JPH11242301A - Silver halide photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a silver halide photographic sensitive material having excellent pressure resistance as well as high sensitivity. SOLUTION: At least one layer selected from layers of photosensitive layers and nonphotosensitive layers on a photographic supporting body contains a gelatin binder having the density between >=1.1 g/cm<3> and <=1.6 g/cm<3> and contains composite polymer fine particles. A gelatin binder layer of one layer in the silver halide photographic sensitive material is formed by dispersing an org. solvent substantially insoluble with water in an aq. soln. of gelatin, then applying the soln., setting and drying. Thus, the density of the gelatin binder can be decreased, while sensitivity and pressure resistance can be improved. By adding a layer containing the gelatin binder and a layer containing composite polymer fine particles as layers of the silver halide photographic sensitive material, preferably adding as a same layer, the sensitivity and pressure resistance can be significantly improved.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a silver halide photographic material. More specifically, the present invention relates to a silver halide photographic material having excellent photographic sensitivity and pressure resistance.

[0002]

2. Description of the Related Art In general, a silver halide photographic light-sensitive material must have various excellent physical or mechanical properties in addition to stable photographic performance so that the material can be used with security at any time in handling. For example, the adhesion between a photographic support and a photographic binder layer, the dimensional stability corresponding to the expansion and contraction of the binder layer, the flexibility of the binder layer related to the expansion and contraction, and the pressure at which the silver halide emulsion fogs due to pressure. Such as pressure resistance to prevent.

[0003] Various improvements in these properties have hitherto been made.

Heretofore, as a method for improving the properties exemplified above, a polymer latex or another polymer compound is added to a gelatin binder layer such as a silver halide emulsion layer, an intermediate layer, a protective layer, or a back layer. , Make that layer flexible,
These polymers have been sought for some kind of weakening effect on the applied force. For example, JP-A-61-6906
Nos. 1 and 61-151527, an acrylamide derivative, U.S. Pat. No. 2,376,005, a vinyl acetate polymer latex, and U.S. Pat. No. 3,325,286, Japanese Patent Publication No. 45-5331 discloses a polymer latex of an alkyl acrylate, a polymer latex such as n-butyl acrylate, ethyl acrylate, styrene, butadiene, vinyl acetate, and acrylonitrile. Polymer latexes of acrylic acid and sulfoalkyl acrylate are disclosed in
No. 17 proposes various proposals such as using a polymer latex of 2-acrylamido-2-methylpropanesulfonic acid.

In order to improve pressure fog (pressure resistance), Japanese Patent Application Laid-Open No. 1-177033 discloses the use of a composite latex containing acrylate and colloidal silica as components in a silver halide photographic material. Are listed. Japanese Patent Application Laid-Open No. 9-146207 describes that an oil agent and the above-mentioned composite latex are contained in any layer on a support at a certain ratio to the amount of gelatin.

[0006]

In order to improve the above-mentioned properties, the polymer latex is added to the gelatin binder or the other is used in combination with the polymer latex, and the level required from the market is still not achieved. The situation is not yet satisfactory.

An object of the present invention is to provide a silver halide photographic material having high sensitivity and excellent pressure resistance.

[0008]

As a method for improving the physical and mechanical properties of a gelatin binder, the addition of some polymer substance or composite latex has been performed as described above. No attention was paid to the gelatin binder itself. We have:
As a result of focusing on the gelatin binder itself, it was found that properties such as pressure resistance were improved by reducing the density of the gelatin binder layer. For further improvement and improvement, this gelatin binder is added to any layer on the photographic support, and the composite polymer fine particles are contained and used in combination, whereby high sensitivity and excellent pressure resistance are obtained. We succeeded in producing a silver halide photographic material.

The above object of the present invention is achieved by the following.

(1) At least one layer selected from a multi-layer photosensitive layer and a non-photosensitive layer on a photographic support has a density of 1.1.
A silver halide photographic material comprising a layer having a gelatin binder of not less than g / cm ^{3 and not} more than 1.6 g / cm ³ .

(2) At least one layer selected from a multi-layer photosensitive layer and a non-photosensitive layer on a photographic support has a density of 1.1.
A silver halide photographic material comprising a layer having a gelatin binder of not less than g / cm ^{3 and not} more than 1.6 g / cm ³ , and having fine composite polymer particles.

(3) The silver halide photographic material as described in (2), wherein the layer having the gelatin binder having the density has the composite polymer fine particles.

(4) The layer having a gelatin binder is formed by dispersing an organic solvent substantially incompatible with water in an aqueous gelatin solution, applying the dispersion, and drying the resulting mixture by set drying. The silver halide photographic light-sensitive material according to any one of (1) to (3).

The present invention will be described in detail.

The density of a usual gelatin binder layer is 1.7 g / cm ³ according to the measuring method specified in the present invention. Therefore, the density of the gelatin binder layer of the present invention is 1.1 g / cm ³ or more and 1.6 g / cm ³ or less, which is clearly different.

The gelatin binder density of the present invention is as follows. A gelatin binder layer having a coating amount of 7.5 g / m ² is prepared at 23 ° C. and 55% RH under a condition of 55% RH. Slice, Pt-P
d (Platinum-Palladium) was coated with a vapor deposition device, and this cross-sectional SEM (scanning electron microscope) S-50
00H (manufactured by Hitachi, Ltd.) at an accelerating voltage of 5 kv and scanning at an inclination angle of 0 °, the thickness (μm) was calculated from the obtained image, and (amount attached) / (thickness) = binder density; And The thickness obtained by SEM images at equal intervals of 10 μm is 20
Measurements are made at various locations, and the average value is defined as the binder density.
In addition, a layer containing only a gelatin binder is prepared in advance under a predetermined condition to determine a binder density, and for a layer containing various additives, a value from a layer containing only a gelatin binder is used.

The low-density gelatin binder layer of the present invention is sufficiently dispersed by adding an organic solvent which is hardly compatible with water (substantially incompatible) to a gelatin solution. The silver halide photographic material is dried by a conventional drying apparatus for a silver halide photographic material. The setting temperature is 20 ° C. or less, preferably 15 ° C. to 3 ° C. Setting time is 1 second to 1 hour, 15 minutes to 3
0 minutes is preferred. The drying temperature is preferably 30 ° C to 80 ° C,
30 ° C to 60 ° C is preferred. For dry humidity, 10
% RH to 50% RH is preferred.

The organic solvent used in the present invention includes:
Methyl acetate, ethyl acetate, i-propyl acetate, acetic acid
t-butyl, pentane, n-hexane, i-hexane,
Those having a boiling point of 40 ° C. or more and 100 ° C. or less, such as cyclohexane, methyl acrylate, ethyl isopropyl ether, ethyl isobutyl ether, dipropyl ether, and dimethyl carbonate, are preferred, and are selected from the viewpoints of almost insoluble in water, safety, and no pollution. Solvents are preferred.

The density of the present invention varies depending on the amount of the organic solvent added, and is from 5% by weight to 45% by weight based on the weight of water used in one layer of the silver halide photographic material.
And preferably 10 to 30% by weight.

As a method for dispersing the organic solvent, ultrasonic dispersion, a homogenizer, a ball mill, a vibration mill, a planetary ball mill, a sand mill, a colloid mill, a jet mill, or the like can be used, and the ultrasonic dispersion method is preferably used in the present invention. Can be

As a method of reducing the density of the present invention, in addition to the method of adding an organic solvent, a method of adding a compound (for example, urea, a urea derivative, thiourea and its derivatives) that lowers the set temperature of gelatin is used. The present inventors have found that there is a method in which a hardener is used in a large amount with respect to gelatin, but the former is not sufficiently set even when a gelatin aqueous solution containing the same is applied, and the film thickness is uneven. And the latter is difficult to penetrate the developing solution, and there is a possibility that the development progress may be slow. Although this is not a preferable method than the method using an organic solvent, it exhibits a preferable effect by combining with the method using an organic solvent. I can do it.

As gelatin used in the present invention, besides lime-processed gelatin, Bulletin of the Society of Scientific Photography of Japan (Bull. Soc. Sci. Photo)
gr. Japan) No. Acid-treated gelatin described on pages 16, 30 (1996) may be used, and hydrolysates or oxygen-decomposed products of gelatin can also be used. As the gelatin derivative, various compounds such as acid halides, acid anhydrides, isocyanates, bromoacetic acid, alkane sultones, vinylsulfonamides, maleimide compounds, polyalkylene oxides, and epoxy compounds are reacted with gelatin. You may use what is obtained by making it.
Specific examples thereof are described in U.S. Pat.
132,945, 3,186,846, 3,3
No. 12,553, British Patent No. 861,414,
Gelatin derivatives described in JP-A Nos. 033,189, 1,005,784 and JP-B-42-26845 can be used.

The reduced density gelatin binder of the present invention may be used in any of the constituent layers of a silver halide photographic material.

Next, another density of the present invention is 1.
The present invention relates to a silver halide photographic material having a gelatin binder of 1 g / cm ³ or more and 1.6 g / cm ³ or less and composite polymer fine particles in any layer on a photographic support.

In the present invention, the composite polymer fine particles are dispersions of composite polymer fine particles comprising inorganic fine particles and a hydrophobic polymer compound, and are preferably obtained by polymerizing a composition having a monomer in the presence of the inorganic fine particles. It is a dispersion of the formed composite polymer fine particles.

As the inorganic fine particles used in the composite polymer fine particles according to the present invention, inorganic oxides, nitrides, sulfides and the like can be mentioned, but oxides are preferable. Specifically, Si, Na, K, Ca, Ba, Al, Zn, Fe,
Cu, Sn, Ti, In, W, Y, Sb, Mn, Ga,
V, Nb, Tu, Ag, Bi, B, Mo, Ce, Cd,
Single or composite oxides such as Mg, Be, Pb, etc. are preferred, especially Si, Y, Sn, Ti, Al, V, Sb, Ib.
A single or composite oxide of n, Mn, 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 to be added is about 1 to 2000% by weight, preferably 30 to 1% by weight, based on the weight of the hydrophobic polymer compound.
000% by weight.

The following are examples of preferred oxides.

SiO ₂ , TiO ₂ , ZnO, SnO ₂ , M
nO ₂ , Fe ₂ O ₃ , ZnSiO ₄ , Al ₂ O ₃ , BeSiO
₄ , Al ₂ SiO ₅ , ZrSiO ₄ , CaWO ₄ , CaSi
O ₃ , InO ₂ , SnSbO ₂ , Sb ₂ O ₅ , Nb ₂ O ₅ , Y ₂
O ₃ , CeO ₂ , Sb ₂ O ₃ .

Particularly preferred among these are S
i, and further, colloidal silica.

As the colloidal silica, a commercially available product can be used as it is. For example, Silica Doll series (manufactured by Nissan Chemical Industries, Ltd.), Ludox series (manufactured by DuPont), Adelite AT series (manufactured by Asahi Denka Co., Ltd.), Snowtex series (manufactured by Nissan Chemical Industries, Ltd.) And the like, but are not limited thereto.

As the monomers forming the polymer portion of the composite polymer fine particles of the present invention, the following can be used, but are not limited thereto.

As the hydrophobic monomer, vinyl esters such as vinyl acetate, vinyl propionate, n-vinyl valerate and vinyl pivalate; methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, t-butyl Acrylates such as acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, benzyl acrylate and glycidyl acrylate; methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, t-butyl methacrylate, cyclohexyl methacrylate, 2-ethylhexyl methacrylate, benzyl Methacrylates such as methacrylate and glycidyl methacrylate; other styrene, vinyl chloride, vinylidene chloride , Acrylonitrile, itaconic acid ester, can be mentioned vinyl ketones.

Hydrophilic monomers include hydroxyethyl acrylate, 3-hydroxypropyl acrylate,
Acrylic esters such as butylene glycol monoacrylate and 3-sodium sulfo-2,2-dimethyl-propyl acrylate; hydroxyethyl methacrylate, 3-hydroxypropyl methacrylate, butylene glycol monomethacrylate, 3-sodium sulfo-2,2-dimethyl Methacrylic acid esters such as -propyl methacrylate; acrylamide, N-methylacrylamide, N-ethylacrylamide, Nn-propylacrylamide, Ni-propylacrylamide, Nn-butylacrylamide, Nt-butylacrylamide, N, N-dimethylacrylamide, N,
N-diethylacrylamide, N, Nn-dipropylacrylamide, N, Nn-dibutylacrylamide, N, Nt-dibutylacrylamide, N-morpholinoacrylamide, N-piperazinoacrylamide,
Diacetone acrylamide, 3-sodium sulfo-
Acrylamides such as 2,2-dimethylpropylacrylamide; methacrylamide, N-methylmethacrylamide, N-ethylmethacrylamide, Nn-propylmethacrylamide, Ni-propylmethacrylamide, N-butylmethacrylamide, N -T-butyl methacrylamide, N, N-dimethyl methacrylamide,
N, N-diethyl methacrylamide, N, Nn-dipropyl methacrylamide, N, Nn-dibutyl methacrylamide, N, Nt-butyl methacrylamide, diacetone acrylamide, 3-sodium sulfo-2,
Methacrylamides such as 2-dimethylpropyl methacrylamide; N-substituted acryloyls such as N-acryloylpyrrole, N-acryloylpyrrolidine, N-acryloylimidazole, N-acryloyltriazole, N-acryloylpiperidine, N-acryloylmorpholine; Methacryloylpyrrole, N-methacryloylpyrrolidine, N-methacryloylimidazole, N-
N-substituted methacryloyls such as methacryloyl triazole, N-methacryloyl piperidine, N-methacryloyl morpholine; p-hydroxystyrene, p-sodium sulfostyrene, p-hydroxymethylstyrene, p
And styrenes such as sulfomethylstyrene.

The polymer compound used in the composite polymer fine particles of the present invention may be a homopolymer or a copolymer of the above monomers. In the present invention, the polymer is preferably a polymer which is hydrophobic or insoluble in water or a developing solution, but a hydrophilic monomer may be copolymerized as long as such a property is maintained.

[0038] Crosslinkable monomers can also be used. For example, ethylene glycol diacrylate, ethylene glycol dimethacrylate, propylene glycol diacrylate, propylene glycol dimethacrylate, butylene glycol diacrylate, polyethylene glycol diacrylate, cyclohexane-1,4-dimethyl diacrylate, trimethylolpropane triacrylate, pentaerythritol Tetramethacrylate,
N, N-ethylenediaminediacrylamide, N, N-
Piperazyl dimethacrylamide and the like can be mentioned. By using a small amount of these crosslinkable monomers and copolymerizing a hydrophilic monomer and another hydrophobic monomer, a water-insoluble polymer compound having hydrophilicity can be obtained.

The method for producing the composite polymer fine particles of the present invention is as follows.
It is obtained by polymerizing the monomer in the presence of the inorganic fine particles. The polymerization method is a normal solution polymerization method,
Emulsion polymerization, radiation polymerization, suspension polymerization, bulk polymerization, and the like can be used, but emulsion polymerization is preferred.

(Emulsion polymerization) A predetermined amount of inorganic fine particles are dispersed in water as a dispersion medium, and 1 to 50% by weight of a monomer based on water and 0.05 to 5% by weight based on a monomer. About 30 to 10 using a polymerization initiator of 0.1 to 20% by weight of a dispersant.
It is obtained by polymerizing under stirring at 0 ° C., preferably 60 to 90 ° C. for 3 to 8 hours.

Examples of the initiator for the emulsion polymerization include water-soluble peroxides (potassium persulfate, ammonium persulfate, etc.) and water-soluble azo compounds (2,2'-azobis- (2-amidinopropane) -hydrochloride). Redox-based polymerization initiators obtained by combining these with a reducing agent such as an Fe ²⁺ salt or sodium bisulfite can be used.

As the dispersant, any of anionic surfactants, nonionic surfactants, cationic surfactants, and amphoteric surfactants can be used. Preferably, anionic surfactants, nonionic surfactants, and the like are used. Agent.

Further, citrate may be added to the dispersion during or after the emulsion polymerization for pH adjustment. Sodium citrate, potassium citrate,
Citric anhydride, citrate anhydride, or a mixture of citric acid and hydroxide are used, but sodium citrate is preferred. The amount of the citrate in the dispersion of the composite polymer fine particles is preferably about 0.4 g per 1 kg of the fine particles.

The composite polymer fine particles of the present invention have an average particle size of 0.00 when incorporated in a silver halide photographic light-sensitive material.
5-3.0 μm is good, preferably 0.01-0.8 μm
m.

(Synthesis Example 1) Composite polymer fine particles (FL-
Synthesis of 1) A stirrer, a thermometer, a dropping funnel, a nitrogen inlet tube, and a reflux condenser were attached to a 1000 ml four-necked flask, and nitrogen gas was introduced to perform deoxygenation.
% By weight of colloidal silica dispersion (average particle size: 12 μm)
240 g was added and the mixture was heated until the internal temperature reached 70 ° C. The following surfactants (3.6 g) were added, ammonium persulfate (0.065 g) was added as a polymerization initiator, and then vinyl acetate (18.0 g) and vinyl pivalate (18.0 g) were added and reacted for 4 hours. After cooling, the pH was adjusted to 6.0 with a sodium citrate solution to obtain composite polymer fine particles FL-1.

[0046]

Embedded image

(Synthesis Example 2) Synthesis of Composite Polymer Fine Particles FL-2 The monomers were 18.8 g of vinyl pivalate and 19.
Except that the amount was changed to 8 g, the mixture was synthesized in the same manner as in Synthesis Example 1 to obtain composite polymer fine particles FL-2.

(Synthesis Example 3) Synthesis of Composite Polymer Fine Particles FL-3 A composite polymer was synthesized in the same manner as in Synthesis Example 1 except that the monomers were changed to 10.8 g of vinyl pivalate and 13.2 g of vinyl caproate. Fine particles FL-3 were obtained.

(Synthesis Example 4) Synthesis of Composite Polymer Fine Particles FL-4 The monomers were 10.8 g of vinyl pivalate and 13.
Except for 2 g, synthesis was performed in the same manner as in Synthesis Example 1 to obtain composite polymer fine particles FL-4.

(Synthesis Example 5) Synthesis of Composite Polymer Fine Particles FL-5 Synthesis Example 1 except that the monomers were 10.8 g of vinyl pivalate and 13.2 g of vinyl propionate, and the inorganic fine particles were changed to tin oxide. Synthesized in the same manner as described above,
5 was obtained.

Synthesis Example 6 Synthesis of Composite Polymer Fine Particles FL-6 Composite polymer fine particles FL-6 were obtained in the same manner as in Synthesis Example 1 except that the inorganic fine particles were changed to titanium oxide.

In addition, as a commercially available composite polymer fine particle, an acrylic ester resin composite polymer VONCOAT DV series manufactured by Dainippon Ink and the like can be used.

The gelatin binder and composite polymer fine particles having a reduced density according to the present invention may be used as a photosensitive material for X-ray photography, a photosensitive material for printing plate making, a photosensitive material for black and white photography, a photosensitive material for color negative, a photosensitive material for color reversal, It can be applied to each layer of a silver halide photographic light-sensitive material such as a photographic paper light-sensitive material.

The preferred silver halide emulsion for use in the silver halide photographic light-sensitive material of the present invention is an emulsion composed of silver chloride tabular grains having a (100) plane as a main plane, preferably (a) 30 mol of chloride. %, A step of introducing a silver salt and a halide salt into the dispersion medium to form nuclei,
(B) following nucleation, Ostwald ripening under conditions that maintain the (100) major plane of the tabular grains;
(C) It is prepared by a step of growing grains so as to have a desired grain size and silver chloride content.

As a method of reacting a silver salt and a halide salt during nucleation, a double jet method is preferably used.

It is preferable to use the double jet method also during grain growth, and it is preferable to use pAg in the liquid phase in which silver halide is formed.
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 during part or all of the steps during grain formation. Since the particle size of the fine particles governs the supply rate of halide ions, it depends on the size and composition of the silver halide grains to be formed, but the preferred size is approximately 0.3 μm or less in terms of the average equivalent sphere diameter, and more preferably 0 μm or less. .1 μm or less. In order for the fine particles to be stacked on the grown particles by recrystallization, the fine particle size is desirably smaller than the sphere equivalent diameter of the grown particles,
More preferably, it is 1/10 or less of the sphere equivalent diameter of the growth particles.

The silver halide emulsion used in the present invention may be subjected to a noodle washing method, flocculation sedimentation method or the like in order to remove soluble salts after the growth of the silver halide grains to obtain a pAg ion concentration suitable for chemical sensitization. As a preferred water washing method, for example, a method using an aromatic hydrocarbon 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 (hereinafter abbreviated as RD) 102, 10208
(October 1972) and 131, 13122 (19
(May, 1975) may be used for desalting.

The silver halide emulsion may be spectrally sensitized with a cyanine dye or the like.

The silver halide photographic light-sensitive material of the present invention includes:
In the steps before and after physical ripening or chemical ripening of the silver halide emulsion, RD-17643, 18716 (November 1979)
Mon) 308119 (December 1989) and the like.

As the support which can be used in the silver halide photographic light-sensitive material of the present invention, those described in the above RD can be mentioned, and a plastic film or the like is suitable. May be provided with an undercoat layer, or may be subjected to corona discharge, ultraviolet irradiation, or the like.

The silver halide photographic light-sensitive material of the present invention comprises
In addition to the silver halide emulsion layer, if necessary, an ultraviolet absorbing layer, an antihalation layer, an intermediate layer, a filter layer, a protective layer and the like can be provided. In some cases, a crossover light cut layer may be provided.

The composite polymer fine particles of the present invention can exhibit an effect when added to any layer of a silver halide photographic material. Further, the density of the present invention is 1.1 g / cm ³ or more and 1.6.
The greatest effect can be obtained by using the composite polymer fine particles and the layer having a gelatin binder of g / cm ³ or less in the same layer.

The coating of the constituent layers of the silver halide photographic light-sensitive material of the present invention can be carried out by a dip coating method, a roller coating method, a curtain coating method, an extrusion coating method, a slide hopper method or the like. Coating Produces, Coatings, pp. 27-28.
Procedures).

The processing solutions that can be used for the silver halide photographic light-sensitive material of the present invention are also described in RD-17643 and RD-17643.
08119 and the like.

Examples of the developer used for black-and-white photography include dihydroxybenzenes (such as hydroquinone), 3-pyrazolidones (1-phenyl-3-pyrazolidone), and aminophenols (N-methyl-aminophenol). In the developer, a preservative, an alkaline agent, p
An H buffer, an antifoggant, a hardener, a development accelerator, a surfactant, an antifoaming agent, a color tone, a water softener, a dissolution aid, a viscosity-imparting agent, and the like can be added. In the fixing solution, a fixing agent such as thiosulfate or thiocyanate is used. In addition, a water-soluble aluminum salt (aluminum sulfate, potassium alum, etc.) as a hardening agent, a preservative, a pH adjuster, and a hardened water softener are used. And the like.

The silver halide photographic light-sensitive material of the present invention was prepared using an automatic developing machine for a total processing time of Dry to dry for 2 hours.
Ultra-rapid processing such as 5 seconds or less can be performed, and processing can be performed with a low replenishment amount of a developing solution or a fixing solution such as 200 ml or less per 1 m ² of a photosensitive material.

[0068]

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

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

(A1 solution) Ossein 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 = 5-7) ) 10% methanol solution 1.20 ml potassium bromide 10.8 g 10% nitric acid 160 ml (solution B1) 2.5N silver nitrate aqueous solution 2825 ml (solution C1) 841 g potassium bromide 2825 ml with water (solution D1) 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 5.70 ml (E1 solution) 1.75N odor Potassium chloride aqueous solution Silver potential control amount Using a mixing stirrer described in JP-B-58-58288, the B1 solution and the C1 solution were each 475.0 at 35 ° C at 355.0 ° C.
ml was added by a double jet method in 2.0 minutes to perform nucleation.

After the addition of the B1 solution and the C1 solution, the temperature of the A1 solution is raised to 60 ° C. over 60 minutes, the entire amount of the D1 solution is added, the pH is adjusted to 5.5 with a 3% aqueous KOH solution, and the B1 solution is 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 completion of the addition, the pH was adjusted to 6 with a 3% aqueous KOH solution.
It was set to 0 and immediately desalted and washed with water to obtain a seed emulsion. Observation of this seed emulsion by an electron microscope revealed that 90% or more of the total projected area of the 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 the hexagonal tabular grains was Is 0.090 μm and the average 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) as a solid particulate dispersion After addition, 4-hydroxy-
6-methyl-1,3,3a, 7-tetrazaindene (T
AI) Aqueous solution containing 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 particle size 0.05 μm) equivalent to 5 mmol, triphenylphosphine Add selenide 6.0 mg dispersion,
Aging was performed for a total of 2 hours and 30 minutes. At the end of ripening, 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. In addition, a dispersion of triphenylphosphine selenide was prepared by mixing 120 g of triphenylphosphine selenide with 50 g of triphenylphosphine selenide.
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 consisting of tabular silver iodobromide grains was prepared using Emulsion Em-1 as a seed emulsion and the following solution.

(A2 solution) Ossein 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 2800 ml with water (solution B2) 1493 g potassium bromide Make up to 3585 ml with water (C2 solution) 2131 g of silver nitrate Finish to 3585 ml with water (solution 2) Solution D2) Fine grain emulsion (*) consisting of 3% by weight of gelatin and silver iodide grains (average grain size: 0.05 μm), equivalent to 0.028 mol *: 5.0 weight containing 0.06 mol of potassium iodide To a solution of 6.64 liters of an aqueous gelatin solution, 2 liters each of an aqueous solution containing 7.06 mol of silver nitrate and 7.06 mol of potassium iodide were added over 10 minutes. During the fine particle formation, the pH was controlled at 2.0 using nitric acid, and the temperature was controlled at 40 ° C. After the formation of the particles, the pH was adjusted to 6.0 using an aqueous solution of sodium carbonate.

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 0.23 μm, average aspect ratio about 4.0, width of particle size distribution (standard deviation of particle size distribution / average particle size)
The emulsion was composed of 5% of tabular silver halide grains.

The obtained emulsion was heated to 47 ° C., and a silver iodide fine grain emulsion (average grain size: 0.05 μm) equivalent to 5 mmol, spectral sensitizing dye A (5,5′-dichloro-9-ethyl-3,3 ′).
-390 mg of di (3-sulfopropyl) oxacarbocyanine sodium salt anhydrous) and spectral sensitizing dye B
(5,5'-di- (butoxycarbonyl) -1,1'-
Diethyl-3,3'-di- (4sulfobutyl) benzimidazolo) anhydride of carbocyanine sodium salt) 4 m
g of adenine 1
Aqueous solution containing 0 mg, 50 mg of ammonium thiocyanate, 2.0 mg of chloroauric acid and 3.3 mg of sodium thiosulfate, 4.0 m of triphenylphosphine selenide.
g of the dispersion was added, and aging was performed for a total of 2 hours and 30 minutes.
At the end of ripening, TAI (4-hydroxy-6) is used as a stabilizer.
-Methyl-1,3,3a, 7-tetrazaindene) 75
0 mg was added.

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

<< Preparation of Sample >> A 175 μm-thick polyethylene terephthalate film base colored blue with a density of 0.15 was coated on both sides with a crossover light cut layer, emulsion layer, intermediate layer and protective layer according to the following formulation (per side). in turn, a grain-weight 1.8 g / m ² per surface, the protective layer gelatin amount 0.4 g / m ^2, an intermediate layer of gelatin weight 0.4 g / m ^2, the emulsion layer gelatin weight 1.5 g / m ^2, the cross-over The light cut layer was coated so as to have a gelatin amount of 0.2 g / m ² and dried to prepare a standard sample. This was designated as Sample No. 1, which was used as a comparative sample.

First layer (crossover light cut layer) Solid fine particle dispersion dye AH 180 mg / m ² Gelatin 0.2 g / m ² Sodium dodecylbenzenesulfonate 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 10,000) 35 mg / m ² styrene-maleic anhydride copolymer 80 mg / m ² Sodium polystyrene sulfonate 80 mg / m ² Trimethylolpropane 350 mg / m ² Diethylene glycol 50 mg / m ² Nitrophenyl-triphenyl-phosphonium chloride 20 mg / m ² Ammonium 1,3-dihydroxybenzene-4-sulfonate 500 mg / m ² 2- Mercaptobenzimidazole-5-sulfonate sodium 5 mg / m ² Compound H 0.5 mg / m ² nC ₄ H ₉ OCH ₂ CH (OH) CH ₂ N (CH ₂ COOH) ₂ 350 mg / m ² Compound M 5 mg / m ² 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 the third layer (intermediate layer) gelatin 0.4 g / m ² Formaldehyde De 10 mg / m ² 2,4-dichloro-6-hydroxy-1,3,5-triazine Na trim salt 5 mg / m ² Bis - vinylsulfonyl methyl ether 18 mg / m ² Latex L 0.05 g / m ² of 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 Fourth layer (protective layer) Gelatin 0.4 g / m ² Matting agent (area average particle size 7.0 μm) Polymethyl methacrylate) 50 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 10,000) 0.05 g / m ² Sodium polyacrylate 20 mg / m ² Polysiloxane S1 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 3mg} / m 2 C 8 F 17 SO 2 N (C 3 H 3) (CH 2 CH 2 O) 15 H 2mg / m 2 C 8 F 17 SO 2 N (C 3 H 3) (CH ₂ CH ₂ O) ₄ (CH ₂ ) ₄ SO ₂ Na 1 mg / m ² Hardener B 160 mg / m ²

[0084]

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[0085]

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[0086]

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[0087]

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Example 1 As shown in Table 1, the above-mentioned silver halide photographic light-sensitive material was prepared by changing the organic solvent layer, the type of organic solvent, and the organic solvent / water (weight ratio). went.

<Evaluation> (Sensitivity) Each sample was sandwiched between fluorescent intensifying screens SRO-250 manufactured by Konica Corporation and irradiated with X-rays through a penetrometer B type manufactured by Konica Medical Co., Ltd. Using an SR-DF processing solution (same as above) in an automatic developing machine SRX-503, processing is performed at a developing temperature of 35 ° C. for 45 seconds in Dry to dry. At this time, the reciprocal of the X-ray dose required to obtain a density of fog density +1.0 is defined as sensitivity, and the sample No. Sensitivity of 1 to 1
The evaluation was made with a relative sensitivity of 00.

(Pressure resistance) An unexposed sample is placed on a flat table,
A sponge scourer stretched on a plate was placed thereon so that the scouring surface hits the light-sensitive material, and a weight of 500 g was placed thereon and fixed, and the sample was pulled out from between the flat base and the sponge. This sample was subjected to a development treatment, and the degree of fogging was evaluated in five levels.

5: Not generated at all 4: Slightly recognized in a part 3: Slightly generated in the whole 2: Occurred in the whole and partially generated 1: Severely generated in the whole I have.

Table 1 shows the above results.

[0093]

[Table 1]

(Result) Sample N in which no organic solvent was used
o. Sample No. 1 in which the weight of ethyl acetate was 1/1 with respect to the weight of water in the formulation of the protective layer. In No. 6, the density of the gelatin binder layer was outside the range of the present invention, the sensitivity did not increase, and the pressure resistance was poor. In contrast, the sample N within the scope of the present invention
o. In Nos. 2 to 5 and 7, the density of the gelatin binder layer was reduced from 1.4 to 1.5 due to the use of an organic solvent, and the sensitivity was 1
The pressure resistance was improved by 7%.

Example 2 As shown in Table 2, the layer containing the organic solvent, the type of the organic solvent, the organic solvent / water (weight ratio) of the layer used, the added layer of the composite polymer fine particles, the seed, and the composite of the added layer The silver halide photographic material was prepared by changing the ratio of polymer fine particles / gelatin (weight ratio) and evaluated.

Table 2 shows the results.

[0097]

[Table 2]

(Results) Sample No. In Nos. 8 and 9, composite polymer fine particles were added to the emulsion layer and the protective layer, and the organic solvent was not used in any of the layers. These showed little increase in sensitivity. On the other hand, Sample No. 1 containing composite polymer fine particles and using an organic solvent was used. 10-18
The density of the gelatin binder layer is 1.3 g / cm ³ to 1.
It became 4 g / cm ³ , and both sensitivity and pressure resistance were improved. In particular, when the layer using the organic solvent and the layer to which the composite fine particles were added were the same, the sensitivity and pressure resistance were significantly improved.

[0099]

The gelatin binder layer of any of the layers of the silver halide photographic light-sensitive material is coated with an organic solvent substantially incompatible with water by dispersing the same in an aqueous gelatin solution.
By forming by drying, the density of the gelatin binder is reduced, and the sensitivity can be increased and the pressure resistance can be improved. The sensitivity and pressure resistance can be improved by adding a layer containing the gelatin binder and containing a layer containing composite polymer fine particles to any layer of the silver halide photographic material, especially to any one of the same layers. It can be significantly improved.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Nobuo Kubo 1 Konica Stock Company, Sakuracho, Hino-shi, Tokyo

Claims (4)

[Claims] 1. A method according to claim 1, wherein at least one layer selected from a plurality of photosensitive layers and a non-photosensitive layer on a photographic support has a density of 1.1 g / g.
A silver halide photographic light-sensitive material comprising a layer having a gelatin binder of not less than cm ^{3 and not} more than 1.6 g / cm ³ . 2. A method according to claim 1, wherein at least one layer selected from a plurality of photosensitive layers and a non-photosensitive layer on the photographic support has a density of 1.1 g / g.
A silver halide photographic material comprising a layer having a gelatin binder of not less than cm ^{3 and not} more than 1.6 g / cm ³ , and having fine composite polymer particles. 3. The silver halide photographic material according to claim 2, wherein the layer having the gelatin binder having the density has the composite polymer fine particles. 4. The layer having a gelatin binder,
The silver halide according to any one of claims 1 to 3, wherein an organic solvent substantially incompatible with water is dispersed in an aqueous gelatin solution, coated, and set and dried. Photosensitive material.