DE3135398A1 - BLACK DYE IMAGE AND METHOD FOR PRODUCING THE SAME - Google Patents

Description

Black dye image and method of making "the same"

The invention relates to a black dye image and method for making the same. Specifically concerns that Invention a black halftone image that is suitable for producing color prints or color separations.

Color separation materials are known. Examples of suitable Examples of light-curable or photo-cured compositions, as well as elements with stained dye images known from US-PS 4,220,700 and BE-PS 871 172. A An example of an element having an image is an element having a carrier with a layer of applied thereon a photosensitive composition with a photohardenable photosensitive Diazo resin and a cationic mordant. Such a layer can be developed by removing the parts which were not cured when exposed to actinic radiation, washed off with water. The pickling agent is with the Diazo resin compatible and is retained in the light-cured layer. Such an element is suitable for example for the production of a dye image by a process with the following process steps: (a) imagewise Exposure of a layer with a photo-curable, photosensitive resin and a cationic mordant with activating Radiation; (b) Development of the layer by rinsing with water while washing away the unexposed parts and (c) application or sucking in an anionic dye onto or into the layer. The colorant is thereby absorbed by the mordant remaining imagewise exposed parts of the layer immobilized

It has been shown that the dyes proposed so far for the generation of black images do not fully meet the requirements placed on them. So it has been shown that the

hitherto known dyes either not the desired Produce a color shade or have inadequate staining properties.

An example of such a proposed black dye, which has not been found to be satisfactory is Eriochrome Blue Black B. The deficiencies of this dye arise from the examples below.

About the dyes that have been tested for suitability so far and which have been found to be unsuitable for producing black images of the type described also black dyes that are not soluble in water. Examples of such dyes are shown in U.S. Patents 4,047,944 and 4,145 known. The bisazo dyes known from these patents require the addition of organic solvents in order to be suitable to reach aqueous solutions.

The invention was based on the object of black image dyes to find which are suitable for the production of black dye images of the specified type and not the disadvantages of the hitherto have known black image dyes.

The invention was based on the knowledge that black dye images, built up from: (a) a photo-cured diazo resin, (b) a cationic mordant compatible with the diazo resin and (c) a black mordant due to the cationic mordant Produce stainable dye with excellent properties thereby let that one uses a bisazo dye of the following formula to prepare the same:

-4T- -40 -

where mean:

R ¹ and R ⁵ individually each -H, -SO ₃ Na, -SO ₃ H-NH ₃ , -SOjH.Pyridine, -SO ₃ HH ₂ NCH ₂ CH ₂ OH, -SO ₃ HN (C ₂ Hg) ₃ , -SO ₂ NH ₂ , -COOH or CH ₂ OH;

R ² and R ⁴ individually are each -H, -OH, -OCH ₃ , -OCH ₂ COOCH ₂ CH ₃ or -OCH ₂ COOH;

R ³ -H, -COOH, -CHjOH or -CONHCH ^ COOH,

12 3 4 5

where the radicals R, R, R, R and R together have a water solubility of at least 0.5g of dye per liter at 21 ° C.

The black bisazo dyes used in the present invention do not require any organic solvent for their solution.

The black disazo dyes which can be used in the present invention can be used, for example, to produce a black dye image use a method that includes the following

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driving levels has:

(a) imagewise exposing an element or recording material with a carrier with a layer of a photo-curable composition with (i) a photo-curable, photosensitive Diazo resin and (ii) a cationic mordant which is compatible with the resin and which is photocured Mass or layer is retained;

Cb) Development of the layer by rinsing with water with removal the unexposed or unexposed parts and

(c) Introducing a black bisazo dye into the remaining ones Parts of the layer with immobilization of the dye by the mordant. According to the invention in the context of a In such a process, a black disazo dye of the specified structure is added to the layer by means of an aqueous solution. As the dye is absorbed, the dye is immobilized in the layer by the mordant.

The black bisazo dyes used in the present invention leave can also be used advantageously in the context of a process for producing a black dye image in a receiving layer which contains a cationic mordant of a predetermined Has pickling strength, the process being characterized by the following stages:

(a) imagewise exposure of a donor layer that contains:

(1) a photo-curable photosensitive diazo resin and

(2) a cationic mordant that is compatible with the resin and is retained in the photocured layer, the mordant of the donor layer in comparison for the mordant of the image-receiving layer, a lower one

-YES-

Has pickling strength with activating radiation;

(b) Development of the donor layer by rinsing with water while removing the unexposed parts;

(c) Coloring the remaining parts of the donor layer with a black bisazo dye, the dye being temporarily immobilized by the donor mordant, and

(d) imagewise transferring the dye into the image receiving layer by contacting dex layers in the presence salt solution or alcohol-water mixture for sufficient time to allow the dye to transfer from the donor layer into the image receiving layer.

The process is characterized in that a dye of the specified structure is used as the black disazo dye.

The described bisazo dyes which can be used according to the invention are particularly advantageous for production of halftone images. They are also suitable for reproducing halftone images in Re, pro copy films (graphic arts print film), micro-copy films (microfile print film) as intermediate stages or copy materials for video discs and as Intermediate copies or intermediate films for UV contact exposure.

Diazo resins suitable for producing the black dye images are water-soluble and light-sensitive. examples for suitable photosensitive diazo resins are disclosed in US Pat. No. 4,220,700 and Research Disclosure, May 1978, No. 16976 known. Particularly suitable diazo resins are those with a comparatively good molecular weight and recurring ones Units of the following formula:

- (CH

in which mean: an an: ion, for example a chloride anion.

Acid condensation products are particularly advantageous diazo resins of a diazonium salt of para-amino diphenyl amine, for example diphenylamino-4-diazonium halide or diphenylamine-4-diazonium phosphate, condensed in an acid with aldehydes, for example paraformaldehyde or formaldehyde, and converted into a double metal salt, for example a chlorozincate or Fluoroborate.

It is known to distribute such diazo resins for Bildhers use. They can be produced by customary known processes. Which can be used to produce images according to the invention Diazo resins are, for example, from Kosar's book, "Light-Sensitive Systems ", pp. 323-324 (1965) and U.S. Patent 3,235,384 known. During exposure, the unexposed layers made from such polymers remain in water

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soluble so that they can be washed or rinsed with water can.'

It may be advantageous to use an acid stabilizer to be used to protect the durability of the photohardenable layer with the diazo resin from undesired degradation. A such acid stabilizer can improve the life of an element or recording material. Commonly known acid stabilizers are acids such as phosphoric acid, citric acid, paratoluene sulfonic acid, methanesulfonic acid, benzene sulfonic acid, naphthalenesulfonic acid and substituted derivatives thereof. Such acid stabilizers can be used more advantageously Use in concentrations of 0.1 to 1.0 mg per dm.

The cationic mordants are used to immobilize the black bis azo dyes in the hardened layers. Suitable cationic mordants must be compatible with the photosensitive diazo resin and must be compatible with the resin on the carrier let apply. The cation: .sche pickling agent should furthermore the Do not adversely affect the adhesive strength or the adhesive properties of the photocurable layers on the carrier. Of Furthermore, the cationic mordant should not impair the hardening properties of the diazo resin. Suitable cationic mordants are generally made up of polymers, including those prepared :; used in the manufacture of photographic materials became. Which can be used to produce images according to the invention Pickling agents are, for example, those with recurring monomeric units with cationic groups carrying charges. Suitable cationic mordants which can be used according to the invention are, for example, from US Pat. No. 4,220,700 and BE-PS 871 172 known. These are particularly advantageous pickling agents with repeating units of the following formula:

- ^ CH ₀ -CH) -

where mean:

2 3

Z and Z that are the same or one of each other

can have different meanings, aryl, aralkyl or alkaryl groups with 6 to 20 carbon atoms or alkyl groups having 1 to 20 carbon atoms;

Z is an alkylene group having 1 to 3 carbon atoms and

Z and Z each represent either a hydrogen atom or together to complete one Ring with 3 to 6 core carbon atoms required atoms;

η = 0, 1 or 2 and

X is an acid anion.

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Examples of suitable pickling agents are:

Poly (styrene-co-3-maleimidopropyl-N, N-dimethy1-N-benzylamraonium chloride) (1: 1) m

Poly (N-alIyI-N, N-dimethyl-vinylbenzylammonium chloride) Poly (N-vinylimidazole)

Poly (Ν, Ν-dimethyl-N-propargyl-vinylbenzylammonium bromide)

Poly (styrene-co-N-alIyI-N, N-dimethyl-vinylbenzylammonium chloride) (1: 1) m

Poly (vinyl acetate pyridinium chloride)

Poly (N, N-dimethyl-N-propyl-vinylbenzylammonium chloride)

Poly (N, N, N, -triethyl-vinylbenzylammonium chloride)

Poly (N, N-dimethyl-N-propargyl-vinylbenzylammonium chloride)

PolyiNjN.N-trimethyl-vinylbenzylammonium chloride-co-ethylene glycol dimethacrylate) (93: 7) m

Poly (N-alIyI-N, N-dimethyl-vinylbenzylammonium bromide-codivinylbenzene) (95: 5) m

Polyistyrene-co-N-allyl-N.N -dimethyl-vinylbenzylammonium bromide-co-divinylbenzene) (49: 49: 2) m

Poly (N-2-butenyl-N, N-dimethyl-vinylbenzylammonium chloride)

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PolyCstyrene-co-N-allyl-NjN-diinethyl-vinylbenzylaminemonium chloride) {1: 4) ra

PolyCstyrene-co-N ^ jN-trimethyl-vinylbenzylammonium chloride)

Poly (styrene-co-N-benzyl-N, N-dimethylacry1amidopropylammonium chloride) (1: 1) m

Poly (N-benzyl-N, N-dimethyl-vinylbenzylammonium chloride)

PolyCstyrene-co-N-butyl-NjN-dimethyl-vinylbenzylammonium chloride (l: 1) m

Poly (I-vinylimidazole-co-3-benzyl-1-vinylimidazolium chloride) 1: 1) m

Poly (1,2-dimethyl-5-vinylpyridinium-p-toluenesiiJ.fonate) Poly (I-benzyl-4-vinylpyridinium chloride) Poly (1-benzyl-2-methyl-5-vinylpyridinium chloride)

PolyiN-carbamoylmethyl-N ^ -dimethyl-vinylbenzylammonium chloride)

Poly (N-cyclohexyl-N, N-dime thy 1-viny Ib enzylammoriiumchl ο rid)

Poly / N, N-dimethyl-N- (3-methyl-2-butenyl) -vinylbenzylammonium chloride 7

Poly (styrene) -co-NjN, N-trimethyl-vinylbenzylammonium chloride)

PolyCN-isobutyl-N ^ -diinethyl-vinylbenzylairanoniumchlorid)

Poly / N-benzyl-NjN-dimethyl- (3-acrylarc: ido-2, Z-dimethy ^ propylanimoniumchlorid /

Poly (N, NjN-trimethyl-vinylbenzylammonium chloride)

PolyCstyrene-co-N-bsnzyl-N, N-dimethyl-4-vinylbenzylanimonium chloride) (1: 1) m

Poly (PjP.P-trioctyLvinylbenzylphosphonium chloride)

PolyCstyrene-co-NjNjN-trihexyl-vinylbenzylammonium chloride) (1: 1) m

PolyCstyrql-co-N ^ .N-trimethyl-vinylbenzylammonium chloride) (1: 1) m

PolyCstyrene-co-N-benzyl-NjN-dimethyl-vinylbenzylanunonium chloride-cc-divinylbenzene) (49.5: 49.5: 1) m

Poly (N-vinylbenzylpiperidinium chloride)

Poly (N, N, N-1 trimethyl-4-vinylphenylcarbamoylmethylammonium chloride)

Poly (N-acetonyl-NjN-dimethyl-vinylbenzylammonium chloride)

Poly (N, N-dimethyl-N-methoxycarbonylmethylvinyIbenzylammonium chloride)

Poly (N-vinylbenzylpyridinium chloride) Poly (N-me thy M-vinylbenzylpyrrolidinium chloride)

Poly (N-methyl-N-vinylbenzylpiperidinium chloride) Poly (N-methyl-N-vinylbenzylmorpholinium chloride) Poly (NjN-dimethyl-N-vinylbenzylanilinium chloride)

Poly (N, N-dimethyl-N-cyclohexyl-vinylbenzylammonium chloride).

Pie cationic pickling agents can be used according to the usual known Process.

The optimal concentration of the mordant and diazo resin in the photohardenable layer may differ depending on the species the desired image, the specially used bisazo dye, the pickling strength of the cationic pickling agent, in the individual case used diazo resin and the concentration of the dye in the dye solution.

The diazo resins are expediently used in one concentration from 0.16 to 1.0 mg per dm used at a preferred concentration of pickling agents from. 0.5 to 5.0 mg / dm. As very special It has generally proven advantageous to use dressing concentrations of 1.0 to 1.5 mg / dm.

Coating compositions of the type described can be used apply conventional known photographic supports. Such carriers are known, for example, from the literature reference "Product Licensing Index", Volume 92, December 1971, Publication No. 9232, page 108 and the reference Research Disclosure ", December 1978, Item 17643.

Suitable supports are, for example, transparent supports, e.g. B. film support and glass support, as well as opaque or opaque carriers, for example made of metal and photographic

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graphic paper. Particularly suitable supports are paper supports and film supports, for example, poly (ethy lent ereph thai filmed) rager.

The carrier can optionally have one or more adhesive layers in order to improve the adhesion of the layers to be applied. The photohardenable composition can be prepared according to the usual known methods Apply methods to the substrate. Such methods are described in more detail, for example, in the aforementioned "Research Disclosure" and the "Product Licensing Index" literature. If necessary, the coating can be used Masses used coating aids added to improve the formation of layers on a suitable support.

A photohardenable layer is thus initially only exposed imagewise to produce a photo-hardened image, and then develop before the material is immersed in a dye bath containing a dye of the invention. The exposure or exposure can be carried out with any activating radiation which is responsive to the diazo resin. Since diazo resins are primarily responsive to ultraviolet light, the light emitted by the radiation source is preferably rich in ultraviolet radiation. Usual contact exposures or contact exposures have proven to be expedient and advantageous.

After the exposure has taken place, the material is developed by washing or rinsing off the unexposed portions of the photohardenable layer. The diazo resin that was cured remains in proportion to the amount of activating radiation that hit the material. The amount of mordant, that remains in the layer is directly proportional to the amount of hardened resin. The development of the hardened layer

takes place in an expedient manner by bringing the layer into contact with a stream of normal tap water or by carefully spraying with tap water. On the other hand, the development can also be done mechanically by rubbing off. Split layers after soaking the layer in water. The duration of the water wash is generally 2 seconds to 1 minute.

The bisazo dye used in accordance with the invention is then incorporated into the developed resin image, specially supplied to the photo-hardened resin image, which contains the mordant, by adding the dye is at least temporarily immobilized. The introduction of the dye into the developed resin image can be carried out by immersion of the element in a suitable dye bath or in some other way, whereby the dye in suitable amounts in the the mordant and the resin-containing layer can penetrate. An aqueous solution or an aqueous solution is preferably used as the bath • Buffered solution of the black bisazo dye is used. The length of the immersion time in the dye bath and the temperature of the bath are adjusted so that optimal dye images are obtained. The immersion time is preferably around 10 to 100 seconds at a dye bath temperature of 10 to 40 ° C. The element is then rinsed off if necessary to remove excess Remove dye and dried. The conditions under which this rinse step is carried out are generally as follows same as the conditions of the development stage.

The concentration of the black disazo dye in a dye bath is advantageously 0.1 to 2.0 percent by weight. The optimal concentration in each individual case depends on various factors Factors such as the type of image to be produced, the duration of immersion, the bath temperature and the pH value. The solvent in the bathroom ordered either from water or water whose pH value is buffered to a pH value suitable for the dye became. For example, the water bath can thus consist of a bath

exist, which was buffered by the addition of potassium phosphate sodium hydroxide to such an extent that a pH value of 5 to 10, for example a pH of 7 is set.

The dye image produced can be from the photocured, developed and colored element, acting as a donor or donor element can serve to be transferred to a receiving element, which consists of a carrier of at least one applied thereon There is a receiving layer which has a cationic pickling agent with a greater pickling strength than the donor or donor layer. Such relative mordant levels are in the photographic field known. When appropriately registered, transferred to a single image receiving element provides color separation positives, including of a color extract positive with a black biazo dye a complete color print.

The image receiving layer can be any polymeric mordant, as described, provided that the stain strength of the receiving layer is greater than the stain strength of the Donor or donor class. Furthermore, the receiving layer contain a binder, e.g. B. gelatin or another suitable binder. Suitable receiving layers are des further hardened or contain hardening agents, e.g. B. formaldehyde or bis (vinylsulfonylmethyl) ether. The concentration of mordant in the receiving layer is generally from 5.0 to 50mg per dm. The concentration of binder in the receiving

layer is usually 0 to 60 mg per dm. The transmission of the dye is preferably carried out in a salt solution or an alcohol-water mixture. To do this you can use either the donor or donor layer or the image receiving layer or both layers are immersed in a solution, the immersion time usually being about 10 to 100 seconds. The two layers are then placed one on top of the other and laminated together, for example by passing them through the

Gap of a pair of printing rollers. The layers are then left in contact with one another for a certain period of time, so that the desired dye concentration can pass into the image receiving layer. The length of this period is in generally at 5 to 100 seconds. The two layers are then separated from one another.

On the other hand, it is also possible to produce a receiving layer, which contains a transfer salt. In this case it can a comparatively short immersion of the donor or donor layer be done in water.

The selection of the salt solution with the transfer function depends primarily on the solubility of the black bisazo dye. The use of salt solutions which contain potassium chloride, potassium bromide or potassium iodide has proven to be particularly advantageous or sodium salicylate and / or potassium thiocyanate. It is expedient to use 0.1 to 1.0 molar solutions.

To suitable alcohol-water solutions for the transfer of Colorants include mixtures in which the alcohol is present in an amount of about 1 to 5 parts by volume per part by volume of water. Suitable alcohols are, for example, methanol, ethanol and isopropanol.

The following examples are intended to further illustrate the invention.

Example 1: Synthesis of a water-soluble black bisazo dye

This example illustrates the synthesis of a suitable one water soluble black dye.

A solution of 3.78g (0.02 mol) 2-aminophenol - 4-sulfonic acid (also known as 4-hydroxymetanilic acid), 1.58g (0.02 mol) Pyridine, 20 ml (0.02 mol) of an IN sodium nitrite solution and 10 ml Water was slowly added to 25 ml (0.05 mol) of 2N hydrochloric acid and 50 g of crushed ice with vigorous stirring. The resulting light brown solution was placed in a refrigerator for half an hour, whereupon it became one at a time cold (0 to 5 ° C) solution of 2.58g (0.0099 mol) 2,3-naphthalenediol-6-sulfonic acid, The sodium salt of a mixture of 50 ml of pyridine and 11 ml of a 29% aqueous ammonium hydroxide solution was added became. (The di-oil was first mixed with pyridine, after which the ammonium hydroxide was added). The purple one obtained Solution was stirred in a cooling bath for 1 hour and then overnight without cooling. The black solution obtained was under Stirring given in 400ml tetrahydrofuran, whereupon the whole thing was stirred for a further hour. The precipitated black precipitate was filtered off and immersed in fresh tetrahydrofuran for one hour slurried. The separated solid mass was then Stirred for a further hour in 300ml boiling ethanol, whereupon was filtered off. The filtered dye was washed and dried in a vacuum oven at 50 ° C. The structure of the dye was determined by customary analytical methods.

Other black dyes were synthesized in a similar manner. The structure of the dyes produced gives from the following table I:

Table I.

R ¹

Example 'No. R.

R *

1 -SOjH, pyridine -OH -H -H -SOjH.pyridine 2 -SOjNa -OCH ₃ -H -H -SOjH.pyridine 3 -SOjNa -OCHj -H -H -CO ₂ H 4th -H -OCHj -H -H -SOjH.pyridine 5 -SOjNa -H -CO ₂ H -H -SO ₂ NH ₂ . 6th -SOjNa -OH, -H -H -SOjNa 7th -SOjNa -H -CONHCH-
I. -H -H CO ₂ H

Example no. R. 8th -SOjNa 9 -SOjNa 10 -SOjNa 11 -SOjNa 12th -SOjNa 13th -SOjNa 14th -SOjNa 15th -SO ₂ NH ₂ 16 -SOjNa 17th -SOjNa 18th -SOjNa 19th -SOjNa 20th -SOjNa 21st -SOjNa

-H -CO 2 ^H -H -CO ₂ H -H -CH ₂ 0H -H -CH ₂ OH -OH -H -H -SOjH.pyridine -OH -H -H -SOjH.H ₂ NCH ₂ CH ₂ OH -OH -H -H -SOjH.NHj -OH -H -H GH 14 Mf PU ΠΙ! "\
- OU _ Π. JN IL / Π- VjFI - J -
J L 3 ύ -OH -H -H -CO ₂ H -OH -H -H -SOjH.pyridine -OH -H -H -SOjH.pyridine -OH -H -H , -SOjH.pyridine -H -H -OH -SO ₂ NH ₂ -OCH ₃ -H -H -SO ₇ NH,
Ct Lt -H -H -OH,
ι , CO ₂ C ₂ H ₅ -H -H -H -OH, .CO.H -H

GO OJ cn co CO OO

Examples 22-42

On a subbed poly (ethylene terephthalate) film base a photo-curable coating compound of the following composition was applied:

Poly (N-cyclohexyl-N, N-dimethyl-4-vinylbenzylammonium chloride) (polymeric mordant) ^ 3.78 mg / dm

light-sensitive diazo resin (Fairmount Diazo Resin No. 4, Type 1) (condensation product of 4-diazo-diphenylamine and Formaldehyde) 0.81 mg / dm

2 phosphoric acid 0.35 mg / dm

The black dye to be tested was dissolved in a concentration of 0.4% by weight in distilled water which had been buffered to a pH of 8.0 by adding sodium phosphate. A portion oes element with the mordant and the light-sensitive diazo resin was imagewise exposed for 30 seconds using a 400 watt mercury vapor lamp. In this way, the layer with the diazo resin is held in an image-wise manner. The following process steps were carried out at a temperature of 21 ^° C.:

(1) Develop the element for 10 seconds with the exposed Diazo resin layer with running tap water;

(2) immersion in the black dye solution for 30 seconds;

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(3) rinse in running tap water for 20 seconds;

(4) Cleaning and drying in the air at room temperature (21 ^° C.).

The density of the colored test piece was determined by means of a conventional densitometer. In each case, the dye image became black obtain. The following dye densities were determined:

. - -so- - Reflective density Table II 0.77 Example no. Dye of 0.51 Example no. 0.75 22nd 2 0.50 23 3 1.28 24 4th 0.98 25th 5 1.01 26th 6th 1.47 27 7th 1.33 28 8th 1.29 29 10 0.52 30th 10 (repeat) 0.49 31 11 0.94 32 12th 0.52 33 12 (repeat) 0.64 34 13th 0.82 35 14th 0.59 36 15th 0.59 37 16 0.46 38 17th 0.40 39 18th 0.43 40 19th 41 21st 42 20th

From the compiled data it can be seen that the maximum Reflection density using the dye from Example 29 was obtained.

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- * ττ ~ ~ *

Example 43

The procedure described in Examples 22-42 was repeated except that this time a black Bisazo dye of the following structural formula was used:

Optionally, the dye can have sodium ions instead of ammonium ions.

When the dye was used, a favorable black dye image was obtained. The dye has a particularly advantageous one Solubility in water.

Comparative examples:

The following dyes were used in solutions of the following composition:

99i "ml of buffered water

, 1 ml of a surface-active compound (Surfactant 10G, corresponding to a nonylphenoxyglycidol, trade name from Olin Corp., U.S.A),

g dye.

The solutions were buffered to pH 7 and 10. None of the dye solutions prepared were found to be suitable due to one or more of the following disadvantages: undesirable hue, poor absorption into the photocured layer or undesirable gray image color.

Chicago Sky Blue (Cl. 24410) Eriochrome Black T (CI. 1464 5) Eriochrome Blue Back B (CI. 14640) Mordant Blue 79 (CI. 14720) Acid Black 24 (CI. 26370) Acid Black 48 (CI. 65005) Acid Blue 25 (CI. 62055) Acid Blue 40 (CI. 62125) Celestine Blue (CI. 51050)

Claims (8)

PATENT LAWYERS Dr.-Ing. Wolff t H. Bartels DipL-Chem. Dr. Brandes Dr.-Ing. Held Diploma Phys. WoHf Reg. No. 126 242 approved by the GERMAN AND EUROPEAN PATENT OFFICE EASTMAN · KODAK COMPANY State Street 8000 Munich 22, Ttiierschstr. Rochester, New York State Tel. <O89) 293297 Telex 0523325 (patwo d) United States of America Telegram address: wolffpatent, mürchen Postscheckkonto Stuttgart 7211 BtZ 60010070 Deutsche Bank AG, 14/28630 BLZ 60070070 August 31, 1981 25/28 Black dye image and Method of making the same. Claims ^ l 1. ) Black dye image, made up of: (a) a photo-cured diazo resin, (b) a cationic mordant compatible with the diazo resin and (c) a black, due to the cationic mordant
pickable, dye, characterized in that it contains a black bisazo dye of the following formula: Telephone information and orders are only possible after written Confirmation binding where mean: R and R each individually represent a hydrogen atom or a remainder of one of the following formulas: -S (X ₅ Na; -SO ₃ H ₁ NH ₃ ; -SO ₃ H.Pyridine; -So ₃ FLH ₂ NCH ₂ CH ₂ OH; -SO ₃ H ₁ N (C ₂ H ₅ ) ₃ ; -SO ₂ NH ₂ ; -COOH or -CH ₂ OH; R and R each individually represent a hydrogen atom or a remainder of one of the following formulas: -OH; -OCH ₃ ; -OCH ₂ COOCH ₂ CH ₃ or -OCH ₂ COOH; a hydrogen atom or a residue of one of the following formulas: -COOH; -CH ₂ OH or -CONHCH ₂ COOh, where the radicals R, R, R, R and R together have a water solubility Ensure at least 0.5 g of dye per liter at 21 ° C. 2. dye image according to claim 1, characterized in that it contains, as a black bisazo dye, the dye of the following formula: NaO ₃ S ΛΤΙ \ 3. dye image according to claim 1, characterized in that that it contains, as a black bisazo dye, the dye of the following formula: NaO ₃ S CONHCh ₂ COOH CONHCH ₂ COOh 4. dye image according to claim 1, characterized in that it is the dye of the black bisazo dye contains the following formula: COOH NaO ₃ S OH ^ GOOH -OH / COOH . COOH 5. dye image according to claim 1, characterized in that that it contains, as a black bisazo dye, the dye of the following formula: NaO ₃ S 6. dye image according to claim 1, characterized in that it is the dye as a black bisazo dye
contains the following formula: HC H ₃ N-HO ₃ S SO ₃ H ^ NH ₃ SO ₃ H ^ NH ₃ 7. A method for producing a dye image comprising: Ca) a photographic recording material composed of a Layer support and a layer applied thereon with (1) a photo-curable, photosensitive diazo resin and (2) a cationic compatible with the diazo resin Pickling agents exposed imagewise to activating radiation; (b) the layer by rinsing with water to remove it of the non-exposed parts developed and (c) colors the parts that have remained on the substrate with a black dye which is produced by the mordant is immobilized, characterized in that an aqueous solution of a bisazo dye according to one of the claims is used for coloring to 6 used. 8. Method of making a black dye image in an image receiving layer with a cationic mordant of a predetermined mordant strength, in which one (a) a donor layer with (1) a photo-curable, photosensitive diazo resin and (2) a cationic mordant compatible with the diazo resin, which compared to the mordant of the Image receiving layer has a lower stain strength, exposed imagewise to activating radiation, (b) the donor layer by rinsing with water with removal of the unexposed parts developed, (c) the remaining parts of the donor layer with a black dye with immobilization by the Colorants of the donor layer and (d) the dye by contacting the layers in Presence of a saline solution or an alcohol-water mixture from the donor layer on the image receiving layer transmits, characterized in that a bisazo dye according to one of Claims 1 to 6 is used as the black dye used.