JPH073568B2 - Silver halide color photographic light-sensitive material - Google Patents

Description

TECHNICAL FIELD The present invention relates to a silver halide color photographic light-sensitive material, and more specifically, it is capable of rapid development processing, the processing stability in the rapid development processing is improved, and The present invention relates to a silver halide color photographic light-sensitive material capable of silver and capable of suppressing fogging.

In general, a silver halide color photographic light-sensitive material has three kinds of photographic silver halide emulsion layers, which are selectively spectrally sensitized to have sensitivity to blue light, green light and red light, coated on a support. ing. For example, in a silver halide photographic light-sensitive material for color photographic paper, a red light-sensitive silver halide emulsion, a green light-sensitive silver halide emulsion layer, and a blue light-sensitive silver halide emulsion layer are generally coated in this order from the exposed side. Similarly to the silver halide photographic light-sensitive material for color negatives, an intermediate layer such as an ultraviolet absorbing layer and a protective layer are provided for each special purpose. It is also known that each of these silver halide emulsion layers is provided in an arrangement different from that described above, and further, as each silver halide emulsion layer, it is photosensitive to each color light in substantially the same wavelength range. It is also known to use a photosensitive silver halide emulsion layer having two layers. In these silver halide color photographic light-sensitive materials, the exposed silver halide grains are developed by using, for example, an aromatic primary amine type color developing agent as a color developing agent, and the generated color developing agent is oxidized. The reaction of the product with the dye-forming coupler forms a dye image. In this method, usually, in order to form a dye image of cyan, magenta and yellow, a phenol or naphthol type cyan coupler, a 5-pyrazolone type, a pyrazolinobenzimidazole type, a pyrazolotriazole type, an indazolone type or a cyano type, respectively. Acetyl magenta couplers and acyl acetamigi yellow couplers are used. These dye-forming couplers are contained in the light-sensitive silver halide emulsion layer or in the developing solution. The present invention relates to a silver halide color photographic light-sensitive material in which these couplers have been previously contained in a silver halide emulsion layer to make them non-diffusible.

[Prior Art] In recent years, a silver halide color photographic light-sensitive material which is capable of rapid processing, has high image quality, excellent processing stability, and low cost has been demanded in the industry in recent years.
In particular, a silver halide color photographic light-sensitive material capable of rapid processing is desired.

In other words, silver halide color photographic light-sensitive materials are run by an automatic processor provided in each laboratory. It is now required to return to users and even to return within a few hours from reception, and the development of silver halide color photographic light-sensitive materials that can be processed more rapidly is urgent. Has been. Further, in the running process, there is a problem in that stable photographic performance cannot be obtained because the photographic characteristics greatly change due to the composition change of the processing liquid and the change of conditions even between the laboratories or even in the same laboratories. Changes in the composition of the processing liquid and changes in conditions are
It is considered that this is due to elution / accumulation of the photographic active substance from the light-sensitive material during development processing (running) and other causes. Therefore, in order to cope with fluctuations in processing conditions, it is required that the developing time, the temperature and pH of the developing solution, and the halogen concentration in the developing solution, particularly the bromide concentration, be highly controlled. However, compared with the development time or the temperature and pH of the developing solution, the concentration of bromide ions in the developing solution is difficult to quantify, and it is difficult to control because of poor measurable property. Therefore, in particular, it is necessary to develop a silver halide color photographic light-sensitive material whose photographic performance has little dependence on the brom concentration and which is highly process-stabilized. Processing stability is problematic even during normal processing time, but in rapid processing, processing stability becomes more problematic. Further, it is a matter of course that such a processing-stabilized silver halide color photographic light-sensitive material is required to be provided economically at low cost.

In view of the prior art, a silver halide color photographic light-sensitive material that can be rapidly processed is disclosed in, for example, JP-A-51
-77223 fine graining technique of silver halide,
A technique for reducing silver bromide of silver halide as described in JP-A-58-184142 and JP-B-56-18939, and JP-A-56-64339.
1-aryl-3- having a specific structure as described in
A technique of adding pyrazolidone to a silver halide color photographic light-sensitive material, further JP-A-57-144547 and JP-A-58-50534,
No. 58-50535 and No. 58-50536, a technique of adding 1-arylpyrazolidones to a silver halide color photographic light-sensitive material is known. In addition, exposed silver halide color A technique of using a color development accelerator when developing a photographic light-sensitive material using an aromatic primary amine type color developing agent is also known. For example, as such a color development accelerator, U.S. Patent No. 2,950,970,
2,515,147, 2,496,903, 4,038,075, 4,1
19,462, British Patents 1,430,998, 1,455,413, JP-A-53-15831, 55-62450, 55-62451, 55.
−62452, 55−62453, 55−62453, Japanese Patent Sho 51
There are compounds described in No. 12422, No. 55-49728 and the like.

However, when using one of these conventional techniques,
Although the processing time is shortened, the processing stability in the rapid development processing is poor, and there is a problem with fogging in the same day performance.

When the above low silver bromide emulsion is used, the amount of brom ions eluted from the silver halide color photographic light-sensitive material containing the low silver bromide emulsion into the processing liquid is small, and the concentration of brom ions in the processing liquid is set low. Although rapid processing can be achieved, the processing stability is poor when a silver halide color photographic light-sensitive material containing a low silver bromide emulsion is processed using a processing solution having a low bromide concentration. Here, the treatment stability is the degree of variation in sensitometry with respect to variations in the composition of the treatment solution, pH, temperature, concentration of bromine ion, etc. and contamination of other compounds other than the composition of the treatment solution.

Further, when the above fine grain silver halide was used, there was a drawback that the processing stability was inferior and that the finer the grain, the lower the sensitivity.

On the other hand, looking at the conventional techniques for improving the processing stability, there are those by improving the processing liquid as disclosed in, for example, JP-A Nos. 59-121036 and 59-120250. As far as is known, there is no example in which the processing stability is substantially improved by the improvement of the silver halide color photographic light-sensitive material, and it is desired to develop a technique for improving the processing stability by improving the light-sensitive material.

On the other hand, silver saving is one technical means for providing a low-cost silver halide color photographic light-sensitive material. Various technologies capable of saving silver are known, and the active point substitution type magenta coupler is one of the main technologies for saving silver. However, it has been pointed out that the active-point-substitution type magenta coupler has a drawback that the occurrence of fog in the same day performance is high and that the development is suppressed when the active-point substituent contains a mercapto group.

Various improvements have been attempted to solve these problems. For example, a technique for solving the development inhibition by adding fine grain silver halide as described in JP-A-58-7632,
Further, there is a technique of suppressing fog by adding a hydroquinone compound as described in JP-A-51-9828.

However, the former method of solving the development inhibition by fine grain silver halide is not preferable because the amount of fine grain silver halide is increased. Further, the latter suppression of fog by hydroquinone or the like causes a substantial decrease in sensitivity, which is not preferable. Therefore, it is desired to develop a silver halide color photographic light-sensitive material that is less susceptible to fog and less affected by development inhibition.

[Problems to be Solved by the Invention] The present invention has been made in view of the above, and is capable of rapid development processing, the processing stability in the rapid development processing is improved, and silver saving is possible. Moreover, it is a technical subject to provide a silver halide color photographic light-sensitive material capable of suppressing the occurrence of fog.

[Means for Solving the Problems] The silver halide color photographic light-sensitive material of the present invention for solving the above technical problems is a blue-sensitive silver halide emulsion layer and a green-sensitive silver halide emulsion layer on a reflective support. And a silver halide color photographic light-sensitive material having a red light-sensitive silver halide emulsion layer in this order, the average grain size of silver halide in the blue light-sensitive silver halide emulsion layer is 0.20 to 0.55 μm, The silver halide content of the silver halide in the silver halide emulsion layer and the red light-sensitive silver halide emulsion layer is 5 to 65 mol%, and the green light-sensitive silver halide emulsion layer is represented by the following general formula [I]. It is characterized by containing at least one of the represented compounds (hereinafter referred to as active site-substituted magenta coupler of the present invention).

General formula [I] In the formula, R ₁ is an arylamino group (eg, phenylamino group, α- or β-naphthylamino group, 4-methylphenylamino group, 2,4,6-trichlorophenylamino group, 4
-[Α- (3-tert-Butyl-4-hydroxyphenoxy) tetradecanamide] -2,6-dichlorophenylamino group) or an acylamino group (for example, acetylamino group, benzamide group, 3- (2,4-di-) tert-amylphenoxy) butyramide group, 3- (3-pentadecylphenoxy) butyramide group, etc., and X is —O—
R ₂ , -S-R ₂ or Wherein R ₂ z is an alkyl group (eg, methyl group, propyl group, t-butyl group, hexadecyl group, 2- (2,4,6
-Trichlorophenyl) ethyl group, 3- (3-pentadecylphenoxy) propyl group, 3- (2,4-di-tert-
Amylphenoxy) propyl group, 2- [α- (3-tert
-Butyl-4-hydroxyphenoxy) tetradecanamidoethyl] group) or an aryl group (for example, phenyl group, α- or β-naphthyl group, 4-methylphenyl group,
2,4,6-trichlorophenyl group, 4- [α- (3-tert
-Butyl-4-hydroxyphenoxy) tetradecane amide] -2,6-dichlorophenyl group) and R ₃
And R ₄ may be the same or different and each represents a hydrogen atom, an alkyl group (for example, methyl group, propyl group, t-butyl group, hexadecyl group, 2- (2,4,6-trichlorophenyl) ethyl group, 3- (3-pentadecylphenoxy) propyl group, 3- (2,4-di-tert-amylphenoxy) propyl group, 2- [α- (3-tert-butyl-4
-Hydroxyphenoxy) tetradecanamidoethyl]
Groups), aryl groups (eg phenyl groups, α or β-
Naphthyl group, 4-methylphenyl group, 2,4,6-trichlorophenyl group, 4- [α- (3-tert-butyl-4-hydroxyphenoxy) tetradecanamido] -2,6-dichlorophenyl group, etc.), hetero Cyclic group (eg pyridyl group, thienyl group, quinolyl group etc.), acyl group (eg acetyl group etc.), alkylsulfonyl group, arylsulfonyl group, carbamoyl group (eg carbamoyl group, dimethylcarbamoyl group etc.), sulfamoyl group (eg sulfamoyl group) Group, methylsulfamoyl group, etc.), alkoxycarbonyl group (eg, methoxycarbonyl group, tetradecyloxycarbonyl group, etc.) or aryloxycarbonyl group (eg, phenoxycarbonyl group, etc.), and R ₃ and R ₄ are both hydrogen atoms. Never be. Also with R ₃
R _{4 s} may combine with each other to form a 5- or 6-membered ring with the nitrogen atom. This 5- or 6-membered ring may be further condensed with a benzene ring or a heterocycle.

X ₁ , X ₂ and X ₃ may be the same or different and each is a hydrogen atom, an alkyl group (eg methyl group, propyl group, t
-Butyl group, hexadecyl group, 2- (2,4,6-trichlorophenyl) ethyl group, 3- (3-pentadecylphenoxy) propyl group, 3- (2,4-di-tert-amylphenoxy) propyl group , 2- [α- (3-tert-butyl-
4-hydroxyphenoxy) tetradecanamidoethyl] group) or a halogen atom (eg chlorine, bromine, fluorine etc.). However, at least one of X ₁ , X ₂ and X ₃
One is not a hydrogen atom.

The active point substitution type magenta coupler used in the present invention is
It is also known that the active site-substituting component is bonded via any of an oxygen atom, a sulfur atom and a nitrogen atom, and such an active site-substituting magenta coupler is used in the specific silver halide as in the present invention. It was not known at all that the processing stability was improved when used in combination with an emulsion, particularly in the rapid processing, and it was surprising to the present inventors. . In addition, as a problem of the active point substitution type magenta coupler, it has been pointed out that the occurrence of the above-mentioned fog is high, and that development is suppressed when the active point substituent contains a mercapto group, When used in combination with the silver halide emulsion of the present invention, generation of the fog and suppression of development can be improved. This fact was completely unexpected even for the inventor who has been involved in research for many years.

Hereinafter, the present invention will be described in more detail.

The silver halide contained in the blue-sensitive silver halide emulsion layer of the present invention has an average grain size (average grain size) of 0.20 to 0.55μ.
m, preferably 0.30 to 0.50 μm. Average particle size is 0.55
When it exceeds μm, the processing stability is poor, and particularly when the amount of potassium bromide varies, the processing stability is significantly deteriorated. on the other hand,
If the average grain size is less than 0.20 μm, the sensitivity of the blue-sensitive silver halide emulsion layer is insufficient and magenta color turbidity occurs.

The average grain size of the silver halide contained in the blue-sensitive silver halide emulsion layer of the present invention can be measured by various methods generally used in the technical field for the above purpose. A typical method is Loveland's “Particle Size Analysis” ASTM Symposium on Light Microscopy, 1955, pp. 94-122 or “Theory of Photographic Processes” co-authored by Mies and James, 3rd.
Edition, published by Macmillan, Inc. (1966), Chapter 2. This particle size can be measured using the projected area or diameter approximation of the particle. If the particles are of substantially uniform shape, the particle size distribution can be fairly accurately expressed as a diameter or projected area.

The silver halide used in the present invention may be a polydisperse emulsion having an average grain size distributed in a wide range, but a monodisperse emulsion is preferable.

The above-mentioned monodisperse silver halide grain in the present invention means that most of the silver halide grains appear to have the same shape when the emulsion is observed by an electron micrograph, the grain sizes are uniform, and It has a particle size distribution as defined. That is, when the standard deviation s of the particle size distribution is divided by the average particle size, the value is 0.15 or less.

The grain size as used herein has the same meaning as the grain size described for the average grain size, and in the case of cubic silver halide grains, the length of one side thereof, or in the case of grains having a shape other than cubic, is the same. It is the length of one side when converted to a cube having a volume, and the individual particle size in this sense is ri, and when the number is ni, is defined by the following formula.

The relationship between particle size distributions is described in "The Empirical Relationship between Sensitometric and Particle Size Distributions in Photography", The Photographic Journal, LXXIX (1949), pages 330-338, by Tribel and Smith. You can decide this in a way.

The silver halide contained in the green light-sensitive silver halide emulsion layer and the red light-sensitive silver halide emulsion layer of the present invention is silver chlorobromide, silver chloroiodobromide or a mixture thereof (or silver chloride,
(A mixture containing a part of silver bromide), and the silver bromide content is 5 to
It is 65 mol%. One or both of the green light-sensitive silver halide emulsion layer and the red light-sensitive silver halide emulsion layer in the present invention may be composed of two or more layers. And in the present invention, the silver bromide content means an all-green light-sensitive silver halide emulsion layer,
Total red light-sensitive silver halide emulsion layer It means the total content of silver bromide in each layer in the total silver halide contained in each layer. When the silver bromide content exceeds 65 mol%, the processing stability becomes poor and magenta color turbidity occurs. On the other hand, when the silver bromide content is less than 5 mol%, the processing stability is significantly deteriorated.
When the silver halide contained in the green light-sensitive silver halide emulsion layer and the red light-sensitive silver halide emulsion layer of the present invention is silver chloroiodobromide, the silver iodide content thereof does not exceed 2 mol%. Those are preferable.

The preferable silver bromide content of the green-sensitive silver halide emulsion layer and the red-sensitive silver halide emulsion layer is 20 to 60 mol%, more preferably 30 to 55 mol%.

The silver halide contained in the green light-sensitive silver halide emulsion layer and the red light-sensitive silver halide emulsion layer of the present invention is also monodisperse like the silver halide contained in the blue light-sensitive silver halide emulsion layer. Are preferred.

The composition of silver halide contained in the blue-sensitive silver halide emulsion layer is not particularly limited, and may be any of silver chloride, silver bromide, silver chlorobromide salt, silver iodobromide, and a mixture thereof. Although it may be present, it is preferably silver chlorobromide and has a silver bromide content of 30 to 95 mol%. Further, the blue-sensitive silver halide emulsion layer in the present invention may be composed of two or more layers.

The average grain size of silver halide contained in the green-sensitive silver halide emulsion layer and the red-sensitive silver halide emulsion layer is not particularly limited, but is preferably 0.1 to 2 μm, more preferably 0.2.
˜1 μm, particularly preferably 0.25 to 0.8 μm.

Next, the active point substitution type magenta coupler of the present invention will be described.

The active point-substituted magenta coupler of the present invention is contained in a green light-sensitive silver halide emulsion layer. When the green light-sensitive silver halide emulsion layer is composed of two or more layers, at least one layer is contained in the layer. It may be contained.

The addition amount of the active site-substituted magenta coupler of the present invention is not limited, but it is preferably 2 × 10 ^{−3 to} 5 × 10 ⁻¹ mol, and more preferably 1 mol per mol of silver in the green light-sensitive silver halide emulsion layer. It is 1 × 10 ^{-2 to} 5 × 10 ^-1 mol.

The active point substitution type magenta coupler used in the present invention is
Examples of the active site-substituting component bonded via an oxygen atom include, for example, U.S. Patents 3,419,391 and 3,311,476.
No. 52-58533, No. 51-108842, No. 51-11703
No. 2, No. 51-112343, No. 52-55529, No. 52-90932
No. 52-20023, No. 51-110328, No. 50-48922,
57-96334, 57-96335, 57-96336, 57
-96337, 57-96338, 57-96339, 57-963
The compounds described in No. 40, No. 57-96341, No. 57-96342, No. 57-96343 and the like can be mentioned.

Further, examples of the active site-substituted component bonded through a sulfur atom include, for example, U.S. Pat.No. 3,227,554, JP-B-53-34044, JP-A-51-16924, JP-A-54-80744,
55-62454, 56-126833, 55-135835, 5
7-4044, 57-17950, 57-35858, 58-505
The compounds described in No. 37, No. 58-58544 and the like can be mentioned.

Furthermore, examples of those in which the active site-substituting component is bound via a nitrogen atom include, for example, Japanese Examined Patent Publication No. 50-40375.
51-10100, JP-A-50-13041, 50-159336,
51-3232, 51-3323, 51-20826, 51-3
No. 0228, No. 51-36938, No. 52-58922, No. 53-123129
No. 55-118034, No. 56-38043, No. 56-38044,
Examples thereof include the compounds described in JP-A-56-40825.

Specific examples of the active point-substitution magenta coupler of the present invention will be given below, but the present invention is not limited thereto.

[Exemplified compound] The silver amount (silver coating amount) of the silver halide emulsion layer in the silver halide color photographic light-sensitive material of the present invention is not particularly limited, but is 0.3 to 1 in total for the light-sensitive silver halide emulsion layer.
It is preferably g / m ² . That is, in order to obtain excellent image quality, the silver amount is preferably 1 g / m ² or less, while in order to obtain high maximum density and high sensitivity, the silver amount is 0.3 g / m ² or more. Is preferred.

The silver halide composition preferably used in the present invention is silver chlorobromide or silver chloroiodobromide. Further, it may be a combination mixture such as a mixture of silver chloride and silver bromide. That is, when the silver halide emulsion according to the present invention is used for color photographic paper, particularly fast developing property is required. Therefore, it is preferable that the halogen composition of the silver halide contains a chlorine atom, and the halogen composition is at least 1%. Particularly preferred is silver chlorobromide or silver chloroiodobromide containing silver chloride.

The crystals of these silver halide grains may be normal crystals, twin crystals or others, and any ratio of [1.0.0] face to [1.1.1] face can be used. Further, the crystal structure of these silver halide grains may be uniform from the inside to the outside, or may have a layered structure (core shell type) in which the inside and the outside are different. Further, these silver halides may be of a type that forms a latent image mainly on the surface or may be of a type that is formed inside the grain. Further, tabular silver halide grains (see Japanese Patent Application No. 59-170070) can also be used.

The substantially monodisperse silver halide grains preferably used in the present invention may be those obtained by any preparation method such as an acidic method, a neutral method or an ammonia method.

Further, for example, a method may be used in which seed particles are formed by an acidic method and further grown by an ammonia method having a high growth rate to grow to a predetermined size. When the silver halide grains are grown, the pH, pAg, etc. in the reaction vessel are controlled, and the amount of silver ions corresponding to the growth rate of the silver halide grains as described in JP-A-54-48521 is used. It is preferable to successively inject and mix the and halide ions simultaneously.

The silver halide grains according to the present invention are preferably prepared as described above. A composition containing the silver halide grains is referred to herein as a silver halide emulsion.

These silver halide emulsions include active gelatin; sulfur sensitizers such as allylthiocarbamide, thiourea, and cystine; sulfur sensitizers; selenium sensitizers; reduction sensitizers such as stannous salt and thiourea dioxide. Noble metal sensitizers such as gold sensitizers, specifically potassium aurithiocyanate, potassium chloroaurate, and 2-aurothio-3-.
Sensitizers of methylbenzothiazolium chloride and the like or water-soluble salts such as ruthenium, palladium, platinum, rhodium and iridium, specifically ammonium chloroparadate, potassium chloroplatinate and sodium chloroparadate (these or Some of them act as sensitizers or antifoggants depending on the amount.) Etc. alone or in combination (for example, gold sensitizer and sulfur sensitizer, gold sensitizer and selenium sensitizer). It may be chemically sensitized by the combined use with a sensitizer).

The silver halide emulsion according to the present invention is chemically ripened by adding a sulfur-containing compound, and before, during, or after the chemical ripening, at least one kind of nitrogen-containing heteroaryl having a hydroxytetrazaindene and a mercapto group. You may make it contain at least 1 sort (s) of a ring compound.

The silver halide used in the present invention contains a suitable sensitizing dye in an amount of 5 × 10 ^{−8 to} 3 × 10 ^{−3 with} respect to 1 mol of silver halide in order to impart photosensitivity to a desired wavelength region. It may be optically sensitized by adding a mole. Various kinds of sensitizing dyes can be used, and one kind or a combination of two or more kinds of sensitizing dyes can be used. Examples of the sensitizing dye that can be advantageously used in the present invention include the following.

That is, as the sensitizing dye used in the blue-sensitive silver halide emulsion layer, for example, West German Patent No. 929,080, U.S. Pat.
1,658, 2,493,748, 2,503,776, 2,519,001
No., No. 2,912,329, No. 3,656,959, No. 3,672,897,
Examples thereof include those described in JP-A-3,694,217, JP-A-4,025,349, JP-A-4,046,572, British Patent 1,242,588, JP-B-4414030 and JP-A-52-24844. Examples of sensitizing dyes used in green-sensitive silver halide emulsions include, for example, U.S. Patents 1,939,201, 2,072,908 and 2,739,14.
Representative examples thereof include cyanine dyes, merocyanine dyes or complex cyanine dyes such as those described in No. 9, No. 2,945,763 and British Patent No. 505,979. Further, sensitizing dyes used in red-sensitive silver halide emulsions include, for example, U.S. Patents 2,269,234 and 2,2
70,378, 2,442,710, 2,454,629, 2,776,28
Representative examples thereof include cyanine dyes, merocyanine dyes, and complex cyanine dyes described in No. 0 and the like. Furthermore, U.S. Patent 2,213,995
, 2,493,748, 2,519,001, West German Patent 929,080
Cyanine dyes, merocyanine dyes or complex cyanine dyes such as those described in JP-A No. 1994-242242 can be advantageously used in green-sensitive silver halide emulsions or red-sensitive silver halide emulsions.

These sensitizing dyes may be used alone or in combination.

The photographic light-sensitive material of the present invention may be optionally optically sensitized to a desired wavelength range by a spectral sensitization method using a cyanine or merocyanine dye alone or in combination.

Particularly preferably, a typical example of the spectral sensitization method is, for example, JP-B-43-4936 relating to a combination of benzimidazolocarbocyanine and benzoxazolocarbocyanine.
No. 43, No. 22884, No. 45-18433, No. 47-37443,
48-28293, 49-6209, 53-12375, JP
52-23931, 52-51932, 54-80118, 58-1
53926, 59-116646, 59-116647 and the like.

Further, as a combination of a carbocyanine having a benzimidazole nucleus and another cyanine or merocyanine, for example, Japanese Patent Publication Nos. 45-25831, 47-11114 and 47
-25379, 48-38406, 48-38407, 54-345
No. 35, No. 55-1569, JP-A No. 50-33220, No. 50-38526
No. 51, No. 51-107127, No. 51-115820, No. 51-135528
No. 52-104916 and No. 52-104917.

Furthermore, examples of combinations of benzoxazolocarbocyanine (oxacarbocyanine) with other carbocyanines include, for example, JP-B-44-32753 and 46-11627.
JP-A-57-1483, and those relating to merocyanine include, for example, JP-B-48-38408, 48-41204, and 50-
40662, JP-A-56-25728, 58-10753, 58-9
1445, 59-116645, 50-33828 and the like.

Further, examples of combinations of thiacarbocyanine with other carbocyanines include, for example, Japanese Patent Publication Nos. 43-4932 and 43-43.
-4933, 45-26470, 46-18107, 47-8741
JP-A-59-114533 and the like, and the method described in JP-B-49-6207 using zeromethine or dimethine merocyanine, monomethine or trimethine cyanine and styryl dyes can be advantageously used.

To add these sensitizing dyes to the silver halide emulsion according to the present invention, a dye solution such as methyl alcohol, ethyl alcohol, acetone, dimethylformamide, or a fluorinated alcohol described in JP-B-50-40659 can be prepared in advance. It is used by dissolving it in a hydrophilic organic solvent such as.

The silver halide emulsion may be added at any time from the start of chemical ripening, during ripening, and at the end of ripening, and in some cases, it may be added immediately before the emulsion coating.

The silver halide color photographic light-sensitive material of the present invention may contain a water-soluble dye in the hydrophilic colloid layer as a filter dye or for various purposes such as prevention of irradiation. Such dyes include oxonol dyes, hemioxonol dyes, merocyanine dyes and azo dyes. Of these, oxonol dyes, hemioxonol dyes and merocyanine dyes are useful. Specific examples of dyes that can be used include British Patents 584,609, 1,277,429, JP-A-48-85130, 49-99620, 49-114420 and 49-114420.
-129537, 52-108115, 59-25845, U.S. Patents 2,274,782, 2,533,472, 2,956,879, 3,1
25,448, 3,148,187, 3,177,078, 3,247,12
No. 7, No. 3,540,887, No. 3,575,704, No. 3,653,905,
No. 3,718,472, No. 4,071,312, No. 4,070,352.

The green light-sensitive silver halide emulsion layer according to the present invention contains the active point substitution type magenta coupler of the present invention, and the green light-sensitive silver halide emulsion layer contains a magenta coupler other than the present invention. Good. However, the magenta couplers outside the present invention are preferably less than 45 mol% with respect to the total amount of magenta couplers. Further, the blue-sensitive silver halide emulsion layer and the red-sensitive silver halide emulsion layer according to the present invention may each contain a coupler, that is, a compound capable of reacting with an oxidized product of a color developing agent to form a dye. it can.

In the present invention, a usual yellow coupler, magenta coupler and cyan coupler can be used as the coupler. These couplers may be so-called 2-equivalent type or 4-equivalent type couplers,
It is also possible to use a diffusible dye-releasing coupler in combination with these couplers.

Examples of the yellow coupler include a closed ketomethylene compound and an active site called a so-called 2-equivalent coupler.
o-aryl substituted coupler, active point-o-acyl substituted coupler, active point hydantoin compound substituted coupler, active point urazole compound substituted coupler and active point succinimide compound substituted coupler, active point fluorine substituted coupler, active point chlorine or bromine substituted Coupler, active point -o
-Sulfonyl-substituted couplers and the like may be used without particular limitation.

Examples of the magenta coupler used in the present invention include pyrazolone-based, pyrazolotriazole-based, pyrazolinobenzimidazole-based and indazolone-based compounds.

These magenta couplers are the same as the yellow couplers 4
Not only the equivalent type coupler but also a two equivalent type coupler may be used. As a specific example of the magenta coupler, US Pat.
600,788, 2,983,608, 3,062,653, 3,127,2
No. 69, No. 3,311,476, No. 3,419,391, No. 3,519,429
No., No. 3,558,319, No. 3,582,322, No. 3,615,506,
No. 3,834,908, No. 3,891,445, West German patent 1,810,464
Issue, West German patent application (OLS) 2,408,665, 2,417,945
No. 2, 2,418,959, 2,424,467, Japanese Patent Publication No. 40-6031
No. 51-20826, No. 52-58922, No. 49-129538.
No. 49-74027, No. 50-159336, No. 52-42121,
49-74028, 50-60233, 51-26541, 53
-55122, Japanese Patent Application No. 55-110943 and the like can be mentioned.

Further, useful cyan couplers used in the present invention include, for example, phenol type and naphthol type couplers. And these cyan couplers may be not only 4-equivalent type couplers but also 2-equivalent type couplers like the yellow couplers. Specific examples of cyan couplers include U.S. Patents 2,369,929 and 2,434,272.
No. 2, 2,474,293, 2,521,908, 2,895,826,
3,034,892, 3,311,476, 3,458,315, 3,4
76,563, 3,583,971, 3,591,383, 3,767,41
No. 1, 4,004,929, West German patent application (OLS) 2,414,830
No. 2,454,329, JP-A-48-59838, 51-26034.
No. 48-5055, 51-146827, 52-69624,
Examples thereof include those described in Nos. 52-90932 and 58-95346.

In order to incorporate the active site-substituted magenta coupler of the present invention and other couplers in the silver halide emulsion of the present invention, when the coupler is alkali-soluble, it may be added as an alkaline solvent and may be oil-soluble. In the case of, for example, U.S. Patent Nos. 2,322,027 and 2,801,170
No. 2,801,171, 2,272,191 and 2,304,
According to the method described in each specification of No. 940, it is preferable to dissolve the coupler in a high boiling point solvent and, if necessary, a low boiling point solvent together, to disperse it in a fine grain form and to add it to the silver halide emulsion. At this time, if necessary, a hydroquinone derivative, an ultraviolet absorber, an anti-fading agent, etc. may be used in combination. It is also possible to use a mixture of two or more couplers. Further, in the present invention, the addition method of the preferred couplers will be described in detail. One or more couplers may be added together with other couplers, hydroquinone derivatives, anti-fading agents, ultraviolet absorbers and the like organic acid amides. , Carbamates, esters, ketones, urea derivatives, ethers, hydrocarbons, etc., especially di-n-butyl phthalate, tri-cresyl phosphate, triphenyl phosphate, di-isooctyl azelate, di-n-
Butyl sebacate, tri-n-hexyl phosphate,
N, N-di-ethyl, caprylamidobutyl, N, N-diethyllaurylamide, n-pentadecylphenyl ether, di-octyl phthalate, n-nonylphenol,
3-pentadecyl phenyl ethyl ether, 2,5-di-s
ec-amyl phenyl butyl ether, high-boiling solvent such as monophenyl-di-o-chlorophenyl phosphate or fluoroparaffin, and / or methyl acetate, ethyl acetate, propyl acetate, butyl acetate, butyl propionate, cyclohexanol, diethylene glycol monoacetate, Anionic surfactants such as alkylbenzene sulfonic acid and alkylnaphthalene sulfonic acid and / or sorbitan, which are soluble in low boiling point solvents such as nitromethane, carbon tetrachloride, chloroform, cyclohexanetetrahydrofuran, methyl alcohol, acetonitrile, dimethylformamide, dioxane and methyl ethyl ketone. Nonionic surfactants such as sesquioleate and sorbitan monolaurate and / or gelatin It was mixed with an aqueous solution containing a hydrophilic binder, a high-speed rotary mixer, and emulsified by a colloid mill or an ultrasonic dispersing device or the like, is added to the silver halide emulsion.

In addition, the coupler may be dispersed by using a latex dispersion method. The latex dispersion method and its effect are described in JP-A-49-74538, JP-A-51-59943, JP-A-54-32552 and Research Disclosure, August 1976, No. 1485.
0, pages 77-79.

Suitable latices include, for example, styrene, acrylates,
n-butyl acrylate, n-butyl methacrylate,
2-acetoacetoxyethyl methacrylate, 2- (methacryloyloxy) ethyltrimethylammonium methosulfate, 3- (methacryloyloxy) propane-1-sulfonic acid sodium salt, N-isopropylacrylamide, N- [2- (2-methyl-4) -Oxopentyl)] acrylamide, 2-acrylamido-2-
Homopolymers, copolymers and terpolymers of monomers such as methyl propane sulfonic acid and the like.

The silver halide color photographic light-sensitive material of the present invention may further contain various photographic additives. For example, anti-cabe agents, stabilizers, UV absorbers, color stain inhibitors, fluorescent whitening agents, color image fading inhibitors, antistatic agents, hardeners, surface active agents described in Research Disclosure Magazine 17643. Agents, plasticizers, wetting agents and the like can be used. In the silver halide color photographic light-sensitive material of the present invention, hydrophilic colloids used for preparing emulsions include gelatin, derivative gelatin, graft polymers of gelatin and other polymers, proteins such as albumin and casein, and hydroxy. Any one of ethyl cellulose derivative, cellulose derivative such as carboxymethyl cellulose, starch derivative, single or copolymer synthetic hydrophilic polymer such as polyvinyl alcohol, polyvinyl imidazole, polyacrylamide and the like is included.

The support of the silver halide color photographic light-sensitive material of the present invention includes, for example, baryta paper, polyethylene-coated paper, polypropylene synthetic paper, a transparent support provided with a reflective layer, or in combination with a reflective material such as a glass plate and cellulose acetate. , Polyester films such as cellulose nitrate or polyethylene terephthalate, polyamide films, polycarbonate films, polystyrene films and the like, and these supports are appropriately selected according to the purpose of use of the photosensitive material.

Various coating methods such as dipping coating, air doctor coating, curtain coating, and hopper coating can be used for coating the emulsion layers and other constituent layers used in the present invention. Further, a simultaneous coating method of two or more layers by the method described in US Pat. Nos. 2,761,791 and 2,941,898 can also be used.

In the present invention, the coating position of each emulsion layer can be arbitrarily determined. For example, in the case of a full-color photographic light-sensitive material for photographic paper, it is preferable to sequentially arrange a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer and a red-sensitive silver halide emulsion layer from the support side. .

In the light-sensitive material of the present invention, it is optional to provide an intermediate layer having an appropriate thickness according to the purpose, and further various layers such as a filter, an anti-curl layer, a protective layer and an antihalation layer are appropriately combined as a constituent layer. Can be used. A hydrophilic colloid which can be used in the silver halide emulsion layer as described above can be similarly used as a binder in these constituent layers, and in the layer, a hydrophilic colloid can be used in the silver halide emulsion layer as described above. Various photographic additives that can be included can be included.

The processing method of the photographic light-sensitive material using the silver halide emulsion according to the present invention is not particularly limited, and any processing method can be applied. For example, as a typical one,
After color development, bleach-fixing treatment followed by washing and / or stabilizing treatment if necessary; after color development, bleaching and fixing treatment are carried out separately, and if necessary, further washing and / or stabilizing treatment; or Pre-hardening, neutralization, color development, stop-fixing, washing, bleaching, fixing, washing, post-hardening, washing in this order, color development, washing, supplemental color development, stopping, bleaching, fixing, washing, stabilizing May be carried out in any order, such as a method in which the developed silver produced by color development is subjected to halogenation bleaching, and then color development is carried out again to increase the amount of dye formed.

The color developing solution used for processing the silver halide emulsion according to the present invention is an alkaline aqueous solution containing a color developing agent, preferably having a pH of 8 or more, more preferably 9 to 12. The aromatic primary amine developing agent as the color developing agent is a compound having a primary amino group on the aromatic ring and capable of developing exposed silver halide. A precursor forming such a compound may be added.

Typical examples of the color developing agent include those of p-phenylenediamine type, and the following are preferred examples.

4-amino-N, N-diethylaniline, 3-methyl-4
-Amino-N, N-diethylaniline, 4-amino-N-
Ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-β-hydroxyethylaniline,
3-methyl-4-amino-N-ethyl-N-β-methoxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3
-Methoxy-4-amino-N-ethyl-N-β-hydroxyethylaniline-3-methoxy-4-amino-N-
Ethyl-N-β-methoxyethylaniline, 3-acetamigi-4-amino-N, N-dimethylaniline, N-ethyl-N-β [β- (β-methoxyethoxy) ethoxy] ethyl-3-methyl-4 -Aminoaniline, N-ethyl-N-β (β-methoxyethoxy) ethyl-3-ethyl-4-aminoaniline and salts thereof such as sulfates, hydrochlorides, sulfites and p-toluenesulfonates. is there.

Further, for example, JP-A-48-64932, 50-131526,
No. 51-95849 and Bent's Journal of the American Chemical Society, Volume 73, 3100-
The one described on page 3125 (1951) is also mentioned as a typical example.

The amount of these aromatic primary amino compounds used depends on where the activity of the developer is set, but it is preferable to increase the amount of use in order to increase the activity. The amount used is in the range of 0.0002 mol / l to 0.7 mol / l. Further, two or more compounds can be used in an appropriate combination depending on the purpose. For example, 3-methyl-4-amino-N, N-diethylaniline and 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl- N-
A combination of β-methanesulfonamidoethylaniline and 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline and the like can be freely combined and used according to the purpose.

In the color developer used in the present invention, various components that are usually added, for example, sodium hydroxide, an alkali agent such as sodium carbonate, an alkali metal sulfite,
Alkali metal bisulfite, alkali metal thiocyanate, alkali metal halide, benzyl alcohol,
A water softening agent, a thickening agent, a development accelerator and the like may be optionally contained.

Examples of additives other than the above that are added to the color developing solution include potassium bromide, bromide such as ammonium bromide, alkali iodide, nitrobenzimidazole, mercaptobenzimidazole, 5-methyl-benzotriazole, and 1-phenyl. Examples include compounds for rapid processing liquids such as -5-mercaptotetrazole, stain inhibitors, anti-sludge agents, preservatives, layering effect accelerators, chelating agents and the like.

As the bleaching agent used in the bleaching solution or the bleach-fixing solution in the bleaching step, those in which metal ions such as iron, cobalt and copper are coordinated with an organic acid such as aminopolycarboxylic acid or oxalic acid, citric acid are generally known. There is. And the following can be mentioned as a typical example of said amino polycarboxylic acid.

Ethylenediaminetetraacetic acid Diethylenetriaminepentaacetic acid Propylenediaminetetraacetic acid Nitrilotriacetic acid Iminodiacetic acid Ethyldiaminediaminetetraacetic acid Ethylenediaminetetrapropionic acid Ethylenediaminetetraacetic acid disodium salt Diethylenetriaminepentaacetic acid pentasodium salt Nitrilotriacetic acid sodium salt May be included. When a bleach-fixing solution is used in the bleaching step, a solution having a composition containing a silver halide stabilizer in addition to the bleaching agent is applied. Further, the bleach-fixing solution may further contain a halogen compound such as potassium bromide. And, as in the case of the bleaching solution, various other additives,
For example, a pH buffer, a fluorescent color enhancer, a defoaming agent, a surfactant, a preservative, a chelating agent, a stabilizer, an organic solvent and the like may be added and contained.

The silver halide fixing agent is, for example, sodium thiosulfate, ammonium thiosulfate, potassium thiocyanate, sodium thiocyanate, or thiourea, thioether, etc. Compounds forming a silver salt of

Color development of the silver halide color photographic light-sensitive material of the present invention,
From the viewpoint of rapid processing, it is preferable that the processing temperature of bleach-fixing (or bleaching / fixing) and, if necessary, various processing steps such as washing with water, stabilization and drying is carried out at 30 ° C. or higher.

Effects of the Invention According to the silver halide color photographic light-sensitive material of the present invention, a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer and a red-sensitive silver halide emulsion layer are provided on a reflective support. In the silver halide color photographic light-sensitive material, the average grain size of the silver halide in the blue-sensitive silver halide emulsion layer is 0.20 to 0.55 μm, the green-sensitive silver halide emulsion layer and the red-sensitive silver halide emulsion layer are The silver halide emulsion layer has a silver bromide content of 5 to 65 mol%, and the green-sensitive silver halide emulsion layer contains the active point-substituted magenta coupler of the present invention. Therefore, rapid development processing is possible, processing stability in the rapid development processing is improved, silver can be saved, and fogging can be suppressed.

[Examples] Specific examples of the present invention will be described below, but embodiments of the present invention are not limited thereto.

Example 1 Silver halide color photographic light-sensitive material samples Nos. 1 to 4 were prepared by sequentially coating the following layers from the support side on a paper support laminated on both sides with polyethylene.

Layer 1 ... 1.2 g / m ² gelatin, 0.32 g / m ² (in terms of silver, the same applies hereinafter) of a blue-sensitive silver chlorobromide emulsion (silver bromide content and average grain size are shown in Table 1), A layer containing 0.80 g / m ² of yellow coupler (Y-1) dissolved in 0.50 g / m ² of dioctyl phthalate.

Layer 2 ... an intermediate layer consisting of 0.70 g / m ² of gelatin.

Layer 3: 1.25 g / m ² gelatin, 0.15 g / m ² green-sensitive silver chlorobromide emulsion (silver bromide content and average grain size are shown in Table 1), 0.30 g / m ² dioctyl 0.52 dissolved in phthalate
Example compound (M / g ² of active site-substituted magenta coupler)
-28) containing layers.

Layer 4: an intermediate layer consisting of 1.20 g / m ² of gelatin.

Layer 5 ··· 1.20g / m ² of gelatin, 0.30 g / m ² of red-sensitive silver chlorobromide emulsion (silver bromide content and an average particle diameter shown in Table 1), dioctyl 0.20 g / m ² 0.45 dissolved in phthalate
A layer containing the following cyan coupler (C-1) of g / m ² .

Layer 6 ... A layer containing 0.30 g / m ² of the following UV absorber (UV-1) dissolved in 1.00 g / m ² of gelatin and 0.20 g / m ² of dioctyl phthalate.

Layer 7 ... A layer containing 0.50 g / m ² of gelatin.

As a hardener, 2,4-dichloro-6-hydroxy-S-triazine sodium was added to layers 2, 4 and 7 so that the amount was 0.017 g per 1 g of gelatin.

Then, for the above-mentioned sample Nos. 1 to 4, the magenta coupler of the green light-sensitive silver halide emulsion was replaced with the above-mentioned (M-1) (silver amount 0.62 g per 1 m ² ), and the green-sensitive salty odor of layer 3 was used. The only difference is that the silver content of the silver halide emulsion was changed to 0.22 g / m ² .
Sample Nos. 5 to 8 corresponding to the sample Nos. 1 to 4 were created.

Each of the above light-sensitive material samples Nos. 1 to 8 was exposed through an optical wedge and then processed in the next step.

Processing step (38 ° C.) Color development 3 minutes Bleach fixing 1 minute 30 seconds Washing with water 1 minute Drying 60 to 80 ° C. 2 minutes The composition of each processing solution is as follows.

[Color developer] Pure water 800 ml Benzyl alcohol 15 ml Hydroxyamine sulfate 2.0 g Potassium bromide 1.5 g Sodium chloride 1.0 g Potassium sulfite 2.0 g Triethanolamine 2.0 g N-ethyl-N-β-methanesulfonamidoethyl-3
-Methyl-4-aminoaniline sulfate 4.5 g 1-hydroxyethylidene-1,1-diphosphonic acid (60%
Aqueous solution) 1.5ml Potassium carbonate 32g Whitex BB (50% aqueous solution) 2ml (Fluorescent brightener, Sumitomo Chemical Co., Ltd.) Add 1 to adjust the pH to 10.1 with 20% potassium hydroxide or 10% dilute sulfuric acid. To do.

[Bleaching Fixing Solution] Pure water 550 ml Ethylenediaminetetraacetic acid iron (III) ammonium 65 g Ammonium thiosulfate 85 g Sodium bisulfite 10 g Sodium metabisulfite 2 g Ethylenediaminetetraacetic acid-2 sodium 20 g Sodium bromide 10 g Add pure water to 1 and ammonia water Or pH with dilute sulfuric acid
Adjust to 7.0.

Separately, 0.5, 1.0, 2.0 of potassium bromide in the color developing solution is added.
Each of the same sample Nos. 1 to 8 as above was subjected to development processing by using color developing solutions which were different from each other by 2.5 and 2.5.

Sensitometry was performed on each of the obtained samples by a conventional method. Table 2 shows gamma values at each potassium bromide concentration.

As is clear from the comparison between Sample Nos. 3 and 7 and Sample Nos. 4 and 8, the present invention was applied to the blue-sensitive silver halide emulsion layer, the green-sensitive silver halide emulsion layer and the red-sensitive silver halide emulsion layer. When the other silver halide emulsion was used, the effect of improving the processing stability was small even when the active point-substitution type magenta coupler of the present invention was used in combination, whereas the comparison of Samples No. 1 and 5 and No. 2 and 6 As is clear from the above, when the silver halide emulsion in the present invention and the active point substitution type magenta coupler of the present invention are used in combination,
It can be seen that the processing stability of the light-sensitive silver halide emulsion layer, especially the green light-sensitive silver halide emulsion layer, is significantly improved.

Further, in Sample Nos. 1 and 4, the silver halide emulsion of the green light-sensitive silver halide emulsion layer is exactly the same, and only the silver halide emulsion of the blue light-sensitive silver halide emulsion layer is different. However, the processing stability of the green-sensitive silver halide emulsion layer was found to be high when the active point-substitution magenta coupler of the present invention is used and the silver halide emulsion of the present invention is used (Sample N
It turns out that only o.1) is improved. As described above, the fact that the developability of the silver halide emulsion in the green light-sensitive silver halide emulsion layer is different when the silver halide emulsion in the blue light-sensitive silver halide emulsion layer is different is Is considered to mean that the developability of No. 1 affects the developability of the green-sensitive silver halide emulsion layer. This is a surprising fact that has never been known before.

Example 2 Using each of the processing solutions of Example 1 using Sample Nos. 1 to 8 (however, the potassium bromide concentration of the color developing solution was set to 1.0 g / l.), The color developing time was 2 minutes. The fog of the green light-sensitive silver halide emulsion layer was examined. The results are shown in Table 3.

As is clear from the results in Table 3, it is understood that the sample No. 1 of the present invention suppresses the generation of fog in spite of using the active site-substituted magenta coupler as the coupler.

Example 3 Sample No. 1 was used to test for rapid processability. That is, when each processing solution of Example 1 was used (however, the potassium bromide concentration of the color developing solution was set to 1.0 g / l), when the color developing time was set to 2 minutes, 2 minutes 30 seconds and 3 minutes The sensitivity (S), gamma (γ), and maximum density (Dm) were examined. The results are shown in Table 4.

As is clear from the results of Table 4, the sample No. 1 of the present invention is 2
It can be seen that sufficient photographic performance can be obtained even with a minute color development time, and the rapid processing property is excellent.

Example 4 Dm of the green-sensitive silver halide emulsion layer was changed except that Sample No. 5 was used instead of Sample No. 1 of Example 1.
The result was the same as that of Sample No. 1 above. As is clear from this, according to the present invention, it was found that a high Dm can be obtained despite the small amount of silver used.

Example 5 A sample was prepared in the same manner as in Example 1 except that magenta coupler (M-28) was replaced with (M-1) and (M-5) in sample No. 1 in Example 1. When the same experiment was conducted, good results equivalent to those of Sample No. 1 in Example 1 were obtained.

Comparative Example A comparative sample was prepared in the same manner as in sample No. 1 except that the silver halide emulsions of the first, third and fifth layers in sample No. 1 of Example 1 were changed as shown in Table 5. A, B and C were prepared and evaluated in the same manner as in Examples 1 to 3 of the present invention. The results are shown in Table 6 together with Sample No. 1 of the present invention.

As is clear from the table, the comparative sample A in which the silver bromide content of the green-sensitive silver halide and the red-sensitive silver halide was 3 mol% had a large process fluctuation range and had a fog in the green-sensitive layer. Is big.

Further, the comparative sample B in which the silver bromide content of the green-sensitive silver halide and the red-sensitive silver halide was 80 mol% had a large process fluctuation range and was inferior in rapid processability. Further, comparative sample C in which the grain size of blue-sensitive silver halide was 0.18 μm
Has a large process fluctuation range, and has a large fog in the green photosensitive layer.

 ─────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Shigeto Hirabayashi 1 Sakura-cho, Hino-shi, Tokyo Within Konishi Roku Photo Industry Co., Ltd. (56) References JP-A-59-160143 (JP, A) JP-A-59 -74546 (JP, A) JP-A-59-9653 (JP, A)

Claims (1)

[Claims] 1. A silver halide color photographic light-sensitive material having a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer and a red-sensitive silver halide emulsion layer in this order on a reflective support. The silver halide in the blue-sensitive silver halide emulsion layer has an average grain size of 0.20 to 0.55 μm, and the silver halide in the green-sensitive silver halide emulsion layer and the red-sensitive silver halide emulsion layer contains silver bromide. The rate is 5 to 56 mol%,
A silver halide color photographic light-sensitive material characterized in that the green light-sensitive silver halide emulsion layer contains at least one compound represented by the following general formula [I]. General formula [I] In the formula, R ₁ represents an arylamino group or an acylamino group, and X is —O—R ₂ , —S—R ₂ or Wherein R ₂ represents an alkyl group or an aryl group,
R ₃ and R ₄ may be the same or different and each is a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an acyl group, a sulfonyl group, a carbamoyl group, a sulfamoyl group, an alkoxycarbonyl group or an aryloxycarbonyl group. And R ₃ and R ₄ are not both hydrogen atoms. R ₃ and R ₄ may be bonded to each other to form a 5- or 6-membered ring with the nitrogen atom. This 5- or 6-membered ring may be further condensed with a benzene ring or a heterocycle. X ₁ , X ₂ and X ₃ may be the same or different and each represents a hydrogen atom, an alkyl group or a halogen atom. However, at least one of X ₁ , X ₂ and X ₃ is not a hydrogen atom.