DE1572225B - Process for producing a silver photographic image with molecular resolution - Google Patents

Description

The invention relates to a method for producing a silver image then .erst with an aqueous place of a photographic silver image, in the solution of a silver salt and then with a silver, a photosensitive layer, which a photolytically halide developer is developed, effective haloalkanes of the formula R - CX _3,. In practice, the amine compound in which R is hydrogen, a halogen atom or a 5 is preferably chosen so that it is with the halogen optionally halogen-substituted alkyl radical and X compound in the presence of light with generation of a halogen atom, and a triphenylmethyllactone, a product with clearer or even more intense Michler's Hydrol, Rhodamine-B-Lactam, 2,5-dichloro color reacts, so that one turns into a silver picture. N-phenylleukauramine, diphenylamine, benzidine, changing molecularly resolved primary image visible-naphthylamine, tribenzylamine, p-toluidine, indole, Ίο bar. If the primary image does not need to be 4,4'-bis- (dimethylaminophenyl) methane, hexylamine, reactants are chosen so that and / or piperidine is dispersed in a binder. A colorless or latent primary image is produced. It contains, initially with the formation of a colored one, therefore certain, an invisible, latent or colorless, latent primary image exposed and tes image resulting light-sensitive systems, which is developed in. . 15 the previous procedures were unusable, as a result

It is known (US Pat. No. 2,981,622), in the subsequent treatment with silver salt solution

a photosensitive recording material which is advantageously used for the production of silver,

a phosphotungstic acid and an image high resolution leuco base may be used. . . ^:

Triphenylmethane dye contains a latent image Examples of suitable amine compounds for a

to generate the primary image colored by treatment with a silver salt in front of a colorless background

solution and a halogen silver developer in one are the following:

Silver image is converted _Ό ■ "'.._'„ ₉ _ „ 3,3-bis- (p-dimethylaminophenyl) -

& is further from the USA patent 1658 510 6-dimethylaminophthalide,

known, in a light-sensitive, em halogen 3,3-bis (p-diethylaminophenyl) phthalide,

alkane and a binder containing recorder 25 Michlers Hvdrol ■. ■

tion material to generate a latent image and this Rhodamine B Lactam

by treating with a silver salt _{solution in a 25} dichloro-N-phenyileukauramine

To convert silver image .'_; ". as well as mixtures of these compounds to any

It is also from U.S. Patent 3,042,519. bieen parts

known, in a photosensitive layer that has a 30 · '' - ■ .-

Haloalkane and an amine containing a latent image Suitable amine compounds for a process

to produce, which by heat treatment in a where no colored primary image is required, are:

visible image is converted. . ,. .

After all, it is from the German interpretation: uipnenyiamin,

1134 587 as well as from British patent specification 35 f.f ': ¹ "'. ...., _{N tU}

917 919 known, light-sensitive layers for M-b.s-PimethylammophenyD-methane,

To use the production of color images that are an i-mpninyiamm,

aromatic amine and a halogen compound result in 1 π Denzyiamine, "·. .,.

keep. These color images are produced by a heat- p-ioiuiain,

treatment fixed in the dry way. 40 '

A disadvantage of these known methods is If no visible primary image is desired,

However, that ^: the images produced by them are also aliphatic as amine components

have limited resolving power and - so - amines, ζ. B. hexylamine or piperidine. However, it is

The well-known processes for the preparation of aliphatic amines are widely used in the present

Silver images concern - no-visible primary 45 of carbon tetrabromide and air humidity (each

images can be made. depending on the environmental conditions) more or less

The object of the invention is to rapidly form the amine hydrobromide salt in a photographic material

To specify the method in which stable silver images with. Invention to increase the haze of the image background

extremely high resolution can be produced.,. would .- \ .s; . . ! s.;: ■:,

can and where, if desired, visible pri- 5 ° Suitable halogenated alkanes are:

march images can be obtained. Iodoform '

The subject matter of the invention is therefore based on carbon tetrabromide, .1 ■

a process for producing emesphotogra- hexachloroethane,

phical silver image in which a light-sensitive carbon tetraiodide - - '

borrowed layer, which is a photolytically effective halogen 55 '/ ...'-. ■ ·

alkane of the formula R - CX ₃ , wherein R is hydrogen, ■ The preferred for the process according to the invention

a halogen atom or an optionally halogenated, water-soluble silver salt is silver nitrate;

substituted alkyl radical and X is a halogen atom, suitable reducing agents are: '. ·· ■. '".

and a triphenylmethyllactone, Michler's hydrol, ' _D -phenylenediamine or any photo-

Rhodam.nB-Lactam, 2,5-dichloro-N-phenylleukaur- 60 _graphic developer or any reducing agent

amm D.phenylam.n Benzid.n, 1-naphthylamm, tincture for silver sizing pictures. benzylamine, p-toluidine, indole, 4,4-bis- (dimethyl-

aminophenyl) methane, hexylamine and / or piperidine The preferred binder for the dispersion is

Contains dispersed in a binder, initially cellulose acetate butyrate. However, others can as well

with the formation of a colored or colorless, lat- 65 binding agent, the light-

th primary image is exposed and developed and are permeable, dissolve or dissolve the reaction part

is characterized in that the image-bearing act as a molecular dispersant and the

Allow layer to convert the primary particle into an application of the silver salt solution by adding it

allow diffusion of the silver salt solution and the reducing agent.

Example!.

A casting solution was prepared according to the following recipe: 20 g cellulose acetate butyrate of a quality that gives a viscosity of half a second (tested according to ASTM-D 817-64; a 2.38 mm chrome steel ball takes ¹ _1/2 seconds to move in a 20 % solution of the polymer (55 mm, the solvent being mainly acetone) were softened to a slurry in 40 g of toluene. This slurry was dissolved in 28 g of methyl ethyl ketone.

0.8 g of 2,5-dichlorophenyl leukauramine was used to form the dye-containing polymer solution and 10 mg of rhodamine B base dissolved in 3 ecm of toluene by heating. This solution were after Cooling to room temperature 7 ecm that prepared in the manner described above Cellulose acetate butyrate solution and 2 g of carbon tetrabromide were added. This dye-polymer solution was poured onto a 3.2 mm thick sheet of polymethyl methacrylate to form a 0.1 mm thick wet layer.

After the layer had dried, it was put through a master copy for 1 minute with a strong metal filament lamp, ζ. Β. a photo lamp, which was arranged at a distance of about 45 cm. The sheet was then washed in ethyl alcohol (95% ethyl alcohol and 5% water) to remove excess dye and carbon tetrabromide. After extracting the solvent, the recording material was dried in an air stream at 6O ⁰ C. At this point in the process, the primary colored image with molecular resolution was clearly visible. .

The subsequently dried recording material was then for 3 to 5 minutes in a 15 g Silver nitrate, 350 ecm of distilled water. 50 ecm of ethyl alcohol and a drop of a wetting agent containing solution soaked. After the treatment with silver nitrate solution, the recording material became rinsed three times with fresh distilled water and three times for 3 to 5 minutes each time washed with fresh ethyl alcohol. The primary image converted to a silver halide image was now very large faint but still visible.

The recording material was then dissolved in a 0.3 percent strength by weight aqueous solution of sodium sulfite washed to remove any silver nitrate that may still be present, and then for the image-wise reduction of the silver bromide first the light of the same photolamp for 1 minute exposed and then using a photographic developing solution (D-76 from Eastman Kodak Company, Rochester, New York, V. St. A). The silver image obtained was brown.

B e i s ρ i e 1 2

Here hardened filter paper was used as the layer support used without watermark. To form the dye-containing film-forming solution 1.8 g of 2,5-dichlorophenylleukauramine and mg of rhodamine B base were added by heating in 19 ecm Toluene dissolved. After cooling to room temperature, this solution became 4 g of carbon tetrabromide

ίο and 1 ecm of the cellulose acetate butyrate solution Example 1 added. The aforementioned filter paper was immersed in this dye solution and then dried.

In contrast to Example 1, a solvent was used in the form of a during exposure and development System, consisting of 50 percent by volume of toluene in petroleum ether, used which the ethyl alcohol as Replaced washing solvent after the first exposure, also one made from 50 percent by volume ethyl alcohol in Acetone existing solvent washing system instead of ethyl alcohol as washing solvent treatment with silver nitrate solution.

Claims (2)

Patent claims: 1. A method for producing a photographic silver image, in which a photosensitive layer which is a photolytically active haloalkane of the formula R - CX ₃ wherein R is hydrogen, a halogen atom or an optionally halogen-substituted alkyl radical and X is a halogen atom, and a Triphenylmethyl lactone, Michler's Hydrol, Rhodamine-B-lactam, 2,5-dichloro-N-phenylleukauramine, Diphenylamio, Benzidine, 1-naphthylamine, Tribenzylamine, p-toluidine, Indole, 4,4'-bis (dimethylaminophenyl) methane, Hexylamine and / or Piperidine contains dispersed in a binder, initially forming a colored or colorless, is exposed and developed latent primary image, characterized in that the image-bearing layer for converting the primary image into a silver image only afterwards developed with an aqueous solution of a silver salt and then with a silver halide developer will. 2. The method according to claim 1, characterized in that that cellulose acetate butyrate is used as a binder.