JPH01213637A - Silver halide emulsion and method for manufacturing and processing same - Google Patents

Abstract

PURPOSE:To improve sensitivity, gradation, graininess, sharpness, resolution, covering power, and image quality by using a silver halide emulsion having the silver halide grains of which >=95% of the total projection area is occupied by flat silver halide grains having parallel twin crystal faces and the size distribution is of a monodispersion type. CONSTITUTION:The emulsion to be used is composed of a dispersion medium and the silver halide emulsion and >=95% of the total projection area of the grains is occupied by flat silver halide grains having 2 parallel twin crystal faces and the size distribution of a monodispersion type. These flat grains have principal hexagonal faces each having an adjacent side ratio (longest side to shortest side ratio) of <=2.0, and an adjacent side ratio of >=4/5, and an aspect ratio of >=2.0, thus permitting the silver halide grains to be uniform in the shapes, good in monodispersion performance, and improved in each of sensitivity, gradation, graininess, sharpness, resolution, covering power, image quality, and pressure resistance.

Description

Detailed Description of the Invention (Technical Field) The present invention relates to a silver halide emulsion useful in the field of photography, and in particular to a silver halide emulsion containing a dispersion medium and tabular silver halide grains (hereinafter referred to as "AgX"). ) Regarding emulsions.

(Prior art and its problems) The photographic properties of tabular silver halide grains containing parallel twin planes (hereinafter referred to as "tabular grains") are the ratio of surface area to volume (hereinafter referred to as specific surface area). is large, and a large amount of sensitizing dye can be adsorbed onto the surface. As a result, the color increase and the degree of confusion are relatively high.

2) When an emulsion containing tabular grains is coated and dried, the grains are arranged parallel to the surface of the support, so the thickness of the coated layer can be reduced, and sharpness and current f# progression are good.

3) In an X-ray photographic system, when a sensitizing dye is added to tabular grains...the extinction coefficient of the dye is greater than the extinction coefficient of indirect transition of silver halogenide (AgX), which causes significant crossover light. Therefore, deterioration of image quality can be prevented.

Hiroshi) Less light scattering, solution rj! A high-quality image can be obtained.

Since both have flat surfaces that are parallel to each other, there is an interference effect of light on parallel plates.Using this metal, the light utilization efficiency =
can be raised.

6) Covering and g-cous are high and silver saving can be achieved.

7) Radiation absorption increases exponentially for each particle, but since tabular grains have thin grains, radiation absorption/
There are fewer particles and less natural radiation build-up due to aging.

? )Currently 11! %% is flattened and mottle silver is hard to form, so the graininess is good.

ri) Because the specific surface area is large, development progresses quickly.

Because of these many advantages, it has been used in high-grade commercially available light-sensitive materials.

Tokukai Akira! ! -//No. 3926, same as r-7i3ri No. 27, same! ! -//JF2r and others disclose emulsion grains having an astect ratio of j or more.

The aspect ratio referred to here is expressed as the ratio of the diameter to the thickness of the tabular grain. Furthermore, the term "grain diameter" refers to the diameter of a circle that covers an area equal to the projected area of the grain when the emulsion is observed under a microscope or an electron microscope. The resulting thickness is indicated by the distance between two parallel surfaces forming a tabular grain T44.

However, as seen in the case of Eiman in the above patent,
Tabular grains according to the known preparation ε:, -" j11 The tabular grain size is not good. This is because ■ S + tabular grains have a wide projected grain size distribution ■ In addition to tabular grains, there are zen-like grains, tetrapod-like grains,
Contains single twin grains and grains with non-parallel twin planes.

■ As tabular grains, hexagonal tabular AgX grains (hereinafter referred to as
This means that hexagonal tabular grains) and triangular tabular AgX grains (hereinafter referred to as triangular tabular grains) are mixed.

For this reason, l) hard contrast of the characteristic curve (so-called high gamma) cannot be expected.

2) When chemically sensitizing an emulsion containing a mixture of large grains and small grains, the optimal conditions for chemical sensitization are different for large grains and small grains, so it is necessary to perform optimal chemical sensitization for both. That's funny.

3) Comparing emulsion coating layers with a mixture of large grains and small grains, a multilayer system in which a heavy dispersion large grain layer is coated on top of the T1 layer and a monodisperse small grain layer is coated on T1 has higher sensitivity in terms of light utilization efficiency. However, it has the disadvantage that this multilayer effect cannot be fully utilized.

Therefore, various attempts have been made to monodisperse tabular grains, and several patents have been disclosed.

Tokukai Akira! λ-/! 3% Jj monodispersed tabular grains have A in the core.
There is a restriction that gI crystal is used, and the obtained grain shape has a small proportion of tabular grains according to the present invention.

Tokukai Akira! ! -/4c23 Co. No. 2 discloses the growth conditions for monodispersing tabular grains, but because the seed crystal nucleation conditions used in that example were inappropriate, the produced grains were subject to I invention. The proportion of tabular grains was low.

After the nucleation of the single twin grain of Akira Sakai/-32027,
This is a method in which AgX solvent is added and ripened, and then the grains are grown, but the resulting grains have a low tabular grain ratio according to the present invention and a low astectonic ratio.

Regarding the particle formation process, there is Tokuyoku Shoti-//λ/4L4, which is a monodisperse twin patent similar to this patent. This patent is also not intended to specifically increase the ratio of uninvented tabular grains, but is lower than the ratio of uninvented tabular grains, and since spherical grains are used as seed crystals, the asquite ratio is λ, λ or less. It is.

The monodisperse tabular grains described in French Patent No. 213≠034 are formed by a method of ripening without using an AgX solvent after nucleation, but when measured from the grain photographs published in the examples, they are triangular. If the projected area of the tabular grains is 10% or more, the grains differ from the grains of the present invention.

The triangular tabular grains were prepared by J.E., Maskasky, J.

Imaging Sci, L/1 iri 17 years, p.
p, /j-J According to A, it is a grain with 3 M parallel twin planes, and has more defects than a hexagonal tabular grain with 2 M parallel twin planes, and due to their synergistic effect. , has the disadvantage of high internal sensitivity.

However, if triangular tabular grains and hexagonal tabular grains are mixed,
Chemical sensitization and hard-boiled methods are inappropriate because their chemical sensitization characteristics are different.
It has great love benefits.

When comparing triangular tabular grains with the same projected area and hexagonal tabular grain color divided by hexagonal tabular grain, the maximum grain size W5 of the former is 1.13 times the maximum color diameter of the latter, which indicates that the granularity of the triangular tabular grain is Getting worse.

Furthermore, it is known that the ideal pixel arrangement in an image sensor for boat fishing is a honeycomb structure, and a two-dimensional arrangement of regular hexagonal pixel elements is preferable. For this, see J.C., Daintyand R.Shaw,
Image 5science.

Academic Press, London.
/27μ, you can refer to the description in Chapter 1.

From this point as well, 1[i! The shape of the AgX particles corresponding to each picture element is preferably a regular hexagon.

#ifa by the present inventors K.
JA/-, xPylrr issue and 42-20343j
No. 1 relates to monodisperse hexagonal tabular grains and circular tabular grains with two parallel twin planes, but the projected area ratio of the tabular grains did not exceed J% gold. That is, triangular tabular grains, single twin grains, annular grains, and tetrapod-like grains 7J: The removal of these grains was a problem because they contained j-73% in total projected area.

(Objective of the Invention) The object of the present invention is to have uniform shape, good monodispersity, and excellent sensitivity, gradation, graininess, sharpness, strength, covering power, image quality, and pressure resistance. It is an object of the present invention to provide a tabular AgX emulsion that can be improved.

(Disclosure of the Invention) The object of the present invention is to provide an AgX emulsion consisting of a dispersion medium and AgX grains, in which 25 or more of the total projected area of the AgX grains are tabular grains having two parallel twin planes M. This was achieved using an AgX emulsion in which the size distribution of the tabular grains is monodisperse.

The tabular grains having two M parallel twin planes in the present invention have the following λ shapes as specific shapes.

(t) The shape of the main plane of the tX tabular grain is determined by the adjacent side ratio (
It is a hexagon with maximum side length / minimum side length) of 2 or less, and the ratio of the straight line part of the hexagon is Hiroshi/! In addition to the above, monodisperse hexagonal dry T with an ast ratio of 2.0 or more! (2) The shape of the main plane of the plate-like tester is 1iiti part ratio X
61) with a circular shape of 4'/z-o, and the asquite ratio is 2
．． Monodispersed circular tabular grains having a particle size of 0 or more.

The adjacent side ratio herein refers to (maximum side length/minimum side length) of sides forming a hexagon in seven hexagonal tabular grains.

The corners of the monodisperse hexagonal tabular grains of the present invention may be somewhat rounded. When the corners are somewhat rounded, the length of the side is varied by extending the straight part of that side and alternating between the intersections with the line extending the straight part of the adjacent side.

The linear portion ratio in the present invention refers to (length of the hexagonal straight portion/distance between the intersections of the extended lines).

The lithographic bao of the present invention has a special feature of having two parallel-twin planes t, which means that an ultra-thick layer (~a/μm thick) section of the cross-section of the emulsion-coated film can be This can be confirmed by observation with a transmission electron S micrometer in the α-form He1 degree).

It is assumed that the uninvented dish tabular hexagonal tabular grains and dish-dispersed circular tabular grains are monodispersed, but monodispersity here refers to the coefficient of variation [the diameter of the projected area of the tabular grains converted to a circle]. It is expressed by dividing the variation (standard deviation) of the expressed particle size by the average particle size.

The grain size distribution of an emulsion consisting of a group of photosensitive silver halide grains with uniform grain morphology and small variations in grain size shows almost a normal distribution, and the standard deviation can be easily determined. The monodispersity of the tabular grains of the present invention has a coefficient of variation of 30% or less, preferably 20% or less, and more preferably 11% or less.

The monodisperse circular tabular grains of the invention and the monodisperse circular tabular grains have an average aspect ratio of 1 or more, preferably 11! ~20
．． More preferably Hiroshi-16.

The average ascent ratio herein refers to the average value of the ascent ratios of all the grains of the invention having an ascite ratio of 2.0 or more present in the emulsion.

The uninvented Agx emulsion consists of minute grains and Ag
As mentioned above, tabular grains having two parallel twins i are preferred above tqb.

The grain size of the tabular grains of the present invention is 0.2 μm or more, preferably Oo−≠μm.

Normally, for untwinned grains such as cubes, O, 0.7
The light scattering efficiency factor (0
sca) is particularly large, which is a problem, but from the viewpoint of using the particles of the present invention in this particle size range and reducing 0sca, the particle size of 0°25 to 0.7 rμm1 as has a ct ratio of 3 to 3. −〇 is preferable.

In addition, since tabular grains usually have a large surface/volume, the number of chemical nuclei generated/particles increases, which tends to cause latent dispersion, but the tabular grains of the present invention can prevent this dispersion. Therefore, it is preferable that the number of chemically sensitized nuclei produced/particles be controlled. The number of chemically sensitized nuclei produced/gL is preferably 20 or less, preferably 10 or less, and more preferably 3 or less.

Furthermore, it is preferable that the location of chemical sensitizing nuclei to be generated is also controlled. The details are as follows.

■ Tabular grains having (100) planes at the edges and chemically sensitized cherry blossoms formed preferentially on the core (100) planes.

Preferential in this case means (number of chemically sensitized nuclei on the crystal face where chemically sensitized nuclei are preferentially formed/cm”)/(number of chemically sensitized nuclei on the crystal face where chemically sensitized nuclei are not preferentially formed) Number of sensitizing nuclei/c
rn2) is 2.1 or more, preferably 1 or more.

In this case, the preferred range of the (100) area of the edge portion is (thorn area of (10O) plane/total surface area of the flat plate or particle) =
0.0r-0.6.

The area ratio of the (///) plane and the (100) plane can be determined using a measurement method (T, Tan1. Journalof
It can be determined using Imaging 5science, 29, /Ayo (/tatori).

■ As shown in Figure 7, there is a core part and an appended part t-1 in the lateral direction, and the halogen composition of the core part and the appended part is different. Using selective adsorption characteristics, chemically sensitized nuclei are cor
A tabular grain formed preferentially on the e part or on the additional part. The definition of preferential in this case follows the above definition.

Also, the area ratio of the core part and the additional part is //2Q~20
is preferred.

In the cases of ■ and ■ above, the number of chemically sensitized nuclei produced/particle is 20
or less, preferably 70 or less, more preferably 3 or less.

Chemical X formed on uninvented tabular grains! It is difficult to observe the number of impressions in place. However, when the AgX emulsion coating is exposed to light (exposure period 10 seconds to '/100 seconds), a residue is formed at the top of the chemical amplification (photosensitivity length), and a suppressive state is formed.
By making the suppression letter visible with an electronic a shukukyo senshi (sword) and counting the number of suppression expressions,
The number of chemically multiplying nuclei and the above ratio can be determined.

Regarding this method, C. Birch et al., Jour
nal of Photographic 5c
ience.

It is described in Volume 13, P, 2-ara (15'7 yo.).

Here, the chemical sensitizing nucleus is a chemical sensitizing nucleus consisting of sulfur, selenium, tellurium, gold, and Group 1 noble metal conjugates alone or in combination, and most preferably a gold-sulfur sensitizing nucleus. It is usually referred to as sulfur-enriched atom, gold-enhanced S nucleus, noble metal-enriched temporary, or a combination thereof, and for details, reference can be made to the literature mentioned below.

The composition of the tabular grains may be any of silver bromide, silver iodobromide, silver chlorobromide, and silver chloroiodobromide.

There are no particular restrictions on the halogen composition K, and it can be used depending on the purpose. In many cases, kgBr,
AgBr1lljI (B content is o -jHd solubility limit, α content is 0 to 0 mol%). The crystal structure is-
It may be similar to the above, or it may be made of different halogen compositions on the inside and outside, or it may have a layered structure. Part 1
The change in halogen content between 1 and 2 is gradual. Any type of shoken type is fine, and each type can be used depending on the purpose.

Further, it is preferable that the particles contain reduction-sensitized silver nuclei. Whether it has this reduction-sensitized silver nucleus can be determined by exposing it to light,
This can be easily determined since the reversal of the existing internal fog is observed when internal development is carried out by a conventional method and the HD curve is filled.

Next, the farming method of the AgX emulsion of the present invention will be described.

The AgX emulsion of the present invention can be produced by any of the following methods: (1) nucleation → ripening (2) nucleation → ripening-growth (2) nucleation → ripening-growth → (4) ripening. Therefore, the basic processes of nucleation, ripening, growth, and ripening will be explained.

/, Nucleation Nucleation uses low molecular weight gelatin as a dispersion medium, pBr/,
Nucleates under conditions of 0-J,j.

In this case, the molecular weight of the low molecular weight gelatin is 60,000 or less, preferably 1000-≠10,000.

When the average molecular weight is 60,000 or more, the uninventive effect (more than 20% of the projected area of the whole human gX grain becomes a tabular grain having two parallel twin planes) becomes less.

It is preferred that 50% or more, preferably 70% or more of the dispersion medium is low molecular weight gelatin.

The concentration of the dispersion medium can vary from o, or to io.

As a seed field for gelatin, alkali-treated gelatin is usually used, but other modified gelatin such as acid-treated gelatin and capped gelatin can also be used.

In addition, it is more preferable that one or both of the AgNO3 aqueous solution and the alkali halide aqueous solution added at the time of nucleation contain gelatin.

The gelatin used here is preferably the low molecular weight gelatin mentioned above. In that case as well, it is preferred that 50% or more, preferably 70% or more of the dispersion medium be low molecular weight gelatin.

In this case, the concentration of the dispersion medium is 0.0 r-j by weight, preferably 0.3 to 0.0 and O1 to 1.

This effect is thought to be due to preventing the gelatin concentration from becoming non-uniform near the addition ports of the λgNo aqueous solution and the norogenide salt aqueous solution, thereby preventing the formation of multiple twin grains.

The frequency with which twin planes are formed during bale formation depends on various supersaturation factors [temperature during nucleation, gelatin concentration, type of gelatin,
Molecular weight of gelatin, addition rate of silver salt aqueous solution and alkali halide aqueous solution, Br concentration, stirring rotation speed, knee content in the alkali halide aqueous solution to be added, amount of silver halide solvent, pH1 salt concentration (KNO3, N a N O3 Such)
(emulsion stabilizer, antifoggant, sensitizing dye concentration), etc., and the dependence is
It is shown in the figure in issue 3rtot.

Normally, nucleation occurs at low temperatures (2J to 3o'C), and then high filtration is carried out at low temperatures without ripening! p! In the sum growth method, if these supersaturation factors are increased during nucleation,
The main particles generated are a) octahedral reginilla ÷ - b
) a single twin plane! Busy → C) Two parallel twin planes! particles (target objects) - d) single grains with non-parallel twins I't- and C) particles growing three or more twin planes.

Therefore, in the present invention, it is preferable to form a square bottom under conditions where the probability of producing C) is as high as possible without increasing the production ratio of particles d) and e).

Specifically, while looking at the dependence in the above diagram, in the A g
These various supersaturation factors are adjusted so that the abundance ratio of ) falls within the range claimed in this patent. More specifically, the saturation factor conditions at the time of nucleation may be adjusted while observing the replicas of the silver halide grains finally produced using a transmission electron microscopy.

Regarding the nucleation of tabular grains with a high iodine content of 7 moles or more in the center, -i? Haraaki A/-23
You can refer to the description in No. 1101.

By adjusting these various factors f: the tabular grains finally obtained, the tabular grains obtained by nucleation using the above conditions have a normal average molecular weight of 100,000 for photographic use. It was found that the proportion of non-tabular grains is particularly low compared to the case where gelatin is used as a dispersion medium.In addition, the proportion of hexagonal tabular grains described in Japanese Patent Application No. 4/2221JJ is high.

The particles of the example of No. 73G were
The ratio of triangular tabular grains (grains with three parallel twin planes) is high, but this is thought to be because nucleation was performed under highly supersaturated conditions.

In addition, preferable conditions during formation of wrinkles in the present invention are as follows.

The temperature can be set at OoC, but when producing fine tabular grains with an average grain size of o, rμm or less, j, u
t' (is preferable. The knee content in the solution added in advance is preferably 0.03 mol/j or less. A g N O
The addition rate of s is preferably 7,jg/min to 3og/min per liter of reaction aqueous solution.

The composition of the alkali halide solution to be added is Br
The I- content relative to - is preferably below the solid solubility limit of Ag13rI to be produced, preferably below 0.0%.

The concentration of irrelevant salt in the reaction solution is preferably O to 1 mol/min. The pH of the reaction solution can be 2 to 10, but when introducing reduction-sensitized silver nuclei, the pH is preferably r, o to IO. The concentration of AgX solvent in the reaction solution is 0 to 3.
xio mol/l is preferred. As for the type of AgX solvent, those mentioned below can be used.

2. Ripening In the nucleation described in 1), minute tabular grain nuclei are formed, but at the same time many other fine grains (especially octahedral and single twin grains) are formed. Before entering into the growth process described below, it is necessary to eliminate grains other than the tabular grain cores to obtain nuclei having the shape of tabular grains and having good monodispersity. To make this possible, Ostwald ripening is performed using the nucleation Ka.

As for this ripening method, the items described in #Gan Sho 67-22 ri/jyo can be used, but in addition to that, the following methods are especially recommended! It is effective.

After nucleation, a portion of the emulsion is taken out as a seed crystal and an aqueous gelatin solution is added, or after nucleation in a dish, an aqueous gelatin solution is added to adjust the p B r s gelatin concentration. In this case, the preferable pBr is low pBr (/, ψ
~C, O), and the gelatin concentration is 1 to IO% by weight. The gelatin used in this case is preferably gelatin which is commonly used in the photographic industry and has an average molecular weight of 300,000, usually 100,000.

Next, when the temperature is raised and a first ripening is performed, tabular grains grow and non-tabular grains disappear. Next A g N 03
Add aqueous solution to raise the pBr of the solution to higher p13r(/,7
~λ, )), an AgX solvent is added and a second ripening is performed. In this case, the concentration of A g X solvent is 10
-' ~JX10-1 mot/l is preferred. Also Ag
As the X solvent, those mentioned below can be used.

After ripening in this manner, only about 100% to 100% tabular grains are obtained.

Basically, with this low pBr filling/ripening, Ostwald ripening occurs between twin grains with troughs and seeds without troughs, and a second ripening using -s, gX solvent at a slightly higher pBr. In this case, Ostwald ripening occurs between the earth i of the tabular grains and the spherical decay surface of the non-tabular grains, and only the tabular grains become almost 100%.

In addition, this second ripening has the effect of bringing the non-tabular grains that could not be eliminated in the first ripening to the tip, and the effect of making the thickness of the seed crystals of the tabular grains uniform. Aging using an AgX solvent at low pAg causes growth of the tabular grains in the thickness direction and the grains become thicker. If this thickness is uneven, the growth rate in the lateral direction will be uneven during the next crystal growth. This phenomenon is particularly noticeable during crystal growth in the low pBr (/, ψ~2.0) region, and is particularly unfavorable in that case.

This ripening progresses slowly in low temperature summers, so from a medicinal point of view, Hiroo'C-to'C1 is preferably jOo(-to
Perform at °C.

The gelatin concentration is o, or to io 1-% by weight, preferably /
, 0-j, 17jit% are preferred. The stage+4 A g The tabular grains are hexagonal tabular grains with slightly rounded hexagonal corners or circular tabular grains.

At the stage where this over-ripening is completed, the emulsion is washed with water by a conventional washing method, and the monodisperse hexagonal tabular grains of the present invention or C〈 may be used as monodisperse circular tabular grains.

After this ripening is completed, the next crystal growth process is usually started in order to further grow the crystals to a desired size.

After the ripening is completed, if the AgX solvent is not needed in the next growth process, the AgX solvent is removed as follows.

■ Wash the emulsion with water.

(1) Conventionally used as a water washing method for emulsions.
Tardel water washing method, (11) Water washing method in which a precipitant is added and sedimentation is performed, (iii) Sedimentation washing method using modified gelatin such as phthalated gelatin, (1■) Limit 7 method, 3! (Details Q, p, 1) uffin.

”Photographic Emulsion Ch.
emistry,'Focal Press,Lon
don, /det6 and the meaning below) can be used.

■ For alkaline A g X solvents such as NH3,
An acid having a large solubility product with Ag'', such as HNO3, is added to neutralize and nullify it.

■ In the case of thioether-based AgX solvent, refer to JP-A-40-
An oxidizing agent such as H20□ is added as described in No. 134734 to neutralize it.

3. The pBr during the crystal growth period following the growth ripening process is preferably maintained at 0. In addition, Ag” in the crystal growth period,
and the addition rate of halogen ions to 1 of the crystal critical growth rate.
It is preferable to set the addition rate to a crystal growth rate of 0 to 700%, preferably 3Q to ioo%.

That is, the higher the p13r and the higher the supersaturation of the growth atmosphere during the crystal growth period, the more the tabular grains become monodispersed as they grow. However, on the high p13r side (pBrλ
~3.0 or the below-mentioned /≠hedral crystal or cubic crystal formation region), the abrasion in the thickness direction is lost, so that monodisperse tabular grains with a low aspect ratio can be obtained.

When grown on the low pBr side (pBr/, G ~!, 0 or the region where (tii) hedral crystals such as hehedral crystals described below are produced) and with high supersaturation, tabular grains with a high ast ratio can be obtained. However, the monodispersity is slightly worse.

In this case, the addition rate of silver ions and halogen ions is increased as the crystal grows.
As described in No. 1, the addition rate (flow rate) of the silver salt aqueous solution and the halogen salt aqueous solution at a constant concentration may be increased, or the concentration of the silver salt aqueous solution and the halogen salt aqueous solution may be increased. good. Also, o, ioμm in advance
An ultrafine grain emulsion having the following size may be prepared in L4 and the addition rate of this ultrafine grain emulsion may be increased. Moreover, these may be superimposed. The addition rate of silver ions and halogen ions may be increased intermittently or continuously.

For details and how to stir, etc., see Kaisho! j-/
Hiroko 3λri No. 751, Special ■Sho 67-λ2ri No. 751, US 5W license, 3. A! No. 0,7!7, UK, etc.

! 3j, octopus! Number mark l! You can refer to it.

Generally, the lower the pBr@ in the growth atmosphere and the lower the degree of supersaturation, the broader the particle size distribution of the resulting particles.

Regarding the monodispersity of tabular grains and the 7-Squid ratio, the same applies as above. Next, the crystal 8 at the edge portion of the tabular grain will be explained.

When crystal growth is performed with the pBr at the time of crystal growth set to the above-mentioned low pBr region, the resulting tabular grains have (///) planes in both the main planes and most of the edge planes. On the other hand, if the pBr during crystal growth is changed to pBr in the high pBr region mentioned above, the grains will grow while becoming thicker.
The main plane is the (///) plane, but the edge part has (100)
My face is covered in rain.

In this case, if it is grown at a higher pBr, it will grow more in the thickness direction and the (10O) surface ratio will increase. This can be learned from the reference book described in Reference Example 1 of Japanese Patent Application No. 62-211377.

Further, if the pBr during this growth is set to the pBr of the cubic crystal generation region and is made to be low supersaturation, a hexagonal flat plate or a circular flat plate with hexagonal corners 5 slightly rounded will be obtained.

Regarding this, reference may be made to the description in Japanese Patent Application No. 1973-JOj6jr.

In addition to the method described above, the following method can also be used for crystal growth. (1) A method in which tabular grains with a high aspect ratio are first formed at low pBr, and then grown under high pBr to form (100) planes at the edges. After the ripening process, when grown under high pBr conditions, (
Although it is possible to form too 1 plane, since it also grows in the thickness direction, only tabular grains with a low aspect ratio can be obtained.

Therefore, first, tabular grains with a high aspect ratio are formed under low pBr, and then a desired area ratio of (1
00) Crystal growth is performed under high pBr in the amount necessary to form a surface, with a high aspect ratio and edge part Kito.
o) It produces tabular grains with faces.

(2) A method in which grains are grown in the thickness direction under high pBr to form tabular grains with uniform thickness, and then grown in the edge direction under low pBr. When grown under low pBr,
Monodispersity is poor because it grows quickly in the edge direction (thinner plates or thicker plates). Therefore, the method is to first uniformize the thickness and then grow in the edge direction to obtain monodisperse tabular grains with high surface area.

Basically, the tabular grains of the present invention can be produced through the nucleation, ripening, and growth processes described above.
If necessary, the next step ① ripening can be performed.

Especially for the halogen composition of AgX, which is layered on top of the nucleus during the growth period! 11! There is no limit. Often -AgBr.

AgBrα■ (Tenjiri content is O-solid solubility limit, α content is O~
0 mol%).

In order to make the intra-grain top-heel distribution into an increasing or gradual type, it is only necessary to gradually increase or gradually decrease the composition ratio of iodide in the α-genide which is added along with crystal growth. In addition to the cane length, the composition ratio of iodide in C-genide should be increased rapidly or the color should be made lighter.

In addition, as a method for supplying natural ions during this crystallization growth period, a method of adding a pre-prepared fine particle λgI (particle size of 0,/am or less, preferably 0.0 Attrn or less) emulsion may be used;・It may be used in combination with the method of supplying an aqueous alkali chloride solution. In this case, fine particles Ag
Since I is dissolved and I- is supplied, the knee is uniformly supplied, which is particularly preferable.

In the present invention, it is preferable that the silver halogenide grains contain reduction-sensitive nuclei, and from this point of view, the pH of the bath solution during the growth period is preferably r, o to -j.

In order to promote growth during the crystal growth period, an AgX solvent, which will be described later, can be used. In that case, the concentration of the AgX solvent is preferably 0 to j, 0x10-'moI/g.

Hiroshi, No. 1 ripening The main purpose of this No. 1 ripening is to convert the 11 hexagonal tabular grains into circular
T! (2) edge part of tabular grain)
00) form a surface, (3) edge 5 with high aspect ratio
(100) side t-! form tabular grains.

Thick and thin hexagonal tabular grains and small grain size (((7,
Aμmφ) When hexagonal tabular grains have sharp hexagonal corners, the sharp corners may dissolve over time and the corners may become rounded. This deformation over time of dissolution can be prevented to some extent by first adsorbing an adsorbent such as a sensitizing dye after particle formation, but more stability is still more preferable. In circular tabular grains, the edges of tabular grains that are easy to dissolve are
Since it dissolves immediately, it has the advantage that the emulsion has good stability over time.

In addition, due to circularization, (100)
A surface is formed.

In addition, if the growth is suddenly performed under high pBr after ripening, a (/(7) plane can be formed at the edge, but
Because it grows also in the thickness direction, only tabular grains with low aberrations can be obtained. Therefore, if tabular grains with a high aspect ratio are first formed under low pBr and then rounded and ripened to the extent necessary to form (100) planes with a desired area ratio at the edges, it is possible to Tabular grains having a spectral ratio and (/(7(7)) planes at the edge portions are formed.

Regarding these and the ripening conditions No. 1 for circular flattening, reference can be made to the description in Japanese Patent Application No. 1973-20 JAJj and FIG. 7 thereof.

Briefly, the degree of circularization mainly depends on the temperature during ripening, the pBr value, and the type and concentration of the AgX solvent used.
Specifically, circular tabular grains are obtained on the shaded side of the curve in FIG. 7 of the above patent.

The ripening conditions are preferably as follows.

That is, the temperature is 4Lo°~J'770C1 preferably jO6
~to°C%lO~/QO9rllII111 Preferably 2Q to 60 minutes, gelatin concentration is 0.06 to 70% by weight, preferably /, 0 to j% by weight,...Silver halide solvent concentration is o-o, gmol /I! , preferably 10~o
, 3m o I/A's The following can be used as the halogenated vR solvent. p
13r is /, r-3,! , preferably λ, O~J, (7
It is.

The aforementioned cubic crystal, l≠hedral crystal or hehedral crystal or (/ll
) The pBr (or pAg) region where hedrons are formed depends on the growing...rogen composition, coexisting solvent eclipse, and degree of hyperporosity during growth; specifically, Murofushi et al., International Congress o.
f Photographic 5science.

Tokyo (/?A 7), J. Rodgers, Symposium Paper
onGrowth of Photosers
sitive Crystals.

Cambridge (/? 7 I), T, G,
Bogg et al., J. Phot, Sci., 2u.

It (/ri76) and reference example of λ of Tokusei Sho tko λ/Tata t2 No. 1l
You can refer to lc. For example, in λg3r, the area where /≠hedron is generated is 5o-to, which is the critical growth rate.
% supersaturation level of pAg7. rj~7. This is the area of μ.

In this way, the Arashi-divided square tabular grains 3 and the monodispersed circular tabular grains of the present invention are formed.

The silver halide grains of the present invention can be used as an emulsion in the form of the above-mentioned silver halide grains, but when the core tabular grains of the present invention are used as a substrate, the heno-logen composition in the gravity direction with respect to the main plane of the tabular grains is AgX layers with different numbers may be stacked. s about this! ! f Gansho 6/-2,! J
You can refer to No. 37.

By using the tabular grains, one A g An X fL agent may be formed. Regarding this, the description in %Gan Shojj-Jj/j77 can be referred to.

Alternatively, using the tabular grain as a core grain, AgX having a halogen composition different from that of the tabular grain may be grown in the direction of the core grain. For example, AgB
The large seismic content of rI may be COre tc >additional part, or may be less than core part. When the flat seeds are grown in the aforementioned low pBr region, p13r
As the platform becomes lower, it becomes larger due to the horizontal direction velocity/the direction speed, and at p13r/, 2 or less, it hardly grows in the vertical direction. It can be prepared by utilizing the growth characteristics of these tabular grains. The crystal growth rate during this growth is 5 to 0% of the critical growth mode, preferably 10-≠O%.
It is preferable to set the growth rate to . This is because increasing supersaturation increases the crystal growth rate in the vertical direction.

In addition, the circular tabular grains are defined as hos particles, and the hos
As shown in FIG. 2, AgX having an I/logen composition different from that of the grains may be selectively grown only at the corners of the circular tabular grains. The growth conditions in this case are the same as above, with low pAg
Regions and supersaturated regions are preferred.

Alternatively, the tabular grains may be used as host grains to form epitaxial grains. Regarding this, please refer to JP-A-5R
-10r! No. 26, No. 133j Hiroo, No. 6λ-
324L Hiro 3, same! j-/λhiro/No. 3, 12-70
Hiro 0 and Tata 762 can be used as Hiro Q and EPoot Tata 17).

The tabular grains may be used as substrate grains to form ruffled grains. Regarding this, U.
S,≠64L3ri No. 46 can be referred to.

Further, a grain having dislocation organs inside may be formed using the tabular grain as a core. Special request for this K! The description in Hiroshi 6 Hiroshi No. 0 can be referred to.

In this way, monodisperse hexagonal tabular grains and monodisperse circular tabular grains are formed, and chemical sensitization is usually then formed on the tabular grains.

It is preferable that the position and number of chemically sensitized nuclei generated on the tabular grains of the present invention are controlled. As a method of controlling this, the following method can be effectively used.

■ Corners and edges of AgX particles with or without adsorption of adsorbents (adsorbents such as sensitizing dyes, antifoggants, stabilizers, etc.), halogen conversion method or A g N O3 and I. A method in which epitaxial particles are grown by adding a rogenated alkali solution, stabilized by adsorbing a counterfeiting agent, and then chemically multiplied to limit the position of latent formation to epitaxial particles.

Regarding this, please tell us about it, Tokukai Akira. -101!26, same j7
-133! Reference may be made to the descriptions in Hirohiro No. 0 and 62-32 Hirohiro No. 3.

■ A method in which adsorbents such as sensitizing dyes are added during particle formation to introduce defective areas into the particles, and sensitizing nuclei are preferentially formed only in these defective areas. This method is described in U.S. Pat.
Yo, 766, same j, A21.

rito, same'A, /13,7! A. Dohiro, 22j.

1101 Research Disclosure, Item/
227.722 volumes, p, /! You can refer to the description of j (/??Q year).

■ At least (/// one side and (
100) Using AgX particles with island surfaces on the plane, chemical -*Ig= is formed only on one crystal plane by utilizing the difference in sulfur increase and reactivity of S agent to those crystal planes. how to.

Regarding this, J, Phot, Sci, 2J, 24L
lyyr, Japan-X Photography Society Journal, Hiroshi Vol. 7, P.

2! ! (/Ri?Hiro) Figure 3 can be referred to.

19. A method of forming gold-sulfur sensitizing nuclei only on one crystal face by utilizing this difference in reactivity is disclosed in Japanese Patent Application No. 6
One-λl tata? You can refer to the description in No. 2.

■ A method of chemically sensitizing AgX particles by adsorbing an adsorbent and then adding a chemical sensitizer. In this method, since chemically sensitized nuclei are formed only in areas where no adsorbent is adsorbed, the number of chemically sensitized nuclei is controlled, but the position is not controlled. For this method, for example -% Kaisho! ! −／／J
Ri No. 26, same! r-//Jri No. 27, jt-//3ri No. 2, U.S. Patent Ko, Ko 32. ! No. 20, μ, tAJ
! .

No. 501, Re5earch Disclosure,
Item.

/ 76 a J, 5ection III, %H Sho 62-62j/, JP-A Sho j♂-/λ6j26, JP-A Sho 6
2-j69 Hiro, and is described in JP-A-62-4'J64'4'.

■ Two or more types of 5 V crystal planes on the surface of seven AgX particles
Using AgX particles, we add an adsorbent (face-selective 'JL adhesive) that is selective for adsorption to the precipitated crystal plane. A method in which a chemical sensitizer is added to form a crystal plane that is adsorbed to the substrate, and then chemically sensitized by adding a chemical sensitizer to form a chemically sensitized nucleus on the crystal plane to which the adsorbent is loosely adsorbed.

This method attempts to control the position of chemically sensitized nuclei.

Regarding this, please refer to Tokukai Shoyo r-//Jri 2 issue, Tokko Sho 62-20343j, same A, 2-2/Tata! 2, 6λ-/ri77hiro 1, &u-J/Tata r3, 6
2-λl Tata r≠ issue, 6λ-23/373 issue, 62
-CoS/No. 377 can be referred to.

■ It has at least (10o) and (///) crystal planes on the surfaces of seven AgX particles, and the no-rogen composition of the crystalline layer on the crystal attachment surface is mutually ((different AgX particles are used). ,
Differences in their crystal planes]・In addition to the N-absorbing agent that has selectivity in the use of the rogen composition, the adsorbent adsorbs to a high 9-degree crystal plane, and the adsorbent adsorbs sparsely to form a 9-degree crystal plane. After that, a chemical enhancer is added to chemically enhance and harden the material, and chemically sensitized nuclei are preferentially formed on the crucible surface to which the adsorbent is sparsely adsorbed. Regarding this, special application 1986-2! /J77 can be referred to.

(2) In AgX particles whose particle surfaces are substantially composed of one type of crystal plane, AgX particles whose surfaces have the same crystal system and different halogen compositions are used, and the adsorptivity differs depending on the halogen composition. A selective adsorbent is added to form a crystal plane where the adsorbent adsorbs at a high density, and a crystal plane where the adsorbent adsorbs to the taste. After that, a chemical sensitizer is added to chemically sensitize the adsorbent. A method in which chemical sensitization is preferentially formed on crystal faces that have loosely adsorbed agents. Here, "substantially" refers to 90% or more of the entire surface, preferably 90% or more of the entire surface. Specifically, as mentioned above, a tabular grain having a core part and an appended part in the direction of the sakaki, and the halogen composition of the core part and the appended part are different, is used, and the difference in halogen composition of the core part and the attached part is 1.・Chemical sensitization method that utilizes the selective adsorption characteristics of the 22 adsorbent to selectively form chemically sensitized girons on the core part or the additional part. Regarding the difference in slope 1% properties of the adsorbent due to the difference in the composition of the adsorbents, reference may be made to the description in Japanese Patent Application No. 7377, No. 62-2-2. In particular, the method of selectively forming chemically sensitized cherry blossoms in the core region can be particularly preferably used as a method of concentrating the m-image of tabular grains that are easily dispersed in the latent f-rays in the central region. In this case, it is preferable to use fine particle monodisperse flat plates as the core particles because the latent image can be more concentrated only in the center. A specific example is the tabular grain shown in FIG. 1, in which the core is AgBr and the adduct is AgBrI (Tennan content: Hiromi-Q mole %).

In addition, as another form, po < shown in FIG. 2, using a tabular grain having the circular tabular host grain part and a hexagonal corner part (additional part) having a halogen composition different from the host B, It is also possible to use the V method, a chemical sensitization method in which chemical sensitization nuclei are selectively formed in the appended portion by utilizing the selective adsorption characteristics of the adsorbent due to the difference in halogen composition between the host portion and the added portion. In this case, the generation of morphological sensitizing nuclei is caused by the hexagonal plate a
Since the latent image is limited to only the six corners of the child, dispersion of the latent image is prevented, which is preferable.

■ Chemistry 1 The adsorbent that is adsorbed to control the formation of nuclei has traditionally served the role of spectral sensitization, etc.; Redispersion → Additive Addition Method A chemical sensitization method that separates functions by using sound. The adsorbent has the advantage that the most suitable adsorbent can be selected in order to control the formation position and number of chemical sensitizing nuclei, ignoring its photographic properties.

■ In order to control both the location and number of chemically increased cherry blossoms at the same time, a combination of the above methods ■ and ■ or ■
It is possible to use a combination of methods (1) and (2) or a combination of (2) and (9).

In this case, it is more preferable because the position and number of chemically augmented temporary molecules can be literally controlled.

If you are like this, IS! - is used to indicate the position of the apex of the chemical amplification, or the number is 1! ! Controlled: Tabular grains of the invention are formed.

Regarding the adsorption characteristics due to differences in the halogen composition and crystals on the AgX particle surface of the N-absorbing agent, which is determined by ε above, T,
H. James, The Theory of the
Photographic Process, p.
oursEdition, Macmillan, Ne
w York, t777, Chap, Ri, Cha
p, /, Chap, /j.

A, Herz and J, Heming, J.
Co11oidInterface Sci,,a
i, 3yi (ttriAA).

S, L, 5crutton, J, Phot, Sci.
22.

Yellowtail (/ri7hiro).

J, Nys, Dye 5ensitization
.

Bressanone Symposium, Foc
al Press.

London, /ri70. P, 26~4L3, j7~j
j.

T, Tan1. Journal of Imagi
ng 5science.

29,/A! (/91ri.Special Fa Showa 1r2-ty774
c/, 4J-2/? ri t3, same 6.2-ko/tata wo hiro, same iG! -231373 and jJ-jj/377 can be referred to.

In practical use, Langmuir of various adsorbents for cubic seeds, octahedral particles, etc. particles with different agen compositions are used.
Adsorption 3! This can be investigated by measuring the temperature curve, which is described in T and H above.

You can refer to the description in James Bian's book.

As a specific example of an adsorbent, a dye that is responsible for halogen composition dependence is i, /'-diethyl-j, 2'-
cyanine chloride, / , /'
,j,j'-tetramethyl-2,2'
-cyanine.

Cyanine dyes such as anionic termethylthiacarbocyanine adsorb to the halogen ion site on the surface of AgX particles, and dyes with crystal m dependence include J, j'
-dimethylthiazolinodicar
bocyanine bromide, i, J'-
bis(IA-5ulfobutyl)-2-met
hyl-thiacarbocyanine and the like can be obtained.

The tabular grains of the present invention may be used by forming a shallow latent type emulsion using the tabular grains as cores. Regarding this, please refer to JP-A Shoj Turf 33 Yoko No. 2, British Patent M/Hiroyo ♂ No. 76 tr
＞It can be considered.

A core/shell type direct inversion emulsion may be formed using the tabular grains as cores, and then used. Regarding this, see Example 13 of ζ Tokuto Numa A/- Kotata/jj, and U.S. Patent No. 3. V4/, No. 274, Hiroshi.

Kootsu No. 2,227, J, 347.77, and R may be referred to.

In addition, by the end of gold sensitization aging, H20 □, Boruo Φ
A method of adding an oxidizing agent such as phosphoric acid and then adding a reducing substance, or a method of reducing free gold ions in the sensitive material after gold sensitization and ripening can be used. Regarding this, JP-A/-j/j section number, A/-j/36,
Patent Application No. 60-26237, JP-A-67-λ19tA
ff issue, AI-co/ri y4c issue, special application show A/-/1
Reference may be made to No. u190 and No. 4/-/r3 Rihiro. The tabular grains may be subjected to spectroscopy (mg) using an antenna dye. Regarding this, Tokusara Sho A/-j/J? No. A
The descriptions in /-λrr, tλ7/, and A/-j Zahiro No. 27- can be referred to.

Regarding the use of the optical coherence of the flat plate, as well as details of the above and other matters, please refer to Tokusho A/
-,! The Tata/jyo issue and its amendments can be referred to.

The tabular grains can also be used in high hardness systems.

Regarding this K, Tokukai Akira! Jr-//Jri No. 24, Re5
You can refer to the section Disclosure%/I Hiromaki, 1997, Item/r≠37%.

The low molecular weight gelatin used in the present invention can usually be produced as follows. Gelatin, which is commonly used and has an average molecular weight of 10,000, is dissolved in water, and a gelatin-degrading enzyme is added to enzymatically decompose the gelatin molecules. This method is described in RoJ, COX.

Photographic Qelatin [[
, Academic Press, London, /
976, p, 233~λr/, P, 33r~3
You can refer to the descriptions in 4 and 6. in this case,#
The Ochiai position where the element decomposes is in the center, so it is a ratio! 12FF
It is preferable because it provides a low molecular weight gelatin with a narrow molecular weight distribution. In this case, increasing the enzymatic decomposition time (1) results in lower molecular weight.

In addition, low pH (p)i/~3) or high pH (pH
10~/λ) There is also a method of heating in an atmosphere to hydrolyze the mixture.

In the bale forming process of the present invention, a silver halide solvent may be used to adjust the supersaturation conditions that determine the frequency of twin plane formation.

Further, in the ripening process of the present invention, a silver halide solvent may be used to promote ripening and crystal growth during the viscous crystal growth period after ripening.

Examples of frequently used silver halide solvents include thiocyanates, ammonia, thioethers, and thioureas.

For example, thiocyanate (U.S. Pat. No. 2,2 λ).

No. 26, No. 2. Hirohiro 1. JJ Hiro issue, same number 3゜320
．． 062 etc.), ammonia, thioether compounds (
For example, U.S. Patent Nos. 3,27/117 and 3.57
Hiroshi, No. 62, No. 3, 70u, No. 130, No. ≠, 4
77, ≠ No. 32, same No. Hiroshi, j74. jμ7, etc.), thione compounds (e.g., JP-A No. 3-7≠4!3/ri, jj-fJtAot, JP-A-77737, etc.),
An amine compound (for example, JP-A Sho! Hiro-1007/7, etc.) can be used.

The sensitizing dye, antifogging agent, and stabilizer used in the present invention can be present in any step of the manufacturing process of a photographic emulsion, or can be present at any stage after manufacturing until immediately before coating.

Examples of the former include a silver halide grain formation process, a physical ripening process, and a chemical ripening process.

The silver halide emulsion of the present invention may be mixed with other emulsions or emulsions as necessary.
One or more layers (for example, two layers, JriJ'') can be provided on the support together with the layer, intermediate layer, and filter layer. Also, it can be provided not only on one side of the support but also on both sides. It can also be layered as a double emulsion.

In the case of the dispersed tabular grains of the present invention, when coated with 31 layers of large grain, medium grain, and small grain emulsions, or with 3 or more layers of emulsions with further fine grain sizes, high absorption ratios can be obtained. Since it consists of plate-like particles, each layer can be made thinner and can be manufactured without significantly increasing the thickness of the emulsion layer, thereby achieving both high sensitivity and high image quality without deteriorating sharpness.

Therefore, an emulsion consisting of monodispersed tabular grains is formed in two or more layers in descending order of grain size from the top layer, preferably 31~! When the monodisperse tabular grains of the present invention are constituted by 1, the effect is further exhibited, which is preferable.

In terms of this layer structure, *G Showa 6 Whoo Tata! You can refer to the description in j.

Usually, when an emulsion consisting of tabular grains with a high aspect ratio is coated and dried, the tabular grains are oriented parallel to the base plane. When the tabular grains of the present invention are oriented parallel to the base surface and oriented so that they overlap each other for light transmission, and there are no gaps between grains through which incident light can pass, the light utilization efficiency is increased. Increases the sensitivity and image quality. Also, current 1j! covering p when
OWER becomes higher. In addition, in color photography, it is possible to obtain the grain disappearing effect with a smaller amount of silver than in the past, resulting in silver-saving fhi,
High image quality is possible. The monodispersed hexagonal tabular grains of the present invention are particularly preferred because these effects are particularly large.

There are no particular restrictions on other components of the emulsion layer of the silver halide photographic material of the invention, and various additives may be used as required.

Chemical sensitizers, spectral sensitizing dyes, antifoggants, metal ion dopes, silver halide solvents, stabilizers, dyes, color couplers, DIR couplers, binders, hardeners, herbal medicines, coating aids, which can be added. Thickeners, emulsion settling agents, sizing agents, dimensional stability improvers, antistatic agents, fluorescent whitening agents, lubricants, matting agents, surfactants, ultraviolet absorbers, scattering or absorbing materials, curing agents, Preventing adhesion and improving JIc characteristics! 1ll (e.g. development accelerator, contrast agent, etc.), developer, etc. Photographically useful fragments (development inhibitor or accelerator, bleach accelerator, developer enhancer, silver halide solvent, toner, hard abrasion) , antifogging columns, competitive couplers, chemical or spectral sensitizing dyes and desensitizers, etc.), dye stabilizers, self-inhibiting developers, and their convenient uses, force, spectroscopy, W8
) is super heavy at 377! , spectral 15 dyes... rogen acceptor effect and electron acceptor effect, antifogging agents, stabilizers, the effects of inhibitors in addition to accelerators, and other manufacturing equipment used to manufacture uninvented emulsions; Reactor, stirring device, coating, drying method, exposure method (light source, exposure atmosphere, exposure method), photographic support, microporous support, 9 layers of undercoat, surface protection layer, matting agent, intermediate layer, etc. Regarding the anti-ration layer, the layer structure of the AgX emulsion, the photographic processing agent, and the photographic processing method, see Research Disclosure Magazine, Vol. 776, /27J', 7
February issue (item/7A Hiro 3), same lt Hiromaki 17 layer 2017 issue (item/g≠37 issue), same lt Hiromaki 13 Hiromaki/275
June 2018 (Itery34csa) Product Licensing Lee/Daesoksu Magazine Volume 22 107-l10 (l!P
7/72), Tokukai Sho! ♂-//3ri 26-1139
No. 21, 6/-313, βjG2-62j1, JCIA Monthly Report/P♂≠, 72, p, //I-, 27,
Patent application 1986-2/2 layer No. 2, T, H, James, T
the theory of the photog
rapicProcess, Fourth Edi
tion, Macmillan.

New York, 1977, V. L., Zelikman et al., Mak.
Ingand Coating Photogra
phic Emulsion (The Focal
You can refer to the description published by Press, /9tu).

The silver halide emulsion of the present invention can be used in black-and-white silver halide photographic materials (e.g., X-ray sensitive materials, lithographic materials, negative films for black-and-white photography, etc.) and color photographic materials (e.g., color negative films, color reversal films, etc.). , Color E/
Qi, silver dye bleached photographs, etc.) can be used.

In addition, photosensitive materials for diffusion transfer (for example, color diffusion transfer
! It can also be used for heat-developable photosensitive materials (black and white, color), etc.

The silver halide color light-sensitive material containing the monodisperse tabular Ag A halogen containing at least one ferric complex salt of a compound selected from (A) and a ferric complex salt of 1,3-diaminopropanetetraacetic acid in a molar ratio of 3 or less. It was found that when processed using the processing method for silver oxide color photographic materials, the desilvering efficiency was significantly higher than that of tabular AgX emulsions with large dispersion. In general, tabular grains have a large specific surface area and can adsorb a large amount of sensitizing dye to the surface, resulting in a relatively high color sensitization sensitivity. In the desilvering process, the dye tends to inhibit the bleaching of silver in the processing solution, resulting in poor desilvering efficiency. However, in silver halide color light-sensitive materials containing the monodispersed tabular AgX emulsion of the present invention, the desilvering efficiency is significantly improved when the processing bath having bleaching ability of the present invention is used.

The bleaching agent of the present invention comprises at least one ferric complex salt of a compound selected from the compound (A) group and a ferric complex salt of 1゜3-diaminopropanetetraacetic acid in a molar ratio of 3 or less. Used together with. The preferred molar ratio is 1.8 to 0.5.
When the molar ratio of 0 exceeds 3, the bleaching strength decreases, resulting in poor desilvering. Furthermore, if the ratio of ferric salt of 1,3-diaminopropanetetraacetic acid becomes extremely high, slight bleaching fog may occur.

The amount of the bleaching agent of the present invention added is 0.05 mol to 1 mol, preferably 0.1 mol to 0.5 mol, per 1z of bath having bleaching ability.

In addition, the above-mentioned aminopolycarboxylic acid is used as a treatment liquid having bleaching ability of the present invention! In addition to (IN) 11, aminopolycarboxylic acid salts can be added. In particular, the compound group (A
) is preferably added.

Hereinafter, the treatment bath having bleaching ability of the present invention will be explained.

In the present invention, immediately after color development, processing is carried out in a processing bath having bleaching ability.

A processing bath having bleaching ability generally refers to a bleaching solution and a bleach-fixing solution, but in the present invention, a bleaching solution is preferable because it has an excellent bleaching blade, and the derailment process of the present invention includes, for example, the following steps. However, it is not limited to these.

■ Bleach-fixing ■ Bleach-bleach-fixing ■ Bleach-fixing ■ Bleach-fixing-bleach-fixing ■ Bleaching-Water-washing and fixing Particularly, steps (1) and (2) are preferred in order to exhibit the effects of the present invention.

The preferred amount added is 0.0001 mol to 0.0001 mol. 1 mole/
It is more preferably 0.003 mol to 0.05 mol/l.

Aminopolycarboxylic acids and their ferric complex salts are usually preferably used in the form of alkali metal salts or ammonium salts, and ammonium salts are particularly preferred because they have excellent solubility and bleaching properties.

Further, the bleach solution or bleach-fix solution containing the above-mentioned ferric ion complex may contain a metal ion complex salt other than iron, such as cobalt or copper.

Various bleach accelerators can be added to the bath having bleaching ability of the present invention.

Such bleach accelerators are described, for example, in US Pat. No. 3,893,858, German Patent No. 1,290.
．． Compounds having a mercapto group or a disulfide group described in Specification No. 812, British Patent No. 1 138.842, JP-A-53-95630, Research Disclosure No. 17129 (July 1978 issue) , thiazolidine derivatives described in JP-A-50-140129, thiourea derivatives described in U.S. Pat. No. 3,706.561, iodides described in JP-A-58-16235, German Patent No. Polyethylene oxides described in specification No. 2,748.430, Japanese Patent Publication No. 1974-
Polyamine compounds described in Japanese Patent No. 8836 can be used. Particularly preferred is British Patent No. 1.138.
Mercapto compounds such as those described in '842 are preferred.

In particular, in the present invention, from the following general formula (IA) (VIA
Bleaching accelerators represented by ) can be preferably used because they have excellent bleaching ability and cause little bleaching fog.

General formula (IA) R-^-3-M'^ In the formula, Ml^ represents a hydrogen atom, an alkali metal atom, or ammonium; RI& represents an alkyl group, an alkylene group, an aryl group, or a heterocyclic residue; The group preferably has 1 to 5 carbon atoms, most preferably 1 to 3 carbon atoms, and the alkylene group preferably has 2 to 5 carbon atoms. Examples of the ring group include phenyl group and naphthyl group, with phenyl group being particularly preferred.Heterocyclic residues include nitrogen-containing 6-membered rings such as pyridine and triazine, azole, pyrazole, triazole, thiadiazole, etc. A nitrogen-containing 5-membered ring is preferred, and particularly preferred is a case where two or more of the ring-forming atoms are nitrogen atoms. R1^ may be further substituted with a substituent. As the substituent, Examples include an alkyl group, an alkylene group, an alkoxy group, an aryl group, a carboxy group, a sulfo group, an amino group, an alkylamino group, a dialkylamino group, a hydroxy group, a carbamoyl group, a sulfamoyl group, and a sulfonamide group.

Among general formulas (IA), preferred are general formulas (IA)
-1) to (IA-4).

General formula (IA-1) RIA R''-N　　　　　(CHx) □-SH (Zl Todoroki) Ei.

(R”)ha In the formula, Rxa, Rsa, and R4^ may be the same or different, and each represents a hydrogen atom, a substituted or unsubstituted lower alkyl group (preferably 1 to 5 carbon atoms, especially a methyl group, an ethyl group, a propyl group) (preferably a group) or an acyl group (preferably having 1 to 3 carbon atoms, such as an acetyl group or a propionyl group), and kA is an integer of 1 to 3.
represents an anion (chloride ion, bromide ion, nitrate ion, sulfate ion, p-toluenesulfonate, oxalate, etc.), kA is O or 1% iA is O or I
represents.

Rlk and R3A may be linked to each other to form a ring
RgA, RSk, and RJ& are preferably a hydrogen atom or a substituted or unsubstituted lower alkyl group.

Here, the substituent that R"% R", R" has is preferably a hydroxy group, a carboxy group, a sulfo group, an amino group, or the like.

General formula CIA-2) General formula (IA-3) C BSk'\N/ゝ5lll General formula (IA-4S)1 In the formula, Rsa is a hydrogen atom, a halogen atom (e.g., a chlorine atom, a bromine atom, etc.) , an amino group, a substituted or unsubstituted lower alkyl group (preferably 1 to 5 carbon atoms, particularly preferably a methyl group, an ethyl group, and a propyl group), an amino group having an alkyl group (a methylamino group, an ethylamino group,
Represents a substituted or unsubstituted alkylthio group (dimethylamino group, diethylamino group, etc.).

Here, the substituents that RIA has include a hydroxy group,
Examples include a carboxy group, a sulfo group, an amino group, and an amino group having an alkyl group.

General formula CII A) R"-3-3-R'^ In the formula, RIA is the same as RIA of general formula CIA),
R" is synonymous with RIA. RIA and RAM may be the same or different.

Among general formulas (IIA), preferred ones are general formulas (H
A-1).

General formula (mA-1) (8 units), 1 In the formula, RIA, Ro, RIA are R2''', R]^, R4
It is synonymous with 1. hA, kA and ZIA are expressed by the general formula (IA
-1) is the same as hA and kASZ'^. iB is 01
Represents 1 or 2.

General formula (III) R11+lI M"- In the formula, RIIA and RIIA may be the same or different, and each represents a hydrogen atom, an alkyl group that may have a substituent (preferably a lower alkyl group, such as a methyl group, ethyl group, propyl group), a phenyl group that may have a substituent, or a heterocyclic residue that may have a substituent (more specifically, a heterocyclic group such as a nitrogen atom, an oxygen atom, a sulfur atom, etc.) R11 & represents a heterocyclic group containing at least one atom, such as a pyridine ring, thiophene ring, thiazolidine ring, benzoxazole ring, benzotriazole ring, thiazole ring, imidazole ring, etc.), and R11 & has a hydrogen atom or a substituent; represents an optional lower alkyl group (for example, a methyl group, an ethyl group, etc., preferably having 1 to 3 carbon atoms).

Here, the substituents from RIIA to R1ff1A include a hydroxy group, a carboxy group, a sulfo group, an amino group,
These include lower alkyl groups.

R13^ represents a hydrogen atom, an alkyl group, or a carboxy group.

General formula (rVA) In the formula, R14A and Rln R14A may be the same or different, and each represents a hydrogen atom or a lower alkyl group (for example, a methyl group, an ethyl group, etc., preferably having 1 to 3 carbon atoms), kB represents an integer from 1 to 5.

XI^ represents an amino group, a sulfo group, a hydroxy group, a carboxy group, or a hydrogen atom which may have a substituent. Examples of the substituent include a substituted or unsubstituted alkyl group (for example, a methyl group, an ethyl group, a hydroxyalkyl group) group, alkoxyalkyl group, carboxyalkyl group, etc.), and two alkyl groups may form a ring.

R14A, R+sa, RlAA may form a mutually linked site ring. RI4A~R"^,
In particular, a hydrogen atom, a methyl group or an ethyl group is preferable, and X1
As for ^, an amino group or a dialkyl 7mino group is preferable.

General formula (VA) Here, AlA is an n-valent aliphatic linking group, aromatic linking group, or heterocyclic linking group; (when n-1, AlA is a simple aliphatic group, aromatic group, or heterocyclic group ) The aliphatic connector group represented by AlA has 3 carbon atoms.
~12 alkylene groups such as trimethylene, hexamethylene, cyclohexylene, etc. may be mentioned.

Examples of the aromatic linking group include arylene groups having 6 to 18 carbon atoms (eg, phenylene, naphthylene, etc.).

Examples of the heterocyclic linking group include a heterocyclic group consisting of one or more heteroatoms (e.g., oxygen atom, sulfur atom, nitrogen atom) (e.g., thiophene, furantriazine, pyridine,
piperidine, etc.).

Here, the number of aliphatic linking groups, aromatic linking groups, and heterocyclic linking groups is usually one, but two or more may be linked (the linking format may be direct or a divalent linking group (for example, −〇−
1-S-1Ht.^-5Ot-N-1 -1-C〇- or a linking group formed from these linking groups, and R11 represents a lower alkyl group).

Further, the aliphatic linking group, aromatic linking group, and heterocyclic linking group may have a substituent.

Examples of the substituent include an alkoxy group, a halogen atom, an alkyl group, a hydroxy group, a carboxy group, a sulfo group, a sulfonamide group, and a sulfamoyl group.

xn is 10-1-S-1R1l & stands for R81^
N- is a lower alkyl group (e.g. methyl group, ethyl group, etc.)
), R"", R"" represents a substituted or unsubstituted lower alkyl group (e.g., methyl group, ethyl group, propyl group, isopropyl group, pentyl group, etc.), and examples of the substituent include a hydroxy group, Lower alkoxy groups (e.g., methoxy, methoxynidoxy, hydroxynidoxy, etc.), amino groups (e.g., unsubstituted amino, dimethylamino, N-hydroxyethyl-N-methylamino, etc.) are preferred. Here, when there are two or more substituents, they may be the same or different.

R1″^ represents a lower alkylene group having 1 to 5 carbon atoms (methylene, ethylene, trimethylene, methylmethylene, etc.), and Z″ represents an anion (halide ion (chloride ion,
(bromine ion, etc.), nitrate ion, sulfate ion, p-toluenesulfonate, oxalate, etc.).

In addition, RlffA and RIIA are carbon atoms or heteroatoms (
For example, they may be linked via an oxygen atom, nitrogen atom, sulfur atom) to form a 5- or 6-membered heterocycle (for example, a pyrrolidine ring, a piperidine ring, a morpholine ring, a triazine ring, an imidazolidine ring, etc.) .

R1T^ (or R11^) and A are connected via a carbon atom or a heteroatom (e.g., oxygen atom, nitrogen atom, sulfur atom), and form a 5- or 6-membered heterocycle (e.g., hydroxyquinoline ring, hydroxyindole ring). , isoindoline ring, etc.).

Furthermore, R1'tA (or R11^) and RII
A is linked via a carbon atom or a hetero atom (e.g., an oxygen atom, a nitrogen atom, a sulfur atom) to form a 5- or 6-membered heterocycle (e.g., a piperidine ring, a pyrrolidine ring, a morpholine ring, etc.) You can.

IA is 0 or tSmA is 0 or 1, nA is 1.2 or 3
, pA represents 0 or 1, and QA represents 0, 1.2, or 3.

General formula (VIA) R寞8＾
It is the same as kB.

M寞＾ is hydrogen atom, alkali metal atom, ammonium S
R■^ represents a hydrogen atom or a lower alkyl group (having 1 to 5 carbon atoms and may have a substituent).

Specific examples of compounds of general formulas (IA) to (VIA) are shown below.

(IA)-(1) (IA)-(2) (IA)-+31 (IA)-+4) (IA)-+51 (IA)-(6) (IA)-(7) (IA)-+8) (IA)-191 (IA) -α・ (IA) −〇υ (IA)-(121 -N (IA)　　-〇l -N (IA)　　−〇〇 -N (IA) -09 -N (IA) -αe -N ■ (IA) −〇η -N (IA) -α Shizuku -N (IA) -α (to) S)! (IA) - (to) -N H (nA) - (1) (IIA)-(21 (IIA)-(3) (IIA)-+41 (IIA)-+5) (nA)-+61 0 ■ (IIA)-(?) (IIA)-+81 (IIA)-(91 (IIA)-Ql (IIA) -00 (It A) - (B) (IIIA)-(1) (IIIA)-(2) (mA) - (31 (IIIA)-(4) (I[A)-+51 (IIIA)-+61 (IVA) - (1) (IVA) - (21 (II/A)-(31 (IYA)-(41 (IVA)-(5) (IYA)-+61 (IVA)-(?) (IVA)-(8) (IVA)-(91 (IVA)-Ql (IVA) -Ql) (VA)　　-　) (VA)-(2) Out (VA)-(3) (VA)-(4) (VA)-(5) CHtN(CHzCHzOH)* (VA) - (61 (VA) - (71 CHtN　(CHzCHtOH)　z CH! N (CHtCHtOH)t (VA)-(91 H3 CHJCHtCHtOH CHJCHtCHtOH H3 (VA)-QI CH.

(VA) -〇〇(VA) -(2) CIleC1θ (VA) -α美(VA) -(B) (VA) -09 Also--ノ' (VA) -αe (VA) -clause (VA)-Q・CHJ(CHzCHtOCHtCHtOH)! (VA)
-(2) H (VA) -■ (VA) -(2) (VA) -(company) (VA) -(to) (VA) =(company) C1θ C1e (VA) -(5) (VA) -(2) H (VIA) -(11 (VIA)-(21 (VIA)-+31 (VIA)-(41 (VIA)-+51) Among the above bleach accelerators, particularly preferred compounds are IA-2, I
A-5, IA-13, IA-14, IA-15, IA-
16, IA-19, IIA-1, IIA-IL VA
-I VIA-1, and Vl-2. The amount of bleaching accelerator added is 0.01g to 20g per 11 liquids having bleaching ability.
Preferably it is 0.1 g to 10 g.

In addition to the bleaching agent and the above-mentioned compounds, the bleaching solution constituting the present invention includes bromides such as potassium bromide, sodium bromide,
Rehalogenating agents such as ammonium bromide or chlorides such as potassium chloride, sodium chloride, ammonium chloride can be included.

The concentration of the rehalogenating agent is 0.00% per 11 parts of the bleaching solution. 1-5
mol, preferably 0.5 to 3 mol. In addition, nitrates such as sodium nitrate and ammonium nitrate, boric acid, borax,
One or more types of inorganic acids and organic acids having pH buffering capacity such as sodium metaborate, acetic acid, sodium acetate, sodium carbonate, potassium carbonate, phosphorous acid, phosphoric acid, sodium phosphate, citric acid, sodium citrate, tartaric acid, etc., and organic acids thereof. Additives commonly known for use in bleaching solutions, such as salt, can be added.

The pH of the bleaching bath of the present invention is generally 6 to 1, preferably 5.8 to 1.5, and most preferably 5.8 to 1.5.
It is 3-2. In a preferred pH range, there is little bleaching fog and excellent desilvering performance.

The replenishment amount of the bath having bleaching ability of the present invention is 50 mJ to 2000 mA per 1 d of photosensitive material, preferably 100 m1 to 100 mA.
It is 0mj.

In the present invention, after treatment with a bath having bleaching ability, treatment is generally performed with a bath having fixing ability.

However, this does not apply when the bath having bleaching ability is a bleach-fixing solution.

The bath having fixing ability in the present invention refers to a bleach-fixing bath and a fixing bath.

Fixing agents for baths having these fixing abilities include thiosulfates such as sodium thiosulfate, sodium thiosulfate, sodium ammonium thiosulfate, and potassium thiosulfate, and thiocyanates such as sodium thiocyanate, ammonium thiocyanate, and potassium thiocyanate. , thiourea, thioether, etc. can be used. The amount of these fixing agents is from 0.3 mol to 3 mol, preferably from 0.5 mol to 2 mol, per 11 of the processing solution.

The fixing bath contains sulfites as preservatives, such as sodium sulfite, potassium sulfite, ammonium sulfite, and bisulfite adducts of hydroxylamine, hydrazine, aldehyde compounds, such as acetaldehyde sodium bisulfite. be able to. Furthermore, various optical brighteners, antifoaming agents, surfactants, polyvinylpyrrolidone, organic solvents such as methanol, etc. can be contained, but in particular, as preservatives, it is possible to contain
It is preferable to use the sulfinic acid compounds described in No. 283831.

The amount of replenishment of the bath having fixing ability is preferably from 300 ml to 3000 mj per 1 d of light-sensitive material, more preferably from 300 ml to 1000 mff1.

Further, it is preferable to add various aminopolycarboxylic acids and organic phosphonic acids to the bath having fixing ability of the present invention for the purpose of stabilizing the solution.

The shorter the total time of the desilvering step of the present invention, the more remarkable the effects of the present invention can be obtained. The preferred time is 1 minute to 4 minutes, more preferably 1 minute 30 seconds to 3 minutes.

Further, the treatment temperature is 25@~50℃, preferably 35℃~4
It is 5°C. In a preferred temperature range, the derailment speed is improved and the occurrence of staining after treatment is effectively prevented.

In the desilvering step of the present invention, it is preferable that the stirring be as strong as possible in order to more effectively exhibit the effects of the present invention.

A specific method for strengthening stirring is disclosed in JP-A-62-18346.
No. 0, No. 62-183461, the method of impinging a jet of processing liquid on the emulsion surface of a photosensitive material, and the method of colliding a jet of a processing liquid on the emulsion surface of a photosensitive material, as described in JP-A No. 62-183-1.
No. 83461, a method of increasing the stirring effect using a rotating means, and further improving the stirring effect by moving the photosensitive material while bringing the emulsion surface into contact with a wiper blade provided in the liquid to create turbulence on the emulsion surface. method, and a method of increasing the circulation flow rate of the entire treatment liquid. Such means for improving agitation is effective for all bleaching solutions, bleach-fixing solutions, and fixing solutions. It is believed that improved stirring speeds up the supply of bleach and fixing agent into the emulsion film, and as a result increases the desilvering rate.

Further, the agitation improving means is more effective when a bleach accelerator is used, and can significantly increase the accelerating effect and eliminate the fixing inhibiting effect caused by the bleach accelerator.

The automatic developing machine used in the present invention is JP-A-60-191
It is preferable that the photosensitive material conveying means described in JP-A No. 257, 191258, and 191259 be provided. As described in the issue, this type of conveyance means can significantly reduce the carry-over of processing liquid from the front bath to the post bath, and is highly effective in preventing the performance price of the processing liquid. This is particularly effective in shortening the processing time and reducing the amount of processing liquid replenishment.

The color developer used in the present invention contains a known aromatic primary amine color developing agent.

A preferred example is p-phenylenediamine WAs,
Representative examples are shown below, but the invention is not limited thereto.

D-IN, N-diethyl-p-phenylenediamine D-22-amino-5-diethylaminotoluene D-32-amino-5-(N-ethyl-N-laurylamino)toluene D-44-(N-ethyl- N-(β-hydroxyethyl)aminocoaniline D-52-methyl-4-[N-ethyl-N-(β-hydroxyethyl)aminocoaniline D-64-amino-3-methyl-N-ethyl-N −(β
-(methanesulfonamido)ethyl)-aniline D-T N-(2-amino-5-diethylaminophenylethyl)methanesulfonamide D-8N, N-dimethyl-p-phenylenediamine D-94-amino-3-methyl -N-ethyl-N-methoxyethylaniline D-104-amino-3-methyl-N-ethyl-N-β
-Ethoxyethylaniline D-114-amino-3-methyl-N-ethyl-N-β
-Butoxyethylaniline Among the above p-fluorinated diamine derivatives, Exemplified Compound D-5 is particularly preferred.

Further, these p-phenylenediamine derivatives may be salts such as sulfates, hydrochlorides, sulfites, p-)luenesulfonates, etc. The amount of the aromatic-grade amine developing agent used is 12 Preferably about 0.1 g to about 20 g,
More preferably, the concentration is about 0.5 g to about lag.

In addition, sulfites such as sodium sulfite, potassium sulfite, sodium bisulfite, potassium bisulfite, sodium metasulfite, potassium metasulfite, and carbonyl sulfite adducts are added to the color developer as preservatives as necessary. be able to.

The preferred amount added is 0.5 g to 1.0 g per 1 j of color developer.
0g1, more preferably 1g to 5g.

In addition, as compounds that directly preserve the color developing agent, various hydroxylamines, Japanese Patent Application No. 61-18655
Hydroxamic acids described in No. 9, hydrazines and hydrazides described in No. 61-170756, and hydrazides described in No. 61-188
Phenols described in No. 742 and No. 61-203253, α-hydroxyketones and α-aminoketones described in No. 61-188741, and/or No. 61-18
It is preferable to add various saccharides described in No. 0616, and in combination with the above compounds, Japanese Patent Application Nos. 61-147823, 61-166674, 61-165621,
Monoamines described in No. 61-164515, No. 61-170789, No. 61-168159, etc., No. 61-173595, No. 61-164515, No. 6
Diamines described in No. 1-186560, etc., No. 61-1
65621 and polyamines described in No. 61-16674, polyamines described in No. 61-188619,
nitroxy radicals described in No. 61-197760,
It is preferable to use the alcohols described in No. 61-186561 and No. 61-197419, the oximes described in No. 61-198987, and the tertiary amines described in No. 61-265149.

Other preservatives include various metals described in JP-A-57-44148 and JP-A-57-53749;
Salicylic acids described in No. 180588, JP-A-Sho s 4-3
Alkanolamines described in No. 532, JP-A-56-9
Polyethyleneimines described in No. 4349, U.S. Patent No. 3
．． The aromatic polyhydroxy compound described in No. 746,544 may be included if necessary, and addition of an aromatic polyhydroxy compound is particularly preferred.

The color developer used in the present invention preferably has a pH of 9
-12, more preferably 9-11.0, and the color developer may contain other known developer component compounds.

In order to maintain the above pi(), it is preferable to use various buffering agents.

Specific examples of buffering agents include sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate, tripotassium phosphate, disodium phosphate, dipotassium phosphate, sodium borate, potassium borate, Sodium tetraborate (borax), potassium tetraborate, 0-
Sodium hydroxybenzoate (sodium salicylate), potassium o-hydroxybenzoate, 5-sulfo-2
-sodium hydroxybenzoate (sodium 5-sulfosalicylate), potassium 5-sulfo-2-hydroxybenzoate (potassium 5-sulfosalicylate), and the like. However, the present invention is not limited to these compounds.

The amount of the buffer added to the color developing solution is 0.1 mol/
It is preferably 1 or more, especially 0.1 mol/1 to 0
．． Particularly preferred is 4 mol/l.

In addition, various chelating agents can be used in the color developer as an anti-settling agent for calcium or magnesium or to improve the stability of the color developer.

As the chelating agent, organic acid compounds are preferred, such as aminopolycarboxylic acids, organic phosphonic acids, and phosphonocarboxylic acids.

Specific examples are shown below, but the invention is not limited to these.

Nitrilotriacetic acid, diethylenetriaminepentaacetic acid, ethylenediaminetetraacetic acid, N,N,N-trimethylenephosphonic acid, ethylenediamine-N,N,N',N'~tetramethylenephosphonic acid, transcyclohexanediaminetetraacetic acid, 1.2- Diaminopropane tetraacetic acid, hydroxyethyliminodiacetic acid, glycol ether diamine tetraacetic acid, ethylenediamine orthohydroxyphenylacetic acid, 2
-phosphonobutane-1,2,4-)licarboxylic acid, 1-
Hydroxyethylidene-1,1-diphosphonic acid, N, N
'-Bis(2-hydroxybenzyl)ethylenediamine-N,N'-diacetic acid Two or more of these chelating agents may be used in combination as necessary.

The amount of these chelating agents added may be sufficient as long as the amount is sufficient to sequester metal ions in the color developer. For example, 11
It is about 0.1g to Log per unit.

Any development accelerator can be added to the color developer if necessary. However, the color developer of the present invention preferably does not substantially contain benzyl alcohol from the viewpoints of pollution, formulation properties, and prevention of color staining. Here, "substantially" means 2. m 1 or less,
Preferably, it means not containing it at all.

Other development accelerators include Japanese Patent Publications No. 37-16088, No. 37-5987, No. 38-7826, No. 44-
No. 12380, No. 45-9019 and U.S. Patent No. 3.
813.247, p-phenylenediamine compounds shown in JP-A-52-49829 and JP-A-50-15554, JP-A-50-137726, JP-B-Sho 44-30074, JP-A-56-156826 and JP-A No. 52-43429,
Quaternary ammonium salts represented by U.S. Patent No. 2,
No. 494,903, No. 3,128゜182, No. 4,2
No. 30.796, No. 3,253.919, Special Publication No. 1977
-11431, U.S. Patent No. 2.482,546, U.S. Pat. 596. 926 and 3,582.346, etc., Japanese Patent Publication No. 37-16088, Japanese Patent Publication No. 42-25201, U.S. Patent No. 3,128.18
No. 3, Special Publication No. 41-11431, No. 42-23883
and U.S. Pat. No. 3,532,501, etc., and other 1-phenyl-3-
Pyrazolidones, imidazoles, etc. can be added as necessary.

In the present invention, any anti-capri agent can be added as required. As anti-capri agents, alkali metal halides such as sodium chloride, potassium bromide, potassium iodide and organic anti-capri agents can be used. Examples of organic anti-capri agents include benzotriazole, 6-nidropenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chloro-benzotriazole, 2-thiazolyl-benzimidazole, Typical examples include nitrogen-containing heterocyclic compounds such as 2-thiazolylmethyl-benzimidazole, indazole, hydroxyazaindolizine, and adenine.

The color developer used in the present invention may contain a fluorescent brightener, and the preferable fluorescent brightener is a 4°4'-diamino-2,2'-disulfostilbene compound. Addition amount is O~5g/l, preferably 0.1g~4g/l
It is.

Further, various surfactants such as alkylsulfonic acid, ary-phosphonic acid, aliphatic carboxylic acid, and aromatic carboxylic acid may be added as necessary.

The processing temperature of the color developer of the present invention is 20 to 50°C, preferably 30 to 45°C. The treatment time is 20 seconds to 5 minutes, preferably 30 seconds to 3 minutes. Although it is preferable that the replenishment amount be small, it is 100 to 1500 m I per 11 photosensitive materials! Preferably it is 100 to 800 m1. More preferably 1
00ml to 400ml.

Further, the color developing bath may be divided into two or more baths as necessary, and the color developing replenisher may be replenished from the first bath or the last bath, thereby shortening the developing time and reducing the amount of replenishment.

The processing method of the present invention can also be used for color reversal processing. In the present invention, the black and white developer used at this time is commonly known as the black and white first developer used for the reversal processing of color photographic light-sensitive materials, or Those used for processing black and white photosensitive materials can be used. In addition, various well-known additives that are generally added to black and white developers can be included.

Typical additives include l-phenyl-3-pyrazolidone, developing agents such as metol and hydroquinone, preservatives such as sulfites, and accelerators consisting of alkalis such as sodium hydroxide, sodium carbonate, and potassium carbonate. ,
Inorganic or organic inhibitors such as potassium bromide, 2-methylbenzimidazole, methylbenzthiazole, water softeners such as polyphosphates, and development inhibitors consisting of trace amounts of iodides and mercapto compounds. I can give it to you.

The processing method of the present invention comprises processing steps such as color development, bleaching, bleach-fixing, and fixing as described above.

Here, after the bleach-fixing or fixing process, processing steps such as water washing and stabilization are generally performed, but after a bath with fixing ability, stabilization processing is performed without substantial water washing. A simple treatment method can also be used.

The rinsing water used in the rinsing process may contain known additives as required. For example, water softeners such as inorganic phosphoric acid, aminopolycarboxylic acid, and organic phosphoric acid;
Disinfectants and anti-fungal agents (for example, isothiazolones, organochlorine disinfectants, benzotriazole, etc.) that prevent the growth of various bacteria and algae, surfactants that prevent drying load and unevenness, and the like can be used. Or L, E
.

West, “Water Quality Cr1t
eria”+Photo, Sci, and Eng,, vo
l, skin! 1h6, Pages 344-359 (1
965) and the like can also be used.

As the stabilizing solution used in the stabilization step, a processing solution that stabilizes the dye image is used. For example, a solution having a buffering capacity of pH 3 to 6, a solution containing aldehyde (for example, formalin), etc. can be used. can. The stabilizing solution may contain ammonium compounds, metal compounds such as Bi and A1, optical brighteners, chelating agents (e.g. 1-hydroxyethylidene-1,1-diphosphonic acid), bactericides, anti-fouling agents, etc. as necessary. A hardening agent, a surfactant, etc. can be used.

In addition, the water washing step and the stabilization step are preferably performed using a multi-stage countercurrent method, and the number of stages is preferably 2 to 4. The replenishment amount is 1 to 50 times the amount brought in from the previous bath per unit area, preferably 2 to 30 times. times, more preferably 2 to 15 times.

The filtrate used in these washing steps or stabilization steps includes tap water, as well as Ca
It is preferable to use water that has been deionized to have an Mg concentration of 5 mg/j or less, water that has been sterilized with halogen, an ultraviolet germicidal lamp, or the like.

In each of the above processing steps for photosensitive materials, when continuous processing is performed using an automatic processor, concentration of the processing solution due to evaporation may occur, especially when the processing amount is small or the opening area of the processing solution is large. becomes. In order to correct such concentration of the processing liquid, it is preferable to replenish an appropriate amount of water or correction liquid.

Further, the amount of waste liquid can be reduced by using a method in which the overflow liquid from the water washing step or the stabilization step is allowed to flow into a bath having a fixing ability, which is a pre-bath.

(Effects of the present invention) The tabular AgX emulsion of the present invention thus obtained has the following characteristics: (1) The grain shape is monodisperse (2) The projected grain size is monodisperse (2) The grain thickness is uniform; Chemical sensitization can be set optimally for each particle, and large particles, medium particles, and small particles can be separated into high-sensitivity layers, medium-sensitivity layers, and low-sensitivity layers, respectively. The effect can be fully demonstrated, and the properties of the tabular grains mentioned above can be fully demonstrated, such as sensitivity, gradation, graininess, sharpness, resolving power, covering power,
It is possible to provide a negative AgX emulsion and a direct reversal AgX emulsion that have excellent properties in image quality, storage stability, latent image stability, and pressure resistance.

Furthermore, when the color light-sensitive material using the emulsion of the present invention is used with the processing bath having bleaching ability of the present invention, the color light-sensitive material using the emulsion of the present invention can
It can exhibit significantly superior desilvering efficiency compared to emulsions.

The present invention will be further explained below with reference to Examples.

[Example] - The present invention will be specifically explained below with reference to Examples, but the embodiments of the present invention are not limited thereto.

An aqueous solution containing gelatin with an average molecular weight (M) of λ 72,000 in K/E was prepared using a double-jet method with stirring.
gNO3 and M20,000 gelatin Q, 7), HN Q 3 (
/ N) 0, / u me ′if have] and k
While stirring the Br aqueous solution (containing 200*ecPO, 7fOM 20,000 f7) and keeping the pBr value constant, add 27.5 min at 2 CC/min.The temperature is 30
It is 0C. Of this emulsion, 3! Use O scrap j as a seed crystal, add gelatin aqueous solution tfOrxlc to it, k
13r/, containing 2%] and the temperature was raised by 77'CK and aged for 4 minutes.
3/, including 7F) between 1/30//,
Then, 6.2 d of NH4No3 (jO wt%) aqueous solution and N
Add 4゜2g of H3 (jj wt%) aqueous solution, and further add μO
Aged for minutes. Next, the emulsion was washed with water using the ultrafiltration method described above, and the same volume was used as I) H7.

After adding kf3r/p, AgNO3 aqueous solution (
AgNO3 in 100xl) and kB
The r aqueous solution was added at r volume for the first 70 minutes, and CDJ was added at a silver potential of −20 mV at a rate of 1 tl/min for the next 20 minutes. This emulsion was washed with water and redispersed, and a replica of the obtained emulsion grains [↑ was observed under TEM (magnification: 3210 times). The characteristics of the grains of the present invention in the emulsion were as follows.

Example In Example 7, M20,000 gelatin was used, M=100,000,
Everything was the same except for replacing the gelatin with Hiroman, /man, and rooo. Everything was the same except that gelatin of each molecular weight was replaced. The TEM images of emulsion grains obtained with gelatin of each molecular weight were used to determine the number ratio of hexagonal tabular grains, as shown in Figure 3.

Implementation Test 13 Nucleation is the same as in Implementation-1/. Gelatin aqueous solution jψjm/(contains gelatin 329, pH 6, j) after nucleation
and raise the temperature to near 0C. After waiting for 1 minute, add 3.21 minutes of AgNO3 aqueous solution (AgNO3
) was added for 3 minutes, followed by NH4No3 (jo
Add 10d of Oat SNH3 (23% by weight) solution and mature for 30 minutes. Next, the ultrafiltration method was washed with water, and 1) H7 was added to the same volume.

O, add k13r/, AjE, A g N 0
3 aqueous solution (/00 rttl with AgNO3 ij'
p) and kBr aqueous solution, and r for the first 10 minutes.
ag/min, and for the next 20 minutes the silver potential -λ at /rxl/min.
CDJ of Om■ was added. This emulsion was washed with water and redispersed. The characteristics of the tabular grains of the present invention determined from the TEM images of the obtained emulsion grains are as follows. The TEMf image of the obtained particles is shown in Figure 3.

Furthermore, according to observation of a cross-sectional thin layer section of a coated emulsion grain using a low-temperature transmission electron hammer, 100% of the observed tabular grains were observed.
% of the particles had one parallel twin plane.

Process, F'ourth Edition,
Macmillan.

New York, 1977, V. L., Zelikman et al., Mak.
Ingand Coating Photog
rapic Emulsion (The Foc
You can refer to the description in ``Al Press, 1964''.

The silver halide emulsion of the present invention can be used in black-and-white silver halide photographic materials (e.g.,
Color negative film, color reversal film, color is -
It can be used for silver dye-bleached photographs, etc.).

Furthermore, it can be used in light-sensitive materials for diffusion transfer (for example, color diffusion transfer elements, silver salt diffusion transfer elements), thermal photosensitive materials (black and white, color), and the like.

(Effects of the present invention) The tabular AgX emulsion of the present invention obtained in this manner: ■ has a monodisperse grain shape; ■ has a monodisperse projected grain size; monodisperse as obtained in Example 3 An emulsion consisting of hexagonal tabular grains was prepared with pBr2 and r%p in AgNO3 aqueous solution and NaOH aqueous solution.
After adjusting to HA, NH4No3(-!wt%
) was added with 10 g of NH3 (lx, weight %)/λrut, and aged for 20 minutes at 7s0 (:).

After aging, the temperature was cooled to 30C, washed with water, and dispersed. The replica r image of the obtained emulsion grain is T E M (times z
Observation was made at a magnification of 12 oo. The characteristics of the emulsion grains were as follows.

Real rabbit example! When the particle growth was completed in Example 3, the silver potential was adjusted to +70 mV using an AgNO3 aqueous solution, and then the AgNO3 and kBr aqueous solutions of the same concentration were further grown for 5 minutes at the same -M degree. The temperature was then cooled to 3 rac, washed with water and dispersed. The properties of the obtained emulsion grains were as follows.

Example 3 Emulsion prepared in Example j (AgB r o , r mol/11 pHA , j, pAgf , 01 temperature ro'c
) to J, J'-dimethyl thiaz
olinodicarbocyanine b r o
The sensitizing dye was added in an amount of 0 to saturately adsorbed, and I) Ag was adjusted to r and o. , after death for 20 minutes, pAg was changed to t, j, triethyl-
thiourea methanol'p='J (0,00
6% by weight) 0, rX/Q-5mol/mol A
Only gBr was added at a constant rate over 10 minutes, and the mixture was aged for 10 minutes. Next, add gold to the compound (gold thiocyanate complex) tO.

! ×10 mol/molAgBr was added and aged for 50 minutes. @ Lower the strength and make this emulsion p13r7
．． Washed twice with water of 6 to remove unreacted sulfur sensitizer, then washed twice with water of pAgj, 0 to remove the dye, and then washed once with water again to redisperse. I let it happen. Next, the temperature was raised to Hiroo'C, Dye/ was added in an amount of ≠Q% of the saturated adsorption amount, and then the turnip) inhibitor TAI (4'-hydrox
y-A-methyl-/.

3, ja, 7-tetraazaindene
) and a coating aid were added.

DYe/ Comparative example/ Special ■ 1986-λ2ri/! ! As in Example 7, the addition of AgNO3 was stopped when the amount of silver added during crystal growth reached /l yVC, and tabular grains with an average grain size of 1.1 μm and an average thickness of 0,076 μm were produced. They were subjected to the same chemical sensitization and spectral sensitization and coated in the same manner.

The coated film thus obtained (the amount of coated silver is /
, j P/l112, base is polyethylene terephthalate film)'' color ant r o o
'/100 with tungsten light with oC filter
Wedge exposure for 2 seconds, then 2o 0C with fAA-/developer
.

Developed for 70 minutes.

The sensitivity granularity determined from the obtained characteristic curves is as shown in Table 1.

It can be seen that the sensitivity and graininess of the non-inventive emulsion are good.

The vine + g degree is the runx in the third degree of 0.2 above Capri.
We will use the reciprocal of the exposure amount that can be displayed in seconds.

The sample was uniformly exposed to a light intensity that gave a density of 0.2 on Capri to IS granularity, and after the development process described above, the sample was exposed to light using the method described in ``The Theory of Photographic Process'' published by Macmillan. Measurement was carried out using a G filter using the method described in 6/Riba Iji.The samples using comparative emulsion (2) were each expressed as 100.

Example 7 The same K was used as in Example 3 before the crystal growth process, and kBr was added to increase the silver potential to -4L! mV and crystal growth of AgNO3
Water bath solution (contains 3oy of AgNO3 in 100ml) and halide aqueous solution (contains k13r and KI, natural content is 5 mol%) for the first 16 minutes! Rei//Next 3C in minutes
Minutes are 10R1Z minutes, -! ? mV CD' J ”T
Added S. This emulsion was washed with water and redispersed (pHa, μ
, pAgJ', j). T E of the obtained emulsion grains
The properties of the tabular grains of the present invention determined from M(rl) were as follows.

The exposed portion is made of AgBrI (5 mol %) and has the structure shown in FIG.

The molar ratio of the core part to the additional part of this particle is about 73.

This unripened emulsion was heated to 0'C,pHA,j,pAgr.
, s, raise the temperature to 0c,...wart aqueous solution to J
, adding only jxlo-5 mol/mol AgBr,
After j minutes, add gold, add sensitizer to X10-"mol/molA
Only gBr was added and aged for 50 minutes. Next, set the temperature to a
o 'CK lower, Dye2(/,/' -diethy
l-2,2'-cyanine chloride
) is the saturated adsorption amount. After adding r% and aging for 2C minutes, anti-fogging agent and coating aid were added and coated.

Example? The unripened emulsion prepared in Example 7 was mixed with Hiro O''('', pH 6,
! , pAgr, j, and DyeJ to the saturated adsorption amount o3r%
3 addition, -209pHa'if! Q I, Ria, High, M / , 2x / O-5mol/mol AgBr
Just add it! diameter gold sensitizer to-o, uxto-5mo
Vmol AgBrff1 was added and aged for 50 minutes. Next, the temperature was brought to ≠00C, and an anti-fogging agent and a coating aid were added and coated. In addition, DyeJ is AgB r
BrI is a dye that selectively adsorbs to the surface.

Example The unripened emulsion prepared in Example 7 was heated to 0°C and dyed.
After adsorbing J for 70 times at saturated adsorption l,! Raise the temperature to o 'C and add hypo to 10 mol/molAg
Only Br was added over io minutes, and after 5 minutes, the gold sensitizer was added to 0.
．． Add only 3x10-5 mol/molAgBr,
Aged for 0 minutes. Then lower the temperature to 3j0C, I) HJ
A portion of the dye was desorbed with , r, pAg Hiro, O, washed with water, and redispersed (pHA, Hiro, pAgr, j). Reflection spectrum measurement when increasing the amount of DyeJ added to this emulsion showed that the amount of residual dye adsorption was Br%. This emulsion was brought to ≠00C and coated with the addition of an antifoggant and a coating aid.

Example 10 The unripened emulsion of Example 7 was changed to ≠o'C and DyeJ (A
pK of gB'r adsorbed on (//i) side
The a value is U, a) is adsorbed at Po% of the saturated adsorption amount, and 20
After waiting for several minutes, the temperature was lowered to 00C and the hypo was set to 0.7
Only X/O-5 mol/mol AgBr was added over 70 minutes, and after 5 minutes, gold sensitizer was added at 0°3×to'm.
Only ol/mol AgBr was added and aged for 50 minutes.

Next, lower the @ degree to Jjo (, lower the pH to 3.
The emulsion was subjected to color-sensitivity desorption, and the emulsion was washed with water at a pH of 3°, and this process was repeated three times. The emulsion was then redispersed and the IAQ °C
37% of the saturated adsorption amount of Dyel (optimal addition amount in terms of sensitivity) was adsorbed, and then antifoggant and coating aid were added and coated (coated silver amount was t, 517 m, Heath was a polyethylene terephthalate film). .

Actual power example 7? When the 10 samples were compared in the same manner as shown in Table 7, the results of 辰λ were obtained.

Table - Examples - // The emulsion obtained in Example 3 was prepared using gold thiocyanate. : Chemical sensitization was performed.

The emulsion thus obtained was used in JP-A-62-K6TATA! A color photographic material having the same composition as Sample 10/ of Sample 10/ of Example 7 of No. R was prepared, except that it was used as the emulsion for the third layer.

When treated in the same manner as in Example 7 of the 1980 62-26 Tata JR, it showed good sensitivity and graininess.

Example 12 On a subbed cellulose triacetate film support,
A sample of a multilayer color light-sensitive material was prepared by coating layers having the compositions shown below.

Emulsion 1 is an emulsion obtained by optimally sensitizing the emulsion shown in Example 1 with gold and sulfur, and has the average grain size l shown in Comparative Example 1.

Emulsion 2 was an emulsion in which tabular grains of 1 μm and average thickness of 0.16 μm were similarly optimally sensitized with gold and sulfur.

A sample using Emulsion 1 was designated as Sample 101, and a sample using Emulsion 2 was designated as Sample 102.

(Photosensitive layer composition) The number corresponding to each component indicates the coating amount expressed in g/nl, and for silver halide, it indicates the coating amount in terms of silver. However, for sensitizing dyes, the halogen in the same layer The coating amount is shown in moles based on 111 moles of chemical compound.

(Sample 101) 1st layer; Haley silane prevention layer black colloidal silver...Silver 0.18 Gelatin...0.40 2nd layer; Intermediate layer 2.5-di-t-pentadecylhydroquinone...0. 18EX-1...
・ 0.07 EX-3... 0.02 EX-12... 0.002 0-1... 0.060-2
...0.08U-3...
0.10 HBS-1... 0.10 8BS-2... 0.02 Gelatin... 1.04 Third layer (first red-sensitive emulsion layer) Monodisperse silver iodobromide emulsion (silver iodide emulsion) 6 mol% average particle size 0.
6 μm, coefficient of variation regarding particle size 0.1... Silver 0.55 Sensitizing dye l... 6.9X10-' Sensitizing dye ■... 1.8XIO-' Sensitizing dye II
I-... 3. lX10°5 sensitizing dye■
・・・ 4.0X10-'EX-2・ ・ ・
0.350 HBS-1・ ・ ・ 0.005 EX-10・ ・ ・ 0.020 Gelatin ・・・ 1.20 4th layer (second red-sensitive emulsion layer) Tabular silver iodobromide emulsion (1110 iodide Mol%, average particle size 0.7μ, average aspect ratio 5.5, average thickness 0.2
μ)...all, 0 Sensitizing dye■...5. lX10-'sensitizing dye■...1.4X10-'sensitizing dye■
...2.3X10-'sensitizing dye■
...3.0X10-'EX-2...0.4
00 EX-3... o, os.

EX-10... 0.015 Gelatin... 1.30 5th layer (third red-sensitive emulsion layer) Emulsion 1 or Emulsion 2... Silver 1.60 Sensitizing dye ■... 5.4XIQ- 'Sensitizing dye■...1.4X10-'Sensitizing dye■
...2.4X10-' sensitizing dye N
・・・-3,1xlO"EX-3... 0.24
0 EX-4... 0.120 HBS-1... 0.22 HBS-2... 0.10 Gelatin... 1.63 6th layer (middle layer) EX-5... 0. 040 HBS-1... 0.020 Gelatin... 0.80 7th layer (first green-sensitive emulsion layer) Tabular silver iodobromide emulsion (silver iodide 6 mol%, average grain size 0
．． 6μ, average aspect ratio 6.0, average thickness 0.15) ・ ・ ・ Silver 0.40 Sensitizing dye ■ ...3.0X10-' Sensitizing dye ■ ...1.0X10-' Sensitizing dye ■
...3.8X10-'EX-6...
0.260 EX-1・ ・ ・ 0.021 EX-7・ −・ 0.030 EX-8・ ・ 0.025 HBS-1・ ・ 0.100 HBS-4・ ・ ・ 0.010 Gelatin ・... 0.75 8th layer (second green-sensitive emulsion layer) Monodisperse iodobromide II! I (silver iodide 9 mol%, average grain size 0.7μ grain size coefficient of variation 0.18)...io,
s.

Sensitizing dye■...2. lX10-'sensitizing dye■...7.0X10-'sensitizing dye■
...2.6X10-'EX-6...0
．． 180 EX-8... 0.010 EX-1... 0.008 EX-7... 0.012 HBS-1... 0.160 HBS-4... 0.008 Gelatin... 1.10 9th layer (third green-sensitive emulsion layer) Emulsion 1 or emulsion 2 ...ill, 2 Sensitizing dye ■ ...3.5X10-' Sensitizing dye ■ ...8.0X10-' Sensitive pigment■
...3.0X10-'EX-6...0
．． 06S EX-11--・0.030 EX-1...0.025 HBS-1...0.25 HBS-2...0.10 Gelatin...1.74 10th layer (
Yellow filter layer) Yellow colloidal silver...Silver 0.05EX-5
・-・ 0.08 HBS-3・ ・ ・ 0.03 Gelatin ・・・ 0.95 11th layer (
1st blue-sensitive emulsion layer) Tabular silver iodobromide emulsion (i!6 mol% iodide, average grain size 0.6μ, average aspect ratio 5.7, average thickness 0.15
μ) ... Daughter 0.24 Sensitizing dye■ ...3.5XIO-'EX-
9... 0.8S EX-8... 0.12 8BS-1... 0.28 Gelatin... 1.28 12th layer (
2nd blue-sensitive emulsion layer) Monodisperse silver iodobromide emulsion (1110 mol% iodide, average grain size 0.8μ, coefficient of variation regarding grain size 0°...!10.
45 Sensitizing dye■...2. lX10-'EX-
9... 0.20 EX-10... 0.015 HBS-1... 0.03 Gelatin... 0.46 13th layer (
Third blue emulsion layer) Emulsion 1 or Emulsion 2...iio, 77 Sensitizing dye ■...2.2X10-'EX-
9... 0.20 HBS-1... 0.07 Gelatin... 0.69 14th layer (
1st protective layer) Cola silver bromide emulsion (iodide w! 11 mol%, average grain size 0.
07μ) ...! IQ, 5 U-4... 0.11 U-5... 0.17 HBS-1... 0.90 Gelatin... 1. OO 15th layer (
2nd protective layer) Polymethyl acrylate particles (approximately 1.5 μm in diameter) ... 0.54S-1.
・ ・ o, 15 S-2 ・ ・ ・ 0.05 Gelatin ... 0.72 In addition to the above components, gelatin hardening agent H-1 and a surfactant were added to each layer.

X-2 0H X-3 H X-4 1l (i) CJ, 0CONII 0CIItC1ltS
CItCOOlX-5 H X-6 3゛X-8 CIls
CH311cOc(CHs)s X-9 EX-10 0H 3CHCOOCHi CH3 EX-11 EX-12 S-I
S-2HBS-1) Liclesil phosphate HBS
-2 dibutyl phthalate HBS-3 bis(2-ethylexyl) phthalate B5
-4 Cllz = CH-3ow-CHtCONHCH
zCL = CB-3(h-CHt-CONHCH
x Sensitizing dye (CHx) ssO3Na ■ N Ct II sJs Sample 101 (invention) and sample 102 (comparative example) prepared as described above were subjected to the following processing steps to increase the tank capacity of color developer. Continuous processing (running test) was performed on each sample until it was replenished twice as much. However, the composition of the bleaching solution was changed as shown in Table 1, and the test was conducted for each of them.

The automatic developing machine used was of the belt conveyance type described in JP-A No. 60-191257, and each processing bath was
The jet stirring method described in No. 183460 was used.

The processing steps are shown below.

Color development 3 minutes 15 seconds 38℃ 38 ugliness Bleaching 1 minute 38℃ 4m&
Fixation 1 minute 38℃ 30
m1 Stable 1 20 seconds 38℃ - Stable 2 20 seconds 38℃ - Stability 3 20 seconds 38℃ 35difficulty* Drying 1 minute 15 seconds 50-70℃
-This stabilizing solution was a 3-tank countercurrent force type: Stable 3 - Stable 2 - Stable 1.

The composition of each treatment liquid used is shown below.

(Color developer) Mother solution (g) Replenisher (g) Diethylenetriaminepentaacetic acid 5.0 6.0 Sodium sulfite 4.0 4.4 Potassium carbonate 30.0 37.0
Potassium bromide 1.3 0.9
Potassium iodide 1.2mg
-Hydroxylamine sulfate 2.0 2.8
Add 4-[N-ethyl-N-β-4,75,3hydroxyethylamino]-2-methylaniline sulfate solution 1. Oj 1.0
1p H10,0010,05 (bleaching solution) Mother liquor Replenisher solution 1.3-diaminopropanetetraacetic acid 4.0g
5.0g ammonium bromide 100.0g
160.0g ammonium nitrate 3
0.0g 50.0g Ammonia water (27%)
20.0 pal 23. Oml! Acetic acid (9
8%) 9.0s+j 15.
0 Steel E Add water 1. On!
1.01 pH See Table 1 HC1 (Fixer) Mother liquor Replenisher 1-Hydroxyethylidene-1,1-diphosphonic acid 5.0g 6.0g
Sodium sulfite 7. Og 8.
0g Sodium bisulfite 5.0g 5
．． 5g ammonium thiosulfate 170.0ml
200.0 mA aqueous solution (70%) Add water 1.01 1.01p
H6,76,6 (Stable solution) Mother liquor, replenisher common formalin (37%) 1.2m+
15-Chloro-2-methyl-4-s, osgisothiazolin-3-one 2-methyl-4-isothiaso゛ 3.0g phosphorus-3-one surfactant 0.4[C, 1-0 +CHzCHtO-) rv +1 ] Ethylene glycol 1.0 Add water
1,01p H5,0-7,0 After exposing the sample to 20 CMS, it was treated with each running equilibrium solution, and the amount of residual silver was determined by fluorescence XAI method.

The relationship between level and effect (residual silver amount) in the example is μgld The effects of the present invention are clear.

Example 13 On a subbed cellulose triacetate film support,
A multilayer color photosensitive material consisting of each layer having the composition shown below was prepared. A sample using Emulsion 1 (invention) in Example 12 was designated as Sample 103, and a sample using Emulsion 2 (Comparative Example) was designated as Sample 103. When these samples were subjected to the same processing steps as shown in Example 12, it was found that sample 103 using the emulsion of the present invention showed good desilvering properties with respect to the processing solution of the present invention. .

(Composition of photosensitive layer) The coating amount is expressed in g/rd$ of silver for silver halide and colloidal silver, and the amount expressed in g/rd for couplers, additives, and gelatin. The number of sensitizing dyes is expressed per 111 moles of halogen in the same layer. Note that the symbols indicating additives have the meanings shown below. However, if a substance has multiple effects, one of them is listed as a representative.

UVi ultraviolet absorber, 3oIV; high boiling point organic solvent, EX
F: dye, ExS: sensitizing dye, RxC: cyan coupler, ExM: magenta coupler, EXY: yellow coupler, cpa: additive first layer (Haley silane prevention layer) black colloidal silver...0.15 gelatin ...2.9UV-1...0
．． 03 UV-2...0.06 UV-3...0.07 S01V-2...0.08 ExF-1...-0,01 ExF-2=0.01 2nd layer (low Sensitive red-sensitive emulsion layer) Silver iodobromide emulsion (Ag 14 mol%, uniform, equivalent sphere diameter 0.
4μ Number of fluctuations in equivalent sphere diameter: 37%, plate-like particle diameter/thickness ratio: 3.0) Coated silver amount: 0.4 gelatin
...0.8ExS-1...2.
3X10-'ExS-2...1.4XlO-' -ExS-5 - ・-2,3x
10-'ExS-7・・・・8. 0xlO-'
Etc-1・-・0. 17 ExC-2-0,03 ExC-3-・・0. 13 3rd layer (medium-sensitivity red-sensitive emulsion layer) II emulsion (Agl 6 mol%, core-shell ratio 2:1, internal height Agl, equivalent sphere diameter 0.65μ, coefficient of variation of equivalent sphere diameter 25%, plate-like) Grain, diameter/thickness ratio 2.0) Coated silver amount...0.65 Silver iodobromide emulsion (Ag1 4 mol%, uniform-Agl type, equivalent sphere diameter 0.4μ, coefficient of variation of equivalent sphere diameter 37%) , plate-like particles,
Diameter/thickness ratio 3.0) Coated silver amount...0.1 Gelatin...1. 0ExS
-1...2X10-' ExS-2...1.2X 10-'ExS-5...-zxlo-'ExS-7...-7xto-' ExC-1... 0. 31 ExC-2-・・0. 01 ExC-3・・・0.06 4th layer (high-sensitivity red-sensitive emulsion layer) Emulsion 1 or Emulsion 2 Diameter/thickness ratio 2.5) Coated silver amount...0.9 Gelatin...0.8ExS −
1...L, 6X10-' ExS-2...1.5x l O-'ExS-5...
・1.6X10-'ExS-7-6xio-' ExC-1...-0,07 ExC-4...-0,05 Solv-1...0.07 Solv-2...0.20 C9d -7...4.6XIQ-' 5th layer (middle layer) Gelatin...0.6UV-4.
・・0.03 UV-5・ ・ ・ 0.04 Cpd-1・ ・ ・ 0. 1 Polyethyl acrylate latex...0.08 Solv-1=0.05 6th layer (low-sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion (Agl 4 mol% uniform type).

Equivalent sphere diameter 0.4μ, equivalent sphere diameter 0.7μ, coefficient of variation of equivalent sphere diameter 37%, plate-like particles, diameter/thickness ratio 2.0) Coated silver amount...0.18 Gelatin...0. 4ExS-
3...2X10-' ExS-4... 7X10-' ExS-5... lX10-' ExM-5...0.11 ExM-1...0.03 ExY-8...0.0I Solv-1...0.09 Solv-4-0,01 7th layer (medium-sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion (Ag1 4 mol%, core shell ratio l:1
Surface height Agl type, legal equivalent type, equivalent sphere diameter 0.5 μ, coefficient of variation of equivalent sphere diameter 20%, plate-like particle, diameter/thickness ratio 4.0
) Coated silver amount...0.27 Gelatin...0.6ExS-3
... 2X10-' ExS-4... 7X10-'ExS-5...txlo-' ExM-5...0.17 ExM-7...0.04 ExY-8...0.02 Solv -1...0.14 SO1v-4...0.02 8th layer (high-sensitivity green-sensitive emulsion layer) Emulsion 1 or emulsion 2 Coated silver amount...0.7 Gelatin...0. 8ExS-
4...5.2X10-' ExS-5・ ・ ・ 1×1O-4 ExS-8・ ・ ・ 0. 3XIO-'ExM-5
・ -・ 0. I ExM-6・・・0.03 BxY-8・・−0,02 ExC-1・・・0.02 ExC-4・−・0. 01 Solv-1・・・・0. 25 Solv-2・・・・0. 06 Solv-4・=0. (11 cp d-7・ ・ ・ lXl0-'9th layer (middle layer) Gelatin...0.6Cpd-1
...0.04 Polyethyl acrylate latex...0.12 Solv-1...0.02 10th layer (donor layer for interlayer effect on red-sensitive layer) Silver iodobromide emulsion (Ag1 6 mol% , internal high Agl type with core-shell ratio 2:1, equivalent sphere diameter 0.7 μ, coefficient of variation of equivalent sphere diameter 2
5%, plate-like grains, diameter/thickness ratio 2.0) Coated silver amount...0.68 Silver iodobromide emulsion (Ag1 4 mol% uniform type, coefficient of variation of equivalent sphere diameter 37%, plate-like grains, Diameter/thickness ratio 3.0) Coated silver amount...0.19 Gelatin...1.0ExS-3
-・-5x1o-' ExM-10...0.19 Solv-1...0.20 11th layer (yellow filter layer) Yellow colloidal silver...0.06 Gelatin...0.8Cpd-' l
...0.13SO1v-1...0
．． 13 Cpd-1...0.07 Cpd-6...0.002 H-1...0.13 12th layer (low sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion (Ag14.5 mol% , uniform Agl type, equivalent sphere diameter 0.7μ, coefficient of variation of equivalent sphere diameter 15%, plate-like grains, diameter/thickness ratio 7.o) Coated silver amount...0.3 Silver iodobromide emulsion (Ag1 3 mol%, uniform Agl type, equivalent sphere diameter 0.3 μ, coefficient of variation of equivalent sphere diameter 30%, plate-like particles,
Diameter/thickness ratio 7.0) Coated silver amount...0.15 Gelatin...1. 8ExS-
6...9xto-' ExC-1...0.06 Exc-4...0,03 ExY-9...l), 14 ExY-11...l), 89 Solv-1...0 .42 13th layer (middle layer) Gelatin...0.7ExY-1
2-0,20 Solv-1... 0.34 14th layer (high-temperature blue-sensitive emulsion layer) Emulsion 1 or Emulsion 2 Coated silver amount...0.5 Gelatin...0.5ExS-6
...txto-' ExY-9--0,01 ExY-11-0.20 ExC-1-0,02 Solv-1-0. 10 15th layer (first protective layer) Fine-grain silver bromide emulsion (All 2 mol%, average - Agz type 8 sphere equivalent diameter 0.07μ) Coated silver amount...0.12 Gelatin...0.9UV- 4.
・・0. 11 UV-5...0.16 SO1v-5...0.02 H-1...0.13 Cpd-5...0.10 Polyethyl acrylate latex...0.09 No. 16 Layer (second protective layer) Fine grain silver bromide emulsion (Ag1 2 mol%, uniform Agl type, equivalent sphere diameter 0.07
μ) Coated silver amount...0.36 Gelatin...0.55 Polymethyl methacrylate particle diameter 1.5μ...0. 2 H-1...0.17 In addition to the above components, each layer contains emulsion stabilizer CPD-3 (
0.07g10f) Surfactant Cpd-4 (0.03g
/nf) was added as a coating aid.

uv-1 uv-2 H V-3 H (t)CJq V-4 CH3CH3 V-5 3o1v-1 tricresyl phosphate 5olv-2 diptyl phthalate olv-4 Solv-5 trihexyl phosphate XF-1 N(CJs)z N (C!Is)t xS-1 xS-2 ExS-3 ExS-4 ExS-5 ExS-6 ExS-7 (CHx)zsOJ-N(CJs)s xS-8 xC-1 H (t)CJ*0CN)l xC-2 H 3CHCO□CR3 CH.

ExC-3 ExC-4 H (i) CJtOCONH0CHxCIhSCHtCOJ
xM-5 CHs C00CJ* I m! 25 m'-25 sol, wt, approximately 20.000 xM-5 I xM-7 xM-10 ExY-3 CH.

ExY-9 ExY-11 ExY-12 pd-7 pd-1 C also HI3 0HCJ13 pd-2 H3SO pd-6 -N Cpd-5 CI(3 I Cpd-3 H Cpd-4 Hz = CI-Sow-CHz- CONCl-
5oC)l! = C0-5O□-CHz-CON
H-CHz

[Brief explanation of the drawing]

In Figure 1, the core part is AgBr and the lateral addition part is Ag.
At Br1, selective adsorbent (cyanine dye) on the adduct
This figure schematically shows a preferred embodiment B of the present invention in which is adsorbed and chemical sensitization is selectively formed on the core region. FIG. 2 schematically shows a hexagonal tabular grain in which an additional portion having a halogen composition different from that of the host grain is grown on a circular tabular host grain. Figure 3 shows the relationship between the molecular weight of gelatin as a dispersion medium and the number of hexagonal tabular grains obtained in Example-2, where the horizontal axis represents the molecular weight of gelatin and the vertical axis represents the hexagonal tabular grains of the present invention. Shows the ratio of the number of items. FIG. 4 is an electron micrograph showing the crystal structure of the particles obtained in Example 3, and the magnification is 3280 times. Patent applicant: Fuji Photo Film Co., Ltd. (Mi Toshii Kazuguchi +0.000 50.000
100.000 Figure 4 1, Indication of the case 1986 Patent Application No. 3yooo 2, Title of the invention Silver halide emulsion and its manufacturing method and processing method 3, Person making the amendment Relationship with the case Patent applicant Location Kanagawa 210 Nakanuma, Minamiashigara City, Prefecture Name (5)
20) Fuji Photo Film Co., Ltd. Contact information: 2-26-30 Nishi-Azabu, Minato-ku, Tokyo 106 Fuji Photo Film Co., Ltd. Tokyo Head Office Date of amendment order: 7th April, 1939 (Shipping) 5. Amendment Subject to specifications and drawings. 1. Indication of the case Patent Application No. 3 yooo 20 of 1988 Name of the invention Silver halide emulsion and its manufacturing method and processing method 3. Person making the amendment Relationship with the case Patent applicant Location 210 Nakanuma, Minamiashigara City, Kanagawa Prefecture Name (520) Fuji Photo Film Co., Ltd. Contact address 2 Nishiazabu, Minato-ku, Tokyo 106
T1126 No. 30 4, Subject of amendment The statement in the "Detailed Description of the Invention" column 5 of the description and the "Detailed Description of the Invention" section of the description of the amendment is amended as follows. 1) Insert appendix l after "Can be used." in the is-th line of page 33. 2) Correct the "performance list price" on page P3, line 77 to "performance deterioration." 3) The entire text of page 144≠ is amended as shown in the attached document. 4) Correct "sample 103" in line j of page 3 of 14c to "sample IO+L". Attachment l "Generally, there are 11 basic processes for processing color photosensitive materials, a color development process and 1 process for desilvering. In other words, the exposed silver halide color photographic material is put into the color development process. The silver halide is reduced to silver by the color developing agent, and the oxidized color developing agent reacts with the color former to give a dye image.The one color photographic material is then subjected to a desilvering process. Here, the silver produced in the previous step is oxidized by the action of an oxidizing agent (commonly called a bleaching agent), and then dissolved and removed by a silver ion complexing agent, commonly called a fixing agent. After nine steps, only a dye image is created on the photographic material.Actual processing consists of the two basic steps of color development and desilvering described above to maintain the photographic and physical quality of the image. Contains auxiliary steps to improve image preservation and image preservation, such as a hardening bath that prevents excessive softening of the photosensitive layer during processing, and effectively stops the development reaction. Examples include a stop bath, an image stabilizing bath that stabilizes the image, and a film removal bath that removes the backing layer of the support.The above-mentioned iron removal process also uses two separate bleaching baths and fixing baths. In some cases, it is carried out in a process, and in other cases, the processing process is simplified for the purpose of speeding up processing and saving labor, and in other cases it is carried out in a single step using a bleach-fixing bath containing both a bleaching agent and a fixing agent. , from the viewpoint of rapid and simple processing and prevention of environmental pollution, ferric ion complex salts (e.g., aminopolycarboxylic acid ferric ion complex salts, etc., especially ethylenediaminetetraacetic acid iron (II) complex salts) are mainly used. However, since ferric ion complex salts have a relatively small oxidizing power and an insufficient bleaching blade, bleaching methods using this as a bleaching agent are, for example, silver chlorobromide emulsions. When bleaching or bleach-fixing a low-sensitivity silver halide color photographic light-sensitive material that mainly contains silver halide, the desired purpose can be achieved, but When processing a color-sensitized silver 10-genide color photographic light-sensitive material, especially a color reversal light-sensitive material for photography, and a negative light-sensitive material for photography that uses a high silver content emulsion, It has the disadvantage that the bleaching effect is insufficient, resulting in poor desilvering, and that it takes a long time to bleach.In addition, in photosensitive materials, sensitizing dyes are used for the purpose of color sensitization. In particular, tabular grains with high silver or an expanded aspect ratio may be used with the aim of increasing sensitivity. The silver halide photosensitive material containing the monodispersed tabular Ag Containing at least one ferrous complex salt of a compound selected from compound group (A) and a ferrous ferric complex salt of l,3-diaminoprocenetetraacetic acid in a molar ratio of 3 or less. It was found that when processed using the characteristic silver halide color photographic light-sensitive material processing method, the desilvering efficiency was significantly higher than that of a tabular AgX emulsion with large dispersion. In general, tabular grains have a large specific surface area and are capable of adsorbing a large amount of sensitizing dye onto their surfaces, resulting in a relatively high color sensitization sensitivity. However, when a large amount of dye is adsorbed, the dye inhibits the bleaching of silver in the processing solution during the desilvering process, and the desilvering efficiency tends to deteriorate. However, the monodisperse tabular AgX emulsion of the present invention Silver halide color photosensitive materials are
When the treatment bath having bleaching ability of the present invention is used, the efficiency of desilvering is significantly improved. ” Attachment ``Relationship between level and effect in Examples (residual silver amount) unit is μg
/3'' The effects of the present invention are clear.

Claims (6)

[Claims] (1) A silver halide emulsion consisting of a dispersion medium and silver halide grains, wherein 9 of the total projected area of the silver halide grains is
A silver halide characterized in that 5% or more is occupied by tabular silver halide grains having two parallel twin planes, and the size distribution of the tabular silver halide grains is monodisperse. emulsion. (2) The shape of the main plane of the tabular grain is a hexagon with an adjacent side ratio (maximum side length/minimum side length) of 2.0 or less, and the straight part ratio of the hexagon is 4/5 or more. A silver halide emulsion according to claim 1, characterized in that: (3) The shape of the main plane of the tabular grain has a linear part ratio of 4/5
Claim 1 characterized in that it has the following circular shape:
The silver halide emulsion described in . (4) A method for producing a monodisperse tabular silver halide emulsion containing two parallel twin planes through nucleation of silver halide grains, Ostwald ripening, and grain growth, in which the dispersion medium has an average molecular weight of 60,000 yen. A method for producing a silver halide emulsion, characterized in that it is a low molecular weight gelatin as shown below and forms nuclei under conditions of pBr 1.0 to 2.5. (5) The aging process is firstly aged at low pBr (1.4-2.0) and then silver salt is added to raise pBr to higher (1.7
The method for producing a silver halide emulsion according to claim 4, characterized in that the method is a two-stage ripening process in which a silver halide solvent is added to ripen the silver halide emulsion. (6) A method in which an imagewise exposed silver halide color photographic light-sensitive material containing a silver halide emulsion according to claim 1 is color-developed and then treated with a processing solution having bleaching ability. The treatment liquid contains at least one ferric complex salt of a compound selected from the following compound group (A) as a bleaching agent and a ferric complex salt of 1,3-diaminopropanetetraacetic acid in a molar ratio of 3 or less. A method for processing a silver halide color photographic material, characterized in that it contains: Compound (A) A-1 Ethylenediaminetetraacetic acid A-2 Diethylenetriaminepentaacetic acid A-3 Cyclohexanediaminetetraacetic acid A-4 1,2-propylenediaminetetraacetic acid