DE1622920C3 - Color photographic recording material - Google Patents

Description

OR ¹

CONH

NHCOOR " ¹

OR "

is where mean:

X is hydrogen or halogen;

R ¹ and R "alkyl with up to 18 carbon atoms, aryl or aralkyl;

R " ^{1 is} alkyl, aryl, or aralkyl;

b to complete an annealing

th benzene or a tetrahydrobenzene ring members required.

2. Color photographic recording material according to claim 1, characterized in that R ¹ and R "each represent an alkyl group having up to 5 carbon atoms.

3. Color photographic recording material according to claim 1, characterized in that R " ¹ denotes an alkyl group substituted by a phenoxy group and having up to 5 carbon atoms.

Image dyes produced by oxidized color developer usually have undesirably strong secondary absorptions. Many dyes separate out as a relatively coarse grain of color, with others the coupling reaction takes place too slow. Generally speaking, those obtainable by chromogenic development have cyan dyes insufficient light stability, unsatisfactory hydrolysis resistance and disruptive sensitivity against reducing agents.

The invention is based on the object of finding cyan couplers which are themselves tropically stable and which lead to tropically stable dyes with high lightfastness.
The invention accordingly provides a color photographic recording material with a red-sensitive silver halide emulsion layer which contains a 1-oxy-2-naphthoic anilide cyan coupler. The recording material is characterized in that the cyan coupler is a compound represented by the following formula

The invention relates to a color photographic recording material with a red-sensitive silver halide emulsion layer.

It is known in color photographic recording materials that are produced by the chromogenic process are processed to color images to build up the blue-green partial image from color couplers, which in general consist of derivatives of phenols or naphthols. Although such cyan couplers in large Number are known, there is still no cyan coupler that meets the diverse requirements that are placed on it are fulfilled in an optimal way. On the contrary, most of the color couplers have serious disadvantages. Inadequate stability of the residual coupler, which has not been coupled with the color developer to form the dye image often to a discoloration of the image whites. With

OH

OR ¹

CONH

NHCOOR ¹ "

OR "

where mean:

X is hydrogen or halogen such as chlorine or

Bromine;

R ¹ and R ″ alkyl with up to 18 carbon atoms, preferably short-chain alkyl with up to 5 carbon atoms, e.g. methyl, ethyl or butyl, aryl, in particular phenyl or aralkyl, in particular benzyl or phenylethyl, the phenyl groups optionally may contain further substituents;

R " ¹ (1) alkyl, especially short-chain alkyl

with up to 5 carbon atoms, the alkyl groups preferably being substituted with Aroxy groups, e.g. B. phenoxy, the phenyl groups containing further substituents can, in particular alkyl with up to 18 carbon atoms, halogen such as chlorine or bromine, alkoxy or nitrile, also (2) aryl, e.g., phenyl or (3) aralkyl, e.g., benzyl or phenylethyl;

b to complete a fused

Benzene or a tetrahydrobenzene ring members required.

For example, the following couplers are suitable:

OH

0-CH ₃

0-CH ₃

CH ₃ CH ₃

NH-CO-O-CH ₂ -CH ₂ -O- ^ Vc-CH ₂ -C-CH ₃

CH ₃ CH ₃

162-164 "C

χ γ OH
I. C. -CO-NH- O-
I. CHj 2. T A. 160— V -Nh 162 O- CHj Fp

NH-CO-O-CH ₂ -CH ₂ -O

y ν

CH ₃ CH ₃

I I

C-CH ₂ -C-CH ₂ -CH ₃

CH ₃

OH

Mp 80-8 TC

0-CH ₃

NH-CO-O-CH ₂ -CH ₂ -O
0-CH ₃

CH ₃ CH ₃

V-CH-CH ₂ -C-CH ₂ CH ₃ CH ₃

OH

0-CH ₃

M.p. 78-80 ° C

CO-NH

CH ₃

NH-CO-O-CH ₂ -CH ₂ -O

- / V

Cl

Mp 155-157 C

OH 0 -C ₂ H ₅

CO-NH- ^

0-C ₂ H ₅ CH ₃ CH ₃

N H-CO-O-CH ₂ -CH ₂ -O- / "" Vc-CH ₂ -C-CH ₃

CH ₃ CH ₃

Mp 154-155 C

OH

M.p. 76-78 "C

OH 0 -C ₂ H ₅

CO-NH

NH-CO-O-CH ₂ -CH ₂ -O-O-C ₂ H ₅

0-C ₂ H ₅

CH ₃ , CH ₃

CH ₃

CO-NH

CH ₃

V ₅ . / -NH-CO-O-CH ₂ -CH ₂ -O- ^ VCl

0-C ₂ H ₅ C,

The color couplers according to the invention are represented in a manner known per se. The manufacture for Coupler 2 is detailed below. Others of the couplers to be used in the present invention are represented in an analogous way.

Coupler 2
step 1

level 3

IO

103 g of 5-nitro-2-amino-1,4-dimethoxybenzene were suspended in 400 ml of pyridine. 134 g of dimethylaniline were added. With stirring, 216 g of p- (1,3,3-trimethylpentyl) phenoxyethanol carbonate chloride were added dropwise at room temperature. The temperature rises to 6O ⁰ C. The mixture was subsequently stirred for 30 minutes without any further supply of heat. The reaction mixture was stirred into about 31 ice water and made Congo acidic with 5NHCl. The oil crystallized through. The crystals were filtered off with suction, washed neutral with water, stirred in about 2 l of methanol, again filtered off with suction and washed with methanol. For purification, the crude product was recrystallized from 3 liters of n-propanol with the addition of activated charcoal.

The yield was 152 g of green-yellow crystals with a melting point of 47-149 ° C.

Level 2

152 g of the nitro product of stage 1 were dissolved in 1.5 1 tetrahydrofuran jo with Raney nickel at 5O ⁰ C and 50 atm catalytically hydrogenated. The solution was filtered from Raney nickel and then evaporated under a water-jet vacuum. The oily residue was stirred with methanol, the oily amine crystallizing through. The 3, crystals were filtered off with suction and washed with methanol.

Yield: 128 g from m.p. 99.5-101 ° C.

lets evaporate. The color couplers according to the invention are also suitable for these processes. These emulsions are then processed into single or multi-layer material on a layer carrier.

The new dye formers can not only apply to the photosensitive halogen silver emulsion layer

itself, but also to an adjacent light-insensitive layer. You can too develop the photographic material together with the color developer.

The cyan couplers of the present invention are used in a red sensitized photographic emulsion added. Such emulsions can also contain chemical sensitizers in the customary manner. These Layers can also be stabilized by known additives, in particular by those in Publication by Birr in Z. wiss. Phot 47 (1952), pages 2-28 described azaindene derivatives.

example 1

3 g of the color coupler 6 are dissolved in 15 ml of ethyl acetate at 55-60 ° C. and 3 g of di-tert-butyl phthalate are added. _r 50 ml of 5% gelatin that 8 g lauryl sulfate per kg 'is added as an emulsifier are combined with the color coupler solution and 10 minutes mixed intensively at 55 ° C. While it is still warm, 50 g of a photographic silver bromide emulsion prepared with 70 g AgNC> 3 per kg are added to this emulsion. The photosensitive mixture is diluted with 100 ml of 7.5% gelatin solution and then applied in the usual way to paper or a transparent support and dried.

The photographic material produced in this way, after exposure in a color developing bath, is the the following composition:

Ν, Ν-diethyl-p-phenylenediamine-

40

87 g of amine of step 2 and 52.8 g Naphthsalol were melted and heated under vacuum to 170-175 ⁰ C, which resulting phenol was distilled off. After 45 minutes of heating, the hot melt was poured into 750 ml of n-butanol. It was filtered off with suction at room temperature and washed with butanol. The crude product was recrystallized from 1.25 l of butanol and washed with butanol and methanol.

The yield was 111.5 Coupler 2, mp 160-161 ⁰ C.

The color couplers according to the invention can be added to the light-sensitive silver halide layers in a non-diffusible form be incorporated. This can be done in a known manner in that the color couplers be emulsified into the emulsion layer. Such methods have long been known and can be used without difficulty in the present case.

By a known method emulsifying the _b0 new links, provided they are hydrophobic, in a solvent with or without oil former in gelatin dries this emulgate, it swells again in water and then mixed it with the silver halide emulsion. Processes are also known in which the color coupler dissolved in an organic solvent is admixed directly with the halogenated silver emulsion, after which the solvent is added

hydrochloride 2.75 g Sodium sulfite 2g Potassium carbonate 75 g Potassium bromide 0.5 g Hydroxylamine hydrochloride Ug Sodium hexametaphosphate 1.0 g water up to 1000 ml

This material is then bleached, fixed and watered as usual. A blue-green color is obtained Dye image with an absorption maximum at 678 ΐημ.

Example 2

3 g of the color coupler 4 is dissolved in 15 ml Essigester at 55-6O ⁰ C. This solution is added to 50 ml of 5% gelatin that was 8 g per kg of lauryl sulfate as an emulsifier added, and this mixture is emulsified at 55-60 ⁰ C in a blender for 10 minutes. 50 g of the photographic silver bromide emulsion described in Example 1 are added to this emulsion while it is still warm. The photosensitive mixture is diluted with 100 ml of 7.5% gelatin solution, then applied in the usual way to paper or a transparent support and dried.

After exposure and development in the developer described under Example 1, afterwards Conventional bleaching, fixing and washing gives a blue-green dye image, its absorption maximum is at 680 ιτιμ.

You can also create the dye image after exposure in the following developer:

Benzyl alcohol 3.8 ml Sodium hexametaphosphate 2g Sodium sulfite sicc. 2g 10% sodium hydroxide 5.5 ml 4-amino-N-ethyl-N- (j9-methane sulfonamidoethyl) -m-toluidine- sesquisulfate monohydrate 5g Potassium bromide ig Sodium carbonate monohydrate 50 g water up to 1000 ml pH at 21 ° C 10.75

After subsequent bleaching, fixing and washing in the usual way, a dye image is obtained, its Absorption maximum is 686 πιμ.

Example 3

A color photographic material is produced as described in Example 2, with the exception that instead of the color coupler 4. equimolar amounts of color coupler, as indicated in the table below, are incorporated into the emulsions. The photographic materials produced in this way are divided into 4 samples and after the individual samples have been exposed, one sample is developed in each case in a color developer of the composition described in Example 1, hereinafter referred to as egg described composition, hereinafter referred to as E2, developed. A third sample each is in a color developer containing N, N-diethyl-3-methyl-p-phenylene-diamine, hereinafter referred to as developer E3, and a fourth sample each in a color developer containing N-butyl-N-zisulfo-butyl- p-phenylenediamine, hereinafter referred to as developer E4, color-developed. After subsequent bleaching, fixing and washing in the usual way, dye images of the individual photographic materials are obtained. Each of the individual dye images is then divided into three parts and a sample is ^{subjected to a tropical test (7 days storage at 6O 0} C and saturated humidity) and a further sample to a light stability test (12 ^{hours exposure to 2.4X10 6} lux hours behind a xenon lamp).

The percentage decrease in density of the tested samples compared to the untested sample is given in given in% in the table below. The percentage decrease was 0.5 and 1.5 at the density Comparative sample determined

Coupler 2 off % Decrease at 1.5 E ₂ density 6th E., 1.5 E ₄ 1.5 Xenon test 1 p E ₂ 1 5 E., 1.5 E ₄ 1.5 1 off Tropical test 0 0.5 0 0.5 4th 0.5 10 egg OS 05 05 12th Coupler E, 12th 10 12th 20th 12th 10 0.5 22nd 18th 14th 15th 0.5 0 1.5 +4 14th 8th 16 36 10 30th 12th 30th 4th + 2 + 29 0 + 15 36 22nd 22nd 28 0 Comparative coupler
DE-PS 11 37 311 18th 0 0 7th 0 0 0 + 20 26th 0 6th 3 0 Comparative coupler
DE-PS 1137311 12th +.18 0 0 0 + 6 12th 6th 10 0 0 + 8 0 0 According to the invention 0 0 + 5 0 0 5 + 3 0 3 0 11th 16 6th 8th 3 1 0 0 0 0 12th 5 14th 0 5 0 0 2 0 0 0 0 0 4th 0 8th 7th

0 0 +7 0 0 +14 +16 12

8 0 8 4 8 0

The comparison shows that the dye images of the samples according to the invention are generally higher Have tropical stability and also form dyes that are much more light-stable. It is to be noted that the dye density of the samples according to the invention when stored in the tropical cupboard is even frequent increases (positive values in the table) and in contrast to the samples of the prior art hardly any percentage decrease in color density can be observed.

030 124/7

Claims (1)

Patent claims: 1. Color photographic recording material with a red-sensitive silver halide emulsion layer, which contains a derivative of 1-oxy-2-naphthoic anilide as a cyan coupler, thereby characterized in that the cyan coupler is a compound represented by the following formula