DE1961920B - Process for the production of polymer images - Google Patents

Description

A- ^ C = CJ _n -B

in which A and B each represent an OH, NH ₂ or NHR group (where R is an alkyl or aryl radical) and π is an integer up to below 7, is used.

6. The method according to any one of claims and 5, characterized in that the exposed Silver halide emulsion layer first in a solution of a conventional photographic silver halide developer, in particular l-aryl-3-oxopyrazolidine or l-aryl-3-iminopyrazolidine or p-methylaminophenol sulfate, developed and subsequently carrying out the polymerization by treating with a solution of the hydrazine derivative.

(H)

where R _{4 is} a hydrogen atom, an alkyl group, a substituted alkyl group, an aryl group or a substituted aryl group, R _{5 is} an alkyl group, a substituted furyl group, a chlorine atom or an aryl group, where the radicals R ₄ and R ₅ together have carbon atoms, nitrogen atoms or sulfur atoms containing ring S5, and R _{6 is} a hydrogen atom, a carbamoyl group or a substituted oxalyl group or an aryl group, where the radicals R ₆ and R ₄ can form a ring, is used.

2. The method according to claim 1, characterized in that that is developed in the presence of sulfite ions.

3. The method according to claim 1, characterized in that the polymer image is selectively with a dye which, when electronically dissociated, has opposite charges to the Has charges of the polymer image. The invention relates to a method of manufacture of polymer images in which one in an imagewise exposed photographic silver halide emulsion layer contained latent image by the action of at least one monomeric vinyl or Vinylidene compound and at least one reducing agent with image-wise polymerization of the monomeric vinyl or vinylidene compound is developed.

There are already various processes for producing polymer images by photopolymerization known from vinyl compounds. It is further known to use photopolymerization directly of a silver halide as a catalyst (British patent specification 866 631 and S. L e ν in ο s and collaborators "Photographic Science & Engineering", Vol. 6, pp. 222 to 226 [1962]). It is believed, that in this reaction the product formed by photodecomposition of the silver halide serves directly as a polymerization catalyst, however, the photographic sensitivity is that Reaction not as high as in the reduction of exposed silver halide particles with the usual one photographic development.

It is also known to generate polymer images using a silver image or not converted silver halide, which after the development of an exposed silver halide emulsion layer is present in an ordinary developer as a catalyst for image-wise polymerization set vinyl compounds (Belgian patent specification 642 477).

This method, however, has the disadvantage that development and polymerization are carried out separately Need to become.

It is now of great theoretical interest, the imagewise polymerization of vinyl compounds

by the oxidation product or an intermediate product of reducing compounds that are involved in the development an exposed silver halide emulsion layer in the presence of vinyl compounds were to be carried out, as can be expected that in such a method, chain polymerization by the enhancement effect of development is facilitated. It is already known this implementation using an aromatic reducing agent with at least two hydroxyl amino or alkyl or aryl substituted amino groups in the ortho or para positions to one another on Carry out benzene ring (USA.-Patent 3019 104 and G. Oster "Nature", Vol. 180, p. 1275 [1957]). However, only an increase in the optical density of the silver image was observed here An increase in the viscosity of the reaction system or the generation of heat of reaction, soft directly Prove the formation of a high molecular compound, as well as the isolation of one by the Implementation of the high molecular weight compound has not yet been confirmed. (See also S. L e ν i η ο s and F. W. H. M u 11 e r, »Photographic Science & Engineering ", Vol. 6, p. 222 [1962].)

It is also a process for producing polymer images by treating an image-wise exposed silver halide emulsion layer containing a monomeric vinyl compound and a reducing compound known (Belgian patent 699 535), in which as reducing compounds Resorcinol, m-aminophenol or their derivatives are used, these derivatives not being used Amino or hydroxyl group in the o- or p-position own.

It is also already known to use hydrazine as a silver halide developer to use (for example G. I. P. L e ν e η s ο n, »Journal of Photographic Science ", 15 (4), pp. 158 to 163 [1967]), where it is also described that it is used as a developer at high pH can be used. It is also known that an aryl hydrazine, an alkyl hydrazine and semicarbazide can be used as a developer (C. E. K. M e s, "The Theory of the Photographic Process", Chapter 14). Hydrazines are also used as reducing agents, polymerization accelerators, or polymerization initiators known for redox polymerizations (Italian patent 541 925, German patent 1,028,782, U.S. Patent 2,822,368, German Patent 1,032,536, U.S. Patent 2,947,118 and K. Rajat et al, Journal of Polymer Science, Part C, No. 16, p. 141 [1966]). However, are the polymerizations described in the above references all so-called redox polymerizations, d. That is, the polymerization of the vinyl monomers takes place in the entire areas where Oxidizing agents and reducing agents are present and independent of the exposure.

The object of the invention is to provide a method for producing polymer images in which a latent contained in an imagewise exposed photographic silver halide emulsion layer Image in the presence of at least one monomeric vinyl or vinylidene compound and at least of a reducing agent is developed and in which dyeable polymer images are obtained that can be transferred, with a large number of copies obtainable from a polymer image is. Furthermore, the development of the polymer images should be carried out in a wide pH range can be.

The invention relates to a process for the production of polymer images in which one in one imagewise exposed photographic silver halide emulsion layer through Action of at least one monomeric vinyl or vinylidene compound and at least one reducing agent is developed with image-wise polymerization of the vinyl or vinylidene compound, and is characterized in that the reducing agent used is at least one hydrazine derivative of the formula I.

Ν — Ν

R ₂

(D

R ₃

wherein R _{1 represents} a hydrogen, a sulfonic group, a water-soluble metal salt or ammonium salt of the sulfonic group, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, an acyl group, a substituted acyl group, an arylhydrazinocarbonyl group, a thiocarbamoyl group, an arylazothiocarbonyl group, an arylsulfonyl group or a substituted arylsulfonyl group, R _{2 is} a hydrogen atom, an alkyl group, a substituted alkyl group or an aryl group, where the radicals R ₁ and R _{2 can} together form a ring containing carbon atoms, oxygen atoms or nitrogen atoms, and R _{3 is} a hydrogen atom, a sulfonic group water-soluble metal salt or ammonium salt of the sulfone group, an aryl group, an acyl group or a substituted acyl group, where the radicals R ₁ and R _{3 can} together form a ring, or of the formula II

I = NNR ₆

(II)

wherein R _{4 is} a hydrogen atom, an alkyl group, a substituted alkyl group, an aryl group or a substituted aryl group, R _{5 is} an alkyl group, a substituted furyl group, a chlorine atom or an aryl group, where the radicals R ₄ and R ₅ together have carbon atoms, nitrogen atoms or sulfur atoms containing ring, and R _{6 is} a hydrogen atom, a carbamoyl group, or a substituted oxalyl group or an aryl group, where the radicals R ₆ and R ₄ can form a ring, is used.

It has been found that the polymerization occurs in the layer parts where the silver halide particles Own development centers takes place at a higher rate than in the shift parts in which the silver halide grains have no development centers, and consequently that by suitable ones Choice of the reaction conditions and the reaction time the polymerization selectively only on the Areas of the silver halide photographic emulsion layer in which the silver halide particles have development centers.

The invention achieves that using of the above compounds of the formula I and II easily transferable polymer color images can be obtained, due to the stability of the compounds mentioned Alkali can develop in a wide range of pH values.

As a method of forming a polymer image by utilizing the photosensitivity of silver halide the so-called tanning development is known, in the case of gelatine due to the oxidation product a super halide developer is crosslinked. However In these known methods, the image produced is dependent on the image-forming material cross-linked gelatin limited

In contrast, according to the invention, polymer images with various properties as desired by suitable choice of the one to be used Vinyl compounds can be obtained and thus polymer images with properties can be obtained as they cannot be obtained with the crosslinking of gelatine (affinity for coloring, chemical Resistance).

Both ordinary negative photographic emulsions can be used in the process of the present invention as well as direct positive halogen silver emulsions can be used. With the latter the latent image is formed by being uniform in the layer obtained by fogging Development centers can be made to disappear in an image-wise manner by means of an image-wise dressing. The development then provides a positive picture (James & Huggins, »Fundamentals of Photographic Theory ", 2nd Edition, Chapters 3 and 4, Morgam & Morgam Co .. 1960).

Conventional photographic silver chloride emulsions can be used as negative silver halide emulsions. Silver bromide. Silver chlorobromide, silver iodobromide and silver chloroiodobromide emulsions can be used, which can be chemically or optically sensitized. Farther For example, the silver halide photographic emulsions can be any of those used in conventional photographic Process usual stabilizer included.

The silver halide direct positive emulsions used in the invention can, by applying solarization, the Herschel effect, the Clayden effect or the Sabatier effect can be produced. These effects are described in Chapters 6 and 7 of C.E.K. Mees, “The Theory of the Photographic Process ", 2nd Edition, McMillan Co., 1954. Method of manufacture a direct positive silver halide emulsion by solarization are in the British patents 443 245 and 462 730. Process for the preparation of direct positive silver halide emulsions using the Herschel effect are in British Pat. No. 667,206 and US Pat U.S. Patent 2,857,273.

The photographic emulsions used according to the invention consist of dispersion systems, in which the silver halide grains in a solution of a polymeric binder, especially gelatin, are dispersed. In addition to gelatin, synthetic high-polymer binders, for example polyvinyl alcohol, polyvinyl pyrrolidone or polyacrylamide, as well as derivatives of natural high polymers such as carboxyethyl cellulose, Celluloseoxyethyl ether or dextran, either alone or in admixture with gelatin, can be used (F. Ewa, »Journal for Scientific Photographic, Photophysics and Photochemistry ", Vol. 52, pp. 1 to 24 (1957]).

The hydrazines of the above formulas used according to the invention can be used as substituted alkyl groups and substituted acyl groups contain those with halogen, carboxyl, Sulfonyl, hydroxyl, amino, alkylamino, acylamino or arylamino groups are substituted, or they can be substituted alkyl groups with functional groups, such as ether, carbonyl or ester groups, include. Examples of substituted aryl groups and arylsulfonyl groups are those which are associated with halogen, nitro, nitroso, sulfonyl, hydroxyl, Carboxyl, acyl, aloxy, amino, alkyl, acylamino or alkylamino groups are substituted.

Examples of the hydrazines used according to the invention are given below:

1. hydrazine sulfate
NH ₂ NH ₂ -H ₂ SO ₄

2 hydrazine D-tartrate
NH ₂ NH ₂ - C ₄ H ₆ O ₆

3. methylhydrazine
H ₃ CNHNH ₂

4. 2-hydroxyethyl hydrazine
HOC ₂ H ₄ NHNH ₂

5. Benzyl hydrazine

CH ₂ -NHNH ₂

6. N, N-dimethylhydrazine
H ₃ C

N-NH ₂

H ₃ C

7. N-amino homopiperidine
CH ₂ -CH ₂

H ₂ C N -NH ₂

CH ₂

8. N-aminomorpholine
CH ₂ -CH,

O N-NH ₂

CH ₂ -CH ₂

9. N-Benzyl-N-phenylhydrazine

N-NH ₂ CH ₂

10. N-methyl-N-phenylhydrazine H ₃ C

N-NH ₂

11. o-nitrophenyl hydrazine

NO ₂

NHNH ₂

12. p-methylphenylhydrazine

13. Ammonium hydrazine disulfonate _{H 4} NO _{3 SNHNHSo 3} NH ₄

14. Azobenzolphenylhydrazine - ^ - sulfonic acid / ~~ V- N = N - ^< \ ~ \ - NHNHSO ₃ H

15. Benzoyl hydrazine

CONHNH ₂

16. α-Picolinic hydrazide

-CONHNH ₂

17. Isonicotinic acid hydrazide CONHNH ₂

18. 1-Hydroxy-S-naphthoetireliydrazide OH

CONHNH ₂

19. Girard T reagent (H ₃ C) ₃ NCH ₂ CONHNH ₂

20. Oxalylhydrazine (CONHNBi) ₂

21. Adipic hydrazine

- (CH ₂ CH ₂ - CONHNH ₂ ) ₂

22. Phenylglycine hydrazine

NH - CH ₂ - CONHNH ₂

23. Luminol H ₇ NO

AA

T NH

1>

NH

24. Carbohydrazine

NH ₂ NHCONHNh ₂

25. / S-Acetylphenylhydrazine / "S-NHNHCOCH ₃

26. Diphenyl carbazide

NHNHCON = N

27. Di - ^ - naphthylthiocarbazone S.

N = N-C-NH-NH

28. Thiosemicarbazide hydrochloride

Il

NH ₂ NHC - NH ₂ - HQ

29. Dithizone

[= N - C-NHNH -f \

30. Nitrofurazone

\ —1

O ₂ NO CH = N-NH-C-NH ₂

31. Cyclopentanone semicarbazone

H ₂ CC = N-NH-C-NH ₂

H ₂ C CH ₂

^ ⁵ 32.Benzene-sulfonylhydrazine SO _{2 NHNH 2}

209538/209

33. p-Toluenesulfonylhydrazine

34. Ethyl a-butyl acetoacetate semicarbazone

I CH

CH ₃ -C COOC ₂ H ₅

NH \

CO

NH ₂

35. Acetophenone hydrazone H ₃ C

C = N-NH ₂

36. p-Aminoacetophenone hydrazine

H ₃ C

= N-NH ₂

H ₂ N

37. o-Tolylhydrazine

CH ₃

NHNH ₂

38. m-Tolylhydrazine

H ₃ C NHNH ₂

39- p-nitrophenylhydrazine NHNH ₂

41. 3-chloroindazole Cl

42. 2-pyrazoline HC CH ₂

N H

43. 3-methylbenzothiazolone hydrazone

f YC = N-NH ₂ 25 N

CH ₃

44. m-Hydroxybenzaldehyde semicarbazone ³⁰ OH

CH = N-NHCONH ₂

45. Phenylhydrazine p-toluenesulfonate

NHNHSO ₂ -

46. 4-Amino-1,2,4-triazole

N-NH ₂

50 47. Acetone-phenylhydrazone H ₃ C

C = N-NH

H ₃ C

NO ₂

Phenylhydrazine nitrate NHNH ₂ (HNOj) ₂

48. Methyl ester of levulinic acid phenylhydrazone 60 H ₃ C CH ₂ CH ₂ CQiCH ₃

ν— around.

49. Cupferazon

HH ₂ C

H ₂ C - CH ₂

H ₂ C-CH ₂

C = NHCOCONHN = C CH ₂

H ₂ C-CH ₂ H ₂ C-CH ₂

50. 4-phenyl semicarbazide

NHCONHNH ₂

51. l-Phenyl-S-pyrazolone-ß-carboxylic acid hydrazide H ₂ NNHCO

52. Phthalic acid monophenyl hydrazide COOH

CONHNH 53. / J-phenoxyacetic acid phenylhydrazide

OCH ₂ CONHNH

54. Succinic acid monophenyl hydrazide

NHNHCOCH ₂ Ch ₂ COOH 55. / J-acetyl-p-tolyl hydrazide

H ₃ C-

-NHNHCOCH ₃

56. l-Phenyl-4Hnethyir-3- ^ yrazoüdoii

led hydrazine derivatives is done until now not clarified, but based on the fact that a compound generally causing radical polymerization is used and

S the polymerization can be carried out in aqueous solution and that by an inhibitor for radical polymerization the reaction is delayed, inferred that the polymerization after a radical mechanism expires however it is not clarified whether the radicals are directly through the reaction of the silver halide and the hydrazine derivatives listed above are formed or whether the radicals by further reaction with water or Oxygen can be formed in the system.

ι s If the vinyl connection to the reaction system is added after reducing the exposed silver halide particles with the above hydrazine derivative, the occurrence of Polymerization reaction observed. As a result is it is clear that the polymerization of the vinyl compound occurs simultaneously when the silver halide is reduced. Therefore, it is believed that an intermediate of silver halide and the hydrazine derivative contributes to initiation of the reaction

It can be assumed that a radical is formed by the oxidation of N ₂ H ₄ (L even son):

N ₂ H ₄ -N ₂ H ₄ -

-e

- »N ₂ H ₃ + H ⁺ (1)

- N ₂ H ₃ - + H ⁺ U-II)

N ₂ H ₃ - + Ag ⁺ -

N ₂ H ₃ + Ag

(MI)

Formula 1 emerged from a study of oxidation using an iron salt obtained as an oxidizing agent, which is also an oxidizing agent with an electron in the alkaline state, such as AgX

It is also known that the radical N ₂ H _{3 is} easily decomposed in nitrogen, from experiments on electrolytic oxidation (GV Vitritskaya & V. S. Daniel-Bek, "Elektro Kimiya", 3 [8], pp. 973 to 977 [1967]) (Chemical Abstract, 67.113165 J), although the experiments in the acidic Field, the hydrazine radical was observed using electron spin resonance absorption spectrum (J. Q. Adams & J. R. Thomas, "Journal of Chemical Physics", Vol. 39, p. 1904 £ 1963]).

Although the constitution of the intermediate oxidation product of the hydrazine derivative, which the polymerization of the Vifiylinonoineren t within the framework of The initiation of the invention has not yet been clarified The fact that the polymerization occurs as a free radical reaction is assumed that the following intermediates are bathed before the polymerization reaction:

These compounds can be prepared according to known methods (R.B. Wagner, "Synthetic Organic Chemistry", New York, 1953, John Wiley & Sons Co.) or are commercially available.

The reaction mechanism according to which the polymerization of the vinyl compounds as a result of the reduction of the Snberfaalogemd with the above R, HO

\ I I

(a) NN ^ CR ₃

<b) RNHN = C-R- * RN-N ==

N-N = C-R

(c) RNHNH ₂

RN ₂ H ₃ -

(H)

Although various other mechanisms may be envisaged, it is believed that a Radical of type (I) or (II) causes the polymerization of the vinyl or vinylidene monomers. the Polymerization of the monomers is carried out in the context of the invention by the oxidation of the silver halide formed radical of the hydrazine causes, and the reaction rate is determined by the Affects the reaction rate of the silver halide, i.e. the presence or absence of the latent image in the silver halide photographic emulsion layer.

If the polymerization reaction is stopped after a suitable period of time, the high molecular weight Connection selectively only to those by electromagnetic waves or particle radiation irradiated areas are formed, but if the polymerization reaction is further prolonged the polymer is also formed on the non-irradiated areas. However, this appearance is the same such as the so-called fogging which occurs when an exposed photographic silver halide emulsion layer is developed over a longer period of time, whereby not only the exposed areas, but also the unexposed areas become black in the same way. To that extent prevents this The practical applicability of the method according to the invention does not appear.

According to one embodiment of the invention, development takes place in the presence of sulfite ions. The sulfite ions can be added to the reaction system either in the form of a compound containing sulfite ions from the beginning, for example alkali or ammonium sulfites or bisulfites, or in the form of a compound which Sulphite ions resulting from hydrolysis, such as pyrosulphites the alkali metals or ammonium or the adducts of bisulfites with aldehydes, such as formaldehyde or glyoxal, can be added. Although the amount of sulfite ions to be added depends on the species and the amount of the reducing agent and the vinyl compound to be used, the pH of the system are more than 0.05, in particular more than 0.2 moles per liter of developer liquid effective.

It is known in the art to add a sulfite to photographic developers and in In these cases, it is believed that the sulfite is responsible for the auto-oxidation of the developer and the occurrence of a uneven development due to reaction with the oxidation product of the developer, for example Hydroquinone or p-aminophenyl (C. E. K. Mees, "The Theory of the Photographic Process ^! Edition, McMillan Co., 1954, p.652). It should be noted that, since in the context of the invention, the polymerization by the Oxidation intermediate formed from hydrazine, a hydrazide, resulting from reduction of the silver halide or a hydrazone is introduced, the polymerization accelerating effect by the Sulphites fundamentally different from the previously discussed effect of the same Removal of the oxidation product is in a common developer

If the sulfite simply removes the oxidation products as in the usual development process the polymerization would be inhibited rather than favored. Sulphites are also used as reducing agents for Oxidation reduction reactions are known and as a result it can be assumed that the polymer

sation is initiated by a silver halide sulfite ion system. However, in the frame The experiments carried out according to the invention practically no polymerization observed by such a system, when the reducing agents listed below were not present in the reaction system.

Although the mechanism of the action of the sulfite in the process according to the invention is not clear, it can be assumed that the sulfite the

¹ S Prevents the oxygen in the system from having a polymerisation-inhibiting effect.

According to a further embodiment of the invention, in the presence of an additional small amount developed by an ordinary photographic developer.

The development and the polymerization by the hydrazine derivatives used in the context of the invention can namely be favored if together with this a small amount of an ordinary photo-

graphic developing agent is used or the silver halide emulsion layer is used in an ordinary one Developer solution is preprocessed. This is a similar appearance to how. the development and Polymerization by a resorcinol, a metaaminophenol, a phenol, a 5-pyrazolone or a naphthol, favored by the use of a small amount of an ordinary developing agent will. As such ordinary photographic developers used in the invention There are two types of connections, one of which is the general basic structure

P4-

A-C = C-B

wherein A and B groups —OH, —NH ₂ or —NHR, R is an alkyl or aryl group or derivatives thereof and η is an integer, preferably less than 7, and the other type of compound consists of 1-aryl -3-oxopyrazolidines and l-aryl-3-iminopyrazolidines.

These ordinary photographic developers themselves have no effect of initiating the poly-

merization of vinyl compounds, however, the Favor the polymerization reaction by reducing the developing action of the reducing agent, which is the Effect to initiate the polymerization of the vinyl compounds has to demand.

The vinyl compounds which can be used in the context of the invention usually include liquid and solid compounds necessary for addition polymerization are capable, as well as mixtures thereof. Examples of such Vinyl compounds are acrylamide, acrylonitrile,

N-hydroxymethylacryiamide, methacrylamide, N-terL-butyacrylamide, Methacrylic acid, acrylic acid, caldum acrylate, Sodium acrylate, methyl methacrylate, methyl acrylate, Ethyl acrylate, vinylpyrrolidone, 2-vinylpyridm, + • Vinylpyridine, 2-methyl-N-uiinidazcJ, potassium vinylbenzenesulfonate and vinyl carbazole. For the present invention, compounds are nm Twei or more vinyl groups particularly suitable these compounds can be used alone or in a mixture with the

IS

I 961 920

the above compound having a vinyl group be used. Examples of such compounds with two or more vinyl groups are N, N'-methylenebisacrylamide, Ethylene glycol dimethacrylate, triethylene glycol dimethacrylate, Diethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, divinyl ether, Divinylbenzene, bisphenol A thin acrylate and trimethylolpropane trimethacrylate

In the context of the invention, water-soluble vinyl compounds are advantageously used, however, water-insoluble vinyl compounds can also be used by adding the compounds can be added to the reaction system as an emulsion. The emulsification needed to make those listed above The emulsion can be mixed in according to the usual methods using suitable stirring devices The presence of surfactants and / or polymeric binders can be carried out.

As electromagnetic waves or particle beams used in the context of the invention, All electromagnetic waves and particle beams can be used for the ordinary photographic light-sensitive emulsions are sensitive. This means that infrared rays, X-rays, y-rays, ultraviolet rays, electron beams or α-rays can be used.

Since the reduction and polymerization take place simultaneously, the reduction must be in the presence the vinyl compound or the vinyl compounds can be carried out, however, within the scope of Invention, both the vinyl compound and the above-mentioned hydrazine derivative can be used in the photographic field Emulsion layer are incorporated before exposure, or just one of these ingredients can be incorporated in the photographic emulsion layer before exposure, and the other can be added to the system after exposure. It is also possible to use both Add ingredients to the emulsion after exposure.

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

In general, the reaction according to the invention proceeds smoothly in an alkaline medium, but hangs the optimum pH of the reaction system depending on the type and concentration of silver halide Reducing agent and polymeric binder. In general, the polymerization reaction at a pH higher than about 8, preferably higher than 9, can be carried out.

In the case of using a photographic silver halide emulsion layer coated on a support the process can be carried out by applying the silver halide emulsion layer is immersed in an aqueous alkaline solution after irradiation. In this case it will The reducing agent or the vinyl compound is preferably incorporated into the aqueous alkaline solution.

The polymerization reaction taking place in the course of the process according to the invention can easily be terminated by acidifying the system, for example to a pH of less than 5, but the reaction can also be carried out by cooling, removing the reaction products by washing, by dissolving the silver halide in a photographic fixing solution or stopped by adding a polymerization inhibitor to the reaction system.
When a photosensitive layer is used which contains the silver halide and the monomeric vinyl compound dispersed in a binder, it is beneficial to add a small amount of a thermal polymerization inhibitor to prevent the spontaneous thermal polymerization of the vinyl compound.

to prevent attachment. As thermal polymerization inhibitors can all be used as thermal polymerization inhibitors for common free radicals Polymerizations known compounds are used. Examples of such compounds are p-MethoxyphenoL hydroquinone, alkylhydroquinones and 2,6-di-tert-butyl-p-cresol.

If the vinyl monomer is contained in the layer from the start, its weight is usually V30 up to 30 times, preferably ¹ Z ₄ . up to 4 times the weight of the polymeric binder. Furthermore, it is preferred that the amount of silver halide V20 is up to 2 times, preferably Vio up to V2 times the weight of the polymeric binder contained in the layer. Furthermore, if the reducing agent is contained in the layer, the amount of the reducing agent is favorably from VI to 20 mol per 1 mol of silver halide used. If a thermal polymerization inhibitor is used, the preferred amount of 10 ppm to ² I ₁₀₀ the weight of the vinyl monomers. If the vinyl compounds are added to the processing solution, it is usually preferred to dissolve them in as high a concentration as possible because the preferred concentration of the monomers is mainly determined by the solubility of the vinyl compounds in the processing solution. If the hydrazine derivatives are added to the processing solution as reducing agents, their optimal concentration depends on the nature of the derivatives used, but is preferably from 500 moles to 5 moles, preferably from 50 to 1 mole per 1 liter of solution.

As in the ordinary silver halide photographic process, any desired time interval can be used between exposure to electromagnetic waves or particle beams and development lie. In some cases it may vary according to the properties of the photographic used Emulsion and the conditions and the time interval that the emulsion layer is allowed to stand, the effect the exposure is reduced to some extent and in such a case the desired effect can be obtained can be obtained by increasing the exposure.

When using the method according to the invention for recording images, it is possible on the differences in solubility, light scattering, stickiness, and dye receptivity and other physical and chemical properties between the unreacted To make use of vinyl compounds and the resulting polymers. A relief image can be formed are dissolved by removing the unpolymerized layer parts after irradiation and polymerization taking advantage of the solubility difference between the polymerized layer parts and the unpolymerized layer parts is made so that the polymerized compound only remains in the irradiated areas.

In this case it is beneficial if this is in the The polymeric binder contained in the layer was washed away together with the unpolymerized vinyl compound will. It is therefore preferred, on the one hand, that the polymeric binder contained in the layer is a linear and practically uncrosslinked or is only so crosslinked that there is a chain fraction or Crosslinking rupture is accessible, and on the other hand that the polymerization of the vinyl compound The high molecular compound formed is a cross-linked compound with a so-called three-dimensional structure is. For this purpose, it is favorable to use a compound having a plurality of vinyl groups as described above listed, either alone or in combination with a compound with just one Use vinyl group. However, it is not essential, necessarily a connection with a plurality of vinyl groups as there are numerous cases where there is a great difference between the layer parts, contain the high molecular compound formed by polymerizing the vinyl compound, and the parts which do not contain such a high molecular compound occurs. Even then, that's that Case when the high molecular compound obtained is a water-soluble two-dimensional compound is because a reaction of the high molecular weight formed by polymerizing the vinyl compound Compound and the polymeric binder originally contained in the layer occurs, so z. B. in the case of polyacrylic acid as a polymer of the monomers Vinyl compound and gelatin as a binder.

The polymer image formed by the process according to the invention can be used for various printing processes can be applied.

The method according to the invention can also can be used to produce color images. Vinyl monomers, one for taking up charges through electronic dissociation or through addition of Have hydrogen cations capable group, used and then selectively the polymerizatbild with a Dyed dye that has the opposite charge to that of the polymer image. That on this Formed color image or colored image can be transferred to other image-receiving materials according to different manner Procedures are transferred.

According to a further embodiment of the invention, the polymer image is selectively made with a dye colored, the charges opposite to the charges of the electrolytic dissociation Having polymer image.

The addition polymerizable vinyl compounds that are used to accept charges through electrolytic Dissociations or by addition of hydrogen cations are capable and that in such color image formation processes which can be used according to the invention are those which lead to the formation of high molecular weight Compounds with negative charges (high molecular weight anions) are capable and those that lead to Capable of forming high molecular weight compounds with positive charges (high molecular weight cations) are.

Examples of vinyl compounds which form high molecular compounds with negative charges are vinyl compounds with carboxyl groups such as acrylic acid, methacrylic acid, itaconic acid and maleic acid, vinyl compounds which are metal salts or ammonium salts of the carboxyl group such as ammonium acrylate, sodium acrylate, potassium acrylate, calcium acrylate, magnesium acrylate, zinc acrylate, cadmium acrylate , Sodium methacrylate, calaum methacrylate, magnesium methacrylate, zinc methacrylate, cadmium methacrylate, sodium itaconate and sodium maleate, vinyl compounds with sulfonic acid groups, such as vinylsulfonic acid and p-vinylbenzenesulfonic acid or their metal salts or ammonium salts, such as ammonium, vinylsulfonate, sodium vinylsulfonate with vinylbenzene and potassium sulfonate compounds, examples of vinylsulfonate vinylsulfonate and potassium vinylsulfonate Form positive charges are vinyl compounds with a basic nitrogen atom, such as 2-vinylpyridine, 4-vinylpyridine, 5-vinyl-2-methylpyridine, N ₅ N ^ dimethylaminoethyl acrylate, Ν, Ν-dimethylaminoethyl methacrylate, N, N - diethylaminoethyl acrylate and Ν, Ν-diethylaminoethyl methacrylate or their quaternary salts, which were prepared by reacting the vinyl compounds with basic nitrogen atoms and methyl chloride, ethyl bromide, dimethyl sulfate, diethyl sulfate, methyl p-toluene. These compounds can be prepared by known methods or are commercially available. The above compounds can be used alone or in combination. They can also be used together with a water-soluble addition-polymerizable vinyl compound having no charges.

As dyes that are capable of forming charges during electrolytic dissociation and which are therefore used for the production of colored polymer images are generally used the usual acidic dyes and basic dyes are used. If a vinyl compound is used, which forms a polymer image from a high polymer with negative charges a basic dye is used for this. On the other hand, when a vinyl compound which is a high polymer is used Forms cation, an acidic dye must be used for staining.

If gelatin is used as a binder for the silver halide photographic emulsion, it must the staining can be carried out taking into account the isoelectric point of the gelatin, since gelatin is an amphoteric electrolyte. Gelatin has a negative charge at a higher one pH than the isoelectric point of gelatin and has a positive charge at a lower one pH as the isoelectric point. If, therefore, a polymer image from a compound of high Molecular weight with negative charge is formed, only the polymer, but not the gelatin colored when the emulsion layer containing the polymer image is at a lower pH than the isoelectric point of the gelatin in the emulsion layer is colored. Also can in this If only the polymer image is colored by first uniformly applying the gelatin silver halide emulsion layer colored with the polymer image with a basic dye at a higher pH than the isoelectric point of the gelatin and then the dye on the areas of the emulsion layer that do not have any polymer formed with a washing solution with a lower pH than the isoelectric point of gelatin being washed away.

In the case of coloring a polymer image with

A positive charge with an acidic dye can start the dyeing process at a higher pH as the isoelectric point of gelatin.

If the pH is too low or too high, the solubility of the dyes used is reduced, and it goes without saying that electrolytic dissociation of the high polymer to be charged will become hampered by it. The optimal pH range of the system depends on the type of vinyl compounds, the color and type of gelatin. In the case of using an ordinary lime-treated Gelatin with an isoelectric point of about 4.9, the pH range is preferably 2.5 to 4.5 when the polymer image is colored with a basic dye, and 5.0 to 8.0 if the polymer image is colored with an acidic dye.

Examples of the acidic dyes that can be used in the present process are C.I. Acid Yellow 7 (CI. 56 205), CI. Acid yellow 23 (CI. 19140). CI. Acid Red 1 (CI. 18050), CI. Acid Red 52 (CI. 45 100), CI. Acid Blue 9 (CI. 42 090), CI. acid Blue 45, C.I. Acid Blue 62 (C.I. 62 045) and similar compounds. Examples of basic dyes that useful in the present method are CI. basic yellow 1 (CI. 49 005), CI. basic Yellow 2 (C 1.41 000), CI. basic red 1 (C 1.45 160), CI. basic red 2 (CI. 50 240), CI. basic Blue 25 (CI. 52 025), CI. basic violet (CI. 42 555), CI. basic violet 10 (CI. 45 170) and similar connections. The Colorindex nunimers given above are from Colorindex, 2nd edition, cited, all of the above dyes are commercially available under various names.

After the irradiation and the subsequent reduction and polymerization of the or of the vinyl monomers, the unpolymerized vinyl monomers are washed away, wherein the Polymer image remains behind. The polymer is generally less soluble than the monomers. Hence, if a polymeric binder such as gelatin is used in the silver halide photographic emulsion layer was present and remains in the development without dissolving in water, the formed may Do not diffuse polymer into the emulsion layer. If in this case a vinyl monomer having two or more vinyl groups used together with a monovinyl compound can cause insolubility and diffusion resistance of the polymer formed therefrom by the polymerization continue to be improved.

By coloring the polymer image, a color image can be obtained, as indicated. The Color image can be obtained as a sharp and good color photographic image by using the silver halide is removed by a fixing process and the silver image is removed by the action of an oxidizing agent and a solvent for the silver salt is dissolved out. If a reducing agent with a very good efficiency is used to initiate polymerization, the polymerization reaction occurs sufficient even in the case where only a small amount of reduced silver was formed, since in this case it is not necessary or practically not necessary, the silver image by oxidation to remove.

The color image formed in this way can be transferred to other layer supports or image-receiving materials be transmitted. The emulsion layer bearing the resulting color image is used to transfer the color image with a solvent for the dye such as methanol, water or an aqueous solution an acid, a base or a salt and then the layer wetted in this way in close proximity Brought into contact with an image receiving material

As the image receiving material, ordinary papers, papers or films with a hydrophilic polymer can be used Layer or a gelatin layer can be used.

When the color image is transferred to a layer of gelatin is preferred, the image receiving layer to add a pickling agent such as an aluminum salt.

Once the polymer image is formed, a plurality of reproductions or copies can be obtained by coloring the polymer image and then the color image on image receiving materials, as stated above. As a plurality of reproductions or copies of a color image can be obtained and the polymer image can be repeatedly colored many times, many reproductions can be easily obtained.

example 1

A fine grain gelatin-silver chlorobromide photographic emulsion with a pH of 5.8 and a pAg of 7.6, the silver chlorobromide (Chlorine to bromine = 7: 3, molar ratio) corresponding to about 42 g of silver and about 60 g of gelatin per liter was divided into two parts. One of them was exposed. For the purpose of exposure were about 200 ml of the above silver halide emulsion which was in the liquid state at about 35 ° C, Spread over the bottom of a 20 χ 25 cm tub and then light about 300 lux for about 5 minutes exposed with stirring. 10 ml each of the exposed and the unexposed silver halide emulsions were poured into separate test tubes 1.6 cm in diameter. After adding of 6 ml of water to each test tube, 4.0 g of acrylamide was dissolved in the mixture and then 10_ moles of the reducing agents listed in Table I. continued to be added to the mixture. After the mass was sufficiently stirred, the Temperature adjusted to the value given in Table I and the test tubes in a heat-insulating Material set. The insulating material consisted of a polystyrene foam with a thickness of about 2 cm, and the system was placed in a water bath maintained at the temperature shown in Table I. immersed. Immediately thereafter, an aqueous 1N sodium hydroxide solution in the in Table I indicated amount added and the change in temperature of the system in each case measured by means of a thermistor-type temperature recorder. In the exposed emulsion the acrylamide was polymerized and the temperature of the system was increased by the heat of polymerization.

On the other hand, no temperature rise was observed in the system with the unexposed emulsion, or it was only very slight when observed. In the system with the exposed emulsion it was also found that the silver halide was reduced to silver, giving a brownish color.

As already explained above, it follows from the heat generation during the polymerization of the exposed emulsion that a polymerization takes place in the system. Although heat can also be generated by reducing the silver halide without polymerizing the vinyl compound, the amount of heat generated in this way is very small and such a small change in temperature cannot be detected by the temperature detector used in the experiment. If z. B. 10 ^-3 moles of hydroquinone are used, the silver halide is reduced to black silver, but no heat generation is observed in this reaction.

In the case of the unexposed emulsion, an increase in temperature can sometimes be observed if

10 the reaction is carried out for a longer period of time than necessary, but this phenomenon is similar to so-called fogging, that is, the phenomenon that in ordinary photographic emulsions the unexposed image parts are also blackened if the emulsion is developed for an extended period of time. This phenomenon therefore does not prevent the method according to the invention from being practical as a photographic process.

The chemicals used in the previous experiment, the temperature of the water bath, the amount of the alkali, the reaction period and the temperature of the reaction system are summarized in Table I.

Table I.

No. connection (A) (B) (Q (I.
(DO (D ") 2 Hydrazine D-tartrate 50 0.5 14th 100 50 13th Ammonium hydrazine sulfonate 50 0.3 26th 89 72 37 o-tolyl hydrazine hydrochloride 50 4.0 33 58 51 47 Acetone phenylhydrazone 60 3.0 21 82 67 48 Leaevulinic acid methylphenylbydrazone 60 1.0 40 100 74 49 Cupferazon 50 2.0 9 . 96 50 50 4-phenyl semicarbazide 50 2.0 18th 89 74 22nd Phenylglycine hydrazide 60 3.0 5 69 61

(A) Temperature of the water bath in ⁰ C, (B) Amount of 1N NaOH in milliliters, (C) Reaction time in minutes, (D) Temperature in ⁰ C after the real time, (C), (D ') exposed emulsion system, (D ") unexposed emulsion system.

In all cases, the polymerization reaction takes place predominantly in the systems in which the exposed emulsions were used.

Example 2

In this example, a photographic light-sensitive material having a Gelatin - silver chloroiodobromide - emulsion layer processed in a solution containing hydrazine and sodium methacrylate contained.

The light-sensitive material was prepared in the following manner: After adhesive layers were applied to both surfaces of a polyethylene terephthalate film, an antihalation layer was coated on one surface and a gelatin-silver halide fine grain emulsion was coated on the other surface. The emulsion contained about 0.7 moles of chlorine, about 0.3 moles of bromine and about 0.001 moles of iodine per 1 mole of silver and about 100 g of gelatin, with the emulsion still containing a merocyanine dye with a maximum sensitivity of 550 ηΐμ, hydrochloric acid in an amount of about 1.5 g to 100 g of gelatin hardening agent, a suitable stabilizer and a surfactant had been mixed. The emulsion was cast in such a way that 50 g of silver were contained in 100 cm ^{2 of} the layer. Subsequently, the silver halide emulsion layer was coated with a protective layer consisting of gelatin in a thickness of about 0.8 μm.

The photosensitive material thus prepared was passed through a negative for 2 seconds exposed to light of 100 lux and then immersed in a solution of the following for 30 minutes at 30 ° C Composition immersed under red light:

Sodium methacrylate 75 g

Hydrazine-D-tartrate-hydro-

chloride (compound 2) .. 1.82 g
2N aqueous sodium hydroxide solution necessary amount

to adjust the pH to 11.5

Potassium metabisulphite 3 g

Water 75 ml

A pale brown image was formed in the exposed parts of the layer as a result of the development. After the sample was washed with an aqueous acetic acid solution of 1.5% for 30 seconds the sample was fixed in a fixing solution with the following composition:

Sodium thiosulphate anhydrous 150 g

Potassium metabisulphite 15 g

Water to 11

After the sample was fixed and sufficiently washed, it was left at room temperature for 5 minutes in a 0.1% aqueous solution of a basic red dye, rhodamine 6 G. C. P. (C. I. basic Red 1) dipped, and then the emulsion layer was for 5 minutes with a Washed 5% aqueous acetic acid solution, whereby the existing in the unexposed parts of the image Dye was washed out, whereas the exposed parts of the image remained red. Since the brown picture consisted of a silver picture, it could easily be washed away by the Farmer's attenuator. After the silver image was removed, a

/ J

Get a sharp red image. The sequence of coloring and removal of the silver image can be reversed will. That bites, a sharp red image could be obtained by first removing the silver image became, whereby the emulsion layer became colorless and transparent, and then the layer was colored in the manner described above.

The color image obtained in this way could be transferred to paper by a simple process, io Ordinary writing paper was slightly moistened with methanol, and the color image thereby obtained was brought into close contact with the wetted paper, followed by the former after 30 seconds was separated from the latter and the color image was transferred onto the paper.

If the above dye is replaced by a 0.1% aqueous solution of crystal violet V. L, basic Violet 3, colored, a purple-blue image was obtained and the color image could also be transferred 20 will.

Even when using a 0.1% aqueous solution of Auramine 0-100, C.I. basic yellow 2, a yellow image was obtained.

By using a 0.1% aqueous solution of basic blue G. O., C. I. basic blue 25, a blue image was obtained.

In the case of transferring the color image, it is not necessary to add the silver image and the silver halide remove. By carrying out development and polymerization, treatment of the image-bearing layer with a demolition process and after washing with water, direct dyeing and transferring the Satisfactory image transfer could be carried out on the color image. 35

Example 3

The same procedure as in Example 2 was carried out, except that those listed in the tables Reducing agents were used. In this example, however, the composition was Processing solution following:

Sodium methacrylate 75 g

Reducing agent according to Table II

Water 75 ml

2 N aqueous sodium hydroxide solution necessary amount

to adjust the pH to the value given in Table II

Potassium metabisulphite 3 g

After the sample has been in the above solution for the period given in Table II 30 ° C, the sample was subjected to the same procedure as in Example 2. With of the sample stained by a 0.1% strength aqueous solution of Rhodamine 5 G.C.P., the permeability densities were determined the exposed parts of the layer and the unexposed parts of the layer for green light definitely. The results are in tables together with the type of reducing agent whose Amount, processing time, pre-staining optical density, and optical density listed after staining.

As can be clearly seen from Table II, it was found that the color density in the exposed parts of the image was higher in all cases and thus a polymerization reaction occurred in all cases was.

Table!! Reducing agent

(A)

(Q

(CI

(D)

(E)

15th
16
17th
18th
19th
20th
21
22nd
23

Hydrazine sulfate

Methylhydrazine

2-hydroxyethyl hydrazine

Benzyl hydrazine

N, N-dimethylhydrazine

N-amino homopiperidine

N-aminomorpholine

N-benzyl-N-phenylhydrazine

N-methyl-N-phenylhydrazine

o-nitrophenyl hydrazine

p-methylphenylhydrazine

Ammonium hydrazine disulibnate

Azobtaizolpb ^ ylhydrazm- ^ suHbfr-

acid

Benzoyl hydrazine

α-picolinic hydrazide

Isonicotinate hydrazide

2-Hydroxy-3-eaphaeiolic acid hydrazide

Girani T reagent

Oxalyl hydrazine

Adipic hydrazide

Phenylglycine hydrazide

Lununol

11.02 2.07 0.02 1.95 0.96 0.10 4.59 234 0.010 1.90 030

10.17

0.03 136 U7 4.61 9.09 1.67

9.27 3.50 25
30th
70
30th
70
70
60
15th
50
70
20th
20th

30th
70
50
30th
70
70
30th
30th
70
70

0.06
0.07
0.08
0.08
0.08
0.07
0.07
0.16
0.06

0.10

0.15
0.07

0.08
0.08
0.14
0.07
0.10
0.15
0.09
0.10
0.00
0.15

0.08
036
0.30
0.31
0.24
0.70
0.11
0.26
0.24
028

052

0.28
0.25
0.26
0.19
058
0.45
O22
O3O
025
035

0.08
0.40
0.08
0.09
034
0.11
0.13

Ul
0.27
0.24
0.54
0.08

0.12
0.13

0.08
020
040
0.45
O20
014
038

1.00 2.06 0.66 087 2.30 1.70 0.48 1.78 0.56 080 1.75 136

1.94 O82 9Θ 1.25 1.52 2.85 2.86 1.75 0.70

11.47

11.50

11.90

9.15

9.20

9.10

9.28

9.00

9.10

11.65

11.70

11.50

9.15 11.60 11.70

9.00

11.55 11.50

11.60 I 9.00 209538/209

25th

continuation

26th

Reducing agent

(B)

(C)
(C) J (C ")

(D) (D ') j (D ")

(E)

24 25 26 27 28 29 30 31 32 33 34

35 36 37 38 39 40 41 42 43 44 45 46 51

52 53 54

Carbohydrazide

/ f-acetylphsnylhydrazine

Diphenyl carbazide

Di-ß-naphthylcarbazone

Thiosemicarbazide

Dithizone

Nitrofurazone

Cyclopentanone semicarbazone

Benzenesulfonyl hydrazide

p-toluenesulfonyl hydrazide

Ethyl-a-butyl acetoacetate-semi-

carbazone

Acetophenone hydrazone

p-aminoacetophenone hydrazone

o-tolylhydrazine

m-tolylhydrazine

p-nitrophenyl hydrazine

Phenylhydrazine nitrate

3-chloroindazole

2-pyrazoline

3-methyl-2-benzothiazolone hydrazone m-hydroxybenzaldehyde semicarbazone

Phenylhydrazine p-toluenesulfonate

4-amino-1,2,4-triazole

l-phenyl-S-pyrazolone - ^ - carboxylic acid

hydrazide

Phthalic acid monophenylhyrirazide

/ S-phenoxyacetic acid phenylhydrazide Berastinic acid monophenyl hydrazide

4.05 0.67 2.42 0.02 1.64 0.50 0.50 1.86 7.12 0.84

10.49 6.03 0.73 0.05 0.05 0.05 0.05 6.84 3.15 2.15 3.00 0.06 3.78

(A) Amount of reducing agent in grams, (B) Processing time in minutes, (C) optical density of the unexposed parts, (C ') before coloring, (C ") after coloring, (D) optical density of the exposed parts , (D ^ before staining, (D ") after staining, (E) pH of the processing solution.

Example 4

The same procedure as in Example 2 was followed except that the system did not contain sulfite ions. Two samples were prepared and in processing solutions having the following compositions treated:

Sodium methacrylate (g)

/ ^ Acetylphenylhydrazine (g)

2n-wa1Br ^ e NaOH solution (ml) System pH

Sample l

75

0.675 75 10.5

sample

75

0.675 75 60 15 15 70 30 50 30 30 6 20

90 70 70 20th 20th 30th 30th 30th 70 70 70 70 30th

70 10 50 10

0.30 0.09 0.12 0.08 0.10 _χ 0.42 ^X 0.09 0.10 0.07 0.09

0.07 0.07 0.07 0.07 0.07 0.33 0.07 0.06 0.09 0.07 0.07 0.12 0.10

0.08 0.13 0.13 0.24

0.54 0.35 0.32 0.30 0.52 0.67 0.27 0.27 0.22 0.24

0.29 0.19 0.19 0.28 0.52 0.52 0.21 0.21 0.18 0.17 0.21 0.79 0.24

0.40 0.24 0.42 0.84

1.58 0.55 0.50 0.08 0.12 0.43 0.15 1.40 0.19 0.15

0.07 0.07 0.07 0.11 0.30 0.42 0.31 0.07 0.10 0.57 0.07 0.39 0.25

0.09 1.80 0.30 1.40

4.00 2.56 1.54 0.66 0.76 1.18 1.44 3.86 0.82 1.16

0.50 0.36 0.26 2.50 1.93 2.26 1.95 2.17 0.38 2.98 0.40 2.10 1.62

1.72 2.78 2.08 2.70

9.30 11.55 11.65 11.90 11.50 11.50 9.00 11.50 11.75 !!, 50

11.50 11.53 11.58 11.50 11.60 11.50 11.50

9.15 11.50

9.10 11.50 11.60 11.70

11.50

9.00

11.55

11.50

The results listed in the following table were obtained:

45 sample (A) Table III (B-) (B ") (D) (D-) (D ") No. (B) 0.07 0.41 0.27 1.52 1
cn 7th 0.20 1.27 1.41 > 4 ⁵⁰ 1 15th 0.08 0.70 035 U5 2 7th 035 1.55 23 « > 4 2 15th

The samples were treated for 7 or 15 minutes at 30 ^° C. and then subjected to the same post-treatments as in example 2. Then, the transmittance density of the same to light was measured, with that in FIG

(A) processing time in minutes, (B) optical density of the unexposed parts for green light, (BO before coloring, (B ") after coloring, (D) optical density of the exposed parts for green light, (D *) before staining, (D ") after staining.

As can be seen from the results of TabeDelll, the polymerization reaction occurred even in the case of the absence of sulfite ions in the reaction system selectively in the exposed parts, even if the optical density corresponds to the pH of the

The response system and the processing period varied.

If the same experiment was carried out at a pH of 11.5 using 7.6 g of 4-methyl

/ Γ

l-phenyl-3-pyrazolidone hydrazide (compound 56) Instead of / f-acetylphenylhydrazine When the emulsion layer was allowed to stand in the processing solution for 35 minutes, the following results were obtained. It follows from this that the presence of sulfite ions is not absolutely necessary in the context of the invention, if it is also preferred.

Optical density of not
exposed parts after
coloring
0.34 Optical density
of the exposed parts after
coloring
0.88 before the
coloring
0.20 before the
coloring
0.23

10

Example 5

The photographic light-sensitive recording material according to Example 2 was exposed imagewise and treated in a solution which contained 1-vinyl-2,3-dimethylimidazolium-ρ-toluenesulfonate, whereby the polymerization of the basic monomer was carried out imagewise.

For this purpose, the photosensitive material was exposed for 2 seconds through a negative with a line image to light of about 100 lux and then immersed in a solution of the following composition under stable red light in order to develop and carry out polymerization:

1 -Vinyl ^^ - dimethyUmid-

azolium p-toluenesulfonate 75 g o-Tolylhydrazine hydrochloride (Compound 37) 30 mg

Potassium metabisulphite 3 g

2N aqueous NaOH solution required amount

to adjust the pH to 11.8 water 75 ml

35

40

The l-vinyl-2,3-dimethylimidazolium-p-toluenesulfonate used above was prepared by reacting l-vinyl-2-methylimidazole and methyl p-toluenesulfonate at room temperature and by recrystallizing the product from ethanol and ether. The melting point of the crystals obtained was 142.5 ⁰ C.

If the silver halide emulsion layer was treated in the above processing solution for 50 minutes at 30 ° C, a polymer image was composed of the polymerized quaternary salt formed with a pale brown Sflberbüd. this was confirmed by the following procedure.

After sufficient fixation and water washing in the same manner as in Example 2, the Polymer image with a 0.1% strength aqueous solution of a blue acidic dye, Suminol Leveling Sky BlueR extra cone, CL Acid blue62, colored and then washed the emulsion layer with a 1% aqueous solution of sodium carbonate, wherein a blue image was obtained.

Since the brown picture consisted of a silver picture, it could easily be through Farmer's attenuators be solved. Removal of the silver image gave a sharp blue image. By reversing the order of staining and removal of the silver image as in Example 2, a sharp blue image was obtained in the same way.

The color image thus formed could be transferred to paper. For this purpose, as in Example 2, the emulsion layer with the blue image in brought into close contact with a paper moistened with methanol and after about 30 seconds the The paper peeled off, causing the blue image to be transferred onto the paper. Gelatin was also used applied to a paper coated with baryta in a thickness of about 10 μ and the paper in a aqueous alum solution and dried to obtain a dye transfer paper. When this dye transfer paper was wetted with water, brought into close contact with the emulsion layer with the colored image, and after When the paper was peeled off for 1 minute, a dense, sharp blue image was obtained on the paper.

When the emulsion layer with the polymer image in a 0.1% aqueous solution of a red acidic Dye, Solar Rhodamine B extra, C.I. Acid Red 52, was immersed for 5 minutes and was then washed with water, a red image was obtained.

The red image could be transferred to a paper moistened with ethanol. In the same way was able to transfer the color image onto the above-mentioned dye transfer paper which wets with water was to be transferred.

Furthermore, when the emulsion layer with the polymer image in an aqueous solution of a yellow dye, Solar Pure Yellow 8 G, C.I. Acid Yellow 7, or tartrazine, C.I. Acid Yellow 23, immersed and then washed with a buffer solution having a pH of 5.0, a yellow image is obtained, soft on a paper wetted with methanol or transferred to the above-mentioned water-wetted color transfer paper could.

Example 6

The light-sensitive photographic recording material according to Example 2 became an optical one for 1 second with light of 50 Lax Wedge exposed with a step of 045 and then The following composition is processed in a treatment solution. In this example, the effect of a so-called ordinary developer is used shown

Sample no.

Sodium methacrylate (g)

^ -AcetylphenyThydrazm (g)

p-methylaminophenol sulfate (mg) l-phenyl-3-pyrazoHdon (mg)

100 0.75 100 0.75 0.75

IQO 0.75 0.75

100 0.75

0.075

continuation

Sample no. 2 3

Potassium metabilsulfite (g) ...
2N aqueous NaOH solution
System pH

100 11.5

100
11.5

100
11.5

100
11.5

After the processing of the sample in the above solution for 20 minutes at 3O ⁰ C, the sample was subjected to the same post-treatments as in Example 4. FIG. After sufficient fixation and water washing, the sample was cut into two parts and one of them was subjected to complete bleaching using the Fanner attenuator. Further, for each sample, the optical densities of the parts corresponding to the optical densities of the second stage and the seventh stage of the wedge and the fog density were determined using a green filter to obtain the results shown in the following table.

Table IV

Sample no. 3 2 1.75 1.62 1.37 1.35 0.07 0.46 15th 15th

Optical density at the 2nd level

Optical density at the 7th level

Optical density of the unexposed parts
Colorable final stage number

0.44 0.07 0.04 8 1.29
1.11
0.29
16

The optical density was the ratio of the density of the dye selectively adhering to the polymer to the amount of irradiation and consequently corresponded to the amount of polymer formed. the Colorable final stage number is the number of the stage at which the increase in the staining density was observed, if the dyed and bleached sample with the parts exhibiting veils with the unarmed one Eye was compared. This value corresponds to the minimum exposure amount required for selective Formation of the polymer, and the greater the number of colorable final stages, the higher the sensitivity.

Since the optical wedge had a step difference of 0.15, the fact shows that the sample 2 has 7 steps more than sample 1 could be observed that sample 2 polymerizes in the same Same extent as for Sample 1 with an exposure amount of about one tenth of that required for Sample 1 Amount took place. In other words, in the case of processing under Applying the treatment solution 2 the same effect was obtained as with the 10 times more exposed Sample processed in treatment solution 1. Furthermore, the comparison shows of sample 1 and sample 4 that the increase in density in dyeing was greater and the amount of through Polymerization formed was greater at the same amount of exposure.

Thus, by using conventional photographic developers together with those of the present invention The reducing agents used effectively accelerate the polymerization

Claims (1)

Patent claims: 1. Process for the production of polymer images, one in an imagewise exposed photographic silver halide emulsion layer contained latent image by the action of at least one monomeric vinyl or vinylidene compound and at least one reducing agent is developed with image-wise polymerization of the monomeric vinyl or vinylidene compound is, characterized in that the reducing agent is at least one hydrazine derivative of formula I. R ₁ N-N R ₂ (D R ₃ wherein R _{1 represents} a hydrogen atom, a sulfonic group, a water-soluble metal salt or ammonium salt of the sulfonic group, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, an acyl group, a substituted acyl group, an arylhydrazinocarbonyl group, a thiocarbamoyl group, an arylazothiocarbonyl group, an arylsulfonyl group a substituted arylsulfonyl group, R ₂ a hydrogen atom, an alkyl group, a substituted alkyl group or an aryl group, where the radicals Rj and R ₂ together can form a ring containing carbon atoms, oxygen atoms or nitrogen atoms, and R ₃ a hydrogen atom, a sulfonic group, a water-soluble metal salt or the ammonium salt of the sulfonic group, an aryl group, an acyl group or a substituted acyl group, where the radicals R ₁ and R _{3 can} together form a ring, or of the formula II I = NNR ₆ 4. The method according to claim 1, characterized in that in the presence of an additional a small amount of a conventional photographic silver halide developer is developed, 5. The method according to claim 4, characterized in that a super halide developer l-aryl-3-oxopyrazolidine or an l-aryl-3-iminopyrazolidine or a conventional silver halide developing agent the general basic structure