JPH05694B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to a silver halide photographic material,
More specifically, the present invention relates to a silver halide photographic material with improved photographic properties such as sensitivity, graininess, sharpness, storage stability, and gradation. [Prior Art] There has been a strong desire to develop silver halide photographic materials (hereinafter referred to as "photosensitive materials") with high sensitivity and fine grains, and for this reason, many improved photosensitive materials, In particular, color photosensitive materials have been proposed. As one of the photosensitive materials suitable for the above purpose,
For example, British Patent No. 923045 discloses a high-sensitivity silver halide emulsion layer (hereinafter referred to as "high-sensitivity emulsion layer") containing a diffusion-resistant coupler that develops substantially the same hue, and a low-sensitivity silver halide emulsion layer. (hereinafter referred to as the low-speed emulsion layer), a silver halide emulsion with the same color sensitivity is coated in separate layers, and the maximum color density of the high-speed emulsion layer is adjusted to a low level to prevent graininess from deteriorating. It is stated that the sensitivity can be increased. However, in recent years, color light-sensitive materials for photographic use, in particular, are required to have increasingly high sensitivity, forcing the use of coarse silver halide with poor graininess and/or couplers with high coupling speed in the silver halide emulsion layer. For this reason, the method described in the above-mentioned British Patent No. 923045 was insufficient in improving the graininess, and further efforts have been made to improve the graininess. For example, Japanese Patent Publication No. 49-15495 states that graininess can be improved by providing a gelatin layer between the high-sensitivity emulsion layer and the low-sensitivity emulsion layer. Although this method improves the graininess in the low density region, it has a significant negative effect on the gradation.On the other hand, in order to restore the gradation, conventional techniques, such as increasing the grain size of silver halide, lower the sensitivity. Increasing the sensitivity of the emulsion layer is undesirable because it deteriorates the graininess particularly in the medium density range, which is important in practice. Furthermore, the multilayer color photosensitive material having the above structure also has the disadvantage that the stability of the color image density deteriorates against changes in development processing conditions, such as pH value, temperature, time, etc. There is. Furthermore, for example, JP-A-57-155536 discloses that between the high-speed emulsion layer and the low-sensitivity emulsion layer, a material having substantially the same hue as that of the photographic diffusion-resistant coupler contained in the high-speed and low-speed emulsion layers is disclosed. By providing a non-light-sensitive hydrophilic colloid layer containing a photographic diffusion-resistant coupler that develops color and has a coupling speed not greater than the coupling speed of the photographic diffusion-resistant coupler contained in the high-speed emulsion layer, graininess can be improved. It is stated that the gradation can be improved. Although this method does not cause gradation failure and improves graininess, it is still insufficient to improve graininess in the low to medium density range. For example, in the above-mentioned Japanese Patent Publication No. 49-15495 and Japanese Patent Application Laid-open No. 53-7230, medium-sensitivity silver halide emulsion layers each having a low coloring density are provided between the high-sensitivity emulsion layer and the low-sensitivity emulsion layer, A method is described in which the layer contains a compound (hereinafter referred to as a DIR compound) capable of reacting with an oxidized form of a color developing agent to release a diffusible development inhibitor. However, these methods have drawbacks such as increased fog due to increased usage of silver halide and increased usage of valuable silver resources. Furthermore, in light-sensitive materials having two or more silver halide emulsion layers with the same color sensitivity, the silver halide emulsion layer with higher sensitivity usually has improved graininess by lowering the coupler density (in this case, The oxidized form of the developing agent generated from the development reaction diffuses over a wide area in search of a partner to couple with.
The developing agent formed by the development of silver halide in the silver halide emulsion layer with higher sensitivity (which is thought to form a large, blurred dye cloud with low density and do not worsen graininess) The oxidized product does not remain only in the formed layer, but also diffuses into the adjacent or adjacent silver halide emulsion layer with higher coupler density and lower sensitivity, forming a conspicuous granular dye cloud there. do. As a result, when viewing light-sensitive materials, the disadvantage is that the developed silver grains of the silver halide emulsion layer, which has higher sensitivity, extend to the problematic density (or exposure) region, resulting in deterioration of graininess. arise. [Object of the Invention] Therefore, the object of the present invention is to provide a photosensitive material that has high sensitivity, good gradation, and further improved sharpness, image storage stability, and graininess, and that requires less silver usage. There is a particular thing. [Effects of the Invention] As a result of various studies by the present inventors, the above object is to provide a silver halide emulsion layer having a plurality of silver halide emulsion layers having substantially the same color sensitivities but different sensitivities, and In a silver halide photographic light-sensitive material having at least one light-sensitive layer containing a photographic diffusion-resistant coupler on a support, at least the silver halide emulsion layer having the highest photosensitivity among the plurality of silver halide emulsion layers. A non-photosensitive intermediate layer is provided adjacent to the support side, and the non-photosensitive intermediate layer (hereinafter referred to as the intermediate layer according to the present invention) is provided with a material that causes a coupling reaction with an oxidized form of a color developing agent. It has been found that this can be achieved by using a light-sensitive material containing a compound capable of forming a run-off type coupling product. That is, the present invention proposes a novel and improved photosensitive material to solve the above-mentioned problems. [Structure of the Invention] The photosensitive material of the present invention will be explained in more detail below. Below, in explaining the present invention, one aspect of the present invention will be explained. That is, in the present invention, for example, photosensitive layers having different photosensitivity, that is, a high-sensitivity emulsion layer and a low-sensitivity emulsion layer, are provided sandwiching the intermediate layer according to the present invention. In this case, the high-sensitivity emulsion layer and the low-sensitivity emulsion layer may each have one layer, but if they have two or more layers, the effect of the method described in British Patent No. 923045 will be added to the effect of the present invention. preferable. In the present invention, the high-sensitivity emulsion layer is preferably provided farther from the support than the low-sensitivity emulsion layer, and when the high-sensitivity emulsion layer and the low-sensitivity emulsion layer each have two or more layers, the support It is preferable that the closer the layer is to the layer, the lower the sensitivity. In addition, the sensitivity difference between the high-speed emulsion layer and the low-speed emulsion layer can be determined by a well-known method by taking into account gradation and graininess, but is generally about 0.1.
It is preferable to have a difference of ~1.0 logE (E; exposure amount). Further, the high-speed emulsion layer and the low-speed emulsion layer have substantially the same color sensitivity, and after color development processing, the two emulsion layers contain coloring dyes having substantially the same hue. It is preferred to contain a photographic diffusion-resistant coupler that can be formed. In this case, the content of the photographic diffusion-resistant coupler contained in each of the high-speed emulsion layer and the low-speed emulsion layer is such that the color density of the color forming dye formed as a result of the coupling reaction with the oxidized form of the color developing agent is determined. It is preferred that the content be higher in the low-sensitivity emulsion layer than in the high-sensitivity emulsion layer. Further, the intermediate layer according to the present invention can also contain the photographic diffusion-resistant coupler contained in the two emulsion layers. The intermediate layer according to the present invention contains a compound (hereinafter referred to as the compound according to the present invention) that can cause a coupling reaction with an oxidized color developing agent to form a run-off type coupling product. The compound according to the present invention can cause a coupling reaction with an oxidized form of a color developing agent to form a run-off type coupling product. The coupling product formed by the coupling reaction with the body has mobility within the light-sensitive material during the development process, that is, during or after the color development process,
It refers to a substance that flows out of the light-sensitive material during or after color development processing and substantially no longer remains in the light-sensitive material. The compound according to the present invention undergoes a coupling reaction with the oxidized form of a color developing agent to form a run-off type coupling product as described above, and it is preferable that the coupling product is a colored dye or a colorless compound. The amount of the compound according to the present invention contained in the intermediate layer according to the present invention is not particularly limited, but the upper limit is preferably 8×10 ^-2 mol/m ² , and more preferably 3×10 ^-2 mol/m 2 ² , and the lower limit is approximately 1
×10 ⁻⁷ mol/m ² . The compound according to the present invention has a stabilizing group that immobilizes the compound according to the present invention at the coupling site, and at the non-coupling site, there is a coupling product formed after the coupling reaction with the oxidized product of the color developing agent. It has a solubilizing group that provides material mobility. When a coupling reaction occurs with an oxidized color developing agent, the stabilizing group is released, and as a result, the coupled product has mobility. The compound according to the present invention forms a coupled product having mobility through a coupling reaction with an oxidized form of a color developing agent, but the mobility in this case is limited to the extent that it flows out of the system of the light-sensitive material as described above. It is sufficient if mobility can be imparted. The compound according to the present invention can be represented by the following general formula []. General formula [] In the formula, COUP represents a coupler core having a coupling site (asterisk *), and BALL is a group that binds to the coupling site of COUP and can be separated from COUP by reaction between COUP and an oxidized form of a color developing agent. It is a stabilizing group having a size and shape that makes the compound of general formula [] diffusion resistant. SOL is a solubilizing group that binds to the non-coupled position of COUP, and transports the coupling product generated by the coupling of COUP and the oxidized color developing agent from the light-sensitive material to the outside of the system during or after color development processing. It is a group that provides outflow mobility. The coupler core represented by COUP is known or used in the art to form a colored or colorless reaction product through a coupling reaction with an oxidized product of a color developing agent. Any coupler core may be mentioned. For example, yellow dye-forming coupler nuclei are acylacetanilides, such as acetoacetanilides and benzoylacetanilides, and magenta dye-forming coupler nuclei are pyrazolones, pyrazolotriazoles, pyrazolobenzimidazoles, and indazolones. The coupler nucleus for cyan dye formation includes phenols and naphthols. BALL is a stable group having a molecular size and shape that makes the compound of the general formula [] diffusion resistant, and is not limited as long as it imparts diffusion resistance to the compound of the general formula []. , BALL include alkyl groups having 8 to 32 carbon atoms, aryl groups and heterocyclic groups. These groups represent unsubstituted or substituted groups, and as substituents, they increase the diffusion resistance of the compound of the general formula [],
It is a group that changes the reactivity of the compound or causes a coupling reaction and increases the diffusivity of BALL after separation. Furthermore, BALL is preferably bound to the coupling site of COUP via a linking group. Typical linking groups include oxy (-o-),
Examples include thio (-s-). The solubilizing group represented by SOL is a group that imparts mobility to the coupling product generated by the coupling reaction to the extent that it can flow out of the light-sensitive material system, such as an ionizable hydroxyl group, carboxyl group, sulfo group, and aminosulfonyl group. , and their ionizable salts. One or more of these groups are also preferably bonded to the non-coupling site of COUP, or are of suitable size, e.g. alkyl groups with 1 to 10 carbon atoms, 6 to 12 carbon atoms. 1 aryl group
Alternatively, one in which a solubilizing group having two or more of the above ionizable groups is bonded to a non-coupling site of COUP is also advantageously used. Also preferred are those that are bonded to the non-coupling site of COUP via a linking group. Typical linking groups include oxy (-o-), thio (-s-),
Examples include carbonyl group, carboxyl group, oxycarbonyl group, amino group, carbamoyl group, aminocarbonyl group, ureido group, sulfamoyl group and aminosulfonyl group. Although useful solubilizing groups have been listed above, particularly preferred solubilizing groups are carboxyl groups, sulfo groups, or ionizable salts thereof that are directly bonded to the non-coupling site of COUP, or those that are directly bonded to the non-coupling site of COUP. , or an alkyl group having 1 to 10 carbon atoms or 6 to 12 carbon atoms containing one or more carboxy groups, sulfo groups, or ionizable salts thereof bonded via an amino group or a carbonyl group An aryl group having an atom can be mentioned. Further, the compounds according to the present invention which can form yellow, magenta and ion dyes preferably used in the present invention can be represented by the following general formulas [] to []. [Yellow pigment-forming compound] General formula [] In the formula, R ¹ is an aryl group (e.g. phenyl group)
or an alkyl group (particularly a tertiary alkyl group, e.g. t-butyl group), R ² is a stabilizing group (BALL) as mentioned above and R ³ is a solubilizing group (SOL) as mentioned above.
, R ⁴ is a hydrogen atom or a halogen atom, an alkyl group or an alkoxy group, and n+m=5
(However, when n≠0 and m≠0, and n and m are 2 or more, they may be the same or different). [Magenta dye-forming compound] General formula []

[Cyan dye-forming compound]

General formula []

[Exemplary compounds]

Next, typical synthesis examples will be given for these compounds according to the present invention, but other compounds can also be easily synthesized according to these synthesis methods. (a) Synthesis of [1] above α-pivalyl-α-bromo-2-chloro-5
-Ethoxycarbonylacetanilide 7.4g
(0.018mol) and 3-phenyl-4-(4-dodecylbenzyl)urazole 8.0g (0.018mol)
was dissolved in 100 ml of ethyl acetate, 1.3 g (0.009 mol) of anhydrous potassium carbonate was added, and the mixture was heated under reflux for 3 hours. 200 ml of water was added to the reaction mixture, and the ethyl acetate layer was extracted and concentrated to obtain the above [1] as a yellow viscous substance. (b) Synthesis of exemplified compound (2) Add [1] obtained in (a) to 50 ml of ethyl alcohol.
Dissolve 5.0 g of potassium hydroxide in 10 g of water.
ml was added and reacted for 2 hours.
When the reaction product was added to ice water containing 10 ml of concentrated hydrochloric acid with stirring, a white solid precipitated. This was filtered, washed with water, dried, and then recrystallized from ethyl acetate-n-hexane to obtain 10.3 g of Exemplified Compound (2). Mass spectrum m/e=731 (M ⁺ +1) Synthesis example 2 Synthesis of exemplified compound (9) 1-(3-carboxyphenyl)-3-methylpyrazolone 10.6g (0.024mol) and 4-octadecyloxybenzaldehyde 9.1 g (0.012 mol) was dissolved in 200 ml of ethyl alcohol, 3 drops of triethylamine were added, and the mixture was reacted for 5 hours. The solid obtained after concentration was washed with ethyl acetate to obtain 14.6 g of exemplified compound (9). Mass spectrum m/e=792 (M ⁺ ) (a) Synthesis of 1 to above 1,4-dihydroxy-2-naphthoic acid 20.4
g (0.1mol) and para-nitrofluorobenzene
14.1g (0.1mol) of dimethylformamide 300
ml, and while bubbling nitrogen gas, a solution of 8.5 g (0.2 mol) of sodium hydroxide dissolved in 20 ml of water was added, and the mixture was allowed to react for 1 hour. When the reaction product was added to ice water containing 20 ml of concentrated hydrochloric acid with stirring, it formed into a candy-like mass. When this was stirred while heating on a water bath, it solidified. The obtained crystals were filtered, washed with water, washed with acetonitrile, and dried to form a pale yellow solid.
23.2g was obtained. (b) Synthesis of 2 to above 21.8 g (0.067 mol) of 1 to obtained in (a) and 11.1 g (0.067 mol) of ethyl p-aminobenzoate were dissolved in 200 ml of dioxane, and 13.8 g of N,N'-dicyclohexylcarbodiimide was dissolved. g (0.067 mol) and reacted for 2 hours. The precipitated urea was filtered off, and the urea was washed three times with 20 ml of hot dioxane. The filtrate was concentrated and the resulting solid was washed with hot ethyl acetate to obtain 21 g of 2~ as a yellow-green solid. (c) Synthesis of 3~ above 21g of 2~ obtained in (b) was added to tetrahydrofuran.
4g of 5% palladium on carbon catalyst dissolved in 450ml
Catalytic hydrogenation was carried out for 10 hours. The catalyst was removed and the solid obtained after concentration was washed with ethyl alcohol. 9.2g of 3~ was obtained as a white solid. (d) Synthesis of 4~ above 9.2 g (0.021 mol) of 3~ obtained in (c) and α-
Dissolve 7.1 g (0.021 mol) of (2,4-di-t-pentylphenoxy)butyroyl chloride in 100 ml of tetrahydrofuran, and dissolve 1.7 g of pyridine.
(0.021 mol) was added and reacted for 2 hours. Pyridine hydrochloride was filtered off and concentrated to give a reddish-brown viscous substance. When silica gel column treatment was performed using a 1:1 mixed solvent of chloroform-n-hexane, 10 g of pale yellow candy-like substance
was gotten. (e) Synthesis of exemplified compound (18) Add 4 to 7 g of ethyl alcohol obtained in (d) to 50 g of ethyl alcohol.
ml, and a solution of 6.0 g of potassium hydroxide dissolved in 10 ml of water was added, and the mixture was reacted for 3 hours. When the reaction product was added to ice water containing 10 ml of concentrated hydrochloric acid with stirring, white crystals were formed. Filter this,
Washed with water and acetonitrile. When recrystallized from acetonitrile-ethyl acetate, 4.7g
Exemplary compound (18) was obtained. Mass spectrum m/e=717 (M ⁺ +1) In addition to the compound according to the present invention, the intermediate layer according to the present invention contains other types of photographic diffusion-resistant couplers and a hydroquinone derivative for controlling the progress of development. , colorless couplers, fine grain silver halide, etc. may also be contained. Moreover, the intermediate layer can also be composed of two or more layers. In general, photosensitive materials containing couplers include a red-sensitive silver halide emulsion layer containing a photographic diffusion-resistant cyan coupler, a green-sensitive emulsion layer containing a magenta coupler, and a blue emulsion layer containing a yellow coupler. In this specification, "having substantially the same color sensitivity" means having a light sensitivity in substantially the same spectral region;
This is a broad meaning indicating three categories of blue, and slight spectral changes are considered to be substantially the same. Further, the photosensitive material of the present invention has red sensitivity, green sensitivity,
When applied to each blue-sensitive layer, remarkable effects related to the present invention are observed, but it is preferable that at least the green-sensitive layer exhibits the embodiment of the present invention, and if the present invention is applied to all color-sensitive layers, ,
Furthermore, the quality of the final color image is excellent. Two or more compounds according to the present invention can also be used in combination in the intermediate layer according to the present invention. When two or more compounds are used in combination, at least one of the compounds according to the present invention contained in the intermediate layer according to the present invention has the highest coupling rate among the photographic diffusion-resistant couplers contained in the high-speed emulsion layer. It is preferable that the coupling speed is the same or higher than that of the conventional one. Compounds according to the present invention having a coupling speed equal to or higher than that of the one having the highest coupling speed among the photographic diffusion-resistant couplers contained in the high-speed emulsion layer are included in the intermediate layer according to the present invention. Compounds related to the present invention other than those mentioned above and/or
Alternatively, it is preferably contained in an amount of 30% or more, particularly preferably 70% or more, of the various compounds described above. In the present invention, a comparison of the coupling speed of the coupler contained in the high-sensitivity emulsion layer and the intermediate layer according to the present invention and the compound according to the present invention was conducted by adding silver halide 1 0.05 mole of the coupler of interest or the compound according to the invention is added per mole, and conventional sensitometry is carried out. On this occasion,
This is done by comparing the amount of developed silver of each sample under the same exposure conditions, which was subjected to a fixing process without bleaching after color development.
The coupling rate is defined as the coupler used in the sample in which a higher amount of developed silver is produced or the compound according to the invention has a faster coupling rate. The method for adding the coupler or the compound according to the present invention is to add the coupler or the compound according to the present invention 2
After heating and dissolving the mole in a mixed solvent of 4 moles of tricresyl phosphate and 50 moles of ethyl acetate, the mixture was mixed with an aqueous gelatin solution containing sodium dodecylbenzenesulfonate, and then emulsified and dispersed with a high-speed rotating mixer, followed by silver halide. This is done by adding it to an emulsion. A coupler that cannot be dissolved in the above-mentioned mixed solvent is dissolved in an equimolar amount of the high-boiling solvent and the coupler in a soluble solvent, and added after being emulsified and dispersed. Preferred compounds according to the present invention are those which produce a large amount of developed silver in the above-mentioned coupling rate comparison method. According to the present invention, in the light-sensitive material of the present invention, a plurality of silver halide emulsion layers each having substantially the same color sensitivity and different light sensitivities are provided. Photographic diffusion-resistant couplers can be included that produce diffusion-resistant color-forming dyes that provide corresponding tones. For example, as described above, the photographic diffusion-resistant cyan coupler used in the present invention is preferably a phenol compound or a naphthol compound, such as those disclosed in U.S. Pat. No. 2,369,929,
Same No. 2434272, No. 2474293, No. 2895826, Same No.
No. 3253924, No. 3034892, No. 3311476, No. 3311476, No.
No. 3386301, No. 3419390, No. 3458315, No. 3458315, No. 3419390, No. 3458315, No.
The compound can be selected from those described in No. 346563, No. 3591383, etc., and methods for synthesizing these compounds are also described in each of these specifications. Examples of the photographic diffusion-resistant magenta coupler used in the present invention include compounds such as pyrazolone, pyrazolotriazole, pyrazolinobenzimidazole, and indazolone.
As pyrazolone magenta couplers, U.S. Patent No. 2600788, U.S. Patent No. 3062653, U.S. Patent No. 3127269, U.S. Pat.
No. 3311476, No. 3419391, No. 3519429, No.
No. 3558318, No. 3684514, No. 3888680, JP-A-Sho
No. 49-29639, No. 49-111631, No. 49-129538,
Compounds described in No. 50-13041, etc.; as pyrazolotriazole magenta couplers,
Compounds described in U.S. Patent No. 1247493 and Belgian Patent No. 792525; pyrazolinobenzimidazole magenta couplers include U.S. Patent No. 3061432, West German Patent No. 2156111, and Japanese Patent Publication No. 46
Compounds described in Belgian Patent No. 60479; and as indazolone magenta couplers, compounds described in Belgian Patent No. 769116 can be advantageously used in the present invention. As the photographic diffusion-resistant yellow coupler used in the present invention, an open chain ketomethylene compound has conventionally been used, and the generally widely used benzoylacetanilide type yellow coupler and bivaloylacetanilide type yellow coupler can be used. . Furthermore, 2-equivalent yellow couplers in which the carbon atom at the coupling position is substituted with a substituent that can be removed during the coupling reaction are also advantageously used. Examples of these are U.S. Pat. No. 2,875,057, U.S. Pat.
3408194, 3447928, 3277155, 3447928, 3277155,
No. 3415652, Special Publication No. 13576, No. 13576, Special Publication No. 13576, No. 48-
No. 29432, No. 48-66834, No. 49-10726, No. 49
-122335, No. 50-28834, No. 50-132926, etc., along with synthetic methods. In the present invention, a colored coupler may be used in combination with the above-mentioned diffusion-resistant couplers for photography, if necessary.For example, the diffusion-resistant colored cyan couplers for photography used are generally phenol or naphthol derivatives. Targeted and
Examples include, for example, U.S. Patent No. 2,521,908;
No. 3034892, British Patent No. 1255111, Japanese Unexamined Patent Publication No. 1973-
Synthesis methods are described in No. 22028, No. 50-123341, No. 50-10135, and US Pat. No. 3,476,563. Furthermore, as the photographic diffusion-resistant colored magenta coupler used in the present invention, a compound in which the coupling position of a colorless magenta coupler is substituted with arylazo is generally used. For example, U.S. Pat. ,same
No. 3005712, No. 3684514, British Patent No. 937621,
Examples include compounds described in JP-A-49-123625 and JP-A-49-31448. Additionally, U.S. Patent No.
Colored magenta couplers of the type described in US Pat. No. 3,419,391, in which the dye flows out into the processing solution upon reaction with an oxidized form of a developing agent, can also be used. In the present invention, the amount of the photographic diffusion-resistant coupler used is generally 2 x 10 ^-3 mol to 5 x 10 -1 mol per mol of silver in the light-sensitive silver halide emulsion layer, preferably 5 x 10 ^-3 mol per mol of silver in the light-sensitive silver halide emulsion layer. ×10 ^-3 mol to 5
x10 ^-2 mol, and 2 x 10 ^-2 mol to 3 x 10 ^-1 mol in the low-sensitivity emulsion layer. In the intermediate layer according to the present invention, an amount of 1×10 ⁻³ mol/dm ² to 8×
10 ^-3 mol/dm ² , preferably 4×10 ^-6 mol/dm ²
or 3×10 ⁻⁵ mol/dm ² may be added. Dispersion methods for the compound of the present invention and other types of photographic diffusion-resistant couplers used in the present invention include so-called alkaline aqueous dispersion, solid dispersion, latex dispersion, oil-in-water emulsion dispersion, and the like. Various methods can be used and can be appropriately selected depending on the chemical structure of the photographic diffusion-resistant coupler. In the present invention, a latex dispersion method and an oil-in-water emulsion dispersion method are particularly effective. These dispersion methods have long been well known, and the latex dispersion method and its effects have been described in Japanese Patent Application Laid-open No. 74538/1983.
No. 51-59943, No. 54-32552 and research
Research Disclosure,
August 1976, No. 14850, pages 77-79. Suitable latexes include, for example, styrene, ethyl acrylate, n-butyl acrylate, n-butyl methacrylate, 2-acetoacetoxyethyl methacrylate, 2-(methacryloyloxy)
Ethyltrimethylammonium methosulfate, 3-(methacryloyloxy)propane-1
- homopolymers, copolymers and copolymers of monomers such as sulfonic acid sodium salt, N-isopropylacrylamide, N-[2-(2-methyl-4-oxopentyl)]acrylamide, 2-acrylamido-2-methylpropanesulfonic acid, etc. It is a terpolymer. As the oil-in-water emulsion dispersion method, conventionally known methods for dispersing hydrophobic additives such as couplers can be applied. That is, the surfactant is dissolved in a single or mixed solvent of a high boiling point organic solvent with a boiling point of 175°C or higher such as tricresyl phosphate and dibutyl phthalate and/or a low boiling point organic solvent such as ethyl acetate and butyl propionate. is mixed with an aqueous gelatin solution containing gelatin, and then emulsified and dispersed in a high-speed rotary mixer or colloid mill, and then added directly into the silver halide emulsion layer or intermediate layer, or the emulsified dispersion is mixed with a low boiling point solvent by a known method. is added to the silver halide emulsion or to the intermediate layer according to the invention. Furthermore, as colorless couplers that can be used in combination with the present invention, British Patent No. 861138, British Patent No. 914145, British Patent No.
No. 1109963, Special Publication No. 14033, U.S. Patent No.
No. 3580722 and Mitsutteilungen Ausden Forestryen.
Der Agfa Rebelkyusen Volume 4, 352~
You can choose from those listed on page 367 (1964), etc. In addition, in order to enhance the effects of the present invention, the high-speed emulsion layer, the low-speed emulsion layer, and/or the intermediate layer according to the present invention sandwiched between these emulsion layers, which are the above-mentioned embodiments, are made to react with the oxide of the developing agent. It is preferable to contain a compound that releases a development inhibitor (hereinafter referred to as a DIR compound). Regarding DIR compounds, for example, U.S. Pat.
It is described in detail in No. 145135. The DIR compounds are used in amounts of up to 2 mg/dm ² , particularly preferably from 0.1 to 0.9 mg/dm ² , based on the constituent layers mentioned above. In addition to the above-described embodiments of the present invention, the present invention can also be preferably applied to photosensitive materials having at least one photosensitive layer having three or more silver halide emulsion layers with different photosensitivity. can.
For example, the photosensitive layer may include a silver halide emulsion layer with the highest photosensitivity on the side farthest from the support, an intermediate layer according to the present invention, and two or more halogenated layers with sequentially decreasing photosensitivity. Those having a structure in which a silver emulsion layer is provided also exhibit the preferable effects of the present invention. Silver halides used in the silver halide emulsion layer of the light-sensitive material of the present invention include silver chloride, silver bromide, silver iodide, silver chlorobromide, silver iodobromide, silver chloroiodobromide, and mixtures thereof. Any of those used in conventional silver halide photographic emulsions, such as, are included. These silver halide grains may be coarse or fine, and the grain size distribution may be narrow or wide. In addition, the crystals of these silver halide grains may be normal crystals or twin crystals, and have [100] planes and [111] planes.
Any surface ratio can be used. Further, the crystal structure of these silver halide grains may be uniform from the inside to the outside, or may have a layered structure with different inside and outside. Further, these silver halides may be of a type that forms a latent image mainly on the surface or of a type that forms a latent image inside the grain. These silver halide grains can be prepared by methods known in the art. It is preferable to remove soluble salts from the silver halide emulsion used in the present invention, but those without removal can also be used. It is also possible to use a mixture of two or more silver halide emulsions prepared separately. As the binder for the silver halide emulsion layer in the light-sensitive material of the present invention, conventionally known binders can be used. For example, gelatin is most preferred, and other binders include phenylcarbamylated gelatin, acylated gelatin, phthalated gelatin, etc. Gelatin derivatives and the like may also be used together. A silver halide photographic emulsion in which the above-mentioned silver halide grains are dispersed in a binder liquid can be sensitized with a chemical sensitizer. Chemical sensitizers that can be advantageously used in the present invention are roughly classified into four types: noble metal sensitizers, sulfur sensitizers, selenium sensitizers, and reduction sensitizers, and these can also be used in combination. As the noble metal sensitizer, gold compounds and compounds such as ruthenium, rhodium, palladium, iridium, and platinum can be used. In addition, when using a gold compound, ammonium thiocyanate and sodium thiocyanate can be used in combination. As the sulfur sensitizer, in addition to activated gelatin, sulfur compounds can be used. As selenium sensitizers, active and inactive selenium compounds can be used. Reducing tube expanders include monovalent tin salts, polyamines, bisalkylaminosulfides, silane compounds,
These include isinoaminomethane sulfinic acid, hydrazinium salts, and hydrazine derivatives. In addition to the above-mentioned additives, the photosensitive material of the present invention contains stabilizers, development accelerators, hardeners, surfactants, anti-staining agents, lubricants, ultraviolet absorbers, and various other additives useful for photosensitive materials. used. In addition to the silver halide emulsion layer and the intermediate layer according to the present invention, the light-sensitive material of the present invention may optionally be provided with auxiliary layers such as a protective layer, other intermediate layers, a filter layer, an antihalation layer, and a back layer. Examples of the support in the photosensitive material of the present invention include plastic film, plastic laminate paper,
Conventionally known materials such as baryta paper and synthetic paper may be appropriately selected depending on the intended use of the photosensitive material. These supports are generally subjected to a subbing process to enhance adhesion with the photographic emulsion layer. Next, preferred embodiments of the main constituent layers in the color photosensitive material according to the present invention are illustrated below.
The order of layer arrangement is written from the surface layer side to the support side. Example 1 1 A blue-sensitive silver halide emulsion layer containing one or more diffusion-resistant yellow couplers for photography 2 A yellow filter layer that absorbs blue light 3 A green-sensitive layer containing a diffusion-resistant magenta coupler for photography 4. Intermediate layer 5 containing the compound according to the present invention. Green-sensitive low-sensitivity emulsion layer 6 containing a photographic diffusion-resistant magenta coupler. One or more layers containing a photographic diffusion-resistant cyan coupler. Red-sensitive silver halide emulsion layer containing 7 Support example 2 1 Blue-sensitive silver halide emulsion layer 2 containing one or more layers of a photographic diffusion-resistant yellow coupler Yellow filter layer that absorbs blue light 3 Green-sensitive high-sensitivity emulsion layer containing a photographic diffusion-resistant magenta coupler 4 Intermediate layer containing a compound according to the present invention 5 Layer 6 containing a photographic diffusion-resistant magenta coupler
The green-sensitive low-sensitivity emulsion layer 6 contains a photographic diffusion-resistant magenta coupler at a low density.
Green-sensitive low-sensitivity emulsion layer 7 containing a high density of red-sensitive silver halide emulsion layer 8 containing one or more diffusion-resistant cyan couplers for photography Support example 3 1 1 layer or 2 A blue-sensitive silver halide emulsion layer 2 containing at least one layer of a photographic diffusion-resistant yellow coupler 2 A yellow filter layer 3 that absorbs blue light A green-sensitive silver halide emulsion layer containing one or more layers of a photographic diffusion-resistant magenta coupler Silver halide emulsion layer 4 Red-sensitive high-sensitivity emulsion layer containing a photographic diffusion-resistant cyan coupler 5 Intermediate layer containing a compound according to the invention 6 Red-sensitive low-sensitivity emulsion layer containing a photographic diffusion-resistant cyan coupler Sensitive Emulsion Layer 7 Support After exposure of the color light-sensitive material of the present invention, an image can be obtained by a commonly used color development method.
The basic processing steps include color development, bleaching, and fixing steps. Each of these basic processing steps may be performed independently, but instead of performing two or more processing steps, a processing solution with each of these functions is used in one process.
Sometimes this is done in one process. For example, a one-bath color processing method containing a color developing agent, a ferric salt bleaching component, and a thiosulfate fixing component, or a one-bath bleach-fixing method containing an ethylenediaminetetraacetate iron() complex salt bleaching component and a thiosulfate fixing component. etc. Any processing method can be applied to the photosensitive material of the present invention. For example, typical methods include a method in which bleach-fixing is performed after color development, followed by washing with water and stabilization treatment if necessary;
A method in which bleaching and fixing are carried out separately, and if necessary, further water washing and stabilization treatment are carried out; Method to perform in order, color development, washing with water, supplementary color development, stopping, bleaching, fixing,
A method in which the developed silver produced by color development is bleached with halogenation, and then color development is performed again to increase the amount of dye produced. Any method may be used for processing, such as a method for processing a low silver content light-sensitive material using a refire agent. The present invention will be illustrated by the following examples. Example 1 Samples 1, 2, 3, 4, 5 and 6 were prepared by sequentially coating the following layers on a support made of subbed cellulose triacetate film from the support side. Sample-1 Layer-1...Green-sensitive low-sensitivity emulsion layer Silver iodobromide emulsion containing 6 mol% silver iodide (average grain size 0.5μ, silver halide per 1 kg of emulsion)
1 kg of this emulsion was chemically sensitized with gold and sulfur sensitizers, and anhydrous 5,5'-dichloro-9 was added as a green-sensitive sensitizing dye. -ethyl-3,
3'-di-(3-sulfopropyl)oxacarbocyanine hydroxide; anhydrous 5,5'-diphenyl-9-ethyl-3,3'-di-(3-sulfopropyl)oxacarbocyanine; anhydrous 9-ethyl -3,3'-di-(3-sulfopropyl)-5,
6,5',6'-dibenzoxacarbocyanine hydroxide; then 4-hydroxy-
Add 0.25 g of 6-methyl-1,3,3a,7-tetrazaindene, 20 mg of 1-phenyl-5-mercaptotetrazole, polyvinylpyrrolidone and 500 ml of the following dispersion (X-1) to make a green-sensitive low-sensitivity emulsion. It was adjusted and applied to a dry film thickness of 3.0 μm. Layer-2: Intermediate layer An aqueous gelatin solution was applied to a dry film thickness of 1.0 μm. Layer-3...Green-sensitive high-sensitivity emulsion layer Silver iodobromide emulsion containing 7 mol% silver iodide (average grain size 0.9μ, silver halide per 1 kg of emulsion)
0.25 mol, containing 30 g of gelatin) was prepared in a conventional manner. 1 kg of this emulsion was chemically sensitized with gold and sulfur sensitizers, and anhydrous 5,5'-dichloro-9-ethyl-3,
3'-di-(3-sulfopropyl)oxacarbocyanine hydroxide; anhydrous 5,5'-diphenyl-9-ethyl-3,3'-di-(3-sulfopropyl)oxacarbocyanine; anhydrous 9-ethyl -3,3'-di-(3-sulfopropyl)-5,
6,5',6'-dibenzoxacarbocyanine hydroxide; then 4-hydroxy-
6-methyl-1,3,3a,7-tetrazaindene 0.25g, 1-phenyl-5-mercaptotetrazole 5mg, polyvinylpyrrolidone 0.2g
added. Next, add the following dispersion (X-2)
200 ml was added to prepare a green-sensitive, high-sensitivity silver halide emulsion, which was coated to a dry film thickness of 2.0 μm. Layer-4...Yellow filter layer An aqueous gelatin solution in which yellow colloidal silver was dispersed was applied at a ratio of 0.9 g/m ² of gelatin and 0.12 g/m ² of silver to a dry film thickness of 1.2 μm. Sample-2 The gelatin aqueous solution used for the layer-2 of sample-1 was used as the intermediate layer of layer-2 of sample-1 and the following dispersion (AS)
2,5-di-t-octylhydroquinone (0.07 g/m ² ) was prepared and applied in the same manner as Sample-1, except that the dry film thickness was 1.0 μm.
2 was created. Sample-3 Dispersion (AS) used for layer-2 of sample-2 above
Sample-3 was prepared in the same manner as Sample-2 except that the following dispersion (X-3) was added instead. Sample-4 Dispersion (AS) used for layer-2 of sample-2 above
Sample-4 was prepared by the same preparation and coating as Sample-2 except that the following dispersion (C-1) was added instead. Sample-5 Dispersion (AS) used for layer-2 of sample-2 above
Sample-5 was prepared in the same manner as Sample-2 except that the following dispersion (Y-1) was added instead of Sample-2. Sample-6 Sample-6 was prepared by sequentially coating the following layers on a support made of a subbed triacetate film from the support side. Layer-1: green-sensitive low-sensitivity emulsion layer Same as layer-1 of sample-1 in Example 1. Layer-2...Intermediate layer Layer-2 of sample-1 in Example 1 was coated to a dry film thickness of 0.5 μm. Layer-3: Intermediate layer Same as layer-2 of sample-5 in Example 1. Layer-4: Intermediate layer Same as layer-2 of sample-6 in Example 1. Layer-5...Green-sensitive high-sensitivity emulsion layer Same as layer-3 of sample-1 in Example 1. Layer-6...Yellow filter layer Same as layer-4 of sample-1 in Example 1. The dispersions used in each of the above emulsion layers or intermediate layers were prepared as follows. Dispersion (X-1): 54 g of magenta coupler (M-1) below, 14 g of colored magenta coupler (CM-1) and the following
DIR compound (D-3) 0.5g, DIR compound (D-
1) 0.5g tricresyl phosphate (TCP)
500 ml of 7.5% gelatin containing 68 g, 8 g of sodium tri-isopropylnaphthalene sulfonate dissolved in a mixture of 280 ml of ethyl alcohol (EA)
Add to the liquid and emulsify and disperse in a colloid mill to 1000ml.
Adjusted to. Dispersion (X-2); 30 g of the following magenta coupler (M-1) and (M
-2) 30g, colored magenta coupler (CM-
1) 12g and 0.3 of the following DIR compound (D-3)
g was dissolved in a mixture of 70 g of TCP and 280 ml of EA, added to 500 ml of 7.5% gelatin containing 8 g of sodium triisopropylnaphthalene sulfonate, and emulsified and dispersed in a colloid mill to adjust the volume to 1000 ml. Dispersion (AS); 2,5-di-tert-octylhydroquinone 50
g was dissolved in a mixed solution of 50 g of TCP and 100 ml of EA, added to 500 ml of a 7.5% aqueous gelatin solution containing 6 g of triisopropylnaphthalene-sodium sulfonate, and emulsified and dispersed in a colloid mill to adjust the volume to 800 ml. Dispersion (X-3); 60g of the exemplified compound (9) of the present invention was mixed with 60g of TCP and 180g of EA.
ml of the mixture, added to 500 ml of 7.5% gelatin containing 8 g of sodium triisopropylnaphthalene sulfonate, and emulsified and dispersed in a colloid mill to adjust the volume to 1000 ml. Dispersion (C-1): Dispersion and preparation were carried out in the same manner as in the above dispersion (X-3) except that the exemplified compound of the present invention (22) was used instead of the exemplified compound of the present invention (9). Dispersion (Y-1); Exemplified compound of the present invention instead of Compound (9) of the present invention
Dispersion and adjustment were carried out in the same manner as the above dispersion (X-3) except that (2) was used. Magenta coupler (M-1); 1-(2,4,6-trichlorophenyl)-3-
[3-(2,4-di-t-amylphenoxyacetamide)benzamide]-5-pyrazolone magenta coupler (M-2); 4,4'-methylenebis(1-(2,4,6-trichloro phenyl)-3-[3-(2,4-di-t
-amylphenoxyacetamido)benzamide]-5-pyrazolone colored magenta coupler (CM-1); 1-(2,4,6-trichlorophenyl)-4-
(1-Naphthylazo)-3-(2-chloro-5-octadecenylsuccinimidoanilino)-5-pyrazolone DIR compound (D-1); 2-(1-phenyl-3-tetrazolylthio)-
4-octadecylsuccinimide-1-indanone DIR compound (D-2); 1-hydroxy-N-(2-m-tetradecyloxyphenyl)-4-[1-phenyl-3-methyl-4-(1- phenyl-5-tetrazolylthio)
Methyl]-5-pyrazolyloxy-2-naphthamide DIR compound (D-3); 2-(2-amino-1,3,4-thiazoazolyl-5-thio)-4-octadecylsuccinimide-1-indanone These samples After a white exposure was applied to each through a light wedge, processing was performed according to the processing steps described below. Processing process (38℃) Processing time Color development 2 minutes 10 seconds Bleach 6 minutes 30 seconds Washing 3 minutes 15 seconds Fixing 6 minutes 30 seconds Washing 3 minutes 15 seconds Stabilization 1 minute 30 seconds The processing liquid composition used in each processing step was It is as follows. Color developer composition; 4-amino-3-methyl-N-ethyl-N (β
-hydroxyethyl)-aniline sulfate 4.8g Anhydrous sodium sulfite 0.14g Hydroxyamine 1/2 sulfate 1.98g Sulfuric acid 0.74g Anhydrous potassium carbonate 28.85g Anhydrous potassium bicarbonate 3.46g Anhydrous potassium sulfite 5.10g Potassium bromide 1.16g Chloride Sodium 0.14g Nitrilotriacetic acid trisodium salt (monohydrate)
1.20g Potassium hydroxide 1.48g Add water to make 1. Bleach solution composition; ethylenediaminetetraacetate iron ammonium salt
100.0g Ethylenediaminetetraacetic acid diammonium salt
10.0g Ammonium bromide 150.0g Glacial acetic acid 10.0ml Add water to adjust to 1 and use ammonia water to pH
Adjust to 6.0. Fixer composition: Ammonium thiosulfate 175.0g Anhydrous sodium sulfite 8.6g Sodium metasulfite 2.3g Add water to 1 and adjust the pH to 6.0 using acetic acid. Stabilizing liquid composition: Formalin (37%) aqueous solution 1.5ml Konidax (manufactured by Konishiroku Photo Industry Co., Ltd.)
Add 7.5ml water to make 1. Next, the coupler images formed on each sample were measured for fog, sensitivity, and gamma on the same day, after being stored for 3 days at 55° C. and 10% relative humidity, and for graininess and sharpness. The results are shown in Table 1. The gamma and graininess of the color image forming unit layer in the table are measured values when exposed to white light, and the graininess (RMS) occurs when scanning with a microdensitometer with a circular scanning aperture of 2.5μ. It is expressed as 1000 times the standard deviation of the variation in concentration value. In addition, the detection of the improvement effect of image sharpness is performed using MTF.
(Modulation Transfer Function) and compared the magnitude of MTF at spatial frequencies of 10 lines/mm and 30 lines/mm.

[Table] As is clear from the results in Table 1 above, Samples 3, 4, 5, and 6 according to the present invention have better storage stability, graininess, and sharpness than Comparative Samples 1 and 2 outside the present invention. It showed excellent characteristics in all respects. In particular, the improvement in graininess is remarkable, and is a surprising effect that far exceeds the results expected from a system using a dispersion (AS). Example 2 Samples 7, 8 and 9 were prepared by sequentially coating the following layers on a support made of subbed cellulose triacetate film from the support side. Sample-7 Layer-1...Green-sensitive low-sensitivity emulsion layer Silver iodobromide emulsion containing 6 mol% silver iodide (average grain size 0.35μ, silver halide per 1 kg of emulsion)
1 kg of this emulsion was chemically sensitized with gold and sulfur sensitizers, and anhydrous 5,5'-dichloro-9 was added as a green-sensitive sensitizing dye. -ethyl-3,
3'-di-(3-sulfopropyl)oxacarbocyanine hydroxide; anhydrous 5,5'-diphenyl-9-ethyl-3,3'-di-(3-sulfopropyl)oxacarbocyanine; anhydrous 9-ethyl -3,3'-di-(3-sulfopropyl)-5,
6,5',6'-dibenzoxacarbocyanine hydroxide; then 4-hydroxy-
6-methyl-1,3,3a,7-tetrazaindene 0.25g, 1-phenyl-5-mercaptotetrazole 20mg, polyvinylpyrrolidone 0.2g
Sensitized emulsion A sensitized with the addition of silver iodobromide emulsion containing 6 mol% silver iodide (average grain size
0.6 µm, containing 0.25 mol of silver halide and 40 g of gelatin per 1 kg of emulsion) was prepared in the usual manner, and separately from emulsion A using the same method as for the above sensitized emulsion A and using half the amount of sensitizer and stabilizer. The sensitized emulsion B was mixed in a 1:1 ratio. Next, 500 ml of the above dispersion (X-1) was added to 1 kg of this mixed emulsion to prepare a green-sensitive low-sensitivity emulsion (1), and the dry film thickness was
It was applied to a thickness of 3.0μ. Layer-2...Green-sensitive medium-sensitivity emulsion layer The above dispersion (X-3) was added to 1 kg of the emulsion obtained by mixing Emulsion A and Emulsion B shown in Layer-1 in a 1:1 ratio.
Add 200ml to adjust the green-sensitive medium-sensitivity emulsion (2).
It was applied to a dry film thickness of 1.5μ. Layer-3: Intermediate layer An aqueous gelatin solution was applied to a dry film thickness of 1.0 μm. Layer-4...Green-sensitive high-sensitivity emulsion layer Silver iodobromide emulsion containing 7 mol% silver iodide (average grain size 0.9μ, silver halide per 1 kg of emulsion)
0.25 mol, containing 30 g of gelatin) was prepared in a conventional manner. 1 kg of this emulsion was chemically sensitized with gold and sulfur sensitizers, and anhydrous 5,5'-dichloro-9-ethyl-3,
3-di-(3-sulfopropyl)oxacarbocyanine hydroxide; anhydrous 5,5-diphenyl-9-ethyl-3,3-di-(3-sulfopropyl)oxacarbocyanine; anhydrous 9-ethyl-3, 3-di-(3-sulfopropyl)-5,
6,5',6'-dibenzoxacarbocyanine hydroxide; then 4-hydroxy-
6-methyl-1,3,3a,7-tetrazaindene 0.25g, 1-phenyl-5-mercaptotetrazole 5mg, polyvinylpyrrolidone 0.2g
added. Next, add the following dispersion (X-2)
200ml was added to prepare a green-sensitive high-sensitivity emulsion, which was coated to a dry film thickness of 2.0μ. Layer-5...Yellow filter layer Same as layer-4 of sample-1 in Example 1. Sample-8 Layer-1...Green-sensitive low-sensitivity emulsion layer Same as Layer-1 of Sample-7 in Example 2. Layer-2...Green-sensitive medium-sensitivity emulsion layer Same as layer-2 of sample-7 in Example 2. Layer-3: Intermediate layer Same as layer-2 of sample-5 in Example 1. Layer-4...Green-sensitive high-sensitivity emulsion layer Same as layer-4 of sample-7 in Example 2. Layer-5...Yellow filter layer Same as layer-4 of sample-1 in Example 1. Sample-9 Layer-1... Green-sensitive low-sensitivity emulsion layer Same as layer-1 of sample-7 in Example 2. Layer-2...Intermediate layer Same as layer-2 of sample-5 in Example 1. Layer-3...Green-sensitive medium-sensitivity emulsion layer Same as layer-2 of sample-7 in Example 2. Layer-4...Green-sensitive high-sensitivity emulsion layer Same as layer-4 of sample-7 in Example 2. Layer-5...Yellow filter layer Same as layer-4 of sample-1 in Example 1. Each of the samples thus obtained was treated in the same manner as in Example 1, and the graininess and sharpness of the green sensitivity were evaluated. Similar to No. 1, the effects of the present invention were exhibited, and the improvement in leg graininess was particularly remarkable.

Claims (1)

[Claims] 1 At least one photosensitive layer on a support, which has a plurality of silver halide emulsion layers having substantially the same color sensitivity but different photosensitivity, and containing a photographic diffusion-resistant coupler. In the silver halide photographic light-sensitive material, a non-photosensitive intermediate layer is provided adjacent to the support side of at least the most sensitive silver halide emulsion layer among the plurality of silver halide emulsion layers, and a non-photosensitive intermediate layer is further provided. The photosensitive intermediate layer includes
1. A silver halide photographic material comprising a compound capable of causing a coupling reaction with an oxidized color developing agent to form a run-off coupling product.