DE2064304A1 - Photosensitive color photographic material - Google Patents

Description

AGFA-GEVAERTAQ

2 8th DEC. 1970

PATENT DEPARTMENT

LEVERKUSEN

Photosensitive color photographic material

The invention relates to a photosensitive color photographic Material having at least one silver halide emulsion layer which uses indazolone derivatives as a coupler to produce the contains purple partial image.

It is known to produce colored photographic images through chromogenic Development, i.e. by having imagewise exposed silver halide emulsion layers in the presence suitable color couplers by means of suitable color-forming developer substances - so-called color developers - developed, wherein the oxidation product of the developer substances, which occurs in accordance with the silver image, with the color coupler reacts to form a dye image. As a color developer usually aromatic, primary amino group-containing Compounds, especially those of the p-phenylenediamine type, are used.

The color couplers, as well as the resulting chromogenic development A number of requirements are made in practice. So should the coupling speed the color coupler with the oxidation product of the color developer should be as large as possible. The color couplers as well as those The dyes obtained therefrom must be sufficiently stable to light, elevated temperature and moisture. this applies to both fresh material and processed material. For example, the one in the image whites of the

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If the material is working, the remaining couplers will not yellow. In addition, the dyes should be sufficiently stable be against gaseous reducing or oxidizing agents. They must also be diffusion-proof in be anchored in the image layer and should be deposited as the finest possible grain during the chromogenic development. Furthermore, the mechanical properties of the layers must not be adversely affected by the color couplers will. After all, the dyes arising from the color couplers during chromogenic development must have a have a favorable absorption curve with a maximum corresponding to the color of the desired partial image, and the lowest possible secondary absorption. Ideally, a purple dye should give almost all of the green light absorb and largely transmit blue and red light.

As magenta couplers, i.e., color couplers suitable for forming the magenta color image, are generally used Compounds used which are derived from 2-pyrazolone-5. Sometimes indazolone derivatives are also used as purple couplers used. Reference is made to German patent specification 918 484, German Auslegeschrift 1 130 and the English patent 1,182,202. The disadvantages of the indazolone couplers exist in addition to a comparative to the pyrazolone couplers of low coupling intensity in a Bx'aun coloration of the couplers on prolonged storage in the light. The latter property in particular makes the use of indazolone couplers for the production of paper images or other color photographic materials exposed to light. Another disadvantage is that the strongly polar structure of the indazolone stem core atcfa for non-polar substituted derivatives Compounds with high melting points leads. In ethyl acetate, methylene chloride and similar organic solutions

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Easily soluble indazolone couplers are hitherto unknown. This property combined with mostly high melting points, hitherto made the use of indazolone couplers in photographic layers difficult.

It has now been found that indazolone couplers which are produced by a new process by nucleus alkylation of anthraniic acid esters obtained with suitably substituted styrene derivatives or the corresponding tf-carbinols and subsequent indazolone ring closure can be distinguished by extremely advantageous properties, both in terms of higher Sensitivity as well as decreased. Tendency to turn brown in light.

The invention therefore relates to a light-sensitive color photographic material with at least one silver halide emulsion layer, characterized by a content of a magenta coupler of the following formula:

where mean:

Hydrogen or alkyl, preferably having 1 to 5 carbon atoms;

Alkyl ait to bu Π C atoms

R ₁ and

= can also form a cycloalkane ring,

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for example a cyclohexane ring;

X and Y = identical or different radicals, namely

Hydrogen, halogen, e.g. chlorine ^ alkyl with -1-18 Carbon atoms, alkoxy with 1-18 carbon atoms, aroxy, for example phenoxy, or acylamino, wherein the acyl group is from aliphatic or aromatic carboxylic acids or Can derive sulfonic acids; the groups mentioned can carry further substituents, e.g., halogen, hydroxy, carboxy, or carbamyl groups;

Z = hydrogen, an alkali-solubilizing group

pe, for example, carboxyl or sulfo, if appropriate in anionic form, or sulfamyl, optionally mono- or dialkyl- or aryl substituted.

In order to achieve sufficient diffusion resistance of the coupler, preference is given to those indazolone derivatives in which at least one of the radicals R 1, R _2, X, Y and Z contains a larger hydrocarbon radical with at least 12 carbon atoms. At least one of the radicals X and Y is preferably halogen, alkyl, alkoxy, aroxy or acylamino.

The following couplers have proven to be particularly suitable.

Coupler SO, H CH, H - C = O
NH Melting point ι ³ (C ⁰ ) C-f = 5 =
I. CH ₃ ^ 230

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A-G

Coupler

Melting point (C ⁰ )

240 -

5) C ₁₆ H ₃₃ -O-

125

6) C ₁

75

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Coupler melting point (C)

COOH

7) HC-Ο

CH,

CH

120

CH,

π ti - ^C 18 ^H 37

C-CH ₂ -O-

JlH

C = V Γ

-CHp-O-

CH

CH,

ί

NH

55-60

SOgH CH

180

CH. CH,

167

A-G

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Coupler

W H

12) C ₁₇ H ₃₅ -C-:

Melting point (C) 140

CH,

CH,

CK

O ₁₇ H ₃₅ -ON-

15) C - ,,, Η, κ-Ό-Η-

105

75

130-133

110

A-G

2 0 3 B 3 U / (J U 3

No.

Coupler

Melting point (C ⁰ )

17)

134

18)

75

19) ^ N-SO ₂ -

83

For the production of the inventive indazolone coupler first a suitably substituted styrene, optionally in dimeric form, or the corresponding ot-carbinol under acidic Catalysis implemented with anthranilic acid esters, the latter in 5-position are alkylated. The indazolone ring closure is then carried out in a known manner. Palis desired, may Finally, a sulfo group is introduced. Hereinafter the production is illustrated by a few examples.

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206430A

lj

> ~ L (.- (4 ^l -hexadecoxy-3 ^f -sulfophenyl) -iaopropylj-indazolon - * -— (Coupler 2)

(D

1 mol of dimeric isopropenylphenol is used in 1 1 of propanol Dissolved heat and treated with 2.4 mol of KOH. 2.6 mol of cetyl bromide are run in, the mixture is heated under reflux for 3 hours and filtered with suction hot off. The diether (I) separates from the filtrate. yield 65

Q .: 64 ⁰ C

COOCH ,,

(II)

210 g of dimeric p-cetoxy-isopropenyl-benzene (i) are heated to 225 ° C. for 30 minutes under nitrogen with 600 g of methyl anthranilic acid and 25 g of catalyst K 20 (montmorillo nite catalyst from Pa. Südchemie, Munich). The rod is sucked off warm and the excess ester is distilled off in vacuo. The residue is triturated with petroleum ether, cooled and filtered off with suction. Yield 160 g, P .: 70 ^° C

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C.

10og (H) are dissolved in 200 ml of glacial acetic acid and diazotized by addition of 50 ml konztrierter hydrochloric acid at 10-15 ⁰ C with amyl nitrite. After 1 hour, excess nitrite is destroyed with urea and leaves the diazonium salt solution into a cooled to 5-10 ⁰ C solution of 87 g of SnCl. ₂ Pour in 2H ₂ O ia 200 ml of concentrated hydrochloric acid. Then it is diluted with water and decanted. After washing twice with water, the residue is boiled for 8 minutes in 2N sodium hydroxide solution, the solution is then stirred into ice / HCl, filtered off with suction and dried. The crude product is recrystallized from ethyl acetate or methanol. Yield 60 g, m.p .: 92 ^° C

SO, H

d.

50 g (III) are introduced into 400 ml of concentrated sulfuric acid ^{at 0} ° C., the mixture is stirred for 1/2 hour at room temperature, poured onto ice and decanted. After boiling with acetonitrile, it is recrystallized from propanol.
Yield 35 g, mp .: 244 ^° C

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5-1 ^ (2'-hexa deooxyphenyl) - ethylj-indazolou. (Coupler 4)

COOH,

16 ⁿ 33 (IV)

o-Hydroxy-acetophenone is etherified alkaline with cetyl bromide by known processes and then the keto group with Sodium borohydride reduced to alcohol.

(o-Cetoxyphenyl-methyl-carbinol F. 43 ⁰ C).

160 g of the alcohol are mixed with 500 g of anthranilic acid methyl ester and

25 g of catalyst K 20 are ^{heated to 190 °} C. while passing in nitrogen, the nitrogen carrying the water of reaction with it. It is filtered off while hot and the excess anthranilic acid ester is distilled off. The residue is recrystallized from ethanol after precipitation with ligroin.

Yield 130 g, P. 65 ⁰ C.

The indazolone ring closure is carried out in the usual way, whereby the coupler 4 is obtained.

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The new purple couplers turn out to be the well-known indazolone couplers superior in three ways. On the one hand, the stability is considerably improved, especially against light. The new couplers show a greatly reduced tendency to brownish in the light. Furthermore, there is no Alkali oil-making agents are present in the molecule, the emul-. yawability significantly improved. It is particularly noteworthy the increase in coupling sensitivity by 3-5 DIN, which means that the new components can also be used for sensitive recording material enables.

The one from the new color couplers with N-N-diethyl-p-phenylenediamine or N-butyl-n - &) - sulfobutyl-p-phenylenediamine draw the purple dyes obtained as a developer are characterized by good spectral properties. The secondary densities in the blue and especially in the red area are very low.

The compounds according to the invention thus represent valuable color couplers which turn purple during chromogenic development Dyes with excellent stability properties result. They are excellent for use in light-sensitive silver halide emulsion layers of color photographic single or multilayer materials. However, the magenta couplers do not necessarily have to be incorporated in the light-sensitive layers; it is much more it is also possible to incorporate them in a binder layer, that of a photosensitive silver halide emulsion layer is adjacent.

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. If the couplers according to the invention are so-called Emulsifying couplers, i.e. hydrophobic compounds, are incorporated in a known manner by dissolving in suitable organic solvents, e.g. in esters aliphatic carboxylic acids, especially in ethyl acetate, or in methylene chloride and emulsifying this solution into the ready-to-use Silver halide emulsion. The method can occasionally A-G 731 - 12 -

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2Ü64304 i3

can be modified advantageously by the simultaneous use of oily coupler solvents. This The method is known from American patents 2,304,940 and 2,322,027.

If the couplers are alkaline, they will added to the casting solutions for the photographic layers 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 MoI- ^ in one of the commonly used hydrophilic Binders such as protein, especially gelatin, polyvinyl alcohol, polyvinylpyrolidone, cellulose derivatives, such as Carboxyalkyl 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, iSodium thiosulfate and the like. as Chemical sensitizers can also be reducing agents, e.g. those in Belgian patents 493,464 or 568 687 described tin compounds, also polyamides such as diethylenetriamine, or aminomethanesulfin-8 acid derivatives, e.g. according to Belgian patent 547 323.

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

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It is also possible to sensitize the emulsions with polyalkylene oxide derivatives, for example with polyethylene oxide having a molecular weight between 1ooo and 2o,000, furthermore with condensation products of alkylene oxides and aliphatic alcohols, glycols, cyclic dehydration products of hexitols, with alkyl-substituted phenols, aliphatic carboxylic acids, aliphatic carboxylic acids , aliphatic diamines and amides. The condensation products have a molecular weight of at least 7oo, preferably of more than I000. To achieve special effects, these sensitizers can of course be used in combination, as described in Belgian patent 537 278 and in British patent 727 982.

The color coupler-containing emulsions can also contain spectral sensitizers, for example the usual mono- or Polymethine dyes such as cyanines, hemicyanines, streptocyanines, merocyanines, oxonols, hemioxonols, styryl dyes or other methine dyes, including trinuclear or polynuclear, for example rhodacyanines or neocyanines. Such Sensitizers are described, for example, in the work by P.M. Hamer ". The Cyanine Deys and Related Compounds ", (1964) Interscience Publishers John Wiley and Sons. The color couplers according to the invention are preferably however, used in emulsions sensitized to green light.

The emulsions can contain the usual stabilizers, such as homopolar or salt-like compounds of mercury with aromatic or heterocyclic rings, such as mercaptotriazoles, simple mercury salts, sulfonium mercury double salts and other mercury compounds. Azaindenes are also suitable as stabilizers, preferably Tetra- or penta-azaindenes, especially those substituted with hydroxyl or amino groups. Such Connections are in the article by Birr, Z. Wiss. Phot.

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47 , 2-58 (1952). Other suitable stabilizers include heterocyclic mercapto compounds, for example phenyl mercaptotetrazole, quaternary benzothiazole derivatives, benzotriazole and the like.

The emulsions can be hardened in the usual way, for example with formaldehyde or halogen-substituted aldehydes that contain a carboxyl group, such as mucobromic acid, Diketones, methanesulfene acid esters, dialdiiydene and the like.

The customary color developers, for example the customary ones, are used to produce the purple partial image aromatic containing at least one primary amino group Para-phenylene type compounds.

Usable color developers are, for example, N, N-dimethylp-phenylenediamine, NN-diethyl-p-phenylenediamine, monomethylp-phenylenediamine, N-butyl-N- ω -sulfobutyl-p-phenylenediamine,

and the same. Other useful color developers are for example described in J. Amer. Chem. Soc. 73, 3I00 to 3125 (I95I). '

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

example 1

A silver bromide emulsion containing 10 g of coupler 2, 77 g of gelatin and 19.25 g of AgBr in 1 kg is cast on a transparent substrate. After drying, it is exposed behind a gray wedge and developed in a color developer with the following composition:

6 g of N-butyl-N - ^ - sulfobutyl-p-phenylenediamine 4 g hydroxylamine hydrochloride 4 g anhydrous sodium sulfite

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1 g of potassium bromide
100 g potassium carbonate

Water to 1000 ml

After bleaching and fixing, you get a purple color Wedge (a) with an absorption maximum at 574 m / rev. On the same A wedge (b) with coupler 1 is made from DAS 1.130.287. The measurement of the wedges results in a sensitivity of 4 DIN greater for wedge (a). Put both wedges to the daylight off, only wedge (b) shows a brown discoloration of the whites.

Example 2

10g coupler 14 are dissolved in 40ml Ithylenchlorid and contains by addition of 10 g Dibytylphthalat in 200ml of a 5 $ aqueous 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 containing 19.25 g of silver bromide in dispersed form, diluted with water until the casting viscosity is reached and poured onto a transparent layer support. After developing with N, N-diethyl-p-phenylenediamine, it is bleached and fixed as usual. The coupler proves to be 4DIN more sensitive than the comparison wedge (coupler 1 of DAS 1.130.287). The absorption maximum is 552 m / rev.

Example3

10 g of coupler 5 are dissolved in 50 ml of ethyl acetate and, after addition of 10 g of dibutyl phthalate, as in Example 2, further processing . A purple wedge is obtained with an absorption maximum at 554 nyu. Compared with wedge b from Example 1, the sensitivity is increased by 4 DIN.

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Example 4

10 g of coupler 19 are cast as in Example 2 , and the film strip is subjected to the usual reversal process with N, N-diethylamino-p-phenylenediamine as the developer substance , and a purple positive is obtained. The increase in sensitivity compared to the similarly developed film material, which contains coupler 1 of DAS 1.130.287, is 3 DIN; Absorption maximum 557 m / rev.

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Claims (4)

Patent claims: Photosensitive photographic material with at least a silver halide emulsion layer characterized by a magenta coupler represented by the following formula in which mean R ^ = hydrogen or alkyl with 1 to 3 carbon atoms; Rp = alkyl with up to 17 carbon atoms; R ^ and Rp can together form a cycloalkane ring; X and Y = identical or different radicals, namely, hydrogen, halogen, alkyl with 1 to 18 carbon atoms. Alkoxy with 1 to 18 carbon atoms, aroxy or acylamino; Z = hydrogen, and an alkali-solubilizing group or sulfamyl 2) Material according to claim 1, characterized in that Z represents a sulfo group. 3) Material according to claim 1, characterized in that at least one of the radicals R ₁ , R ₂ tXf Y or Z contains a larger hydrocarbon radical with at least 12 carbon atoms. 4) Material according to claim 1, characterized in that at least one of the radicals X and Y is halogen, alkyl, alkoxy, aroxy or acylamino. A-G 731 209830/0838