DE1289421B - Photographic recording material - Google Patents

Description

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The invention relates to a photographic silver or antimonate in acidic, aqueous solution, insbehalogenidhaltiges recording material with a special phosphonic acid compound with such salts of alkali metals, which treat the formation of stains. According to US Pat. No. 2,239,284, the emulsion may be caused by particles of heavy metals, if necessary with alkali pyro and / or heavy metal compounds, alkali metaphosphates, alkalides mixed with phosphates. tripolyphosphates and alkali hexametaphosphates are added to, albeit in the manufacture of photosensitive. Although the addition of the material is extremely careful to avoid turbidity when diluting the Ent it is difficult to completely prevent curling, but it is stated that the phosphates particles of heavy metals, such as iron particles, or io possibly as a sequestering agent for Iron, from heavy metal compounds, such as rust particles, to copper and aluminum ions are used. In the German settle the photosensitive material. This partial laid-open publication 1121,467 is referenced to these U.S. patents generally arise during wear and writing and states that these phosphates do not completely eliminate the corrosion of the coating machines, but the staining. traces of these metals or metal compounds are also found there that phosphoric acid, sometimes fertilize in the photochemicals used arsenic acid or antimonic acid or salts thereof which are present or also in the carrier, e.g. B. Documents Formation of paper, film and glass caused by iron dust, which the light-sensitive black points do not prevent. In this German emulsion is applied. Auslegeschrift are now to prevent such particles of metals or metal stains from metal dust no longer phos compounds are particularly harmful, per compounds, but derivatives of amino because they are chemically reactive, ie a secondary carboxylic acids, especially amino acetic acid, acting on the light-sensitive emulsion layer called. From the German patent specification 1 074 975 is exercise. The adverse effects of these particles, the use of phosphoric acid or phosphonic acid esters, which are usually invisible to the naked eye to avoid yellowing, are so intensified that, depending on the photographic images, especially those, the nature of the particle and the species of the respective light and dark spots are produced after treatment according to the halogen silver diffusion transfer process emulsion and which contain alkalis and development of the exposed photosensitive material in the substances. The compounds photographic baths become visible. 30 neutralize the yellowing alkali. The metal particles in the photographic layers can be attacked, and the dust formed in the process cannot be seen there, the corrosion products can diffuse away from the internal disadvantage of the known compounds to the core. These corrosion products, preventing the formation of stains by metal dust, can have a sensitizing or desensitizing effect - they have insufficient activity or activity only to influence the emulsion, so that in certain emulsions and in a certain photographic material it is rather narrow after the normal bath Show pH range or secondary treatment shows black or white spots. Most of these metals or metal compounds can also have effects on the silver halide emulsion layer, such as desensitization, fogging and fertilization, acting as reducing agents and a spontaneous 4 ° discoloration. Experiments have shown that sodium evolve which leads to black spots, hexametaphosphate according to the U.S. patent. Other influences, such as the impairment of the 2,239,284 at pH 6 hardly and at pH 4 latent image and the hindrance to development, are of little use. Dioxyethyliminoacetic acid, however, lead to white spots. In all cases, German Auslegeschrift 1121 467 Although the resulting spot is always greater than the dust ⁴⁵ improves, but 6 also particles at pH 4 at pH still insufficient, which is the cause of this undesirable object of the invention to provide a photographic phenomenon is . This can easily be checked by bleaching the silver halide-containing recording material, for example the silver from the material which has a ben in which the formation of stains from metal dust shows black spots, with a conventional bleaching agent at all pH values occurring in practice. The 50 that is completely avoided almost always disappears.

black spot but remains in its center. This is achieved by making the recording very small core, the material in the substrate and / or in at least one of them is visible. water-permeable layer, which is on the same Also fine metal particles or dust from the metal side of the substrate as the light-sensitive Compound located in a non-photosensitive silver halide emulsion layer, a few milli-neighbors Layer are present, practice one gram to 10 g per square meter on at least one equally detrimental influence on the above-phosphonic acid of the following general formula or underlying photosensitive layer.

The harmful corrosion products of the metal ^

particles or the dissolved components of the metal 60 τ

Compounds can form the light A — alkylene — P — OH by diffusion

reach the sensitive layer and there the top!

cause mentioned errors. OH

It is known from German patent specification 486 964, to avoid white spots on photo 65 in which A is a carboxyl group, a phosphonic acid graphic Development paper means the base paper or group or a hydroxyl group and / or the barytaed paper with phosphoric acid, arsenic acid at least one water-soluble salt of such or contains antimonic acid or with phosphates, arsenates phosphonic acid.

3 4

As water-soluble salts of such phosphonic acid has a hydroxyl group, this book will refer to

Sodium, potassium, ammonium or amino- the pages 156 and 157 may be mentioned. Let (1-hydroxy-

called salts. heptyl) phosphonic acid, [(l-hydroxy-l, 3-dimethyl) -

These phosphonic acids and phosphonates are in all butyl] phosphonic acid and [(I - hydroxy-1-methyl) -

Kinds of light-sensitive silver halide materials 5 ethylj-phosphonic acid as suitable for the present invention

were mentioned regardless of the pH value and the sensitivity.

possibility of the silver halide emulsion layer in tech- The compounds according to the invention can be used in

nisch progressively active; they also practice different concentrations in the substrate,

possibly also an antistatic and veil z. B. a paper backing, the photosensitive

reducing effect on the photosensitive recording material and / or in at least one

Material from. of the water-soluble layers that are included

The phosphonic acids in which A has a carboxyl on the same side of the support as the photosensitive

group, silver halide emulsion layer can be produced, among other things. Preferably

by reacting halocarboxylic acid esters with the compounds according to the invention are in the

Trialkyl phosphites and subsequent saponification of the light-sensitive silver halide emulsion layer

Ester functions in an acidic medium. Details present themselves; the concentrations can thereby

about this manufacturing method can be found in vary greatly and range from a few milli-

Chem. Ber. (1924), pp. 1023 to 1038, and (1927), grams to 10 g per square meter of light-sensitive

Pp. 291-295, J. Am. Chem. Soc. (1946), p. 1103 to recording material.

1105, and J. Gen. Chem. U.S.S.R. (1927), p. 237, and 20 The phosphonic acids or their salts are

(1929), p. 619. usually initially dissolved, for example in water.

Suitable compounds in which A is a carbon. The support can then with such a

acid group will be soaked in Kosolapoff, solution if the invention

Organophosphorus compounds (John Wiley & Sons, compounds to be incorporated into it. If

Inc., New York, 1950), pp. 160/161. 25, however, the connections in a water-permeable

As particularly suitable according to the invention, the solution to be incorporated into the layer is

to mention: usually related to the casting composition of the

HO ₂ C CH ₂ PO (OH) ₂ added layer or layers.

Carboxymethylphosphonic acid, in a photographic material have the

30 compounds used according to the invention have the

pjQ Q qjj PO (OH) ^th * '' ^ ^a ^ ^e ^ ^s * ^{e to e} g desired photographic properties

² ν 2 shafts do not affect at all, e.g. B. the

Contrast, sensitivity and stability. To the-

³ accordingly, these connections can be too high

1-carboxyethylphosphonic acid, ₃₅ sensitive as well as too low-sensitive

Emulsions, too high in contrast as well as too

HO ₂ C - CH ₂ - CH ₂ - PO (OH) ₂ soft emulsions, both acidic and alkaline

2-Carboxyäthylphosphonsäure see emulsions are added.

and Another advantage is that the invention

HO ₂ C-Ch ₂ -CH ₂ -CH ₂ -PO (OH) ₂ 40 compounds the others in the preparation of the

3-carboxypropyl phosphonic acid. products used in photosensitive materials

such as dispersants, color couplers, surface-active agents

As a phosphonic acid according to the invention, in which A is a substance, optical brighteners, antioxidants, sensiti-phosphonic acid group is, is particularly suitable meters, anti-fogging agents, stabilizers, hardhylene diphosphonic acid. This compound can in no way affect the manufacture or plasticizer, are made by reacting the diethyl ester of Accordingly, the invention Chloromethanephosphonic acid with triethyl phosphite and compounds in all photographic negatives subsequent saponification of the ester functions. Other and positive materials can be used, e.g. Am suitable phosphonic acids in which A is a phosphonic copying materials, X-ray films, graphic mateic acid group can be prepared by using ambient, infrared-sensitive silver halide material between an α, ω-dihaloalkane with the lien and in materials for the application of the silver double molar amount of triethyl phosphite and subsequent salt diffusion process.

ßende saponification of the ester function in dilute The invention is in the following on the basis of acids. Details of these manufacturing methods and examples explained
can be found in an article by K. Moedritzer55 _R. -I ₁
and RR Irani, J. Inorg. Nucl. Chem. (1961), Example 1
P. 297 to 304. Other particularly suitable phosphonic A not yet completely dry adhesive layer, which is applied to acids of this type are ethylene-1,2-diphosphonic acid, a cellulose triacetate carrier, with propylene-1,3-diphosphonic acid and butylene-l , 4-finely divided iron powder dusted. A strip of A phosphonic acid. 60 of this carrier treated in this way is coated with a bromide emulsion corresponding to the above general formula for A = hydroxyl-sensitive, panchromatically sensitized silver. A strip B of the carrier treated by reaction of aldehydes or ketones is coated with the same silver bromide with phosphoric acid or phosphorus trichloride. Coated because of emulsion, which, however, per kilogram of further details of this production method is 65 emulsion 3 g of carboxymethylphosphonic acid added to J. Am. Chem. Soc. (1921), pp. 1928 to 1935, and are. After these two test strips have dried onto the above-mentioned book by Kosolapoff, they are exposed in such a way that, after 9 minutes, pages 129 to 132 are referred to. Compounds in which A Developing at room temperature, fixing and rinsing

Claims (1)

1 249 421 5 6 a density of 0.6 is achieved. To develop is described, fixed, then 1 hour in a solution of the following composition is rinsed with running water and finally dried. used: The paper strip shows numerous white spots. \ y _water 800 ml If, however, 4 g carboxymethylphosphonic acid per Monomethyl-p-aminophenoisulfate ". '.'. '. 2 g of ⁵ kilograms of the photosensitive emulsion added Sodium sulfite (crystallized) 200 g JfVlT ^E ™ ^u f ° ⁿ ^ f ^{6 others} . ^Helped . ^te _t ^{B des} Hydroquinone .4g baryüerten strip is applied, shows this D ^ 2 g half B after the same treatment as for the ^ _ater kjg looo ml half A a uniform appearance with no white ίο stains. Both strips are rinsed for a few seconds and Example 6 then 10 minutes in a solution of the following Fixed composition: Example 5 is repeated, but the carboxy Sodium thiosulfate 200 g methylphosphonic acid with the same amount of methyl Potassium metabisulfite 25 g 15 lendiphosphonic acid replaced. Water up to 1000 ml. The result was similar to that in Example 5 The strips are then made in flowing for 30 minutes. Rinsed with water and finally dried. The B e i s d i e 1 7 Strip A shows numerous black spots while the strip B, which is produced according to the invention 20 Example 5 is repeated, but the carboxy shows a uniform appearance and over methylphosphonic acid by an equal amount its entire surface has the same density. Replaced ethylene-1,2-diphosphonic acid. It became a _. . , “A result similar to that in Example 5 was achieved. Example2 Example 1 is repeated, but the carboxy-25 Example 8 methylphosphonic acid by an equal amount of Example 5 is repeated, but the carboxy Replaced methylenediphosphonic acid. methylphosphonic acid by an equal amount A result similar to that in Example 1 was replaced with propylene-1,3-diphosphonic acid. It became a achieved. similar result as in Example 5 was achieved. Example 3 ³ ° Example 9 Example 1 is repeated, but the carboxy example 5 is repeated, but the carboxymethylphosphonic acid replaced by an equal amount of methylphosphonic acid by an equal amount of butylene-1,4-diphosphonic acid. A butylene-1,4-diphosphonic acid was replaced. It became a similar result as in example 1 was achieved. 35 similar result as in example 5 was achieved. Example 4 Example 10 Example 1 is repeated, but the carboxy example 5 is repeated, but the carboxymethylphosphonic acid replaced by an equal amount of methylphosphonic acid by an equal amount of (l-hydroxyheptyl) phosphonic acid. 40 (1-hydroxyheptyl) phosphonic acid was replaced. It was a result similar to that in Example 1 was achieved. a result similar to that in Example 5 was achieved. Example 5 Example 11 A strip of paper from conventional photographic example 5 is repeated, but the carboxy- Quality is achieved with a barite layer of the following compound 45 methylphosphonic acid by an equal amount composition coated: f (l-hydroxy-l, 3-dimethyl) -butyl] -phosphonic acid 50 weight percent aqueous suspension sets. The result was similar to that in Example 5 sion of barium sulfate achieved 2 kg. 10 weight percent aqueous solution _R =, -, ₉ of gelatine 1000ml 50. Example iz One half A of this barite-coated strip is repeated with Example 5, but the carboxy- a light-sensitive, high-contrast silver bromide methylphosphonic acid with an equal amount emulsion coated that contains iron powder. Replaced after [(l-hydroxy-l-methyl) ethyl] phosphonic acid, After drying, this strip is exposed in such a way that a result similar to that in Example 5 was obtained that after 90 seconds of development, fixation and 55 achieved. Rinse a density of 0.6 is achieved. Go to development example 13 ment is a solution of the following composition used: Example 5 is repeated, but the carboxy Water 800 ml of methylphosphonic acid by an equal amount Monomethyi-p-äminophenoisulfat '.'. '.'. '. 1.5 g ^6o DiKl-carboxy-1-hydroxy-ethyl-phosphonic acid replaced Sodium sulfite (crystallized) 50 g ^Es .7 ^{rde a} similar result as in Example 5 Hydroquinone 6 g ^achieved - Sodium carbonate (crystallized) 100 g Claims: Potassium bromide Ig. ,. «,,. _{Water up to} 1000 ml ^6s 1. Photographic silver-halogenated composition drawing material with a phosphonic acid The strip is rinsed for 5 seconds and then bonded, characterized Minutes in a solution as in Example 1 that it is in the support and / or in at least a water-permeable layer on the same side of the support as the photosensitive layer Silver halide emulsion layer is a few milligrams to 10 grams per square meter of at least one phosphonic acid of the following general formula A - alkylene - P - OH
OH wherein A is a carboxyl group, a phosphonic acid group or a hydroxyl group and / or contains at least one water-soluble salt of such a phosphonic acid.
2. Recording material according to claim 1, 10 characterized in that it is the phosphonic acid and / or its water-soluble salt in the photosensitive Contains silver halide emulsion layer. 3. Recording material according to claim 1 and 2, characterized in that it contains, as phosphonic acid, carboxymethylphosphonic acid, 1 - carboxyethylphosphonic acid, 2 - carboxyethylphosphonic acid or 3-carboxypropylphosphonic acid. 4. Recording material according to claim 1 and 2, characterized in that it contains methylenediphosphonic acid, ethylene -1,2-diphosphonic acid, propylene-1,3-diphosphonic acid or butylene-1,4-diphosphonic acid as phosphonic acid. 5. Recording material according to claim 1 and 2, characterized in that it is phosphonic acid, (1 - hydroxyheptyl) - phosphonic acid, [(I - hydroxyl, 3-dimethyl) butyl] phosphonic acid or [(1-hydroxy-l-methyl ) ethyl] phosphonic acid. 909507/1496