JPS6172237A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To make possible a quick developing process and to improve the process stability by forming the sensitive silver halide emulsion layer provided on the side nearest a reflection type base so as to contain the silver halide particles having the average grain size not larger than or equal to the average grain size of the silver halide particles of the sensitive silver halide emulsion layer which is provided on the upper side thereof and having the color sensitivity different therefrom. CONSTITUTION:The average grain sizes of the silver halide particles of the sensitive silver halide emulsion layers having different color sensitivities are successively larger from the base side and the ratio of the average grain size of the silver halide particles in the respective sensitive silver halide emulsion layer is 1:1-2:1-3 from the base side. The silver halide particles of either one or both of the green sensitive silver halide emulsion layer and red sensitive silver halide emulsion layer are larger or substantially the same in the average grain sizes thereof than or as the silver halide particles of the blue sensitive silver halide emulsion layer in the case of having the configuration consisting, successively from the base side, of the blue sensitive silver halide emulsion layer, green sensitive silver halide emulsion layer and red sensitive silver halide emulsion layer.

Description

Detailed Description of the Invention [Industrial Application Field] The present invention relates to a silver halide color photographic light-sensitive material, and more specifically, it is a silver halide color photographic material that can be rapidly developed and that has improved processing stability in the rapid development process. This invention relates to silver chemical color photographic materials.

In general, silver halide color photographic light-sensitive materials have three types of photographic silver halide emulsion layers selectively sensitized to have sensitivity to blue light, green light, and red light, coated on a support. For example, in silver halide photographic light-sensitive materials for color negatives, a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, and a red-sensitive silver halide emulsion layer are generally coated in this order from the exposed side. A bleachable yellow layer is provided between the blue-sensitive silver halide emulsion layer and the green-sensitive silver halide emulsion layer to absorb the blue light that passes through the blue-sensitive silver halide emulsion layer. A single layer of filter is provided. Further, each emulsion layer is provided with other intermediate layers for various special purposes, and a protective layer as the outermost layer. Furthermore, for example, in a silver halide photographic light-sensitive material for color photographic paper, generally from the side to be exposed to light, a red-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, and a blue-sensitive silver halide emulsion layer are formed in this order. It is painted with
As in silver halide photographic materials for color negatives, intermediate layers such as ultraviolet absorbing layers, protective layers, etc. are provided for special purposes. It is also known that each of these silver halide emulsion layers is provided in a different arrangement from the above, and each silver halide emulsion layer is sensitive to substantially the same wavelength range for each dye. having sex 2
Using a photosensitive silver halide emulsion layer consisting of layers.
is also known. In these silver halide color photographic materials, exposed silver halide grains are developed using, for example, an aromatic primary amine color developing agent as a color developing agent, and the resulting color developing agent is oxidized. A dye image is formed by reaction of the product with the dye-forming coupler. In this method: typically a phenolic or naphtholic cyan coupler, 5
- Pyrazolone, pyrazolinobenzimidazole, pyrazolotriazole, indacylon or cyanoacetyl magenta couplers and acylacetamide yellow couplers are used. These dye-forming couplers are contained in the light-sensitive silver halide emulsion layer or in the developer.The present invention is directed to the use of halogen-forming couplers that are previously contained in the silver halide emulsion layer and are rendered non-diffusible. This invention relates to silver oxide color photographic materials.

[Prior Art] In recent years, there has been a demand in the industry for silver halide color photographic materials that can be processed quickly, have high image quality, have excellent processing stability, and are low cost.
In laboratories, there is a particular desire for silver halide color photographic materials that are capable of rapid development, have improved processing stability in the rapid development, and reduce maintenance during processing.

In other words, silver halide color photographic light-sensitive materials are subjected to running processing in automatic processing machines installed in each laboratory, but as part of an effort to improve service to users, processing is carried out on the same day that processing is received. In recent years, it has become necessary to process and return the material to the user within a few hours of receipt, and there is an urgent need to develop silver halide color photographic materials that can be processed even more rapidly. It's broken. Furthermore, in running processing, there is a problem in that photographic properties vary greatly between laboratories or even within the same laboratory due to changes in the composition of the processing solution and fluctuations in conditions, making it impossible to obtain stable photographic performance. Such changes in the composition of the processing solution and fluctuations in conditions are thought to be due to elution and accumulation of photographically active substances from the light-sensitive material during development processing (running), and other causes.

Therefore, in order to respond to variations in processing conditions, it is required that the development time, temperature and pH of the developer, as well as the halogen concentration, especially the bromine ion concentration, etc. in the developer are highly controlled. However, compared to the development time or the temperature and pH of the developer, the bromide ion concentration in the developer is difficult to quantify and therefore difficult to control.

Therefore, it is particularly necessary to develop a silver halide color photographic light-sensitive material whose photographic performance has little dependence on bromine concentration and is highly process-stabilized. Processing stability is a problem even with current processing times, but processing stability becomes more of a problem in rapid processing. With the rise of small-sized laboratories capable of processing relatively small amounts, the problem of processing stability in such rapid development processing is an important problem that must be solved in order to reduce processing maintenance.

Furthermore, there is an increasing demand for such process-stabilized silver halide color photographic materials to be economically available at low cost.

Therefore, if we look at the conventional techniques for silver halide color photographic materials that can be processed rapidly, for example,
Silver halide micrograining technology as described in No. 1-77223, ■ JP-A-58-184142, JP-A-56-1
A technique for reducing the silver bromide of silver halide as described in No. 8939, and (1) producing a silver halide color photographic light-sensitive material using l-7 ly-3-pyrazolidone having a specific structure as described in JP-A No. 56-64339. Addition technology, and JP-A-57
-144547, 58-50534, 58-5
0535 and No. 58-50536 are known, in which 1-arylpyrazolidones are added to silver halide color photographic light-sensitive materials; A technique of using a color development accelerator when developing a photosensitive material using an aromatic primary amine color developing agent is also known. For example, such a color development accelerator is disclosed in US Pat. ,35
No. 0.970, No. 2,515,147, No. 2,496
, No. 903, No. 4.038.075, No. 4,119,
482, British Patent No. 1,430.888, British Patent No. 1,45
No. 5,413, JP-A-53-15831, JP-A No. 55-6
No. 2450, No. 55-62451, No. 55-6245
No. 2, No. 55-62453, No. 51-12422,
There are compounds described in Japanese Patent Publication No. 55-62453, Japanese Patent Publication No. 51-12422, Japanese Patent Publication No. 55-49728, and the like.

However, when using ■ or ■ of these conventional techniques,
Although the processing time is shortened, the processing stability is poor, especially in rapid development processing.

When the low silver bromide emulsion (2) is used, less bromide ions are eluted into the processing solution from the silver halide color photographic light-sensitive material containing the low silver bromide emulsion, and the concentration of bromide ions in the processing solution is low. Although it is possible to achieve rapid processing because the bromine ion concentration can be set low, 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 with a low bromine ion concentration. Processing stability here refers to the degree of variation in sensitometry with respect to fluctuations in the processing solution composition, pH 1 temperature, protom ion concentration, etc., and to the contamination of other compounds other than the processing solution composition.

Furthermore, when the fine grain silver halide of (1) was used, there was a drawback that the processing stability was poor, and the sensitivity was impaired as the grains became finer.

On the other hand, if we look at conventional techniques for improving processing stability, for example, as disclosed in JP-A-59-121036 and JP-A-59-120250, there are techniques that involve improving the processing solution. To the best of our knowledge, there is no example in which the processing stability has been substantially improved by improving silver halide color photographic materials.

[Problems to be Solved by the Invention] The present invention has been made in view of the above, and provides a silver halide color photographic light-sensitive material that can be rapidly developed and has improved processing stability in the rapid development process. The technical challenge is to provide the following.

[Means for Solving the Problems] The silver halide color photographic light-sensitive material of the present invention which solves the above-mentioned technical problems has a blue-sensitive silver halide emulsion layer and a green-sensitive silver halide emulsion layer on a reflective support. In a silver halide color photographic light-sensitive material having a red-sensitive silver halide emulsion layer and a red-sensitive silver halide emulsion layer, the silver halide grains in the light-sensitive silver halide emulsion layer provided on the side closest to the reflective support are silver halide grains in at least one light-sensitive silver halide emulsion layer having substantially different color sensitivities, provided above the light-sensitive silver halide emulsion layer provided on the side closest to the reflective support; are characterized in that their average particle diameters are larger or substantially the same.

In a preferred embodiment of the present invention, in the light-sensitive silver halide emulsion layers having different color sensitivities, the average grain size of the silver halide grains increases sequentially from the support side, and the halogen of each light-sensitive silver halide emulsion layer is The ratio of average particle diameters of silver oxide particles is 1=1 to 2:1 to 3 from the support side,
Still another preferred embodiment is that the average grain size of silver halide in the blue-sensitive silver halide emulsion layer is 0.20 to 0.55 pm.
and the silver bromide content of silver halide in the green-sensitive silver halide emulsion layer and the red-sensitive silver halide emulsion layer is 5 to 5.
It is 65 mol%.

The present invention will be explained in more detail below.

In addition, in this specification, "lower layer" or "lower side" refers to the side closer to the support or its layer, and "upper layer" or "upper side" conversely refers to the side farther from the support or its layer. .

The silver halide color photographic light-sensitive material of the present invention comprises three light-sensitive silver halide emulsion layers having substantially different color sensitivities, namely, a blue-sensitive silver halide emulsion layer and a green-sensitive silver halide emulsion layer. layer and a red-sensitive silver halide emulsion layer. The coating positions of the three light-sensitive silver halide emulsion layers having different color sensitivities do not matter, but the green-sensitive silver halide emulsion layer and/or the red-sensitive silver halide emulsion layer are placed above the blue-sensitive silver halide emulsion layer. It is desirable that a silver halide emulsion layer is coated. In the silver halide color photographic light-sensitive material of the present invention, the silver halide grains in the photosensitive silver halide emulsion layer provided on the side closest to the reflective support are larger than the silver halide grains provided on the side closest to the reflective support. Silver halide grains in at least one light-sensitive silver halide emulsion layer having different color sensitivities provided above the silver emulsion layer have larger average grain sizes or are substantially the same. It has a configuration. A specific example will be explained as follows. That is, when a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, and a red-sensitive silver halide emulsion layer are arranged sequentially from the support side,
l & halogen in either or both of the light-sensitive silver halide emulsion layer and the red-sensitive silver halide emulsion layer (silver halide grains in the arsenic emulsion layer, silver halide grains in the blue-sensitive silver halide emulsion layer) The average particle size is larger than or substantially the same.

The blue-sensitive silver halide emulsion layer, the green-sensitive silver halide emulsion layer and the red-sensitive silver halide emulsion layer in the present invention may each consist of two or more layers, and the two or more layers are However, in the present invention, the requirement for the average grain size of the silver halide grains in the silver halide emulsion layer is based on the silver halide grains having the same color sensitivity. This does not mean a comparison between emulsion layers, but a comparison between silver halide emulsion layers having different color sensitivities. Further, to explain the above specific example, the silver halide grains in the green-sensitive silver halide emulsion layer have a larger average grain size than the silver halide grains in the blue-sensitive silver halide emulsion layer. If they are substantially the same, the average grain size of the red-sensitive silver halide emulsion layer is larger than that of the silver halide grains of the green-sensitive silver halide emulsion layer and/or the blue-sensitive silver halide emulsion layer. The silver halide grains in the red-sensitive silver halide emulsion layer, on the other hand, may be substantially the same, or may be relatively small in size, while the silver halide grains in the red-sensitive silver halide emulsion layer The average grain size is larger than or substantially the same as that of the silver halide grains in the layer.

The average grain size of the green-sensitive silver halide emulsion layer may be larger than the silver halide grains of the blue-sensitive silver halide emulsion layer and/or the red-sensitive silver halide emulsion layer,
They may be substantially the same or may be smaller than each other. In this way, at least one of the upper light-sensitive silver halide emulsion layers having different color sensitivities with respect to the lowermost light-sensitive silver halide emulsion layer has silver halide grains with an average grain size of It only needs to be larger or substantially the same.

However, in the most preferred embodiment of the present invention, the average grain size of the silver halide grains in the light-sensitive silver halide emulsion layer gradually increases from the support side, and the average grain size of the silver halide grains in each light-sensitive silver halide emulsion layer The average grain size ratio from the support side is l:(~2:1-3. That is, from the support side, the blue-sensitive silver halide emulsion layer, the green-sensitive silver halide emulsion layer,
Taking the above specific example in which the red-sensitive silver halide emulsion layers are arranged as an example, the blue-sensitive silver halide emulsion layer, the red-sensitive silver halide emulsion layer, the red-sensitive silver halide emulsion layer, For example, (1) l:1:1, (2)
1:1:2, (3) 1:l:3, (4)
Preferred examples of the present invention include average grain size ratios of silver halide grains such as 1:2:2 and (5) 1:2:3.

In a preferred embodiment of the present invention, the average grain size of silver halide in the blue-sensitive silver halide emulsion layer is not limited to 0.2.
The silver bromide content of the silver halide in the green-sensitive silver halide emulsion layer and the red-sensitive silver halide emulsion layer is preferably 5-5 mol %.

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 0.20-0.
55 pLm is preferable, more preferably 0.30 to 0.
It is 50Bm.

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 commonly used in the art for the above purpose. A method that can be used is Loveland's "Particle Size Analysis Method" A, S, T, M, Symposium on Light Microscopy, 1955, 94-1.
22 pages or "Theory of the Photographic Process" by Mies and James, 3rd edition, published by Macmillan (1988)
Some of them are listed in Chapter 2 of . The particle size can be measured using the particle's projected area or diameter approximation. If the particles are of substantially uniform shape, the particle size distribution can be described fairly accurately as diameter or projected area.

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

In the present invention, the above-mentioned monodisperse silver halide grains mean that most of the silver halide grains appear to have the same shape when the emulsion is observed using an electron microscope, have uniform grain sizes, and have the following formula: It has a particle size distribution as defined by . That is, when the standard deviation S of the particle size distribution is divided by the average particle size f, the value is 0.15 or less.

One ≦ 0.15? The grain size here has the same meaning as the grain size described above regarding the average grain size, and in the case of cubic silver halide grains, the length of its side, or in the case of grains with shapes other than cubes, The length of one side when converted to a cube having the same volume, where the individual grain size in this sense is ri and the number is ni, - is defined by the following formula. be.

Σni * ri Σni The relationship between particle size distribution is described in "Empirical Relationship between Sensitometric Distribution and Particle Size Distribution in Photography," The Photographic Journal, Vol. LXXIX (1949) 330-3.
In the method described in the paper by Tribel and Smith on page 38,
The silver halide contained in the green-sensitive silver halide emulsion layer and red-sensitive silver halide emulsion layer of the present invention that can determine this is silver chlorobromide, silver chloroiodobromide, or A mixture of the following is preferred, and the silver bromide content is 5 to 65 mol%.
In the present invention, the silver bromide content refers to the silver bromide content of each layer in the total silver halide contained in each of the all-green light-sensitive silver halide emulsion layer and the all-red light-sensitive silver halide emulsion layer. The content of total silver bromide.

When the silver halide contained in the green-sensitive silver halide emulsion layer and the red-sensitive silver halide emulsion layer of the present invention is silver chloroiodobromide, the silver iodide content does not exceed 2 mol%. Preferably.

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

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

The composition of the silver halide contained in the blue-sensitive silver halide emulsion layer is not particularly limited, and may be silver bromide, silver chlorobromide, silver chloroiodobromide, or a mixture thereof. However, silver chlorobromide is preferable, with a silver bromide content of 30
~95 mol%.

The average grain size of the 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 gm, more preferably 0.2 to 14 gm. , particularly preferably from 0.25 to 0.8 lm
It is.

The amount of silver (silver+i amount) in the silver halide emulsion layer in the silver halide color photographic light-sensitive material of the present invention is not particularly limited, but the total amount of silver halide emulsion layer is 0.3 to Ig.
/rrr' is preferable. That is, in order to obtain excellent image quality, the silver amount is preferably less than Ig/m', and in order to obtain high power, high maximum density, and high sensitivity, the silver amount is 0.38/rn. ' or more is preferable.

Silver halide compositions preferably used in the present invention include silver chlorobromide and silver chloroiodobromide. Furthermore, it may be a combinatorial mixture such as a mixture of silver chloride and silver bromide.
That is, 1. When the silver halide emulsion according to the present invention is used in color photographic paper, particularly fast developability is required, so it is preferable that the halogen composition of the silver halide contains chlorine atoms, and at least 1% of the chlorine atoms. Silver chlorobromide or silver chloroiodobromide containing silver chloride is particularly preferred.

Monodisperse silver halide grains preferably used in the present invention may be obtained by any preparation method such as an acid method, a neutral method, or an ammonia method.

For example, when growing silver halide grains, p) 1. It is preferable to control PAg and the like, and to sequentially and simultaneously implant and mix silver ions and halide ions in amounts commensurate with the growth rate of silver halide grains as described in, for example, JP-A No. 54-48521.

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

These silver halide emulsions contain activated gelatin: V#, yellow sensitizers such as allylthiocarbamide, sulfur sensitizers such as thiourea and cystine; selenium sensitizers; reduction sensitizers such as stannous salts; thiourea dioxide, polyamines, etc.; noble metal sensitizers such as gold sensitizers, specifically potassium aurithiocyanate, potassium chloroaurate, 2-aurothio-3-methylbenthiazolium chloride, etc.; or ruthenium, palladium, platinum, etc. Sensitizers of water-soluble salts such as rhodium and iridium, specifically ammonium chlorovaladate, potassium chlorooleate, and sodium chloroparadate (these types can be used as sensitizers or fog suppressors depending on the amount) chemically sensitized by using sensitizers alone or in appropriate combinations (for example, a combination of a gold sensitizer and a sulfur sensitizer, a combination of a gold sensitizer and a selenium sensitizer, etc.). It's okay.

The silver halide emulsion according to the present invention is chemically ripened by adding a sulfur-containing compound, and before, during, or after this chemical ripening, a nitrogen-containing emulsion having at least one hydroxytetrazaindene and mercapto group is produced. It may also contain at least one type of terocyclic compound.

The silver halide used in the present invention is mixed with an appropriate sensitizing dye in an amount of 5 X 10-'' to 3
Optical sensitization may be achieved by adding Q-3 moles.

Various sensitizing dyes can be used, and each sensitizing dye can be used alone or in combination of two or more types. Examples of the sensitizing dyes that can be advantageously used in the present invention include the following: I can list kimono.

That is, examples of sensitizing dyes used in the blue-sensitive silver halide emulsion layer include West German Patent No. 929.080, US Patent No. 2,231,858, US Pat. ? 7f3, 2,519,001, 2,912,329, 3,658,959, 3
, No. 872,897, No. 3,894.217, No. 4.
Examples include those described in Japanese Patent Publication No. 025.349, British Patent No. 4,048.572, British Patent No. 1,242,588, Japanese Patent Publication No. 44-14030, Japanese Patent Publication No. 52-24844, and the like. In addition, examples of sensitizing dyes used in green-sensitive silver halide emulsions include U.S. Pat.
Typical examples include cyanine dyes, merocyanine dyes and composite cyanine dyes as described in British Patent No. 2,945.783 and British Patent No. 505,979. Furthermore, as sensitizing dyes used in red-sensitive silver halide emulsions, for example, US Pat.
No. 39,234, No. 2,270,378, No. 2,44
No. 2.710, No. 2,454,629, No. 2,778
Typical examples thereof include cyanine dyes, merocyanine dyes, and composite cyanine dyes as described in , No. 280, etc. Furthermore, U.S. Patent 2.2
No. 13,995, No. 2,493,748, No. 2.51
! Cyanine dyes, merocyanine dyes or composite cyanine dyes such as those described in No. 3.001, West German Patent No. 929.080, etc. 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. Combinations of sensitizing dyes are often used, especially for the purpose of supersensitization.

Typical examples are U.S. Pat. Nos. 2,888,545 and 2,9
No. 77.229, No. 3,397,060, No. 3,52
No. 2.052, No. 3,527.841, No. 3,817
, No. 293, No. 3,828,984, No. 3.868,
No. 480, No. 3,872,898, No. 3,879,4
No. 28, 3,703,37? No. 3,789,30
No. 1, No. 3,814.809, No. 3,837,882
No. 4,028,70? No., British Patent No. 1,344,2
No. 81, No. 1,507,803, Special Publication No. 43-493
No. 6, No. 53-12375, JP-A No. 52-11061
No. 8, l'1J52-109925.

In the silver halide color photographic light-sensitive material of the present invention, it is used as a filter dye in the hydrophilic colloid layer.

Alternatively, water-soluble dyes may be contained for various purposes such as prevention of irradiation. Such dyes include oxonol dyes, hemioxonol dyes, merocyanine dyes, and azo dyes. Among them, oxonol dyes,
Hemioxonol dyes and merocyanine dyes are useful. Specific examples of dyes that can be used include British Patent No. 584.809.
No. 1,277.429, Japanese Unexamined Patent Publication No. 1977-8513
No. 0, No. 49-99620, No. 49-114420, No. 49-129537, No. 52-108115,
No. 59-25845, U.S. Patent No. 2,274,782, U.S. Patent No. 2.533,472, U.S. Patent No. 2,958,879,
No. 3,125,448, No. 3,148,187, No. 3,177.078, No. 3,247.127, No. 3
, No. 540,887, No. 3.575.704, No. 3.
No. 853,905, No. 3,718,472, No. 4.0
No. 71,312.

It is described in No. 4,070,352.

Each of the silver halide emulsion layers according to the present invention contains a coupler, that is, a compound capable of reacting with an oxidized product of a color developing agent to form a dye.

color and cyan couplers can be used. These couplers may be so-called 2-equivalent type couplers or 4-equivalent type couplers, and in combination with these couplers, it is also possible to use diffusible dye-releasing type couplers.

The yellow couplers mentioned above include conventionally used open-chain ketomethylene compounds, active point-0-7 aryl substituted couplers called 2-equivalent type couplers, active point-0-acyl substituted couplers, active point-0-acyl substituted couplers, active point Effective yellow couplers include hydantoin compound substituted couplers, active point urazole compound substituted couplers, active point succinimide compound substituted couplers, active point fluorine substituted couplers, active point chlorine or bromine substituted couplers, active point -〇-sulfonyl substituted couplers, etc. Can be used. Specific examples of yellow couplers that can be used include U.S. Pat. No. 2,875,057, U.S. Pat.
, No. 582.322, No. 3,725,072, No. 3,
No. 891,445, West German Patent No. 1,547,888,
West German Application Publication 2,219,91? No. 2.281, 3
No. 61, No. 2,414.006, British Patent No. 1.425
．． No. 020, Japanese Patent Publication No. 51-10783, Japanese Patent Publication No. 1977-
No. 26133, No. 48-73147, No. 51-102
No. 636, No. 50-6341, No. 50-123342
No. 50-130442, No. 51-21827,
No. 50-87650, No. 52-82424, No. 52
Examples include those described in No. 115219, No. 58-95346, and the like.

Examples of magenta couplers used in the present invention include pyrazolone, virazolotriazole, pyrazolinobenzimidazole, and inodasilon compounds.

These magenta couplers are similar to the yellow couplers 4
A specific example of a magenta coupler that may be not only an equivalent coupler but also a two-equivalent coupler is U.S. Pat.
, No. 800,788, No. 2,983,808 No. 3.
No. 062,653, No. 3,127,289, No. 3,3
No. 11.476, No. 3,419,391, No. 3,51
No. 8,429, No. 3.558,319, No. 3.582
．． No. 322, No. 3,815,508, No. 3.834
,! No. 308, No. 3,891,445, West German Patent 1,
No. 810.464, West German Patent Application (OLS) 2,4
No. 08,885, No. 2,417,945, No. 2,41
No. 8,959, No. 2,424.467, Special Publication No. 1973-
No. 6031, JP-A-51-20826, JP-A No. 52-58
No. 922, No. 49-129538, No. 49-7402
No. 7, No. 50=159336, No. 52-42121, No. 49-74028, No. 50-60233, No. 5
No. 1-26541, No. 53-55122, Patent Application No. 1982
-110943 etc. can be mentioned.

Further, useful cyan couplers used in the present invention include, for example, phenolic and naphlic couplers. 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. Pat. No. 2,3H,929;
No. 434,272.

2.474.293, 2.521. ! No. 308,
No. 2,895,828, No. 3,034.892, No. 3,311,478, No. 3,458.315, No. 3
, No. 478,583, No. 3,583,971, No. 3.
No. 591.383, No. 3,787,411, No. 4.0
No. 04,929, West German patent ratio jiQli (OLS)
2,414,830, q 2,454.329, JP 48-59838, JP 51-26034, JP 4
No. 8-5055, No. 51-146827, No. 52-6
No. 9624, No. 52-90932, No. 58-9534
Examples include those described in No. 6 and the like.

In order to incorporate these couplers into the silver halide emulsion according to the present invention, if the couplers are alkali-soluble, they may be added as an alkaline solution.
If it is oil-soluble, for example, U.S. Pat. No. 2,322,
No. 027, No. 2.801,170, No. 2,801
, No. 171, No. 2,272,191 and No. 2.
It is preferable to dissolve the coupler in a high boiling point solvent, optionally in combination with a low boiling point solvent, according to the method described in each specification of No. 304.340, disperse it in the form of fine particles, and add it to the silver halide emulsion. At this time, if necessary, other hydroquinone derivatives, ultraviolet absorbers, anti-fading agents, etc. may be used in combination.

It is also possible to use a mixture of two or more couplers.Moreover, to explain in detail the preferred method of adding couplers in the present invention, one or more of the couplers may be used in combination with other couplers, if necessary. hydroquinone derivatives,
Along with anti-fading agents and ultraviolet absorbers, organic acid amides, caloctamates, esters, ketones, urea derivatives, ethers, hydrocarbons, etc., especially di-n-butyl phthalate, triresyl phosphate, and Phenyl phosphate, di-yne octyl azelate, di-n-phthyl sehecate, tri-n-hexyl phosphate, N,N
-Di-ethyl-caprylamidobutyl, N,N-diethyl laurylamide, n-pentadecyl phenyl ether, di-octyl phthalate, n-nonylphenol, 3
- high boiling point solvents such as pentadecyl phenylethyl ether, 2.5-di-5ec-amylphenylbutyl ether, monophenyl-di-0-chlorophenyl phosphate or fluoroparaffin, and/or methyl acetate, ethyl butyrate, propyl acetate, butyl acetate, Dissolved in a low boiling point solvent such as butyl propionate, cyclohexanol, diethylene glycol monoacetate, nitromethane, carbon tetrachloride, chloroform, cyclohexanetetrahydrofuran, methyl alcohol, acetonitrile, dimethylformamide, dioxane, methyl ethyl ketone, etc.
Mixed with an aqueous solution containing an anionic surfactant such as alkylbenzene sulfonic acid and alkylnaphthalene sulfonic acid and/or a nonionic surfactant such as sorbitan sesquioleate and sorbitan monolaurate and/or a hydrophilic binder such as gelatin. Then, it is emulsified and dispersed using a high-speed rotating mixer, colloid mill, ultrasonic dispersion device, etc., and added to a silver halide emulsion.

In addition, the above couplers may be dispersed using a latex dispersion method.The latex dispersion method and its effects are described in JP-A-49-74538, JP-A No. 51-59943, JP-A No. 51-59943;
4-32552 and Research Disclosure, August 1878, No. 14850, pages 77-79.

Suitable latexes include, for example, styrene, acrylate,
n-butyl acrylate, n-butyl methacrylate,
2-7 Cetoacetoxyethyl methacrylate, 2-(methacryloyloxy)ethyltrimethylammonium methosulfate, 3-(methacryloyloxy)propane-1-sulfonic acid sodium salt, N-isopropylacrylamide, N-(2-(2-methyl- 4-oxopentyl)] acrylamide, 2-acrylamide-2-
Seven-dimensional homopolymers, copolymers and terpolymers such as methylpropanesulfonic acid and the like.

The silver halide color photographic light-sensitive material of the present invention may contain various other photographic additives, such as antifoggants, stabilizers, ultraviolet absorbers, etc. described in Research φ Disclosure Magazine No. 17643, 9. Silver halide color photographic light-sensitive material of the present invention in which a color stain preventive agent, a fluorescent whitening agent, a color image fading preventive agent, an antistatic agent, a hardening agent, a surfactant, a plasticizer, a wetting agent, etc. can be used. Hydrophilic colloids used to prepare emulsions include gelatin, derivative gelatin, graft polymers of gelatin and other polymers, proteins such as albumin and casein, and cellulose conductors such as hydroxyethyl cellulose derivatives and carboxymethyl cellulose. , starch derivatives, polyvinyl alcohol, polyvinylimidazole, polyacrylamide, and other single or copolymer synthetic hydrophilic polymers.

The support for the silver halide color photographic light-sensitive material of the present invention is
It may be any of the so-called reflective supports, such as baryta paper, polyethylene coated paper, polypropylene synthetic paper,
A transparent support with a reflective layer or a reflector,
Examples include glass plates, polyester films such as cellulose acetate, cellulose nitrate, and polyethylene terephthalate, polyamide films, polycarbonate films, and polystyrene films, and these supports are appropriately selected depending on the intended use of the photosensitive material.

Various coating methods such as dipping coating, air doctor coating, curtain coating, and hopper coating can be used to coat the emulsion layer and other constituent layers used in the present invention. Also, U.S. Patent No. 2.761,791;
It is also possible to use a simultaneous coating method of two or more layers by the method described in No. 941,898.

As mentioned above, in the present invention, the coating position of each emulsion layer can be arbitrarily determined. For example, in the case of a full-color photosensitive material for photographic paper, the blue-sensitive silver halide emulsion is sequentially applied from the support side. It is preferable to have an arrangement of a green-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, and a red-sensitive silver halide emulsion layer.

In the photosensitive material of the present invention, it is optional to provide an intermediate layer with an appropriate thickness depending on the purpose, and a filter layer,
Various layers such as an anti-curl layer, a protective layer, and an antihalation layer can be used in appropriate combinations as constituent layers.

Hydrophilic colloids that can be used in the emulsion layers as described above can be used as binders in these constituent layers, and various types of colloids that can be contained in the emulsion layers as described above can be used in these layers. Photographic additives may be included.

There are no particular limitations on the method of processing photographic materials using the silver halide emulsion according to the present invention.

Various processing methods can be applied.6 For example, representative methods include a method of performing W:4 self-sufficiency treatment after color development and further washing with water and/or stabilization treatment if necessary;
After color development, bleaching and fixing are performed separately, and if necessary, further water washing and/or stabilization treatment is performed; or pre-hardening, neutralization, color development, stop fixing, water washing, bleaching, fixing, water washing, and post-hardening. A method of performing hardening, then washing with water, a method of performing color development, washing with water, supplementary color development, stopping, bleaching, fixing, washing with water, and stabilization in that order. After the developed silver produced by color development is bleached with norogenation. The processing may be performed using any method, such as a development method in which color development is performed again to increase the amount of produced dye.

The color developing solution used for processing the silver halide emulsion of the present invention is an alkaline aqueous solution containing a color developing agent and preferably having a pH of 8 or higher, more preferably a pH of 9 to 12. The aromatic primary amine developing agent used as the color developing agent is a compound having a primary amino group on an aromatic ring and has the ability to develop silver halide exposed to light. Precursors that form such compounds may also be added.

The color developing agents mentioned above are typically p-phenylenediamine type ones, and preferred examples include primary ones.

4-7 minnow N, N-diethylaniline, 3-methyl-
4-Amino-N,N-diethylaniline, 4-7minor N-ethyl-N-β-hydroxyethylaniline 13-
Methyl-4-7 minnow N-β-hydroxyethylaniline, 3-methyl-4-7 minnow N-ethyl-N-β-methoxyethylaniline, 3-methyl-4-7 minnow N-
Methyl-N-β-methanesulfonamidoethylaniline, 3-methoxy-4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methoxy-4-amino-
N-ethyl-N-β-methoxyethylaniline, 3-acetamido-4-7 minnow N, N-dimethylaniline,
Toethyl-N-β-[β-(β-methoxyethoxy]ethoxy]ethyl-3-methyl-4-7minoaniline, N
-ethyl root β-(β-methoxyethoxy)ethyl-3
-Methyl-4-aminoaniline, and salts thereof such as sulfates, hydrochlorides, sulfites, and P-toluenesulfonates.

Furthermore, for example, JP-A-48-64932, JP-A-50-1
No. 31526, No. 51-95849, and Bent et al.'s Journal Fist of the American Chemical Society, Vol. 73, pp. 3100-3125 (1951)
The ones described above are also listed as representative ones.

The amount of these aromatic primary amino compounds used depends on where the activity of the developer is set, but in order to increase the activity, it is preferable to increase the amount used, and the amount used is 0. It is used in a range from 0,002 mol/view to O.7 mol/view. In addition, two or more compounds may be used in combination depending on the purpose.For example, 3-methyl-4-amino-N, todiethylaniline and 3-methyl-4-7minorN-ethyl-N-β-methanesulfone. Amidoethylaniline, 3-methyl-4-7mi/-toethylute β-methanesulfonamidoethylaniline and 3
-Methyl-4-amino-N-ethyl root β-hydroxyethylaniline, etc. can be freely used in combination depending on the purpose.

The color developer used in the present invention further contains various commonly added components, such as alkaline agents such as sodium hydroxide and sodium carbonate, alkali metal sulfites,
Alkali metal bisulfites, alkali metal thiocyanates, alkali metal halides, benzyl alcohol,
A water softener, a thickening agent, a development accelerator, etc. can also be optionally included.

Examples of additives other than the above added to the color developing solution include bromides such as potassium bromide and ammonium bromide;
Compounds for quick processing solutions such as alkali iodide, nitrobenzimidazole, mercaptobenzimidazole, 5-methyl-benzotriazole, 1-phenyl-5-mercaptotetrazole, as well as anti-stain agents, anti-sludge agents, and preservatives. , interlayer effect promoter, chelating agent, etc.

Bleaching agents used in bleaching solutions or bleach-fixing solutions in the bleaching process are generally known to be those in which metal ions such as iron, cobalt, and copper are coordinated with aminopolycarboxylic acids or organic acids such as oxalic acid and citric acid. There is. Representative examples of the above-mentioned 7-minopolycarboxylic acids include the following.

Ethylenediaminetetraacetic aciddiethylenetriaminepentaacetic acidpropylenediaminetetraacetic acidnitrilotriacetic acidiminodiacetic acid ethyl etherdiaminetetraacetic acidethylenediaminetetraprobionic acidethylenediaminetetraacetic aciddisodium saltdiethylenetriaminepentaacetic acid pentasodium saltnitrilotriacetic acid sodium saltBleaching solutions can be used with various bleaching agents as mentioned above. It may contain additives, and if a bleach-fix solution is used in the bleaching process,
In addition to the above bleaching agent, a solution containing a silver halogen fixing agent is applied. In addition, the bleach-fix solution may further contain /\\rogen compounds such as potassium bromide, and as in the case of the bleach solution described above, various other additives such as pH buffering agents, optical brighteners, etc. Agents, antifoaming agents, surfactants, preservatives, chelating agents, stabilizers, organic solvents, etc. may be added or contained.

The silver halide fixing agent is, for example, sodium thiosulfate, ammonium thiosulfate, potassium thiocyanate, sodium thiocyanate, or thiourea, thioether, etc., which react with silver halide and become water-soluble. Compounds that form silver salts can be mentioned.

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

The silver halide color photographic light-sensitive material of the present invention is disclosed in Japanese Unexamined Patent Publication No. 58
-14834, 58-105145, 58-1
No. 34634 and No. 58-18631 and patent application 1973
A stabilizing treatment as an alternative to washing may be performed as shown in Japanese Patent No. 8-2709 and Japanese Patent No. 59-89288.

[Effect of the invention 1] 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 are formed on a reflective support. In a silver halide color photographic light-sensitive material having a silver halide layer, a photosensitive halogen layer provided on a side closer to the reflective support than the silver halide grains of the photosensitive silver halide emulsion layer provided on the side closest to the reflective support. Silver halide grains in at least one light-sensitive silver halide emulsion layer provided above the silver emulsion layer and having substantially different color sensitivities have a larger average grain size or substantially Since they are the same, it is possible to provide a silver halide color photographic material which is capable of rapid development and has improved processing stability in the rapid development.

[Examples] Specific examples of the present invention will be described below, but the 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 on a paper support laminated with polyethylene from the support side.

Layer L @--1,20 g/rn' of gelatin, 0.
A blue-sensitive silver chlorobromide emulsion (silver bromide content and average grain size are shown in Table 1) of 32 g/ln' (in terms of silver, the same applies hereinafter).

0 dissolved in 0.50 g/m' of dioctyl phthalate
, 80 g/g of yellow coupler (Y-1).

Layer 2---0.70g/rrf gelatin, 105g
/ln” irradiation dye (AI-1), 5mg
/ m” c7) (A I-2).

Layer 3・Φ@1.25g/n'l' gelatin, 0.2
2g/rf of green-sensitive silver chlorobromide emulsion (silver bromide content as well as average grain size are shown in Table 1), 0.82g/rrf of magenta coupler dissolved in 3 layers g/rn' of dioctyl phthalate. A layer containing (M-1).

Layer 4 - Intermediate layer consisting of 1.20 g/g of gelatin.

Layer 5 #II 61.40g/rr? ty) gelatin, 0.20 g/m' red-sensitive silver chlorobromide emulsion (silver bromide content as well as average grain size are shown in Table 1), 0.45 g/m' dissolved in 0.20 g/m' dioctyl phthalate; rn”
A layer containing a cyan coupler (C, -1).

Layer 6---1.0 g/m' gelatin and 0.20 g/m'
0,30 g/m dissolved in m' dioctyl phthalate
A layer containing the following ultraviolet absorber (UV-1).

Layer 7.e. Layer containing 0.50 g/rrf of gelatin.

C Stand-I-I 0 Text I-I I-2 UV-1 In addition, as a hardening agent, 2,4-dichloro-8-hydroxy-s-h riazine sodium was added in layers 2, 4 and 7.
Each was added in an amount of 0.017 g per 1 g of gelatin.

Table 1 tlR: blue-sensitive silver halide emulsion, the same applies hereinafter.

20: Green-sensitive silver halide emulsion, the same applies hereinafter.

*3F, red-sensitive silver halide emulsion, the same applies hereinafter.

Each of the photosensitive material samples Nos. 1 to 4 was exposed through an optical wedge and then processed in the following steps.

Treatment process (38°C) Color development 3 minutes Bleach fixing 1 minute Wash with water 1 minute Drying 60-80℃ 2 minutes The composition of each treatment liquid is as follows.

[Color developer] Pure water 8QOmM benzyl alcohol 15IIIfL hydroxyamine sulfate 2.0g Potassium bromide
1.5g sodium chloride
1.0g potassium sulfite
2.0g triethanolamine
2.0g N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-7 minoaniline sulfate 4.5g 1-hydroxyethylidene-1,1-diphosphonic acid (80% aqueous solution) 1.5 Kokubun potassium carbonate 32gWhite
x BB (50% aqueous solution) 2tJL (
Fluorescent brightener, manufactured by Sumitomo Chemical Co., Ltd.) Add pure water to make 20% potassium hydroxide or 10%
Adjust the pH to 1O, 1 with dilute sulfuric acid.

[? *Shirojisaku liquid] Pure water 550 Japanese ethylenediaminetetraacetic acid iron (II [) Ammonium 85g Ammonium thiosulfate 85g Sodium hydrogen sulfite log Sodium metabisulfite
2g ethylenediaminetetraacetic acid m-2 sodium 2
Add 0g sodium bromide and 10g pure water to make one sentence, and add aqueous ammonia or dilute sulfuric acid to pl=
Adjust to 7.0.

Separately, add 0.5°1.0 potassium bromide to the above color developer.
, 2.0 and 2.5 were used to develop each of the same samples Nos. 1 to 4 as above.

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

As is clear from Table 2, samples Nos. 011 and 2 of the present invention show less gamma movement when the potassium bromide concentration fluctuates, indicating that they have excellent processing stability. That is,
Comparison of samples No. 3 and 4 shows that the average grain size of silver halide grains in the blue-sensitive silver halide emulsion layer is 0.20 to 0.5.
5 p-tn, and the silver bromide content of silver halide in the green-sensitive silver halide emulsion layer and the red-sensitive silver halide emulsion layer is 5 to 85 mol% (Sample No. 3)
According to Sample N of the present invention, the processing stability is improved.
Further, the effect of improving the processing stability was observed in No. 2, and the average silver halide grains in the blue-sensitive silver halide emulsion layer were lower in both the green-sensitive silver halide emulsion layer and the red-sensitive silver halide emulsion layer. The most preferred sample No. larger than the particle size,
It can be seen that in No. 1, the improvement effect on processing stability is particularly remarkable.

Example 2 Sample No. 1 was used to test for rapid processability.

That is, each processing solution of Example 1 was used (however, the potassium bromide concentration of the color developer was set at 1-0 g/L; L).
The sensitivity (S), gamma (γ), maximum density CD, etc. were investigated at color development times of 2 minutes, 2 minutes and 30 seconds, and 3 minutes, and the results are shown in Table 3.

J6: Relative sensitivity when the sensitivity during 3 minutes development is set as 100.

7. Sensitometric slope from concentration 0.8 to 1.8.

As is clear from the results in Table 3, it can be seen that the samples of the present invention can provide sufficient photographic performance even with a color development time of 2 minutes. Therefore, it was found that the silver halide photosensitive material of the present invention has excellent rapid processability.

Patent applicant Roku Konishi Photo Industry Co., Ltd. Agent
Patent attorney Nobuaki Sakaguchi (and 1 other person)

Claims (1)

[Claims] 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 on a reflective support,
The upper side of the photosensitive silver halide emulsion layer provided on the side closest to the reflective support is higher than the silver halide grains in the photosensitive silver halide emulsion layer provided on the side closest to the reflective support. Silver halide grains in at least one light-sensitive silver halide emulsion layer having substantially different color sensitivities provided in the present invention are characterized in that their average grain sizes are larger or substantially the same. A silver halide color photographic light-sensitive material.