JPH05188540A - Manufacture of photograph coupler - Google Patents

Abstract

PURPOSE: To form an intermediate useful to form a photographic coupler by reaction with phosgene or a bisthio compd. CONSTITUTION: This photographic coupler contg. a coupler part(COUP) having a phenoxy group releasable by coupling and having an aminomethyl. group at the 2-position is produced by allowing a coupler part having a phenoxy group releasable by coupling and having a hydroxyalkyl or hydroxyaryl group whose hydroxy group exists on the α-carbon atom of an alkyl or aryl group at the 2-position to react with a halogenating agent under ambient conditions and allowing the resultant product to react with an amine compd.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a process for preparing a photographic coupler comprising an original coupler moiety (COUP) containing a phenoxy coupling-off group having an aminoalkyl group or an aminoaryl group at the 2-position of the phenoxy coupling-off group. Regarding

[0002]

BACKGROUND OF THE INVENTION It is known in the photographic art to use dye couplers to form dye images. It is also known to use various couplers which release a photographically useful group (PUG) from the coupler moiety (COUP) in a photographic light-sensitive material or a processing solution. Such couplers are described, for example, in Research Disclosure , 1989 1
February, Item No. 308119, paragraph VII, and the references listed in this publication. They are also described, for example, in U.S. Pat. No. 4,482,629 and Begley et al. Under the title "Photographic Material and Process Comprising a compound containing a compound capable of forming a washout dye."
Compound Capable of Forming a Wash-Out Dye) "1
U.S. Patent Application No. 483,60, filed February 22, 990.
It is also described in specification No. 0.

[0003]

In the production of such couplers, it has been desired to provide a method in which a substituent can be introduced as desired under harsh reaction conditions without complicated multistep synthetic steps. .. It has been particularly desirable to provide a method capable of forming couplers containing substituents useful in photographic materials and processing.

In this regard, it is particularly desirable to provide a method of making couplers containing groups useful in releasable photographs which allows the introduction of substituents as desired. This is especially necessary for couplers that have a water-solubilizing group on the original coupler moiety that allows the dye from the coupler to be washed out from photographic materials containing such couplers by processing.

[0005]

SUMMARY OF THE INVENTION The advantages as described above include the preparation of a photographic coupler comprising an original coupler moiety (COUP) containing a phenoxy coupling-off group having an aminomethyl group at the 2-position of the phenoxy coupling-off group. (A) (a) a coupler moiety containing a phenoxy coupling-off group having a hydroxyalkyl group or a hydroxyaryl group (wherein the hydroxyl group is on the α carbon atom of the alkyl or aryl group) at the 2-position,
It has been found that this can be achieved by the above-mentioned production method comprising (b) a step of reacting with a halogenating agent, followed by (B) a step of reacting the product derived from step (A) with an amine compound.

Among other things, this method allows the use of various substituents on the amine compound and the substitution of the amine by carrying out step (B), which would not otherwise be possible. For example, the Schiff base method of making a compound as described would not facilitate displacement of the methylamino group to the resulting compound.

The coupler portion (COU as described
P) can be any coupler moiety known in the photographic art, but is preferably a naphthol-based coupler moiety or an acetanilide coupler moiety. Especially preferred coupler moiety is a naphtholic coupler moiety containing a water solubilizing groups such as -CONH ₂ or -CONHCH ₃ at the 2-position of the naphthol skeleton. Typically, such coupler moieties react with developing agents that are oxidized during photographic processing to give colorless or colored compounds.

The coupler moiety may or may not have a ballast group. It can be monomeric and can be dimeric, oligomeric or polymeric couplers.

Generally, the coupler moiety is a dye-forming coupler, such as a colored or colorless dye-forming coupler, which can be diffusible or non-diffusible. The coupler moiety is preferably a divalent, open chain ketomethylene, pyrazolone, known in the photographic art.
Pyrazolotriazole, pyrazolobenzimidazole,
It is a phenol or naphthol type coupler.

The phenoxy coupling-off group is any coupling-off group known in the photographic art provided such that the phenoxy group contains a substituted or unsubstituted hydroxyalkyl as described at the 2-position of the phenoxy group. Can be

The phenoxy coupling-off group can be unsubstituted except for substituted or unsubstituted hydroxyalkyl groups. In some cases, the phenoxy coupling-off group may be substituted by a group that does not adversely affect the coupler or photographic material when the coupler is used or reacts as described. As such a substituent, a group known to be useful as a phenoxy coupling-off group in the photographic art, for example, a ballast group, an alkyl group, an aryl group, a nitro group, a sulfonamide group, a sulfamyl group, a carbamoyl group. , An ether group, an ester group, a carbonamide group and the like.

The hydroxyalkyl groups mentioned preferably contain from 1 to 40 carbon atoms and have a hydroxyl group on the alpha carbon of the alkyl group. This hydroxyalkyl group is represented by the formula:

[0013]

[Chemical 3]

In the above formula, R ¹ and R ² independently represent a hydrogen atom or a substituent which does not adversely influence the synthesis described, such as an alkyl group or a phenyl group (preferably a hydrogen atom). The hydroxyalkyl group is preferably a hydroxymethyl group. Unsubstituted or substituted hydroxyalkyl groups, as described, preferably have 1 to 4 carbon atoms.
Contains 0 and carries a hydroxyl group on the α carbon atom. Substituents on the hydroxyalkyl group that can adversely affect the synthesis as described include other hydroxyl groups and amino groups.

The halogenating agent as described may be any halogenating agent known in the organic compound synthesis art. Such halogenating agent is preferably a brominating agent, but may be a chlorinating agent. Specific examples of such a halogenating agent do not adversely affect the rest of the molecule,
HBr, phosphorus tribromide, SOCl ₂ , PCl ₂ and PC
₁₅ may be mentioned.

The halogenation reaction is carried out under pressure and temperature conditions depending on the halogenating agent used. For example,
When phosphorus tribromide is used, the pressure and temperature are near atmospheric conditions. If HBr is used, it is preferred to use elevated temperatures up to about 60 ° C. This reaction need not be carried out above or below atmospheric pressure. Generally, this reaction is carried out at a temperature within the range of about 0-100 ° C. The halogenation reaction is carried out until completion. Therefore, excess halogenating agent is used in the reaction.

Step (B) as described is carried out with any amine compound which reacts with the product of step (A). The amine compound is typically an alkylamine having 1 to 40 carbon atoms, such as methylamine,
Ethylamine, n-propylamine, i-propylamine, n-butylamine, t-butylamine, ethanolamine, chloroethylamine or other substituted alkylamines. Arylamines are typically unsubstituted or substituted phenylamines having 6 to 40 carbon atoms. Specific examples of such arylamines include aniline, methoxyaniline, chloroaniline and nitroaniline. A specific phenylamine compound is represented by the following formula.

[0018]

[Chemical 4]

In the above formula, R ³ is --NHSO ₂ R ⁴ , --SO
₂ NHR ⁵ , -NHCOR ⁶ , -CONHR ⁷ , -CO
₂ R ₈ , —OR ⁹ or a hydrogen atom, wherein R ⁴ ,
R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ are independently substituents which do not adversely affect the synthesis, such as an alkyl group (eg,
An alkyl group having 1 to 40 carbon atoms) or an aryl group such as phenyl. As the arylamine, the following are preferred.

[0020]

[Chemical 5]

The reaction between the product of step (A) and the amine compound as described above is carried out under the pressure and temperature conditions suitable for the amine compound used, preferably at 0 ° to 100 ° C. It is typically carried out under normal atmospheric conditions of temperature and pressure. May be necessary with some amines at elevated temperatures and reduced pressure or pressure. The desired reaction is 0
It is carried out at a temperature in the range of 100 ° C. Low nucleophilic amines, such as nitroanilines, may require elevated temperatures. Highly nucleophilic amines can be stored at room temperature (20
Reactions below (° C) may be necessary.

The reaction of the product of step (A) with the amine compound as described above is typically carried out until the reaction is completed. The concentrations of the reactants can be mixed in stoichiometric proportions, but generally the amine compound is added in excess of the required amount.

The product of step (B) is typically reacted with phosgene at atmospheric pressure and ambient temperature and then the product of this reaction is reacted with a photographically useful compound. This is because of the processing, in the photographic material, a group useful for photography (PU
It enables the production of couplers which allow the release of G).

Optionally, the product resulting from the reaction of step (B) can be reacted with bismercaptotetrazole compounds known in the photographic art such as bisphenylmercaptotetrazole or benzotriazole carbonyl chloride. This reaction can also be carried out under atmospheric pressure and atmospheric temperature (preferably in the range 0-100 ° C). This allows the processing to form a releasable coupler of the mercaptotetrazole development inhibitor moiety in the photographic material.

The bismercaptotetrazole moiety is
It can be any compound known in the organic compound synthesis art, preferably capable of forming a useful development inhibitor releasing compound in photographic silver halide materials known in the photographic art.

The preferred method described is:

[0027]

[Chemical 6]

Wherein PUG is a photographically useful group, R ¹⁰ is a hydrogen atom or a photographic ballast group known in the photographic art, and R ¹¹ is an unsubstituted or substituted aryl or alkyl group. , R ¹² and R ¹³ are independently a hydrogen atom or a substituent (preferably a hydrogen atom) that does not adversely affect the coupler, and R ¹⁰ , R ¹¹ , R ¹² or R ^{12
One of 13} is a method for producing a photographic coupler, wherein R ¹¹ is preferably a photographic ballast group), wherein (A) (a)

[0029]

[Chemical 7]

The step of reacting the coupler moiety represented by: (b) with a brominating or chlorinating agent under ambient conditions, followed by (B) the product from step (A) with an unsubstituted or substituted arylamine or alkyl. A step of reacting with an amine, followed by a step of reacting a product derived from (C) step (B) with phosgene, and a subsequent step of (D) producing a product derived from step (C) to a photographically useful compound
Preferred is a method comprising the step of reacting with a development inhibitor compound.

Photographically useful groups (PUG) are, for example, B
It may be any photographically useful compound described in U.S. Patent Application No. 483,601 filed by Eggley et al. on Feb. 20, 1990. This specification is incorporated herein by reference. PUG
Can be any group that can be utilized in a photographic element in an imagewise fashion. PUG can be a photographic reagent or photographic dye. Photographic reagents herein refer to moieties released by further reaction with components of the photographic element, such as development inhibitors, development accelerators, couplers (eg, competing couplers,
Dye forming couplers or development inhibitor releasing couplers [D
IR coupler]), dye precursor, dye, developing agent (for example, competitive developing agent, color developing agent or silver halide developing agent), silver complexing agent, fixing agent, image toner, stabilizer, curing agent, tanning agent , Fogging agents, UV absorbers, antifoggants, nucleating agents, chemical or spectral sensitizers or desensitizers.

The PUG can be present in the coupling-off group as a preformed species or in blocked form or as a precursor. The PUG can be, for example, a preformed development inhibitor or one whose development inhibitory action can be blocked by the position attached to the carbonyl group attached to the PUG.

Another example is a preformed dye,
It is a dye or leuco dye that is blocked to shift its absorption. A preferable naphthol compound is produced according to the following method which specifically shows the above method.

[0034]

[Chemical 8]

[0035]

[Chemical 9]

[0036]

[Chemical 10]

[0037]

[Chemical 11]

[0038]

[Chemical 12]

[0039]

[Chemical 13]

[0040]

[Chemical 14]

[0041]

[Chemical 15]

These compounds are photographic couplers which can be used in photographic materials and also compounds which can be used in the preparation of the other photographic couplers mentioned above, such as DIR and DIAR couplers.

The image dye-forming coupler is a photographic element and / or
Alternatively, they can be incorporated into photographic processing solutions, such as developers, whereby development of exposed photographic elements will cause them to be reactively combined with oxidized color developing agent. Coupler compounds incorporated into photographic processing solutions must be of a molecular size and shape such that they can diffuse through the photographic layer with the processing solution. When incorporated into photographic elements, coupler compounds should, in principle, be non-diffusible. That is, they must be of molecular size and shape such that they do not significantly diffuse or migrate from the applied layer.

The photographic elements of this invention can be processed in the conventional manner in which the color coupler and color developing agent are separately incorporated in the processing solution or composition, or incorporated into the element.

Photographic elements incorporating the compounds of this invention are simple elements consisting of a support and a single silver halide emulsion layer or are multicolor elements in which the silver halide emulsion layers are multilayer. be able to. The compounds of the present invention are made reactive in combination with at least one silver halide emulsion layer and / or an oxidized color developing agent and at least one such layer as the adjacent layer in which the silver halide is developed in the emulsion layer. It can be incorporated into other layers. The silver halide emulsion layer contains or is combined with other photographic coupler compounds such as dye-forming couplers, color mask couplers and / or competing couplers. These other photographic couplers can produce dyes of the same or different colors or hues as the photographic couplers of this invention. Further, the silver halide emulsion layers and other layers of the photographic element can contain addenda conventionally contained in such layers.

A typical multilayer, multicolor photographic element comprises a red-sensitive silver halide emulsion unit in combination with a cyan dye image-forming material, a green-sensitive silver halide emulsion unit in combination with a magenta dye image-forming material and It can consist of a support carrying a blue-sensitive silver halide emulsion unit in combination with a yellow dye image-forming material and carrying at least one silver halide emulsion unit in combination with a photographic coupler of the invention. .. Each silver halide emulsion unit can be composed of one or more layers, and the various units and layers can be arranged in different locations in relation to each other.

The couplers of this invention can be incorporated or combined in one or more layers or units of a photographic element. For example, the layer or unit affected by the PUG can be controlled by incorporating scavenger layers in appropriate locations in the element that limit the action of the PUG to the desired layer or unit. At least one of the photographic elements
The two layers can be, for example, mordant layers or barrier layers.

Light-sensitive silver halide emulsions can include coarse, uniform or fine silver halide crystals or mixtures thereof, and silver chloride, silver bromide, silver bromoiodide, silver chlorobromide, salts. It can be composed of silver halides such as silver iodide, silver chlorobromoiodide and mixtures thereof. The emulsions can be negative-working or direct positive emulsions. They can form a latent image preferentially on the surface of silver halide grains or inside silver halide grains. This emulsion is of the type used in reversal color photographic materials such as motion picture films, color negative photographic materials. They can be chemically and spectrally sensitized. The emulsion will typically be a gelatin emulsion, but other hydrophilic colloids can be used. Research Disclosure , January 1983,
Item No.22534, and US Pat. No. 4,434,226
Particularly preferred are tabular grain photosensitive silver halides as described in US Pat.

The support can be any support used with photographic elements. Representative supports include cellulose nitrate films, cellulose acetate films, polyvinyl acetal films, polyethylene terephthalate films, polycarbonate films and related films or resin materials, as well as glass, paper and metals. The paper support is acetylated or has valita and / or 2-1 carbon atoms, especially polyethylene, polypropylene, ethylene-butene copolymers and the like.
It can be coated with a polymer of 0 α-olefin.

The coupling-off group of the present invention is a releasable PUG.
Those containing are preferred. Depending on the nature of the particular PUG,
Couplers can be incorporated into photographic elements for other purposes and can be incorporated elsewhere.

In the following discussion of materials suitable for use in the emulsions and elements of this invention, Research Disclosur
e , December 1978, Item 17643 (Industrial Opport
unities Ltd., Publisher: Howewell Havant, Hampshire, PO9 1
EF, UK). The contents of the description are incorporated herein by reference. This publication will hereinafter be abbreviated as "Research Disclosure".

Photographic elements are Research Disclosure, XV
It can be coated on a variety of supports as described in Section II and the references cited therein. Photo Diary is Research Di
Sclosure, which can be exposed to actinic radiation, typically in the visible region of the spectrum, to form a latent image, as described in Section XVIII, and then processed as described in Research Disclosure, Section XIX. To form a visible dye image. Processing to form a visible dye image includes the step of reducing developable silver halide by contacting the element with a color developing agent and oxidizing the color developing agent. The oxidized color developing agent then reacts with the coupler to give the dye.

Preferred color developing agents that can be used in the present invention are p-phenylenediamines. Particularly preferred are 4-amino-N, N-diethylaniline hydrochloride, 4-amino-3-methyl-N, N-diethylaniline hydrochloride, 4-amino-3-methyl-N-ethyl-N.
-Β- (methanesulfonamido) ethylaniline sulfate hydrate, 4-amino-3-methyl-N-ethyl-N-β-
Hydroxyethylaniline sulfate, 4-amino-3-β
-(Methanesulfonamide) -ethyl-N, N-diethylaniline hydrochloride and 4-amino-N-ethyl-N-
(2-Methoxyethyl) -m-toluidine di-p-toluenesulfonic acid may be mentioned.

With negative-working silver halide, the processing step described above provides a negative image. To obtain a positive (or reversal) image, this step develops the exposed silver halide by developing with a non-color developing agent (but does not produce a dye) and then develops the unexposed silver halide. The element is covered uniformly in order to do so. Alternatively, a direct positive emulsion can be used to obtain a positive image.

The photographic and processing materials described are described, for example, in Research Disclosure , December 1989, Item N.
Photographic silver halide emulsions known to be useful in the photographic art as described in O. 308, 119, as well as addenda. The contents of the reference are the contents of the present specification by reference. Bleaching, fixing or bleach-fixing to remove silver and silver halide after development,
Further common steps of washing and drying are carried out.

[0056]

The present invention will be described in more detail with reference to the following examples.

Example 1: Synthesis The following process illustrates the preparation of compounds according to the present invention.

[0058]

[Chemical 16]

[0059]

[Chemical 17]

[0060]

[Chemical 18]

Experimental Compound (8) : Compound (7) (20 g, 87.26 mmol) was taken up in deoxygenated DMSO (200 mL) and stirred under nitrogen atmosphere. Add 85% KOH (10.0
6 g, 152.71 mmol) was added, followed by deoxygenated water (20 mL). The reaction mixture was thoroughly stirred at room temperature for about 30 minutes. Then 2-chloro-5-nitrobenzaldehyde (16.2 g, 87.26 mmol) was added and stirring was continued for another hour at room temperature. The thick reaction mixture was poured into 2N HCl (1 L) with good stirring. When it became a homogeneous thick suspension, ethyl acetate (2
00 mL) was added and stirring was continued for another 15 minutes. The product precipitated in the solution was collected by filtration and washed with a small amount of ethyl acetate to obtain 25.7 g (78%) of pure compound (8).

Compound (9) : Compound (8) (43.63)
Mmol) in THF (100 mL) and then Me
OH (100 mL) was added. Sodium borohydride (1.65 g, 43.63 mmol) was then added in small portions with cooling as needed. At the end of the addition, the dark colored solution was stirred at room temperature for a further 15 minutes and then poured into 2N-HCl with stirring. The yellow solid was filtered off, washed thoroughly with water and methanol and finally dried. Yield 11.0 g (66%).

Compound (10) : Compound (9) (11.0)
g, 28.92 mmol) in water (140 mL),
Then methanol (20 mL) was added. Then 85% KOH (15.25 g, 231.38 mmol) was added to this suspension. The resulting mixture was refluxed for about 20 minutes, cooled to room temperature and then poured into 2N-HCl. The precipitated yellow solid was collected by filtration, washed with a small amount of water, and then air dried. Yield 10 g (about 100%).

Compound (11) : Compound (10) (13.
6 g, 38.8 mmol) was dissolved in THF (100 mL) and methanol (100 mL) was added. After adding Raney nickel pre-washed with water and methanol, the mixture was hydrogenated at 50 psi at room temperature. When the consumption of hydrogen had ended, the catalyst was filtered off and the filtrate was concentrated under reduced pressure until almost dry. The residue thus obtained was treated with acetonitrile. The obtained solid was collected by filtration and then air-dried to obtain 10.1 g (81%) of the compound (11) as a product.

Compound (12) : Compound (11) (10.
1 g, 31.14 mmol) of dry pyridine (100 m
L) and n-hexadecylsulfonyl chloride (11.13 g, 34.25 mmol) was added to this solution. After 15 minutes, the color of the reaction solution changed from dark yellow to pale red. Next, the reaction solution was concentrated under reduced pressure, and the residue was dissolved in ethyl acetate. The ethyl acetate solution was then washed 3 times with 2N HCl, dried over MgSO ₄ , filtered and then the ethyl acetate solution was passed through a short silica gel column eluting with ethyl acetate. The eluent was concentrated and treated with acetonitrile to give the product compound (12) as 1
5.8 g (83%) was obtained.

[0066]Compound (13): Compound (12) (15.
78 mmol) was suspended in dry ether (150 mL),
Then THF (30 mL) was added. Dry ether (30
phosphorus tribromide (2.7 mL, 28.36 mmol) in
The mixture was added dropwise, and the reaction solution was stirred at room temperature for about 15 minutes. This end
After that, the reaction solution was diluted with ether and washed 3 times with 2N-HCl.
Clean, MgSO _FourDried over, filtered, then concentrated the solution.
Shrink to give a solid. In this reaction, compound (13) was added to 10
Presumed to have progressed to yield 0% yield
It was This crude product was used as such in the next step.

Compound (14) : The crude compound (13) (25.78 mmol) as described above was added to DMF (100 mL).
Dissolved in. Potassium iodide (4.3 g, 2
5.78 mmol) was added, followed by aniline (12 mL,
128.9 mmol) was added and the mixture was gradually heated on a steam bath for about 10 minutes. A fine precipitate of potassium bromide remained when all the potassium iodide had dissolved. Then the reaction mixture was cooled to room temperature, diluted with ethyl acetate,
Wash 3 times with 2N HCl, dry over MgSO ₄ , filter, and concentrate under reduced pressure. The obtained semi-solid substance was treated with acetonitrile to obtain 16.1 g (91%) of the product compound (14) as a yellow powder.

Compound (15) : Compound (14) (2.5
g, 3.63 mmol) in THF (50 mL),
Then bis-phenylmercaptotetrazole carbonyl (1.4 g, 3.63 mmol) was added. The resulting solution was stirred for 1 hour at room temperature. At the end of that time, another batch of bis-phenylmercaptotetrazolecarbonyl (1.4 g, 3.63 mmol) was added,
It was stirred for another hour. Then, the reaction solution was concentrated under reduced pressure, the resulting residual oily substance was dissolved in ethyl acetate, and 2.
Wash 3 times with 5% Na ₂ CO ₃ and 3 times with 2N HCl, then dry over MgSO ₄ , filter, and concentrate to an oil. 35% oil in a little heptane
It was dissolved in ethyl acetate and chromatographed on pressurized silica gel eluting with the same solvent mixture. The first major absorption band (product), compound (15), was collected. Yield 2.0g (62
%).

Calculated as C ₄₈ H ₅₇ N ₇ O ₆ S ₂ : C, 64.62%; H, 6.44%; N, 1
0.99%; S, 7.19%. Experimental value: C, 64.33%; H, 6.30%; N, 1
0.65%, S, 7.82%.

Example 2: Photographic Application Compound I-4 (15) was prepared as described in Example 1. Compounds I-1, I-2 and I-3 were similarly prepared. Photographic elements were made by coating the following layers on a cellulose ester support (amounts of each component are mg / mg):
m ² ).

Emulsion layer 1: Gelatin-2420: Red sensitized silver iodide (as Ag) -1615; Yellow image coupler dispersed in dibutyl phthalate. (Receiver layer)

Intermediate layer: Gelatin-860; didodecylhydroquinone-113

Emulsion Layer 2: Gelatin-2690; green sensitized silver bromoiodide (as Ag) -1615; magenta image coupler dispersed in tritolyl phosphate; D of Table 1.
The IR compound was dispersed in N, N-diethyl-dodecanamide and applied at levels of 5, 10, 15 and 20 μm / ft ² . (Causer layer)

Protective Overcoat: Gelatin-538
0: Bisvinylsulfonyl methyl ether (2% of total gelatin)

The structural formulas of the image couplers are as follows.

[0076]

[Chemical 19]

For the purpose of measuring sharpness, strips of each element were exposed to green light through a step density tablet or a modulation fringe chart and then developed with the following color developers at 38 ° C. for 3.25 minutes. , Stopped, washed, bleached, fixed, washed and then dried.

Color developer Distilled water 800 mL Sodium metasulfite 2.18 g Sodium sulfite anhydride 0.38 g CD-4 (color developing agent) ^* 4.52 g Potassium carbonate anhydride 34.3 g Potassium bicarbonate 2.32 g Bromide Sodium 1.31 g Potassium iodide 1.20 mg Hydroxylamine sulfate (HAS) 2.41 g Diethylenetriaminepentaacetic acid-5 sodium salt (40% solution) 8.43 g Distilled water adjusted to 1 L (adjusted to pH 10.0) * CD -4 is 4-amino-3-methyl-N-ethyl-
N-β-hydroxyethylaniline sulfate

The processed image was read with green light and the contrast and AMT acutance were measured. The values obtained are shown in Table I for those defined as 10 micromoles of compound per square foot. For the AMT calculation, the cascade region under the system modulation curve is “Theory of the
Photographic Process ”, 4th Edition, 1977 (THJame
The equation on page 629 of the s edition): AMT = 100 + 6
6Log [Cascade region / 2.669M] was used. Where the multiple factor M is 3.8 for the 35 mm system AMT. Use of CMT acutance is described in “An Improved Objective Method of Rating” in Journal of SMPTE, Vol.82, 1009-1012 (1973).
Picturp Sharpness: CMT acutance ”by RG Gendron. AMT is a further modification of CMT useful for evaluation systems involving the observation of positive prints made from negatives.

The overlay effect (degree of color correction) was evaluated after daylight exposure. As shown in Table I, the layering effect is that the red-sensitive layer (receiver) is sensitive to gamma and the line-sensitive layer (coser) is used.
Was expressed as a gamma ratio of.

[0081]

[Table 1]

[0082]

[Chemical 20]

[0083]

[Chemical 21]

[0084]

[Chemical formula 22]

[0085]

Industrial Applicability A method for introducing a substituent as intended, which is a method for producing a photographic coupler comprising a coupler moiety containing a phenoxy coupling-off group having an aminomethyl group at the 2-position of the phenoxy coupling-off group is provided. Provided. This method allows the use of various substituents on the amine compound and the introduction of a substituted aminomethyl group at the 2-position of the phenoxy group, which would not be possible with conventional methods.

Claims (2)

[Claims] 1. An original coupler moiety (COU) containing a phenoxy coupling-off group having an aminoalkyl group or an aminoaryl group at the 2-position of the phenoxy coupling-off group.
A method for producing a photographic coupler comprising P), which comprises (a) a phenoxy coupling-off group having a hydroxyalkyl group or a hydroxyaryl group at the 2-position, the hydroxyl group of which is present on the α-carbon of the alkyl or aryl. Reacting a coupler moiety comprising a halogenated compound to form a first product, (b) reacting the product from step (a) with an amino compound to form a second product. (C) reacting the second product with phosgene and then with a photographic development inhibitor compound to form a photographic coupler that releases the development inhibitor compound into the photographic material upon exposure and processing of the photographic material. And a manufacturing method comprising: 2. (A) (a) The following formula: (In the above formula, R ¹⁰ is a hydrogen atom or a photographic ballast group, R ¹² and R ¹³ are independently a hydrogen atom or a substituent, and one of R ¹⁰ , R ¹² and R ¹³ is a photographic ballast group. A coupler moiety represented by the group (b) is reacted with a brominating agent or a chlorinating agent under ambient conditions, followed by (B) the product from step (A) being an unsubstituted or substituted arylamine Alternatively, a step of reacting with an alkylamine, followed by a step of reacting a product derived from (C) step (B) with phosgene, and a subsequent step (D) reacting a product derived from step (C) with a photographically useful compound. Comprising the steps: (In the above formula, PUG is a photographically useful group, 10 ¹⁰ is a hydrogen atom or a photographic ballast group, R ¹¹ is an unsubstituted or substituted aryl group or an alkyl group, and R ¹² and R ¹³ are independently Is a hydrogen atom or a substituent, and R
^{10. The} method for producing a photographic coupler according to claim 1, wherein one of ¹⁰ , R ¹¹ , R ¹² and R ¹³ is a photographic ballast group.