JPH06504384A - Novel magenta coupler for color photography - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] A novel magenta coupler for color photography The present invention is (1, 2-b) (1, 2, 4 ) Concerning a new magenta coupler for color photography selected from triazoles. Ru. In the triazole according to the present invention, the dye (or pigment) in the photographic layer is an oxidized coupler. The magenta coupler used in the silver halide image system formed by related.

Research Disclosure 162, pages 73-75 (1977) (Bog ie and Norris) are p-aminophenol developers and p-phenylene Imidazo(1,2-b)(1,2,4 )) describes the use of lyazole couplers. The two sides described are blue or black. Give undye. Details on the synthesis of the coupler and the resulting dye in ethyl acetate. The hue in the file is given. The same two compounds are photographed by Roku Konishi. Found in European Patent No. EP-A-252,288 by Kogyo Corporation ( 1988, p. 25, compounds 190 and 191), and that these compounds were synthesized. No evidence is given in this document to support this. The compound of the invention is , which provides a practical coupler that provides magenta dyes.

According to the invention, the formula (In the formula, R1 and R2 are the same or different, H, alkyl, substituted alkyl aryl, substituted aryl, heteroaryl, alkylthio, carboxylic acid or is an ester, - or secondary amide, sulfonamide, mono- or di-substituted selected from amino, alcoquine, or aryloxy: and X is selected from H or a group that can be released upon oxidative coupling with a color developer. color photographic couplers are provided. In a preferred embodiment of the present invention, The color developer is p-phenyl diamine, more preferably R', R' or X contains a group capable of immobilizing the coupler in the photographic layer. Furthermore, R1 When aryl, R2 is not aryl or substituted by a -NO□ group. Preferably, it is an aryl.

Preferably R2 is alkyl and R1 is aryl, substituted aryl or alkyl. Selected from Kirthio.

X is preferably a group that can be released during oxidative coupling, such as hydrogen, halogen , or alkyl or arylthiols.

Couplers of the above type of formula (I) are available from other couples currently in use. Exhibits improved hue properties compared to Zenta couplers.

The dye absorption of the present invention has no significant secondary absorption in the blue region of the spectrum. is particularly important. This leads to better color reproduction.

Second, the coupler of the present invention can be easily synthesized in high yield from inexpensive intermediates in a few steps. This is an advantage in terms of production costs.

Specific compounds related to the applications specified above are listed below.

N-(4-(1-H-6-methylimidazo(1,2-b) (1,2°4) lyazol-2-yl)-phenyl)-2-(4-n-butylsulfonamide phenoxy)tetradecanamide 2,4) triazol-2-yl)-phene Photographic elements incorporating couplers of the present invention are monochromatic elements. or multicolored elements. In multicolor elements, the magenta of the present invention Dye-forming coupler mixtures are usually associated with green-sensitive emulsions, but are different. Orthochromate, sensitive to a range of spectra, or panchromatic It can also be associated with emulsions that are photosensitive or non-photosensitive. multicolor The element contains dye image-forming units sensitive to each of the three primary regions of the spectrum. have

Each unit consists of a single emulsion layer or multiple emulsion layers sensitive to a given region of the spectrum. Become. The layers of the element containing image-forming units can be formed in various orders in a manner well known in the art. It can be placed in

Typical multicolor photographic elements each contain at least one yellow, one magenta , or at least one blue dye having associated therewith a cyan dye-forming coupler. colors, yellow, magenta and The cyan image-forming unit consists of a support on which the cyan image-forming units are grown.

This element can further include additional layers such as filter and barrier layers. Ru.

In the following description of materials suitable for use in the emulsions and elements of this invention. Industry Obotunity (Old Barbers 8 North Street) Research data published by Emsworth Hump POIO7DD UK) See Disclosure, December 1989, No. 308119. this publication are identified herein as "Research Disclosure."

The halogenated emulsions used in the elements of this invention can be either negative-working or positive-working. Can be used. Suitable emulsions and their preparation methods are described in Research Disclosure, Part 1. and Chapter ■ and the publications cited therein. Elements of the invention Suitable vehicles for emulsion layers and other uses are listed in Research Disclosure Section ■ Chapters and publications cited therein.

In addition to the coupler combinations of the invention, elements of the invention also include research disclosures. -Chapter ■, Sections E, F and G of - and publications cited therein. may contain other couplers such as those described in . Couplers of the present invention - combinations and optionally added couplers are subject to Research Disclosure. Chapter ■, Section C, and the publications cited therein. Incorporated into sea urchin elements and emulsions.

The photographic elements of this invention and their individual layers are coated with a fluorescent brightener (Research Disc. (see Chapter V of the Research Disk), antifoggants, and stabilizers (see Research Disc. stain inhibitors and image dye stabilizers (research (see Chapters ■, ■, and Section 5 of the Disclosure), light-absorbing and scattering substances ( (see Research Disclosure Chapter 1), hardeners (Research Disclosure, Chapter 1), plasticizers and lubricants (Research Disclosure) (see Chapter X■), antistatic agents (see Research Disclosure Chapter X■) ), adhesives (see Research Disclosure Chapter (see Chapter XVI of Research Disclosures) and color improvers (research Closures (see Chapter XXI).

The above photographic elements are included in Chapter X of the Research Disclosure and cited therein. It can be coated onto a variety of supports, as described in the published publication.

Research by exposing photographic elements to actinic radiation (typically in the visible spectral region) Form a latent image as described in Section X■ of Disclosure, then reprocess. Processed and visible dyed as described in Chapter XIX of the can form a free image. The process of forming a visible dye image involves contacting the element with a color former. The color forming agent is melted by reducing silver halide capable of forming a color by melting the color forming agent. oxidized The color former then reacts with the coupler to form a dye.

Suitable color formers are p-phinidine diamines. Particularly preferably, 4-amino -3-methyl-N, N-diethylaniline hydrochloride, 4-amino-3 -Methyl-N-ethyl-N-β-(methanesulfonamide)-dithylaniline Sulfuric acid hydrate, 4-amino-3-methyl-N-ethyl-N-β-hydroxyethyl Aniline sulfate, 4-amino-3-β-(methanesulfonamido)ethyl-N .

N-diethylaniline hydrochloride and 4-amino-N-ethyl-N-( 2-methoxyethyl)-m-toluidine di-p-toluenesulfonate Ru.

With negative-working halogenated emulsions, this processing step produces a negative image.

In order to obtain a positive (or reversal) image, this step requires non-chromatic color development. This can be done by developing exposed silver halide by developing it with a chemical agent. However, the unexposed halogen does not form dye and then uniformly fogs the element. To enable silver oxide to develop color. Alternatively, the positive image can be directly Emulsions can be used.

Development is followed by conventional steps: bleaching, fixing, bleach-fixing, silver and silver halide Wash and dry to remove.

The present invention also includes a process for preparing the compounds according to the invention. Tuning of other types of heterocyclic couplers Considering the production method, the compounds of the present invention can be produced relatively easily and in high yields. Because it can be done, the expense cost is low. Of course, manufacturing costs may vary in particular cases. Although this will vary depending on the particular substituents selected, the basic imidazozotope of the invention will nevertheless Riazoles are easy and economical to produce.

For example, prepare pyrazolotriazole couplers such as control coupler 02. from readily available starting materials to the final compound according to the text below. Up to 7 synthesis steps are required. This makes the manufacture of couplers economical It is. For example, the pyrazolone type couplers CI and C given below 2 is cheaper to prepare, the imidazotriazole couplers of the present invention are only It can be prepared in six or seven steps with high yields from inexpensive starting materials.

The method for preparing the basic imidazotriazole ring system is shown in Reaction Method 1 below. vinegar.

Reaction method l.

According to another feature of the invention, therefore, the formula where R', R'' and X are as shown above.

A method for preparing an imidazotriazole is provided, which comprises: a) 3-amino-1,2 , 4-) by reacting lyazole with 2-haloketone in the presence of a solvent and a base to form the corresponding providing a 2-ketoalkyl substituted triazole; b) dehydrating the product of step a) in the presence of a dehydrating agent; and C) optionally dehydrating the product of step b). It consists of attaching a coupling-off group to the product.

In a preferred embodiment of the invention, the solvent in step a) is acetonitrile and the base is tetramethylguanidine, and this solvent/base combination provides the best yield and selection. This is because alkylation does not occur on the 4-nitrogen of the triazole ring. It is.

In a further preferred embodiment of the invention, the dehydrating agent in step b) is concentrated sulfuric acid or other strong It is a mineral acid.

In a preferred embodiment of the invention, the coupling-off group (X) is a halogen, an alkyl Kirchisu or arylthio.

Preferred synthesis method for intermediate triazole when substituent R1 is aryl (Method 2) involves reacting an aryl hydrazide with S-alkylisothiourea. to provide an acrylaminoguanidine derivative, which is subsequently treated with 3-amino-5-a Thermal dehydration to reel-1,2,4-triazole.

Route R1 to the imidazotriazole used in the invention = optionally substituted aryl rule R = alkyl In a preferred embodiment of the present invention, when the substituent R1 is arylthio, a suitable intermediate A preferred synthesis method (Method 3) for 3-amino-5-mercapto-1 , 2,4-1 riazoaryl and alkyl halide are reacted in the presence of a base. to give 3-amino-5-alkylthio-1,2,4-triazole.

Method 3゜ A specific example of the synthesis of one suitable type of coupler is illustrated in the example below. Ru.

Nucleophilic substitution E-nitrobenzamide (Dissolve without stirring) Guanidine Final dehydration 5-amino-3-L- 1,2,4-triazole Stabilization by acylation 1-H-6-t-butyl-2-(4-acrylaminof phenyl) triazole The embodiments of the invention are presented for illustrative purposes only. Special mention of compounds Unless you are satisfied with proton cough magnetic resonance spectra, mass spectra, infrared gives the line spectrum. Comparison couplers were prepared using standard synthetic methods and are specifically described. do not.

Aminoguanidine bicarbonate (136.1 g, 1.0 mol) was added to acetic acid (IL). The mixture is heated gently on a steam bath until the evolution of carbon dioxide subsides, and the mixture is clarified. A solution was obtained. The solution was cooled to a temperature of 15-20 °C and added with sodium acetate (8 2.0 g, 1.0 mol) was added and the mixture was stirred until the solids were dissolved. ben Zirchloride (140.5 g, 1.0 mol) was cooled (<20 °C) Stir dropwise and the mixture is then brought to room temperature and stirred overnight (15 hours). did. The white precipitate (benzoic acid) was filtered off and discarded. Rotary evaporation of the filtrate Concentrate in a vacuum evaporator to obtain a clear oil, dissolve it in water (500 ml), and add IOH. The base was basified to 14 with sodium hydroxide solution. filtered and dried lilac A colored solid was obtained with a yield of 116.6 g, 65%.

C.H. Calculation for N and O Theoretical value: C53.9%, N5.7%, N31.4% Actual value: C54.5%, 85 ．． 7%, N 31. ．． 2% henzamide guanidine (91.0g, 0.51 Wood's mole) was placed in a round bottom flask and maintained at +50°C. Immersed in a metal bath. The temperature was raised to 220°C. Dissolve in day crepe dye (D[CREP[TATION) at °C, approx. It was re-solidified at 0°C. The dissolution was maintained at 220°C for 10 minutes and then cooled to room temperature. Rejected. The solid was crystallized from a minimum amount of water, yielding 77.7 g of the product as a white crystalline solid. , 95! Obtained in %.

Calculation for Cm H-N4 Theoretical value: C60.0%, N5.0%, N 35.096 Actual value: C60.2% , N5.15%, N34.9% base-promoted cyclization of benzamide guanidine Midoguanidine (1.78 g, 10 mmol) was added to 2M NaOH (50 mmol). 100 mmol) and heated on a steam bath for 1 hour. Analysis of TCL (EtOAc/silica) indicated that the reaction was complete. Mixture at 20° It was cooled to 7°C and the pH was adjusted to 7 with acetic acid. The product precipitated as a white solid, It was collected by filtration and air-dried at room temperature. The yield was 1.26g, 7996. TLC and I R was the same as the sample prepared above.

(c) 5-amino-1-acetylmethyl-3-phenyl-1,2°4-triazo rule 5-Amino-3-phenyl-1,2,44 lyazole (1,60 g.

10 mmol) was suspended in dry acetonitrile (25 ml) and chloroacetone ( 90% experimental grade, 1.13 g, 10 mmol) was added. in acetonitrile (5 ml) of tetramethylguanidine (1.27 g, 11 mmol) without stirring. dripped. The solid dissolved (slightly exothermic), producing a slightly light brown solution. mixture The mixture was stirred overnight (16 hours) and the solution was poured into water (400ml). Vinegar the product Extracted with ethyl acetate, dried, and concentrated to obtain a yellow glass (1.91 g, 88 %). This material is a TLC spot (EtOAc/silica) and further refined. It was used without being manufactured.

(d) 6-methyl-2-phenyl-1-H-imidazoN, 2-b) 5-amino- 1-acetylmethyl-3-phenyl-1,2,4-triazole (1.9 g, 8.8 mmol) was stirred with cold concentrated sulfuric acid (25 ml) for 1 hour. TLC minute Analysis (ethyl acetate/silica) showed complete conversion to product. This brown solution was added dropwise to sodium bicarbonate solution (1.5 L) and the pale yellow solid was collected by filtration, washed and dried. Drying yielded pure product (0.98g, 56%).

C,,H,. Calculation for N4 Theoretical value: C66,65%, H5,1%, N28.3% Actual value: C66,6%, 85.4%, N28.1% Example 2 N-(4-(1-H-6-t-butylimidazo(1,2-b) [1°2.4) -triazol-2-yl)phenyl)-2-(2,4-di-t-pentylphenyl) Preparation of noxy)-butanamide (coupler 16) (a) 4-nitrobenzamide guanidine S-methyl-2-thiopseudourea Sulfate (32.6 g, 117 mmol) was added to ice-cooled 1M sodium hydroxide (2 4-nitrobenzoic acid hydra in ethanol (120 ml) Jido slurry (21.2g.

117 mmol) was added. The mixture was stirred at room temperature for 1.5 days, during which time the color changed. The color changed from yellow to bright red. The solids were isolated by filtration and slurried in water (5 00ml) and dried under vacuum at 40°C to obtain 24.5g of red product. release The discarded filtrate was allowed to stand overnight, yielding an additional 1.5 g of fine, dark red needles.

Total pure product yield was 26.0 g, 99%.

(b) 5-amino-3-(4-nitrophenyl)-1,2,4-to-4-nitrobe nzamide guanidine (25.8 g, 116 mmol) for 15-20 minutes. Heat to 220-240"C with occasional stirring.During this time, the color of the solid changes to bright red. The color changed to light yellow and water was removed from the container.

The yield of pure product was 21.05 g, 88%. thin layer chromatography - (1% acetic acid/silica gel in ethyl acetate) indicates that the product is pure. did.

5-amino-3-(4-nitrophenyl)-1,2,4-triazole (21 , 0 g, , 102 mmol) was suspended in acetonitrile (200 ml), and Bromovina Colon (90% experimental grade, 20.6g, 115%) Then add 13.8g of tetramethylguanidine, 120ml mol), a slight exotherm was observed upon addition of the base and the solid partially dissolved. . The mixture was stirred overnight (for 19 hours), the solids were filtered off and washed with acetonitrile. As a slurry in water (200ml), air dried, 27.6g, 91% pure raw A product was obtained.

Analysis -; Calculated theoretical value for C+-HlyNs O-: C55, 4%, H5 , 65%, N23.1% Actual value: C55,2%, 85.5%, N23.2%5- Amino-1-(3,3-dimethyl-2-oxbutyl)-3-(4-nitrophe) Nyl)-1,2,4-triazole (27.5 g.

91.1 mmol) was added to the stirring concentrated sulfuric acid (80 ml) in divided portions. . The mixture was stirred until all solids were dissolved and stirred for an additional hour. second viscous Pour the solution into stirring water (600 ml) and stir for 30 minutes, leaving a slight A yellow solid was collected by filtration and washed with water. Moist solid saturated sodium bicarbonate solution (1.5 L), filtered, washed with water and placed in a vacuum oven at 70°C. Dry. Product yield was determined by TLC (1:l ethyl acetate/60-80'C petroleum ether). ether, silica gel) and was 25.2 g, <970.

Analysis; Calculated theoretical values for C,, H, 5N, O: C58.9%, H5.3 %, N 24.559 (i actual value: C58, 8%, H5, 35%, N24. 2% 1-H-6-t-butyl-2-(4-nitrophenyl)imidazo(1,2- b) C1,2,4)-triazole (60 g, 210 mmol) in ethanol Raney nickel (approximately 6 g) was added. mix 30 Hydrogenate at room temperature under ATM pressure and filter through diatomaceous earth to obtain a colorless solution. This was evaporated to dryness. Yield of gray solid is 50.65g, 95% there were.

2-(2,4-di-pentylphenoxy)butanoic acid (64 g, 200 mmol) ) was dissolved in ether (300 ml) and thionyl chloride (100 ml) was added. Then 2-34! i of pyridine was added. This mixture was gently refluxed for 1 hour. Then excess reagents and solvent were removed by rotary evaporation. stone Add oil ether (bp 60-80°C) to remove remaining thionyl chloride. It was removed by rotary evaporation in order to Repeat this twice, and A qualitatively pure acid chloride was obtained.

1-H-6-t-butyl-2-(4-aminophenyl)imidazo(1,2-b) (1,2,4)-triazole (50 g, 196 mmol) in tetrahydrocarbon Dissolved in furan (300ml) and pyridine (300ml). Tetrahydro Acid chloride (above) dissolved in furan (150 ml) was stirred at 5-8 °C for 0.5 h. While stirring, it was poured into stirring water (containing 500 ml of concentrated sulfuric acid) (8 L). tree The fatty solid was extracted into ethyl acetate (2L), washed and dried. solvent was removed and replaced with acetonitrile (1, SL) and then stirred for 2-3 hours. Conclusion Crystallization occurred after 10-15 minutes. Filter the faint cream-colored solid and add it to the acetate. Washed with nitrile and dried at room temperature. The yield of pure product was 92g, 84%. It was.

Analysis; Calculated theoretical value for C5=H4tN-Os: C73.2%, H8.5 %, N12.6% Actual side f: C73,0%, H8,2%, N12.4% or less The coupler is 1-H-6-t-butyl-2-(4-aminophenyl)imidazo(1 , 2-b) (1,2,4)-) Prepared in the same manner as lyazole (purification method and Yield and analytical values are given): coupler crystallized from ethyl acetate (22 ), 75% analysis; Calculated theoretical value for C24H4TNI Ox: C73 ,2%, H8.5%, N12.6% Actual value: C73.1%, H8.3%, N12 ．． 3% coupler (25) chromatography/silica gel/1: 1 ethyl acetate Le: 60-80℃ gasoline, 57% analysis; total for C2=HssN-Ox Theoretical value: C72.5%, H8.8%, N11.1% Actual value: C72.2%, 8 8.8%, N11.1% coupler (26) chromatography/silica gel/1 : 1 Ethyl acetate 60-80℃ gasoline, 60% analysis, C,, H,, N, O , Calculated theoretical values for S: C65.9%, H8.15%, N12.1%, 3 4.6% actual value: C65.7%, H8.3%, N11.9%, 34.5% coupler -(27) Chromatography/silica gel/1:1 ethyl acetate: 60-80°C Gasoline, 51% analysis; Calculated theoretical value for C2=H47N60-S: C 66.5%, H6.9%, N10.2%, 34.7% Actual value: C66.4%, H6.7%, N9.8%, 34.3% coupler (33) chromatography/silicon Lycagel/1:1 ethyl acetate: 60-80℃ gasoline, 58% analysis; Cs4H Calculated theoretical values for 4sNs Oz: C71.4%, N7.9%, N12 ．． 25% actual position: C71.6%, H8.0%, N12.1% 5-amino-3-methane Capto-1,2,4-triazole (50.0 g, 0.43 mol) was added to a dry aliquot. Suspend in setonitrile (435 ml) and stir to remove methyltetrazoka ate (144.5 g, 0.45 mol) was added. This is followed by acetonitrile (25 ml) of tetramethylguanidine (85.0 g, 0.44 mol) dropwise I put it down. The temperature of the mixture was maintained near room temperature with a water bath. solid or slightly soluble (exotherm), and was stirred for 2 hours to obtain a light brown solution, which was poured into water (5 L). the product Extracted into ethyl acetate, dried and concentrated to give a yellowish oil, which It was dissolved in gasoline at 60-80''C and stirred until crystallization was completed.

The pure white solid was filtered off, washed with a little gasoline, and air dried, 63.9 g. 42%.

Analysis; C1vH**N40t Calculated theoretical value for S: C57, 3%, 8 9.05%, N 15.7%, 39.0% actual value + C57.4%, H9, 0%, N15.9%, 88.7% Methyl 2-(5-amino-1,2,4-t lyazol-3-ylthio]tetrazocaate (22.2 g, 0.060 mole bromochloride) was suspended in dry acetonitrile (135 ml) and stirred. Vinacolin (12.9 g, 0.072 mol) was added. This is followed by acetonitol. Tetramethylguanidine (8.3 g, 0.072 mol) in lily (10 ml) was dripped. The temperature of the mixture was maintained near room temperature with a water bath. Stir the solution overnight (18 hours) and then poured into water (1.5 L). The product was extracted into ethyl acetate. , dried and concentrated to give a yellowish oil, 25.8 g.

95%. TLC (1:I EtOAc:Gasoline), NMR, and MS The product was sufficiently pure to proceed to the next step.

The crude product from (3c) (25.7 g, 0.057 mol) was dissolved in concentrated sulfuric acid (6 0 ml) and stirred for 1.5 hours, then added dropwise into saturated sodium bicarbonate solution (2 L). This solution was adjusted to pH 7 with further sodium bicarbonate and then dissolved in ethyl acetate. extracted. The extract was washed with water and dried to remove the solvent. Column crude product Purification by chromatography: 1:2 ethyl acetate: 60-80℃ gasoline/silica ), a cream powder product was obtained, 15.4 g, 62%.

Analysis,C,,H,. Calculated theoretical values for N, O, S: C63.3%, N9.2 %, N12.8%, 37.3% Actual value: C63.1%, N9.0%, N12.9 %, 37.1% (d) Methyl-2-(1-H-6-t-butylimidazo(1,2 -b) (1,2,4))lyazol-2-ylthio)tetradecanoic acid (coupler 14) Methyl-2-(1-H-6-t-butylimidazo(1,2-b)(1,2,4) -triazol-2-ylthio)tetrazocanny) (3.5 g, 8.03 mm Limol) in ethanol (35 ml) and sodium hydroxide in water (5 ml). (1.0 g, 25 mmol) was added at room temperature and stirred for 1.5 hours. acetic acid (5 ml) This solution was added dropwise to an aqueous solution (400 ml) and extracted with ethyl acetate. A milky emulsion was obtained. This extract was washed with water, dried and dried with diethyl ether ( 50 ml), distilled to a light oil and stirred until crystallization was complete (l- 2 hours). The white product was collected by filtration, washed with ether and air dried to yield 2.07g. . A second product was obtained from the filtrate upon standing, 0.24 g, total yield of product was 2 ．． It was 31g, 68%.

Analysis: Calculated theoretical values for C, 2H,, N, 02S: C62.5%, N9. 1%, N13.3%, 37.6% Actual value: C62.2%, N9.0%, N13. 0%, 37.6% comparison coupler Comparison coupler Cl N-((3-((1-(2,4,6-drichlorophenyl)pyrazol-5-o -2-(2,4-di-t-pentylphenyl) (oxy)acetamide comparison coupler C2 N-((4-(3-(6-methyl-7-chloropyrazole[2,3-C]tri azol-3-yl)propyl)phenyl))-2-(4-(4-hydroxyphenyl)) phenylsulfonyl) phenoxy) dodecanamide Control coupler C3 N-(4-chloro-3-(1-(2,4,6-)lichlorophenyl)pyrazole -5-one-3ylamine)')-2-(4-(4-hydroxyphenylsulfur) (onyl) phenoxycodedecaneamide Some imidazotriazoles of the invention Spectrophotometric data for the couplers are set forth in Table 1 below. In particular, certain triazo gives the hue of azamethine dyes derived from alcohol couplers in ethyl acetate.

Coupler λmax/nm CD4 λwax/nm CD2 number (HBW/ nm) (HBW/nm) (+3) 542 (82) 534 (84) --- − (16) 538 (80) ss2 (85) (CI) 538 (82) 526 (74) (C2) 531 (71) 524 (71) 9 Dye is E It is insoluble in tAOC and unstable in aqueous base.

CD4 CD2 Example 5 The photographic data for these imidazotriazole couplers is the standard KODAK Experiments were conducted on coatings treated in the C-41 process.

This C-41 process is the standard K-41 process for developing color negative films. Odak's commercial process, the E6 process is a used in film development.

Sensitizing layer Ag emulsion (standard 1.61 gm-2 factor Ricoda color emulsion) Coupler Laydown 1.04 mmolm-2 Gelatin Laydown 2. 42 gm-2 hardening agent 0.06 gm-2 Dispersant formulation 6% w/w gelatin, 8.8% coupler, coupler: KSr: KSA48 1:0.5:1.5KSI=) Recrecil phosphate KSA48 = 2-(2-butoxyethoxy)ethyl acetate imidazotriazo Coupler photo result coupler Dmax Dmin □ (14)" 0.44 0.14 0.35 204 - - (16) 0.6 3 0.09 0.31 - 551 (104) (17) 1.77 0,1 1 1.15 214 547 (101) (1g) 0.37 0.09 0 ．． 29 208 - - (19) 0.61 0.10 0.31 235 5 50 (98) (20) 1.74 0.13 1.17 214 549 ( 101) (25) 1.10 0.09 0.57 225 546 (110 ) (26) 129 0.11 0.91 185 552 (102) (27 ) 2.2Q O, 251, 36230554 (104) (33) 0.73 0.11 0.43 203 551 (100) (35) 1.29 0.2 6 1.12 243 544 (103) (36) 1.75 0.25 1 ．． 97 205 547 (103) (CI) 2.38 0.15 2.29 212 555 (96) Therefore, the present invention provides a new magenta for color photography. Couplers and methods of making the same are provided.

Submission of translation of written amendment (Article 184-8 of the Patent Law) July 2, 1993

Claims (14)

[Claims] 1. formula ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formula, R1 and R2 are the same or H, alkyl, substituted alkyl, aryl, substituted aryl, hetero aryl, alkylthio, carboxylic acid or ester, primary or secondary amide, Sulfonamide, mono- or disubstituted amino, alkoxy or arylox selected from; and X is H or a group that can be released upon oxidative coupling with a color coupler. ) photo coupler. 2. The coupler according to claim 1, wherein R2 is substituted or unsubstituted alkyl. -. 3. In the preceding claims, R1 is selected from substituted aryl or alkylthio. Coupler listed in any of the above. 4. X is released upon oxidative coupling, and hydrogen, halogen, alkyl group A capacitor according to any of the preceding claims selected from a Ra. 5. wherein R1 or R2 is composed of or includes a ballast chain; A coupler according to any of the claims. 6. formula ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R1, R2 and X are as shown in claim 1) a) 3-amino-1,2,4-triazole with 2-haloketone, solvent and base reacting in the presence of to produce the corresponding 2-ketoalkyl substituted triazole; b) dehydrating the product of step a) with a dehydrating agent; and c) optionally the product of step b) The production of an imidazotriazole of the above formula comprising the steps of attaching a coupling group to Law. 7. The solvent in step a) is acetonitrile, and the base is tetramethylguanidine. The method according to claim 6. 8. The method according to claim 6 or 7, wherein the dehydrating agent in process type b) is concentrated sulfuric acid. . 9. The coupling-off group (X) in step c) is halogen, alkylthio or 9. The method according to any one of claims 6 to 8, which is reelthio. 10. The substituent R1 is aryl, and the intermediate ketokyl-substituted triazole or aryl or an alkylthio-substituted aminotriazole. The method described in any of the boxes below. 11. Aryl-substituted aminotriazole converts acyl hydrazide to S-alkyl- Reaction with isothiourea to form an intermediate product, followed by thermal dehydration to obtain the target compound. 11. A method according to claim 10, wherein the method is formed by producing. 12. The target compound is 3-amino-5-aryl-1,2,4-triazole. 12. The method according to claim 11. 13. Alkylthio-substituted aminotriazole is 3-amino-5-mercapto-1 , 2,4-triazole and alkyl halide are selectively reacted in the presence of a base. 11. The method according to claim 10, wherein the method is formed by providing the target compound. 14. The color coupler according to claims 1 to 5, or the claim The range includes magenta couplers prepared by the method described in items 6 to 13. Photographic elements.