JPS6152644A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To enable rapid development processing by specifying the average grain diameter of the silver halide of a blue-sensitive silver halide emulsion layer, and the silver bromide contents of the silver halide of a green-sensitive silver halide emulsion layer and a red-sensitive silver halide emulsion layer. CONSTITUTION:The silver halide incorporated in the blue-sensitive silver halide emulsion layer formed on a support has an average grain diameter of 0.20- 0.55mum. The silver halides incorporated in the green-sensitive silver halide emulsion layer and the red-sensitive silver halide emulsion layer may be silver chlorobromide, chloroiodobromide, or their mixture, and contains silver bromide in an amt. of 5-65mol%, and the blue-sensitive layer contains a yellow coupler high in reaction speed having a relative coupling reaction speed of >=about 0.3, thus permitting rapid development to be executed, processing stability in rapid development processing to be improved, and occurrence of fog to be suppressed.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a silver halide color photographic light-sensitive material, which is capable of rapid development processing and has improved processing stability in the rapid development processing. The present invention also relates to a silver halide color photographic material which can suppress the occurrence of fog.

In general, silver halide color photographic light-sensitive materials have three types of photographic silver halide emulsion layers selectively sensitized to be sensitive 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 filter layer 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, a red-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, and a blue-sensitive silver halide emulsion layer are generally arranged in this order from the exposed side. Similarly to silver halide photographic materials for color negatives, intermediate layers such as an ultraviolet absorbing layer, 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 furthermore, each silver halide emulsion layer is sensitive to substantially the same wavelength range for each color light. It is also known to use a photosensitive silver halide emulsion layer consisting of two layers. In these silver halide color photographic materials, exposed silver halide grains are developed using 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, phenolic or naphtholic cyan couplers, 5-pyrazolones, pyrazolinobenzimidazoles, pyrazolotriazoles, indacylones or cyanocoupler couplers, 5-pyrazolones, pyrazolinobenzimidazoles, pyrazolotriazoles, indacylones or cyanocouplers are typically used to form cyan, magenta and yellow dye images, respectively. An acetyl-based magenta coupler and an acylacetamide-based or benzoylmethane-based yellow coupler are used.

These dye-forming couplers are photosensitive/contained in the silver halide emulsion layer or in the developer.The present invention is based on the fact that these couplers are preliminarily contained in the silver halide emulsion layer and rendered non-diffusible. This invention relates to silver halide 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 particular, silver halide color photographic materials that can be processed rapidly are desired.

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, the temperature and pH 2 of the developer, as well as the halogen concentration, especially the bromide ion concentration, etc. in the developer are highly controlled. However, compared to the development time or the temperature and pH of the developer, the bromine 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 in normal processing times, but processing stability becomes more of a problem in rapid processing. 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
1-7 ly-3-pyrazolidone having a specific structure as described in JP-A No. 56-64339 in a silver halide color photographic light-sensitive material. Addition technology, and JP-A-57
-144547, 58-50534, 58-5
l-7 as described in No. 0535 and No. 58-50536
A technique is known in which lilyvilazolidones are added to a silver halide color photographic light-sensitive material; For example, such a color development accelerator is disclosed in U.S. Pat. No. 2,950.
．． No. 970, No. 2,515,147, No. 2,496,
No. 903, No. 4.038.075, No. 4,119,4
No. 62, British Patent No. 1,430.888, British Patent No. 1,455
, No. 413, JP-A-53-15831, JP-A No. 55-62
No. 450, No. 55-62451, No. 55-62452
No. 55-62453, No. 51-12422, No. 55-62453, Special Publication No. 51-12422, No. 5
There are compounds described in No. 5-49728 and the like.

However, when using ■ or ■ of these conventional techniques,
Although the processing time was shortened, the processing stability in the rapid development processing was poor, and there were also problems with fogging in the same-day performance.

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. However, when silver halide color photographic materials containing low silver bromide emulsions are processed using a processing solution with a low bromide ion concentration, processing stability is poor. have Processing stability here refers to processing liquid composition, pH1 temperature,
This is the degree of variation in sensitometry due to variations in the bromide ion concentration, etc., and the contamination of other compounds other than the treatment liquid composition.

Furthermore, when using the fine-grained silver halide described in (1) above, there is a drawback that processing stability is poor, and the sensitivity deteriorates as the grains become 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.

By the way, silver halide color for color photographic paper
j In photographic materials, as mentioned above, the blue-sensitive silver halide emulsion layer is coated at the position closest to the support, and is most required to have improved developability. Therefore, as part of the development of a silver halide color photographic light-sensitive material that enables rapid development processing, the present inventor attempted to use a fast-reactive yellow coupler in a blue-sensitive silver halide emulsion layer. As a result, it was found that although rapid development processing was indeed possible, there was a drawback in that rapid development processing was accompanied by a significant amount of fog.

[Problems to be Solved by the Invention] The present invention has been made in view of the above, and is capable of rapid development, improves processing stability in the rapid development, and suppresses the occurrence of fog. Our technical objective is to provide a silver halide color photographic material that can produce high-quality silver halide color photographs.

The silver halide color photographic light-sensitive material of the present invention which solves the above technical problems has a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer and a red-sensitive silver halide emulsion layer on a support. In the silver halide color photographic light-sensitive material, the average grain size of silver halide in the blue-sensitive silver halide emulsion layer is 0.20 to 0.5571 m, and the average grain size of silver halide in the blue-sensitive silver halide emulsion layer is 0.20 to 0.5571 m, and the silver halide emulsion layer in the green-sensitive silver halide emulsion layer and the red-sensitive halogen A fast-reactive yellow coupler having a silver bromide content of /\silver halide in the silver emulsion layer of 5 to 65 mol % and a relative coupling reaction rate of 0.3 or more to the blue-sensitive silver halide emulsion layer. It is characterized by having the following.

The present invention will be explained in more detail below.

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.
55pm, preferably 0.30-0.50pm. When the average particle size exceeds 0.55 g va, the processing stability is poor, and the deterioration of the processing stability is particularly noticeable when the amount of potassium bromide changes.On the other hand, when the average particle size exceeds 0.20 #Lm
If the value is less than 1, the sensitivity of the blue-sensitive silver halide emulsion layer is insufficient and magenta color becomes cloudy.

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 good method 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 (1968)
Some of them are listed in Chapter 2 of . This 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 will describe this fairly accurately as a diameter or projected area. be able to.

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 are those in which 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. 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.

7 lower 7 Σni ≦ 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 the -side, Or, in the case of particles having a shape other than a cube, the length of one side when converted to a cube having the same volume, where the individual particle size in this sense is ri and the number is ni. 7 is defined by the following formula.

Σni ri r== Σni The relationship between particle size distribution is "Empirical relationship between sensitometric distribution and particle size distribution in photography" The Photographic Journal, Volume LXXIX (1f349) 330-
The silver halide contained in the green-sensitive silver halide emulsion layer and the red-sensitive silver halide emulsion layer of the present invention can be determined by the method described in the article by Tribel and Smith on page 338. , silver chlorobromide, silver chloroiodobromide, or a mixture thereof, and the silver bromide content is 5 to 65 mol %.0 Green-sensitive silver halide emulsion layer in the present invention, red-sensitive silver halide One or both of the emulsion layers may consist of two or more layers, and in the present invention, the silver bromide content refers to the total green-sensitive silver halide emulsion layer and the total red-sensitive silver halide emulsion layer, respectively. When the silver bromide content exceeds 65 mol%, which refers to the total silver bromide content in each layer in the total silver halide contained in the layer, processing stability deteriorates and magenta color becomes cloudy. On the other hand, if the silver bromide content is less than 5 mol %, processing stability will be significantly degraded.

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 any of silver chloride, silver bromide, silver chlorobromide, and silver chloroiodobromide, or a mixture thereof. Although it may be present, silver chlorobromide is preferred, and the silver bromide content is from 30 to 95 mol%. Furthermore, the blue-sensitive silver halide emulsion layer in the present invention may consist of two or more layers.

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 0.1 to 2ILII+, more preferably 0.
2 to 1 m, particularly preferably 0.25 to 0.8 m.

The fast-reactive yellow coupler used in the blue-sensitive silver halide emulsion layer according to the present invention is a yellow coupler having a relative coupling reaction rate of 0.3 or more, preferably a relative coupling reaction rate of 0.5 or more. It is a yellow coupler.

The coupling reaction rate of the couplers is determined by the rate of the coupling reaction of the two couplers M and N, which give different dyes that can be clearly separated from each other, in the color image obtained by mixing the mixture and adding it to a silver halide emulsion for color development. It can be determined as a relative value by measuring the amount of pigment.

The maximum concentration of coupler M (DM)wax,, If we express the color development of the concentration DM in the middle stage, and the color development of coupler N (DN) mtsx,, then the reaction activity of the bipolar puller is The ratio RM/RN is expressed by the following formula.

DM In other words, a silver halide emulsion containing a mixed coupler is exposed to light at various stages, and several pairs of DM and DN obtained by color development are plotted on two orthogonal axes. From the slope of the straight line, the coupling activity ratio RM/RN
The value of can be found.

Here, using a fixed coupler N and calculating the value of RM/RN for various couplers as described above, 1. Relative values of coupling reaction rates are determined.

In the present invention, as the above coupler N, the following Let's calculate the RM/RN value when using the coupler.

The amount of the fast-reacting yellow coupler of the present invention is not limited, but is 2 X + o-3 to 5 5X+o-' moles.

Specific examples of the fast-reacting yellow coupler of the present invention are listed below, but the invention is not limited thereto.

[Exemplary compounds]

(Y-1) (y-z) (Y-3) (Y-4) (Y-5) (Y-6) (Y-7) (Y-8) (RM/RN-0,65) ( Y-9) (Y-10) (Y-11) (Y-12) (Y-13) (Y-14) HOH3 (RM/'RN=0.96) (Y-15) t (Y-16 ) (Y-17) t (Y-18) (Y-19) at (Y-20) t (RM/RN=0.88) (Y-21) (γ-27-) Silver halide of the present invention The amount of silver (bank iL) in the silver halide emulsion layer in the color photographic light-sensitive material is preferably 0.3 to Ig/m' in the entire photosensitive silver halide emulsion layer, that is, excellent image quality is obtained. For this purpose, the amount of silver must be Ig
On the other hand, in order to obtain a high maximum density and high sensitivity, the amount of silver is preferably 0.3 g/m' or less.
In the present invention, it is particularly preferable that the silver amount is 0.4 to 0.8 g/m'.

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, the silver halide emulsion according to the present invention is colored! When used in photographic paper, especially fast developability is required, so it is preferable that the halogen composition of silver halide contains chlorine atoms, and silver chloride bromide or chloride iodine containing at least 1% silver chloride is used. Particularly preferred is silver bromide.

The monodisperse silver halide grains preferably used in the present invention may be obtained by any conventionally known preparation method such as an acidic 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 preferably prepared in the manner described above. A composition containing the silver halide grains is hereinafter referred to as a silver halide emulsion.

These silver halide emulsions contain active gelatin; sulfur sensitizers such as allylthiocarbamide, thiourea, cystine; selenium sensitizers; reduction sensitizers such as primary
tin salts, thiourea dioxide, polyamines, etc.; noble metal sensitizers such as gold sensitizers, specifically potassium aurithiocyanate, potassium chloroaurate, 2-aurothiocyanate, etc.
- Sensitizers such as methylbendithiazolium chloride or water-soluble salts such as ruthenium, palladium, platinum, rhodium, iridium, in particular ammonium chloroparadate, potassium chloroplatinate and sodium chloroparadate (these These substances act as sensitizers or fog suppressants depending on the amount. It may also be chemically sensitized (for example, in combination 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 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 halogenated with an appropriate sensitizing dye in order to impart photosensitivity to the desired wavelength range, and 5X+o-8 to 3X per mole of 4ml.
Optical sensitization may be carried out by adding 10 −3 mol.

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

That is, examples of sensitizing dyes used in the blue-sensitive silver halide emulsion layer include West German Patent No. 929,080, US Pat. No. 2,231,658, US Pat.
2.503,778, 2,519,001, 2,912,329, 3,858,959, 3
, No. 672,897, No. 3,694.217, No. 4,
No. 025,349, No. 4.04B, No. 572, British Patent No. 1,242,588, and Japanese Patent Publication No. 14030/1984.

Examples include those described in 52-24844 and the like. It is also used in green-sensitive silver halide emulsions.

As a sensitizing dye, for example, U.S. Pat. No. 1,939,201
No. 2,072. Representative examples include cyanine dyes, merocyanine dyes, and complex cyanine dyes as described in SOB No. 2,739,149, No. 2,945,783, British Patent No. 505,979, etc. I can do it. Further, as sensitizing dyes used in red-sensitive/X silver halide emulsions, for example, U.S. Pat.
No. 269,234, No. 2,270,378, No. 2.4
No. 42,710, No. 2,454. [12i No. 9, same 2,
Typical examples include cyanine dyes, merocyanine dyes, and composite cyanine dyes such as those described in No. 778,280. Furthermore, U.S. Patent Nos. 2,213,995, 2,493,748, and 2
．． 51! Cyanine dyes, merocyanine dyes, or composite cyanine dyes such as those described in II. .

These sensitizing dyes may be used alone or in combination, and combinations of sensitizing dyes are often used particularly for the purpose of supersensitization.

Typical examples are U.S. Pat. Nos. 2,688,545 and 2,9
No. 77.228, No. 3,397,080, No. 3,52
No. 2,052, No. 3,527.841, No. 3,817
, No. 293, No. 3.828.984, No. 3.668,
No. 480, No. 3,872,888, No. 3.67fl,
No. 428, 3,703,37? No. 3,769,3
No. 01, No. 3,814.608, No. 3,837,88
No. 2, No. 4.028.707, British Patent No. 1,344,
No. 281, No. 1.507.803, Special Publication No. 43-49
No. 36, No. 53-12375, JP-A No. 52-1106
No. 18, No. 52-109925.

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 irradiation prevention and other various purposes. Included are 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 Nos. 584.60S and 1,277.
．． No. 429, JP-A-48-85130, JP-A No. 49-99
No. 620, No. 49-114420, No. 49-1295
No. 37, No. 52-108115, No. 59-25845
No. 2,274,782, U.S. Patent No. 2.533,4
No. 72, No. 2,958,879, No. 3,125,44
No. 8, No. 3,148,187, No. 3,177.078
No. 3,247.127, No. 3,540,887, No. 3,575,704, No. 3,653.905,
It is described in No. 3.718.472, No. 4,071,312, and No. 4.070.352.

The blue-sensitive silver halide emulsion layer according to the present invention contains the fast-reactive yellow coupler of the present invention, but the blue-sensitive silver halide emulsion layer contains less than 45 mol % of the present invention. It is preferable that Further, the green-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 form of a color developing agent to form a dye. can.

In the present invention, conventionally known yellow couplers, magenta couplers, and cyan couplers can be used as the couplers. 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 coupler may be a closed ketomethylene compound or a so-called two-equivalent type coupler.
〇-7 aryl substituted coupler, active point -〇-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 Substituted coupler, active point -〇-
Sulfonyl-substituted couplers and the like may be used without particular limitation.

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

These magenta couplers are similar to the yellow couplers 4
A specific example of a magenta coupler, which may be not only an equivalent type coupler but also a two-power type coupler, is disclosed in U.S. Pat.
, No. 800,788, No. 2,983,608, No. 3,
No. 062,853, No. 3,127,289, No. 3,3
No. 11.47B, No. 3,419,391, No. 3,51
No. 9,429, No. 3.558,319, No. 3,582
, No. 322, No. 3,815,508.

3.834.908, 3,891,445, West German Patent No. 1,810.484, West German Patent Application (OLS)
No. 2,408.6flS, No. 2,417,945, No. 2,418,959, No. 2,424.487,
JP 40-6031, JP 51-20826,
No. 52-58922, No. 49-129538, No. 4
No. 9-74027, No. 50-159336, No. 52-
No. 42121, No. 49-74028, No. 50-602
Examples include those described in No. 33, No. 51-26541, No. 53-55122, and Japanese Patent Application No. 110943/1983.

Furthermore, useful cyan couplers used in the present invention include, for example, phenolic couplers, naphthol couplers, and the like. 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. Patent No. 2.3Ef9,929, U.S. Pat.
, No. 521,908, No. 2,895,828, No. 3,
No. 034,892, No. 3,311.478, No. 3,4
No. 58.315, No. 3,478,583, No. ff, 5
No. 83,971, No. 3.591.383, No. 3,78
No. 7,411, No. 4,004,929, West German patent application (OL S,) No. 2,414,830, M 2,4
54.329, JP-A-48-59838, JP-A No. 51-
No. 26034, No. 48-5055, No. 51-1468
Examples include those described in No. 27, No. 52-69624, No. 52-90932, No. 58-95346, and the like.

In order to incorporate the fast-reacting yellow coupler of the present invention and other couplers into the silver halide emulsion of the present invention, if the coupler is alkali-soluble, it may be added as an alkaline solution; In some cases, for example, U.S. Pat. No. 2,322,027, M2
, No. 801, 17o, fis 2,801.171
No. 2,272,191 and No. 2,304,
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. 940, 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, or two or more couplers may be used in combination.

Further, to explain in detail the preferred method of adding couplers in the present invention, one or more of the couplers are added to the alpha-acid amide along with other kabuchi, hydroquinone derivatives, anti-fading agents, ultraviolet absorbers, etc. as necessary. carbamates, esters, ketones, urea derivatives, ethers, hydrocarbons, etc., especially di-n-butyl phthalate, triresyl phosphate, triphenyl phosphate, di-isooctyl azelate, di-n- -butyl sebacate, tri-n-hexyl phosphate, N,N-di-
Ethyl-caprylamidobutyl laurylamide, n-pentadecyl phenyl ether,
Di-octyl phthalate, n-nonylphenol, 3-
Pentadecyl phenylethyl ether, 2.

High boiling point solvents such as 5-di58G-amylphenylbutyl ether, monophenyl-di-rochlorophenyl phosphate or fluoroparaffin, and/or methyl acetate, ethyl acetate, propyl acetate, butyl acetate, butyl propionate, cyclohexanol, diethylene glycol Monoacetate, nitromethane, carbon tetrachloride,
Dissolved in a low boiling point solvent such as chloroform, cyclohexanetetrahydrofuran, methyl alcohol, acetonitrile, dimethylformamide, dioxane, methyl ethyl ketone, anionic surfactants such as alkylbenzenesulfonic acids and alkylnaphthalenesulfones and/or sorbitan sesquioleate and sorbitan. It is mixed with an aqueous solution containing a nonionic surfactant such as monolauric acid ester and/or a lignophilic binder such as gelatin, and emulsified and dispersed using a high-speed rotary mixer, colloid mill, or ultrasonic dispersion device to form a silver halide emulsion. added.

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-51-59943, and JP-A-54.
-32552 Specification Publication and Research Number Disclosure August 1378, No. 14850, pages 77-78.

Suitable latexes include, for example, styrene, acrylate,
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 -oxobentyl)] acrylamide, 2-acrylamide-2-
Seven-dimensional homopolymers, copolymers and terpolymers such as methylpropanesulfuric acid and the like.

The silver halide color photographic light-sensitive material of the present invention may contain various other photographic additives. For example, antifoggants, stabilizers, ultraviolet absorbers, color stain inhibitors, optical brighteners, color image fading inhibitors, antistatic agents, r
ig! A film agent, a surfactant, a concavity agent, a wetting agent, etc. can be used.

In the silver halide color photographic light-sensitive material of the present invention, the hydrophilic colloids used to prepare the emulsion include gelatin, derivative gelatin, graft polymers of gelatin and other polymers, proteins such as albumin and casein, and hydroxyl colloids. Examples include any cellulose derivatives such as ethyl cellulose derivatives and carboxymethyl cellulose, starch derivatives, single or copolymer synthetic hydrophilic polymers such as polyvinyl alcohol, polyvinylimidazole, and polyacrylamide.

Examples of the support for the silver halide color photographic light-sensitive material of the present invention include paratai paper, polyethylene-coated paper, polypropylene synthetic paper, a transparent support provided with a reflective layer or 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, etc., 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. 2.781,791;
It is also possible to use a simultaneous coating method of two or more layers by the method described in No. 941,898.

In the present invention, the coating position of each emulsion layer can be determined arbitrarily.For example, in the case of a full-color photosensitive material for photographic paper, the blue-sensitive silver halide emulsion layer, the green-sensitive silver halide emulsion layer, and the green-sensitive silver halide emulsion layer are sequentially applied from the support side. A preferred arrangement is a silver 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 anti-halation layer can be used in appropriate combinations as constituent layers.

Hydrophilic colloids that can be used in the silver halide emulsion layer as described above can be similarly used as a binder in these constituent layers, and hydrophilic colloids that can be used in the silver halide emulsion layer as described above can also be used in these layers. Various photographic additives can be included.

There are no particular restrictions on the method of processing photographic light-sensitive materials using the silver halide emulsion according to the present invention, and any processing method can be applied. For example, typical methods include:
After color development, a bleach-fixing treatment is carried out, and if necessary, washing and/or stabilization treatment is carried out; after color development, bleaching and fixing are carried out separately, and if necessary, further washing and/or stabilization treatment is carried out; or Pre-hardening, neutralization, color development, stop fixing, washing with water, bleaching, fixing, washing with water, post-hardening, washing with water in that order, color development, washing with water, supplementary color development, stopping, bleaching, fixing, washing with water, stabilization Processing may be carried out using any method, such as a method in which the developed silver produced by color development is bleached with halogen acid, and then color development is performed again to increase the amount of dye produced.

The color developing solution used in the processing of the silver halide emulsion according to 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 amine group on an aromatic ring and has the ability to develop exposed silver halide. Precursors that form such compounds may also be added.

The color developing agent mentioned above is typically p-phenylenediamine type, and the following are preferred examples.

4-7 minnow 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-acetamido-4-amino-N,N-dimethylaniline,
N-ethyl-N-β-[β-(β-methoxyethoxy)
ethoxy]ethyl-3-methyl-4-7minoaniline,
N-ethyl root β-(β-methoxyethoxy)ethyl-
These include 3-methyl-4-aminoaniline and salts thereof such as sulfates, hydrochlorides, sulfites, p-)luenesulfonates, and the like.

Furthermore, for example, JP-A-48-64932, JP-A-50-1
No. 31526, No. 51-95849, and Bent et al., Journal 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 amine compounds to be 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/liter to 0.7 mol/l. In addition, two or more compounds may be used in appropriate combination depending on the purpose. For example, 3-methyl-4-amino-N,N-diethylaniline and 3-methyl-4-amino-N-ethyl-N-β-methane. Sulfonamidoethylaniline, 3-methyl-4-amino-N
-Ethyl-N-β-methanesulfonamidoethylaniline and 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline, etc. may be used in any 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 that may be added to the color developing solution include 1, bromides such as potassium bromide and ammonium bromide;
In addition to compounds for rapid processing solutions such as alkali iodide, nitrobenzimidazole, mercaptobenzimidazole, 5-methyl-benzotriazole, and 1-phenyl-5-mercaptotetrazole, stain inhibitors, stain inhibitors, preservatives, There are multilayer effect promoters, chelating agents, 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, @acids, and organic acids such as citric acid. ing. The following are representative examples of the above-mentioned 7-minoboricarboxylic acid.

Ethylenediaminetetra-drunkDiethylenetriaminepentaacetic acidPropylenediaminetetraacetic acidIminodiacetic acid with nitriloacetic acid Ethyl ether diaminetetraacetic acidethylenediaminetetraprobionic acidEthylenediaminetetraacetic acid disodium saltDiethylenetriaminepentaacetic acidpentasodium saltNitrilotriacetic acid sodium saltBleach solution is used with the above bleaching agent It may contain various additives, and when a bleach-fixing solution is used in the bleaching step, a solution containing a silver halide fixing agent in addition to the bleaching agent is used. Further, the bleach-fix solution may further contain a halogen compound such as potassium bromide. Then, as in the case of the bleach solution mentioned above, various other additives such as pH buffers, optical brighteners, antifoaming agents, surfactants, preservatives, chelating agents, stabilizers, organic solvents, etc. are added. It may be added or contained.

Silver halide fixing agents include, for example, sodium thiosulfate, ammonium periosulfate, potassium thiocyanate, sodium thiocyanate, thiourea, thioether, etc., which react with silver halide and dissolve in water. Compounds that form a silver salt 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 performed as necessary, is preferably 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, as well as special patent application filed in 1973.
A washing stabilization treatment as shown in No. 8-2709 and No. 59-89288 may also be performed.

[Effects of the Invention] According to the silver halide color photographic light-sensitive material of the present invention, the average grain size of silver halide in the blue-sensitive silver halide emulsion layer is 0.20 to 9.554 m, The silver bromide content of the silver halide in the silver emulsion layer and the red-sensitive silver halide emulsion layer is 5 to 65 mol%, and the relative coupling reaction rate to the blue-sensitive silver halide emulsion layer is 0.
Since it is characterized by containing three or more fast-reacting yellow couplers, rapid development processing is possible, processing stability in the rapid development processing is improved, and the occurrence of fog can be suppressed.

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

Example 1 On a paper support laminated with polyethylene, the following layers were sequentially coated from the support side to prepare silver halide color photographic light-sensitive material samples Nos. 011 to 6.

Layer 1・Strategy・1.2g/m' Nogelatin, 0.32g/m
A blue-sensitive silver chlorobromide emulsion (silver bromide content and average grain size are shown in Table 1).

0 dissolved in 0.50 g/m'' dioctyl phthalate
, 80 g/m' of the fast-reacting yellow coupler (Y-
6) A layer containing.

Layer 2: Intermediate layer consisting of gelatin of φ 0.7 g/m''.

Layer 3 ・e a 1.25 g/m' gelatin, 0
．． 22 g/m' green-sensitive silver chlorobromide emulsion (silver bromide content and average grain size are shown in Table 1), 0. 0,62 g/rrr' dissolved in aog,/m'' of dioctyl phthalate
A layer containing the following magenta coupler (M-1).

Layer 4: Intermediate layer consisting of -1,2 g/m' gelatin.

Layer 5...1.4 g/m' gelatin, 0.20 g/m
' red-sensitive silver chlorobromide emulsion (silver bromide content and average grain size are shown in Table 1), 0.45 g/m' of the following cyan coupler (c - a layer containing i).

Layer 6---1.0g/rn' (7) gelatin and 0.2
0,30 dissolved in 0 g/m' dioctyl phthalate
A layer containing the following ultraviolet absorber UV-1 in g/m'.

Layer 7--Layer containing 0.5 g/rn' of gelatin.

In addition, sample No. 1. Samples Nos. 3.4 and 6 used a fast-reacting yellow coupler (Y-6), and samples Nos. 2 and 5 used the following yellow coupler (yy-i) instead of the fast-reacting yellow coupler (Y-6).

Y-I -I 0 Sentence V-1 H In addition, as a hardening agent, 2,4-dichloro-6-hydroxy-S-) riazine sodium was added in layers 2.4 and 7.
Gelatin IgM was added in an amount of 0.017 g.

Table 1 $lR: Blue-sensitive silver halide emulsion, the same applies hereinafter.

120, green-sensitive silver halide emulsion, the same applies hereinafter.

J3P: Red-sensitive silver halide emulsion, the same applies hereinafter.

Each of the photosensitive material samples No. 1 to B was exposed through an optical wedge and then processed in the following steps.

Treatment process (38℃) Color development 2 minutes Bleach fixing 1 minute 30 seconds Wash with water 1 minute Drying 60-80℃ 2 minutes The composition of each treatment liquid is as follows.

[Color developer] Pure water 800ml benzyl alcohol 15ml hydroxyamine sulfate 2.0g potassium bromide
1.5g sodium chloride
1.0g potassium sulfite
2.0g triethanolamine
2.0g Aniline sulfate 4.5
81-hydroxyethylidene-1,1-diphosphone m,
(60% aqueous solution) 1.5mM potassium carbonate 32gWhitex BB
(50% aqueous solution) 2mM (fluorescent brightener, manufactured by Sumitomo Chemical Co., Ltd.) Add pure water to make one sentence 20% potassium hydroxide or 10%
Adjust p)I to 10.1 with dilute sulfuric acid.

[Bleach-fix solution] Pure water 550m Iron ethylenediaminetetraacetate (m) Ammonium 135g Ammonium thiosulfate 85g Sodium hydrogen sulfite 10g 77 Sodium bisulfite
2g ethylenediaminetetraacetic acid-disodium 2
Add 0g sodium bromide and 10g pure water to make 1fL, and adjust the pH to 1fL with aqueous ammonia or dilute sulfuric acid.
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. 011 to 6 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, even if a silver halide emulsion according to the present invention is used in a blue-sensitive silver halide emulsion, processing stability is improved when a silver halide emulsion other than the present invention is used in a green-sensitive silver halide emulsion or a red-sensitive silver halide emulsion. is inferior. This means that the developability of blue-sensitive silver halide emulsions is different from that of green-sensitive silver halide emulsions and red-sensitive silver halide emulsions, and that of green-sensitive silver halide emulsions and red-sensitive silver halide emulsions. This is thought to mean that the developability of the blue-sensitive silver halide emulsion mutually influences the developability. Furthermore, if a fast-reactive yellow coupler is not used, the processing stability of blue-sensitive silver halide emulsions is extremely poor in processing with a development time of 2 minutes, but samples Nos. 1 and 6 of the present invention have improved this point and have improved processing stability. It turns out that it is excellent.

Example 2 Samples Nos. 1.2 and 4 were tested for rapid processability. That is, using each treatment solution of Example 1 (however,
The potassium bromide concentration of the color developer was set at 1.0 g/7 g. ) Sensitivity (S), gamma (γ
), maximum density (Dm) and fog (Fog) were investigated. The results are shown in Table 3, where the sensitivity is expressed as a relative value, with the sensitivity when developed for 3 minutes and 30 seconds being 100.

Table 3 As is clear from the results in Table 3, one sample of the present invention.

It can be seen that No. 1 can obtain sufficient photographic performance even with a color development time of 2 minutes, has excellent rapid processing properties, has excellent processing stability in the rapid processing, and suppresses the occurrence of fog. .

Procedural amendment (voluntary) August 18, 1982

Claims (1)

[Claims] In 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 support, the blue-sensitive silver halide emulsion layer is The average grain size of silver halide is 0.
20 to 0.55 μm, 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 65 mol%, and the blue-sensitive silver halide emulsion layer has a silver bromide content of 5 to 65 mol%. A silver halide color photographic light-sensitive material characterized in that the silver emulsion layer contains a fast-reactive yellow coupler having a relative coupling reaction rate of 0.3 or more.