JPS61110136A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To improve dispersibility and colorability by providing a silver halide emulsion layer contg. the coupler dispersed by the high boiling org. solvent expressed by the specific chemical formula and the compd. expressed by the specific chemical formula on a base. CONSTITUTION:The silver halide emulsion layer contg. the coupler dispersed by using the high boiling org. solvent contg. the compd. expressed by the formu la II is provided on the base to form the silver halide photographic sensitive material. The compd. expressed by the formula I is requird to be incorporated into at least one layer of the above-mentioned silver halide emulsion layer. In the formula I and the formula II, R<1> denotes an alkyl group, aryl group, etc., R<2> denotes a univalent group, S denotes 0-3 integer, R<4> denotes an alkyl group of 1-20C, R<2> denotes an alkyl group and cycloalkyl group of 1-20C. The total sum of members of carbon atoms of the groups R<3> and R<4> is 4-24 and n is 0-3 integer.

Description

[Detailed description of the invention] [Industrial application field] The present invention relates to a silver halide photographic material.

This type of material is used as a light-sensitive material for color photographic film.

[Conventional technology]

As is well known in silver halide color photographic light-sensitive materials, when the silver halide in the emulsion layer is exposed to light, silver is partially precipitated there to form a latent image, and when this is developed, the color developer in the developer solution is released. It is oxidized to silver to become an oxidant, and the oxide of the color developing agent reacts with the coupler previously contained in the emulsion to form a dye, thereby producing color. By the way, in color photography technology in recent years,
As a result of careful technology accumulation, the ISO sensitivity is 1000 or 1.
600 is being developed. Attempts have been made to develop color negative films having sensitivities higher than these, but in this case, means such as chemical sensitization and spectral sensitization are used. However, in addition to such chemical enhancement and spectral sensitization, approaches from coupler dispersions are also very effective.

That is, when preparing an emulsion for forming an emulsion layer, a coupler is dissolved in a high boiling point solvent and then dispersed to form an emulsion.

This is because it is advantageous to dissolve in a high boiling point solvent in terms of color development. (However, due to the solubility of the coupler, there are cases where it is first dissolved in a low boiling point solvent and then dissolved in a high boiling point solvent.) Phenol-based solvents are known as high boiling point solvents.
This is known to have excellent dispersion stability and to be a highly color-forming solvent. However, phenolic high boiling point solvents may result in insufficient density of images formed in low exposure ranges.

That is, when a phenolic high-boiling point solvent is used, the curve is shifted to the left side of the figure, and the sensitivity is faster, as shown by the solid line, than the characteristic curve for using a conventional high-boiling point solvent, which is shown by the single-dot chain point in Fig. 1. be able to. In other words, a lower exposure amount is required to reach the same density value. However, as shown by the broken line in the same figure, the sensitivity at the lower end of the characteristic curve decreases, and when a so-called "low-out" phenomenon occurs, the density in the low-exposure region ends up decreasing. Even if the ratio of high boiling point solvent/coupler is increased, the value of the maximum concentration O1 can be increased, but a decrease in concentration in this low exposure region is unavoidable.For this reason, when a phenolic high boiling point solvent is used, This had the problem of decreased sensitivity in the low exposure range.

[Purpose of the invention]

The present invention has been made in view of the above circumstances, and its purpose is to obtain stable dispersibility and high color development by using a phenolic high-boiling point solvent as a coupler solvent, and to obtain stable dispersibility and high color development. The object of the present invention is to provide a silver halogenide photographic light-sensitive material that can avoid a decrease in density in a low exposure region, has good color development, and has high sensitivity.

[Structure and operation of the invention]

In order to achieve the above object, the present invention provides a silver halide photographic light-sensitive material having a silver halide emulsion layer containing a coupler dispersed using a high boiling point organic solvent on a support. At least one of the silver emulsion layers contains a compound represented by the following general formula (1), and the high boiling point organic solvent is configured to contain at least a compound represented by the following general formula [II]. .

(1) (II) However, in the above formula, R1 represents an alkyl group, an alkyl group, an alkoxy group, or an amino group, Rz represents a monovalent group, S represents an integer from 0 to 3, and S represents an integer from 0 to 3. When 2 or more, R1 may be the same or different R4 has 1 to 2 carbon atoms
0 straight-chain or branched alkyl group, R3 represents a straight-chain or branched alkyl group or cycloalkyl group having 1 to 20 carbon atoms, and the total number of carbon atoms of the groups represented by R3 and R4 is 4 to 20. 24, and n represents an integer from 0 to 3.

In the [I] formula, each group represented by R1 preferably has a total number of carbon atoms of 40 or less, and S is preferably O, and when S is 1 or more, R2 is a hydrogen atom,
halogen atom, alkyl group, alkoxy group, amino group,
or an aryl group. Among the groups represented by R', each carbon-containing group preferably has a total number of carbon atoms of 40 or less. -5ozR' is -OH
It is preferable to be at the p-position.

By adding the compound represented by the general formula CI), the decrease in sensitivity of the foot can be suppressed. Further, the compound represented by the general formula CI) also has a function as a contrast enhancer. The compound represented by the general formula (II) is a type of phenolic high-boiling point solvent, and provides high color development. In this way, compound (1) (I
As a result of using f) in combination, stable dispersion and high color development can be obtained with compound (II), and the decrease in sensitivity of the foot, which was a conventional drawback in that case, can be suppressed by compound CI). Good sensitivity can also be obtained.

Moreover, since the sensitivity is improved by the compound CI), it is expected that sufficient concentration and sensitivity can be obtained without necessarily increasing the relative amount of the high boiling point solvent (compound [■]).

That is, by using the above compound CI)(n), it becomes possible to increase the sensitivity and solve the conventional difficulties when using a high boiling point solvent. It is possible to fully demonstrate the effect. Compound CI) also has a sharpening effect.

When a phenolic high-boiling point solvent is used for monodispersed particles, the concentration decreases greatly in the low exposure range mentioned above. Therefore, in such cases, when compound [I] that exhibits a high contrast effect is used, the effect is particularly remarkable. This is particularly advantageous for monodisperse particles.

The compound represented by the above general formula [I] is preferably 0.2 to 40 g per mole of silver, and more preferably 0.5 to 40 g per mole of silver.
It can be used in an amount of 10g. Similarly, the compound represented by the general formula (II) is preferably 0.1 to 1 mole of silver.
It can be used in an amount of 100g, more preferably 0.3-40g.

Next, specific examples of the compound of the above general formula [I](n) that can be used in the present invention will be shown, but it goes without saying that the present invention is not limited thereto.

Examples of compounds of general formula CI) ([-1+ (I-2) (1-4+ ([-5) (I-81 ([-91 ([-10) ([-11) <1-121 ([ -14) (I-16) (I-17) (I-191 (I-20) (I-22) ([-24) ([-251 (I-271 (1-28> ([-291 0C14H2O I-321 (I-331 (I-34) Examples of compounds of general formula (III) (II-11 (II-2) (I-5) (II-7) fn-8) (II-9) (n -101 (n-12) (II-131 (II-141 (l[-161 (If-171 1) The phenolic high-boiling point solvent of the present invention represented by general formula (II) has a can also be used in combination with other high boiling point organic compounds above 1501.

Such high boiling point organic compounds that can be used in combination are
Preferably, it is a J-acid ester compound represented by the following general formula (I[), or a phthalate ester compound represented by (rV).

General formula (I[[)% formula% In the formula, R2°, R□, and R12 each represent an alkyl' or an aryl group.

In the phosphoric acid ester metal product represented by the general formula (I[I), Rzl and R1 each represent a linear or branched alkyl group or an ary group, but especially R2゜, R8 The total number of carbon atoms in the groups represented by and Rtt is preferably 6 to 50, and R2°, R11 and Rat may be the same or different.

The alkyl group represented by R2 or Ro is, for example, ethyl group, propyl group, t-butyl group, hexyl group, heptyl group, 1so-octyl group, 5eC-nonyl group, dodecyl group, 1so-pentadecyl group, hexadecyl group. Examples of the aryl group include a phenyl group, a naphthyl group, and the like. These alkyl groups and aryl groups may have a substituent, and examples of the substituent for the alkyl group include a halogen atom, an alkoxy group, an aryl group, an aryloxy group, an alkenyl group, an alkoxycarbonyl group, etc. Examples of substituents on the aryl group include a halogen atom, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an alkenyl group, and an alkoxycarbonyl group. Two or more of these substituents may be introduced into the alkyl group or aryl group.

Typical specific examples of the phosphoric acid ester compound represented by the general formula CDI are shown below, but the invention is not limited thereto.

([-6) [Dan-8] General formula CIY) In the formula, Ro and R24 each represent an alkyl group, an alkenyl group, an aryol group, or a cycloalkyl group,
R23 and R□4 may be the same or different, and each has 3 to 20 carbon atoms.

The alkyl group represented by R8 and R14 is, for example, a methyl group, a propyl group, a t-butyl group, a methyl group,
Heptyl group, 1so-octyl group, nonyl group, decyl group, dodecyl group, pentadecyl group, heptadecyl group, octadecyl group, etc., aryl group is phenyl group, naphthyl group, etc., and alkenyl group is butenyl group, pentenyl group. group, heptenyl group, octadecenyl group, etc., and the cycloalkyl group is cyclohexyl group, etc. These alkyl groups, alkenyl groups, aryl groups and cycloalkyl groups may have substituents, and alkyl groups,
Examples of substituents for alkenyl groups and cycloalkyl groups include halogen atoms, alkoxy groups, aryl groups, aryloxy groups, alkenyl groups, and alkoxycarbonyl groups. Examples of substituents for aryl groups include:
Examples include a halogen atom, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an alkenyl group, and an alkoxycarbonyl group. These substituents are part 2
One or more may be introduced into an alkyl group, alkenyl group, aryl group or cycloalkyl group.

Typical specific examples of the phthalate ester compound represented by the general formula (rV) are shown below, but of course the present invention is not limited thereto.

CIV-1) (■-2) (IV-3) CIV-43 C2H4 C,ru(IV-5] ([V-6) CIY-7] (ff -8) The solvent used in combination depends on the type It can be used within a range that does not impair the effect of the high boiling point solvent of general formula (n).

The high boiling point solvent of general formula (1) of the present invention can be applied, for example, to a coupler-containing coloring emulsion layer. When the layer 211 has a high-speed layer and a low-speed layer, it is preferably applied to the high-speed layer, but is not limited thereto. Of course, it can be applied to other emulsion layers, such as a layer adjacent to a coloring layer, alone or It can also be used in combination with a coloring layer. The same holds true when other solvents are used in combination with the solvent [■]. General formula (If
) can also be used in the same way.

The dispersion state may be polydisperse or substantially monodisperse; preferred states of these are discussed below.

When dissolving the coupler using the high boiling point solvent of general formula [I], various techniques regarding high boiling point solvents can be applied and used.

For example, as described in U.S. Pat. No. 2,322,027, a coupler can be dissolved and used in such a high boiling point solvent.
As described in No. 01170, the coupler and the high boiling point solvent may be separately dispersed into fine particles and then mixed for use. Further, in these dispersion methods, it is also preferable to use a low boiling point solvent.

In this case, the compound that can be used in combination can be mixed with the coupler and dispersed, or it can be used separately from the coupler, and when a low boiling point solvent is used, the compounds described in U.S. Pat. No. 2,801,171 or Special Public Service 1978-8
It is also possible to remove the low boiling point solvent from the dispersion by the method described in Japanese Patent No. 099.

In addition to the above-mentioned solvents, preferred among the solvents that can be used in combination are diethyl laurylamide as a high boiling point solvent;
Dibutyl laurylamide, phenoxyethanol, diethylene glycol monophenyl ether, hexamethylphosphoramide, and furthermore, U.S. Pat.
Examples include high-boiling organic solvents that are immiscible with water and are described in Japanese Patent No. 29060. In addition, as a low boiling point solvent,
For example, methyl isobutyl ketone, β-ethoxyethyl acetate, methoxy triglycol acetate, acetone, methyl acetone, methanol, ethanol, acetonitrile, dioxane, dimethyl formamide, dimethyl sulfoxide, ethyl acetate, butyl acetate, isopropyl acetate, butanol, chloroform, cyclohexane, Examples include cyclohexanol and fluorinated alcohol. The low boiling point solvent can be used in place of the high boiling point solvent used in combination with the compound of formula (n) of the present invention, and can also be used in combination with the high boiling point solvent. Furthermore, each of these solvents can be used alone or in combination with the compound of formula [■] by using two or more of them.

Alternatively, in the case of a coupler having a water-soluble group, it is also possible to use the Fischer type, ie, by dissolving it in an alkaline solution. It is also possible to add one of the coupler and the compound that can be used in combination in the same layer by a dispersion method and the other by a Fischer type method.

The silver halide photographic material according to the present invention is produced by coating a silver halide emulsion layer and other constituent layers containing various photographic additives as described above on a support. be done.

Advantageously used supports include, for example, baryta paper, polyethylene-coated paper, polypropylene synthetic paper, glass paper, cellulose acetate, cellulose nitrate,
Supports include polyvinyl acetal, polypropylene, polyester films such as polyethylene terephthalate, and polystyrene, and these supports are appropriately selected depending on the purpose of use of each silver halide photographic light-sensitive material.

These supports are subjected to undercoat processing if necessary.

Next, silver halide that can be used in the silver halide photographic material of the present invention will be described. The silver halide may be any one used in ordinary silver halide photographic emulsions, such as silver chloride, silver bromide, silver iodide, silver chlorobromide, silver iodobromide, and silver chloroiodobromide. Included.

These silver halide grains may be coarse or fine (the grain size distribution may be narrow or wide, and the crystals of these silver halide grains may be normal or twin). It may be crystalline, but if anything, it is better to have coarse particles (,
In addition, it is preferable that the grain size distribution is narrow and the crystals are normal crystals.The grain size of the silver halide used in the present invention is arbitrary, but preferably 0.6 to 2.0μ, and monodisperse. However, monodispersity is substantially more effective. Here, the monodisperse halogenation l! (Grains) means that when the standard deviation S and average grain size of the grain size distribution of silver halide grains is divided by the average grain size T, the value is 0.20 or less, which is defined by the following formula. Preferably.

□　≦0.20 〒 Furthermore, it is particularly preferable that −7≦0.15.

The average grain size r referred to here means the diameter in the case of spherical silver halide grains, or the diameter when the projected image is converted into a circular image of the same area in the case of grains with shapes other than cubic or spherical. The average value, and the individual particle size is r! , and when the number is nm, r is defined by the following 2.

The crystal structure of these silver halide grains may be uniform from the inside to the outside, or may be of a so-called core-shell type in which the inside and outside have a different layered structure.

In this case, the surface layer (double layer with two or more shells)
In the case of core-shell type, it means the outermost shell. It is preferable that each silver halide grain is structured so that the silver iodide content of the silver halide (the same applies hereinafter) does not substantially change. This means that the silver iodide content in the surface layer does not substantially change even if the diameter changes. Specifically, it means that the difference in the silver iodide content in the surface layer between grains is less than 0.5 mol%. It is preferable not to exceed it. This makes it possible to equalize the development activity and to stabilize the chemical ripening. When core-shell type silver halide grains are used in the present invention, the surface layer accounts for 50% or less of the total grain weight, especially 20% of the total grain weight. % or less. Further, the silver iodide content of the surface layer is silver iodobromide of 10 mol% or less, particularly preferably silver bromide with a silver iodide content of substantially 0, and in the core-shell type. The silver iodide content of the core (other than the surface layer, hereinafter the same) is preferably silver halide containing 0 to 15 mol% of silver iodide.

Furthermore, these silver halide grains 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. can do. This silver halide is generally dispersed in gelatin, but other than gelatin, polymers such as polyvinyl alcohol may also be used instead of gelatin or mixed with gelatin.

Photographic emulsions containing the above silver halide can be sensitized with various chemical sensitizers. As the chemical sensitizer, noble metal sensitizers, sulfur sensitizers, selenium sensitizers, and reduction sensitizers can be used alone or in combination.

Furthermore, the silver halide photographic emulsion used in the present invention can be spectrally sensitized using various sensitizing dyes, if necessary. In other words, it is possible to optically sensitize to a desired wavelength range, for example by using optical sensitizers such as cyanine dyes such as zeromethine dyes, monomethine dyes, dimethine dyes, trimethine dyes, or merocyanine dyes alone or in combination (for example, ultra Color sensitization) Can be optically sensitized.

Further, the silver halide photographic light-sensitive material according to the present invention has an emulsion layer and/or other constituent layers (
For example, the intermediate layer, subbing layer, filter layer, protective layer, image-receiving layer, etc.) may contain various photographic additives depending on the purpose.

For example, stabilizers and antifoggants such as azaindenes, triazoles, tetrazoles, imidazolium salts, tetrazolium salts, polyhydroxy compounds; aldehyde-based, aziridine-based, inoxazole-based, vinyl sulfone-based,
Hardening agents such as acryloyl, albodiimide, maleimide, methanesulfonic acid ester, and triazine;
Tone adjusters such as Group 8 metals (e.g. rhodium, ruthenium) or cadmium, thallium; development accelerators such as benzyl alcohol, polyoxyethylene compounds;
Examples include image stabilizers of chroman type, claman type, bisphenol type, and eltel phosphite type; lubricants such as waxes, glycerides of higher fatty acids, and higher alcohol esters of higher fatty acids. In addition, anionic, cationic, and nonionic surfactants are used as coating aids, emulsifiers, permeability improvers for processing solutions, antifoaming agents, and materials for controlling various physical properties of photosensitive materials. Alternatively, N-guanylhydrazone compounds, quaternary onium salt compounds, and the like are effective as the zero mordants that can be used with various amphoteric compounds.

As antistatic agents, diacetyl cellulose, styrene perfluoroalkyl rhidium maleate copolymer, alkali salts of reaction products of styrene-maleic anhydride copolymer and p-aminobunzenesulfonic acid, etc. are effective. 0 Preventing color turbidity Examples of the agent include polymers containing vinylpyrrolidone monomers and polymers containing vinylimidazole monomers. Cloaking agents include polymethyl methacrylate, polystyrene, and alkali-soluble polymers. It is also possible to use colloidal silicon oxide. Further, examples of the latex added to improve the physical properties of the film include copolymers of acrylic esters, vinyl esters, etc., and other monomers having ethylene groups. Examples of gelatin plasticizers include glycerin and glycol compounds, and examples of thickeners include styrene-sodium maleate copolymers and alkyl vinyl ether-maleic acid copolymers.

Furthermore, p-alkoxyphenols and phenolic compounds can be added to the emulsion layer or its adjacent layer in order to improve the light fastness of the color image formed from the coupler that can be used in the present invention.

In addition, the light-sensitive material of the present invention can prevent unnecessary fogging and contamination due to air oxidation of the aromatic primary amino developing agent.
In order to prevent color mixing due to diffusion of oxidized products of the developing agent into adjacent layers during development, silver halide emulsion layers or intermediate layers are coated with U.S. Pat.
No. 0, No. 3700453 and JP-A No. 1983-154
Alkyl-substituted hydroquinone compounds disclosed in Publication No. 38 and Japanese Patent Application No. 54-2551 can be used.

Various couplers can be used as the couplers of the present invention, and useful couplers include magenta couplers such as open-chain methylene yellow couplers, pyrazolone magenta couplers, bilatroriazole magenta couplers, indashilon magenta couplers, and phenol couplers. Examples include cyan couplers based on cyanide or naphthol.

For example, among pyrazolotriazole type couplers, that is, IH-pyrazolo(3,2-C)-3-triazole type couplers, preferred ones are represented by the following general formula (V).

In the formula, R13 and RI4 represent an alkyl group or an aryl group, and 2 represents a hydrogen atom or a group that can be separated by a coupling reaction with an oxidation product of a color developing agent.
The alkyl group represented by RIS and 1fl14 is a linear or branched alkyl group having 1 to 18 carbon atoms (excluding substituent carbon atoms), such as methyl group, methoxymethyl group, ethyl group, tert- These include butyl group, octyl group, etc. This alkyl group may have a substituent, and the aryl group represented by 113 and R14 in general formula (V) is preferably a phenyl group. This aryl group can have substituents. Examples of substituents for these alkyl groups and aryl groups include halogen atoms, alkoxy groups, acylamino groups, aryl groups, and alkyl groups. HI4 is preferably an alkyl group substituted with an aryl group, ie an aralkyl group, particularly preferably a ballasted aralkyl group. Further, R13 is preferably an alkyl group, particularly preferably a methyl group.

Specifically, the group that can be separated by the coupling reaction with the oxidation product of the color developing agent represented by 2 in general formula (V) includes a halogen atom (for example, a chlorine atom, a bromine atom,
iodine atom, fluorine atom), aryloxy group (e.g.
phenoxy group, P-methoxyphenoxy group, P-butanesulfonamidophenoxy group, P-tart-butylcarboamidophenoxy group, etc.), substituted aryl group (e.g., methoxyphenyl group, etc.), arylthio group (e.g.,
phenylthio group), heterocyclic thio group (e.g., 1-ethyltetrazole-5-thioyl group), etc.
Preferred is a halogen atom, particularly preferred is a chlorine atom.

The magenta coupler represented by the general formula (V) is more preferably a two-carrier magenta coupler represented by (VI), where HI3. z has the same meaning as the above definition. RIS and 1716 represent a hydrogen atom, an alkyl group, and the alkyl group is preferably a straight or branched alkyl group having 1 to 20 carbon atoms, such as a methyl group, an ethyl group,
n-propyl group, 1so-propyl group, 130-butyl group, n-butyl group, n-octyl group, n-decyl group, n
-dodecyl group, stearyl group, etc., and RIS and RIS may each be the same or different.

X is a linear or branched alkyl group having 1 to 20 carbon atoms, (
For example, it represents a methyl group, an ethyl group, a t-pentyl group, a t-butyl group, an n-pentadecyl group, etc.), a halogen atom (such as a chlorine atom, a bromine atom, a fluorine atom, etc.), and a hydroxy group.

11, p, and q each represent an integer from O to 4, preferably l represents an integer from O to 3, p represents an integer from 1 to 3, and q represents an integer from 1 to 2, respectively.

Typical specific examples of magenta couplers that can be used in the practice of the present invention will be described below by specifying R", R", and Z in general formula (V). The magenta couplers used in the following description and the examples below can be preferably used, but the present invention is not limited thereto.

In addition to the commonly used phenolic cyan couplers, examples include ureido couplers in which the 2-position is substituted with a ureido group. Examples of these ureido couplers include those represented by the following general formulas [■] and [■].

RI!
represents an alkyl group, a cycloalkyl group, a phenyl group, or a heterocyclic group, each group may or may not have a substituent, as shown in formula 1, and R' is hydrogen. Represents an atom, alkyl group, aryl group, heterocyclic group, alkoxy group, aryloxy group, carboxy group, carbonyl group, ester group, amide group, imido group, sulfonyl group, sulfamide group, cyano group, nitro group , n represents an integer of 1 to 5, and when a plurality of substituents are substituted, they may be the same or different.

A coupler in which R'' is a halogen atom, a substituted sulfonyl group, a sulfonamide group, a sulfamoyl group, a polyfluoroalkyl group, an acyl group, an alkoxycarbonyl group, or a cyano group, particularly substituted at the m or p position, and n is 1 or 2. can be used.

Typical specific examples of cyan couplers that can be used in carrying out the present invention are described below. Those used in the following examples and the examples described later can be preferably used. However, as a matter of course, the cyan coupler is not limited to this in this case as well.

Next, specific examples of yellow couplers will be illustrated.

Those described below and those used in Examples described later can be preferably used, but of course they are not limited thereto.

5OsCHS 9H, (-7) CtHu(-tl (:11H1, (-nl) Colored couplers for auto-masking in combination with these couplers (e.g. split-off group having an azo group as a bonding group at the active site of the coupler) coupled couplers), osazone-type compounds.

Development-diffusible dye-releasing couplers, development inhibitor-releasing compounds (compounds that release development-inhibiting compounds by reacting with the oxidized form of aromatic primary amine developing agents; It is also possible to use so-called DIR couplers, which react with oxidants to form colored dyes, as well as so-called DIR substances, which form colorless compounds. In order to incorporate these couplers into a silver halide color photographic light-sensitive material, various techniques used for couplers can be applied.

For example, when using a high boiling point solvent for compound (If), it can be dissolved therein and incorporated, or the coupler and the high boiling point solvent can be separately dispersed into fine particles and then mixed for use. Furthermore, in these dispersion methods, in addition to the other high-boiling point solvents mentioned above, a low-boiling point solvent can also be used in combination. Of course, each of these solvents can be used alone or in combination of two or more.

Moreover, a colored coupler can also be used as a masking coupler. As the colored magenta coupler used as this masking coupler, a compound in which an arylazo group is substituted at the active site of a colorless magenta coupler is generally used, for example, US Pat.
No. 1, No. 2983608, No. 3005712,
Compounds described in JP-A No. 3684514, British Patent No. 9321, JP-A-49-123625, and JP-A-49-131448 can be mentioned.

Additionally, colored magenta couplers of the type described in U.S. Pat. No. 3,419,391, in which the dye flows out into the processing tower upon reaction with the oxidation products of the color developing agent, may also be used.

As a colored cyan coupler as a masking coupler, a compound in which the active site of a colorless cyan coupler is substituted with an arylazo group is used; for example, as disclosed in U.S. Pat.
No. 521908, No. 3034892, British Patent No. 1
Examples thereof include compounds described in No. 255111, JP-A-48-22028, and the like.

Furthermore, U.S. Patent No. 3,476,563 and Japanese Patent Application Laid-Open No. 1983-101
Colored cyan couplers of the type in which the dye flows out into the processing solution by reaction with the oxidation product of a color developing agent, such as those described in No. 35 and No. 50-123341, can also be used.

Furthermore, in order to improve photographic properties, a so-called competing coupler, which forms a colorless dye, can be included.

Further, each coloring layer can be configured to have two or more layers having substantially the same color sensitivity but different sensitivities, and each of these high-sensitivity emulsion layers can contain a DIR compound, a mordant, etc. as necessary. can. (However, it is not limited to the high-sensitivity layer.) In order to incorporate these various compounds into the light-sensitive material, they can be incorporated in various forms into the coating solution of the constituent layer to be contained, and in this case, e.g. Various techniques currently used for couplers can be applied.

The silver halide photographic material according to the present invention includes a silver halide emulsion layer containing the various photographic additives as described above and other constituent layers (for example, a yellow filter layer, a protective layer, etc.). Manufactured by coating on a support.

The emulsion layer for color development can be composed of a high-speed layer and a low-speed layer, as described above. Supports that are advantageously used to support these constituent layers include, for example, baryta paper, polyethylene-coated paper, polypropylene synthetic paper, glass paper, cellulose acetate, cellulose nitrate, polyvinyl acetal, polypropylene,
Examples include polyester films such as polyethylene terephthalate, polystyrene, and the like, and these supports are appropriately selected depending on the purpose of use of each silver halide photographic light-sensitive material.

These supports are subjected to undercoat processing if necessary.

After exposure, the silver halide photographic material of the present invention can be developed by various commonly used methods. That is, the color developing agent that can be used in processing the light-sensitive material of the present invention preferably has a pH of 8 or higher, more preferably an alkaline aqueous solution having a pH of 9 to 12.

This aromatic primary amino developing agent as a developing agent is
It means a compound having a primary amino group on an aromatic ring and capable of developing exposed silver halide, or a precursor for forming such a compound.

The above-mentioned developing agent 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-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-
Methyl-4-amino-N-ethyl-N-β-methoxyethylaniline, 3-β-methanesulfonamidoethyl-
4-amino-N,N-diethylaniline, 3-methoxy-4-aminoethyl-N-β-hydroxyethylaniline, 3-methoxy-4-amino-N-ethyl-N-
β-methoxyethylaniline, 3-acetamido-4-
Amino-N, N-diethylaniline, 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-1 luenesulfonate and the like.

Furthermore, JP-A-48-64932 and JP-A-50-131526
No. 51-95849, and compounds described in Bent et al., Journal of the American Chemical Society, Vol. 73, 3100-3125 (1951), can also be used. These color developing solutions may also contain various additives such as alkaline agents, p.
H regulator or buffer, development accelerator, antifoggant,
Preservatives etc. may be added. .

After the photosensitive material of the present invention is imagewise exposed and color developed, it can be bleached by a conventional method. This treatment may be carried out simultaneously with or separately from fixing, and this treatment solution can be made into a bleach-fixing solution by adding a fixing agent if necessary. Various compounds can be used as bleaching agents, and various additives including bleaching accelerators can also be added.

[Embodiments of the invention]

Next, one embodiment of the present invention will be described. It should be noted that, as a matter of course, the examples shown below are illustrative of the present invention, and the present invention is not limited thereby.

Here, we will discuss the case where the present invention was applied to a sample made of an optical material consisting of one emulsion layer containing a coupler and a protective layer (Examples 1 to 3), and the case where the emulsion layer containing a coupler was formed into multiple layers. A case in which the present invention is applied to a photosensitizer sample (Example 4) will be illustrated and explained.

(Example 1) In this example, a magenta coloring coupler was used.

Specifically, in this example, a pyrazolotriazole coupler represented by the following formula A was used as the magenta coloring coupler. This corresponds to coupler C-19 mentioned above.

The high boiling point solvent of general formula (n) used as a solvent for dissolving the coupler is ditertiary-nonylphenol (D
NP) was adopted. This is a compound represented by the above-mentioned formula (n-13).

As a comparative example, tricresyl phosphate (TC
Data were collected for the case where P) was used as a solvent.

As the compound represented by the general formula [I], one represented by the following 2B1 formula C was used.

The above compound B is represented by the above formula (1-1),
C corresponds to that shown in formula (1-14).

As a comparative example, data was also collected in the case where such a compound of general formula (1) was not added.

Each layer of this example was dried in the following manner.

1st layer... 1.8 g of high-sensitivity green-sensitive monodisperse silver iodobromide emulsion color sensitized to green sensitivity (Imo1%□3.0mo1%, r.1.
6u*S/r'' is preferably selected in the range 0.1 to 0.15) 0.06 g dissolved in 1.9 g gelatin and 0.20 g magenta coupler and 0.049 g colored magenta coupler A high-sensitivity green-sensitive emulsion layer containing DNP (ditertiary-nonylphenol) (herein, "monodisperse" means substantially monodisperse.

same as below).

2nd layer... Yellow filter layer containing 0.15 g yellow colloidal silver, 0.11 g DBP with 0.2 g antifouling agent dissolved and 1.5 g gelatin.

In addition to the above composition, a gelatin hardener and a surfactant were added to each of the two layers.

Each sample was processed with the following processing steps.

Processing process The composition of the treatment liquid used in each treatment step is shown below.

[Color developer]

[Bleach solution] [Fixer] [Stabilizing liquid] The results obtained for each sample are shown in Table 1.

Table 1 shows fog (Fog), foot sensitivity S 1 (Fog+0.1),
The data of Sz (Fog+0.3) are shown respectively.

As is clear from Table 1, samples 1-1 to 1- using TCP without using the high boiling point solvent according to the present invention
In No. 3, the relative sensitivity of the feet is low, causing the phenomenon of foot breakage. In addition, samples that do not use the compound of formula (1) according to the present invention include those that use TCP (1-1) and those that use DNP, which is a high boiling point solvent of the present invention (1-1).
Regarding 4), it still exhibits the phenomenon of running out, which is not preferable. On the other hand, for Sample 1-5.1-6, which is the present example, the sensitivity of the foot portion was good, no foot breakage occurred, and a decrease in density in the low exposure region could be avoided.

(Example 2) In this example, a cyan coloring coupler was used.

As the high boiling point incubator solvent of the present invention, the same <DN
P was used. As a comparative example, a case where TCP is used is shown.

As the contrast enhancing agent of formula CI), the above-mentioned B and C are used, and the data for samples using each are described, as well as the case where such compounds are not used.

The cyan color forming coupler used is a ureido coupler represented by the following formula or E formula.

S　Ot　Ca　H9 H In this example, each layer was adjusted as follows.

1st layer...1.8g of highly sensitive red-sensitive monodispersed silver iodobromide holes (Imo1%=3.0mo1%, r-1,6μ)
, 2.1 g of gelatin and 0.40 g of DNP in which 0.40 g of cyan coupler was dissolved.

2nd layer: 0.04g of n in which 0.07g of 2.5-di-t-octylhydroquinone (antifouling agent) was dissolved.
- Interlayer containing dibutyl phthalate (DBP) and 0.8 g gelatin.

In addition to the above composition, a gelatin hardener and a surfactant were added to each of the two layers.

The results are shown in Table 2.

In the case of this example as well, the tendency is similar to that of the previous example, and the one to which the present invention is applied shows good results. Note that when coupler E is used, the fog is generally larger and the sensitivity is lower than when coupler D is used (see comparison between 2-1 and 2-2), so Example 2-11 is compared to Comparative Example 2-3. Although the sensitivity etc. are lower, as is clear from the comparison with Comparative Example 2-5.2-6 using the same coupler E, the present invention shows a remarkable effect if the same type of coupler is used. be.

(Example 3) In this example, a yellow coloring coupler was used.

The high boiling point organic solvent of the present invention is <DNP, which is the same as the above example.
was used. As a comparative example, a case where TCP is used is shown.

As the contrast enhancing agent of formula (1), the above-mentioned B and C are used, and the data for samples using each are described, as well as the case where such compounds are not used.

The yellow coloring coupler used is the F type below.

It is represented by the G formula or the H formula.

In this example, each layer was prepared as follows.

1st layer: 2 to 3 g of high-sensitivity monodisperse iodobromide [l (Imo1%-10mo1%, r-1) with color enhancement to blue sensitivity
,6,c+) emulsion, 1.9g gelatin and 0.80
A high-speed blue-sensitive emulsion layer containing 0.80 g of DNP in which g of yellow coupler was dissolved.

2nd layer...protective layer with 2.3g of gelatin.

In addition to the above composition, a gelatin hardener and a surfactant were added to each of the two layers.

The results are shown in Table 3.

This example also had the same tendency as the above two examples, and the one to which the present invention was applied showed good results.

(Example 4) Next, an example in which a multilayer structure is used will be described.

In this example, the following layers were coated in order on a transparent support made of subbed cellulose triacetate film and having an antihalation layer (containing 90.40 g of black colloid and 3.0 g of gelatin). A sample protein was prepared by this method.

As in the above examples, in all of the examples below, the amount added to the light-sensitive material is expressed per unit, and the amounts of silver halide emulsion and colloidal silver are expressed in terms of silver.

Each layer is as follows. Note that the emulsion layer was prepared in the same manner as in the previous example.

Layer 1: 1.4 g of low-sensitivity red-sensitive monodispersed silver iodobromide (Imo1%g2.6mo1%, r
-0.8 μ) emulsion and 1.2 g gelatin and 0.8
g of 1-hydroxy ``-4-(β-methoxyethylaminocarbonylmethoxy)-N-(δ-(2,
4-di-t-amylphenoxy)butyl]-2-naphthamide (a type of cyan coupler), 0.075 g of 1-
Hydroxy-4-(4-(1-hydroxy-δ-acetamido-3,6-disulfo-2-naphthylazo)phenoxy) -N-(δ-(2,4-di-t-amylphenoxy)butyl-2- naphthamide disodium (a type of colored cyan coupler), and 0.015 g of 1-
Hydroxy-2-[δ-(2,4-di-amylphenoxy)-n-butyl]naphthamide, 0.07 g of 4-octadecylstacynimide-2-[1-phenyl-5-
Low red light emulsion layer containing 0.65 g of tricresyl phosphate (TCP) in which tetrazolylthio)-1-indanone (a type of DIR compound) is dissolved.

Layer 2...1.8g of highly sensitive red-sensitive monodispersed silver iodobromide emulsion (Imo1%g3.oa+o1%, r-1,6μ, 2
．． A high-speed red-sensitive emulsion layer containing 0.40 g of DNP in which 7 g of gelatin and 0.40 g of the cyan coupler described above were dissolved.

Layer 3: Contains 0.04 g n-dibutyl phthalate (DBP) and 0.8 g gelatin dissolved in 0.07 g 2.5-di-t-octylhydroquine (antifouling agent). middle class.

Layer 4: 0, 80 g of low-sensitivity monodisperse iodide 1 color sensitized to green sensitivity! (Imo1%-2,6mo1%, r-0
, 8 μ) emulsion and 2.2 g gelatin and 0.8 g 1-(2,4,6-trichlorophenyl”)-3-
(3, (2,4-di-t-amylphenoxyacetamide)benzamidocou-5-pyrazolone (a type of magenta coupler), 0.15 g of 1-(2°4.6-)lichlorophenyl)-4-(1 -saphtylazo)-3-(2
-Chloro-5-octadecenylstacynimidoaniline)-5-pyrazolone (a type of colored magenta coupler), containing 0.95 g of TCP in which 0.016 g of DIR compound (same as above) was dissolved. A low-speed green-sensitive emulsion layer.

Layer 5: 1.8 g of highly sensitive green-sensitive monodispersed silver iodobromide (Imo1%g3.omo1%, r
-1,6μ) emulsion, 1.9g gelatin and 0.20
g magenta coupler (coupler to above) and 0.0
0,60 with 49g of colored magenta coupler dissolved
A highly sensitive green-sensitive emulsion layer containing g DNP.

Layer 6...0.15g yellow colloidal silver, 0.2g anti-staining agent (same as contained in layer 3) dissolved in 0,11
One layer of yellow filter containing g DBP and 1.5 g gelatin.

Layer 7: 0.2 g of low-sensitivity monodisperse silver iodobromide color sensitized to blue sensitivity (Imo1%-2.6mo1%, r-0,
8#) Emulsion and 1.9g gelatin and 1.5g α
-pivaloyl-α-(1-benzyl-2-phenyl-3
, 5-dioxoimidazolidin-4-yl)-2'-chloro-5'-(α-dotecyloxycarbonyl)ethoxycarbonyl]acedoanilide (a type of yellow coupler) containing 0.6 g of TCP. A low-speed blue-sensitive emulsion layer.

Layer 8: 2 to 3 g of high-sensitivity monodispersed iodobromide i11 (Imo1%-1 (1++o1%, r
-1,6u) emulsion, 1.9g gelatin and 0.80
A high-speed blue-sensitive emulsion layer containing 0.80 g of DNP in which g of yellow couplers (couplers F, G, H) were dissolved.

Layer 9: Protective layer with 2.3 g of gelatin.

The subsequent processing steps in this example are as follows. That is, each of these samples was exposed to neutral light through an optical wedge and then processed through the processing steps described below to obtain a dye image.

Processing process Color development 3 minutes 15 seconds bleaching 6 minutes 30 seconds water washing 3 minutes 15 seconds fixing 6 minutes 30 seconds water washing 3 minutes 15 seconds stabilization 1 minute 30 seconds drying Processing liquid composition used in each processing step is as follows.

(Color developer) 4-amine-3-methyl-N-ethyl (β-hydroxy ethyl)-aniline sulfate 4.75g anhydrous sodium sulfite 4.25g hydroxylamine 1/2 sulfate 2.0g anhydrous potassium carbonate 37.5 g Sodium Bromide 1.3 g Nitrilotriacetic acid 3
Sodium salt (monohydrate) 2.5g Potassium hydroxide 1.0g Add ice to make 11.

[Bleach solution]

Ethylenediaminetetraacetic acid iron ammonium salt 100.
0g Ethylenediaminetetraacetic acid diammonium salt 10.0
g Ammonium bromide 150.0g Glacial acetic acid 10.0μl Add water to make 11, and adjust to pH 6.0 using aqueous ammonia.

[Fixer]

Ammonium thiosulfate 175.0g Anhydrous sodium sulfite 8.6g Sodium metasulfite 2.3g Add water to 1
1 and adjust the pH to 6.0 using acetic acid.

[Stabilizing liquid]

Formalin (37% aqueous solution) 1.5+
ol Konidax (manufactured by Konishiroku Photo Industry Co., Ltd.) 7.5
Add ml water to make 11.

The results are shown in Table 4. From Table 4, it is clear that the present invention is effective in improving density reduction in low exposure regions even when multilayered as in this example.

Furthermore, the color development was extremely good.

Table 4 (Effects of the Invention) As described above, according to the present invention, since a phenolic high-boiling solvent is used as the coupler solvent, stable dispersibility and high color development can be obtained. In this case, it is possible to avoid a decrease in density in a low exposure region, and it is therefore possible to obtain a silver halide photographic material with good color development and high sensitivity.

[Brief explanation of drawings]

FIG. 1 is a characteristic curve for explaining the present invention in detail.

Claims (1)

[Scope of Claims] 1. In a silver halide photographic light-sensitive material having a silver halide emulsion layer containing a coupler dispersed using a high-boiling organic solvent on a support, at least The silver halide layer contains a compound represented by the following general formula [I], and the high boiling point organic solvent contains at least a compound represented by the following general formula [II]. Photographic material. [I] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [II] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ However, in the above formula, R^1 is an alkyl group, aryl group, alkoxy group, or amino group, R ^2 represents a monovalent group, S represents an integer from 0 to 3, and when S is 2 or more, R^2 may be the same or different. R^4 represents a straight chain or branched alkyl group having 1 to 20 carbon atoms;
^3 represents a linear or branched alkyl group or cycloalkyl group having 1 to 20 carbon atoms, the total number of carbon atoms of the groups represented by R^3 and R^4 is 4 to 24, and n is 0. Represents an integer from ~3.