JPS59184342A - Photosensitive silver halide material - Google Patents

Abstract

PURPOSE:To improve the solubility of a coupler in a high b.p. solvent and the dispersibility and stability in a silver halide emulsion by using a specified compound as the coupler. CONSTITUTION:This photosensitive silver halide material has a silver halide emulsion layer contg. a couler represented by fromula I . In the formula, Cp<1> is a coupler component which forms a dye (A) and can release Cp<2>-X when the coupler represented by the formula I reacts with the oxidized product of a color developing agent, Cp<2> is a coupler component which forms a dye (B) assuming the practically same hue as the dye (A) and can release X when the released Cp<2>-X reacts with the oxidized product of the color developing agent, and X is a group or a hydrogen atom which is released from the Cp<2>-X when the Cp<2>-X reacts with the oxidized product of the color developing agent. A compound represented by formula II, III or IV is used as the coupler represented by the formula I .

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to photographic technology, particularly the production wave of photographic light-sensitive materials.
It can be used for techniques.

The present invention relates to a silver halide photographic C material, and more particularly to a silver halide color photographic material with improved image quality, particularly image graininess.

As is well known in the art, in general subtractive color photography, an aromatic primary amine color developing agent reduces exposed silver halide grains to form an oxidized product of the color developing agent. A color image is formed by oxidative coupling of yellow, macenta, and cyan dye-forming couplers in a silver halide emulsion.

In the above, as a yellow filler for forming a yellow pigment,
Compounds containing i-sumethylene are used (1), compounds such as pyrazolone, pyrazolinobenzimidazole, indashilon thread, etc. are used as magenta couplers to form a magenta color, and cyan dyes are used. Compounds having G, I phenol and naphtholic hydroxyl groups are used as cyan couplers for the formation.

Each coupler is actually 6) highly water-insoluble.
Point A J' or this 71. The first silver halide is dissolved in the silver halide emulsion using an auxiliary solvent if necessary.
or dissolved in an alkaline aqueous solution and added to the emulsion. The former is an oil γ1 dispersion method, and the latter is an alkali dispersion method, but it is generally said that the former is superior to the latter in terms of heat resistance, moisture resistance, granularity, color sharpness, etc. There are n.

The basic properties required of each coupler include not only the ability to form dyes, but also high solubility in high-boiling axial solvents, as well as dispersibility and stability in silver halide emulsions. The dye formed by the dye has good resistance to roundness, heat, Wni air, etc.
Spectral absorption characteristics are +B favorable, transparency is good,
It is desired to improve various characteristics such as high color density and clear 1111 images.

In this way, it can be used by adding it to a silver halide agent.
Most of the dye-forming couplers G are 4-functional;

A coupler is called a coupler. That is, it is a coupler that requires development of four molecules of silver halide in order to produce one molecule of the above-mentioned dye. Apart from this 4-equivalent coupler, 2-equivalent, 6-equivalent, 4-equivalent, and 8-equivalent couplers are also commonly known, and these couplers each produce one molecule of dye. For this purpose, it is necessary to develop 2, 6 or 8 molecules of silver halide. Is there another one? (
In the case of couplers, photochemical modification can be achieved by introducing various substituents into the coupling active site.
I was able to add some useful performance and functionality to it.

For example, by using a so-called 2-t coupler, which has a group that easily escapes from the active site and is photochemically sensitive to heat, the coupling property can be improved, and the silver needed to obtain a black color image (9!) can be improved. 7, and as a result, the emulsion layer can be made thinner, improving sharpness.Also, so-called colored couplers, in which dyes are bonded to the active sites, are used for color correction of color-representative images. In other words, the KN DIR coupler, which has a development inhibitor bound to its active site, has functions such as controlling image tone, making the dye image finer, and interlayer effect. However, attempts have also been made to attach other chemically useful substituents to the active site.

On the other hand, if we look at the styles of color photography, even if we look only at 17iJ over the past ten years, there are two distinct styles.

One is the gradual trend toward smaller film sizes, and the other is higher sensitivity.

However, small-sized films still lack sufficient graininess, color reproducibility, and sharpness.
Therefore, it is not possible to meet the demand for smaller film sizes. Furthermore, high-power films have the disadvantage that image quality deteriorates due to the basic property of silver halide photography that the higher the sensitivity, the larger the silver halide grains become.

In order to improve these drawbacks, various methods have been devised in the past. The aforementioned DIR couplers and colored couplers are one such method.Another method is to form a thin film of the light-sensitive emulsion layer and separate the light-sensitive layer in the same wavelength range into a high-sensitivity silver halide layer and a low-sensitivity silver halide layer. , improvements in silver halide manufacturing technology, improvements in antihalation technology, improvements in anti-irradiation technology, and improvements in couplers. However, it is still insufficient, and further improvement technology is desired.

One such example is, for example, U.S. Pat.
No. 0,618 describes a multifunctional coupler 314 using a blocking group as a technique for improving the graininess of couplers.
There is a precept. The coupler used as the above-mentioned blocking group is a type that releases the coupler by coupling with an oxidized color developing agent, and the coupler itself flows out into the developer, and is generated in the photosensitive material. excessive oxidation
The objective is to improve graininess by trapping the color developing agent. However, this method has the serious drawback that the dye flows into the developer and contaminates the developer. Also, JP-A-56-13584
According to No. 1, after the coupling reaction with the oxidized color developing agent, the magenta dye-forming coupler is protected and the ortho-sensitivity is Improve the graininess of the yC layer,
Additionally, a coupler with improved storage stability of magenta dye-forming couplers is described. However, even with this method, contamination of the developer occurs due to the dye flowing out, and the coloring sensitivity is not sufficient because the magenta dye-forming coupler only contributes after separation from the blocking group.11.
There are some drawbacks.

Furthermore, according to a publication in JP-A No. 57-82837, a coupler is disclosed that generates a mobile dye that suppresses image blurring upon a coupling reaction with an oxidized color developing agent. However, this method (4) has the drawback that the dye cloud is blurred due to the movement of the produced dye, which deteriorates the sharpness of the image.

OBJECTS OF THE INVENTION The first object of the present invention is to improve the above-mentioned drawbacks and provide desirable properties, while improving solubility in high boiling point solvents and dispersibility and stability in silver halide agents. The object of the present invention is to provide a silver halide color material containing a coupler such as fQ-H.

A second object of the present invention is to provide a silver halide color photographic light-sensitive material containing a coupler that maintains the l-shaped property and has improved image resolution in the low X' and ! light ranges. It is in.

A third object of the present invention is to provide a silver halide color photographic material containing a coupler which exhibits excellent interlayer effects and markedly improved sharpness.

Roughly speaking, the fourth object of the present invention is to provide a silver halide color photographic material containing a coupler with high sensitivity, high color density, good brown color reproducibility, and no color staining. be.

A fifth object of the present invention is to provide a silver halide color photographic C-phase material containing a coupler that has a wide exposure latitude and does not cause developer contamination.

Finally, the sixth object of the present invention is to provide a silver halide color photographic material containing a coupler which can reduce the amount of coupler depending on the amount of silver.

Structure of the Invention As a result of various test printings to solve the above problem, the present inventors have developed a silver halide photographic photosensitive material having a silver halide emulsion layer containing a coupler represented by the following general formula [I] on a support. It has been found that the above object can be achieved by using the second material.

General formula [1] % formula % In the formula, Q p I is a dye (
represents a coupler moiety which forms A) and releases Qp 2
represents a coupler component capable of reacting with an oxidized form of a color developing agent to form a dye (B) exhibiting substantially the same hue as the dye (A) and releasing X, where X represents a coupler component capable of releasing X; ``-x represents an n group or a hydrogen atom released from Qp2-x when it reacts with an oxidized product of a color developing agent.

Further, at least one of the dye (A) and the dye (B) has substantially the same color sensitivity as the silver halide emulsion layer containing the coupler represented by the general formula [I] and the layer. represents a dye that is diffusible within adjacent silver halide emulsion layers.

Silver halide color photosensitive material L-4 of the present invention (hereinafter referred to as
The above-mentioned -l' represented by the formula [I] contained in the silver halide emulsion layer of the light-sensitive material of the present invention (abbreviated as 2.)
The couplers related to ゛jy plar C, unexploded, IIj and u-P s) form two dyes exhibiting substantially the same hue through a two-step reaction with an oxidized product of a color developing agent, or At least one of the dyes is a diffusible dye.

Such a 6 coupler according to the present invention has at least one extension in a site other than the coupling active site of the coupler molecule;
It has a group that gives the monomer character ζ], and Cp2 is Cp l
The coupling active field binds to the 2nd position, and the Gatsu□ pl
and Cp2 are actually combined with a coupler that forms a dye of the same hue, and color A1 is preferably a magenta or cyan dye.

In the present invention, the above-mentioned dyes having practically the same hue include, for example, a combination of T couplers, or in the case of forming a magenta dye, a combination of two couplers or a coupler having pyrazolone rings. This means that the other substituents may be any group, and all magenta dyes obtained from such couplers are considered to have substantially the same hue. In addition, in combination of couplers, 119 to form a cyan dye (well, in combination of 0 couplers, phenolic thread 11, metal material and naphthol compound, 7t,
Any combination may be used, and the intention is that all cyan dyes obtained from such couplers will have the same hue. Further spread calendar J
The diffusion IQ of the dye (A) and the dye (B), 1) or the range of diffusion of the coupler according to the present invention is as described above.・, η is close to 14% I is limited to the 1.6th area of the halogenated milking layer having the same color sensitivity as the first layer.Therefore, the above-mentioned same 1) Even if there is an intervening layer, for example, in the layer 1t1 of the two halogenated αγ scavenging agent layers that provide scolding properties, the range of expansion covered by the present invention can be achieved without any support. A.

Furthermore, -hi+jl-': 1.11-'s j・■ chromaticity is iJ.
If the material is a green material containing a magenta coupler, a green layer containing a magenta coupler and a red layer containing a cyan coupler, or a wave that does not affect normal color reproduction, respectively. "l?" Those that have the same characteristic as i(rξtf) have substantially the same I+!
*Introduced as having a color wart.

In the present invention, the coupler capable of forming the above-mentioned wide color J has a substituent capable of imparting a necessary degree of diffusivity to the dye formed at a site other than the coupling active site of the coupler. The substituent that imparts the required degree of diffusivity is, for example, an alkyl group having 4 to 20 carbon atoms, or an alkyl group having 6 carbon atoms.
~20 groups may be mentioned. Both of these substituents may further have substituents, and in this case, the substituents include basic ionizing ability 7',
A C group is preferable, and examples thereof include a bitroxyl group, a carboxyl group, a sulfo group, and an aminosulfonyl group.

In the present invention, the above-mentioned group imparting the required degree of diffusivity by +1 is, for example, ether, thioether, ester, amino, cylamino, carbamoyl, sulfonamide,
It is preferable that the coupler be bonded to a site other than the kabu-1 non-coupled active site of the coupler via a bonding group such as sulfamoyl or ureido.

The coupler according to the present invention preferably has the following general formula [n
] to [rV].

General formula [II] In the formula, B and R3 represent an alkyl group, an alkylcarboxamide group, an arylcarboxamide group, or an arylamino group, and R2 and R1 represent a Represents a carboxamide group, x, 4B hydrogen atom, /.rogen atom, and an alkoxy group. In addition, l and m represent integers from O to 5, and R
At least one of 8 and R3 is a diffusible group.

General formula [111] (wherein, R6 represents an alkyl group or an aryl group,
R1 represents an alkylcarboxamide group, an arylcarboamide group, an alkylcarbamoyl group, an arylcarbamoyl group, or an arylureido group, and R2 and R each represent a hydrogen atom, a halogen atom, an alkyl group, or an alkylcarboxamide group. represents a group. Also R1 and R1
may be combined with each other to form a 5- or 6-membered ring. Further, X2 represents a hydrogen atom, a halogen atom, or an alkoxy group, and R6, R, and R1 are at least one of the diffusible groups.

General formula [Iv] H S In the formula, R represents an alkylcarboxamide group, an arylcarboxamide group, or an arylureido group; 't'
RIO represents a hydrogen atom, a halogen atom, an alkyl group or an alkylcarboxamide group, and R81 represents the general formula [
It represents a group having the same meaning as R6 in January, and also represents a group having the same meaning as R7 and R8 in the above general formula Eill'3. xs l:i represents a hydrogen atom, a halogen atom, or an alkoxy group, n represents an integer of 1 to 2, and when n is 2, RIG may be the same or different. At least one of R10, R(RH and RI3) is a diffusible group. Note that the general formulas [II], [lil] and [
In [V], when each of the groups R1 to R13 has a substituent, the substituent is when the combined coupler is associated with a coupler that forms a diffusion-resistant dye. , as described below, is a substituent found in conventionally known diffusion-resistant couplers, and when it is associated with a coupler that forms a diffusible dye, OJ, the basic ionizable group described above, Examples include hydroxyl group, carboxyl group, sulfo group, aminosulfonyl group, and the like.

(11 cans if the coupler forms a pigment that
As for the other coupler, that is, the coupler that forms the diffusion-resistant dye, a conventionally known coupler can be used. can.

For example, for magenta couplers, U.S. Pat.
No. 369,489, No. 2,343. 'i' No. 03,
Same No. 2,311.082, Same No. 2,600,788, Same No. 2.908,573, Same No. 3,062,653
No. 3,152,896, No. 3.519,42
No. 9 specifications and the Agfa Mitteilung (BandIr) 1
There are various magenta couplers, such as pyrazolone magenta couplers and indacylon magenta couplers, which are described in 26-156* (1961).

Furthermore, as a cyan coupler, U.S. Patent No. 2.367
, No. 531, No. 2,423,730, No. 2.47
4; No. 293, No. 2', No. 772,162, No. 2,
No. 895,826, No. 3,002,836, No. 3
, 034,892, 3,041.236, 3,880,661, 4,124,3967,
No. 4,333,999 and Japanese Unexamined Patent Publication No. 4'7-211
There are naphthol-based or phenol-based couplers described in various specifications or publications such as No. 39.

Typical specific examples of couplers according to the present invention are listed below, but the couplers used in the present invention are not limited thereto.

(Exemplary compound) -1 -2 M-3 M-5 M-6 -1 H " -2 H -3 H Ci, H9 -4 H 2H5 -5 H C8U, 1 -6 O/ -7 0T( Cor 8 H C-9 00H, (!0NHO4H.

-10 H -12 H Below, a synthetic route and a synthetic example of a typical magenta coupler according to the present invention are shown.

(C) (E,)
1++L' on υ5 (Exemplified Compound M-3) Synthesis Example 1 (Synthesis of Exemplary Coupler M3) i! Add 67.2 g of your own coupler (C), 19.5 g of diethyl chloromalonate, and 27.6 g of potassium carbonate to DMFGoo.
ml, heated to 50-60°C, and reacted for 200 hours. After the reaction solution was allowed to cool to room temperature, it was added to water, and the resulting oil was extracted with ethyl acetate. After washing with water three times, the oil layer was separated, dried, and concentrated under reduced pressure. The residue was purified using silica gel column chromatography to obtain 62 g of a pale yellow oil.

Regarding the structure of the compound, use NMR to calculate the structure of the compound (
D).

100 g of potassium t-butoxide was dissolved in anhydrous T, HoF
.

3,001 nl of anhydrous T, H, F, 50 M solution of 60 g of the compound (D) obtained above was added thereto under stirring at room temperature.

After 15 minutes, add 1+1 liters of m-nitrophenyl isocyanide dichloride to anhydrous T, H, F. 50ml solution was slowly added dropwise. After the dropwise addition was completed, the mixture was stirred for 1 hour, nitrogen gas was introduced, and 1 liter of pentachlorophenylhydrazine was added under stirring.
A solution of s, zp in anhydrous methanol was added dropwise. After stirring for 30 minutes, the mixture was further stirred vigorously, and a solution of 7.8 g of sodium methylate in anhydrous methanol Group 300 was added dropwise little by little over a period of 30 minutes. After the reaction solution was further stirred for 3 hours, water was added and the mixture was neutralized with acetic acid and acidified with concentrated hydrochloric acid. The resulting oil was extracted with ethyl acetate, washed with water three times, and then the oil layer was separated, dried, and concentrated under reduced pressure. The residue was recrystallized using acetonitrile.

Pale yellow crystal 24. 'i', got 9. The structure was determined using NMR and mass spectra, and the above coupler (E)
It was confirmed that

20 g of the above coupler (E) was dissolved in 200 g of T, H, F, and hydrogenated at atmospheric pressure using 4 g of palladium-carbon catalyst. After consuming a specified amount of hydrogen, the catalyst was separated from P, and 1.9 g of succinic anhydride was added to the p liquid, heated to 70 to 80°C, and reacted for 3 hours. The reaction solution was added to water and extracted using ethyl acetate. After washing with water and drying the oil layer separately,
It was concentrated under reduced pressure. Solidify the residue using n-hexane,
White crystal 149 was obtained. It was determined by thin 1·η chromatography that the starting amine had disappeared, and the structure was determined to be the desired exemplary compound M-3 by mass spectroscopy.

Next, a synthesis route and a synthesis example of the cyan coupler according to the present invention will be shown.

H 02H.

H Synthesis Example 2 (Synthesis of Exemplary Coupler 0-4) 204I-1,
1.51 of 4-dihydroxy-2-naphthoic acid,
In addition to M and F, a caustic soda water bath solution consisting of 84 g of caustic soda and 125 ml of water is added in a nitrogen gas stream while cooling to 30°C.

Thereafter, 3-fluoro-4-nitroα-(2゜4-ditθrt-amylphenoxybutane anilide 550
Add & in small portions over 30 minutes. Then 50°C
The reaction mixture was heated to 3 hours and the reaction was carried out for 3 hours. Reaction liquid? ! j1 Hydrochloric acid-
If added to ice, an oil will form. Since this oil solidifies afterwards, it is filtered, washed with water, washed with acetonitrile, and dried. A light dry color powder 4189 was obtained.

400 g of the obtained crude crystals were added to 41 ml of ethyl acetate, and 75.6 g of hexylamine and 1,419 g of dicyclohexylcarbodiimide were added, followed by boiling and reaction for 5 hours. The mixture was allowed to cool to room temperature, the insoluble matter was filtered, the liquid F was washed with water, the oil layer was separated, dried, concentrated under reduced pressure, and then recrystallized from acetonitrile to obtain 245 g of pale yellow powder. Structure @ is NM
Determined using R and mass spectra, the compound (I
') was confirmed.

Compound (F) 200. jil was added to ethanol 21, and hydrogenation was performed at normal pressure using 10 g of palladium-carbon catalyst at Z. After consuming a specified amount of hydrogen, the catalyst was filtered and the iH solution was concentrated under reduced pressure. Residual G toluene obtained
1. p-ethanesulfonylphenyl, 93 g of phenyl carbamate, 1.9 g of imidazole,! ? Add and boil to 811'? The reaction was carried out for a while. After the reaction solution was allowed to cool to room temperature, it was concentrated under reduced pressure, and the residue was solidified using ethyl acetate and n-hexane, and further recrystallized using methanol. 855 g of white crystals were obtained. The disappearance of the amine was determined by thin layer chromatography at 66+ BM L , and the structure was determined using mass spectrometry to confirm the target exemplified coupler (C-4).

The coupler according to the present invention produced by the above synthesis method is a combination of two couplers having a color image forming ability in one molecule, and at least one of the two dyes obtained by the coupling reaction. Because the pigment is diffusible, it can have various photographic characteristics.

That is, since the coupler according to the present invention has a coloring ability (or pigment forming ability) of 24'f compared to a normal σ coupler, it is possible to drastically reduce the amount of use thereof. Therefore, when it is applied to an emulsion layer, the amount of gelatin as a binder and the amount of coupler solvent can be greatly reduced. As a result, the silver halide emulsion layer containing the coupler becomes thinner, resulting in an effective effect of 1! without inhibiting J-, and (
It can also improve the sharpness of a blood-colored fish. At the same time, the thin layer allows for good permeability of the developer, and prevents it from developing.
Since it does not contain a +1 floc group, it is convenient for obtaining high sensitivity.

In addition to the above, the effect of the present invention is that the coupler according to the present invention forms a diffusive dye. i
'Since it is limited to one layer or the same color-sensitive emulsion layer adjacent to this (1), the blurring effect due to the spread of the dye ν3 on the image is effective and improves the graininess. It is also possible to improve the quality of jtl and Ij images.Furthermore, the coupler according to the present invention has two couplers bonded to each other in the coupling active site of the coupler molecule, so it is similar to a normal two-to-one coupler. It also has the advantage of not requiring the use of benzyl alcohol in the color developing solution, since silver can be saved and the coupling reaction rate is high.

Hereinafter, the photosensitive material of the present invention containing the coupler according to the present invention will be explained in more detail.

The couplers according to the invention are applied to sensitizers by methods similar to those used for conventional couplers.

Typically, the coupler according to the present invention is added and blended into a silver halide emulsion, and this emulsion is coated on a support to form a light-sensitive material.

The light-sensitive material of the present invention may be a monochrome element or a multicolor element. When a multicolor element, the couplers of the invention are usually included in the emulsion of the green-sensitive layer or the red-sensitive layer, or in a dye image-forming composition sensitive to each of the three primary regions of the spectrum. In a multicolor element having the unit, it may be included in a color-sensitive layer other than the above-mentioned green-sensitive and red-sensitive layers.

The arrangement of the iij+i image-forming structural unit layers in such a multicolor element light-sensitive material can be arranged in each i.gamma. as known in the industry. In a typical multicolor element photosensitive material, at least one blue 1e halogen 1
A yellow image forming unit consisting of a 1Z silver emulsion layer; a magenta image forming unit consisting of at least one green-sensitive silver halide emulsion layer; It is constructed by layering cyan image-forming structural units consisting of a red-sensitive silver halide emulsion layer on a support, and in the present invention, among the magenta image-forming structural units and cyan image-forming structural units,
At least one of the units contains a coupler according to the present invention.

In the photosensitive material of the present invention, when each of the above-mentioned image-forming structural units is composed of at least one constituent layer, for example, two constituent layers with different photosensitivity, the upper layer has more than one constituent layer. It is preferable that the coupler according to the present invention be contained in a high-strength constituent layer.

In addition to the color-sensitive silver halide emulsion layer consisting of hole-forming units of each color described above, the light-sensitive material of the present invention includes auxiliary layers such as a filter layer, an intermediate layer, a retention layer, and an undercoat layer on a support. It may be on top.

In order to incorporate the coupler according to the present invention into an emulsion, a conventionally known method may be followed. For example, high boiling point organic solvents with a boiling point of 175°C or higher, such as tricresyl phosphate and dibutyl phthalate, or low boiling point solvents, such as butyl acetate and butyl propionate, as explained in detail later, may be used alone or in combination as necessary. After dissolving the II-related couplers that do not erupt in liquid, either alone or in combination, they are mixed with an aqueous gelatin solution containing a surfactant, and then high ia P
After emulsifying with J-times E mixer or colloid mill, add to silver halide to make unexploded I■ (4+, 41-4l
It is possible to FL the silver halide emulsion with mQ%. When the coupler according to the present invention is added to the silver halide emulsion used in the present invention, it is usually about 0.01-0.0% per mole of silver halide. The coupler according to the present invention is added in an amount of 0.02 to 0.2 mol, ie, 0.02 to 0.2 mol.

Examples of the silver halide used in the silver halide emulsion used in the present invention include silver bromide, Xai chloride, silver iodobromide, silver chlorobromide, and silver halide @iI! Any used in emulsions is included.

The silver halide emulsion used in the present invention can be manufactured by various manufacturing methods including the usual manufacturing method, such as Japanese Patent Publication No. 4G-777.
No. 2 describes a method for producing a so-called conversion emulsion, in which the solubility is greater than that of silver bromide, or the average grain size is less than 0.1μ. It can be produced by any production method such as the production method of a Lippmann emulsion consisting of fine grain silver halide having the following properties.

Furthermore, silver halide used in the present invention? L agents include sulfur sensitizers, such as luthiocarbamide, thiourea, cystine, etc., active or inactive selenium sensitizers, and reduction sensitizers, such as stannous! 'l, a % polyamine 28, noble metal enrichment 11 dust agent, such as gold enrichment IHM agent, specifically potassium aurithi A cyanate, potassium chloroaurate, 2-oresulbobenzthiol methyl chloride, etc., or e.g. Water-soluble 11, such as ruthenium, rhodium, iridium; j) Sensitizers, specifically ammonium chlorovaladate, potassium chloroaurate, and sodium chlorovaladite, etc. alone or in combination with suitable chemical agents. It can be increased or decreased.

Furthermore, the silver halide emulsion used in the present invention has a green sensitivity of 5.
Spectral sensitization is carried out by selecting an appropriate f-enhancing dye in order to impart sensitivity to the IIi light wavelength range required for U formulations and red-sensitive emulsions.

Various spectral sensitizing dyes can be used, and these can be used alone or in combination.Spectral sensitizing dyes that are advantageously used in the non-exploding 5j-J include, for example, the US standard Permit No. 2,269,234, same No. 2
．． 2 'i' 0.3 '78 No. 2,442,7
No. 10, No. 2.454,620, No. 2. 'i”i
Typical examples include cyanine dyes, merocyanine dyes, and complex cyanine dyes, which are described extensively in the specifications of No. 6,280.

Furthermore, the silver halide emulsion used in the present invention may contain any known photographic additives. For example, Re
Photographic additives such as those described in Research Disclosure, December 1978, Item 17643.

According to the present invention, in order to further increase the effectiveness of the present invention, an RD coupler can be used in combination with the coupler according to the present invention.

The DIR coupler effectively used in the present invention is 1
It is a compound that can react with an oxidized form of a color developing agent to release a development inhibitor (1).

Typical IR compounds have introduced into the active site of the coupler a group that can form a compound having a development function when ηF is released from the active site.
couplers, such as British Patent No. 935.454;
U.S. Patent No. 3,227,554, U.S. Patent No. 4,095.9
No. 84 and No. 4,149,886.

The above-mentioned DIR coupler has a property of forming a dye while releasing a development inhibitor when the coupler core undergoes a coupling reaction with a fused form of a color developing agent. The present invention also includes U.S. Pat. Nos. 3,652,345 and 3,928,
No. 041, No. 3,959,993, No. 3.961
．． No. 959, No. 4,052,213, 2iiil, 1te f Kaikyo No. 53-11, No. 529, No. 54-1333
No. 3, No. 55-161237. When the light color j'J is reacted with the oxidized product of the main mulberry as described in each publication, the developer J1'il inhibitor is released υN. , compounds that do not form pigments are also included.

Furthermore, in Japanese Patent Application Laid-open No. 145135, JJ1
When reacted with the oxidized color developing agent as described in No. 6-114946 and Japanese Patent Application No. 56-39766, the mother nucleus forms a dye or a colorless compound of C1;
The present invention also includes so-called timing DIR compounds, which are compounds in which the false timing group releases a development inhibitor through an intramolecular nucleophilic plate reaction or dethermal reaction. 57-45807
It also includes a timing DIR compound in which a timing group as described above is bonded to a coupler core that produces a completely diffusible dye when reacted with an oxidized color developing agent as described in the above.

Typical specific examples of the D-R compound preferably used in combination with the coupler according to the present invention in Immortal I-J are described below.

(Flash compound) (D-IJ 1 (D-2) 1 H8 awl(s CD-4) H (D-5) H No.

N07 (D-8) 01 Next, in the present invention, the diffusion-resistant coupler that produces a diffusion-resistant dye used together with the coupler according to the present invention is a known dye that produces a diffusion-resistant dye of an appropriate color tone. Any of the generation couplers may be used. Such couplers may be included in lower IM 134 silver halide emulsion layers, in which case couplers according to the invention that produce diffusible dyes are included in silver halide emulsion layers with the highest sensitivity. However, conversely, the above-mentioned known couplers may be contained in the maximum 11 ω degree emulsion layer, and the couplers according to the present invention may be contained in the low (i,!' 4 degree emulsion layer).

In the present invention, the amount of the DIR compound contained in the same layer as the layer containing the coupler according to the present invention is generally suitably in the range of 10 to 10 moles per mole of silver.

The above again? When using a diffusion-resistant coupler that generates a diffusion-resistant dye in the diffusion agent layer, the ratio of 1150 to 10
It is selectively used in the range of I weakening.

Furthermore, a colored coupler as a masking coupler can also be used in the light-sensitive material of the present invention.The colored magenta coupler as a masking coupler is generally used at the active site of a colorless magenta coupler. Compounds substituted with a ruazo group are used, for example, in the United States! ff n's' No. 2゜801, l'i'1,
Same No. 2,983,608, Same No. 3,005. '712
No. 3,684,514, British Patent No. 93'7
．． 621 and JP-A-49-123625, JP-A No. 49-1
Compounds and products described in No. 31448 and the like can be mentioned.

Additionally, colored magenta couplers of the type described in U.S. Pat. No. 3,419,391, in which the dye is leached into the processing bath 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 an arylazo group is substituted at the active site of a cuffless cyan coupler is used, for example, U.S. Pat. No. 2,521,908 and U.S. Pat. No. 1,255,111, Japanese Unexamined Patent Publication No. 48-22028, and the like.

Furthermore, U.S. time d1 No. 3,476,563, Japanese Unexamined Patent Application Publication No. 1973-
It is also possible to use colored cyan couplers of the type in which a color patch flows out into the processing bath by reaction with the oxidation product of a color developing agent, such as those described in No. 101-35 and No. 50-123341. can.

Further, in order to improve photographic properties, a coupler that forms a colorless dye, sometimes called an i'4 concatenating coupler, can be included.

1.4 yl used in the present invention
, a reducing agent or an anti-butylation agent, such as 1lIi (rQ !
Induction (M (tic t'! Sodium, potassium sulfate, etc.), J] (hydroxylamine, N-methylhydroxylamine, N-phenylhydroxylamine, etc.), sulfinic acids (sodium phenylsulfinate, etc.), hydrazines (N.

1-dimethylhydrazine, etc.), reductones (ascorbic fermentation, etc.), aromatic hydrocarbons containing one or more hydroxyls (p-teriminophenol, gallic acid, catechol, pyrokarol, resorcinol, '2.3
-Dihydroxynaphthalene, etc. 2 may be preferably used in combination with 2, etc. in order to sufficiently enhance the effects of the present invention.

Furthermore, in order to further improve the light fastness of the color image formed from the coupler used in the present invention, p-alkoxyphenols or phenolic compounds may be added to the emulsion layer containing the coupler or the V/R contact layer. can be added.

The layer structure of the light-sensitive material of the present invention may be formed by a conventional subtractive color method, and in principle, a yellow coupler to form a yellow dye in the blue-sensitive light-sensitive layer is mixed with a green! +j%ness 1+i;',
, a magenta coupler for forming a magenta dye in the T0 layer, and a cyan coupler for forming a cyan dye in the red-sensitive photosensitive layer, each having a multilayer structure of three layers. It is also preferable to improve photographic properties such as color development, color reproducibility, and granularity of coloring dyes. In addition to these basic emulsion layers, each layer such as a protective layer on the top layer, an intermediate layer between the layers, a single filter layer, an undercoat layer and an anti-drifting layer on the bottom layer are appropriately used. , storage stability, prevention of color staining, improvement in graininess, improvement in color reproduction, improvement in film adhesion time, etc.

These emulsion layers as well as other layers are made of laminated paper,
It is coated on a suitable support such as cellulose acetate or polystyrene by a known method.

The above silver halide emulsions include 1-phenyl-5-mercaptotetrazole, 3-methylbenzothiazole, 4- hydroxy-6
Various compounds such as heterocyclic compounds such as -methyl-1,3゜3a, 7-tetrazyindene, mercapto compounds, metal salts, etc. can be added.

The hardening of the emulsion is carried out according to conventional methods.

A surfactant may be added alone or in combination to the above silver halide emulsion. These surfactants include coating aids, emulsifiers, permeability improvers for processing solutions, antifoaming agents, antistatic agents, anti-corrosion agents, and various other agents for improving photographic properties or controlling physical properties. activators can be used.

In addition, in the silver halide photographic and optical materials of the present invention, unnecessary fogging and contamination due to air oxidation of the aromatic primary amino developing agent can be prevented, and the order of the developing agent to the i-contact layer during development can be improved. In order to prevent color mixing due to diffusion of reaction products, the silver halide emulsion layer or intermediate layer is coated with U.S. Pat.
No. 659, No. 2,732,300, No. 3,700
It is useful to use alkyl-substituted hydroquinone compounds disclosed in , 453, JP-A-5Q-15438, and Japanese Patent Application No. 54-2551.

The outline of the method for incorporating the coupler according to the present invention into the photosensitive material of the present invention has been described above, but in more detail, the coupler can be incorporated in the coating solution of the constituent layers in various forms by the following method. .

For example, as described in Honjin Patent No. 2,322,027 (
It can also be contained dissolved in a high boiling point solvent as described in US Pat. No. 2,801.1 '70
As described in the specification, the coupler and the high-boiling point solvent can be separately dispersed into fine particles and then mixed for use, and in the method using these dispersions, a low-boiling point solvent can be used. is also cited as a preferred method. In this case, the compound according to the invention (': i coupler and:
ll'i', it is possible to use a combined IFZ or to use ITJ separately from the coupler,
In addition, low υ (when using a point solvent, U.S. Patent No. 2
, 801.1 Specification No. '71 or Special Publication No. 1984-8
It is also possible to remove the low boiling point solvent from the dispersion by the method described in Japanese Patent No. 099.

Among the applicable solvents, +X(6
iJ point m fJJ, then dibutyl phthalate, dioctyl phthalate, diindecyl phthalate, triphenyl phosphate, tricresyl phosphate, diethyl laurylamide, dibutyl lauryl amide, pencil phthalate, monophenyl-p-1-butylphenyl phosphate, phenoxyethanol, Diethylene glycol monophenyl ether, di-methoxyethyl-7
talate, hexamethylphosphoramide, and further US Pat. No. 3, '779. '765 Meikyogata, JP-A-49-
No. 90523 and Japanese Patent Publication No. 48-29060 mention 1 (high-temperature point solvents that are immiscible with water). Also, as low Jtj point solvents, for example, methyl isobutyl ketone, β-ethoxy ethyl acetate,
Methoxytriglycol acetate, acetone, methyl acetate, methanol, ethanol, acetonitrile,
Examples include dioxane, dimethylpolamide, dimethyl sulfoxide, ethyl acetate, butyl acetate, isopropyl acetate, butanopechloroform, cyclohexane, cyclohexanol, fluorinated alcohol, etc. These low boiling point solvents can be replaced with high boiling point solvents. It can be used in combination with a high boiling point solvent, and each of these solvents can be used alone or in combination of two or more.

In the case of the coupler according to the present invention, it is also possible to use the Fischer type, that is, by dissolving it in an alkaline solution, and one of the coupler and the coupler according to the present invention can be used by a dispersion method, and the other can be used by a Fischer type method. They can also be added in the same layer.

The older color developing agent used in processing the photosensitive material of the present invention is:
pH including developing agent is 8 or more, preferably Gt pH 9
It is an alkaline aqueous solution. This aromatic primary amino developing agent as a developing agent is a compound having 7 primary amino groups on an aromatic ring and has the ability to develop exposed silver halide, or forms such a compound. Preparation of the precursor.

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

4-amino-N, N-diethylaniline, 3-methyl-4-termino-N, N-diethylaniline, 4-amino-N-ethyl-N-β-hydroxyethyluniline, 3-methyl-4-terminol Minnow N-engine f/L'= N-β-
Hydroxyethyl Ryoji'Jl/, 3-Methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-N-
β-Methoxyethylaniline, 3-β-methanesulfonamidoethyl-4-ami/-N,N-diethylaniline, 3-methoxy-4-diminol: J-ethyl-N-β
-Hydroxyethylaniline, 3-methoxy-4-amino-N-ethyl-β-methoxyethylaniline, 3-acetamido-4-amino-N,N-diethylaniline,
4-ami/-N,'N-dimethylaniline, N-ethyl-N-β-[β-(β-methoxyethoxy]ethoxy]
Ethyl-3-methyl-4-aminoaniline, N-ethyl-N-β-(β-methoxyethoxylessethyl-3-methyl-4-aminoaniline and salts thereof, such as sulfate, hydrochloride, sulfite, p -) luenesulfonate, etc.

Furthermore, JP-A-48-64932@, JP-A No. 50-131526
No. 51-95849, and the compounds described in Bent et al., Journal of American Chemical Society, Vol. 73, pp. 3100-3125 (195), etc. can also be used. The color developing solution may contain various additives as necessary, such as alkaline agents, pHB buffers or buffering agents, development accelerators,
Antifoggants, preservatives, etc. are added.

1. of the present invention. The f3 optical material is imagewise exposed (1), and after a color development process, a bleaching process is carried out by a conventional method (4).

This place 8! C. It may be done simultaneously with the fixation or separately. This processing solution can also be used as a bleach-fixing bath by adding a fixing agent if necessary. Various compounds can be used as bleaching agents, and bleaching accelerators and other additives can also be added.

Hereinafter, misfired IIA will be specifically described using actual ffR examples, but the present invention is not limited thereto.

Example 1 On a subbed cellulose triacetate film support, a coupler according to the present invention and a comparative coupler as shown in Table 1 below were placed on a subbed cellulose triacetate film support, each having the same type as the coupler! A mixture of tricresyl phosphate and 3 times 1 liter of ethyl acetate was dissolved in a 10% water bath solution of 20M and 5% of alkanol B (argylnaphthalene sulfonate, manufactured by DuPont). Gelatin aqueous solution 2
00ml and ci were combined and emulsified in a colloid mill to obtain an IL compound.Additionally, 1'j of this amount was added to 1:JI chromaticity iodobromideffl+< emulsion (7 mol% iodide) A hardening agent and 40 rnl of a 2% aqueous solution of 1,2-bis(hinylsulfonylnoethane) were added and coated.

Coating of the obtained halogenated poly(J), i-sensitive (C) material
2 Y / 100 crl, and the molar ratio of coupler and silver is 5%, and the coupler is equivalent to 5%, and 2 of the sum of the weights of gelatin, coupler salt At, and tricresyl phosphate.
The coupler according to the present invention and the comparative coupler were each adjusted so as to be twice as old as 6 as shown in Table 1.
Seed samples were prepared.

Comparison coupler [A] e Comparison coupler [B] (JP-A-57-82837@iie
Comparative Coupler [C] (Special U Ishisho 56-135841-kun/Sidadaki Cabrara Comparison Coupler "D") (American Material II'i-No. 4,310.
(No. 618, 1, 21, 4 couplers) Each sample thus prepared was subjected to wedge exposure using the usual method, and then subjected to the following process (1) and color development using a processing solution to obtain LI-resistance. The characteristic values of each sample are shown in Table 1 below.

[Treatment Step] Treatment Step (38° C.) The composition of the treatment liquid used in the js4j treatment step during treatment is as follows.

[Light color developer composition] [Bleaching solution composition] [Fixer composition] [Stabilizing solution composition] The results of the samples developed as described above are shown in Table 1 below. It was expressed as relative sensitivity 11α when set to 100.

Table 1 above t! As is clear from Table 31, compared to sample GJ of the present invention containing 6 ka'7' 5- and samples other than the present invention containing comparative sword blur, there was no fogging. You can see that it is low, has high sensitivity, and has a large color development.

Embodiment 2 In the example, the removal rate of the coupler according to the present invention was controlled, and as shown in Table 2 below, the amount used was decreased compared to the soft coupler, and the characteristic curve was changed compared to that of the soft coupler. After adjusting the additive i11 so that it did not match with the soft coupler [A], an emulsified dispersion was prepared in the same manner as in Fruit Densei 1, and six types of 0-sensitivity materials were prepared.

The obtained 61F+li sample was treated in the same manner as in Example 1, and the MT? A curve was created and the MTF (support) at 1 spatial frequency 30 cycles/dragon and the RMS granularity at a concentration of 0.6 were determined by Zu (the
Theory of Photographic Processes, 4th Edition, p. 619, by T.H. It is shown in Table 2.

Table 2 As shown in the results of Table 2 above, the coupler according to the present invention does not deteriorate the compatibility with photographic materials even when the amount used is reduced, and is effective in thinning the film compared to the 1:2 coupler. It also turned out to be a suitable coupler. Moreover, it has excellent sharpness, and even when it has graininess, it is better able to fit in than the comparison sample! +ta.

Example 3 On a subbed cellulose triacetate film support, the couplers and occlusion couplers according to the present invention as shown in Table 3 below were coated with the same amount of tricresyl phosphate as the occlusion couplers. Mixture of 3 different amounts of vinegar with Iψethyl/Iri ni Wei! ! l'tL/, this bath liquid? Emulsification and dispersion was carried out in the same manner as in Example 1, and the same 4=
1. A sample of Sensitive C material was obtained by performing the following operations to bring the Comparative Coupler [1] below into contact with the Special White White.

Ratio t; Coupler EE] H Comparison coupler [F] (special fur JIJ 57-8283
No. 7 4-mounted coupler] H 00HOI4H2p No. 00H Comparison coupler [G] (US L1,! Call number 4,310, 6
Caprano comparative coupler [H] described in No. 18 (Special L3 () IT%j 50-91
No. 3.23 Power Plano (IOH, C0NHCH20H200H).

Sample obtained as above (:↓, Jufugin: “l+’<
1j) 12 rru; 1/100-, the molar ratio of the coupler to the carbon dioxide corresponds to 25% of the coupler, and the gelatin is the sum of the volume of the coupler and the tricresyl phosphate mass σ'+ 2 (ilf' This is a 1:I compound obtained by adjusting a coupler according to the present invention and a comparative coupler so as to have a 1:I ratio.

The above test'; Shown in Figure 3.

Table 3 As shown in Table 3 above, based on the characteristic values exhibited by the samples of the present invention, the turnips according to the present invention can reduce the number of feet used, and have better sharpness and graininess than the comparative samples. It can be seen that it is excellent.

Example 4 11 g of the comparative coupler [E] was applied to the body of a subbed cellulose triacetate film support, and 11 ml of the comparative coupler [E] was applied! and 30 ml of ethyl acetate, and this solution was mixed with 20 10% aqueous alkanol solution and 200 M of 5% seratin water bath solution, and emulsified in a colloid mill to create an emulsified dispersion. 11i silver iodobromide emulsion (containing 4 mol% silver iodide), coating scissors ht 2 o my / 100 c
rl, the molar ratio of coupler to silver was adjusted so that the coupler was 10%, and this was coated and dried. On the sample obtained in this way, 8 types of samples prepared in Example 3 (13 to 20 test samples) were coated in layers, respectively. 1,2-
Bis-(vinylsulfonylnoethane 2% water '76 W
I kept 40 ml of water in one cup.

The obtained sample was treated in the same manner as in Example 2, and the MTF (MTF) and RMS (im) were determined in one filtration, and the obtained results are shown in Table 4 below.

Table 4 According to Table 4 above, the samples of the present invention (sample 'ji'r&2
5-28), in addition to the improvement in sharpness due to the reduction in the use of couplers, it is thought that the contrast effect due to the diffusive color formation has a synergistic effect on the improvement of sharpness. The sharpness is much better than that of the . Regarding granularity, the sample containing the comparative coupler [H] showed significant deterioration, and even the sample containing the comparative coupler [3] showed some deterioration in granularity. In the sample (ia), the graininess was also improved.

This is considered to be due to the wideness of the pigment cloud of the unidirectional dye according to the present invention.

Example Middle - Connecting to the formulation of sample 526 prepared in Example 4, the following Toko R coupler [technique] was used in the high-sensitivity emulsion layer so that the molar ratio of the coupler to the DIR compound was 5%. This was added to obtain a photosensitive material sample with a stable coating film on the entire surface. This sample was subjected to G treatment in the same manner as in Example 2, and the MTF (%) and RystHm were measured.

The edge effect is further accentuated by the action of the development inhibitor released from the DIR coupler.
Colors with outstanding graininess W tj! II statue? I was rejected.

DIR Coupler [1] Effects of the Invention The silver halide color photographic photosensitive material containing the coupler according to the present invention not only has high sensitivity and a large maximum density, but also has significantly improved graininess especially when it comes to sharpness. be done.

Yoshimi Kuwabara

Claims (1)

[Scope of Claims] A silver halide photographic material comprising, on a support, a silver halide emulsion layer containing a coupler represented by the following general formula [I]. General formula [I] Op'-Cp''-X [In the formula, OpI is a dye (A
), and Cp2 represents a coupler component capable of releasing ap'-x.
) to form a dye (B) exhibiting substantially the same hue as
represents a coupler component capable of releasing X, where X is the Qp
When tz reacts with the oxidized color developing agent,
represents a group or a hydrogen atom released from Op"-X. At least one of the color X (A) and the dye CB) is a silver halide emulsion layer containing a coupler represented by the general formula [I]. and represents a dye that is diffusible within an adjacent silver halide emulsion layer having substantially the same color sensitivity as that layer.]