DE2032171A1 - Photosensitive color photographic material - Google Patents

Description

AGFA-GEVAERTAG

PATENT DEPARTMENT

LEVERKUSEN JUNE 29, 1970

Photosensitive color photographic material

The invention relates to a light-sensitive color photographic material having at least one silver halide emulsions layer, the indazolone derivative contains as a coupler for generating the purple partial image.

It is known to produce color photographic images by chromogenic development, i.e. by being imagewise exposed silver halide emulsion layers in the presence of suitable color couplers by means of suitable color-forming developer substances - so-called color developer - developed, with the resultant in accordance with the silver image Oxidation product of the developer reacts with the color coupler to form a dye image. As a color developer are usually aromatic, primary amino group-containing compounds, especially those of the p-phenylenediamine type, used.

The color couplers, as well as the dyes obtained therefrom by chromogenic development, are in practice a Set of demands. So the coupling rate of the color coupler with the oxidation product of the The largest possible color developer. The color couplers as well as the The dyes obtained therefrom must be sufficiently stable to light, increased! temperature and humidity. This applies to both fresh material and processed material Material. For example, in the image white of the processed Remaining couplers still present in the material are not

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yellow. In addition, the dyes should be sufficiently resistant to gaseous reducing or oxidizing agents Agents. They must also be anchored in a diffusion-proof manner in the image layer and should be at the Separate chromogenic development as the finest possible grain. Furthermore, the mechanical properties of the layers must not be impaired by the color couplers. After all, they have to produce a cheap dyes from the color couplers during chromogenic development Have an absorption curve with a maximum that corresponds to the color of the respective desired partial image, and if possible low lifting absorption. Ideally, this should be a purple dye Absorb green light almost completely and largely allow blue and red light to pass through.

Compounds which are derived from 2-pyrazolone-5 are generally used as magenta couplers, ie as color couplers which are suitable for producing the purple color image. Indazolone derivatives are also sometimes used as magenta couplers. Reference is made to German Patent 918 484, German Auslegeschrift 1 130 287 and English Patent 1 182 202. It is advantageous here that the dyes made from the indazolones have only low secondary absorptions in the blue and red spectral range with high resistance to the tropics . A fundamental disadvantage of all previously known indazolone derivatives is that many common color-forming developers, such as 2-amino-5-diethylaminotoluene or 2-amino-5- (n-ethyl-n-β-methanesulfonamidoethylamino) toluene, have no or only an extremely high level of toluene result in a faint purple image. The previously known patents are limited in their examples to the use of Ν, Ν-diethyl-p-phenylenediamine as a color developer, which delivers brilliant dyes with absorption maxima around 560 nin. .,. . . _ί4; .,.

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However, this developer is for various reasons, mainly because of its toxicity for the production of paper- pictures and other color material not very suitable. Instead of this Often N-Butyl-N-oj-sulfobutyl-p-phenylenediamine is used, which, with indazolones, produces purple images with good color density. However, in this way, dyes with absorption maxima are produced around and above 580 nm. Even the relatively short wave absorbing dye derived from that in the German Auslegeschrift 1 130 287 described coupler 1 with N-butyl-N - ^ - sulfobutyl-p-phenylenediamine is formed as a developer, has an absorption maximum at 577 nm. This leads to bluish tints Purple pictures.

The invention is based on the object of having magenta couplers Find indazolone structure with N-butyl-U-ίλ) -sulfobutylp-phenylenediamine as a developer, form purple dyes with a suitable absorption maximum below 580 nm.

It has now been found that such dyes are obtained can be used if indazolones are used which have an alkoxy, cycloalkoxy, aroxy or aralkyl group on the benzene ring wear. The subject of the invention is therefore a light sensitive Lich color photographic material with at least one silver halide emulsion layer, characterized by a content of a magenta coupler of the following formula I;

Z alkoxy with up to 20 carbon atoms, preferably methoxy, substituted by a phenyl group (benzyloxy) or an alkoxy radical with 8 to 20 carbon atoms;

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Cycloalkoxy, for example cyclohexoxy;
Aroxy, preferably phenoxy; or aralkyl, especially benzyl.

In order to achieve sufficient diffusion resistance of the couplers, those indassolone derivatives are preferred in which Z contains a larger hydrocarbon radical with at least 8 carbon atoms. The above-mentioned substituents can therefore in turn be further substituted.

* Couplers that use either of the two are particularly suitable. Formulas II and III correspond to:

II

III

Ν-t

wherein:

R is hydrogen or alkyl;

R alkyl with up to 20 carbon atoms, preferably benzyl or

an alkyl radical with 8 to 20 carbon atoms, or cyclohexyl; X -O- or -CH ₂ -; and

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1 U98 837 1 8.0

Y hydrogen, sulfo, carboxyl, carbamyl, sulfonyl, Alkoxy or aroxy;

2 1

R and at least one of the substituents R and Y contain a larger hydrocarbon with at least 8 carbon atoms. *

The following couplers have proven to be particularly suitable proven. The absorption maximum (A-max) of the with N-Buty1-N-OJ -sulfobutyl-p-phenylenediamine obtained dye is in mn specified.

CH, GH ₉ - ^ - ^ CH, 564

^ ^ά CH. °

C = O NH

CH,

N '
ι

iso

O = O ⁵⁶⁵

k
N '"

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° 16 ^H 33 ° "

, = 0

NH 569

CH,

CH ₃ -CH-

CH,

I -CH-CH ₅

-CH ₂ -OC = O NH

CH

CH ₃ CH ₃ 561

O = C NH

CBU.

N-

C ₁₈ H ₃₇

C = O

N "
H

SO, H 573

/ Ho

O = C I CH ₀ -NC ₀ H,

C = O NH

N'H

571

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CH.

C = O NH 565

iso

C = O
NH

H-

CH

C = O

NH

^l 2 H

569

573

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83 /, '!

The preparation of the .Purpurkuppler according to the invention generally starts from suitably substituted o-nitrobenzoic acids, which are reduced to the o-amino benzoic acids, diasotized with sodium nitrate or amyl nitrite and then reduced _{with SnCl 2.} The o-hydrazine p-benzoic acids formed can easily be converted into the indazolones with ring closure. The indazolone couplers of the formula II, in which X denotes -GHp-, can be prepared by reacting indazolone carboxylic acid chloride (doubly acetylated) in the presence of AlCl with a suitably substituted benzene (for example cetylbenzene) to give the ketone, the keto group of which is then reacted with hydrazine hydrate to form the methylene group is reduced. For illustration, the preparation of some couplers is described in detail below

Coupler 1

60 g of 3-bromo-6-nitrobenzoic acid and 90 g of p- (1,1,3,3-tetramethyl-butyl) -phenol are dissolved in 700 ml of butanol, adjusted to pH 10 with solid KOH and boiled for 15 hours heated. The solution is diluted with water and extracted twice with ether, 'The ether phase is concentrated, the residue was dissolved in hot acetonitrile and cooled. 50 g of oily 2-nitro-5- (p-1,1,3,3-tetramethyl-butylphenoxy) benzoic acid are obtained (A).

2-Amino-5 "~ (p ~ 1> 1 _S 3 _? 5 ~ tetraiaethyl ~ butyl ~ ph.enoxy) benzoic acid methyl ester (B;

5OgA be atm in 750 ml of methanol at 50 C and hydrogenated for 70 ⁰ in the presence of palladium carbon. It is filtered, adjusted to pH 4 with concentrated hydrochloric acid and concentrated in vacuo. An excess of an ethereal solution of diazomethane is added to the residue. After one hour, the mixture is filtered and concentrated. Yield: 40 g of B; Oil.

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5— (ρ — 1-, 1,3,3-tetramethyl-butyl-phenoxy) -indazolone (coupler 1)

4OgB are dissolved in glacial acetic acid, treated with 100 ml of concentrated hydrochloric acid, and at 10 - diazoti 15 ⁰ C with amyl nitrite mixture is stirred for 1 hour at 10 - 15 ⁰ C after destroying the excess nitrite with urea and available at 5 - 10 ⁰ C, 65 g of SnCl ₂ .2H ₂ O in 150 ml of concentrated hydrochloric acid are added. After one hour, it is diluted with water and decanted from the precipitated grease. The latter is heated to boiling with 2N KOH for 7 minutes, precipitated in ice / HCl, filtered off with suction and washed with water. The water-containing grease is taken up with hot ethyl acetate, the ethyl acetate phase is separated off and dried over calcium chloride. After the solvent has evaporated, the residue is digested with hot ligroin and filtered off with suction. If further purification is required, it can be chromatographed over silica gel (mobile solvent: ethyl acetate). Yield: 10 g of Coupler 1; M.p. 189 ^° C

Coupler 3

45 g of 2-nitro-4-hydroxy-benzoic acid, 100 ml of water, 200 ml Propanol, 30 g of KOH and 90 g of cetyl bromide are heated to boiling for 15 hours, with the addition of further KOH pH is kept at 9. It is cooled, filtered off with suction and recrystallized from ethanol.

Yield: 30 g of 2-nitro-4-cetoxy-benzoic acid (C); Mp. 70 ⁰ C.

2-amino-4-cetoxy-benzoic acid (D)

30 g of C are hydrogenated in 250 ml of propanol at 60 ^° C. and 50 atm. In the presence of palladium carbon. It is filtered hot, acidified with concentrated hydrochloric acid, cooled and filtered off with suction.
Yield: 18 g of D.

^A " ^{G 664} 1.0 9'aeV / 1-5 0 9

η η Ο O Λ · Ί

2-Amino-4-cetoxy - benzoic acid methyl ester (E) c. \ Joc. \ Ι

An excess of diazomethane in ether is added to 18 g of D at 20 ^° C. After one hour, the mixture is filtered and concentrated.
Yield: 16 g of E.

6-cetoxy-indazolone (coupler 3)

16 g of E are dissolved in hot glacial acetic acid, 50 ml of concentrated hydrochloric acid are added and the ^{mixture is diazotized at 10-15 °} C. with amyl nitrite. It is stirred for 1 hour at 20 ⁰ C after destroying the excess nitrite with urea and mixed at 0 - 5 ⁰ C with a solution of 28 g of SnCl ₂ .2H ₂ O in 60 ml of concentrated Salzsäux'e "Bach one hour, is diluted with water , suctioned off, boiled for 5 minutes in 2N KOH and precipitated with ice / HCl. After suctioning off, it is recrystallized once from methanol and once from ligroin. Yield: 5 g of coupler 3; Mp. 203 ⁰ C,

Coupler 5

3-methyl-4-nitrophenyl-3-methylphenyl ether (P)

200 g of 3-bromo-6-nitro-toluene _II 600 g of m-cresol and 450 ml of sodium methylate solution (which contains 2 mol of Na dissolved in methanol) are heated to the boil in the presence of a little Cu powder. After distilling off the methanol is heated for 5 hours at 130 ⁰ C. After cooling, it is stirred into water with 2N K0H made alkaline and extracted with ether. The ether phase is extracted with 2N-KOH, treated with activated charcoal and fuller's earth and concentrated. The residue is recrystallized from methanol with the addition of activated charcoal. Yield: 100 g of E; Ip. 47 - 48 ⁰ Co

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.'I

3- (4'-nitro-3'-carboxy-phenoxy) -benzoic acid (G)

70 gF are dissolved in 1.4 liters of water and 1.4 liters of pyridine.

At 80 - 9O ⁰ C are added in portions 900 g KMnO. added.

After 12 hours, it is suctioned off with concentrated hydrochloric acid acidified and etherified twice.

The ether phase becomes over Ma ₂ SO. dried and evaporated.

The residue is dissolved in dilute potassium hydroxide solution and washed with Acetic acid adjusted to pH 5. One cools and sucks off.

Concentrated hydrochloric acid is added to the filtrate, cooled and vacuumed.

35 g of G are obtained; Pp. 110 ⁰ C.

Hydrochloride of 3- (4 ^f -amino-3 ^l -carboxy-phenoxy) -benzoic acid (H)

The reduction of G takes place in water at pH 9, 80 ⁰ C and 50 atm. H ₂ in the presence of Pd-charcoal.

After the piltration, it is acidified with concentrated hydrochloric acid, cooled and filtered off with suction.
Yield $ 80> of theory.

5— (3'-carboxy-phenoxy- y ± uu.a.zoXon (I)

50gH are dissolved in 150 ml of dilute sodium hydroxide solution. Are employed 15 g of NaNO ₂ to and makes this solution at 0 ° - 10 ⁰ C dropwise in 150 ml konsentrierter hydrochloric acid and 50 ml of water. After stirring at 10 ^° C. for 1 hour, the excess nitrite is destroyed with urea and the solution is then allowed to drip into a solution of 130 g of SnCl ₂ .2H ₂ O in 300 ml of concentrated hydrochloric acid. After 1 hour, the mixture is filtered off with suction and the residue is boiled for 30 minutes in a mixture of 2.7 liters of water and 800 ml of concentrated hydrochloric acid. After cooling, it is filtered off with suction, washed with a little ice water and dried.
Yield: 35 g I; -Fp. 210 ⁰ C. ''

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5 ~ l ~ 3 '- (2 "-N-methyl-N-octadecvlainino-S" -sulfophenyl-carbamyl) -phenoxyy-indazolone (coupler 5)

10gI are heated to boiling for 15 minutes in 50 ml of acetic anhydride. The excess acetic anhydride is removed in vacuo and the residue is heated to boiling for 1 hour with 60 ml of thionyl chloride and a few drops of dimethylformamide. The excess thionyl chloride is then distilled off, the residue is triturated with petroleum ether and filtered off with suction. 10 g of acid chloride of I (twice acetylated) are obtained. 6 g of acid chloride are added to a hot solution of 7.5 g of 3-amino-4- (N "methyl-N» octadecylaraino) benzenesulfonic acid in 100 ml of tetrahydrofuran and 20 ml of triethylamine. The mixture is refluxed for 4 hours and stirred in up / HOL a decanted t off koeht 2 minutes with 2 N NaOH and precipitated with ice / HCl. After filtration with suction is washed with water, the residue dissolved in methanol hot Geust and filtered. After cooling, it is filtered again and dae filtrate evaporated to dryness. Msh 2-maIigem boiling with acetone obtained as a residue 4 g of pure coupler 5} mp. over 20Q ⁰ O,

Coupler 7

0.1 mol of DiaQetyl-Indazßlon ~ 4 '»oar'bon ^ ftureohlorid _i! which is easily accessible from 5-afflinophthalic acid via indazelone ring closure, aoetylation and reaction with thionyl chloride, and 0.1 moles of ethylbenzene are heated to the boil in 100 ml of dry carbon disulfide * Naoh in portions! ¹ addition of 0.5 mol AlOl.? it is heated to reflux for 10 boilers, then poured onto Eifl / HGl, the carbon disulfide is evaporated and filtered off with suction. The residue is boiled for 5 meows in 2N KaOH, cooled, decanted, washed with water and crystallized after the cooks This gives 4 ~ (p-cetylbenzoyl) indaaolone (K) in a yield of 60%, pp. 109 ⁰ O.

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1Ü38Ö3 / 150S

4- (p-cetylbenzyl) indazolone (coupler 7)

23 g K are heated for 1 hour at 200 ⁰ C with 5 g NaOH, 25 ml and 200 ml Hydraζinhydrat triglycol in an open vessel. After stirring into ice, the mixture is acidified with dilute hydrochloric acid and filtered off with suction. 5 g of coupler 7 are obtained;

Pp. 114 ⁰ C. -

The magenta couplers according to the invention give in the coupling with color developer oxidation products, especially those of the p-phenylenediamine type, brilliant dyes with very little Secondary absorptions. It turns out to be a particular advantage that the couplers are especially compatible with N-butyl-N-iJ-sulfobutyl-p-phenylenediamine As color developers, dyes result in a very favorable position of the absorption maximum around 550 to 570 nm. The absorption maximum is thus compared with the absorption maximum of comparable dyes from the same developer and known indazolones shifted significantly in the direction of smaller wavelengths. The dyes turn out to be very stable, especially given over moist heat.

The compounds according to the invention are thus valuable Color couplers are which, in the chromogenic development, give purple dyes with excellent stability properties. They are eminently suitable for use in light-sensitive silver halide emulsion layers of color photographic single- or multilayer materials. The purple couplers however, they do not necessarily have to be the photosensitive one To be incorporated into layers; rather, it is also possible to use them to be accommodated in a binder layer, which is a photosensitive Silver halide emulsion layer is adjacent.

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The magenta couplers according to the invention can be prepared by one of the known methods of the silver halide emulsion or else be incorporated into a different binder mixture, provided that it is The couplers according to the invention are so-called emulsifying couplers, i.e. hydrophobic compounds Incorporation in a known manner by dissolving in suitable organic solvents, 2.B. in esters, more aliphatic Carboxylic acid, especially in ethyl acetate or methylene chloride, and emulsifying this solution into the ready-to-cast silver halide emulsion. These. Method can advantageously be achieved through the simultaneous use of oily coupler solvents be modified. This method is known from American patents 2,304,940 and 2,322,027.

So much for the purple couplers according to the invention however, alkali-soluble couplers are used, they are conventionally used in the silver halide emulsion or the casting solution for a another binder layer added in the form of an aqueous-alkaline solution.

Suitable light-sensitive emulsions are emulsions of Silver halides such as silver chloride, silver bromide or mixtures thereof, possibly with a low content of silver iodide up to 10 mol $ in one of the commonly used hydrophilic ones Binders such as protein, especially gelatin, polyvinyl alcohol, polyvinylpyrolidone, cellulose derivatives such as carboxy

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alkyl cellulose, in particular. Carboxymethyl cellulose -. Or Derivatives of alginic acid.

The emulsions can also be chemically sensitized, e.g. by adding sulfur-containing compounds during chemical ripening, e.g. allyl isothiocyanate, Allyl thiourea, sodium thiosulfate and the like. · As a chemical Sensitizers can also be reducing agents, e.g.

the tin compounds described in Belgian patents 493,464 or 568,687, and also polyamides such as Disthylenetriamine, or aminomethanesulfinic acid derivatives, for example according to the Be3g patent specification 547,323.

Precious metals are also suitable as chemical sensitizers or precious metal compounds such as gold, platinum, palladium, iridium, Ruthenium or rhodium. This method of chemical sensitization is in the article by R. Koslowsky, Z.Wiss.Phot. 46, 65-72, (1951).

It is also possible to use the emulsions with polyalkylene oxide derivatives to sensitize, e.g. with polyethylene oxide with a molecular weight between 1000 and 20,000, also with condensation products of alkylene oxides and aliphatic alcohols, Glycols, cyclic dehydration products of hexitols, with alkyl-substituted phenols, aliphatic carboxylic acids, aliphatic amines, aliphatic diamines and amides. The " Condensation products have a molecular weight of at least 700, preferably greater than 1000. To achieve special These sensitizers can of course have effects use in combination, as in the Belgian patent specification 537,278 and in British patent specification 727,982.

The color coupler-containing emulsions can also be spectral Contain sensitizers, e.g. the usual mono- or Polymethine dyes such as cyanines, hemicyanines »Strepto * - cyanines, merocyanines, oxonols, hemioxonols, styryl dyes

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or other methine dyes, including trinuclear or polynuclear c. . for example rhodacyanines or neocyanines. Such • sensitizers are described, for example, in the work by PM Hamer "The Cyanine Deys and Related Compounds", (1964) Interscience Publishers John Wiley and Sons. However, the color couplers according to the invention are preferably used in emulsions which are sensitized to green light.

The emulsions can contain the customary stabilizers, such as, for example, homopolar or salt-like compounds of mercury with aromatic or heterocyclic rings, such as mereäptotetriazoles, simple mercury salts, sulfonium-mercury double salts and other mercury compounds are substituted by hydroxyl or amino group. Such compounds are described in the article by Birr, Z.Wiös.Phot. 4I _x . 2 - 50X ^ 52). Further suitable stabilizers are Uia * heterocyclic mercapto compounds, for example phenyl mercapto-feetrazole, quaternary benzothiazole derivatives, benzotriazM and SMiiiche "

The emulsions can be giMSaEHbe ^ is ^? eltij | for example with formaldehyde or halo-ensubittiBrien # which contain a carboxyl group, such as ucobromsiurfev tonen, methane sulfon acid esters, dialdohydes and others

The usual Color developers used, for example the usual aromatic ones containing at least one primary amino group Compounds of the p-phenylenediamine type. Usable color developers are, for example, N, W-Dim'ethylp-phenyleMiamin-, Ν, Ν-diethyi-p-phenylenediamine, monbraethylp-phenylondiamine, N-butyl-N-'tü-sulfobütyi-p-ph'enylen'diamin and the like. Other useful color developers are described, for example, in J. Amer. Chem. Soc. 73, 3ooo to 3025

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Those developers in which the two positions adjacent to the primary amino group are unsubstituted.

example 1

10 g of coupler 1 are dissolved in 50 ml Essigester and after adding 10 g of dibutyl phthalate in 200 ml of a 5 #igen gelatin solution containing 1.6 g dodecylbenzenesulfonate sodium salt, emulsified at 60 ⁰ C. Then it is mixed with 850 g of a 7.5% gelatin solution which contains 19.25 g of silver bromide in dispersed form and, after dilution with water, is poured onto a transparent layer support until the pouring viscosity is reached. After drying, the film is exposed behind a gray wedge and developed in a color developer of the following composition.

6 g. N-Butyl-N-ocJ-sulfobutyl-p-phenylenediamine 4 g hydroxylamine hydrochloride 4 g anhydrous sodium sulfite 1 g potassium bromide
100 g potassium carbonate

Water to 1ooo ml

After exposure and fixing, a purple-colored wedge is obtained (λ-max. 564 nm).

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Example 2 AS

10 g of coupler 5 are dissolved in 500 ml of diluted NaOH and "at pH 9 with emulsion containing 19.25 g of AgBr, and 750 g of 7.5% gelatin added and diluted with water to the casting viscosity. Further processing is as made in Example 1 and gives a purple color wedge (X max. 573 nm).

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Claims (2)

Patent claims: Light sensitive photographic material having at least one silver halide emulsion layer, characterized by a content of a magenta coupler of the following Formula: wherein Z alkoxy with up to 20 carbon atoms, cycloalkoxy, aroxy, or aralkyl means. 2. Photographic light-sensitive material according to claim 1, characterized by a content of a magenta coupler one of the following formulas: , = 0 N-H III -Ö- A-G 664 , = 0 109-883 / 1509- where mean: R is hydrogen or alkyl; 2 ■ R alkyl with up to 20 carbon atoms or cyclohexyl; X -0- or -CH ₂ -; and Y hydrogen, sulfo, garboxy1, carbamyl sulfonyl, alkoxy or aroxy; 2 1 R and at least one of the substituents R waä. ϊ develop larger hydrocarbon residues with at least 8 carbon atoms. A-G 664-20 1 0 988 3 / 1SQ-.9