JPS6263936A - Multi-color photographic element - Google Patents

Abstract

PURPOSE:To obtain a titled element having high sharpness and good granular characteristic by disposing low-sensitivity layers on the side further from a base than high-sensitivity emulsion layers. CONSTITUTION:A high-sensitivity unit UH having a high-sensitivity red-sensitive emulsion layer RH and high-sensitivity green-sensitive emulsion layer GH and a low-sensitivity unit UL having a low-sensitivity red-sensitive emulsion layer RL and low-sensitivity green-sensitive emulsion layer GL are formed on a base A successively from the base side and further a blue-sensitive emulsion layer B is formed thereon. Layer order of the layers GL and RL in the unit UL and the unit UH and layer order of the layers GH, RH are optional but the layers GL, GH are positioned on the side further from the base A than the layers RL, RH. The images which are not affected by the high-sensitivity layers are thereby formed in the low-sensitivity layers and since the low-sensitivity layers have smaller silver halide particles in general, the sharpness and granular characteristic are excellent and other photographic performances (sensitivity, etc.) are satisfactory as well.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention This invention relates to multicolor photographic elements. In particular, at least a high-sensitivity green-sensitive silver halide emulsion layer, a low-sensitivity green-sensitive silver halide emulsion layer, a high-sensitivity red-sensitive silver halide emulsion layer, and a low-sensitivity red-sensitive halogen emulsion layer are formed on the support. The present invention relates to a multicolor photographic element having a silveride emulsion layer.

[Conventional technology]

Multicolor photographic elements are required to improve their performance in various respects, and in particular, as photographic light-sensitive materials have become smaller in format in recent years, photographic elements are required to have higher image quality.

In the past, many proposals have been made in this type of technical field with the aim of increasing sensitivity or improving graininess, but among them:
Some attempts have been made to improve performance by improving the layer structure on the support.

For example, instead of containing red-sensitive, green-sensitive, and blue-sensitive silver halide emulsion layers alone, each color sensitivity may contain a highly sensitive emulsion layer (fasteremulsion layer).
1 ayer) and a low-speed emulsion layer (slowerem)
ulsion 1ayer) exist at the same time,
A technique is known in which each color sensitivity is composed of a high-sensitivity layer and a low-sensitivity layer.

It is also known to apply to photographic elements for color photography a unit composed of a plurality of layers, each layer of which is sensitized to the same three sets of visible spectra. GB 818,687 discloses that a relatively high sensitivity cyanogenic silver halide emulsion (sensitized for red light) is coated, for example, on another relatively low sensitivity emulsion with similar properties. As a result, it is disclosed that an increase in sensitivity (speed) can be obtained and an improvement in latitude can also be achieved.

It is believed that similar effects can be obtained if the technique disclosed in this British patent is applied to all three types of color composite units. However, sharpness and graininess are not a problem, and these points are still unsatisfactory.

Further, in U.S. Pat. No. 3,662,228, for example, in FIG. 1C thereof, a layer having relatively high sensitivity and having undergone blue light sensitization, green light sensitization, and red light sensitization is shown to have a relatively low sensitivity. It is shown coated above a sensitized emulsion layer corresponding to the above-mentioned layer. This allows the normal 3
It is contemplated to obtain photographic elements with increased latitude compared to layered color film elements. However, in the case of this US patent, the respective units of the relatively high-sensitivity emulsion layer and the relatively low-sensitivity emulsion layer are separated by an ND (neutral density) filter. Therefore, as will be clear from this, increasing speed and sensitivity are not problems of this US patent, nor are sharpness and graininess a particular problem. In this US patent,
It seems that these sharpness and graininess are still insufficient.

Next, in the specification of US Pat. No. 3,658,536, as shown in FIG. Although a technique has been disclosed in which the exposure loss of the layer is eliminated by locating the layer on the surface side farther away, this patent also fails to improve sharpness and graininess sufficiently.

For other techniques related to changing the layer structure, see JP-A No. 51. 49027, 53-97424, and US Pat. No. 4,129,446, etc. are known. However, in all of these, the effect of improving image quality such as graininess and especially sharpness of green-sensitive and red-sensitive emulsion layers was insufficient.

[Purpose of the invention]

An object of the present invention is to solve the problems of the prior art described above, and to provide an advantageous multicolor photographic element that has excellent sharpness and graininess, and also has sufficient other photographic performance (sensitivity, etc.). It is about providing.

[Structure and operation of the invention]

As a result of intensive research, the present inventors have discovered that a multicolor photographic element having the following layer structure satisfies the above object.

That is, the multicolor photographic element of the present invention comprises at least a high-sensitivity green-sensitive silver halide emulsion layer, a low-sensitivity green-sensitive silver halide emulsion layer, and a high-sensitivity red-sensitive silver halide emulsion layer on a support. A multicolor photographic element comprising a red-sensitive silver halide emulsion layer and a low-speed red-sensitive silver halide emulsion layer is characterized by the following (a) to (c).

(a) The high-sensitivity green-sensitive emulsion layer and the high-sensitivity red-sensitive emulsion layer constitute a high-sensitivity emulsion unit (g)) The low-sensitivity green-sensitive emulsion layer and the low-sensitivity The red-sensitive emulsion layer constitutes a low-sensitivity emulsion unit (c1) The high-sensitivity emulsion unit is located closer to the support than the low-sensitivity emulsion unit 7. thing.

Conventionally, it was common sense to arrange a high-sensitivity emulsion unit at a position far from the support and receive incident light with the high-sensitivity unit, thereby achieving high sensitivity. It has never been thought of to arrange this highly sensitive emulsion unit in a position close to the support as in the above-mentioned FCL of the present invention, and the structure of the present invention is completely new and difficult to predict. However, the fact that the above-mentioned improvement in sharpness and graininess is achieved by the configuration of the present invention means that
This is truly surprising.

The effect of the present invention is not necessarily clear, but since the low-sensitivity emulsion layer makes a large contribution to the formed image, the low-sensitivity layer is disposed on the side farther from the support than the high-sensitivity emulsion layer. By doing this, an image is formed in the low-speed layer that is not affected by the high-speed layer, and since the silver halide grains are generally smaller in the low-speed layer, it is possible to obtain images with high sharpness and good graininess. It is assumed that.

According to the present invention, the graininess in the high exposure range, which has been a problem in the past, can be made particularly good.

In the present invention, the high-sensitivity green-sensitive emulsion layer and the high-sensitivity red-sensitive emulsion layer are preferably arranged adjacent to each other in the high-sensitivity emulsion unit. When they are placed adjacent to each other, it is preferable to insert an intermediate layer between them. The order of the green-sensitive emulsion layer and the red-sensitive emulsion layer is arbitrary. Preferably, the green-sensitive emulsion layer is located farther from the support than the red-sensitive emulsion layer.

In the present invention, it is also preferable that the low-sensitivity green-sensitive emulsion layer and the low-sensitivity red-sensitive emulsion layer are arranged adjacent to each other in the low-sensitivity emulsion unit. In this case as well, an intermediate layer may be inserted between them, and the order of the green-sensitive emulsion layer and the red-sensitive emulsion layer is arbitrary. Preferably, the green-sensitive emulsion layer is located farther from the support than the red-sensitive emulsion layer.

In the present invention, the sensitivity difference between the high-sensitivity emulsion layer and the low-sensitivity emulsion layer is preferably 0.2 to 2.0 [ogE (E; exposure amount)].

When implementing the multicolor photographic element of the present invention, a configuration as illustrated in FIG. 1 can be adopted.

That is, in order from the support A side, the high-speed red-sensitive emulsion layer RH
and a high-sensitivity green-sensitive emulsion layer GH)
H1 low-sensitivity red-sensitive emulsion layer RL and low-sensitivity green-sensitive emulsion layer GL
A photographic element for color photography can be obtained by further forming a blue-sensitive emulsion layer B on the low-sensitivity unit UL.

It is preferable to cover the blue-sensitive emulsion layer B and provide a protective layer P on the outermost surface. The protective layer P is preferably one or two layers. In terms of protective function, two layers are preferred.

When a blue-sensitive emulsion layer is provided, it is preferably one or more than two layers and three or less layers. As shown in the figure, it can be composed of two layers: high-speed and low-speed blue-sensitive emulsion layers BH and BL.

A yellow filter layer Y is placed on the support side of the blue-sensitive emulsion layer B.
It is preferable to provide C. This is a single layer of filter that is yellow and contains colloidal silver, yellow dye, etc. For example, blue absorption of 0.05 or more can be used.

The layer order of the low-sensitivity green-sensitive and red-sensitive emulsion layers OL and RLO in the low-sensitivity unit UL and high-sensitivity unit UH, and the layer order of the high-sensitivity green and red-sensitivity emulsion layers GH1RH are arbitrary as described above, but the diagram In both cases, green-sensitive emulsion layers GL and GH
is located on the side farther from the support A than the red-sensitive emulsion layers RL and RH. In addition, in the illustration, the emulsion layers of each unit UL and UH are adjacent to each other, and the emulsion layers of each unit are adjacent to each other.
and RL,,GH11! :RH can be formed adjacent to each other.

An intermediate layer can be provided between each layer. For example, as shown in the figure, an intermediate layer IL can be provided between the UL and UH units. The intermediate layer contains scavengers, DIR compounds,
It may contain dyes (which may be diffusible or non-diffusible) and the like.

Each color sensitive layer may have a medium speed emulsion layer. When a medium-sensitivity layer is provided, the sensitivity difference between the high-sensitivity layer and the medium-sensitivity layer is 0.
1~1.0 j! It is preferable that the difference in sensitivity between the medium sensitivity layer and the low sensitivity layer is 0.1 to 1.0 ffogE.

Next, the emulsion used in the present invention will be described.

The silver halide emulsion used in the present invention includes any silver halide used in conventional silver halide emulsions such as silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide, and silver chloride. You can use things.

In the present invention, the silver halide grains used in the silver halide emulsion may have a uniform silver halide composition distribution within the grain, or a core/shell in which the silver halide composition differs between the grain interior and the surface layer. Although they may be particles, those having a core-shell structure are preferred. In the case of a core-shell structure, it is preferable to use silver iodobromide as the silver halide.

For example, a core having a silver halide composition of silver halide containing 3 to 40 mol% of silver iodide and a silver halide coated with silver halide having a silver iodide content of 0 to 10 mol% It is possible to use a shell consisting of a shell having the same composition and a difference in silver iodide content between the shell and the core being 2 to 30 mol%.

The change in the silver iodide content at the boundary between the core and the cylinder may be continuous or stepwise. There is no problem even if there is a part of the silver iodide content (for example, the part corresponding to the seed grain -t in manufacturing) where the silver iodide content is 0.The thickness of the shell is 217. It is preferable that the thickness of the shell is sufficient to hide the undesirable qualities of the core.
Preferably, the silver halide grains are in the range of 0.01 to 0.3 pm.

The silver halide grains used in the present invention have the above-mentioned core/
It is preferable that shell type silver halide grains account for 70% or more of all grains in the same silver halide emulsion layer, and it is particularly preferable that all the grains are core/shell type silver halide grains.

Such core/shell type silver halide grains may be used alone, or it is preferable to use a mixture of two or more types of silver halide grains having different average grain sizes.

Further, two or more kinds of core/shell type silver halide grains having different silver iodide contents can be preferably used as a mixture.

Further, in the present invention, the emulsion is preferably monodisperse. That is, when the standard deviation S of the particle size distribution is divided by the average particle size 〒, the value is preferably 0.20 or less. More preferably, it is 0.15 or less. Note that in the case of spherical silver halide grains, the grain size here refers to the diameter,
Alternatively, in the case of particles having a shape other than a cube or a sphere, the diameter is the diameter when the projected image is converted into a circular image with the same area.

The average grain size of silver halide grains in each high-speed emulsion is 0.4~
The average grain size of the silver halide grains in each low-speed emulsion is preferably 0.1 to 1.0 .mu..

When a medium-speed emulsion is used, the average grain size of the silver halide grains is preferably 0.2 to 1.5 microns.

In the green-sensitive silver halide emulsion layer of the present invention, pyrazolone compounds, indacylon compounds, cyanoacetyl compounds, etc. can be used as magenta couplers.

A specific example of a magenta coupler that can be used is disclosed in JP-A-49-1
No. 11631, No. 56-29236, No. 57-947
No. 52, Japanese Patent Publication No. 48-27930, U.S. Patent No. 2,60
No. 0,788, No. 3,062, No. 653, No. 3,408
．． No. 194-, No. 3,519.429 and Research
There is one described in Disclosure No. 12433.

Furthermore, a pyrazoloazole compound represented by the following formula and other pyrazoloazole compounds can be used.

XI N -----, -N In the formula, Z represents a group of nonmetallic atoms necessary to form a nitrogen-containing heterocycle.

XI represents a hydrogen atom or a substituent that can be separated by reaction with an oxidized product of a color developing agent.

R represents a hydrogen atom or a substituent.

Colored magenta couplers can be used in combination with the green-sensitive silver halide emulsion layer, and examples of colored magenta couplers that can be used in combination include U.S. Pat. Examples include those listed in No.

The red-sensitive silver halide emulsion layer of the present invention contains a phenolic compound as a cyan coupler, such as a group selected from a phenylureido group, a naphthylureido group, and a peterocyclic ureido group at the 2-position, and a ureido compound having an acylamino group at the 5-position. Type phenolic cyan color-forming couplers, nephthol compounds, etc. can be used.

Specific examples include U.S. Patent No. 2,423,730;
474, No. 293, No. 2,895,826, and Japanese Unexamined Patent Publication No. 117422/1983.

A common colored cyan coupler can be used in combination with the red-sensitive silver halide emulsion layer. As a colored cyan coupler, Japanese Patent Publication No. 55-32461 and British Patent No. 1
, No. 084,480, etc. can be used.

Further, when a blue-sensitive silver halide emulsion layer is provided, various closed ketomethylene couplers can be used as the yellow coupler used in the layer. Among these, benzoylacetanilide and pivaloylacetanilide compounds can be advantageously used. For example, a benzoyl type yellow coloring coupler represented by the following formula can be used.

In the formula, R1, R2, and R3 may be the same or different, and each is a hydrogen atom, a halogen atom, or an alkyl group.

Aryl group, alkoxy group, acylamino group, carbamoyl group, alkoxycarbonyl group, sulfonamide group,
Or represents a sulfamoyl group.

R4, R9, Rh and R? may be the same or different,
Each represents a hydrogen atom, an alkyl group, an alkoxy group, an aryloxy group, an acylamino group, or a sulfonaromide group.

W is a halogen atom, an alkyl group, or an alkoxy group.

Represents an aryloxy group or a dialkylamiquino group.

X represents a hydrogen atom or a detachable group.

Specific examples of yellow couplers are disclosed in Japanese Patent Application Laid-Open No. 47-26133,
No. 48-29432, No. 50-87650, No. 51
-17438, No. 51-102636, Special Publication No. 1977
-19956, 46-19031, 51-33
No. 410, No. 51-10783, U.S. Patent No. 2,875
, No. 057, No. 3,408,194, No. 3,519.
There are those described in No. 429, etc.

The amount of coupler used in the multicolor photographic elements of this invention is generally preferably from 2X10-3 to 1 mole per mole of silver in the emulsion layer, more preferably from 1X10-'' to 8X10-
'Use moles.

The silver halide emulsion used in the present invention can be used after being sensitized by appropriate means.

That is, the silver halide emulsion contains activated gelatin; sulfur sensitizers such as allylthiocarbamide, thiourea, and cystine; selenium sensitizers; reduction sensitizers such as stannous salts, thiourea dioxide, and polyamines. etc.1 Noble metal sensitizers such as gold sensitizers, specifically potassium aurithiocyanate,
Sensitizers such as potassium chloroaurate, 2-orothio-3-methylbenzothiazolium chloride, or water-soluble salts such as ruthenium, palladium, platinum, rhodium, iridium, specifically ammonium chlorovaladate, potassium chloroaurate, etc. (These kinds of substances act as sensitizers or fog suppressants depending on the amount.) alone or in combination as appropriate.
For example, chemical sensitization may be performed using a combination of a gold sensitizer and a sulfur sensitizer, a combination of a gold sensitizer and a selenium sensitizer, etc.).

The silver halide emulsion used in the present invention is chemically ripened by adding a sulfur-containing compound, and before, during, or after this chemical ripening, the silver halide emulsion is converted into a nitrogen-containing emulsion having at least one hydroxytetrazaindene and mercapto group. It may also contain at least one type of terocyclic compound.

The silver halide used in the present invention is mixed with an appropriate sensitizing dye at 5X10-1' to 3X10-' per mole of silver halide in order to impart photosensitivity in the desired wavelength range.
Optical sensitization may be achieved by adding molar amounts.

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

That is, examples of the sensitizing dye used in the blue-sensitive silver halide emulsion layer include West German Patent No. 929.080, US Patent No. 2,231.658, US Pat.
, No. 503.776, No. 2,519,001, No. 2,
No. 912.329, No. 3.656,959, No. 3.6
No. 72.897, No. 3,694,217, No. 4,02
No. 5,349, No. 4,046,572, British Patent No. 1,
No. 242.588, Special Publication No. 44-14030, No. 52
-24844 etc. can be mentioned. In addition, as sensitizing dyes used in green-sensitive silver halide emulsions, for example, U.S. Pat.
, No. 072,908, No. 2,739.149, No. 2,
Typical examples include cyanine dyes, merocyanine dyes, and composite cyanine dyes as described in No. 945,763, British Patent No. 505.979, and the like. Further, as sensitizing dyes used in red-sensitive silver halide emulsions, for example, U.S. Patent No. 2,269,23
No. 4, No. 2,270.378, No. 2.442.710
No. 2,454,629, No. 2, 776, 280
Typical examples thereof include cyanine dyes, merocyanine dyes, and composite cyanine dyes as described in No. Furthermore, U.S. Patent 2,213,9
No. 95, No. 2,493.748, No. 2.519,00
Cyanine dyes, merocyanine dyes or composite cyanine dyes such as those described in German Patent No. 1, German Patent No. 929.080, etc. can be advantageously used in green-sensitive silver halide emulsions or red-sensitive silver halide emulsions.

These sensitizing dyes may be used alone or in combination.

The multicolor photographic element of the present invention may be optically sensitized in a desired wavelength range by a spectral sensitization method using cyanine or merocyanine dyes or a combination thereof, if necessary.

A typical particularly preferred spectral sensitization method is, for example, Japanese Patent Publication No. 43-493 concerning the combination of benzimidazolocarbocyanine and benzoxazolocarbocyanine.
No. 6, No. 43-22884, No. 45-18433,
No. 47-37443, No. 48-28293, No. 49
No.-6209, No. 53-12375, JP-A-52-2
No. 3931, No. 52-51932, No. 54-8011
No. 8, No. 5B-153926, No. 59-116646
No. 59-116647 and the like.

Further, regarding the combination of carbocyanine having a benzimidazole nucleus with other cyanine or merocyanine, for example, Japanese Patent Publication Nos. 45-25831 and 47-11
No. 11.4, No. 47-25379, No. 48-3840
No. 6, No. 4B-38407, No. 54-34535,
No. 55-1569, JP-A No. 50-33220, No. 5
No. 0-38526, No. 51-107127, No. 51-
No. 115820, No. 51-135528, No. 52-1
No. 04916, No. 52-104917, and the like.

Furthermore, regarding combinations of benzoxazolocarbocyanine (oxa-carbocyanine) and other carbocyanines, for example, Japanese Patent Publication Nos. 44-32753 and 46
-11627, Japanese Unexamined Patent Publication No. 1483/1983, and Japanese Patent Publication No. 38408/1983 regarding merocyanine.
No. 48-41204, No. 50-40662, JP-A No. 56-25728, No. 58-10753, No. 5
B-91445, No. 59-116645, No. 50-
No. 33828 etc. are mentioned.

Regarding combinations of thiacarbocyanin and other carbocyanins, for example, Japanese Patent Publications Nos. 43-4932, 43-4933, 45-26470, and 46
No.-18107, No. 47-8741, JP-A-59-4
No. 14533, etc., and the method described in Japanese Patent Publication No. 49-6207, which uses zeromethine or dimethine merocyanine, monomethine or trimethine cyanine, and styryl dye, can be advantageously used.

In order to add these sensitizing dyes to the silver halide emulsion used in the present invention, a dye solution containing, for example, methyl alcohol, ethyl alcohol, acetone, dimethylformamide, or a fluorinated alcohol as described in Japanese Patent Publication No. 40659/1982 is added in advance. It is used by dissolving it in a hydrophilic organic solvent such as

The addition may be made at any time such as at the start of chemical ripening of the silver halide emulsion, during ripening, or at the end of ripening, and in some cases, it may be added at a step immediately before coating the emulsion.

In a preferred embodiment of the present invention, a compound (hereinafter referred to as a DIR compound) that releases a development inhibitor or its precursor by reacting with an oxidized form of a color developing agent is added to at least one of the light-sensitive silver halide emulsion layers. More preferably, when the light-sensitive silver halide emulsion layer is composed of two or more layers having different sensitivities, the high-sensitivity layer (BH) of the blue-sensitive silver halide emulsion layer , the high-speed layer (GH) of the green-sensitive silver halide emulsion layer, and the high-speed layer (RH) of the red-sensitive silver halide emulsion layer.

Typical examples of DIR compounds include DIR couplers in which a group capable of forming a compound having a development-inhibiting effect when separated from the active site is introduced into the active site of the coupler; for example, British Patent No. 935,454; US Patent 3,
227, No. 554, 4. Q95,984, same 4,
No. 149,886, JP-A-57-151944, etc. The above-mentioned DIR coupler has the property that, when subjected to a coupling reaction with an oxidized form of a color developing agent, the coupler core forms a dye while releasing a development inhibitor.

Further, the present invention is disclosed in US Pat. No. 3,852,345 and US Pat.
No. 928.041, No. 3,958,993, No. 3,9
No. 61.959, No. 4,052,213, JP-A-53
-110529, 54-13333, 55-1
Also included are compounds that release a development inhibitor when subjected to a coupling reaction with an oxidized form of a color developing agent, such as those described in No. 61237, but do not form a dye.

Furthermore, JP-A-54-145135 and JP-A-56-1
When reacted with oxidized color developing agents such as those described in No. 14946 and No. 57-154234, the mother nucleus forms a dye or a colorless compound, while the released timing group undergoes an intramolecular nucleophilic substitution reaction. Or so-called timing D, which is a compound that releases a development inhibitor through an elimination reaction.
IR compounds are also included in the invention.

Also, JP-A-58-160954, JP-A No. 5B-16294
Timing DI 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 described in No. 9.
It also includes R compounds.

More preferred DIR compounds used in the present invention can be represented by the following general formulas (1) and [■], and among these, the most preferred DIR compound is a compound represented by the following general formula (H).

General formula (1) % formula % In the formula, Coup is a coupler component (compound) that can couple with the oxidized form of a color developing agent, such as open chain ketomethylene compounds such as acylacetanilides and acylacetic acid esters, pyrazolones, and pyrazolones. Zolotriazoles,
These are dye-forming couplers such as pyrazolinobenzimidazoles, indasilones, phenols, and naphthols, and coupling components that do not substantially form dyes such as acetophenones, indanones, and oxacylones.

In addition, the inhibitor in the above formula is a component (compound) that is released by reaction with a color developing agent and inhibits the development of silver halide.
and preferred compounds include benztriazole,
There are heterocyclic compounds and heterocyclic mercapto compounds such as 3-octylthio-1,2°4-triazole and the like.

Examples of the above-mentioned heterocyclic group include a tetrazolyl group, thiadiazolyl group, oxadiazolyl group, thiazolyl group, oxasilyl group, imidazolyl group, triazolyl group, and the like. Specifically, 1-phenyltetrazolyl group, 1-ethyltetrazolyl group, 1-(4-hydroxyphenyl)tetrazolyl group, 1,3.4-thiazolyl group,
Examples include 5-methyl-1,3,4-oxadiazolyl group, benzthiazolyl group, benzoxasilyl group, benzimidazolyl group, and 4H-1,2,4-triazolyl group.

In addition, in the above general formula (1), the inhibitor is bonded to the active site of (:oup.

General formula [■] Coup-TIME-inhibitor In the formula, the inhibitor is the same as defined in general formula N) above. Coup also includes a coupler component that produces a diffusible dye, similar to that defined in general formula N). TIME is the general formula (Tl'['l (I
V) is represented by (V'l and [VI), but is not limited to these.

It represents the general formula (I11'1, where X2 represents an atomic group necessary to complete the benzene ring or naphthalene ring. Y' represents an alkyl group or an alkyl group), and the coupling position is combined. Further, R'' and R12 are bonded to U7 atom 7-, each of which represents a group having the same meaning as the above-mentioned RIff.

-・General formula (IV)! ? 15 In the formula, W is a group having the same meaning as Y in the general formula Cl11), and R14 and RI5 are also each represented by the general formula (II[
) in R eyes and 6R' which is a group synonymous with RI 2
6 is a hydrogen atom, an alkyl group, an aryl group, an acyl group, a sulfone group, an alkoxycarbonyl group, a heterocyclic residue; It represents an amino group, an acylamido group, a sulfonamide group, a carboxy group, an alkoxycarbonyl group, a carbamoyl group, and a cyan group. This timing group is then bound by W to the coupling position of Coup, forming I5.

Next, an example of a timing group that releases an inhibitor by an intramolecular nucleophilic substitution reaction is shown by the general formula [■].

General formula (V) Nu ■ V-1! In the formula, Nu is a nucleophilic group having an electron-rich oxygen, sulfur or nitrogen atom and is attached to the CoupO coupling position. E is an electrophilic group having a carbonyl group, a thiocarbonyl group, a bosphinyl group, or a thiophosphinyl group that is electron symmetric, and is bonded to the heteroatom of the inhibitor. ■ is Nu! =IF, and after Nu is released from Coup, it undergoes an intramolecular nucleophilic substitution reaction accompanied by the formation of a 3- to 7-membered ring, and thereby releases the inhibitor. It is a bonding group that can

General formula (Vl) Coup-OCtt2-inhibitor Coup and inhibitor have the same meanings as above.

The DIR compound described above is preferably added to the photosensitive silver halide pore agent layer.

In the present invention, two or more types of DIR compounds may be included in the same layer. The same DIR compound may also be included in two different layers.

These DIR compounds are generally preferably used in amounts of 2X10-' to 5XIO-' moles, more preferably 2X10-' to 5X10-2 moles per mole of silver in the emulsion layer.

In the silver halide emulsion layer and other photographic constituent layers in the multicolor photographic element of the present invention, non-diffusible couplers, polymer couplers, etc., which react with the oxidized form of a developing agent to form a diffusible dye that bleeds moderately, are included. The real groan [ri double gotokinno (1 k 1-' L-lassies-so-t and Yashima 12 Mahi =
You may also use the couplers of shi(ri5tokuL11-sai1-tsu14) and φrumor=. Regarding the non-diffusible couplers that react with the oxidized form of these development-1 pigments to produce a diffusible dye that bleeds moderately, the present applicant's patent application No. 59-193611
For the description of the issue, and for the polymer coupler, please refer to the patent application filed in 1973.
9-172151 can be referred to.

The method of adding the DIR compound and the like is substantially the same as that of adding the magenta coupler and the like. That is, in order to incorporate the DIR compound etc. into a coating solution for a silver halide emulsion or other photographic constituent layer, if the DIR compound etc. is alkali-soluble, it may be added as an alkaline solution; In the case of silver halide, silver halide is dissolved in a high boiling point solvent (HBS) in combination with a low boiling point solvent (LBS) as necessary according to the method described in the above-mentioned US patent specification, and dispersed in fine particles. Preferably, it is added to the emulsion. At this time, if necessary, other hydroquinone derivatives, ultraviolet absorbers, anti-fading agents, etc. may be used in combination. It is also possible to use a mixture of two or more DIR compounds. Furthermore, to explain in detail the preferred method of adding DIR compounds, etc. in the present invention, one or more kinds of DIR compounds, etc. are added together with other couplers, hydroquinone derivatives, anti-fading agents, ultraviolet absorbers, etc. as necessary. Organic acid amides, carbamates, esters, ketones, urea derivatives, ethers, hydrocarbons, etc., especially those dissolved in the high boiling point solvent (TBS) and/or the low boiling point solvent (LBS). is mixed with an aqueous solution containing the anionic surfactant and/or nonionic surfactant and/or hydrophilic binder, emulsified and dispersed using a high-speed rotating mixer, and added to the silver halide emulsion.

In addition, the above-mentioned DIR compounds and the like may be dispersed using a riot latex dispersion method.

The multicolor photographic elements of this invention may contain various other photographic additives. For example, JP-A-46-212
8, U.S. Patent No. 2.72El, 659, and Research Disclosure Magazine 17643.
Antifoggants, stabilizers, ultraviolet absorbers, color stain inhibitors, optical brighteners, color image fading inhibitors, antistatic agents, hardeners, surfactants, plasticizers, wetting agents listed in the No. etc. can be used.

In the multicolor photographic elements of this invention, the hydrophilic colloids used to prepare the emulsion include gelatin, derivative gelatins, graft polymers of gelatin and other polymers, proteins such as albumin and casein, hydroxyethyl cellulose derivatives, Any of cellulose derivatives such as carboxymethyl cellulose, starch derivatives, single or copolymer synthetic hydrophilic polymers such as polyvinyl alcohol, polyvinylimidazole, and polyacrylamide are included.

Supports for the multicolor photographic elements of the present invention include, for example, baryta paper, polyethylene-coated paper, polypropylene synthetic paper, transparent supports provided with a reflective layer or in combination with a reflective material,
Alternatively, there are transparent supports such as glass plates, polyester films such as cellulose acetate, cellulose nitrate, or polyethylene terephthalate, polyamide films, polycarbonate films, and polystyrene films, and these supports are appropriately selected depending on the intended use of the photosensitive material. be done.

Various coating methods such as tipping coating, air doctor coating, curtain coating, and hopper coating can be used to coat the emulsion layer and other constituent layers used in the present invention. Also, U.S. Patent No. 2.76L791,
It is also possible to use a simultaneous coating method of two or more layers according to the method described in No. 941,898.

There are no particular limitations on the method of processing the multicolor photographic elements of the present invention, and any processing method can be applied.

For example, typical methods include a method in which bleach-fixing is performed after color development, followed by further washing and/or stabilization treatment if necessary; bleaching and fixing are performed separately after color development; A method of performing water washing and/or stabilizing treatment; or a method of performing prehardening, neutralization, color development, stop fixing, water washing, bleaching, fixing, water washing, post hardening, water washing, color development, water washing, supplementary color development There are two methods: developing, stopping, bleaching, fixing, washing, and stabilizing in the order of development, and halogenation bleaching of the developed silver produced by color development, followed by color development again to increase the amount of dye produced. It may be processed using a method.

The color developing solution used is, but is not limited to, an alkaline aqueous solution containing a color developing agent and having pi (preferably 8 or more, more preferably p) I of 9 to 12. The aromatic primary amine developing agent used as the color developing agent is a compound having a primary amino group on an aromatic ring and has the ability to develop silver halide exposed to light. Precursors that form such compounds may also be added.

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

4-Amino-N, N-diethylaniline, 3-methyl-
4-amino-N, N-diethylaniline, 4-amino-N-ethyl-N-β-hydroxyethylaniline, 3
-Methyl-4-amino-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-
Methoxyethylaniline, 3-methyl-4-amino N
-Methyl-N-β-methanesulponamidoethylaniline, 3-methoxy-4-amino-N-ethyl-N-β-
Hydroxyethylaniline, 3-methoxy-4-amino-N-ethyl-N-β-methoxyethylaniline, 3-
Acetamido-4-amino-N.

N-dimethylaniline, N-ethyl-N-β-[β-(
β-methoxyethoxy)ethoxy]ethyl-3-methyl-4-aminoaniline, N-ethyl-N-β-(β-methoxyethoxy)ethyl-3-methyl-4-aminoaniline, and salts thereof such as sulfate, hydrochloric acid salt, sulfite,
p-) luenesulfonate and the like.

Furthermore, for example, JP-A-48-64932, JP-A-50-1
No. 31526, No. 51-95849, and Bent et al., Journal of the American Chemical Society, Vol. 73, pp. 3100-3I25 (1951).
The ones described above are also listed as representative ones.

The amount of these aromatic primary amino compounds to be used depends on where the activity of the developer is set; however, in order to increase the activity, it is preferable to increase the amount used. The amount used is 0.0002 mol/7! 0.7 mol/7!
It is used in the range up to. Moreover, two or more compounds can be used in appropriate combination depending on the purpose. For example 3
-methyl-4-amino-N,N-diethylaniline and 3
-Methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline and 3-methyl-4- Amino-N-ethyl-N-β
-Hydroxyethylaniline, etc. can be freely used in combination depending on the purpose.

The color developing solution used also contains various commonly added components, such as alkaline agents such as sodium hydroxide and sodium carbonate, alkali metal sulfites, alkali metal bisulfites, alkali metal thiocyanates, and alkali metal halogens. A chemical compound, benzyl alcohol, a water softener, a thickening agent, a development accelerator, and the like may optionally be included.

Examples of additives other than the above added to the color developing solution include bromides such as potassium bromide and ammonium bromide;
In addition to compounds for quick processing solutions such as alkali iodide, nitrobenzimidazole, mercaptobenzimidazole, 5-methyl-benzotriazole, 1-phenyl-5-mercaptotetrazole, anti-stain agents, anti-sludge agents, preservatives, There are multilayer effect promoters, chelating agents, etc.

Bleaching agents used in bleaching solutions or bleach-fixing solutions in the bleaching process are generally known to be those in which metal ions such as iron, cobalt, and copper are coordinated with aminopolycarboxylic acids or organic acids such as oxalic acid and citric acid. There is. Representative examples of the above aminopolycarboxylic acids include the following.

Ethylenediaminetetraacetic aciddiethylenetriaminepentaacetic acidpropylenediaminetetraacetic acidnitrilotriacetic acidiminodiacetic acid ethyl etherdiaminetetraacetic acidethylenediaminetetrabrobionic acidethylenediaminetetraacetic aciddisodium saltdiethylenetriaminepentaacetic acidpentasodium saltnitrilotriacetic acid sodium saltBleaching solutions can be used with various bleaching agents as mentioned above. It may also contain additives. When a bleach-fixing solution is used in the bleaching step, a solution containing a silver halide fixing agent in addition to the bleaching agent is used. Further, the bleach-fix solution may further contain a halogen compound such as potassium bromide. Then, as in the case of the above-mentioned bleaching solution, various other additives such as pH buffers, antifoaming agents, surfactants, preservatives, chelating agents, stabilizers, organic solvents, etc. are added and contained. Good too.

The silver halide fixing agent is, for example, sodium thiosulfate, ammonium thiosulfate, potassium thiocyanate, sodium thiocyanate, or thiourea, thioether, etc., which react with silver halide and become water-soluble. From the viewpoint of rapid processing, the processing temperature for various processing steps such as color development, bleach-fixing (or bleaching and fixing), and optionally washing, stabilizing, and drying should be 30°C or higher - No. 14834, No. 5B-105145 No. 5B-
Stabilization treatment as an alternative to water washing may be performed as shown in Japanese Patent Application No. 134634 and No. 58-18631, Japanese Patent Application No. 58-2709 and No. 59-89288, and the like.

〔Example〕

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

In all the examples below, the amount added in the silver halide photographic light-sensitive material is per 1 rrr unless otherwise specified. In addition, silver halide and colloidal silver are shown in terms of silver.

A multilayer color photographic element was prepared by sequentially forming each layer having the composition shown below on a triacetyl cellulose film support from the support side.

Sample-1 (comparison) First layer; antihalation layer (■C-1) Gelatin layer containing black colloidal silver.

Second layer; Intermediate layer (1,L,) Gelatin layer containing an emulsified dispersion of 2.5-di-t-octylhydroquinone.

3rd layer; low sensitivity red-sensitive silver halide emulsion layer (RL-1)
Average grain size (r) 0.30#m, monodisperse emulsion consisting of AgBrI containing 6 mol% Agl (emulsion ■)...silver coating amount 1.8 g/rrf
Sensitizing dye I... 6 x 10-' mol per mol of silver Sensitizing dye ■... 1.0 x 10-5 mol cyan coupler ((,-1) per mol of silver ...0.06 mol colored cyan coupler (cC-1) per 1 mol of silver...1 silver
0.003 mol per mol DIR compound (I)-1)...0.0015 mol per mol silver DIR compound (D-2)... 0.0015 mol per mol silver 0.002 mol 4th layer; Highly sensitive red-sensitive silver halide emulsion N (R■-1
) Average particle size (r) 0.5 pm, AgI 7.0
Monodispersed emulsion (emulsion ■) consisting of AgBrI containing mol%...silver coating amount 1.3 g/rrr
Sensitizing dye I... 3 x 10-5 mol per mol of silver Sensitizing dye ■... 1. OX 10-'Morsian coupler (c-1)...0.03 mol per mol of silver DIR compound (D-2)... o, ooi per mol of silver Molar 5th layer; middle layer (1, L,) Same as the second layer, gelatin layer.

6th layer; low sensitivity green-sensitive silver halide emulsion layer (GL-1)
Emulsion - ■... Coated silver amount 1.5 g/a Sensitizing dye ■... 2.5 x 10-' mol sensitizing dye ■ per 1 mole of silver
...Colored magenta coupler (cM-1) ...0.009 mol per 1 mol of silver DIR compound (I)-1) ... 0.009 mol per 1 mol of silver 0.0010 mol DIR compound (D-3) 0.0030 mol per mol of silver 7th layer; Highly sensitive green-sensitive silver halide emulsion layer (Gl+-1
) Emulsion - ■... Coated silver amount 1.4 g /
rd sensitizing dye ■... 1.5 x 10-5 mol sensitizing dye ■ per 1 mol of silver
...... 1 mole of silver. OX 10-' mole magenta coupler (M-1)...0.03 per mole of silver
0 mol DIR compound (D-3) 0.0010 mol per mol of silver 8th layer; Yellow filter single layer (VC-1') Yellow colloidal silver and 2,5-di-t- and an emulsified dispersion of octylhydroquinone.

9th layer; low sensitivity blue-sensitive silver halide emulsion layer (BL-1)
Average particle size 0.48 μm, containing 6 mol% Agl^g
Monodisperse emulsion (emulsion ■) consisting of RrI... Silver coating amount 0.9 g/rJ sensitizing dye ■... 1.3 x 10' mol yellow coupler (Y-1) per 1 mol silver. ...0.29 mol per mol of silver 10th layer; high sensitivity blue-sensitive emulsion layer (formerly 1-1) average grain size 0
．． 8 μm, monodisperse emulsion (emulsion ■) consisting of AgBrI containing 15 mol% of AgI...Silver coating amount: 0.5 g/n (sensitizing dye ■...... i = 1.5 g/n per 1 mol). 0.08 mol of OX 10-'Mole Yellow coupler (Y -1) per mol of silver DIR compound 1-2) 0.08 mol per mol of silver. 0015 mol 11th layer; 1st protective layer (Pro-1) Silver iodobromide (Ag
l 1 mol% average particle size 0.07zzm) Silver coating amount 0.5
g/% Gelatin layer containing UV absorbers UV-1 and UV-2.

12th layer; Second protective layer (Pro-2) Gelatin layer containing polymethyl methacrylate particles (1.5 μm in diameter) and formalin scavenger (R5-1) In addition to the above composition, each layer also contains gelatin. Hardening agent (i(-
1) and a surfactant were added.

Hereinafter, each layer of the above composition was prepared using the above HC-1゜.
RI L RH-1, GL-1, GH-1, YC-LB
L-1, B11-1. They shall be indicated by the abbreviations Pro-1 and Pro-2.

Sample-2 (comparison) This sample-2 was produced as follows.

The 1st to 3rd layers are the same as Sample-1, the 4th layer is the same as the 2nd layer of Sample-1 (1, 17,) 5th layer
Layer Same as the 6th layer of sample-1 (GL-1) 6th layer Same as the 2nd layer of sample-1 (1,ll,)7th layer Sample-
Same as the 4th layer of Sample-1 (RH-1) 8th layer Same as the 2nd layer of Sample-1 (1, L,) 9th layer Same as the 7th layer of Sample-1 (Gl(-1>10th layer) Layer Same as the 8th layer of sample-1 (Yt, -1) 11th layer Same as the 9th layer of sample-1 (BL-1) 12th layer Same as the 10th layer of sample-1
(BB-1) 13th layer Same as the 11th layer of sample-1 (
1”ro-1) 14th layer Same as the 12th layer of sample-1
(Pro-2) Sample-3 (present invention) Sample-3 was prepared as follows.

The first layer and the second layer are the same as the first layer and the second layer of Sample-1.

Third layer: Same as the fourth layer of sample-1 (R11-2) except that the emulsion (2) had an average grain size (r) of 0.75 μm.

The emulsion was changed to a medium-dispersion emulsion (emulsion = ■) consisting of 8 gRrl containing 6.0 mol% of Agl.

4th layer; same as the 2nd layer of sample-1 (I, 11.) 5th layer
Layer: Same as the 7th layer of sample-1 except that (Gl(-2) emulsion-■) was changed to (emulsion-V).

6th layer; same as the 2nd layer of sample-1 (1, 1,,) 7th layer
Layer: Same as the third layer of sample-1 (1?L-2) except that emulsion I) has an average grain size (r) of 0.22 μm and Agl 7.
Monodisperse emulsion (emulsion v) consisting of AgBrT containing 5 mol%
r) i;it did.

8th layer: Same as the 2nd layer of sample-1 (1,L,) 9th layer: Same as the 6th layer of sample-1 (GL-2) However, emulsion ■
) was changed to (emulsion ■).

The 10th to 14th layers are the same as the 10th to 14th layers of Sample-2. Hereinafter, each layer having the above composition is indicated by the abbreviations of RH-2, GH-2°RL-2, and GL-2.

In the same manner, multilayer coating samples were prepared with the contents shown in Table 1 below.

Table 1 also shows the layer configurations of Sample-1 and Sample-2. The layer structure of each sample-1 to sample-8 is the first layer to
The 14th layer (Sample-1 is the 1st layer to the 12th layer) is specified by using the abbreviations mentioned above in Table-1.

The compounds contained in each layer are as follows.

Sensitizing dye '1.5.5°-dichloro-9-ethyl-3,
3'-di(3-sulfopropyl)thiacarbocyanine hydroxide sensitizing dye ■; 9-ethyl-3,31-di(3-sulfopropyl)-4,5,4'.

51-dibenzothiacarbocyanine hydroxide sensitizing dye 1[;5,5'-diphenyl-9-ethyl-3
, 3'-di(3-sulfopropyl)oxacarbocyanine hydroxide sensitizing dye ■; 9-ethyl-3,31-di(3-sulfopropyl)-5,6,5'.

61-Dibenzoxacarbocyanine hydroxide sensitizing dye V, 3.3”-di(3-sulfopropyl)-
4,5-Benzo-5'-methoxythiacyanine h IE I υV-1 Of (UV-2 M-2 nt+ Each of the samples 1 to 8 thus prepared was exposed to a wedge using white light. , the following development treatment was performed.

Processing steps (38°C) Color development 3 minutes 15 seconds bleaching 6 minutes 30 seconds washing 3 minutes 15 seconds fixing 6 minutes 30 seconds washing 3 minutes 15 seconds stabilization 1 minute 30 seconds drying The composition of the processing solution used in each processing step is as follows. It is as follows.

[Color developer]

4-Amino-3-methyl-N-ethyl-N-(β-hydroxyethyl)-aniline sulfate 4.75g anhydrous sodium sulfite 4.25g hydroxylamine 1/2 sulfur hexasalt 2.0g anhydrous potassium carbonate
37.5 g sodium bromide
163g Nitrilotriacetic acid trisodium salt (monohydrate) 2.5 g
Potassium hydroxide 1.0g Add water and bring to 1°C.

[Bleach solution]

Ethylenediaminetetraacetic acid iron ammonium salt 100. g Ethylenediaminetetraacetic acid 2 Ammonium salt 10.0 g Ammonium bromide 150.0 g Glacial acetic acid 10.0 ml 1 Add water and II! Bind and use ammonia water to pH-6.0
Adjust to.

[Fixer]

Ammosorum thiosulfate 175. Og Anhydrous sodium sulfite 8.5g Sodium metasulfite 2.3g Add water to make 11, and adjust to pH = 6.0 using acetic acid.

[Stabilizing liquid]

Formalin (37% aqueous solution) 1.5nl
Konidax (manufactured by Konishiroku Photo Industry Co., Ltd.) 1.5 tal
Add 1 water to make 1β.

Relative sensitivity (S), sharpness (MTF), and RMS of each sample obtained were measured using white light (W). The results are shown in Table 2.

Note that the relative sensitivity (S) is the relative value of the reciprocal of the exposure amount that gives the fog density +0.1, and the W sensitivity of the sample Ncl is 10
It is shown as a value of 0. The sharpness improvement effect is due to the M of the dye image.
T F (Modulation Transfer
Find the MTF at 10 lines/mm
It is expressed as a relative value (with sample size 1 set as 100).

The RMS value is the minimum density + 1.2 when the circular scanning aperture is 2.
It is expressed as a value 1000 times the standard deviation of the variation in density value that occurs when scanning with a 5 μm microdecimometer.

Table-2

Claims (1)

[Claims] 1. On a support, at least a green-sensitive silver halide emulsion layer with high sensitivity, a green-sensitive silver halide emulsion layer with low sensitivity, and a red-sensitive silver halide emulsion layer with high sensitivity; A multicolor photographic element comprising a red-sensitive silver halide emulsion layer of low sensitivity, characterized in that it has the following (a) to (c). (a) The high-sensitivity green-sensitive emulsion layer and the high-sensitivity red-sensitive emulsion layer constitute a high-sensitivity emulsion unit. (b) The low-sensitivity green-sensitive emulsion layer and the low-sensitivity The red-sensitive emulsion layer constitutes a low-sensitivity emulsion unit. (c) The high-sensitivity emulsion unit is disposed closer to the support than the low-sensitivity emulsion unit. 2. Claim 1, wherein the high-sensitivity green-sensitive emulsion layer and the high-sensitivity red-sensitive emulsion layer are disposed adjacent to each other in the high-sensitivity emulsion unit. Multicolored photographic elements described in . 3. Claim 1, wherein the low-sensitivity green-sensitive emulsion layer and the low-sensitivity red-sensitive emulsion layer are disposed adjacent to each other in the low-sensitivity emulsion unit. or a multicolor photographic element according to paragraph 2.