DE1597554B - Photographic recording material - Google Patents

Description

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soluble. For the production of solvents diluted with water developers of the following additions are expediently

solutions, however, only solvents with a low polar composition:

did used because the silver pi complexes concerned water (about 50 ⁰ C) 750 ml

p-methylaminophenol sulfate ". '.'. '.'. Υ. 2 g

The pi complexes according to the invention have their 5 sodium sulfate, dried 100 g

greatest sensitivity in the ultraviolet range. You hydroquinone 5 e

can, however, also by dyes that contribute to the spec- Borax 2 ε

central sensitization of photographic silver _with water 'top up '. '.'. '.'. '.'. '.'. 1 liter
halide emulsions are used opposite

Light of other spectral ranges (spectrally) sensitized io developed and then washed in the usual way

will. and fixed with sodium thiosulfate. Here was a

The individual pi-complexes differ in obtained stable, sharp copy,
among themselves something in their solubility properties

in a wide variety of organic solvents. Example 2

Thus, for example, silver nitrate complexes 15 solve _a \ producing a

of cycloheptatriene, N-vinylcarbazole and pyridine cycloheptatriene silver nitrate complex
m methanol, chloroform and ethanol essential

better than the rest of the complexes. By mixing 5 g of silver nitrate, 10 ml

Since the complexes both heat and light cycloheptatriene and 15 ml of absolute ethanol and

are sensitive, can be added to them either by shaking the mixture obtained for 20 liters for 5 hours

Exposure to light or heating images at a temperature of 10 ° C became a clear liquid

produce. Solution of the cycloheptatriene silver nitrate complex

According to an advantageous embodiment, one received. As the complex obtained in absolute

Photographic recording material according to which ethanol is completely soluble, was none in the solution

Invention contains this sediment, which is common to determine in addition to pi complexes,

photographic developer compounds, preferred,. _TT ",".,

wise those of the hydroquinone type. Such a ^b > production of the recording material

photographic material can be used according to the Beiich

develop through heat and z. B. by showing a heptatriene silver nitrate complex

Treatment with aluminum sulfate or sodium sulfite 30 so that the most diverse photographic materials

fix. lien made.

_{Polyvinyl hydrogen phthalate L} are used as a binder.

and copolymers of vinyl hydrogen phthalate nitrate complex was applied to a paper backing

preferably used with Malemsaureimid applied and dried. The received photo

The following examples are intended to _{approximate the invention. 35 grams of rap} hical material was then contacted

illustrate. For the production of the pt complexes _with a printing template by a thermo

however, no protection is sought. graphical copier out. The co-

piercing device worked at maximum exposure

Example 1 setting. On the thermographically

⁴⁰ wrapped photographic material appeared

a) Production of a brown picture on a white background. The

Cyclopentadiene silver nitrate complex image was obtained by treatment with a

". ., ",,. , τ ^, η,, · common sodium thiosulphate fixing agent stabili-

A pressure bottle with a capacity of about 1.2 l was filled with · _t

wrapped in adhesive tape and covered with black. 45 2. A correspondingly coated paper has been made

Varnish sprayed to make them translucent. _{χ minute} \ _{from a distance of 2032 cm}

_{A nitraphot lamp was then placed in a nitraphoto lamp filled} with dry nitrogen through a photo

reeled pressure bottle 680 ml absolute ethyl alcohol graphic negative exposed. That exposed

and 34 g (0.2 mol) of silver nitrate were incorporated. The photographic material was then incorporated in one

Pressure bottle was sealed and its contents at 50 En _{twick he} i the following composition:

Cooled to 0 ° C. ^{Thereupon 39.6 g 6 6} were put into the bottle

(0.6MoI) freshly distilled cyclopentadiene in water (about 50 C) 750 ml

fills. Finally the bottle was immersed in a water p-methylaminophenol sulfate ... 2.5 g

bath shaken at O ⁰ C for 5 hours. The sodium sulfite here, dried 50.0 g

obtained pi-complex of cyclopentadiene and silver ₅₅ hydroquinone 2.5 g

Nitrate was until used at a tempera-alkali 20.0 g

stored at -20 ° C. Potassium bromide 0.5 g

made up to 1 liter with water

b) Production of the recording material developed and finally treated in a customary The resulting solution of the pi complex (cyclo-sodium thiosulphate fixing bath. Pentadiene-silver nitrate complex) was obtained on a sharp silver image.
Paper backing applied and dried. The paper support provided with a photosensitive layer from the dried photographic material was then provided with a cycloheptatriene silver nitrate complex for 1 minute at a distance of 10.16 cm and was exposed to a UV lamp from a distance of through a negative. 65 6 inches for 30 seconds with an altitude post exposure, the photographic sunlamp was exposed. A good AusMaterial was obtained for 30 to 60 seconds in a copy image, which was then stabilized in a conventional 1: 3 acidic fixing bath in a light silver halide.

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The pi complex of cycloheptatriene and silver and cycloheptatriene was added. The solution obtained

On treatment with aqueous potassium, nitrate can then be coated with a barite layer

chloride or potassium bromide solution in silver chloride provided paper and on the other hand on a white

or convert silver bromide. pigmented film base in one layer thickness (in

. 5 measured wet) of 0.0762 mm.

Example 3 _{After the} χ ^^ η of the layers, the

In a similar manner to the photographic materials described in Example 1 for 5 seconds

ben, the following pi complexes were made: long from a distance of 30.5 cm through a

AgNO-phenylacetylene step wedge with increments of 0.3 log E using a

AgNO ³ cyclopentadiene ^{10 Nitra} P ^hotlam P ^e exposed. The one by the exposure

Ag ₂ SO ² 3-cyclopentadiene, latent images obtained were physically de-

AsNO Pvridin wraps by putting on one with a for 2 minutes

AgNOÜ-N-Vinyicarbazole and silver halide coated film strips, which

AgNO ₃ maleic acid imide. Immersed in developer solution for ^{5 seconds}

15 had been pressed. The design used

All of the prepared pi-complexes proved to have the following composition:

proved to be extremely light-sensitive. Methylaminoethanol-SO ₂ (19.9%

Example 4 SO ₂ ) 190.0g

,,, _,, Hydroquinone 11.6 g

■ In a 100 ml Erlenmeyer flask wur- ao i-phenyl-4,4-dimethyl-3-pyrazolidone. ^J "1.0 g

'to 20 ml of a 10 / _o by weight solids content up of sodium thiosulfate pentahydrate .... 60.0 g. .

pointing solution of polyvinyl hydrogen phthalate in potassium iodide 0 42 g

l ^ner , S ^SC ? ^Un ^ ^aUS , ethoxyethanol and methanol, _{1Q0 /} j _{e me} thanoiische 'solution of'

20 ml of methanol and 0.3 ml of the S-MethyW-piperidinylmethyl-

made up a solution of the pi-complex of Silbermtrat and 25 2-thiooxazolidine "" "■" 10 0 ml

Cycloheptatriene introduced. Fill up with water under safety light !!!! '. !!' !!! l'ljter
0.15 g of hydroquinone developer was added to the solution

added, whereupon the resulting coating mass. The results obtained with the baryta-coated paper carrier were applied to baryta-coated paper and the results in the air were somewhat better than those obtained with the white-dried. The obtained photographic pigmented film base gave results.
Paper was then in a copier ^ for 1 second. .
device of the Besseler Slido-O-Printer type with a B e 1 s ρ 1 e 1 6
Negatively I exposed to ultraviolet light, a latent image of the type described in Example 5 being formed. This was heated for less than 3 seconds as a coating compound and thereby produced into a compound. High density visible image developed into the coating composition. 1-carboxymethyl-

In another series of experiments, corresponding 5- [3-ethyl-2 (l) -benzoxazolylidene-ethylidene] -3-phenyl-

Such photographic materials at elevated 2-thiohydantoin at a concentration of 2.5 ml

Temperatures exposed to ultraviolet light. added per 380 ml of coating material. Which he-

In this case, without additional heat treatment, 40 coating compounds were applied

Obtain immediately visible high density images. paper provided with a baryta layer in one thickness

A standard sun light (measured when wet) of 0.0762 mm was used for exposure Used as a light source so it was often worn. After drying, this was obtained required, distances of at least 25.4 cm photographic material, as described in Example 5 and exposure times of less than 15 seconds, exposed and treated. The results obtained choose to damage the photographic nisse showed that when using the above material to avoid. The images obtained could be 32 times that of said sensitizing dye increased sensitivity by treatment with aqueous aluminum sulfate. Next or Sodium sulfite solution are stabilized. due to the alkali permeability of the verr> · · 1 c 50 applied binder the contact time of the silver P * ■ supplying film strip with the exposed photo-

To 10 ml of a 4 ° _ / ₀ solution of phthaliertem photographic material for 2 minutes to 5 seconds

Polyvinyl acetate in 2-ethoxyethanol were 0.1 ml of the can be shortened without affecting the image quality

pi complex of silver nitrate obtained in Example 2 suffered.

Claims (5)

1 2 like watering and in particular the relative patent claims: difficult to control chemical ripening, can be dispensed with. 1. Photographic recording material, This object was achieved in such a way that "consisting of a carrier as well as 5 pi-complexes of a water-soluble silver applied thereon, a light-sensitive silver salt and certain unsaturated organic compounds and if necessary, use a water-permeable poly bond. merisate as a binder-containing layer, the subject of the invention is therefore from a characterized in that it consists of a photographic recording material pi-complex of a water-soluble silver salt io from a carrier and an applied, and an alicyclic polyene, phenylacetylene, a photosensitive silver salt and optionally N-vinylcarbazole, pyridine or maleic acid imide a water-permeable polymer as a binder contains. containing layer, and is thus characterized 2. Photographic recording material characterized in that it is a pi-complex of a water claim 1, characterized in that it contains a 15 soluble silver salt and an alicyclic polyene, pi complex of silver nitrate and cyclopentadiene phenylacetylene, N-vinylcarbazole, pyridine or maleic or Contains cycloheptatriene. acid imide contains. 3. Photographic recording material according to the preparation of the photographic recording claims 1 and 2, characterized in that voltage material according to the invention suitable light As a binder polyvinyl hydrogen phthalate or ao sensitive pi-complexes can be made from water-soluble a copolymer of vinyl hydrogen phthalate silver salts and the specified organic unsuitable and maleimide. saturated compounds in alcohols, ethers and 4. Photographic recording material according to other organic solvents and in Mi claims 1 to 3, characterized in that such solvents are prepared with water it contains a hydroquinone developer. 25 become. Since the light-sensitive pi complexes in 5. Photographic recording material are soluble in organic solvents, they can Claims 1 to 4, characterized in that from organic solutions on conventional layer supports a spectral sensitizing dye can be applied. Due to their solubility in holds. organic solvents they can also be used jointly 30 sam can be used with film-forming binders, which are only sparingly soluble in water. The light- sensitive layer of a recording material according to the invention can thus contain a binder or be binder-free. The invention relates to a photographic recording material, consisting of a carrier as well as practically speaking of the photosensitivity of silver purifier a light-sensitive halide applied to it. For making photographic images The recording materials according to the invention polymer can contain a silver salt and, if appropriate, a water-permeable one as a binder-containing layer. generation according to those for photographic silver halide Exposed, developed and fixed in the usual known photographic processes processes will be known to be photosensitive. Recording materials used whose light- For the production of pi complexes with especially sensitive layers containing a silver halide or advantageous photographic properties have contained mixtures of different silver halides. aliphatic, isocyclic polyenes, such as triene and vinylcyclohexene, since light-sensitive silver halides are easily produced by way of cyclopentadiene, cycloheptatriene, cyclododeca-precipitates in aqueous media. .
can, the usual silver halides in the reaction with pi-electron containing Usually in the form of aqueous suspensions or emulsified unsaturated organic compounds, suitable sions are applied to the substrate. The film-forming water-soluble silver salts are, for example, silver, the binders of such emulsions consist of 5 ° nitrite, silver sulfite and preferably silver nitrate,
hydrophilic colloids, for example gelatin, or The preparation of those used in the photographic the most diverse other, used in water dispersing materials according to the invention, lightable, natural or synthetic substances. In the case of the sensitive pi complexes it is expedient to carry out Such silver halide emulsions are produced by reacting the mentioned silver salts with the however usually several operations required, 55 called pi-electron-containing unsaturated ones namely, precipitation of silver halides in the case of similar organic compounds in a suitable solvent Dispersion in the solution of the binder, solvent. Suitable solvents are for example solidification, in order to show a subsequent rinsing short-chain alcohols such as methanol, ethanol possible, said watering to remove excess and butanol, hydrocarbons, such as hexane, heptane To wash out salts that are otherwise sensitiv- 60 and cyclohexane, ethers, such as ethyl ether, tetrahydromend would act, as well as the final chemifuran and dioxane, as well as dimethylformamide, chloroshe Maturation, the control of which is a great experience form and acetone. Mixtures of these can also be used requires a professional. Solvents can be used with water. The object of the invention is therefore to provide the pi complexes obtained are in particular to indicate drawing material that such silver is special due to its favorable solubility in organic contains compounds whose photosensitivity is made from solvents of low polarity. A big after all, chemically ripened silver halides are equal in number of these complexes also in mixtures of some comes, but in their production on operations, the organic solvents mentioned with water