DE1942168A1 - Process for the production of polymer image reproductions - Google Patents

Description

The invention relates to a method for producing Poiymerbi ldv / i ed resulted, in particular, a method for their selective training on the surfaces that the the photographic, latent image-bearing surfaces correspond, by the action of a photographic Silver halide emulsion and a reducing agent. There are already various methods of manufacture of image reproductions "through the formation of highly polymerized compounds due to photopolymerization suggested by vinyl compounds. Ss has also been suggested to direct the photopolymerization by using silver halides as catalysts to effect (British Patent 866,631 and S. Levinos et al, "Photographic Science

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and Engineering ", Volume 6, pages 222-22 (1962)). It is assumed in this reaction that the light-induced decomposition product of the silver halide acts as an oil polymerization analyzer and that this reaction is not sensitive to light V / ert achieved, as is easily achieved in the ordinary development of silver halide particles. It has also been proposed that in the form of an image reproduction ' ^: ' there would be highly polymerized compounds by polymerizing vinyl compounds using a SiI- ·: Over image as a catalyst or an unreacted "silver halide" after the development of an exposed "th" silver halide emulsion with an ordinary developing solution (Belgian patent specification 642 477). This method has the disadvantage that development and polymerization are carried out separately ^: It is theoretically of great interest to control the polymerization of vinyl compounds by the oxidation product or the Zv formed therefrom in the course of the development of a photographic silver halide emulsion; A chemical product to be carried out by means of a reducing agent in opposition to vinyl compounds, since in this case it is to be expected that in this process the polymerization is brought about by both the reinforcing effect of the development and that of the chain polymerization, and it has already been proposed that such a reaction be carried out using benzenoid compounds with at least two hydroxyl-, amino- or alkyl- or aryl-substituted amino groups in the o- or p-position to one another on the benzene ring as reducing agent (TJS-Pat ent 3 019 104, G. Oster "Nature * '\' ^y '' ^r -;, Volume 180, page 1275 (1957). However, Beis ipieien

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for this ~ J ~ ß et zünder, only an increase in the optical density of the silver image "observed - and the facts that the formation of connections of high
"No molecular evidence, i.e. increase in viscosity, formation of heat of reaction or isolation of the cooking porosity, were not confirmed.

Other researchers have also reported that attempting these procedures has not been successful could (S. levinos and P.V. '. H. I ^ ueller "Photographic-,

Science and Engineering ", Vol. 6, page 222 (19.62)).

One object of the invention is to transfer a through electromagnetic waves or particle radiation The image formed on a silver halide photographic emulsion turns into an image reproduction from a highly polymerized substance by means of • a simple process ...

Another object of the invention is to achieve a polymer image with the desired properties, this method being used for recording or printing.

In the context of the invention it was found that the

Polymerization of vinyl compounds by reducing | Silver halide in the presence of the vinyl compound with
one of the naphthols described in more detail below,
Eaphthylamines, oxyquinolines or derivatives thereof
is achieved and that in cases, v / o the silver halide is in the form of a photographic silver halide emulsion, the reaction proceeds at a higher rate when the silver halide grains contain development centers than when the grains contain no development centers, so that the polymerization with a suitable choice of the reaction conditions and of

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Response period selectively in those areas of the Emulsion can be run wherever Silberhalogenidteijlcheh with development centers, i.e. where the photographic emulsion layer bears a latent image.

The method according to the invention is achieved using the facts set out above. Invention Accordingly, it becomes a silver halide photographic emulsion layer having a photographic latent image of exposure to those described in detail below Naphthols, naphthylamines or. Oxyquinolines in the presence of a polymerizable vinyl compound subjected and thereby the vinyl compound selectively in the areas of the emulsion layer which the latent Image bears, polymerizes.

The feature for the naphthols, naphthylamines, oxyquinolines or derivatives which can be used in the context of the invention of this, if the compound bears two or more amino groups or hydroxyl groups, its oxidized form can be represented by the following conjugated-type Kekule structure:

Example 1,.

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11421ft

Example 3

Especially when the above compounds are two Carrying amino groups and / or hydroxyl groups on a ring represent the compounds 1,2- or 2,3-substituted represents, which is also a feature of the invention,

Typical examples of naphthols, naphthylamines, oxyquinolines and derivatives thereof, which are part of the Invention to use are the following:

(1) a-naphthol or derivatives thereof:

* ^: OH "-

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- ο - ■. ■. -

wherein .Rg; a hydrogen atom »a sulfonic group, a substituted aryl group, or a chlorate, R, a hydrogen atom or a sulfaemoyl group, R. a hydrogen atom, a sulfonic group or a chlorine group, Rc a hydrogen atom» a sulfonic group, a hydroxyl group, an araino group or an acylamino group , Rg a V / Aäserstöffatorri »a carboxyl group or a sulfone group and R ~ a V / hydrogen atom, a hydroxyl group or an amino group. ₍

(2.) ß-Naphthol or derivatives thereof:

wherein R _{1 is} a hydrogen atom, a pormyl group, a sulfone group, a Garboxy1gruppe, an ITitroso group, an arylazo group or an amino group, R, a hydrogen atom, a hydroxyl group or the group. -COlTHR '(R ¹ is an aryl group or an alkyl group), R. is a hydrogen atom, a sulfone group, a -chlorine, atom or a sulfone group, R _{5 is} a hydrogen atom or a nitro group and Rg to Rg are each a Mean hydrogen atom or a sulfonic group. (3) a-l-taphthylamine or derivatives thereof:

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BATH ORIGINAL

t · ■ ■ ■ * -

where R is a hydrogen atom, a substituted alkyl group, an amino group or a hydroxyl group, K. is a hydrogen atom or a sulfonic group and R _{5 is} a hydrogen atom, an amino group or a hydroxyl group.

(4) ß-liaphthylamine or derivatives thereof:

n.

wherein R ₁ . a hydrogen atom or an amino group, R, a hydrogen atom, a sulfonic group or an amino group, R. a hydrogen atom or a sulfonic group, Rg a hydrogen atom or a sulfonic group and Rg a hydrogen atom, a sulfonic group or a hydroxyl group "mean.

(5) Oxychinoline derivatives:

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wherein, if Rq represents a hydroxyl group, R2 is Hydrogen atom or a carboxyl group and R, a hydrogen atom or represent a hydroxyl group and, if R. represents a hydroxyl group, R “represents a carboxyl group and Rg represent a hydrogen atom.

The photographic latent image is an invisible image formed in the silver halide photographic emulsion by the action of electromagnetic waves or particle radiation and can be converted into a visible image by development. In the photographic emulsion layer for negative image formation, the latent image is formed by forming the development centers of the silver halide grains formed by electromagnetic waves or particle radiation, while in the photographic emulsion layer for a direct positive image, the latent image is formed by forming development centers in all silver halide present in the layer - grains and subsequent removal of the development centers is formed by exposure to electromagnetic waves or particle radiation, for which reference is made, for example, to James and H. Huggins, "Fundamentals © f Photographic Theory", Chapters 3 and 4 * 2, edition, Morgam & Morgam Co * . -

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Both the above-mentioned photographic silver halide emulsions can be used in the process of the present invention for negative image reproductions and the photographic silver halide emulsions for positive ones Image reproductions are used.

In the present invention, as silver halide photographic emulsions giving a negative image, emulsions suitable for ordinary development processes can be favorably used. Thus, silver chloride, silver chlorobromide, silver chlorobromide, silver iodobromide and silver chloroiodobromide photographic emulsions can be used. The chemical sensitizations and optical sensitizations applicable to ordinary photographic emulsions can also be applied to the silver halide emulsions to be used in the present invention. Sulfur sensitization and noble metal sensitization can thus be used for chemical sensitization, for which reference is made, for example, to P. Glafkides, "Chemie Photographique ¹¹ , 2nd edition, Phot ocinema Paul Mont el, Paris 1957, pages 247-301. For optical sensitization, the optical sensitizers for ordinary photographic emulsions, e.g. Emulsions which can be used in the invention can also contain the stabilizers used in conventional photographic processes.

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The direct positive silver halide emulsions which can be used in the context of the invention can be achieved by using solarization, the Herschel effect, Clayden effect or Sabatier effect can be produced. The explanations of these effects are in chapter 6 and 7 by C. E. K. Mees, "The Theory of the Photographic Process", 2nd Edition, MacMillan Co., 1954. For the preparation of direct-positive photographic silver halide emulsions by solarization, a solarized silver halide emulsion was prepared and then subjected to uniform exposure Exposed to light or the action of a chemical, so that it becomes capable of development without exposure to images. Processes for making such emulsions are z. B. in British Patents 443 245 and 462 730 described.

The Herschel effect is made by exposure to a photographic emulsion which is developable by uniform exposure to shorter wavelength light or uniform exposure of a chemical reagent, exposed to light from caused longer Ytellenlänge. In this case it will it is preferred to use silver halide emulsions which mainly contain silver chloride and a desensitizer such as pynakryptol yellow or phenosafranine to increase the effect. The procedure for the production of direct-positive emulsions using the Herschel effect is for example in British Patent 667,206 and US Patent 2,857,273.

To get a positive image straight away using the

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To achieve the Clayden effect, it is necessary to use an emulsion with a relatively low total exposure to light To expose intensity after imagewise exposure to light of high intensity for a short period of time, where those areas of the emulsion which not exposure to the high intensity light were exposed to become viable after this overall exposure.

The Sabatier effect is produced when a

photographic silver halide emulsion layer which ■ an imagewise exposure to light and thereby an increase in the developability of the areas which not exposed to imagewise exposure in the state of immersion in a developing solution exposed to uniform exposure to light or a chemical reagent. The Clayden Effect and the Sabatier effect are easily and conveniently available in such silver halide emulsions that a tendency towards the formation of development centers of the first exposure in the inner part and not in the surface part of the grains of the silver halide show.

Process for the preparation of such emulsions, g

a tendency towards the formation of inner development centers are disclosed in, for example, U.S. Patents 2,592,250 and 2,497,876, British Patent Specification 1 011 062 and the German patent specification 1 207 791.

The photographic emulsions listed above consist of dispersion systems in which particles of silver halides are dispersed in a solution of a high polymer and is called high polymer

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gelatin is widely used for this purpose, while polyvinyl alcohol, polyvinylpyrrolidone, Polyacrylamide, carboxymethyl cellulose, oxyethyl ether and dextran are used alone or in admixture with gelatin v / ground, for example on P. Ewa, "Zeitschrift für Wissenschaftliche Photographie, Photophysik und Photochemie * Volume 52, page 1-24, (1957) is referred to. ·

Examples of naphthols, uaphthylamines, oxyquinolines and derivatives thereof suitable for practice, which can be used in the context of the invention are as follows:

(1) a-Naphthol

(2) Potassium 1-naphthoil-2-sulfonate

'OH

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(3) sodium 1-naphthol-4-sulfonate

OH

(4) Sodium 1-naphthol-5-sulfonate

OH

(5) β-naphthol

OCT

(6) 2-hydroxy-1-naphthaedehyde

CHO

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- H-

(7) 2-Naphthol-i-sodium eulfonate.

(θ) 2-naphthol-6-sodium sulfonate

(9) 2-naphthol-8-sodium eulfonate

(10) 2-naphthol-8-sodium sulfonate

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(11) 2-Hydroxy-1-naphthoic acid

'• OCH

OH "

(12) m-N- (Hydroxy-3-naphthoyl) phenylenediamine

X O MiH

κ)

(13) β- (2-Hydroxy-3-naphthoyl) aminoethanol

(U) a-nitro ae-ß-naphthol

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(15) Naphtho orange

(16) 1- (a-Hydroxy-2'-naphthylazo) -5-nitro-2-naphthol « 4-sodium sulfonate ''

NO,

X17) 2,3-naphthalene diol

(18) 2,3-hydroxynaphthalene-6-sodium 8ulfonate

* O H

(19) 1,5-dihydroxynaphthalene

M!

(20.) 1,7-Dihiydronaphthalene

(21) 1,7-Dinydro3ty-6-naphthoic acid

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-Ί8 -

(22) α-naphthylamine

(25) ß-Diethylaminoethyl-cc-naphthylamine

CaHs

^N Ca Hs

(24) thionalide

(25) 2-Haphthylamine-8-sodium sulfonate

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(26) 2-naphthylamine-4,8-disodium eulfonate

(27) 1,2-naphthalenediamine

(28) 1, 5-naphthalenediamine

(29) 2-Anino-8-naplitliol-3,6-aleulfonic acid

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(30) t-amino »2-naphthol-4-sodium 8ulfonate

(31) α-amino-5-naphthol

(32) 5-methacryloylamino-1-naphthol

CHj

(33) 8-Oacyehinoline

COC

OH

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(34) 4-8-Hydro3cychinoline-2-earbon8 acid

OH

⁰ ^ ¹ SfS

QH

(35) 4-Hydroxyohlnoline-2-carboxylic acid

(36) 1-Naplithol-3-sulfonamide-sodium

(37) 2,4-dichloro-i-naphthol

OH

'a

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1942108

(38) 2,3-naphthalenediamine

Methods for making the above compounds are known, as are the above compounds are customary in trade.

In the context of the invention, the silver halide is in Form of a silver halide photographic emulsion layer to increase the diversity of the reactivity, i.e. the selectivity of the implementation between the surfaces irradiated with electromagnetic waves or particle radiation and the surfaces not exposed to any such Irradiated areas applied "

Up to now it was not known that the polymerization according to the invention by compounds of those Kind is initiated by the joint action of silver halide and the above-listed naphthols, naphthylamines, oxyehinolines ode? Deri-

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derivatives represent intermediate products formed therefrom, even if there are numerous reports on the oxidation of ITaphthols and also those obtainable from them Describe intermediate products. For example, see T. J. Stone & V, '. A. Waters, "Chera. & Ind.", Page 213 (1964), M. Adams, M.S. Blois Jr., and R. H. Sands, "Chem. Phys.", Vol. 28, p. 774 (1958) and R. Pummer and I. Veit, "Chem, Ber.", Volume 86, Page 412 (1953). According to these reports, results the formation of the following 'intermediate products.

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x-

IVa

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The oxidation of naphthylamines is for example by L. Homer and J. Dehnert, "former Ber.", Volume 96, Page 786 (1963). According to the reporter the formation of the intermediate products should proceed as follows:

- €

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In the references listed above ^Λ , the polymerization of a vinyl or vinylidene monomer using the intermediate formed by oxidation was not attempted * It is also known that 1,2-dihydroxynaphthalene or 1 _t 5-dihydroxynaphthalene is effective as a developing agent (CEK Wees, " The Theory of the Photographic Process ", Chapter H, 2nd Edition, McMillan Co., 1954, New York).

When each of the two rings of the naphthalene ring has a hydroxyl group or amino group as in the context of Invention is believed to cause polymerization of the vinyl or vinylidene compound because the radical formed during development is not so stable. If continued a ring of naphthalene has two hydroxyl groups or amino groups at the 1,4-position, is that formed during development Radically too stable to initiate the polymerization, but is if the groups are in the 1,2-position or 2,3-position, the radical formed during development is not so stable and, as a result, the Polymerization of the vinyl or vinylidene compound caused. It is believed that the above phenomenon is related to the fact that in so-called aromatic photographic developing agents with hydroxyl groups or amino groups, the activity of a developing agent having p-substituent is generally higher than that of an o-substituted developing agent, in other words that There are differences in the stabilities of the radicals between the two cases.

The reaction mechanism of the polymerization of a vinyl or vinylidene compound due to the reduction

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of silver halides through the naphthols, naphthylamines, Oxyquinolines or derivatives thereof according to the invention is not yet clear. However, it is to be assumed that because one is accessible to radical polymerization Compound is used and implemented in aqueous media will and also inhibitors for the radical polymerization delay the implementation, the Polymerieation takes place via a radical polymerization mechanism. Until now it is not clear whether the radical is generated directly by the reaction of the reducing agent according to the Invention and the silver halide is formed or whether the radical is formed by the combined action of water, oxygen and the like in the system. Even though ' however the influence of oxygen is not clear from the above, it is assumed that if z. B. a naphthol is used as a reducing agent, the following reaction takes place;

■ .S

Ί 'j

X-C

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• ■ "■! * $: ■■■

IS 4 216-

Furthermore, in accordance with the above Implementation of radicals formed the following resonance structures are present, one or more of which for initiation should contribute to the polymerization:

.R

Further, it is clear that the polymerization of the vinyl compound or vinylidene compound occurs simultaneously with the reduction of the silver halide, since if the vinyl compound or vinylidene compound is added to the reaction system after the reduction with a reducing agent, no polymerization is observed. Therefore, it is assumed that the intermediate from silver halide, and the present invention the reducing agent used, the initiation of the reaction i tion causes .. Even if the reaction is discontinued after a suitable period, is in the irradiated parts selectively the formation of highly polymerized material before, during, if the reaction is continued, the highly polymerized material will also be formed on the parts that have not been irradiated. This fact is believed to be due to the occurrence of a difference in the rate of formation of (IC) due to the difference between the reactivity of the irradiated silver halide and that of the non-irradiated

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., ο- 1942188

Silver halides. The foregoing fact that the density of the unexposed parts becomes that of the exposed parts if the implementation is continued for an extended period of time presents the same phenomenon that occurs when a development is continued for a longer period of time in conventional photographic processes, with all parts including the exposed Parts and the unexposed parts are blackened. In this respect, the above-mentioned phenomenon does not worsen the process according to the invention practical feasibility of the present invention.

As a method of forming an image reproduction from a high molecular weight material using the photosensitivity of silver halide the so-called tanning development is known, whereby gelatine is caused by the oxidation product of a known developer is crosslinked, however, in this method, the material for forming the image reproduction is only on the crosslinking product of gelatin is limited. In contrast, in the process according to the invention, image reproductions from highly polymerized compounds with different Properties corresponding to the vinyl compounds or vinylidene compounds used can be obtained, so that image reproductions are quite excellent Properties such as coloring properties and chemical resistance that have never been seen before achieved in the case of the application of a crosslinked product could be obtained. can.

Furthermore, it was found in the context of the invention that, if sulfite ions in the reaction system according to the

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Invention present the polymerization of vinyl compounds or vinylidene compounds can still be accelerated.

The sulfite ions can add to the reaction system either in the form of compounds originally the sulfite ions contained in the molecule, such as alkali sulfites or ammonium sulfite, or in the form / compounds, the sulfite ions due to hydrolysis in aqueous solution, such as the pyrosulfites of alkali metals or des Ammonium or the adducts of bisulfites with aldehydes, such as formaldehyde or glyoxal can be added. Albeit the appropriate amount of that to be added to the system Sulphite ions of the type and amount of the reducing agent and the vinyl or vinylidene compound, the pH of the Systems and similar factors are generally more than 0.04, especially more than 0.2 Mol / liter of the reaction system β effective.

It is well known in the art to add sulfites to photographic processing solutions. However, in these cases, it is believed that the sulfite inhibits autoxidation of the developing agent and uneven development occurrence by reacting with the oxidation products of the developing agents such as hydroquinone or p-aminophenol, including e.g. See, for example, CEK Meee, ^ Theory of the Photographic Process ¹¹ , 2nd Edition, p. 652, McMillan Co., 1954. It should be noted that, since the intermediates of the oxidation of the naphthols, naphthylamines, oxyohinolines or derivatives thereof, initiate the polymerization of a vinyl compound or a vinylidene compound in the process of the invention, which the

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Polymerization-promoting effect of sulfite ions in principle different from the effect of removing the oxidation products in the ordinary, developing solutions listed above.

If the sulfite just like the oxidation products If the normal development process were to remove, the polymerization would be inhibited and not favored will.

Although the mechanism of the action of the sulfite ions in the process according to the invention is not clear, is believed to be likely to be the sulfite ions prevent the polymerization-inhibiting effect of oxygen '. The development and polymerization by the Reducing agent according to the invention can also by common use of a usual photographic Developing agent or a quaternary salt are favored. This presents the same appearance appear as if a resorcinol, a phenol or a 5-pyrazolone is used as a reducing agent, so that development and polymerization by the addition of a small amount of an ordinary photographic Developing agent can be favored.

Common developing agents are compounds of the formula A (C =C) B, in which A and B each _{denote -OH, -NH 2} or -NHR, so-called phenidones, ie i-aryl-3-oxopyrazolidines or derivatives thereof and i-aryl -3-iminopyrazolidine. As mentioned above, the above developing agents themselves have no effect of promoting polymerization in development, but are believed to promote the developing effect of the reducing agents with a polymerization inducing effect and

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then favor the polymerization of the monomers. Quaternary salts of pyridine, such as lauryl pyridinium chloride can be used. The fact, that the use of the quaternary salts favors development and polymerization is likely to result are based on the fact that, after an ordinary silver halide photographic emulsion, halogen in an excessive amount and the surface of the silver halide particles in the emulsion is negatively charged, the quaternary salt acts to neutralize the charges, making the approximation the reducing agent and favoring the implementation is facilitated.

The vinyl compounds used in the context of the invention are addition-polymerizable vinyl compounds which are liquid or solid at normal temperature, or mixtures of such vinyl monomers. Examples of such vinyl compounds are acrylamide, acrylonitrile, N-hydroxymethyl-acrylamide, N-tert-butyl acrylamide, methacrylic acid, acrylic acid, calcium acrylate, sodium acrylate, methyl methacrylate, ethyl acrylate, vinyl pyrrolidone, dicyelopentadiene methacrylate, vinyl butyrate, 2-vinyl pyridine, 4-vinyl pyridine, 2-methyl-N-vinylimidazole, potassium vinylbenzenesulfonate or vinylcarbazole. In the method of the present invention, vinyl compounds having more than 2 vinyl groups are particularly preferred, and these compounds can be used together with the above vinyl compounds having a vinyl group or they can also be used alone. Examples of vinyl compounds with more than two vinyl groups are !!, N'-methylene-bis-aerylamide, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, polyethylene glycol dimethacrylate,

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Divinylbenzene, bisphenol-A-dimethacrylate, butylene dimethacrylate, Trimethylolpropane trimethacrylate, pentaerythritol tetraacrylate and similar compounds.

In the context of the invention, water-soluble Vinyl compounds are favorably used, but water-insoluble vinyl compounds can also be used if they are added to the reaction system as an emulsion be admitted. The emulsification can be carried out by means of suitable stirring in the presence of a surface-active agent Carried out by means of and / or a high molecular weight compound according to conventional procedures will.

All electromagnetic waves or particle radiation, to which ordinary photographic photosensitive emulsions are sensitive are used in the process according to the invention. This means that visible rays, ultraviolet rays, Infrared rays with wavelengths shorter than 1.3 microns, X-rays, gamma rays, and alpha rays Electron beams are used.

To carry out the method according to the invention it is necessary to the two stages of irradiation by electromagnetic waves or particle radiation and carry out the reduction and polymerization. Particularly when recording images, it is necessary to that the silver halide particles in the emulsion their Was at most during the period between the irradiation by electromagnetic waves or particle beams and the polymerization in the reaction system change little and therefore it is preferred that the reaction system in highly viscous, liquid feed

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stood or is held in the gel state. Although photographic emulsions have a certain viscosity or can be gelled as they are natural or synthetic high molecular weight materials further high molecular weight materials can be added to the emulsion, if any this property is insufficient.

When irradiated with electromagnetic waves or particle beams, the silver halide | particles be dispersed in an aqueous solution or kept in a dry gel. Thus can a highly viscous or gelled photographic emulsion of radiation on a support in the undried state be subjected or the emulsion can be the Exposed to radiation on a support in the dry state. There reduction and polymerization take place at the same time, the reduction must take place in the present the vinyl connection or vinylidene compound carried out will. Even if within the scope of the invention, both the above-listed compounds accordingly of the general formula (I) or (II) as well as the vinyl compound in the photographic emulsion J can be incorporated prior to exposure, one of these can first be incorporated into the emuleion prior to exposure and the other to the emulsion after the Exposure can be added. Furthermore, both components can be added to the system after the irradiation will.

Since the reduction and polymerization according to the invention must be carried out in the presence of water, it is necessary to carry out the reaction in an aqueous solution or in a moist gel state.

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19A2168

The implementation according to the invention goes smoothly in the alkaline state and the most favorable pH values of the reaction systems depend on the types and concentrations of the silver halide, the reducing agent and the highly polymerized compound used as a medium, and further on the reaction temperature. The reaction can be carried out at pH values higher than 6, but pH values higher than 7 become particular preferred. .

Palls the silver halide photographic emulsion is applied as a coated emulsion layer on a support, the reaction can be carried out by immersing the photographic emulsion layer formed on the support in an alkaline, aqueous solution after the emulsion layer with the has been exposed to electromagnetic waves or particle radiation. In this case it is beneficial to go to the alkaline, aqueous solution to incorporate the reducing agent or the vinyl compound.

Although the implementation is easy by reducing the pH of the reaction system, for example, to one Value less than 5 can be canceled, it can also by cooling down, removing the reactants by washingV dissolving the sirber halide see a photographic solution or the addition of a poly- : mer-isatiörishemms toffee 2U canceled the system.

If.the combination of high molecular weight as a carrier for the silver halide; and the vinyl monomer zii a layer processed _s call it _f wirfi preferably a low / Metige a thei ^ ^ ISOH heiöiistoffes aur Verhinäertmg the spon Gesä.tatpolymerisation of Viiiylinonomeren fifuaüsetsen * As

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Such thermal polymerization inhibitors can be used all known thermal polymerization inhibitors for radical polymerization. Examples are p-methoxyphenol _r hydroquinone, alkylhydroquinones, 2, 6-3) i-tert. -butyip'-kre.sol and similar compounds.

When the vinyl monomer is incorporated into the system from the beginning, its weight is usually 1.30 to 30 times, preferably t / 4 to 4 times the weight of the high molecular weight compound originally present in the system. The silver halide is usually used in an amount by weight of 1.20 to 2 times, preferably 1/10 to 1/2 times the amount of the high molecular weight compound originally present in the system. Even if the reducing agent is incorporated in the system from the beginning, the amount of the reducing agent is preferably 1/1000 to 20 moles per mole of silver halide, and when the above-mentioned thermal polymerization inhibitor is added to the system, its amount is desirably 1/100 000 to 2/100 the weight of the vinyl monomer. If the vinyl monomer is incorporated in the processing solution, it is preferred to dissolve it therein in as high a concentration as possible, and therefore the amount of the vinyl monomer is mainly determined by the solubility thereof in the processing solution. Case, is incorporated in the processing solution, the naphthol, naphthylamine, or Qxychinolin, which is used as a reducing agent, the concentration thereof 1/2000 to 5 moles, particularly from 1/100 to 1 mole per liter.

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V / ie in the ordinary silver halide photographic process can be a time gap between exposure to electromagnetic waves or particle radiation and the polymerisation stage. According to the properties of the photographic emulsion, the environment in which the system is allowed to stand, and the length of the time interval can be _ Irradiation effect reduced to a certain extent. Who-- " ™ den and in such a case the desired Effect can be obtained by increasing the amount of exposure.

In the case of using the method according to the invention for recording image reproductions, it is possible to identify the various differences in solubility, light scattering, stickiness, dye receptivity and other physical and historical properties between the To exploit vinyl monomers and their polymers. By Taking advantage of the difference in solubility can be a Relief image made from the high molecular weight material

6 are formed by the non-polymerized parts after irradiation and polymerization are dissolved away, so that the material is high molecular weight only remains on the irradiated parts.

In this case, it is favorable if the high molecular weight compound originally present in the reaction system is dissolved away together with the unreacted monomer. In this respect it is preferred that the compound of high molecular weight originally present in the system is a so-called two-dimensional linear and practically non-crosslinked or

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is such a crosslinked one that the main chain or the crosslinking bond is easily broken and that the high molecular weight compound formed by the polymerization of the monomer through the reaction a so-called three-dimensional network is. For this purpose it is beneficial to connect with multiple vinyl groups as listed above, either alone or in conjunction with a compound to be used with a vinyl group. However, it is usually not essential to have a compound with multiple vinyl groups apply because even if the high molecular weight compound formed is only a water-soluble one two-dimensional compound is, often a notable difference in solubility between the areas where the high molecular weight compound is formed by the reaction and the areas where where such a connection is not formed, as a result of the interaction with the originally in high molecular weight compound present in the system occurs, for example in the case of polyacrylic acid and gelatin *

The formed by the inventive method Image reproductions from the high molecular weight compound can be used for various printing processes can be used.

Furthermore, the method according to the invention can be used for imaging color images. In these Cases "consists of the vinyl compound used. a vinyl monomers "with one to take up charges by electrolytic dissociation or by the addition of groups capable of hydrogen cations, so that

00981 2 / U87

Polymers capable of absorbing charges through electrolytic dissociation or addition of hydrost of fcations are formed, whereupon the polymer images selectively by a dye of the opposite Charge to that of the polymer to be colored. The resulting color reproductions can also be transferred to other carriers by various methods.

Examples of such vinyl compounds which can be polymerized by addition and which accept charges by electrolytic dissociation or addition of hydrogen cations are capable and those in the frame The following can be used in accordance with the invention: vinyl compounds which absorb negative charges are capable of high molecular weight compounds formed are vinyl compounds with for example carboxyl groups such as acrylic acid, methacrylic acid, itaconic acid and maleic acid, vinyl compounds as a metal salt or ammonium salt of carboxylic acids, such as ammonium acrylate, sodium acrylate, potassium acrylate, Calcium acrylate, magnesium acrylate, zinc acrylate, cadmium acrylate, Sodium methacrylate, calcium methacrylate, magnesium methacrylate, Zinc methacrylate, cadmium methacrylate, sodium itaconate and sodium maleate, vinyl compounds with a sulfonic acid group such as vinyl sulfonic acid and p-Vinylbenzenesulfonic acid and vinyl compounds as metal salt or ammonium salt of a sulfonic acid, for example ammonium vinyl sulfonate, sodium vinyl sulfonate, Potassium vinyl sulfonate and potassium p-vinyl benzene sulfonate. As examples of vinyl compounds that are used to achieve are capable of positive charges on the high molecular weight compound formed therefrom are listed

0098127U87

Vinyl compounds with a basic nitrogen atom, such as 2-vinylpyridine, ♦ -vinylpyridine, 5-vinyl-2-methylpyridine, NjN-dimethylaminoethyl acrylate, N, N-dimethylaminoethyl methacrylate, N, N-diethylaminoethyl acrylate and Ν, Ν-diethylaminoethyl methaerylate and vinyl compounds as a quaternary nitrogen salt, which is derived from a base of the the above vinyl compound having a basic nitrogen atom and e.g. B. methyl chloride, ethyl bromide, dimethyl sulfate , Diethyl sulfate, methyl p-tpluenesulfonate or similar connections were made. These compounds can be prepared by processes known per se are or are customary in the trade. These compounds can also be used alone or in combination of several be used. Furthermore, they can be used together with water-soluble, polymerizable vinyl compounds which carry no charges by addition can be used. As vinyl compounds of this type are listed acrylamide, K-hydroxymethyl acrylamide, methacrylamide, Methyl methacrylate, vinyl pyrrolidone, N, N-methylenebis-acrylamide, Triethylene glycol dimethacrylate, polyethylene glycol dimethacrylate and similar connections. In the pail of the application of vinyl compounds without charges, the reactivity and the proportion of Vinyl compound should be chosen to be a high molecular weight compound which is' practically non-electrolytic Has dissociating groups, in the polymerization only the vinyl compound without charges is formed.

Dyes used to form charges electrolytic dissociation are capable and within the framework of the invention can be used, the generally applicable

0OS812 / U87

applied common acidic dyes and basic dyes. Thus, if one is used to form a high molecular weight compound with negative charges. Suitable vinyl compound is used, a basic dye is used, while, if a * for Formation of a high molecular weight compound vinyl compound suitable with positive charges is applied an acidic dye is used. At-

In other words, a basic dye stains because it has positive charges, selectively high molecular weight compounds with negative charges, while a acidic dye, since it has negative charges, selectively high molecular weight compounds with colors positive charges. Thus, a color picture or a colored picture can be reproduced in accordance with the imagewise formed compound of high molecular weight can be obtained »

If gelatin as a binder for the photographic If emulsions are used, the isoelectric point of gelatine must be taken into account when dyeing, since gelatine is an amphoteric electrolyte. If

If the pH of the system is lower than the ispelectric point of the gelatin, then the gelatin has negative charges, while if the pH is higher is, the gelatin has positive charges * If so a high molecular weight compound with negative When charges are formed, only the image reproduction from the compound of high molecular weight can be achieved. ■ weight can be stained without staining the gelatin by the image-bearing emulsion layer is colored with a basic dye. On the other hand, if an emulsion layer initially uniformly with the polymer image

009812 / U87

a higher pH than the isoelectric point of the Gelatin is colored and then the layer colored in this way with a washing solution at a lower pH value as the isoelectric point is washed, only the color on the faces of the emulsion layer becomes Washed away without a polymer image and therefore only the areas with the polymer image in the colored state obtain.

If you look at the image reproduction from the compound of high molecular weight with positive charges with a Desires to color acidic dye, the image can be reproduced at a higher pH than the isoelectric Point the gelatin to be colored. Of course, if the pH of the reaction system is too high or too low, the solubility of the dye is reduced and the electrolytic dissociation of the compound to be charged is reduced hindered by high molecular weight. Thus, although the optimal pH range of the system is of the species the vinyl compounds used and the dyes used and the types of binder, such as gelatin, is dependent, in the case of a chalk treatment, normal gelatin with an isoelectric point of about 4.9 the pH value favorably 2.5 to 4.5, if a high molecular weight compound having negative charges is colored with a basic dye will, and. 5.0 to 8.0 if a high molecular weight compound having positive charges with an acidic one Dye is colored.

Typical examples of acidic balms according to the invention Dyes that can be used in processes are 0. I. Acid Yelbw 7 (C. I. 56205), C I. Acid Yellow 23 (C I. 19U0), C. I.

009812 / U87

Acid Red 1 (C.I. 18050), -C. I. Acid Red 52 (G. I. 45100), C. I. Acid Blue 9 (C I. 42090), C. I. Acid Blue 45, C. I. Acid Blue 62 (C. I. 63045), C. I. Acid Violet 7 (C.I. 18055) and similar dyes. Typical Examples of those which can be used in the context of the invention basic dyes are C. I. Basic Yellow 1 (C. I. 49005), C I. Basic Yellow 2 (G. I. 41000), C. I. Basic Red 1 (C. Γ. 45160), C. I. Basic Red 2 (C. I. 50240), C. I. Basic Blue 25 (C I. 52025), C I. Basic Violet 3 (C I. 42555), C I. Basic Violet 10 (C. Γ. 45170) and similar dyes.

The number of the dyes indicated above corresponds to the color index.

To carry out the process according to the invention, it is necessary to carry out the reduction and polymerization after to carry out the irradiation with electromagnetic waves or particle radiation and then make the staining.

By washing off only the unreacted Viny! Monomers after irradiation and reduction and Polymer images can be obtained by polymerization. A polymer is generally less soluble in water than the monomer and consequently remains behind if a silver halide emulsion originally present in the photograph and no molecular weight compound used as a binder without dissolution in wetness, as with gelatine, only remains the polymerized © part to form an image reproduction, since the polymer hardly diffuses into the gel avalanche phase can. If a. Mdnomeres with two or more Vinyl groups are also used, can cause loss of solubility and never Sigensehofft -]) iffu8ioti defl polymers

009812/14

continue to be increased.

By coloring the polymer images with the above Listed dyes can be colored pictures or colored Image reproductions corresponding to the polymer images were obtained will. The color images obtained in this way can be seen as clear, colored image reproductions by removing the Silver halides after a fixing process and further dissolution of the silver images through the effects an oxidizing agent and a solvent for the silver salts are used «if a reducing agent with a fairly high effect to initiate the polymerization is used, the polymerization reaction occurs sufficiently even in a state where a very small amount of the reduced silver is formed and therefore it is in such a case no or hardly necessary, the silver images through Oxi-. dation to remove. .

Furthermore, the color images formed can be transferred to other carriers. To carry out the transfer, the emulsion layer with the color images thereon is moistened with a solvent for dye, for example methanol, water, an aqueous solution of an acid, a base or a salt, and then the layer is brought into intimate contact with the surface of a support which the reproduction of color images. Ordinary paper, papers with a hydrophilic polymer layer or gelatin layer and films with a hydrophilic polymer layer or gelatin layer can be used as a carrier for receiving the color images.

If the color images are transferred to a carrier with an attached gelatin layer, it is better to

0098-127i4 & 7

V. 19421S8

stig, one, with a pickling agent, for example one Aluminum salt, treated carrier apply like them used in the usual Parb transmission methods will. After a picture playback from a connection of high molecular weight necessary for carrying charges capable of being formed, it is possible to make a plurality of copies thereof by coloring and transferring in the manner described above. Since there continue to be numerous copies of the transferred Images can be obtained from a single color image reproduction and a polymer image can be repeatedly colored, numerous copies can be made according to the present invention can be easily obtained.

example 1

A photographic, fine-grain silver chlorobromide emulsion with a content of about 60 g / l of gelatin ... "and about 42 g / l (as silver) of silver chlorobromide with a ratio of chlorine to bromine of 7: 3 and a pH V. ert ^r of 5.8 and a pAg of 7.6 was divided into two parts, a portion of which was exposed to a fluorescent lamp. to carry out the exposure, were etv / a 200 ml of the emulsion at about 35 ° C melted and spread over a barrel 20 cm χ 25 cm, and then exposed the thus spread liquid layer with stirring to a fluorescent lamp of about 300 lux for about 5 minutes. In a test tube 1.6 cm in diameter were each 2 ml of the exposed and of the unexposed emulsion and after adding 6 ml of water to each glass, 4.0 g of acrylamide was dissolved in each solution and

.00 * 812 / U 87

then 10 "^ moles of IJatriun-i-naphthol-4-sulfonate (compound 3) added to this. After sufficient stirring was the temperature of the system is set to 60 ° C and the test tubes are placed in a heat-insulating material. The insulating material was made with a polystyrene foam about 2 cm thick and the entire system in a water bath kept at 60 ° C immersed. Subsequently, 4.0 ml of an aqueous In-sodium hydroxide solution was immediately added to the system and the change in temperature using a Thermister-type temperature recorder registered. The temperature / of the exposed emulsion was determined by the due to the polymerization of the The heat of polymerization produced by acrylamides increased and reached after about 118 minutes from the start of the reaction the temperature a 91 »5 ° C and the contents of the test tube increased its viscosity due to the resulting polyacrylamide and became itself in a large amount of methanol not dissolved.

On the other hand, the temperature of the system in which the unexposed emulsion was applied only reached 75 ° C

It results from the formation of the heat of polymerization and the change in the flowability of the overall system that the polymerization took place in the exposed emulsion system. In fact, the reduction of the silver halide can also generate heat in addition to the polymerization conversion, but the amount of heat generated by the reduction of the silver halide is too low, especially as a temperature change in this system. If z. B. Hydroquinone in the presence of

009812/14 87

the method instead of sodium i-naphthol-4-sulfonate was used, the silver halide was reduced to black silver, but no heat generation was observed. If, on the other hand, sodium 2-naphthol-i-sulfonate (compound 7) used instead of sodium 1-naphthol-4-sulfonate the temperature of the system in which the exposed emulsion was used reached 94 ° C after 123 minutes, while the temperature of the system where the unexposed emulsion was used only reached 80 ° C.

From the above fact that in the system using the exposed emulsion, the polymerization is preferred under the same conditions to the system using the unexposed emulsion, it is clear that the exposed Emulsion participates in the implementation and causes the reaction.

- ■ ■ ' Example 2

A photographic photosensitive film with Photographic gelatin silver a solution containing 1,7-dihydroxy-6-naphthoic acid (compound 22), acrylamide, and methylene-bis-acrylamide, to carry out the polymerization imagewise processed. The photographic film used was produced in the following way: Both surfaces of a polyethylene terephthalate film received an undercoat * whereupon one of the surfaces was then covered with an atrium protective layer and the other with a finely divided layer Gelatitte silver halide emulsion containing 100 g of gelatin

00981.2 / U 87

and about 0.7 moles of chlorine, about 0.3 moles of bromine and about Contains 0.001 mol of iodine per 1 mol of silver and incorporates a merocyanine dye with maximum sensitivity at 550 mu as a sensitizing dye, about 1.5 g of mucochloric acid per 100 g of gelatin as a hardening agent and a suitable stabilizer and a suitable surfactant, coated so that the coated layer 50 mg of silver each Contained 100 cm of layer. Then there was a Schutzschüit made of gelatin about 0.8 microns thick applied to the emulsion layer. This type of photographic film is commonly used for Production of network images or line images by Photogravure used.

A negative with a line tape was applied to the photographic photosensitive film, and the system for 2 seconds with light of about 100 lux exposed and then the emulsion layer became under steady red light in a solution of the following. Composition immersed;

Acrylamide

Methylene-bis-acrylamide 1,7-dihydroxy-6-naphthoic acid (Compound 22) potassium metabisulfite water

2N NaOH solution required amount for adjustment the pH to TI, 5

When the film was left to stand at 30 ° C. for 30 minutes , it became a. weak image on the exposed

90 G 10 G 0 , 3 g 3 , 0 g 100 ml

000812/1407

19421S8

th surfaces observed. After the reaction was terminated by a 1 ^ strength aqueous acetic acid solution and the layer was washed with 'Nasser, the gelatin of the emulsion layer under application of an aqueous solution containing 1? * A gelatin decomposing enzyme (V, ^r arenbezeichnung Bioprase PF. 4) decomposed and the gelatin on the unexposed areas was completely washed away and the undecomposed film remained on the exposed areas, indicating that the polymerization occurs selectively in the exposed areas. ^w hen the same procedure using 0.07 g of 5-amino-1-naphthol (Compound 32), instead of 1, T-dihydroxy-G-naphthoic acid was performed, showed similar results.

Example 3 , -

The same photographic photosensitive film as in Example 2, exposure was carried out there and in a Solution of the following composition for implementation processed during development and polymerization:

1-vinyl-2,3-dimethylimidazolium p-toluenesulfonate

1,2-diaminonaphthalene (compound 28)

Potassium metabisulphite solution of sodium hydroxide

water

75 g

10 mg 2 g

amount necessary to adjust the pH value to 11.6

75 ml

00 9S12 / 1487

Pas 1-vinyl-2,3-dimethylimeaazolium-p-toluenesulfonate was made by reacting 1-vinyl-2-methylimidazole and methyl p-toluenesulfonate at normal temperature and recrystallization of the product from ethanol and Ether made. The melting point of the crystals was 142.5 ° C

If the layer is in the above solution was treated, a pale brown silver image and at the same time an image of the quaternary salt polymers, which was confirmed by the following method.

For this purpose, the layer was washed for 30 seconds with a 1.5 ″ aqueous acetic acid solution and fixed by a fixing solution having the following composition:

Sodium thiosulphate anhydrous 150 g Potassium metabisulphite 15g

Water to 1 1

After sufficient fixation and washing, the image thus obtained was replaced by a 0.15 aqueous solution of a blue, acidic dye, Suminol Leveling Sky Blue R-extra cone, C.I. Acid Blue 62, colored and then for 5 minutes with a 1 # aqueous Sodium bicarbonate solution to give a blue image.

Since the brown picture consisted of a silver picture, it could easily be through the reducing agent according to Farmer removed "After the silver image was peeled off, a clear" blue image could be obtained.

00 9812 / U8 7

overimage has been carried out, d. H. if the silver picture first with the formation of a colorless and transparent one The image was removed and then the image was colored in the above manner, could become the same blue Image to be received *

The color image formed in this way could be printed on paper be transmitted. When an ordinary writing paper was slightly wetted with methanol, the one obtained Color image was brought into close contact with the moistened paper and separated therefrom after 30 minutes the color image was transferred to the paper.

Even if a layer of gelatin about 10 microns thick on the surface of one coated with barite Paper was applied, the paper in an aqueous Solution of Alavin was immersed and then was dried to obtain a transfer paper, became narrower after being moistened with water Contact with the color image listed above and separation of the transfer paper after 1 minute obtain a clear, high-density, blue image from the color image on the transfer paper.

If. Furthermore the polymer image for 5 minutes in an aqueous solution with 0.1 $ of a red, acidic Dye, Solar Rhodamine B extra, C. I, Acid Red 52, instead of immersion in the above aqueous Solution of Suminol Leveling Sky Blue E extra cone was immersed and then washed with water likewise an image, with only the image parts colored red.

Auöh the Eotbild could be on a with ethanol "moistened Writing paper are transferred. Furthermore, the color image could be applied to the above, loaded with water

09812/1487

Moistened transfer paper with gelatin layer transfer will.

Even if the polymer image by a yellow dye , Solar Pure Yellow 8 G, G. Γ. Acid Yellow 7, or Tartrazine C.I. Acid Yellow 23, colored and with washed in a buffer solution with a pH of 5.0 a yellow image was obtained and the image could be on writing paper moistened with methanol or the above, water-moistened paper with a gelatin layer can be transferred.

When the above reaction is repeated at pH 11.5 using 2,3-dioxynaphthalene (Compound 17) instead of 1,2-diaminonaphthalene for 30 minutes became practically the same Get results.

Example 4

The same photographic photosensitive film as in Example 2 was exposed as in Example 2 and in a solution of the following composition, which contained the reducing agents listed in Table I, processed:

Methacrylic acid 58.9 ml

Sodium carbonate (monohydrate) 4-3.0 g

Reducing agent according to Table I.

Potassium metabisulphite 3.0 g

Water 87.5 ml

2n sodium hydroxide necessary amount for

Adjustment of the pH value to the value given in table I.

009 81 2XU 87

after a processing during the in Table I. The film was fixed at 30 ° C. for the period indicated and washed with · water as in Example /, where a Image from polymethacrylic acid was obtained, which by a T ^ 'ige solution of a basic dye, Rhodamine 6 GCP, was stained. The permeability densities opposite green light were exposed to and the unexposed parts of the photographic film measured before and after staining. Type of reducing agent, pH of the system during processing, processing period and the optical densities before and after staining are summarized in Table I.

009812/14 87

Table I - 1

No reducing agent

Amount d. Processing density of the density of the reduction period not exposed by means of (g) (min.) ned area area

PH

α-naphthol

i-Ifaphthol-2-potassium sulfonate 1-Uaphtho1-4-sodium sulfonate i-ITaphthol-5-sodium sulfonate β-haphthol

2-Hydroxy-1-naphthaldehyde 2-ITaphthaol sodium sulfonate 2-sodium-6-sodium sulfonate 2-ITaphth.ol-7-sodium sulfonate 2-lTaphthfll-8-sodium sulfonate

2-hydroxy-1-naphthoic acid

m-N- (2-hydroxy-3-naphthoylphenylenediamine

ß- (2-Hydroxy-3-naphthoyl) aminoethanol

α-ETitroso-β-naphthol Naphtliol orange

1- (1-Hydroxy-2-naphthylazo) -5-thiitro-2-naphthol-4-sodium sulfonate

.2,3-naphthalenediol

2,3-dihydroxynaphthalene-6-sodium sulfonate

1,5-hydroxy naphthalene

CD 7th O CO 8th CO 9 10 J * 11th OO -O 12th

15th before after before after 11.53 I. 2.05 2Ό 0.22 0.64 0.72 2.41 H., 55 I.
VJl
VJI 1.18 50 0.10 1.07 0.11 2.88 11.55 1.07 ■ 30th 0.09 1.16 0.09 1.41 11.50 1.11 30th 0.12 1.30 0.13 2.25 11.50 6.48 50 0.08 0.71 o, Q9 ^ 2.54 11.50 7.74 50 0.14 0.54 0.1.6 1.90 11.60 11.07 70 0.07 0.35 0.09 0.48 11.50 11.07 40 0.10 1.46 0.14 1.68 11.33 11.07 40
40 0.25 1.12 0.20 1.78 11.50
11.50 11.07
8.46 0.13
0.17 1.60
1.00 0.14
0.18 2.09
2.23

0.22 3.10 0.32 3.62

10.40 70 0.10 0.61 0.13 2.51 9.00 approx 0.08 70 0.07 0.46 0.08 1.07 9.10 1.00 70 0.10 0.37 0.12 1/64 11.55 GD 0.50 30th 0.40 1.37 0.44 2.73 11.45 OO 7.20 15th 0.17 0.92 0.68 3.70 11.50 11.79 40 0.08 0.28 0.06 1.32 11.50 7.20 20th 0.08 0.55 0.28 1.63 9.00

No reducing agent

20 1,7-dihydroxynaphthaJin

21 1 ^ -dihydroxy-ö-naphthoic acid

22 α-naphthylamine

23 ß-Diethylaminoethyl-α-naphthylamine '

24 thionalide

ο 25 2-naphthylamine-8-sodium

o sulfonate

oo 26 2-N "aphthylamine-4,8-disodium

- ». sulf onate ^ 27 1,2-naphthalene diamine ^ 28 1,5-naphthalenediamine 29 ^ -amino-S-naphthol-S, 6-di- ■ * · * ■ sulfonic acid

30 1-Amino-2-naphthol-4-sodium sulfonate

31 1-amino-5-naphthol

32 5-methaacryloylamino-ynaphthol

33 8-oxyquinoline

34 4,8-dihydroxyquinoline-2-carboxylic acid

35 4-Hydroxyquinoline-2-cartonic acid

m- 0.71 Table I. - 2nd after Density of
exposed
area after pH Amount d.
induction
by means of (g) 7.11 , Processing
time
(Min.) 0.35 before 1.84 14.35 Density of
non-apo-
ned area 1.34 ' 0.14 2.10 9.15 0.16 m-
0.01 30th before 0.42 0.10 0.57. 9.05V 0.156 7.16 60 0.08 0.52 0.05 0.66 9.05 ^V 0.44 10.22 50 0.10 0.69 0.12 1.77 10.50 8.32 6.53 70 0.08 0.43 0.16 1.12 10.50 3.52 6.00 70 0.12 0.41 0.07 0.91 ti, 50 10.04 8.50 70 0.15 0.25 0.15 2.93 11.50 70 0.09 0.30 0.48 1.90 9.00 10 0.10 0.85 0.16 2.54 11.50 .30 0.09 0.51 0.12 1.41 11.50 20th 0.11 0.84 0.22 3.10 9.03 40 0.12 0.25 1.21 1.80 11.50 7th 0.12 0.22 0.26 0.56 11.50 25th 0.22 0.29 0.08 2.24 11.50 70 0.18 0.36 0.12 0.63 11.50 30th 0.08 0.12 11.50 70 0.09 0.1T

VJ «

CD

OO

Mr. Reducing agent

36 i-Naphthol-3-sulfonamide sodium salt

37 2,4-Bichloro-i-naphthol

38 2,3-diaminonaphthalene

Table I. - 3 after Density of
exposed
area after pH 50
50
50 Amount of
Reduction
by means of (g) Processing
time
(Min.) 2.51
3.70
0.62 before 3.34
above
4th
2.44 Density of
nonexpo
ned area 0.19
1.05
0.07 11
11
11. 1.00
0.96
3.50 30th
30th
T5 before 0.18
0.99
0.07

K> CO

Ul

CD

ro

OD OD

From the above values it follows that the density of the color image is higher in the exposed parts than in the unexposed parts and thus the exposed parts were selectively colored. This was also confirmed by the fact that after the silver image was removed from each sample with the Farmer reducing agent, a clear red image was obtained. ,

Ytenn as a reducing agent compound 13 or 14 was used, the increase in density was large and then a clear, red image was obtained even without the fading of the silver with the reducing agent Farmer received. The color images obtained could also can be transferred to writing papers using methanol as in Example 3.

Example 5

Using the following films A and B was made the polymerization of a system made of sodium methacrylate and 2,3-haphthalenediol (compound 17).

FlIaA: After a base coat had been applied to both surfaces of a cellulose triacetate carrier, a surface was covered with an antihalation layer. The other surface was covered with a medium grain gelatin silver halide emulsion containing about 225 g gelatin and about 0.015 mole iodine and about 0.985 mole bromine per 1 pint of silver and incorporated about 0.5 g mucochloric acid per 100 g gelatin as a hardening agent A suitable stabilizer and a suitable surface-active agent, so that the layer contained 60 mg of silver per 100 ca ⁵ . At-

009812 / U87

Finally, a protective layer made of gelatin was added about 1 micron thick is applied to the emulsion layer. The film thus made is iet from the to the production of positives by photogravure used type.

Film B: A film base with layers of primer and an antihalation layer as in Film A. coated with a fine grain gelatin-silver halide emulsion comprising about 204 grams of gelatin and about 0.012 mole Iodine and about 0.988 moles of bromine per 1 mole of silver, sensitized by a rhodan complex of monovalent gold, contained and incorporated 0.3 g of 6-methyl-4-hydroxy-1,3-3a, 7-tetraazaindene 1 mole of silver each as stabilizer, about 0.7 g of mucochloric acid per 100 x g of gelatin as a hardening agent and a suitable surfactant so that the layer contained 60 mg of silver per 100 cm. There was also a protective layer made of gelatin applied to the emulsion layer at a thickness of about 0.8 microns. The produced in this way, photographic photosensitive film is of the type used to produce line images or hard images. Positives of continuous tinting by photogravure used Art.

The two film samples were exposed as in Example 2 and processed in a solution of the following composition:

Sodium methacrylate 75 g

2,3-naphthalenediol (Compound 17) 0.72 g Potassium metabisulphite 3.0g

Water 75 ml

2n sodium hydroxide necessary amount for

Adjustment of the pH value to 11.5

009 81 2 / U 8 7

After the films for 20 minutes at 30 ° C after being edited, the images became faint brown obtain. Each of the samples was fixed and washed as in Example 3 and divided into two parts, one of which was using Rhodamine 6 GCP was dyed as in Example 4. After drying became the density of the colored sample and the unprocessed Sample as in Example 4, the results are summarized in Table II:

density
ned Tabel II exposed lim before the
coloring the non-expo
area Density of
area after
coloring 0.06 after
coloring before the
coloring 2.73 A. 0.06 0.50 0.07 2.28 B. 0.43 0.07

A color image was formed in the exposed areas, although the formation of a silver image was hardly observed, indicating that the polymerization was occurring the reduction of a very small amount of silver could be initiated.

Furthermore, each colored sample was moistened with water under pressure on the surface of a transfer paper a, as used in Example 3 and treated with an aqueous solution containing i # sodium bicarbonate wetted and allowed to stand for 3 minutes, after which the transfer paper was removed from the sample and obtain a color reproduction on the transfer paper became.

009812 / U87

Example 6

Six of the same films as in Example 2 were made with light of 50 lux for 1 second through an optical Step wedge exposed with a step difference of 0.15 and processed in solutions of the following compositions. This example shows the effect of a common developing agent.

Sample No. 1 2 34 5 6 Component

Sodium methacrylate (g) 100 100 100 180 100 100

«-Naphthol (g) 1.73 1.73 1.73

2,3-naphthalenediol 0 0.96 0.96 0.96

(ß)

Ka te chin (mg) 0.171.7

p-methylaminophenol sulfate (mg) potassium metabisulfite (g) water (ml)

2N sodium hydroxide required amount for adjustment

the pH values of the systems to 11.5

After processing for 10 minutes at 30 ° C., each sample was processed further as in Example 4. After sufficient fixation and washing, the samples were cut into two parts, one of which was treated in the Farmer reducing agent to completely bleach the silver. In addition, for samples 1, 2 and 3, the optical densities were determined in the 5th stage and in samples 4, 5 and 6 the optical densities in the 6th stage were determined using a green filter

1 4th 4th 4th 0.01 0.1 '4 00 100 100 4th 4th 100 100 100

009812/1487

certainly; the results are given in Table III.

Density of
nonexpo
ned area Table III Number of output stage,
the dyeing
is accessible sample
No. 0.26 Density of
exposed
area 8th 1 0.28 0.44 10 2 0.25 0.72 11th 3 0.27 0.93 10 4th 0.61 1.10 11th 5 0.44 ¹ .5 ¹ 11th 6th 1.59

The density listed above corresponds to Amount of dye colored on the selectively formed polymer corresponding to the amount of exposure and consequently corresponds to the amount of that formed Polymers. The number of the final stage accessible to coloring, which is given in the table above, denotes the number of stages through which the increase in color density could be observed in comparison to veiled Split when the specimen thus dyed and bleached was observed with the naked eye. I.e. the number corresponds to the minimum amount of exposure required to selectively form the polymer, so that the larger the number of final stages, the higher the sensitivity of the film.

Because the difference of a level of applied optical Wedge was 0.15, the result means that Sample 2 two levels higher than Sample 1 in terms of

09812/1487

Number of the final stage according to Table III was that the sample 2 the same degree of polymerization as example 1 at half that required for sample 1 Suspension amount. In other words, the development, treatment solution has the same effect as in the case where the sample was exposed twice as long in the processing of the sample in the one used for processing "sample 1" Development solution. Also when comparing sample 4 with sample 6, the density increased accordingly a so-called haze, however, was when the optical densities at the same 6th level were compared , the increase in the density of dyeing in Sample 4 was far greater, and it was confirmed that the Amount of polymerization in the same amount of exposure polymer formed in sample 4 was larger. It was thus confirmed that by applying a conventional developing agent together with the reducing agent according to the invention, the polymerization of the system is effectively favored.

Example 7

Five film samples were produced as in Example 6 and, after exposure, they were processed in a solution of the following composition. In this Example is the effect of using a quaterary Salt shown with the reducing agent according to the invention. Laujzylpyridiniumohlorid was used as a quaternary salt used.

009812/1487

Sample no, component

Sodium methacrylate (g)

2,3-haphthalenediol (g)

1 $ Lauryl pyridine urachloride (ml) potassium metabisulphite (g) Ml water)

2n-iiatrium hydroxide required amount for adjustment

of the system to 11.5

After processing for 1: 0 minutes at 30 ° C., the samples were processed further as in Example 6 The results are summarized in Table V «

100 100 100 100 100 0 * 96 0.96 0.96 0.96 0.96 2.5 9 22.5 40 4th 4th 4th 4th 4th 100 100 100 100 100

Table Y 1.10
1.91
1.97
2.15
1.77 Number of end
Btufe that the
Coloring access
is borrowed Trial
Kr _e Density of density of
non-expo- 6th level
ned area 10
11th
12th
12th
12 ' 1
2
3
4th
5 .0.27
0.51
0.46
0.46
0.53

The analysis of the values can be carried out as in Example 6. From the results, it can be seen that in the case of using the quaternary salt together with the reducing agent according to the invention, practically the same amount of polymer was obtained when the amount of exposure was lower or when the processing period was shorter.

009812/1487

Example 8

The same film as in Example 2 was exposed to X-rays. Then the Film in the solution with compound 17 according to example 4 processed.

The exposure to X-rays was carried out using a Cobalt C beam tube from Philips Co. at 30 kv and 10 ma. The sample was the X-ray tube at a distance of 1 cm from the window of the X-ray tube exposed while part of the sample is covered with a razor blade 0.2 mm thick became.

The samples exposed for 1 second, 3 seconds or 10 seconds were then exposed during Machined for 20 minutes at 30 ° C. In this procedure only the parts exposed to the X-rays gave silver images and when subjected to image reproduction After the post-processing described in Example 7, the image parts were colored, which proves that polymethacrylic acid had been formed.

The method according to the invention can thus also are applied to silver halide emulsion layers, the rays of high energy such as X-rays, were exposed. ■ .. '

009812/1487

Claims (4)

Claims 'Iy method sur Preparation of Polymer images, characterized in that at least one Vinylidenmonomeres or Vinylmonoineres exposure subjected to a photographic silver halide emulsion layer having a latent image in the presence of at least one compound corresponding to the following general formulas ι.
(1) α-waphthol or derivatives thereof ' '' OH wherein R «is a hydrogen atom, a sulfon group, a substituted arylazo group or a chlorine group, R ~ a hydrogen atom or a sulfamoyl group, R. a A hydrogen atom, a sulfon group or a chlorine atom, Rc is a hydrogen atom, a sulfone group, a hydroxyl group, an amino group or an acylamino group, Rg a hydrogen atom, a carboxyl group or a Sulfon group and R- denote a hydrogen atom, a hydroxyl group or an amino group, (2) ß-Uaphthol or derivatives thereof 009812/1 U 8 7 where R | a hydrogen atom, a formyl group, a sulfon group, a carboxyl group, a nitroso group, an arylazo group or an amino group, R, a hydrogen atom, a group -CONHR '(R ¹ represents an aryl group or alkyl group) or a hydroxyl group, Ri is a hydrogen atom or a Sulfon group, Rc is a hydrogen atom or a nitroso group and Rg, R ₇ and Rq each represent a hydrogen atom or a sulfon group,,. (3) oc-naphthylamine or derivatives thereof wherein Rp is a hydrogen atom, a substituted alkyl group, an amino group or a hydroxyl group ", R. is a hydrogen atom or a SuIfongruppe and Rc is a hydrogen atom, an amino group or a hydroxyl _i group mean <j (4) β-naphthylamine or derivatives thereof 009812/1487 wherein R-, a hydrogen atom or an amino group, R, a hydrogen atom, a sulfonic group or an amino group, R. a hydrogen atom or a sulfonic group, 'Rg a hydrogen atom or a sulfonic group and R ₈
represent a hydrogen atom, a sulfonic group or a hydroxyl group, and
(5) Oxyquinoline derivatives in which Rq is a hydroxyl group, R _{2 is} a hydrogen atom or a carboxyl group and R. is a hydrogen atom or a hydroxyl group or in which, if R. is a hydroxyl group, R _{2 is} a carboxyl group and Rg is a hydrogen atom, and polymerizing the monomer selectively in the areas bearing the "latent image". 2. The method according to claim 1, characterized in that that the polymerization reaction in the presence of sulfite ions - is carried out. 3. The method according to claim 1 or 2, characterized in that the polymerization in the presence of a small amount of a developing agent or a quaternary one Salt is carried out. 4. The method according to claim 1 to 3, characterized ge indicates that the polymer image formed continues selectively with a dye of opposite charge 09812 / .H8 to charge the polymer when the polymer image is electrolytic dissociated or combined with hydrogen cations, is colored. 00981-2 / U87