JPH05297499A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To provide the silver halide color photographic sensitive material high in sensitivity and superior in storage stability by spectrally sensitizing silver halide grains with a specified spectral sensitizing dye and chemically sensitizing them in the presence of a specified compound. CONSTITUTION:At least one of silver halide emulsion layers formed on a support contains the silver halide grains spectrally sensitized with the spectrally sensitizing dye represented by formula 1 and chemically sensitized in the presence of the compound represented by formula II, and in formulae I and II, each of Y1 and Y2 and Y3 and Y4 is an atomic group combining with each other to form two symmetrical naphtoxazole rings; R1 is H or alkyl; each of R2 and R3 is alkyl; X1 is an anion; (m) is 1 or 2; X2 is an H or alkali metal atom; and R4 is H, halogen, or 1-5C alkyl.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide color photographic light-sensitive material, and more specifically, it has high sensitivity and has the highest density in fog or color reversal photographic light-sensitive material under various storage conditions. The present invention relates to a silver halide color photographic light-sensitive material having a small change in.

[0002]

2. Description of the Related Art In recent years, a silver halide color photographic light-sensitive material for photographing has a high sensitivity so that a scene with insufficient light quantity or a subject requiring a high shutter speed can be photographed regardless of whether it is negative or reversal. Is required. On the other hand, from a practical point of view, there is a demand for a silver halide color photographic light-sensitive material which not only has high sensitivity but also retains a stable image under any conditions.

As a means for sensitizing a silver halide color photographic light-sensitive material, for example, increasing the grain size,
It is generally known that chemical sensitization is sufficiently performed.

[0004]

However, in any of the above-mentioned high-sensitivity techniques, fogging is likely to occur in silver halide grains in any of the methods, and in conventional silver halide color photographic light-sensitive materials, high sensitivity and stability with time are required. It has not been achieved sufficiently.

An object of the present invention is to provide a silver halide color photographic light-sensitive material which has high sensitivity and has a small change in the maximum density in a fog or color reversal photographic light-sensitive material under various storage conditions. ..

[0006]

The present invention relates to a silver halide color photographic light-sensitive material having at least one silver halide emulsion layer on a support, and the silver halide grains contained in the silver halide emulsion layer. Is represented by the general formula (I)
A silver halide color photographic light-sensitive material characterized by being spectrally sensitized by a spectral sensitizing dye represented by the formula (1) and chemically sensitized in the presence of the compound represented by the general formula (II) shown in Chemical formula 4.

[0007]

[Chemical 3] (In the formula, Y ₁ and Y ₂ and Y ₃ and Y ₄ each represent an atom group forming a ring by connecting to each other to form a symmetrical naphthoxazole ring. Further, R ₁ represents a hydrogen atom or an alkyl group. R ₂ and R ₃ each represent an alkyl group, X ₁ ⁻ represents an anion, and m represents an integer of 1 or 2. provided that when m represents 1, R ₂ or R ₃ is an intramolecular group. Represents a group capable of forming a salt.)

[0008]

[Chemical 4] (In the formula, X ₂ represents a hydrogen atom or an alkali metal atom, and R ₄ represents a hydrogen atom, a halogen atom or a carbon number 1
Represents an alkyl group of ~ 5. ) Hereinafter, the present invention will be described in more detail.

The silver halide grains contained in the silver halide emulsion layer of the silver halide color photographic light-sensitive material of the present invention are
It is spectrally sensitized with the spectral sensitizing dye represented by the general formula (I).

In the above general formula (I), Y ₁ and Y ₂ and Y ₃ and Y ₄ are connected to each other to form a ring. As a result, naphthoxazole rings such as naphtho [2,3
The -d] oxazole ring, the naphtho [1,2-d] oxazole ring or the naphtho [2,1-d] oxazole ring is symmetrically formed in the molecule of the spectral sensitizing dye represented by the general formula (I).

The alkyl group represented by R ₁ is
Lower alkyl groups are preferred, for example methyl, ethyl,
There are groups like propyl. Examples of the alkyl group represented by R ₂ and R ₃ include groups such as methyl, ethyl, sulfoethyl, carboxypropyl, butyl and sulfobutyl. R ₂ and R ₃ may be the same or different from each other. Furthermore, X ₁ ^- as an anion represented by the, for example, chloride, bromide, iodide, thiocyanate, Sarufuameto, methylsulfate,
There are anions of ethyl sulfate, perchlorate, p-toluene sulfonate.

Typical examples of the spectral sensitizing dyes I-1 to I-7 represented by the general formula (I) are shown below.

[0013]

[Chemical 5]

[0014]

[Chemical 6] Further, the silver halide grain of the present invention is chemically sensitized in the presence of the compound represented by the general formula (II) (hereinafter referred to as compound (II)). That is, in the silver halide emulsion of the present invention, at least one kind of compound (II) is allowed to be present during chemical sensitization. The compound (II) may be added, for example, in the ordinary emulsion preparation step, during grain formation, during subsequent desalting, immediately before chemical sensitization of silver halide grains by redispersion thereafter, or during chemical sensitization. But it's okay. When it is added at the time of grain formation, it is preferably added after 50%, more preferably after 80% of the total silver nitrate.

The addition amount of the compound (II) is preferably 1 × 10 ^-5 mol to 1 × 10 ^-3 mol per 1 mol of total silver halide in the emulsion. When added at the time of particle formation, it is preferable to add a large amount as compared with when added after desalting,
For example, about 5 times the amount is added.

In the above general formula (II), X ₂ represents a hydrogen atom or an alkaline metal atom (eg lithium, sodium, potassium). Preferably, a hydrogen atom,
It is sodium or potassium, more preferably a hydrogen atom or sodium.

R ₄ represents a hydrogen atom, a halogen atom (eg, fluorine, chlorine, bromine) or an alkyl group having 1 to 5 carbon atoms. The alkyl group may be substituted. Preferred are a hydrogen atom, a fluorine atom, a chlorine atom and an alkyl group having 1 to 5 carbon atoms. The number of substituents represented by R ₄ is preferably 1 or 2.

Preferred specific examples II-1 to II-8 of the compound (II) are shown below.

[0019]

[Chemical 7]

[0020]

[Chemical 8] Here, the total projected area of the silver halide grains of the present invention is 50
% Or more is preferably occupied by tabular silver halide grains (hereinafter referred to as tabular grains). In the present invention, the tabular grain has an aspect ratio, that is, two parallel or nearly parallel main planes facing each other, and a main circle equivalent diameter (diameter of a circle having the same projected area as the main plane) A particle having a ratio of the distance between planes (that is, particle thickness) of 3 or more.

The average aspect ratio of the silver halide emulsion having tabular grains of the present invention is preferably from 3 to 12, and particularly preferably from 5 to 10. Here, the average aspect ratio can be obtained by averaging the grain diameters / thicknesses of all tabular grains, but a simple method is as a ratio of the average diameter of all tabular grains to the average thickness of all tabular grains. You can also ask.

The diameter (corresponding to a circle) of the tabular grains of the present invention is, for example, 0.5 μm or more, preferably 0.5 to 10 μm,
The thickness is more preferably 0.5 to 5.0 μm, still more preferably 0.5 to 2.0 μm.

The thickness of tabular grains is, for example, 0.5.
The thickness is less than or equal to μm, preferably 0.05 to 0.4 μm, and more preferably 0.08 to 0.3 μm.

The diameter and thickness of the tabular grains used in the present invention can be determined from electron micrographs of the grains as in the method described in US Pat. No. 4,434,226. Specific examples of the halogen composition of the tabular grains include silver chloroiodide, silver iodobromide, silver chloride, silver chlorobromide, silver bromide, and silver chloroiodobromide. Further, it may contain, for example, silver thiocyanate or silver cyanate.

The method for producing tabular grains includes, for example, US Pat. Nos. 4,434,226, 4439520 and 4th.
No. 414310, No. 4399215, No. 4433.
No. 048, No. 4386156, No. 4400463
Nos. 4,414,306 and 4,435,501 may be appropriately combined.

For example, a relatively high pAg of pBr 1.3 or less
By forming a seed crystal in which tabular grains are present in an amount of 40% or more by weight in an atmosphere of a certain value, and adding a silver and / or halogen solution while maintaining a pBr value of the same level or more to grow the seed crystal. can get.

In the grain growth process by adding silver and / or halogen, it is desirable to add a silver and halogen solution so that new crystal nuclei are not generated.

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

The surface of the silver halide grain of the present invention is chemically sensitized.

The above-mentioned chemical sensitization is performed by James (T.H.
James), The Theory of Photographic Process, 4th edition, published by Macramin, 1977.
Year, (TH James, The Theory o
f the Photographic Procedures
s, 4th ed, Macmillan, 1977)
It can be carried out using activated gelatin as described on pages 67-76. Research Disclosure, Volume 120, April 1974, 12008; Research.
Disclosure, Volume 34, June 1975, 134
52, U.S. Pat. Nos. 2,642,361 and 3,29.
7,446, 3,772,031, 3,85
7,711, 3,901,714, 4,26
6,018, and 3,904,415, and British Patent 1,315,755,
It can be carried out at a pAg of 5-10, a pH of 5-8 and a temperature of 30-80 ° C with sulfur, selenium, tellurium, gold, platinum, palladium, iridium, rhodium or combinations of these sensitizers. Chemical sensitization is optimally
In the presence of a gold compound and a thiocyanate compound, US Pat. Nos. 3,857,711 and 4,266,018 are also available.
No. 4,054,457, or in the presence of a sulfur-containing compound such as hypo, a thiourea compound, and a rhodanine compound. It is also possible to carry out chemical sensitization in the presence of a chemical sensitization aid. As the chemical sensitization aid to be used, compounds such as azaindene, azapyridazine and azapyrimidine which are known to suppress fog and increase sensitivity in the process of chemical sensitization are used. Examples of chemical sensitization aid modifiers are:
US Pat. Nos. 2,131,038 and 3,411,91
No. 4, 3,554, 757, JP-A-58-1265.
No. 26 and the above-mentioned "Photographic Emulsion Chemistry" by Duffin, 13
8 to 143. In addition to, or as an alternative to chemical sensitization, reduction sensitization can be performed with, for example, hydrogen as described in US Pat. Nos. 3,891,446 and 3,984,249. Further, as described in US Pat. Nos. 2,518,698, 2,743,182 and 2,743,183, a reducing agent such as stannous chloride, thiourea dioxide and polyamine is used. Thus, reduction sensitization can be achieved by treatment with low pAg (eg less than 5) and / or high pH (eg greater than 8). US Pat. Nos. 3,917,485 and 3,
The chemical sensitization method described in 966,476 can also be applied.

Further, JP-A-61-3134 and 61-3
A sensitizing method using an oxidizing agent described in JP-A No. 136 can also be applied.

In the present invention, the following monodisperse hexagonal tabular silver halide grains can be used as the tabular grains.

The emulsion in this case is a silver halide emulsion composed of a dispersion medium and silver halide grains, and 70% or more of the total projected area of the silver halide grains is the side having the minimum length. A tabular silver halide grain (hereinafter, referred to as a tabular grain and a hexagonal hexagon in which the ratio of the length of the side having the maximum length to the length is 2 or less) and having two parallel parallel surfaces as outer surfaces. And the coefficient of variation of the grain size distribution of the tabular grains (variation (standard deviation) in grain size represented by the circle-equivalent diameter of the projected area divided by the average grain size). Has a monodispersity of 20% or less. Further, the tabular grains have an aspect ratio of 2.5 or more and a grain size of 0.2 μm or more.

The composition of the tabular grains may be any of silver bromide, silver iodobromide, silver chlorobromide and silver chloroiodobromide. When the iodide ion is contained, its content is 0 to 30 mol%, and it may have a uniform crystal structure, a halogen composition having different internal and external halogen compositions, or a layered structure. Further, it is preferable that the grains contain reduction-sensitized silver nuclei.

The tabular grains can be produced by nucleation-Ostwald ripening and grain growth, the details of which are described in JP-A-63-151618.

When the tabular grains of the present invention are produced, the addition rate, amount and concentration of the silver salt solution (eg AgNO ₃ aqueous solution) and the halide solution (eg KBr aqueous solution), which are added to accelerate the grain growth, are increased. The method is preferably used.

Regarding these methods, for example, British Patent No. 1,335,925 and US Pat. No. 3,672,9 are described.
No. 00, No. 3,650,757, No. 4,242,
No. 445, JP-A-55-142329 and JP-A-55-15.
The description of No. 8124 can be referred to.

A silver halide solvent is useful for promoting the ripening. For example, it is known to have an excess of halogen ions present in the reactor to accelerate aging. Therefore, it is clear that mere introduction of a halide salt solution into the reactor can accelerate aging. Also,
Other ripening agents can also be used. All of these ripening agents can be incorporated in the dispersion medium in the reactor before adding the silver and halide salts, and one or more halide salts, silver salts or peptizers can be added. It is also possible to add the agent and introduce it into the reactor. As another variation, the ripening agent can be introduced independently at the halide salt and silver salt addition stages.

As ripening agents other than halogen ions, ammonia compounds, amine compounds, thiocyanate salts [eg alkali metal thiocyanate salts (particularly sodium and potassium thiocyanate salts), ammonium thiocyanate salts] can be used. The use of thiocyanate ripening agents is described in US Pat. No. 2,222,264,
Teachings can be found in U.S. Pat. Nos. 2,448,534 and 3,320,069. Also, US Pat. No. 3,271,15
No. 7, No. 3,574,628, and No. 3,737,
A conventional thioether ripening agent as described in No. 313 can also be used. Furthermore, JP-A-53-82
The thione compounds as disclosed in No. 408 and No. 53-144319 can also be used.

The properties of the silver halide grains can be controlled by allowing various compounds to be present in the silver halide precipitation forming process. Such a compound may be initially present in the reactor, or may be added together with one or more salts by a conventional method. US Patent Nos. 2,448,060 and 2,628,167
Issue 3, Issue 3,737,313, Issue 3,772,031
No. and Research Disclosure, 134
Vol., June 1975, 13452,
Silver halide grains by allowing compounds such as copper, iridium, lead, bismuth, cadmium, zinc, chalcogen compounds (sulfur, selenium and tellurium), gold and compounds of Group VII noble metals to be present during the silver halide precipitation process. You can control the nature of. Japanese Patent Publication 58-141
Issue 0, Moisar et al., Journal of Photographic Science, 25, 197.
As described on pages 7 and 19 to 27, the silver halide emulsion can reduce and sensitize the inside of the grain during the precipitation formation process.

In the tabular grains used in the present invention,
Silver halides having different compositions may be bonded by the epitaxial bonding, or may be bonded with a compound other than silver halide such as silver rhodanide and lead oxide. These emulsion grains are described in US Pat. No. 4,094,
No. 684, No. 4,142,900, No. 4,459,3
53, British Patent No. 2,038,792, U.S. Patent Nos. 4,349,622, 4,395,478, 4,433,501, 4,463,087, and 3, respectively. Nos. 656,962, 3,852,067 and JP-A-59-162540.

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

Non-photosensitive layers such as various intermediate layers may be provided between the above-mentioned silver halide photosensitive layers and as the uppermost layer and the lowermost layer.

For the intermediate layer, Japanese Patent Laid-Open No. 61-43748 is used.
No. 59-113438, No. 59-113440
Nos. 61-20037 and 61-20038, the couplers, the DIR compounds, etc. may be contained, and a color mixing inhibitor may be contained as is usually used.

A plurality of silver halide emulsion layers constituting each unit photosensitive layer are a high sensitivity emulsion layer and a low sensitivity emulsion layer as described in West 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 that the layers are arranged so that the sensitivities are gradually lowered toward the support, and a non-photosensitive layer may be provided between each halogen emulsion layer. Also,
JP-A-57-112751, JP-A-62-200350
No. 62-206541, No. 62-206543, etc., a low-sensitivity emulsion layer may be provided on the side farther from the support, and a high-sensitivity emulsion layer may be provided on the side closer to the support.

As a specific example, from the side farthest from the support,
Low sensitivity blue photosensitive layer (BL) / high sensitivity blue photosensitive layer (BH)
/ High sensitivity green photosensitive layer (GH) / Low sensitivity green photosensitive layer (G
L) / high-sensitivity red photosensitive layer (RH) / low-sensitivity red photosensitive layer (RL), or BH / BL / GL / GH / RH /
RL order or BH / BL / GH / GL / RL / RH
Can be installed in order.

Further, as described in JP-B-55-34932, the layers can be arranged in the order of blue-sensitive layer / GH / RH / GL / RL from the side farthest from the support. Also, JP-A-56-25738 and 62-6393.
As described in No. 6, it is also possible to arrange in the order of blue-sensitive layer / GL / RL / GH / RH from the side farthest from the support.

As described in JP-B-49-15495, the upper layer is the silver halide emulsion layer having the highest sensitivity, the middle layer is the silver halide emulsion layer having a lower sensitivity, and the lower layer is the middle layer. Another example is an arrangement in which a silver halide emulsion layer having a lower photosensitivity is arranged and three layers having different sensitivities are sequentially lowered toward the support. Even when it is composed of three layers having different sensitivities, as described in JP-A-59-202464, a medium-sensitivity emulsion from the side remote from the support in the same color-sensitive layer. It may be arranged in the order of layer / high-speed emulsion layer / low-speed emulsion layer.

In addition, the layers may be arranged in the order of high-speed emulsion layer / low-speed emulsion layer / medium-speed emulsion layer, or low-speed emulsion layer / medium-speed emulsion layer / high-speed emulsion layer. Also, 4
In the case of more than one layer, the arrangement may be changed as described above.

In order to improve color reproducibility, US Pat. Nos. 4,663,271, 4,705,744, 4,707,436 and JP-A-62-160448,
BL, GL, described in the specification of 63-89850.
It is preferable that the RL has a multilayer effect donor layer (CL) having a spectral sensitivity distribution different from that of the main photosensitive layer and is disposed adjacent to or in proximity to the main photosensitive layer.

As described above, various layer configurations and arrangements can be selected according to the purpose of each light-sensitive material.
The preferred silver halide contained in the photographic emulsion layer of the photographic light-sensitive material used in the present invention is silver iodobromide, silver iodochloride, or silver iodochlorobromide containing about 30 mol% or less of silver iodide. .. Particularly preferred is silver iodobromide or silver iodochlorobromide containing from about 2 mol% to about 10 mol% silver iodide.

The silver halide grains in a photographic emulsion have regular crystals such as cubes, octahedra and tetradecahedrons, grains having irregular crystal forms such as spheres and plates.
It may have a crystal defect such as a twin plane or a composite form thereof.

The grain size of silver halide may be fine grains of about 0.2 micron or less, or large grains having a projected area diameter of up to about 10 microns, and may be a polydisperse emulsion or a monodisperse emulsion.

The silver halide photographic emulsion which can be used in the present invention is, for example, Research Disclosure (RD) N.
o. 17643 (December 1978), pages 22-23,
"I. Emulsion preparation
ion and types) ”and ibid. 187.
16 (November 1979), p. 648, ibid. 307
105 (Nov. 1989), pages 863-865, and Graphide, "Physics and Chemistry of Photography," published by P. Glafkides, Chemieet P.
hisque Photographaque Pa
ul Montel, 1967), "Photoemulsion Chemistry" by Duffin, published by Focal Press (G.F. Duffi).
n, Photographic Emulsion C
chemistry (Focal Press, 196)
6)), "Production and coating of photographic emulsions" by Zelikmann et al., Published by Focal Press (VL Zelikman et.
al, Making and Coating Ph
otographic Emulsion, Focal
It can be prepared using the method described in Press, 1964).

For example, US Pat. No. 3,574,628,
No. 3,655,394 and British Patent No. 1,413,
The monodisperse emulsion described in No. 748 is also preferable.

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

The above-mentioned emulsion may be either a surface latent image type in which a latent image is mainly formed on the surface, an internal latent image type in which a latent image is formed, or a type having a latent image both on the surface and inside. Must be a type of emulsion. Among the internal latent image types, the cores described in JP-A-63-264740 /
It may be a shell type internal latent image type emulsion. The preparation method of this core / shell type internal latent image type emulsion is described in JP-A-59-13.
3542. The thickness of the shell of this emulsion varies depending on development processing and the like, but is preferably 3 to 40 nm, particularly preferably 5 to 20 nm.

The silver halide emulsion is usually used after physical ripening, chemical ripening and spectral sensitization. Additives used in such a process are Research Disclosure No. 17643, No. 17643. 18716 and No. 18716. No. 307105, the relevant parts are summarized in the table below.

The light-sensitive material of the present invention comprises a photosensitive silver halide emulsion having a grain size, a grain size distribution, a halogen composition,
Two or more kinds of emulsions having different characteristics of at least one of grain shape and sensitivity can be mixed and used in the same layer.

The fogged silver halide grains described in US Pat. No. 4,082,553 and the fogged grains described in US Pat. No. 4,626,498 and JP-A-59-214852 are fogged. The prepared silver halide grains and colloidal silver can be preferably used in the photosensitive silver halide emulsion layer and / or the substantially non-photosensitive hydrophilic colloid layer.
The fogged silver halide grain inside or on the surface means a silver halide grain which enables uniform (non-imagewise) development regardless of the unexposed portion and exposed portion of the light-sensitive material. .. A method for preparing a silver halide grain whose inside or surface is fogged is described in US Pat. No. 4,626,498 and JP-A-59-214852.

The silver halide forming the inner nucleus of a core / shell type silver halide grain having a fogged inside may have the same halogen composition or different halogen compositions. As the silver halide having the inside or surface of the grain fogged, any of silver chloride, silver chlorobromide, silver iodobromide and silver chloroiodobromide can be used. The grain size of these fogged silver halide grains is not particularly limited, but the average grain size is 0.01 to 0.7.
It is preferably 5 μm, particularly preferably 0.05 to 0.6 μm. Also,
The grain shape is not particularly limited, and may be regular grains or polydisperse emulsion, but monodisperse grains (at least 95% of the weight or the number of silver halide grains are within ± 40% of the average grain size) It is preferable that the particles have a particle size of

In the present invention, it is preferable to use a non-photosensitive fine grain silver halide. The non-photosensitive fine grain silver halide is a fine grain of silver halide which is not exposed to light during imagewise exposure for obtaining a dye image and is not substantially developed in the developing treatment, and it is preferable that the fog is not fogged in advance. ..

The fine grain silver halide has a silver bromide content of 0 to 100 mol%, and if necessary, silver chloride and / or
Alternatively, it may contain silver iodide. Preferred is one containing 0.5 to 10 mol% of silver iodide.

The fine grain silver halide preferably has an average grain size (average diameter of circles corresponding to the projected area) of 0.01 to 0.5 μm, more preferably 0.02 to 0.2 μm.

The fine grain silver halide can be prepared in the same manner as in the case of ordinary photosensitive silver halide. In this case, the surface of the silver halide grain does not need to be optically sensitized,
Also, spectral sensitization is not necessary. However, prior to adding this to the coating solution, it is preferable to add a known stabilizer such as a triazole-based, adadeindene-based, benzothiazolium-based, or mercapto-based compound or a zinc compound in advance. Colloidal silver can be preferably contained in the layer containing the fine grain silver halide grains.

The amount of silver coated on the light-sensitive material of the present invention was 6.0 g.
/ M ² or less is preferable, and 4.5 g / m ² or less is most preferable.

Known photographic additives that can be used in the present invention are described in the above-mentioned three Research Disclosures, and the related portions are shown in the following table.

Types of additives RD17643 RD18716 RD307105 1. Chemical sensitizer Page 23 Page 648 Right column Page 866 2. Sensitivity enhancer Page 648, right column 3. Spectral sensitizer, pages 23 to 24, page 648, right column to pages 866 to 868, supersensitizer, page 649, right column 4. Whitening agent Page 24 Page 647 Right column Page 868 5. Antifoggant, pages 24 to 25, page 649, right column, pages 868 to 870, stabilizer 6. Light absorber, pages 25 to 26, page 649, right column to page 873, filter dye, page 650, left column, ultraviolet absorber 7. Anti-staining agent Page 25 Right column Page 650 Left column Page 872 Right column 8. Dye image stabilizer Page 25 Page 650 Left column Page 872 9. Hardener 26 pages 651 left column 874 to 875 10. Binder page 26 651 left column 873 to 874 page 11. Plasticizers and lubricants 27 pages 650 right column 876 pages 12. Coating aids, 26 to 27 Page 650 page right column 875 to 876 surface active agent 13. static, page 27 page 650 right column 876 to 877 page inhibitor 14. matting agent page 878 to 879 To prevent deterioration of photographic performance due to formaldehyde gas U.S. Pat. Nos. 4,411,987 and 4,
It is preferable to add to the light-sensitive material a compound capable of immobilizing by reacting with formaldehyde described in JP-A No. 435,503.

The light-sensitive material of the present invention can be prepared by the method of US Pat.
0,454, 4,788,132, JP-A-62.
It is preferable to incorporate the mercapto compounds described in JP-A-18539 and JP-A-1-283551.

The light-sensitive material of the present invention can be incorporated into Japanese Patent Laid-Open No. 1-1060.
It is preferable to contain a compound which releases a fogging agent, a development accelerator, a silver halide solvent or a precursor thereof, as described in No. 52, regardless of the amount of developed silver produced by the development processing.

In the light-sensitive material of the present invention, the international publication WO88 /
No. 04794, Dyes or EP No. 317,308A dispersed by the method described in Japanese Patent Publication No. 1-502912.
No. 4,420,555, Japanese Patent Laid-Open No. 1-25
It is preferable to incorporate the dye described in No. 9358.

Various color couplers can be used in the light-sensitive material of the present invention. Specific examples thereof include Research Disclosure No. 17643, VII-C-
G, and the same No. 307105, VII-C to G.

Examples of yellow couplers include US Pat. Nos. 3,933,501 and 4,022,620.
Issue No. 4,326,024, No. 4,401,75
No. 2, No. 4,248,961, Japanese Patent Publication No. 58-107.
39, British Patent Nos. 1,425,020 and 1,4
76,760, U.S. Pat. Nos. 3,973,968, 4,314,023, 4,511,649,
The ones described in EP 249,473A are preferred.

As the magenta coupler, 5-pyrazolone type compounds and pyrazoloazole type compounds are preferable, for example, US Pat. Nos. 4,310,619 and 4,351,89.
7, EP 73,636, US Pat. No. 3,06
1,432, 3,725,067, Research
Disclosure No. 24220 (June 1984)
Mon.), JP-A-60-33552, Research Disclosure No. 24230 (June 1984), JP-A-60-43659, 61-72238 and 60.
-35730, 55-118034, 60-1
Those described in U.S. Pat. No. 8,5951, U.S. Pat. Nos. 4,500,630, 4,540,654, 4,556,630 and International Publication WO88 / 04795 are particularly preferable.

Examples of cyan couplers include phenol-type and naphthol-type couplers. For example, US Pat. Nos. 4,052,212, 4,146,396, 4,228,233, and 4 are cited. , 296,200,
No. 2,369,929, No. 2,801,171
No. 2, No. 2,772,162, No. 2,895,82
No. 6, No. 3,772,002, No. 3,758,3
08, 4,334,011, 4,327,
173, West German Patent Publication No. 3,329,729, State Patents 121,365A, 249,453A, US Patents 3,446,622, 4,433,99.
9, No. 4,775,616, No. 4,451,5
No. 59, No. 4,427, 767, No. 4,690,
889, 4,254,212 and 4,29
Preferred are those described in JP-A No. 6,199 and JP-A No. 61-42658. Furthermore, JP-A-64-553 and 64-64
Nos. 554, 64-555 and 64-556, and pyrazoloazole-based couplers described in U.S. Pat.
The imidazole couplers described in No. 8,672 can also be used.

Typical examples of polymerized dye-forming couplers are, for example, US Pat. Nos. 3,451,820, 4,080,211, 4,367,282, and 4,409. No. 320, No. 4,576,910,
British Patent No. 2,102,137, European Patent 341,
188A.

As couplers in which the color forming dye has an appropriate diffusibility, US Pat. No. 4,366,237, British Patent 2,125,570, European Patent 96,570,
Those described in West German Patent (Publication) No. 3,234,533 are preferable.

Colored couplers for correcting unwanted absorption of color-forming dyes are Research Disclosure N.
o. 17643, Item VII-G, ibid. 307105
VII-G, U.S. Pat. No. 4,163,670, JP-B-57-39413, U.S. Pat. No. 4,004,92.
9, U.S. Pat. No. 4,138,258, and U.S. Pat. No. 1,14.
Those described in No. 6,368 are preferable. Further, a coupler described in US Pat. No. 4,774,181 for correcting unnecessary absorption of a coloring dye by a fluorescent dye released upon coupling, and a reaction with a developing agent described in US Pat. No. 4,777,120. It is also preferable to use a coupler having a dye precursor group capable of forming a dye as a leaving group.

Compounds that release a photographically useful residue upon coupling are also preferably used in the present invention. The DIR coupler releasing a development inhibitor is the above-mentioned R
D17643, Item VII-F and No. 30710
5, patents described in section VII-F, JP-A-57-15
1944, 57-154234, 60-184.
No. 248, No. 63-37346, No. 63-37350.
U.S. Pat. Nos. 4,248,962 and 4,782,0
Those described in No. 12 are preferable.

For example, R. D. No. 11449 and 24
241, the bleaching accelerator releasing coupler described in JP-A No. 61-201247 is effective for shortening the processing time having a bleaching ability, and particularly, the light-sensitive material using the tabular silver halide grains described above. The effect is great when it is added to. Examples of couplers that release a nucleating agent or a development accelerator imagewise during development are described in British Patent 2,097,
140, 2,131,188, JP-A-59-15.
Those described in 7638 and 59-170840 are preferable. In addition, JP-A-60-107029 and 60-
252340, JP-A-1-44940, and 1-45.
Compounds which release a fogging agent, a development accelerator, a silver halide solvent and the like by an oxidation-reduction reaction with an oxidized product of a developing agent described in No. 687 are also preferable.

Other compounds that can be used in the light-sensitive material of the present invention include, for example, US Pat.
Competitive couplers as described in US Pat. No. 4,427, for example US Pat.
283,472, 4,338,393, 4,310,618, and other multiequivalent couplers, such as JP-A-60-185950 and JP-A-64-2425.
No. 2, etc., DIR redox compound releasing coupler,
DIR coupler-releasing coupler, DIR coupler-releasing redox compound or DIR redox-releasing redox compound, EP Nos. 173,302A and 313,
No. 308A, a coupler which releases a dye that recolors after separation, a ligand-releasing coupler described in U.S. Pat. No. 4,555,477, and a coupler which releases a leuco dye described in JP-A-63-75747, for example, U.S. Pat. No. 4,7
No. 74,181, the couplers which release the fluorescent dye are mentioned.

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

Examples of the high boiling point medium used in the oil-in-water dispersion method are described in, for example, US Pat. No. 2,322,027. The boiling point at atmospheric pressure used in the oil-in-water dispersion method is 1
Specific examples of the high boiling point organic solvent having a temperature of 75 ° C. or higher include phthalic acid esters (for example, 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 (eg triphenyl phosphate, tricresyl phosphate, 2 -Ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-
2-ethylhexyl phosphate, tridodecyl phosphate, tributoxyethyl phosphate, trichloropropyl phosphate, di-2-ethylhexylphenylphosphonate), benzoic acid esters (eg 2-ethylhexylbenzoate, dodecylbenzoate, 2
-Ethylhexyl-p-hydroxybenzoate), amides (e.g., N, N-diethyldodecane amide, N,
N-diethyllaurylamide, N-tetradecylpyrrolidone), alcohols or phenols (eg isostearyl alcohol, 2,4-di-tert-amylphenol), aliphatic carboxylic acid esters (eg bis (2-ethylhexyl)) Sebacate, dioctyl azelate, glycerol tributyrate, isostearyl lactate, trioctyl citrate), aniline derivatives (eg N, N-dibutyl-2-butoxy-5-te).
rt-octylaniline), hydrocarbons (eg paraffin, dodecylbenzene, diisopropylnaphthalene)
Is mentioned. The auxiliary solvent has a boiling point of about 30 ° C.
Above, preferably, an organic solvent having a temperature of 50 ° C. or higher and about 160 ° C. or lower can be used, and typical examples thereof include ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone,
Examples thereof include cyclohexanone, 2-ethoxyethyl acetate, dimethylformamide and the like.

The steps and effects of the latex dispersion method and specific examples of latex for impregnation are described in, for example, US Pat. No. 4,19.
No. 9,363, West German Patent Application (OLS) No. 2,541
274 and 2,541,230.

In the color light-sensitive material of the present invention, phenethyl alcohol, JP-A-63-257747 and JP-A-62-257747 are used.
272248 and, for example, 1,2-benzisothiazolin-3-one described in JP-A No. 1-80941, n.
-Butyl, p-hydroxybenzoate, phenol,
It is preferable to add various preservatives or antifungal agents such as 4-chloro-3,5-dimethylphenol, 2-phenoxyethanol, and 2- (4-thiazolyl) benzimidazole.

Suitable supports which can be used in the present invention are, for example, those described in RD. No. 17643, page 28, ibid.
18716, page 647, right column to page 648, left column, and ibid. 307105, page 879.

In the light-sensitive material of the present invention, the total thickness of all hydrophilic colloid layers on the emulsion layer side is preferably 28 μm or less, more preferably 23 μm or less, and 18 μm or less.
m or less is more preferable, and 16 μm or less is particularly preferable.
The film swelling speed T _1/2 is preferably 30 seconds or less, more preferably 20 seconds or less. The film thickness means a film thickness measured under a humidity condition of 25 ° C. and a relative humidity of 55% (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 (A. Gr
een, et al., Photographic Science and Engineering (Photogr. Sci. E)
ng. ), Vol. 19, No. 2, pp. 124-129, can be measured by using a swellometer (swelling meter) of the type, and T _1/2 is treated with a color developer at 30 ° C. for 3 minutes 15 seconds. 90% of the maximum swollen film thickness reached at that time is defined as the saturated film thickness, and is defined as the time required to reach 1/2 of the saturated film thickness.

The film swelling speed T _1/2 can be adjusted by adding a film hardening agent to gelatin as a binder or changing the aging condition after coating. The swelling rate is preferably 150 to 400%. The swelling rate is calculated from the maximum swelling film thickness under the conditions described above, using the formula:
It can be calculated according to (maximum swollen film thickness-film thickness) / film thickness.

The color developing solution used in the development processing of the light-sensitive material of the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine type color developing agent as a main component. Although aminophenol compounds are also useful as the color developing agent, p-phenylenediamine compounds are preferably used, and representative examples thereof include 3-methyl-4-amino-N, N diethylaniline and 3- Methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline, 3
-Methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-β-methoxyethylaniline and their sulfates, hydrochlorides or p-toluene Examples include sulfonates. Of these, 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline sulfate is particularly preferable. Two or more kinds of these compounds can be used in combination depending on the purpose.

The color developer contains a pH buffer such as an alkali metal carbonate, borate or phosphate, a chloride salt, a bromide salt, an iodide salt, a benzimidazole compound, a benzothiazole compound or a mercapto compound. It is common to include such a development inhibitor or an antifoggant. If necessary, hydroxylamine, diethylhydroxylamine, sulfite, hydrazines such as N, N-biscarboxymethylhydrazine, phenylsemicarbazides, triethanolamine, various preservatives such as catecholsulfonic acids, ethylene glycol, Organic solvents such as diethylene glycol, benzyl alcohol, polyethylene glycol, quaternary ammonium salts, development accelerators such as amines, dye-forming couplers, competing couplers, auxiliary developing agents such as 1-phenyl-3-pyrazolidone, viscosity imparting Agents, aminopolycarboxylic acids, aminopolyphosphonic acids, alkylphosphonic acids, various chelating agents represented by phosphonocarboxylic acids, for example, ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclo Hexane diamine tetraacetic acid, hydroxyethyliminodiacetic acid, 1-hydroxyethylidene--
1,1-diphosphonic acid, nitrilo-N, N, N-trimethylenephosphonic acid, ethylenediamine-N, N, N, N
-Tetramethylenephosphonic acid, ethylenediamine-di (o-hydroxyphenylacetic acid) and their salts can be mentioned as representative examples.

Next, processing liquids and processing steps of the color reversal light-sensitive material of the present invention other than color development will be described.

Among the processing steps of the color reversal light-sensitive material of the present invention, the steps from black development to color development are as follows.

1) Black-white development-water washing-reversal-color development 2) Black-white development-water washing-light reversal-color development 3) Black-white development-water washing-color development Steps 1) to 3) are all performed in US patents. 4,8
In place of the rinse process described in No. 04,616, it is possible to simplify the process and reduce waste liquid.

Next, the steps after color development will be described.

4) Color development-adjustment-bleaching-fixing-washing-stable 5) Color development-washing-bleaching-fixing-washing-stable 6) Coloring development-washing-bleaching-washing-fixing-washing-stable 7) Color development Development-washing-bleaching-washing-fixing-washing-stable 8) Color development-bleaching-fixing-washing-stable 9) Color development-bleaching-bleaching fixing-washing-stable 10) Color development-bleaching-bleaching fixing-fixing- Washing-stable 11) Color development-bleaching-washing-fixing-washing-stable 12) Color development-adjusting-bleach-fixing-washing-stable 13) Coloring development-washing-bleach-fixing-washing-stable 14) Color development-bleach-fixing -Washing-Stable 15) In the processing steps of color development-fixing-bleach-fixing-water washing-stable 4) to 15), the washing step immediately before the stabilizing step may be eliminated, or conversely, the stabilizing step of the final step may be omitted. You don't have to do it. Any one of the above steps 1) to 3) and any one of steps 4) to 15) are connected to form a color reversal step.

Next, the processing liquid in the color reversal processing step of the present invention will be described.

Known developing agents can be used in the black and white developing solution used in the present invention. As a developing agent,
For example, dihydroxybenzenes (eg hydroquinone), 3-pyrazolidones (eg 1-phenyl-
3-pyrazolidone), aminophenols (eg N
-Methyl-p-aminophenol), 1-phenyl-3
-Pyrazolines, ascorbic acid and US Pat.
The heterocyclic compounds described in No. 67,872 in which a 1,2,3,4-tetrahydroquinoline ring and an indole ring are condensed can be used alone or in combination.

The black-and-white developer used in the present invention may include, if necessary, preservatives (eg, sulfite, bisulfite), buffers (eg, carbonate, boric acid, borate, alkanolamine), alkaline agents. (Eg, hydroxide, carbonate), dissolving tablets (eg, polyethylene glycols,
Containing these esters), pH adjusters (eg organic acids such as acetic acid, sensitizers (eg quaternary ammonium salts), development accelerators, surfactants, defoamers, hardeners, viscosity imparting agents) Can be made

The black-and-white developing solution used in the present invention must contain a compound acting as a silver halide solvent.
The sulfite, which is usually added as a preservative, plays the role. The sulfite and other silver halide solvents that can be used include, for example, KSCN and NaSC.
N, K ₂ SO ₃ , Na ₂ SO ₃ , K ₂ S ₂ O ₅ , Na ₂
It can be exemplified _{S 2 O 5, K 2 S} 2 O 3, Na 2 S 2 O 3.

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

In order to carry out a sensitizing process using such a black-and-white developing solution, it is usually necessary to extend the time by up to about 3 times the standard process. At this time, if the processing temperature is increased, the extension time for the sensitization processing can be shortened.

PH of these color developing solution and black and white developing solution
Is generally 9 to 12. The replenishing amount of these developing solutions depends on the color photographic light-sensitive material to be processed, but is generally 3 liters or less per 1 square meter of the light-sensitive material, and it is 500 ml or less by reducing the bromide ion concentration in the replenishing solution. You can also do it. When the replenishment amount is reduced, it is preferable to prevent the liquid evaporation and air oxidation by reducing the contact area with the air in the processing tank.

The contact area between the photographic processing liquid and air in the processing tank can be expressed by the aperture ratio defined below.

That is, aperture ratio = [contact area between treatment liquid and air (cm ² )] ÷ [volume of treatment liquid (cm ³ )] The above aperture ratio is preferably 0.1 or less, and more preferably It is preferably 0.001 to 0.05. As a method of reducing the aperture ratio in this way, in addition to providing a shield such as a floating lid on the surface of the photographic processing liquid in the processing tank, JP-A-1-82
No. 033, a method using a movable lid, JP-A-63-63
-216050 can be mentioned as a slit developing treatment method. To reduce the aperture ratio, not only the steps of color development and black and white development, but also the subsequent steps,
For example, it is preferably applied in all steps such as bleaching, bleach-fixing, fixing, washing with water, stabilization and the like. Further, the amount of replenishment can be reduced by using a means for suppressing the accumulation of bromide ions in the developing solution.

The reversal bath used for black and white development may contain a known fogging agent. That is, for example, stannous ion-organic phosphoric acid complex salt (US Pat. No. 3,617,28)
2), stannous ion organic phosphonocarboxylic acid complex salt (Japanese Patent Publication No. 56-32616), stannous ion-aminopolycarboxylic acid complex salt (US Pat. No. 1,20).
9,050) stannous ion complex salts such as borohydride compounds (US Pat. No. 2,984,567), heterocyclic amine borane compounds (US Pat. No. 1,0).
11,000) and boron compounds.
The fogging bath (reversal 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 10, and particularly preferably 3 to 9. A light reversal process by re-exposure may be performed instead of the reversal bath, and the reversal step can be omitted by adding the fogging agent to the color developing solution.

The silver halide color photographic light-sensitive material of the present invention is subjected to bleaching treatment or bleach-fixing treatment after color development. These treatments may be carried out immediately after the color development without passing through other processing steps, in order to prevent unnecessary post-development and air fog, and to reduce the carry-in of the color developing solution to the desilvering process. In addition, in order to wash out and detoxify the sensitizing dyes and dyes contained in the photographic light-sensitive material and the color-developing agent impregnated in the photographic light-sensitive material, stop, adjust, and wash with water after color development processing. A bleaching treatment or a bleach-fixing treatment may be carried out after the treatment steps such as.

The photographic emulsion layer after color development is usually bleached. The bleaching process may be performed at the same time as the fixing process (bleach-fixing process) or separately. Further, in order to speed up the processing, a processing method of bleach-fixing processing after bleaching processing may be used. Further, treatment with two continuous bleach-fixing baths, fixing treatment before the bleach-fixing treatment, or bleaching treatment after the bleach-fixing treatment can be optionally carried out. As the bleaching agent, compounds of polyvalent metals such as iron (III), peracids, quinones, nitro compounds and the like are used. A typical bleaching agent is an iron (III) complex salt,
For example, aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid, glycol etherdiaminetetraacetic acid, or complex salts of citric acid, tartaric acid, malic acid, etc. Can be used. Among these, aminopolycarboxylic acid iron (II) complexes including ethylenediaminetetraacetic acid iron (III) complex salts and 1,3-diaminepropanetetraacetic acid iron (III) complex salts.
I) Complex salts are preferable from the viewpoint of rapid processing and prevention of environmental pollution. Further, the aminopolycarboxylic acid iron (III) complex salt is particularly useful in both the bleaching solution and the bleach-fixing solution. The pH of the bleaching solution or bleach-fixing solution using these iron (III) aminopolycarboxylic acid complex salts is usually 4.0 to 8, but it is also possible to process at a lower pH for speeding up the processing.

If necessary, a bleaching accelerator can be used in the bleaching solution, the bleach-fixing solution and their pre-bath.
Specific examples of useful bleach accelerators are described in the following specifications. For example, U.S. Pat. No. 3,893,858, West German Patents 1,290,812, and 2,059,988,
JP-A Nos. 53-32736, 53-57831, 53-37418, 53-72623, 53-
No. 95630, No. 53-95631, No. 53-104
No. 232, No. 53-124424, No. 53-1416
No. 23, No. 53-28426, Research Disclosure No. 17129 (July 1978), a compound having a mercapto group or a disulfide group;
Thiazolidine derivatives described in JP-A-50-140129; JP-B-45-8506, JP-A-52-20832
No. 53-32735, U.S. Pat. No. 3,706,5
Thiourea derivatives described in No. 61; West German Patent No. 1,12
7,715, iodide salts described in JP-A-58-16,235; West German Patent Nos. 966,410 and 2,748,
Polyoxyethylene compounds described in JP-A No. 430; polyamine compounds described in JP-B-45-8836; other JP-A-49-40,943, 49-59,644, 5
3-94,927, 54-35,727, 55
Nos. 26,506 and 58-163,940; bromide ions can be used. Among them, a compound having a mercapto group or a disulfide group is preferable from the viewpoint of a large accelerating effect, and in particular, US Pat. No. 3,893,85
No. 8, West German Patent No. 1,290,812, JP-A-53-
The compounds described in No. 95,630 are preferable. Further, the compounds described in US Pat. No. 4,552,834 are also preferable. These bleaching accelerators may be added to the light-sensitive material. These bleaching accelerators are particularly effective when bleach-fixing a color light-sensitive material for photographing.

In addition to the above compounds, the bleaching solution and the bleach-fixing solution preferably contain an organic acid for the purpose of preventing bleach stain. Particularly preferable organic acid is a compound having an acid dissociation constant (pKa) of 2 to 5, and specifically, for example, acetic acid, propionic acid and hydroxyacetic acid are preferable.

Examples of the fixing agent used in the fixing solution and the bleach-fixing solution include thiosulfates, thiocyanates, thioether compounds, thioureas and a large amount of iodide salts. Use of thiosulfates Is most commonly used, with ammonium thiosulfate being the most widely used. Further, for example, a combination of thiosulfate, thiocyanate, thioether compound and thiourea is also preferable. As a preservative for the fixing solution and the bleach-fixing solution, sulfites, bisulfites, carbonyl bisulfite adducts or sulfinic acid compounds described in European Patent 294769A are preferable. Further, various aminopolycarboxylic acids and organic phosphonic acids are preferably added to the fixing solution and the bleach-fixing solution for the purpose of stabilizing the solution.

The total time of the desilvering process is preferably as short as possible so long as no desilvering failure occurs. Preferred time is 1 to 3 minutes
Minutes, more preferably 1 minute to 2 minutes. The processing temperature is 25 ° C to 50 ° C, preferably 35 ° C to 45 ° C.
In the preferable temperature range, the desilvering rate is improved and the stain generation after the processing is effectively prevented.

In the desilvering process, it is preferable that the stirring is strengthened as much as possible. As a specific method for strengthening the stirring, a method of causing a jet of a processing solution to collide with the emulsion surface of the light-sensitive material described in JP-A-62-183460, or stirring using a rotating means of JP-A-62-183461. Method to increase the effect, further moving the photosensitive material while contacting the emulsion surface with the wiper blade provided in the solution, to improve the stirring effect by making the emulsion surface turbulent, circulation of the entire processing solution There is a method of increasing the flow rate. Such stirring improving means includes a bleaching solution, a bleach-fixing solution,
It is effective with any of the fixing solutions. It is considered that the improvement of the stirring speeds up the supply of the bleaching agent and the fixing agent into the emulsion film and, as a result, increases the desilvering rate. Further, the above-mentioned stirring improving means is more effective when a bleaching accelerator is used, and it is possible to remarkably increase the accelerating effect or eliminate the fixing inhibiting action of the bleaching accelerator.

The automatic developing machine used for the light-sensitive material of the present invention is disclosed in JP-A-60-191257 and 60-19125.
It is preferable to have the photosensitive material conveying means described in No. 8 and No. 60-191259. JP-A-60-1
As described in No. 91257, it is possible to remarkably reduce the carry-in of the treatment liquid from the front bath to the rear bath of such a conveying means, and it is highly effective in preventing the deterioration of the performance of the treatment liquid. Such effects are particularly effective in shortening the processing time in each step and reducing the amount of processing liquid replenishment.

The silver halide color photographic light-sensitive material of the present invention is generally washed with water and / or stabilized after desilvering. The amount of rinsing water in the rinsing process depends on the characteristics of the photosensitive material (for example, depending on the materials used such as couplers), application, and further, the rinsing water temperature, the number of rinsing tanks (number of stages), replenishment system such as countercurrent, forward flow, and other various conditions. It can be set in a wide range.
Among these, the relationship between the number of washing tanks and the amount of water in the multi-stage countercurrent system is described in the Journal of the Society
y of Motion Picture and T
Evolution Engineers Volume 64,
P. 248 to 253 (May 1955 issue). According to the multi-stage counter-current method described in the above literature, the amount of washing water can be significantly reduced, but due to the increase in the residence time of water in the tank, bacteria propagate, and the suspended matter produced adheres to the photosensitive material, etc. Problems arise. In the processing of the color light-sensitive material of the present invention, as a solution to such a problem, JP-A-62-288,838 has been proposed.
The method of reducing calcium ion and magnesium ion described in No. 10 can be used very effectively. Further, isothiazolone compounds and siabendazoles described in JP-A-57-8,542, chlorine-based bactericides such as chlorinated sodium isocyanurate, and benzotriazole are also described by Hiroshi Horiguchi in "Bacterial and Antifungal Agents". Chemistry "(1986)
Sankyo Publishing Co., Ltd., Sanitary Technology Association, "Microbial Sterilization, Sterilization, and Antifungal Technology" (1982), Industrial Technology Association, Japan Antibacterial and Antifungal Society, "Antibacterial and Antifungal Encyclopedia" (1986). Can also be used.

The pH of the washing water in the processing of the light-sensitive material of the present invention is 4-9, preferably 5-8. The washing water temperature and washing time can be variously set depending on the characteristics of the light-sensitive material, the use, etc., but generally 15 to 45 ° C. for 20 seconds to 10 minutes,
A range of 30 seconds to 5 minutes at 25 to 40 ° C. is preferably selected. Further, the light-sensitive material of the present invention can be directly processed with a stabilizing solution instead of the above washing with water. In such stabilizing treatment, JP-A-57-8543 and 58-58 are used.
All known methods described in JP-A-148344 and JP-A-60-220345 can be used.

In addition, the washing treatment may be followed by a further stabilizing treatment. As an example of the stabilizing treatment, a stabilizing agent containing a dye stabilizer and a surfactant, which is used as a final bath of a color light-sensitive material for photographing, is used. You can mention the bath. Examples of dye stabilizers include aldehydes such as formalin and glutaraldehyde, n-methylol compounds, hexamethylenetetramine, and aldehyde sulfite adducts. Various chelating agents and antifungal agents can also be added to this stabilizing bath.

The overflow solution accompanying the above washing with water and / or supplementation of the stabilizing solution can be reused in other steps such as the desilvering step.

In the processing using an automatic processor or the like, when each processing solution described above is concentrated by evaporation, it is preferable to add water to correct the concentration.

The silver halide color light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and accelerating the processing. For incorporation, it is preferable to use various precursors of color developing agents. For example, US Pat.
Indoaniline compounds described in No. 342,597, No. 3,342,599, Schiff base type compounds described in Research Disclosures 14,850 and 15,159, aldol compounds described in No. 13,924, USA The metal salt complexes described in Japanese Patent No. 3,719,492 and the urethane compounds described in JP-A No. 53-135628 can be mentioned.

The silver halide color light-sensitive material of the present invention comprises
In order to accelerate color development, various 1-
Phenyl-3-pyrazolidones may be incorporated. Typical compounds are, for example, JP-A Nos. 56-64339 and 57-57.
-144547 and 58-115438.

Various processing solutions used in the present invention are 10 ° C. to 50 ° C.
Used at ° C. Usually, a temperature of 33 ° C. to 38 ° C. is standard, but a higher temperature is used to accelerate the processing to shorten the processing time, and a lower temperature is used to improve the image quality and the stability of the processing liquid. be able to.

[0122]

EXAMPLES The present invention will now be specifically described by way of examples, which should not be construed as limiting the invention. Preparation of Samples 101 to 124 On each undercoated 127 μm-thick cellulose triacetate film support, from each layer having the following composition in which the kind of silver halide grains used in the 11th layer was different as shown in Tables 1 and 2. Multi-layer color light-sensitive material samples 101 to 124 were prepared. The numbers represent the amount added per m ² . The effect of the added compound is not limited to the described use. First layer: antihalation layer Black colloidal silver 0.20 g Gelatin 1.9 g UV absorber U-1 0.1 g UV absorber U-3 0.04 g UV absorber U-4 0.1 g High boiling organic solvent Oil-1 0.1 g Dye E -1 microcrystalline solid dispersion 0.1 g Second layer: intermediate layer Gelatin 0.40 g Compound Cpd-C 5 mg Compound Cpd-J 5 mg Compound Cpd-K 3 mg High boiling point organic solvent Oil-3 0.1 g Dye D-4 0.4 mg Third layer: intermediate layer Finely grained silver iodobromide emulsion on the surface and inside (average grain size 0.06 μm, coefficient of variation 18%, AgI content 1 mol%) Silver amount 0.05 g Gelatin 0.4 g Fourth layer : Low sensitivity red-sensitive emulsion layer Emulsion A Silver amount 0.1 g Emulsion B Silver amount 0.4 g Gelatin 0.8 g Coupler C-1 0.15 g Coupler C-2 0.05 g Coupler C-3 0.05 g Coupler C-9 0.05 g Compound Cpd-C 10 mg High boiling point organic solvent Oil 2 0.1 g Additive P-1 0.1 g Fifth layer: Medium speed red-sensitive emulsion layer Emulsion B Silver amount 0.2 g Emulsion C Silver amount 0.3 g Gelatin 0.8 g Coupler C-1 0.2 g Coupler C-2 0.05 g Coupler C- 3 0.2 g High boiling point organic solvent Oil-2 0.1 g Additive P-1 0.1 g Sixth layer: High-sensitivity red-sensitive emulsion layer Emulsion D Silver amount 0.4 g Gelatin 1.1 g Coupler C-1 0.3 g Coupler C-2 0.1 g Coupler C-3 0.7 g Additive P-1 0.1 g Seventh layer: Intermediate layer Gelatin 0.6 g Additive M-1 0.3 g Color mixing inhibitor Cpd-I 2.6 mg UV absorber U-1 0.01 g UV absorber U- 2 0.002 g UV absorber U-5 0.01 g Dye D-1 0.02 g Compound Cpd-C 5 mg Compound Cpd-J 5 mg Compound Cpd-K 5 mg High boiling point organic solvent Oil-1 0.02 g Eighth layer: Intermediate layer Surface and internal fogged silver iodobromide emulsion (average grain size 0.06 μm , Variation coefficient 16%, AgI content 0.3 mol%) Silver amount 0.02 g Gelatin 1.0 g Additive P-1 0.2 g Color mixing inhibitor Cpd-A 0.1 g 9th layer: low-sensitivity green-sensitive emulsion layer Emulsion E Silver amount 0.1 g Emulsion F Silver amount 0.2 g Emulsion G Silver amount 0.2 g Gelatin 0.5 g Coupler C-4 0.1 g Coupler C-7 0.05 g Coupler C-8 0.20 g Compound Cpd-B 0.03 mg Compound Cpd-C 10 mg Compound Cpd- D 0.02g Compound Cpd-E 0.02g Compound Cpd-F 0.02g Compound Cpd-G 0.02g High-boiling point organic solvent Oil-1 0.1 g High-boiling point organic solvent Oil-2 0.1 g 10th layer: Medium sensitivity green sensitive emulsion layer Emulsion G silver amount 0.3 g emulsion H silver amount 0.1 g gelatin 0.6 g coupler C-4 0.1 g coupler C-7 0.2 g coupler C-8 0.1 g compound Cpd-B 0.03 g compound Cpd-D 0.02 g compound Cpd-E 0.02 g Compound Cpd -F 0.05g Compound Cpd-G 0.05g High boiling point organic solvent Oil-2 0.01g 11th layer: High sensitivity green sensitive emulsion layer Emulsion: See Table 1 Silver amount 0.5 g Gelatin 1.0 g Coupler C-4 0.3 g Coupler C- 7 0.1 g Coupler C-8 0.1 g Compound Cpd-B 0.08 g Compound Cpd-C 5 mg Compound Cpd-D 0.02 g Compound Cpd-E 0.02 g Compound Cpd-F 0.02 g Compound Cpd-G 0.02 g Compound Cpd-J 5 mg Compound Cpd-K 5 mg High-boiling organic solvent Oil-1 0.02 g High-boiling organic solvent Oil-2 0.02 g 12th layer: Intermediate layer gelatin 0.6 g 13th layer: Yellow filter layer Yellow colloidal silver Ag amount 0.07 g Gelatin 1.1 g Color-mixing inhibitor Cpd-A 0.01 g High boiling point organic solvent Oil-1 0.01 g Microcrystalline solid dispersion of dye E-2 0.05 g 14th layer: intermediate layer gelatin 0.6 g 15th layer: low-sensitivity blue-sensitive emulsion Emulsion J Silver amount 0.2 g Emulsion K Silver amount 0.3 g Emulsion L Silver amount 0.1 g Gelatin 0.8 g Coupler C-5 0.2 g Coupler C-6 0.1 g Coupler C-10 0.4 g 16th layer: Middle-speed blue-sensitive emulsion layer emulsion L silver amount 0.1 g Emulsion M silver amount 0.4 g Gelatin 0.9 g Coupler C-5 0.3 g Coupler C-6 0.1 g Coupler C-10 0.1 g 17th layer: High-sensitivity blue-sensitive emulsion layer Emulsion N Silver amount 0.4 g Gelatin 1.2 g Coupler C-5 0.3 g Coupler C-6 0.6 g Coupler C-10 0.1 g 18th layer: 1st protective layer Gelatin 0.7 g UV absorber U-1 0.2 g UV absorber U-2 0.05 g UV absorber U -5 0.3 g Formalin scavenger CpD-H 0.4 g Dye D-1 0.1 g Dye D-2 0.05 g Dye D-3 0.1 g 19th layer: 2nd protective layer Colloidal silver Ag amount 0.1 mg Fine grain silver iodobromide emulsion ( Average particle size 0.06 μm, A I content 1 mol%) Silver amount 0.1 g Gelatin 0.4 g 20th layer: Third protective layer Gelatin 0.4 g Polymethylmethacrylate (average particle size 1.5 μm) 0.1 g Methylmethacrylate-acrylic acid copolymer (methylmethacrylate: acrylic) Acid = 4: 6) (Average particle size 1.5 μm) 0.1 g Silicone oil 0.03 g Surfactant W-1 3.0 mg Surfactant W-2 0.03 g In addition to the above composition for all emulsion layers Additive F-
1-F-7 were added. In addition to the above composition, gelatin hardener H-1 and coating and emulsifying surfactants W-3, W-4, W-5 and W-6 were added to each layer.

Further, phenol, 1,2-benzisothiazolin-3-one, 2-phenoxyethanol and phenethyl alcohol were added as antiseptic and antifungal agents.

[0124]

[Table 1]

[0125]

[Table 2] The silver iodobromide emulsions used in Samples 101 to 124 were as follows.

[0126]

[Table 3]

[0127]

[Table 4]

[0128]

[Table 5]

[0129]

[Chemical 9] The structural formulas of various compounds used in Samples 101 to 124 were as follows.

[0130]

[Chemical 10]

[0131]

[Chemical 11]

[0132]

[Chemical 12]

[0133]

[Chemical 13]

[0134]

[Chemical 14]

[0135]

[Chemical 15]

[0136]

[Chemical 16]

[0137]

[Chemical 17]

[0138]

[Chemical 18]

[0139]

[Chemical 19]

[0140]

[Chemical 20]

[0141]

[Chemical 21]

[0142]

[Chemical formula 22] The following incubation test was carried out to examine the change in fog during storage.

Three sets of sample pieces were prepared for each of the samples 101 to 124, one set was stored at 50 ° C. and 30% RH, and the other set was stored at 50 ° C. and 80% RH for 3 days. The remaining one set was stored at room temperature and used as a control. These samples were subjected to wedge exposure with a light source of 4800 ° K, and subjected to the following treatment and sensitometry for comparison. The results are shown in Table 6.

[0144]

[Table 6] [Treatment process] Treatment process time Temperature Tank capacity Replenishment amount Black and white development 6 minutes 38 ℃ 12L 2.2 L / m ² First washing 2 minutes 38 ℃ 4L 7.5 L / m ² Inversion 2 minutes 38 ℃ 4L 1.1 L / m ² Color development Development 6 minutes 38 ℃ 12L 2.2 L / m ² adjustment 2 minutes 38 ℃ 4L 1.1 L / m ² Bleach 6 minutes 38 ℃ 12L 0.22L / m ² Settlement 4 minutes 38 ℃ 8L 1.1 L / m ² Second water wash 4 minutes 38 ° C. 8 L 7.5 L / m ² stability 1 minute 25 ° C. ² L 1.1 L / m ^{2 In the} above treatment process, the composition of each treatment liquid was as follows.

Black and White Development Mother Liquor Replenisher Nitrilo-N, N, N-trimethylene phosphonic acid pentasodium salt 2.0 g 2.0 g Sodium sulfite 30 g 30 g Hydroquinone monopotassium sulfonate 20 g 20 g Potassium carbonate 33 g 33 g 1 -Phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone 2.0 g 2.0 g Potassium bromide 2.5 g 1.4 g Potassium thiocyanate 1.2 g 1.2 g Potassium iodide 2.0 mg-Add water 1000 ml 1000 ml pH 9.60 9.60 pH was adjusted with hydrochloric acid or potassium hydroxide.

Inversion solution Mother liquor Replenisher Nitrilo-N, N, N-Trimethylene Same as mother liquor Phosphonic acid / 5-sodium salt 3.0 g Stannous chloride / dihydrate 1.0 g p-Aminophenol 0.1 g Sodium hydroxide 8 g Ice Acetic acid 15 ml Water was added to 1000 ml pH 6.00 pH was adjusted with hydrochloric acid or sodium hydroxide.

Color developer Mother liquor Replenisher Nitrilo-N, N, N-trimethylene phosphonic acid pentasodium salt 2.0 g 2.0 g Sodium sulfite 7.0 g 7.0 g Trisodium phosphate dodecahydrate 36 g 36 g Potassium bromide 1.0 g-potassium iodide 90 mg-sodium hydroxide 3.0 g 3.0 g citrazinic acid 1.5 g 1.5 g N-ethyl- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline sulfate 11 g 11 g 3,6 -Dithia-1,8-octanediol 1.0 g 1.0 g Water was added to 1000 ml 1000 ml pH 11.80 12.00 pH was adjusted with hydrochloric acid or potassium hydroxide.

Preparation liquid Mother liquor Replenishing liquid Ethylenediaminetetraacetic acid-The same as the mother liquor Disodium salt / dihydrate 8.0 g Sodium sulfite 12 g 1-Thioglycerin 0.4 ml Sorbitan ester * 0.1 g Water 1000 ml pH 6.20 pH is , Hydrochloric acid or sodium hydroxide.

[0149]

[Chemical formula 23] Bleaching solution Mother liquor Replenishing solution Ethylenediaminetetraacetic acid ・ 2 sodium salt ・ dihydrate 2.0 g 4.0 g Ethylenediaminetetraacetic acid ・ Fe (III) ・ Ammonium ・ dihydrate 120 g 240 g Potassium bromide 100 g 200 g Ammonium nitrate 10 g 20 g Water was added to 1000 ml 1000 ml pH 5.70 5.50 pH was adjusted with hydrochloric acid or sodium hydroxide.

Fixing solution Mother liquor Replenishing solution Ammonium thiosulfate 8.0 g To the mother liquor, the same sodium sulfite 5.0 g sodium bisulfite 5.0 g water was added and 1000 ml pH 6.60 pH was adjusted with hydrochloric acid or ammonia water.

Stabilizer Mother liquor Replenisher Formalin (37%) 5.0 ml Same as mother liquor Polyoxyethylene-p-monononyl phenyl ether (average degree of polymerization 10) 0.5 ml Water was added to 1000 ml As shown in Table 6 Sample 10 in which the spectral sensitizing dye I-7 of the present invention and the antifoggant II-1 were used before the start of chemical sensitization
8, 109, 111, 112, 120, 121, 12
Nos. 3,124 have high magenta image relative sensitivities, and the change in maximum density due to incubation is relatively small. In addition, samples 108, 109, 1 using cubic particles
11, 112 and samples 120, 12 using tabular grains
Comparing 1,123 and 124, it is understood that the effect of the present invention in the latter case is more clear and the effect of the present invention is more remarkably exhibited when tabular grains are used.

[0152]

As described above, the silver halide color photographic light-sensitive material of the present invention has high sensitivity, and at the same time reduces fog under various storage conditions or changes in the maximum density of the color reversal photographic light-sensitive material. Can be achieved.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI Technical indication G03C 7/26

Claims (2)

[Claims] 1. In a silver halide color photographic light-sensitive material having at least one silver halide emulsion layer on a support, the silver halide grains contained in the silver halide emulsion layer are represented by the general formula (1) I) a silver halide color photographic light-sensitive material which is spectrally sensitized by a spectral sensitizing dye and chemically sensitized in the presence of a compound represented by the general formula (II) shown in Chemical formula 2. material. [Chemical 1] (In the formula, Y ₁ and Y ₂ and Y ₃ and Y ₄ each represent an atom group forming a ring by connecting to each other to form a symmetrical naphthoxazole ring. Further, R ₁ represents a hydrogen atom or an alkyl group. R ₂ and R ₃ each represent an alkyl group, X ₁ ⁻ represents an anion, and m represents an integer of 1 or 2. provided that when m represents 1, R ₂ or R ₃ is an intramolecular group. Represents a group capable of forming a salt.) (In the formula, X ₂ represents a hydrogen atom or an alkali metal atom, and R ₄ represents a hydrogen atom, a halogen atom or a carbon number 1
Represents an alkyl group of ~ 5. ) 2. 50% of the total projected area of silver halide grains
2. The silver halide color photographic light-sensitive material according to claim 1, wherein the above is occupied by tabular silver halide emulsion grains having a thickness of 0.5 .mu.m or less, a diameter of 0.5 .mu.m or more and an aspect ratio of 3 or more. material.