JPS63305355A - Silver halide color reversal photographic sensitive material - Google Patents

Abstract

PURPOSE:To improve sensitivity by using silver halide particles which are fogged on the surface or in the inside into an intermediate layer adjacent to the lowermost sensitive layer of the other silver halide emulsion layers having different color sensitivities near a base. CONSTITUTION:This photosensitive material has blue-, green- and red sensitive silver halide emulsion layers constituted of the plural silver halide emulsion layers having the same color sensitivity and different sensitivities as well as the nonphotosensitive intermediate layer on the base and >=50% of the total projection area of the silver halide particles incorporated into at least one layer of one color sensitive layer positioned furthest from the base is occupied by the planar silver halide particles having <=0.5mum thickness, >=0.5mum diameter, and >=3:1 average aspect ratio. In addition, the silver halide particles which are fogged on the surface and/or the inside are incorporated into at least one silver halide emulsion layer each of the other two color sensitive layers and/or the nonphotosensitive intermediate layer adjacent to the lowermost sensitive layer. The sensitivity is thereby improved.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a silver halide color reversal photographic light-sensitive material which has excellent sharpness and is suitable for sensitization development.

(Prior Art) High image quality and high sensitivity are always required for silver halide color reversal photographic light-sensitive materials for photography, and sharpness, for example, is one of the important factors for image quality.

Usually, in a multilayer color photographic light-sensitive material having blue-sensitive, green-sensitive, and red-sensitive silver halide emulsion layers, light scattering by silver halide grains occurs in the silver halide emulsion layer closer to the support (and farther from the incident light source). It is known that the sharpness of images is reduced, and as an improvement method, for example, the US patent DA, RI3RI,! - The tabular silver halide grains described in 〇 can be used.

On the other hand, in color reversal photographic materials, so-called sensitization development, in which the development time of the first development (black and white negative development) is extended, is usually carried out to substantially increase the sensitivity when photographing scenes with insufficient light intensity. . Therefore, it is required to provide a color reversal photosensitive material in which the sensitivity of the silver halide emulsion layer having the above three different color sensitivities is greatly increased during sensitization development, and each sensitivity and gradation are well balanced. has been done.

Originally, tabular silver halide grains have a high activity in dissolution physical development using silver halide solvents such as potassium thiocyanate and sodium sulfite produced in the first development, and have a characteristic suitable for sensitization. Furthermore, in the case of multilayer silver halide photographic light-sensitive materials, in general, the silver halide emulsion layer closer to the coating film surface is It is known that the developing activity is relatively high. Therefore, when tabular silver halide grains are used in the silver halide emulsion layer near the coating film surface farthest from the support as described above, the dissolution and physical development activity of the silver halide emulsion layer is extremely high. When performing sensitization development, the magnitude of sensitization of the silver halide emulsion layer and the magnitude of sensitization of other silver halide emulsion layers with different color sensibilities closer to the support (further from the coating film surface) are determined. A problem arises in that differences occur between the colors and the density balance of the color image deteriorates.

As described above, it has been extremely difficult to provide a silver halide color reversal photographic light-sensitive material that effectively uses tabular silver halide grains to improve sharpness and is suitable for sensitization development.

(Problems to be Solved by the Invention) The object of the present invention is to provide a silver halide color reversal photograph with excellent sharpness and a uniform increase in sensitivity due to sensitization development of all silver halide emulsion layers having different color sensitivities. Our purpose is to provide photosensitive materials.

(Means for Solving the Problems) The above problems are caused by silver halide emulsion layers having the same color sensitivity but different sensitivities on a support. J- of the total projected area of silver halide grains contained in at least seven layers of one color-sensitive layer having a silver halide emulsion layer and a non-light-sensitive intermediate layer located farthest from the support. 04 or above has a thickness of 0.3-
μm or less, the diameter is 0.1 μm or more, and the average aspect ratio is 3.
occupied by two/or more tabular silver halide grains;
and silver halide coated on the surface and/or in the at least seven silver halide emulsion layers of each of the other two color-sensitive layers and/or in the non-light-sensitive intermediate layer adjacent to the lowest-sensitive layer. The problem was solved by a silver halide color reversal photographic material characterized by containing grains.

The present invention will be explained in detail below.

The color reversal process to which the present invention is applied usually consists of the following steps.

First development - Water washing - Reversal bath - Color development - Adjustment bath - Bleaching fixation - Water washing - Stabilizing bath Light-sensitive silver halide grains with their surfaces or interior covered are placed in the emulsion or in an adjacent non-light-sensitive intermediate layer. The mechanism by which the sensitivity of the light-sensitive silver halide emulsion layer increases during sensitization development by using it is as follows.

The silver halide grains whose surfaces or interiors are fogged are chemically developed into developed silver at the beginning of the first development or at an appropriate time, regardless of exposure. Dissolution physical development of undeveloped photosensitive silver halide grains in the vicinity is promoted using these developed silver as nuclei.

The present invention relates to a silver halide color reversal photographic light-sensitive material using tabular silver halide grains in a color-sensitive silver halide emulsion layer located near the surface of a coated film, which has a different color sensitivity closer to the support. For other silver halide emulsion layers, the above-mentioned surface is present in these silver halide emulsion layers and/or in an intermediate layer adjacent to the lowest sensitive layer of each of these color-sensitive silver halide emulsion layers. and/or intended to greatly and uniformly increase the sensitivity of all silver halide emulsion layers with different color sensitivities during sensitization development by using internally fogged silver halide grains. It is.

The present invention relates to the specific use of surface and/or internally fogged silver halide grains in combination with tabular silver halide grains to improve sharpness and sensitization development. U.S. patent for using surface-fogged silver halide grains in a light-sensitive silver halide emulsion layer to increase interimage effect, θ♂λ,! ! No. 3,
U.S. Pat. JP-A-2003-279911, which does not particularly limit the usage of the shell-type fogged silver halide grains.
, can be clearly distinguished from No. 2.

The silver halide color reversal photographic light-sensitive material of the present invention has a back-sensitive, green-sensitive, and red-sensitive silver halide on a support. It has an emulsion layer and a non-photosensitive intermediate layer. Although the arrangement of the blue-sensitive layer, green-sensitive layer and red-sensitive layer is arbitrary, the blue-sensitive layer is usually arranged farthest from the support. Further, each color-sensitive silver halide emulsion layer is composed of a plurality of silver halide emulsion layers having the same color sensitivity but different sensitivities. The number and arrangement of these silver halide emulsion layers having the same color sensitivity but different sensitivities are arbitrary, but the silver halide emulsion layer with higher sensitivity is often arranged farther from the support. Furthermore, these silver halide emulsion layers with the same color sensitivity but different sensitivities are often placed adjacent to each other, but they may also be placed alternately with parts of silver halide emulsion layers with different color sensitivities. I can do it. In the present invention, it is preferable that a non-photosensitive intermediate layer is disposed adjacent to the lowest sensitive layer of each of the two color sensitive layers closer to the support.

In the present invention, tabular silver halide grains are used in at least seven silver halide emulsion layers among the color-sensitive layers located farthest from the support. Furthermore, among the silver halide emulsion layers having different sensitivities constituting the color-sensitive layer, the position of the emulsion layer using tabular silver halide grains is not necessarily limited, but the position of the emulsion layer using tabular silver halide grains is not necessarily limited, but the position of the emulsion layer furthest from the support is It is often preferable to use tabular silver halide grains in the silver halide emulsion layer.

The tabular silver halide grains that can be used in the present invention will be explained below.

In the present invention, tabular silver halide grains (hereinafter referred to as "tabular grains") have λ opposing parallel principal planes, and have a circular equivalent diameter of the principal planes (a circle having the same projected area as the principal planes). diameter) is the distance between principal planes (i.e. particle thickness)9
Particles that are three times or more larger.

It is preferable that the average grain diameter/grain thickness ratio of the emulsion having tabular grains of the present invention is 3 to 1, and especially VC! ~/θ
It is preferable that

Here, the average grain diameter/grain thickness ratio is obtained by averaging the grain diameter/grain thickness ratio of all tabular grains, but a simple method is to calculate the average diameter of all tabular grains and the average of all tabular grains. It can also be determined as a ratio to the thickness.

The diameter (equivalent to a circle) of the tabular grain of the present invention is 0.3 to /θμm
Preferably 0. ! ~6.0μm1, more preferably 0.
It is 3 to 2.0 μm.

The particle thickness is θ,! μm or less, preferably θ, θ! ~θ,
jμm, more preferably θ, θt~0°3 μm.

The particle diameter and particle thickness in the present invention can be determined from electron micrographs of the particles by the method described in US Patent No. Q, <t34t, 224.

Specifically, silver chloroiodide, silver iodobromide, silver chloride, silver chlorobromide, steel bromide, and silver chloroiodobromide can be used as the halogen composition of the tabular grains used in the present invention. Silver bromide is preferred. It may also contain silver thiocyanate, silver shea/acid, and the like.

As a general method for producing tabular grains, U.S. Patent No. 4t31
No. 12λ, No. 4t4t3, No. 520, No. 41/
4t370, same number 3 wata 2/j, same number 3 aiio
4ter issue, 4t3/≦/66, 94Loo
4tt No. 3, same No. 414t/41306, same No. 41
This can be accomplished by appropriately combining the methods described in No. 3110/.

For example, in an atmosphere with a relatively high pAg value of pBr/7 or less, seed crystals containing 410% or more of tabular grains by weight are formed, and a silver and halogen solution is added while maintaining the pBr value at the same level or higher. It is obtained by growing seed crystals.

In the above grain growth process, it is desirable to add a silver and halogen solution to prevent the generation of new crystal nuclei.

The size of the tabular grains can be adjusted by controlling temperature, selection of the type and amount of solvent, silver salt used during grain growth, rate of addition of halide, etc.

The tabular grains that can be used in the present invention are manufactured by increasing the addition rate, amount, and concentration of silver salt solutions (e.g., AgNO3 aqueous solution) and halide solutions (e.g., KBr aqueous solution), which are added to accelerate grain growth. A method is preferably used.

Regarding these methods, for example, British Patent No. 1゜33j,
U.S. Pat. No. J,472, U.S. Pat. No. 00, U.S. Pat. -/4ko3.29, same! j-/6/12
You can refer to the description in No. 41 etc.

Silver halide solvents are useful to accelerate ripening.

For example, it is known to have an excess of halogen ions present in the reactor to promote ripening. It is therefore clear that ripening can be accelerated simply by introducing a halide salt solution into the reactor. Other ripening agents can also be used, and these ripening agents can be incorporated in their entirety into the dispersion medium in the reactor prior to addition of the silver and halide salts, and/or two or more ripening agents can be used. A rhodanide salt, a silver salt or a peptizer can also be added and introduced into the reactor. As a further variant, the ripening agent can also be introduced independently at the halide salt and silver salt addition stages.

As ripening agents other than halogen ions, ammonia or amine compounds, thiocyanate salts such as alkali metal thiocyanate salts, especially sodium and potassium thiocyanate salts, and ammonium thiocyanate salts can be used. The use of thiocyanate ripening agents is described in U.S. Pat.
4t<td', No. 639 and 3.3-0, 0g
The teaching can be found in No. 2. Also, U.S. Patent No. 3,271.7
No. 57, j, j74t, j, No. 2/, and No. 3,
737. It is also possible to use commonly used thioether ripening agents such as those described in No. J/3. Or Tokukai Akira!
It is also possible to use thione compounds as disclosed in No. 3-/Kota O♂ and JJ-/4-Ta No. 379.

The properties of silver halide grains can be controlled by allowing various compounds to be present during the silver halide precipitation formation process. Such compounds may be initially present in the reactor or may be added in accordance with conventional methods and/or along with the addition of two or more salts. U.S. Patent Interval 2,
4t4tl, No. 040, same, 6λ/, No./47, same J, 737.

3/3 issue, same! ,? 7.2.03j issue and Research Disclosure, volume /34, /2t year 4
Copper, iridium, as described in /34t1λ
The presence of compounds such as lead, bismuth, cadmium, zinc, (chalcogenic compounds such as sulfur, selenium and tellurium), gold and compounds of group II noble metals during the silver halide precipitation process results in the formation of silver halide. Characteristics can be controlled. Special public Akira! ? -/4t No. 10, Moisar et al., Journal of Photographic Science, Volume 2t, /ri 77, /day 27
As described on page 1, silver halide emulsions can undergo reduction sensitization of the interior of the grains during the precipitation formation process.

In the present invention, the following monodisperse hexagonal tabular grains can be used. The emulsion is a silver halide emulsion consisting of a dispersion medium and silver halide grains, in which 70% or more of the total projected area of the silver halide grains has a maximum area of 70% or more relative to the length of the side having the minimum length. The ratio of the lengths of the sides with length is
occupied by tabular silver halide grains having a hexagonal shape of 2 or less and having two parallel surfaces as outer surfaces, and K, a coefficient of variation of the grain size distribution of the hexagonal tabular silver halide grains; [The value obtained by dividing the variation (standard deviation) of particle size expressed by the circular diameter of the projected area by the average particle size] is monodispersity of 20% or less, and the aspect ratio is ! Above, the particle size is O9,
It is 2 μm or more.

The hexagonal tabular grains may have a composition of silver bromide, silver iodobromide, silver chlorobromide, or silver chloroiodobromide. When the natural ion is contained, the content thereof is θ to 30 molti, and the crystal structure may be uniform, the inside and outside may have different halogen compositions, or the crystal structure may be a layered structure. Further, it is preferable that the particles contain reduction-sensitized silver nuclei.

The silver halide grains can be produced by undergoing nucleation-Ostwald ripening and grain growth, but
For details, please visit Tokugan Akiotsu/-λ Tata/! ! Follow the instructions.

The tabular silver halide grains that can be used in the present invention may have a uniform halogen distribution or may have two or more phases having different halogen compositions.

For example, the silver iodobromide tabular grains used in the present invention may have a layered structure consisting of a plurality of phases each having a different iodide content. JP-A-61-//,? ,
Octopus No. 7, Tokukai Sho Jrl-//3.921, Tokukai Sho J
Tar? ? , No. 4133, Tokukai Sho! Tar/l? , No. 1, Tokukai Akira! Preferred examples of the halogen composition of tabular silver halide grains and the intragrain distribution of halogen are described in No. 9.3!0 and the like.

In the tabular grains used in the present invention, silver halides of different compositions may be bonded by epitaxial bonding, or compounds other than silver halide such as silver rhodan or lead oxide may be bonded. These emulsion grains are described in U.S. Pat. No. 9.353, British Patent No. 2.03/, 7 Octopus, U.S. Patent No. 9,319
．． Go, No. 2-, 4t, 39! , No. 4171, a, t
lj3. jO/ issue, same evening, 4t to j, <7J'7 issue, same J, tjt.

R6λ, same! , No. 152,067, Tokukai Sho! ? -/4
It is disclosed in No. 2!4IO, etc.

The tabular grains can be selected from those formed from (///) planes, (/θθ) planes, or a mixture of (///) planes and (/+170) planes.

In addition, the tabular silver halide grains that can be used in the button of the present invention are produced by depositing silver and halogen on the tabular grains in the presence of various additives while adjusting the pBr value and temperature at any stage during grain formation. By doing so, specific surfaces can be grown in the form of pits on the surface of the tabular grains to increase the surface area.

Typical additives that can be used to grow specific surfaces include the following.

Examples of additives that create pits formed by (2//) planes include compounds (1) to (Vl).

Examples of additives that create pits formed by (33/) planes include compounds (■) to (X).

It is also possible to grow singular surfaces consisting of (/θO) planes, (//Q) planes, (210) planes, (3co/) planes, etc. by selecting other additives.

Compound Example (I) (n) H3 (IV) (V) H2CH3 (M) (CH2) 3 0aH (■) (■) (K) h2 (X) Tabular silver halide grains that can be used in the present invention may be ordinary surface latent image type silver halide grains, or may be internal latent image type silver halide grains which mainly form a latent image inside. Also, the ratio of surface sensitivity to internal sensitivity is 0. j〜
Tabular grains with improved pressure properties of λ can also be preferably used. In order to develop internal sensitivity in tabular grains, there are two methods: chemical sensitization at a certain stage before grain formation, doping with electron-trapping metal ions, or creating lattice mismatches due to gaps in the halogen composition within the grains. A method is used that causes this to occur.

Chemical sensitization of tabular grains that can be used in the present invention is carried out by James (
T. H. James), The -1=O1J--Off'' Photographic Process, QL Macmillan Publishing Co., Ltd., 7977, (T. H. James).

The Theory of the Pho
tographicProcess, 4t the e
d, Macmillan, /ri77>47-7g
It can also be carried out using activated gelatin as described in Research Disclosure, Vol. 20, /74, /2θ0/; Research Disclosure, Vol. 734tj2,
U.S. Patent No. 4&2.34/3. Kota 7, 4
t4t4 issue, 3,772,03/issue, 3.1!7,
7// issue, same 3. ri0/, 7/, same, -6 Otsu, 0
pAgr~10, par~? and temperature 30~. roo
C can be carried out using sulfur, selenium, chiru, gold, platinum, )R radium, iridium, or a combination of multiple of these sensitizers. Chemical sensitization is optimally carried out in the presence of a gold compound and a thiocyanate compound and as described in US Pat. /! Sulfur-containing compounds described in No. 7,77/, same, 2≦3.0// and same <1,0j4t, 4tJ-7, or hypo, thiourea-based compounds, rhodanine-based compounds, etc. Performed in the presence of the compound. Chemical sensitization can also be carried out in the presence of chemical sensitization aids. Chemical sensitization aids used include compounds known to suppress capri and increase sensitivity during the chemical sensitization process, such as azaindene, azapyridazine, and azapyrimidine. Examples of chemical sensitizer modifiers include U.S. Pat.
/J/, 03? Same issue! , 4t//, issue 9/4, same 3. ! ! No. 41,752, Tokukai Sho! ! -/26! ,2/
, issue and the aforementioned Duffin, "Photographic Emulsion Chemistry J, /3/~
/4t page 3. In addition to or in place of chemical sensitization, US Pat. ? ♂Q, 24t? Reduction sensitization can be carried out, for example, using hydrogen, as described in U.S. Pat. //J with reducing agents such as stannous chloride, thiourea dioxide, polyamines, and/or low pAg (e.g. less than 5) and/or high pH (e.g. pAg) treatment. Reduction sensitization can be performed by Also, U.S. Patent No. 3. ri/7
, 4tr! No. and 3. Color sensitization can also be improved by the chemical sensitization method described in No. 44,4t74.

See you again! Tar/22ri♂/ya same! ter/2j9/<
The sensitization method using an oxidizing agent described in < can also be applied.

In the present invention, the thickness of the layer containing tabular silver halide grains is 0.3 to .theta..mu., especially 0.3 g. It is preferable that j~ri and θμ.

In conventional technology, in an emulsion layer containing grains with large grain diameters, it was necessary to make the coating layer thick in order to avoid the phenomenon that the emulsion grains themselves protrude from the coated layer. If you use particles,
Since the thickness of the tabular grains can be made very small, the coating layer can be thinned to further improve sharpness.

In the present invention, a silver halide emulsion layer containing tabular silver halide grains, which is located farthest from the support among the three color-sensitive layers, is surface and in at least seven silver halide emulsion layers of each of the other two color-sensitive layers near the surface and/or in the non-light-sensitive intermediate layer adjacent to the lowest sensitive layer of each of these color-sensitive layers /or contains internally covered silver halide grains. As a layer using silver halide grains whose surfaces and/or interiors are covered, a non-sensitive intermediate layer is preferable to a light-sensitive silver halide emulsion layer, since the density of unexposed areas during sensitization development is less likely to decrease. preferable.

When silver halide grains whose surfaces and/or interiors are covered are used in a light-sensitive silver halide emulsion layer, it is better to use them in a less sensitive silver halide emulsion layer so that they can be unexposed during sensitization development. It is preferable because it causes less decrease in the concentration of the liquid. Additionally, surface and/or internally fogged silver halide grains may be used in both the light-sensitive silver halide emulsion layer and the non-light-sensitive interlayer.

Silver halide grains whose surfaces and/or interiors are coated and which can be used in the present invention will be described below.

In the present invention, silver halide grains whose surfaces and/or interiors have been fogged (hereinafter referred to as "fogged silver halide grains") are particles that have fogged nuclei on their surfaces and/or interiors by chemical methods or light. Refers to silver halide grains prepared to be developable regardless of exposure.

Surface-fogged silver halide grains (surface-fogged silver halide grains) are produced during the formation of silver halide grains and/or
Alternatively, the silver halide grains can be prepared by fogging these silver halide grains by a chemical method or by light after grain formation.

The above-mentioned fogging step can be carried out by adding a reducing agent or gold salt under appropriate pH and pAg conditions, or by adding a low pAg
This can be carried out by a method of heating under a lower temperature, a method of providing uniform exposure, or the like. Chloride No. 1 is used as a reducing agent.
Tin, hydrazine-based compounds, ethanolamine, thiourea dioxide, etc. can be used.

The fogging step using these fogging substances is preferably carried out before the water washing step for the purpose of preventing fogging over time due to diffusion of the fogging substance into the photosensitive emulsion layer.

In addition, the internally fogged silver halide grains (internally fogged silver halide grains) form an outer shell (shell) on the surface of these grains with the above-mentioned surface fogged silver halide grains as the core. It can be prepared by Such internally fogged silver halide is described in detail in Japanese Patent Application Laid-Open No. 2003-200012/2/4tJ. The effect of these internally fogged silver halide grains on sensitization and development can be controlled by controlling their shell thickness.

Further, silver halide grains with internally fogged can also be formed by using the above-mentioned fogging method from the start of grain formation, forming a core with a fog, and then adding an unfogged shell. If necessary, it is also possible to cover everything from the inside to the surface.

These fogged silver halide grains include silver chloride, silver bromide,
It does not matter if it is silver chlorobromide, silver iodobromide, or silver chloroiodobromide, but if it is silver halide containing iodide, the iodide content is preferably less than j molti, and λ molti The following are more preferred.

Further, these fogged silver halide grains may have internal structures with different halogen compositions inside the grains.

'The average grain size of the fogged silver halide grains that can be used in the present invention is not particularly limited, but when these fogged silver halide grains are added to a light-sensitive silver halide emulsion layer or a non-light-sensitive intermediate layer. is preferably smaller than the average size of silver halide grains in the adjacent lowest sensitive layer. Specifically, it is preferably 0.jpm or less,
More preferably, K is 0.2 μm or less, and most preferably, K is 0.7 μm or less.

Further, there is no particular limitation on the grain shape of these fogged silver halide grains, and they may be regular grains or irregular grains. Although these fogged silver halide grains may be polydispersed, it is preferable that they be monodispersed.

Here, monodisperse silver halide emulsion (non-tabular grain) is
9 of the total amount or total number of silver halide grains contained therein! It is defined that the average particle diameter is within ±4 tO%, preferably within ±30% of the average particle diameter.

The amount of these fogged silver halide grains used can be arbitrarily changed depending on the degree required in the present invention, but
When used in a light-sensitive silver halide emulsion layer, the ratio of the amount of silver to the light-sensitive silver halide grains, or when used in a non-light-sensitive interlayer, the lowest window halogen adjacent to the non-light-sensitive interlayer. 0.0 for the ratio of silver amount to silver oxide particles!
~SO molti is preferred, 0.7 to 2j molti is even more preferred, and Q, j-20 molti is most preferred. In terms of fogging efficiency based on the amount of silver used, surface fogging type silver halide having a smaller average size (specifically, O02μ or less) has the highest fogging efficiency and is preferred.

Other photosensitive silver halide grains that can be used in the present invention include regular grains having regular crystal bodies such as cubes, octahedrons, and tetradecahedrons, and irregular grains such as spherical and potato-shaped grains. Examples include particles having a typical crystal shape. Further, as the silver halide for these grains, any one of silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide, and silver chloride may be used.

Preferred silver halides are silver iodobromide or silver iodochlorobromide containing up to 30 moles of silver iodide. Particularly preferable is Morchi 2! It is silver iodobromide containing silver iodide up to molti.

The grain size of the silver halide grains used here may be fine grains of 0.67 microns or less, large grains with a projected area diameter of up to 70 microns, monodisperse emulsions with a narrow distribution, or polydisperse emulsions with a wide distribution. An emulsion may also be used.

These silver halide grains used in the present invention are described in "Physics and Chemistry of Photography" by Grafkide, published by Paul%7Tel (
P, Glafkides, Chimie etPh
ysique Photographique P
aulMontel, /ri67), "Photographic Emulsion Chemistry" by Duffin, published by Focal Press (G, F, Duf
fin.

Photographic Emulsion Che
mistry(Focal Press, /9 d
& ), “Production and Coating of Photographic Emulsions” by Zelikman et al.
, Published by Focal Press (V, L, Zelikman
et al, Making and Coating
Photographic Emulsion.

It can be prepared using the method described in Focal Press, /ri a4t). That is,
Any of the acidic method, neutral method, ammonia method, etc. may be used, and the method for reacting the soluble complex salt and the soluble halogen salt may be any one-sided mixing method, simultaneous mixing method, or a combination thereof. It is also possible to use a method in which particles are formed in an excess of silver ions (so-called back-mixing method). As one form of the simultaneous mixing method, a method in which PAg in the liquid phase in which silver halide is produced can be kept constant, that is, the so-called Nilchondrold double jet method can also be used. According to this method, a silver halide emulsion having a regular crystal shape and a nearly uniform grain size can be obtained.

Two or more types of silver halide emulsions formed separately may be mixed and used.

The silver halide emulsion consisting of the regular grains described above can be obtained by controlling pAg and pH during grain formation. For more information, see Photographic Science and Engineering (Photographic Science and Engineering).
5science and Engineering) No. 6
roll,/! Ri~/ko! Page (/Riza 2); Journal of Photography Sciences (Journal
of Photographic Science),
Volume 72, 2412-2! /page (/ri≦9), U.S. Patent No. 3. T! Jr. 3ri No. 9 and British Patent No. 1. <173
, 7', No. 11.

Regarding monodispersed emulsions, please refer to JP-A-4T? -/40θ, same! /-39027, same 3l-t30ri No.2, same!
3-/37/33 issue, same j4t-4tl! Ko/No., same!
Q-wata 4t79, same jr-37tjj, same! /-
9ri? 3? No. 4T7-//3♂, U.S. Patent No. 3. Otsu! J, 3ri No. 9 and British Patent No. 1, 4t/
3, No. 74tJ', etc.

The crystal structure of these silver halide grains may be uniform, the inside and outside may have different halogen compositions, or they may have a layered structure.

These emulsion grains are described in British Patent No. 1.027, /4t
No. t, U.S. Patent No. j,! 0! , 0i No. 1, same q.

Da4t4t, /77 and special request show! ? -24t! It is disclosed in the Naburi issue, etc.

In the present invention, a non-photosensitive fine grain emulsion having no fog nuclei of θ, 4 μ or less, preferably O, μ or less, has improved shelf life,
It may be added to a silver halide emulsion layer, intermediate layer or protective layer for the purpose of effectively utilizing reflected light.

In the present invention, a monodisperse silver halide emulsion is formed using a photosensitive halogen emulsion layer adjacent to the photosensitive silver halide emulsion layer using the fogged silver halide grains or a non-photosensitive intermediate layer using the fogged silver halide grains. It is preferable to use it in the silveride emulsion layer in terms of graininess and gradation.

Furthermore, in the present invention, by using tabular silver halide grains and monodisperse non-tabular silver halide grains in the same and/or different emulsion layers, it is possible to improve sharpness and granularity at the same time. There is.

The use of a monodisperse silver halide emulsion in a silver halide photographic light-sensitive material to improve granularity is described in the above-mentioned Japanese Patent Publication No. 4T7-//316. Tokukai Show 3! -/4t, 2
3 pieces, same j7-/7 pieces 3! , same j wharf 24t1. t
It is described in O et al.

As mentioned above, all the photosensitive silver halide grains used in the present invention are usually those that have been subjected to physical ripening, chemical ripening, and spectral sensitization.

Additives used in such processes are listed in Research Disclosure A/7t4tJ and Research Disclosure A//
7/B, and the relevant parts are summarized in the table below.

Known photographic additives that can be used in the present invention are also described in one of the above research disclosures, and the relevant descriptions are shown in the table below.

/ Chemical sensitizers, page 23, page 1t, right column Sensitivity increasing agent Same as above Brightener, page 24 to 7 Anti-stinting agent, page 25, right column Page 120, left to right column
Dye image stabilizer - page 5 Hardener - page 6 6j/page left column 10
Binder page 2g Same as above // Plasticizer, lubricant page 22 6. tO Right Column Various color couplers can be used in the present invention, and specific examples thereof can be found in the Research Disclosure (RD) shop 77 mentioned above.
tj, ■-C, GK.

As a yellow coupler, for example, U.S. Patent No. 3.93
No. 3,507, same No. 9. θkoλ, Go No. 20, Same No. 3, 3
2, 0.2'1, same number, ri θ/.

7! λ, special public Akira! ? -70739, British Patent No. 7,
Preferred are those described in 4t2j, No. 020, No. 1, 4t74.7Jθ, and the like.

As magenta couplers, pyrazolone and pyrazoloazole compounds are preferred, and US Pat.
0. tjri issue, same issue Q,! ! / .

I97, European Patent No. 73. No. I3, U.S. Patent No. 3.
0go/, No. 4132, same No. J, 7.2j, 067
No., Research Disclosure A, 2Q 220 (
0-33362 in Japanese Patent Publication No. 0-33362, Research Disclosure AJ4t2Jθ (J'4 in June 2007), Japanese Patent Application Publication No. 6O-4t3, US Patent No. 0-33362, ! 00. Otsu 3θ issue, same issue! Particularly preferred are those described in No. 0, I4, etc.

Cyan couplers include phenolic and naphthol couplers, as described in US Pat.

062, core No. 2, same No. g, /4 Otsu, 39g No., same No. Q, 227.233, same No. '1.29 &, 20
No. 0, No. 2, 36, Takota No., No. λJO/.

No. 777, No. 2,772.162, No. 2゜? Rij
J2 No. Otsu, No. 3,772,002, No. J, 76
r, No. 307, No. 33, No. 0//, No. 4.
No. 327.773, West German Patent Application No. 3.3.29,72
No. 1, European Patent No. 1/.

JtjA, U.S. Patent No. j, 4t4t, 2nd Co., 333. Data issue, same issue, ¥it/,;! ? No. 41.4t27.7g7, European Patent No. 1j/,
Those described in No. 124A and the like are preferred.

Research Disclosure A/2≦4t, ?A colored coupler for correcting unnecessary absorption of coloring dyes?
Section ■-G of U.S. Pat. No. 1, I63.

Go No. 70, Special Publication Sho J2-394T/3, U.S. Patent No. Q
, oo<t, Takota, No. 4t, /3? , 2!
Preferred are those described in British Patent No. 1, No. 4,361.

Couplers whose colored dyes have appropriate diffusivity include U.S. Patent No. Q, 344,232 and British Patent No. 2.723.
．． No. 570, European Patent No. 1+G, No. R70, West German Patent (
Public) No. ? , 23'l, ! The one described in No.-33 is preferred.

A typical example of a polymerized dye-forming coupler is US Pat. No. 3,41! /, No. 120, <t, o♂θ, 2/
/ No. Q, j, No. 47.122, British Patent No. 2
．． 102.173 etc.

Couplers that release photographically useful residues upon coupling are also preferably used in the present invention. The DIR coupler releasing the development inhibitor is the aforementioned RD/7t4tj
, the patents described in Sections 4 and 2, JP-A-2-IjiI1
Same issue! 7-7! e239, same otsu θ-/141ko 4J
', U.S. Patent No. q.

24t? , No. 962 is preferred.

A coupler that releases a nucleating agent or a development accelerator imagewise during development is disclosed in British Patent No. 2. Ori7, 7410
No., No. 2, /J/, No. 171, Tokukai Sho! Tar/
, r7t3r issue, same! The one described in No. 770/qO is preferred.

Other couplers that can be used in the photosensitive material of the present invention include US Pat. No. 4t, I30. Competitive couplers such as those described in Il22 et al., U.S. Pat.

-♂J, 4t7.2, same No. 331, Jri No. 3,
Patent No. Q, 310.671, DIR redox compound releasing couplers described in JP-A No. 173. Examples include couplers that release a dye that exhibits an aftercolor after separation, as described in No. jO2A.

The coupler used in the present invention can be introduced into the light-sensitive material by various known dispersion methods.

An example of a high boiling point solvent used in the oil-in-water dispersion method is given in US Patent No. 2. J, No. 2.2.027, etc.

The steps and effects of latex dispersion methods and specific examples of latex for impregnation are described in U.S. Patent No. 9. /? Wow.

No. 333, West German Patent Application (OLS) No. 3, j4t/.

No. 22q and No. λ,,! Examples include r4t/ and 23θ.

Suitable supports that can be used in the present invention include, for example, the above-mentioned R
D, A/7 to 3/2/page, and wholesaler/77/l from <t7 page right column to g4t♂4! column.

The color photographic material according to the present invention has the above-mentioned RD,
A / 7g < t3 λt ~ λ page, and the same A//
It can be developed by the usual methods described in 43/left column to right column of 7/2.

The silver halide color photographic light-sensitive material of the present invention is generally subjected to a water washing and/or stabilization step after desilvering treatment such as fixing or bleach-fixing.

The amount of water used in the washing process depends on the characteristics of the photosensitive material (for example, depending on the materials used such as couplers), the application, the temperature of the washing water, the number of washing tanks (number of stages), the replenishment method such as countercurrent or forward flow, and various other conditions. Can be set over a wide range. Among these, the relationship between the number of flushing tanks and the amount of water in the multi-stage countercurrent method is described in the Journal on the Society on Motion Picture and Television Engineers (Jo).
Urnal of the 5ociety of
MotionPicture and Te1evi
sion Engineers) Volume ≦ Volume, P, Coq?
- Ko! You can obtain it by the method described in 3 (/rij! Year! Month issue).

According to the multi-stage countercurrent method described in the above-mentioned literature, the amount of water used for washing can be greatly reduced, but the increased residence time of water in the tank causes bacteria to propagate and the generated suspended matter to adhere to the photosensitive material. Problems such as this arise. In the processing of the color light-sensitive material of the present invention, as a solution to such problems, the method for reducing calcium and magnesium described in Japanese Patent Application No. 4/737632 can be used very effectively. In addition, chlorine-based disinfectants such as inteazolone compounds and thiabendazoles, chlorinated sodium isocyanurate, and other benzotriazoles described in JP-A No. 7-#, JT4T, No. 2, and other chlorine-based disinfectants such as benzotriazoles, etc. "Chemistry of Agents", "Microbial Sterilization, Disinfection, and Anti-Mold Technology" edited by Sanitation Technology Society,
It is also possible to use fungicides listed in the "Encyclopedia of Antibacterial and Antifungal Agents" edited by the Japan Antibacterial and Antifungal Society.

The pH of the washing water in the processing of the photosensitive material of the present invention is preferably tartaric. −? It is. The washing water temperature and washing time can be set in various ways depending on the characteristics of the photosensitive material, its use, etc., but in general, a range of 20 seconds to 70 minutes for /r-4tr'c, preferably 5r-4to 0CClO2-j minutes is selected. be done.

Furthermore, the photosensitive material of the present invention can also be directly processed with a stabilizing solution instead of washing with water. In such a stabilization process, Japanese Patent Application Laid-Open No. 7-T! "!', No. 13, j7-
/4t739,! Day! r4t3'A3, 6O-2
2034tj issue, tO-7!31r3.2, Otsu 0-2
397?9, 60-ko3ri7tata, g/-4tO!
All known methods described in No. '/-, No. 4/-//♂2-9, etc. can be used. In particular, /-hydroxyethylidene-/, /-diphosphonic acid! A stabilizing bath containing -chlorocomethyl-q-inthiacylyly/-3-one, a bismuth compound, an ammonium compound, etc. is preferably used.

Further, following the water washing treatment, a further stabilization treatment may be carried out; an example of this is a stabilizing bath containing formalin and a surfactant, which is used as the final bath for photographic use 2-photosensitive materials. Can be done.

(Examples) The present invention will be explained in detail below using Examples, but the present invention is not limited thereto.

Example: Multilayer color reversal photographic material sample 10/ was prepared by coating each layer having the composition shown below on a triacetate support. In sample /θ/, the blue-sensitive layers (1st! layer, 76th layer, and 77th layer) are the color-sensitive layers furthest from the support. The ninth layer is the red-sensitive layer, and the second layer is the lowest-sensitive layer of the green-sensitive layer. On the other hand, the third and second layers are non-photosensitive intermediate layers adjacent to the respective lowest sensitive layers.

Sample 102 is /-2? the law of nature/! ! Emulsions B and A containing monodispersed tabular silver halide grains prepared by the method described in 1) were used in the first layer and the 77th layer, respectively. Sample 1
For sample 03, silver halide grains were used to cover only the third layer for sample /θλ, and for sample /o<t, silver halide grains were used for cover only for the first layer for sample 10.2. . Samples 10j to //3 used silver halide grains with roughened surfaces or insides in the light-sensitive silver halide emulsion layers of both the red-sensitive layer and the green-sensitive layer and/or the adjacent non-sensitive intermediate layer. be.

Sample 10/~/θq is a comparative example, sample 10j~//
3 is an example of the present invention.

Sample 10/ 1st layer: Antihalation layer black colloidal silver 0. ．． 2jg/m2 UV absorber U-/θ, /g/m2 UV absorber
U-20,/g/m2 High boiling point organic solvent 0il-/gelatin/g/m2
λth layer: Intermediate layer -/Cpd D /θmg/m2 High boiling point organic solvent 0il-j Q0mg/m2 Gelatin
0.1. tg/m2 3rd layer: Intermediate layer - cogelatin 0.4 tg/m2 Q-layer: 1st red-sensitive emulsion layer Silver iodobromide emulsion spectrally sensitized with sensitizing dyes S-/ and S-,2 (average Silver content 0.4 tg/m2 Coupler C-/0.2 ilm2C-2
0, Org/m2 High boiling point organic solvent 0il-/θ, / cc/m
2 gelatin 0. rg/m2 No.
Layer: 1st green-sensitive emulsion layer Silver iodobromide emulsion spectrally sensitized with sensitizing dyes S-/ and S-2 (average grain size θ, 3 μm, AgI content 9 tilt-dispersed cubic emulsion) Silver amount Q, 41ilm2 Coupler C-10, 2ilm2 Coupler C-30, 2ilm2 C-20, Ojg/m2 High boiling point organic solvent 0il-/ 0. /cc/m2 Gelatin 0. J'g/m2 Second layer: Third red-sensitive emulsion layer Silver iodobromide emulsion spectrally sensitized with sensitizing dyes S-7 and S-1 (AgI content 2 tilt dispersed cubes with average grain size θ0 gμm) Silver amount 0.4tg/m2 Coupler C-J θ, 7g/m2 Gelatin /, /g/m2 2nd layer: Intermediate layer-3 Dye D-10,02ilm2 Gelatin 0.4 g/m 2nd!
Layer: intermediate layer compound CpdA o, 2ilm2 gelatin /, 0ilm2 9th layer; 1st
Green-sensitive emulsion layer A silver iodobromide emulsion spectrally sensitized with sensitizing dyes S-3 and S-<t (average grain size 0.μmAgI content! mole-monodisperse cubic and average grain size θ, /μmAgI /:/mixture of monodisperse cubes with content j morti) Silver content 0.6ilm2 Coupler C-<t o, 3g7m2 Compound CpdB O,03ilm2 Gelatin
θ, jg/m2 1st O layer: 1st silver emulsion (AgI content 5 tilt dispersed cubes with average grain size o.qμm) Silver content 0.4tg/m2 Coupler C-<t 0.3ilm2 Compound CpdB O. 03ilm2 gelatin
0.6ilm2 1st/layer: 3rd green-sensitive emulsion layer Silver iodobromide emulsion containing sensitizing dyes S-s and S-<t (monodisperse cubic with average grain size O1 and μmAg1 content λ morch) Silver amount 0. jg/m2 Coupler C-i, t O, d'g/m2
Compound CpdB O, OJ'g/m2 Gelatin /, Og/m2 1st co-layer:
Intermediate layer-j Dye D-x O, Org/m2 Gelatin O00g/m2 13th layer: Yellow filter layer Yellow colloidal silver 0. /g/m2 compound
CpdA O, θ/g/m2 Gelatin
/, 1g7m2 74th layer: middle layer - gelatin 0.4tg/m2 1st!
Layer: First blue-sensitive emulsion layer Silver iodobromide emulsion containing sensitizing dyes S-s and S-≦ (
A monodispersed cubic emulsion with an average grain size of O0-μm and an AgI content of 3 molti and an average grain size of 0. /μmAgI content 3 molar content 3 public ru ♂g/m2 First layer: Second sensitive emulsion layer Silver iodobromide emulsion containing sensitizing dyes S-r and S-
Same emulsion as the third green sensitive layer) (average grain size θ, 4tμm, Ag
I content comolti cubic content 2 dispersion) Silver content Q, g/m2 Coupler C-j O, Jg/m2 C-4
0,'3g/m2 Gelatin 0.9g7m2 No. 17
Layer: j1r emulsion layer silver iodobromide emulsion containing sensitizing dyes S-z and S-j (
Same emulsion as the third green-sensitive layer) (average grain size 0, lpm, AgI
Content (Content: 2 tilt parallelepiped monodispersed emulsion) Silver content θ, 4tg/m2 Coupler C-/ho, 2g/m2
Gelatin /, 2g/m2 1st/layer: 1st protective layer Ultraviolet absorber U - / 0.01tg/m2 Ultraviolet absorber U-j 0.03g7m2' [J-
<t o, 0gg/m2U-r θ, OJ
rg/m2 U-to θ, Ojg/mZ Compound CpdCO,tg/m2 Dye D-3θ, 0! g/m2 Ze2tin 0.7 g/m2 First layer: Second protective layer Fine grain silver iodobromide emulsion (average grain size 0.θ?μmAgI content 1 mol%) Silver amount θ, /g/m2 Polymethyl Methacrylate particles (average particle size/.

jμ) 0.1g7m2 Copolymer of 4t:j of methyl methacrylate and acrylic acid (average particle size/,!μ) (7,/g/m2 Silicone oil 0.03g/m2 Fluorine-containing surfactant W-/ jmg/m2 gelatin
In addition to the above composition, a gelatin hardener H-/ and a surfactant were added to each O3♂g/rn2 layer.

Examples/Structures of compounds used in λ -a U4Mc+(t) IJ-<t U-J- U-Oil / diptyl phthalate O112 tricresyl phosphate pdA pdB ptic H D-/ D-koH-/ CH2=C) LSO2CH2CONf (CH2CH2=
CH-802CH2CONHCH2W-/Samples 10/~//3 were wedge-exposed with a light source at roo 0 and noe for MTF measurement.
The samples exposed through the turn were subjected to the following processing.

The treatment steps and treatment liquid used here are as follows.

Processing process Process time temperature First development 6 minutes 310C Wash with water 2 minutes Reversal - minutes Coloring current price per minute Adjustment 2 minutes bleached white in minutes Fixed Arrival Evening Water washing amount Stable for 7 minutes at room temperature drying The composition of the treatment liquid used is as follows.

No.-Developer water 200m
1 Sodium tetrapolyphosphate, 2 g Sodium sulfite - 0 g Hydroquinone monosulfonate 30 g Sodium carbonate (/hydrate) 30 g/-Phenyl q Methyl 9-Hydroxymethyl-3 Pyrazolidone - 2 g Potassium bromide 2.5 g Thiocyanate Potassium 7.2g Potassium iodide (
0.7 chloride solution) Add 2 ml water
/θθ, Oml (pH 10, i) Inverted liquid water 700m
1 nitro・N −N −N −)rimethyleneoschinic acid・Na salt 3g stannous chloride (dihydric acid) /gp-aminophenol O・7g sodium hydroxide
♂g glacial acetic acid
/rmJl Add water 10θOm
1 color developer water 7θO
ml sodium tetrapolyphosphate, 2g sodium sulfite, 7g sodium triphosphate (/cohydrate), 36g potassium bromide, 7g potassium iodide (
0.7% solution) Oml sodium hydroxide
3g citradi/acid
/,! gN・Ethyl-N-(β-methanesulfonamidoethyl)-3・Methyl-q-aminoaniline・Sulfur salt 11g Ethylenediamine 3g Add water
7000m1 Adjustment liquid water 700m
! Sodium sulfite 72g ethylene diamino, sodium tetraacetate (dihydrate) /g Thioglycerin o, <t ml Glacial acetic acid 3mJl Add water
10100O bleach solution water 10
0g ethylenediami/sodium tetraacetate (dihydrate) 2.0g ethylenediami/iron(II) tetraacetate ammonium (dihydrate)/coθ,og potassium bromide 100.0g Add water
10100O fixer water ♂θOm
l Ammonium thiosulfate 2090g Sodium sulfite! , Og Sodium Bisulfite! , θg water added
10100t) Stabilizer water 200m
1 Formalin (37% by weight) r, Oml
Fuji Drywell z, add o ml water and boil to 10100O.
Sample 10/wedge exposed by a light source at oo 0
A sensitization process was carried out in which the development time of the first development was extended to 2 minutes.

After processing, the cyan, magenta, and yellow images formed on these samples were measured by regular sensitometry for the wedge-exposed samples, and microdensitometry for the samples exposed through the setan for MTF measurement. The MTF value was determined.

Table 3 shows the yellow image at a frequency of 30 lines m/m,
The MTF values of magenta and cyan images are shown. Table 9 also shows the first development time of 6 minutes and 2 minutes (sensitized development).
The relative sensitivities of the six layers and the density of the unexposed areas are shown.

As shown in Table 3, in contrast to sample 10/ which does not use tabular silver halide grains in the 1st layer and 77th layer, sample θco~//3 which uses tabular grains is Freshness has been improved. In addition, in samples 703 to //3, the sharpness of the color image shown by the color-sensitive layer using silver halide grains in the emulsion layer and/or the adjacent non-light-sensitive intermediate layer was improved, but this was due to the use of fogged halogen grains. This is due to an increase in the edge effect due to silver oxide particles. On the other hand, as can be seen from Table 9, in sample 102, only the yellow image was sensitized during sensitization development compared to sample 10/, and the sensitization was not balanced with the magenta and cyan images. In addition, samples 103 and 104t, in which silver halide grains were used to cover only one adjacent intermediate layer of the red-sensitive layer or the green-sensitive layer, had an increased magenta image (sample 103) and cyan image (sample 10<1), respectively. The color balance is poor and the color balance is poor. However, the sample of the present invention/Q! In ~//3, the magnitude of sensitization of each house is increased compared to Comparative Example Sample 10/, and Comparative Example Sample 7
For 02 to io<t, the color balance during sensitization development is improved. As described above, it can be said that only the samples of the present invention are excellent in terms of sharpness, increased sensitivity during sensitization development, and good color balance.

Table 3 Example-2 For sample 10/, tabular silver halide emulsions C and F of Table 1 were used in the 76th layer and 72nd layer as shown in Table 6 to prepare sample 20/ and sample 204t. Created. Sample 20
/ and sample θ9, as shown in Table 1, sample 10
Samples 0, λθ3.20j, and θg were prepared using the surface fogging emulsions used in Examples 3 to 107. Samples 10/1.2θ/ and θ9 are comparative examples, and samples 02, λθJ, 20j, and λθt are examples of the present invention.

These samples 20/ to 20≦ and sample 10/ were subjected to wedge exposure and exposure for MTF measurement, and were subjected to the treatments described in Examples. For the wedge-exposed sample, sensitization development was also performed in which the development time of the first development was set to 2 minutes. Table 3 and Table 7 each show 30 lines/m.
MTF values and sensitometric results at frequencies of m are shown.

As can be seen from Tables 4 and 7, samples 203 and Ko0da, which are examples of the present invention, are different from the corresponding comparative samples /θ/ and 202, which are also examples of the present invention. Sample 206 and θg are the corresponding comparative example samples/θ
/ and λQ4t, the sharpness and the magnitude and balance of 6-image sensitization during sensitization development are improved.

Claims (1)

[Claims] It has blue-sensitive, green-sensitive, and red-sensitive silver halide emulsion layers composed of a plurality of silver halide emulsion layers having the same color sensitivity and different sensitivities on a support, and a non-light-sensitive intermediate layer. , and at least 50% of the total projected area of the silver halide grains contained in at least one color-sensitive layer located farthest from the support have a thickness of 0.5 μm or less and a diameter of 0.5 μm.
occupied by tabular silver halide grains with an average aspect ratio of 3:1 or more, and in at least one silver halide emulsion layer of the other two color-sensitive layers and/or in these other two color-sensitive layers. A silver halide color reversal photographic method characterized by containing silver halide grains whose surfaces and/or interiors are covered in a non-light-sensitive intermediate layer adjacent to each lowest-sensitive layer among two color-sensitive layers. material.