DE1954768C - Process for the production of polymer images - Google Patents

Description

* T method according to claim 1, characterized in that that is developed and polymerized in the presence of sulfite ions.

3 The method according to claim 1, characterized that the polymer image dyes selectively with Sem dye, which in electrolytic Dissociation has opposite charges to the Laduneen of the polymer.

R,

CH

C. O

I! ο

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 Ri can optionally _{form a ring with the radicals R 2} or R ₃ , of the formula ( b):

CH

Y-R, The invention relates to a method of manufacture of polymer images, in which one in one imagewise exposed photographic silver halide emulsion layer through Exposure to a monomeric vinyl or vinyldene compound and a reducing agent developed "" 's is known, an imagewise photopolymerization using a silver halide as a kSvsator (cf. British patent specification 866 631 S. L e ν i η ο s et al., »Photographic Science

or

R, C CYR ₂

I Il

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 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):

CN

CH
R ₁

be reduced. . ,,

It is also known to produce polymers by polymerizing vinyl compounds using a silver image or unreacted silver halide after development an exposed silver halide emulsion with a

common 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.

Theoretically, exposed halogen silver with a reducing compound is now of great interest to develop in the presence of a vinyl compound and the polymerization of the vinyl compound by the oxidized product or by a during

to effect the intermediate product formed during the reduction as the enhancement effects of silver halide development and the chain polymerization can be used to generate the polymer image be able. It is also known this reaction

using a common aromatic silicon halide developer compound, the z. B. two or more hydroxyl groups, amino groups or has alkyl- or aryl-substituted amino groups in the o- or p-position of the benzene ring to one another.

to be carried out (see USA.-PatentschrH.3 Π 104, G Oster, "Nature", Vol. 180, p. 1275 [1957]). When developing with these benzenoid compounds however, only an increase in the optical density of a silver image was observed.

Facts which would directly support the formation of a high molecular weight compound, i. H. one An increase in viscosity or generation of a heat of reaction was not observed. It was

■ J

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", Vol. 6, p. 222 [1962]).

E? is also a method for producing photographic polymer images by treatment an imagewise exposed silver halide emulsion layer containing a monomeric vinyl compound and a reducing compound in which the reducing compound is 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 also known that active methylene compounds ij fertilize door used to initiate polymerization (cf. H. Bredereck, B Foehlisch & R. Franz. »Makromoleculare 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 "· CP and oxygen or peroxide. However, oxygen is at work in this system. Cu "" or peroxide as the oxidizing agent and accordingly the polymerization has no selectivity with respect to irradiation. It has also been reported that a complex compound of / i-diketone. e.g. Acet \! acetone as Po! ^1st merization initiator, can be used (cf. CAl Bamford & D. H. Li η d. "Chemistry & In- 3c dusiry". 1627 [1965] and the references made therein). It is stated here that the polymerisation is initiated by the following radical:

CH ₃ *

CH Mn '"(Acac),

'V /

C-O

/
CH ₃

CH ₃

C = O

CH

+ Mn "(Acac), layer with a monomeric vinyl compound and to indicate a reducing compound that is easy to implement and polymer images with variable Provides properties that can be dyed, transferred and thus used in the production of a large number of copies can be used and a higher color density than previously possible, exhibit.

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):

CH

40

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

R ₃

R, CH YR ₂

Il II

X O

R ₁ CC — Y — R,

X O

or

C = O

/
CH ₃

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

The tanning development process is also used as a method for producing images made of polymeric material 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 cross-linked gelatin are limited.

The object of the invention is a process for the production of polymer images by treating an image-wise exposed silver halide emulsion in which R _{1 is} a hydrogen atom or an alkyl group.

R _{2 is} an alkyl group. a substituted aromatic ring or sodium. R ₃ denotes a hydrogen atom, an alkyl, substituted alkyl or cyano group or a chlorine atom, where R ₂ and R _{3 can} optionally form a ring with one another.

55 R _{7 represents} an aromatic ring when X represents the - NH - group, and represents an acyl or alkylu group when X represents the - O - group. X the remainder - O -. - NH -

60 -ν-NH-^ ' y

and Y denotes the radical O or NH, or the Formula | c |:

CN R ₁

65 \ /

CH

i 954

_{in which R 1} denotes a hydrogen atom, an acyl or phenyl group and R 1 denotes an ethoxycarbonyl or cyano group, or their iautomeric isomers and / or their metal complex salts are used.

The invention achieves that, as a result of the low pH dependency, the reducing agent used active methylene compounds of formula (a). (b) and (c) or their tautomeric Isomers and their metal complexes cause the production of the polymerization color images within a wide pH range 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 images obtained in the tanning development process, those according to the invention show obtained polymer images depending on the vinyl compounds used changeable Properties, being 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 in the places of the photographic Halide silver emulsion in which the silver halide crystals have development centers which Polymerization takes place faster than at the sites. their silver halide crystals free of development centers are 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 negative silver halide photographic emulsions can silver chloride. Bromide silver. Chlorhromite silver. Iodobromosilver and chloroiodobromosilver emulsions can be used, which can be chemically or optically sensitized in the usual way.

For optical sensitization, optical sensitizers can be used in addition to conventional photographic emulsions. /..B. Cyanine dyes and merocyanine dyes. can be used expediently and conveniently (see, for example, Kikuchi et al. "Kagaku Shashin Bernau [Handbook of Scientific Photography]". Vol. II. pp. 15 to 24. Maruzen Co .. 1959) The to be used according to the invention Emulsion can also contain stabilizing agents such as those used in conventional photography procedures.

The photographic direct-positive silver halide emulsions which can be used in the process according to the invention can be prepared using solarization. of the Herschcl-FITekls. the Clayden effect and the Sabalier effect. These effects are /. B. in C. EK M oes. "The Theory of ihc Photographic Process". 2nd edition, published on McMillan Co. (1954). Kapileld and 7. explained.

In the pholographic limulfosions that are used, the halosilver grains are dispersed in a solution of a polymeric binder. Gelatin is usually used as the polymeric Uindemittcl, although synthetic high-molecular compounds./. B. Polyvinyl alcohol. Polwinylpyrro- fts lidon and polyacrylamide, or natural high molecular derivatives. / B carboxymethyl cellulose. CcIIuluseowäthvlather and dextran. Can be used without or together with gelatine (cf. FE ν ν a, Zeitschrift für Wissenschaftliche £ hoto «£ ph« ■ otophvsik und Photochemie «, Vol. 52, pp. 1 to _4 Lip / J). Examples of reducing agents to be used according to the invention corresponding to the general formulas (a), (b) and (c) given above are listed below:

» I.

O O

Acetylacetone

1,3-cyclohexanedione

H ₃ C

CH,

6-acetyl-3-methyl-2-cyclohexen-1-one

CH,

CH, CH, CH CH,

\ / N / \ / C CH ₂ C

Ii Il

ο ο

3-acetyl-2,6-heptanedione

CH, CH, OC ₂ H ₅

■ · ". / ^X ~ /
CC

ο ο

Ethyl acetoacetate

HIGH,

CH, CH, N [

"c c 1 i | II Il \ /

ο ο

o-acetoacetanisidide

CH ₃

CH ₃ CH OC ₂ H ₅

Il Il ο ο

Ethyl-a-methylacetoacetate

nC ₆ H ₁₃

CH ₃ CH OC ₂ H ₅ CC

Il Il ο ο

Ethyl-a-n-hexylacetoacetate

CN

CH ₃ CH OC ₂ H ₅

Il Il ο ο

Ethyl-a-cyanoacetoacetate

CH ₃ CH ₃ -COC = CH-C-OC ₂ H ₅ O

Ethyl ß-acetoxycrctonate

H CH i _N / OC = H ₅

ϊ Ϊ

NH O

Ethyl 3-aniline crotonate

CH OC ₂ H ₅ • \ /

f ί

OC ₂ H ₅ O

Ethyl 0-ethoxyacrylate CH ₃ CH ₂ OC ₂ H ₅

Y ι

NH

Ethyl - /? - iminobutyrate

(14)

(15)

(16)

(17)

35

40

(18)

5 °

(19)

6o

(20)

CH ₃ CH ₂ OCH ₃

C C

Il l \

OH OCH ₃

Acetoacetaldehyde dimethyl acetal

CN CN malononitrile

C ₆ H,

CH OC ₂ H ₅

CN C

Ii ο

Ethyl-a-phenylcyanoacetate

CH ₃ CH OC ₂ H ₅

I Il

O 0

Ni ₁ , 2
Ethyl nickel acetoacetate

nC ₄ H ₉

CH ₃ CH OC ₂ H ₅ \ / \ / CC

Ii il

O 0

Ethyl-a-n-butyl acetoacetate

H CH ₃ CH ₂ N

c c T j

Ii Ii V

O O

Acetoacetanilide

0 0

Il I!

c c

CH ₂ CH ₃

Benzoylacetone

CH, CH ₂ OCH ₃

Methyl acetoacetate

n-CjH ,,

ί CH, CH OC ₂ H ₅

Ethyl a-n-amylacetoacetate

CH ₃

CH ₂

ONa

Sodium acetoacetate

CH, CH ₂

CH ₃

CH

2-acelylbutyrolactone

CH,

Cl

CH

Athvl-fi-chloroacetoacetal

CH ₃

Phenylhydrazone dehydroacetate

The compound (26) is obtained by reaction of dehydroacetic acid with an equivalent amount of phenylhydrazine in tetrahydrofuran under cooling at - received "15 ^C 'C, the temperature being gradually returned to OC, and the resulting precipitate is recrystallized from tetrahydrofuran to give a product with the following properties is obtained:

Melting point: 199 to 202 ⁰ C: Ultraviolet absorption spectrum:

}. _max , 99% EthOH: 245 ma, log _f :

'' ■ maxi 99% EthOH: 352 mx log, -: infrared absorption spectrum:

• COC (-coc): 1250cm- '. ; NH 3360 cm " ¹ .

4.01, 3.60:

: 3405 cm "

The synthesis methods of the compounds (1) to (25) are well known, and these compounds are commercially available. In addition, these compounds can be shown in Foi m a metal complex salt can be used. 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 of these metal complex salts, in particular the complex salts of acetylacetone derivatives. are general known (cf. M ar part and Calvin, "Chemistry of the Metal Chelate Compounds", published by Prentice-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) under introduction the polymerization in reaction. However, it is believed that the polymerization after a Radical chain mechanism occurs due to the fact that monomers that lead to radical chain polymerization tend to be used and that the reaction proceeds in aqueous solution and is retarded by a radical polymerization inhibitor. It is not clear whether this is Radika directly by reacting the compound of the general formulas given above (a), (b or (c) with silver halide or by interaction with water or oxygen in the system is produced. It is clear, however, that the polymerisation of a vinyl compound occurs simultaneously with the reduction of the silver halide takes place since when the vinyl compound added to the reaction system after the irradiated silver halide with de Compound of the above general formulas (a), (b) or (c) is reduced, no pole; merization is found.

An intermediate product that has been oxidized / J-diketone or / ϊ-keto acid ester with a mom electron oxidant, namely cerium sulfate, is available from G.A. Russian 1 & curls gard.

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

-H ⁺

O '0'

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. z. B. formaldehyde or glyoxal are supplied. Although the appropriate amount of sulfide ions. which is to be added to the system, of 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 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 (cf. CEK Mees, "The Theory of the Photographic Process," 2nd edition, edited by MacMillanCo. [1954], p. 652). It is now 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 product 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, e.g. B. acrylamide, acrylonitrile, N-hydroxymethylacrylamide, methacrylic acid. Acrylic acid, calcura acrylate. Sodium acrylate. Methyl methacrylate. Methyl acrylate, ethyl acrylate, vinyl pyrrolidone. 2-vinyl pyridine. 4-vinyl pyridine. 2-methyl-N-Vin) ! imidazo !. Potassium vinylbenzenesulfonate and N-vinyicarbazole. 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. Triethylene glycol dimethacrylate, polyethylene glycol dimethacrylate. Divinyl ether or divinyl benzene.

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 according to the invention. So can be visible rays, ultraviolet rays. Infrared rays 1.3 microns or less. X-rays. v-rays and corpuscular rays, e.g. B. Electron beams and u-rays. 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 deposited on a suitable The support can be used in an undried state, or it can be used as a layer on top of a suitable substrate in a dried state.

Since the reduction and polymerization take place simultaneously, the reduction in the presence of a Vinyl compound are carried out. In the method according to the invention, both the above described active methylene compound, which acts as a reducing agent for the silver halide, as well as the vinyl compound to be polymerized in the emulsion layer in advance Recording material may be contained, or the one component may be contained therein alone, while the other is added to the system after irradiation. In certain cases, both components be added after irradiation.

Since the presence of water is necessary for the practical execution of the reduction and polymerization reactions. the reaction must be in aqueous Solution or in a moist gelled state.

This reaction takes place in an alkaline medium, i. H. at a pH 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. z. B. p-methoxyphenol. Hydroquinone, alkyl hydroquinone or 2,6-di-tert-butyl-p-cresol.

When the monomeric vinyl compound is incorporated in the emulsion layer, it is used in an amount by weight ranging from ¹ ^ ₃₀ to 30 times. preferably ^l _{4 to 4} times the amount by weight of the previously added polymeric binder is used. The silver halide is used in an amount by weight of the '^; ₂₀ - to 2 times. preferably ¹ I ₀ - to ¹ J times the previously added polymeric binder used. When the reducing agent is incorporated into the layer, the amount of the reducing agent is preferably about ₁₀ to 20 moles per 1 mole of the silver halide used. When a is 1 nhibitor added compared to the thermal polymerization, it is preferably present in an amount by weight of the Vi ₀₀ O oar Vioofiidien to the amount by 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} _{× 20} to 5 mol, in particular from 1 to 1 mol (per 1 mol of the silver halide used).

As with conventional silver halide photography, there may be a time lag between exposure 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, e.g. B. Solubility, light scattering, adhesive or stickiness or staining affinity are exploited. When used the difference in solubility can e.g. B. an image by dissolving the after irradiation and development non-polymerized parts of the layer, leaving behind a relief of high molecular weight material can be obtained only in the irradiated layer parts.

In this case, the polymeric binder contained in the layer is preferably used together with the unreacted monomers dissolved away. To achieve this, a polymeric binder is added to the layer, whose structure is two-dimensional or linear and which is essentially free of crosslinking or whose main chain or crosslinking can be broken easily, added. That with exposure In contrast, the polymerizate formed and subsequently developed has a three-dimensional one networked structure and is accordingly sparingly soluble. To be an insoluble, crosslinked polymer To achieve, it is advantageous to have a compound having a plurality of vinyl groups alone or together to use with a compound with 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 polymer image is which consists of a salt-like polymer 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 forms an ionic charge through ionization or the addition of hydrogen cations can get used. A polymer is then formed which is capable of accepting a charge by ionization or addition of hydrogen cations. The color image obtained after staining can be transferred to another substrate using various methods.

Addition polymerizable vinyl compounds, which odei to take up a charge by ionization Addition of hydrogen cations are capable and used in the case described above are the following:

a) Compounds that provide a polymer image with a negative ionic charge are vinyl compounds with a carboxyl group, ^ B. acrylic acid, methacrylic acid, itaconic acid and maleic acid, as well as derei Metal or ammonium salts, e.g. B. ammonium acrylate, sodium acrylate, potassium acrylate, calcium acrylate Magnesium acrylate, zinc acrylate, cadmium acrylate, Na trium methacrylate, calcium methacrylate. Magnesium methacrylate, zinc methacrylate, cadmium methacrylate Sodium itaconate and sodium maleate, vinyl verb fertilize with a sulfonic acid group, e.g. Viny sulfonic acid and p-vinylbenzenesulfonic acid and viny

compounds and their metal or ammonium salts, z. B. ammonium vinyl sulfonate, sodium vinyl sulfonate, Potassium vinyl sulfate and potassium p-vinylbenzenesulfonate.

b) Compounds which produce a polymer image with a positive ion charge are vinyl compounds with a basic nitrogen atom, e.g. B. 2-vinylpyridine, 4-vinylpyridine, S-vinyl-1-methylpyridine, N, N - dimethylaminoethyl acrylate, N, N - diniethylaminoethyl methacrylate, N, N - diethylaminoethyl acrylate and Ν, Ν-diethylaminoethyl methacrylate, and Vinyl compounds with a quaternary nitrogen atom, which by reacting these bases with methyl chloride, Ethyl bromide, dimethyl sulfate, diethyl sulfate and methyl p-toluene sulfonate were produced.

These compounds mentioned are commercially available and can be according to generally known Working methods are produced. These compounds can be used 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. z. B. acrylamide, N-hydroxymethylacrylamide. Methacrylamide, methyl methacrylate, vinyl pyrrolidone. N.N-methylenebisacrylamide. Triethylene glycol dimethacrylate and triethylene glycol dimethaerylate. 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 when using a vinyl compound, 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 image becomes obtained, which 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 is formed with a negative ion cuadunc dyeing with a basic dye at a pH below the isoelectric point carried out by gelatin, with only the image of the polymerized vinyl compound being colored can without coloring the gelatin. On the other hand, the staining can be uniform initially at a pH above the isoelectric point of gelatin, whereupon washed with a washing solution with a pH lower than the isoelectric point of gelatin is, as a result of which those parts of the layer which do not contain any polymer formed are 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 kinds of to be used 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 has been treated with lime in the usual way, and contains a Polymer image with a negative ionic charge is to be colored with a basic dye. Furthermore, a preferred pH range is a range from 0.5 to 8.0 when a polymer image with a positive ion charge is colored with an acidic dye.

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

18 050), C. I. Acid Red 52 (C. I. 45 100). C.I. Blue 9 (CI. 42090), CI. Acid blue 45, C.I. Acid Blue 62 (CI. 62 045) and CI. Acid Violet 7 (CI. 18 055). and dyes useful as basic dyes are C I. Basic Yellow I (C 1.49 005), C I. Basic Yellow 2 (C.I. 41,000), CI. Basic Red 1 (C I. 45 160). C. I. Basic Red 2 (C I. 50 240), C. I. 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 transfer should 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 Gclatineschicht is applied. used.

One treated with a pickling agent is preferred

Image-receiving layer, for example an image-receiving layer treated with an aluminum salt, as in the usual transmission method. After once a polymer image that is used for

309 619/341

Formation of ion charges is capable of being formed. it can be reproduced several times by staining and transferring in the manner described above will. One coloring can have several transfer images result, and the polymerized image can be subjected to repeated staining to obtain a Number of copies to be obtained with ease.

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

IO

example 1

A fine-grain photographic gelatin-chlorochromium emulsion with a chlorobromosilver content accordingly about 42 g of silver and with a molar ratio of chlorine to bromine of 7: 3. the one pH 5.8 and pAg 7.6 was divided into two parts and 1 part was taken with exposed to a fluorescent lamp. For exposure, 200 ml of the emulsion liquid were added at about 35.degree Spread out in a curse of 20 χ 25 cm and shaking or moving for about 5 minutes left under an illumination of about 300 lux.

2.5 in! the exposed emulsion and the unexposed emulsion were each taken up in test or test tubes with a diameter of about 1.6 cm, including 6 ml of water. 4.0 g acrylamide and 10 ~ ^J Mo! Acetylacetone were added. After adequate stirring and setting the temperature to 60.degree. C., the test glasses were immersed in a thermostat at 60.degree. C. in a heat-insulating material made from foamed polystyrene about 2 cm thick. 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 the 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 was raised 78 "C was only reached during the same reaction time. From the heat generation it can be seen that the polymerization took place. Although heat can be generated by the reduction of the silver halide in addition to the polymerization reaction, this is too small to be a temperature change using the one used in this example When using hydroquinone instead of acetylacetone, for example, silver ha'.osenide was reduced to black silver, but no heat generation was found.

Even when the unexposed emulsion was used, the polymerization occurred with generation of heat. when the reaction time has been extended. This corresponds to the general appearance of a It is found that conventional photographic emulsions are used with an increase in the development time too much, the silver halide in an unexposed area is also formed the so-called veil is reduced and finally the image is barely perceptible or noticeable. Accordingly, the utility of the photographic material according to the invention is enhanced by them Appearance is never impaired.

Example 2

The same working method, as described in example I, was repeated under the same conditions except that an active methylene compound as indicated in the first line of Table I ^ used in place of acetylacetone and the amount of sodium hydroxide was changed. The amount of active methylene compound is in Table I in the second column, the temperature of a thermostat in the third column, the Menee of 1N sodium hydroxide in the fourth column, the length of time for 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 point in time in the seventh column of Table I.

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

Table I.

Reducing agents

Acetoacetanilide

Benzoylacetone

Methyl acetoacetate

Ethyl-n-amyk'ce'ioacetate ..

Sodium acetoacetate

2-acetylbutyrolactone ....

fi-acetoxycrotonate

Ethyl O-chloroacetoacetal

Phenvlhydra.rX dehydroacetate

crowd

(mg)

177
162
116
200
124
128
172
165

258

Bath temperature

(Cl

50 60

57

57

58

48.5

57

58

55 quantity
of I n-NaOH

2 '

9.1

0.5

1.0

1.0

Duration
(min)

30th
58
27
30th
54
65
150
20th

38

Temperature of
exposed
emulsion

75
99.5
78
63.5
69.5
94
69
107

Temperature of

unexposed

emulsion

54
86
70
57
62
69
59
83

71.5

Example 3

A photographic recording material coated with a chloroiodobromide silver gelatin photographic emulsion. was exposed to light and then treated with a solution containing ethyl u-phenyl vanoacetate (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 support made of polyethylene terephthalate with an adhesive layer, on one surface an antihalation layer and on the other surface a fine-grained gelatin-halosilver emulsion containing about 0.7 moles of chlorine, about 0.3 mol of bromine and about 0.001 mol of iodine and about 100 g of gelatin ie I MoF silver were applied, the Ictz-K'ren being a merocyanine dye with a maximum sensitivity of 550 ηΐμ as a sensitizing color \ ΐκίϊ. about 1.5 a Tviucuchlois column per KiOi; Gelatine, hardening agent and a suitable stabilizing agent or surface-active agent had been added and the said emulsion η was applied in such a ^{way that 50 mg of silver were applied to each ItH) cm 2 layer area.} Finally, a protective layer of gelatin of about i'.S: j. Thickness applied to the emulsion layer. This photographic material is commonly used for the production of line and halftone images for photomechanical reproductions.

The photographic material thus prepared was based on a master copy, consisting of a negative of a line image with light from about 100 lux. exposed for 2 seconds, whereupon the material is converted into a solution with the following , given composition under red safety light was immersed:

Sodium methacrylate .... 75 g

Ethyl-n-phenylcyano-

acetate (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 mil a 1.5% aqueous solution of acetic acid for 40 seconds and washed with a fixing solution fixed with the following composition:

Sodium thiosulphate (anhydrous) .. 150 g

Potassium octabisullite 15 g

Water rest to 1000 ml

The sample, which had been sufficiently fixed and washed with water, was dissolved in a 0.1% strength aqueous solution red basic dye, namely Rhodamine 6 Ci. C. P. (Cl. Basic redl) at room temperature immersed for 5 minutes and then with a 5% aqueous solution of acetic acid during Washed for 5 minutes. The dye was washed out of the unexposed parts of the layer while the exposed parts of the layer retained their red color.

The brown silver picture could easily be matched with the

Farmer's reducing solution to be removed. 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

ίο 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, through tight 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

by Crystal-Violet (C.I. Basic Violet 3) for coloring.

the formation of a color image and the transfer being carried out in a similar manner.

an ulau violet transferred image was obtained.

When using a 0.1 ", o igen aqueous solution a yellow image was obtained with Auramine 0-100 (CI. Basic Yellow 2) as the dye.

When using a 0.1% aqueous solution from Basic Blue B. O. (CI Basic'ßlue 25) as a 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 immediately after developing. Polymerize. Interrupt and wash with water.

Example 4

The same recording material as in Bcii piel 3 described, was exposed as in Example 3! and then with different solutions with the one below specified composition and with a content of the various reducing agents, such as h the Table II below, treated.

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 that indicated in Table 11 worth

The sample was treated, fixed and with at 30 ° C. for a period of time as indicated in Table II Water, as described in Example 3, washed and then colored using O.r'oigem rhodamine 6 G. C P .. in a similar way to example 3.

f> o The permeable wedge densities to green light before and after staining were an exposed area and an unexposed area of dimensioned for each sample.

The type of reducing agent used, the

f> 5 amount, the pH during treatment that Treatment time, the optical density before staining and the optical density after staining are compiled in Table II below.

21

Table II

22nd

Reducing agent

Acetylacetone

1,3-cyclohexanedione

o-acetyl-S-methyl-I-cyclohexane
-on.

3-acyl-2,6-heptadione

Ethyl acetoacetate

o-methoxyacetoacetanilide

Ethyl a-methylacetoacetate

Ethyl-a-n-hexylacetoacetai

Ethyl u-cyanoacetate

Ethyl fi-acetnxycrotonate

Aihv! - ^ - aniüncrotonat

Ethyl - ^ - ethoxyacrylate

Ethyl fi-iminobutyrate

Acetylacetaldehyde dimethyl acetal

Malononitrile

Ethyl a-phenyl cyanoacetate

Nickel ethyl acetoacetate

Ethyl a-butyl acetoacetate

Mense

IgI

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 negotiation

(mini

70
30th

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

60
64

Density of the unexposed area

before after

Staining 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

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

• staining after staining

0.11 0.1 ί

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

0.70 2.20

11.60 11.50

1.52 1.50 1.6 " 0.35 11.50 0.76 12.40 0.38 0.40 0.25 0.22 0.84 0.26 0.22 2.00 0.23 11.50 2.42 11.50 1.51 11.50 1.48 11.50 0.95 1.50 1.:"!) i.öu \ S>) 9.1! « ll.oi 11.5! :

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 has been removed, leaving a clear red image stayed behind. In the sample, the density of the silver image was low. became a clear red picture itself found without removing the silver image. These color images could be made using writing paper from methanol in a similar manner to Example 3.

Example 5

35

40

45 zondehydroacetat used with a metal salt to test its effect. The sample wun! * introduced the following treatment solution:

Potassium metabisulphite 3 g

Sodium methacrylate .... 75 g

Phenylhydrazone dehydroacetate 12g

Metal salt 4.5 10 ⁺ mol

Water 75 ml

amount of n-NaOH required

for setting the specified in the table below pH value

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 III, treated

Combination with an active methylene compound delt. and the results obtained are as in

executed. Phenylhydra- Example 4 was summarized in Table 111 as the reducing agent.

Table III

Metal scrap

No

Nickel chloride.
Barium chloride
Copper acetate.

pH

9.10

9.40
9.30
9.20

! Temperature (Ci

40
40
40

'

Duration (mini

Density of the unexposed area

before staining

0.08 0.16 0.07 0.22

after staining

0.20 0.27 0.34 1.98

Density of the exposed area

before staining

0.09 0.57 0.18 0.97

after staining

1.30

3.47

2.07

over

It can be seen from Table III above. Change in the reactivity of the active methylene digester the image density is converted by the dyeing using 65 binding or that the metal salt

generation of a metal salt was increased. This is possibly due to the fact that the reducing agent and the metal salt partially in a C'helal under the redox reaction of the silver halide with the Reducing agent catalyzed. However, the mechanism of this has not yet been clarified.

Example 6

The recording material described in Example 3 was similar to that described in Example 3, treated with a solution of the composition given below. Under use of a basic monomer became a polymer suitable for coloring with an acidic dye is suitable to receive.

1 -Vinyl-2,3-dimethylimide-

azolium p-toluenesulfonate .. 75 g
Ethyl d-phenyl cyanoacetate

(No. 16) 0.85 g

Potassium metabisulphite required for

the setting
the pH to 9 or 11.5
Water 85 ml

l-vinyl ^ .S-dimethylimidazolium-p-toluenesulfonate with a melting point of 142.5 ° C was by reacting 1-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 washed with water, as described in Example 3, with a 0.1% strength 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, whereby a blue image was obtained. It was confirmed that when the pH of the system was higher, the sharpness of an image by coloring was greater and the polymerization reaction proceeded more.

When the silver image was removed as described in Example 3, a sharp blue image could be seen can be obtained. The image could be obtained by pressing it onto a with methanol; as in example 3 described, wetted paper can be transferred. When an image-receiving sheet that is coated by of a baryta paper with a gelatin layer

ίο thickness of about 10 microns, immersion in an aqueous one Solution of alum and drying had been made, wetted with water, in intimate contact brought with the color image described above. Left for 1 minute and then separated a sharp, high density blue image was obtained. The sample was in a 0.1% strength aqueous solution of a red acidic dye, namely Solar Rhodarnine B extra (C.I. Acid Red 52), the ar Place of Suminol Leveling Sky Blue R extra concentrated was used for 5 minutes for a total staining immersed, then in a Kolthoff buffer solution with a pH of 5.0 for 3 M inu Then immersed and washed with water, if a sample was obtained in which only di < 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, to be carried over.

The sample was colored with Solar Pure Yellow 8 G (C. I Acid Yellow 7) and mixed with a buffer solution Washed to pH 5.0 to give a yellow image that was moistened with methanol tetes writing paper or transferred to an image-receiving sheet wetted with water by pressing could.

Claims (1)

Claims: wherein 1. A process for the production of polymer images, in which an image-wise exposed in one A latent image contained in the pholographic silver halide emulsion layer 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 formula (a): hydrogen atom, an acyl or e and R, an ethoxycarbonyl or means ", or their tautomeric iso- ■ their metal complex salts