JPH0378740A - Silver halide color reversal photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain satisfactory color reproducibility by incorporating silver chlorobromoiodide particles contg. silver chloride chiefly in the surfaces of the particles into an emulsion layer and incomporating an emulsion contg. surface-fogged or internally fogged silver halide particles into the emulsion layer or a nonphotosensitive layer. CONSTITUTION:A silver chlorobromoiodide emulsion (A) contg. silver chloride chiefly in the surfaces of the particles is incorporated into at least one silver halide emulsion layer and an emulsion (fogged emulsion) (B) contg. surface- fogged or internally fogged silver halide particles into the emulsion layer or a nonphotosensitive layer. The emulsion A, B may be incorporated into any color-sensitive layer but are preferably incorporated into a green- or red-sensitive layer. The emulsion A may be incorporated into plural color-sensitive layer having different color sensitivities or the same color sensitivity. A photographic sensitive material having an enhanced interimage effect, that is, improved color reproducibility, especially saturation is obtd.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a silver halide color reversal photographic light-sensitive material exhibiting good color reproducibility.

(Prior Art) Color reversal photographic materials usually have a plurality of silver halide emulsion layers having different color sensitivities, such as a red-sensitive layer, a green-sensitive layer, and a blue-sensitive layer, on a support.

These color reversal photographic light-sensitive materials imagewise exposed for multicolor subjects are first subjected to black and white silver development in a first development step, and then undergo a chemical or optical fogging step to remove residual halogenation in a second development step. The silver is developed in color to form cyan, magenta, yellow, etc. statues. By the way, the dye image formed in each color-sensitive layer during normal multicolor exposure is different from the color image formed during monochrome exposure, and in the case of color reversal photographic materials, this difference is mainly due to the different sensitivity in the first development step. It occurs due to the movement of development inhibiting substances such as iodide ions between emulsion layers having color properties. The difference in color image between polychromatic exposure and monochromatic light produced by such development is described by Hudson and Horton, Journal of the Optical Society of America, Vol. 42, No. 9, 663.
As described on page 669 (published in 1976), it is called an inter-image effect and is known to be useful for improving sharpness and color reproducibility.

(Problems to be Solved by the Invention) On the other hand, in JP-A-51-128528, an emulsion having a surface covered with silver halide grains is introduced into a light-sensitive silver halide emulsion layer. A method of increasing the inter-image effects experienced by emulsion layers is disclosed. However, the above-mentioned invention does not describe the properties of the more preferable light-sensitive silver halide emulsion when the fogged silver halide emulsion is used to enhance the inter-image effect; However, there is still no sufficient means for improving color reproducibility and color reproducibility, and a solution to this problem has been desired.

Also, Re5earch Disclosure 13
553 (1975), as a preferred way to apply a multilayer effect using iodine ions in a reversal photosensitive material, AgBrI, Ag(1!I and A g
An emulsion containing silver iodide such as B r C (l I) is included, and a hydrophilic colloid is included in addition to normal emulsion grains as a layer that receives at least one interlayer effect, and a surface fogging emulsion is included. However, the technical report mentioned above only describes the characteristics of a light-sensitive silver halide emulsion that is more preferable for enhancing the interimage effect using a fogging emulsion. 3-4 It is still insufficient as a means to achieve good color reproducibility even in a short development time (standard 75 seconds), especially in the first development of color reversal paper. Understood.

The multilayer effect of color reversal photosensitive materials is substantially determined by the first development, and in systems with short processing times such as color reversal paper, sufficient multilayer effects cannot be obtained unless the emulsion is carefully designed. Our research found that no.

Therefore, an object of the present invention is to provide a silver halide color reversal photographic material that provides good color reproducibility.

(1! Means for Solving Problem I) The above object of the present invention is to provide a silver halide color reversal photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer on a support. The layer mainly contains silver chlorobromoiodide grains containing silver chloride on the surface of the grain, and the at least one emulsion layer or non-photosensitive layer is covered with the surface or inside of the silver halide grain. A silver halide color reversal photographic light-sensitive material characterized in that it contains an emulsion, and the silver chlorobromoiodide grains containing silver chloride mainly on the surface of the grains have a silver iodide content of 1 to 10 moff%. and the content of silver chloride between O and 50 IIlOfA% of the total silver amount from the center of the grain is x (mo1%), and the content of silver chloride between 0 and 50 mog% of the total silver amount from the grain surface The content rate of y (mo
1%), and the content of silver chloride on the grain surface as determined by Content ratio [(AgCl content on the outside)/(A on the inside)
g (content rate of 4)] as y/x, y/x>10+y
≧10. z≧10. (Achieved by the silver halide color reversal photographic material described in (1) above, where 0≦x<l.

The present invention will be explained in detail below.

The color reversal photographic light-sensitive material of the present invention usually has emulsion layers of different color sensitivities, such as a red-sensitive layer, a green-sensitive layer and a blue-sensitive layer, on a support. Further, these color-sensitive layers are usually composed of a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities.

At least one silver halide emulsion layer of the color reversal photographic light-sensitive material of the present invention contains a silver chlorobromoiodide emulsion (hereinafter referred to as surface Ca emulsion) containing silver chloride mainly on the surface of the grains, and the above-mentioned At least one emulsion layer or non-light-sensitive layer contains an emulsion in which the surfaces or interiors of silver halide grains are fogged (hereinafter referred to as a fogged emulsion).

The surface CQ emulsion and fogging emulsion used in the present invention are:
Although it may be contained in any color-sensitive layer, it is preferably contained in the green-sensitive layer or the red-sensitive layer. In addition, the surface CI2 emulsion is
It is also possible to apply several different or the same color-sensitive layers. The present invention may be applied to silver halide emulsion layers of any sensitivity among the same color-sensitive layers, but it is preferably applied to silver halide emulsion layers of higher sensitivity.

The surface CQ emulsion that can be used in the present invention will be explained below. In the present invention, the surface CU emulsion refers to the following.

In other words, in a silver halide grain made of silver chlorobromoiodide, "J containing mainly silver chloride on the surface of the grain" means: If J contains silver chloride mainly on the surface of the grain, then Ag in the three regions x, y, and z
A "surface CQ emulsion" is defined by the CQ content and the combination of these ratios as follows.

1. Silver chlorobromoiodide containing silver chloride mainly on the surface of the grains has a silver iodide content of 1 to 10 mol%, and y/x>2. Refers to something that satisfies all of y≧1 mou% and Z≧1 moβ%.

7 8-2, preferably the silver iodide content is 1 to 10 moβ%, and y/x>10. y≧10moff%
, 2≧mo11%, and y/x)100.
V≧25mo1%, 2≧50mofi% (O≦X<(
If1oQ'l=5 all τ and 19 are also false.

4. Most preferably silver iodide content is 2 to 8 mol%
and y/X −) 00 (In other words,
1%.

The silver chloride content on the grain surface is determined by measuring the silver halide grains by XPS (X-ray Photoelectro
It is the average silver chloride content in the surface area of silver halide grains obtained by nS spectroscopy) analysis.

This content analysis can be performed, for example, by exciting the core electrons in the 3d and 2P orbits of Ag in the silver halide with soft X-rays characteristic of Ag, Mg, etc., and analyzing the binding energy. can.

Next, the silver halide grains used in the present invention whose surfaces or interiors are covered will be explained.

In the present invention, silver halide grains whose surfaces and/or interiors are fogged are those prepared by chemical methods or light so that they have fogging nuclei on their surfaces and/or interiors and are developable regardless of exposure. Refers to silver halide grains.

Surface-fogged silver halide grains (surface-fogged silver halide grains) are produced by fogging these silver halide grains by chemical methods or light during and/or after grain formation. It can be prepared by

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 at a lower temperature, or by a method of providing a negative exposure.

As the reducing agent, stannous chloride, hydrazine compounds, ethanolamine, thiourea dioxide, etc. can be used.

The fogging step using these fogging substances is preferably performed 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 In this way, the internal fogging type silver halide was disclosed in Japanese Patent Application Laid-open No. 59.
It is described in detail in No.-214,852. The effect of these internally fogged silver halide grains on sensitization development can be controlled by controlling their shell thickness.

Furthermore, silver halide grains with a fogged interior can be formed either from the start of grain formation or by forming a fogged core using the fogging method described above 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 may be silver chlorobromide, silver iodobromide, or silver chloroiodobromide, but if it is silver halide containing iodide, the iodide content is preferably 5 mol% or less, and 2 More preferably, it is less than mol%.

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 used in the present invention is not particularly limited, but when added to a light-sensitive silver halide emulsion layer or a non-light-sensitive layer to which these fogged silver halide grains are added, adjacent It is preferably smaller than the average size of silver halide grains in the lowest sensitive layer. Specifically, it is preferably 0.5p or less, and 0.2μs
It is more preferable that it is less than or equal to 0.1 μm.
The following is most preferable.

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.

The amount of these fogged silver halide grains to be used can be arbitrarily changed depending on the degree required in the present invention, but the amount of the photosensitive silver halide grains contained in all layers of the color reversal light-sensitive material of the present invention is When expressed as a percentage of the total amount,
0.05-50 mol% is preferable, and 0.1-25 mol% is more preferable. When viewed from the viewpoint of fogging efficiency per amount of silver used, surface fogging type silver halide having a smaller average size (specifically, 0.2 μm or less) has the highest fogging efficiency and is preferred.

The colloidal silver used in the present invention may be yellow, brown, blue, black, etc., and the layer containing colloidal silver is not particularly limited, and any one of the emulsion layer and the non-photosensitive layer may be used. The layer can be selected as appropriate. Preferably, it is contained in the emulsion layer containing the surface C2 emulsion. Further, when it is contained in a non-photosensitive layer, it is preferably contained in a layer adjacent to the emulsion layer containing the emulsion.

Moreover, in order to have the function of a filter, it is preferable to use yellow colloidal silver in the lower layer of the blue-sensitive layer. The amount of colloidal silver added is preferably 0.0001 to 0.4
g/i, more preferably 0.0003 to 0.3 g/i.

The preparation of various types of colloidal silver is described in the literature, for example by Wile
Published by Y & 5ons, New York, 1933,
Co11oidal Element by Weiser
s (yellow colloidal silver by Carey Lea's dextrin reduction method) or as described in DE 1096193 (brown and black colloidal silver) or US Pat. No. 26886 x (blue colloidal silver) .

Note that the non-photosensitive layer as used in the present invention means an intermediate layer, a protective layer, and an antihalation layer that do not contain a photosensitive emulsion.

The silver halide grains of the present invention may be so-called regular grains having regular crystal bodies such as cubes, octahedrons, and dodecahedrons, or may have irregular crystal shapes such as tabular or spherical shapes. , particles with crystal defects such as twin planes, or a composite thereof, but regular particles are more preferable. Also, mixtures of various crystal forms may be used.

The grain size of the silver halide may be fine grains of about 0.1 micron or less, large grains with a projected area diameter of about 10 microns, or a polydisperse emulsion with a wide distribution. Monodispersed emulsions are preferred in terms of improving graininess.

A typical single emulsion is one in which at least 95% by weight of the emulsion is within ±40% of the average grain diameter. Emulsions having an average grain diameter of 0.05 to 2 microns and having at least 95% by weight or at least 95% (by number of grains) of silver halide grains within a range of ±20% of the average grain diameter are used in the present invention. can. Methods for producing such emulsions are described in U.S. Pat. Nos. 3,574,628 and 3.
, 655,394 and British Patent No. 1.413,748.
listed in the number. Also, JP-A-48-8600,
No. 51-39027, No. 51-83097, No. 53
-137133, 54-48521, 54-9
No. 9419, No. 58-37635, No. 58-4993
Monodispersed emulsions such as those described in No. 8 can also be preferably used in the present invention.

The silver halide photographic emulsion that can be used in the present invention can be produced by a known method, such as Research Disclosure,
Volume 176, Nα17643 (December 1978), 22
~Page 23, ``1. Emulsion production
187, &18716 (November 1979), 64
The method described on page 8 can be followed.

The photographic emulsion used in the present invention is described in "Physics and Chemistry of Photography" by Grafkide, published by Paul Montell (P.

Glafkides, Chimie at Phys
iquePhotographique Paul M
ontel, 1967), "Photographic Emulsion Chemistry" by Duffin, published by Focal Press (G.F. Duffin,
Photographic Emulsion Chem
istry (Focal Press, 1966)
, Zelikman et al., “Production and coating of photographic emulsions”, published by Focal Press (V, L. Zelikman et al.
al, Making and Coating Ph
otographic Emulsion, Foca
1Press, 1964). That is, any of the acidic method, neutral method, ammonia method, etc. may be used, and the method for reacting the soluble silver salt with the soluble halogen salt may be any one-sided mixing method, simultaneous mixing method, or a combination thereof. good. A method in which particles are formed in an excess of silver ions (so-called back-mixing method) 15-6- can also be used. 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, a so-called Chondrald 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.

Also, known silver halide emulsions (e.g. ammonia, rhodalin potassium or U.S. Pat. No. 3,271,157,
JP-A-51-12360, JP-A-53-82408, JP-A-53-144319, JP-A-54-1007
Physical ripening can also be carried out in the presence of thioethers and thione compounds (described in No. 17 or JP-A-54-155828).

The above-mentioned silver halide emulsion is composed of PAg and pH during grain formation.
obtained by controlling the For more information, see Photographic Science and Engineering.
dE engineering) Volume 6, 159-165
Page (1962); Journal of Photographic Science
graphic 5science), vol. 12, 242~
251 pages (1964), U.S. Patent No. 3,655,394
and British Patent No. 1,413,748.

Further, tabular grains having an aspect ratio of 5 or more can also be used in the present invention. Tabular grains are described in Cutoff, Photographic Science and Engineering.
engineering), 1st
4, pp. 248-257 (1970); U.S. Patent No. 4
, 434,226, 4,414゜310, 4,
433,048, 4,439,520, and British Patent No. 2,112,157. When tabular grains are used, there are advantages such as increased covering power and increased color sensitization efficiency by sensitizing dyes, and the above-mentioned US Pat.
, 434, 226.

Chemical sensitization was performed by James (T.
), The Theory of Photographic Process, 4th edition, Macmillan Publishing, 1977, (T.

H. James, The Theory of th
e PhotographicProcess, 4t
h ed, Macmillan, 1977) 67
It can be carried out using activated gelatin as described in p.
U.S. Patent Nos. 2,642,361 and 3,297,44
No. 6, No. 3,772゜031, No. 3,857,711
No. 3,901,714, No. 4,266°018, and No. 3,904,415, and British Patent No.
．． pAg5-10 as described in No. 315,755
, pH 5-8 and temperature 30-80 DEG C. using sulfur, selenium, tellurium, gold, platinum, palladium, iridium or combinations of these sensitizers. Chemical sensitization is optimally carried out in the presence of a gold compound and a thiocyanate compound and as described in U.S. Patent No. 3,857,711.
No. 4,266.018 and No. 4,054,45
The reaction is carried out in the presence of a sulfur-containing compound described in No. 7 or a sulfur-containing compound such as hypo, a thiourea compound, or a rhodanine compound. Chemical sensitization can also be carried out in the presence of chemical sensitization aids. The chemical sensitization aid used is a compound known to suppress fog and increase sensitivity during the chemical sensitization process, such as azaindene, azapyridazine, and azapyrimidine. Examples of chemical sensitization aid modifiers are U.S. Pat. No. 2,131,038;
No. 11,914, No. 3, 554, 757, JP-A-58-126526, and the aforementioned "Photographic Emulsion Chemistry J+" by Duffin, pages 138-143.In addition to or in place of chemical sensitization, U.S. Patent No. 3,891
, 446 and 3,984,249, reduction sensitization can be performed, for example, using hydrogen, and U.S. Pat.
182 and 2,743,183 using reducing agents such as stannous chloride, thiourea dioxide, polyamines and ascorbic acid, or with low pA
g (e.g. less than 5) and/or high pH (e.g. less than 8
can be reduced sensitized by treatment (larger). Also, U.S. Patent Nos. 3,917,485 and 3,966
．． Color sensitization can also be improved by the chemical sensitization method described in No. 476.

The crystal structure may be one in which the inside and outside have different halogen compositions, or it may have a layered structure.

These emulsion grains are described in British Patent Nos. 1,027,146 and 19-20;
No. 7 and Japanese Patent Application No. 58-248469. For example, silver halide grains containing silver chloride in the grain surface phase can be used. Furthermore, silver halides having 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.
, 142,900, 4,459,353, British Patent No. 2.038,792, U.S. Patent No. 4,349,6
No. 22, No. 4,395゜478, No. 4,433,50
No. 1, No. 4,463,087, No. 3,656°962
No. 3,852,067, JP-A-59-16254
It is disclosed in No. 0, etc.

In the process of silver halide grain formation or physical ripening,
Cadmium salts, zinc salts, lead salts, thallium salts, iridium salts or complex salts thereof, rhodium salts or complex salts thereof, iron complex salts, etc. may be present.

In order to remove soluble silver salts from the emulsion before and after physical ripening, the Nudel water washing proculation sedimentation method or the ultrafiltration method is used.

Additives used in the manufacturing process of silver halide emulsions are Research Disclosure Nα17643 and Nα
18716, 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 the two Research Disclosures mentioned above, and the relevant descriptions are shown in the table below.

(Left below) 1-22 Additive type 1 Chemical sensitizer 2 Sensitivity enhancer 3 Spectral sensitizer Super sensitizer 4 Brightener 5 Antifogging agent and stabilizer 6 Light absorber, filter dye Ultraviolet absorber Anti-stin agent Dye image stabilizer Hardener Binder Plasticizer, lubricant Coating aid, Surface active agent 13 Static inhibitor RD 17643 23 pages 23-24 pages 24 pages 24-25 pages 25-26 pages 26 pages right column 25 Page 26 Page 26 Page 27 Page 26-27 Page 27 RD18716 Page 648 Right column Same as above Page 648 Right column - Page 649 Right column Page 649 Right column - Page 649 Right column - Page 650 Left column Page 650 Left - Right column Page 651 Left column Same as above, page 650 Right column Same as above Same as above As for preservatives, in addition to phenol, there are phenoxyethanols, meccins, and proxel.

Such as salicylic acid sodium salt can be added.

Various color couplers can be used in the present invention, specific examples of which can be found in the above-mentioned Research Disclosure (
RD) Nα17643, described in the patent described in ■-〇-G.

As a yellow coupler, for example, U.S. Patent No. 3.93
No. 3,501, No. 4,022,620, No. 4,
Preferred are those described in British Patent No. 326,024, British Patent No. 4,401,752, Japanese Patent Publication No. 58-10739, British Patent No. 1,425,020, British Patent No. 1,476.760, and the like.

As the magenta coupler, 5-pyrazolone and pyrazoloazole compounds are preferred, and U.S. Pat.
No. 0,619, No. 4,351,897, European Patent No. 73,636, US Patent No. 3,061,432, US Patent No. 3,725°067, Research Disclosure Nα24220 (June 1984) ), Japanese Patent Application Publication No. 1983-
No. 33552, Research Disclosure Nα24
230 (June 1984), Jikai 23-24-Sho 60-43659, U.S. Patent No. 4,500,630
Particularly preferred are those described in No. 4, 540.654, and the like. Furthermore, pyrazolone-based and pyrazoloazole-based magenta couplers can be used in combination, if necessary.

Cyan couplers include phenolic and naphthol couplers, and are described in U.S. Patent No. 4.052,2.
No. 12, No. 4,146,396, No. 4,228
, No. 233, No. 4,296,200, No. 2,369
, No. 929, No. 2,801゜171, No. 2,772
, No. 162, No. 2,895,826, No. 3, 7
No. 72,002, No. 3,758,308, No. 4,334゜011, No. 4,327,173, West German Patent Publication No. 3,329゜729, European Patent No. 121
, 365A, U.S. Patent No. 3.446.622, U.S. Pat. No. 4.33:3,999, U.S. Pat.
European Patent No. 4,427,767, European Patent No. 161,626
Those described in No. A etc. are preferred.

The colored coupler for correcting unnecessary absorption of coloring dyes is Research Disclosure Nα17643.
■-G section, U.S. Patent No. 4,163,670, Japanese Patent Publication No. 57-39413, U.S. Patent No. 4,004,929
No. 4.138,258, British Patent No. 1,14
6,368 is preferred.

Couplers whose coloring dyes have appropriate diffusivity include U.S. Patent No. 4,366.237 and British Patent No. 2,125.
Preference is given to those described in No. 570, European Patent No. 96,570, and German Patent Publication No. 3.234,533.

Typical examples of polymerized dye-forming couplers are described in U.S. Pat. No. 3,451. ．． No. 820, No. 4,080,214
No. 4, . No. 367.282, British Patent No. 2,10
It is described in No. 2,173, etc.

Couplers that release photographically useful residues upon coupling are also preferably used in the present invention. DIR couplers that release development inhibitors include the aforementioned RD 17643.
, Patents described in sections ■ to F, Japanese Patent Application Laid-Open No. 57-15194
No. 4, No. 57-154234, No. 60-184248
Preferred are those described in US Pat. No. 4,248,962.

Couplers that release a nucleating agent or a development accelerator imagewise during development include British Patent No. 2,097°140;
No. 2,131,188, JP 59-157638
No. 59-170840 is preferred.

25-26 Other couplers that can be used in the photosensitive material of the present invention include competitive couplers described in U.S. Pat. No. 4,130,427, U.S. Pat. No. 4,283.4'72,
Multi-equivalent couplers described in JP-A Nos. 4,338,393 and 4,310,618, etc., JP-A-60-185950
Examples thereof include DIR redox compound releasing couplers described in E.P. No. 173.302A and couplers that release dyes that recover color after separation as described in European Patent No. 173.302A.

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

Examples of high boiling point solvents used in the oil-in-water dispersion method are described in US Pat. No. 2,322,027 and the like.

The steps and effects of latex dispersion methods and specific examples of latex for impregnation are described in U.S. Pat. No. 4,199,363, West German Patent Application No. It is written in the number etc.

Further, the photosensitive material of the present invention includes U.S. Patent No. 3,379,52.
9 and 3,639,417, and Research Disclosure Nα18264 (197
Naphthohydroquinones which release development-inhibiting compounds described in June 1999) can be preferably used.

Suitable supports that can be used in the present invention include, for example, the above-mentioned R
D, page 28 of Nα17643 and Nα18716
It is described from the right column on page 647 to the left column on page 648.

The color developing solution used in the development of the light-sensitive material of the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine color developing agent as a main component. Aminophenol compounds are also useful as color developing agents, but p-phenylenediamine compounds are preferably used, representative examples of which include 3-methyl-4-amino-N, N-diethylaniline, 3- Methyl-4-amino-N-ethyl-N
-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-N
-β-methoxyethylaniline and their sulfates, hydrochlorides, and P-toluenesulfonates. Two or more of these compounds can be used in combination depending on the purpose.

7 28- The color developer contains pH buffering agents such as alkali metal carbonates, borates or phosphates, bromide salts, iodide salts,
Development inhibitors or antifoggants such as benzimidazoles, benzothiazoles or mercapto compounds are generally included. If necessary, hydroxylamine, diethylhydroxylamine, sulfite hydrazines, phenyl semicarbazides, triethanolamine, catechol sulfonic acids, triethylenediamine (1,4-diazabicyclo[2°2.2]octane), etc. Various preservatives, organic solvents such as ethylene glycol, diethylene glycol, development accelerators such as benzyl alcohol, polyethylene glycol, quaternary ammonium salts, amines, dye-forming couplers, fogging agents such as competing couplers sodium boron hydride, It may contain an auxiliary developing agent such as 1-phenyl-3-pyrazolidone, a viscosity imparting agent, and various chelating agents such as aminopolycarboxylic acid, aminopolyphosphonic acid, alkylsulfonic acid, and phosphonocarboxylic acid. .

Further, when performing reversal processing, black and white development is usually performed and then color development is performed. This black and white developer contains dihydroxybenzenes such as hydroquinone, 1-phenyl-3-
Known black and white developing agents such as 3-pyrazolidones such as pyrazolidone or aminophenols such as N-methyl-p-aminophenol can be used alone or in combination.

The pH of these color developing solutions and black and white developing solutions is generally 9 to 12.

After color development, the photographic emulsion layer is usually bleached.

The bleaching process may be carried out simultaneously with the fixing process (bleach-fixing process) or separately. Furthermore, in order to speed up the processing, a processing method may be used in which bleaching is followed by bleach-fixing. Furthermore, treatment with two consecutive bleach-fixing baths, fixing treatment before bleach-fixing treatment, or bleaching treatment after bleach-fixing treatment can be carried out as desired depending on the purpose. Examples of bleaching agents include iron (■) and cobalt (m).
, 9 30- Compounds of polyvalent metals such as chromium (■) and copper (II), peracids, quinones, nitro compounds, etc. are used.

Typical bleaching agents include ferricyanide; dichromate: organic complex salts of iron (m) or cobalt (III), such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, and 1,3-diaminoacetic acid. Aminopolycarboxylic acids such as propanetetraacetic acid, glycol ether diamine tetraacetic acid, or complex salts of citric acid, tartaric acid, malic acid, etc.; persulfates; bromates; permanganates; nitrobenzenes, etc. can be used. Among these, aminopolycarboxylic acid iron(III) complex salts and persulfates, including iron(m) complex salt of ethylenediaminetetraacetate, are preferable from the viewpoint of rapid processing and prevention of environmental pollution. Furthermore, aminopolycarboxylic acid iron(III) complexes are particularly useful in both bleach and bleach-fix solutions.

The pH of the bleach solution or bleach-fix solution using these aminopolycarboxylic acid iron (m) complex salts is usually 5.5 to 8,
For faster processing, it is also possible to process at lower pH.

A bleach accelerator may be used in the bleaching solution, bleach-fixing solution, and their prebaths, if necessary.

Examples of fixing agents include thiosulfates, thiocyanates, thioether compounds, thioureas, and large amounts of iodide salts, but thiosulfates are commonly used, with ammonium thiosulfate being the most widely used. Can be used for As the preservative for the bleach-fix solution, sulfites, bisulfites, or carbonyl bisulfite adducts are preferred.

The silver halide color photographic light-sensitive material of the present invention is generally subjected to water washing and/or safety steps after desilvering treatment.

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 washing tanks and the amount of water in the multistage countercurrent method is
Urnal of the 5ociety of M
tion Picture and T elevis
on Engineers Volume 64, P, 248-
It can be determined by the method described in 25331-2- (May 1955 issue).

The pH of the washing water used in processing the photosensitive material of the present invention is 4-9.
and preferably 5-8. The washing water temperature and washing time can also be set variously depending on the characteristics of the photosensitive material, its use, etc., but generally it is 20 seconds to 10 minutes at 15-45°C, preferably 20 minutes.
A range of 30 seconds to 5 minutes at 5-40°C is selected. Furthermore,
The photosensitive material of the present invention can also be directly processed with a stabilizing solution instead of washing with water.

In such stabilization treatment, JP-A-57-8゜5
No. 43, 5g-14,834, 60-220,345
All known methods described in this issue can be used.

Further, following the water washing treatment, a further stabilization treatment may be carried out, such as a stabilizing bath containing formalin and a surfactant, which is used as a final bath for color photosensitive materials for photography. .

Various chelating agents and antifungal agents can also be added to this stabilizing bath.

The overflow liquid from water washing and/or replenishment of the stabilizing liquid can be reused in other processes such as the desilvering process.

Various treatment liquids in the present invention are used at 10°C to 50°C. Normally, the standard temperature is 33°C to 38°C, but higher temperatures can be used to accelerate processing and shorten processing time, or lower temperatures can be used to improve image quality and stability of the processing solution. be able to.

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

(Preparation of emulsion) Silver iodide emulsion A was prepared as follows. First, solutions I to ■ were prepared as shown in Table 1.

Table 1 3 - One Word - Milk fton N (AgBrI) For the ■ solution, double the ■ solution and ■ solution while keeping PAg at 7.1 in the first and second stages as shown in Table 2. It was added by jet method. After addition, desalt by a known method, add Na2S2O3 and KAuCn, and heat at 70°C.
Chemical sensitization was carried out for 50 minutes.

AgBrI The temperature of the reactor was raised for emulsion A, and the
Particle formation was achieved by decreasing the addition rate in the steps. Details are shown in Table 2.

After the addition is complete, desalt in the same manner as Emulsion A to remove Na2S2O3 and K.
AuCQ4 was added and chemically sensitized at 70°C for 50 minutes.

Emulsions A and B have average grain sizes of 0.3 μs and 0.7 μs, respectively.
It was a cubic monodisperse emulsion of silver iodobromide containing 3.0 mol% of silver iodide.

2N (AgBr(II)) Next, various CN silver chlorobromoiodide emulsions containing 3.0 mol % of silver iodide were prepared as follows.

First, as shown in Table 3, apart from solution ■, solutions ■～■
prepared.

35-36- In the preparation of silver chlorobromoiodide emulsion C-N, PA was added to the I solution in the first, second and third stages as shown in Table 4.
While maintaining g at 7.1, liquids (1) and (2) to (2) were added by a double jet method.

Emulsions C, E, G, I, K and M were kept at the same temperature as Emulsion A (6
Emulsion F, H, J, L and N were prepared at the same temperature as Emulsion B (80°C).

After addition, desalt in the same manner as emulsions A and B to remove Na2
S, O, and KAuCfi were added and chemically sensitized at 70°C for 50 minutes.

The obtained emulsions C, E, G, I, K and M had an average grain size of 0.
．． 3tm, emulsions F, H, J, L and N were cubic monodispersed emulsions made of silver chlorobromoiodide containing 3.0 mol % of silver iodide with an average grain size of 0.7 μs.

The structure of the emulsion from A to N and the inside/outside of the grains.
The AgCQ content on the surface is summarized in a table and classified based on the above regulations, as shown in Table 5.

Furthermore, phenoxyethanol was added as a preservative to emulsion A-N at a ratio of 1.6 g/100 g AgNO3.

37-38-39- Next, color photographic materials Nα1 to Nα18 were prepared by multilayer coating with the compositions shown below on a paper support laminated on both sides with polyethylene. The silver halide emulsions contained in the third, fourth and seventh layers of these samples are as shown in Table 6. Note that the average grain size of emulsion SF is 0.06. It is a monodisperse silver iodobromide emulsion covered with a surface containing 1 moff% of silver iodide, and emulsion I
F has an average particle size of 0.08 mof, 1 mof1%
It is a monodisperse silver iodobromide emulsion with a capped interior containing silver iodide.

(Photosensitive layer composition) The components and coating amounts in g/rrF units are shown below.

Regarding silver halide, the coating amount is shown in terms of silver.

1st layer (gelatin layer) Gelatin...1.30 2nd layer (antihalation layer) Black colloid layer...0.10 Gelatin...0.70 3rd layer (low sensitivity red sensitivity layer) Red enhancement Silver iodobromide emulsion A spectrally sensitized with sensitive dyes (ExS-1, 2, 3) (silver iodide 3 mol%, average grain size 0.
3μ, size distribution 10%, cubic, uniform type)
...0.06 red sensitizing dye (
Silver iodobromide EMI spectrally sensitized with ExS-1, 2, 3)
(Silver iodide 5 mol%, average grain size 0.45 μ, size distribution 20%, flat plate (aspect ratio = 5))
...0.10 gelatin
...1.00 cyan coupler (ExC-
1) -0,14 cyan coupler (EXC-2
) -0,07 Antifading agent (Cpd-2,3
, 4,9 equivalents) 0.12 Coupler dispersion medium (CPd-5)...0.
03 coupler solvent (Solv-1,2,3) -0,
06 4th layer (high sensitivity red-sensitive layer) Silver iodobromide emulsion B spectrally sensitized with red sensitizing dyes (ExS-1, 2, 3) (silver iodide 3 mol%, average grain size 0.
7μ, size distribution 15%, cubic, uniform type)
...0.151 2 Gelatin ...1.00
Cyan coupler (ExC-1) -0,20 Cyan coupler (ExC-2) -0,10 Antifading agent (Cpd-2,3,4,9 equivalent) 0.15 Coupler dispersion medium (Cpd-5) ・・・0.
03 coupler solvent (Solv-1,2,3) -0,
10 5th layer (intermediate layer) Magenta colloid silver...0.02 Gelatin...1.00 Color mixing prevention agent (Cpd-6,7)...0.0
8 Color mixing inhibitor solvent (Solv-4,5) -0,1
6 polymer latex (Cpd-8)...0
．． 10 6th layer (low sensitivity green sensitive layer) Silver chloroiodobromide EM2 spectrally sensitized with green sensitizing dye (ExS-4) (silver chloride 1 mol%, silver iodide 2.5 mol%, average grain Size: 0.28μ, grain size distribution: 12%, cubic, core-normal type (core-shell)...Silver iodobromide EMS spectrally sensitized with 0.04 green sensitizing dye (ExS-4)
(Silver iodide 2.8 mol%, average grain size 0.45μ,
Size distribution 12%, flat plate (aspect ratio = 5))
...0.06 gelatin
...0.80 Magenta coupler (ExM -1) -0.10 Antifading agent (C
pd-9)...0.10 Stain inhibitor (Cpd-10)...0.01 Stain inhibitor (Cpd-11)...0.00
1 Stain inhibitor (Cpd-12)...
0.01 force puller dispersion medium (Cpd-5) ・
・・0.05 coupler solvent (Solv-4,6)
-0,15 7th layer (high sensitivity green sensitive layer) Silver iodobromide emulsion B spectrally sensitized with green sensitizing dye (ExS-4) (silver iodide 3.0 mol%, average grain size 0. 7μ
, particle size distribution 15%, cubic, uniformity type)
...0. lO gelatin
...0.80 magenta coupler (ExM-1) -0.10 antifading agent (Cp
d-9)...0.10 Stain inhibitor (C, pd-10)...0.01 Stain inhibitor (Cpd-11)...0.00
143- 44- Stin inhibitor (Cpd-12) Coupler dispersion medium (Cpd-5) Coupler solvent (Solv-4, 6) 8th layer (yellow filter layer) Yellow colloidal silver gelatin color mixing inhibitor (Cpd-7) Color mixing Inhibitor solvent (Solv-4, 5) Polymer latex (cpd-8) 9th layer (low sensitivity blue sensitive layer) Silver chloroiodobromide EM4 spectrally sensitized with blue sensitizing dye (ExS-5) <chloride 2 mol% silver, 2.5 mol% silver iodide,
Average grain size 0.35μ, grain size distribution 8%, cubic, core density type (core shell)...0.07 Silver iodobromide EM5 (iodine Silver bromide 2.5 mol%, average grain size 0.45 μ, grain size distribution 16%, tabular (aspect ratio = 6)) ... 0.10 gelatin
・・・ 0.50... 0.
05 0.20 1.00 0.06 0.15 0.10 ... 0.15 ... 0.01 Yellow coupler (ExY-1) Anti-stinting agent (Cpd-11) Anti-fading agent (Cpd-6 ) Coupler dispersion medium (Cpd-5) Coupler solvent (Solv-2) 10th layer (highly sensitive blue-sensitive layer) Silver iodobromide EM6 spectrally sensitized with blue sensitizing dye (ExS-5, 6) Silveride 2.5 mol%, average grain size 1
．． 2μ, grain size distribution 21%, flat plate (aspect ratio =
14) )...0.25 Gelatin...1.00 Yellow coupler (ExY-1) -0,40 Stain inhibitor (Cpd-11)...0.002
Antifading agent (Cpd-6)...0.
10 coupler dispersion medium (CPd-5)...
0.15 coupler solvent, (Solv-2)
-0,10 11th layer (ultraviolet absorption layer) Gelatin ultraviolet absorber (CPd -1, 3, 13) Color mixing prevention agent (
Cpd-6,, 14) ... 1.00 ... 1.50 ... 0.06 ... 0.20 ... 0.001 ... 0.10 ... 0.05 ・... 0.05 45- 46- Dispersion medium (Cpd-5) Ultraviolet absorber solvent (Solv-1, 2) -0,1
5 Irradiation prevention dye (Cpd-15, 16) ...0.02 Irradiation prevention dye (Cpd-17, 18) ...0.02 12th layer (protective layer) Fine particle silver chlorobromide (silver chloride 97 mol) %, average size 0.2
μ) ...0.07
Modified Poval...0.02 Gelatin...1.50 Gelatin hardener (H-1)...0.17 Furthermore, in each layer, Alkanol XC (D
upont) and sodium alkylbenzenesulfonate as a coating aid, succinate ester and M
Agefac F-120 (manufactured by Dainippon Ink Co., Ltd.) was used. (Cpd-19, 20, 21) was used as a stabilizer in the silver halide or colloidal silver containing layer. Table A below shows the compounds used in the examples.

47- Three film pieces were each made from these samples Nα1 to Nα18, and one film piece each was subjected to wedge exposure using a white light source, wedge exposure using a red light source, and wedge exposure using a green light source. The exposed samples were processed in the following steps.

[Processing process]

First development (black and white development) 38℃ Water washing 38℃ Reversal exposure 100 Lux or more Color development
38℃ Water washing 38℃ Bleach-fixing 38℃ Water washing 38℃ [Processing liquid composition] Millet nitrilo-N,N,N-trimethylenephosphonic acid, pentasodium salt Diethylenetriaminepentaacetic acid, pentasodium salt 1' 15 "1' 301 11 or more 2'15'45'2'OO'2'15" 0.6g 4.0g Potassium sulfite Potassium thiocyanate Potassium carbonate Hydroquinone monosulfonate Potassium salt Diethylene glycol 1-phenyl-4-hydroxyl-4 -Methyl-3-pyrazolidone Potassium bromide Potassium iodide Add water 30.0 g 1.2 g 35.0 g 25.0 g 15.0 g 2.0 g 0.5 g 5.0 IQ (pH 9,70 ) Benzyl alcohol diethylene glycol 3.6-cythyl 1,8-octanediol nitrilo-N,N,N-trimethylenephosphonic acid pentasodium salt 15.0 12.0d 0.2g 0. 5g 49- 50- Diethylenetriaminepentaacetic acid pentasodium salt Sodium sulfite Potassium carbonate Hydroxylamine sulfate N-ethyl-N-(β-methanesulfonamidoethyl)-3-methyl-4-aminoaniline sulfate Potassium bromide iodide 2-Mercapto-1,3,4-triazoleethylenediaminetetraacetic acid disodium dihydrate Ethylenediaminetetraacetic acid Fe(Ill) ammonium hydrate Sodium sulfite (pH 2, 0g 2.0g 25.0g 3.0g 5.0g 0.5g 1.0■ IQ 10.40) 1.0g 5+0g 80.0g 15.0g Sodium thiosulfate (700g / Q liquid) 16
0.0m! l glacial acetic acid
Add 5.0ntQ water
IQ (pH 6,50) After processing, sensitometry was performed on the cyan and magenta images formed on the sample, and for each sample, the sensitivity ratio of the cyan image of the white exposed sample and the cyan image of the red monochrome exposed sample, and the white The sensitivity ratio between the magenta image of the exposed sample and the magenta image of the green monochrome exposed sample was determined. These results are shown in Table 7. For each color image, the higher the sensitivity ratio during monochrome exposure to the sensitivity during white exposure, the greater the interimage effect, and the color reversal photographic light-sensitive material exhibits color reproducibility with high saturation.

(Left below) 1-2- As seen from Table 7, Sample N using silver iodobromide emulsion
Compared to Sample No. 111 and Sample Nα2 using a homogeneous silver chlorobromoiodide emulsion, Samples Nα3 and 4 using a surface Cρ emulsion have higher monochromatic exposure sensitivity and a greater interimage effect on other layers and the white layer. .

Also, for samples Nα1 and 2, like samples Nα5 and 6,
Even when silver iodobromide or homogeneous silver chlorobromide emulsions are used,
When used in combination with a surface-fogged silver halide emulsion, the interimage effect on other layers and the white layer is enhanced. However, when a surface 0°C emulsion is contained in the same highest sensitivity layer as the comparative emulsion and a surface fogging emulsion is also used, as in samples Nα8 to Nα11 according to the present invention, the interimage effect on other layers and the white layer is , is much larger than that of the sample, and it can be seen that both the interimage effect on other layers and the interimage effect on the white layer are greater than the sum of the individual effects of each of the above.

Furthermore, there are differences in the magnitude of the interimage effect among the sample groups of the present invention (samples Nα8 to Nα11), and in general, there are differences between the groups of 1 to 453-1, which are defined as surface Ca emulsions, or Differences in interimage effects between emulsions within the same group are determined by the following factors.

(i) In a group of emulsions in which the values of X and y used in the definition of surface CQ emulsions are equal, the larger the value of 2, the faster the dissolution rate of grains becomes, which is preferable in terms of increasing the interimage effect. (Comparison of samples Nn8 and 10 or 9 and 11) Therefore, even in a surface Cβ emulsion with a certain silver chloride content, in order to better express its performance, silver chloride must be unevenly distributed on the outermost surface of the emulsion grains. (Increasing the Z value) is preferable.

Sample Nα11 used together with surface-fogged emulsion SF,
In a comparison of sample Nα12 in which an emulsion with an internally fogged surface was used, the effect was higher when an emulsion was also used with an emulsion in which the surface was fogged.

Regarding the sensitivity of the emulsion layer suitable for containing the surface C2 emulsion, samples Nα8 to Nα11 used in the highest sensitivity layer have an increased interimage effect at high concentrations compared to samples Nα13 and Nα14 used in the lowest sensitivity layer. is significantly more preferable.

Further, the surface C1 emulsion can be used in the same color-sensitive layers having different sensitivities, as in sample Nα15, or in a plurality of different color-sensitive layers, as in sample Nα18.

[Effects of the Invention] According to the present invention, a silver halide color reversal photographic light-sensitive material can be obtained in which the interimage effect is significantly increased, that is, the color reproducibility, particularly the chroma, is significantly improved.

(Left below) 55 G Table A ExS-1 ExS -3 ExS-4 pd-4 pd-5 (CH, -CH) - (n = 100 to 1000) CONH
C4H9(t) pd-6 pd-7 pd-8 59- ExS -5 pd-1 pd-2 pd-3 pd-9 pd-10 pd-11 =60- cpd, -13 Cpd-14 Pd-15 61 - Cpd-21 xC-1 xC-2 xM-1 63- Cpd-16 Cpd-17 Cpd-18 Cpd-19 Cpd -20 62- xY-1 olv-1 di(2-ethylhexyl) phthalate olv-2 trinonyl Phosphate olv-3 Di(3-methylhexyl) phthalate olv-4 Tricresyl phosphate olv-5 Dibutyl phthalate olv Trioctyl phosphate- (1) 1.

2bis(vinylsulfonylacetamido)ethane - Diagram - Procedural amendment 4. Subject of amendment Column of “Detailed Description of the Invention” of the specification Indication of the case 1999 Japanese Patent Application No. 215600 Name of the invention Silver halide color reversal photographic light-sensitive material 3 Person making the amendment Relationship to the case

Claims (2)

[Claims] (1) In a silver halide color reversal photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer and at least one non-light-sensitive layer on a support, the at least one
one emulsion layer contains silver chlorobromoiodide grains containing silver chloride mainly on the surface of the grain, and the at least one emulsion layer or non-photosensitive layer covers the surface of the silver halide grain or the inside of the grain. A silver halide color reversal photographic light-sensitive material characterized by containing a silver halide color reversal emulsion. (2) The silver chlorobromoiodide grains containing silver chloride mainly on the surface of the grains have a silver iodide content of 1 to 10 mol%, and range from 0 to 50 mol% of the total silver amount from the grain center. The content of silver chloride at
Let y (mol%) be the content of silver chloride between 0 mol%, let z (mol%) be the content of silver chloride on the particle surface measured by X-ray photoelectron spectroscopy (XPS), and When divided in half, the content ratio of outer and inner silver chloride [(outer AgCl content)/(inner AgCl content)] is y/x, y/x>10, y≧10 ,z
2. The silver halide color reversal photographic material according to claim 1, wherein x is 10 and 0≦x<10.