DE1772146C3 - Process for the production of color photographic images - Google Patents

Description

The invention relates to a decay for the production of photographic color images in which an imagewise exposed photographic silver halide emulsion layer by the action of a monomeric vinyl compound from the group of vinyl carboxylic acid, vinyl sulfonic acid or basic Vinyl compounds with a nitrogen atom and their salts, and of resorcinol, its derivatives, m-aminophenol, its derivatives or naphthol derivatives with two hydroxyl groups or one Hydroxyl group and an amino group in the 1.6, 1.8, 2.5 or 2.7 positions on the naphthalene ring is being developed as a reducing agent.

Process for the formation of color images using a silver halide photographic emulsion are known. It has been suggested that in a silver halide photographic emulsion latent images formed with p-phenylenediamine as a developer in the presence of couplers to form of color images consisting of the oxidation products of the developer and a coupler to develop (see E. M u 11 e r, color photography, theory and practice [1967] Springer-Verlag).

Here, however, a free choice of dyes for the colored images is not possible, and it cannot be excellent in hue or light resistance or fastness can be obtained because the dyes for the colored images are limited to those obtained by the Reaction between the oxidation product of the developer and the coupler are formed.

A tanning development process was also used in which gelatin relief images were used accordingly the latent images formed in gelatin-silver halide emulsion layers by development with tanning developers, for example pyrogallol, in the absence of sulfite to harden the Emulsion layer through the oxidation products of the developer and through removal of the uncured Parts can be obtained by washing with water [I.e. E. Mother, Color Photography, Theory and Practice, especially page 78).

Color images can then be obtained by absorbing the gelatin relief image with a mordant dye leaves and transfers the mordant to a suitable image receiving material. Although the colors can be used in this process with excellent tone and fastness the soft gelatin relief images can be scratched easily and are therefore suitable for use inconvenient and unsuitable.

In the German patents 17 20 665 and! 7 20 778 it is described that if a latent image, that by imagewise exposure of a photographic silver halide emulsion layer to electromagnetic Waves or corpuscular rays formed with resorcinol, or m-aminophenol a naphthol derivative is developed in the presence of a vinyl or vinylidene compound, a Polymierisatbila is formed in accordance with the exposed parts.

Also in DT-AS 11 19 120 and in US-PS 30 19 104 a development process is described wherein an exposed silver halide emulsion layer in the presence of a polymerizable monomer Vinyl compound is developed with a silver halide developer, which as an intermediate product free Forms radicals. In particular, a benzoid developer substance is used as the developer, such as B. p-aminophenol. The difficulties outlined above also arise here.

The object of the invention is therefore to create a method for producing colored polymer images, in which by converting a latent image in a silver halide photographic emulsion layer into an image of a highly polymerized substance using a simple one Polymer images that can be dyed well can be obtained with a large selection can be colored by dyes, of which color images can be easily transferred to an image-receiving material can be transferred and can therefore be used to produce a large number of copies, which show clear color images with great durability and lightfastness.

The object of the invention is a process for the production of photographic Color images in which an imagewise exposed photographic silver halide emulsion layer passes through Action of a monomeric vinyl compound from the group of vinyl carboxylic acid, vinyl sulfonic acid or basic vinyl compounds with a nitrogen atom and their salts, and of resorcinol, its derivatives, m-aminophenol, its derivatives or naphthol derivatives with two hydroxyl groups or a hydroxyl group and an amino group in the 1.6, 1.8, 2.5 or 2.7 positions on the Naphthalene ring is developed as a reducing agent, and is characterized in that one has the The resulting polymer images selectively dyes with a dye which corresponds to the charge on the polymer has opposite electrical charge, and that if necessary, the color images on a Transmits image receiving material.

According to the invention, clear color images of great durability and lightfastness are obtained, wherein the selection of dyes for the colored images

20th

within a very wide range

It was found that when the above said vinyl compound has a group which is capable of carrying an electrical charge, due to electrolytic dissociation or addition of a hydrogen ion, one to have an electric charge capable polymer due to the electrolytic dissociation or the Addition of hydrogen ions is obtained; the image consisting of the polymer can then selectively colored with a dye with an electrical charge opposite to that of the polymer be, moreover, it was found that so educated Color images can be transferred to an image receiving material according to various working methods. A conventional silver halide emulsion for negative images can be used in practicing the invention or direct positive emulsions are used.

For example, chlorosilver, silver bromide, silver chlorobromide, silver iodobromide, and silver chloroiodobromide can be used as photographic emulsions be used. The silver halide emulsions can be used in the customary manner be chemically or optically sensitized, as described in the literature (see P. Glafkides, Chemie Photographique, 2nd edition, Photocinema Paul Montel, Paris 1957, pp. 247-301, and K i k u c h 1 et al., Kagaku Shashin Benran (Handbook of Scientific Photography), Vol. II, pp. 15-24, Maruzen Co., Tokyo [1959]) · The emulsion to be used according to the invention can also contain stabilizers, as in the commonly used photographic techniques.

The direct positive silver halide emulsion can be produced using solarization, the Herschel effect, Clayden effect or Sabatier effect can be produced. These effects are discussed in Chapters 6 and 7 of “The Theory of the Photographic Process "by C. E. K. M e e s (2nd edition, edited by McMillan & Co. [1954]) is fully explained. Procedures for preparing such emulsions include: in British patents 443 245, 462 730, 6 67 206 and 10 11062, in US patents 28 57 273, 25 92 250 and 2497 876 and the German Patent 1207791 described.

The photographic emulsions described above consist of dispersion systems, in which particles of silver halide are dispersed in a solution of a high polymer. As a high polymer Gelatin is widely used for this purpose. However, synthetic ones can also be used High polymers, e.g. B. polyvinyl alcohol, polyvinylpyrrolidone, polyacrylamide or naturally occurring High polymers, e.g. B. carboxymethyl cellulose, oxyethyl cellulose and dextran, either alone or can be used in the form of mixtures with gelatine (cf. F. E ν ν a: Journal for scientific Photographic, Photophysik und Photochemie, Vol. 52, pp. 1-24 [1957]). .

The reducing agents to be used include resorcinol, m-aminophenol and their derivatives as indicated below:
HO

O- ° ^H

Resorcinol

35

40

45

55

HO

/ VO-CO-CH ₃ resorcinol monoacetic acid ester HO

Resorcinol monomethyl ether HO CH ₃

O- ° ^h

2-methylresorcinol

HO

5-methylresorcinol

HO

Q-OH

QH ₅

4-ethylresorcinol

HO

^Oh

4-hexylresorcinol

HO

COOH
3,5-dihydroxybenzoic acid

HO

COOH

2,6-dihydroxybenzoic acid HO NO ₂

\ I> - ^oh

2-nitroresorcinol

HO

OH

OH

1,3-naphthalenediol

HO

-NH ₂ m-aminophenol

HO

CH ₃ m- (dimethylamino) phenol

HO

4-hydroxy-N, N-dimethyl-o-toluidine HO

NH (CH ₂ )., SO., II

V-

3- (m-Hydroxyanilino) -l-propanesulfonic acid HO

/ "V-NHCHjCOOH

m-hydroxyphynylglucine HO

NHCH ₂ m- (benzylumino) -phonol HO

45

55

'' S.

HO

\ ~ \ - NHCH ₂ CH ₂ CI mi / i-chloroethylaminoJ-phenol OH

OC ₂ H ₅ resorcinol monoethyl ether

OH

Resorcinol monobutyl ether

OH
/ Γ

C ₂ H ₄ OH

OH o-hydroxyethyl scorcinol

OH

OH

nC., H ₇ 4-n-propy! resorcinol

OH

OH

1-C ₈ H ₁₇

rfMert.-Octylresorcinol

m - (/ i-HydfoxylUhylumino) phenol OH Ji-C ₁₂ H _2. ,

4-n-luurylresorcinol

OH

OH

OH

CH ₂

4-benzylcorcinol

COOH HO I OH

OH

2,4,6-trihydroxybenzocic acid

CH,
HO I OH

Oil

2,4,6-trihydroxytoluene

2,4,6-trihydroxybenzene chloride COOH

HO I OH

CM., J.S.Dihydmxy ^ -methylbenzoestlure

fio

OH

CONH,

OH

2,6-dihydroxybenzamide

H ₁ NC
O

OH

3,5-dihydroxybenzamide

OH

CHO

CH, OH

2,6-dihydroxy-4-methylbenzaldchy (

COCH,

OH 2,6-dihydroxyacctophynone

OH COC ₂ H, 2,4-dihydroxypropiophenone

COCH.,

HO OH

2,4,6-trihydroxyucctophynone

HO OH

2.2 ', 4.4' "ToiruhydiOxybcn /, ophcn

HO

COC ₂ H ₄ -

OC ₆ H ₁₁ 0 ₅ (/ (- gl ucosc) phlorizin

OH

N-OH / f-resorcinal doxime

Cl
4-chlorocorcinol

OH

Cl

Cl 4,6-dichlorocorcinol

OH

OH

SOjII

2,4-I) iliydroxybonzenesulfonstiurc

NHCOCH ₁ , m-Hydroxy-n-oclunoylunilide

NHCOCjlIj m- (propionylumino) «phenol

IO

'5

40

JS

60

NHCOCH = CH ₂ m- (propenoylamino) -phanol

OH

NHCOCH = Ch-COOI malcinsic acid mono- (m-hydroxyanilide)

OH

NHCOC ₂ H ₄ COOH Succinic acid mono- (m-hydroxyanilide)

NHCOCh ₂ COCH., M-Acctoacetylaminophenol OH

NCO ■ Il

m-Hun / .oyliiminophciiol

OH

COOII

I'hlhalsiiiircmono-dn-hydioxyanilid) OH

NHSO ₁ ~ <f V-CKi m-llydroxy. (P.toluolsuironyl) -unilide

HO

Uv

OH (!) 5,7 dihydroxy-4-hydroxyi1uvon

11th

HO

OCH ₁

OH O

5,7-dihydroxy-4'-methoxyflavone

OH

OH O Morin

NHC ₂ H ₅ CH,

3-ethylamino-4-cresol OH

NI IC, H ₇ m- pylarninophenol

OH

NHC ' _H H, _r n m-Uclylaminophcnul

OH

NHC ₁₀ H ₂₁ -Ii mn-DecyluminophcnoI

OH

NHC ₁ HhSO ₁₁ U 4 "im-Hydroxyuni! Ino) -l" buUin8ulfonsllurc

OH

QH ₅

C ₂ H ₅ m-diithylaminophynol

OH

NH
m-hydroxydiphenylamine

Examples of naphthol derivatives are given:

OH

HO

1,6-dihydroxynaphthalene

OH OH

I, K-dihydroxy naphthalene

110

Oil

2.7-1) ihydri) xynaphthalir

OU OH

SO., H

SO., H 1,8-Dihydroxynuphthulin-2,4-disu

SO ₁ H

SOjH

1,8-Dihytlroxynuphthulin-3,5-dl8t

HO ₃ S SO ₃ H

1,8-dihydroxynaphthalene-3,6-disulfonic acid

ΛΑ / *

HO ₃ S SO ₃ H

2,7-dihydroxynaphthalene-3,6-disulfonic acid

NH,

HO
I-amino-6-naphthol

NHCH ₂ CH ₂ CH ₂ SO ₃ H

HO

6-hydroxy-1-naphthylamino) propane-1-sulfonic acid

OH NH,

I-amino-8-naphthol OH NHCOCH ₃

OH NH,

SO ₃ H

N-acetyl-1-amino-8-naphthol

NH,

OH

2-amino-5-naphthol

HO

NH,

2-Amino-7-nanohthol SO ₃ H
l-amino-8-naphthol-2,4-disulfonic acid

2,7-dioxynaphthalene monomethyl ether,
l-amino-8-naphthol-3,5-disulfonic acid,
l-Amino-e-naphthol-So-disulfonic acid,
l-amino-e-naphthoI- ^ ö-disulfonic acid,
1-amino-S-naphthol-SJ-disulfonic acid,

1-amino-S-naphthoM-sulfonic acid,
8-amino-l-naphthol-4-sulfonic acid,
2-Amino-5-naphthol-7-sulfonic acid and the like

The process for preparing such phenolic and naphtholic compounds is well known in the art and the compounds are commercially available.
The vinyl compounds to be used usually include liquid and solid compounds, the

are capable of addition polymerization and an electrical charge due to ionization or addition of hydrogen cations.

Examples of suitable vinyl carboxylic acids are

Acrylic acid, methacrylic acid or maleic acid, ammonium salts of such carboxylic acids with a Vinyl group, e.g. B. ammonium acrylate, metal salts of carboxylic acids with a vinyl group, e.g. B. Sodium Acrylate, Potassium acrylate, Calciumacry'.at, magnesium

acrylate, zinc acrylate, cadmium acrylate, sodium methacrylate, Calcium methacrylate, magnesium methacrylate, zinc methacrylate, cadmium methacrylate, sodium itaconic acid or sodium maleic acid. Examples of suitable vinyl sulfonic acids are vinyl sulfonate or p-vinylbenzenesulfonate, an ammonium salt of a sulfonic acid with a vinyl group, e.g. B. ammonium vinyl sulfonate, a metal salt of a sulfonic acid with . a vinyl group, e.g. B. sodium vinyl sulfonate. Potassium vinyl sulfonate or potassium p-vinylbenzenesulfonate.

Examples of suitable basic vinyl compounds with a basic nitrogen atom are 2-vinylpyridine, 4-vinylpyridine, 5-vinyl-2-methylpyridine, N, N - dimethylaminoethyl acrylate, N, N - dimethyl I-aminoethyl methacrylate, Ν, Ν-diethylaminoethyl acrylate, Ν, Ν-diethylaminoethyl methacrylate and quaternary Salts with a vinyl group obtained by reacting a compound with a vinyl group and a basic nitrogen atom with methyl chloride, ethyl bromide, Dimethyl sulfate, diethyl sulfate or methyl p-toluene sulfonate getting produced. Vinyl carboxylic acids and vinyl sulfonic acids obtained on polymerization a negative electrical charge, while said basic vinyl compounds upon polymerization have a positive charge.

The vinyl compounds can be used alone or in the form of a mixture. You can also together with a water-soluble, polymerizable and non-ionizable vinyl compound, for example with acrylamide, N-hydroxymethylacrylamide, Methacrylamide, methyl methacrylate, vinylpyrrolidone, Ν, Ν-methylenebisacrylamide, triethylene glycol dimethacrylate, Polyethylene glycol dimethacrylate and the like can be used.

When using a non-ionizable vinyl Bond together with the ionic vinyl compound the ratio of the amounts of the respective vinyl compounds must be carefully matched with their reactivity are regulated so as to ensure that a substantial amount of ionizable compound is incorporated into the polymer formed.

As the dye capable of exhibiting an electric charge upon ionization, an ordinary Acid dye or basic dye can be used.

When using a vinyl compound, which leads to the formation of a polymer with a negative electrical A basic dye with a positive electrical charge should be used and when using a vinyl connection, which is capable of forming a polymer with a positive electrical charge is said to be an acidic dye can be used with a negative electric charge.

Furthermore, when using gelatin as a binder for the photographic emulsion which is an amphoteric electrolyte, coloring under consideration of the isoelectronic point of gelatin. Gelatin, for example, has a negative • Electric charge at a pH above the isoclectic point of gelatin and a positive one electrical charge at a pH below the isoelectronic point of gelatin. Accordingly can in the case in which a polymer is generated with a negative electrical charge, the Polymerisal images without coloring the gelatin by coloring the images with a basic dye at a pH lower than the isoelectric point of gelatin. One can also color the emulsion layer uniformly first and then with a solution with a lower pH as the isoelectric point of the gelatin wash to remove dye in the areas in which no polymer image is formed, a colored polymer image remaining. In a similar way Way, if polymerisal images with a positive electrical charge were generated and to be colored with an acidic dye, the polymer images at a higher pH than the isoelectric point of gelatin.

Although the particularly suitable pH for coloring varies with the type of vinyl compound, des The most preferred is the dye or binder to be used Range of pH values between 2.5 and 4.5 in the case of a basic dye and between 5.0 and 8.0 in the case of an acidic dye, when a lime-treated gelatin with an isoclectic as the binder Point of about 4.9 is used.

Examples of dyes that can be used according to the invention are acidic dyes, such as C. 1. Acid Yellow 7 (C. 1. 56 205), C. 1. Acid Yellow <> o 23 (C. 1. 19 140 ), C. 1. Acid Red 1 (C. 1. 18 050), C. 1. Acid Red 52 (CI. 45 100), CI Acid Blue 9 (Cl. 42090), CI Acid Blue 45 (C I. 63 010) and C I. Acid Violet 7 (Cl. 18 055), and basic dyes, e.g. CI. Basic Yellow 1 (CI. 49005), CI. Basic ^ Yellow 2 (C I. 41 000), CI Basic Red 1 (C 1. 45 160), C I. Basic Red 2 (C I. 50 240), C 1. Basic Blue 25 (C I. V ( PSl. C I. Basic Violet 3 (C 1.42 555) and CI Basic

Violet 10 (C.I. 45 170). The ones given above Color numbers refer to Color Index (2nd edition).

When irradiated with electromagnetic waves or corpuscular rays, the silver halide grains be dispersed in an aqueous solution or kept in a dry gel. So can a highly viscous or gelled photographic emulsion on a suitable radiation support be subjected both in the undried and in the dried state. Because the reduction and polymerization take place simultaneously, the reduction in the presence of a vinyl compound or carried out by vinyl compounds. The vinyl compound and that used as a reducing agent Compounds can be incorporated into the photographic emulsion prior to exposure; but you can also incorporate only one of these into the emulsion before exposure and the other compound add to the system after exposure, or both compounds can be added after exposure.

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

In general, the reaction is carried out in the presence of a suitable amount of an alkali, since it progresses smoothly under alkaline conditions. Although the appropriate amount of for the reaction Alkali of the silver halide type of reducing agent and high polymer in the system and their respective concentrations and the reaction temperature depends, it is preferably sufficient Amount used to bring the system pH to 7.5 or above.

In addition, it was found that the polymerization of the vinyl compound was caused by the presence of Sulfite ions in the system is accelerated.

Sulphite ions can enter the reaction system either in the form of a compound that was originally the Sulfite ion contained in the molecule, for example alkali metal sulfites or ammonium sulfite, or in the form of a Compound which gives sulfite ions as a result of hydrolysis, for example pyrosulfites of alkali metals and ammonium, or the addition products of bisulfites with aldehydes, for example formaldehyde or glyoxal, can be added. Although the amount of sulfite ions added depends on the type and amount of Reducing agent and the vinyl monomer used as well as the pH of the system and others Factors dependent are more than 0.05, in particular more than 0.2 mol per liter of the system effective.

The reaction can be carried out by dipping the exposed silver halide emulsion layer in an alkaline one aqueous solution are carried out, wherein the vinyl compound or the vinyl compounds and / or the reducing agent can be easily dissolved in the aqueous alkaline solution,

Although interruption of the reaction is easy by adjusting the pH of the system to e.g. B. 5 or less is achieved, the interruption can also be achieved by cooling, removing the reactants by washing, dissolving the silver halide by fixing or by adding a polymerisation inhibitor to the system can be achieved

When the high polymer used as a binder door the silver halide grains and the monomeric Vinyl compound can be mixed and put together as a coating to form a layer on top of one Substrate are applied, is preferably a small amount of an inhibitor for one; thermal Polymerization added to cause undesirable thermal polymerization of the vinyl monomer impede. As such a polymerization inhibitor, any of the known thermal radical polymerization inhibitors, such as p-methoxyphenol, hydroquinones, 2,6-di-tert-butyl-p-cresol, naphthol or the like. Can be used.

If the vinyl monomer in the. System is included from the beginning, the vinyl monomer is used in an amount by weight of the V30 "to 30 times and preferably incorporated from the ^l l ₄ bis 4 times the amount of the initially present in the system high polymers. The silver halide is suitably present in an amount by weight of the ¹ I ₂₀ - to 2 times and preferably of the ¹ I ₁₀ - "^ s ^! / 2f ^acnen the amount of the high polymer present as a binder used. If the reducing agent is to be incorporated into the system before the reaction, it is expediently added in an amount of 0.1 to 20 moles per 1 mole of silver halide. The thermal polymerization preventing inhibitor is expediently added in an amount of 10 to 2000 parts per million by weight of the vinyl compound. When using the vinyl monomers in the treatment solution, they are preferably dissolved in as high a concentration as possible, since the preferred concentration of the monomer is mainly determined by the solubility of the monomer in the solution. If the reducing agent is used in the treatment solution, it is expediently dissolved in a concentration between ¹ l _2n and 5 mol per 1 liter and preferably between 0.1 and 1 mol per liter.

Similar to conventional silver halide photographic processes, / 'can wipe the There must be a time interval between exposure and the execution of the polymerization. In some cases may according to the properties of the photographic emulsion or the conditions and the Duration of the time interval the effect of the exposure may be reduced to some extent and in this In this case, the decrease in this effect can be eliminated by increasing the amount of exposure will.

Polymer images can be formed by adding only the unpolymerized portion of the vinyl monomer After exposure, reduction and polymerization, you wash away the polymer less is soluble than the monomer and is hardly absorbed by the high polymer, e.g. B. Gelatin, which acts as a binder is used for a silver halide photographic emulsion, can diffuse through. Using of monomers with at least two vinyl groups in combination can reduce the insolubility and the diffusion resistance of the polymer obtained can be increased. Color images according to the Polymer images are obtained by staining as described above after the polymerization. The images formed by this method can be converted into clear color images by fixing the Silver halide to remove it, and then to dissolve it from the silver image, using an oxidizing agent and a solvent for silver Application, be used.

When using a reducing agent with a high efficiency for initiating the polymerization it is not necessary to remove the silver images through the oxidation, as a sufficient polymerization reaction has already taken place under such conditions that a very small amount of reduced silver was produced.

The invention achieves that exposed silver halide emulsion layers in one development step can be developed into polymer images that can be easily colored with dyes can, and which are useful for printing purposes.

In particular, according to the invention, it is possible to obtain a plurality of images relating to depending on the dye absorption capacity, chemical resistance and other properties on the type of vinyl compounds used are particularly advantageous and variable.

The color images formed according to the invention can be transferred to image receiving materials, by placing an image receiving material in intimate contact with a layer bearing the color image, is brought, the color image with a solvent for the dye, for example methanol, Water or an aqueous solution of an acid, base or salt, is moistened. As image receiving material, On which the color image is to be transferred, an ordinary paper or a paper can be used or a film coated with a hydrophilic polymer of gelatin can be used. If the color image is to be transferred to an image-receiving material coated with gelatin, it is preferably with a tanning agent, e.g. B. aluminum salts, in advance in the same way as treated in the usual dye transfer process. After one off from an ionizable Polymeric existing image is formed, it is possible to make a number of copies by staining and surpassing to form in the manner described above, as some copies are formed with a tint graze and the polymer image can be repeatedly colored.

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

example 1

A photographic recording material with a layer of a gelatin-silver chloroiodobromide emulsion became after exposure to one containing both resorcinol and sodium methacrylate Solution treated to form an image-forming polymerisation to effect. Then the resulting image, which was made of polyacrylic acid, was treated with a basic dye colored. The recording material used was by applying a Adhesive layer on both sides of a polyethylene terephthalate film. Applying an antihalation layer one of the so coated surfaces of the film and by application to the other surface one photographic silver halide emulsion obtained by adding an appropriate amount of merocyanine dyes with a sensitization maximum of about 550 ιτίμ for optical sensitization and 1.5 g of chloromuconic acid as a hardening agent and also by adding suitable stabilizers and Wetting agents to form a gelatin silver chloroiodobromide

17th

Emulsion containing 1 mole of silver, about 0.7 mole of chlorine, about 0.3 mole of bromine, about 0.001 mole Iodine and about 100 g gelatin had been produced, the coated film having a silver content of 50 mg per 100 cnr, and further by Auf- s bring a gelatin protective layer to this emulsion layer in a thickness of about 0.8 μm and the formation of line and raster images is suitable for graphic technology. A sample of the film was seen with light of 100 lux for 2 see through a negative of a line image or a line drawing and then immersed in a solution under a red darkroom lamp immersed with the following composition:

15 sodium acrylate 36 g

Resorcinol 2.6 g

2 n-sodium hydroxide 16 cm ³

Water 4.4 cm ³

After soaking for 8 minutes at 35 ° C, the exposed area turned brown. The sample was then soaked for 30 seconds in a 1.5% aqueous solution of acetic acid and then with a Fixing solution of the following composition is fixed.

Sodium thiosulphate (anhydride) .... 150 g

Potassium pyrosulfite 15g

Water, rest to 1000 cm ³

The sample was fixed and washed completely and then in a 0.1% aqueous solution of a red basic dye (Rhodamine 6 GCP, C. 1. Basic Red 1, CI. 45 160) for 5 minutes Immersed in room temperature. After staining, the sample was washed with a 5% aqueous solution of Acetic acid washed for 5 minutes to remove the dye from the parts of the sample in which no brown image was developed, leaving the portion of the image containing the red dye. Since the brown image was made of silver, it was easily replaced by a ferricyanide thiosulfate containing it Reducing agent (Farmer's reducing agent) dissolved out. After the silver image was removed get a clear red image. A similar red image could also be obtained by viewing the Reverse the order of staining and removal of the silver image, d. H. first the silver picture removed and then stained the apparently colorless sample thus obtained.

The sample bearing the color image thus formed was printed on ordinary paper that had been mixed with methanol Rubbing with a sponge containing methanol had been moistened, pressed, and when the sample had been moistened after 30 seconds of being removed from the paper, the red image was transferred to the paper.

If the same procedure outlined above using a 0.1% aqueous Solution of crystal violet (C. I. Basic Violet 3, C. 1. 42 555), Auramine 0-100 (C. I. Basic Yellow 2, ho C. 1. 41 000) or Basic Blue G. O. (C. I. Basic Blue 25, C. 1. 52 025) was repeated instead of Rhodamine 6 GCP, transferred images were shown in blue-violet, yellow or blue color respectively preserved.

In the case of transferring the color images, it was not necessary to remove the silver images. A satisfactory image could be obtained by direct printing after a water wash in connection 146

development and polymerization and rinsing in an intermittent bath,

Example 2

A sample of the recording material as used in Example 1 was, as indicated in Example 1, exposed and treated with a solution of the following composition:

Sodium methacrylate 75 g

Resorcinol 4.95 g

Sodium sulfite 3.0 g

2 n-sodium hydroxide 22 cm ³

Water, remainder to 75 cm ³

On treatment at 30 ^° C. for 8 minutes, pale brown silver images and images made from polymethacrylic acid were obtained.

If the same procedure as indicated in Example 1, using an acidic dye, for example from Rhodamine 6 GCP (C. 1. Basic Red CI No. 45 160) or Crystal Violet CI. Basic Violet 3 (CI No. 42 555) was repeated, color images were obtained which could be transferred onto paper using methanol as in Example 1.

Example 3

A sample of the recording material used in Example 1 was, as described in Example 1, exposed and treated with a solution of the following composition:

Acrylamide 9 g

Potassium p-vinylbenzenesulfonate .... 68 g

Resorcinol 4.95 g

2N sodium hydroxide 38 cm

Water, remainder to 110 cm ³

Treatment at 30 ° C. for 15 minutes gave pale brown silver images and polymer images receive. The polymer images could with an acidic dye by the same procedure be dyed as in Example 1.

If in this case p-vinylbenzenesulfonate in the When the treatment solution was not contained, an image receptive to staining did not become was received.

Example 4

A sample of a recording material as used in Example 1 was, as described in Example 1, exposed and treated with a solution of the following composition:

l-vinyl-2,3-dimethylimidazolium

p-toluenesulfonate 75 g

5-methylresorcinol 5.6 g

Potassium pyrosulfite 3.0 g

2.1 sodium hydroxide 19 g

Water, remainder to 75 cm ³

l-vinyl-2,3-dimethylimidazolium-p-toluenesulfonate was prepared by reacting l-vinyl-2-methylimidazole with methyl p-toluenesulfonate at room temperature and crystallizing the reaction products with ethanol and ether and had a melting point of 142.5 ⁰ C.

Treatment at 30 ° C. for 30 minutes gave pale brown silver images and polymer images formed from the quaternary salt.

17th

After fixing and washing, as indicated in Example 1, the sample was converted into a 0.1% igc aqueous solution of Solar Rhodamine B extra (C. 1. Acid Red 52, C. I. 45 100) for 5 minutes immersed, this dye being an acidic dye <red in color. Then the sample was in immersed and washed a Kolthoff buffer solution having a pH of 5.0 for 3 minutes. After washing, the sample was obtained with a red-colored image area. By dissolving the ic Silver image, as indicated in Example 1, a clear red image was obtained. The color images thus formed could on ordinary paper that was moistened with methanol as in Example 1. transfer will.

In addition, clear, high-density, red images were obtained when the color images were viewed with a Baryta paper brought into contact for 1 minute, this paper with a gelatin layer with a Thickness of 10 μm coated in an alum solution: o dipped and dried.

A similar sample was made with a 0.1% solution of Suminol Leveling Sky Blue R extra cone. (C.I. Acid Blue 62. Cl. 62045), an acid dye with a blue tint instead of solar:? Rhodamine B extra, colored. Blue color images were when washing the recording material with a 1% solution of sodium bicarbonate echo. These images could be transferred onto ordinary paper moistened with ethanol. Similar results were obtained when water was used in place of ethanol. Yellow color image cr were obtained by treating the sample with Solar Pure Yellow 8 G (CI. Acid Yellow 7. C.I. 56 205) or Tartrazine (Cl. Acid Yellow 23 Cl. 19 140) is instead of Solar Rhodamine B C. 1. Add Red 52 (C. 1. No. 45 100), extra colored and with a buffer solution with a pH of 5.0. These yellow color images were printed on a mil methanol or Water moistened paper is transferred by pressing the images onto the paper.

Example 5

A sample of a recording material as used in Example I was drawn as in Example I

Table I.

¹⁴⁶ / 12

lei and with a solution of the following composition treated:

^ -Dimethylaminoäthylmethacrylat 40 u

Acrylamide 2Og

Resorcinol 5.0 g

Potassium pyrosulfite 3.0 g

Water 85 cm ^J

After treatment at 30 ° C. for 20 minutes, basic polymer images with pale brown silver images were obtained. Blue color images were obtained by treating the polymer images with a solution of Suminol Leveling Sky Blue R extra cone. (C.I. Acid Blue 62, Cl. No. 62045) such as colored in Example 4 and washed with an aqueous solution of sodium bicarbonate.

Example 6

A sample of the recording painting. as in Example 1, used, was exposed as described in Example 1 and with a solution of the following Composition treated:

Methacrylic acid 58.9 cm '

Sodium carbonal monohydrate ... 43.0 g
Reducing agents as indicated in Table 1 below

Water 87.5 cm ³

1 η-sodium hydroxide sufficient

Amount to

attitude

of

pH value

to 10.0

After treatment at 30 "C for a period as indicated in Table 1, the samples were fixed, washed with a 0.1 ⁰ Oigen solution of Rhodamine 6GCP CM. Basic Red 1 (C. 1. 45 160 no.) After the same procedure as described in Example 1, colored.

The transmission density to green light in the exposed and unexposed areas dei Samples were measured before and after dyeing. The results are in the table below compiled.

No Reducing agent Kfcngv iki treat Density itci unexposed Density vle exposed Reduction"· lung »· Areas Areas miiicU length of time voi that after YOi dem after (SI (Min) Iftrbcn Karben l'Htben tiirbcn I. 5-methylcorcinol 5.6 10 0.02 0.12 0.04 0.08 2 Phloroglucine 7.3 IO 0.03 0.22 0.09 0.55 3 nvAminophcnol 4.9 15th 0.13 0.19 0.17 0.83 4th 2-methylcorcinol 5.6 20th 0.44 1.00 0.72 2.28 5 4-ethylcorcinol 6.3 IO 0.14 0.61 0.68 6th 4- (m-Hydroxyanilino) - I -butane
«Ulfonic acid c 11.0 20th 0.12 0.24 0.87 7th OwIlWIl 3d MIV
2-nilrorcsorcinol 7.0 4th 0.15 0.50 0.29 8th 1,3-nuphthalenediol 7.2 4th 0.26 0.92 0.47 9 2.7-naphthalenediol 7.2 30th 0.14 0.35 0.26 .18 .63 .48 .60 25th

l-s became bcsitttigi. that the increase in density by staining in the exposed area urööcr is than in the unexposed areas, i.e. the images, corresponding to the exposed areas

were selectively stained. It was also evident that clear red-colored images can be obtained by linearly removing the silver images from the samples using the Laimersehen reducing agent were obtained. Since the density of the silver images in Samples Nos. 1 and 2 was low, clear red-yellow images were obtained even without removing the silver images.

These color images were printed on ordinary paper by the same procedure as in Example 1 be described, transferred.

Example 7

Samples of the recording material as in Example 1 ι as described in Example I.

f  24

exposed and treated with solutions of the following composition:

Methacrylic acid 75 g

Reducing agents as in Table U

specified

Sulphites as indicated in Table 11

Water 75 cm ¹

n-NaOH sufficient '

Amount to

Changeover

of

pH value.

as in

Table Il

specified

labile Il

Ni. - Kcdukiionsmiilcl Mcnyc
(μι SuIIiI 12th pll VnbnuUin, (i, 2 connection 12th K) N.N-dimethylmethaminophenol 10.8 Nitrile sulfil 12th 9.0 Il 1-Arnim i-K-naphl hol-3-sulfonsiiurc 15.1 the same 3 10.2 12th l-Amino-8-naphthol-3, (> - disulfonic acid 19. (i the same 3 12.0 13th Sodium-1,8-dioxynaphlhalin-3, ii-disiilfonsiiiire 15.3 Potassium pyrosulite 3 1. 5 14th l-Amino-8-napilhol-2,4-disulfonic acid 7.2 the same 3 1.4 15th 5-amino-2-naphlhol 11.4 the same 3 1. 5 ld Nalrium-2,7-dioxynaphlhalin-3, (i-disilfonic acid f., 5 ilesgl. 3 1.5 17th 4-ChIm resorcin 8.0 the same 3 9.0 I « 4.0-dichlorocorcinol 0.70 ilesgl. 3 1.5 19th // - Resoreylaldoxime 8.0 the same 3 1.5 20th 2,4-Dihydioxyben / olsulfonic acid (i, 9 the same 3 1.5 21 o-llvdroxyalhyhesorcinol 7, (i the same 3 1.5 22nd 2,4. (Ι-Ί riliydroxyacetophenon (i, 8 the same 3 1.5 23 3,5-dihydroxy benzamide IU ilesgl. 3 1.5 24 2,2 ', 4,4-elrahydroxyben / ophenone 0.9 the same 3 1. 5 25th 2,4, (i-trihydroxybenzaldehyde 1.0 the same 3 1. 5 2 (i 4-letl .- () ctylresorcinol I O. (i the same 3 1. 5 27 m-l hydroxy-n-oclanoyl anilide 9.3 ilesgl. 3 I. 1. 5 2S Maleinsiiuie- (mono-m-hydioxyanilid) 8.3 ilesgl. 3 1. 5 29 m-l hydroxydiphenylamine 11.8 the same 3 I.5 30th m-llydioxy- (p * toliiolstilfoiiyl) -aiilide 0.75 ilesgl 3 1.5 31 Resin cinmonobuiyliilhci y.o the same 3 I. OK 32 4-Ik ¹ IiZyIrCSOrCiIi 0.2 desyl 3 1.5 33 Rosorein monol ethylthei ^ι λ (ι ilesgl. J I I.Ci 34 Rosorcin monobes / oal 0.08 the same 3 y.o 35 3-ethylamino-4-cresol 0.3 the same J I I.5 3d 2.4-Ο-Ί rihydroxyloluene 8, (i the same .1 ι y.o 37 4-cyclohexylrcorcinol 0.72 ilesgl 3 I. I.5 38 I.O-Dioxynaphthluilin 13.0 the same I.5 V; Morin ilesgl 1.5

After cooling at .V) C "for a period of time , as indicated in the following table III, fixing, washing and tinting were repeated. The optical density of the resultant image

/ EiL'hnungsmaierlalien was measured, as in lkis | described, and the lirgebn are summed up in Table III below

25 '~ 26

C'hlormuconsäure as hardening agent and a suitable one Contains stabilizers and surfactants and the emulsion in an amount for Creating a coating layer with a content

of 60 mg of silver per 100 cm ^{2 is} applied, and finally a protective layer of gelatin is applied to a thickness of 1 micron.

The material B consists of a material usually used in the production of line or line images

ίο or continuous tone images with steep gradation recording material used in the photogravure process, which is produced by that on the same base as for material A, a gelaline silver halide emulsion of

is fine grain size with a content of about 0.012 mole of iodine and about 0.988 mole of bromine and 204 g of gelatin per 1 mole of silver, which are with a rhodanate complex sensitized by monovalent gold and with about 0.7 g per HM) g gelatin of chloromuconic acid

as hardening agent, 0.3 g per 1 mol of silver of 6-methyl-4-hydroxy-1,3,3a, 7-tetrazaindcn as a stabilizing agent and a suitable surfactant is combined in an amount to provide a Coating layer with a content of 60 mg of silver

100 cm ² each and then a protective layer of gelatin with a thickness of about 0.8 microns.

Each sample of materials A and B was illuminated through a step wedge with light from a lighting

.10 intensity of 1000 lux and a color temperature of 2880 K for half a second and then exposed to a solution of the following Composition treated.

.15 sodium methacrylate 60 μ

l-Amino-S-naphthol-.U-disiiironic acid c 12 µ

Potassium pyrosulite 2.4 μ

Water W) env ¹

ι »2n-Na () || 22 cm ¹

After treatment at 30 C, pale brown images were observed. Each sample, which was fixed and washed in the same way as indicated in Example 1, was then divided into two parts, the other part was mixed with Rhodamine 6 GCP, CM. Basic Red I (CM. 45 160), as in example I gcRlrbt. The density of both parts was as indicated in Example 6-Example 8 ^hc . ⁿ · Dimension.

The following recording material A and B "KuA AAAiAAA '^

äiesb: sjiHÄ % käöäs sssssr ^ι ■ * "■

tion of the vinyl compounds. Fig. 2 shows similar kminkurvLntr the up

The material A consisted of a customary "zciehmmusmuieriul B ^{" code}

in the production of a positive Wr the photo I _n each of the Fiu'l and 2 zoii-t diu curve I the

gravure density of silver images used in photogravure processes before dyeing and the

Recording material produced thereby. Curve 2 the aeeunitdlchiB vnn Knrh «d silver

dall form on both sides of a cellulose triacetate!

or a Cellulosetriaceia.unterlage a lilfs- or "amount of FarbsSlT, An A.tsmall der bSKh

Interlayer is applied, uui an increase. In particular, she knew about a ηViltlcreii

curses the so loaded pad erne anti I.

Horbildungsschtcht and formed on the other Oberllüehe image. wilhrond diis Srh iTt »S» ι nincrk

an aela.ine silver hulogenide emulsion was borrowed from the base, vodSh, ^ f "S

table III 1, Density of after the Density of Areas No. Treat l'ar exposed lung- after length of time unexposed 0.26 1 before lärbeii Areas 1.06 l'irben before the 0.11 0.95 (min) l'arden 0.15 0.13 3.58 10 10 1.34 1.32 2.30 Il 3 0.09 0.50 0.59 1.86 12th 10 0.34 0.11 0.09 3.49 13th 25th 0.08 0.28 2.02 2.34 14th 4th 0.07 0.45 1.15 1.2 « 15th 5 0.47 0.22 0.57 1.6 " 16 20th 0.20 0.31 0.13 2.20 17th 20th 0.08 0.1 « 0.70 2.11 18th 5 0.08 0.28 0.31 1.81 19th 30th 0.10 0.08 0.68 1.42 20th 6th 0.08 0.36 0.14 0.93 21 20th 0.10 0.38 0.17 1.05 22nd 20th 0.07 1.10 0.43 0.98 23 20th 0.12 0.28 0.01 2.76 24 30th 0.08 0.34 0.38 2.57 25th 30th 0.08 0.38 0.44 0.54 26th 30th 0.36 0.66 0.1 « 0.48 27 50 0.12 0.42 0.07 0.96 28 50 0.14 2, (K) 0.15 2.10 29 25th 0.07 0.23 0.27 2.06 30th 20th 0.13 1.53 0.35 2.93 31 50 0.28 0.31 0.58 1.73 32 3 0.19 0.73 0.13 1.95 M. 10 0.07 0.92 0.06 1.56 34 50 0.0 « 0.61 0.45 1.92 35 20th 0.06 1.2 « 0.20 1.8 « 36 20th 0.10 0.57 1.46 37 3 0.1 « 0.66 2.09 38 3 0.07 0.64 example 39 30th 0.17 • results as in lis were 0.22 iM'haltci similar I.

of medium grain size are applied, wherein

an addition of about 0.5 g per KH) g of gelatine to ^ Ρ ^ & ^^^^^ Ά IS

the emulsion is about (U) 15 moles of iodine and about 0.9 moles in the case of ^ SgSi ^ tA "itw S 'Jff K" vS "rom and about 255 g« clutlne per 1 mole of silver and drive LnUU £ Prn, Ä " i ..? ί I ^{d Y}

27 '28

of halftone images can be applied. The graphic film using the inheritance

Samples showing colored images were given the effect was with light from a 2 kW xenon

Moistened with water and with the papers attached to the arc lamp at a distance of 50 cm during

were the same as in Example 4, and exposed through an original for 2 minutes, the

1% solution of sodium bicarbonate wetted s light was passed through a yellow filter. then

v'uren. brought into contact and pressed. The material was then dissolved in a solution of the

Allowing to stand for 3 minutes, the papers were immersed in the composition:

and the samples were separated and there were 50 μ on the sodium methacrylate

Papers produce clear color images. l-amino-8-naphthol-3,6-disulfone-

^{1 (1} acid 13 g

Example 9 Potassium Pyrosulnt 1.3g

The following panchromatic recording NaC I. ... ...... ... ... ■ ■. ■ ■ · ^^^

material was with a solution as in the example K w

treated. The material consisted of one at the is setting

Manufacture of color dividers for the photo.

engraving process commonly used mate- nH value

rial, which is produced by one on both j _er lö _sui1 ,,

Sides of a polyethylene terephthalate carrier intermediate ^ 10 0

layers, on a surface that is marked with · ο _u , _v “,»,, ,, _r . _m,. 'j

-,. , ι · ι ι 11 ι · α · water, kcsi aui ivaj nii

Underlay provided with an anti-

halo formation layer and on the other side of the after immersion at 30 C for 7 minutes

The recording material was fixed and washed on the base of a gclatin silver halide emulsion

average grain size applies, which is about 0.05 mol and with rhodamine 6GCP, Cl. Basic Red I (C. I.

.Iodine and 0.95 mol of bromine and about 180 g of gelatin ■> 45 IW)), colored as in Example I. They turned brown

each containing 1 mole of silver and formed with a rhodanate syllable image in the unexposed areas

The complex of monovalent gold was sensitized and selectively colored. The coloring of the unexposed

and then with a thioearbocyanine derivative with ranges alone is due to the fact

a sensitization maximum of about 630 ιημ that polymethacrylic acid only in the exposed

and with oxacarbocyanine with a sensitizing _v > areas was formed what from the fact

maximum of about 550 ιημ was scnsibilisierl and it was evident that the thickness of the unexposed

an addition of 6-methyl-4-hydroxy-1,3,3a, 7-tetra-area about 2 microns larger than that of the

/ ainden was used as a stabilizer, dimethylol urine-exposed areas.

As a hardening agent and a curse-active agent, the emulsion was mixed with the Farmer's reducing agent to create a clear, pink-colored, positive content of 80 mg of silver per HK) cnr recorded images according to the original,
is brought, and finally a protective ... . ...

layer of gelatine. 3 samples of this H c ι s ρ ι e I Il
Materials were exposed to light with an illumination.) <> A recording material, as in Example I, a gain of 1000 I.ux and a color temperature of wends, was exposed to x-rays for 3 seconds 2KW) K for 1/1 second through a step wedge and with the same solution as in the example, each sample with a red and green game I being used. A cobalt X-ray tube at 30 kV, 10 mA was used for color separation. The samples were then partially covered with a razor blade the same solution as in Example 8 at 30 "C for a thickness of 2 mm and treated in a period of 14 minutes. When the fixation, washing stood from 1 cm from the window of the tube angeordvu \ d dyeing according to the net described in Example K. The recording material was then carried out with the procedure was established: same solution as in Example I Iki 35 C while the amount of color in the exposed areas _M Treated for 1 minute, fixed, washed and colored with the recording mutation here proportionally with Rinulamine 6 GCP, CM. Basic Red I (CI 45 160). The increase in exposure increased. For this reason, silver images were only found in this full surface The relative ratio of the exposed areas was generated, and the exposed surfaces against red, green, and blue rich were selectively colored.
Similar to the wrapping with a Uh- ss Hs, Mimil was shown that the process according to borrowed wrapping methods, for example monomethyl of the invention, can be applied to the photographic silver halo-aminophenol sulfate or hydroquinone nidemuNion. the one with another

... , ,, Radiation of higher energy than with visible

^{Uci) (} P ^{| t; lm} exposed to light

Hine photographic (leluline-C'hlorsilhcr-Htnul- in

sion with veil scenes, which are similar to "e ι s ρ ι e ι ι-

Described in British Patent 667 206, line polymerization and dyeing were under

was manufactured. the Plnakryplolgelbuls Desen- use of a photographic emulsion which

Sealing agent sealed fluid containing no gelatine and by inserting η of

containing surfactants was reduced to a ^ silver level mi; an alkali halide in a Li) -

uinc interlayer carrying polythylene solution of polyvinylpyrrolidone to seal the SiI

phlhululillm uufgebraucht. Dus photogruphinche Aufberhalogenids. Coagulation of polyvinylpyrrolidone

zelchnungsmuteriul, dus a so-called uulopositivcr, photo * and silver halide with acetone. distance from

17th

By-products from decanting, dispersing the coagulated masses and subsequent ripening had been prepared, the emulsion being chlorine and bromine in a molar ratio of 7: 3, K) Og polyvinylpyrrolidone, 300 g polyvinylalcohol .s hol and 2.4 · 10 ~ "moles of sodium thiosulfal as chemical Sensibilisicrungsmiltcl contained per 1 mole of silver.

The emulsion so formed was beautified to one with an intermediate coat in a dark room Cllulosctriacelate film forming a coating layer about 5 microns thick upset. After drying, the photographic recording material was exposed to a 5 (K) -WaIl-Xcnon lamp with a distance of 50 cm for 10 seconds by a line or line image of a Originals exposed and with a solution of the following Composition treated.

Sodium methacrylate 75 g

Methylenebisacrylamide Hg

Resorcinol 4.95 g

Potassium Pyrosulfil 12g

Borax 7.5 g

Water 75 cm '

2N NaOH 94 cm ¹ "

After treatment at 30 ° C. for 15 minutes, pale brown silver images were observed. The Material was immersed in a 1% aqueous acetic acid solution to interrupt the reaction and washed directly with running water. The image areas were left behind, and the image-free ones However, areas were cleared away with the water.

The image areas could be colored with basic dyes as described in Example 1. Clear color images were obtained when the silver images were removed from the recording material. In addition, the color images could be transferred to papers that had been moistened with methanol with the transfer being carried out in the same manner as in Example 1.

When using methacrylamide instead of sodium methacrylate in the method described above Solution, a polymer image was also obtained, but this was not done with basic dyes 45; could be colored.

If the treatment solution is not methylenebisacrylamide contained, the washing also swelled and loosened the image area. From this In fact, it can be seen that the polymer, so consisting of both sodium methacrylate and

146 from methylenebisacrylamide, in which the image area is formed.

Example i3

A recording material was prepared by a Gclatinc silver chlorobromide emulsion of fine grain size containing silver chlorobromide corresponding to an amount of about 64 g of elemental silver and chlorine and bromine in a molar ratio of 7: 3 and about 35 g of gelatin per 1 l emulsion, This fine-grained gclatin silver chlorobromide emulsion for photographic purposes had a pH value of 5.8 and a pAg value of 7.7, 35 cm ^{3 of} this photographic emulsion being treated with a solution which contained 100 cm ^{1 of} a 0, 43molaren aqueous solution of methacrylic acid, 1 cm x ¹ a lgcw.% aqueous solution of Natriumdodccylbcnzolsulfonsäurc, 1 cnv ¹ a '/ "" molar aqueous solution of Chlormuconsäurc, 1 cnv' a '/ snmolarcn aqueous solution of p-Mcthoxjphcno) and 6.5 g gelatin contained, was prepared and applied to a cellulose triacetate recording base provided with an intermediate layer so that the thickness of the emulsion layer after drying n was 8 microns.

The material thus formed was in intimate contact with a transparent original, the Slrichodcr Linicnbildcr, brought, with a 500 watt Xcnonlampc exposed for 1 second at a distance of 50 cm and exposed to a solution of the the following composition coated.

Resorcinol 6.6 g

Potassium pyrosulite 8.0 g

Water 90 cnv '

33% by weight igc NaOH 16 cm '

A spongy synthetic material was immersed in the processing solution, and the recording material was coated with it. A glass slide was made on the recording material laid to cover the surface of the wet emulsion. After leaving the material to stand At room temperature for 20 minutes, the exposed areas changed color and became faint silver images perceived. When treated according to the procedure described in Example 1 the exposed areas were selectively colored.

As in Example 1, it was possible to obtain clear color images by removing the silver images that were on a paper could be transferred using methanol.

Ilicr / u 2 sheet drawings

Claims (1)

Claim: Process for the production of color photographic images in which one is exposed imagewise photographic silver halide emulsion layer by the action of a monomeric Vinyl compound from the group of vinyl carboxylic acid, vinyl sulfonic acid or basic vinyl compounds with a nitrogen atom and its ι ο salts, and of resorcinol, its derivatives, m-amine phenol, its derivatives or naphthol derivatives with two hydroxyl groups or one hydroxyl group and one amino group Developed in the 1.6, 1.8, 2.5 or 2.7 positions on the naphthalene ring as a reducing agent is characterized by the fact that one the resulting polymer images selectively colors with a dye which corresponds to the charge on the polymer has opposite electrical charge, and that, if necessary, the color images transfers to an image receiving material.