DE1720778B - Process for the production of polymer images - Google Patents

Description

The invention relates to a method for producing η polymer images, in which one in one image-wise exposed silver halide emulsion layer latent image due to the action of a monomeric vinyl compound and an aromatic dihydroxy or hydroxyamino compound is developed as a reducing agent.

There are various methods of producing images with the help of the formation of highly polymerized Compounds known by means of photopolymerization of vinyl compounds. So is known, the photopolymerization to be carried out directly using silver halides as a catalyst (cf. British U.S. Patent 866,631; S. Le vinos et al, Photographic Science and Engineering, Vol. 6, pp. 222-226 [1962]). It is believed that the photo-generated decomposition product of Silver halide serves as a polymerization catalyst, being sensitive to light from this Reaction does not reach the extent easily achieved by an ordinary evolving process will. It is also known to form polymerizates by polymerizing vinyl compounds under Use of a silver image or unreacted halogen silver as a catalyst after development an exposed halide silver emulsion layer with a customary developer solution to produce (see Belgian patent specification 642477). However, this procedure has the disadvantage that development and polymerization must be carried out separately.

It is of particular interest to investigate the polymerization of vinyl compounds by the oxidation product, that in the course of developing a photographic silver halide emulsion by means of a reducing agent was formed, or an intermediate product of the same, to effect, as expected in this The way of working the polymerization through the reinforcing effect of both the development and caused by the chain polymerization. Such an implementation is already known using an aromatic developing agent with at least 2 hydroxyl, amino or amino groups substituted by alkyl or aryl groups in the o or p positions on the benzene ring, to be carried out as a reducing agent (see US Pat. No. 3,019,104, German Auslegeschrift 1,119,120, G. O s t e r. Nature, Vol. 180, p. 1275 [1957]). It was however, found that in the reactions with such aromatic developing agents an increase in the optical density of the silver image takes place, while such features indicating the formation of highly polymerized compounds, namely increase in viscosity, generation of heat of reaction or deposition of a polymer, z. B. in the form of a relief image, were not observed (see also S. L e ν i η 0 s and F. W. H. M u 11 e r. Photographic Science and Engineering. Vol. 6, p. 222 [1962]).

The object of the invention is to provide a method for producing polymer images in which by converting a latent image in a photographic silver halide emulsion layer to an image of a highly polymerized substance using a simple procedure. Polymer images with such solubility. Dye receptivity and other physical and chemical Properties can be obtained as they are for various printing or copying processes are necessary.

The object of the invention is based on a process rare production of polymer images, in which a latent image contained in an imagewise exposed silver halide emulsion layer by the action of a monomeric vinyl compound and an aromatic dihydroxy or hydroxyamino compound is developed as a reducing agent and is characterized in that as Reducing agent a dihydroxynaphthalene or a hydroxyaminonaphthalene, the functional groups of which are in the 1,6-positions, the 1,8-positions, the 2.5 or 2.7 positions, or derivatives thereof are used.

In practicing the method according to the invention, an ordinary silver halide emulsion can be used used by the development centers in the by electromagnetic waves or Corpuscular rays irradiated areas forms and, after normal development, delivers negative images. On the other hand, so-called direct positive emulsions can also be used come to the application, the development centers in halogen silver particles in the Have areas that have not been subjected to imagewise exposure.

Suitable photographic silver halide emulsions for negative images are silver chloride, silver bromide, Cbiorbromosilver, iodobromosilver and chloroiodobromosilver emulsions, which, if desired, have been sensitized chemically and / or optically in the usual way are.

For a chemical sensitization, a sulfur sensitization or a noble metal sensitization can be used can be used (cf. for example P. G1 a fkides, Chimie Photographique, 2nd edition, Photocinema Paul Montel, Paris, 1957, pp. 247 to 301). for optical sensitization may include optical sensitizers for photographic emulsions, e.g. B. Cyanine dyes and merocyanine dyes, are expediently used (cf., for example, K i k u c h i et al, Kagaku Shashin Benran (Handbook of Scientific Photography), Vol. 2. pp. 15-24, Maruzen Co., Tokyo. 1959). In addition, the emulsion to be used according to the invention can be a common stabilizer contain.

The direct positive halogen silver emulsion applicable according to the invention can be produced using solarization, Herschel effect, Clayden effect or Sabatier effect, whereby these effects in chapters 6 and 7 of C. E. K. M e s in "The Theory of the Photographic Process ", 2nd Edition, edited by McMillan & Co., 1954, are fully explained. Procedure for Manufacture of direct positive silver halide photographic emulsions using solarization are z. B. in British Patents 443 245 and 462 730 described. A manufacturing process for direct positive emulsions using the Herschel effect. being a halogen silver emulsion is used, which preferably contains predominantly silver chloride and a Desensitizers may contain is, for example, in British Patent 667,206 and in US Pat U.S. Patent 2,857,273.

To obtain a positive image using the Clayden effect, it is necessary to an emulsion of an overall exposure to light of a relatively low intensity after one Subjecting image exposure to light of high intensity for a short period of time. Be there the areas of the emulsion not exposed to high intensity light irradiation were developable after the overall exposure.

To achieve the Sabatier effect, a photographic silver halide emulsion layer that had been imagewise exposed during the Subjected to uniform exposure to light by immersion in a developing solution. Through this

ίο a development capability is achieved in the area which had not been subjected to the image exposure.

The Clayden effect and the Sabatier effect become effortless and effective in halogen silver emulsions obtained that tend to form development centers by the first exposure in the inner part than tend to be on the surface part of halogen silver grains. The production of such emulsions is, for example, in U.S. Patents 2,592,250 and

ίο 2,497,876, British Patent i 011 062 and the German patent 1 207 791 described.

The photographic emulsions listed above consist of dispersion systems, in what parts of halogen silver are dispersed in a solution of a polymeric binder. Examples such polymeric binders are gelatin, polyvinyl alcohol, polyvinyl pyrolidone, polyacrylamide as well as carboxymethyl cellulose, oxyethyl cellulose or dextran. Derivatives of naturally occurring high polymers Materials can also be used, alone or in admixture with gelatin (see for example F. Ewa: Journal for Scientific Photographic, Photophysik und Photochemie, Vol. 52, pp. 1 to 24 [1957]).

The reducing agents to be used according to the invention include e.g. B. the following dihydroxynaphthalenes or hydroxyaminonaphthalenes:

OH

HO
1,6-dihydroxynaphthalene

HO OH

1,8-dihydroxynaphthalene
HO OH

2.7-dihydroxynapnthalin

SO ₃ H

SO ₃ H
1.8-dilute-naphthalene-2,4-disulfonic acid

SO ₃ H SO ₃ H

1,8-dihydroxynaphthalene-3,5-disulfonic acid HO OH

/ HO ₃ S SO ₃ H

1,8-dihydroxynaphthalene-3,6-disulfonic acid

20th

XA /

HO ₃ S SO ₃ H

2,7-dihydroxynaphthalene-3,6-disulfonic acid 25

30th

35

HO

l-amino-6-naphthol

NHCH ₂ CH ₂ CH ₂ SO ₃ H

40

HO

3- (6-Hydroxy-1-naphthylamino) propane-1-sulfonic acid

HO NH ₂

45

HO

NH,

l-Amino-8-naphthol HO NHCOCH ₃

N-acetyl-1-amino-8-naphthol
NH ₂

55

60

OH 2-amino-5-naphthol

SO ₃ H

SO ₃ H 1 -amino-8-naphthol-2,4-disulfonic acid

2,7-dihydroxynaphthalene monomethyl ether,

l-amino-8-naphthol-3,5-disulfonic acid,

l-amino-8-daphthol-3,6-disulfonic acid,

1-amino-e-naphthol- ^ n-disulfonic acid,

l-amino-S-naphthol-SJ-disulfonic acid,

l-amino-e-naphthol- ^ sulfonic acid,

e-amino-l-naphthol- ^ sulfonic acid,

l-amino-S-naphthol-V-sulfonic acid.

The vinyl compounds to be used according to the invention normally include liquid and solid compounds capable of addition polymerization, as well as mixtures thereof. Examples are acrylamide, acrylonitrile, N-hydroxymethylacrylamide, methacrylic acid, acrylic acid, calcium acrylate, sodium acrylate, methacrylamide, methyl methacrylate, methyl acrylate, ethyl acrylate, vinyl pyrrolidone, vinyl methyl ether, vinyl butyl ether, vinyl isobutyl ether, vinyl butyrate, 2-vinylpyridine, 2-vinylpyridine, -vinylimidazole, potassium vinylbenzenesulfonate or vinylcarbazole. According to the invention, compounds having two or more vinyl groups are particularly suitable, and the compounds can be used alone or in admixture with any of the above-mentioned monovinyl compounds. Examples of such compounds with two or more vinyl groups are N, N-methylenebis (acrylamide), ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, divinyl ether or divinylbenzene.

Although it is convenient and convenient to use water-soluble vinyl compounds in the method according to the invention, water-insoluble ones can be used Vinyl compounds in the form of emulsions are used. The emulsification can take place in can usually be carried out using suitable stirring equipment in the presence of a surfactant and / or a polymeric binder.

In recording or copying images, it is necessary that the halogen silver grains change their position little during the period between irradiation and polymerization in the reaction system, and therefore the system is preferably kept in a highly viscous liquid state or in a gel state. The silver halide photographic emulsion coated on a suitable support can be subjected to irradiation either in the undried or in the dried state. In the presence of the vinyl compound or vo · - · vinyl compounds, reduction and polymerization take place simultaneously. When "according to the procedure

of the invention, both the vinyl compound and the naphthol compound of the photographic Emulsion can be incorporated prior to exposure. However, it can only be one of these connections can be incorporated into the emulsion before exposure and the other can be incorporated into the system after exposure be added, it is also possible to add both compounds only after exposure.

The reduction and polymerization are supposed to be carried out in the presence of water, and it is therefore necessary to carry out the reduction and polymerization in an aqueous solution or in a moist gel.

Usually the reaction is carried out in the presence of a suitable amount of alkali, since it is under alkaline conditions progresses more smoothly. The suitable amount of alkali usually depends on the Type of silver halide, reducing agent and polymeric binder and their concentrations as well as the reaction temperature. Preferably the alkali is used in sufficient amount used to bring the pH of the system to 7.5 or above. When the silver halide photographic emulsion layer was applied to a layer support, this photographic recording material can after exposure to an alkaline aqueous solution to be immersed for carrying out the reaction. In this case, the Vinyl compounds and / or the reducing agents are expediently dissolved in the aqueous alkaline solution will.

The reaction can be interrupted easily by adjusting the pH of the system to about S or below; the interruption can also be carried out by cooling, removing the reactants Washing, dissolving the silver halide by fixing or adding a polyene; isation inhibitor to the system.

When the halogen silver grains and the monomeric vinyl compound in a polymeric binder are distributed and applied as a layer on a substrate, is preferably a low Amount of an inhibitor for a thermal polymerization added to an unwanted thermal Prevent polymerisation of the vinyl monomer. Examples of such polymerization inhibitors are p-methoxyphenol, hydroquinone, 2,6-di-tert-butyl p-cresol or / S-naphthol.

When the vinyl monomer is initially included in the system, it is incorporated in an amount by weight from V30 to 30 times the amount of the polymeric binder, and preferably Y4 to ₄ times that amount originally present in the system is expediently used in an ^{amount by weight of 1} Z _{20 to 2} times and preferably ¹ Z ₁₀ to Y 2 times the amount of the polymeric binder originally present in the system expediently added in an amount of ¹ J ₁₀ to 20 moles per mole of halosilver. The thermal polymerization inhibitor is suitably added in an amount of 10 to 20,000 parts per million by weight of the vinyl compound. If the vinyl monomers are to be dissolved in the treatment solution, they are preferably dissolved in as high a concentration as possible, since the preferred concentration of the monomer is mainly determined by the solubility of the monomer in the solution. If the naphtholic reducing agents are dissolved in the treatment solution, they are expediently dissolved in a concentration between V20 and 5 mol per liter and preferably between 1/10 and 1 mol per liter.

If the effect of exposure to some extent over the course of time between the exposure and the execution of the polymerization is weakened, this weakening can be caused by Increase in the exposure level can be counteracted.

The invention achieves that exposed silver halide emulsion layers in one development step can be developed into polymer images which are useful for printing purposes.

in contrast to the Gerbuügsentwicklungsverfahren, in which gelatin molecules are cross-linked with the oxidation products of a developing agent, it is possible according to the invention to obtain a large number of images which, with regard to the dye receptivity, chemical resistance and other properties depending on the type of vinyl compound used are different.

When applying the method according to the invention for recorded images can of the Differences in solubility, light scattering, stickiness, dye receptivity and other physical and chemical properties between the monomeric vinyl compounds and their polymers Be made use of. A relief image made of polymers! Material can be formed by one dissolves away non-polymerized parts of the image after irradiation and polymerization, using the difference in solubility between the polymerized image parts and the unpolymerized Image sharing leaving the highly polymerized compound thus formed as an image alone is made in the irradiated areas

In this case it is appropriate that the originally polymeric binders present in the system washed away with the unpolymerized vinyl compound can be. Accordingly, it is the polymeric binder originally present in the system preferably a linear, essentially non-crosslinked polymer or such a crosslinked polymer Polymer that it is sensitive to chain breakage or breaking of crosslinking bonds On the other hand, there is the photopolymerized compound that builds up the BQd, which is created by the poly merization of the vinyl compound is formed before preferably from a crosslinked polymer with a so-called three-dimensional structure. From these The reason is a monomeric vinyl compound formation with a plurality of vinyl groups as indicated above, either alone or in conjunction used with a compound with only one vinyl group, however, it is not necessarily » required to connect with a plurality of voi Use vinyl groups as there are many systems with simple vinyl compounds that are sufficient large differences in solubility between the popular polymerized and unexposed buds share deliver. This also applies if the bud

6s supplying polymerized substance from a linear] soluble material is due to the interaction between the by the Polymerisa tion formed polymerized substance and the ή

9 ίο

polymer originally present in the system as in the customary development process

Binder, for example as in the case of poly- only removed.

acrylic acid as a polymerized compound and gela- Although the mechanism of action of

tine as a polymeric binder. Sulphite ions in the process according to the invention

The image produced by this procedure, which cannot be seen, may be that the sulfite ions

Consists of polymerizing substances, the polymerization-inhibiting effect of free

prevent different printing or copying processes for the application of oxygen,

get dung. The invention is illustrated below with reference to

Although the mechanism of initiating the poly examples is explained in more detail,

merization of vinyl compounds with the reduction to

of halogen silver with the mentioned naphthol B e i s d i e 1 1

derivatives is not yet clarified, it is assumed ^p

that the polymerization according to a radical poly- A photographic recording material with The merization mechanism advances as the mixture becomes a layer of a gelatin-chloroiodobromide silver on any vinyl compound that became a radi- 15 emulsion after imagewise exposure kaiischen polymerization are capable of being applicable with a solution containing 2,7-dihydroxynaphthalene as and the reaction by radical polymerization inhibitor reducing agent and sodium methacrylate as monobitoral is delayed. It is not yet clear whether mere Viiiyfvei contained binding, treated to the to effect the polymerization initiating the radical directly forming the image. That included photographic material used by the reaction between naphthol derivatives and silver halide is formed or whether it had been produced by placing one on both sides a further reaction with other components of the polyethylene terephthalate support an adhesive the system, e.g. B. water or oxygen, formed layer applied to one of the surfaces of the sun will. a substrate provided with adhesive layers

According to one embodiment of the invention, the antihalation layer is applied to the other surface

Development in the presence of sulfite ions recorded by a photographic silver halide emulsion

was brought out, whereby the photographic halogen

It was found that the polymerization of the silver emulsion per 1 mol of silver, about 0.7 mol of chlorine,

Vinyl compound in the process according to the invention - about 0.3 mol of bromine, about 0.001 mol of iodine and about

by the presence of sulfite ions in the 30 100 g of gelatin together with a suitable amount

System is accelerated. of a merocyanine dye with a sensitizing

Sulphite ions can give the reaction system either a maximum of about 550 ηΐμ 1.5 g mucochlorin form of a compound which originally contained the sulphic acid as hardening agent and suitable stabilization ion in the molecule, for example alkali and wetting agents. It was a recording sulfite or ammonium sulfite or in the form of a 35 material containing 50 mg of silver per 100 cm ^{2 of} compound that obtained sulfi as a result of hydrolysis. On this emulsion layer an ion was supplied, for example pyrosulphites of alkali metals, gelatin protective layer with a thickness of about 0.8 μ and ammonium ions or the plant connections were applied. The material is used to fertilize bisulfites with aldehydes, e.g. B. Formal- of line or halftone formers for graphic dehydration or glyoxal are added. Although the technique is suitable, this material was a suitable amount of sulfite ions with light to be added from 100 lux for 10 seconds through a line image master bearing negative image from the type and amount of reducing agent and the pH of the vinyl monomer used Value and then depends on the system and other factors under a red darkroom, more lamps are immersed in a developer solution of the following ingredients 0.05 MoL, in particular more than 0.2 Moi per liter 45 saminenseizuag:
of the system effective. Sodium methacrylate 50 g

E ^ is well known in the art, ui photo- 2J-Dmydroxyna _P hthalin 4.8 g

graphic developing solutions a sulphite aqueous 2N sodium hydroxide. 17 to ³

bring, and in these cases it is assumed that _w ° _R __ _t _ " _f ^JJ innn ~~ 3

the sulphite the autoxidation of a developing agent 50 ^water ' ^{kest at} 1000 cm

and uneven development by post immersion for 30 minutes at 35 ° C

Reaction with the oxidation products of the decolorized the exposed areas, wodurci

Winding agent, for example hydroquinone, or it has been indicated that the halosilver grains in dec

p-AminophenoL prevented (cf. for example exposed areas were reduced. The material

C.E. K. Mees, "Theory of the Photographic Process" 55 was then dissolved in 1.5% aqueous acetic acid

2nd Edition, p. 652, edited by McMillan & Co. soaked, washed with running water and mi;

[1954]). ^emer 1% aqueous solution of a Gelatmezer

It should be noted that, since the intermediate enzyme is treated, in the disregard

Product of the oxidation of naphthol derivatives by the affected areas of gelatine decomposed and washed away

Silver halide the polymerization of a vinyl Ver- 60 was, while in the exposed areas d «

bond or vinyl compounds in which the emulsion layer was not washed away and en

drive according to the invention initiates the polymer-positive ReBef image corresponding to the exposure

sation-promoting effect of sulfite ions essentially used copy master remained. The under

is different from the effect of removal differed in the resistance to cerium

of oxidation products as in the above 65 placement between the exposed and the unexposed

common developing solutions mentioned. The dead area was not detected when you

Polymerization would rather be inhibited than required. Treatment solution no sodium methacrylate ent

when the sulfite ion stopped the oxidation products

! 720 778

11 12

Sodium methacrylate 50 g
Example 2 Naphthol derivative ... as given below

Sulfite as indicated below

Samples of the same recording material, such as NaOH, amount to sufficient

used in Example 1, the pH was adjusted to the following

exposed in Example 1, the working method indicated and the value indicated standing

adjust with solutions of the following composition

treated: "Water rest on 1000 cm ³

No. Naphthol derivative 13.0 g sulfite Potassium pyrosulfite 2g PH value 1 1,8-dihydroxynapthalene 3,6-disulfonic acid 10.0 g Sodium sulfite 8g 9 2 1 -amino-8-naphthol- 3,6-disulfonic acid 10.0 g Kaiiumpyrosuint 2g 11.5 3 l-amino-8-naphthol- 3,6-disulfonic acid 10.0 g Addition product of 10.5 4th l-amino-8-naphthol- Sodium sulfite with formaldehyde 3,6-disulfonic acid (Monohydrate) 8g 100 g Potassium pyrosulfite 2g 10.5 5 l-amino-8-naphthol- 4.7 g Potassium pyrosulfite 2g 2,4-disulfonic acid 10.0 6th 1-amino-6-naphthol 12.0 g Potassium pyrosulfite 2g 9.0 7th 3- (6-hydroxynaphthylamino) - 4.8 g Potassium pyrosulfite 2g propane-1-sulfonic acid 9.0 8th 1,5-dihydroxynaphthalene 11.5

Each sample was mixed with the solution at 35 ° C for the time period given below and then treated with an enzyme as described in Example 1. The results were similar in each case obtained as in example 1.

Treatment time (min).

Treatment solution

25th

15th

10

10

Example 4

The following recording materials A and B were treated with the processing solution used in Example 2 3 treated.

Recording material A is produced by applying an adhesive layer to both sides of a cellulose triacetate substrate, applying an antihalation layer to one surface of the substrate provided with adhesive layers, and applying a gelatin-halosilver emulsion with an average grain size of about 0.015 mol to the other surface of the substrate Contains iodine and about 0.985 mol of bromine and about 255 g of gelatin per 1 mol of silver, to which about 0.5 g per 100 g of gelatin of mucochloric acid as a hardening agent and a suitable stabilizing agent and surface-active agent have been added. The gelatin-silver halide emulsion was applied in an amount to give a layer containing 60 mg silver per 100 cm ² 2x1. A protective layer of gelatin 1 micron thick was applied over this layer

The recording material B is a material having a steep gradation. This material is prepared by applying a fine-grained gelatin-halosilver emulsion with a content of about 0.012 mol of iodine and about 0.988 mol of bromine and 204 g of gelatine per 1 mol of silver to the same base as for material A. The emulsion is with a Rhodamate complex of monovalent gold sensitized and treated with about 0.7 g of mucochloric acid per 100 g of gelatin as hardening agent, 0.3 g of 6-methyl-4-hydroxy-13.3a, 7-tetrazaindene as stabilizing agent per mole of silver and a suitable surface-active agent The gelatin-halosilver emulsion is applied in an amount which results in a layer with a content of 60 mg silver per 100 cm ^2. A protective layer of gelatin with a thickness of about 0.8 microns is applied over it

After the same exposure as in Example 1, the recording materials A and B were ^{soaked in the treatment solution 3 described in Example 2 at 30 °} C. for 15 and 10 minutes, respectively, in order to obtain an indecomposable image with the gelatin decomposition enzyme, as in Example 1.

Example 4a

A solution in the additions given below

The composition was added to 100 cm ^{3 of} a fine-grain photographic gelatme chlorobromide silver emulsion, the chlorobromide silver corresponding to about 42 g of elemental silver and chlorine and bromine in a molar ratio of 7: 3 and 60g of gelatin per liter of the emulsion and a pH of 5.8 and a pAg of 7.6.

Acrylamide 8 g

NjN'-methylenebisacrylamide 0.8 g

Potassium pyrosulfite 4 g

0.02 moles of p-methoxyphenol 1.0 cm ³

Water 15 cm ³

10% chrome alum 0.3 cm ³ ,

2533

The mixed solution was applied as a layer to an undercoated cellulose triacetate support and dried in a darkroom to obtain a dry thickness of 10 μm. That so Photographic material 5 obtained was exposed to light of 1000 lux for 5 seconds from the surface opposite the emulsion layer through a negative image The supporting line image master is exposed and covered with a solution of the following composition ι ο and left in a dark room.

1 -amino-8-naphthol-

3,6-disulfonic acid 10g

Potassium pyrosulfite 2.5 g

2N NaOH 20 cm ³ " ⁵

NaCl Ig

Water, remainder to 100 cm ³

The exposed areas of the material were found to discolor, which indicated that a faint silver image was produced in the exposed areas.

After standing for one hour the material was washed with hot water, whereupon in the gelatin was washed away from the unexposed areas, and a positive relief image accordingly the negative image used for exposure remained.

When the same procedure as described above has been repeated with the modification, that 8 g of acrylamide was replaced by less than 4 g of acrylamide, it was difficult to identify the exposed areas from the unexposed areas because of the difference in strength between the exposed areas and the unexposed areas after the treatment was small.

Example 5

A photographic gelatin-silver chloride emulsion containing fog centers, which had been chemically prepared as described in British Patent 667,206 in a similar manner, wherein the emulsion pinacryptol yellow as a desensitizing agent, suitable curing agents and surface nak tive agent was contained in an intermediate or Polyethylene terephthalate film bearing auxiliary layers applied a line art master was passed, whereupon it was immersed in a solution of the following composition:

Sodium methacrylate 50 g

l-Ammo-8-naphthol-3,6-disulfonic acid 13 g

Potassium pyrosulfite 1.3 g

NaQ 1.0 g

NaOH sufficient amount

to adjust the pH of the solution to 10.0

Water, remainder to 100 cm ³

After immersion at 30 ⁰ C for 7 minutes, the Aiifzeichmingsmaterial would with a l, 5ge-

weight percent aqueous acetic acid to interrupt the polymerization reaction soaked with Washed with water and decomposed with enzyme, according to the procedure described in Example 1.

This left polymerized areas corresponding to the copied positive image. Another one Example of a sample obtained by the same procedure as described above, but without the Decomposition had been produced by the enzyme, was converted into a 1.5% aqueous acetic acid for interruption immersed in the reaction and then treated with an ordinary photographic fixing solution. Pale brown silver color images were found in the exposed areas approximately around 2 microns thicker than the unexposed areas.

In the case of treatment with the same solution, but without methacrylate, the thickening in the image areas are not observed, so that it is believed that the thickening is due to the polymerization of methacrylate decreases.

Example 6

The same recording material as in Example 1 was exposed to X-rays and treated with the same solution as in Example 1 using a cobalt X-ray tube at 30 kV and 10 mA. The sample of the material was partially covered with a razor blade 0.2 mm thick and placed at a distance of 1 cm from the window of the tube. The sample was then ^{treated with a solution as in Example 1 at 30 °} C. for 9 minutes. Only the irradiated areas were blackened, and a polymer relief remained after the enzyme decomposition in a manner similar to that in Example 1.

Example 7

Polymerization was carried out using a photographic emulsion containing no gelatin and reacting silver nitrate with an alkali halide in a solution of polyvinyl pyrrolidone to produce silver halide, coagulating the polyvinyl pyrrolidone and silver halide with acetone. Removal of the salts produced as a by-product by decanting, redispersing the coagulated mass and subsequent ripening had been carried out, the emulsion being chlorine and bromine in a molar ratio of 7: 3.100 g polyvinylpyrrolidone, 300 g polyvinyl alcohol and 2.4 x 10 " ⁶ Contained moles of sodium thiosulfate as a chemical sensitizer per 1 mole of silver

The emulsion thus formed was adhered to an adhesive layer in a dark room Cellulose triacetate base applied to form a dried layer approximately 5 microns thick After drying, the photographic material was exposed to a 500 W xenon lamp in exposed at a distance of 50 cm for 10 seconds through a line image master copy and treated with a solution of the following composition:

Sodium methacrylate 75 g

N ^ i'-methylenebisacrylamide 8 g

l-amino-S-naphthol ^ ö-disulfon-

acid sodium salt 19.7 g

Potassium pyrosulfite 12 g

2553

15 16

Borax 7.5 g solution of acetic acid to interrupt the

Immersed water 75 cm ³ reaction and immediately with flowing

Washed 2N NaOH 116 cm ^{3 of} water. Then the unexposed ones became

Areas with water leaving the un-

After treatment at 30 ⁰ C during 15 for minutes 5 dissolved unexposed areas washed to a

th, pale brown-colored silver images were observed

The material was then obtained in a 1% aqueous solution.

Claims (6)

Patent claims: 1. A process for the production of polymer images, in which an image-wise exposed in one Silver halide emulsion layer containing a latent image by the action of a monomeric Vinyl compound and an aromatic dihydroxy or hydroxyamino compound as a reducing agent is developed, characterized that the reducing agent is a dihydroxynaphthalene or a hydroxyaminonaphthalene, their functional groups are in the 1,6-positions, 1,8-positions, the 2,5- or 2,7 positions, or derivatives thereof are used will. 2. The method according to claim 1, characterized in that the development in the presence of Sulfite ions is carried out. 3. The method according to claim 1 or 2, characterized in that the naphthol derivative 1,6 - dihydroxynaphthalene, 1,8 - dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 2,7-dihydroxynaphthalene monomethyl ether, 1,8 - dihydroxynaphthalene - 2.4 - disulfonic acid, 1,8 - dihydroxynaphthalene - 3,5 - disulfonic acid, 1,8 - dihydroxynaphthalene - 3,6 - disulfonic acid, 2,7 - dihydroxynaphthalene - 3,6 - disulfonic acid, 1 -amino - 6 - naphthol, 3 - (6 - hydroxy -1 - naphtholamino) - propane-1-sulfonic acid, 1-amino-8-naphthol, N-acetyl- 1 - amino - 8 - naphthol, 2 - amino - 5 - naphthol, 2 - amino - 7 - naphthol, 1 - amino - 8 - naphthol-2,4 - disulfonic acid, 1 - amino - 8 - naphthol - 3,5 - disulfonic acid, 1 - amino - 8 - naphthol - 3,6 - disulfonic acid, 1 - amino - 8 - naphthol - 4,6 - disulfonic acid, 1-amino-e-naphthoI-SJ-disulfonic acid, 1-amino-8-naphthoi-4-sulfonic acid, 8-Amino-1-naphthol-4-sulfonic acid or 2-amino-5-naphthol-7-sulfonic acid used 4. The method according to any one of claims 1 to 3, characterized in that the vinyl compound Acrylamide, acrylonitrile, N-hydroxymethylacrylamide, methacrylic acid, acrylic acid, calcium acrylate, Sodium acrylate, methacrylamide. Methyl methacrylate, methyl acrylate, ethyl acrylate, vinyl pyrrolidone, Vinyl methyl ether, vinyl butyl ether, vinyl isopropyl ether, vinyl isobutyl ether. Vinyl butyrate, 2-vinyl pyridine, 4-vinyl pyridine, 2-methyl-N - vinylimidazole, potassium vinylbenzenesulfonic acid or vinylcarbazole are used. 5. The method according to any one of claims 1 to 3, characterized in that the vinyl compound Ν, Ν'-methylenebisacrylamide, ethylene glycol dimethacrylate, Diethylene glycol dimethacrylate. Triethylene glycol dimethacrylate, polyethylene dimethacrylate, Divinyl ether or divinylbenzene is used. 6. The method according to any one of the claims! to 5. characterized in that the sulfite ions in the form of sodium sulfite. Potassium sulfite. Sodium pyrosulfite, potassium pyrosulfite, a formaldehyde addition product of sodium bisulfite or ammonium sulfite supplies.