JPH04229862A - Color developing method - Google Patents

Abstract

PURPOSE: To provide a color coupler which can be applied as a color developing color coupler that forms a magenta or cyan dye each having a bright color tone by using a specific color coupler compound. CONSTITUTION: In this method, the color coupler used is a heterocyclic imidazo compound represented by the formula. In the formula: each of R<1> and R<2> is H, a halogen, a -SCN, alkyl, aryl or alkoxyl group, or the like, wherein at least one of R<1> and R<2> is H, a halogen or an eliminable group under the conditions of color development; and Q is a compound necessary to completely form a fused heterocycle contg. at least one nitrogen atom. A color photographic material contg. an exposed silver halide emulsion is developed with a p- phenylenediamine type color developer compound.

Description

[Detailed description of the invention]

The present invention relates to a color photographic process in which the coupling product with a color developer of the 2-methyl-4-dialkylaminoaniline type exhibits an absorption in the green and/or red spectral range and a strong absorption in the infrared region. Concerning a novel color coupler for.

More particularly, this invention relates to new highly reactive cyan couplers.

The color couplers used according to the invention are heterocyclic imidazo[1,5-a] compounds.

Certain compounds used according to the invention, such as compounds 1, 2, 3, 6 below, are known per se and contain imidazo[1,5-a] as a coupling component.
The corresponding azo dyes prepared with pyridine or by other methods [DE-A-30 47 305
and DE-A-31 15 648]. The abovementioned azo dyes exhibit orange to violet hues which, after metallization, are shifted into the cyan region.

[0005] Chromogenic method
imidazo for coupling in cess) [
1,5-a] type of heterocyclic imidazo compounds was unknown.

It has also been found that magenta-cyan dyes are obtained as a result of color coupling reactions which have a light tone and, in some cases, a high degree of resistance to light fading and dark fading under conditions of high air humidity. is new.

The present invention provides that the color coupler compound has the formula (I).

[0008]

embedded image In the formula, R1 and R2 are H, halogen (e.g. Cl, Br
), -SCN, alkyl, aryl, alkoxy, aryloxy, alkylthio, arylthio, a heterocyclic group optionally bonded to the S-atom, an azo group, acylamino, carbamoyl or alkoxycarbonyl, with the proviso that a substituent At least one of R1 and R2 is H,
Represents a halogen or a group that can be removed under color development; Q
completes a fused heterocyclic ring containing at least one nitrogen atom, in the presence of a color coupler compound, at least one
This invention relates to a photographic color development process consisting of developing a color photographic material consisting of a silver halide emulsion layer with exposed seeds with a color developer compound.

The heterocyclic ring completed by Q preferably has 5 or 6 ring members and is, for example, pyridine,
It is a pyrimidine, triazine, pyridone, pyrimidone or thiadiazine-1,1-dioxide ring. The above rings may optionally contain other fused rings, especially benzene rings, and may be substituted with suitable substituents. R
1. The alkyl group represented by R2 or present in R1, R2 can contain, for example, from 1 to 18 carbon atoms and can be straight-chain or branched,
It can also have other substituents as needed.

R1, R2 or R
The aryl group present in 1.R2 is, for example, a phenyl group, which may be substituted, for example, by Cl, -OH, alkyl, alkoxy, alkylthio or sulfamoyl.

R1, R2 or R
1. Heterocyclic groups present in R2 include, for example, pyridine, thiazole, thiadiazole, imidazole, 1,2,3
-triazole, 1,2,4-triazole or tetrazole group.

Depending on the fused heterocycle, the coupling position and substituents, and also the color developer and oil former used, the dye exhibits strong absorption in the linear and red regions of the spectrum, and also strongly in the infrared region. The new absorbable couplers are characterized by a high degree of coupling activity and do not require any rapid conversion from the leuco stage to the dye. The absorption band is generally characterized by a small half band width. 1-arylimidazo[1,
5-a] Pyridine has a high color yield (color yie
ld) and are cyan couplers characterized by a light tone, while imidazo[1,5-b]1,2,4-triazoles are very suitable as magenta couplers. Depending on the substituents in the 1 and 3 positions that can be coupled, the substituents are based on the 4-equivalent principle (H, -SO3H, -N=N
-aryl) or as a two-equivalent color former; cleavage of the nucleophilic group can produce specific photographic effects. In addition, after removal of the intermediate element, the nucleophilic groups that develop its photographic effect can be removed.

The groups represented by R1, R2 in formula I which are removable under color development conditions are, for example, themselves residues of photographically active compounds or are formed by oxidation of the silver halide developer. It is a group which, after being removed from the coupling position of the coupler during its coupling with a substance, can release the residue of the photographically active compound attached to it during the subsequent reaction. Such groups may also be used as timing elements (timi
ng element) because the residues of the photographically active compound bound to it are often released and activated with a delay. Known timing elements, e.g. groups where the C atom is bonded to the N atom of the photographically active compound (e.g. DE-A-27 03 145), allow intramolecular spherical nuclear reactions to occur after removal of the coupler. and a group that releases the photographically active compound (e.g. DE-A-28
55 697), after removal from the coupler, electron rearrangements can occur along the bonding system, thus releasing the photographically active compound (e.g. DE-A-31
05 026 is attached to the reference ring position, while the C atom is attached to the atom of the photographically active compound and R represents, for example, aryl (e.g. EP-A-0 127 063
reference). Additionally, the timing element is a group that, after removal from the coupling position of the coupler, can itself enter into a coupling or redox reaction and, as a result of that reaction, releases the photographically active compound bound to it. can be.

Groups which can be removed under color development conditions are, for example, organic groups, which are generally attached to an oxygen, sulfur or nitrogen atom in the coupling position of the coupler molecule. If the releasable group is a cyclic group, it can be bonded directly to an atom that is part of the ring, such as a nitrogen atom, at the coupling position of the coupler molecule, or indirectly via an intermediate atom. Many such releasable groups are known, for example as 2-equivalent couplers.

Examples of releasable groups bonded by oxygen correspond to the following formulas:

[0016]

##STR00003## where R3 is an acyclic or cyclic organic group, such as an alkyl, aryl, a heterocyclic group or an acyl derived from, for example, an organic carboxylic or sulfonic acid. In particularly preferred releasable groups of this type, R3 is an optionally substituted phenyl group. Groups of this type are e.g. US-A-3,408,194, DE-A-2
4 56 076.

Examples of releasable groups bonded by nitrogen can be found in the following German patent publications:
ungsschrifts (DE-A): 20 57 941, 21 63 812,
22 13 461, 22 19 917, 22 61
361, 22 63 875, 23 18 807,
23 29 587, 23 44 155, 23 63
675, 24 33 812, 24 41 779,
24 42 703, 25 28 638, 25 28
860, 26 37 817, 28 18 373,
30 20 416.

The heterocyclic rings are all 5- or 6-membered heterocyclic rings that are attached to the coupling position of the coupler by a ring nitrogen atom. Often the heterocyclic ring contains an activating group, such as a carbonyl or sulfonyl group or a double bond, adjacent to the nitrogen atom that establishes the linkage to the coupler molecule.

Photographically active compounds include development inhibitors, bleach inhibitors, development accelerators, and "nucleating agents."
ing agents"), soluble development-promoting mercaptan compounds, stabilizers, white couplers, scavengers such as phenidone-type electron transfer agents, or color coupler compounds.

Development inhibitors are in particular benzotriazoles,
Thienotriazole, non-fused monocyclic 1,2,3-triazole, 3-alkylthio-1,2,4-triazole; 5-mercapto-1-alkyl or 5-mercapto-1-aryltetrazole and 2-mercapto- 5
-Alkylthio-1,3,4-thiodiazole.

Photographically useful leaving groups, such as development inhibitors, development activators or nucleating agents, can be attached in a variety of ways.

For example, the introduction of thiol or thiocyanate groups directly into the fighting ring and subsequent reduction with borohydride generates thiol groups with halogenated heterocyclic precursors of the inhibitor, such as 1- Aryl-5
-chlorotetrazole or a reactive halogen atom, such as bromine or chlorine, can be exchanged at the coupling position with a photographically active leaving group. This can be defined, for example, by leaving groups, in particular 1,2,
It applies to development activators containing leaving groups of the 3- or 1,2,4-triazole type or benzotriazole type, or development inhibitors or free thiol groups. The presence of an inorganic or organic auxiliary base is preferred for the reaction.

In addition, the color couplers according to the invention can be provided with ballast groups. Ballasting groups are groups that make it possible or easy to incorporate the color couplers according to the invention into non-dispersed form in the hydrophilic colloids typically used in photographic materials. Preferred ballast groups are generally organic groups with straight or branched aliphatic groups and optionally carbocyclic or heteroaromatic groups, generally containing from 8 to 20 carbon atoms. These groups are linked directly or indirectly to the rest of the molecule, for example by one of the following groups: -NHC
O-, NHSO2-, -NR-, where R is hydrogen or alkyl, -O- or -S-. In addition, the ballast group may also contain water-soluble groups, such as sulfonic or carboxyl groups, which may be present in anionic form.

Although the new coupler itself shows a clear affinity for absorption for silver halide, it also
The absorbency of in) can be improved by incorporation of additional functional particle-absorbent groups in addition to or instead of ballast groups. Reference may be made to this for the sensitized particle-absorbing couplers described in DE-A-3900 115.

Examples of color couplers according to the invention are:

[0026]

embedded image The color coupler according to the invention can be produced by the following method: 1. Synthesis of ring Q from the existing imidazole substructure by condensation reaction, e.g. imidazo[1,5-2]
Pyrimidines, such as those described by Novinson, J.; Med.
Chem. 19, 517-520 (1976), J. H
eterocycle. Chem. 11, 873-878
(1974).

2. via acylamino compounds or by ring fighting with cyanogen chloride or thiocarbonyldiimidazole or isothiocyanete.

[0028]

Synthesis of imidazole ring from [Chemical formula 5] 2.1. Preparation of 2-aminoalkylheterocycles by direct introduction of N atoms as electrophilic groups and reduction of e.g. arylazo, nitro, nitroso, azide groups, the reducing agent is inter alia H2(+catalyst), base metals, e.g. Zn, H2S+base, dithionite, tin(I) in the medium
I) It is a salt.

2.2. Mitsunobu (M) in thiazole type
For example, the introduction of carbinol groups with electrophilic substituents by reactions [Schmidt, Utz
, Angew. Chem. 96, 723 (1984),
Also Mitsunobu, Synthesis 19
81, 1 and zviral, Helv. Chim. A
cta 2100 (1976)]: in this case the azide is first introduced and then reduced.

2.3. Introduction by reduction of oximes or hydrazones obtained from 2-acyl heterocycles by derivatization.

Examples of such methods are:2.
4. Introduction of amino groups in free or masked form during the synthesis of heterocycles (Q), e.g. α-amino,
By synthesis from acylamino or alkoxycarbonylaminocarboxylic acids, nitriles, thioamides or amidoximes.

Example: Johnson, Gatewood:
J. Am. Chem. Soc. 51, 1815-182
0 (1929).

Other examples include Pyl et al., Liebigs
Ann. Chem. 676, 141-150 (1964
) can be found in

2.5. In an electrophilic substitution reaction, an aminoalkyl group is indirectly substituted with an alkylthio group, a sulfone group, or a reactive halogen via the corresponding electrophilic nitroalkane, which is substituted with the corresponding heterocycle or heterocycle precursor. introduction. A corresponding example is a series of 3 that yields 3-aminomethylpyrazolones upon reduction.
- Schaefer for nitromethylpyrazole
, Gewald, J. Prakt. Chem. 325,
Volume 1, 41-48 (1983). 2.3. Reference: Synthesis of oximes via 2-acyl heterocycle: metalation → carbonyl → debenzylation -
2-Aroylimidazole with oxide, (CrO3), Bastiaansen, Godefroy, Sy
nthesis 1978, p. 675, Ohta et al.
Heterocycles 23, Volume 7, 1759~
1764, Tetrahedron Lett. 25,
Vol. 30, 3251-3254 (1984) 2-benzoylbenzimidazole a. Carbinol (mandelic acid) m. CrO3, Przeworski, Ber. 45
, 3249, (Beilst.24 I 292; melting point 209°C) 1-phenyl-3-acylimidazole B
orsche, Butetschli, Ann. 522 [
1936], 285, 2952-thiazolylketone (ketoximine), Ermolaeva, Shchu-ki
na, Zhur. Obshch. Khim. 32, 26
64 (1962), 33, 825 [1963], 33,
2716 [1963] 2-Acylpyridine: Direct acylation of 2-picolinic acid, Karlivan, Walter
; Khim. Geterotsikl. Soedin.
9, 1231-1234 (1984) 3-acylpyrazoles by direct ring fighting via the intermediate acylhydrazone (most common method) by reaction of Grignard compounds or organolithium compounds with 2-cyanopyridines [Eastman , Detert;J. Am. Chem
．． Soc. 70, 962-964 (1948)] 1-acylisoquinol from isoquinoline-N-oxide by base-induced fragmentation/rearrangement of the corresponding acylalkoxyisoquinolinium salt [Sliwa, Gu
attara; Heterocycles 26, 1st
2, 3065-3069 (1987)] from phenacyl azide by thermal decomposition [Boyer, Straw; J. A
m. Chem. Soc. 74, 4506-4508 (1
952)], or from phenylglyoxal by the action of ammonia [Pinner; Ber. Dt. Che
m. Ges. 38, 1531-1538 (1905)]
Specific 2-benzoylimidazole production example compound 3 3.1. 2-benzoyl oxime was refluxed in ethanol for 2 hours with a 1.2 times molar amount of hydroxylamine aqueous solution of 2-benzoylpyridine.
A mixture of species isomers was prepared and used without further purification. Melting point: 131-140°C.

3.2. 2-(α-amino)-benzylpyridine: A document states that the desired results cannot be obtained by reducing phenyl-2-pyridylketoximine with zinc dust, Boyer, Wolford; Org. Ch
em. 23, 1953 (1958), contrary to Joch
ims method, Monash. Chem. 9
4, 677 (1964), the amine was obtained in a yield of 76% of theory by reduction with zinc dust in the presence of ammonia.

3.3. 1-phenylimidazo[1,5
-a] pyridine as described by Bower, Ramage: J. C
hem. Soc. 1955, 2834 by heating 2-(α-formamido)-benzylpyridine with phosphorus oxychloride in toluene or dichloromethane on a steam bath for several hours. Melting point 104-105°C.

Compound 11 11.1. 4-n-Dodecyloxybromobenzene was etherified with 1-bromododecane for 6 hours at reflux temperature after addition of 1.1 times the molar amount of potassium tert-butyrate to 4-bromophenol in dimethylformamide. It was manufactured by hand. Melting point 34-35°C.

11.2. 51 g of 4-dodecyloxybromobenzene were added over a period of 3 hours to a stirred suspension under reflux of 4.1 g of magnesium flakes and 3 g of bromobenzene in 150 ml of anhydrous tetrahydrofuran. After dissolving the magnesium, the Grignard solution, which turned dark in color, was cooled to 0°C and 2-
A solution of 60 g of cyanopyridine was added with stirring. 1
After an hour, the reaction mixture was treated by addition of tetrahydrofuran containing 10% water and acidification. Yield after crystallization from methanol: 23 g, mp 57-58°C after recrystallization from methanol.

11.3. By refluxing the ketone 11.3 (20 g) in 200 ml of ethanol together with a 1.5-fold molar amount of an aqueous hydroxylamine solution, 17 g of an oxime consisting of two isomers having a melting point range of 115-125°C was obtained.

11.4. 4-n-dodecyloxy-α
-2-Pyridylbenzylamine A suspension of 6 g of compound 11.3 and 9 g of zinc dust in 100 ml of 25% NH3 and 100 ml of ethanol was heated under reflux for 2 hours after addition of 1.5 g of ammonium acetate. The solution was filtered hot from the residue and concentrated under reduced pressure. After stirring with water, 4.5 g of a white waxy substance was obtained which melts at 74-78°C.

11.5. 2-(4-dodecyloxy-
3.2 g of the compound 3.2 g of α-formamide)-benzylpyridine are left for 1 hour with a freshly prepared mixture of 3 ml of formic acid and 3 ml of acetyl pyridine, then heated on a steam bath for 30 minutes and finally , concentrated by evaporation to dryness under reduced pressure. The reaction mixture was taken up in 10 ml of 10% sodium acetate solution, filtered with suction and air-dried. Yield: 2.95g, melting point: 82-83°C
.

11.6. 2g formamide compound 2
g was heated under reflux for 2 hours with 4 ml of phosphorus oxychloride in 12 ml of toluene and concentrated by evaporation under reduced pressure. The residue was dissolved in 50 ml of 10% potassium carbonate solution and 5 ml of ethyltoluene.
After taking up 0 ml and separating the organic phase and drying over sodium sulfate and filtration, the product was chromatographed on 500 g of silica gel with an increasing gradient of ethyl acetate using toluene as eluent. After concentration by evaporation and recrystallization from ethyl acetate/hexane, 0.78 g of pale brownish crystals melting at 175-178°C are isolated from the eluent, which contains as the main component the color After coupling with developer/alkaline persulfate, it contained bright cyan spots (TLC
:Silica gel, eluent: toluene/ethyl acetate 7:30
).

Compound 25 25.1. Isonitrosobenzo 1,2,4-sulfonediazine-3-acetic acid ethyl ester DE-A 3 9
25 438, 27 g of benzo-1,2,4-sulfonediazine-3-acetic acid ethyl ester was dissolved in 250 ml of acetic acid at 70°C, and after cooling to 25°C, 13.8 g of sodium nitrite was dissolved in 1 Added small amounts over time. The mixture was stirred for 30 minutes and, after addition of 200 g of ice, filtered with suction. Yield: 20.1 g (67% of theory). Melting point 2
24-226°C (decomposition).

25.2. Ethyl-α-formamide benzo-1,2,4-thiadiazine-1,1-dioxide-3-acetate 18 g of isonitroso compound 25.1. 200m of formic acid
1 of zinc powder by heating, and 12 g of zinc powder was added to the resulting solution.
was added little by little while stirring. After decolorization, the residue was filtered off with suction, and 50 ml of acetate and 50 ml of formic acid were added.
A freshly prepared mixture of was added. The mixture was heated in a steam chamber on a steam bath and then concentrated by evaporation under vacuum. The residue was stirred with water and filtered with suction. Yield: 16.4 g (88% of theory). Melting point: 188
~190℃.

25.3. 10 g of compound 25.2 and 12 g of triphenylphosphine were dissolved in 200 g of acetonitrile.
After addition of 15 ml of triethylamine and 30 ml of carbon tetrachloride, the resulting mixture was left overnight. Then 1 kg of ice was added and after extraction three times with 500 ml of toluene, the organic phase was treated with diatomaceous earth. After filtration through a glass frit, the reaction mixture was concentrated by evaporation under vacuum, taken up in toluene and chromatographed on 250 g of silica gel with toluene and an increasing gradient of ethyl acetate as eluent. The product eluted as a strong cyan coupling spot [thin layer chromatogram on silica gel, eluent dichloromethane/ethyl acetate 7:3, color developer CD in the eluent.
3 (3-methyl-4-amino-N-ethyl-N-methanesulfonamidoethyl-aniline sulfate) and detected by spraying with an alkaline potassium persulfate solution]. Yield: 2.5 g after stirring with petroleum ether and crystallization from methanol Compound 26 26.1. A mixture of 279 g of dodecylcyanoacetate N-dodecanol and 128 g of cyanoacetic acid was heated to 120° C. with stirring after addition of 3 g of p-toluenesulfonic acid.
for 3 hours while passing a nitrogen stream through it. After cooling, 336.8 g of solid was obtained.

26.2. 3-Imino-3-epoxypropionic acid dodecyl ester/HCl dichloromethane 5
253 g of compound 26.1 in 00 ml. A solution of 53 g of ethanol was saturated with HCl gas at 0°C. 0℃
After leaving it for 40 hours, add 1000ml of toluene,
Approximately 500 ml of solvent was evaporated under vacuum. The precipitated salt was filtered off with suction, washed with a little toluene and dried under vacuum at room temperature. Yield: 300g. Melting point 65-67°C.

26.3. dodecyl-benzo-1,2,
153 g of 4-thiadiazine-1,1-dioxide-3-acetate 2-aminobenzenesulfonamide was heated to 100°C in 250 ml of methyl glycol, and 149 g
Compound 26.2. was introduced with stirring, and the mixture was reduced to 1
00° C. for 30 minutes, and then added 149 g of compound 26.
．． 2. was introduced and the mixture was heated to 100° C. for a further 30 minutes. It was then allowed to cool to room temperature, introduced into 1000 g of ice, the crystalline material was filtered off with suction, and the product was washed with water. After drying, 7
283 g of compound 26.3. melting at 6-81°C. was gotten.

26.4. 27.2 g of benzo-1,2,4-sulfonediazine-3-(α-isonitroso)-acetic acid dodecyl ester 20 g of sodium nitrite heated to 50°C
Compound 26.3. was added little by little to the suspension with stirring, and the temperature rose to 70°C as nitrogen oxide was generated. After stirring for 30 min, the reaction mixture was introduced into 400 g of ice and, after neutralization with sodium bicarbonate to a pH value = 5, extracted 3 times with 300 ml of dichloromethane, the dichloromethane phase was dried over Na2SO4 and concentrated under vacuum. and dispersed in 90% aqueous methanol. 8 g of yellowish crystals melting at 138-142°C were obtained.

26.5. Dodecyl (formamide benzothiadiazine-1,1-dioxide)-acetate 1
0.9 g of compound 26.4 in 110 ml of formic acid at 80°C
heated to. After introducing 5 g of zinc dust, decolorization occurred with increasing temperature and foaming. After the temperature had fallen to 50° C., a freshly prepared mixture of 20 ml acetanhydride and 20 ml formic acid was introduced. After heating on a steam bath for 20 minutes, the off-white zinc salt was filtered off with suction and the reaction product was concentrated by evaporation under vacuum and recrystallized from cyclohexane. Yield: 8.3 g of a compound with a decomposition melting point of 120-127°C.

26.6. A mixture of 4 g of compound 26.5 and 8 g of phosphorus oxychloride was heated in 25 ml of toluene on a steam bath for 4 hours. After cooling, the mixture was poured onto 200 ml of saturated sodium bicarbonate solution and 200 g of ice;
The organic phase was separated after addition of 200 ml of ethyl acetate and
Dry over 2SO4 and concentrate by evaporation. Two coupling spots appeared in the thin layer chromatogram (eluent: dichloromethane/methanol 95:1, propellant: 3-methyl-4-amino-N-ethyl-N-hydroxyethylanilinosulfate + alkaline). persulfate solution). By column chromatography,
0.9 g of cyan-coupled spots were recovered from the corresponding eluate after evaporation and co-disintegration with methanol. Melting point: 98-180°C. In the proton resonance spectrum (60 MHz), the signals of the dodecyl ester group were 0.8 to 1.9 ppm and 4.2 to 4.5 ppm.
other signals (aromatic) appeared at 7.1-8.1
and 9.15 ppm (NH).

[0051] In the method according to the invention, at least one
A color photographic material containing two exposed silver halide emulsions is developed with a color developer compound of the p-phenylenediamine type. Color couplers according to the invention can be present in materials in spatial and spectral association with the light-sensitive silver halide emulsion layer.

In the context of the present invention, the spatial association is based on the specific halogenation with which the two can interact such that the color coupler forms a corresponding image between the silver image produced during development and the dye image produced by the color coupler. It means that they exist in spatial relationship with each other in the silver emulsion layer. Generally this result is achieved by including color couplers in the silver halide emulsion layer itself or optionally in an adjacent light-insensitive binder layer.

Spectral relatedness means that the spectral sensitivities of each of the colors of the component dye images resulting from a light-sensitive silver halide emulsion layer and a particular spatially related color coupler have a certain relationship to each other. Generally, component dye images for other colors (eg cyan, magenta, yellow) are associated with each of the spectral sensitivities (red, green, blue). Depending on the color resulting from the color couplers according to the invention (cyan vs. magenta), these couplers are preferably associated with silver halide emulsion layers that are spectrally sensitive to red and/or green light.

In addition, the material may contain compounds different from the coupler, which compounds may include releasable compounds, such as development inhibitors, development accelerators, bleach accelerators, developing agents, silver halide solvents, fogging agents, etc. agents or anti-fogging agents, such as the so-called DIR hydroquinone, as well as e.g. US-A-4
,636,546,4,345,024,4,684,
604 and DE-A-31 45640, 25 15
213, 24 47 079 and EP-A-198
438. These compounds function similarly to DIR, DAR, and FAR couplers, except that they do not produce coupling products.

High molecular weight color couplers are, for example, DE-
C-1 297 417, DE-A-24 07 56
9, DE-A-31 48 125, DE-A-32
17 200, DE-A-33 20 079, DE-
A-33 24 932, DE-A-3331 743
, DE-A-33 40 376, EP-A-27 2
84, US-A-4,080,211. Generally, high molecular weight color couplers are prepared by polymerization of ethylenically unsaturated monomeric color couplers. However, they can also be obtained by polyaddition or polycondensation. Color couplers according to the invention can be incorporated into silver halide emulsion layers by first preparing a solution, dispersion or emulsion of the particular compound and then adding it to the casting solution for the particular layer. The selection of the appropriate solvent or dispersant depends on the particular solubility of the compound.

Methods for introducing substantially water-insoluble compounds by milling are described, for example, in DE-A 26 09 741.
and DE-A-26 09 742.

Hydrophobic compounds can also be introduced into the pouring solution using high-boiling solvents, so-called oil formers. Corresponding methods are described, for example, in US-A 2,322,02
7, US-A-2,801,170, US-A-2,8
01,171 and EP-A-0 043 037.

Oligomers or polymers, so-called polymeric oil formers, can be used instead of high-boiling solvents.

The compounds can also be introduced into the casting solution in the form of a charged latex, eg D
E-A-25 41 230, DE-A-25 41
274, DE-A-28 35 856, EP-A-0
014 921, EP-A-0 069 671, E
P-A-0 130 115, US-A-4,291,
See 113.

Anionic water-soluble compounds (eg dyes) can also be introduced in a non-dispersed manner using cationic polymers, so-called mordant polymers.

Suitable oil formers are, for example, phthalic acid alkyl esters, phosphonic esters, phosphoric esters, citric esters, benzoic esters, amides, fatty acid esters, trimesic esters, alcohols, phenols, aniline derivatives and hydrocarbons. be.

Examples of suitable oil formers are dibutyl phthalate, dicyclohexyl phthalate, di-2-hexyl phthalate, decyl phthalate, triphenyl phosphate, tricresyl phosphate, 2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate. , tri-2-ethylhexyl phosphate, tridecyl phosphate, tributoxyethyl phosphate, trichloropropyl phosphate, di-2-ethylhexyl phenyl phosphate, 2-ethylhexyl benzoate, dodecyl benzoate, 2-ethylhexyl p-hydroxybenzoate , diethyldodecaneamide, N-
Tetradecylpyrrolidone, isostearyl alcohol,
2,4-di-t-amylphenol, dioctyl azelate, glycerin tributyrate, isostearyl lactate, trioctyl citrate, N,N-dibutyl-
2-butoxy-5-t-octylaniline, paraffin, dodecylbenzene and diisopropylnaphthalene.

Color photographic negative materials are usually developed, bleached,
Processed by fixing and washing or by developing, bleaching, fixing and stabilizing without subsequent washing. Bleaching and fixing can be combined in one processing step. Suitable color developer compounds are any compounds capable of reacting in the form of their oxidation products with any color coupler according to the invention to form an azomethine dye. Suitable color developer compounds are aromatic compounds of the p-phenylenediamine type containing at least one primary amine, such as N,N-diethyl-p-phenylenediamine, 1-(N
-ethyl-N-hydroxyethyl)-3-methyl-p-
such as phenylenediamine, 1-(N-ethyl-N-hydroxyethyl)-3-methyl-p-phenylenediamine and 1-(N-ethyl-N-methoxyethyl)-3-methoxyethyl)-p-phenylenediamine. N, N,
-dialkyl-p-phenylenediamine. Other suitable color developers include, for example, J. Amer. Che
m. Soc. 73, 3106 (1951) and G.
．． Mod-ern Pho from Haist
tpgraphic Processing, 1979
, John Wiley & Sons
ley and Sons), New York, 54.
It is described from page 5 onwards.

If the color couplers according to the invention are alkali-soluble compounds, they can also be added to the color developer bath (in contrast to the photographic material).

Color development can also be followed by an acidic stop bath or water wash.

Normally, the material is bleached after color development and fixed directly. Suitable bleaching agents include, for example, hexacyano salts,
Fe(III) salts such as dichromate and Fe(II)
I) Complex salt, a water-soluble cobalt complex salt. Particularly suitable bleaching agents are iron(III) complex salts of aminopolycarboxylic acids, more particularly for example ethylenediaminetetraacetic acid, propylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, nitrilotriacetic acid, imidodiacetic acid, N-hydroxyethylethylenediaminetriacetic acid. , alkyliminodicarboxylic acids, and the corresponding iron(III) complex salts of phosphonic acids. Other suitable bleaching agents are persulfates and peroxides, such as hydrogen peroxide.

The bleaching/fixing bath or fixing bath is generally followed by a water wash, which is carried out as a countercurrent water wash and consists of several vessels, each with a water supply.

Good results are obtained if a finishing bath containing little or no formaldehyde is subsequently used.

However, the water wash can be completely replaced by a stabilizing bath, which is usually operated in countercurrent. If formaldehyde is added, this stabilizing bath also serves as a finishing bath.

The color reversal material is first developed in a black and white developer in which the oxidation products cannot react with the color couplers. This initial development step is followed by a second diffusion
se) Exposure and development by color developer, bleaching and fixing.

[0071]

EXAMPLE 1 A color photographic recording material was prepared by applying the following layers in the indicated order to a transparent support layer of cellulose triacetate (interlayer relationship 1A - comparative example). The quantities indicated are each based on 1 square meter. If silver halide was used, the corresponding amount of AgNO3 is indicated. The silver halide emulsion is 100g of AgNO3
per 0.1 g of 4-hydroxy-6-methyl-1,3
, 3a,7-tetraazaindene.

Interlayer relationship 1A (comparative example) Layer 1 (antihalation layer) 0.2 g Ag Black colloidal silver layer containing 1.2 g gelatin Layer 2 (micrate intermediate layer) 1.0 g
Ultrafine silver bromide silver iodide emulsion of 0.25 g AgNO3 containing gelatin (0.5 mol% iodide;
(average grain size 0.07 μm) Layer 3 (red photosensitive layer) Red-sensitive silver bromide silver iodide emulsion of 5.35 g AgNO3 containing 3.75 g gelatin 1.33 g cyan coupler C-1 1.33 g TCP ( 4.0 mol% iodide; average particle size 0.45μ
m) Layer 4 (protective and hardening layer) 0.68g gelatin 0.73g hardening agent (CAS registration number 65411-60
The layer cyan coupler C-1 containing -1) has the following formula:

0073
]

Interlayer Association 1B (Invention) Similar to Interlayer Association 1A, but with the following points: instead of cyan coupler C-1, layer 3 contains 1.4 g of compound 2.
The difference is that it includes 6.

Development was carried out by Brit. J. Photo. 1
974, pages 597-598 after exposure of a gray wedge on the material.

Cyan wedges are obtained for both interlayer association 1A and interlayer association 1B (invention); interlayer association 1
In B, the color tone shifts slightly towards green. Maximum density measured behind red filter 1
．． 6 and 1.45.

This example demonstrates the suitability of compounds of the invention as cyan couplers when the 2-position of the imidazole ring is vacant.

[Chemical formula 1]

[Chemical formula 1]

Claims (1)

[Claims] 1. A color coupler compound having the formula (I) [Image Omitted] wherein R1 and R2 are H, halogen (for example, Cl,
Br), -SCN, alkyl, aryl, alkoxy,
Aryloxy, alkylthio, arylthio, optionally S
- represents a heterocyclic group, azo group, acylamino, carbamoyl or alkoxycarbonyl which may be bonded to an atom, provided that at least one of the substituents R1 and R2 is H, halogen or a group that can be removed under color development represents at least one exposed halogenated compound in the presence of a color coupler compound, characterized in that Q is a compound corresponding to; Q completes a fused heterocyclic ring containing at least one nitrogen atom; A photographic color development method consisting of developing a color photographic material consisting of a silver emulsion layer with a color developer compound.