DE1253049B - Aqueous black and white developer for photographic reversal processing of color photographic materials - Google Patents

Description

GERMAN PATENT OFFICE

EDITORIAL

German class: 57 b -18/13

Number: 1253 049

File number: A 41160IX a / 57 b

1253049 Filing date: September 15, 1962

Opening day: October 26, 1967

The invention relates to a black and white developer for the initial development of color reversal materials.

When processing color photographic reversal materials, very special requirements are placed on the black-and-white developer for the first development, which are generally not met by the known developers of conventional black-and-white materials, so that new developers are found for the reversal process in color reversal materials had to. For example, black-and-white developers that are to be used for the process under discussion may only contain relatively little sulfite, since the dissolution of silver chloride is to be avoided. Developer substances, which are widely used in normal black-and-white development, show in the present process in the processing of color reversal papers disadvantageous effects that their use Aqueous black-and-white developers for
reversal photographic processing
color photographic materials

Applicant:

Agfa Aktiengesellschaft,
Leverkusen, Kaiser-Wilhelm-Allee 24

Named as inventor:

Dr. Heinz Meckl, Cologne-Flittard;

Helmut Häseler,

Dr. Bernhard Morcher, Leverkusen

Silver chloride emulsions containing a silver emulsion, has the advantage of the various fatigue in this field of photographic tech version 20 layers in the stack of layers equal to corresponds

prevent nik. This applies, for example, to hydroquinone, which for reasons that have not yet been clarified is a causes uneven formation of larger image color areas.

Developers for the reverse process have already been described, which are used as the developer substance Contain 3-pyrazolidones. However, such developers are practically useless because they are due to their low activity low sensitivity utilization of the photographic emulsions used allow sions.

The object of the invention is to find a first developer for the color reversal process who is at satisfactory activity, the uniform formation of larger image color areas in the further course of processing allowed.

It has now surprisingly been found that for the initial development of color reversal materials In an excellent manner, a developer is useful, which as developer substances 3-pyrazolidones and Contains o-phenylenediamine. The presence of o-phenylenediamine increases the activity of the 3-pyrazolidones considerably increased, so that with the same halogen silver emulsions a significantly higher sensitivity is achieved. This finding was all the more surprising as it was found that m- and p-phenylenediamine cause only a slight increase in activity. o-Phenylenediamine develops in a developer alone with a pH value of 10.0 no halogen silver.

The claimed combination of 3-pyrazolidones with o-phenylenediamine in the processing of Color reversal materials that wrap in layers alongside.

For the reproduction of saturated hues, it is particularly advantageous that the inventive Reversal developer only forms photographically inactive oxidation products.

Furthermore, it has been found that the activity of an initial reversal developer for color reversal film material, in addition to a silver halide solvent, e.g. B. sodium rhodanide, as developer substances 3-pyrazolidones and contains hydroquinone, is increased by the addition of o-phenylenediamine so that the Halogen silver solvent can be omitted as an activity-enhancing substance. This gives you with the same sensitivity and equally good color rendering by reducing the physical Development of a much finer grain, since o-phenylenediamine has no noticeable solution effect.

For the developer combinations according to the invention, the known developer substances can be used 3-pyrazolidone series can be used. Pyrazolidones of the following general types are particularly suitable Formula:

O = C

HN

CR _i

R ₃
■ R,

709 679/494

therein R ₁ denotes hydrogen, alkyl up to 4 carbon atoms or a phenyl group which can be substituted, for example with lower alkyl groups such as methyl or ethyl, also with chloroalkoxy groups such as methoxy, amino, acylamino, for example acetamino or hydroxy; R ₂ to R _{5 are} hydrogen, alkyl up to 4 carbon atoms or phenyl radicals.

The following compounds may be mentioned in detail, for example:

l-phenyl-3-pyrazolidone,

5-phenyl-3-pyrazolidone,

5-methyl-3-pyrazolidone,

l-p-chlorophenyl-3-pyrazolidone,

l-phenyl-5-phenyl-3-pyrazolidone,

l-phenyl-5-methyl-3-pyrazolidone,

l-acetaminophenyl-3-pyrazolidone.

The substances are known as developing substances and are described, for example, in the article by J. D. K e η d al 1, Brit. J. phot. (1951), p. 539. The concentration ratio of 3-pyrazolidone and o-phenylenediamine is arbitrary and can meet the requirements of the the respective copying process or the properties of the color reversal material used. In general, these two substances are used in a weight ratio of 60:40 to 40:60 be applied. According to a preferred embodiment, the two substances are approximately equal amounts are used. The developer combination according to the invention is in principle independent the type of color photographic material; in this the color couplers can be found in water-soluble, contain diffusion-proof form or emulsified as a solution in organic solvents be. The developer of the present invention is also applicable to such reversal processes in which the Color generation takes place according to the so-called development process. The developers of the invention Otherwise you can use the usual additives of stabilizers, antioxidants, alkalizing agents Contain substances, etc.

example 1

In a first reversal developer of the following composition, a multilayer material on paper backing, which has a bromide silver layer with 3 - (ρ - stearoylamino - benzoylacetamino) - isophthalic acid as a yellow coupler and two chlorosilver layers with 1 - (3 '- sulfo - 4' - phenoxy) - phenyl - 3 - heptadecyl-pyrazolone (5) as a magenta coupler and I-hydroxy-4-sulfo-2-naphthoic acid octadecylamid as cyan couplers, 4 designed to 5 minutes at 20 ⁰ C:

3 g sodium hexametaphosphate,
15 g sodium sulfite (sicc),

5 g o-phenylenediamine,
60 g soda (sicc),

5 g potassium bromide,

5 g of l-phenyl-3-pyrazolidone,

0.05 g benzotriazole,

Make up to 11 with water.

After rinsing, it is post-exposed diffusely and developed for 8 minutes in the following color developer:

2 g sodium hexametaphosphate,

4 g hydroxylamine sulfate,

4 g sodium sulfite, (anhydrous),

1 g potassium bromide,
100 g potassium carbonate (anhydrous),
5 g of N-butyl- C'j -sulfobutyl-paraphenylenediamine.

This is followed by watering and bleaching in a bleach-fix bath, as is done e.g. B. in the German patent 605 is described.

Then it is watered and, after treatment with a final bath containing formalin, dried,
xo Developed without the addition of o-phenylenediamine in a developer with the following composition at 20 ° C for 5 to 6 minutes:

3 g sodium hexametaphosphate,

15 g sodium sulfite (sicc),

60 g soda (sicc),

5 g potassium bromide,

5 g of l-phenyl-3-pyrazolidone,
0.05 g benzotriazole,

fill up with water to 11,

and processed further as stated above, one obtains, compared to the first developer mentioned above, a significantly lower sensitivity, which means a 3 to 4-fold increase in the exposure time as requires.

Example 2

A multilayer film, consisting of three layers of bromide silver, used as a yellow coupler 3- (p-stearoylamino - benzoylacetamino) - isophthalic acid, as purple coupler 1 - (3 '- sulfo - 4' - phenoxy) - phenyl-3-heptadecyl-pyrazolone- (5) and as the cyan coupler - hydroxy - 2 - naphthoic acid - [2 '- (methyl - η - octadecylamino) -5'-sulfonic acid] anilide contains, is developed in a first developer with the following composition at 20 ° C for 15 minutes:

3 g sodium hexametaphosphate,

70 g sodium sulfite (sicc),

6 g o-phenylenediamine,
6 g potassium bromide,

5 g of l-phenyl-3-pyrazolidone,

6 g hydroquinone,
60 g soda (sicc),

0.1 g benzotriazole.

This is followed by rinsing, stop bath, washing and post-exposure, then 14 minutes of color development in:

5 g of N, N-diethyl-p-phenylenediamine hydrogen sulfate,

1.2 g hydroxylamine sulfate,
5 g sodium sulfite,

2 g hexametaphosphate,
75 g potash,

2 g potassium bromide,

5 ml ethylenediamine.

It is then watered, stopped, watered again. This is followed by a potassium ferricyanide bleach bath, rinsing, Fixing bath, washing and finally a formalin bath.

Developed without the addition of o-phenylenediamine at 20 ° C for 15 minutes in a first developer as follows:

3 g sodium hexametaphosphate,
70 g sodium sulfite (sicc),

6 g potassium bromide,

Claims (3)

60 g of soda, 5 g of 1-phenyl-pyrazolidone, 6 g of hydroquinone, 0.1 g of benzotriazole, and processed as above, results in images that are significantly less sensitive than those of the developer above. The sensitivity-increasing effect was determined as follows: A silver-gray wedge is exposed to a sample of color reversal paper, the step spacing of which is] / 2. When processing in the first developer specified above, the sensitivity to o-phenylenediamine-free development is increased by seven levels. Patent claims: 1. Aqueous black-and-white developer for reversal photographic processing of color photographs Materials, characterized by a content of a known developer substance the 3-pyrazolidone series in combination with a known o-phenylenediamine developer. 2. Aqueous black and white developer according to claim 1, characterized in that the 3-pyrazolidone developer of the general formula ^R 6 O = C CR ₄ HN \ / R ₂ corresponds to where R ₁ to R _{5 are} hydrogen, alkyl up to 4 carbon atoms or phenyl. 3. Aqueous black and white developer after. Claim 1, characterized in that the Developer substance o-phenylenediamine and 3-pyrazolidone in a weight ratio of 60 to Contains 40 to 40 to 60. 709 679/494 10.67 ® Bundesdruckerei Berlin