JPS623248A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To improve rapid processability and stability of processability by specifying the silver bromide content of each of blue-sensitive, green-sensitive, and red-sensitive silver halide emulsion layers, and specifying the grain diameter range of silver halide grains. CONSTITUTION:The silver bromide content of the silver halide contained in each of blue-sensitive, green-sensitive, and red-sensitive silver halide emulsion layers is controlled in the range of 70-100mol%, 5-65mol%, and 5-65mol%, respectively. A ratio of the average grain diameter taumax of the silver halide grains having the maximum average grain diameter to the average grain diameter taumin of the silver halide grains having the minimum average grain diameter is set so as to satisfy the inequality as shown on the right, taumax/taumin<=1.2. The average grain diameter of the silver halide grains contained in the blue-sensitive silver halide emulsion layer is in the range of 0.20-0.65mum, and those in the green-sensitive and red-sensitive silver halide emulsion layers are not especially limited but, preferably, in the range of 0.2-0.6mum.

Description

[Detailed Description of the Invention]; A [Field of Industrial Application]; A.1. The present invention relates to a silver halide photographic light-sensitive material.
1'□] or rapid development processing is possible, and processing stability is
,! has been improved. Silver halide color photographic material
,.

Regarding.
, 3,] [Background of the invention]
4.51,'.

-@I,: A O"＞"°"1"5-1m""'"
``'': ffi 18, y; Three types of photographic materials selectively spectrally sensitized to have sensitivity to blue light, green light, and red light on a rigid body.
'λ・7,.

A silver halide emulsion layer is coated. For example, in a silver halide photographic material for 1° color negative, -1,
Blue-sensitive silver halide emulsion from the generally exposed side
22 layers, a green-sensitive silver halide emulsion layer, a red-sensitive silver halide emulsion layer, and a blue-sensitive silver halide emulsion layer.
゛7. Gai, 7. □, □22,. Kera. □
A bleachable yellow filter layer is provided between the blue-sensitive silver halide emulsion layer and the blue light-sensitive silver halide emulsion layer.

Furthermore, each emulsion layer 5, □, ・ has other intermediate layers for various special purposes, and
・□゛:.

In addition, for example, in a silver halide photographic light-sensitive material for color printing, a red-sensitive silver halide emulsion layer, a green-sensitive halogen emulsion layer, and a green-sensitive halogen emulsion layer are generally formed from the exposed side. A silver halide emulsion layer and a blue-sensitive silver halide emulsion layer are coated in this order, and as in the case of the silver halide photographic light-sensitive material for color negatives, each layer is coated with intermediate layers such as an ultraviolet absorbing layer for a special purpose. , a protective layer, etc. 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 provided with a different arrangement for each color light. It is also known to use a photosensitive silver halide emulsion layer consisting of two layers that are sensitive to substantially the same wavelength range. In these silver halide color photographic light-sensitive materials, for example, aromatic The exposed silver halide grains are developed using a group primary amine color developing agent, and a dye image is formed by the reaction between the oxidation product of the color developing agent and the dye-forming coupler.

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 rapidly processed 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 1 of the developer, as well as the halogen concentration, especially the bromine ion concentration, etc. in the developer are highly controlled. However, compared to controlling the development time or the temperature and DH of the developer, controlling the bromine ion concentration in the developer to a constant value is difficult in general laboratories.
Have difficulty.

Particularly in rapid processing, the development speed is largely dependent on the bromide ion concentration, and therefore more processing stability is required. Furthermore, it is a matter of course that such processing-stabilized silver halide color photographic materials are required to be economically provided at low cost.

Therefore, conventionally proposed silver halide color photographic materials that can be processed rapidly include, for example:
A technology for making silver halide into fine grains as described in JP-A-51-77223; (2) A technology for making silver halide into a low silver bromide as described in JP-A No. 58-184142 and JP-B No. 56-18939; A technique of adding 1-aryl-3-pyrazolidone having a specific structure as described in JP-A-56-64339 to a silver halide color photographic light-sensitive material, as well as JP-A-57-144547 and JP-A-58-50534. , No. 5J3-50535, No. 58-50536, 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 silver color photographic material using an aromatic primary amine color developing agent is also known. - Development accelerators include U.S. Pat. No. 2,950,970;
No. 2,515,147, No. 2,496,903, No. 4,038,075, No. 4,119,462, British Patent No. 1,430,998, No. 1,455,413,
JP-A-53-15831, JP-A No. 55-62450,
'No. 55-62451, No. 55-62452, No. 55-62453, No. 51-12422, No. 5
No. 5-62453, Special Publication No. 51-12422,
There are compounds described in No. 5, No. 55-49728, etc.. However, among these conventional techniques, ■ or ■ is used.

If the
In addition, there were problems with fogging and storage stability in same-day performance.

When the low silver bromide emulsion (2) above is used, less bromide ions are eluted into the developer from the silver halide color photographic light-sensitive material containing the low silver bromide emulsion, and the concentration of bromide ions in the developer is low. Although it is possible to achieve rapid processing due to the ability to set
It has been found that when a silver halide color photographic light-sensitive material containing a low silver bromide emulsion is processed, it has a drawback of poor processing stability. Processing stability here refers to processing liquid composition,
This is the degree of variation in sensitometry due to variations in pH 1 temperature, bromine ion concentration, etc., and contamination of other compounds other than the treatment liquid composition.

Further, 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.

[Object of the Invention] The present invention was made in view of the above-mentioned conventional problems, and an object of the present invention is to provide a silver halide photographic material that can be rapidly processed and has improved processing stability.

[Structure of the Invention] The above object of the present invention is to provide a silver halide photograph 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. Photosensitive material l': F3°゛1・front 2 blue photosensitive A
0:・The silver bromide content of the silver halide in the silver emulsion layer is □70 to 10070 to 100 mol green-sensitive halogen □, the silver emulsion layer and the red-sensitive silver halide emulsion 1 layer The average grain size of silver halide grains having a silver halide silver bromide content of 5 to 65 mol % and having the maximum average grain size among the silver halide grains contained in each silver halide emulsion layer. diameter (rmax) and the average grain size of silver halide grains having a minimum average grain size--this was achieved by providing a silver halide photographic light-sensitive material.

・
The present inventors have discovered that the halogen composition of silver halide grains,
- As a result of intensive study by varying the average particle diameter over a wide range, it was discovered that the desired rapid processability and 91U mechanical stability were specifically satisfied with the above-mentioned sheath circumference, leading to the present invention.

[Specific structure of the invention] The present invention will be explained in further detail below.

The silver bromide content of the silver halide contained in the blue-sensitive silver halide emulsion layer in the present invention is limited to 70 to 100 mol%, preferably 80 to 100 mol% of silver chlorobromide or silver bromide. be.

If the silver bromide content is less than 70 mol %, the sensitivity of the blue-sensitive emulsion layer will drop sharply, making it difficult to achieve fine grain size and rapid development while maintaining sensitivity. It is preferable that the blue-sensitive silver halide emulsion consists essentially of silver chlorobromide or silver bromide, but it may also contain silver iodide having very fine concavities in its grain structure. In such a case, the content of silver iodide is preferably 1 mol % or less, but from the viewpoint of desilvering speed, it is preferable that no silver iodide is contained.

The silver halide contained in the green-sensitive silver halide emulsion layer and the red-sensitive silver halide emulsion layer in the present invention is
Silver chlorobromide, silver chloroiodobromide, or a mixture thereof is preferred, and the silver bromide content is 5 to 65 mol%, preferably 20 to 60 mol%, preferably coarse.
When silver iodide is used, the content thereof is preferably 1 mol % or less, and it is most preferable that no silver iodide is contained at all.

The green-sensitive silver halide emulsion layer in the present invention,
・□One or both of the red-sensitive silver halide emulsion layers are 2
The silver bromide content may consist of a total line-sensitive silver halide emulsion layer, (
゛tag N Contained in each red-sensitive silver halide emulsion layer
1. = The total silver bromide content of each layer in the total silver halide. If the silver bromide content exceeds 65 mol %, the development speed of the blue-sensitive emulsion layer is reduced, and the bromide ion concentration in the developer during low replenishment processing is increased, making rapid development difficult. On the other hand, when the silver bromide content is less than 5 mol%, the processing stability becomes markedly * (e I,
,! fr IZ 3J! @ ) If $ (D '7
CI A it > la S H4,'',' The occurrence of fog increases rapidly when the change is made in the negative direction.

The silver halide contained in the blue-sensitive silver halide emulsion layer in the present invention has an average grain size (average grain size) of 0.20.
~0.65 μm, preferably 0.30 to 0.60 μm. When the average particle size exceeds 0.65 μm, processing stability is poor, and particularly when the amount of potassium bromide is varied, the developability is significantly lowered. On the other hand, if the average grain size is less than 0.20 am, the sensitivity as a blue-sensitive silver halide emulsion may become insufficient.

Furthermore, the average grain size of the silver halide contained in the green-sensitive silver halide emulsion layer and the red-sensitive emulsion layer is not particularly limited, but is 0.
．． 2 to 0.6 μm, more preferably 0.3 to 0.5 μm.

In the present invention, the average grain size of the silver halide contained in the blue-sensitive, green-sensitive and red-sensitive silver halide emulsion layers is as follows:
This can be measured by various methods commonly used in the art for the above purposes.

A representative method is Loveland's [Particle Size Analysis Method J
A, S, T.

M, Symposium on Light Microscopy,
1955, pp. 94-122, or Chapter 2 of ``Theory of Photographic Processes'' by Mies and James, 3rd edition, published by Macmillan (1966). 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.

In the present invention, the silver halide contained in the blue-sensitive, green-sensitive, and red-sensitive silver halide emulsion layers may be a polydisperse emulsion in which the average grain size is distributed over a wide range.
Monodispersed emulsions are more 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 approximation S of the particle size distribution is divided by the average particle size T, the value is 0.15 or less.

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, It is the length of one side when converted to a cube having the same volume, and when the individual grain size in this sense is ri and the number is nl, the average grain size r is defined by the following formula. It is something that

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 (1848), 330-3.
In the method described in the paper by Tribel and Smith on page 38,
You can decide this.

In the present invention, the grain size ratio of the silver halide grains contained in each layer of the blue-sensitive emulsion layer, the green-sensitive emulsion layer, and the red-sensitive emulsion layer is specified. It is an essential condition that the average grain size (r max ) of silver halide grains having a minimum average grain size is ≦1.2. If the particle size ratio is greater than 1.2,
Processing stability deteriorates and the specific effects of the present invention are not exhibited. That is, the range of variation in the photographic performance of the three layers is different in response to variation in the bromine ion concentration in the developer, which causes a fatal defect in the finished print. Furthermore, if the particle size ratio is greater than 1.2, the processing fluctuation range of the three layers tends to increase due to mixing of the bleach-fixing solution into the developer. Further, when the above particle size ratio is satisfied, the particle size can be freely selected as long as the set particle size is within the range described above. Generally, the average grain size of the silver halide grains contained in the blue-sensitive emulsion layer, which has strict requirements in terms of sensitivity and rapid processability, is set, and the green-sensitive emulsion layer matches the above grain size ratio to that grain size. A method is used to set the average grain size of silver halide grains in the emulsion layer, but the method can be selected as appropriate depending on various purposes.

In the silver halide photographic light-sensitive material of the present invention, the amount of silver (silver coating amount) in the silver halide emulsion layer is preferably 0.3 to 'IQ/f in the entire photosensitive silver halide emulsion layer. That is, in order to obtain excellent image quality, the silver amount is preferably 1 Q/f or less, while in order to obtain high maximum density and high sensitivity, the silver amount is 0.3 g/f or more. It is preferable. In the present invention, the silver amount is particularly preferably 0.4.
~0.8Q/f.

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.

Alternatively, for example, seed particles may be produced using an acidic method, and then grown using an ammonia method, which has a high growth rate, to grow to a predetermined size. When growing silver halide grains, the pH in the reaction vessel is controlled such as 1DAΩ, and the amount of silver ions and halides is adjusted to the growth rate of silver halide grains, as described in JP-A No. 54-48521, for example. It is preferable to implant and mix the ions sequentially and simultaneously.

The rA production of silver halide grains according to the present invention is carried out as described above.

The crystal habit of the silver halide grains used in the present invention is as follows:
Cubic silver halide grains such as cubic, tetradecahedral, octahedral, twinned, etc. are not particularly limited, but cubic silver halide grains are generally preferred since they have good color sensitization efficiency and can provide high contrast gradations.

The silver halide emulsion used in the present invention has an active
・Gelatin; Sulfur sensitizers, such as allylthiocarbamide, thiourea, cystine; Selenium sensitizer; Dual reduction sensitizers, such as stannous salts, thiourea dioxide, polyamines, etc.; sensitizers such as gold sensitizers, specifically potassium aurithiocyanate, potassium chloroaurate, 2-orothio-3-methylbenzothiazolium chloride, etc. or water-soluble salts such as ruthenium, palladium, platinum, rhodium, iridium, etc. Sensitizers, specifically ammonium chlorovaladate, potassium chloroplatinate, and nathorum chloroplatinate (these types act as sensitizers or fog suppressants depending on the amount), etc., alone or as appropriate. Chemical sensitization may be carried out by using a combination (for example, a combination of a gold sensitizer and a sulfur sensitizer, a combination of a gold sensitizer and a selenium sensitizer, etc.).

The silver halide emulsion used in the present invention may be chemically ripened by adding a sulfur-containing compound, and may contain at least one hydroxytetrazydene before, during, or after the chemical ripening.

The silver halide used in the present invention has 5 x 10-8 to 3 x 10-3 mol of a suitable sensitizing dye added to each mol of silver halide in order to impart photosensitivity to the desired wavelength range. It may also be optically sensitized.

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. No. 776, No. 2,519,001,
No. 2,912,329, No. 3,656,959, No. 3,672,897, No. 3,694,217,
No. 4,025,349, No. 4,046,572, British Patent No. 1,242.588, Japanese Patent Publication No. 14030/1973
No. 52-24844, etc. can be mentioned. In addition, as a sensitizing dye used in green-sensitive silver halide emulsions, for example, US Patent No. 1,939,2
No. 01, No. 2,072.908, No. 2,739,14
No. 9, No. 2,945,763, British Patent No. 505,97
Cyanine color as described in No. 9 etc.
Typical examples include merocyanine dyes or complex cyanine dyes. Roughly,
Examples of sensitizing dyes used in red-sensitive silver halide emulsions include U.S. Pat. Nos. 2,269,234 and 2,27
No. 0,378, No. 2,442,710, No. 2,454
Typical examples thereof include cyanine dyes, merocyanine dyes, and composite cyanine dyes as described in , No. 629, No. 2.776.280, and the like. Furthermore, U.S. Pat. No. 2,213,995, U.S. Pat.
No. 3,748, 2,519,001 Ji! Cyanine dyes, merocyanine dyes or composite cyanine dyes such as those described in German Pat.

These sensitizing dyes may be used alone or in combination. Combinations of sensitizing dyes are often used, especially for the purpose of supersensitization.

A typical example is U.S. Patent No. 2,688,545;
, No. 977.229, No. 3,397,060, No. 977.229, No. 3,397,060, No.
No. 3,522,052, No. 3,527,641, No. 3
, No. 617,293, No. 3,628,964, No. 3,
No. 666.480, No. 3,672,898, No. 3,6
No. 79,428, No. 3,703,377, No. 3,76
No. 9,301, No. 3,814.609, No. 3,837
, 862 bow, 4,026.707@, British patent 1,3
No. 44,281, No. 1,507,803, Special Publication No. 43
No.-4936, No. 53-12375, JP-A-52-1
No. 10618, No. 52-109925, etc.

The silver halide photographic material of the present invention may contain a water-soluble dye in the hydrophilic cotoid layer as a filter dye or for various purposes such as preventing irradiation. Such dyes include oxonol dyes, hemioxonol dyes and merocyanine dyes and azo dyes. Among them, oxonol dyes, hemioxonol dyes and merocyanine dyes are useful. Specific examples of dyes that can be preferably used include British Patent Nos. 584,609 and 1, 2.
No. 77.429, JP-A-48-85130, JP-A No. 49-
No. 99620, No. 49-114420, No. 49-1
No. 29537, No. 52-108115, No. 59-2
No. 5845, U.S. Pat. No. 2,274.782, U.S. Pat.
33.412, 2,956,879, 3,
No. 125,448, No. 3, No. 148.187, No. 3,
No. 177.078, No. 3,247,127, No. 3,
No. 540,887, No. 3,575,704, No. 3,6
No. 53,905, No. 3,718,472, No. 4,07
No. 1,312 and No. 4,070.352.

Each of the silver halide emulsion layers used in the present invention can contain a dye-forming coupler, that is, a compound capable of reacting with an oxidized form of a color developing agent to form a dye.
In the present invention, conventionally known yellow couplers, magenta couplers and cyan couplers can be used as the dye-forming couplers. These dye-forming couplers may be so-called 2-equivalent type couplers or 4-equivalent type couplers, and in combination with these dye-forming couplers, it is also possible to use diffusible dye-releasing couplers and the like. .

The cyan coupler is, for example, a phenol- or naphthol-based cyan coupler; the magenta coupler is, for example, a 5-pyrazolone-, virazololinobenzimidazole-, pyrazolotriazole-, indashilon-, or cyanoacetyl-based magenta coupler; and the yellow coupler is, for example, For example, acylacetamide-based or benzoylmethane-based yellow couplers are used.

In order to incorporate these dye-forming couplers into the silver halide emulsion used in the present invention, if the couplers are alkali-soluble, they may be added as an alkaline solution; if they are oil-soluble, they may be added, e.g. US Patent Nos. 2 and 3
No. 22,027, No. 2,801.170, No. 2,
No. 801.171, No. 2,272,191 and No. 2,304,940, dye-forming couplers are used in a high boiling point solvent, and optionally in combination with a low boiling point solvent. It is preferable to dissolve it, 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 dye-forming couplers. Furthermore, to explain in detail the preferred method of adding dye-forming couplers in the present invention, one or more of the couplers are added to an organic acid along with other couplers, hydroquinone derivatives, anti-fading agents, ultraviolet absorbers, etc. as necessary. Amides, 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-hexyl phosphate, N,N~di-ethyl-caprylamidobutyl, N,N-diethyl Laurylamide, n-pentadecyl phenyl ether, di-octyl phthalate, n-nonylphenol, 3-pentadecyl phenylethyl ether, 2,5-di5eC-amyl phenyl butyl ether, monophenyl-di-O-lophenyl phosphate Alternatively, a high boiling point solvent such as fluoroparaffin, and/
Or methyl acetate, ethyl acetate, propyl acetate, butyl acetate, butyl propionate, cyclohexanol, diethylene glycol monoacetate, nitromethane, carbon tetrachloride, chloroform, cyclohexane tetrahydrofuran, methyl alcohol, acetonitrile, dimethylformamide, dioxane, methyl ethyl ketone, etc. Dissolved in a low boiling point solvent, the alkylbenzene sulfone'I/M
and an aqueous solution containing an anionic nasal surfactant such as alkylnaphthalene sulfonic acid and/or a nonionic surfactant such as sorbitan sesquioleate and nlupitan monolaurate and/or a hydrophilic binder such as gelatin, It is emulsified and dispersed using a high-speed rotating mixer, colloid mill, ultrasonic dispersion device, etc., and then added to a silver halide emulsion.

Alternatively, the couplers formed above may be dispersed using a latex dispersion method. Latex dispersion method and its effects are as follows:
JP-A-49-74538, JP-A No. 51-599434, JP-A No. 54-32552M Research Disclosure August 1976, No. 14850, 77-19
It is written on the page.

Suitable latexes include, for example, styrene, acrylate,
n-butyl acrylate, n-butyl methacrylate,
2-7 Cetoacetoxyethyl methacrylate, 2-(methacryloyloxy)ethyltrimethylammonium methosulfate, 3-(methacryloyloxy)pan-1-sulfone sodium salt, N-isopropylacrylamide, N-[2-(2- methyl-4-oxopentyl)] acrylamide, 2-acrylamide-2-
Homopolymers, copolymers and terpolymers of monomers such as methylpropane sulfone and the like.

The silver halide photographic material of the present invention may contain various other photographic additives, such as antifoggants, stabilizers, ultraviolet absorbers, and colorants described in Research Disclosure No. 17643. anti-pollution agent,
Fluorescent whitening agent, color image fading prevention agent, antistatic agent, hardening agent,
Surfactants, plasticizers, wetting agents, etc. can be used.

In the silver halide 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 human O2. Examples include cellulose derivatives such as xyethyl cellulose derivatives and carboxymethyl cellulose, starch derivatives, single or copolymer synthetic hydrophilic polymers such as polyvinyl alcohol, polyvinylimidazole, and polyacrylamide.

The support for the silver halide photographic material of the present invention includes:
For example, baryta paper, polyethylene-coated paper, polypropylene synthetic paper, transparent supports with a reflective layer or a reflector, such as glass plates, polyester films such as cellulose acetate, cellulose nitrate, or polyethylene terephthalate, polyamide films, polycarbonate. There are films, polystyrene films, etc., and these supports are appropriately selected depending on the intended use of the photosensitive material.

Emulsion layers and other layers used in the present invention
・Dipping coating and aired coating are used for coating the constituent layers.
Various coating methods such as lid coating, curtain coating, and hopper coating can be used. Also, U.S. Patent 2.7
61,791 and 2,941,898 can also be used to simultaneously coat two or more layers.

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, it is preferable to sequentially arrange a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, and a red-sensitive silver halide emulsion layer from the support side. .

In the silver halide photographic material of the present invention, it is optional to provide an intermediate layer with an appropriate thickness depending on the purpose, and various layers such as a filter layer, an anti-curl layer, a protective layer, an antihalation layer, etc. They 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 processing method for the silver halide photographic material of the present invention, and any processing method can be applied. For example, typical methods include a method in which bleach-fixing is performed after color development, followed by further washing and/or stabilization treatment if necessary, and a method in which bleaching and fixing are carried out separately after color development, followed by further washing with water if necessary. and/or stabilizing treatment method: or pre-hardening, neutralization, color development, stop-fixing, water washing, bleaching, fixing, water washing, fast hardening, water washing, color development, development, water washing, supplementation. A method in which color development, stopping, bleaching, fixing, washing, and stabilization are performed in the order of color development, and after halogenation bleaching is applied to the developed silver produced by color development, color development is performed again to increase the amount of dye produced. The treatment may be performed using any method.

The color developing solution used in the processing of the silver halide photographic light-sensitive material of the present invention is an alkaline aqueous solution containing a color developing agent and preferably having l)H of 81X or more, more preferably l)H of 9 to 12. This aromatic first as a color developing agent
A primary amine developing agent is a compound that has a primary amino group on an aromatic ring and has the ability to develop exposed silver halide. May be added.

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

4-Amino-N, N-diethylaniline, 3-methyl-
4-amino-N, N-diethylaniline, 4-amino-
N-ethyl-N-β-hydroxyethylaniline, 3-
Methyl-4-amino-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methoxyethylaniline, 3-methyl-4-amino-N-
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-amino-N.

N-dimethylaniline, N-ethyl-N-β-[β-(
β-methoxyethoxy)ethoxy]ethyl-3-methyl-4-aminoaniline, N-ethyl-N-β-(β-methoxyethoxy)ethyl-3-methyl-4-aminoaniline, and salts thereof such as sulfates, hydrochloride, sulfite,
p-toluenesulfonate and the like.

Furthermore, for example, JP-A-48-64932, JP-A-50-1
No. 31526, No. 51-95849@, and those described by Bent et al., Journal of the American Chemical Society, Vol. 73, pp. 3100-3125 (1951) are also mentioned as representative examples.

The amount of these aromatic primary amine compounds to be used can be determined by setting the activity of the developer, but in order to increase the activity, it is preferable to increase the amount. The amount used ranges from 0.0002 mol/2 to 0.7 mol/2. Moreover, two or more compounds can 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-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-
Ethyl-N-β-methanesulfonamidoethylaniline and 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline may be used in any combination depending on the purpose.

The color developing solution used in the present invention further contains various commonly added components, such as tetralim hydroxide, alkaline agents such as sodium carbonate, alkali metal sulfites,
Alkali metal bisulfites, alkali metal thiocyanates, alkali metal halides, benzyl alcohol,
A water softener, an 81 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;
Alkali iodide, nido Ω benzimidazole, mercaptobenzimidazole methyl-benzotriazole, 1-
In addition to compounds for rapid processing solutions such as phenyl-5-mercaptotetrazole, there are anti-stain agents, anti-sludge agents, preservatives, interlayer effect promoters, chelating agents, and the like.

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 aminopolycarboxylic 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 also contain additives. 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. As in the case of the above-mentioned bleaching solution, various other additives such as pHIII agents, optical brighteners, bleaching 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 temperatures for various processing steps such as bleach-fixing (or bleaching and fixing), washing with water, stabilization, and drying as necessary are as follows:
From the viewpoint of rapid processing, it is preferable to conduct the treatment at a temperature of 30°C or higher, preferably 35°C or higher.

The silver halide photographic light-sensitive material of the present invention is disclosed in Japanese Unexamined Patent Publication No. 58-14
No. 834, No. 5B-105145, No. 58-1346
No. 34 and No. 5g-18631 and patent application No. 58-2
709 and No. 59-89288, etc., as an alternative stabilization treatment to washing with water.

You may go.

Specific examples of the present invention will be described below.
8 [Example] The embodiments of the present invention are not limited to these.

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 materials n samples Nos. 1 to 11. Note that the amount added is expressed in J per 11j unless otherwise specified.

Layer 1...1.2g gelatin, 0.32g (in terms of silver,
0.50 g of a blue-sensitive cubic silver chlorobromide emulsion (silver bromide content and average grain size are shown in Table 1) of
A layer containing 0.80 g/f of yellow coupler (Y-1) dissolved in ethylhexyl phthalate (hereinafter abbreviated as DOP).

Layer 2 - 0.7 g/1 gelatin, 10 ma/v' anti-irradiation dye (AI-1), 5II 1 g/V
(AI-2) and 0.05 g of the following color stain inhibitor H
Intermediate layer containing 0.051 J DOP in which Q-1 was dissolved.

Layer 3: 1.25 g gelatin, 0.229 green-sensitive cubic silver chlorobromide emulsion (silver bromide content and average grain size are shown in Table 1), dissolved in 0.301; l DOP 0, 6
2! Layer containing I+ magenta coupler (M-1).

Layer 4...1゜2g of gelatin and o, oag of HQ-
1 and o, sg UV absorber LIV-1 dissolved in 0,
Intermediate layer containing 35g DOP.

Layer 5: 1.4 g of gelatin, 0.209 g of red-sensitive cubic silver chlorobromide emulsion (silver bromide content and average grain size are shown in Table 1)
), 0,451 dissolved in a DOP of 0.209;
1 cyan coupler (C-1).

Layer 6: Layer containing 0,309 LIV-1 dissolved in 1.0 g gelatin and 0.2 h DOP.

Layer 7: A layer containing gelatin of -o, so/f.

Note that a vinyl sulfone organic hardener was used as the hardener.

Table 1 *IR: Night-sensitive halodane recording emulsion.

*20; Green-sensitive silver halide emulsion.

*3 P: Red-sensitive silver halide emulsion.

-IC6 HQ-1 V-1 (:5Htt() AI-'J.

I-2 Each of the above photosensitive material samples Nos. 1 to 11 was exposed to white light through an optical wedge and then processed in the following steps.

Processing process (38℃) Color development 2 minutes 30 seconds bleach fixing
Wash with water for 1 minute and dry for 1 minute.
80°C for 2 minutes The composition of each treatment solution is as follows.

[Color developer J pure water 800d benzyl alcohol 151Af! Triethanolamine 10. OQ sulfuric acid and droxyamine 2.0g potassium bromide
1.5g sodium chloride
1.0g potassium sulfite
2609 N-Ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfur salt 4.5 g 1-Human O-xyethylidene-1.1-diphosphone M (60% aqueous solution > 1.5.1
Potassium 2 carbonate 32 QWh
itex B B (50% aqueous solution>2
i12 (fluorescent brightener, manufactured by Sumitomo Chemical Co., Ltd.).

Add pure water to make 11 and 20% potassium hydroxide or 10%
MU to pHio, i with dilute sulfuric acid.

C Bleach-fix solution j Pure water 550 v1 Ethylenediaminetetraacetic acid iron(III) Ammonium 65 Q Ethylenediaminetetraacetic acid-2-Ca,,tsu,,,5゜ i Ammonium thiosulfate as g Sodium bisulfite 10 Q Sodium metabisulfite 2g Ethylenediamine Tetraacetic acid-2 Sodium 20 Q Sodium Bromide 10 Q
, add pure water to bring the pH to 12, and adjust the pH to 7.0 with aqueous ammonia or dilute sulfuric acid.

Separately, add 0.9 g of potassium bromide of the above color developer, 1.
2fJ, 1.8 (7 and 2.10) using the same color developer as above.

Each of samples Nos. 1 to 11 was developed.

Sensitometry was performed on each sample obtained by a conventional method. Table 2 shows the sensitivity, fog, and gamma value when the potassium bromide concentration was varied, assuming that the sensitivity of each sample was 100 when the potassium bromide concentration was 1.5 g/Il.

S in Table 2 is potassium bromide concentration 1.5g#! Relative sensitivity when the sensitivity at 100, γ is reflection density 0.5
The slope (gamma value) on the characteristic curve of ~1.8, F is the fog density, and ΔS is S when the potassium bromide concentration is 2.1 g/2
Δγ is the ratio of S at 0 and 9all to γ, Δγ is the ratio of γ at 0 and 9Q/e to γ at potassium bromide concentration of 21o/l, and B, G and R are the ratio of blue, green and red, respectively. It represents what was determined from the characteristic curves obtained by measuring with each monochromatic light.

Furthermore, the sensitivity of the blue-sensitive emulsion layer at a potassium bromide concentration of 1.5o/ffi (obtained from the characteristic curve measured with blue monochromatic light) is also shown as the relative sensitivity when sample N 0.1 is taken as 100. .

As is clear from Margin Table 2 below, the samples (1, 2, 6) with particle size ratios outside of the present invention have large fluctuations in sensitivity and gamma to changes in potassium bromide concentration, and the balance of the three layers cannot be maintained. Not yet. In addition, samples (3, 4) having the grain size ratio of the present invention but in which the silver bromide composition of the blue-sensitive silver halide emulsion is 70 mol% or less have low sensitivity and low sensitivity, although the sensitivity of the blue-sensitive layer is low. Gamma processing variation range has not been improved. Furthermore, in sample (7) in which a silver chlorobromide emulsion with a silver bromide composition of 3 mol % was used in the green-sensitive layer and the red-sensitive layer, fog increased rapidly due to a decrease in potassium bromide in the developer. be. In addition, sample (5) in which a silver chlorobromide emulsion with a silver bromide composition of more than 65 mol % was used in the green-sensitive layer and the red-sensitive layer had a processing fluctuation range of sensitivity and gamma (especially in the blue-sensitive layer). is not improved.

On the other hand, the samples (8 to 11) of the present invention have a small sensitivity to changes in potassium bromide concentration and a small range of gamma fluctuations, and are well balanced at 311. Moreover, there is no increase in fog, and the processing stability is low. has been significantly improved.

Example 2 Using the sample 1.2.6.8°10 prepared in Example 1, mixing the color developer (potassium bromide 1.50/2) with a bleach-fix solution (1.0 cc/l) ), and the results are shown in Table 3.

Margin Table 3 Below, gamma in the table was determined in the same manner as in Example-1, and gamma balance indicates the ratio of B and R to G.

From the results shown in Table 3, the gamma balance of comparative samples (1, 2, 6) is disrupted due to the contamination of the bleach-fix solution, and in particular, the balance of B with respect to G is greatly disrupted, and the cisetone part is blue to blue.
This indicates a significant shift towards the green trend. On the other hand, although the gamma of samples (8, 10) of the present invention increases slightly due to the mixing of the bleach-fix solution into the color developing solution, the gamma balance is not significantly disrupted, and the finished prints have good color reproduction. In addition, neutral (black) reproduction is possible.

Claims (1)

[Claims] In a silver halide photographic 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 silver bromide content of silver halide is 7
0 to 100 mol%, and 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 5 to 65 mol%, respectively;
Among the silver halide grains contained in each silver halide emulsion layer, the average grain size of the silver halide grains having the maximum average grain size (@r@max) and the average grain size of the silver halide grains having the minimum average grain size The ratio to the diameter (@r@min) is @r@max
A silver halide photographic material, characterized in that /@r@min≦1.2.