JPH04301838A - Method for processing silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain enough density even in the case of using a developing solution containing substantially no benzyl alcohol at the time of processing the silver halide color photographic sensitive material having a reflective support and containing silver iodide by a color reversal process. CONSTITUTION:Silver halide grains contained in at least one of the photosensitive emulsion layers of the silver halide color photographic sensitive material has an average diameter of the spheres corresponding to the grains of <=0.3mum and contains silver iodide, or further continuous flat silver halide grains having an aspect ratio of >=5. This photosensitive material is exposed and developed by the developing solution containing substantially no benzyl alcohol.

Description

[Detailed description of the invention]

0001

[Field of Industrial Application] The present invention relates to a processing method for processing a silver halide color photographic light-sensitive material through a color reversal processing step, and in particular, the present invention relates to a processing method for processing a silver halide color photographic light-sensitive material through a color reversal processing step, and in particular, in the color reversal processing step, a color developing solution containing substantially no benzyl alcohol is used. This invention relates to a method for processing so-called color reversal paper, which performs color development.

0002

2. Description of the Related Art Conventionally, various measures have been taken to speed up color development in the processing of silver halide color photographic materials. Among them, color developing agents, which play a major role in color development, have low hydrophilicity, so they have the problem of slow penetration into photosensitive materials.In order to speed up this process, various penetrants have been studied, and in particular, benzyl alcohol is used in color development. The method of adding a liquid to speed up color development has a large effect of promoting color development, and is therefore widely used in processing color photographic materials, especially color reversal papers.

[0003] However, if benzyl alcohol is used in a color developing solution in an amount exceeding the currently widely used amount of 10 to 15 ml/liter, its water solubility is low, so diethylene glycol, triethylene glycol, or alkanolamine is required as a solvent. However, these benzyl alcohol, glycols, alkanolamines, etc. have high BOD and COD when they enter wastewater. Therefore, in order to reduce the burden of photographic processing wastewater, it is preferable not to use benzyl alcohol or the like.

Furthermore, benzyl alcohol is used during processing.
When the photosensitive material is transferred from the color developing bath to the bleach-fixing bath, if the color developing solution adheres to the moving photosensitive material and is brought into the bleaching bath or bleach-fixing bath which is the bath after the color developing bath, the cyan coupler is removed. This may cause the formation of leuco dyes, resulting in a decrease in cyan color density. Moreover, if it is brought into the washing water that is a post-bath, the storage stability of color images will be deteriorated. For this reason as well, it is preferable that the color developer does not contain benzyl alcohol.

However, when benzyl alcohol is removed from the color developer, the color density is significantly reduced. Instead, various conventionally known color development accelerators (for example, U.S. Pat. No. 2,304,925, U.S. Pat. No. 2,496,
No. 903, No. 2,515,147, No. 2,950,9
No. 70, No. 4,038,075, No. 4,119,
462, British Patent No. 1,430,998, British Patent No. 1,
No. 455,413, JP-A-53-15831, No. 55
-62450, 55-62451, 55-62
No. 452, No. 55-62453, Special Publication No. 51-124
No. 22 and No. 55-49728) were used in combination, but sufficient color density could not be obtained.

[0006] For this reason, when processing ordinary silver halide color photographic materials, it is difficult to process them using a color developing solution that does not contain benzyl alcohol or contains a very small amount of benzyl alcohol to the extent that it does not cause problems in subsequent processing steps. Attempts have been made to improve color development regardless of the conditions.

[0007] For example, Japanese Patent Application Laid-Open No. 61-70552, WO
No. 87/04534 discloses a technique for improving color development using a silver halide emulsion containing a large amount of AgCl, but regarding color photographic materials using a silver halide emulsion that does not contain a large amount of AgCl, cannot be applied.

JP-A-62-30250 discloses a method of color development using a specific magenta coupler with a color developer that does not contain benzyl alcohol or contains a very small amount of benzyl alcohol. Techniques for improving this are not disclosed. Also, JP-A-62-324
No. 56 discloses a method in which a color photographic light-sensitive material made from a tabular silver halide grain emulsion is developed with a color developing solution that does not contain or contains a very small amount of benzyl alcohol. The silver halide composition is AgBr or AgBrCl, and there is no mention of improvement in color development when AgI is contained.

[0009]

[Problems to be Solved by the Invention] On the other hand, in the color reversal process of silver halide color photographic light-sensitive materials, as mentioned above, the basic steps are first development, color development, and desilvering treatment. The process is almost the same as the color development process in the processing of ordinary silver halide color photographic light-sensitive materials, and the color developer used there is also almost the same, so benzyl alcohol is used as the color developer. It is preferable to use one that does not contain or contains a very small amount.

[0010] From this point of view, the
In No. 820, a silver halide reversal color photographic light-sensitive material containing 13 mg or more of silver per 100 square cm is developed with a color developing solution containing 7.0 ml or less per 1 liter of benzyl alcohol after image exposure, and then immediately washed with water. A processing method is described which is characterized in that the film is then processed with a bleach-fix solution containing an organic acid metal complex salt.

[0011]In the processing method of carrying out a color reversal processing step of a silver halide color photographic light-sensitive material, when the light-sensitive material to be processed is a color reversal light-sensitive material, the light-sensitive silver halide emulsion is The halogen composition has important technical significance. That is, a color reversal light-sensitive material has multiple emulsion layers, such as a red-sensitive emulsion layer, a green-sensitive emulsion layer, and a blue-sensitive emulsion layer, on a support, but the emulsion is composed of a silver halide emulsion containing iodine. When this is the case, as development progresses during black-and-white development, iodine ions diffuse from the developed emulsion layer to other layers, producing a multilayer effect in which development of the emulsion layer is suppressed. Color reproduction is improved by masking using this multilayer effect. In order to provide this multilayer effect and to control the effect, it is necessary for the color reversal light-sensitive material to contain iodine in its light-sensitive emulsion layer.

[0012] For this reason, the above-mentioned Japanese Patent Application Laid-open No. 62-3 does not mention anything about the improvement in color development when AgI is contained.
The technique of No. 2456 cannot solve the above-mentioned problems of color reversal photosensitive materials. In addition, the above-mentioned Japanese Patent Publication No. 61-46820 only mentions silver chlorobromide as an emulsion, and it is recommended to wash with water immediately after color development or to specify the composition of the bleach-fix solution to prevent poor color restoration. Therefore, this problem cannot be solved.

In the present invention, a silver halide color photographic light-sensitive material containing silver halide containing silver iodide in at least one light-sensitive emulsion layer is processed using a color developer substantially free of benzyl alcohol. It is an object of the present invention to provide a method for processing a silver halide color photographic material that undergoes a color reversal processing step.

[0014]

[Means for Solving the Problems] As a result of intensive research, the present inventors have discovered that by controlling the size of silver halide emulsion grains, even when there is substantially no benzyl alcohol in the color reversal process, It has been found that the color density can be increased. Moreover, at the same time, by making the shape of the silver halide grains tabular,
Furthermore, it has been found that the color density can be increased. It has also been found that by controlling the size and shape of the silver halide emulsion grains or setting them to specific values as described above, a preferable effect can be exerted on the multilayer effect. It has also been found that the shorter the color development processing time in the color reversal processing step, the better the effect. The present invention was completed based on the above findings.

That is, the present invention consists of the following means. 1. A silver halide color photographic light-sensitive material having a light-sensitive emulsion layer on a reflective support is subjected to black-and-white development, color development, and then desilvering treatment. The silver halide emulsion grains contained in at least one light-sensitive emulsion layer of the material have an equivalent sphere average grain size of 0.30 μm or less and contain silver iodide, and substantially absorb the color developing solution. 1. A method for processing a silver halide color photographic material, characterized in that the processing is carried out using a color developing solution containing no benzyl alcohol.

2. The silver halide emulsion grains contained in the light-sensitive emulsion layer of the silver halide color photographic light-sensitive material are:
Tabular silver halide grains with an aspect ratio of 5 or more are present in the same layer, making up 50% of the total projected area of all silver halide grains.
2. The method for processing a silver halide color photographic material as described in item 1 above, wherein the silver halide color photographic material is contained in an amount equal to or more than 10%.

3. 3. The method for processing a silver halide color photographic light-sensitive material according to item 1 or 2 above, wherein the color development is carried out for a processing time of 135 seconds or less. The present invention will be explained in detail below, but first, one of the features of the present invention is the silver halide emulsion grains contained in the light-sensitive emulsion layer constituting the silver halide color photographic light-sensitive material used in the present invention. explain.

In the silver halide color photographic light-sensitive material used in the present invention, the silver halide emulsion grains contained in at least one light-sensitive emulsion layer have an average equivalent spherical grain diameter of 0.30 μm or less.

Further, the average equivalent sphere grain diameter of the silver halide emulsion grains contained in at least one emulsion layer is 0.25.
It is preferably less than μm. Further, from the viewpoint of sensitivity, it is preferable that the lower limit is 0.1 μm.

The method for measuring the equivalent sphere diameter of silver halide grains is described in detail in, for example, "The Theory of Photographic Processes" (by James, 4th edition, p. 100). Examples include methods using an optical microscope, an electron microscope, a Coulter counter, etc., but in the measurement of the emulsion grain size of the present invention, an electron microscope is used, and the thickness of the grain is determined from the projected area of the grain and the length of the shadow caused by shadowing. Preferably, a method is used in which the volume of each particle is determined from these and the equivalent sphere average particle diameter is determined from the average value.

[0021] The sphere-equivalent average particle diameter used in the present invention is 0.
The silver halide grains of 30 μm or less may be a polydisperse emulsion in which the grain sizes are distributed over a wide range, but are preferably monodisperse emulsions with a narrow grain size distribution. Specifically, it is preferable that 60% by weight of the particles be no more than 20% away from the average particle diameter.

The method for producing the monodisperse emulsion is, for example, the double jet method described in Japanese Patent Publication Nos. 48-36870, 54-48520, 54-65521, etc., or the double jet method described in JP-A-54-158220. The method described in et al. can be used.

Furthermore, in the present invention, at least one
The two light-sensitive emulsion layers contain tabular silver halide grains with an equivalent spherical average grain size of 0.30 μm or less and an aspect ratio of 5 or more, and the projected area of the tabular silver halide grains with an aspect ratio of 5 or more is the same. The content is preferably such that it occupies 50% or more of the total projected area of the silver halide grains present in one layer. The aspect ratio herein means the diameter/thickness ratio of emulsion grains.

Further, the diameter of a silver halide grain refers to the diameter of an area equal to the projected area of the grain. Generally, tabular silver halide grains are tabular with two parallel surfaces, and the thickness herein is expressed as the distance between the two parallel surfaces constituting the tabular silver halide grain.

Next, a method for producing tabular silver halide grains will be described. The tabular silver halide grains can be produced by appropriately combining methods known in the art.

For example, a relatively low pB of pBr1.3 or less
It is obtained by adding silver and halogen solutions simultaneously while maintaining the r value. 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 may be used if necessary. Often used silver halide solvents include ammonia, thioethers and thioureas. For thioethers, U.S. Pat. No. 3,271
, No. 157, No. 3,790,387, No. 3,574,
628 etc. can be referred to.

[0028] In addition, regarding the manufacturing method of tabular silver halide grains, see Gatoff, Photographic Science.
and Engineering (Gutoff, Photo
Graphic Science and En
gineering), Volume 14, pp. 248-257 (
1970), U.S. Patent No. 4,434,226,
, No. 414,310, No. 4,433,048, No. 4,
439,520 and British Patent No. 2,112,157
It is detailed in the number etc.

The above-mentioned at least one photosensitive emulsion layer is:
It means at least one of a red-sensitive emulsion layer, a green-sensitive emulsion layer, and a blue-sensitive emulsion layer. Even when each of the emulsion layers described above is composed of a plurality of layers having similar spectral sensitivities, it is sufficient that at least one layer among them satisfies the above conditions, but from the viewpoint of sensitivity, a low-sensitivity emulsion layer is preferred. When a layer containing yellow colloidal silver is included, it is preferable that the emulsion layer closest thereto satisfies the above conditions.

The silver halide emulsion of the light-sensitive emulsion layer in the color photographic light-sensitive material used in the present invention contains silver iodide based on the above-mentioned purpose. The silver iodide may be contained in any of silver iodobromide, silver iodochloride, and silver iodochlorobromide. The content of silver iodide in the emulsion layer is preferably 30 mol % or less (in total silver halide), more preferably 10 mol % or less, but at least 0.
It is preferable that the content is 1 mol%. If the content of silver chloride in the silver halide is too high, the solubility of silver halide in the processing solution becomes too high, which is not preferable. It is preferably 30 mol % or less, and does not need to contain any silver chloride at all.

Although the characteristic parts of the silver halide color photographic light-sensitive material used in the present invention have been described above, other structures already known for the light-sensitive material can be used as they are. The other configurations mentioned above will also be briefly explained below.

The light-sensitive material used in the present invention has at least one blue-sensitive layer, one green-sensitive layer, and at least one green-sensitive layer on a reflective support.
It is sufficient that a silver halide emulsion layer as a red-sensitive layer is provided, and there are no particular restrictions on the number and order of the silver halide emulsion layer and the non-photosensitive layer. A typical example is a silver halide photographic photosensitive material having on a reflective support at least one light-sensitive layer consisting of a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities. The photosensitive layer is a unit photosensitive layer sensitive to blue light, green light, or red light, and in a multilayer silver halide color photographic light-sensitive material, the photosensitive layer is generally a unit photosensitive layer. A red-sensitive layer, a green-sensitive layer, and a blue-sensitive layer are arranged in this order from the support side. However, depending on the purpose, the order of installation may be reversed, or the order of installation may be such that different photosensitive layers are sandwiched between the same color-sensitive layer.

[0033] Non-photosensitive layers such as various intermediate layers may be provided between the above-mentioned silver halide photosensitive layers and between the uppermost layer and the lowermost layer. The intermediate layer includes JP-A No. 61-43748, JP-A No. 59-113438, JP-A No. 59-113440, JP-A No. 6
1-20037 and 61-20038, such as couplers, DIR compounds, etc., may be included, and a commonly used color mixing inhibitor may be included.

The plurality of silver halide emulsion layers constituting each unit photosensitive layer include a high-speed emulsion layer and a low-speed emulsion layer as described in German Patent No. 1,121,470 or British Patent No. 923,045. A two-layer structure of emulsion layers can be preferably used. Usually, it is preferable to arrange the layers so that the photosensitivity decreases toward the reflective support, and a non-photosensitive layer may be provided between each halogen emulsion layer. Also, JP-A-57-112751, JP-A No. 62-20035
Even if a low-sensitivity emulsion layer is placed on the side away from the reflective support and a high-sensitivity emulsion layer is placed on the side close to the reflective support, as described in No. 0, No. 62-206541, No. 62-206543, etc. good.

In order to improve color reproducibility, US Pat.
, No. 663,271, No. 4,705,744, No. 4,707,436, JP-A-62-160448,
BL, GL, R described in the specification of No. 63-89580
A multilayer effect donor layer (CL) having a different spectral sensitivity distribution from the main photosensitive layer such as L may be arranged adjacent to or close to the main photosensitive layer.

As described above, various layer structures and arrangements can be selected depending on the purpose of each photosensitive material. Silver halide grains in photographic emulsions include those with regular crystals such as cubes, octahedrons, and tetradecahedrons, those with irregular crystal shapes such as spherical and plate shapes, and those with twin planes. may have crystal defects, or a composite form thereof.

Silver halide photographic emulsions that can be used in the present invention include, for example, Research Disclosure (RD) No.
．． 17643 (December 1978), pp. 22-23, “
I. Emulsion preparation
ion and types)”, U.S. Pat. No. 3,57
Monodisperse emulsions such as those described in No. 4,628, No. 3,655,394 and British Patent No. 1,413,748 are also preferred.

The crystal structure may be uniform, the inside and outside may have different halogen compositions, or it may have a layered structure. Further, silver halides having different compositions may be joined by epitaxial joining,
Further, it may be bonded with a compound other than silver halide, such as silver rhodan or lead oxide. Also, mixtures of particles of various crystal forms may be used.

The silver halide emulsion used is usually one that has been subjected to physical ripening, chemical ripening and spectral sensitization. Additives used in such processes are listed in Research Disclosure No. 17643 and the same No. 18716, and the relevant parts are summarized in the table below.

Known photographic additives that can be used in the present invention are also described in the above two Research Disclosures, and the relevant descriptions are shown in the table below. Additive type RD17
643 RD18716 1 Chemical sensitizer
23 pages 6
Page 48 right column 2
Sensitivity enhancer
Same as above
3 spectral sensitizer,
Pages 23-24 Page 648 Right column ~ 64
Page 9 right column Super sensitizer


4 Brightener page 24

5 Antifoggant
Pages 24-25 Page 649 right column to page 650 left column and stabilizers


6 Light absorber, 25-26
Pages Page 649 right column to page 650 left column
filter dye,

UV absorber


7 Stain inhibitor Page 25 right column Page 650 left to right column
8 Dye image stabilizer page 25

9 Hardener
26 pages
Page 651 left column
10 Binder 26 pages
Same as above
11 Plasticizer, lubricant
Page 27 Page 650 Right column 12 Coating aid, Pages 26-27 6
Page 50 right column
surfactant

13 Static inhibitor Page 27 Same as above In addition, in order to prevent deterioration of photographic performance due to formaldehyde gas, U.S. Pat.
It is preferable to add to the light-sensitive material a compound that can be immobilized by reacting with formaldehyde as described in No. 35,503.

Various color couplers can be used in the present invention, specific examples of which are shown in Research Disclosure (RD) No. 1, cited above. 17643, VII-C~G
It is described in the patent described in .

Examples of yellow couplers include US Pat. No. 3,933,501, US Pat. No. 4,022,620, US Pat.
No. 4,248,961, Special Publication No. 1973-1073
9, British Patent No. 1,425,020, British Patent No. 1,47
6,760, US Pat. No. 3,973,968, US Pat. No. 4,314,023, US Pat. No. 4,511,649, European Patent No. 249,473A, etc. are preferred.

As the magenta coupler, 5-pyrazolone and piazoloazole compounds are preferred, and are described in US Pat. No. 4,310,619, US Pat. No. 3,061,
No. 432, No. 3,725,067, Research Disclosure No. 24220 (June 1984),
Japanese Patent Publication No. 60-33552, Research Disclosure No. 24230 (June 1984), Japanese Patent Application Publication No. 1986
-43659, 61-72238, 60-35
No. 730, No. 55-118034, No. 60-18595
1, U.S. Patent No. 4,500,630, U.S. Patent No. 4,54
No. 0,654, No. 4,556,630, International Publication W
Particularly preferred are those described in No. 088/04795 and the like.

Cyan couplers include phenolic and naphthol couplers, and are described in US Pat.
No. 52,212, No. 4,146,396, No. 4,
No. 228,233, No. 4,296,200, No. 2
, No. 369,929, No. 2,801,171, No. 2,772,162, No. 2,895,826, No. 3,772,002, No. 3,758,308 ,
4,334,011, 4,327,173, West German Patent Publication No. 3,329,729, European Patent No. 1
No. 21,365A, No. 249,453A, U.S. Patent No. 3,446,622, U.S. Patent No. 4,333,999,
Same No. 4,775,616, Same No. 4,451,559, Same No. 4,427,767, Same No. 4,690,889
No. 4,254,212, No. 4,296,19
No. 9, JP-A No. 61-42658, etc. are preferred.

Colored couplers for correcting unnecessary absorption of coloring dyes are available in Research Disclosure No.
．． Section VII-G of 17643, U.S. Patent No. 4,163,
No. 670, Japanese Patent Publication No. 57-39413, U.S. Patent No. 4,
No. 004,929, No. 4,138,258 and British Patent No. 1,146,368 are preferred. Additionally, there are couplers that correct unnecessary absorption of coloring dyes using fluorescent dyes released during coupling, as described in U.S. Pat. No. 4,774,181, and U.S. Pat. No. 4,777,120.
It is also preferable to use a coupler having as a leaving group a dye precursor group capable of reacting with a developing agent to form a dye as described in the above-mentioned issue.

[0046] Couplers whose coloring dyes have appropriate diffusivity include US Pat. No. 4,366,237, British Patent No. 2,125,570, European Patent No. 96,570,
Preference is given to those described in German Patent No. 3,234,533.

Typical examples of polymerized dye-forming couplers are US Pat. Nos. 3,451,820 and 4,08.
No. 0,211, No. 4,367,282, No. 4,4
No. 09,320, British Patent No. 4,576,910, British Patent No. 2,102,173, etc.

Couplers that release photographically useful residues upon coupling are also preferably used in the present invention. DIR couplers that release development inhibitors are the aforementioned RD
17643, patents listed in sections VII to F, JP-A-5
No. 7-151944, No. 57-154234, No. 60
-184248, 63-37346, 63-3
7350, U.S. Patent No. 4,248,962, U.S. Patent No. 4
, 782,012 is preferred.

As a coupler which releases a nucleating agent or a development accelerator imagewise during development, British Patent No. 2,097
, No. 140, No. 2,131,188, JP-A-59-
Those described in No. 157638 and No. 59-170840 are preferred.

Other couplers that can be used in the photosensitive material of the present invention include US Pat. No. 4,130,42
Competitive couplers such as those described in U.S. Pat. No. 4,283, et al.
No. 472, No. 4,338,393, No. 4,310
, 618, etc., JP-A-60-1
D described in No. 85950, JP-A No. 62-24252, etc.
IR redox compound-releasing couplers, DIR coupler-releasing couplers, DIR coupler-releasing redox compounds or DIR redox-releasing redox compounds, couplers that release dyes that recolor after separation as described in EP 173,302A and EP 313,308A. , R. D. N
o. 11449, 24241, JP-A-61-2012
Bleach accelerator-releasing couplers described in U.S. Pat. No. 47, etc., ligand-releasing couplers described in U.S. Pat. , 774, 181, etc., which emit a fluorescent dye.

The coupler used in the present invention can be introduced into the light-sensitive material by various known dispersion methods. Examples of high boiling point solvents used in the oil-in-water dispersion method are U.S. Pat.
It is described in No. 027, etc.

Specific examples of high-boiling organic solvents with a boiling point of 175° C. or higher at normal pressure used in the oil-in-water dispersion method include phthalic acid esters (dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate,
(decyl phthalate, bis(2,4-di-t-amylphenyl) phthalate, bis(2,4-di-t-amylphenyl) isophthalate, bis(1,1-diethylpropyl) phthalate, etc.), phosphoric acid or Phosphonic acid esters (triphenyl phosphate, tricresyl phosphate, 2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, tributoxyethyl phosphate, trichloropropyl phosphate, di-2-ethylhexyl phenylphosphonate, etc.), benzoic acid esters (2-ethylhexylbenzoate, dodecylbenzoate, 2-ethylhexyl-p-hydroxybenzoate, etc.), amides (
N,N-diethyldodecanamide, N,N-diethyllaurylamide, N-tetradecylpyrrolidone, etc.), alcohols or phenols (isostearyl alcohol, 2,4-di-tert-amylphenol, etc.)
, aliphatic carboxylic acid esters (bis(2-ethylhexyl) sebacate, dioctyl azelate, glycerol tributyrate, isostearyl lactate, trioctyl citrate, etc.), aniline derivatives (N,N-dibutyl-2-butoxy-5 -tert-octylaniline, etc.), hydrocarbons (paraffin, dodecylbenzene, diisopropylnaphthalene, etc.), and the like. Further, as the auxiliary solvent, an organic solvent having a boiling point of about 30°C or higher, preferably 50°C or higher and about 160°C or lower can be used, and typical examples include ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone,
-Ethoxyethyl acetate, dimethylformamide and the like. Examples of latex dispersion process steps, effects, and latex for impregnation are described in U.S. Patent No. 4,199.
, No. 363, West German Patent Application (OLS) No. 2,541,2
No. 74 and No. 2,541,230.

The color photographic material of the present invention is described in US Pat. Nos. 3,379,529 and 3,639,417.
Hydroquinones releasing development-inhibiting compounds as described in JP-A No. 64-546, and Research Disclosure No. 18264 (June 1979)
Naphthohydroquinones and the like that release the development-inhibiting compounds described above can be preferably used.

The color reversal photographic material of the present invention includes:
1,2-benzisothiazolin-3-one, n-butyl-p-hydroxybenzoate, phenol, 4-chlor- 3,5-
Dimethylphenol, 2-phenoxyethanol, 2-
It is preferable to add various preservatives or antifungal agents such as (4-thiazolyl)benzimidazole.

The color photographic material used in the present invention is a so-called color reversal paper. Suitable reflective supports that can be used in the present invention include, for example, the above-mentioned RD. No. 17
643, page 28, and the same No. 18716, from the right column on page 647 to the left column on page 648. In addition to paper, Al foil can also be used as a reflective support.

In the photosensitive material used in the present invention, the total thickness of all the hydrophilic colloid layers on the side having the emulsion layer is preferably 28 μm or less, more preferably 23 μm or less,
More preferably, the thickness is 20 μm or less. Also, membrane swelling rate T (1/
2) is preferably 30 seconds or less, more preferably 20 seconds or less. Film thickness means the film thickness measured at 25° C. relative temperature and 55% humidity control (2 days), and the film swelling rate T (1/2) can be measured according to a method known in the art. . For example, A. Green et al., Photographic Science and Engineering (Photogr. Sci. Eng.), 1
It can be measured by using a swellometer of the type described in Vol. 9, No. 2, pp. 124-129, and T(
1/2) is defined as the time it takes to reach 1/2 of the saturated film thickness, which is 90% of the maximum swelling film thickness reached when processed with a black and white developer at 30°C for 3 minutes and 15 seconds. .

The membrane swelling rate T (1/2) can be adjusted by adding a hardening agent to gelatin as a binder or by changing the aging conditions after coating. Further, the swelling rate is preferably 150 to 400%. The swelling rate is calculated from the maximum swollen film thickness under the conditions mentioned above, using the formula:
It can be calculated according to (maximum swelling film thickness - film thickness)/film thickness.

The processing method of the present invention basically consists of black-and-white development, color development, and desilvering steps, and a reversal step such as optical fogging or chemical fogging may be included after black-and-white development. . Further, steps such as a stop bath, water washing, stabilization, and adjustment are inserted between these steps as necessary.

One of the features of the processing method of the present invention is color development, which is carried out using a color developer containing substantially no benzyl alcohol, as stated for the purpose of the present invention. "Substantially free of benzyl alcohol" means that it is better not to contain benzyl alcohol, but 5
There is no problem even if it contains up to ml/liter.

Further, in the processing method of the present invention, it is preferable that the processing time in color development is 135 seconds or less, so that the effect of increasing the color density can be further improved.

The color reversal processing step carried out in the processing method of the present invention will be explained below, but first the black and white development (first development) carried out will be explained. Black and white development is performed using a black and white developer.

Conventionally known developing agents can be used in the black and white developer used in the present invention. As developing agents, dihydroxybenzenes (e.g. hydroquinone, hydroquinone monosulfonate), 3-pyrazolidones (e.g. 1-phenyl-3-pyrazolidone, 1
-phenyl-4-methyl-4-hydroxymethyl-3-
pyrazolidone), aminophenols (e.g. N-methyl-p-aminophenol), ascorbic acid and 1,2,3,4 as described in U.S. Pat. No. 4,067,872.
-Heterocyclic compounds such as a fused tetrahydroquinoline ring and an indolene ring can be used alone or in combination. The amount of these developing agents added is about 1.times.10@-5 to 1 mol/liter per liter of developer.

The black and white developer used in the present invention may contain other preservatives (for example, sulfites, bisulfites, etc.) as necessary.
, buffering agents (e.g. carbonates, boric acid, borates, alkanolamines), alkaline agents (e.g. hydroxides, carbonates)
, solubilizing agents (e.g. polyethylene glycols, esters thereof), pH adjusters (e.g. organic acids such as acetic acid), sensitizers (e.g. quaternary ammonium salts), development accelerators, surfactants, erasers. A foaming agent, a hardening agent, a viscosity imparting agent, etc. can be included.

The black and white developer used in the present invention preferably contains 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 KSCN, NaSCN,
K2 SO3 , Na2 SO3 , K2 S2 O5
, Na2 S2 O5 , K2 S2 O3 , Na
2 S2 O3, 2-methylimidazole, etc. can be mentioned.

A development accelerator is used to impart a development accelerating effect, and thioether compounds described in JP-A No. 57-63580 are particularly preferred. S
CN- is 0.005 to 0 per liter of developer.
．． 02 mol, especially 0.01 to 0.015 mol, and SO3 2- is preferably 0.05 to 1 mol, especially 0.1 to 0.5 mol.

Various antifoggants may be added to the black and white development process of the present invention for the purpose of preventing development fog. Preferred antifoggants include alkali metal halides such as potassium bromide, sodium bromide, and potassium iodide, and organic antifoggants. Examples of organic antifoggants include benzotriazole, 6-nitrobenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chloro-benzotriazole, 2-thiazolyl-benzimidazole, 2 -Nitrogen-containing heterocyclic compounds such as thiazolylmethyl-benzimidazole, hydroxyazaindolizine, and 1-phenyl-5-mercaptotetrazole 2
Mercapto-substituted heterocyclic compounds such as -mercaptobenzimidazole, 2-mercaptobenzothiazole, and also mercapto-substituted aromatic compounds such as thiosalicylic acid can be used. These antifoggants are
This includes substances that are eluted from color reversal light-sensitive materials during processing and accumulate in these developers.

Among these, bromide is preferable for preventing fogging, and the preferable concentration is 1×10 −3 mol to 0.1 m
ol/liter, more preferably 0.01 to 0.05 mo
It is about l/liter.

Furthermore, the black and white developer of the present invention may contain a swelling inhibitor (for example, an inorganic salt such as sodium sulfate or potassium sulfate).
or a water softener. As the water softener, those having various structures such as aminopolycarboxylic acid, aminopolyphosphonic acid, phosphonocarboxylic acid, and organic-inorganic phosphonic acid can be used. Specific examples are shown below, but the invention is not limited to these.

Ethylenediaminetetraacetic acid, hydroxyethyliminodiacetic acid, propylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, triethylenetetraminehexaacetic acid,
Nitrilo-N,N,N-trimethylenephosphonic acid, ethylenediamine-N,N,N',N'-tetramethylenephosphonic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, these water softeners are two types The above may be used in combination. A preferable addition amount is 0.1 g to 20 g/liter, more preferably 0.5 g to 10 g/liter.

The pH value of the developer thus adjusted is selected to be sufficient to provide the desired density and contrast, but is in the range of about 8.5 to about 11.5. The processing time for black and white development is 20 seconds to 3 minutes, preferably 30 seconds to 90 minutes.
Seconds. The treatment temperature is 30°C to 50°C, preferably 35°C.
℃~45℃. The amount of replenishment of black and white developer is 1 m of photosensitive material.
2 50ml to 500ml, preferably 50ml to 500ml
It is about 330ml.

In the processing of the present invention, after black-and-white development, the film is washed and/or rinsed with water, and then, if necessary, is processed in a reversal processing step, followed by color development processing.

[0072] Although a single water washing or rinsing bath may be used, it is more preferable to adopt a multistage countercurrent system with two or more tanks in order to reduce the amount of replenishment. Here, washing with water is a method in which a relatively large amount of water is replenished, whereas rinsing is a method in which the amount of replenishment is reduced to the level of other processing baths. The amount of washing water to be replenished is preferably about 3 liters to 20 liters per m@2 of photosensitive material. Further, the replenishment amount of the rinse bath is preferably about 100 ml to 500 ml, more preferably about 50 ml to 2 liters,
The amount of water used is significantly reduced compared to the washing process.

[0073] Further, an oxidizing agent, a chelating agent, a buffering agent, a bactericidal agent, a fluorescent whitening agent, etc. can be added to the rinsing bath of the present invention, if necessary. In the reversal process in the processing method of the present invention, optical fogging is more preferable than chemical fogging. This is because when using a chemical fogging process, a chemical fogging agent may be brought into the color developing bath and cause unevenness, but with optical fogging there is no such concern.

Although not preferred, if a chemical fogging treatment is performed, the fogging bath may contain a known fogging agent. That is, stannous ion-organophosphate complex salt (U.S. Pat. No. 3,617,282)
, stannous ion complex salts such as stannous ion organic phosphonocarboxylic acid complex salts (Japanese Patent Publication No. 56-32616), stannous ion-aminopolycarboxylic acid complex salts (British Patent No. 1,209,050), hydrogen Boron compounds (U.S. Patent No. 2,984,567), heterocyclic aminoborane compounds (British Patent No. 1,011,000)
boron compounds, such as those in the patent specification). The pH of this fogging bath (reversal bath) ranges over a wide range from the acidic side to the alkaline side, with a pH of 2 to 12, preferably 2.
．． The range is from 5 to 10, particularly preferably from 3 to 9.

The color developing solution used for color development in the present invention is preferably an alkaline water-soluble one containing an aromatic primary amine color developing agent as a main component. As this color developing agent, p-phenylenediamine compounds are preferably used. Representative examples of p-phenylenediamine compounds are 3
-Methyl-4-amino-N,N-diethylaniline, 3
-Methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3
-Methyl-4-amino-N-ethyl-N-β-methoxyethylaniline and their sulfates, hydrochlorides, phosphates or p-toluenesulfonates, tetraphenylborate, p-(t-octyl ) Benzene sulfonate, etc.

In addition, the concentration and pH of the developing agent in the color developer are very important factors in shortening the development time.
g to about 15 g, more preferably about 3.0 g to about 8.0 g per liter of color developer. Further, the pH of the color developing solution is usually 9 or higher, and most preferably about 9.5 to about 12.0.

[0077] The processing temperature of the color developing solution in the present invention is as follows:
Preferably 30°C to 50°C, more preferably 31°C to
The temperature is 45°C. Further, in the present invention, various development accelerators may be used in combination as necessary.

[0078] Also, as a development accelerator, US Pat.
, 648,604, Japanese Patent Publication No. 44-9503, and US Pat. Neutral salts such as, Japanese Patent Publication No. 44-9304, U.S. Patent No. 2,533,990, U.S. Patent No. 2,531,832,
Nonionic compounds such as polyethylene glycol and its derivatives, polythioethers, etc. described in US Pat. No. 2,950,970 and US Pat. No. 2,577,127, US Pat.
, 242 may be used.

In the color development step of the present invention, various antifoggants may be used in combination for the purpose of preventing development fog. As the antifoggant used in these developing steps, alkali metal halides such as potassium bromide, sodium bromide, and potassium iodide, and organic antifoggants are preferred. Examples of organic antifoggants include benzotriazole, 6-nitrobenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chloro-benzotriazole, 2-thiazolyl-benzimidazole, 2 -Nitrogen-containing heterocyclic compounds such as thiazolylmethyl-benzimidazole, hydroxyazaindolizine, and 1-phenyl-
Mercapto-substituted heterocyclic compounds such as 5-mercaptotetrazole, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, as well as mercapto-substituted aromatic compounds such as thiosalicylic acid can be used. These antifoggants include those that are eluted from color reversal photosensitive materials during processing and accumulate in these developers.

[0080] In addition, the color developer in the present invention includes:
pH buffering agents such as alkali metal carbonates, borates or phosphates; hydroxylamine, diethylhydroxylamine, triethanolamine, catechol-3
, 5-disulfonate, West German Patent Application (OLS) No. 2,
622,950, preservatives such as sulfites or bisulfites; organic solvents such as diethylene glycol, triethylene glycol; dye-forming couplers; competitive couplers such as citradinic acid, J acid, H acid. ; nucleating agents such as sodium boron hydride; auxiliary developers such as 1-phenyl-3-pyrazosolidone; viscosity-imparting agents; ethylenediaminetetraacetic acid, nitrilotriacetic acid, cyclohexanediaminetetraacetic acid, iminodiacetic acid, N-hydroxymethyl Aminopolycarboxylic acids such as ethylenediaminetriacetic acid, diethylenetriaminepentaacetic acid, triethylenetetraminehexaacetic acid, and the compounds described in JP-A-58-195845, 1-hydroxyethylidene-
1,1'-diphosphonic acid, Research Disclosure No. 18170 (May 1979), aminophosphonic acids such as aminotris (methylenephosphonic acid), ethylenediamine-N,N,N',N'-tetramethylenephosphonic acid, JP-A-52-1027
No. 26, No. 53-42730, No. 54-121127
No. 55-4024, No. 55-4025, No. 55
-126241, 55-65955, 55-6
No. 5956, and Research Disclosure No.
．． 18170 (May 1979), a chelating agent such as a phosphonocarboxylic acid can be contained.

The pH of the color developing solution is preferably in the range of about 8-13. The temperature of the color developing solution is selected within the range of 20°C to 70°C, preferably 30°C to 60°C. More preferably the temperature is 35°C to 45°C. In addition, the replenishment amount of color developer replenisher is 50ml to 1000ml per 1m2 of photosensitive material.
1, preferably 100 ml to 500 ml.

The color reversal photosensitive material after color development is then subjected to desilvering treatment. The desilvering process is usually carried out as follows. 1. (Color development) - Adjustment - Bleaching - Fixing 2. (Color development) - Washing - Bleaching - Fixing 3. (Color development) - Bleaching - Fixing 4. (Color development) - Water washing - Bleaching - Water washing - Fixing 5. (Color development) - Bleaching - Washing - Fixing 6. (Color development) - Washing - Bleach fixing 7. (Color development) - Adjustment - Bleach-fixing 8. (Color development) - Bleach fixing 9. (Color development) - Washing - Bleaching - Bleach-fixing 10. (Color development) - Bleaching - Bleach-fixing 11. (Color Development) - Washing - Bleaching - Bleach-Fixing - Fixing Among the above steps, 6 and 8 are particularly preferred.

[0083] As for the replenishment method in the above treatment steps, the replenisher solution for each bath may be replenished individually into the corresponding treatment bath as in the conventional method, or in steps 9 and 10, the overflow solution of the bleaching solution may be replenished. It may be introduced into a bleach-fix bath, and the bleach-fix bath may be replenished only with the fixer composition. Further, in step 11, a method is carried out in which the overflow solution of the bleach solution is introduced into the bleach-fix solution, the overflow solution of the fix solution is introduced into the bleach-fix solution in a countercurrent manner, and both are allowed to overflow from the bleach-fix bath. You can.

As the bleaching agent for the bleaching bath or bleach-fixing bath of the present invention, aminopolycarboxylic acid iron (III) complex salts are currently most commonly used. Representative examples of these aminopolycarboxylic acids and their salts include A-
1 Ethylenediaminetetraacetic acid A-2 Ethylenediaminetetraacetic acid disodium salt A-3 Ethylenediaminetetraacetic acid diammonium salt A-4 Diethylenetriaminepentaacetic acid A-5 Cyclohexanediaminetetraacetic acid A-6 Cyclohexanediaminetetraacetic acid disodium salt A-7 Iminodiacetic acid A-8 1,3-diaminopropane tetraacetic acid and the like can be mentioned, but of course the compounds are not limited to these exemplified compounds.

The ferric aminopolycarboxylic acid complex salt may be used in the form of a complex salt, or a ferric ion complex salt may be formed in a solution using the ferric salt and the aminopolycarboxylic acid. Furthermore, one type or two or more types of aminopolycarboxylic acids may be used. In any case, the aminopolycarboxylic acid may be used in excess of the amount required to form the ferric ion complex.

The bleaching solution or bleach-fixing solution containing the above-mentioned ferric ion complex may also contain a metal ion complex salt other than iron, such as cobalt or copper. Various bleach-fix accelerators can be added to the bleach bath, bleach-fix bath of the present invention, or a conditioning bath which is a pre-bath thereof.

[0087] Examples of such bleaching accelerators include those described in US Pat.
Various mercapto compounds as described in the publication No.
Compounds having a disulfide bond as described in JP-A-53-95630, JP-A-53-9854
Thiazolidine derivatives such as those described in Japanese Patent Application Publication No. 1982-94927, isothiourea derivatives such as those described in Japanese Patent Publication No. 1983-8506, Japanese Patent Publication No. 1985-1984,
Thiourea derivatives as described in JP-A No. 9-26586, thioamide compounds as described in JP-A-49-42349, dithiocarbamates as described in JP-A-55-26506, etc. can be given.

Further, as a bleach accelerator, alkyl mercapto which is unsubstituted or substituted with a hydroxyl group, a carboxyl group, a sulfonic acid group, an amino group (the alkyl group and the acetoxyalkyl group may have any substitution), etc. Compounds can be used. Examples include tothioglycerin, α,α'-thiodipropionic acid, and δ-mercaptobutyric acid. Additionally, U.S. Patent No. 45528
Compounds described in No. 34 can also be used.

The amount of the compound having a mercapto group or disulfide bond in the molecule used in the present invention, thiazoline derivative, or isothiourea derivative to be added to the bleaching solution depends on the type of photographic material to be processed, the processing temperature, and the intended processing. Although it differs depending on the time required for processing, etc., 1 x 10-5 to 10-1 mol per liter of processing solution is appropriate.
Preferably it is 1 x 10-4 to 5 x 10-2 mol.

In addition to the bleaching agent and the above compounds, the bleaching solution used in the present invention may contain bromides such as potassium bromide, sodium bromide, ammonium bromide, or chlorides such as potassium chloride, sodium chloride, ammonium chloride, etc. rehalogenating agents. In addition, nitrates such as sodium nitrate and ammonium nitrate, boric acid, borax,
pH of sodium metaborate, acetic acid, sodium acetate, sodium carbonate, potassium carbonate, phosphorous acid, phosphoric acid, sodium phosphate, citric acid, sodium citrate, tartaric acid, etc.
Additives known to be commonly used in bleaching solutions, such as one or more inorganic acids, organic acids, and salts thereof, having a buffering capacity can be added.

In the present invention, the amount of bleaching agent per liter of bleaching solution is 0.1 mol to 1 mol, preferably 0.1 mol to 1 mol.
．． The amount is 2 mol to 0.5 mol. Further, the pH of the bleaching solution is preferably 4.0 to 8.0, particularly 5.0 to 6.5 during use.

In the present invention, the amount of bleach per liter of bleach-fix solution is 0.05 mol to 0.5 mol, preferably 0.1 mol to 0.3 mol. The bleach-fix solution also contains thiosulfates such as sodium thiosulfate and ammonium thiosulfate, sodium thiocyanate, and other fixing agents.
Thiocyanates such as ammonium thiocyanate and potassium thiocyanate, thioureas, thioethers, and the like can be used. The amount of these fixing agents is 0.3 mol to 3 mol, preferably 0.5 mol to 2 mol, per liter of bleach-fix solution.
It is a mole.

The replenishment amounts of the bleaching solution, fixing solution, bleach-fixing solution, etc. in the present invention can be set arbitrarily, but are preferably 30 ml to 900 ml per 1 m 2 of the light-sensitive material. More preferably, it is 50 ml to 150 ml.

In the present invention, known fixing agents such as ammonium thiosulfate and sodium thiosulfate, sulfites, bisulfites, various buffering agents, and chelating agents such as sulfinic acids can be added to the fixing agent-containing solution. All additives can be added. The concentration of each component in these fixer-containing solutions can be set so that when mixed with the overflow solution of the bleach bath and diluted, it will reach the concentration required as a bleach-fix solution, and is usually replenished into the fixer bath. It can be made more concentrated than usual. As a result, the amount of liquid discharged also decreases, and the burden of recovery processing can be reduced. The concentration of the fixing agent contained in the fixing agent-containing liquid is preferably 0.5 to 4 mol/liter, more preferably 1 to 3 mol/liter. Further, the pH of the fixing agent-containing liquid is preferably 6 to 10, more preferably 7 to 9. Furthermore, ferric aminopolycarboxylic acid complex salts, ammonium halides such as ammonium bromide, sodium bromide, and sodium iodide, and alkali metal halides may be added. The pH of the bleach-fixing bath according to the present invention is from 5 to 8, preferably from 6 to 7.5.

In the processing method of silver halide color reversal photographic light-sensitive materials, after the above-mentioned desilvering step, processing steps such as water washing and/or stabilization are generally carried out. A simple treatment method that performs stabilization treatment without washing with water can also be used.

[0096] The washing water used in the washing step may contain known additives, if necessary. For example, chelating agents such as inorganic phosphoric acid, aminopolycarboxylic acid, and organic phosphoric acid, bactericides and fungicides that prevent the growth of various bacteria and algae, hardening agents such as magnesium salts and aluminum salts, drying load, and unevenness. A surfactant or the like can be used to prevent this. Or L. E. West, “
WaterQuality Criteria”Ph
ot. Sci. and Eng. , Vol. 9No.
6 p. Compounds described in 344-359 (1965) and the like can also be used. In addition, the water washing process may be performed using two or more tanks if necessary, and multistage countercurrent water washing (
For example, 2 to 9 stages) may be used to save washing water.

As the stabilizing liquid used in the stabilizing step, a processing liquid that stabilizes the dye image is used. For example, pH3
A solution having a buffering capacity of ~6, a solution containing an aldehyde (for example, formalin), etc. can be used. Optical brighteners, chelating agents, bactericidal agents, fungicides, hardeners, surfactants, and the like can be used in the stabilizing liquid as necessary.

Furthermore, the stabilization step may be carried out using two or more layers if necessary, and multi-stage countercurrent stabilization (for example, two or more layers) may be carried out.
to 9 stages), the stabilizing liquid can be saved and the water washing step can also be omitted.

Each treatment bath may be provided with a heater, a temperature sensor, a liquid level sensor, a circulation pump, a filter, various floating pigs, various squeegees, nitrogen stirring, air stirring, etc., as necessary.

[0100]

[Operation] The present invention provides a silver halide color photographic light-sensitive material having a reflective support, in which silver halide emulsion grains contained in at least one light-sensitive emulsion layer have an average equivalent spherical grain diameter of 0.30 μm or less. The silver halide emulsion grains contain silver iodide, and the color developing solution does not substantially contain benzyl alcohol, which is extremely effective as a color accelerator, although it has other drawbacks. Although it is possible to obtain a sufficiently high color density for practical use, its detailed mechanism of action has not been elucidated. Furthermore, if tabular silver halide grains with an aspect ratio of 5 or more are contained as the silver halide grains so as to account for 50% or more of the total projected area of all the silver halide grains present in the same layer, the effect will be further enhanced. Increased. Further, if color reversal processing steps are generally performed continuously, black and white developing agents will be mixed into the color developer, thereby inhibiting color development. This phenomenon is particularly pronounced in color reversal development, particularly in the processing of color reversal papers that include only a water wash bath between the black and white developer bath and the color color developer bath. However, when the above-mentioned silver halide grains of the present invention are used,
This inhibition can also be alleviated.

[0101] The shorter the processing time for color development in the present invention, the more remarkable the effect, and the time is preferably 13
It is 5 seconds or less. Therefore, the present invention speeds up the processing.

[0102]

[Examples] The present invention will be further explained below with reference to Examples, but the present invention is not limited thereto. Example 1 (Emulsion A) Cubic grains of silver iodobromide (silver iodide 2.5 mol %) were prepared by a controlled double jet method in the presence of ammonia. The spherical equivalent average particle size of the obtained particles was 0.35 μm. This was chemically sensitized using a combination of gold and sulfur. The emulsion thus obtained will be referred to as Emulsion A hereinafter. 60% by weight of the emulsion grains had a grain size within 18% of the average grain size. (Emulsions B and C) In emulsion A, a cubic emulsion having the following spherical equivalent average grain size was prepared by adjusting the temperature during grain formation. All are silver iodobromide grains containing 2.5 mol % of silver iodide.

In emulsion B, 60% by weight of these emulsion grains are within 15% of the average grain size, and in emulsion C, 60% by weight are within 12% of the average grain size.
It had a particle size within %. (Emulsion D) 30 g of gelatin and 10.3 g of potassium bromide were added to 1 liter of water, and Solutions I and II in Table 1 were added simultaneously over 15 minutes while stirring into a container kept at 60°C.

In the obtained tabular silver halide grains, grains having an aspect ratio of 5 or more accounted for 53% of the total projected area of the grains, and silver iodide accounted for 2.5 mol %. This emulsion was chemically sensitized using a combination of gold and sulfur. The tabular silver halide emulsion thus obtained is referred to as Emulsion D. This emulsion D had a sphere-equivalent average grain diameter of 0.35 μm.

[0105]

[Table 1] (Emulsion E) In Emulsion D, by adjusting the temperature during grain formation, grains with an equivalent spherical average grain diameter of 0.28 μm and an aspect ratio of 5 or more accounted for 53% of the projected area of the total grains.
%, and emulsion E containing 2.5% of silver iodide was obtained. (Emulsion F) In Emulsion E, by adjusting pAg during grain formation, grains with an equivalent spherical average grain diameter of 0.28 μm and an aspect ratio of 5 or more account for 80% of the projected area of all grains, Emulsion F containing 2.5% silver iodide was obtained.

Phenoxyethal was added as a preservative to emulsions A to F at a ratio of 40,000 ppm to gelatin. (Preparation of Photosensitive Material) A color photographic material was prepared by coating the following 1st to 12th layers in multiple layers on a paper support laminated on both sides with polyethylene, and designated Sample 101. The first coated polyethylene layer contains titanium white as a white pigment and a trace amount of ultramarine as a bluish dye.

The composition of the photosensitive layer is shown below. The composition is g/m2
Indicates the coating amount in units. Regarding silver halide, the coating amount is shown in terms of silver. 1st layer (gelatin layer) Gelatin
・・・
・ 1.30 2nd layer (antihalation layer) Black colloid layer
...
0.07 gelatin

... 0.70 Third layer (low sensitivity red sensitive layer) Silver iodobromide EM1 spectrally sensitized with red sensitizing dye (ExS-1, 2, 3) (silver iodide 4 mol%, average grain Size 0.4μm, cube)
0.06 Silver iodobromide EM2 spectrally sensitized with red sensitizing dye (ExS-1, 2, 3) (silver iodide 5 mol%, average grain size 0.50μ, cubic)...
0.05 gelatin

... 1.00 Cyan coupler (ExC-1)
... 0.14 Cyan coupler (
ExC-2)
... 0.07 Antifading agent (Cpd
-2, 3, 4, 9 equivalents)...
0.12 Coupler dispersion medium (Cpd-5)
...
0.03 Coupler solvent (Solv-1,2,3
) ... 0.0
6 Fourth layer (high sensitivity red-sensitive layer) Silver iodobromide EM3 (silver iodide 6 mol%, average grain size 0.75 μm, twin Akira) ... 0
．． 14 Gelatin

... 1.00 Cyan coupler (ExC
-1)
... 0.20 Cyan coupler (ExC-
2)・
... 0.10 Anti-fading agent (Cpd-2,3
, 4, 9 equivalents) ... 0
．． 15 Coupler dispersion medium (Cpd-5)
... 0.
03 Coupler solvent (Solv-1, 2, 3)
... 0.10 5th layer (middle layer) Yellow colloidal silver
...
0.02 gelatin

... 1.00 Color mixing prevention agent (Cp
d-6,7)
... 0.08 Color mixing prevention agent solvent (S
olv-4,5) ・
・・0.16 Polymer latex (Cpd
-8) ・・・
0.10 6th layer (low sensitivity green sensitive layer) Emulsion A spectrally sensitized with green sensitizing dye (ExS-4) 0.09 Gelatin

... 0.80
Magenta coupler (ExM-1)
... 0.05 Magenta coupler (ExM-2)
... 0.05 Anti-fading agent (Cpd-9)
...0.10 Stain inhibitor Cpd-10)
... 0.01 Stain inhibitor (Cpd-11)
... 0.001 Stain inhibitor (Cpd-12)
... 0.01 Coupler dispersion medium (Cpd-5)
...0.05 Coupler solvent (S
olv-4,6)
... 0.15-7 layer (high sensitivity green sensitive layer) Silver iodobromide EM4 spectrally sensitized with green sensitizing dye (ExS-4) (silver iodide 3.5 mol%, average grain size 0) .6μm, twin crystal)...
0.09 Magenta coupler (ExM-1)
... 0
．． 05 Magenta coupler (ExM-2)
... 0.0
5 Anti-fading agent (Cpd-9)
... 0.
10 Stain inhibitor Cpd-10)
... 0.0
1 Stain inhibitor (Cpd-11)
... 0.001
Stain inhibitor (Cpd-12)
... 0.01
Coupler dispersion medium (Cpd-5)
...0.05 Coupler solvent (Solv-4,6)
... 0.15 8th layer (yellow filter layer) Yellow colloidal silver
...
0.14 Gelatin

... 1.00 Color mixing prevention agent (Cp
d-7)
...0.06 Color mixing inhibitor solvent (Solv-4,5)
...0.15 Polymer latex (C
pd-8) ・・
- 0.10 9th layer (low sensitivity blue sensitive layer) Silver iodobromide EM5 spectrally sensitized with blue sensitizing dye (ExS-5, 6) (silver iodide 2.5 mol%, average grain size 0) .40μm, cube)...0.0
7 Silver iodobromide EM6 (2.5 mole iodide) spectrally sensitized with blue sensitizing dye (ExS-5)


%, average particle size 0.4
5 μm, cube) ... 0.06
gelatin
・・・
・0.50 Yellow coupler (ExY-1
)...
0.20 Stain inhibitor (Cpd-11)
...
0.001 Anti-fading agent (Cpd-6)
...
0.10 Coupler dispersion medium (Cpd-5)
...
0.05 Coupler solvent (Solv-2)
...
0.05 10th layer (high sensitivity blue sensitive layer) Silver iodobromide EM7 (silver iodide 25 mole) spectrally sensitized with blue sensitizing dye (ExS-5)


．． %, average particle size 1.2μm
, twin) ... 0.25
gelatin
・・・
・ 1.00 Yellow coupler (ExY-1
)...
0.40 Stain inhibitor (Cpd-11)
...
0.002 Anti-fading agent (Cpd-6)
...
0.10 Coupler dispersion medium (Cpd-5)
...
0.15 Coupler solvent (Solv-2)
...
0.10 11th layer (ultraviolet absorption layer) Gelatin
・・・
・1.50 Ultraviolet absorber (Cpd-1,3
,13)...
1.00 Color mixing prevention agent (Cpd-6,14)
... 0.
06 Dispersion medium (Cpd-5)
...
UV absorber solvent (Sol
v-1,2)...
0.15 Anti-irradiation dye (Cpd-
15,16) ... 0.02 Anti-irradiation dye (Cpd-17,18)
... 0.02 12th layer (protective layer) Fine grain silver chlorobromide (silver chloride 97 mol%, average size 0
．． 2μm)・0.07 Modified Poval

... 0.02 Gelatin
... 1
．． 50 Gelatin hardening agent (H-1)
...
0.17 Furthermore, in each layer, Alkanol XC (DuPont) and sodium alkylbenzenesulfonate were used as emulsification dispersion aids, and succinate ester and Magefac F-120 (manufactured by Dainippon Ink Co., Ltd.) were used as coating aids. . (Cpd-19, 20, 21) was used as a stabilizer in the silver halide or colloidal silver containing layer. The compounds used in the examples are shown below.

[0108]

[Chemical formula 1]

[0109]

[Case 2]

[0110]

[Chemical formula 3]

[0111]

[C4] Cpd-8 Polyethyl acrylate

[0112]

[C5]

[0113]

[C6]

[0114]

[C7]

[0115]

[Chemical formula 8]

[0116]

[Chemical formula 9]

[0117]

embedded image Solv-1 Di(2-diethylhexyl) phthalate Solv-2 Trinonyl phosphate Solv-
3 Di(3-methylhexyl) phthalate Solv-
4 Tricresyl phosphate Solv-5 Dibutyl phthalate Solv-6 Trioctyl phosphate H-1
Samples 102 to 106 are obtained by replacing emulsion A in the sixth layer with emulsions B to F in 1,2 bis(vinylsulfonylacetamido)ethane sample 101. Table 2 shows the relationship between each sample and each emulsion.

[0118]

[Table 2] The above samples 101 to 106 were exposed through a sensimetry wedge and subjected to processing 1 and processing 2, respectively.
The maximum density of magenta color development was measured. The processing contents of processing 1 and processing 2 are shown below. Processing 1 Processing process Black and white development 38℃
Wash with water for 75 seconds at 38℃
90 seconds reverse exposure 100
Lux or higher Color development for 60 seconds or more
Wash with water at 38℃ for 135 seconds
38℃ 45 seconds bleach fixing 38℃ 1
Wash with water for 20 seconds at 38℃
Drying for 135 seconds Composition of processing solution (black and white developer) Nitrilo-N,N,N-trimethylenephosphonic acid
pentasodium salt

0.6g diethylenetriaminepentaacetic acid.
pentasodium salt
4.0g potassium sulfite

30.0g Potassium thiocyanate

1.2g potassium carbonate
35.
0g Hydroquinone monosulfonate potassium salt 25.0g Diethylene glycol
15.0
ml 1-phenyl-4-hydroxymethyl-4-methyl-3-pyrazolidone

2.0g potassium bromide

0.5g potassium iodide

Add 5.0mg water

1 liter

(p
H 9.70) (Color developer) Benzyl alcohol

15.0ml diethylene glycol

12.0ml 3,6-dithia-1,
8-octanediol
0.2g Nitrilo-N,N,N-trimethylenephosphonic acid, pentasodium salt

0.5g diethylenetriaminepentaacetic acid, pentasodium salt
2.0g sodium sulfite

2.0g potassium carbonate

25.0g Hydroxylamine sulfate

3.0g N-ethyl-N-(β-methanesulfonamidoethyl)-3-methyl-4-aminoaniline sulfate
5.0g potassium bromide

0.5g potassium iodide

Add 1.0mg water

1 liter

(pH
10.40) (bleach-fix solution) 2-mercapto-1,3,4-triazole
1.0g Ethylenediaminetetraacetic acid disodium dihydrate
5.0g Ethylenediaminetetraacetic acid/Fe (trivalent)/ammonium monohydrate

8
0.0g Sodium sulfite

15.0g Sodium thiosulfate (70
0g/liter liquid) 16
0.0ml glacial acetic acid

Add 5.0ml water

1 Liter Process 2 Process 2 is the same as Process 1 except that the benzyl alcohol in Process 1 was removed using a color developer.

Table 3 shows the measurement results of magenta color density obtained by the above processing.

[0120]

[Table 3] According to Table 3, it can be seen that in the present invention, a practically effective high coloring density can be obtained even without benzyl alcohol, which is extremely preferable for practical use. Example 2 Samples 101 to 106 in Example 1 were subjected to wedge exposure using white light exposure and wedge exposure using green light exposure. Processing 2 in Example 1 was performed on this sample.

After the processing, the ratio of magenta sensitivity when white exposure was performed to magenta sensitivity when green exposure was performed for each sample was determined for the formed magenta image. The results of these measurements are shown in Table 4. In this case, the higher the sensitivity during green exposure compared to the sensitivity during white exposure, the greater the multilayer effect, which is preferable in terms of color reproduction.

[0122]

[Table 4] According to Table 4, it can be seen that the weight effect is large and preferable in the present invention. Example 3 The sample in Example 1 was exposed to light through a sensitometric wedge, and then developed using an automatic developing machine in the following manner.

Processing process Time Temperature Mother liquor tank capacity Replenishment amount First development 75 seconds 38
°C 8 liters 330ml/m
2 First water washing (1) 45〃 33〃
5 〃 ───
First water wash (2) 45〃
33 5 500
0 〃 Reversal exposure 15〃
100lux color development
135〃 38℃ 15 liters 330ml/m2 Second water washing
45〃 33〃 5
〃 1000 〃 Bleach fixing (
1) 60〃 38〃 7〃
─── Bleach fixing (2) 60〃 38〃 7
〃 150 〃 Third washing (1) 45〃 33〃 5
〃 ────
Third washing (2) 45〃 33〃
5 〃 ───
Third flush (3) 45〃 33〃
5 〃 5000〃
Drying 45〃75
Here, the first water washing and the third water washing were each performed using a countercurrent washing method. That is, the washing water is passed through the first washing (2), the overflow is led to the first washing (1), and the third washing (3) is conducted.
), and the overflow is poured into the third wash (2).
), and the overflow of the third water wash (2) was led to the first water wash (1).

The composition of each treatment liquid was as follows. First development

Mother solution Replenisher Nitrilo-N, N
,N-trimethylene
Phosphonic acid pentasodium salt
1.0g 1.0g Diethylenetriaminepentaacetic acid, pentasodium salt
3.0g 3.0g Potassium sulfite

30.0g 30.0g Potassium thiocyanate
1.2g 1.2g
potassium carbonate
35.0g 3
5.0g Potassium hydroquinone monosulfonate
25.0g 25.0g
1-phenyl-4-hydroxymethyl-4-methyl-3-pyrazolidone
2.0g 2.0g Potassium bromide
0.5g ---
potassium iodide
5.0mg
─── Add water

1000ml 1000ml pH

9.60
9.70 pH was adjusted with hydrochloric acid or potassium hydroxide. color development

Mother solution Replenisher diethylene glycol
12.0ml 14.0ml 3,6-
Dithia-1,8-octanediol 0.2
0g 0.25g Nitrilo-N,N,N-trimethylenephosphonic acid
・5sodium salt

0.5g 0.5g Diethylenetriaminepentaacetic acid, pentasodium salt 2.0g
2.0g sodium sulfite

2.0g 2.5g Hydroxylamine sulfate
3.0g 3.6g N-ethyl-N-(β-methanesulfonamidoethyl)-
3-Methyl-aminoaniline sulfate 5.0
g 8.0g Fluorescent brightener (diaminostilbene type) 1.0g
1.2g potassium bromide

0.5g --- Potassium iodide

1.0mg ─── Add water
1000ml
1000ml pH

10.25 10.40 pH was adjusted with hydrochloric acid or potassium hydroxide. bleach-fix solution

Mother solution Replenisher Ethylenediaminetetraacetic acid
Disodium/dihydrate 5.0g Same ethylenediaminetetraacetic acid/Fe (trivalent)/ammonium/monohydrate in the mother liquor
80.0g sodium sulfite
15.0g ammonium thiosulfate (700g/liter) 160ml2
-mercapto-1,3,4-triazole
Add 0.5g water
1
000ml pH

6.50
The pH was adjusted with acetic acid or aqueous ammonia.

Table 5 shows the results. here,
Perform sensitometry with the new solution, record the maximum magenta image density at that time, and also
After processing m2 daily for two weeks, similar sensitometry was performed and the measured magenta maximum image density is also shown.

[0126]

[Table 5] According to Table 5, it can be seen that in the present invention, the maximum image density decrease before and after running is small, which is preferable. Example 4 The sample 102 in Example 1 was uniformly exposed to light, and the treatment in Example 3 (new solution) was performed. At that time, the exposure amount was adjusted so that the image became gray with an optical density of about 1.0.

Next, the sample 102 exposed in the same manner was subjected to the following treatment. Development processing time Temperature Mother liquor tank capacity Replenishment
Amount First development 75 seconds
38℃ 8 liters 330ml
/m2 First washing (1) 45〃 3
3〃 5 〃 ───
Second water wash (2) 45〃
33〃 5 〃 5
000 Inversion 4
5〃 38〃 5 〃
330 〃 Color development 1
35〃 38〃 15〃
330 〃 Second washing
45〃 38〃 5 〃
1000 〃 Bleach fixing (1) 6
0〃 38〃 7 〃
─── Bleach fixing (2
) 60〃 38〃 7 〃
150 〃 Third washing (1)
45〃 33〃 5 〃
─── Third washing (2) 45〃 33〃 5
〃 ───
Third flush (3) 45〃 33〃
5 〃 5000〃 Dry
Dry 45〃 75〃This is
The processing in Example 3 is the same except that the reversal exposure step is changed to a reversal step.

The composition of the reversal treatment solution was as follows. Reversal

Mother solution Replenisher Nitrilo-N, N, N
-trimethylenephosphonic acid pentasodium salt

3.0g Same as mother liquor Stannous chloride
1.0g p-aminophenol
0.1g sodium hydroxide

8.0g glacial acetic acid

Add 15.0ml water
1
000ml pH

6.0 The measurement results at this time are shown in Table 6.

[0129]

[Table 6] According to Table 6, it can be seen that when chemical fogging treatment is performed, unevenness is more likely to occur than when optical fogging treatment is performed.

[0130]

Effects of the Invention The present invention provides color development using a color developing solution that does not substantially contain benzyl when processing a silver halide color photographic light-sensitive material having a reflective support through a color reversal processing step. It is also possible to obtain a sufficiently high color density. Since the color developing solution does not substantially contain benzyl alcohol, BO in wastewater can be
The D content can be reduced, and the production of leuco dye from the cyan coupler is small, so there is no decrease in cyan coloring density.

Furthermore, the present invention provides a method in which the silver halide emulsion grains of at least one light-sensitive emulsion layer of the light-sensitive material mainly consist of tabular silver halide grains having an aspect ratio of 5 or more. By doing so, the color density can be further increased. In particular, when color reversal processing is performed continuously, it is possible to avoid the problem of black and white developing agents being mixed into the color developing solution and inhibiting color development.

Further, the present invention further improves the effect of increasing the color density by setting the color development processing time to 135 seconds or less in the color reversal processing step.
Moreover, in this case, rapid processing can be performed.

Claims (3)

[Claims] Claim 1: In a color reversal processing step in which a silver halide color photographic light-sensitive material having a light-sensitive emulsion layer on a reflective support is subjected to black-and-white development, color development is performed, and then desilvering processing is performed, in which the halogen The silver halide emulsion grains contained in at least one light-sensitive emulsion layer of the silver color photographic light-sensitive material have an equivalent sphere average grain diameter of 0.30 μm or less and contain silver iodide, and the color forming 1. A method for processing a silver halide color photographic material, characterized in that development is carried out using a color developing solution containing substantially no benzyl alcohol. 2. The silver halide emulsion grains contained in the light-sensitive emulsion layer of the silver halide color photographic light-sensitive material are:
Tabular silver halide grains with an aspect ratio of 5 or more are present in the same layer, making up 50% of the total projected area of all silver halide grains.
2. The method for processing a silver halide color photographic material according to claim 1, wherein the silver halide color photographic material is contained in an amount equal to or more than 10%. 3. The method for processing a silver halide color photographic material according to claim 1, wherein the color development is carried out for a processing time of 135 seconds or less.