DE1287439B - Photographic recording material - Google Patents

Description

1 2

The present invention relates to a stabilized desired stabilization and the type of layer, photographic recording material with a silver ■ · to which propiolic acid is added; in general halide emulsion layer and an unsaturated one, it is in the range of 10 mg to 1 g per liter of the aliphatic acid. Emulsion or overlay solution. It's purpose-photographic silver halide recording 5 moderately, the propiolic acid in a suitable solvent materials tend to be medium when stored for a long time, such. B. water, dilute sodium carbonate Decrease in their sensitivity to light and add to the solution, methanol or ethanol, dissolved, Fogging. To avoid this undesirable provided the addition to a liquefied emulsion The effects of adding stabilizers are known. he follows.

A disadvantage of admixing the known stabilizers is that the stabilizers according to the invention However, in addition to a desired effect, the stabilized photographic fog reduction is achieved mostly also the photosensitive drawing material safely over a long period of time Liability of the photographic recording material can be stored without the photosensitivity being reduced. Also from the USA. Patent speed decreases or the veil increases. 2,380,280 known silver halide emulsions water- 15 In cases where propiolic acid becomes a photographic to add soluble salts of unsaturated aliphatic acids to the emulsion during its chemical ripening, which is named in this patent specification is another advantage of the present one Lent listed compounds each as unsaturated invention to be seen in the fact that it is possible to Bonds one or more double bonds, but never one because of the slower formation of fog Have triple bonds. These connections mean an increase in photosensitivity also act as chemical sensitizers, range.

d. That is, they increase photosensitivity, amplify. The use of is particularly advantageous

but with it also the tendency to fogging of the propiolic acid as a stabilizer in a color photo

sensitized material. graphic recording material that is in large quantities

The object of the invention is to provide a photographic recorder containing 25 color former, because fog and desensitivity

drawing material to indicate that a stabilizer is used, both of which are common during storage of a

that the fogging occurs without causing such a recording material to detrimentally occur, thereby

Influence on photosensitivity can be prevented and effectively prevented,

the recording material an improved storage _. . , "

ability. 30 Example 1

The object of the invention is therefore based on a highly sensitive silver iodobromide emulsion,

a stabilized, photographic recording produced by the boiling process and suitable for

material with a silver halide emulsion layer negative that contains 3 mole percent silver iodide

and an unsaturated aliphatic acid and is undergoing chemical ripening at 60 ° C for 75 minutes

characterized in that it is subjected to propiol-35 as a stabilizer. After this ripening is finished

contains acid. divided the emulsion into two parts, one of which

The propiolic acid is in at least one of the ways to produce a control film, the other after

Layers of the photographic composition according to the invention. Addition of propiolic acid in an amount of 70 mg / l

Drawing material, this layer being used as an emulsion. Become of every part

an emulsion layer, undercoat, interlayer, 40 coatings made that for 3 days at 55 ° C

Be a protective layer or a primer layer and then another 3 days at 55 ° C and one

can. relative humidity of SO ⁰ J ₀ .

The inclusion of propiolic acid in a layer Samples of these coatings are then in a

or in layers of a photographic recording sensitometer provided with an intensity scale

materials according to the present invention can be exposed for 45 and 5 minutes in a developer

take place at any point in time. For example, the following composition has been developed:

it is useful in cases where propiolic acid in a _p -methylaminophenol sulfate 2.0 g

This emulsion layer Aufzeichnungsmatenals corresponds triumsulfit _Na (anhydrous) 50.0 g

should be, the propiolic acid of the emulsion just hydroquinone 40g

before, during or after their chemical ripening 50 sodium carbonate (monohydrate) ". '.'. '. 1,0g

admit. The addition of the propiolic acid after the potassium bromide 0.75 g

however, chemical ripening is preferred. On the other ^ _{water on füIlt to 10 L}

on the other hand, propiolic acid can be used as a starting material

Preparation of the emulsion, e.g. B. the gelatin itself, The development is carried out using dilute acetic acid

be added. 55 stopped, and the samples are then fixed,

The amount of propiolic acid to be added varies in washing and drying. The results are in Table I.

Depending on the type of emulsion, the degree of reproduced.

Table I.

Fresh sample
Sensitivity [veil

3 days storage at 55 ° C

Sensitivity I veil

Another 3-day storage

at 55 ° C and 80%

relative humidity

Sensitivity I veil

Control film

Propiolic acid film

100
100

0.03
0.03

40 95

0.80
0.05

25 85

1.20 0.07

Sensitivity is based on optical density at 0.1 above fog. The results of the Table I clearly show that propiolic acid is suitable for preventing undesirable fogging is.

Example 2

The highly sensitive emulsion for negatives according to Example 1 is a chemical ripening in the in the same manner as described in Example 1 subjected. The treated emulsion is made by adding chemically sensitized by dodecylethylene oxide lauryl ether in an amount of 100 mg / 1 of the emulsion. The emulsion is divided into two parts, one of which is propiolic acid in an amount of 90 mg / l Emulsion is added. A comparative experiment is described in the same way as in Example 1 carried out. The results obtained are shown in Table II.

Table II

Fresh sample sensitivity veil

3-day storage
at 55 ° C

sensitivity

veil

Another 3-day storage

at 55 ^o C and 80 ° / ₀
relative humidity
Sensitivity veil

Control film

Propiolic acid film

100
100

0.05
0.05

40
100

1.50
0.10

0
80

1.80
0.15

The results of Table II clearly show that chemically sensitized more to fogging Tending emulsions can be safely stabilized by adding propiolic acid.

Example 3

Sodium thiosulfate is added as a sulfur sensitizer to the highly sensitive emulsion for negatives according to Example 1 added in an amount of 2 mg / 1 emulsion. The resulting emulsion is in two parts divided, one used as a control and the other used for the following test. Propiolic acid

as becomes this other proportion in an amount of 10 mg / 1 emulsion added and the resulting mixture subjected to chemical ripening at 60 ° C, while samples are taken after 20, 40, 60, 80 and 100 minutes after the start of ripening and with them Film base are coated. The coatings obtained are rated in terms of photosensitivity and fogging according to Example 1 measured. The results are given in Table III.

Table III

Sample taken after 60 Minutes 100 20th 40 100 80 90 60 90 0.04 105 0.19 0.02 0.02 80 0.12 120 40 50 0.03 100 0.05 0.02 0.02 0.03

Control film

sensitivity

veil

Propiolic acid film

sensitivity

veil

In the table above, the relative photosensitivity in terms of the value of 60 minutes is long matured control sample is defined as 100. As can be clearly seen from Table III, it was found that the photosensitivity of the films to which propiolic acid was added, according to the progression of the Ripening was effectively increased; it was found that there was less tendency to fog was given and the photosensitivity of the films produced in this way in comparison with the control sample was not increased to such an extent during the beginning of the second ripening, but in the end it did a higher sensitivity is achieved.

Example 4

The highly sensitive emulsion for negatives according to Example 1 is subjected to chemical ripening at 60 ° C. for 75 minutes, then a solution of 1- (4'-phenoxy-3'-sulfophenyl) -3-heptadecyl-5-pyrazolone is added as a color former and a carrier coated therewith. A 3% gelatin solution is applied to the surface which, on the one hand, contained no propiolic acid and, on the other hand, contained propiolic acid in an amount of 200 mg / l of the gelatin solution used as a protective layer. The resulting film was stored for 3 days at 55 ° C. and then for a further 3 days at 55 ° C. and a relative humidity of 80 ° / ₀ in the same manner as described in Example 1. The film treated as described above as well as the untreated film were developed with a color developing solution containing diethyl-p-phenylenediamine. The developed film was bleached, fixed and washed with water by commonly known methods. The results obtained are shown in Table IV.

5 1,287,439
Table IV be
veil 3 day location
at 55 ° C
sensitivity 6th Another 3-day storage
at 55 ^o C and 80%
relative humidity
Sensitivity I veil 0.65
0.12 Fresh Pro
sensitivity 0.06
0.05 40
90 tion
veil 30th
80 Control flag 100
100 0.50
0.15 Propiolic acid film

The results in Table IV clearly show that fogging is caused by the presence of propiolic acid can be prevented.

Claims (1)

Claim: Stabilized photographic recording material with a silver halide emulsion layer and an unsaturated aliphatic acid, characterized by that it contains propiolic acid as a stabilizer.