JPH10148904A - Silver halide photographic sensitive material and silver halide emulsion - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the silver halide photographic sensitive material not liable to be adversely affected by vibration energy, that is, capable of reducing pressure fog by incorporating uniaxially orientable fine flat particles in a hydrophilic colloidal layer. SOLUTION: The silver halide photographic sensitive material is provided on a support with the hydrophilic colloidal layer and this layer contains the uniaxially orientable fine flat particles having 550kg/mm<2> -850kg/mm<2> of average elastic modules and an average surface roughness value Ra of 1-220nm and a value Rz of 10-220nm, and further, fine flat particles each having a soaking heat of >=1.0J/g at 25 deg.C and these fine flat particles are surface-treated with a metallic oxide.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a silver halide photographic material and a silver halide emulsion.

[0002]

2. Description of the Related Art A silver halide photographic light-sensitive material (hereinafter, also simply referred to as a photographic light-sensitive material) has a photosensitive functional material, for example, silver halide in a binder, thereby having an image forming ability. This photosensitive functional material, even with a small amount of radiation such as light, preferably forms a good image, that is, preferably has high sensitivity, but generally has a high sensitivity and is easily affected by stimuli other than light. . Especially,
When stress is applied locally in a vibrating manner, for example, when the surface is rubbed by minute foreign matter,
Even if there are few scars, the properties of the photosensitive material inside change due to vibration energy, and the performance (eg, sensitivity, density, fog, etc.) required of the photosensitive material is fully satisfied. May not be obtained.

Conventionally, materials that attenuate vibration energy have been known as anti-vibration materials and sound absorbing materials. For example, it is known that a polymer resin contains plate-like fine particles such as mica.

Therefore, the present inventors have proposed a photographic material
We examined whether similar effects could be obtained by incorporating flat particles such as mica, but in order to apply it to photographic light-sensitive materials, a hydrophilic material containing a photosensitive functional material on a support was used. In the case of a photosensitive material in which a thin film is formed using a colloid as a binder, it has been found that the flat fine particles to be used cannot be solved by mere diversion because of the characteristics and thin film of the hydrophilic colloid which are not in the conventional concept.

[0005]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a silver halide photographic light-sensitive material which is less susceptible to vibration energy, that is, reduces pressure fog. Materials and silver halide emulsions.

[0006]

The above object of the present invention is attained by the following constitutions.

[0007] 1. In a silver halide photographic material having at least one hydrophilic colloid layer on a support,
A silver halide photographic light-sensitive material, characterized in that at least one of said hydrophilic colloid layers contains uniaxially oriented tabular fine particles.

[0008] 2. ^{2. The} silver halide photographic light-sensitive material as described in 1 above, wherein the uniaxially oriented tabular fine particles have an average elastic modulus of 550 kg / mm ^{2 to} 850 kg / mm ² .

3. A silver halide photographic material having at least one hydrophilic colloid layer on a support,
At least one of the hydrophilic colloid layers has an average surface roughness of Ra: 1 to 200 nm, and Rz: 10 to 10 nm.
A silver halide photographic light-sensitive material characterized by containing tabular fine particles of 200 nm.

[0010] 4. A silver halide photographic material having at least one hydrophilic colloid layer on a support,
A silver halide photographic material, characterized in that at least one of the hydrophilic colloid layers contains tabular fine particles having a heat of immersion in water at 25 ° C. of 1.0 J / g or more.

5. A silver halide photographic material having at least one hydrophilic colloid layer on a support,
At least one of the hydrophilic colloid layers has an average surface roughness of Ra: 1 to 200 nm, and Rz: 10 to 10 nm.
A silver halide photographic material characterized by containing tabular fine particles having a thickness of 200 nm and an immersion heat in water at 25 ° C of 1.0 J / g or more.

6. A silver halide photographic material having at least one hydrophilic colloid layer on a support,
At least one layer of the hydrophilic colloid layer, the average modulus of elasticity is the ^{550kg / mm 2 ~850kg / mm 2} , the average value of the surface roughness Ra: 1 to 200 nm deli and Rz: 1
A silver halide photographic light-sensitive material comprising 0 to 200 nm and tabular fine particles having a heat of immersion in water at 25 ° C of 1.0 J / g or more.

7. 7. The silver halide photographic material as described in 3, 4, 5 or 6, wherein the tabular fine particles are surface-treated with a metal oxide.

8. A silver halide emulsion containing uniaxially oriented tabular fine grains.

9. The silver halide emulsion according to the 8 the average elastic modulus of the uniaxially oriented flat particles is characterized by a ^{550kg / mm 2 ~850kg / mm 2} .

10. The average value of the surface roughness is Ra: 1 to 20
A silver halide emulsion characterized by containing tabular fine particles of 0 nm and Rz: 10 to 200 nm.

A silver halide emulsion characterized by containing tabular fine grains having a heat of immersion in water at 11.25 ° C. of 1.0 J / g or more.

[12] The average value of the surface roughness is Ra: 1 to 20
A silver halide emulsion characterized by containing tabular fine particles having a thickness of 0 nm, an Rz of 10 to 200 nm, and a heat of immersion in water at 25 ° C. of 1.0 J / g or more.

13. Average modulus of elasticity is 550 kg / mm ² or more
850 kg / mm ² , average surface roughness Ra: 1-2
00 nm, and Rz: 10 to 200 nm,
A silver halide emulsion characterized by containing tabular fine grains having a heat of immersion in water at 25 ° C of 1.0 J / g or more.

[14] Wherein the flat plate-like fine particles are surface-treated with a metal oxide.
Or a silver halide emulsion according to item 13.

Hereinafter, the present invention will be described in more detail.

The tabular fine particles in the present invention are not particularly limited as long as the following conditions (A), (A) and (C) are satisfied.

(A) Flat plate: The ratio of the major axis diameter to the thickness (long axis diameter / thickness) passing through the center of gravity of the main plane for at least 60% of the total projected area is 8 or more on average, and the main plane The ratio of the minor axis diameter to the thickness passing through the center of gravity (minor axis diameter / thickness) (minor axis diameter / thickness) is 3 or more. (A) Fine particles: average particle diameter is 20 μm or less.

The particle size and volume fraction were measured by the following method using a laser microsizer LMS-24 manufactured by Seishin Enterprise. A sample is added to 300 to 400 ml of the dispersing medium in an amount within a concentration of 500 to 250 mV for measurement. The particle size at a cumulative volume of 50 vol% was defined as the average particle size.

Examples of such tabular fine particles include talc, mica, glass flake, and synthetic hydrotalcite.

Talc is called “hydrated magnesium silicate” and can be represented by 4SiO ₂ .3MgO.H ₂ O. The crystal structure is a three-layer structure in which silicic acid is present on the surface, magnesium oxide having a hydroxyl group is in the second layer, and silicic acid is in the third layer. In fact, dozens of these crystals overlap.

Mica is a group of layered silicate minerals, and the general composition formula of natural mica is A _1-x B _{2 -3} [(OH, F) ₂ X ₄ O ₁₀ ] (A = K , Na, Ca, Ba, NH ₄ , H ₃ O, B = A
1, FeIII, Mg, FeII, Mn, Li, Zn, VII
I, CrIII, T, X = Si, Al, Be, FeIII, x
= 0 to 0.5).

A is located between the octahedral and tetrahedral layers constituting the layered structure and is called an interlayer cation.

B is called an octahedral cation constituting a layer composed of an octahedron of BO ₆ .

X forms a tetrahedral layer, so to speak, a framework and is called a tetrahedral cation.

These form a unit having an octahedral layer on both sides of a tetrahedral layer, which are connected by interlayer ions.

In addition to the above natural mica, there is synthetic mica. Synthetic mica has the same crystal structure as natural mica,
It is common to replace the water of crystallization of natural mica with the same type of F.

[0033] As a general formula as synthetic hydrotalcite, in _{[Mg 1-x Al x (} OH) 2] x + [Y n- x / n · m H 2 O] x- ( this formula, 0 <x ≦ 0.33, 0 <m <2, Y
^n- represents an n-valent anion. ).

The crystal structure has a layered structure in which a positively charged magnesium hydroxide type basic layer and a negatively charged intermediate layer comprising anions and interlayer water are alternately stacked.

The uniaxial orientation (flat fine particles) of the present invention means that the orientation ratio is 70% (number) or more, preferably 80%.
It is a tabular fine particle of (number) or more.

The orientation ratio mentioned here can be determined by the following method.

That is, 7 g of gelatin / 3 g of fine particles (for example, S
nO ₂ surface treated mica) / glyoxal (1 wt% based on gelatin) mixed aqueous solution (total binder concentration 10 wt%)
%) On a support provided with an undercoat layer at 10 ° C. and a relative humidity of 40% so as to have a dry film thickness of 10 μm, and a cross section of the sample obtained by drying was coated with a scanning electron microscope (SEM).
Observation using a
It refers to the ratio of tabular fine particles oriented in the direction of 10 ° to 10 ° to all tabular fine particles.

The uniaxially oriented tabular fine particles are not particularly limited as long as they are formed under the above conditions.

The above uniaxially oriented tabular fine particles may be used alone or in combination of two or more.

The average elastic modulus of the uniaxially oriented tabular fine particles of the present invention is 550 kg / mm ^{2 from} the viewpoint of improving the pressure in liquid.
It is preferably ８850 kg / mm ² .

The average elastic modulus of the tabular fine particles was measured by the following method.

That is, a mixed aqueous solution (total binder concentration: 10 wt%) of 7 g of gelatin / 3 g of uniaxially oriented tabular fine particles (for example, mica treated with SnO ₂ surface) / glyoxal (1 wt% based on gelatin) at 10 ° C. and 40% relative humidity was used. A sample obtained by coating and drying a support having no undercoat layer underneath to a dry film thickness of 10 μm was obtained by measuring 9 cm × 1 cm.
The elastic modulus was determined from the slope of a stress-strain curve obtained by using a tensile tester at 23 ° C. and a relative humidity of 55% at a tensile speed of 40 mm / min.
The average value of the elastic modulus of the 20 samples measured by the above method was defined as the average elastic modulus.

The uniaxially oriented tabular fine particles may be surface-treated with a surfactant, a silane coupling agent, or a metal oxide.

The average values Ra and Rz of the surface roughness of the tabular fine particles of the present invention are, for example, ERA-80 manufactured by Elionix.
It can be determined by measuring particles one by one using a scanning electron microscope equipped with a plurality of detectors such as a 00FE type, or a microscope capable of outputting numerical values of surface irregularities such as an atomic force microscope (AFM). . The “average value of the surface roughness” here is a value obtained as an arithmetic average of Ra and Rz of each fine particle when at least 50 flat fine particles are measured by AFM, for example.

A specific method for measuring Ra and Rz of each fine particle using AFM is as follows.

First, a sample powder is sprayed and adhered on an optically smooth substrate dried and coated with a toluene solution containing 2% neoprene. Next, particles that are not directly adhered to the substrate are removed by using a blower or the like, and a platinum-palladium alloy is coated with a magnetron sputter metal coater to a thickness of 1 nm.
Coat ~ 3 nm. As the AFM, a commercially available general device can be used. For example, it is desirable to use a model such as an Olympus NV2000 type that can confirm particles to be measured with an optical microscope and to perform measurement in an AC mode. As measurement parameters in the AC mode, referring to a cantilever spring: 0.16 N / m and a resonance frequency / amplitude: 68.2 kHz / 54.3 nm, be careful not to cause movement of the sample particles due to movement of the cantilever. It is preferable to measure.

It is preferable to select, as the fine particles to be measured, those having no other fine particles adhered or deposited, and one outer surface of the fine particles having the largest area adhered to the substrate. The scanning range of the cantilever is arbitrary, but when measuring the roughness, the roughness of each point
It is preferable to measure at intervals of not more than nm.
When scanning a range of 000 nm × 1000 nm, 12
What is necessary is just to obtain a value of 8 points × 128 points. From the array of data obtained in this way, avoid the part where foreign substances etc. are thought to be attached and the part where cracks or chipping of the tabular particles on the substrate are likely to occur. At least 64 points are selected and used as a roughness curve f (x) in the following calculation. When a roughness curve is used, it is desirable to correct the inclination, and Ra and R
z may be obtained by integrating the entire range of the roughness curve according to the following equation.

Ra = 1 / L∫ ｛f (x)｝ dx Rz = (P1 + P2 + P3 + P4 + P5 + V1 + V2 +
V3 + V4 + V5) / 5 (However, P1, P2, P3, P4, and P5 are the top five places of the peak height of the roughness curve, V1, V2, V3, V4, and V5 are the top five places of the valley depth, and L is In the case where the plate-like fine particles are provided in a coating film with an organic binder, for example, J.I. Tech.
R. Conf. Medi. and Bio. Elect
ron Microsco. Vol9 No. 2 (1
995) If the organic binder is removed with an ion beam with reference to the example described on page 68, the measurement can be performed in the same manner as described above.

The flat fine particles of the present invention have an average surface roughness Ra of 1 to 200 nm and an Rz of 10 to 200 nm.
nm.

The heat of immersion in the present invention means the calorific value of a plate-like fine particle powder per unit mass immersed in water at a constant temperature, specifically, pure water kept at 25 ° C. Means the amount of heat generated when the powder is immersed in the powder. As a measuring method, for example, it can be measured using a multi-micro calorimeter manufactured by Tokyo Riko Co., Ltd. In addition, in the measurement, pressure reduction (1E-0.3 mmHg) and heat drying (200 ° C., 5 hours) were performed as a pretreatment for the purpose of removing water adhering to the powder surface.

The heat of immersion of the flat particles of the present invention is as follows:
1.0 J / g or more, preferably 1.0 to 00 J / g
g or less, more preferably 50 J / g or more to 100.
J / g, particularly preferably 10 J / g to 50 J / g.
It is.

The flat fine particles according to the fifth and twelfth aspects have an average surface roughness of Ra: 1 to 200 nm,
z: 10 to 200 nm, and plate-like fine particles having a heat of immersion in water at 25 ° C. of 1.0 J / g or more.

The flat fine particles of the invention according to claims 6 and 13 have an average elastic modulus of 550 kg / mm ^{2 to} 850 kg / m ^2.
m ² , and the average value of the surface roughness of the tabular fine particles is Ra:
It is 1 to 200 nm, Rz: 10 to 200 nm, and the heat of immersion of the tabular fine particles in water at 25 ° C. is 1.0 J / g or more.

As another preferred embodiment of the flat fine particles of the present invention, 1) the average elastic modulus of the flat fine particles is 550 kg / mm ² or more.
850 kg / mm ² , the average value of the surface roughness of the plate-like fine particles is Ra: 1 to 200 nm, and Rz: 10 to 2
2) The average elastic modulus of the plate-like fine particles is 550 kg / mm ² or more.
850 kg / mm ² , and the heat of immersion of the flat fine particles in water at 25 ° C. is 1.0 J / g or more. 3) Each of the above flat fine particles is surface-treated with a metal oxide described below. And so on.

Examples of the metal oxide include the following.

Examples of preferred metal 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-19 CeO ₂ SO-10 Al ₂ SiO ₅ SO-20 Sb ₂ O ₃ Of these, tin oxide is particularly preferred. Tin oxide may be a solid solution with, for example, antimony. A preferred surface treatment method is disclosed in
No. 50813, a method of treating a flat particle with antimony-doped tin oxide for surface treatment.

The flat fine particles of the present invention have a total projected area of 60.
% Or more, preferably 80% or more, has a ratio of the major axis diameter to the thickness passing through the center of gravity of the main plane and the thickness (major axis diameter / thickness) of 8 or more, preferably 10 or more, more preferably 20 or more, and preferably The ratio between the minor axis diameter passing through the center of gravity of the main plane and the thickness (minor axis diameter / thickness) is 3 or more, preferably 5 or more, and more preferably 300 or less. The average particle size of the tabular fine particles is 20 μm or less, but preferably 1 μm.
It is 5 μm or less, preferably 10 nm or more.

The addition layer of the tabular fine particles of the present invention may be a hydrophilic colloid layer, but is preferably added to a silver halide emulsion layer or a layer above the emulsion layer. It is more preferably a silver halide emulsion layer, and further preferably, it is added to both the silver halide emulsion layer and the layers above it. In particular, it is preferable to add a layer containing no tabular fine particles between the silver halide emulsion layer and the layer added above the emulsion layer, and between the emulsion layer and the layer added above the emulsion layer.

The amount of the tabular fine particles to be used is 0.1% by weight based on the weight of the binder in the hydrophilic colloid layer containing the fine particles.
001 to 0.4 are preferable, and 0.01 to 0.4 are more preferable.
0.3.

A preferred silver halide emulsion for use in the light-sensitive material of the present invention is an emulsion comprising silver chloride-based silver halide tabular grains having a (100) plane as a main plane, and preferably (a) 30 mol% of chloride. Under the above conditions, 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 silver halide tabular grains, and (c) grains having a desired grain size and silver chloride content. It was prepared by the step of growing.

As a method of reacting a silver salt and a halide salt at the time of nucleation, it is preferable to use a double jet method.

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 of the present invention may be washed with a noodle washing method in order to remove soluble salts after the completion of the growth of silver halide grains to obtain a pAg ion concentration suitable for chemical sensitization.
A flocculation sedimentation method or the like may be used. A preferred washing method is, for example, a method using an aromatic hydrocarbon aldehyde resin containing a sulfo group described in JP-B-35-16086, or JP-A-2-7037. A desalting method using Exemplified Compounds G-3, G-8, etc., which are the described polymer flocculants, can be mentioned. Also, Research Disclosure (RD) Vol. 102 (1972) Oct. It
em10208 and Vol. 131 (1975) Ma
r. Desalting may be performed using the ultrafiltration method described in Item 13122.

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

As the binder used for the hydrophilic colloid layer, gelatin, polyvinyl alcohol,
Synthetic polymers such as polyacrylamide, acrylic latex, vinyl ether latex, colloidal albumin, polysaccharide, dextran, dextrin,
A hydrophilic colloid such as a cellulose derivative 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.

The light-sensitive material of the present invention has an RD No. 1 before and after physical ripening or chemical ripening of a silver halide emulsion. 17
643, no. 18716 (November 1979), N
o. 308119 (December 1989) and the like can be used.

The support which can be used in the light-sensitive material of the present invention includes those described in the above RD.
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, and the like. 176, p. 27-28 "Coa
Ting procedures "in detail.

The processing liquid which can be used for processing the light-sensitive material of the present invention is also the same as that of RDNo. 17643 and 3081
19 etc.

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 light-sensitive material of the present invention is prepared by using an automatic developing machine.
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.

In practicing the present invention, various techniques used in photographic techniques can be applied.

[0076]

EXAMPLES 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.

(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 (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 5.70 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 was raised to 60 ° C. over 60 minutes, the entire amount of the D1 solution was added, the pH was adjusted to 5.5 with a 3% aqueous KOH solution, and the B
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. 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 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) D2 solution) Fine grain emulsion composed of 3% by weight of gelatin and silver iodide grains (average particle size: 0.05 μm) Equivalent to 0.028 mol * 5.0% by weight containing 0.06 mol of potassium iodide 2 g of an aqueous solution containing 7.06 mol of silver nitrate and 7.06 mol of potassium iodide were added to 6.64 l of an aqueous gelatin solution over a period of 10 minutes. During the formation of fine particles, 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 with water 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 by 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) × 1
00] An emulsion comprising 20.5% of 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 dispersed in the form of solid fine particles corresponding to 5 mmol of a silver iodide fine grain emulsion (average particle size: 0.05 μm). 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 ripening, 750 mg of TAI was added as a stabilizer.

A sample was prepared according to the following formulation using an emulsion prepared by mixing Em-1 and Em-2 in 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 , dried and dried No. 1 was produced.

First layer (crossover 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 polystyrenesulfonate 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 ammonium 500 mg / m ² 2 -Sodium mercaptobenzimidazole-5-sulfonate
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 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 Third 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-vinylsulfonyl methyl 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 Fourth layer (protective layer) Gelatin 0.4 g / m ² Matting agent (polymethyl methacrylate having an area average particle size of 7.0 μm) 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) 0.05g / 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 hardener B 1.5 mg / ^{m 2}

[0092]

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[0093]

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[0094]

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[0095]

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As shown in Tables 1 and 2, no. 2-No. No. 6 was created.

<< 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%)] A methyl ethyl ketone solvent was added to a composition consisting of 2 g of nitrocellulose (digestibility: 11.5%), and the mixture was dispersed with a propeller type mixer to prepare a coating solution for forming a phosphor layer having a viscosity of 25 ps (25 ° C.). Prepared (binder / phosphor = 1)
/ 22).

Further, methyl ethyl ketone was added to 90 g (solid content) of a soft acrylic resin and 50 g of nitrocellulose as a coating liquid for forming an undercoat layer, and dispersed and mixed to obtain a viscosity of 3 to 6 c.
A ps (25 ° C.) dispersion was prepared.

Thickness 250 μm incorporating titanium dioxide
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 thereon with a doctor blade to a 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 >> The obtained samples were evaluated for sensitivity and pressure resistance as follows.

(Sensitivity) Each sample was sandwiched between the prepared fluorescent intensifying screens, and irradiated with X-rays through a penetrometer type B manufactured by Konica Medical Co., Ltd., and an automatic developing machine SRX-5 manufactured by Konica Co., Ltd.
03, using the SR-DF processing solution (same as above), at a developing temperature of 35
Processing is performed at 45 ° C. for 45 seconds at 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. The relative sensitivity was evaluated with the sensitivity of 1 as 100.

<Evaluation of resistance to pressure in liquid> In a dark room, the surface of the sample was wound around a rubber roller b having a smooth surface by 180 ° with the rubber roller a having a smooth surface, and the surface A of the sample was intentionally roughened. The sample is passed between the rollers once with an arbitrary pressure. Thereafter, a developing process is performed, and a pressure fogging occurrence level is visually determined. The pressure applied between the rollers was determined by the comparison sample No. It is adjusted in advance so that the pressure fog level of 1 becomes 3.

The pressure fog level is better as the numerical value is larger, and is a level at which 5 does not occur at all.

Sample No. 1 to No. Table 2 shows the results obtained for No. 6.

[0107]

[Table 1]

[0108]

[Table 2]

Em: emulsion layer, Pro: protective layer Fine particles A: pulverized mica (WK941 manufactured by Otsuka Chemical Co., Ltd.) surface-treated with SnO ₂ and Sb ₂ O ₅ Fine particles B: hydrophobic synthetic mica (Corp Chemical) Fine particles of water-swellable synthetic mica (Corp Chemical Co., Ltd.)
The following can be seen from the pulverized product of ME100) produced in Table 2.

In the case of No. 1 where the heat of immersion of the plate-like fine particles was 1.0 J / g or more. Nos. 2, 3, 5, and 6 are Nos. Compared to 1, the relative sensitivity and the resistance to pressure in liquid are improved. The average value of the surface roughness of the tabular fine particles is Ra: 1 nm to 200 nm,
And Rz: 10 to 200 nm. 2,3
No. 6 is No. Compared to 1, the relative sensitivity and the resistance to pressure in liquid are particularly improved.

Further, it can be seen that when the tabular fine particles of the present invention are added to the emulsion layer or the emulsion layer and the protective layer, the results are more preferable than when they are added to the protective layer.

Incidentally, regarding the transparency of the sample after the development processing, Sample No. 2 containing the tabular fine particles of the present invention was used.
Nos. 3, 5, 6 and Nos. Comparison with No. 1 showed no decrease in transparency.

Example 2 << Preparation of Emulsion EM-3 >> (A3 solution) Ossein gelatin 37.5 g Potassium iodide 0.625 g Sodium chloride 16.5 g Make up to 7,500 ml with distilled water (B3 solution) Silver nitrate 1500 g With distilled water Make up 2500 ml (C3 solution) Potassium iodide 4 g Sodium chloride 140 g Make up to 684 ml with distilled water (D3 solution) 375 g Sodium chloride Make up to 1816 ml with distilled water Put the A3 solution into the mixing stirrer described in JP-B-58-58288. Then, at 40 ° C., 684 ml of the B3 solution and the total amount of the C3 solution were added thereto over 1 minute. 149m silver potential E _Ag
After Ostwald ripening for 20 minutes while holding at V, B
After the entire remaining amount of Solution 3 and the total amount of Solution D3 were added over 40 minutes, desalting and washing were immediately performed to obtain seed emulsion EM-3.

When the obtained silver halide seed emulsion was observed with an electron microscope, the total projected area of the silver halide grains was 6%.
0% or more is composed of tabular grains having a (100) plane as a main plane, and has an average thickness of 0.07 μm and an average equivalent circle diameter of 0.5 μm
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-4 >> Emulsion EM
Emulsion EM-4 consisting of tabular high silver chloride grains was prepared using the following solution, using -3 as a seed emulsion.

(A4 solution) Ossein 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-3 0.98 mol equivalent Make up to 3000 ml with water (B4 solution) 3.50 N silver nitrate aqueous solution 2240 ml (C4 solution) Sodium chloride 455 g Finish up to 2240 ml with distilled water (D4 solution) 1.75 N chloride Aqueous sodium solution Silver potential control amount A4 solution was put into the mixing stirrer, and at 40 ° C, B
The total amount of solution 4 and solution C4 was adjusted by the double jet method so that the flow rate at the end of the addition was three times the flow rate at the start of the addition.
It was added over 0 minutes to grow.

The silver potential during this time was +120 using the D4 solution.
It controlled so that it might be set to mV.

After completion of the addition, in order to remove excess salts,
Precipitation desalting was performed by the following method.

[0119] 1. The temperature of the reaction mixture after completion of mixing is raised to 40 ° C.
Exemplified flocculant gelatin agent G- described in JP-A-2-7037.
20g per mole 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. Perform the above step 2 again. 15 g of gelatin, sodium carbonate, and water are added per mole of silver halide, and the mixture is redispersed to pH 6.0 to finish the solution to 450 cc per mole of silver halide.

When about 3,000 silver halide grains contained in the obtained emulsion EM-4 were observed by an electron microscope, it was found that 80% of the total projected area had a (100) plane as a main plane and an average circle equivalent diameter of 1 .17μm, average thickness 0.12μ
m, and the coefficient of variation was 24%.

The obtained emulsion EM-4 was heated to 55 ° C., and 5 mmol of a silver iodide fine grain emulsion (average particle diameter: 0.05 μm), 250 mg of spectral sensitizing dye (1) and 30 mg of spectral sensitizing dye (2) were added. After addition as a solid particulate dispersion, 2.0 mg of ammonium thiocyanate, 1.0 mg of chloroauric acid, 1.0 mg of triphenylphosphine selenide
mg of the dispersion was added, and aging was performed for a total of 90 minutes. At the end of ripening, 50 mg of TAI was added as a stabilizer to prepare an emulsion.

[0122]

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<< Preparation of Sample >> The silver halide emulsion was
Sample No. 4 except that the sample No. 4 was changed. Sample N in the same manner as
o. 7 was created. Sample No. Tables 3 and 4
As shown in Table 2, each tabular fine particle was added to both emulsion layers, 8 to No. 10 was created.

<Evaluation of Scratch Pressure Resistance> An unexposed sample was placed on a flat table, and a sponge scourer stretched on a plate was placed on the sample so that the scrubbing surface hit the light-sensitive material, and a weight of 300 g was placed thereon and fixed. Then, the photosensitive material was pulled out from between the flat table and the sponge.

Development processing is performed on such a sample.
The degree of fogging was evaluated on a 5-point scale.

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.

The sample No. 7-No. Table 4 shows the obtained results.

[0128]

[Table 3]

[0129]

[Table 4]

Fine particles D: mica surface-treated with a silane coupling agent.

The synthesis method is described below.

Methyl methoxysilane is used as a coupling agent, dissolved in distilled water, and then sprayed onto mica powder which is stirred under high pressure in a mixing vessel. Thereafter, the mica fine powder surface-treated with silane is produced by a drying treatment.

Table 4 shows the following.

Sample N in which tabular fine particles have uniaxial orientation
o. Nos. 8 and 9 are Nos. In comparison with No. 7, both the abrasion pressure resistance and the relative sensitivity were improved, but the surface elasticity was particularly increased by the metal oxide and the average elastic modulus was 550 kg / mm ^{2 to} 85.
No. 0 kg / mm ² . No. 8 has a large improvement in scratch resistance and relative sensitivity.

With respect to the transparency of the sample after the development processing, Sample No. 8 containing the tabular fine particles of the present invention,
9, 10 and No. As a result, no decrease in transparency was observed.

[0136]

As demonstrated in the Examples, the silver halide photographic light-sensitive material and the silver halide emulsion according to the present invention are hardly affected by vibration energy, that is, can reduce pressure fog and have an excellent effect. Having.

 ──────────────────────────────────────────────────の Continuing on the front page (72) Inventor Jin Adachi In-house Konica Corporation, 1 Sakura-cho, Hino-shi, Tokyo In-house

Claims (14)

[Claims] 1. A silver halide photographic material having at least one hydrophilic colloid layer on a support, characterized in that at least one of said hydrophilic colloid layers contains uniaxially oriented tabular fine particles. Silver halide photographic material. 2. A silver halide photographic material as claimed in claim 1, the average modulus of uniaxial oriented tabular fine particles are characterized by a ^{550kg / mm 2 ~850kg / mm 2} . 3. A silver halide photographic material having at least one hydrophilic colloid layer on a support, wherein at least one of the hydrophilic colloid layers has an average surface roughness Ra: 1 to 200 nm. And Rz: 10 to 2
A silver halide photographic light-sensitive material containing tabular fine particles of 00 nm. 4. A silver halide photographic material having at least one hydrophilic colloid layer on a support, wherein at least one of the hydrophilic colloid layers has a heat of immersion in water at 25 ° C. of 1.0 J / A silver halide photographic light-sensitive material characterized by containing tabular fine particles of at least g 5. A silver halide photographic material having at least one hydrophilic colloid layer on a support, wherein at least one of the hydrophilic colloid layers has an average surface roughness Ra: 1 to 200 nm. And Rz: 10 to 2
A silver halide photographic light-sensitive material characterized by containing tabular fine particles having a thickness of 00 nm and a heat of immersion in water at 25 ° C of 1.0 J / g or more. 6. A silver halide photographic material having at least one hydrophilic colloid layer on a support, wherein at least one of the hydrophilic colloid layers has an average elastic modulus of 5 or more.
^{50kg / mm 2 ~850kg / mm 2} , the average value of the surface roughness Ra: is 1 to 200 nm, and Rz: 10 to 2
A silver halide photographic light-sensitive material characterized by containing tabular fine particles having a thickness of 00 nm and a heat of immersion in water at 25 ° C of 1.0 J / g or more. 7. The silver halide photographic material according to claim 3, wherein the tabular fine particles are surface-treated with a metal oxide. 8. A silver halide emulsion containing uniaxially oriented tabular fine grains. 9. The silver halide emulsion of claim 8, the average modulus of uniaxial oriented tabular fine particles are characterized by a ^{550kg / mm 2 ~850kg / mm 2} . 10. The average value of the surface roughness is Ra: 1 to 200.
A silver halide emulsion characterized by containing tabular fine particles having a thickness of 10 nm to 200 nm. 11. A silver halide emulsion characterized by containing tabular fine grains having a heat of immersion in water at 25 ° C. of 1.0 J / g or more. 12. The average value of the surface roughness is Ra: 1 to 200.
A silver halide emulsion characterized by containing tabular fine particles having a thickness of 10 J / g or more and a immersion heat of 1.0 J / g or more in water at 25 ° C. 13. An average elastic modulus of 550 kg / mm ² to 8
50 kg / mm ² , average surface roughness Ra: 1 to 20
A silver halide emulsion characterized by containing tabular fine particles having a thickness of 0 nm, an Rz of 10 to 200 nm, and a heat of immersion in water at 25 ° C. of 1.0 J / g or more. 14. The plate-shaped fine particles are surface-treated with a metal oxide.
Or a silver halide emulsion according to item 13.