Examples of the support usable in the light-sensitive material of the present invention include those described in RD above.
A plastic film or the like is suitable, and a subbing layer may be provided on the surface of the coating layer for adhesion, or corona discharge, ultraviolet irradiation, or the like may be applied.

The light-sensitive material of the present invention may be provided with an antihalation layer, an intermediate layer, a filter layer and the like, if necessary.

The constituent layers of the light-sensitive material of the present invention can be coated by a dip coating method, a roller coating method, a curtain coating method, an extrusion coating method, a slide hopper method or the like. 176, p. 27-28 "Coa
Ting procedures "in detail.

The processing solution which can be used for processing the light-sensitive material of the present invention is also the above-mentioned RD No. 17643 and 3081
19 etc.

Examples of developers used for black-and-white photographs include dihydroxybenzenes (hydroquinone etc.), 3-pyrazolidones (1-phenyl-3-pyrazolidone), aminophenols (N-methyl-aminophenol) and the like. , A developer, if necessary, a preservative, an alkaline agent, a pH buffering agent, an antifoggant, a hardener, a development accelerator,
Surfactants, defoamers, colorants, water softeners, dissolution aids,
A viscosity imparting agent or the like can be added. Further, a fixing agent such as thiosulfate or thiocyanate is used in the fixing solution, and further, a water-soluble aluminum salt (aluminum sulfate, potassium alum, etc.) as a hardening agent, a preservative, a pH adjuster, and water softening. You may contain an agent etc.

The light-sensitive material of the present invention was processed by D using an automatic processor.
Ultra-rapid processing such as 25 seconds or less in the total processing time of ry to dry can be performed, and processing can be performed with a low replenishment amount of a developing solution or a fixing solution of 200 ml or less per 1 m ² of the photosensitive material.

[0057]

The present invention will be described in detail below with reference to examples, but the embodiments of the present invention are not limited thereto.

Example 1 <Preparation of Emulsion Em-1> An emulsion Em-1 comprising tabular silver iodobromide grains was prepared as follows.

(Liquid A) Ocein gelatin 24.2 g Water 9657 ml HO (CH ₂ CH ₂ O) _n [CH (CH ₃ ) CH ₂ O] ₁₇ (CH ₂ CH ₂ O) _m H (n + m = 5 to 7) ) 10% methanol solution 1.20 ml potassium bromide 10.8 g 10% nitric acid 160 ml (B1 solution) 2.5N silver nitrate aqueous solution 2825 ml (C1 solution) potassium bromide 841 g water 2825 ml (D1 solution) ossein gelatin 121 g water 2040 ml 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 5.70ml (E1 solution) 1.75 n odor Potassium iodide aqueous solution Silver potential control amount Using a mixing stirrer described in Japanese Patent Publication No. 58-58288, liquid A1 is liquid B1 and liquid C1 is 475.0 each at 35 ° C.
Nucleation was performed by adding ml in 2.0 minutes by the double jet method.

After the addition of the solutions B1 and C1 was completed, the temperature of the solution A1 was raised to 60 ° C. over 60 minutes, the whole amount of the solution D1 was added, the pH was adjusted to 5.5 with a 3% KOH aqueous solution, and the solution B was added again.
Solution 1 and Solution C1 were added at a rate of 55.4 ml / min.
Added for 2 minutes. During this period, the silver potential (measured with a silver ion selective electrode using a saturated silver-silver chloride electrode as a reference electrode) was controlled to +8 mV and +30 mV using the E1 solution.

After the addition was completed, the pH was adjusted to 6 with a 3% aqueous KOH solution.
It was set to 0, and desalting and washing were carried out immediately to obtain a seed emulsion. Observation of this seed emulsion with an electron microscope revealed that 90% or more of the total projected area of silver halide grains consisted of hexagonal tabular grains having a maximum adjacent side ratio of 1.0 to 2.0, and the average thickness of hexagonal tabular grains was Is 0.090 μm, and the equivalent circle diameter is 0.5
It was 10 μm.

The obtained seed emulsion was heated to 53 ° C., and the spectral sensitizing dye A (5,5′-dichloro-9-ethyl-3,3′-di- (3-sulfopropyl) oxacarbocyanine sodium salt anhydrous Product) 450 mg, spectral sensitizing dye B (5,
8 mg of 5'-di- (butoxycarbonyl) -1,1'-di-ethyl-3,3'-di- (4-sulfobutyl) benzimidazolocarbocyanine sodium anhydride) as a solid fine particle dispersion After the addition, 4-hydroxy-
6-methyl-1,3,3a, 7-tetrazaindene (T
AI) 60 mg, adenine 15 mg, ammonium thiocyanate 50 mg, chloroauric acid 2.5 mg and sodium thiosulfate 5.0 mg, silver iodide fine grain emulsion (average grain size 0.05 μm) equivalent to 5 mmol, triphenylphosphine Add 6.0 mg of selenide dispersion,
Aging was performed for a total of 2 hours and 30 minutes. At the end of aging, 750 mg of TAI was added as a stabilizer.

The dispersion of the solid fine particles of the spectral sensitizing dye is as follows:
The dye was added to water at 27 ° C., and 3500 rpm with a high-speed stirrer (dissolver). p. m. For 30 to 120 minutes. Also, a dispersion of triphenylphosphine selenide was prepared by adding 120 g of triphenylphosphine selenide to 50 g of the dispersion.
C. in 30 kg of ethyl acetate at 30.degree. C. and stirred to completely dissolve, while 3.8 kg of gelatin was dissolved in 38 kg of pure water, and sodium dodecylbenzenesulfonate was added thereto.
93 g of a 5% by weight aqueous solution was added, and these two liquids were mixed and dispersed by a high-speed stirring type disperser having a 10 cm diameter dissolver at 50 ° C. and a dispersion blade peripheral speed of 40 m / sec for 30 minutes. Then, ethyl acetate was removed while stirring until the residual concentration of ethyl acetate became 0.3% by weight or less, and the resultant was diluted with pure water to obtain a finished product of 80 kg.

<< Preparation of Emulsion Em-2 >> Emulsion Em-2 comprising tabular silver iodobromide grains was prepared using Emulsion Em-1 as a seed emulsion and the following solution.

(Solution A2) Oscein gelatin 19.04 g HO (CH ₂ CH ₂ O) _n [CH (CH ₃ ) CH ₂ O] ₁₇ (CH ₂ CH ₂ O) _m H (n + m = 5 to 7) 10 % Methanol solution 2.00 ml Potassium iodide 7.00 g Em-1 1.55 mol Equivalent to make water 2800 ml (solution B2) Potassium bromide 1493 g Water to make 3585 ml (C2 solution) Silver nitrate 2131 g Water to make 3585 ml ( D2 liquid) Fine particles composed of 3% by weight of gelatin and silver iodide grains (average particle size: 0.05 μm) Emulsion (*) Equivalent to 0.028 mol * 5.0% by weight containing 0.06 mol of potassium iodide To 6.64 l of the above gelatin aqueous solution, 2 l of an aqueous solution containing 7.06 mol of silver nitrate and 7.06 mol of potassium iodide were added over 10 minutes. The pH during fine particle formation was controlled to 2.0 using nitric acid, and the temperature was controlled to 40 ° C. After forming the particles, the pH was adjusted to 6.0 using an aqueous sodium carbonate solution.

The solution A2 was vigorously stirred in the reaction vessel while maintaining the temperature at 55 ° C., and half of each of the solutions B2 and C2 was added to 35
Over a period of minutes, the mixture was added by the simultaneous mixing method. During this time, the pH was 5.8
Kept. The pH was adjusted to 8.8 with a 1% aqueous KOH solution,
Solution 2, Solution C2 and Solution D2 were added by the simultaneous mixing method until Solution D2 disappeared. The pH was adjusted to 6.0 with a 0.3% aqueous citric acid solution, and the remaining amounts of the B2 solution and the C2 solution were added by a simultaneous mixing method over 25 minutes. During this time, the pAg was kept at 8.9. The addition rates of the B2 liquid and the C2 liquid were changed in a function according to the critical growth rate to suppress generation of small particles and polydispersion due to Ostwald ripening.

After completion of the addition, desalting, washing and redispersion were carried out in the same manner as in Em-1, and after redispersion, the pH was adjusted to 5.80 at 40 ° C.
The pAg was adjusted to 8.2.

When the obtained silver halide emulsion was observed with an electron microscope, the average circle-equivalent diameter was 0.91 μm.
Average thickness of 0.23 μm, average aspect ratio of about 4.0, width of particle size distribution (standard deviation of particle size distribution / average particle size) 20.
The emulsion consisted of 5% tabular silver halide grains.

The resulting emulsion was heated to 47 ° C., and 390 mg of spectral sensitizing dye A and 4 mg of spectral sensitizing dye B were added as a dispersion in the form of solid fine particles, equivalent to 5 mmol of a silver iodide fine grain emulsion (average particle size: 0.05 μm). After addition, adenine 10m
g, ammonium thiocyanate 50 mg, chloroauric acid 2.
An aqueous solution containing 0 mg and 3.3 mg of sodium thiosulfate, and a dispersion of 4.0 mg of triphenylphosphine selenide were added, and aging was performed for a total of 2 hours and 30 minutes. At the end of aging, 750 mg of TAI was added as a stabilizer.

A sample having the following formulation was prepared using an emulsion prepared by mixing the prepared Em-1 and Em-2 at a weight ratio of 6: 4.

<< Preparation of Sample >> A crossover cut layer, an emulsion layer, an intermediate layer and a protective layer were formed on both sides of a polyethylene terephthalate film base having a thickness of 175 μm and colored blue at a concentration of 0.15 in the following order (per side). , 1.8 g / m ² of silver on one side, gelatin of protective layer 0.1 g / m ² .
4 g / m ² , intermediate layer gelatin amount 0.4 g / m ² , emulsion layer gelatin amount 1.5 g / m ² , crossover cut layer gelatin amount 0.2 g / m ² , coated and dried to obtain a sample Was produced.

First layer (crossover cut layer) Solid fine particle dispersion dye AH 180 mg / m ² gelatin 0.2 g / m ² sodium dodecylbenzene sulfonate 5 mg / m ² compound I 5 mg / m ² latex L 0.2 g / m ² 2,4-dichloro-6-hydroxy-1,3,5-triazine sodium salt 5 mg / m ² colloidal silica (average particle size 0.014 μm) 10 mg / m ² hardener A 2 mg / m ² second layer (Emulsion layer) Silver halide emulsion Silver amount 1.8 g / m ² Compound G 0.5 mg / m ² 2,6-bis (hydroxyamino) -4-diethylamino-1,3,5-triazine 5 mg / m ² t-butyl-catechol 130 mg / m ² polyvinylpyrrolidone (average molecular weight 10000) 35 mg / m ² styrene-maleic anhydride copolymer 80 mg / m ² po Sodium lystyrenesulfonate 80 mg / m ² trimethylolpropane 350 mg / m ² diethylene glycol 50 mg / m ² nitrophenyl-triphenyl-phosphonium chloride 20 mg / m ² 1,3-dihydroxybenzene-4-ammonium sulfonate 500 mg / m ² 2 -Sodium mercaptobenzimidazole-5-sulfonate 5 mg / m ² compound H 0.5 mg / m ² n-C ₄ H ₉ OCH ₂ CH (OH) CH ₂ N (CH ₂ COOH) ₂ 350 mg / m ² compound M 5 mg / M ² compound N 5 mg / m ² colloidal silica 0.5 g / m ² latex L 0.2 g / m ² dextran (average molecular weight 1000) 0.2 g / m ² compound P 0.2 g / m ² compound Q 0.2 g / M ² 3rd layer (intermediate layer) Gelatin 0.4 g / m ² Formaldehyde 10 mg / m ² 2,4-dichloro-6-hydroxy-1,3,5-triazine sodium salt 5 mg / m ² bis-vinylsulfonylmethyl ether 18 mg / m ² latex L 0.05 g / m ² sodium polyacrylate 10 mg / m ² compound S-1 3 mg / m ² compound K 5 mg / m ² hardener B 1 mg / m ² 4th layer (protective layer) gelatin 0.4 g / m ² matting agent (area average particle size 7.0 μm Polymethylmethacrylate)
50 mg / m ² formaldehyde 10 mg / m ² 2,4-dichloro-6-hydroxy-1,3,5-triazine sodium salt 5 mg / m ² bis-vinylsulfonylmethyl ether 18 mg / m ² latex L 0.1 g / m ² Polyacrylamide (average molecular weight 10000) 0.05 g / m ² sodium polyacrylate 20 mg / m ² polysiloxane SI 20 mg / m ² compound I 12 mg / m ² compound J 2 mg / m ² compound S-1 7 mg / m ² compound K 15 mg / m ² compound O 50 mg / m ² compound S-2 5 mg / m ² C ₉ F ₁₉ O (CH ₂ CH ₂ O) ₁₁ H 3 mg / m ² C ₈ F ₁₇ SO ₂ N (C ₃ H ₇ )- _{(CH 2 CH 2 O) 15} H 2mg / m 2 C 8 F 17 SO 2 N (C 3 H 7) - (CH 2 CH 2 O) 4 - (CH 2) 4 SO 3 Na 1mg / m 2 dura Amount of gelatin as described in B 1.5 mg / m ² Table 1 (in the table Gel volume), the amount of oil in the intermediate layer, (labeled in the table Lx) composite latex in the emulsion layer, the amount with gelatin per side ( In the same manner as in the sample No. except that the amount of gel in the table) was adjusted. 2-46 were produced.

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[Chemical 6]

<< Preparation of fluorescent intensifying screen >> Gd ₂ O ₂ S: Tb phosphor (average particle size 1.8 μm) 200 g Polyurethane thermoplastic elastomer 20 g [Sumitomo Bayer Urethane Co., Ltd .: Demolac TPKL-5-2625] (Solid content 40%)] To a composition consisting of 2 g of nitrocellulose (digestibility 11.5%), a methyl ethyl ketone solvent was added and dispersed with a propeller mixer to obtain a coating liquid for forming a phosphor layer having a viscosity of 25 ps (25 ° C). Prepared. (Binder / phosphor =
1/22) Also, a soft acrylic resin 90 g as a coating liquid for forming an undercoat layer
(Solid content), methyl ethyl ketone was added to 50 g of nitrocellulose, dispersed and mixed to have a viscosity of 3 to 6 ps (25 ° C.)
Was prepared.

Thickness 250 μm in which titanium dioxide is kneaded
The polyethylene terephthalate support is placed horizontally on a glass plate, and a coating solution for forming an undercoat layer is uniformly applied using a doctor blade, and then gradually heated from 25 ° C. to 100 ° C. and dried. An undercoat layer of 15 μm was formed.

The coating liquid for forming a phosphor was uniformly applied on this with a doctor blade to a film thickness of 240 μm, dried, and then compressed at 80 ° C. using a calender roll at a pressure of 800 kgw / cm ² . .

Further, Example 1 of JP-A-6-75097
A transparent protective layer having a thickness of 3 μm was formed by the method described in 1. to prepare a fluorescent intensifying screen comprising a support, an undercoat layer, a phosphor layer and a transparent protective layer.

<Evaluation> Each of the obtained samples was evaluated for sensitivity, covering power and pressure resistance as follows.

(Sensitivity) Each sample was sandwiched between the prepared fluorescent intensifying screens and irradiated with X-rays through a penetrometer B type manufactured by Konica Medical Co., Ltd., and an automatic processor SRX-5 manufactured by Konica Co., Ltd. was used.
03 using the SR-DF treatment liquid (the same), the development temperature 35
The treatment is carried out at 45 ° C. for 45 seconds in Dry to dry. At this time, the reciprocal of the X-ray dose required to obtain the fog density + 1.0 density is taken as the sensitivity, and the sample No. The evaluation was made by the relative sensitivity with the sensitivity of 1 being 100.

(Covering Power) The value obtained by dividing the maximum density by the amount of coated silver was sample No. It evaluated by the relative value which made 1 that of 100.

(Pressure resistance) An unexposed sample was placed on a flat table, and a sponge scrubbing stretched on a plate was placed on this so that the scrubbing surface hits the sample, and a weight was placed on the sample to fix it.
The degree of occurrence of fog was evaluated according to the following criteria.

5: No fog is generated at all 4: Fog is slightly observed at part 3: Fogging is slightly generated at the whole 2: Fog is entirely generated, and a part of the fog is severely generated 1: Fog is severely generated on the whole.

The above results are shown in Table 1.

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[Table 1]

From Table 1, a photosensitive silver halide emulsion layer,
An intermediate layer and a protective layer containing an oil agent in a weight ratio of 0.2 to 1.0 with respect to gelatin are provided in this order, and the intermediate layer has a composite latex of 0.3 to 1.1 with respect to gelatin. All layers of the photosensitive silver halide emulsion layer contained in a weight ratio,
It has an intermediate layer and a protective layer containing an oil agent in a weight ratio of 0.2 to 1.0 with respect to gelatin in this order, and the gelatin content per one side is 1.7 g / m ² or less, and It has a photosensitive silver halide emulsion layer, a protective layer, an intermediate layer containing a composite latex in a weight ratio of 0.3 to 1.1 with respect to gelatin, and has a gelatin content of 1.
It can be seen that the light-sensitive materials of the present invention having an amount of 7 g / m ² or less are excellent not only in pressure resistance but also in sensitivity and covering power.

Example 2 << Preparation of seed emulsion >> (A3 solution) Ocein gelatin 37.5 g Potassium iodide 0.625 g Sodium chloride 16.5 g Distilled water to 7500 ml (B3 solution) Silver nitrate 1500 g 2500 ml with distilled water (C3 solution) Potassium iodide 4 g Sodium chloride 140 g Distilled water to 684 ml (D3 solution) Sodium chloride 375 g Distilled water to 1816 ml A3 solution is charged into a mixing stirrer described in JP-B-58-58288. At 40 ° C., 684 ml of solution B3 and the total amount of solution C3 were added thereto over 1 minute. 149m silver potential E _Ag
After aging Ostwald for 20 minutes while holding at V, B
After adding the remaining whole amount of the 3rd liquid and the whole amount of the D3 liquid over 40 minutes, the mixture was immediately desalted and washed with water to obtain a seed emulsion EM-1.

Observation of the obtained silver halide seed emulsion with an electron microscope revealed that the total projected area of the silver halide grains was 6
0% or more consists of tabular grains having the (100) plane as the main plane, and has an average thickness of 0.07 μm and an average equivalent circle diameter of 0.5 μ.
m and the coefficient of variation (standard deviation of particle size distribution × 100 / average particle size) were 25%.

<< Preparation of High Silver Chloride Emulsion EM-2 >> Emulsion EM
Using -1 as a seed emulsion, the following solution was used to prepare an emulsion EM-2 composed of tabular high silver chloride grains.

(Liquid A4) Ocein gelatin 29.4 g HO (CH ₂ CH ₂ O) _n [CH (CH ₃ ) CH ₂ O] ₁₇ (CH ₂ CH ₂ O) _m H (n + m = 5 to 7) 10 % Methanol solution 1.25 ml EM-1 0.98 mol equivalent Finish with water to 3000 ml (B4 solution) 3.50N silver nitrate aqueous solution 2240 ml (C4 solution) sodium chloride 455 g Finish with distilled water to 2240 ml (D4 solution) 1.75 N chloride Aqueous sodium solution Silver potential control amount A4 liquid was put into the mixing stirrer, and at 40 ° C., B was added thereto.
Using the double jet method, make sure that the flow rate at the end of addition is 4 times the flow rate at the start of addition.
It was added over 10 minutes and grown.

During this period, the silver potential was +120 using D4 solution.
It controlled so that it might be set to mV.

After the addition is completed, in order to remove excess salts,
Precipitation desalting was performed by the method shown below.

1. The temperature of the reaction mixture after completion of mixing is raised to 40 ° C.
Exemplified flocculating gelatin agent G- described in JP-A-2-7037
20 g per mol of silver halide, 56% by weight
The pH is lowered to 4.30 by adding acetic acid, and the mixture is allowed to stand and decanted. 2. Pure water at 40 ° C. is 1.8 l per mol of silver halide.
2. Add 10 minutes of stirring and then decant. 3. Repeat step 2 above 4. Gelatin (15 g), sodium carbonate and water are added per mol of silver halide, and the mixture is redispersed to have a pH of 6.0, and finished to 450 cc per mol of silver halide.

When about 3000 silver halide grains contained in the obtained emulsion EM-2 were observed by an electron microscope, 80% of the total projected area had a (100) plane as a main plane and an average equivalent circle diameter of 1 .17 μm, average thickness 0.12 μ
The coefficient of variation was 24% for tabular grains of m.

The obtained emulsion EM-2 was heated to 55 ° C., and 5 mmol of silver iodide fine grain emulsion (average grain size: 0.05 μm), spectral sensitizing dye (1) 250 mg and spectral sensitizing dye (2) 30 mg were added. After addition as a solid fine particle dispersion, 2.0 mg of ammonium thiocyanate, 1.0 mg of chloroauric acid, 1.0 of triphenylphosphine selenide
The dispersion liquid (mg) was added, and the mixture was aged for a total of 90 minutes. At the end of ripening, 50 mg of TAI was added as a stabilizer to prepare an emulsion.

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<< Preparation of Sample >> EM-
No. 2 except that the oil agent was added to the O-4 intermediate layer in a weight ratio of 0.15 with respect to gelatin. Sample No. 47 was created. In addition, sample No. In No. 47, the oil amount of the intermediate layer on both sides was adjusted as shown in the table below. 48-59 were created.

<< Evaluation of Pressure Resistance >> A sample is wound around a rubber roller having a smooth surface by 180 ° in a dark room, and the surface on the rubber roller side is referred to as B surface. A rubber roller with a roughened surface is pressed against the outer surface (A surface) of the sample, and the sample is
After passing between the two rollers once, development is performed in the same manner as in Example 1 and the fog generation level is evaluated according to the same evaluation criteria as in Example 1. Note that the roller nip pressure was Sample No. 47
The pressure fog level of was adjusted in advance to 3.

The results are shown below.

Sample No. Side A Side B Pressure fog Oil agent Oil agent / Gelatin Oil agent Oil agent / Gelatin generation level Weight ratio Weight ratio 47 O-4 0.15 O-4 0.15 3.0 48 O-4 0.25 O-4 0.25 4 0.049 O-4 0.40 O-4 0.40 4.5 50 O-4 0.70 O-4 0.70 4.5 51 O-4 0.70 O-4 0.70 4.5 O-7 O-7 52 O-7 0.70 O-4 0.70 4.5 53 O-9 0.70 O-9 0.70 4.5 54 O-4 0.95 O-4 0. 95 4.5 55 O-4 1.20 O-4 1.20 3.0 56 O-4 0.70-0 3.3 57-0 O-4 0.70 3.0 58-0-0 3 .0 59-0-0 2.5 Sample No. Sample No. 59 was Sample N except that the uppermost layer on both surfaces contained oil agent O-4 in an oil agent / gelatin weight ratio of 0.9.
o. It is the same as 58.

As a result, when the weight of the oil agent of the layer containing the oil agent is 0.2 to 1.0 with respect to the weight of gelatin,
It turns out that it is excellent in pressure resistance.

Example 3 The silver halide emulsion was changed to EM-2 and latex L- was used.
Sample No. 1 except that 1 was added as follows. Sample No. 60 was created. In addition, sample No. Sample No. 60 was prepared by adjusting the amount of latex on both sides as shown in the table below. 61 to 72 were prepared and the pressure resistance was evaluated in the same manner as in Example 2.

The results are shown in Table 2 below.

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[Table 2]

Sample No. In No. 68, coating and drying fog occurred, and pressure fog could not be evaluated.

From this, it is understood that the composite latex is excellent in pressure resistance in the weight ratio range of 0.3 to 1.5 with respect to the gelatin of the containing layer.

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According to the present invention, not only the pressure resistance of the silver halide photographic light-sensitive material but also the sensitivity and the covering power can be improved.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Reference number within the agency FI Technical indication location G03C 1/76 502 G03C 1/76 502 (72) Inventor Chiaki Otani 1 Sakura-cho, Hino-shi, Tokyo Konica Stock Company In-house

Claims (6)

[Claims] 1. At least one side of the support is provided on all sides of the photosensitive silver halide emulsion layer on that side, a layer containing an oil agent in a weight ratio of 0.2 to 1.0 with respect to gelatin, and a non-layer. It has a photosensitive layer in this order as viewed from the support, and at least one layer on this side has a composite latex of 0.3 to gelatin.
A silver halide photographic light-sensitive material, characterized in that the silver halide photographic light-sensitive material is contained in a weight ratio of 1.5. 2. At least one side of the support has at least one side of the photosensitive silver halide emulsion layer on that side, a layer containing an oil agent in a weight ratio of 0.2 to 1.0 with respect to gelatin, and a non-layer. A silver halide photographic light-sensitive material having a light-sensitive layer in this order from the support, and having a gelatin content per surface of 1.7 g / m ² or less. 3. A photosensitive silver halide emulsion layer and a non-photosensitive hydrophilic colloid layer are provided on a support, and at least one layer selected from the emulsion layer and the hydrophilic colloid layer is a composite latex for gelatin. And the gelatin content per one side is 1.7 g / m.
^{2. A} silver halide photographic light-sensitive material, wherein the number is ² or less. 4. The gelatin content per side is 1.7 g.
/ M ² or less, the silver halide photographic light-sensitive material of claim 1. 5. Both sides of the support are provided with all layers of the photosensitive silver halide emulsion layers on each side, a layer containing an oil agent in a weight ratio of 0.2 to 1.0 with respect to gelatin, and a non-photosensitive layer. A silver halide photographic light-sensitive material having a photosensitive layer in this order. 6. A support has a photosensitive silver halide emulsion layer and a non-photosensitive hydrophilic colloid layer on both sides, and at least one layer selected from the emulsion layer and the hydrophilic colloid layer on each side is a composite. Latex is 0.3 to gelatin
A silver halide photographic light-sensitive material, characterized in that it is contained in a weight ratio of 1.5.