DE1522407A1 - Blue-green dyes for the silver dye bleaching process - Google Patents

Description

Blue-green dyes for the silver color bleaching process The invention relates to the use of novel triazole group-containing blue-green pigments for light-sensitive color photographic material after silver color bleaching procedure. It is known to take color photographic images after color bleaching process to produce, it is in a homogeneous Colored collector layer in the places where it was previously ßilberb @ ld. , was produced photographically, the dye, mostly an azofsr1astpff, in a strongly acidic bath, must be blgiehtt _ Both negatives and reversal images can be produced by this process. If one wants to achieve positive paper images or duplicate positives directly from slides, one works with simple black-and-white development to generate the silver image, which then represents a negative of the original. Since the image dye homogeneously distributed in the layer (or the 3 layers of a multicolor material) is destroyed according to the size of the silver image, the desired dye image positive for the original is obtained (reversal image). If an image is generated that is positive for the original (silver reversal image). For example, by a black-and-white reverse development or by means of the bromine ion diffusion process or the silver diffusion process, a dye image with the opposite gradation of the original is created after the color bleaching, i.e. a positive color image if the original is a color negative. The requirements that are placed on dyes for the standard processes are '. special high because müesen serve not only be spectrally suited eondern, challenges in addition to high. beds good bleaching barges should also cry. They also have a detrimental effect on the photographic impulse and have to be completely different in the gelatine, which is almost always used as a layer-forming agent . Of particular importance is a high level of authenticity, which contributes to the glare effect of light and is also resistant to acidic substances, as is the case in the air in areas of exposure. The invention is based on the object of developing new cyan azo dyes which are particularly suitable for use in the silver dye bleaching process.

It has now been found that novel azo dyes containing at least one triazole group are outstandingly suitable as cyan dyes for the silver dye bleaching process. They correspond to the general formula:. where: A = radical of a diazo component, preferably a monoazo compound, optionally with a triazole group X = any substituent such as H, SO H, halogen, amino, optionally substituted with alkyl or acyl, in particular acyl, which is derived from aliphatic short-chain carboxylic acids.

Y = a triazole ring bonded to the naphthalene nucleus, which is bonded to the naphthalene nucleus by a single bond or in fused form, e.g. B. is shown in formulas II and III. R = a radical of the phenyl or naphthyl series, for example phenyl, naphthyl or diphenyl, which can optionally be mono- or polysubstituted, for example with sulfo, amino, acylamino, alkylamino, sulfonamide, alkyl alkoxy and other groups. The benzene nucleus is linked to the triazole ring with a simple bond or in fused form.

Compounds of the formula IV are preferred. In the formula, X, Y and R. have the meanings already given in formula I. The symbols are: Rt, Rtt = alkyl, preferably up to two carbon atoms, optionally further substituted, for example alkoxyalkyl, hydroxyalkyl or sulfoalkyl.

Rt and R "can be identical but also different. R"'= an aromatic radical, preferably of the phenyl or naphthalene series, in particular a naphthalene radical which is substituted by at least one hydroxyl or alkoxy group, but can also contain further substituents. The dyes of the formula V have proven to be particularly suitable Rvlj ORw OR 'OH N - N - i, i - N = N - `@, - N = N - OR, 503H X Riv R v proven. Therein mean: RIV, RV = H, SO3 H, amino, optionally substituted z.8. Alkyl or acylamino, Oh. Generally are where RIv and -RV for a given connection except for RIVY R v = H. different. RVI = H, alkyl, preferably up to 2 carbon atoms, given if substituted, for example with alkoxy. RVII = H, or any substituent such as SO'ZH, COOH, J Halogen such as chlorine or bromine, alkyl, preferably up to to 3 carbon atoms, optionally substituted with, for example Halogen such as trifluoromethyl, alkoxy, acylamino such as Acetamino. The symbols X, RI and RII have those given above Meaning. Anindinemn Parbut * fitn aeita zupiela indicates the Chewing dye containing triazole groups The dyes are produced by methods known per se in azo chemistry. Compound 1 is obtained, for example, as follows: 295-dimethoxy-4-nitro-aniline is diazotized in a known manner, coupled to the triazole of 1-amino-8-hydroxynaphthalene-4,6-disulfonic acid in an alkaline solution and reduced Nitro group of the originated monoazo dye with sodium sulfide in aqueous solution. After renewed diazotization, coupling is carried out on 2-Ibdrogynaphthalene-7-sulfonic acid.

The triazole compound required for the first coupling is produced by diazotization of p-sulfanilic acid, acidic coupling to 1-amino-8-hydroxynaphthalene-4,6-disulfonic acid and ring closure of the o-amino coupling product with ammoniacal copper sulfate solution to the triazole.

Dye No. 17 in the table was represented by diazotization of 4-acetylamino-2,5-dimethoay-aniline and coupling of an alkaline solution the hydroxynaphthalene triazole compound. After splitting off the acetyl group of the Diazofarbatoffes in alkaline solution, the mixture was diazotized again and coupled to 2-naphthol.

The other dyes in the table can be used in an analogous manner or according to that in the German patent. ... ... registration no. can be obtained as described. The hydroxy-naphthalenetriazole component according to formula I. where X, Y and R have the meaning given, offers wide possibilities for variation for dyes according to the invention, especially with regard to X and R.

As the naphtholsulfonic acid residue, for example, the residues of the following are suitable Acids: 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid (H-acid), 1-amino-8-hydroxynaphthalene-4,6-disulfonic acid (K-acid), 2-amino-8-hydroxynaphthalene-6-sulfonic acid (G-acid), 2-amino-8-hydroxynaphthalene-5-sulfonic acid, 1-Amino-7-hydroxynaphthalene-3 or 4-sulfonic acid, 1-amino-8-hydroxynaphthalene-4 or 6-sulfonic acid, 1-amino-6-hydroxynaphthalene-3-sulfonic acid, 2-amino-6-hydroxynaphthalene-8-sulfonic acid, 2-Amino-5-hydroxy-naphthalene-7-sulfonic acid, (I-acid), as well as the 1-sulfo-I-acid and the 1-chloro-I-acid.

The triazole ring, as defined in formula V, can be bonded to the naphthalene nucleus via 2 nitrogen atoms or via a nitrogen atom. Suitable naphthol sulfonic acid triazole components are, for example, the following: In suitable cases, it can be advantageous to replace the individual sulfo groups in the formulas given in the previous text with sulfonamide groups.

As a particularly suitable naphthol or. Alkoxynaphthalene component of general formula IV R "') may be mentioned: 2-naphthol, 2-ethoxynaphthalene, 2-naphthol-7-sulfonic acid, 2-methoxy- 'or. 2-ethoxynaphthalene-7-sulfoic acid, 2-naphthol-6-sulfonic acid, 2-methoxy or 2-ethoxy-naphthalene-6-sulfonic acid, 2,8-dihydroxynaphthalene-6-sulfonic acid, 2-ethoxy-8-naphthol-6-sulfonic acid, 2-naphthol-8-amino-6-sulfonic acid, 1-acylamino-6-hydroxynaphthalene-3-sulfonic acids, 2Z-6-Hydroxy-2J-triazo.1-6-sulfonic acid. 3-sulfo-naphthyl- (1) j naphtho-`1. Preferred are 2-naphthol-7-sulfonic acid or 2-ethoxynaphthalene-7-sulfonic acid and ß-naphthol with the azo group in the 1-position. As the center piece of the dye molecules of the formulas IV and V are mainly benzene nuclei, those in the 1,4-position are the azo bonds wear and those in the 2,5-position by ethoxy or methoxy groups but possibly also by hydroxyethoxy, ethoxyethoxy or l (j-sulfopropoxy or W-sulfobutoxy groups are substituted. 2,5-dimethoxy and 2,5-diethoxy-benzene residues are specifically used (Azo groups in 1,4-position). The residues in the 2,5-position can be but also be different. The high diffusion resistance of the invention Dyes, especially if they have three or fewer sulfonic acid groups in the molecule , allows their use without additional pickling agents in the layer former.

Through a suitable choice of the solubilizing groupings, this can be done for the optimum between sufficient diffusion resistance required in each case one and sufficient solubility on the other hand set without difficulty will.

The dyes according to the invention are extremely lightfast. They also have very long-wave absorption maxima, some of which in gelatine are above 700 nm. In most cases they can be bleached very easily and show only an extremely low tendency towards the formation of disruptive red shades or monoazo forms with incomplete bleaching in the presence of a little silver, for example in low color densities. The dyes have little absorption in the blue spectral range. They can be cast in layers on any substrate.

The dyes according to the invention can be used in the context of the silver dye bleaching process for the production of direct positive images. can be used from a copy, such as by a simple black and white development and subsequent color bleaching Azo dye-containing halogen silver layers arise and also for images with a for the submission of opposing gradation, as e.g. by a black and white reversal development, obtained by the bromine ion diffusion method or the silver salt diffusion method will. Both acidic thiourea baths and acidic baths can be used as dye bleach baths Baths containing quinoline and iodide can be used. Such baths are known. Their application is evident from the examples.

The dyes according to the invention can be mixed with all customary layer additives, such as hardening agents, plasticizers, netmetteln etc. shed. With the new dyes Layers produced may be those disclosed for the silver dye bleaching process Sensitizers are made sensitive to light in the red spectral range, as they e.g.

in the German Auslegeschrift 1? 13 240 were described. as Gelatin is preferred as a binder, but it can whole or partly by other synthetic or natural polymers, such as polyvinyl alcohol, its esters or ethers, alginates, cellulose derivatives, etc. may be replaced as long as sufficient layer strength is guaranteed.

The following examples explain the use of the dyes according to the invention without restricting them to the cases mentioned. Example 1 : 300 ml of a 2% gelatin solution containing 2.8 g of dye 17 and 0.35 g of saponin are added to 500 ml of an iodide-containing silver bromide emulsion. The emulsion is sensitized to red light with 12 mg of the sensitizer according to Example 11 of German Auslegeschrift 1 213 240 and poured onto a base made of barytized paper or cellulose triacetate. Of the. The silver application is around 0.8 g Ag / m2. After drying, it is exposed to yellow light under a stepped gray wedge and processed as follows: 1) 5 min. Develop in a solution of 1 gp "methylaminophenol 13 g Na 2 SO 3 sicc. 3 g hydroquinone, 26 g soda sicc. And 1 g potassium bromide in 1000 ml water 2) Soak for 1 min. 3) Fix for 5 min. In a solution of 200 g of crystalline sodium thiosulphate.

20 g potassium metabisulphite in 1000 ml water 4) soak for 5 min. 5) 5 min. Harden in a solution of 60 ml formalin (30%) 5 g sodium bicarbonate in. 1000 ml water 6) 5 min. Watering 7) 15 min. Color bleaching in a solution of 10 g potassium iodide 10 g sodium hypophosphite 25 ml sulfuric acid 50 ml quinoline 10 mg 2,3-dimethylquinoxaline in 1000 ml water 8) 5 min. Watering 9) 5 min. Bleach in a bath of 25 g - copper chloride 5 ml hydrochloric acid conc. in 1000 ml of water 10) 10 Min. fix as in 2. 11) 20 min. Water After drying, one obtains a diffusion-resistant blue-green Parbstoffkeil with clean stepped gradation and proper white people who do not discolor even after prolonged exposure. The low color densities of the wedge are without any reddish tinge and are highly lightfast. Example -2 : The procedure is as indicated in Example 1, but the dye is replaced by 3.1 g of the dye of the formula 16 and poured onto a white-pigmented cellulose triacetate. After exposure and processing with baths 1-6 as in Example 1, proceed as follows: 7) 5 min. Color bleaching in a reading from 28g thiourea 18g potassium bromide 3 mg 2-amino-3-hydroxyphenazine 400 ml hydrochloric acid conc. in 1000 ml of water 8) soak for 5 min. 9) bleach-fix for 10 min. in a solution of 26 g of tetrasodium ethylenediamine tetraacetate 24 g of soda sicc.

15 g iron (III) chloride 13 g sodium sulfite sicc.

200 g sodium thiosulphate sicc. soak in 800 ml of water 10) for 20 min. A result very similar to that in Example 1. Both layers are outstandingly suitable as part of a three-layer color photographic material. Example 3 : The procedure is as described in Example 1, but instead of the dye indicated there, approximately the same amounts of dye 17, for example, or any other dye from the table are used. After exposure and processing as in Example 1, similar results are obtained.

Example 4 : The procedure described in Example 2 is followed, but after exposure it is processed as follows: 1) 5 Yin. develop in a bath as given in Example 1. 2) 1 yin. water 3) 1 yin. bleach in a solution of 10g potassium dichromate 5 g sulfuric acid conc. in 800 ml of water 4) 1 yin. water 5) 1 yin. clear sicc in a bath of 5 g sodium sulfite. in 1000 ml of water 6) soak for 1 min. 7) 2.5 min. second exposure with a 40W lamp at a distance of 20 cm ..

8) Second development as under 1.

9) Curing and further processing as in Example 1 with the baths 5 - 11.

A blue-green pigment wedge is obtained with a gradation running in the opposite direction to the original. EXAMPLE 5: A color photographic multilayer material for the silver dye bleaching process is produced as follows: The following layers are arranged one after the other on a base made of barytaised paper: 1) a red-sensitized layer, as indicated in Example 1, 2) an intermediate layer of 2% gelatin solution, 3) a green-sensitized layer containing, on 500 g of an iodide-containing silver bromide emulsion, 15 mg of a sensitizer such as is listed in German Auslegeschrift 1 213 240, Examples 2-10, and 3.1 g of the dye of the formula its description from German patent specification 1 039 840 is known, dissolved in 250 ml of a 2% gelatin solution, and pickled with -1.2 g of 4,4'-diphenyldibiguanide. The GieB solution contains the usual quantities of hardening agents ao, like: 0.4 g saponin. The silver application is approx. 0.75 gAm. 4) an intermediate layer, including a 2% gelatin layer, which Per ornament S- g of tertrazine eatable. 5) an unsensitized silver bromide-containing emulsion layer which, in 500 g, contains 2.8 g of the yellow dye of the formula contains, its representation according to the German patent specification '. ... . . (A 50 510 IXa / 57b) takes place in addition to the usual hardening agents and 0.4 g of saponin. The silver application is about 0.65 g / m².

6) A protective layer made from a 2% gelatin solution. Processing: After drying, it is exposed behind a multicolored slide and processed as described in Example 1, except that 50 mg of 2,3-dimethylquinozaline are added to the bleach bath added and the duration of treatment increased to 20 minutes.

After washing and drying, you get a lifelike reproduction: the original in brilliant colors.

Claims (3)

Claims : 1. Light-sensitive photographic material, characterized by the content of an azo dye. Of the following formula: in which: A = radical of a diazo component; X = hydrogen or any substituent; Y = a triazole ring bonded to the naphthalene nucleus, which is bonded by a single bond or in fused form; R = a radical from the phenyl or naphthyl series. 2. Photosensitive photographic material according to claim 1, characterized by the content of an azo dye of the following formula: where: R ', R "= Alky1 R"' = an aromatic radical which is substituted by at least one hydroxyl or alkoxy group. 3. Photosensitive photographic material according to claim 1, characterized by a content of an azo dye of the following formula: where mean: RIv9 Rv = H1 SO 3Hg @ amino; RvI = H, Alkgl; RvII = H, or any substituent.