DE1954768B - Process for the production of polymer images - Google Patents

Description

It also reports that other researchers have had no success in following up this procedure (S. Le vinos and F. W. H. Mueller, "Photographic Science & Engineering", Ed. 6, p. 222 [1962]).

It is also a method of preparing photographic polymer images by treatment an imagewise exposed silver halide emulsion layer containing a monomeric vinyl compound and a reducing compound known in which the reducing compound resorcinol, m-aminophenol or derivatives thereof are used, these derivatives not being amino or Have hydroxyl group in the o- or p-position (Belgian patent 699 535).

It is wide ^one "known to be active Methylenverbindüngen used for initiating the polymerization can werütn (see. H. Bredereck, B. Föhlisch & R. Franz," Macromolecular Chemistry ", 92 [1966], pp 70 to 90).

According to the above publication, the active methylene compound ^{can initiate polymerization of a vinyl compound in the presence of Cu ++} , Cl ~ and oxygen or peroxide. In this system, however, oxygen, Cu ^{+ +} or peroxide act as oxidizing agents and accordingly the polymerization has no selectivity with respect to irradiation. It has also been reported that a complex compound of / ϊ-diketone, e.g. B. acetylacetone can be used as a polymerization initiator (cf. CH. Bamford & D.H. Lin d, "Chemistry &Industry", 1627 [1965] and the references made therein). It is stated here that the polymerization is initiated by the following radical:

CH ₃

C = O

CH
\

CH ₃
CH ₃

Mn ⁱⁿ (Acac) ₃

C-O

C = O

CH

+ Mn "(Acac) ₂

C = O

CH ₃

In the system of this initiator is also the reaction due to the by oxidation with a Metal salt generate radicals and is thus independent of the irradiation.

Also, as a method for producing images made of polymeric material, the tanning development method is used known in which one crosslinked with an oxidation product of a developer Gelatin builds up the image. In this process, the properties of the image formed are dependent on the Properties of crosslinked gelatine are limited.

The object of the invention is a method for production of polymer images by treatment of an imagewise exposed silver halide emulsion

layer with a monomeric vinyl compound and a reducing compound to specify that easy is to be carried out and provides polymer images with variable properties that can be colored, transferred and can therefore be used to produce a large number of copies and which have a higher color density than previously possible.

The subject matter of the invention relates to a process for the production of polymer images that of a latent contained in an image-wise exposed photographic silver halide emulsion layer Image obtained by the action of a monomeric vinyl or vinylidene compound and a reducing agent is developed from and is characterized in that at least one reducing agent is used active methylene compound of formula (a):

R,

R ₃

CH

wherein R ₁ and R ₂ each represent an alkyl, a substituted alkyl or phenyl group and R _{3 represents} a hydrogen atom, an alkyl or substituted alkyl group and where R _{1 can} optionally form a ring with the radicals R ₂ or R ₃ , of the formula (b):

R,

R,

CH

Y-R,

or

R,

X O

C C-Y-

C C

X O

wherein R _{1 is} a hydrogen atom or an alkyl group, R _{2 is} an alkyl group, a substituted aromatic ring or sodium, R _{3 is} a hydrogen atom, an alkyl, substituted alkyl or cyano group or a chlorine atom, where R ₂ and R ₃ optionally form a ring with one another R _{7 represents} an aromatic ring when X represents the - NH - group, and represents an acyl or alkyl group when X represents the - O - group. X the remainder - O -, - NH -,

- N-NH

and Y denotes the radical O or NH, or of the formula (c):

CN R ₂

CH

where R _{1 is} a hydrogen atom, an acyl or phenyl group and R _{2 is} an ethoxycarbonyl or cyano group, or their tautomeric isomers and / or their metal complex salts are used.

The invention achieves that, as a result of the low pH dependency, the reducing agent active methylene compounds of the formulas (a), (b) and (c) or their tautomeric compounds used Isomers and / or their metal complex salts produce the polymerization color images within of a broad pH value serum can be carried out, moreover, when using the same Treatment times obtained polymer color images with a higher color density than was previously possible was.

Compared to the tanning development process The images obtained show the polymer images obtained according to the invention as a function of the vinyl compounds used have changeable properties, some of the properties, for example the coloring power and the chemical resistance are better than the corresponding ones Properties of cross-linked gelatin.

It was found that at the points of the photographic halogen overemulsion in which the silver halide crystals Own development centers, the polymerization takes place faster than in the places, whose silver halide crystals are free of development centers and that therefore the polymerization of the monomeric vinyl compound in areas in which silver halide particles have development centers, can be effected selectively with a suitable choice of reaction conditions.

As the photographic silver halide emulsions, conventional negative emulsions or direct positive emulsions can be used be used.

As photographic negative halosilver emulsions, chlorosilver, bromosilver, chlorobromosilver, Iodobromosilver and chloroiodobromosilver emulsions are used which are chemically or optically can be sensitized in the usual way.

Optical sensitizers for conventional photographic emulsions, z. B. cyanine dyes and merocyanine dyes can be used appropriately and conveniently (cf. e.g. K i k u c h i et al. "» Kagaku Shashin Benran [Handbook of Scientific Photography] ", Vol. II, pp. 15-24. Maruzen Co., 1959). According to the invention The emulsion to be used can also contain stabilizers, as seen in conventional photography Working methods used are included.

The ^r in the inventive Ver Ahren usable photographic direct-positivist liven silver halide emulsions könren using the Sun! Arisa-tion, the Herschel effect of Clayder. effect and the Sabatier effect can be produced. These effects are e.g. B. in CEK M ees, "The Theory of the Photographic Process", 1st edition, published by McMillan Co. (1954), Chapters 6 and 7 explained.

In the photographic emulsions to be used are the halogen silver grains in a solution of a polymeric binding agent. As a polymer Binder is usually gelatii., Used, however, synthetic high molecular weight compounds such. B. polyvinyl alcohol, polyvinyl pyrrolidone and polyacrylamide, or natural high molecular weight derivatives, e.g. B. carboxymethyl cellulose. CeIIuloseoxväthvläther and dextran, alone or together with gelatin can be used (cf. F. E ν ν a. "Journal for Scientific Phctography, Photophysics and Photochemistry", Vol. 52, p. 1 to 24 [1957] (. Examples of reducing agents to be used in accordance with the invention correspond to those given above general formulas (a), (b) and (c) are given below:

H ₃ C CH ₂ CH ₃

C C

Il Il ο ο

Acetylacetone

1,3-cyclohexanedione

H, C

o-Acetyl-S-methyW-cyclohexen-1-one

CH,

C = C

CH ₃ CH ₂ CH CH ₃

</ </ \ / C CH ₂ C

Il Il

ο ο

3-acetyl-2,6-heptanedione

CH ₃ CH ₂ OC ₂ H ₅ CC

O

Ethyl acetoacetate

o-acetoacetanisidide

7th 1 954 768 CH ₃ CH, CH OC ₂ H ₅
\ / \ /
CC
Il Il 5 (14) Il Il
OO Ethyl M-melhylaceloacetate
HC ₆ H ₁₃ IO (15) CH ₃ CH OC ₂ H ₅ \ / \ /
CC
Il Il "5 Il Il
OO Ethyl-u-n-hexylaceloacetate 20th (16) CN CH ₃ CH OC ₂ H ₅ 25th \ / \ /
CC
Il π Il Il
ο ο Ethyl u-cyanoacetoacetate l \ 7 \

CH ₃
(10) CH ₃ -COC = CH-C-OC ₂ H ₅

Il Il

ο ο

Ethyl - ^ - acetoxycrotonate H

CH ₃ C OC ₂ H ₅

I Il

NH O

Ethyl 3-aniline crotonate

CH OC ₂ H ₅

/ "\ /
(12) CH C

I Il

OC ₂ H ₅ O
EthyI-0-ethoxyacrylate CH ₃ CH ₂ OC ₂ H ₅

Y Y

NH O
Ethyl - /? - iminobutyrate

35

40

45

55

60

CH ₁ CH ₂ OCH ₃

c c

Il l \

0 H OCH ₃

Acetoacelaldehyde dimethyl acetal

_{/ C} H,

CN CN

Malononitrile

QH ₅

CH OC ₂ H ₅

/ \ / CN C

Il ο

Ethyl u-phenyl cyanoacetate

CH, CH OC ₂ H ₅

I Il

0 O

Ni ,, ₂ ethyl nickel acetoacetate

CH ₃ CH OC ₂ H ₅ CC

Il Il ο ο

Ethyl-a-n-butyl acetoacetate

H CH ₃ CH ₂ N

c c

O 0

Acetoacetanilide

O

Il Il

c c

CH ₂ CH ₃

Benzoylacetone

CH ₁ CH ₂ OCH ₁

Il Ii ο ο

Methyl acetoacetate

CH ₃

CH OC ₂ H ₅

c c

Il Il ο ο

Ethyl a-n-amylacetoacetate

CH ₃ CH ₂ ONa

Il Il ο ο

Sodium acetoacetate CH ₂ CH ₂ O

CH ₃

CH

\ C C

Il Il ο

2-acetylbutyrolactone

Cl

CH ₃ CH OC ₂ H ₅

Il Il ο ο

Ethyl a-chloroacetoacetate

Phenylhydrazone dehydroacetate

The synthesis methods of the compounds (1) to (25) are well known, and these compounds sinvi available in stores.

The compound (26) is obtained by reacting before dehydroacetic acid with an equivalent amount before phenylhydrazine in tetrahydrofuran under freezer at - I5 ° C, the temperature is gradually reduced to 0 ⁰ C, obtained, and the resulting precipitation is recrystallized in tetrahydrofuran with a Product with the following characteristics is obtained:

ίο Melting point: 199 to 202 "C;

Ultraviolet absorption spectrum:
'· «« .99% AthOH: 245mn lied _f -: 4,0I,
W ₂ .99% ÄthOH: ηΐμ 352, log f: 3.60;
Infrared absorption spectrum:

>'C0C(>' C0c): 1150cm- ',, -NH: 3405cm' ¹ , 3360 cm " ¹ .

moreover, these compounds can be used in the form of a metal complex salt. In this Case, the compound isolated as the metal complex salt may be used, or it may be a Complex salt can be formed in the solution by adding a metal salt. The stability constants these metal complex salts, especially the complex salts of acetylacetone derivatives, are general known (cf. Marte 11 and Calvin, »Chemistry of the Metal Chelate Compounds ”, published by Preniice-Hall Inc. [1962], in particular table on page 549).

in contrast to the ratios in the known non-image-wise polymerization of vinyl compounds Silver halide acts with / i-dicarbonyl compounds in the process according to the invention as an oxidizing agent, so that the rapidity of initiation of polymerization with the presence or absence of development centers in the silver halide particles, d. H. with the presence or lack of exposure to electromagnetic waves or corpuscular rays varies. this is a very important feature. The mechanism of the reaction has not yet been clarified with regard to in what manner exposed silver halide with the methylene compound of the above general formulas (a), (b) or (c) with initiation of the polymerization in reaction. It will, however assumed that the polymerization proceeds according to a radical chain mechanism due to the The fact that monomers prone to free radical polymerization can be used and that the reaction proceeds in aqueous solution and is delayed by a radical polymerization inhibitor will. It is not clear whether the radical is generated directly by the reaction of the compound of the above given general formulas (a), (b) or (c) with silver halide or by interaction is generated with water or oxygen in the system. However, it is clear that the polymerization of a vinyl compound takes place simultaneously with the reduction of the silver halide, since when the vinyl compound is added to the reaction system after the irradiated silver halide with the Compound of the general formulas (a), (b) or (c) given above is reduced, no polymerization Is found.

An intermediate product obtained by oxidation of /? - diketone or / f-keto acid ester with a Munoelectronic oxidizing agent, namely cerium sulfate, is from G.A. R u3seI & curls gard. in

"Journal of the American Chemical Society". 89, 5059 (1967).

In this report the intermediate product is explained in the radical state, with the following reaction scheme relating to the oxidation of 1,3-cyclopentanedione Is accepted.

O ^- O "

The initiation of image-wise polymerization in the process of the invention is likely to occur by a radical of the active methylene compound that occurs during the reduction of the silver halide is formed.

If the reaction is interrupted after a certain time, the polymer is selective in the irradiated layer parts have been formed alone. If the reaction time is extended, polymer formation continues also in the non-irradiated parts of the layer. However, the usefulness of the procedure according to the invention by this phenomenon, that of so-called fogging in silver halide photography corresponds, not restricted.

It was also found that in the process according to the invention, the polymerization of the monomeric Vinyl compound is accelerated by the presence of sulfite ions.

According to one embodiment of the invention, development and polymerization are carried out in the presence of sulfite ions.

The sulfite ions can be added to the system either by adding a compound containing sulfite ions, e.g. B. of alkali and ammonium sulfites and disulfites or by adding a to form sulfite ions material capable of hydrolysis in aqueous solution, e.g. B. of alkali and ammonium pyrosulfite and addition compound of bisulfite and aldehyde, e.g. B. formaldehyde or glyoxal are supplied. Although the appropriate amount of sulfite ions to be added to the system depends on the type and Amount of reducing agent and vinyl monomers used and the pH of the system depends, however, an amount of 0.05 mol or more per 11 of the system, particularly 0.2 mol or more above, preferred.

The addition of sulfite to photographic developers is well known. In this case it is assumed that the sulfite prevents the autoxidation of the developer, for example of hydroquinone or p-aminophenol, as well as a non-uniform development reaction (see CEK Mees, "The Theory of the Photographic Process", 2nd edition, published by MacMillanCo . [1954], p. 652). Hs can now be observed that the polymerization accelerating effect of the sulfite according to the invention is completely different from the effect of removing an oxidation product in the usual developer as described above, since according to the invention an oxidized intermediate with an active methylene compound with a silver halide the Initiates polymerization. If the sulfite were only used to remove the oxidized product, the polymerization would have to be suppressed.
5 Although the mechanism of the action of sulfite according to the invention has not yet been clarified, it is believed that the addition of sulfite cancels the polymerization-inhibiting effect of oxygen.

ίο useful for the method according to the invention Vinyl compounds are addition-polymerizable compounds that are liquid at normal temperature or are solid or mixtures thereof, ζ. Π. Acrylamide, acrylonitrile, N-hydroxymethylacrylamide, methacrylic acid, Acrylic acid, calcium acrylate, sodium acrylate, methyl methacrylate, methyl acrylate, ethyl acrylate, Vinylpyrrolidone, 2-vinylpyridine, 4-vinylpyridine, 2-methyl-N-vinylimidazole, Potassium vinyl benzene sulfonate and N-vinyl carbazole. When performing the invention Process, vinyl compounds with two or more vinyl groups are particularly suitable, these alone or together with the above-mentioned compound having a vinyl group can be used. Examples of such compounds having two or more vinyl groups are Ν, Ν-methylenebisacrylamide, ethylene glycol dimethacrylate, Diethylene glycol dimethacrylate, triaibvlenglycol dimethacrylate, polyethylene glycol methacrylate, Diviryl ether or divinylbenzene.

A water-soluble vinyl compound is expedient and advantageous for the process according to the invention used, but also a water-insoluble vinyl compound by addition in the form an emulsion can be polymerized. The emulsification can be carried out by means of suitable stirring devices in the presence of a surface-active agent and / or a polymeric binder in the usual manner are executed.

Any electromagnetic waves or corpuscular rays against which the usual photographic emulsion is sensitive can be used in accordance with the invention. So can include visible rays, ultraviolet rays, infrared rays of 1.3 microns or less, x-rays, y-rays and corpuscular rays, ζ. Β electron beams and α-rays can be applied.

Upon exposure, the silver halide can either be in an aqueous solution or in the form of a gel exist, d. i.e., a highly viscous or gelled photographic emulsion can be coated on a suitable one The support can be used in an undried state, or it can be used as a layer on a: suitable substrate in a dried state.

Since the reduction and polymerization take place simultaneously, the reduction must be carried out in the presence of a Vinyl compound are carried out. In the process according to the invention, both the before active methylene compound described above, which acts as a reducing agent for the silver halide as well as the vinyl compound that is to be polymerized in the emulsion layer from the start Recording material, or the eirii Component can only be included in it, according to which the other is added to the system after irradiation will. In certain cases, both components can be added after irradiation.

The presence of water allows the reduction and polymerisation reactions to be carried out in practice is necessary, the reaction must be in an aqueous solution or in a moist gelled state are executed.

This reaction takes place in an alkaline medium, i. H. at a pH value above about 6, preferably above about 7, well, the particularly suitable pH of the species and the Concentrations of silver halide, reducing agent and the high molecular compound as Medium and the reaction temperature depends.

When a photographic emulsion coated on a support is used, it will After exposure, photosensitive material is preferably developed with an aqueous alkali solution. The reducing agent or the vinyl compound can preferably be contained in this solution.

The image-providing development can easily be interrupted by leaving the system in the acidic Area transferred (pH below 5), a reactant by washing, cooling, dissolving removed from silver halide in a fixing solution for photographic use or a polymerization inhibitor adds to the system.

When a layer of silver halide in a polymeric binder and a vinyl monomer is used, it is desirable to add a small amount of a thermal polymerization inhibitor, to prevent spontaneous polymerization of the vinyl compound. As a thermal polymerization inhibitor Compounds are used for the customary radical polymerization are well known, e.g. B. p-methoxyphenol, hydroquinone, alkylhydroquinone or 2,6-di-tert-butylp-cresol.

When the monomeric vinyl compound is incorporated into the emulsion layer, it is used in an _{amount by weight ranging from V 30} to 30 times, preferably ¹ Z _{4 to 4} times, the amount by weight of the polymeric binder previously added. The silver halide is in an amount by weight of the Z ¹ ₂₀ - to 2 times, preferably until VIO '^ fold of the previously added polymer binder used. When the reducing agent is incorporated into the layer, the amount of the reducing agent is preferably about 1/10 to 20 moles per 1 mole of the silver halide used. When an inhibitor to thermal polymerization is added, it is preferably used in an amount by weight of from one thousandth to ^{two hundredth of} the weight of the vinyl compound.

When adding the monomeric vinyl compound to a treatment solution, it is usually convenient and desirable that its concentration is as high as possible, in which case the amount to be added is limited by the solubility of the vinyl compound in the treatment solution. When an active methylene compound used as a reducing agent is added to a treatment solution, its concentration is preferably in the range from ¹ Z ₂ O to 5 mol, in particular ¹ Z ₁₀ to 1 mol (per 1 mol of the silver halide used).

As with usual silver halide photography there may be a time gap between irradiation and development (polymerization).

To record an image, the differences between unchanged monomeric vinyl compound and their polymer with regard to their physical and chemical properties, ζ. Β Solubility, light scattering, adhesive ode. · Adhesive strength or staining affinity, exploited. When utilizing the difference in solubility can e.g. B. a Bile by dissolving away the layer parts not polymerized after irradiation and development under back leave a relief of high molecular weight material only in the irradiated layer parts the.

In this case, the polymeric binder contained in the layer is preferably dissolved away together with the unreacted monomers. In order ^{to achieve 1} , a polymeric binding agent, the structure of which is two-dimensional or linear and which is essentially free of crosslinking or whose main chain or crosslinking can be easily broken, is added to the layer. In contrast, the polymer formed during exposure and subsequent development has a three-dimensional crosslinked structure and is accordingly less soluble. In order to achieve an insoluble, crosslinked polymer, it is advantageous to use a compound having a plurality of vinyl groups alone or together with a compound having a vinyl group.

Even if the polymer formed consists of a two-dimensional high molecular weight material however, there is often a difference in solubility between the exposed and unexposed parts of the layer obtained because the polymer formed and the polymeric binder contained in the layer below Cross-link formation of insoluble parts of the image, for example in the case of polyacrylic acid as formed Polymer and gelatin as a polymeric binder. Thus it is not always necessary to use a monomer to be used with a plurality of vinyl groups. In the method according to the invention it is possible Receive color images. For this purpose, a poly-

Merisatbild, which consists of a salt-like rOlymerisat with ion charges, is generated and this selectively colored with a dye with opposite ionic charge. To achieve this, a vinyl monomer is used with a group that receives an ion charge through ionization or the addition of hydrogen cations can, used. A polymer is then formed which is capable of accepting a charge by ionization or addition of hydrogen cations. The color obtained after staining

image can be transferred to another substrate using various methods.

Addition-polymerizable vinyl compounds that accept a charge by ionization or Addition of hydrogen cations are capable and which

can be used in the case described above are the following:

a) Compounds that provide a polymer image with a negative ion charge are vinyl compounds with a carboxyl group, e.g. B. acrylic acid, methacrylic acid, itaconic acid and maleic acid, as well as their Metal or ammonium salts, e.g. B. ammonium acrylate, sodium acrylate, chewing acrylate, calcium acrylate, Magnesium acrylate, zinc acrylate, cadmium acrylate, sodium methacrylate, Calcium methacrylate, magnesium

methacrylate, zinc methacrylate, cadmium methacrylate, sodium itaconate and sodium maleate, vinyl compounds with a sulfonic acid group, e.g. B. vinyl sulfonic acid and D-vinyl benzene sulfonic acid and vinyl

compounds and their metal or ammonium salts, e.g. B. ammonium vinyl sulfonate, sodium vinyl sulfonate, Potassium vinyl sulfonate and potassium p-vinyl benzene sulfonate.

b) Compounds which give a polymer image with a positive ionic charge are vinyl compounds with a basic nitrogen atom, e.g. B. 2-vinylpyridine, 4-vinylpyridine, 5-vinyl-2-methylpyridine, N, N - dimethylaminoaälhylacrylat, N, N - dimethylaminoethyl _{methacrylate, N 7} N - diethylaminoethyl acrylate and NN-diethylaminoethyl methacrylate, and vinyl compounds with a quaternary nitrogen atom, which by reaction these bases were prepared with methyl chloride, ethyl bromide, dimethyl sulfate, diethyl sulfate and methyl p-toluenesulfonate.

These compounds mentioned are commercially available and can be according to generally known Working methods are produced. These compounds can be shipped alone or in the form of mixtures Be, moreover, these compounds can be combined with a charge-free water-soluble and addition polymerizable monomeric vinyl compound, e.g. B. acrylamide, N-hydroxymethylacrylamide. Methacrylamide. Methyl methacrylate. Vinyl pyrrolidone, N.N-methylenebisacrylamide, triethylene glycol dimethacrylate and triethylene glycol dimethacrylate. used will.

As a dye capable of ionizing. in this case the common acidic and basic ones can be used Dyes are used. When using a vinyl compound that has a polymer image with a provides a positive charge, an acidic dye is used, while if a vinyl compound is used, which provides a polymer image with a negative charge, a basic dye is used. An acidic dye, the dye molecule of which is negatively charged, colors a high molecular compound with a positive charge, while a basic dye, whose dye molecule is positively charged is, a high molecular compound having a negative charge colors well. Hence, a dye ' biid obtained that corresponds to the primarily generated polymer image.

When gelatin is used as a binder of a photographic emulsion, the coloring is necessary of the polymer image taking into account the isoelectric point of gelatine, since gelatin is an amphoteric electrolyte. At a pH above the isoelectric point of the gelatin used, the gelatin has a negative charge and a lower pH value a positive charge. Therefore, when a polymer image having a negative ionic charge is formed dyeing with a basic dye at a pH below the isoelectric point carried out by gelatin, whereby only the image from the polymerized vinyl compound are colored can without coloring the gelatin. On the other hand, the staining may initially be uniform at a pH above the isoelectric point of gelatin, whereupon washed with a washing solution having a pH lower than the isoelectric point of gelatin is, whereby those layer parto. which do not contain any polymer formed, washed out and only an image consisting of colored polymer remains.

When a polymer image with a positive ionic charge is colored with an acidic dye, can stain similarly at a higher pH than the isoelectric point of Gelatin run. If the pH is too high or too low, the solubility becomes one Dye is reduced or the dissociation of the salt structure of the polymer image is disturbed, see above that of course the most suitable range of pH in accordance with the types of

ro end vinyl compound, the dye and the binder, e.g. B. gelatin, must be determined. A preferred pH range is from 2.5 to 4.5 when the layer is a gelatin with a isoelectric point of about 4.9, which in common

rs way was treated with lime, contains and a Polymer image with a negative ionic charge is to be colored with a basic dye. Further, a preferred pH range is a range of 0.5 to 8.0 if a polymer image with a positive ionic charge is made with an acidic dye is colored.

Dyes that can be used as acidic dyes are C.I. Acid Yellow 7 (C.I. 56 205). C. I Acid Yellow 23 (C. 1.19 140). C. I. Acid Red 1 (C. I.

18 050), C.I. Acid Red 52 (CI. 45,100). C.I. Blue 9 (CI. 42 090), C.I. Acid Blue 45. C.I. Acid Biue 62 (CI. 62 045) and C.I. Acid Violet 7 (CI. 18 055). and dyes useful as the basic dyes are C. I. Basic Yellow I (C. I. 49 005). C. I. Basic Yellow 2 (C I. 41,000), C I. Basic Red 1 (C I. 45 160). CI. Basic Red 2 (CI. 50 240), CI. Basic Blue 25 (C I. 52 025), C I. Basic Violet 3 (C 1.42 555) and C. I. Basic Violet 10 (C 1.45 170). The C.I. numbers of these Dyes correspond to the Color Index (2nd edition).

The colored polymer image contains silver or unreacted silver halide in individual areas. This colored polymer image can be converted into a color image with clear colors by one silver halide by fixing with a solvent for the silver salt and the silver image with an oxidizing agent removed.

When using a reducing agent with a very high polymerization initiation effect occurs the polymerization reaction sufficiently occurs. even if only a very small amount is formed on reduced silver. Accordingly, in this case it is hardly or not at all necessary to remove the silver images by oxidation.

The color image formed can be transferred to an image receiving material. The transfer will carried out by the layer having the colored polymer image in a solvent for the dye, e.g. B. methanol, water or an aqueous solution of an acid, a base or a Salt, wetted and the wetted layer in intimate contact with an image receiving material on which the (transmission is to take place, brings. As image receiving material ordinary papers are used for the transfer. Papers on which a hydrophilic Polymer or gelatin layer is applied. and films on which a hydrophilic polymer or gelatin layer is applied.

An image-receiving layer treated with a mordant, for example with an aluminum salt, is preferred treated image-receiving layer, as in the usual transfer process, used. After once a Polvmorisatbild that for

Formation of ion charges is capable, is formed, it can be stained and transferred in the above can be reproduced several times as described. One coloration can result in several transfer images and the polymer image can produce one repeated staining to obtain a number of copies with ease.

The invention is explained in more detail below with the aid of examples.

example 1

A fine grain gelatin-chlorochrome photographic emulsion with a chlorobromosilver content corresponding to about 42 g of silver and with a molar Ratio of chlorine to bromine of 7: 3, which has a pH value of 5.8 and a pAg value of 7.6, was divided into two parts, and 1 part was exposed to a fluorescent lamp. For exposure 200 ml of the emulsion liquid were spread out at about 35 C in an area of 20 χ 25 cm and below Shaking or moving for about 5 minutes under an illumination of about 300 lux.

2.5 ml of the exposed emulsion and the unexposed emulsion were each taken up in test or test tubes with a diameter of about 1.6 cm, to which 6 ml of water, 4.0 g of acrylamide and 10 " ³ mol of acetylacetone were added. m agitation and adjusting the temperature to 60 "C vvere the test tubes in a heat insulating material made of foamed polystyrene of about 2 cm thickness, dipped in a thermostat at 60 ⁼ C, allowed to stand. 3 ml of 1N sodium hydroxide was added directly to each of the two test tubes, and the change in temperature was recorded by means of a thermistor or thermometer. In the system from the exposed emulsion, the acrylamide was polymerized, and the temperature was raised by the heat of polymerization, the temperature of the system reaching 108 ° C. in about 20 minutes from the start of the reaction, while in the system from the unexposed emulsion the temperature 78 ° C reached only during the same reaction time.

It can be seen from the generation of heat that the polymerization took place. Although warmth by that Reduction of the silver halide can be generated in addition to the polymerization reaction

this is too small to be measured as a temperature change by means of the measuring instrument used in this example to be perceived. When using hydroquinone instead of acetylacetone was z. B. silver halide reduced to black silver,

however, no heat generation was found.

Even when the unexposed emulsion was used, the polymerization occurred with the generation of heat, when the reaction time has been extended. This corresponds to the general appearance of a

customary photographic emulsions becomes that, namely, if the development time is extended too much, the silver halide will be removed is also reduced in an unexposed area with the formation of so-called haze and

borrowed the image is barely perceptible or noticeable. Accordingly, the utility of the photographic material according to the invention is enhanced by them Appearance not affected.

B e i s ρ i e 1 2

The same procedure as described in Example 1 was carried out under the same conditions with the Deviation repeats that an active methylene compound as in the first line of Table I indicated, was used in place of acetylacetone and the amount of sodium hydroxide was changed would. The amount of active methylene compound is in Table I in the second column, the temperature of a thermostat in the third column, the amount of 1 n-nitrium hydroxide in the fourth column, the length of time door the maximum temperature in the system using the exposed emulsion in the fifth column, the temperature at that time in the sixth column and the temperature of the System using the unexposed emulsion at the same time in the seventh column given in Table I.

In each case, the polymerization took place preferentially with the exposed emulsion.

Table I.

No. Reducing agent crowd
(mg) bath
temperature
(C) crowd
of In-NaOH Duration
(min) Temperature of
exposed
emulsion Temperature of
unexposed
emulsion 19th
20th
21
22nd
23
24
10
25th
26th Acetoacetanilide
Benzoylacetone
Methyl acetoacetate
Ethyl-n-amylacetoacetate ..
Sodium acetoacetate
2-acetylbutyrolactone ....
/ i-acetoxycrotonate
Ethyl 2-chloroacetoacetate
Phenylhydrazone dehydro-
acetate 177
162
116
200
124
128
172
165
258 50
60
57
57
58
48.5
57
58
55 2
3
3
3
3
9.1
0.5
1.0
1.0 30th
58
27
30th
54
65
150
20th
38 75
99.5
78
63.5
69.5
94
69
107
80 54
86
70
57
62
69
59
83
71.5

1 S54 768

Example 3

A photographic material coated with a chloroiodobromide silver gelatin photographic emulsion was exposed to light and then treated with a solution containing ethyl α-phenyl cyanoacetate (No. 16) and sodium methacrylate to effect image-wise polymerization. The polymer image obtained in this way was well colored with a basic dye. The photographic material was prepared by providing both surfaces of a substrate made of polyethylene terephthalate with an adhesive layer, on one surface an antihalation layer and on the other surface a fine-grain ge' ^ tine-halosilver emulsion with a content of about 0.7 mol Chlorine, about 0.3 mol of bromine and about 0.001 mol of iodine and about 100 g of gelatin per 1 mol of silver were applied, the latter being a merocyanine dye with a maximum sensitivity of 550 πΐμ as a sensitizing dye, about 1.5 g of mucochloric acid per 100 g of gelatin had been added as a hardening agent and a suitable stabilizing agent or surface-active agent and the said emulsion was applied in such a way that 50 mg of silver were applied to each 100 cm ^{2 of} layer film. Finally, a protective layer of gelatin about 0.8 μm thick was applied to the emulsion layer. This photographic material is usually used for the production of line and halftone images for photomechanical reproductions.

The photographic recording material thus produced was composed of a master copy from a negative (a line picture with light of about 100 lux, exposed for 2 seconds, whereupon the material in a solution with the composition given below under a red safety light was immersed:

Sodium methacrylate .... 75 g

Ethyl a-phenyl cyanoacetate (No. 16) 8.5 g

Water 75 ml

2 n-NaOH amount required

for the setting
the pH to 11.6.

After standing at 30 ^° C. for 5 minutes, a light brown image appeared. The sample was washed with a 1.5% aqueous solution of acetic acid for 40 seconds and fixed with a fixing solution of the following composition:

Sodium thiosulphate (anhydrous) .. 150 g

Potassium Metabisi'Tit 15g

Water rest to 1000ml

The sample, which had been sufficiently fixed and washed with water, was poured into a 0.1% strength aqueous solution. red basic dye, namely .Rhodamine 6 G. C. P. (CI. Basic real) at room temperature immersed for 5 minutes and then in a 5% aqueous solution of acetic acid during Washed for 5 minutes. The dye was washed out of the unexposed parts of the layer during the exposed parts of the layer the red coloration The brown silver image could easily with the Farmer's reducing solution are dissolved away. When the silver image was removed, it became a clear red image receive. By reversing the order of staining and removing the silver image, i. H. through Removing the silver image first, leaving an apparently colorless and transparent image, and then staining in the manner described above could similarly produce a red clear picture can be obtained.

The color image thus obtained could be transferred onto a sheet of paper, e.g. B. by wetting a Writing paper with methanol by rubbing with a sponge containing methanol, by dense Bringing the color image into contact with the writing paper under pressure and by separating the two after about 30 seconds.

When using a 0.1% aqueous solution of Crystal Violet (C. I. Basic Violet 3) for staining, where the production of a color image and the transfer were carried out in a similar manner, a blue-violet transferred image was obtained.

When using a 0.1% aqueous solution of Auramine 0-100 (CI. Basic Yellow 2) as the dye a yellow image was obtained.

When using a 0.1% aqueous solution of Basic Blue B. O. (C I. Basic Blue 25) as the dye a blue image was obtained.

When transferring a color image, it is not necessary to add the silver image and the silver halide remove. Accordingly, a satisfactorily transferred image was also obtained by coloring and transferring obtained immediately after developing, polymerizing, breaking and washing with water.

Example 4

The same recording material as described in Example 3 was exposed as in Example 3 and then with various solutions with the following composition and content treated with various reducing agents as indicated in Table II below.

Sodium methacrylate .... 75 g

Reducing agents as in Table II

specified

Water 75 ml

2 n-NaOH necessary amount for

the adjustment of the pH

Value to the value given in Table II

The sample was treated at 30 ° C. for a period of time as indicated in Table II, fixed and washed with water, as described in Example 3, and then dyed using 0.1% rhodamine 6 G. C P., in a similar way to example 3. ₍

^A : Green light transmittance densities before and after staining were measured on an exposed area and an unexposed area of each sample.

The type of reducing agent used, the amount, the pH during the treatment, the Tape duration, the optical density before staining and the optical density after staining are compiled in Table II below.

21

Table II

Reducing agent

Acetylacetone

1,3-cyclohexanedione

o-acetyl-S-methyl-l-cyclohexane

1-on.

3-acetyl-2,6-heptadione

Ethyl acetoacetate

o-methoxyacetoacetaniüd

Ethyl a-methylacetoacetate

Ethyl ci-n-hexylacetoacetate

Ethyl a-cyanoacetate

Ethyl jS-acetoxycrotonate

Ethyl ß-aniline crotonate

Ethyl - /? - ethoxy acrylate

Ethyl ß-iminobutyrate

Acetylacetaldehyde dimethyl acetal

Malononitrile

Ethyl a-phenyl cyanoacetate

Nickel ethyl acetoacetate

Ethyl a-butyl acetoacetate

Amount (g)

5.00 5.04

6.84 7.60 5.85 0.32 6.48 9.63 6.97 7.74 9.22 5.40 5.85 5.94 2.97 8.50 1.17 8.37 Duration of treatment

70
30th

10
70
70
70
70
70
70
70
70
70
70
70
30th
5

60
64

Density of
unexposed area

before
Staining

0.07
0.08

0.18
0.09
0.08
0.09
0.08
0.08
0.07
0.07
0.11
0.09
0.17
0.10
0.08
0.09
0.08
0.07

after
Staining

0.27
0.44

0.35
0.20
0.29
0.25
0.18
0.19
0.17
0.22
0.17
0.17
0.34
0.19
0.23
0.26
0.28
0.17

Density of the exposed area

before staining

0.11 0.11

0.33 0.10 0.08 0.08 0.08 0.08 0.06 0.08 0.12 0.09 0.08 0.10 0.09 0.29 0.09 0.08

after staining

0.70 2.20

1.52 0.35 0.76 0.38 0.40 0.25 0.22 0.84 0.26 0.22 2.00 0.23 2.42 1.51 1.48 0.95

pH

11.60 11.50

11.50 11.50 12.40 11.50 11.50 11.50 11.50! 1.50 11.50 11.60 11.50 9.00 9.00 11.60 11.50 11.60

In each case, the dyeing increased the density in the exposed parts of the image more than in the unexposed parts of the image. This shows that the exposed image parts were selectively colored. That was also shown by the fact that the silver image of each sample was caused by the Farmer's reducing agent was removed leaving a clear red image. In the sample, the density of the silver image was low, a clear red image was found even without removing the silver image. This Color! !: r could be using on a writing paper of methanol in a similar manner to Example 3.

40

Example 5

45

zondehydroacetat used with a metal salt to test its effect. The sample was in introduced the following treatment solution:

Potassium metabisulphite 3 g

Sodium methacrylate .... 75 g

Phenylhydrazone dehydroacetate 12 g

Metal salt 4.5 χ ΙΟ " ⁴ mol

Water 75 ml

2 n-NaOH amount required

for setting the pH value given in the table below

An experiment similar to that in Example 4 was carried out. The sample was kept at a temperature during

described, using a metal salt for a period of time as indicated in Table Hl, treated

Combination with an active methylene compound de'.t, UiiG the results obtained are as in

executed. Phenylhydra- 50 Example 4 was summarized in Table III as the reducing agent.

Metal salt pH No 9 10 Nickel chloride 9.40
9.30
9.20 Barium chloride. .. Copper acetate

Table III Duration Density of after Density of ι area unexposed area Staining exposed after temperature (min) before 0.20 before Staining 30th Staining 0.27 Staining 1.30 ("C) 30th 0.08 0.34 0.09 3.47 40 30th 0.16 1.98 0.57 2.07 40 30th 0.07 0.18 over 4 40 0.22 0.97 to

From the above table IU can be seen. Change in the reactivity of the active methyl

that the image density is converted by the dyeing under binding, or that the metal salt

generation of a metal salt was increased. This is possible - the redox reaction of the silver halide with the

This can be attributed to the fact that the reducing agent catalyzes. The mechanism here-

medium and Mctallsalz partially in a C'helat below of is not ⁿ .och clarified.

m m time:

Example 6

The recording material described in Example 3 was, similarly to that described in Example 3, with a solution of the following Composition treated. Using a basic monomer, a polymer was suitable for staining with an acidic dye.

1 - vinyl 2,3-dimethylimide

azolium p-loluenesulfonate .. 75 g
Ethyl-fi-phylcyanoacetate

(No. 16) 0.85 g

Potassium metabisulphite required for

the setting
the pH to 9 or 11.5
Water 85 ml

l-vinyl-2,3-dimethylimidazolium-p-toluenesulfonate with a melting point of 142.5 ° C was by Reaction of l-vinyl-2-methylimidazole with methyl p-toluenesulfonate obtained at ordinary temperature and recrystallization from ethanol and ether.

The sample was ^{treated at 30 °} C. for 30 minutes in such a way that a light brown silver image was obtained together with a polymer image of the quaternary salt. The sample was fixed and treated with water, as in the example! 3 described, washed, with a 0,!% Aqueous solution of an acidic dye, namely Suminol Leveling Sky Blue R extra conc. (CI Acid Blue 62) and washed with a 1% sodium bicarbonate solution for 5 minutes to obtain a blue image. It was confirmed that when the pH of the system was higher, the sharpness of an image by coloring was higher and the polymerization reaction was more likely to proceed.

When the silver image was viewed as described in Example 3, a sharp blue image could be obtained. The image could be transferred by pressing it onto a paper wetted with methanol, as described in Example 2

ίο thickness of about 10 microns, immersion in an aqueous one Solution of alum and drying was made, wetted with water, in intimate contact with the color image described above brought to stand for 1 minute and then gctrcnnl a sharp blue image of high density was obtained. The sample was in a 0.1% igc aqueous solution of a red acidic dye, namely Solar Rhodamine B extra (C.I. Acid Red 52), the ar Instead of Suminol Leveling Sky Blue R extra conc, was used for 5 minutes for an overall staining immersed, then in a Kolthoffschc buffer solution immersed at pH 5.0 for 3 minutes and washed with water, wobc a sample was obtained in which only the exposed parts of the layer were colored red.

The image could be moistened with methanol; Writing paper and on a moistened with water Image receiving sheet, as described above, over-

The sample was stained with Solar Pure Yellow 8 G (C 1 Acid Yellow 7) and treated with a buffer solution mil washed to pH 5.0 to give a yellow image which was based on a methanol wash tctes writing paper or can be transferred to an image-receiving sheet wetted with water by pressing could.

Claims (3)

Patent claims: 1. A process for the production of polymer images, in which an image-wise exposed in one photographic silver halide emulsion layer containing latent image by exposure a monomeric vinyl or vinylidene compound and a reducing agent is developed, characterized in that at least one active methylene compound is used as the reducing agent of the formula (a): where R _{1 is} a hydrogen atom, an acyl or phenyl group and R _{2 is} an ethoxycarbonyl or cyano group, or their tautomeric isomers and / or their metal complex salts are used. 2. The method according to claim 1, characterized in that developed in the presence of sulfite ions and is polymerized. 3. The method according to claim 1, characterized in that the polymer image is selectively with stains a dye which, upon electrolytic dissociation, has opposite charges to the Has charges of the polymer image. R ₁ CH wherein R ₁ and R ₂ each represent an alkyl, a substituted alkyl or phenyl group and R _{3 represents} a hydrogen atom, an alkyl or substituted alkyl group and where R _{1 can} optionally form a ring with the radicals R ₂ or R ₃ , of the formula (b): ^CH I! ο C.
X Il ο wherein R _{1 is} a hydrogen atom or an alkyl group, R _{2 is} an alkyl group, a substituted aromatic ring or sodium, R _{3 is} a hydrogen atom, an alkyl, substituted alkyl or cyano group or a chlorine atom, where R ₂ and R ₃ optionally form a ring with one another R _{7 represents} an aromatic ring when X represents the group - NH -, and an acyl or alkyl group when X represents the group - O-, X represents the radical - O -, - NH -, - N-NH- and Y denotes the radical O or NH, or the Formula (c): CH R. The invention relates to a process for the production of polymer images, in which one in one image-wise exposed photographic silver halide emulsion layer through Developed the action of a monomeric vinyl or vinylidene compound and a reducing agent will. It is known, an imagewise photopolymerization using a silver halide as To effect a catalyst (see British patent specification 866 631, S. Le vino s et al., "Photographic Science & Engineering ", Vol. 6, pp. 222 to 226 [1962]). In this reaction, the photographic sensitivity is not as high as when exposed halogen silver particles through customary development be reduced. It is also known to produce polymer images by polymerizing vinyl compounds using a silver image or unreacted silver halide after development an exposed silver halide emulsion with a customary developer solution as a catalyst (see Belgian patent specification 642 477). This implementation has the disadvantage that the operations development and polymerization must be carried out separately. It is now theoretically of great interest, exposed To develop halogen silver with a reducing compound in the presence of a vinyl compound and the polymerization of the vinyl compound by the oxidized product or by a during intermediate product formed after reduction, since the enhancing effects of silver halide evolution and chain polymerization can be used to generate the polymer image be able. It is also known to carry out this reaction using a customary aromatic SiI berhalogenident developer compound, the z. B. two or more hydroxyl groups, amino groups or alkyl or aryl-substituted amino groups in o- or p-position of the benzene ring to each other, to perform (cf.USA patent 3G19I04, G. Oster, "Nature", Vol. 180, p. 1275 [1957]). However, in the development with these benzenoid compounds, there has only been an increase the optical density of a silver image. Facts which would directly support the formation of a high molecular weight compound, i.e. H. one An increase in viscosity or generation of a heat of reaction was not observed. It was