DE1285303B - Stabilized photographic recording material - Google Patents

Description

The present invention relates to a stabilized photographic A recording material comprising a gelatin-halosilver emulsion layer and a adjoining gelatin layer.

It is known that photographic recording materials containing halosilver a decrease in sensitivity and after prolonged storage after their preparation suffer the formation of an undesirable veil. To these adverse effects A wide variety of stabilizers have already been proposed to prevent this. That However, introducing the known stabilizers is disadvantageous because it is usually causes a decrease in sensitivity, and the desire of the professional world is directed to the development of a stabilizer that allows concealment without to prevent any adverse influence on the sensitivity.

The object of the invention is to provide a photographic recording material which does not show any decrease in sensitivity over long periods of time and does not tend to form fog. The subject matter of the invention is based on a stabilized photographic recording material with a gelatin-halosilver emulsion layer and an adjacent gelatin layer and is characterized in that it contains a compound of the general formula QC - CR in the emulsion layer and / or in the gelatin layer, in which R is a hydrogen atom or a carboxyl, alkoxycarbonyl, phenyl or substituted phenyl radical and Q is an alkoxycarbonyl, carbamoyl, Denotes phenyl, substituted phenyl or naphthyl radical and in which, if R represents a hydrogen atom, Q is a group of the formula where R1 is a hydrogen atom, a lower alkyl, phenyl, substituted phenyl or aralkyl radical and Rr is a lower alkyl, phenyl, substituted phenyl, naphthyl or aralkyl radical and both radicals R1 and R2 together represent a cycloalkyl radical and R3 denotes a hydrogen atom or an acyl radical.

The gelatin layers include sub-layers, intermediate layers and protective layers. The introduction of the compounds according to the invention of the general Formula in one layer or in layers of the photographic according to the invention Recording material can be made in a manner known per se. if for example the compound is present in an emulsion layer of this material If you want, it is possible to straight the compound into the emulsion at any time before, during or to introduce this emulsion after the second ripening. The addition the compound at a stage after the second ripening of the emulsion is preferable. Optionally, the compound can be used in a starting material for making the emulsion be introduced, for example into the gelatin. The amount of added according to the invention Compound changes depending on the type of emulsion, the type of compound used, the degree of stabilization desired and the type of layer to which the connection is made is added, but is generally in the range of 10 mg to 2 g per liter the emulsion or coating solution. It is desirable to keep the compound in solution, add dissolved water, diluted alkalis, methanol or ethanol, for example, if the addition is to be made to an emulsion.

The invention achieves that the recording material according to the invention Stored for longer periods of time without any loss of sensitivity or fogging can be. Another advantage of the present invention is that when adding the compound according to the invention to a halogen silver emulsion during the prevention of fogging during their ripening or digestion is possible and accordingly an increase in sensitivity due to the tire or the Digestion is facilitated.

According to one embodiment of the invention, the emulsion layer contains additionally a color former.

This ensures that concealment and desensitization or Decrease in the sensitization effect, both of which are common during storage of a Color photographic material occurs that contains large amounts of color former in the emulsion, effectively prevented by the use of a compound of the present invention can.

The following compounds are examples of compounds according to the invention according to the general formula Some of the compounds shown above are new substances which have not yet been made and used, and in order to provide sufficient information about the present invention to those skilled in the art, the preparation of such new compounds is given below. l-Tolyl-2-propyne-l -ol (XX) A solution containing NaC mm CH was prepared from 4.6 g of metallic sodium, about 200 cc of liquid ammonia, a small amount of ferric nitrate, Fe (NO3) 3, and gaseous acetylene in produced in a known manner. A solution of 24 g of p-methylbenzaldehyde in 30 cc of dry ether was added dropwise at 80 ° C. to the resulting solution. After the addition had ended, the mixture was stirred at -35 to -40 ° C. for 5 hours. Then 15 g of ammonium chloride were added and the ammonia was evaporated at room temperature. Ether and water were added to the residue obtained. The deposited ethereal layer was removed and then combined with the essential extract obtained by shaking the aqueous layer with ether. The combined essential components were washed with dilute sulfuric acid, aqueous sodium bicarbonate and water and then dried over sodium sulfate. After evaporation of the ether, the remaining liquid mass was subjected to distillation under reduced pressure, whereby a fraction of 18 g with a boiling point of 96 to 98 ° C./0.8 mmHg was obtained. This fraction was called 1.Tolyl-2-propyn-1-ol of the formula identified.

1-p-Chlorophenyl-2-propyn-1-ol-O-acetylate (XXIII) A solution with a content of NaC - Cli was made from 2.3 g of metallic sodium, 150 ccm of liquid Ammonia, a small amount of ferric nitrate and acetylene gas in a manner known per se manufactured. A solution of 14 g of p-chlorobenzaldehyde in 20 ccm of dry ether were added dropwise at -80 ° C. When the addition was complete the mixture was stirred at -35 to -40 ° C. for 6 hours. Then there was 10 g of solid ammonium chloride added and the ammonia evaporated at room temperature; The residue obtained was shaken with ether and water.

The ethereal layer was separated and the aqueous layer extracted with ether. The ethereal components were combined, washed with dilute sulfuric acid, sodium bicarbonate and water and dried over sodium sulfate. After evaporation of the ether, the remaining liquid mass was distilled, giving 10 g of l- (p-chlorophenyl) -2-propyn-1-ol with a boiling point of 80 to 82 ° C / 0.3 mmltg. The free alcohol obtained was in Dissolve 100 cc of pyridine and add 30 cc of acetic anhydride. The mixture was left to stand at room temperature overnight. Then the mixture was poured into water and extracted with ether. The essential extract was washed with dilute hydrochloric acid, aqueous sodium bicarbonate and then with water, and dried over anhydrous sodium sulfate. After evaporation of the ether, the remaining liquid mass was distilled in vacuo, giving 10 g of 1- (p-chlorophenyl) -2-propin-1-ol-O-acetylate with a boiling point of 99 to 1000 ° C./1 mmHg, which has the formula corresponded. l-Phenyl-3-butyn-2-ol (XXV) A Grignard solution containing HC C - Mg - Br was prepared from 12 g of magnesium, 60 g of ethyl bromide, 300 cc of tetrahydrofuran and gaseous acetylene according to the method described in Organic Synthesis, 39, 56, method described.

A solution of 55 g of fresh phenylacetaldehyde in 30 cc of tetrahydrofuran was added to the prepared solution while cooling with ice. After the addition was complete, the resulting mixture was stirred at room temperature overnight. A solution of 50 g of ammonium chloride in 300 cc of water was then added while cooling with ice. Aether was also added. The deposited organic solvent layer was removed and the remaining aqueous layer was extracted with ether. The ethereal components were combined, washed with water until the litmus sample showed a neutral reaction, and then dried over sodium sulfate. After evaporation of the organic solvent, the remaining liquid mass was distilled in vacuo. where 30 g of 1-phenyl-3-butyn-2-ol (b.p. 65 to 66 ° C / 0.23 mmHg) of the formula were obtained.

The following examples serve to explain the invention in more detail.

Example 1 A highly sensitive silver bromide emulsion for negatives with a content of 3 mol percent silver iodide is produced by the boiling process.

This emulsion undergoes a second ripening at one for 75 minutes Subject to temperature of 60 ° C.

After this ripening, the emulsion is divided into 12 parts, one of which is used for the production of the control film and the other 11 parts are used in each case in combination with one of the compounds according to the invention given below. The samples obtained are then stored for 3 days at 55 ° C., then exposed in a Sensitorneter and developed for 5 minutes in a developer with the following composition: p-methylaminophenol sulfate 2, (3 2.0 g sodium sulfite (anhydrous).... 50.0 g hydroquinone 4.0 g sodium carbonate (monohydrate) ... 7.0 g potassium bromide ......... ........... 0.75 g water made up to .. ............ 1.01 The developed samples were stopped with dilute acetic acid and then fixed, washed and dried The results are given in Table 1. Table I Amount of compound freshly extracted oven values after 3 days at 55 ° C Compound per liter of emulsion relative relative (mg) obfuscation obfuscation Sensitivity sensitivity Control .......... - 100 0.04 42 0.75 1 300 100 0.04 80 0.15 II 350 100 0.04 80 0.10 III. ... 200 100 0.03 85 0.05 IV ... ... 600 100 0.04 95 0.07 VI ..... 450 100 0.03 95 0.06 VII ......... 400 100 0.04 80 0.06 VIII 200 100 0.04 60 0.10 Ix 400 100 0.02 95 0.05 X .. 400 100 0.04 70 0.25 XI ........... 420 100 0.04 70 0.30 XII. . . . . . . . . 420 100 0.04 85 0.15 XIII ......... 450 100 0.04 75 0.28 XIV ......... 400 100 0.04 85 0.08 The information on the relative sensitivity is based on a density of 0.1 above the haze.

The values in Table I clearly show. that the specified according to the invention Compounds are valuable in preventing undesirable fogging.

Example 2 The highly sensitive negative emulsion used in Example 1 is subjected to a second ripening in the same manner as in Example 1. the treated emulsion is by adding Dodecyläthylenoxydlauryläther in a a lot of 100 mg per liter of emulsion sensitized. The emulsion is divided into parts, each of which is admixed with the respective compound according to the invention. the Comparative test is carried out in the same manner as in Example 1. the The results obtained are shown in Table II.

Table II Amount of compound Fresh values Oven values after 3 days at 55 ° C Compound per liter of emulsion relative. ... relative .. ..... (mg) Sensitivity obfuscation Sensitivity obfuscation Control. . . . . . - 100 0.05 40 0.97 IV 1000 100 0.05 130 0.07 V 1000 100 0.03 90 0.05 VII 400 100 0.05 120 0.10 XV .... 500 100 0.05 125 0.15 XX ............. 800 100 0.05 110 0.20 the values in Table II clearly show. that chemically sensitized photographic ereulsions could be effectively stabilized by adding the compounds according to the invention.

Example 1 of the high sensitivity used in Example 1 Negative emulsion is @sodium thiosulfate as a sulfur sensitizer in a Amount of ven 2 mg per liter of emulsion added, the emulsion obtained is in drel Parts shared. one of which is used as a control and the other for the the following test can be used.

The bond of formula (IV) becomes the second part in a set of 300 mg per liter of this part was added. and the compound of formula (VIII) is added to the third part in an amount of 20 mg each. The received Mixtures are subjected to a second ripening at 60 ° C., with samples in each case removed at 20, 40, 60, 80 and 100 minutes and coated on film support will. The films obtained are rated in terms of sensitivity and fogging measured according to the method described in Example 1. The results are in Table III given.

Table III Additional 20 minutes 40 minutes 60 minutes 80 minutes 100 minutes Reia @ ive sensitivity ... 60 90 n100 104 9 .. @@@ trolie { Concealment .... ..... 6.0 @ @ 0.0 @ 0, @@ @@ @elative sensitivity ... 36 @@ 92 @ 3 @@@ @@ { concealment ............ 0.02 0.93 0.03 0.07 0.08 Relative sensitivity .... 36 55 95 115 120 @V { Concealment ............ 0.02 0. @ 3 0.03 0.07 0.08 In the table above, the relative sensitivity was based on that of the control sample which had been matured for 60 minutes and whose value was set equal to 100. As can be seen clearly from Table III. an effective increase in the sensitivity of the emulsions to which the compounds according to the invention were added as a function of the progress of the ripening process, with a lower tendency to fogging occurring, while the sensitivity of these emulsions compared with the control sample was not as noticeable during the initial stage of the second ripening increased.

Example 4 e 1 4 The @@ Beisptel 1 used highly sensitive @@@ @@@@@@ @@@@@@ Min @ te lang emer second @@@@@@@@@@@ a solution containing - (4'-phenoxy-3'-sulfophenyl) -3-heptadecyl-5-pyrazolone contained, added as a color former. The resulting emulsion was applied to a film support layered. A 3% gelatin solution was applied to the surface of the film obtained, in which the specified compound was introduced, if applicable. as a protective layer applied to produce a layered film. The obtained film became 3 days at 55 C in the same way as described in the example. stored. Of the film treated as above, as well as the untreated film. were with a Developed a color developing solution containing diethyl-p-phenylenediamine. The developed Films were based on the conventional. known type bleached and fixed with water washed. The results obtained are given in Table IV.

Table IV Amount that 11 3% fresh values oven values after 3 days at 55 ° C Used gelatin solution Compound added was relative relative (mg) Sensitivity obfuscation Sensitivity obfuscation Control; . . . . . 100 0.08 90 0.40 1,500 100 0.07 105 0.15 II 800 100 0.06 110 0.10 III 700 100 0.08 95 0.12 XV 500 100 0.08 95 0.20 XX .......... 700 100 0.07 95 0.18 5CXIII 1000 100 0.06 100 0.15 The values in Table IV clearly show that the formation of fog can be prevented by the presence of the compounds according to the invention in a protective layer.

Example 5 A highly sensitive silver bromide emulsion for negatives with a content of 3 mol percent silver iodide is produced by the boiling process. This emulsion lasts for 75 minutes subjected to a second aging at 60 ° C. To when the ripening is complete, the emulsion is divided into 11 parts, one of which is a control is used and of which the other 10 each in combination with one of the compounds according to the invention given below is used.

Samples are made with all parts and are stored at 55 ° C for 3 days. The sensitivity and fogging of the films are determined in the same manner as in Example 1. The results are given in Table V. Table V Amount of compound Fresh values Oven values after 3 days at 55 ° C Compound per liter of emulsion relative .. ... relative .. ... (mg) Sensitivity obfuscation Sensitivity obfuscation Control. . . . . . 100 0.04 42 0.75 XV 300 100 0.04 95 0.18 XVI 250 100 0.04 - 90 0.25 XVII 300 100 0.04 85 0.20 XVIII 300 100 0.04 80 0.30 XIX 400 100 0.03 90 0.12 XXI 500 100 0.04 90 0.10 XXII 600 100 0.04 85 0.13 XXIII 400 100 0.03 85 0.15 XXIV 400 100 0.04 80 0.20 XXV. 400 100 0.04 80 0.22 The values in Table V clearly show that the formation of fog is prevented by adding the compounds according to the invention.

Of course, changes can be made in the implementation of this Invention to be made. Thus, instead of the compounds of the above Examples of any other of the present invention as defined by the general formula Connections can be used, or several such connections can be used come. The compounds in question here can also be used alone or in combination with the usual known stabilizers and prevent fogging Means can be used without any undesirable effects.

Claims (2)

Claims: 1. Stabilized photographic recording material with a gelatin-halosilver emulsion layer and an adjacent gelatin layer, characterized in that in the emulsion layer and / or in the gelatin layer it contains a compound of the general formula QC CR, in which R etn hydrogen atom ttdLt is a carboxyl - Alkowearbonyl- ,. Phenyl-substituted phenyl radical and Q is an alkoxycarbonyl, carbamoyl, Denotes phenyl, substituted phenyl or naphthyl radical and in which, if R represents a hydrogen atom, Q is a group of the formula may mean in which R1 is a hydrogen atom, a lower alkyl, phenyl, substituted phenyl or aralkyl radical and R is a lower alkyl. Represents phenyl, substituted phenyl, naphthyl or aralkyl radical and both radicals R and R2 together can represent a cycloalkyl radical and Ra represents a hydrogen atom or an acyl radical. 2. Photographic recording material according to claim 1, characterized characterized in that the emulsion layer additionally contains a color former.