DE1258265B - Photosensitive photographic layer - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Int. Cl .:

G03c

German class: 57 b-10

Number: 1 258 265

File number: E 20480IX a / 57 b

Filing date: January 21, 1961

Open date: January 4, 1968

The invention relates to a photosensitive photographic layer, which is preferably on a support is arranged and contains an azide.

It is known that certain organic azides are photosensitive and used for the production of printing forms are suitable. For the production of such printing forms, photosensitive layers are made from Azides and binders, such as albumin, starch and the like, applied to the support. When exposing a With such a recording material, the exposed parts of the image become hard and insoluble. By detaching of the unhardened image parts can in this way be used as printing forms relief images manufacture of which can be printed with bold color. According to the British patent specification 765 909, certain light-sensitive azidobenzimidazoles can also be used for the production of binder-free Use printing forms.

The object of the invention is to provide a photosensitive photographic layer which is suitable for Production of high-contrast copy images is suitable.

The subject matter of the invention is based on a photosensitive photographic layer an azide and is characterized in that the azide has one of the formulas

Photosensitive photographic layer

Applicant:

Eastman Kodak Company,

Rochester, N. Y. (V. St. A.)

Representative:

Dr.-Ing. W. Wolff and H. Bartels,

Patent Attorneys, 8000 Munich 22, Thierschstr. 8th

Named as inventor:
John Joseph Sagura,
James Albert VanAllan,
Rochester, NY (V. St. A.)

Claimed priority:

V. St. v. America 5 February 1960 (6888) -

mean, and that the layer contains a coupling component which has the formula

Ar - N,

I!

Ar - C -

Il

Ar - CH - CHC - N,

corresponds, in which Ar is an aryl group, Y is a nitrogen, oxygen or sulfur atom, Q is a 3 or 4-membered, hydrocarbon and / or nitrogen and / or oxygen and / or sulfur-containing group, the is optionally linked to one or more carbocyclic or heterocyclic rings,

in which the aryl rings are optionally substituted or fused with other aryl rings and wherein X is an oxygen, sulfur or selenium atom or a methylene or imino group.

In the formulas given for suitable azides, the group denoted by Q can be unsubstituted or form substituted rings. Substituted azides can e.g. B. alkyl, alkoxy, nitro or halogen groups exhibit. Generally the lower alkyl and alkoxy groups are of up to 4 carbon atoms advantageous.

The aryl nucleus denoted by Ar can also have one or more heterocyclic or carbocyclic rings. Rings with up to 8 atoms, preferably rings with 6 atoms, are suitable. Heterocyclic azides are particularly advantageous. The azides of the four general formulas can also use the Ar and Q marks

709 717/568

Rings carry azide substituents, although such polyazides are generally no more effective than that Are monoacides.

Particularly suitable heterocyclic azides are, for example:

2-azidobenzoxazole

Ν — Ν
5-azidotetrazole [a] phthalazine

; Νν

4-Azido-6-methyl-1,3,3a, 7-tetrazaindene

2,4-diazido-6-methylpyrimidine

and 2-azido -1 - carbobutoxymethylcarbamylbenzimidazole and 2 -azido -1 - phenylcarbamylbenzimidazole.

Particularly advantageous coupling components are those with one or more alkyl, alkoxy, Nitro or halogen groups in the aryl rings, preferably with alkyl and alkoxy groups with 1 to 4 carbon atoms. Also suitable are those coupling components whose rings with carbocyclic or heterocyclic rings, as in the case of the azides described, are substituted.

It has been found that substituents on the aryl rings reduce the coupling rate between the Strongly affect coupling components and the light decomposition products of the azides.

This can be related to the increase in electron density in the coupling position or because of it be conditional on the coupling components having a sensitizing effect on the azide. Indeed are the coupling components that react fastest with the light decomposition products of the azides usually those that act as sensitizers in other azide systems that do not require coupling takes place, are effective.

The dyes that form on exposure of the layers appear to be a group of the following structure to contain:

Here, X has the same meaning as in the formula given for the coupling component. the Dyes produced by exposure are therefore obviously related to the merocyanines. the The absorption spectra of these dyes often depend on the type of solvent used, which is also the case with the merocyanines. The influence of the absorption by the solvent can be useful when coloring agents with an absorption in a certain range should be generated. The introduction of substituents on the azide or the coupling component also often leads to shifts in the color spectra, so that by a suitable combination the azide and the coupling component give dyes which produce yellow to blue images.

Those listed in the second and third of the above

Azides represented by formulas, namely the aroyl azides and their vinyl homologues, are generally fewer active than the other azides when not in the presence of an inorganic ammonium salt or one Salt, an organic derivative of ammonia, can be used.

The photosensitive layer therefore preferably additionally contains an inorganic ammonium salt or a salt of an organic derivative of ammonia.

The salts of the strong mineral acids, in particular the hydrochlorides and sulfates, are particularly suitable and nitrates, such as ammonium chloride, the hydrochloride of 4-aminodiphenylamine, 3,3-dimethoxybenzidine, 2-aminobenzothiazole, Ι, Γ-diphenylhydrazine, poly (aminostyrene), diethylamine, Guanidine, 2-aminobiphenyl, p-toluene or phenothiazine.

The light-sensitive photographic layers can be in the form of binder layers on conventional be applied photographic supports, the azides and coupling components in the Binder layer are dissolved or dispersed. The one containing the azides and the coupling components However, the layer can also be self-supporting. The photosensitive layer preferably contains additionally one or more binders and is present without a substrate.

Although it has been found that many organic azides contain a large number of nitrogenous React heterocyclic compounds, it has been shown that only some of the azides for the production of the layers according to the invention are suitable, since many azides are too slow for photographic purposes react or do not form sufficiently strongly colored compounds, so that the desired high Contrast is not maintained in the copy image.

A self-supporting photosensitive layer preferably contains 2-azidobenzoxazole, 2-azido-

1 - carbobutoxymethylcarbamyl - benzimidazole or

2 - azido -1 - phenyl - carbamylbenzimidazole and as Coupling component benzophenthiazine or benzophenoxazine.

It has been shown that the color of the image depends on the pH of the photosensitive layer, if the layer is an aroyl azide or a vinyl homologue of such an azide, a heterocyclic coupling component and contains an organic derivative salt of ammonia. The color base of this system is red while its salts are blue. Therefore the color of the picture is determined by the ratio of color base to color salt and can range from blue to violet to red-violet, as can also be seen from Table I.

Used for recording material containing a salt of an organic derivative of ammonia for amplification used for dye formation and if the photosensitive layer is water-permeable, so can the copied images obtained by washing with warm water for a few minutes or a dilute acid. The unreacted salts are removed during washing. The images stabilized in this way can be preserved for a long time without being changed.

It has been found that in certain cases the layers are also sensitive to heat. This property can be used in an advantageous manner. For example, some azides can be deactivated by the action of heat or removed from the layer by thermal diffusion by heating the layer to temperatures of 75 to 150 ^° C. for 10 to 30 seconds. This enables these images to be stabilized well. 2-Azido-benzoxazole and 2,4-diazido-6-methylpyrimidine, by thermal diffusion from the layer are removed or deactivated by heating for 20 seconds at 95 to 13O ⁰ C.

In other cases, the copy-out image obtained by exposure can be intensified by heating. This is the case, for example, when a layer is used which contains 1-phenylcarbamido-2-azidobenzimidazole and benz (a) contains phenothiazine.

The quantitative ratio of azide to the coupling component is not critical, although approximately stoichiometric ratios of azide to coupling component the best results can be obtained.

The coupling components required to produce a layer according to the invention can be produced by known methods. Process for the preparation of the azides are for example in Chem. Revs., 54, No. 1, February 1954, and J. Am. Chem. Soc, 76, 1859 (1954).

The photosensitive layers according to the invention can be coated by the usual coating method can be produced on all types of substrates. In general, the azides and the coupling components with a natural or synthetic binder in a suitable solvent dissolved or dispersed and applied to a layer support. The binder can be from anyone natural or high molecular weight synthetic polymers or mixtures of these polymers, as they are usually used for the production of photographic layers, such as gelatin, Casein, polystyrene, vinyl resins, polyvinyl alcohol, polyvinyl butal and cellulose derivatives. Of the The support for the light-sensitive layer can be a plate, film or strip of paper, cellulose derivatives, Glass, synthetic high molecular weight polymers and the like. As a solvent are all known solvents normally used for coating purposes. A special one an advantageous solvent is 2-butanone.

Self-supporting, photosensitive layers can be produced by adding the azide the coupling component and a binder, for example cellulose triacetate, in a suitable one organic solvents, e.g. B. a mixture of methylene chloride and methanol, are dissolved and that the solution obtained is applied to a glass plate. When the layer has dried sufficiently it is peeled off the glass plate and forms a self-supporting film.

The usual light sources, e.g. B. arc lamps, mercury lamps, nitrophot and sun lamps can be used.

The photosensitive layers according to the invention have the effect that they are more imagewise Exposure a colored copy-out image of high contrast and uncolored which is negative in relation to the original Deliver underground.

example 1

A coating solution consisting of 50 g of a 10 weight percent solution of a copolymer of vinyl chloride and vinyl acetate with 85 to 88 percent by weight vinyl chloride and a molecular weight of 6000 in 2-butanone, 1.0 g of 2-azido-1-phenylcarbamylbenzimidazole and 0.3 g of benzo [b | - phenoxazine was applied to a support and dried. The obtained photographic light-sensitive material was then exposed by means of a mercury vapor lamp through a negative halftone master copy, an almost neutral positive print-out image was obtained.

Example 2

20 g of 2-azido-1-carbobutoxymethyl-carbamylbenzimidazole and 1.0 g of benzene phenoxyzine were dissolved in 600 g of a 10 weight percent solution of cellulose acetate propionate dissolved in 2-butanone. This solution was applied to a paper support and exposed according to Example 1 to produce a blue-black image.

B e i s ρ i e 1 3

A coating solution was obtained by dissolving 0.3 g of 2-azido-1-carbobutoxymethyl-carbamylbenzimidazole and 0.1 g of acridan in 25 g of a 10 percent strength by weight solution of that described in Example 1 Copolymer produced in 2-butanone.

Became the recording material obtained by applying the coating solution on a support exposed to UV light, a purple image was obtained.

Example 4

By dissolving 0.3 g of 2-methoxy-6-chloro-9-azidoacridine and 0.2 g of phenothiazine in 25 g of a 10 weight percent Solution of the described in Example 1

A coating solution was prepared with the same copolymer in 2-butanone. Became this mix When applied to a photographic support and exposed to UV light, a red-brown image preserved.

Example 5

14 g of 2-azidobenzoxazole, 1.8 g of benzoylphenothiazine and 0.5 g of 4-quinolizone were in a solution consisting of 105 g of 2-butanone and 150 g of vinyl polymer solved. 40% of the vinyl polymer consisted of the polymer described in Example 1 and 60% from a copolymer of vinyl chloride and vinyl acetate with a vinyl chloride content from 85 to 88 percent by weight and a molecular weight of 10,000. The resulting mixture was applied to a layer support made of cellulose acetate and dried.

The recording material obtained contained 0.0032 g of solids per square centimeter. When the recording material was exposed to UV light through a transparent negative copy original, a positive image was obtained. The image was stabilized by brief heating to a temperature of 95 to 100 ^{° C.}

Example 6

A coating solution consisting of 0.4 g of 2-azidobenzoxazole, 0.25 g of phenothiazine and 25 g of a benzene solution containing 1 percent by weight of rubber and 5 percent by weight of polystyrene was applied to a paper support and allowed to dry. The recording material obtained was then exposed through a transparent negative copy master for 30 seconds with a sun lamp set up at a distance of 25.4 cm. The result was a positive black and white image. The image was stabilized by heating to a temperature of 100 to 130 ^{° C. for 20 seconds.}

Example 7

A coating solution consisting of 0.3 g of 1 - carboethoxymethyl - 3 - (2 - azidobenzimidazole -1) urea, 0.1 g of phenothiazine and 25 g of a benzene solution containing 1 percent by weight of rubber and containing 5 percent by weight of polystyrene was applied to a paper support and left to dry. The recording material obtained was through a transparent negative Copy original exposed for 30 seconds with a sun lamp set up at a distance of 25.4 cm. It a positive blue-white image was obtained.

55 Example 8

40 ml of a 10 percent strength by weight solution of the copolymer described in Example 1 in 2-butanone were admixed with 0.176 g of 2,4-diazido-6-methylpyrimidine and 0.4 g of phenothiazine. The mixture was shaken until a solution was obtained. The solution was then applied to a paper support and allowed to dry. The layer side of the recording material was then exposed through a transparent negative copy master for 30 seconds with a sun lamp set up at a distance of 25.4 cm. A positive sepia and white image was obtained. The image was stabilized by heating at 100 to 130 ^{° C. for 20 seconds.}

Example 9

50 ml of a 10 percent strength by weight solution of the copolymer described in Example 1 in 2-butanone were -with 0.1 g of 2,4,6-triazido-sym-triazine, 0.3 g of phenothiazine and 5 drops of dimethyl sulfoxide offset. The resulting mixture was shaken until a solution had formed. the Solution was then applied to a paper support and allowed to dry. The received Recording material was then passed through a transparent negative for 30 seconds Copy master exposed with a sun lamp set up at a distance of 25.4 cm. It turned out to be a positive one Preserved sepia and white image.

Example 10

By dissolving 0.1 g of 5-azidotetrazol [a | phthalazine and 0.2 g of phenothiazine in 100 ml of a 10 weight percent Solution of the copolymer described in Example 1 in 2-butanone was a Coating solution prepared. This solution was applied to a paper support and spun dry. The light-sensitive material obtained was then passed through a transparent one negative master copy for 1 minute with one set up 10 inches away Sun lamp exposed. A positive violet-white image was obtained.

Example 11

A 10 weight percent solution of the copolymer described in Example 1 in 2-butanone, the 0.1 g phenothiazine and 0.13 g 4,4'-diazidodiphenyl sulfide was applied to a paper support using a spinner and left to dry. The recording material obtained was copied from a negative master Exposed for 1 minute with a sun lamp placed at a distance of 25.4 cm. It turned out to be a positive one Preserved purple and white image.

Example 12

A 5 weight percent solution of polyvinyl butal in methanol was made with 2-aminobiphenyl hydrochloride saturated. Equivalent proportions of phenothiazine and benzoylazide were then added. the The resulting solution was then applied to a paper support by means of a spinner. That dry recording material was then through a negative master copy for 1 minute with in one Exposed from a distance of 25.4 cm. It became a positive red-purple image obtain. The image was stabilized by washing with warm water for 5 minutes.

Example 13

A 5 weight percent solution of polyvinyl butal in methanol was saturated with aniline hydrochloride. Equivalent proportions of 2,4,6-triazido-sym-triazine and phenothiazine were then added to the solution. The solution obtained was then applied to a substrate using a centrifuge Paper applied. The dry recording material was replaced by a negative master copy

For 1 minute with one at a distance of 10 inches exposed sun lamp. A good quality blue image was obtained.

The procedure was carried out using some other ammonia derivatives in place of the aniline hydrochloride repeated. In the following table I are the ammonia derivatives used and the colors of the obtained images compiled.

Table I.

IO

Ammonia derivatives Color of
Image 4-aminodiphenylamine hydrochloride ... Brown 3,3'-dimethoxybenzidine hydrochloride Blue black 2-aminobenzothiazole hydrochloride ... blue Ι, Γ-diphenylhydrazine hydrochloride ... violet Polyamino-styrene hydrochloride Blue-gray Diethylamine hydrochloride Blue-gray Guanidine hydrochloride Blue green Hydroxylamine hydrochloride Brown 2-aminobiphenyl hydrochloride Red-violet p-toluidine hydrochloride blue Ammonium hydrochloride blue Phenothiazine hydrochloride blue

Be i s ρ i e 1 14

30th

A coating solution was prepared by dissolving 5 g of 1-phenylcarbamido-2-azidobenzimidazole, 1 g of benzene phenothiazine and 20 g of cellulose triacetate in 162 g of methylene chloride and 18 g of methanol. The resulting solution was applied to a glass plate. The layer thickness was 0.889 mm. The layer was dried at room temperature for 6 hours. The layer was then peeled off the glass plate and exposed for 2 minutes to a sun lamp through a step wedge. The resulting image was enhanced by heating at 65 ° C for several minutes. In the image, a maximum density of 3.3 (D _max ) and a minimum density of 0.22 (D _min ) were obtained.

Claims (4)

Patent claims: 1. Photosensitive photographic layer with an azide, thereby marked 10 net that the azide is one of the following formulas Ar-N ₃
O Ar-C-N, Ar - CH - CHC - N, corresponds to where Ar is an aryl group, Y is a nitrogen, oxygen or sulfur atom, Q is a 3- or 4-membered, hydrocarbon- and / or nitrogen- and / or oxygen- and / or sulfur-containing Group optionally bearing one or more carbocyclic or heterocyclic rings is connected, mean, and that the layer contains a coupling component which has the formula in which the aryl rings are optionally substituted or condensed with other aryl rings and in which X is an oxygen, sulfur or selenium atom or a methylene or imino group means. 2. Photosensitive photographic layer according to claim 1, characterized in that they additionally contain an inorganic ammonium salt or a salt of an organic derivative of Contains ammonia. 3. Photosensitive photographic layer according to claim 1, characterized in that it additionally contains one or more binders and is present without a substrate. 4. Photosensitive photographic layer according to claim 3, characterized in that they as azide 2-azidobenzoxazole, 2-azido-1-carbobutoxymethylcarbamyl-benzimidazole or 2-azido-1-phenylcarbamyl-benzimidazole and contains benzophenthiazine or benzophenoxazine as a coupling component. 709 717/568 12.67 © Bundesdruckerei Berlin