JPH03264949A - Sheet of silver halide photographic sensitive material improved in pressure characteristics - Google Patents

Abstract

PURPOSE:To restrain occurrence of pressure fog by coating a specified support with a specified silver halide photographic emulsion and executing corner cut. CONSTITUTION:The silver halide grains amounting to >=50% of the total projec tion area are composed of silver halide twin grains having a diameter to thick ness ratio of <5 and forming a monodispersion system, and having only one peak in (420) X-ray diffraction signals using CuKa rays as a ray source, and a diffraction ray with of <1.5 deg. in diffraction angle (2theta) and a maximum peak height of 0.13. This silver halide emulsion containing these grains are applied to the surface of the support of >= 500cm<2> area and the corner cut is carried out, thus permitting occurrence of pressure fog along the corner cut to be restrained.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a sheet-shaped photographic material. More specifically, there is provided a sheet-shaped silver halide photographic light-sensitive material in which the occurrence of pressure blur that may occur in the process of forming an obtuse angle or curved corner cut is suppressed even when the corners are formed with an obtuse angle or a curved corner cut. It is related to.

[Background of the invention]

When a sheet-shaped photographic material has a large area, it may bend during handling, and in this case, the bent portion is developed black, making the image extremely difficult to see. Therefore, a thick support is often used to increase the stiffness of the support so that bending is less likely to occur. However, when this is done, the stiffness is strong, and if the corners remain at right angles, it is easy to injure hands. Therefore, it is preferable to make the corners obtuse or curved, so-called corner cuts, to improve handling safety.

In the process of making corner cuts, a large number of sheets of film are usually stacked one on top of the other, and a circular blade, for example, is lowered from above.
- Perform corner cuts on a large number of films. At this time, since the lower film is subjected to pressure from the lower blade stand, fogging may occur along the corner cuts after development, making the image difficult to see and at the same time, it may significantly reduce the commercial value.

By the way, tabular silver halide grains are advantageous because they have high covering power and high color sensitization sensitivity, so various photosensitive materials using tabular silver halide grains are being researched. Photosensitive materials using silver halide grains are prone to failures associated with corner cuts as described above.

[Purpose of the invention]

In order to solve the above-mentioned problems, an object of the present invention is to provide high sensitivity and to prevent the occurrence of pressure burr along the corner cut even when the corner cut is made to have an obtuse angle or a curved corner. It is an object of the present invention to provide a sheet-like silver halide photographic light-sensitive material that is suppressed.

[Structure of the invention]

The above object of the present invention is that 50% or more of the projected area consists of silver halide twin grains with a grain diameter/grain thickness ratio of less than 5, and that the silver halide grains are monodisperse, and that CuKα radiation is used as a radiation source. (420) A silver halide photographic emulsion in which the X-ray diffraction signal has a unique peak and the diffraction line width at the highest peak height x 0.13 is less than 1.5 degrees at the diffraction angle (2θ) is 5001. This was achieved using a sheet-like silver halide photographic material which is coated on a support having the above area and is characterized by having corner cuts.

In addition, in the sense that the effects of the present invention are more fully exhibited, claims 2 to 3
The silver halide photographic material described in No. 4 is a preferred embodiment.

That is, when the above-mentioned silver halide photographic emulsion uses CuKα radiation as a radiation source (420), the line segment where the horizontally drawn line is cut by the signal at the maximum peak height of the X-ray diffraction signal x 0.13 is called AA'. When the intersection with the line drawn from the highest peak position is B, the silver halide is separated so that the ratio of the length of line segment AB to the length of line segment BA' is 1.0 or less. Preferably it is a photographic emulsion.

Further, it is preferable that the silver halide grains mainly consist of silver iodobromide having a high silver iodide content phase inside the grains.

In addition, more than 50% of the silver halide grains are (1
It is preferable to use an emulsion having both a 11) plane and a (100) plane.

The present invention will be explained in more detail below.

First, the silver halide emulsion constituting the silver halide photographic material of the present invention will be explained. 50% or more of the projected area consists of silver halide twin grains with a grain diameter/grain thickness ratio of less than 5, and is monodisperse,
Halogenated X-ray diffraction signal using CuKα radiation as a radiation source (420) has a single peak and the diffraction line width at the highest peak height x 0.13 is less than 1.5 degrees in diffraction angle (2θ) It is a silver photographic emulsion (hereinafter also referred to as "silver halide emulsion according to the present invention").

In the silver halide emulsion according to the present invention, the term "twin" refers to a silver halide crystal having one or more twin planes within one grain. The classification of the morphology of twins is based on the paper “Photografiche” by Klein and Moyser, Collesbonden J.
(Photographische K.

rrespondenz) Volume 99, Page 99, Volume 100,
It is explained in detail on page 57. Two or more twin planes of a twin may or may not be parallel to each other. Twin planes can be observed directly with an electron microscope, but silver halide grains can also be dispersed and hardened in a resin and observed from the cross section as an ultrathin section sample.

The silver halide twin grains constituting the silver halide emulsion according to the present invention preferably have two or more parallel twin planes, more preferably an even number, particularly preferably two. It has twin planes.

Here, "consisting mainly of twins having two or more parallel twin planes" means that the number of twin grains having two or more parallel twin planes is 50 when counted from large grain size particles. % or more, preferably 60% or more, particularly preferably 70% or more.

The silver halide emulsion according to the present invention comprises silver halide twin grains in which 50% or more of the projected area has a grain diameter/grain thickness ratio of less than 5 (hereinafter also referred to as "silver halide grains of the present invention"). ), preferably 70% or more of the projected area, particularly preferably 90% or more. Further, the ratio of particle diameter/particle thickness is preferably 1.0 to 4.5, particularly preferably 1.1 to 4.0. The particle size here is the diameter when the projected image of the particle is converted into a circular image with the same area.

The projected area of a particle can be determined from the sum of the particle areas. Both can be obtained by observing with an electron microscope a silver halide crystal sample distributed on a sample stage to such an extent that grains do not overlap. The thickness of the particles can be obtained by obliquely observing the sample using an electron microscope.

The expression that the silver halide emulsion according to the present invention consists of the grains of the present invention means that the emulsion mainly consists of the grains of the present invention. The expression that the emulsion consists mainly of the silver halide grains of the present invention This means that the ratio of the silver halide grains of the present invention to the total grains is 60% or more in number. Preferably 80% or more, particularly preferably 95-100
%.

The silver halide emulsion according to the present invention is monodisperse, and is particularly preferably a silver iodobromide monodisperse emulsion.

In the present invention, a monodisperse silver halide emulsion is one in which the weight of silver halide contained within a grain size range of ±20% around the average grain size d is 70% or more of the total weight of silver halide. Good, preferably 80% or more, more preferably 90%
% or more.

Here, the average particle size d is the frequency ni of particles having the particle size di
It is defined as the particle diameter di when the product ni Xdi3 of and di3 becomes the maximum (3 significant figures, minimum digit is rounded down to 4 to 5).

The particle size here is the diameter when the projected image of the particle is converted into a circular image with the same area.

The particle size can be obtained, for example, by photographing the particles with an electron microscope at a magnification of 10,000 to 50,000 times, and actually measuring the particle diameter or projected area on the print (the number of particles measured is (assumed to be at least 1000 indiscriminately)
.

Preferred highly monodispersed emulsions of the present invention have a distribution width defined by 20% or less, more preferably 15% or less, particularly preferably 12% or less.

Here, the particle size measurement method shall follow the measurement method described above,
The average particle size is a simple average.

Next, in the silver halide emulsion according to the present invention, the (420) The angle (2θ) is less than 1.5 degrees,
This will be explained below.

X-ray diffraction is known as a method for investigating the structure of silver halide crystals.

Various characteristic X-rays can be used as the X-ray source. Among them, CuKα rays targeting Cu are the most widely used.

The grain structure of various silver halides can be determined by this X-ray diffraction method. This will be explained below using silver iodobromide as an example.

Silver halides, such as silver iodobromide, have a rock salt structure and are C-
The (420) diffraction line of the uKα line is observed at 2θ71 to 74 degrees. Since the signal intensity is relatively strong and the angle is high, the resolution is good and it is ideal for investigating crystal structures.

When measuring X-ray diffraction of a photographic emulsion, it is necessary to remove gelatin, mix a standard sample such as silicon, and measure the powder.

Regarding the measurement method, reference can be made to Basic Analytical Chemistry Course 24 "X-ray Analysis" (Kyoritsu Publishing).

The emulsion according to the present invention uses CuKα radiation as a radiation source (420
) The diffraction line width is less than 1.5 degrees at the diffraction angle (2θ) at the maximum peak height of the X-ray diffraction signal x 0.13. More preferably, the diffraction line width is less than 1.0 degrees, particularly preferably 0.90 degrees.
degree or less.

The diffraction signal of the silver halide emulsion according to the present invention has only one peak. When counting the number of peaks, measurement noise and peaks less than 4% of the height of the highest peak shall not be counted.

The silver halide emulsion according to the present invention uses CuKα radiation as a radiation source (420) The line segment where a line drawn horizontally at the maximum peak height of the X-ray diffraction signal x 0.13 is cut by the signal is defined as AA'. , when the intersection with a line drawn perpendicularly from the highest peak position is defined as B, it is preferable that the division is performed such that the ratio of the length of the line segment AB to the length of the line segment BA' is 1.0 or less. Here, the line segment AA' is drawn from the low angle side of the diffraction angle to the high angle conversion side. Also, the ratio of the length of line segment AB to the length of line segment BA' is 0.9
It is more preferably 5 or less, particularly preferably 0.
60 to 0.90.

The silver halide twin grains according to the present invention have (111) planes and (
Particles having both 10(1) planes are preferable, 20% or more of the particle surface is (100) planes, and more preferably 30(1) planes.
% or more, particularly preferably 40 to 70%, are (100) planes. The surface other than the (100) chamfer is preferably a raw surface (1111 surface).

The ratio of the (100) plane to the (111) plane is the signal of the (200) plane, (222) plane, and (220) plane of a sample in which silver halide grains are distributed so as not to overlap on a flat sample stage. It can be determined by comparing the intensity ratio with the signal intensity ratios of the (200) plane, (222) plane, and (220) plane in the powder sample.

The silver halide emulsion of the present invention is preferably a silver halide emulsion containing silver iodide, in which case it is particularly preferable that the average silver iodide content is less than 6 mol %, more preferably 0 to 5 mol %. mol %, particularly preferably 1 to 4 mol %.

Further, the silver halide emulsion of the present invention is preferably a silver iodobromide emulsion, but in that case, it may contain silver chloride to the extent that the effects of the present invention are not impaired.

The silver halide emulsion of the present invention is preferably one obtained by localizing silver iodide within the grains. A particularly preferred embodiment is one in which silver iodobromide having a lower silver iodide content is deposited in a layered structure on the inner core having a higher silver iodide content.

The silver iodide content of the inner core is preferably 18 to 45 mol%. Particularly preferably 25 to 40 mol%.

The difference in silver iodide content between the outermost shell and the inner core is preferably 10 mol% or more, more preferably 2
The difference is 0 mol% or more, particularly preferably 30 to 40 mol% or more.

In the above embodiment, another silver halide phase may be present at the center of the inner core or between the inner core and the outermost shell.

The volume of the outermost shell is preferably 10 to 90 mol% of the entire particle, and more preferably 50 to 80 mol%. The inner core, the outermost core, and other silver halide phases may have a uniform composition, or may be a phase group consisting of multiple phases with a uniform composition and whose composition changes in a stepwise manner, Alternatively, it may be a continuous phase in which the composition changes continuously within the phase, or a combination thereof.

Another embodiment of the present invention is an embodiment in which the silver iodide localized within the grain does not form a substantially uniform phase, but the silver iodide content changes continuously from the center of the grain toward the outer part. can be mentioned. In this case, it is preferable that the silver iodide content decreases monotonically from the point where the silver iodide content within the grain is maximum toward the outer side of the grain.

The silver iodide content at the point where the silver iodide content is maximum is preferably 15 to 45 mol%, more preferably 2
It is 5 to 40 mol%.

Further, the silver iodide content on the grain surface is preferably 3 mol% or less, more preferably 0 to 2 mol%, particularly preferably 0.1 to 1.0 mol% of silver iodobromide. That's good.

As a method for obtaining the silver halide emulsion of the present invention, a method in which silver iodobromide or a silver bromide-containing phase is precipitated on monodisperse seed crystals is preferably used. Particularly preferred is the method described in JP-A-61-6643, which includes a growth step for enlarging a monodisperse spherical twin seed emulsion. Specifically, in a method for producing a silver halide photographic emulsion, which is carried out by supplying a water-soluble silver salt solution and a water-soluble halide solution in the presence of a protective colloid, (a) a silver iodide content of 0 to 5 mol%; The pBr of the mother liquor was kept at 2.0 for at least 1/2 period from the beginning of silver halide precipitate formation.
(b) Following the core particle generation step, a silver halide solvent is added to the mother liquor at a concentration of 10 to 2.0 per mole of silver halide.
(c) Next, a water-soluble silver salt solution and a water-soluble halide solution and/or The emulsion of the present invention can preferably be obtained by a method that includes a growth step in which fine silver halide grains are added to enlarge seed grains.

Here, the mother liquor is a liquid (also containing a silver halide emulsion) used for preparing a silver halide emulsion to produce a finished photographic emulsion.

The silver halide grains formed in the core grain forming step (a) above are twin grains made of silver iodobromide containing 0 to 5 mol % of silver iodide.

The term "twin" here refers to a silver halide crystal that has one or more twin planes within one grain, but the classification of twin crystal morphology is as per Klein and Moyser, supra, vol. 99, p. 99.
It is described in detail in Volume 100, page 57. Two or more twin planes of a twin may or may not be parallel to each other. In addition, the outer wall of the crystal is composed of (1 river surface), (1
00) surface or both surfaces.

In the above manufacturing method, the twin core particles are produced by controlling the bromide ion concentration in the protective colloid aqueous solution to 0.01 to 5 mol/l, that is, p B
Keep r2.0 to -0.7, preferably 0.03 to 5 mol/i! (pBr = 1.5 to -0.7) and can be obtained by adding a water-soluble silver salt or a water-soluble silver salt and a water-soluble halide.

The core particle generation step in the above manufacturing method refers not only to the period from the time when the water-soluble silver salt is added to the protective colloid solution until substantially no new crystal nuclei are generated, but also the period after which the particles grow. It may include a period, and is defined as a step before the seed particle formation step.

In the above manufacturing method, the size distribution of the core particles is not limited and may be monodisperse or polydisperse. What is polydispersity here?
Particles with a coefficient of variation (synonymous with the width of the distribution described above) of 25% or more. In this case, the core particles preferably contain at least 50% or more twin grains based on the total number of core particles, more preferably 70% or more, and 9
Most preferably it is 0%.

Next, in the case of the above production method, the seed grain forming step in which the core grains obtained in the core grain forming step are ripened in the presence of a silver halide solvent to obtain seed grains consisting of monodisperse spherical grains will be explained. .

Ripening in the presence of a silver halide solvent (hereinafter simply referred to as ripening) is thought to generally lead to a broader grain size distribution, with the small grains dissolving and the larger grains growing when large and small grains coexist. This seems to be different from the Ostwald ripening that has been described. The conditions for ripening the seed grains from the core grains obtained in the core grain generation step include the core grain generation step in which twin core grains are produced using silver halide with a silver iodide content of 0 to 5 mol%. Substantially monodisperse spherical seed grains are obtained by ripening the emulsion mother liquor that has undergone the process in the presence of a silver halide solvent of 10 -5 to 2.0 mol/silver mol. Substantially monodisperse means that the width of the distribution as defined above is less than 25%.

Substantially spherical grains are defined as (111) planes or (111) planes or (111) planes or (
100) When a surface such as a plane is rounded to the extent that it cannot be clearly distinguished, and three-dimensional axes that are orthogonal to each other are set at one point near the center of gravity within the particle, the vertical, horizontal, and height of the plane image of the particle It refers to particles in which the ratio C=□ of the maximum particle diameter L and the minimum particle diameter l in the direction is from 1.0 to 2.0, preferably from 1.0 to 1.5.

Further, in forming the emulsion of the present invention, it is preferable that the spherical particles account for 60% or more, preferably 80% or more, and more preferably most of the total number of seed grains.

Examples of the silver halide solvent used in the seed grain forming step include (a) U.S. Pat. No. 3,271.157;
No. 31,289, No. 3.574.628, Japanese Unexamined Patent Publication No. 1974
-1019, No. 54-158917, and Special Publication No. 1983
-30571, organic thioethers (b
) Thiourea derivatives described in JP-A-53-82408, JP-A-55-29829, JP-A-55-77737, etc.; (C) Oxygen or sulfur atoms and nitrogen described in JP-A-53-144319. Silver halide solvent having a thiocarbonyl group sandwiched between atoms, (d) JP-A-54-10
Imidazoles described in No. 0717, (e) sulfites, (f) thiocyanates, (g) ammonia, (h
) hydroxyalkyl-substituted ethylenediamines described in JP-A-57-196228, (i) substituted mercaptotetrazoles described in JP-A-57-202531, (D water-soluble bromide, (k) JP-A-57-202531); Showa 58 = 5
Examples include benzimidazole derivatives described in No. 4333.

Next, specific examples of these silver halide solvents (a) to (k) will be given.

(a) (b) HOCHzCHtSCHzCHzSCHzCHzOH(
C) CHzNHCOCsHv CHgSCHtCHzSCHzCHtCOOH(d) (e) K,SO3゜azSOz (f) NH,SCN.

SCN (g) NH3 (h) ()lOcHzGHz) JCHzCHzN (C)l
zc)lzOH) z(k) (CJs) JCfbCIhN (CHzCFlzO)
1) z(i) CHzCH*N(CHs)z CHzCHzNHz N) NaBr+ H4Br1 Br Two or more of these solvents can be used in combination. Preferred solvents include thioethers, thiocyanates, thioureas, ammonia, and bromides, and particularly preferred is a combination of ammonia and bromide.

These solvents are preferably used in an amount of 10 to 2 mol per mol of silver halide.

In addition, the pH is 3 to 13, and the temperature is 30 to 70.
℃ is preferred, particularly preferably pH 6 to 12, temperature 35
~50°C.

One example of a preferred embodiment when the above manufacturing method is adopted is that the pH is 10.8 to 11.2, the temperature is 35 to 45°
Ammonia 0.4-1.0 mol/I in C! , and potassium bromide in combination of 0.03 to 0.5 mol/l, 3
By aging for 0 seconds to 10 minutes, an emulsion containing suitable seed particles was obtained.

During the seed particle forming step, a water-soluble silver salt may be added for the purpose of adjusting ripening.

The seed grain growth process that enlarges the silver halide seed grains is performed during precipitation of silver halide, during Ostwald ripening, PAg, P
This is accomplished by controlling the H1 temperature, the concentration and silver halide composition of the silver halide solvent, and the rate of addition of the silver salt and halide solution.

The conditions for enlarging the obtained seed particles are as follows:
-39027, 55-142329, 58-1
No. 13928, No. 54-48521 and No. 58-49
As seen in No. 938, a water-soluble silver salt solution and a water-soluble halide solution are added by the double jet method, and the addition rate is adjusted to a range that does not cause new nucleation and Ostwald ripening depending on the enlargement of the particles. One example is a method of gradual change. As another condition for enlarging the seed grains, a method of enlarging the seed grains by adding silver halide fine grains, dissolving and recrystallizing can be used, as shown in the Proceedings of the 1988 Annual Conference of the Photographic Society of Japan, page 88, but the former The method is preferred.

In producing the silver halide emulsion according to the present invention, the growth conditions for silver halide grains are preferably pAg 5 to 11, temperature 40 to 85°C, and pH 1.5 to 5.8. pH
Particularly preferred is 1.8 to 3.5. The pAg is particularly preferably 6.0 to 9.5, and the temperature is 60 to 9.5.
Particularly preferred is 80°C.

During growth, it is preferable to add a silver nitrate aqueous solution and a halide aqueous solution by the double jet method, and the state change can also be supplied into the system as silver iodide. The addition rate should be such that new nuclei are not generated and the size distribution does not widen due to Ostwald ripening.
That is, it is preferable to add at a rate of 30 to 100% of the rate at which new nuclei are generated.

In the silver halide grains having a preferable internal high silver iodide content contained in the silver halide emulsion according to the present invention, the concentration of the silver nitrate aqueous solution used during the growth of the high silver iodide content phase (internal core) in the center thereof is IN or less is preferable, especially 0.3 to 0.8N
is preferred.

In producing the silver halide emulsion of the present invention, stirring conditions during production may be extremely important.

As the stirring device, the device shown in JP-A-62-160128, in which an additive liquid nozzle is installed in the liquid near the mother liquor inlet of the stirrer, is particularly preferably used. Also, at this time,
The stirring rotation speed is preferably 400 to 120 rpm.

Removal of soluble salts (desalting) during production of the emulsion according to the present invention
It can be performed. In order to remove soluble salts from the emulsion after precipitation or physical ripening, the tardel water washing method, which involves gelatinization of gelatin, may be used.
For example, a precipitation method (flocculation method) using gelatin derivatives (eg, acylated gelatin, carbamoylated gelatin, etc.) may be used. The process of removing soluble salts may be omitted.

In the light-sensitive material of the present invention, one type of silver halide emulsion according to the present invention may be used, or several types of emulsions may be mixed and used.

The emulsion used in the light-sensitive material of the present invention is preferably subjected to gold sensitization, sulfur sensitization, or reduction sensitization, and it is also preferable to use a combination of these sensitizations.

That is, a sulfur-containing compound (
Sulfur sensitization using reducing substances (e.g., stannous salts, amines, hydrazine derivatives, formamidine sulfinic acid, silane compounds); Reduction sensitization method used; noble metal compounds (e.g., gold complex salts, Pt,
Ir.

A noble metal aggravation method using complex salts of metals in group (I) of the periodic table such as Pd can be used alone or in combination.

Specific examples of these include U.S. Patent No. 1.574.944, U.S. Pat. No. 3,410,689, U.S. Pat.
U.S. Patent No. 3.656,955, etc., and U.S. Patent No. 2.983609 and U.S. Pat.
No. 2,599,083, US Pat. No. 2,448.
No. 060, British Patent No. 618.061, and other specifications.

In carrying out the present invention, a combination of internal latent image type silver halide grains and surface latent image type silver halide grains described in Japanese Patent Publication No. 41-2086 may be used as an emulsion.

The sheet-shaped silver halide photographic material of the present invention has corner cuts. A corner cut is generally formed such that at least one corner is obtuse or curved. The photosensitive material of the present invention has high resistance to pressure such as corner cutting, has round corners,
It is preferable to have a curved shape such as an ellipse, or it may be cut in a straight line, but in this case, it is preferable to cut it in two or more straight lines.

When the emulsion according to the present invention is used, or when an emulsion layer is formed using other emulsions as necessary, the emulsion layer consists of two or more types of emulsions having substantially different photographic properties, for example, two to six emulsions.
The emulsion can be formed by containing various silver halide emulsions. Here, ``j with substantially different photographic characteristics refers to sensitivity,
Among the photographic properties, including gradation, color sensitivity, coloration, developability, image sharpness, graininess, etc., the difference in sensitivity and gradation.

The emulsions having different photographic properties may be contained in separate emulsion layers.

In terms of graininess and drying properties, the silver halide photographic light-sensitive material of the present invention has silver halide particles when immersed in an aqueous solution of 1.5 weight percent sodium hydroxide at 50.0°C without stirring. It is preferable to harden the emulsion layer by adding a hardening agent so that the time required for detachment from the support is 10 minutes or more, more preferably 15 minutes or more.

When the silver halide photographic material of the present invention is processed, for example, in a roller conveyance type automatic processing machine, it is often processed in a state from development to drying. The water content of the photographic material is 6.0.
The range is preferably from 15.0 g/rrf to 15.0 g/rrf, particularly preferably from 9.0 to 14.0 g/rrr. In this specification, the water content of the silver halide photographic material is
Measured using the following measurement method under conditions of 25°C and 75% relative humidity. That is, 20C1lX20C1l,
The sample is exposed to just enough light to achieve maximum density.
Using Konica's automatic developing machine 5RX-501 (processing speed selector switch at 45 seconds), the developer was Konica's XD-3.
A predetermined amount of Starter
Automatic development was carried out using SR (manufactured by the same company) at 32° C., with tap water at 18° C. being supplied at a rate of 31 minutes per minute. The drying rack of the automatic developing machine was removed, and 101 sheets of the same sample as the sample for moisture content measurement were processed in succession at an interval of 1 sheet/12 seconds, and the 101st sample was used as the sample for moisture content measurement. Take it out and measure the weight 15 seconds later. (At this time, make adjustments in advance so that the power to the drying system does not turn on.) Let the weight at this time be W%, l (g).

Next, after thoroughly drying the sample, dry the sample at 25°C for at least 1 hour.
The sample was left under conditions of 1°C, 55% RH, and its weight was measured. Let this be Wa (g). The water content is calculated from the following formula.

Water content (g/a) = (ww - Wd) x (10
000c1i/ 20cm x 20C11) The location for weight measurement must be a location where the wind speed is 0.5 m/sec or less.

The photographic material of the present invention may contain a dispersion of a water-insoluble or sparingly soluble synthetic polymer in the photographic emulsion layer or other hydrophilic colloid layer for the purpose of improving dimensional stability.

For example, alkyl (meth)acrylate, alkoxyalkyl (meth)acrylate, glycidyl (meth)acrylate, (meth)acrylamide, vinyl ester (e.g. vinyl acetate), acrylonitrile, olefin, styrene, etc. alone or in combination, or these and acrylic acid. , methacrylic acid, α,β-unsaturated dicarboxylic acid, hydroxyalkyl (meth)acrylate, sulfoalkyl (meth)acrylate, styrene sulfonic acid, and the like can be used. Note that the term (meth)acrylate mentioned above is an abbreviation for both acrylate and methacrylate.

The silver halide photographic material of the present invention is preferably provided with a protective layer, and this protective layer is a layer made of a hydrophilic colloid, and any hydrophilic colloid such as gelatin can be used.

Further, the protective layer may be a single layer or a multilayer.

A matting agent and/or a smoothing agent may be added to the emulsion layer or protective layer of the silver halide photographic material of the present invention, preferably to the protective layer. Although known matting agents can be used, polymer matting agents are more preferred, and the average particle size thereof is preferably from 0.3 .mu.m to 12 .mu.m, particularly preferably from 3 .mu.m to 9 .mu.m.

Specific examples of polymer matting agents used in the practice of the present invention include water-dispersible vinyl polymers such as polymethyl methacrylate, cellulose acetate propionate, starch, and the like. In particular, matting agents of water-dispersible vinyl polymers such as homopolymers of acrylic esters such as methyl methacrylate, glycidyl acrylate, and glycidyl methacrylate, or copolymers of these acrylic esters with each other or with other vinyl monomers are used. preferable. Among these, spherical matting agents of polymethyl methacrylate having an average particle diameter of 3 μm to 9 μm are particularly preferred.

The matting agent is usually added to the protective layer above the emulsion layer, the protective layer on the back side, etc., but the above polymer matting agent is added to the protective layer on the emulsion layer side. It is more preferable to do so. As a result, when a photographic material containing a polymer matting agent is processed with a roller conveyor type automatic developer, for example, the photosensitive material will not slip.

Smoothing agents help prevent adhesion failure similar to matting agents, and
It is particularly good for improving frictional properties related to the projection of motion picture films or camera compatibility during projection. Specific examples include liquid paraffin, waxes such as esters of higher fatty acids, polyfluorinated hydrocarbons or derivatives thereof, polyalkylpolysiloxanes, polyarylpolysiloxanes, polyalkylarylpolysiloxanes, or their like. Silicones such as alkylene oxide addition derivatives are preferably used.

It is preferable to use a plasticizer in the light-sensitive material of the present invention in order to prevent fog during coating and drying, and to prevent fog and desensitization caused by bending under low humidity conditions. Examples of plasticizers include JP-A No. 48-63715 and JP-A No. 43-4
No. 939, No. 47-8745, U.S. Patent No. 306, 47
No. 0, No. 2,960.404, No. 3,412.159
issue.

Those described in No. 3,791,857 and the like can be used. Preferably, the melting point is 40°C or higher (both 2
Polyhydric alcohol compounds with three or more hydroxyl groups are
It is to contain one type of both. Such compounds include alcohols that have 2 to 12 hydroxyl groups and 2 to 20 carbon atoms, and in which the hydroxyl groups are not conjugated with a conjugated chain, that is, an oxidized form cannot be written. It is preferable that the melting point is 50°C or more and 300″C or less.
There is one described in No. 49.

In carrying out the present invention, surfactants can be used in the photosensitive material for various purposes.

The silver halide photographic light-sensitive material of the present invention can be exposed to exposure light suitable for each light-sensitive material, and can be subjected to processing such as development processing depending on each light-sensitive material.

〔Example〕

Hereinafter, the present invention will be explained in detail by giving Examples.

However, as a matter of course, the present invention is not limited to the examples.

Example 1 (Preparation of spherical seed emulsion) A monodisperse spherical seed emulsion was prepared by the method disclosed in JP-A-61-6643.

D. Ammonia water (28%) 705
d Add B, liquid and 0 to liquid A1 which was stirred vigorously at 40°C.
1 liquid was added in 30 seconds using a double jet method to generate nuclei. The pBr at this time was 1.09 to 1.15.

After 1 minute and 30 seconds, liquid C1 was added for 20 seconds and aged for 5 minutes. The KBr concentration during aging was 0.071 mol/i, and the ammonia concentration was 0.63 mol/1.

Thereafter, the pH was adjusted to 6.0, and the solution was immediately desalted and washed with water. When this seed emulsion was observed under an electron microscope, it was found to be a monodisperse spherical emulsion with an average grain size of 0.36 μm and a distribution width of 18%.

Comparative Example 1 Using the seed emulsion of Example 1, a tabular comparative emulsion Em-A having an average silver iodide content of 1.93 mol % was prepared.

Made by Danko and Nigiri Liquid B and Ct were added over 40.5 minutes to liquid A2, which was vigorously stirred at 65°C, by the double jet method.

During this time, the pH was maintained at 2.0 with nitric acid, and the pAg was maintained at 9.0 throughout. The addition rates of B2 liquid and 02 liquid were increased linearly so that the initial and final addition rates were 2.95 times.

After the addition, in order to adjust the pti to 6.0 and remove excess salts, precipitation desalination was performed using an aqueous solution of Demol (manufactured by Kao Atlas Co., Ltd.) and an aqueous solution of magnesium sulfate, and the pA
g 8.5. An emulsion with a pH of 5.85 was obtained at 40°C. When the obtained emulsion was observed with an electron microscope, the average grain size was 0.92 μm, the width of the distribution was 14%, and the projected area was 88.
The grains were tabular silver halide grains consisting of (111) planes with a ratio of 100%.

The average grain diameter/grain thickness ratio of the tabular silver halide grains was 3.6. Cu of this emulsion Em-A
The (420) diffraction line using Kα radiation as the source has a peak l5F
It consisted of two sharp peaks separated by 0.27 degrees (2θ). FIG. 2 shows the X-ray diffraction signal of this emulsion Em-A.

In all the measurements of the emulsion samples in the examples described in this specification, a JDX-11 model manufactured by JEOL Ltd. was used as the device, a graphite monochromator was used as the monochromator for the diffraction line, and the measurement conditions were a tube voltage of 40 kV. , tube current 5
The test was performed at 0 mA and a step angle of 0.02 degrees (2θ). Under these measurement conditions, the half-width of the (331) diffraction signal of the silicon powder used as a standard sample is 0.33 degrees (2θ)
(The X-ray diffraction pattern of this standard sample is shown in FIG. 4).

Comparative Example 2 The seed emulsion of Example 1 was used, the average grain volume was the same as Em-A, and the average silver iodide content was 8.0 mol%.
A comparative emulsion Em-B, which is a monodisperse twin emulsion having a high silver iodide content phase inside the grains, was prepared.

Liquid 83-1 and liquid C3-1 were added to liquid A3, which was vigorously stirred at 75°C, by a double jet method. At this time, the pH was maintained at 2.0 with nitric acid and the pAg was maintained at 8.0.

The addition time was 45 minutes, and the addition rate was increased linearly by a factor of 1.9 between the initial and final times. Next, add L-z in the same solution.
Liquid and 03-2 liquid were added by double jet method. At this time, the pH was maintained at 2.0 and the PAg was maintained at 8.0. The addition time was 28 minutes, and the addition rate was increased linearly by a factor of 1.75 between the initial and final times. After the addition was completed, the pH was adjusted to 6.0, and in order to remove excess salts, precipitation desalting was performed using an aqueous Demol solution and an aqueous magnesium sulfate solution to obtain an emulsion with a pAg of 8.5 at 40°C.

When the obtained emulsion was observed with an electron microscope, the average grain size was 0.75 μm, the distribution width was 15%, and the (100) plane and (1
11) It was a monodisperse tabular silver halide emulsion with planes.

The CuKα radiation of this emulsion Em-B was used as a radiation source (420)
The diffraction line was a wide signal consisting of two peaks with a peak interval of 1.32 degrees. Figure 3 shows that this emulsion Em
-B shows the X-ray diffraction signal.

Example 2 Using the seed emulsion of Example 1, the average grain volumes were EmA, Em-
Same volume as B and average silver iodide content of 2.25 mol%
Milk IJEm-1 of the present invention was prepared.

The 84- and C,- solutions were added by a double jet method to the A4 solution that was vigorously stirred at 75"C. At this time, the pH was maintained at 2.0 with nitric acid and the PAg was maintained at 8.0. The addition time was 16 minutes, and the addition rate was linearly increased to 1.27 times between the initial and final times. 84-Z liquid and 04-2 liquid were added to the same liquid using the double jet method. At this time, the pH
was kept at 2.0, and p, Ag was kept at 860. The addition time was 38 minutes, and the addition rate was increased linearly by a factor of 1.80 between the initial and final times. After the addition was completed, desalination and precipitation were performed in the same manner as in Comparative Examples 1 and 2, and pA g8.5 at 40°C.
An emulsion with a pH of 5.85 was obtained.

When the obtained emulsion was observed with an electron microscope, it was found that 100
The silver halide emulsion consisted of % twin grains, had an average grain size of 0.73 μm, and had a distribution width of 11%. In addition, 100% of the projected area has a particle diameter/particle thickness ratio of 1.0 to 1.5.
It had a (100) plane and a (11,1) plane, and the ratio was 64:36.

The CuKα radiation of this emulsion Em-1 was used as a radiation source (420)
The diffraction line had only one peak. FIG. 1 shows the X-ray diffraction signal of this emulsion Em-1. The diffraction width at the highest peak height x 0.13 of this signal was 0.816 degrees (2θ), and the line drawn vertically from the highest peak intersects the line drawn horizontally at the peak height x 0313. Let point B be peak height x
If AA' is the line segment where the line drawn horizontally at 0.13 is cut by the signal, then AA' is AB by B.
: BA' = 0.85:1 (B and A
For A', see Figure 1).

Example 3 Emulsion Em-2 of the present invention having an average silver iodide content of 2.02 mol % was prepared in the same manner as in Example 2 except that the solution B4-2 in Example 2 was replaced with the following solution. .

A, Same as solution A4 of Example 2 B, -1 Same as solution B4-1 of Example 2 C! l-1 Same as solution C4-5 of Example 2 C5-t Same as solution C4-2 of Example 2 When the obtained emulsion was observed under an electron microscope, it was found that it consisted of 100% twin grains, and the average grain size was 0.7
It was a silver halide emulsion with a diameter of 3 μm and a distribution width of 11%. In addition, 100% of the projected area has a particle diameter/particle thickness ratio of 1.0 to 1.5, and (too1 surface and jllll
The ratio was 65:35.

The diffraction line of this emulsion using CuKα radiation as a radiation source had only one peak, and the diffraction width at the maximum peak height x 0°13 was 0.820° (2θ).

Also, a line drawn perpendicularly from the highest peak and peak height x 0
．． 13, the point where the horizontal lines intersect is B, and the line segment where the horizontal lines cut the signal at peak height x 0.13 is AA', then AA' is AB by B.
: BA'=0.8671.

Example 4 Each of the silver halide emulsions Em-A, Em-B, Em-1, and Em-2 obtained in Comparative Examples 1 to 2 and Examples 2 to 3 was optimally subjected to gold-sulfur sensitization. .

Immediately before the end of this chemical sensitization, the following sensitizing dye was added to Dye A:
Dye B = 20:1 ratio, total amount 1000 ■ 1 mol A,
and 4-hydroxy-6-methyl 1.3.3a
, 2.5 g of 7-chitrazaindene, 1 mole of Ag.

Spectral sensitizing dye A Spectral sensitizing dye B Furthermore, in each emulsion, as emulsion layer additives, 400 μg of t-butyl-catechol per mole of silver halide, 1.0 g of polyvinylpyrrolidone (molecular weight 10.000), styrene/anhydrous 2.5 g of maleic acid copolymer, 10 g of trimethylolpropane, 5 g of diethylene glycol, 50 g of nitrophenyl-triphenylphosphonium chloride, 4 g of ammonium 1,3-dihydroxybenzene-4-sulfonate, 12-mercaptobenzimidazole-5-sulfonate sodium 15 ml, 2-mercaptobenzothiazo-υi tyrol-1-bromo-1-nitromethane 10 ml, and the following compound as a protective layer additive were added. That is, per 1 g of gelatin, 0xNa CJ+f'-0+CHzCHzO+-r-r-CHzC
HzOHCsF+, SOsK 2wg, 3■, 7■ of a matting agent made of polymethyl methacrylate with an average particle size of 5 μm, and 70■ of colloidal silica with an average particle size of 0.013 μm were added.

Furthermore, as a hardening agent, the following compound was added at 7% per 1g of gelatin.
■Added.

CH,=cnsogocuzso□CO=cut The resulting emulsion and protective film solution were colored blue to a thickness of 180t.
It was coated on both sides of a 1 m long subbed polyethylene terephthalate sheet to obtain a double-sided emulsion sheet-like photosensitive material. At this time, the amount of silver per side was 1.9 g/rrr, the gelatin of the emulsion was 2 g/rrf, and the gelatin of the protective film was Ig/rrf.
It was applied so that

(Sensimetry Evaluation) The obtained sample was sandwiched between X-ray photographic intensifying screens KO-250 (manufactured by Konica Corporation) and irradiated with X-rays through a venetrometer type B (manufactured by Konica Medical Corporation). after that,
Using Konica Corporation's 5RX-501 automatic processor,
Processing was performed for 45 seconds using a D-SR developing solution.

The sensitivity of each sample developed as described above was evaluated. Sensitivity was expressed as a relative value, with 100 being the reciprocal of the amount of irradiation energy required to give sample 1 a density of fog+1.0.

The results obtained are shown in Table-1.

(Creating a corner cut) Cut the coated sample into the size shown in Table 1, randomly stack 1000 pieces of each type of sample of the same size, including dummies, and cut the sample into a round with a radius of curvature ICII using a round blade. Corner cuts were made by cutting off the corners. These samples were developed using the above-mentioned developing machine, and the degree of blackening of the corner cut portions was visually evaluated. 1 is black and not practical, 2 is better than 1 but still not practical, 3 is practical, 4
5 indicates that there is a slight blackening, and 5 indicates that there is no blackening at all. Table 1 shows the average value of 10 sheets.

(Comprehensive evaluation) As shown in Table 1, the samples of the present invention have high sensitivity, and the corner cut evaluation is 3 or more, so there is no problem in practical use. On the other hand, comparative samples other than those of the present invention were inferior in both sensitivity and corner cut evaluation.

Em-1 × 匡β times 1 (20) [Effects of the Invention] As described above, the sheet-shaped silver halide photographic light-sensitive material of the present invention has high sensitivity and has obtuse or curved corners. Even when a corner cut is made in this way, the effect is that the occurrence of pressure fog along the corner cut is suppressed.

[Brief explanation of drawings]

Figures 1, 2, and 3 are graphs showing X-ray diffraction signals of emulsion grains, and Figure 1 is a graph showing the X-ray diffraction signals of milk JlqEm-
1. FIG. 2 shows the signals for emulsion Em-A, and FIG. 3 shows the signals for emulsion Em-B. FIG. 4 is a (331) powder X-ray diffraction pattern of silicon powder.

Claims (1)

[Claims] 1. 50% or more of the projected area consists of silver halide twin grains with a grain diameter/grain thickness ratio of less than 5, and are monodisperse, and CuKα radiation is used as a radiation source. The (420) X-ray diffraction signal has only one peak, and the highest peak height ×
The diffraction line width at 0.13 is 1.5 at the diffraction angle (2θ)
Silver halide photographic emulsion of less than 500cm^2
1. A sheet-shaped silver halide photographic light-sensitive material characterized in that it is formed by coating on a support having the above area and has corner cuts. 2. At the highest peak height x 0.13 of the (420) X-ray diffraction signal using CuKα rays as the radiation source, let AA' be the line segment where the horizontal line is cut by the signal,
When the intersection with the line drawn from the highest peak position is B,
The halogen sheet according to claim 1, characterized in that it contains a silver halide photographic emulsion separated so that the length ratio of the length of line segment AB to the length of line segment BA' is 1.0 or less. Silver chemical photographic material. 3. The sheet-shaped silver halide photographic light-sensitive material according to claim 1 or 2, wherein the silver halide grains mainly consist of silver iodobromide having a high silver iodide content phase inside the grains. 4. More than 50% of the silver halide grains are {11
4. The sheet-like silver halide photographic material according to claim 1, which has both a {1} plane and a {100} plane.