JPH0610757B2 - Silver halide color reversal light-sensitive material - Google Patents

Description

TECHNICAL FIELD The present invention relates to a silver halide color photographic light-sensitive material, and more specifically, it has excellent color reproducibility and processing variation, that is, processing solution composition and processing time. The present invention relates to a silver halide color photographic light-sensitive material in which the tone of the highlight portion of the characteristic curve due to variations in processing temperature and the like is small.

(Prior Art) Silver halide color photographic light-sensitive materials are broadly classified into color negative photographic light-sensitive materials and color reversal photographic light-sensitive materials. A color negative photographic light-sensitive material refers to a material capable of forming a negative image by subjecting it to a color negative treatment after exposure, while a color reversal photographic light-sensitive material is capable of forming a positive image by subjecting it to a color reversal treatment after exposure. Refers to what can be done.

The color reversal photographic light-sensitive material referred to in the present invention is described by T. H. Edited by James, “The Theory of the Photograp
hic Process) ”, 4th edition, p. 336, McMilan (M
acmillan) published (1977) "inversion process (revers
al process) ”, the development processing step is a step of first development in which black and white development is performed, and a step in which silver halide not developed in the first development is activated by exposure or a chemical method to enable development. Means a color photographic light-sensitive material which is subjected to a color developing process in the presence of a coupler, a bleaching process of returning developed silver to silver halide, and a fixing process of dissolving and removing it, and a negative-type silver halide is used. To do.

The first developer in this step contains a silver halide solvent such as KSCN in order to impart a development acceleration effect by dissolution physical development. Therefore, in the first development processing step, the unexposed grains are dissolved to some extent at the same time as the development of the exposed silver halide grains, and dissolution physical development occurs using the developed silver or colloidal silver in the yellow filter layer as nuclei. become.

The silver halide grains left undeveloped and dissolved in the first development are fogged in the reversal bath and contribute to color development. The complexity of this step of the color reversal processing compared to the color negative photographic materials makes the fluctuation of the photographic performance to the fluctuation of the development processing conditions of the color reversal photographic materials. It has long been desired to stabilize the photographic performance of color reversal light-sensitive materials against variations in development processing.

It is known in the art that the sharpness is improved by using tabular silver halide grains in the color-sensitive layer, and further, US Pat. Nos. 4,434,226 and 4,439,
No. 520, it is disclosed that the technique of using tabular silver halide grains is effective in order to reduce the development processing dependency. This is because the tabular silver halide grains form a visible image in a shorter time from the start of development, as compared with the spherical silver halide grains.

However, the tabular silver halide grains reduce the inter-image effect due to the specific development speed, and when applied to a silver halide color reversal light-sensitive material, the color reproducibility, which is an important characteristic of photographic performance, is significantly deteriorated. It had a drawback.

An inter-image effect is expressed as one means for improving color reproducibility. For the inter-image effect, see, for example, Hanson et al., “Journal
Of the Optical Society of America
(Journal of the Optical Society of America) ", Vol. 42, pp. 663-669, and A. Teels.
(A. Thiels), “Zeitscrift fr Wis
senschaftliche Photographie, Photophysique und Phot
o-chemie), Vol. 47, pp. 106-118 and 2.
46-225.

U.S. Pat. No. 3,536,486 discloses the incorporation of diffusible 4-thiazoline-2-thiones into exposed color reversal photographic elements and also U.S. Pat. No. 3,536,4.
No. 87 describes the introduction of diffusible 4-thiazoline-2-thiones into unexposed color reversal photographic elements to obtain the desired interimage effect.

Further, in Japanese Patent Publication No. 48-34169, when a color photographic light-sensitive material is developed to reduce silver halide to silver, the presence of an N-substituted 4-thiazoline-2-thione compound causes a remarkable interimage effect. It is described that appears.

It is also possible to provide a colloidal silver-containing layer between the cyan layer and the magenta layer of a color reversal photographic element to obtain a preferable inter-image effect by Research Disclosure (R
esearch Disclosure), No. 131, Item 13116 (1)
975).

Further, U.S. Pat. No. 4,082,553 discloses a color reversal light-sensitive material having a layer arrangement capable of moving iodide ions during development, in which one layer contains latent image-forming silver haloiodide grains. , Another layer with latent image forming silver halide grains,
A method for obtaining a good inter-image effect by including silver halide grains whose surfaces have been fogged so as to be developed independently of image exposure is described.

However, in the above method, the inter-image effect is insufficient, the use of a colloidal silver-containing layer, the introduction of fogged silver halide grains, and the like cause a large decrease in color density in a color reversal light-sensitive material. It has drawbacks.

In addition to the above, for example, a coupler (DIR coupler) capable of releasing a development-inhibiting substance such as a benzotriazole derivative or a mercapto compound at the time of a coupling reaction with an oxidized product of a color developing agent in a color development processing step is used. Alternatively, it is also known that an inter-image effect can be produced by using a hydroquinone compound or the like that can release a development-inhibiting substance such as an iodine ion or a mercapto compound during development, but if these compounds are used, Their use has been limited because of marked desensitization and a decrease in color density.

(Problems to be Solved by the Invention) Therefore, the first object of the present invention is
It is an object of the present invention to provide a silver halide color reversal photographic light-sensitive material having less variation in photographic performance.

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

(Means for Solving Problems) The inventors of the present invention have conducted extensive studies to develop a silver halide color reversal photographic light-sensitive material satisfying such demands, and as a result, have developed a silver halide color reversal photographic light-sensitive material. In the color reversal process, when processing with the first developing solution containing hydroquinone or a 3-pyrazolidone compound, halogen for the sensitivity of the sensitometric curve and the change of the tone of the highlight part with respect to the change of the condition of the first developing solution is used. It has been found that the crystal form of the silver halide emulsion grains influences and the change in processability is small in the case of tabular silver halide grains. Further, the present inventor uses tabular silver halide grains and uses all silver halide emulsions as silver iodobromide emulsion grains containing 4 mol% or less of silver iodide without deteriorating color reproducibility. Sensitometry for changes in conditions of the first developer
It was found that the sensitivity of the curve and the change in the tone of the highlight part can be significantly reduced. The present invention has been accomplished based on this finding.

That is, an object of the present invention is to carry out a black and white development containing a thiocyanate and having a red-sensitive, green-sensitive and blue-sensitive emulsion layer of at least one layer each on a support, and then perform color development. In the reversal light-sensitive material, (1) the silver halide grains contained in all silver halide emulsion layers consist essentially of silver iodobromide containing 4 mol% or less of silver iodide, and (2) The total projected area of silver halide grains having at least one emulsion layer containing tabular silver halide grains having a grain size of 5 times or more the grain thickness, and the grains being present in the same layer. Of at least 50% of the silver halide color reversal light-sensitive material.

The 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 are substantially composed of silver iodobromide containing 4 mol% or less of silver iodide. Particularly preferred is silver iodobromide containing 1.0 to 3.0 mol% of silver iodide.

Here, “substantially” means that the average is 4 mol% or less even if the mol% of silver iodide produced in the process of producing silver halide exceeds 4 mol% and a small amount of silver iodobromide is contained. Show.

The silver halide grains in the photographic emulsion may be so-called regular grains having regular crystal bodies such as cubes, octahedra and tetradecahedrons, and those having an irregular crystal shape such as spheres, It may have a crystal defect such as a twin plane or a composite form thereof. Also, a mixture of particles having various crystal forms may be used.

The grain size of the silver halide may be fine grains of about 0.1 micron or less, or large grains with a projected area diameter of up to about 10 microns, a monodisperse emulsion having a narrow distribution, or a polydisperse grain having a wide distribution. It may be an emulsion.

The silver halide photographic emulsion which can be used in the present invention can be produced by a known method, for example, Research Disclosure,
Volume 176, No.17643 (December 1978), 22
Pp. 23, "I. Emulsion Preparation and
Types) ”and ibid., 187, No. 18716 (197).
No. 9, pp. 648, can be followed.

The photographic emulsion used in the present invention is described in "Physics and Chemistry of Photography" by Graphide, published by Paul Montel (P.Glafkides, Chim.
ie et Physique Photographique Paul Montel, 196
7), "Photoemulsion Chemistry" by Duffin, published by Focal Press (GFDuffin, Photographic Emulsion Chemistry (F
Ocal Press, 1966), "Manufacturing and coating of photographic emulsions" by Zelikmann et al., published by Focal Press (VLZelikman e
t al, Making and Coating Photographic Emulsion, Foca
l Press, 1964) and the like. That is, any of an acidic method, a neutral method, an ammonia method and the like may be used, and a method of reacting a soluble silver salt and a soluble halogen salt may be a one-sided mixing method, a simultaneous mixing method or a combination thereof. Good.
A method of forming grains in the presence of excess silver ions (so-called reverse mixing method) can also be used. PAg in liquid phase produced by silver halide as one type of simultaneous mixing method
To keep constant, that is, so-called controlled
The double jet method can also be used. According to this method, a silver halide emulsion having a regular crystal form and a substantially uniform grain size can be obtained.

Known silver halide solvents (for example, ammonia, rhodancal or U.S. Pat. No. 3,271,157, JP-A-51-12360, JP-A-53-82408, JP-A-53-144319, JP-A-53-144319, JP-A-53-144319, SHO 54-100717
Physical aging in the presence of thioethers and thione compounds described in JP-A No. 54-155828. Also by this method, a silver halide emulsion having a regular crystal form and a nearly uniform grain size distribution can be obtained.

The silver halide emulsion composed of the regular grains can be obtained by controlling the pAg and pH during grain formation. For details, see, for example, Photography Science
And Engineering (Photographic Science and
Engineering) Volume 6, 159-165 (1962);
Journal of Photographic Science (Jou
rnal of Photographic Science), Volume 12, 242-2
51 (1964), U.S. Pat. No. 3,655,394 and British Pat. No. 1,413,748.

The monodisperse emulsion comprises silver halide grains having an average grain diameter of greater than about 0.1 micron, at least 9
Emulsions such that 5% by weight are within ± 40% of the average grain diameter are typical. The average grain diameter is 0.25 to 2 microns and at least 95% by weight or (number of grains) at least 95% of the silver halide grains have an average grain diameter of ± 2.
Emulsions such as within 0% can be used in the present invention.
A method for producing such an emulsion is described in US Pat. No. 3,574,6.
28, 3,655,394 and British Patent 1,413,748. In addition, JP-A-4
8-8600, 51-39027, 51-83
097, 53-137133, and 54-4852.
1, No. 54-99419, No. 58-37635,
Monodisperse emulsions such as those described in JP-A-58-49938 can also be preferably used in the present invention.

On the other hand, in the silver halide color reversal photographic light-sensitive material of the present invention, when each silver halide emulsion layer having the same color sensitivity has two or more layers having different sensitivities, the upper layer as viewed from the support is the lower layer. The silver iodobromide having a smaller mol% of silver iodide than that of the above is preferable, and the difference between the mol% of silver iodide in the upper layer and the mol% of silver iodide in the lower layer is 0.5 mol% to
3.5 mol% is preferable, and 1.0 mol% to 3 mol% shows more preferable color reproducibility, and the change in tone of the highlight portion of the characteristic curve due to process variation is 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. Here, the diameter of a silver halide grain means the diameter of a circle having an area equal to the projected area of the grain. In the present invention, the tabular silver halide grains have a diameter of 0.4 to 5.0, preferably 0.6 to 4.
0 μ.

In general, tabular silver halide grains are tabular having two parallel planes, so that the "thickness" in the present invention is represented by the distance between two parallel planes constituting the tabular silver halide grain. .

The tabular silver halide grains have a halogen composition substantially consisting of silver iodobromide in which the mol% of silver iodide is 4 mol% or less. Tabular silver iodobromide grains containing 0.5 to 3.5 mol% of silver iodide are preferred, and 1 to 3 are more preferred.
It is a tabular silver iodobromide grain containing mol% of silver iodide.

Further, the silver halide color reversal light-sensitive material of the present invention contains an emulsion containing tabular silver halide grains in at least one of the blue-sensitive layer, the green-sensitive layer and the red-sensitive layer, so that the development processing can be varied. Changes in photographic performance can be reduced. Further, a silver halide color reversal light-sensitive material using an emulsion containing tabular silver halide grains in each of the high-sensitivity emulsion layers of the blue-sensitive layer, the green-sensitive layer and the red-sensitive layer is particularly preferable.

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

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

For example, it can be obtained by simultaneously adding silver and halogen solutions while maintaining a relatively low pBr value of pBr 1.3 or less and growing the crystal.

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

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

Examples of the silver halide solvent often used include ammonia, thioethers and thioureas. For thioethers, US Pat. No. 3,271,
No. 157, No. 3,790,387, No. 3,57.
No. 4,628 can be referred to.

These silver halide solvents are added during the production of the tabular silver halide grains of the present invention to accelerate grain growth.
A method of increasing the addition rate, the addition amount, and the addition concentration of the silver salt solution (eg, AgNO ₃ aqueous solution) and the halide solution (eg, KBr aqueous solution) is preferably used.

For these methods, see, eg, US Pat. No. 4,43.
No. 6,226, No. 4,439,520, No. 4,41
4,310, 4,425,425, 4,39
9,215, 4,435,501, 4,38
6,156, 4,400,463, 4,41
4,306, 4,425,426, European Patent No. 84,637A2, JP-A-59-99433,
Research Disclosure No. 22534 (1983)
(January year) etc. can be referred to.

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

The chemical sensitization may be performed inside the silver halide grain or on the surface of the silver halide grain. It may be carried out either inside or on the surface of the silver halide grain.

As the chemical sensitization method, a gold sensitization method using a so-called gold compound (for example, US Pat. Nos. 2,448,060 and 3,32) is used.
No. 0,069) or a sensitization method using a metal such as iridium, platinum, rhodium or palladium (for example, US Pat. No. 2,4,4).
48,060, 2,566,245, 2,56
No. 6,263) or a sulfur sensitizing method using a sulfur-containing compound (for example, US Pat. No. 2,222,264), or a reduction sensitizing method with tin salts, polyamines and the like (for example, US Pat. No. 2,487,850). No. 2,518,698, No. 2,521,925), or a combination of two or more thereof.

From the viewpoint of sensitization, the tabular silver halide grain of the present invention is preferably gold-sensitized or 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 be contained in 50% or more of the total projected area of silver halide grains present in the layer. More preferably, the diameter / thickness ratio (aspect ratio) is 5 or more and 30.
Up to 50% of the total projected area of the silver halide grains contained in the layer.

The thickness of the layer containing tabular silver halide grains is 0.3-
It is preferably 6.0 μ, and particularly preferably 0.5 to 4.0 μ.

The coating amount of tabular silver halide grains is 0.1 to 6 g /
It is preferably m ² , particularly 0.3 to 3 g / m ² .

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

Further, as described later, a dye-forming coupler is used in the silver halide color reversal light-sensitive material of the present invention. 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. Although a yellow dye-forming coupler is used in the blue-sensitive layer, 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 above red-sensitive, green-sensitive and blue-sensitive layers.
When these color-sensitive layers are composed of two or more photosensitive layers, they may be used in any of the layers, but particularly preferably, they are used in the layer farthest from the support. Also,
It is preferable that the 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 a blue-sensitive layer (especially when it is composed of two or more layers, the layer on the side farther from the support). , When it is at the farthest position with respect to the support than the other color-sensitive layers.

To process 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. In this step, a pre-bath, a pre-hardening bath, a neutralizing bath and the like may be further provided.
The reversal may be carried out in a fogging bath or re-exposure. It can also be omitted by adding a fogging agent to the color developing bath. Furthermore, the conditioning bath can be omitted.

Known developing agents can be used in the first developing solution used in the present invention. Examples of developing agents include dihydroxybenzenes (eg hydroquinone), 3-pyrazolidones (eg 1-phenyl-3-pyrazolidone), aminophenols (eg N-methyl-p-).
Aminophenol), 1-phenyl-3-pyrazolines, ascorbic acid, and U.S. Pat. No. 4,067,872.
A heterocyclic compound such as 1,2,3,4-tetrahydroquinoline ring and an indole ring described in No.
They can be used alone or in combination.

In the black-and-white developer used in the present invention, if necessary, a preservative (for example, sulfite, bisulfite, etc.), a buffer (for example, carbonate, boric acid, borate, alkanolamine),
Alkaline agents (eg hydroxides, carbonates), solubilizers (eg polyethylene glycols, their esters), pH adjusters (eg organic acids such as acetic acid), sensitizers (eg quaternary ammonium) Salt), a development accelerator, a surfactant, a color tone agent, a defoaming agent, a film hardener, a viscosity imparting agent and the like.

The first developing solution used in the present invention needs to contain a compound which acts as a silver halide solvent, and the sulfite salt added as the preservative usually plays the role. Specific examples of the sulfite and other silver halide solvents that can be used include KSCN, NaSCN, K ₂ SO ₃ , and N.
_{a 2 SO 3, K 2 S} 2 O 5, Na 2 S 2 O 5, K 2 S 2
O _3, etc. _Na 2 _S 2 _{O 3} can be mentioned.

Further, a development accelerator is used for imparting a development accelerating action. Particularly, a compound represented by the following formula (I) described in JP-A-57-63580 is used alone or in combination of two or more kinds, May be used in combination with the above silver halide solvent.

General formula (I) If the amount of these silver halide solvents used is too small, the progress of development is slowed, and if the amount is too large, fogging occurs in the silver halide emulsion, and therefore, there is a preferable amount used by itself. Can be prepared by those skilled in the art.

For example, SCN ⁻ is 0.005 to 0.0 per developer.
It is preferably 2 mol, particularly 0.01 to 0.015 mol, and SO ₃ ²⁻ is 0.05 to 1 mol, particularly 0.1
It is preferably ˜0.5 mol.

When the compound of the general formula [1] is used by adding it to the black and white developer of the present invention, the addition amount is preferably 5 × 10 ⁻⁶ mol to 5 × 10 ⁻¹ mol, and more preferably ¹ × 10 ⁻⁶ mol. It is 1 × 10 ⁻⁴ mol to 2 × 10 ⁻¹ mol.

The pH value of the developer thus adjusted is selected to an extent sufficient to give the desired density and contrast, but it is preferably in the range of about 8.5 to about 11.5.

To perform a sensitization process using such a first developing solution,
The time may be extended up to about 3 times the standard processing.
At this time, if the processing temperature is raised, the extension time for the sensitization processing can be shortened.

The fogging bath used in the present invention may contain a known fogging agent. That is, stannous ion-organic phosphoric acid vinegar (US Pat. No. 3,617,282), stannous ion organic phosphonocarboxylic acid vinegar (Japanese Patent Publication No. 56
-32616), stannous ion-aminopolycarboxylic acid complex salts (British Patent No. 1,209,050), and other stannous ion borohydride compounds (US Pat. No. 2,984,567). ), A boron compound such as a heterocyclic amine borane compound (British Patent No. 1,011,000), and the like. The fogging bath (inversion bath) has a wide pH range from the acidic side to the alkaline side and has a pH of 2 to 12, preferably 2.5 to.
The range is 10, particularly preferably 3 to 9.

The color developer used in the present invention has a composition of a general color developer containing an aromatic primary amine developing agent. Preferred examples of aromatic primary amine color developing agents are the following p-phenylenediamine derivatives. N, N-diethyl-p-phenylenediamine, 2-amino-5-diethylaminotoluene, 2-amino-5- (N-ethyl-
N-laurylamino) toluene, 4- [N-ethyl-N
-(Β-Hydroxyethyl) amino] aniline, 2-methyl-4- [N-ethyl-N- (β-hydroxyethyl) amino] aniline, N-ethyl-N- (β-methanesulfoamidoethyl) -3 -Methyl-4-aminoaniline, N- (2-amino-5-diethylaminophenylethyl) methanesulfonamide and salts thereof (for example, sulfate, hydrochloride, sulfite, p-toluenesulfonate, etc.) are preferable. This is a typical example.

The color developer may contain other known developer component compounds. For example, caustic soda, caustic potash, sodium carbonate, potash carbonate, and the like can be used as the alkaline agent and the buffer.
Tertiary sodium phosphate or potassium, potassium metaphoric acid, borax, etc. may be used alone or in combination.

The photographic emulsion layer after color development is usually bleached. The bleaching process may be performed at the same time as the fixing process, or may be performed individually.

The bleaching or bleach-fixing solution is described in U.S. Pat. Nos. 3,042,520 and 3,241,966, JP-A-45-85.
In addition to the bleaching accelerators described in JP-B No. 06, JP-B-45-8836, etc., various additives can be added.

Other constitutions of the layer containing the tabular silver halide grains of the present invention, for example, binder, curing agent, antifoggant, silver halide stabilizer, surfactant, spectral sensitizing dye, dye, ultraviolet absorber There is no particular limitation on the chemical sensitizer, and for example, Research Disclosure 176, 22
The description on page 28 (December 1978) can be referred to.

Known photographic additives that can be used in the present invention are Research Disclosure No. 17643 (December 1978).
And No. 18716 (November, 1979), and the locations described in the table below are shown.

Various color couplers can be used in the present invention, specific examples of which are mentioned above in Research Disclosure.
No. 17643, VII-C to G. As the dye-forming coupler, a coupler which gives the three primary colors (that is, yellow, magenta and cyan) of the subtractive color method by color development is important, and specific examples of the diffusion-resistant hydrophobic 4-equivalent or 2-equivalent coupler are described above. Research Disclosure No.17643, VII-C
In addition to the couplers described in the patents described in paragraphs D and D, the following can be preferably used in the present invention.

A typical example of the yellow coupler that can be used in the present invention is a hydrophobic acylacetamide coupler having a ballast group. A specific example is US Pat. No. 2,
No. 407,210, No. 2,875,057 and No. 3,265,506. In the present invention, it is preferable to use a two-equivalent yellow coupler, and US Pat. Nos. 3,408,194 and 3,447,928 are preferred.
No. 3,933,501 and No. 4,022.
No. 620 and other yellow couplers of oxygen atom elimination type or Japanese Patent Publication No. 58-10739, U.S. Pat. Nos. 4,401,752, 4,326,024, R
D18053 (April 1979), British Patent No. 1,42
No. 5,020, West German Application Publication No. 2,219,917,
Typical examples thereof include nitrogen atom releasing yellow couplers described in Nos. 2,261,361, 2,329,587 and 2,433,812. The α-pivaloyl acetanilide type coupler is excellent in the fastness of the color forming dye, especially the light fastness, while
The benzoylacetanilide coupler provides high color density.

Examples of magenta couplers that can be used in the present invention include hydrophobic indazolone or cyanoacetyl, preferably 5-pyrazolone and pyrazoloazole couplers having a ballast group. The 5-pyrazolone-based coupler is preferably a coupler in which the 3-position is substituted with an arylamino group or an acylamino group, from the viewpoint of the hue and color density of the color forming dye, and a representative example thereof is US Pat.
311,082, 2,348,703, 2,600,788, 2,908,573, 3,062,653, 3,152,896 and No. 3,936,015.
As the leaving group of the 2-equivalent 5-pyrazolone-based coupler, the nitrogen atom leaving group described in US Pat. No. 4,310,619 or the arylthio group described in US Pat. No. 4,351,897 is particularly preferable. European Patent No. 7
The 5-pyrazolone-based coupler having a ballast group described in JP-A No. 3,636 provides high color density. As a pyrazoloazole coupler, US Pat. No. 3,061,43
2 pyrazolobenzimidazoles, preferably pyrazolo [5,1-C] [1,2,4] triazoles described in US Pat. No. 3,725,067, Research Disclosure No. 24220 ( 1984 6
And the disclosure of pyrazolotetrazole and research disclosure described in JP-A-60-33552.
No. 24230 (June 1984) and JP-A-60-
The pyrazolopyrazoles described in 43659 are mentioned. The imidazo [1,2-b] pyrazoles described in U.S. Pat. No. 4,500,630 are preferable in view of low yellow sub-absorption of a color forming dye and light fastness, and are described in European Patent 119,860A. Pyrazolo [1,5-b]
[1,2,4] triazole is particularly preferred.

Cyan couplers that can be used in the present invention include hydrophobic and diffusion-resistant naphthol-based and phenol-based couplers. The naphthol-based couplers described in U.S. Pat. No. 2,474,293, preferably U.S. Pat. 052
No. 212, No. 4,146, 396, No. 4,22
Typical examples are the oxygen atom desorption type two-equivalent naphthol couplers described in JP-A-8,233 and JP-A-4,296,200. Further, specific examples of the phenol-based coupler are described in US Pat. Nos. 2,369,929 and 2,8.
01,171, 2,772,162, 2,
No. 895,826.

Cyan couplers which are fast against humidity and temperature are preferably used in the present invention, and typical examples thereof include an alkyl group having an ethyl group or higher at the meta-position of the phenol nucleus described in US Pat. No. 3,772,002. A phenolic cyan coupler having a group, US Pat. No. 2,772,162,
No. 3,758,308, No. 4,126,396
No. 4,334,011, No. 4,327,17
3, 2,5-diacylamino-substituted phenol-based couplers described in West German Patent Publication No. 3,329,729 and European Patent 121,365, and US Pat. Nos. 3,446,622 and 4 , 333, 999, 4,451, 559 and 4, 427, 767.
And the like, which have a phenylureido group at the 2-position and an acylamino group at the 5-position.

The graininess can be improved by using a coupler in which the color forming dye has an appropriate diffusibility. Such couplers are
U.S. Pat. No. 4,366,237 and British Patent No. 2,
Specific examples of magenta couplers are disclosed in 125,570, European Patent No. 96,570 and West German Patent Application Publication No. 3,2.
No. 34,533 describes specific examples of yellow, magenta or cyan couplers.

The dye-forming coupler and the above-mentioned special coupler may form a dimer or higher polymer. Typical examples of polymerized dye forming couplers are found in US Pat. No. 3,451,82.
0 and 4,080,211. Specific examples of polymerized magenta couplers are described in British Patent No. 2,102,173 and US Patent No. 4,367,
282.

Couplers that release a photographically useful residue upon coupling are also preferably used in the present invention. As the DIR coupler releasing a development inhibitor, the couplers of the patents described in the above-mentioned Research Disclosure, No. 17643, VII to F are useful.

The coupler used in the present invention can be introduced into the light-sensitive material by various known dispersion methods, for example, a solid dispersion method, an alkali dispersion method, preferably a latex dispersion method, more preferably an oil-in-water dispersion method, etc. are typical examples. be able to. In the oil-in-water dispersion method, after dissolving in either a single liquid of a high boiling organic solvent having a boiling point of 175 ° C. or higher and a so-called auxiliary solvent having a low boiling point or a mixed liquid of both, water or gelatin is added in the presence of a surfactant. Finely dispersed in an aqueous medium such as an aqueous solution. Examples of high boiling organic solvents are US Pat. No. 2,32
2, 027 and the like. The dispersion may be accompanied by phase inversion, and if necessary, the auxiliary solvent may be removed or reduced by distillation, washing with noodles or ultrafiltration, and then used for coating.

The steps of latex dispersion method, effects, and specific examples of latex for impregnation are described in US Pat. No. 4,199,363, West German Patent Application (OLS) Nos. 2,541,274 and 2,541,230. It is described in.

The light-sensitive material produced by using the present invention, as a color antifoggant or color mixing inhibitor, is a hydroquinone derivative, an aminophenol derivative, an amine, a gallic acid derivative, a catechol derivative, an ascorbic acid derivative, a colorless coupler, a sulfonamidephenol. You may contain a derivative etc.

Various anti-fading agents can be used in the light-sensitive material of the present invention. Hydroquinones as organic anti-fading agents,
6-hydroxychromans, 5-hydroxycoumarans, spirochromans, p-alkoxyphenols,
Typical are hindered phenols centered on bisphenols, gallic acid derivatives, methylenedioxybenzenes, aminophenols, hindered amines and ether or ester derivatives obtained by silylating or alkylating the phenolic hydroxyl groups of these compounds. Take as an example. Further, a metal complex represented by (bissalicylaldoximato) nickel complex and (bis-N, N-dialkyldithiocarbamato) nickel complex can also be used.

The light-sensitive material according to the present invention, in addition to the silver halide emulsion layer,
Protective layer, intermediate layer, filter layer, antihalation layer,
It is preferable to appropriately provide an auxiliary layer such as a back layer.

In the photographic light-sensitive material of the present invention, the photographic emulsion layer and other layers are coated on a flexible support such as a plastic film, paper or cloth usually used for a photographic light-sensitive material or a rigid support such as glass, pottery or metal. To be done. Useful as flexible supports are cellulose derivatives (cellulose nitrate,
Films made of cellulose acetate, cellulose acetate butyrate, etc.), synthetic polymers (polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate, etc.), baryta layers or α-olefin polymers (eg polyethylene, polypropylene, ethylene / butene copolymers), etc. It is a paper or the like coated or laminated with. The support may be colored with a dye or pigment. It may be black for the purpose of shading. The surface of these supports is generally
It is subjected to a subbing treatment to improve the adhesion with the photographic emulsion layer and the like. The surface of the support may be subjected to glow discharge, corona discharge, ultraviolet irradiation, flame treatment or the like before or after the undercoat treatment.

For coating the photographic emulsion layer and other hydrophilic colloid layers, for example, dip coating method, roller coating method, curtain coating method,
Various known coating methods such as extrusion coating method can be used. US Pat. No. 2,681,294 as required
No. 2761791, No. 3526528, No. 3508947, and the like, the multilayers may be simultaneously coated by the coating method.

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

Example-1 A tabular silver halide emulsion was prepared by the following method.

Gelatin 30g and potassium bromide 10.3g were added to water 1 and kept at 60 ° C in a container (pAg 9.1, pH, 6.5).
Solutions I and II of Table 1 were simultaneously added by the double jet method over 65 minutes with stirring.

In the resulting tabular silver halide grains, grains having a diameter / thickness number average of 7.0 accounted for 50% of the projected area of all grains, and silver iodide was 5.5 mol%. . This emulsion was chemically sensitized by using gold and sulfur together. The tabular silver halide emulsion thus obtained is hereinafter referred to as Emulsion A.

For comparison with Emulsion A, spherical grains of silver iodobromide (5.5 mol% silver iodide) were prepared by the double jet method in the presence of ammonia. The average grain size of the obtained emulsion grains was 0.7 μm. Chemical sensitization was performed by using gold and sulfur together. The emulsion thus obtained is hereinafter referred to as Emulsion B.

Next, the 101st to 13th layers were apply | coated in the following order on the triacetate film base, and the sample 101 was created.

1st layer; antihalation layer UV absorber 5-chloro-2- (2-hydroxy-3,
5-di-t-butylphenyl) -2H-benzotriazole 15 g, 2- (2-hydroxy-5-t-butylphenyl) -2H-benzotriazole 30 g, 2- (2
-Hydroxy-3-sec-butyl-5-t-butylphenyl) -2H-benzotriazole 35 g, and dodecyl 5- (N, N-diethylamino) -2-benzenesulfonyl-2,4-pentadienoate 100 g. When,
200 ml of tricresyl phosphate, 200 of ethyl acetate
ml, sodium dodecylbenzenesulfonate 20g, 1
An emulsion obtained by stirring a 0% gelatin aqueous solution at high speed (hereinafter referred to as emulsion (a)) is mixed with 10% gelatin, black colloidal silver, water, and a coating aid to give a dry film thickness of 2μ. Applied.

Second layer: gelatin intermediate layer 2,5-di-t-octylhydroquinone is dissolved in 100 cc of dibutyl phthalate and 100 cc of ethyl acetate to prepare 1
2 kg of an emulsion (hereinafter referred to as emulsion (b)) obtained by high-speed stirring with 1 kg of 0% gelatin aqueous solution was mixed with 1.5 kg of 10% gelatin, and the mixture was applied so as to have a dry film thickness of 1 μm.

Third layer; low red-sensitive emulsion layer 100 g of 2- (heptafluorobutylamide) -5- {2 '-(2 ", 4" -di-t-aminophenoxy) butylamide} -phenol which is a cyan coupler, 100cc of tricresyl phosphate and 100cc of ethyl acetate
And 500 g of an emulsion (hereinafter referred to as emulsion (c)) obtained by high-speed stirring with 1 kg of a 10% gelatin aqueous solution,
1 kg of red-sensitive silver iodobromide emulsion (70 g of silver, 60 g of gelatin)
Was added, and the iodine content was 7.5 mol%), and the coating was applied so that the dry film thickness was 1 μm. (Silver amount: 0.5 g / m ² ) Fourth layer: High-sensitivity red-sensitive emulsion layer The emulsion (c) was mixed with 1 kg of a red-sensitive silver iodobromide emulsion (70 g of silver,
The mixture was mixed with 60 g of gelatin and had an iodine content of 5.5 mol%) and coated so that the dry film thickness was 2.5 μm. (Silver amount: 0.8 g / m ² ) Fifth layer: Intermediate layer 1 kg of the emulsion (b) was mixed with 1 kg of 10% gelatin and coated so as to have a dry film thickness of 1 μm.

Sixth layer: low-green emulsion layer Magenta coupler instead of cyan coupler 1-
(2,4,6-Trichlorophenyl) -3- {3-
An emulsion obtained in the same manner as the emulsion of the third layer except that (2,4-di-t-amylphenoxyacetamide) benzamide} -5-pyrazolone (hereinafter referred to as emulsion (d)). ) 300 g to 1 kg of green-sensitive silver iodobromide emulsion (70 g of silver)
g and 60 g of gelatin, and the iodine content was 6.5 mol%), and the mixture was applied to give a dry film thickness of 2.0 μm. (Silver amount: 0.7 g / m ² ) Seventh layer: Highly sensitive green sensitive emulsion layer 1000 g of emulsion (d) was added to 1 kg of a green sensitive silver iodobromide emulsion.
(It contains 70 g of silver and 60 g of gelatin, and the iodine content is 5.
5 mol%) and coated so that the dry film thickness would be 2.0 μm. (Silver amount: 0.7 g / m ² ) Eighth layer: Gelatin intermediate layer 1 kg of the emulsion (b) was mixed with 1 kg of 10% gelatin, and the mixture was applied to give a dry film thickness of 0.5 μm.

Ninth layer: Yellow filter layer An emulsion containing yellow colloidal silver was applied so as to have a dry film thickness of 1 μm.

10th layer: Low-blue emulsion emulsion layer α- which is a yellow coupler instead of a cyan coupler
(Pivaloyl) -α- (1-benzyl-5-ethoxy-
1000 g of an emulsion (hereinafter, referred to as emulsion (e)) obtained in the same manner as the emulsion of the third layer except that 3-hydantoinyl) -2-chloro-5-dodecyloxycarbonylacetanilide was used was blue-sensitive. 1 kg of silver iodobromide emulsion (70 g of silver
g, and 60 g of gelatin, and the iodine content was mixed at 6.0 mol%), and the mixture was applied to give a dry film thickness of 1.5 μm. (Silver amount: 0.6 g / m ² ) Eleventh layer; High-sensitivity blue-sensitive emulsion layer 1000 g of emulsion (e) was added to 1 kg of blue-sensitive silver iodobromide emulsion B
(It contains 70 g of silver and 60 g of gelatin, and the iodine content is 5.
5 mol%) and coated so that the dry film thickness would be 3 μm. (Amount of silver: 1.1 g / m ² ) Twelfth layer; Second protective layer Emulsion (a) was mixed with 10% gelatin, water, and a coating aid, and coated so that the dry film thickness was 2 μm.

13th layer; 1st protective layer Fine grain emulsion (grain size 0.06μ,
A 10% aqueous gelatin solution containing 1 mol% silver iodobromide emulsion) was applied so that the silver coating amount was 0.1 g / m ² and the dry film thickness was 0.8 μ.

A gelatin hardener 1,4-bis (vinylsulfonylacetamide) ethane and a surfactant were added to each layer.

Then, instead of the spherical emulsion B, the tabular emulsion A was
Layer: A sample 102 was prepared in the same manner as the sample 101 except that it was applied to the high blue sensitive emulsion layer. Further, according to Table 2, Samples 103 to 103 were prepared so that each emulsion layer can be compared with iodomol% of silver iodobromide and silver halide having a spherical crystal shape.
114 was created. What is described as (tabular) in Table 2 is an emulsion containing tabular silver halide grains in the present invention.

These samples 101 to 114 were exposed through a wedge for sensitometry with a light source of 4800 ° K and an exposure amount of 50 lux · second white light, and then subjected to the following color reversal development processing. However, in order to investigate the fluctuations in photographic performance under varying developing conditions, the developer Nos. In which the amount of potassium bromide in the first developing solution was 2.5 (type amount), 3.5, 4.5, 5.5 g / Nos. 1 to 4 were prepared and subjected to development processing at the same time.

Treatment process Time Temperature First development 6 minutes 38 ° C Water wash 2 minutes 〃 Inversion 2 minutes 〃 Color development 6 minutes 〃 Adjustment 2 minutes 〃 Bleach 6 minutes 〃 Soaking 4 minutes 〃 Water washing 4 minutes 〃 Safety 1 The composition of the normal-temperature drying treatment liquid is as follows.

First developer Water 700 ml Nitrilo-N, N, N-trimethylenephosphonic acid pentasodium salt 2 g Sodium sulfite 20 g Hydroquinone monosulfonate 30 g Sodium carbonate (monohydrate) 30 g 1-Phenyl-4methyl-4- Hydroxymethyl-3 pyrazolidone 2 g Potassium bromide 2.5 g Potassium thiocyanate 1.2 g Potassium iodide (0.1% solution) 2 ml Water was added 1000 ml Inversion solution water 700 ml Nitrilo-N, N, N-trimethylenephosphonic acid・ Pentasodium salt 3 g Stannous chloride (dihydrate) 1 g p-Aminophenol 0.1 g Sodium hydroxide 8 g Glacial acetic acid 15 ml Water was added 1000 ml Color developer water 700 ml Nitrilo-N, N, N-trimethylenephosphone Acid, pentasodium salt 3
g Sodium sulfite 7g Tribasic sodium phosphate (12-hydrate) 36g Potassium bromide 1g Potassium iodide (0.1% solution) 90ml Sodium hydroxide 3g Citrazine acid 1.5g N-ethyl-N- (β-methanesulfone Amidoethyl) -3-methyl-4-aminoaniline / sulfate 11 g 3,6-dithiaoctane-1,8-diol 1 g Water was added to 1000 ml Preparation liquid water 700 ml Sodium sulfite 12 g Sodium ethylenediaminetetraacetate (dihydrate) 8 g Thioglycerin 0.4 ml Glacial acetic acid 3 ml Water added 1000 ml Bleached water 800 ml Sodium ethylenediaminetetraacetate (dihydrate) 2 g Ethylenediaminetetraacetic acid iron (III) ammonium (dihydrate) 120 g Potassium bromide 100 g Water added 1000 ml Fixer Water 800 ml Sodium thiosulfate 0.0g Sodium sulfite 5.0g Sodium bisulfite 5.0g Water is added 1000ml Stabilizer Water 800ml Formalin (37% by weight) 5.0ml Fuji Drywell (Fuji Film Co., Ltd. Surfactant 5.0ml Water In addition, 1000 ml of these treated samples were subjected to yellow, magenta and cyan density measurements to determine their respective characteristic curves.

The red, green, and red sensitivities (S _B , S _G , and S _R ) were calculated from the reciprocal of the exposure amount required to obtain a constant density (D = 1.00) from the characteristic curve, and potassium bromide in the first developing solution was obtained. Change in sensitivity when developed with the first developer (No. 1) of 2.5 g / amount and No. 2 to 4 (Δ
S _1.0 ). Similarly to the change in sensitivity, the tone of the highlight parts of blue, green and red ( _B ,
_G and _R ) (log E from the sensitivity point of D = 1.0)
= 0.5 Color density and density 1.0 with increasing exposure
The change in the tone of the highlight part is larger as the difference is larger. ) Was also examined at the same time.

The results are shown in Tables 3 and 4.

As is clear from Tables 3 and 4, in Samples 107 to 114 according to the present invention, the fluctuations in sensitivity and fluctuations in the tone of the highlight portion due to fluctuations in the development processing are extremely small, and stable with respect to fluctuations in the development processing. You can see that it has good sex. Further, it can be seen that Samples 111 to 114 have particularly good stability against fluctuations in development processing.

Example-2 For each of the samples 101 to 114 prepared in Example-1, a part of each is subjected to red wedge exposure, green wedge exposure, and blue wedge exposure, and another part is subjected to white wedge exposure (red + Green + blue light). The exposure amounts of red light, green light, and blue light during white exposure were the same as those of red exposure and green exposure, respectively.

These exposed samples were treated with the No. 1 developing solution of Example-1.
Except for setting 1, the same processing was performed.

The yellow, magenta, and cyan densities of these treated samples were measured, and the cyan at the time of red light exposure and the cyan at the time of white exposure were compared, and the difference ΔlogE in the exposure amount giving a density of 1.00 was measured.

The larger the ΔlogE value, that is, the larger the inter-image effect, the better the color reproducibility.

In the case of green light exposure and blue light exposure, Δ
log E was measured. These are shown in Table 5.

As is clear from Table 5, Samples 107 to 107 according to the present invention
At 114, samples 101-10 of the prior art
It is clear that the inter-image effect is remarkably larger than 6 and the color reproducibility is improved.

Claims (1)

[Claims] 1. A silver halide color reversal in which black and white development containing thiocyanate is carried out, followed by color development, having at least one each of a red-sensitive, green-sensitive and blue-sensitive emulsion layer on a support. In the light-sensitive material, (1) the silver halide grains contained in all the silver halide emulsion layers are substantially composed of silver iodobromide containing 4 mol% or less of silver iodide, and 2) The total projected area of silver halide grains comprising at least one emulsion layer containing tabular silver halide grains having a grain size of 5 times or more the grain thickness, and the grains being present in the same layer. A silver halide color reversal light-sensitive material characterized by occupying at least 50% of