JPS6218552A - Silver halide color reversal photosensitive material - Google Patents

Abstract

PURPOSE:To reduce fluctuation of photographic performance in development processing by forming all the silver halide emulsion layers containing silver halide grains made of silver iodobromide, and specifying the aspect ratio and the projection area ratio of the grains. CONSTITUTION:The silver halide grains contained in all the silver halide emulsion layers are made of silver iodobromide containing 1-3mol% silver iodide, and at least one emulsion layer contains flat silver halide grains having a grain diameter to thickness ratio of 5-30:1, and the flat grains have at least 50% of the projection area of the total silver halide grains in the same layer. It is preferred to apply the flat silver halide grains especially in an amount of 0.3-3g/m<2>.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a silver halide color photographic light-sensitive material, and more specifically, a silver halide color photographic material having excellent color reproducibility and no processing fluctuations, that is, a processing liquid composition. The present invention relates to a silver halide color photographic light-sensitive material in which the tone of a highlight portion of a characteristic curve has little variation due to variations in processing time, processing temperature, etc.

(Prior Art) Silver halide color photographic materials are broadly classified into two types: color negative photographic materials and color reversal photographic materials. Color negative photographic materials are those that can form a negative image by performing color negative processing after exposure, while color reversal photographic materials can form a positive image by performing color reversal processing after exposure. Refers to something that can be done.

The color reversal photographic material referred to in the present invention is T.

The Theory of the Photographic Process (The Theory of the Photographic Process), edited by James H.
theory of the Photographic
Process)', φth edition, page 336, published by Macmi 11an (1977) [
reversal process
s) As described in J, the development process is
A first development in which black and white development is carried out, a step in which the silver halide that was not developed in the first development is activated by exposure or a chemical method to make it developable, a step in which color development is carried out in the presence of a coupler, a step in which the developed silver is converted into a halogen A bleaching process that reverts to silver,
A color photographic light-sensitive material that undergoes a fixing process to dissolve and remove silver halide, and uses negative silver halide.

The first developer in this step contains a silver halide solvent such as KSCN in order to provide the full development accelerating effect through dissolution physical development. Therefore, in the seventh development process, at the same time as development of exposed silver halide grains, dissolution of unexposed grains progresses to some extent, and dissolution physical development occurs with developed silver and colloidal silver in the yellow filter layer as cores. become.

Silver halide grains remaining without being developed and dissolved in the first development are covered by the reversal bath and contribute to color development. Compared to color negative photographic materials, the complexity of this step in color reversal processing makes the photographic performance of color reversal photographic materials subject to greater fluctuations in response to changes in development processing conditions. It has long been desired to stabilize the photographic performance of color reversal sensitive materials against fluctuations in development processing.

It is known in the art that sharpness is improved by using tabular silver halide grains in all color-sensitive layers, and US Pat.
32. No. jJO discloses that a technique using tabular silver halide grains is effective in reducing development dependence on i-processing. This is because tabular silver halide grains form a visible image in a shorter time from the start of development than do spherical silver halide grains.

However, tabular silver halide grains have a unique development speed that reduces interimage effects and improves color reproducibility, which is an important characteristic of photographic performance, when applied to silver halide color reversal light-sensitive materials. It had the disadvantage of causing significant deterioration.

Regarding the interimage effect, which is sometimes used as a means to improve color reproducibility, see, for example, Hanson et al., 'Journal of the Optical Society of America. of the 0ptica
5ociety of America)',
Volume ≠ 2, pp. 663-6, and A, Thels, 'Zeitschrift 7 Jür Guitsenschaftriche Fotografie Fotophysik Land Fotohiemi ( Z
eitscrift f'ur Wissenscha
ftliche Photography.

Photophysique and Photo
-chemie), Vol.

US Patent 3. ! 3t, ≠♂, describes the introduction of diffusible thiazoline-cochions into exposed color reversal and reversal photographic elements, and U.S. Pat.
≠♂7 describes a method for introducing diffusive ≠-thiazoline-λ-thiones into unexposed color reversal photographic elements to obtain desirable interimage effects.

In addition, in the special issue No. Sho≠r-31Ait, when developing a color photographic light-sensitive material and reducing silver halide to silver, N-
It has been described that the presence of a substituted≠-thiazoline-cochion compound produces a remarkable interimage effect.

Research Disclosure (
Research Disc Iosure), A/j/
, No. 1j// is described in the section (17!).

Furthermore, U.S. Patent No. A, O♂2.163 discloses that in a color reversal photosensitive material having a layer arrangement in which iodide ions can move during development, silver haloiodide particles having latent image forming properties are included in one layer of the color reversal photosensitive material. and latent image-forming silver halide grains in another layer,
A method is described in which a good interimage effect is obtained by including silver halide grains whose surfaces are fogged and which can be developed independently of imagewise exposure.

However, in the above method, the interimage effect is insufficient, and the use of a colloidal silver-containing layer, the introduction of fogged silver halide grains, etc. lead to a decrease in color density in color reversal light-sensitive materials. It has major drawbacks.

In addition to the above, for example, in the color development process, a coupler (DIR coupler) that can release a development-inhibiting substance such as a benzotriazole derivative or a mercapto compound during a coupling reaction with an oxidized form of a color developing agent is used. It is also known that interimage effects can be produced by using hydroquinone compounds that can release development-inhibiting substances such as iodide ions and mercapto compounds during development. Their use has been limited because they are accompanied by significant desensitization and a decrease in color density.

(Problems to be Solved by the Invention) Therefore, the first object of the present invention is to:
An object of the present invention is to provide a silver halide color reversal photographic material with little variation in photographic performance.

A second object of the present invention is to provide a silver halide color reversal photographic material with excellent color reproducibility and a processing method.

(Means for Solving the Problems) The present inventor has conducted extensive research in order to develop a silver halide color reversal photographic light-sensitive material that satisfies these undesirable demands. When processing with a first developing solution containing hydroquinone and 3-pyrazolidone compounds in color reversal processing, the sensitivity of the sensitometric curve to changes in the conditions of the first developing solution and changes in the tone of highlighted areas are It has been found that the crystal shape of the silver halide emulsion grains has an effect, and in the case of tabular silver halide grains, the change in processability is small. Furthermore, the present inventors have determined that the silver halide emulsion grains are silver iodobromide emulsion grains containing less than Damorthite silver iodide by using tabular silver halide grains without deteriorating the F color reproducibility. 1. It has been found that the sensitivity of the sensitometric curve to changes in developer conditions and changes in the tone of highlighted areas can be significantly reduced. The present invention has been made based on this knowledge.

That is, the object of the present invention is to provide a silver halide color reversal photographic light-sensitive material having at least one layer each of red-sensitive, green-sensitive and blue-sensitive emulsion layers on a support, (1) All silver halide The silver iodide grains contained in the emulsion layer are each substantially composed of silver iodobromide containing less than or equal to 100% silver iodide, and (2) the grain size is 1 times the grain thickness. At least the total projected area of the silver halide grains in which the emulsion layer containing all of the above tabular silver halide grains is composed of at least seven layers, and the grains are present in the same layer! This was achieved by using a silver halide color reversal light-sensitive material, which is characterized by the fact that all of the oxides are occupied.

Preferred embodiments of the present invention will be described below.

The silver halide grains other than the tabular silver halide grains used in the present invention consist essentially of silver iodobromide containing less than ≠moleth of silver iodide. Particularly preferred is 1. Silver iodide ranging from 0 mol to 3.0 mol S.

Here, "substantially" means that even if the molten silver iodide produced in the silver halide production process contains a small portion of silver iodobromide exceeding damol%, the average thereof is ≠molti or less.

Silver halide grains in photographic emulsions form regular crystal bodies like cubes, octahedrons, and dodecahedrons! They may be so-called regular particles, or may have irregular crystal shapes such as spherical shapes, particles with crystal defects such as twin planes, or composites thereof. Also, mixtures of particles 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, monodispersed emulsions with a narrow distribution, or polydisperse emulsions with a wide distribution. A dispersed emulsion may also be used.

The silver halide photographic emulsion that can be used in the present invention can be produced by a known method, such as Research Disclosure,
/74 volume, &/76 Hiro J (/27 in 72), 22~
Page 23, ″′1. Emulsion Pre
"Paration and Types)" and the same, vol. 117, Jli/J'7/7
, page 6≠g 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 et Phy
siquePhotographique Paul
Montel, /rit7), "Photographic Emulsion Chemistry" by Duffin, published by Focal Press (G, F, Du
ff in, PhotographicEmu
lsion Chemistry (Focal
Press.

``Production and Coating of Photographic Emulsions'' by Zelikman et al.
, published by Focal Press (V, L.

Zelikman et al., Making
andCoating Photographic
Emulsion.

It can be prepared using the method described in Focal Press, /rit4t). 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. It is also possible to use a method in which the particles are formed under an excess of tg ions (so-called back-mixing method). As one form of the simultaneous mixing method, a method in which the 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.

In addition, known silver halide solvents (for example, ammonia, Rodankali or U.S. Pat.
Japanese Patent Publication No. 33-/≠≠3/ri, Japanese Patent Publication No. Shoj≠-1007/
No. 7 or Tokukai Shoj≠−/! Physical ripening can also be carried out in the presence of thioethers (such as thione compounds described in No. 312r, etc.). This method also yields a silver halide emulsion with a regular crystal shape and a nearly uniform grain size distribution.

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, please see Photographic Science and Engineering.
5science and Engineering)
Volume, /! ri~itr page (/ri t2); Journal・
Of Photographic Science (Journal
ofPhotographic 5science
), Volume 72, 2≠λ~2! /page (/ri6≠), U.S. Patent No. 3.6! , 3 ≠ and British Patent No. 1. μ/3,
7≠described in issue g.

A typical ratio-dispersed emulsion is an emulsion in which silver halide grains have an average grain diameter larger than about 0.17 microns, and at least 5% by weight of the silver halide grains are within ±10% of the average grain diameter. The average particle diameter is 0.21 to λ microns, and at least R! Emulsions containing at least 100% silver halide grains and an average grain diameter within the range of 20 inches can be used in the present invention. A method for producing such an emulsion is described in U.S. Patent No. 3. j7≠.

1.21, same No. 3. T! j, 3 ≠ and British Patent No. 1. IA/! , 7μ in issue.

Also, JP-A-Sho μg-ttoo issue, JP-A-Sho 11-jri issue 017,
same! /-4.3097, 33-/37/33, same! Goo 4 #j2/issue, same! Gutata≠／ri issue, 31-
3763! Monodispersed emulsions such as those described in No. JR-41993 and the like can also be preferably used in the present invention.

On the other hand, when the silver halide color reversal photographic light-sensitive material of the present invention has a structure in which silver halide emulsion layers having the same color sensitivity have different sensitivities, the upper F layer is lower than the lower layer when viewed from the support. It is preferable to use silver iodobromide with less silver iodide mole than that of silver iodide, and furthermore, the difference between the silver iodide mole in the upper layer and the silver iodide mole in the lower layer is Q, j mole 3. ! Morti is preferable; /, 0 molti, 3 molti exhibits more preferable color reproducibility, and changes in the tone of the highlighted portion of the characteristic curve due to processing variations are also small.

Next, the tabular silver halide grains used in the present invention will be described.

The tabular silver halide grains used in the present invention have a diameter/thickness ratio of 5 times or more.

The diameter of a silver halide grain herein refers to the diameter of a circle having an area equal to the projected area of the grain. In the present invention, the diameter of the tabular silver halide grains is O0≠μ~j.

θμ, preferably o, t~≠, θμ.

In general, tabular silver halide grains are tabular with two parallel planes, and therefore, "thickness" in the present invention is expressed as the distance between the λ parallel planes constituting the tabular silver halide grain. .

The halogen composition of the tabular silver halide grains consists essentially of silver iodobromide in which the mole of silver iodide is less than or equal to the mole of silver iodide. Preferably 0. Tabular silver iodobromide grains containing silver iodide of 3 molti or more, more preferably 1
These are tabular silver iodobromide grains containing ~3 mol of silver iodide.

However, the silver halide color reversal light-sensitive material of the present invention contains an emulsion containing tabular silver halide grains in at least seven or more of the blue-sensitive layer, green-sensitive layer, and red-sensitive layer, thereby facilitating development processing. Changes in photographic performance due to fluctuations can be reduced. Furthermore, a silver halide color reversal light-sensitive material is particularly preferred, in which each of the high-sensitivity emulsion layers of the blue-sensitive layer, the green-sensitive layer and the red-sensitive layer uses an emulsion containing all tabular silver halide grains.

Next, a method for producing tabular silver halide grains will be described.

The tabular silver halide grains can be produced by appropriately combining five methods known in the art.

For example, it can be obtained by simultaneously adding silver and halogen solutions and growing crystals while maintaining a relatively low pBr value of pf3r/, 3 or less.

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

When producing the tabular silver halide grains of the present invention, a silver halide solvent can be used if necessary.

Often used silver halide solvents include ammonia, thioethers and thioureas. Regarding thioethers, U.S. Pat. ．． 27/,
No. 117, No. 3,720. JIr No. 7, same No. 3. j7
≠, you can refer to the number etc. for 6.

These silver halide solvents are added in order to accelerate grain growth during the production of tabular silver halide grains of the present invention.

A method of increasing the addition rate, amount, and concentration of a silver salt solution (for example, AgNO3 aqueous solution) and a halide solution (for example, KBr aqueous solution) is preferably used.

Regarding these methods, see for example U.S. Pat.

≠34,221. No., same≠,≠32. ! No. 20, Dohiro,
≠l≠, No. 310, same≠, ≠23. ≠2j issue, same gu, 3
Tata, Ko/J No., Same Da, ≠33.101, Same μ, 31
6. /11. No., same≠,≠00. ≠No. 63, same≠, $/
#, jOj issue, Douhiro, ≠2! .

No. ≠2, European Patent No. r≠, A37A2, JP-A-Sho! Tata P4cJJ issue, research disclosure 2 shops 2 shops! You can refer to descriptions such as 3≠ (January 3rd year).

The tabular silver halide grains of the present invention can be chemically sensitized if necessary.

Chemical sensitization can be carried out either inside the silver halide grains or on the surface of the silver halide grains. -! The coating may be carried out either inside or on the surface of the silver halide grains.

As a chemical sensitization method, so-called gold sensitization method using a gold compound (for example, US Patent No. λ, ≠≠r, ot).

No. 3,3, No. 0,01) or iridium, platinum,
Sensitization method using metals such as rhodium and palladium (for example, U.S. Pat.
No., same, jA4. ZAj) or a sulfur sensitization method using a sulfur-containing compound (for example, U.S. Patent Nos. 2.λ, 2co, 26)
φ), or reduction sensitization using tin salts, polyamines, etc. (for example, U.S. Pat. No. J, 1117.1jO, 2.
j/r, t22, same λ,! 2/, 2nd issue), or a combination of two or more of these can be used.

Particularly from the viewpoint of high sensitivity, the tabular silver halide grains of the present invention are preferably gold sensitized, sulfur sensitized, or a combination thereof.

In the layer containing the tabular silver halide grains of the present invention,
It is necessary that tabular grains having a diameter/thickness ratio (aspect ratio) of 5 or more are included in the layer in an amount of 0% or more of the total projected area of the silver halide grains present in the layer. More preferably, tabular grains having a diameter/thickness ratio (aspect ratio) of 5 or more and 30 or more are present over the total projected area of the silver halide grains contained in the layer.

The thickness of the layer containing tabular silver halide grains is from 0.3 to
It is preferably 1.0μ, particularly 0.2-Hiro, Oμ.

Further, the coating amount of tabular silver halide grains is O8/~6f/
It is preferable that nL2, % KO, J ~ j r/m2.

The silver halide color reversal photosensitive material of the present invention has at least one layer each of red-sensitive, green-sensitive, and blue-sensitive emulsion layers, but the order of these photosensitive layers is not particularly limited and may be changed depending on the purpose. determined.

Furthermore, as will be described later, dye-forming couplers are used in the silver halide color reversal photosensitive material of the present invention, and usually a cyan dye-forming coupler is used in the red-sensitive layer and a magenta dye-forming coupler is used in the green-sensitive layer. , a yellow dye-forming coupler is used in the blue-sensitive layer, but different combinations may be used depending on the purpose.

The tabular silver halide emulsion used in the present invention may be used in any of the red-sensitive, green-sensitive and blue-sensitive layers.

When these color-sensitive layers consist of two or more photosensitive layers, they may be used in any layer, but it is particularly preferable to use them in the layer furthest from the support. Also,
Preferably, that layer has the highest sensitivity among the same color-sensitive layers.

The effect of the present invention is maximized when a tabular silver halide emulsion is added to the blue-sensitive layer (particularly the layer farthest from the support when it consists of two or more layers), and when the blue-sensitive layer is , when the other color-sensitive layer weights are also at the furthest positions with respect to the support.

In the processing of the color reversal light-sensitive material of the present invention, the steps of black and white development (first development) → washing → reversal → color development → conditioning bath → bleaching → fixing → washing → stabilization → drying are used. This step may further include a prebath, a hardening bath, a neutralization tower, and the like.

Reversal may be performed in a fogging bath or may be performed in re-exposure. It is also possible to omit Lv when adding a fogging agent to the color developing bath. Furthermore, the adjustment tower can also be omitted.

Known developing agents can be used in the first developer used in the present invention. As developing agents, dihydroxybenzenes (e.g. hydroquinone), 3-pyrazolidones (e.g. /-phenyl-3-pyrazolidone), aminephenols (e.g. N-methyl-p-
amine phenol), /-phenyl-3-pyrazolines, ascorbic acid, and U.S. Patent ≠, 01r7.17.
/, 2, 3 described in No. 2. A heterocyclic compound in which a ≠-tetrahydroquinoline ring and an intrene ring are condensed can be used singly or in combination.

In addition, the black and white developer used in the present invention may include preservatives (e.g., sulfites, bisulfites, etc.), buffers (e.g., carbonates, boric acid, borates, alkanolamines),
Alkaline agents (e.g. hydroxides, carbonates), solubilizing agents (
(e.g. polyethylene glycols, esters thereof), E)H regulators (e.g. organic acids such as acetic acid), sensitizers (e.g. quaternary ammonium salts), development accelerators, surfactants, color toning agents, erasers. A dampening agent, a hardening agent, a viscosity imparting agent, etc. can be included.

The first developer used in the present invention must contain a compound that acts as a silver halide solvent, and the above-mentioned sulfite added as a preservative usually plays this role. The sulfite and other usable silver halide solvents include specifically K S CN , Na S CN ,
K 2 S O3, Na 2 S O3, K2S2
O5, Na2S2O5, K2S2O5, Na2S2O3
etc. can be mentioned.

In addition, a development accelerator is used to impart a development accelerating effect, and in particular, a compound of the following general formula (1) described in JP-A-17-1S JJlO is used alone or in combination of two or more; Furthermore, the above-mentioned silver halide solvents may be used in combination.

General formula (1) ゛ If the amount of these silver halide solvents used is too small, the progress of development will be slowed down, and if it is too large, fog will occur in the silver halide emulsion, so there is a preferable amount to use. However, the amount can be easily determined by those skilled in the art.

For example, 5CN- has o, ooz ~ 0.0 per developer/l.
2 moles, especially 0,0/, 0,0/! S03 is preferably 0.01 to 1 mol, especially o, i
-o,z moles are preferred.

When the compound of general formula [1) is added to the black and white developer of the present invention, the amount added is preferably g per 1 developer.
zxi o-' mole to zxi O-1 mole, more preferably /X10-' mole to cox16-1 mole.

The pH value of the developer thus adjusted is selected to be sufficient to provide the desired density and contrast, but is preferably in the range from about t,j to about //,j.

To carry out sensitization using such a seventh developer, usually,
It is sufficient to extend the time up to about three times the standard processing time.

If the treatment temperature is raised at this time, the extension time for the sensitization treatment can be shortened.

The fogging bath used in the present invention can contain a known fogging agent. Namely, stannous ion-organophosphoric acid acetate (U.S. Pat. No. 3,6/7゜-rco specification), stannous ion-organophosphonocarboxylic acid acetate (Japanese Patent Publication No. 74
-J, No. 24/A), stannous ion complex salts such as stannous ion-aminopolycarboxylic acid complex salts (British Patent No. 1, 20, No. 010), etc. (U.S. Patent No. 2. and boron compounds such as heterocyclic amine borane compounds (UK Patent No. 1.0//, 000). The pH of this fogging bath (reversal bath) ranges over a wide range from acidic to alkaline, with pI (J~lλ, preferably ko,!).
-io, particularly preferably 3-io.

The color developer used in the present invention has the composition of a general color developer containing an aromatic primary amine developing agent. Preferred examples of aromatic primary amine color developing agents are p-phenylenediamine derivatives as shown below. N,N-diethyl°-p-7 2-diamine, λ-amino! -diethylaminotoluene, 2-amino-t-(N-ethyl-N-laurylamino)toluene, 'l-CN-ethyl-N-(β-hydroxyethyl)aminecoaniline, 2
-Methyl-Hiro-[N-ethyl-N-(β-hydroxyethyl)aminocoaniline, N-ethyl-N-(β-methanesulfamidoethyl)-3-methyl-p-aminoaniline, N-(2 Preferred representative examples include -amino-!-diethylaminophenylethyl) methanesulfonamide and salts thereof (eg, sulfate, hydrochloride, sulfite, p-toluenesulfonate, etc.).

The color developer may also contain other known developer component compounds. For example, alkali agents, buffering agents, etc. include caustic soda, caustic potash, soda carbonate, potassium carbonate,
Tertiary sodium phosphate or potassium, potassium metaphosate, borax, etc. are used alone or in combination.

After color development, the photographic emulsion layer is usually bleached. The bleaching process may be performed simultaneously with the fixing process, or may be performed separately.

For bleaching or bleach-fixing solutions, see US Pat. Specification No. 20, Hiroshi 32/Specification No. 66, Tokko Sho≠yo-gr
Various additives can be added, including the bleaching accelerators described in Japanese Patent Publication No. 3-1136 and Japanese Patent Publication No. 3-1136.

Other constituents of the layer containing the tabular silver halide grains of the present invention, such as a binder, a curing agent, an antifoggant, etc.
・Silver halogenide stabilizers, surfactants, spectral sensitizing dyes,
There are no particular restrictions on dyes, ultraviolet absorbers, chemical sensitizers, etc.
Volume 7 of re/page 2+2~2 (Li7≠72
You can refer to the description of month).

Known photographic additives that can be used in the present invention are listed in Research Disclosure JA/7A! J (/ri7≠/February)
and A/♂7/A (/7/January), and the locations are shown in the table below.

1 Chemical sensitizer page 23 6≠r page right column 2
G degree increaser Same as above 3 Spectral sensitizer, page 23-2 μ tttr page right column ~ Super sensitizer 6 ≠ page right column 4 Brightening agent
2≠Page 5 Anti-fogging agent λ≠~Page 2j 6 Large page right column and stabilizer 6 Light absorber, F page 27-2A 6≠Right column~Eater dye 120 Left column Ultraviolet absorber 7 Anti-staining agent - 2≠Page right column 6≠0 Page left~
Right column 8 Dye image stabilizer 2≠page 9 Hardener page 26 Pages 1 and 31 Left column 10 Binder 2≦page Same as above 11
Plasticizer, lubricant page 27 AjO right column 12 Coating aid, table pages 26-27 Same top surface activator 13 Static prevention page 27 Same top stop agent Various color couplers can be used in the present invention, specific examples thereof is the aforementioned research disclosure &
/76≠3, ■-C, described in the patent described in G. As dye-forming couplers, couplers that can be obtained by full color development of the three primary colors (i.e., yellow, magenta and cyan) using the subtractive color process are important, and specific examples of diffusion-resistant, hydrophobic, high-equivalent or 2-equivalent couplers are given below. In addition to the couplers described in the above-mentioned Research Disclosure A/76 Ko 3, Sections 1-C and D, the following can be preferably used in the present invention.

A representative example of the yellow coupler that can be used in the present invention is a hydrophobic acylacetamide coupler having a pallast group. A specific example is U.S. Pat.
No. 1707.210, No. 2. -173.037 and the same No. 3. It is written in Korot, rot issue, etc.

The use of dual-strength yellow couplers is preferred for the present invention and is described in U.S. Pat.
7,9JIr No.

Same 3rd. No. 33.301 and same No. ≠, 022゜6λ
Oxygen atom separation type yellow coupler described in No. O etc. or Tokuko Sho! r-10732, U.S. Patent No.
≠0/, No. 732, No. ≠, 32t, No. 0217, R
D/10j! (15'75' ≠ month), British Patent No. 1
, 4 (λ!, No. 020, West German Application Publication No. 2. A typical example is the nitrogen atom separation type yellow coupler described in No. 33, r/2, etc. α-piparoylacetanilide couplers have excellent color fastness, especially light fastness; α-Benzoylacetanilide couplers provide high color density.

Magenta couplers that can be used in the present invention include hydrophobic indacylon or cyanoacetyl couplers having a ballast group, preferably yoichi pyrazolo/pyrazolo/pyrazoloazole couplers. ! -Pyrazolone couplers are preferably substituted at the 3-position with an arylamino group or an acylamino group from the viewpoint of the hue and color density of the coloring dye.
3ii, orx issue, same number, 2, Jlfil, 703
No. x, tsoo, yrr, No. 2,901
, No. 173, No. 3,062. T! No. 3, same No. 3. l!
λ, rYt No. 3,936,0/! It is listed in the number etc. Two cars! - As a leaving group for pyrazolone caprani, the nitrogen atom leaving group described in U.S. Patent No. is particularly preferred.

Further, the pyrazolo/type couplers having a ballast group described in European Patent No. 73.436 can provide high color density. Examples of pyrazoloazole couplers include pyrazolobenzimidazoles described in U.S. Pat. No. 3.0t/≠3.2, preferably U.S. Pat. No. 3,72! Pyrazolo [r, t C) [/12, ≠] described in t, No. 067
Triazoles, Research Disclosure Shop 2≠
220 (/Yr≠June) and JP-A-60-331
Pyrazolotetrazoles described in No. 3-2 and Research Disclosure, Muda 230 (/91 Hiroyuki ≦
) and pyrazolopyrazoles described in JP-A No. 3612. U.S. Pat.
.

The imidazo[:'+2 b]pyrazoles described in EP-A-630 are preferred, as are the pyrazolo[l,j-b][l,2. ≠] Triazoles are particularly preferred.

Cyan couplers that can be used in the present invention include hydrophobic and diffusion-resistant naphthol and phenolic couplers, as described in US Pat. ≠7≠.

Naphthol couplers described in US Pat. No. 223, preferably US Pat.

/4ct, J Riwo No. '1,221,233, Kohi Dodai Hiro, λri No. 6,200, an oxygen atom detachment type two-car mass 7 toll coupler is a typical example. It is mentioned as. Further, specific examples of phenolic couplers include U.S. Patent Nos.
2, 77λ, 742, 2. It is described in Turij, No. 124, etc.

Cyan couplers that are robust to humidity and temperature are preferably used in the present invention, and a typical example thereof is described in U.S. Pat. Phenolic cyan couplers having the following properties, U.S. Pat. Nos. 2,772,112 and 3,711.

No. 301, No. 1t, /24,394, No. ≠.

33≠, No. 077, No. 327,173, West German Patent Publication No. 3,3 Kota, No. 722 and European Patent No. 1λ/
, 361, etc., and fcλ, j-diacylamino substituted phenolic couplers, and US Pat. ≠Hirot
, l, No. 22, Hiroshi No. 333, Tatata No. 1. three! /, 16th issue ≠, ≠ 27,747, etc., and has a phenylureido group at the t-position and has a j-
These include phenolic couplers having an acylamino group in the position.

Granularity can be improved by using a coupler in which the coloring dye has an appropriate diffusibility. Such a coupler is
U.S. Patent No. 4c, jA4. ．． 2J7 and British Patent No. 2. /2! , No. 370 contains a specific example of a magenta coupler,
Also, European Patent No. A, T70 and West German Application Publication Tube J
, 2j4', No. 4133 describes specific examples of yellow, magenta or cyan couplers.

The dye-forming couplers and the special couplers described above may form dimers or more polymers. Typical examples of polymerized dye-forming couplers are described in U.S. Patent No. 3. psi, rx
No. o and No. +, otro.

It is described in No. 277. Specific examples of polymerized magenta couplers are described in British Patent No. 2,102,173 and U.S. Pat. ．． It is described in No. 2r2.

Couplers that release photographically useful residues upon coupling are also preferably used in the present invention. DIR couplers that release development inhibitors are described in the above-mentioned Research Disclosure, /, /74 Hiroj, sections ① to F, and the couplers of the following patents are useful.

The coupler used in the present invention can be introduced into the light-sensitive material by various known dispersion methods, such as solid dispersion method, alkaline dispersion method, preferably latex melting method, and preferably oil-in-water dispersion method. This can be cited as an example. In the oil-in-water dispersion method, the boiling point is /7! After dissolving in either a high boiling point organic solvent of 0C or higher and a low boiling point so-called auxiliary solvent, either alone or in a mixture of both, it is finely dispersed in an aqueous medium such as water or an aqueous gelatin solution in the presence of a surfactant. Examples of high boiling point organic solvents are U.S. Pat.
No. 22,027, etc.

Phase inversion may be used for dispersion, and if necessary, the auxiliary solvent may be removed or reduced by total distillation, noodle washing, or ultrafiltration before use for coating.

Latex dispersion process, effects, specific examples of latex for impregnation, US Patent No. .

, 3t3, West German Patent Application (OLS) No. 2,141/.

Core No. 4' and Core No. 2. ! ≠/, No. 230, etc.

The light-sensitive materials produced using the present invention contain hydroquinone derivatives, aminophenol derivatives, amines, gallic acid derivatives, catechol derivatives, ascorbic acid derivatives, colorless couplers, and sulfonamide phenols as color-fogging inhibitors or color-mixing inhibitors. It may also contain derivatives and the like.

Various anti-fading agents can be used in the light-sensitive material of the present invention. Organic anti-fading agents include hydroquinones,
t-Hydroxychromans! Hindered phenols, mainly t-hydroxycoumarans, spirochroman Lp-alkoxyphenols, and bisphenols,
Representative examples include gallic acid derivatives, methine/dioxybenzenes, amine phenols, hindered amines, and ether or ester derivatives obtained by silylating or alkylating the phenolic hydroxyl group of each of these compounds. Metal complexes such as (bis-N, N-dialkyldithiocarbamado) nickel complexes can also be used.

In addition to the silver halide emulsion layer, the light-sensitive material according to the present invention is preferably provided with all auxiliary layers such as a protective layer, an intermediate layer, a filter layer, an antihalation layer, and a back layer.

In the photographic material of the present invention, the photographic emulsion layer and other layers are coated on a flexible support such as plastic film, paper, or cloth, or a rigid support such as glass, ceramic, or metal that is commonly used in photographic materials. be done. Useful flexible supports include cellulose derivatives (cellulose nitrate,
cellulose acetate, cellulose acetate butyrate, etc.), films made of synthetic polymers (polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate, etc.), baryta layers or α-olefin polymers (e.g. polyethylene, polypropylene, ethylene/butene copolymers), etc. Paper coated or laminated with The support may be colored using dyes or pigments. It may be made black for the purpose of blocking light. The surface of these supports is generally treated with an undercoat to improve adhesion to photographic emulsion layers and the like.

The surface of the support may be subjected to glow discharge, corona discharge, ultraviolet irradiation, flame treatment, etc. before or after the undercoating treatment.

For coating the photographic emulsion layer and other hydrophilic colloid layers, for example, dip coating, roller coating, curtain coating,
Various known coating methods such as extrusion coating can be used. U.S. Pat. No. 241/λ9≠ as appropriate
No. 27 Otsu/7ri No. 7, No. 3j24121r,
Same number 3!01? Multiple layers may be coated simultaneously using coating methods such as those described in 'l-7.

(Examples) Next, the present invention will be described in more detail based on Examples, but the present invention is not limited thereto.

Example - Engineering A tabular silver halide emulsion was prepared by the method shown below.

Gelatin JOt, potassium bromide 10. Add all Jt in a container kept at too much temperature (pAg, /.

p'H, A, t) while stirring solutions I and 1 of Table 1.
They were added simultaneously by the double jet method over 14 j minutes.

In the obtained tabular silver halide grains, grains having a number average diameter/thickness of 7.0 accounted for SO% of the total grain projected area, and silver iodide! ,! It was morchi. This emulsion was chemically sensitized using a combination of gold and sulfur. The tabular silver halide emulsion thus obtained will hereinafter be referred to as an emulsion.

For comparison with Emulsion A in Table 1, spherical grains of silver iodobromide (silver iodide 5.3 mol tlb) were prepared by the double jet method in the presence of ammonia. The average grain size of the resulting emulsion grains was 0.7 μm. This was chemically sensitized using a combination of gold and sulfur. The emulsion thus obtained will be referred to as emulsion B hereinafter.

Next, the first to thirteenth layers were coated on the triacetate film base in the following order to prepare sample 10/''Ik.

1st layer: Antihalation layer UV absorber 3-chloroco-(co-hydroxy-3.
j-di-t-butylphenyl)-2H-benzotriazole/jf, λ-(2-hydroxy-5-titylphenyl)-2H-penztriazole 30? , 2-
(2-hydroxy-3-sec-butyl-j-i-butylphenyl)-coH-benzotriazole J j f,
and dodecyl j-(N,N-diethylamino)-2
-benzenesulfonyl-J,4C-pentagenoate 100 and tricresyl phosphate 2o orn
1, 200 ml of ethyl acetate. Emulsion obtained by stirring sodium dodecylbenzenesulfonate 20f and 10% gelatin aqueous solution at high speed (hereinafter referred to as emulsion (a)) f
, 10% gelatin, black colloidal silver, water, and coating aids and coated to a dry film thickness of 2 μm.

2nd layer; gelatin intermediate layer λ, J--G-t-octylhydroquinone gold, an emulsion obtained by dissolving in 100cc of dibutyl phthalate and 10cc of ethyl acetate and stirring at high speed with an aqueous solution of 70% gelatin ( Hereinafter referred to as emulsion (b)) 2 to 9 to 10
% gelatin/, j1g, and applied to the surface to a dry film thickness of □/μ.

3rd layer: low sensitivity red sensitive emulsion layer cyan coupler λ-(heptafluorobutyramide)-j-(λ'-(=“,≠”-di-t-aminophenoxy)butyramide)-Funino- le 100tf,)
licresyl phosphate 100Cc and ethyl acetate 10
Dissolved in 0 countries, 10% gelatin dissolved in water? ffl/kli!
The emulsion obtained by stirring at high speed (hereinafter referred to as emulsion (c)) was converted into a red-sensitive silver iodobromide emulsion/ki9 (silver 70f, gelatin toy2 content, iodine content 7.jmol). The mixture was mixed and applied to a dry film thickness of lμ.

(Silver amount: 00 jf/m2) Third layer: Highly sensitive red-sensitive emulsion layer The emulsion (c) was mixed with a red-sensitive silver iodobromide emulsion/kg (silver 7
0f1 Contains gelatin tOff, iodine content is j.

3 mol%), and the dry film thickness was 2. ! I applied the sea urchin so that it becomes μ. (Silver amount o, If/m") Third layer: Intermediate layer emulsion (b)/lcl?'t,/"% Gelatin was mixed with the intermediate layer and coated to a dry film thickness of lμ.

6th layer: Low green sensitivity emulsion layer Al/- with magenta coupler instead of cyan coupler
(λ, μ, 4-trichlorophenyl)-j-(3-(2
, μm di-t-amylphenoxyacetamido)benzamide)-yo-pyrazolone was used, but an emulsion (hereinafter referred to as emulsion (d)) obtained in the same manner as the emulsion of No. 3 J* was prepared. , green-sensitive silver iodobromide emulsion 7 kg (silver 70
? , contains 6 oy of gelatin, and has an iodine content of 6. J'mol%) and coated to a dry film thickness of 2.0μ. (Silver amount o, 7 t/, m2) 7th layer; Highly sensitive green-sensitive emulsion layer Emulsion (d)/000 t'k, green-sensitive silver iodobromide emulsion/9 (silver 701, gelatin tOf) (with an iodine content of 5.5 mol%) and coated to a dry film thickness of λ and Oμ. (Amount of silver: 0, 7 f/@2) R-th layer: Gelatin intermediate layer emulsion (b) was mixed with 9% gelatin/kg and coated to a dry film thickness of 0.1μ.

Second layer: Yellow filter First layer: An emulsion containing yellow colloidal silver was coated to a dry film thickness of lμ.

10th layer: low-sensitivity blue-sensitivity emulsion layer with yellow coupler instead of cyan coupler
(piparoyl)-α-(/-benzyl-yo-ethoxy-
3-Hydantoinyl)-Cau Chloro! -1000f of an emulsion obtained in the same manner as the emulsion for the third layer except that dodecyloxycarbonylacetanilide (hereinafter referred to as emulsion (e)) was added to a blue-sensitive silver iodobromide emulsion/9 ( 70? of silver, 60f of gelatin, and iodine content of 6.0 mol%), and the dry film thickness was 1. It was applied so that it became jμ. (Amount of silver 0, 6 f/nL2) 11th layer;
Highly sensitive blue-sensitive emulsion layer Emulsion (e) / 00 (7f?, blue-sensitive silver iodobromide emulsion 13 i kg (701 silver, 60 gelatin)
(with an iodine content of j mole %) and coated to a dry film thickness of 3 μm. (Amount of silver / , / 97m
2) Seventh λ layer: The seventh protective layer emulsion (a) was mixed with 10% gelatin, water, and a coating aid, and coated to a dry film thickness of 2μ.

13th layer: Fine grain emulsion (grain size 0°06μ,
An aqueous solution of io% gelatin containing a 7 molar silver iodobromide emulsion was coated with a silver coating amount of 0. If/m2, the coating was applied to a dry film thickness of O1tμ.

A gelatin hardener, ≠-bis(vinylsulfonylacetamido)ethane, and a surfactant were added to each layer.

Next, Sample IO- was prepared in the same manner as Sample 10/, except that instead of the spherical emulsion B, a tabular emulsion Ai was coated on the first/highly blue-sensitive emulsion layer. Furthermore, according to Table 2, samples 103-/
/uf was created. Those described as (tabular) in Table 2 represent emulsions containing all tabular silver halide grains as used in the present invention.

These samples 10/, l/IA as a light source for aroo',
It was exposed through a sensitometry wedge at an exposure amount of jOlux and Sunayama color light, and then subjected to the following color reversal development process. However, in order to examine changes in photographic performance due to varying development conditions, the amount of potassium bromide during the first development night was set to 2. ! (type it), 3. ! ,Ge,! ,j,
A developing solution and a l-μ each having a concentration of t/l were prepared, and development processing was performed at the same time.

Processing process Step Time Temperature first development 6 minutes j I o (: water
Washing 2 minutes inversion 2 minutes color development 6 minutes adjustment 2 minutes bleaching Separate fixing μ minute water Washing μ minute stabilization 1 minute Drying at room temperature The following composition is used for the processing solution.

No.-Developer water 70
0 GonitriloN, N, N-)rimethylenephosphonic acid, pentasodium salt 27 Sodium sulfite Coy Hydroquinone
Monosulfonate JOf Sodium Carbonate (-
water salt) 3091-phenyl-≠methyl-μm hydroxymethyl-3 pyrazolidone 2? Potassium bromide λ, jf Potassium thiocyanate /, 49 Potassium iodide (o, i% bath solution Add Kogo water /
000m1 inverted liquid water 700
Punitrilo N, N, N-trimethylenephosphonic acid pentasodium salt 3 was converted into stannous chloride (
double salt) /fp-aminephenol O, no? Sodium hydroxide
♂2glacial acetic acid
/ Add water / 000 ml Color developer water 700
Punishment nitrilo-N, N, N-)rimethylenephosphonic acid pentasodium salt 3v Sodium sulfite 71 Tertiary phosphorous disodium (lλ hydrate) 36? potassium bromide
/f Potassium iodide (0, /% soluble
70ml sodium hydroxide
3? Citrazic acid /, j?
N-ethyl-N-(β-methanesulfonamidoethyl)-3-methyl 1μm aminoaniline sulfate //fJ, &-dithiaoctane-i,r-diol l? Add water to make 1o00yil adjusted liquid water 70
0 Sodium sulfite / 21 Sodium ethylenediaminetetraacetate (trihydrate)? 1,000 glycerin O0ψ1 glacial acetic acid
Add 3mJ water
100θ Go bleach solution water 1r 00 ml Ethylenediaminetetraacetic acid 2 Sodium (trihydrate) 29 Ethylenediaminetetraacetate iron(III) ammonium (trihydrate) /20? Potassium bromide 100f/water 1000rnl Fixer water 100
m1 Sodium thiosulfate to, oy Sodium sulfite, r, 09 Sodium bisulfite j, Of Add water
to00tnl stable liquid water 7
00ml formalin (37% by weight) 2.0
Add M Fuji Drywell (surfactant made by Fuji Film ■) and water.
10100O By measuring the yellow, magenta and cyan densities of these treated samples, respective characteristic curves were determined.

From the characteristic curve, red, green, and red sensitivity (SE
, SG%SR), and the change in sensitivity (ΔS1. 0) was investigated. Also, similar to the change in lacrimal sensitivity, the characteristic curve is blue,
The tone of the green and red highlights (GBX Gc and GR) (Gl), =/, logE = from the sensitivity point of O
θ,! It is expressed as the difference between the color density at the point where the exposure amount is increased and the density 1.0, and the larger the difference, the greater the change in the tone of the highlight area. ) changes were also investigated at the same time.

The results are shown in Table 3 and Table J.

As is clear from Table 3 and Table μ, in Samples 107 to //44 according to the present invention, the fluctuations in sensitivity and the fluctuations in the tone of highlight areas due to fluctuations in development processing were extremely small, and the fluctuations in the tone of highlighted areas were extremely small. It can be seen that the stability is good. Furthermore, in samples ///, //u,
It can be seen that the stability is particularly good against fluctuations in development processing.

Example 2 For the good sample 10/~iiu prepared in Example 7, each part was exposed to red wedge exposure, green wedge exposure, and blue wedge exposure in different parts, and white wedge exposure was applied to other parts. Light exposure (red + green + blue light) was given. During white exposure, the exposure amounts for red light, green light, and back color are as follows:
The exposure amount was the same as that of green light exposure.

These exposed samples were treated with the first developer of Example-7 A/
The process was exactly the same except that it was closed.

The yellow, magenta, and cyan densities of these treated samples were measured, and the cyan when exposed to red light and the cyan when exposed to white were compared, and the density/QOt-difference in the given exposure amount ΔA'ogE was measured.

The larger the ΔlogE value, the greater the interimage effect and the better the color reproducibility.

Similarly, in the case of green light exposure and blue light exposure, Δ
IlogEi was measured. These are shown in Table 3.

As is clear from Table 3, samples 107 to 107 according to the present invention
At 17μ, the conventional technique sample/01. /
It is clear that 06 and 06 also have a significantly large interimage effect and improve color reproducibility.

Claims (1)

[Scope of Claims] A silver halide color reversal light-sensitive material comprising at least one red-sensitive, green-sensitive, and blue-sensitive emulsion layer on a support, comprising: (1) all silver halide emulsions; The silver halide grains contained in the layer are substantially composed of silver iodobromide each containing 4 mol% or less of silver iodide, and (2) the grain size is a flat plate with a grain size of 5 times or more the grain thickness. consisting of at least one emulsion layer containing shaped silver halide grains,
A silver halide color reversal light-sensitive material, wherein said grains occupy at least 50% of the total projected area of silver halide grains present in the same layer.