DE1797193C - Process for the production of optionally colored polymer images - Google Patents

Description

IO

wherein R is a hydrogen atom, an alkyl group, a substituted alkyl group, an acyl group, an aryl group, a substituted aryl group or a heterocyclic group, R _{2 is} a hydrogen atom, a hydroxyl group, an amino group, a substituted amino group, an alkyl group, a substituted alkyl group, a Carboxyl group, an ester of a carboxyl group, an aryl group or a substituted aryl group and R ₃ denotes a hydrogen atom, an alkyl group or a substituted formyl group, the Carbony'lgruppe in the 5-position can also be aeylated with isomerization to the enol form and bis-compounds by Compounds via the groups R ₂ or R ₃ or can be formed directly in the 4-position, or a 3 · pyrazolin-5-one of the formula

N C

R ₅ NO

R4

wherein R ₁ ^ is a hydrogen atom or an aryl group, R _{5 is} a hydrogen atom or an alkyl group, R ₆ , a hydrogen atom, a hydroxyl group, an amino group, a substituted amino group; an alkyl group, a substituted alkyl group, a carboxyl group, an ester of a carboxyl group, an aryl group or a substituted aryl group and R _{7 represents} an amino group or a substituted amino group is used.

2. The method according to claim 1, characterized in that the development in the presence of Sulfite ions is carried out.

3. Process for the production of colored polymer sheets according to claim 1, characterized in that the monomeric vinyl compound is at least a vinyl carboxylic acid, a vinyl sulfone-The invention relates to a method for manufacturing

of optionally colored polymer images, be

(I) the one in an imagewise exposed silver halide

Emulsion layer contained latent image by the action of a monomeric vinyl compound and a

Reducing agent is developed.

1 mnd various methods of making voi Pn |> merisate images known by photopolymerization of vinyl compounds. So is known the picture moderate photopolymerization using a silver halide catalyst directly to effect (see British patent specification 836 631 and S. L e ν i η ο: and employees. "Photographic Science and Engineering". R.I ö. Pp. 222 to 226 fl962]). It wi-d jedocl accepted. that in the above-mentioned reaction that is caused by the photodecomposition of the silver The product formed by halides acts directly as a catalyst for the polymerization and, as a result, you Conversion is not as sensitive as in the case of the reduction of silver halide grains by a common silver halide developers.

It is also known to polymerizate images by Ent winding exposed silver halide grains in a conventional developer and then? Carrying out the polymerization of a vinyl compound using the SiI thus formed over image or the unreacted silver halide as a catalyst (cf. Belgian patent 642 477). However, this method has the disadvantage that the development process must be carried out separately from the polymerization process.

A method in which exposed silver halide grains be developed by a reducing compound in the presence of a vinyl compound and in which the vinyl compound is formed by the oxidation product des Silver halide developer, or an intermediate product thereof, is polymerized in theoretical terms of particular interest, since in such a process both an amplifying effect through Ui development reaction as well as a reinforcing effect by chain polymerization can be used. It is already known in this regard that the above described reaction using an aromatic developing agent as a reducing agent perform, namely with a compound that is in the o- or p-positions on a Benzolrin.g at least two hydroxyl groups, amino groups or amino groups substituted by alkyl or aryl groups carries (cf. USA.-Patent 3 019 104, German Auslegeschrift 1 119 120 and G. O s t e r, "Nature", Vol. 180, p. 1275 [1957]). However, this known implementation is used in the exemplary embodiments

(H)

using an aromatic developing agent, an increase in optical density observed from silver image reproductions, but no direct indication of the formation of a high molecular weight compound such as e.g. B. Increase in viscosity, occurrence of heat of reaction or deposition of a high molecular weight compound formed (cf. also S. L e ν i η ο s and F. W. H. M u 11 e r, »Photographic Science and Engineering ", Vol. 6, p. 222 [1962]).

The object of the invention is to provide a process for the preparation of optionally colored Polymerisatbildern in which a contained in an imagewise exposed Silberhalogemdemulsionsschicht latent image connection by action of a monomeric vinyl and a reducing agent is developed, which method is to be executed in a simple manner and in which Polymerisatbilder with such characteristics, r 2 of solubility, dye receptivity u: .d other physical and chemical properties can be obtained, which are necessary for various printing or copying process.

The invention relates to a process for the production of optionally colored polymer images in which a latent contained in an image-wise exposed silver halide emulsion layer Image is developed by the action of a monomeric vinyl compound and a reducing agent and which is characterized in that the reducing agent is a 2-PyrazoIin-5-one of the formula

N2

1
N

wherein R _{1 is} a hydrogen atom, an alkyl group, a substituted alkyl group, an acyl group, an aryl group, a substituted aryl group or a heterocyclic group, R _{2 is} a hydrogen atom, a hydroxyl group, an amino group, a substituted amino group, an alkyl group. a substituted alkyl group, a carboxyl group, an ester of a carboxyl group, an aryl group or a substituted aryl group and R ₃ denotes a hydrogen atom, an alkyl group or a substituted formyl group, where the carbonyl group in the 5-position can also be acylated with isomerization to the enol form and Bis compounds can be formed by connection via the groups R ₂ or R ₃ or directly in the 4-position, or a 3-pyrazolin-5-one of the formula

R ₆ R ₇

N
R ₁

where R _{4 is} a hydrogen atom or an aryl group, R _{5 is} a hydrogen atom or an alkyl group, R $ is hydrogen atom, a hydroxyl group, an amino group, a substituted amino group, an alkyl group, a substituted alkyl group, a carboxyl group, an ester of a carboxyl group, an aryl group or a substituted aryl group and R _{7 represents} an amino group or a substituted amino group.

In an emulsion layer for negative image formation, a latent image is formed upon exposure by developing centers of development on the silver halide grains, while in an emulsion layer for direct positive image, the latent image is formed by first forming development centers on all silver halide grains and then destroyed image by image by exposure (cf. James and Huggins, "Fundamentals of Photographic Theory" 2nd edition, Morgan & Morgan Co. [1960]). Paragraphs 3 and 4).

According to the invention, a silver halide emulsion can be used for negative images as well as for positive ones Images to apply. Suitable photographic silver emulsions for negative images are chlorosilver, ßromsilver-. Silver chlorobromide, silver iodobromide and silver chloroiodobromide emulsions. which, if desired, have been sensitized chemically and / or optically.

For a chemical sensitization, a sulfur iron sensitization or a noble metal sensitization can be used (cf. e.g. P. G Ia fk id es. "Chimie Photographique". 2nd Edition. Pp. 247 to 301 11957]. Photocinema Paul Montel, Paris) and for an optical sensitization can optically; Sensitizers for photographic emulsions, ζ. Β. Cyanine dyes and merocyanine dyes are expediently used, in addition, the silver halide photographic emulsions used according to the invention can be used contain common stabilizers.

The direct positive halogen silver emulsion which can be used according to the invention can be produced using solarization, the Herschel effect. Clayden effect or Sabatier effect, these effects being fully explained in chapters 6 and 7 of CEK M ees in "The Theory of the Photographic Process", 2nd edition, published by McMillan & Co., 1954. Process for the preparation of photographic direct positive halogen silver emulsions using solarization are, for. B. in British Patents 443 245 and 462 730 described. A manufacture.; Procedure for direct positive emu'sions using the Herschel effect. where a halide silver emulsion is used, which preferably contains predominantly silver chloride and may contain a desensitizing agent, is described, for example, in British Pat. No. 667,206 and in US Pat. No. 2,857,273.

To obtain a positive image using the Clayden effect, it is necessary to an emulsion of a total exposure with light of a relatively low intensity after an image exposure subject to light of high intensity for a short period of time. Be there the areas of the emulsion not exposed to high intensity light exposure, after the total exposure, develop no

To achieve the Sabatier effect, a photographic silver halide emulsion layer is used had undergone imagewise exposure while being immersed in a developing solution of the uniform Subject to exposure to light or a chemical reagent. This creates an ability to develop obtained in the area not subjected to the image exposure.

The Ciayden effect and the Sabatier effect are easily and effectively obtained in halogen silver emulsions, those to form development centers by the first exposure in the inner part rather than the Tend surface part of halogen silver grains. The production of such emulsions is z. Tie U.S. Patents 2,592,250 and 2,497,876, British Patent 1,011,062 and German U.S. Patent 1,207,791.

The aforementioned photographic emulsions

Sions are made by dispersing halide silver grains in a solution of a polymeric binder manufactured. Suitable polymeric binders are gelatin, synthetic compounds, e.g. B. polyvinyl alcohol, Polyvinylpyrrolidone or polyacrylamide, as well as derivatives of natural compounds of high Molecular weight, such as carboxymethyl cellulose, oxyethyl cellulose, dextrans and similar compounds, these compounds can be used alone or in a mixture with gelatin (cf. z. B. F. Ewa, Journal for Scientific Photographic, Photophysik und Photochemie, Vol. 52, pp. 1 to 24 [1957]).

Examples of those to be used according to the invention Pyrazolin-5-one compounds are listed below.

Examples of the groupings R ₁ , R ₂ and R ₃ in the above formula (I) are as follows:

Table I.

N C

connection
No. R ₁ R ₂ - H cn R ₃ H 1 O - OH - NHCOC = CH ₂ H . 2 the same -NH ₂ - OH H 3 the same -COOH -COOC ₂ H ₅ H 4th the same -CH ₃ - QHg-n 5 the same -CH ₃ H 6th the same -CH ₃ H 7th the same on / ^ U / ""! J H 8th the same - CH ₂ COOC ₂ H ₅ -CH ₃ 9 the same -CH ₃ - C ₄ H ₉ -Ii * 10 the same -CH ₃ H 11th the same -CH ₃ H 12th the same -CH ₃ -C ₂ H ₄ OH 13th the same -CH ₂ - ^ 3 14th also *. -CHO 15th the same -CH = N-NH ^ T _y 16 the same

Connection no.

17 18

22 23 24

25th

26th

27

28

29

30 31 32

. b

R,

NH ₂

HOjS

CH ₃ Cl

Cl Cl

Cl Cl

Cl

HO ₃ S

H H H

Continuation

-CH ₃ -CH ₃

- CHj -CHj

-CHj

-CH ₃

-CHj

- CHj

NH ₂

-NH ₂

-NH ₂

- COOH

H
-CH ₃

OH3

continuation

-CHj -CH ₃ - CH ₂ CH ₂ CH Cl

Cl

OCH ₃

CH ₃ O

-CH ₃ -CH ₃ -CH ₃ -CH ₃

NH ₂

CONH -

the same

10

connection
No. R. -CH ₃ K 33 H -CH ₃ -C ₂ H ₃ M. H -CH ₃ -C ₂ H ₄ OH 35 H -CH ₃ -CH (CHj) ₂ 36 H -CH ₃ - CH ₂ CH (CH ₃ I ₂ 37 H -CH ₃ -C ₄ H ₉ -D 38 H -CH ₃ -C ₅ H ₁₁ H 39 H -CH (CH ₃ J ₂ -CH ₂ - <3 40 H - C (CH ₃ ) ₃ H 41 H Qa ^H 3- H 42 H -CH ₂ CH ₂ CH ₃ H 43 H H 44 H O 3,4-tetramethylene 45 H H

-C ₄ H ₉ -Ii -C ₂ H ₄ OH-C ₄ H ₉ -Ii

and
60

,, S

continuation

H ₃ C NH ₂

ΛΑ

H ₃ CN

12th

61

N CO

_Ν Q-CO-CH ₃

63

H ₂ j j-

IN

A /

O N

N O

H ₃ C

SO, K

SO ₃ K

H ₃ C

CH ₃

NC

CN

N 0 O N

H ₁ C

CH ₂ - CH, - OH

The compounds listed above can be prepared by processes known per se, how they z. B. von R. E i 1 e y and P. W i 1 e y, "The Chemistry of Heterocyclic Compounds", Vol. 20, 1964, John Wiley and Sons, New York.

It was reported recently that 5-pyrazolone derivatives are used to initiate polymerization, for example, H. Bredereck, B. Föhnlisch and R. F ra η ζ, "Macromolecular Chemistry", Vol. 92, S ^"7 O up 90 (1966). There it was described that, according to the studies there, a 5-pyrazo] one derivative initiates the polymerization of a vinyl compound in the presence of Cu ⁺⁺ , Cl ~ and oxygen or a peroxide. Copper (II) or a peroxide as an oxidizing agent, and consequently the polymerization takes place independently of the irradiation with light or rays of high energy The rate of final polymerization is influenced by the presence of development nuclei on the silver halide particles, ie by exposure to light or a beam treatment of high energy.

The reaction mechanism whereby the polymerization of a vinyl compound as a result of the reduction of silver halide has not yet been clarified. In general, however, it is assumed that the polymerization mechanism takes place as a radical polymerization, due to the The fact that initiators of free radical polymerization can be used that the reaction can be carried out in an aqueous solution can and that the use of a radical polymerization inhibitor can prevent the progress of the Can delay implementation. It has not yet been clarified whether the radical initiating the polymerization directly by reacting Compounds I or II with a silver halide or by any Implementation in the reaction system, e.g. B. is formed with water or oxygen. Since no polymerization was observed when an irradiated silver halide was previously mixed with Compound I or II was reduced and vinyl compound to the react

4,

tion system has been added, it is clear that that the polymerization of the vinyl compound takes place simultaneously with the editing of the silver halide It can therefore be assumed that an intermediate product of silver halide and the compound I or II leads to the reaction With regard to the air oxidation of 5-pyrazolone, there is a study by S. V e i b e 1 and S.C. Linhold, "Acta Chem. Scand.", Vol.9, Pp. 963-969 (1955) which states that the pyrazolone forms 1.5 molar equivalents of oxygen of a radical absorbed

It is believed that the polymerization according to the invention is caused by the radicals of pyrazolones which are formed when they are oxidized by a silver halide. When the reaction after a suitable period of irradiation is discontinued, a compound of high molecular weight only formed on the irradiated areas during when the reaction Continuing further, the high molecular weight compound also irradiated on the η ι ht Surfaces is formed. However, this phenomenon is similar to the fog that occurs when a conventional silver halide photographic light-sensitive material is exposed for an excessively long period of time, wherein also the entire areas are blackened regardless of the imagewise exposure.

According to one embodiment of the invention, the development is carried out in the presence of sulfite ions

It was found that if there is sulfite ion in the reaction system are present according to the invention, accelerates the polymerization of the vinyl compounds can be.

Sulphite ions can be added to the reaction system either in the form of a compound which originally was the sulphite ion contains in the molecule, for example alkali sulfites or ammonium sulfite, are added or in Form of compounds that give off a sulfite ion as a result of hydrolysis, for example pyrosulfites of Alkalis or ammonium or adducts of bisulfites with aldehydes, for example formaldehyde or glyoxal. Although the appropriate amount of the sulfite ion to be added depends on the type and amount of the reducing agent and the vinyl monomer to be used, the pH of the system, and other factors is dependent, more than 0.05, in particular more than 0.2 mol per liter of the system are effective.

It is well known in the art to add a sulfite to photographic processing solutions and in such cases it is believed that the sulfite is an autoxidation of the developing agent and prevents uneven development by using the products of oxidation the developing agent, for example hydroquinone or p-aminophenol, reacts, including e.g. B. on C. E. K. M e s, "Theory of the Photographic Process", 1st Edition, p. 652, McMillan Co., 1954, is referenced. It it should be pointed out, however, that although the intermediate product is the oxidation of 2-pyrazolin-5-ones or 3-pyrazolin-5-ones by silver halide the polymerization of one or more vinyl compounds initiates in the process according to the invention, the effect which promotes the polymerization of sulfite ion fundamentally different from the effect of removing oxidation products is, as with the commonly used developing solutions listed above. The polymerization would be inhibited, promoted in place if the sulphite simply remove the oxidation products would, as is the case with standard development processes

Although the mechanism of the action of the sulfite ion in the process according to the invention is not known, it can be assumed that the sulfite ion is the one that inhibits polymerization Effect of free oxygen prevented

As vinyl compounds in the context of the invention, addition-polymerizable vinyl compounds, which are liquid or solid at normal temperature, and mixtures of such vinyl compounds are used. Examples of such compounds are acrylamide, acrylonitrile, N-hydroxymethacrylamide, methacrylic acid, Acrylic acid, calcium acrylate, sodium acrylate, acrylamide, methyl methacrylate, methyl acrylate, Ethyl acrylate, vinyl pyrrolidone, vinyl methyl ether, vinyl biityl ether, Vinyl isoprene, vinyl isobutyl ether, vinyl butyrate, 2-vinylpyridine, 4-vinylpyridine, 2-methyl-N-vinylimidazole, potassium vinylbenzenesulfonate and vinyl carbazole.

In the method according to the invention, the use is of vinyl compounds with two or more vinyl groups are particularly favorable. Such connections may or may together with the above vinyl compounds having a vinyl group can be used alone. Examples of vinyl compounds having a plurality of vinyl groups are N, N'-methylene - bis - acrylamide, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, Polyethylene glycol dimethacrylate, divinyl ether and divinyl benzene are listed.

According to the invention, water-soluble vinyl compounds are conveniently employed, but can also water-insoluble vinyl compounds are polymerized by adding them to the reaction system can be added in the form of an emulsion.

Visible rays, ultraviolet rays, infrared rays can be used in the method of the present invention with a wavelength shorter than 1.3 microns. X-rays, gamma rays, alpha rays and Electron beams are used.

When recording or copying images, it is necessary that the halogen silver grains keep their position change little during the period between irradiation and polymerization in the reaction system, and therefore the system is preferably in a still viscous liquid state or in a Gel condition held. The silver halide photographic emulsion coated on a suitable support can be subjected to irradiation either in the undried or dried state will. In the presence of a vinyl compound or in front of vinyl compounds, reduction and polymerization can take place at the same time. In the method according to the invention, both Vinyl compound as well as the compound I or the compound II of the photographic emulsion voi incorporated into the exposure. However, only one of the compounds mentioned in the emulsion can also be used before exposure, and the other can be applied by the dsm system after exposure it is also possible to add both compounds only after exposure.

Since the reduction and polymerization have to be carried out in the presence of water, it is necessary

necessary, the reduction and polymerization ui in an aqueous solution or in a moist gel.

In general, the reaction is carried out in the presence of an appropriate amount of an alkali since it proceeds smoothly under an alkaline condition. Although the amount of the alkali suitable for the reaction depends on the kind of the silver halide, the reducing agent and the high polymer in the system and their concentrations and the reaction temperature, a pH of the system of 6 or more, preferably more than 7, is preferred , set. When the photographic emulsion in the form of a layer is applied on a base, the reaction can be carried out by the photosensitive Au thus obtained ^f / iichnungsmaterial is immersed after exposure in an alkaline aqueous solution. In this case, the vinyl compounds and / or the reactants can be conveniently dissolved in the aqueous alkaline developing solution.

Lin interrupting the implementation is easy by adjusting the pH of the system to, for example 5 or less; the interruption can also be done by cooling down. Removal of the reactants by washing, dissolving the silver halide by fixing or adding a polymerization inhibitor to the system.

If the polymeric binder door the silver halide grains and the monomeric vinyl compound are mixed and together 11 ter formation of a Layer are applied to a support, preferably a small amount of an inhibitor for thermal polymerization added to allow spontaneous thermal polymerization of the vinyl monomer to prevent. Such polymerization inhibitors can be, for example, p-methoxyphenol, Hydroquinones, 2,6-di-tert-butyl-cresol, / i-naphthoi and the like.

If the vinyl monomer is initially included in the system, it is present in an amount by weight from V ₃₀ to thirty times, preferably 1/4 to four times the amount of the polymeric binder originally present in the system . The silver halide is usually used in an amount by weight VOmV ₂₀ times to two _{times, preferably 7 ic} times to ^{72 times} the amount of the polymeric binder originally present in the system. If the reducing agent is to be added to the system before the reaction, it is advantageous to add it in an amount of up to 20 moles per mole of silver halide. It is preferable to add the thermal polymerization inhibitor in an amount of 10 to 20,000 ppm by weight of the vinyl compound. If the vinyl monomers are dissolved in the casting 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 monomer in the solution. If the reducing agent are dissolved pyrazolone type in the developing solution, it is favorable to it ^un d 5 moles per liter, to dissolve in a concentration of between '/ 20, preferably between V10 and 1 mole per liter.

If the effect of the exposure is to some extent over the lapse of time between I.

the exposure and the execution of the polymerization is weakened, this weakening can be counteracted by increasing the exposure amount will.

The invention achieves that exposed Silver halide emulsion layers with a single development step in a very simple one Process for Pdlymerisatbilder can be developed which are useful for printing purposes.

In contrast to the tanning development process, at using the photosensitivity of silver halide in a tanning process of gelatin is crosslinked by a developer oxidation product, polymerization images can be used in the process according to the invention with different properties according to the many different usable Vinyl compounds are made. As a result, Polymmsationsbilder with completely different Properties such as B. in terms of colorability or chemical resistance, can be obtained, wi. > So far, never with networked products of (lelatine were achievable.

When using the method i; em according to the invention for recorded images it is possible to use the Differences in solubility. Light scattering, confusion. Dye absorbency and other physical and chemical properties between the unpolymeris L.icn from monomeric vinyl compounds consist of using the layer parts and the polymerized layer parts. A relief image can be formed are dissolved away by the unpolymerized layer parts after the irradiation and polymerization be taking application of the dissimilarity of solubility between the polymerized Layer parts and de "unpolymerized Layer parts is made so that the in this way the polymerized compound only in the irradiated Image sharing remains.

In this case it is advantageous if the polymeric binder originally present in the system can be washed away together with the unpolymerized vinyl compound. F ^ will therefore it is preferred that the polymeric binder is practically non-linearly crosslinked, or at most one such is crosslinked polymer that is accessible for chain breaking or breaking of the crosslinking, whereas the high polymer formed by polymerizing the vinyl compound as a crosslinked polymer is present with a three-dimensional structure. For this reason, it is favorable as a monomeric vinyl compound a compound having a plurality of vinyl groups as listed above, either to be used alone or in a mixture with compounds with only one vinyl group. However, it is ηκΜ necessarily required. Connections with a Use the majority of vinyl groups, as there are many systems with simple vinyl compounds that sufficient differences, e.g. with regard to the solubility between the parts of the image, which are caused by polymerization the high molecular weight substance formed of the vinyl compound, and the bicomponents that contain do not contain such a high molecular substance. This also applies if the received Polymerisatsubstanz is a soluble linear substance due to the interaction between the highly polymerized substance formed upon exposure and dsm originally in the system existing polymeric binders, as is the case

in the case of polyacrylic acid as the polymerized vinyl compound and gelatin as the binder.

The image reproduction that is achieved by the method according to the invention and from highly polymerized Substances can be used in various printing processes.

Furthermore, the method according to the invention can be used to produce color image reproductions will. In this case, a vinyl monomer is used to accept a charge by electrolytic Dissociation or addition of a group suitable for hydrogen cation as a polymerizable vinyl monomer used and the polymer is selectively colored with a dye which is the opposite Charge to that of the polymer. The resulting color reproductions can be based on other substrates can be transferred in various ways known per se.

Examples of such du ^r c * i addition polymerizable vinyl compounds which are capable of taking up a charge through electrolytic dissociation or addition of hydrogen cations and which are used in the context of the invention are vinyl compounds without a carboxyl group, for example acrylic acid, methacrylic acid, itaconic acid and maleic acid, ammonium acrylate, sodium acrylate, potassium acrylate, calcium acrylate, magnesium acrylate. Zinkacryict, Cadmiumacrylat, sodium methacrylate, potassium methacrylate, magnesium methacrylate CaI-ciummethacrylat, zinc methacrylate, Cadmiummethacrylat, Natriumitakonat and sodium maleate, vinyl compounds containing sulfonic acid groups, such as vinyl sulfonic acid and p-vinylbenzenesulfonic acid and Atnmoniumvinylsulfonat, sodium vinylsulfonate, Kaliumvinylsulfonat and Potassium-p-vinylbenzolsulfoi.at. Furthermore, vinyl compounds with positive charges of the high molecular weight compounds formed from the monomers can be vinyl compounds with basic nitrogen offatom, for example 2 - vinylpyridine, 4 - vinylpyridine, 5 - vinyl-2 - metr-ylpyridine, N, N - dimethylaminoethyl acrylate, N, N - diroethylaminoethyl methacrylate, N, N - diethylaminoethyl acrylate, N, N - diethylaminoethyl methacrylate and similar compounds and vinyl compounds a quaternary ammonium salt obtained from a Ba <5e of the above vinyl compounds and methyl chloride, ethyl bromide, dimethyl sulfate, diethyl sulfate, methyl p-toluene sulfonate and the like can be used.

These compounds can be prepared by processes known per se or are available at hand. D ^; ^ se compounds can be used alone or as a mixture of two or more such compounds. Also, the above vinyl compounds can be used together with a water-soluble addition polymerizable vinyl compound which has no charge. As compounds of the latter type of vinyl compounds, acrylamide, N-hydroxymelhylacrylamide, methacrylamide, methyl methacrylamide, vinyl pyrrolidone, N, N-methylene-bis-acrylamide, triethylene glycol dimethacrylate, polyethylene glycol dimethacrylate and similar compounds can be used. In the event that vinyl compounds become uncharged, the reactivity and proportions of the vinyl compounds must be chosen so that high molecular weight compounds are virtually non-electrolytically dissociative

Group due to the polymerization of the vinyl polymer only cannot be trained without charge.

According to a further embodiment of the invention, the monomeric vinyl compound is at least a vinyl carboxylic acid, a vinyl sulfonic acid, a basic nitrogen-containing vinyl compound or a Salt of these compounds is used, and the polymer image is developed with a dye colored, which has a charge opposite to the charge of the polymer.

Dyes to be used which have a charge due to electrolytic dissociation can generally Customary acidic and basic dyes can be used. If one is polymerized for delivery Layer parts with negative charge suitable vinyl compound is applied, becomes a basic dye used, while with a vinyl compound that is used to deliver polymerized layer parts with a positive charge is suitable, an acidic dye

In other words, a basic dye has a positive charge and particularly selectively colors polymerized parts of the layer «\ s compounds with a negative charge, while an acidic dye has a negative charge and selectively

colored parts of the layer composed of compounds with a positive charge.

If gelatin is used as a binder in photographic applications If emulsion is used, the isoelectric point of the gelatin must be taken into account when staining because gelatin is an amphoteric electrolyte. In other words, if the The pH of the system is lower than the isoelectric point of the gelatin to be used. the gelatin be positively charged, while with a Sv star whose

pH is higher than that which makes gelatin negative is loaded. If consequently a Pu'ymerisatbild with negative charge is formed, only the polymer parts of the image reproduction can be colored, without the gelatin being colored if the polymer image is provided with a basic dye is colored at a pH lower than the isoelectric point of the gelatin. Even if one photographic emulsion layer initially uniform after development of the polymer image

is colored at a higher pH than the isoelectric point of the gelatin and then the Layer with a washing solution with a lower pH than the isoelectric point of the gelatin is washed off, eliminating the areas that are no

polymerized portions of vinyl compound are washed out and color image reproducing areas left from polymerized fractions of vinyl compound, so is the procedure. If one desires image parts from a polymerized vinyl compound having a positive charge with an acidic To color dye, the coloration can take place at a higher pH than the isoelectric point of gelatin are executed. Of course, if the pH of the system is too high or too low, the solution will

The ability of the dye is lowered and the electrolytic dissociation of the compound to be charged is reduced high molecular weight can be inhibited. Thus depends on the optimal range of the pH value of the types of vinyl compounds and that

Color and the type of binder, such as gelatin. In the case of using a common gelatin, which has been subjected to lime processing and has an isoelectric point of about 4.9 is the

1,797

suitable pH of the system 2.5 to 4.5, if any High molecular weight compound with a negative charge through a basic dye to be colored and 5.0 to 8.0 layer parts made of a polymerized vinyl compound with a positive one Charge to be colored with an acidic dye.

Examples of dyes to be used in the context of the invention are acidic dyes, such as. B. CI. Acid Yellow 7 (CI. 56 205), CI. Acid Yellow 23 (CI. 19 140), CI. Acid Red 1 (CI. 18 050), CI. Acid red 52 (C. 1.45 100), C. I. Acid blue 9 (C 1.42 090), C. I. Acid blue 45, C. I. Acid blue 62 (C. I. 62 045), C. I. Acid violet 7 (CI. 18 055) and the like. As basic dyes are just CI. basic yellow (CI. 49 005), CI. basic yellow 2 (CI. 41,000), Cl. basic red (CI. 50 240), CI. basic violet 3 (CI. 42 555), CI. basic violet 10 (C. [. 45 170) and the like listed.

The number of the specified dyes corresponds to the Color Index (2nd edition), and the above Dyes are commercially available.

With this type of implementation of the invention It is necessary to process the process steps of irradiation by electromagnetic Rays or particle radiation to perform the reduction and polymerization and then the stage of coloring.

Pulymens bands can be obtained by only the unpolymerized parts of the vinyl monomer after exposure, reduction and Polymerization washed away, since the polymerized layer parts less soluble than the monomer are. By using monomers with at least two vinyl groups in combination the insolubility and non-insolubility of the polymerized layer part obtained can be increased.

The colored polymer images obtained by this process can be used as clear dye images after fixing the unexposed silver halide for its removal and subsequent dissolution the silver picture with an oxidizing agent and a solvent for the Silver salts are produced.

If a reducing agent with a high effectiveness is used to initiate the polymerization it is not necessary to remove the silver images by oxidation, as a sufficient polymerization reaction already done in such a state where a very small amount of reduced Silver is formed.

According to a further embodiment of the invention, of the colored ones obtained in this way Polymerization images, color images can be transferred to other substrates. To carry out a he such The image-receiving material must be in intimate contact with the layer that is to be transferred to the above transfer Way caused colored polymer images and containing a solvent for the Dye, such as methanol, water or an aqueous solution of a base, an acid or a salt moistened is to be brought. As an image receiving material onto which the color images are transferred can, can be ordinary paper or a paper or film made with a hydrophilic polymer z. B. coated from gelatin, can be used. When the colored image is transferred to a base be sol !, which is coated with a gelatin layer, it is preferable to use a pickling agent such as

fTum salt, proceeding in the same way before to be treated as in the usual dye transfer process. When an image reproduction made up of the ionizable polymer is produced it is possible to make a number of copies by coloring and transferring as above carried out, as some copies can be made with a single stain and the polymer images can be colored repeatedly.

The following examples are provided for further explanation of the invention without being limited to this.

example 1

A fine grain silver chlorobromide photographic emulsion containing about 60 grams per liter of gelatin and about 42 grams Silver chlorobromide / 1 with a molar ratio of Chlorine to bromine of 7: 3 and a pH of 5.8 and a PAg value of 7.6 was divided into two parts, one of which with a fluorescent lamp was exposed. When the exposure was carried out, about 200 ml of the emulsion,

melted at 35 ° C, spread out in a trough of 20 x 25 cm and the liquid layer was exposed to a lamp of about 300 lux for 5 minutes with stirring. Then, 2 xn \ were each poured the emulsion be exposed and the unexposed Etnulsion in a test tube of 1.6 cm diameter, and after addition of 6 ml of water in the test tube, 4.0 g of acrylamide were added and continued to 10 ~ ⁴ mol of 3 -Methyl-5-pyrazolone added. After sufficient stirring, the temperature became

of the system in the test tube adjusted to 60 ° C and the test tube inserted into a heat-insulating material. The overall system including the heat insulating material was placed in a water bath at 60 ⁰ C. Thereafter, 0.01 ml of an aqueous 1N-Natriumbydroxydlösung zugefüg directly to the system. and the change in temperature was followed by means of a thermal resistance type recording thermometer. The pH of this system was 6.2. The result

nits are listed in the drawing, where the extended one Line (1) the temperature change of the exposed emulsion and the dotted line (2) the Indicates temperature dependence of the unexposed emulsion. Aery I-amide was used in the exposed emulsion polymerized and gave a temperature rise, making the temperature of the system 100 ° C after about 98 minutes from the beginning of the reaction and the contents: de »test tubes rubber-like due to the resulting polyacrylamide.

On the other hand, there was no temperature limit in the unexposed emulsion, and the contents of the test tube could easily be poured out. In the system using the exposed emulsion, it was also found that the fat of the system was brown due to the reduction in the oversupply.

When the proportion of acrylamide was increased from 4 to 8 g in the above system, the reaction

Fion period abbreviated Using 8 g of the acrylamide, the system in which the exposed emulsion was used reached 100 ° C after about 40 minutes while the system

thinned emulsion only 63 ° C at the same target point reached.

It clearly results from the generation of the heat of polymerization and the change in the Flowability of the overall system that polymerization took place. Except for the polymerization reaction the heat could be generated by the reduction of the silver halide, but here would be the heat generated The amount of heat is so low that it cannot be determined by increasing the temperature. For example, when hydroquinone was used in place of 3-methyl-5-pyrazolone, that was Silver halide reduced to black silver, but no heat generation was observed. Farther testified to the fact mentioned above that the amount of tub formed by the amount of Acrylamide was influenced by the fact that the temperature rise of the system was mainly caused by the heat generated by the polymerisation reaction.

When the unexposed emulsion was used, the emulsion generated heat and lost its heat Flowability only if it has been implemented over a relatively long period of time. This he-

However, the appearance corresponds to the appearance when a conventional photographic emulsion is used too long periods of time is developed, with the unexposed areas under formation of so-called Veils are reduced and finally the picture details are no longer detectable.

Example 2

ίο The same experimental set-up as in example 1 was repeated, but the pyrazolone compounds listed in Table I below were used Instead of 3-methyl-5-pyrazolone used and also changed the amount of sodium hydroxide. In the following table shows the amounts of pyrazolone, the temperature of the system and the amount of 1N sodium hydroxide, the period of time until the temperature of the system using the exposed Emulsion reached the maximum value, and the temperature of the system, if the unexposed emulsion was used. All of the experiments clearly show that the exposed Emulsions the polymerization preferably took place (Table I).

Table I.

attempt No

17th
18th
20th
26th
27
28
64

l-phenyl-3,5-diccto-4-butyl-

pyrazoline

l ^ -Dimethyl-S-pyrazolone

1,3-dimethyl-4-butyl-

5-pyrazolone '(I)

1, S-DimethyM-Zf-hydroxyathy 1-

5-pyrazolone (2)

3-methyl-4-butyl-1 - / J-hydroxy-

ethyI-5-pyrazolone (3)

1 - Phen yi-3- «tr boxy-5-pyrazolone 1-phenyl-3-methyl-5-pyrazolone. I -phenyl-3-ethoxycarbonyl-

methyl-5-pyrazolone

1,3-diphenyl-5-pyrazolone

1- {2-pyridyl) -3-methyl-5-pyrazolone

1-p-nitrophenyl-3-methyl-5-pyrazolone

H2,6-dichlorophenyl) -3-aniino-5-pyrazolone , ....

1- (2,6-DicMoro-4-cyano-phenyl) -3-amino-5-pyrazolone

H4-methoxyphenyl) -3-amino-5-pyrazolone

4,4'-methylidenebis ^ (1-p-potassium m-sulfonylphenyl) -3-methyl-5-pyrazolone

4,4'-Bi & - {1-phenyl-3-methyl-5-pyrazolone)

5-pyrazolone

-
3 sound
(mg) Badicmp.
CC)
- - 248
11th 30th
30th 18th 30th 16 30th 20th
204 30th
50 174 50

232 236

175 219 255 280 213

291

346 84 50
50

50
50
50
50
50

50

50 50

4th ₅ n-NaOH
(ecm) Time to
max temp.
(Min.) 0.0
0.1 52
140 0.05 93 1.0 145 1.0
2.0
0.5 32
! 70
18th 0.2 95 0.2 53 0.5 75 0.2 115 2.0 20th 0.2 23 2.0 30th 0.2 195 2.0
0.5 27
40

Temp.

( ⁰ C)

66
64.7

73.8
73.3

48
78
97

above

100
above

100

95
99
89
89
62

92.5

64
54

Temperature at Application of

may be lighted

emulsion

30 30.3

39 31 35 50 50 50

57 59 55 50 59

55 51

attempt

No.

31
32
33

34

37
38
45

46
56

2
3

10
14th

11th
16

19th

21
22nd
23
24

25th
29

36
42
44
54

3-methyl-5-pyrazolone S-methyl- ^ methyl-S-p 3-methyl-4-ethyl-5-pyratolone ... 3-MethyI-4 - / <- hydroxyälhyl-

5-PyrazoIon

3-methyl-4-butyl-5-pyrazolone ... 3-methyl-4-amyl-5-pyruzoIon ... 3-phenyl-5-pyrazolone

S-p-methoxyphenyl-S-pyra- ^ ion

H2-methylphenyl) -3- {3-nitrobenzoylamino) -5-pyrazolone ...

! -PhcnyI-5-PyrazoIon

l-phenyW-hydroxy-S-pyrazolone l-phenyl-3-amino-5-pyrazolone .. l-phenyl-3-ethoxycarbonyl-

5-pyrazolone

] -Phenyl-3-methyl-4-butyl-

5-pyrazoion

l-phenyl-S-methyM - ^ - hydroxy-

ethyl 5-pyrazolone

l-PhenylO-propyl-S-pyrazolon .. l-Phcnyl-S-methyM-formyl-

5-pyrazolone phenyl hydrazone. · l- (2-quinolyl) -3-methyl-

5-pyrazolone

l-m-aminophonyl-3-methyl-

5-pyrazolone

l-p-aminophenyl-3-methyl-

5-pyrazolone

l-p-sulfonyl-3-methyl-

5-PyrazoIon

l-o-methylphenyl-3-methyl-

5-pyrazolone

1- (3,5-dichloro-4-sulfonyl) -3-methyl-5-pyrazolone

1- (4-sulfonyl) -3-carboxyi-5-pyrazolone

3-methyl-4-isobutyl-5-pyrazolone

3-octadccyl-5-pyrazolone

3,4-tetramethylene-5-pyrazolone ..

1- {5-Ch! or-2-methy] -phenyl) -3- (3-nitrobenzylamino) - " 5-pyrazolone

H5-chloro-2-methoxyphenyl) -. 3- (3-nitrobenzoylamino) -5-pyrazolone

l-Pheflyl-3-mei.hacryIamino-5-pyrazoIon

I-Phenyl-S-methyl-1-methyl-5-pyrazolone

continuation

2 I 3 j 4 I 5

I! i j

! j ι / eil to the |

Amount of bath temp. j n-NaOH j max.temp.

292
235
226
226
154
188

(Ci

50
50

50
50
50
50

50
55
55
55

55
55

55
55

55
60
55
55
55
55

55
60

55
55

55
55
60

I ecm I

0.5 0.5 0.02

0.5 0.1 0.02 0.5

0.3

2.0 0.5 0.5 0.2

1.3 4.0

3.0 0.02

3.0 1.0 4.0 0.5 1.0 0.2

1.5

1.5 0.03 4.0 1.0

4.0 1.0 0.5

60 2.0

{Min.ι

40 y

25th

41

65 21 62.

72

130

55 65 60 67

106 28

10

35

193 17 43 78 12

34

69 40 81 46

130 78 18

Temp.! Cl

98 90 99

93

100

96

above 100 95

65 80.5 64 66.2

86

74

73 100

75

88

85.5

95

99

above 100

99

95 97 94 77

72.3

above 100

above 100

100

Temperature at Application of

not necessary

emulsion

56

54 52

50 50 50 50

50

50 78 55.2 62.2

48 81.5

58 58

65 72 61 85 101 59

57.5

57 66 79 73

66 87

60, 89

attempt
No.

40
41
63
61

43
66

58
62

continuation

l-phenyl-3-methyl-4-formyl-

5-pyrazo! On 202

S-isopropyl-S-pyrazolone 126

3-t-butyl-5-pyrazolone 140

p-Di-3-pyrazolonyl-benzene 242

2-phenyl-4-benzoylamino

3-pyrazolin-5-one 293

3-propyl-5-pyrazolone 126

l-p-nitrophenyl-3-methyi-

4-j3-hydroxyethyl-5-pyrazolone 163

l-acetyl-3-phenyl-5-pyrazolone .. 202

S-phenyl-S-acetylpyrazolone j 2OJ

Amount (mg)

Bath cmp. ( ⁰ C)

60
60
60
60

60

55

55
57.8

58.5

n-NaOH
(ecm)

0.3
0.05
10.0

1.0
0.2

2.0
0.5

1.0

5 6th 7th 7cil to 7ur Temperature at max temp. Temp. Application of
do not reveal (Min.) ! C) emulsion 90 93 85 41 100 60 63 77 60 120 90 78 11th 63 60 53. 94.5 62.5 36 84.5 67.5 10 above 57.5 100 108 81.5 78

Example 3

The polymerization was carried out using polyvinyl alcohol and polyvinyl pyrrolidone instead of gelatin as a protective colloid. A silver chlorobromide emulsion containing about 100 g / l polyvinyl alcohol, about 30 g / l polyvinylpyrrolidone and 20 g / l finely divided silver chlorobromide with a molar ratio of chlorine to bromine of 7: 3, was exposed for 10 minutes as in Example 1 and compared the results against the same emulsion but not exposed. The trials were carried out by adding 4 g of acrylamide, 2 ml of water, 1 ml of a solution of 1 mol / l the pyrazolones listed in Table Ii and an aqueous 1N sodium hydroxide solution in the amount listed in Table II.

Table II

sample
No. l-Phenyl-3-methacrylamino-5-pyrazolone ...
lp-sulfophenyl-S-pyrazolone-S-carboxylic acid
lp-sulfophenyl-3-methyl-5-pyrazolone In-NaOH
(ecm) Time until
Reaching the
Maximum-
temperature temperature
CC) Temperature at
Use of
not exposed
emulsion 4th
29
23 2.0
0.3
1.0 140
90
25th 82
61
100 61
55
56

As can be seen from Table II, the reaction is preferably carried out in the exposed emulsion.

Example 4

In Examples 1 to 3, water-soluble vinyl compounds were used, but could water-insoluble monomers, tetraethylene glycol dimethacrylate to produce an emulsion thereof are polymerized.

The tetraethylene glycol dimethacrylate emulsion was prepared by mixing 10 ml of tetraethylene glycol and 10 ml of a 4% gelatin solution and emulsifying the system using a high-speed emulsifier after adding 0.2 g of sodium dodecylbenzenesulfonate. After mixing 8 ml of the emulsion obtained in this way and 2 ml of the emulsion prepared according to Example 1, the resulting mixture was mixed with 1 ml of an aqueous 1 η solution of 3-muyl-4- / I-hydroxyethyl-5-pyrazolone, 0 , 3 ml of an aqueous 1N sodium hydroxide solution and 10 ^"5 mol of sodium sulphate is mixed and the same experiments as stated in example 1 with the mixture. in the system where the exposed emulsion was used stie _fc the tem perature of the system by the heat of reaction after 66 minutes 66.7 ⁰ C while the system was used in which the non-exposed emulsion, single lent reached 62.5 ⁰ C. Thus, it could also appli cation in a water-insoluble or slightly löslichei monomers in the form of an emulsion, the monomials polymerized selectively in the presence of a silver halide since it was irradiated by electromagnetic rays or particle radiation.

Example 5

After imagewise exposure of a photographic photosensitive recording material rials with a photographic gelatin silver chloro iodobromide emulsion, the material with a Solution, the l-phenyl-S-methyl-S-pyrazolone. acrylic amide and methylene-bis-acrylamide contained, for through Conducting an imagewise polymerization treated the photosensitive used in this example Material was made in the following manner: After applying an adhesive layer to both surfaces surfaces of a polyethylene terephthalate layer carrier

an antihalation layer was coated on one surface thereof and a fine grain gelatin silver halide emulsion was coated on the opposite surface. The silver halide emulsion contains 100 g of gelatine and 0.7 mol of chlorine, 0.3 mol of bromine and 0.001 mol of iodine per mol of silver together with a merocyanine dye with a maximum light sensitivity of 550 ηΐμ as the sensitizing dye, about 1.5 g of mucochloric acid per 100 g of gelatine as hardeners and stabilizers and surface-active agents, the applied layer containing 50 mg of silver per 100 cm ² . A protective layer of gelatin to a thickness of about 0.8 Mik ^r on was further coated on the emulsion layer. Such types of photographic materials are commonly used for making photographic reproductions and halftone reproductions.

After a negative line image copy original on the recording material produced in this way had been hung up. the material was exposed to light of about 100 lux for 2 seconds and then immersed in a solution of the following composition under red light:

Acrylamide 90 g

Mrth., Lenbisacrylamid Sg

1-phenyl-3-methyl-5-pyrazoloii .... 7.8 g

Water 100 ml

2 N NaOH 23 ml

If the recording material was left to stand at 30 ° C. for 20 minutes, the exposed material could be exposed Observe a delicate picture. After stopping the reaction by applying an aqueous Solution of about 1% acetic acid and subsequent washing with water became the gelatin by using an aqueous solution with 1% of a gelatin-decomposing monyme (Bioprase PN 4) decomposed, whereby the gelatin in the unexposed parts of the layer was completely removed, while in the exposed parts of the layer left undecomposed areas, which led to the occurrence of selective polymerization covered in the exposed parts of the layer.

Example 6

45

The photographic photosensitive recording material according to Example 5 was exposed as there and treated in a solution of sodium methacrylate and l-phenyl-3-methyl-5-pyrazolone, wherein a polymer image was obtained which could be colored with a basic dye. That exposed Material was immersed in a solution of the following composition:

. Sodium methiK rv'at 60 g

l-phenyl-3-meth},

5-pyrazolone 6.2 g

2 n-sodium hydroxide

solution Required amount

for setting
the pH value
on 9
Water 60 ml

When the recording material treated in this way was left to stand at 30 ° C for 30 minutes an imagewise light brown deposit was formed on the exposed parts of the layer. The material was with an aqueous 1.5% acetic acid solution

⁵⁵

washed for 30 seconds and in a fixing solution fixed by the following composition:

Sodium thiosullate anhydrous 150 g

Potassium metabisulphite 15 g

Water to 11

After sufficient fixation and rinsing with water, the material was dissolved in a 0.1% aqueous solution Solution of a red basic dye (Rhodamine 6 G. C P., C. I-Basic Red 1) for 5 minutes Immersed in room temperature. If then the sample with an aqueous 5% acetic acid solution was washed for 5 minutes, the dye was washed out on the unexposed parts of the layer, while the exposed parts of the image are colored red, the image rendering is brown Represents the silver image, the silver image could through the Reducing agent after Farmer- are removed. After the removal of the silver image, a clear one became received red image. When the order of coloring and removal of the silver image has been changed, i.e. H. first the silver image was removed and a colorless transparent image was obtained and then the image was colored, it also became clear received red image.

The color image reproduction produced in this way could be transferred onto a paper. This was done lightly rubbed the surface of a conventional writing paper with a sponge containing methanol, to wet the surface with methanol, then the color image prepared in the above manner closely brought into contact with the wet surface of the paper and the two parts after about Taken apart 30 seconds, which transferred the red image onto the paper.

Using crystal violet (CI. Basic Violet 3) as a 0.1% aqueous solution was also a color image reproduction was made by the same procedure and the blue-violet image could be printed on Paper to be transferred.

By applying a 0.1% aqueous Lo ^ Solution of auramine 0-1000 (CI. Basic Yellow 2), a yellow image reproduction was obtained, and upon application a 0.1% aqueous solution of basic blue G.O. (C.I. Basic Blue 25) became a blue image receive.

In the case of transferring the color image, it was not necessary to remove or remove the silver image Silver halide could be removed and it could therefore be removed by immersing the material after development and polymerization in a break bath, washing with water and immediate dyeing and transfer good transferred images can be obtained during image reproduction.

Example 7

The same photographic light-sensitive material as in Example 5, exposure was carried out as there and in a liquid of the following composition treated to carry out the development and polymerization:

Sodium methacrylate 75 g

3-methyl-4-ethyl

5-pyrazolone 5.7 g

Potassium pyrosulfite 3.0 g

2 n-sodium hydroxide

solution Required amount

to adjust the pH to 9.0

Water 75 ml

When treated for 60 minutes at 30 ° C, a delicate sweet image and one made of polymethacrylic acid existing polymer image obtained. The image was made possible by Rhodamine 6 G.C. P. or crystal violet and similar compounds as in Example 6 could be colored, and the color image reproduction could be transferred to a paper moistened with methanol will.

Example 8

The same photographic light-sensitive material as in Example 5, exposure was carried out as there and in a solution of the following composition to carry out the development and polymerisation:

1-vinyl-2-methylimidazole 40 g

1-phenyl-3-methyl-5-pyrazolone 3.7 g

Potassium metabisulphite 3.0 g

Water ".. 75 ml

2N sodium hydroxide .... Required amount

to adjust the pH to 10.5

When the recording material was treated at 30 ° C. for 1 minute, it became a pale brown Silver picture together with the picture from polyvinylmethylimidazole educated. After fixation and rinsing

After treatment with water, the image was colored with a blue acid dye (CI. Acid Blue 62) and the image was washed for 5 minutes with a 1% aqueous solution of sodium bicarbonate, whereby a blue image reproduction was obtained. The image could be transferred onto a sheet of writing paper moistened with ethanol. The image could also be transferred onto a transfer paper moistened with water (Table III).

Example 9

The same recording material as in Example 5 was exposed as there and in a solution of the following Composition treated:

Methacrylic acid 58.9 ml

sodium
(Monohydrate) 43.0 g

For reducing agents see Table III

Water 87.5 ml

2n sodium hydroxide

solution Required amount

to adjust the pH to 10.0 or 9.0

After a treatment at 30 "C for the period listed in Table III, then fixed, rinsed with water and dyed as in example 5 with 0.1% rhodamine 6 G.C.P. The permeability density for green light of the exposed parts of the layer and of the unexposed parts of the layer ^ was measured before and after staining. The types of reducing agents, external quantities, the pH value in the treatment, the treatment time and the optical density before and after staining Coloring are listed in Table III.

20th

Table III

attempt

Reducing agent

1 - Phenyl-5-pyrazolone-3-carboxylic acid

1- (4-methoxyphenyl) -3-amino-5-pyrazolone

1 - PheuyI-3-methy 1-5-pyrazolone

1- (2,6-dichlorophenyl) -3-amino-5-pyrazolone

Amount of reducing agent (g)

9.18

9.58 7.83

11.48 treatment time (min.)

30th
10

30th
30th

before the coloring

0.24

0.20
0.18

0.14

do not read
len part Density of
exposed part after
coloring after
coloring before the
coloring 0.56 0.25 0.28 0.46
1.66 0.26
0.26 0.31
0.30 1.36 0.35 0.20

PH value

It can be seen that in all cases the density of the coloration of the exposed parts of the layer was higher than that of the unexposed layer parts and that the exposed layer parts are selectively colored. This gives can also be seen clearly from the fact that after removing the silver image, every attempt with the Reducing agent according to Farmer a clear red image was obtained. Even if the sample is a silver picture of low density, a clear or sharp red image was obtained without removing the silver image receive. These color images could also be reproduced on paper moistened with methanol, as in Example 6 be transmitted.

B e i s ρ i e 1 10

The recording material according to Example 5 was exposed as there and in a solution of the following Composition treated:

Sodium methacrylate 7.5 g

For reducing agents see Table IV

Sulphite see Table IV

Water 7.5 ml

I n-Sodium Hydroxide Required amount

to adjust the pH value to 9

33

1,797

It was found that the exposed parts were selectively colored as in Example 9.

Table IV

Attempt no.

Reduction fee!

crowd to reducers medium

(S)

Treatment time (min.)

Density of the unexposed part *

before the coloring

after staining

Density there exposed part

front coloring

after

Sulfite (E)

1-phenyl-3-methyl-5-pyrazolone

4-methoxyphenyl-3-asnino-

pyrazolone

3-phenyl-5-pyrazoloD

l-Py-idyl-3-methyl-5-pyrazolone S-amino-l-phenyl-S-pyrazolone. 4-n-buty 1-3,5-diketo-1-phenyl-

pyrazolone

Bis-1-phenyl- 3-methyl-

5-pyrazolone

3-methyl-5-pyrazolone

l-phenyl-3-hydroxy-5-pyrazolone 3-methyl-4- (2-hydroxyethyl) -

5-pyrazolone

1 -p-nitropbenyl-3-melhy 1-

5-pyrazolone

l-PhenyI-5-pyrazo! on-3 · nthyl-

acetate

1,3-dimethyl-5-pyrazolone

l-phenyl-3-methacrylamino

5-pyrazolone

1 -p-sulfony 1-5-pyrazolone-

3-carboxylic acid

l-p-sulfonyl-3-methyl-

5-p> tazolone

S-methyl-l-O-tolyl ^ -pyrazoIin-

5-on

l-m- (aminophenyl) -3-methyl-

5-pyrazolone

1 -p- (aminophenyl) -3-methyl-

5-pyrazolone

4-aminoantipyrine

3-methyl-4-isobutyl-5-pyrazolone 3-methyl-4-ethyl-5-pyrazolone 3-methyl-4-isopropyl

5-pyrazolone

3-methyl-4-amyl-5-pyrazolone 1 -PhenylO ^ imethyl-

5-PyrazoIon

3-t-butyl-5-pyrazoloiu

3,4-tetramethylene-5-pyrazoles

3,4-dimethyl-5-pyrazolone

3-phenyl-pyrazolone

l-phenyl ^ -methyl ^ n-butyl-

5-pyrazolone

1-phenyl ^ methyl ^ B-hydroxyethyl-5-pyrazolone

13-DJmethyl-4-butyl-5-pyrazolone

0.783

0.96

0.71

0.79
0.79 '

1.04

1.55
0.44
0.79

0.64
0.99

1.11
1.06

1.1

1.3

1.1

0.85

1.0

0.85
0.91
0.69
0.57

0.51
0.76

0.74
0.63
0.62
0.50
0.72

0.59

0.98
0.76

30th

10 90

40 45

30th

30 30

25th

20 30

7 30

12 25 60 60 13

13 4

30 60

60 30

20 60 60 30 60

60 9

0.08

0.19
0.08

0.08
0.07

'■ 07

0.06
0.06
0.06

0.06
0.08

0.07
0.74

0.11
0.08
0.07
0.08
0.26

0.08
0.07
0.08
0.08

0.07
0.07

0.07
0.07
0.07
0.07
0.08

1.44

0.21 0.75.

0.14 0.48

0.85

0.27 0.4S '0.33

0.30 0.35

0.70 2.55

0.24 0.13 0.15 0.15 0.37

0.18 0.14 0.17 0.15

0.20 0.16

0.16 0.14 0.29 0.16 0.24

0.47

0.26 0.24

0.09

0.41 0.08

0.08 0.09

0.07

0.35 0.07 0.09

0.00 0.14

0.35 0.84

0.16 0.08 0.08 0.08 0.43

0.19 0.11 0.09 0.08

0.08 0.08

0.09 0.08 0.07 0.11 0.11

0.60

0.14 0.14

1.97

0.53 0.93

0.49 1.12

1.89

1.08 U2

1.07 1.22

1.52 2.58

l / M) 0.25 035 0.3 *

Sodium sulfate,

the same

Potassium meta-

btsuhlt, 0.3

the same

the same

the same

1.55 032 1.54 1.58

1.62 1.45

1.72 0.27 0.52 1.75 0.34

L96 2.9!

despj

the same

desgl desgl.

like. like. like. like.

like. like. like. like.

desgl desgl.

like. like. like. like.

the same

the same.

35

continuation

Attempt no.

Reducers

1, S-dimethyl- ^ B-hydroxyethyl-5-pyrazolone

l - ^ - hydroxyethyl-3-methyl-4-butyl-5-pyrazolone

crowd Treat Density of not after Density of after to Re- lungs time exposed part coloring exposed part coloring duzier- (Min.) 0.64 2.82 medium before the 0.31 before the 3.33 (G) 60 coloring coloring 0.70 30th 0.07 0.16 0.89 0.08 0.14

Sulfite (g)

the same. the same. '

example

As in Example 10, the exposed recording material was in a solution of the following composition treated:

Methacrylic acid 7.5 g

Reducing agent ... see Tabei'e V

Sulphite see Table V.

Water 7.5 ml

1 n-sodium hydroxide Amount required for adjustment

the pH value to the value given in Table V.

Table V

Attempt no.

5-pyrazolone

ί -Phenyl-S-amino-S-pyrazoIon 3,4-dimethyl-5-pyrazolone .... ^ n-butyl-S.S-diketo-

pyrazoion

3-methyl-5-pyrazolone l-phenyl-3-methyl- 4 - /? - hydroxyethyl

5-pyrazolone

1,3-Dimethyl-5-pyrazolone 1,3-Dimethyl-4-butyl-

5-pyrazolone

1,3-dimethyl-4- / S-hydroxy-

ethyl-5-pyrazolone 1-hydroxyethyl-3-methyl-4-butyl-5-pyrazolone

0.39 0.79 0.50

1.05 0.44

0.98 0.50

0.76 0.70 0.88

Treatment time (mm.)

40

5 5

30 60

37 18

40 60 60 Density of the unexposed part

before the coloring

0.08

0.08
0.10

0.10
0.08

0.24
0.07

0.18
0.36
0.21

after staining

0.10 0.49 0.62

0.42 0.25

0.46 0.20

0.31 0.60 0.62

Tight
exposed
before the
coloring 1
edes
en part
after
coloring sulfite
Potassium-
meta-
bisulnt
(G) pH 0.12
0.22
0.60 0, b6
1.64
1.22 0.3
0.3
0.3 10.4
11.5
11.5 U, 10
0.10 1.47
1.56 0.3
0.3 11.5
11.65 0.48
0.17 2.43
1.51 0.3
0.3 11.7
11.65 0.62 3.56 0.3 12.0 3.38 3.83 0.3 12.05 0.46 2.87 0.3 11.65

example

It was obtained by coating a silver halide emulsion without using gelatin as in Example 3 prepared photographic material used. It became a support made of cellulose triacetate used:

Emulsion as in Example 3 75 ml

Water · · · · 100 ml

p-methoxyphenol (V ₅₀ molar

aqueous solution) 1.0 ml

Sodium dodecylbenzenesulfonal

(1% aqueous solution) 1.0 ml

65 The above mixture was applied to the layer support approximately 5 microns thick (dry) and the layer was dried by heating.

A line art master was placed on the emulsion layer of the material for 10 seconds irradiated with a xenon lamp of 500 watts at a distance of 50 cm. Then the recording material became into a solution having the following composition for carrying out development and polymerization immersed:

3,4-dimethyl-5-pyrazolone 5 g sodium methacrylate (20% solution) 75 ml

1

Potassium metabisulphite 12 g

Borax 7.5 g

Water 100 ml

Methylenebisacrylamide ... 8 g

2n-NaOH Required amount

for setting
the pH value
on 9

The recording material was developed for 15 minutes at 30 ^° C., whereupon a delicate image reproduction was discernible in the exposed parts of the layer. When the material was fixed and washed with water, the unexposed parts of the layer were peeled off. When the remaining image reproduction was colored by an aqueous solution of Rhodamine 6 GCP, the exposed parts of the image were colored, which shows that a polymer with a negative charge had been formed. In this example, a synthetic polymeric binder was used in place of gelatin for the silver halide photographic emulsion.

Example 13

An emulsion of the following composition was coated on a cellulose triacetate support Applied to a dry thickness of about 8 microns:

Emulsion according to Example 1 35 ml

Calcium methacrylate (66%

aqueous solution) 75 ml

Gelatin 6.5 g

Water 30 ml

p-methoxyphenol (Vsomolare

aqueous solution) 1 ml

Mucochloric acid (2% aqueous

Solution) 1.2 ml

Sodium dodecylbenzenesulfonate

(1% aqueous solution) ImI

The recording material thus obtained was passed through a line image master for 1 second irradiated with a xenon lamp of 500 watts at a distance of 50 cm and then the emulsion layer moistened with a sponge containing a developer of the following composition:

1-phenyl-3-methyl-5-pyrazolone ... 0.783 g

Potassium metabisulphite 1.6 g

Water 10 ml

2N NaOH 7.9 ml

The entire layer was then covered with a glass plate in order to carry out the development and polymerization for 1 hour at 30 ^° C., whereby a delicate image was formed. The layer was fixed and rinsed with water and the image reproduction was colored as in Example 6. With this procedure it was found that the exposed parts of the layer were selectively colored and a polymer image had thus formed in these parts of the image. Thus, by incorporating the monomer in the emulsion layer in advance, it was possible to reduce the concentration of the monomer and to simplify the development and polymerization process.

Example 14 **

Using recording materials A and B using the following two

193 Ol

LJ 38

Types of silver iodobromide emulsions was the polymerization of sodium methacrylate with 3,4-dimethyl-5-pyrazolone accomplished.

Material A

The two surfaces of a cellulose triacetal support were provided with an adhesive layer, one surface being coated with an antihalation layer and the other surface being coated with a medium grain photographic silver halide photographic emulsion containing about 225 g of gelatin and 0.015 moles of iodine and 0.985 moles of bromine per mole of silver together with 0.5 g of mucochloric acid per 100 g of gelatin and conventional additives such as stabilizers and surface-active agents . The emulsion was applied to the adhesive layer in a layer weight of 60 mg of silver per 100 cm ^{2 of} the emulsion layer, and a protective layer of gelatin in a thickness of about 1 micron was further applied to the emulsion layer. Such types of photographic materials are commonly used for the production of positive images for the photographic printing process.

Material B

A fine-grain photographic gelatin silver halide emulsion containing about 204 g of gelatin, 0.0! 2 Mo! Iodine and 0.988 mol of bromine per mol of silver, sensitized with a gold thiocyanate complex, together with 0.3 g of 6- methyl-4-hydroxy-1,3,3a-7-tetrazaindene per 1 mol of silver as a stabilizer, about 0.7 g Mucochloric acid contained per 100 g of gelatin as hardening agent and suitable surface-active agents and which ^{resulted in a proportion of the silver of 60 mg per 100 cm 2 of} the emulsion layer. Such photographic materials are commonly used for the production of line copies and continuous tone images of steep gradation for photographic printing. ^

2 seconds were recording materials' / exposed with 1000 lux and a Farbtemperai ^<0 of 2880 K through an optical step prism having a stage difference of 0.15 and then developed with a solution of the following composition:

Sodium methacrylate 60 g

3,4-dimethylpyrazolone ... 6.4 g

Potassium pyrosulfite 2.4 g

Water 60 ml

2 n-sodium hydroxide

solution Required amount

to adjust the pH to 9.0

After 25 minutes of development at 30 ⁰ C a delicate brown image was obser tet in both cases. The emulsion layers were fixed and washed with water as in Example 6 , and then colored with Rhodamine 6 GCP to obtain color image reproductions.

Example IS

A fine grain silver chloride emulsion wherein the Approach cores have been chemically sensitized «rare and practically by the same process as in the British Patent 667206

was, was with

mixed was on «^^^^ SÄg StaUetenPolyathylentereph ^ atSchM

carry. It became a ^ t- ^ mves A ^{u |} MJchnunp matena vom Hcrschcl-E (Tci t-Typ £ ™ _u ^ line image copy template was au d ^ E ™ ™

ÄS5 ^ «vi Solva ^ Sito long ÄSdtaKKuter irradiated from a distance of 50 cm The exposed recording material was developed in a solution of the following composition: ·

Sodium methacrylate «J g

l-phenyl-3-metnyi-

5-pyrazolone. β

Potassium pyrosuint, β

l-phenyl-5-mercapto- ^

tetrazole 60 ml

Υ ä; _{an unNecessary} amount

-Solution ^ setting

the pH value to 10

SÄKn ^ lSÄC was that

Material fixed, rinsed with water and the thereby _ene ^ _{e rhodamine 6} GCP _{be by}

torn, creating a light brown silver image in the night

exposed layer parts was formed and only

_{be) exposed parts of the image were ßrbl} , so that a

positive image reproduction of the master copy was obtained.

B e i s ρ i e 1 16

^ _{photographic recording material} | as in Example 6, it was exposed to X-rays and

if «the same solution as in the example! 6 treated. _The | _{X-ray treatment} was carried out under

Winding of a cobalt X-ray tube with 30 kV and 10 m-Anip. carried out for 3 seconds.

The sample was attached to the window of the X-ray

The nozzle at a distance of 1 cm,

while a part of it was covered with a sheet of paper 0.2 mm thick.

After 30 minutes of development at 30 ° C., the layer was fixed and washed with water and with rhodamine ό Ci. C. P. colored.

1 sheet of drawings

Claims (1)

Patent claims: 1. A process for the production of optionally colored polymer images, in which one in one imagewise exposed silver halide emulsion layer containing latent image by exposure a monomeric vinyl compound and a reducing agent is developed, characterized in that that the reducing agent is a 2-pyrazolin-5-one of the formula acid, a basic nitrogenous vinyl compound or a salt of these compounds and the developed polymer image one Dye which has a charge opposite to that of the polymer is dyed 4. The method according to claim 3, characterized in that the colored Polymerisatbik colored image reproductions are transferred to an image receiving sheet.