DE2516174B2 - PHOTOGRAPHIC RECORDING MATERIAL AND PHOTOGRAPHIC PROCESS FOR PRODUCING IMAGES - Google Patents

Description

The invention relates to a photographic recording material comprising a layer support and at least a radiation-sensitive layer containing a cobalt (III) complex, and also relates to a photographic one Process for the production of images in which a photographic recording material imagewise exposed to rays having a wavelength longer than 300 nm and then to an image-receiving layer is brought into contact, and a photographic positive-positive method of manufacture of images in which a photographic material is in contact with an image-receiving layer exposed to radiation with a wavelength longer than 300 nm and heated to a temperature is heated from 80 to 150 C.

It is well known that conventional photographic recording materials contain radiation-sensitive materials Component silver halide. In the exposure and development of such a material the silver halide is reduced to metallic silver, creating an image. Disadvantageous at The well-known classic development process is the use of aqueous baths, which is the immediate Production of photographic images prevented by exposure of the recording material. Another disadvantage of the known classical photographic process is that the price of silver is in has risen sharply in recent years. As you know, go during the development process photographic recording materials of the type described contain considerable amounts of silver lost, which significantly increases the cost of the known photographic process.

There has therefore been no lack of attempts to develop photographic systems in which the Silver halide is replaced by other photosensitive components. Typically were such systems are designed to shorten the photographic processing process and to capture images without the delay in the development process that is common in conventional photographic processes to be able to manufacture. However, the known methods of this type require at least a process step using a liquid to produce the photographic Freeze images. In addition, the systems that have become known have serious disadvantages. For example, many of the systems that have become known that do not use silver are only suitable for making negative images or for making positive images only. Further it has been shown that these systems are a comparatively

have only very low photographic sensitivity, since these systems do not have the amplification capability of the silver halide can be exploited. Many of the known systems suffer from this further including that the image-background contrast is lost or at least severely impaired over time will.

US Pat. No. 3,152,903 also discloses photographic recording materials with cobalt III complexes known. In the case of these recording materials, photographic images are spoiled Oxidation-reduction reaction star obtained. A cobalt (III) complex is used as a Photocatalyst used to stimulate the oxidation-reduction reaction. As a reducing agent A wide variety of hydroxvaromatic compounds can be used, including of dihydrophenols. for example hydroquinones The oxidizing agent can consist of various metals, e.g. B. silver. Mercury. Lead. Gold. Manganese. Nickel. Tin. Chrome. Platinum and copper The reducing agents used in the case of the known recording materials are sensitive to oxygen, therefore careful handling of the recording materials must be carried out. too early a response without imaging to prevent. In order to produce visible and permanent images, the photographic Images are fixed to a continued oxidation-reduction reaction to prevent, since this adversely affects the image quality, such However, fixing increases the cost of the development process.

It is the object of the invention. a radiation sensitive. to indicate silver-free photographic material suitable for the production of both positive and negative photographic images and was / was either in a radiation sensitive layer of the material or in a separate internal layer of the material or an external imaging layer. The photographic material of the invention, hereinafter referred to as the most radiation-sensitive material, is also to establishing lasting images allow good quality without the need for a fixing process, and it is thermally can be stabilisieri without there "

τ-- ■ c \ ·· ι ■. ■: _l. ^ I. 1 ". ..ti

CHIC Γ IAlCl IlUbM ^ Ktll ClllWUZLlll ttldSätil rtwiui.li men. ·.

The invention is based on the knowledge that the task at hand by selecting certain cobalts! 111! Complexes and certain spectral sensitizers can solve.

The invention relates to a photographic one Recording material composed of a layer support and at least one radiation-sensitive layer a cobalt! 111 (complex, which is characterized is. that the radiation-sensitive layer (a) as the only photolytic component is one of sensitizable Anion-free cobalt! III! Complex with at least two unidentical ligands and (b | a sensitizer. emitting a wavelength of longer than 300 nm \ erm is able to absorb. contains, where (el applies that it is a Cobaltlllllkomplex contains, its reduction potential between the oxidizing and reducing potential of the sensitizing agent in the ground state

The invention also relates to a photoi'r: inherent Recording material on a layer support and at least one radiation-sensitive layer with a cobalt (III) complex, which thereby is characterized in that the radiation-sensitive layer (a) as the only photolytic component a Coball (III) -koimplex free of sensitizable anions with at least two unideal ligands and fb) a sensitizer. the radiance of one Able to absorb wavelength longer than 300 nm / u, contains its reduction polentiai between

ίο the oxidation and reduction potential of the sensitizing agent is in the basic condition, and that the recording material (d) contains an image-receiving layer.
The invention also relates to a photographic process for producing images, in which a photographic recording material is exposed imagewise to rays having a wavelength longer than 300 nm and then brought into contact with an image-receiving layer, which is characterized in that a photographic recording material of the specified Type and an image receiving layer with a compound which is with at least one of the unidental ligands of the cobalt! 111 l complex reacts to form an optically different compound in the image-receiving layer, is used.

The invention also relates to a photographic positive-positive process for production of images in which a photographic recording material in contact with an image-receiving layer with radiation of a wavelength of long exposed as 300 nm and heated to a temperature of 80 to 150 C, which is characterized is. that a photographic recording material of the specified type and as an image-receiving layer a photosensitive layer of a two-part diazotype material is used and that the photosensitive layer of the two-component diazotype material than imagewise exposed and the photographic material uniformly with rays a Wavelength \ on is exposed for longer than 300 nm.

The drawing serves to explain the in more detail

Invention. In detail are shown in

Fig. 1 is a radiation sensitive photographic Material according to the invention in the scheme.

2 shows the schematic representation of the production a photographic image using

; tUi ^^ ι; ι uu: i xm ^

. _η ^ _π ^ ι; _η ι. _πη ^ u ~ «~ u: _-. i

ipmiinnuvll puuiu ^ l ajjlli: s \ inll

teriais according to the invention in contact with a template through reflex exposure,

3 shows the schematic representation of the production of a photographic image using a radiation sensitive one according to the present invention Material in combination with a copy sheet during thermal development.

F1 g. 4 shows the schematic representation of an image having copy sheet.

5 shows the schematic representation of a comparatively more complicated radiation-sensitive ho recording materials according to the invention.

6 and 7 the schematic representation of a an image having an original and a radiation-sensitive Materials according to the invention.

8 shows the schematic representation of a multiple

f> 5-layer, multi-colored, radiation-sensitive Image recording material according to the invention and 9 shows a diagram with reduction potentials

of cobalt) II D-complexes in the ground state apart

depending on the logarithm of the dye fading rate in units of optical density.

I. For the production of photographic recording materials suitable cobalt after the discovery! UI) -

complex

In the manufacture of photographic materials Cobalullll complexes suitable according to the invention are molecules with a cobalt atom or coballion. that of a group of atoms. Ions or other molecules are surrounded, commonly referred to as ligands will. The cobalt atom or C'obaltion in the center of these complexes is a Lewis acid. whereas the Ligands are Lewis bases. It is known that (obalt complexes capable of forming with both divalent and trivalent cobalt ions. In the case of the present So-called trivalent cobalt complexes are found used, i.e. CobaltUIll complexes. there the ligands in these complexes compared to the corresponding cobalt! II I (complexes firmly held will.

Particularly beneficial cobalt! 111 (-complexes 7ur Manufacture of photographic materials according to the invention are those referred to as inert complexes will. Inert complexes are those which have no or practically no exclusion of uncoordinated or coordinated ligands within a period of at least one Minnie and preferably show for several hours up to 5 hours or more if a Test sample of the complex is dissolved in a 0.1 molar concentration at 20 C in a solvent, which also has a labeled uncoordinated ligand of the same in 0.1 molar concentration Type as the coordinated ligand contains. The test is carried out in an advantageous manner under the conditions carried out, to which the radiation-sensitivec Material after the discovery is subject.

Lots of cobalt! 1II (complexes show practically none Exchange of uncoordinated and coordinated ligands over the course of several days. The definition of inert complexes and methods for measuring ligand exchange using radioactive ones Isotopes for labeling ligands are known. Reference is made, for example on the work of Taube, published in »Chem. Rev «. Vol. 50, p. 69 (1952). and the work of B a sο 1ο and Pearson, “Mechanism of Inorganic Reactions. A Study of Meta] Complexes and Solutions «. 2nd edition. 1967. John Wiley and Sons publisher. P. 141. More details of the measurement of a Ligand exchanges can also be found in a work by A d a m s ο η and co-workers in »J. At the. Chem ", Vol. 73, p. 4789 (1951).

Cobalt (III) complexes suitable for the production of photographic materials according to the invention are, in particular, those with a coordination number of 6. A wide variety of ligands can be present in the complexes. Virtually all Lewis bases can ligands in cationic cobalt! 111 (represent complexes. Typical ligands. Which can be present in the complexes are halide ligands. 7. B chloride, bromide and fluoride ligands, furthermore nitrate.

Nitrite, superoxide, aquo and amine ligands, e.g. B. ethylenediamine, diethylenetriamine, triethylenetelramine, diaminodiacetic acid and ethylenediamine telraacetic acid ligands, also NH ₃ , azide, glyoxime, thiocyanide, cyanide and carbonate ligands and other ligands, such as those described, for example, on p. 44 of the cited literature by B. as ο I ο and Pearson are described. It is characteristic of the cobalt (III) complexes used according to the invention. that they

ίο have at least two unidentical ligands.

Particularly advantageous cobalt! II! Complexes for Production of photographic materials according to the invention are those in which the cobalt (III) atom and the ligands associated with the atom form a cationic radical. Such complexes are hereinafter referred to as cationic cobalt (III) complexes designated. They preferably have an absolute positive charge of +3. For education In a complete connection, the cationic cobalt III complex has one or more non-sensitizable Anions according to the charge neutralization rule! on.

For the purposes of the invention, anions are referred to as being insensitive if they are used in combination with known sensitizing agents for photographic silver halide emulsions, their photographic response to exposure not stimulated with electromagnetic radiation of a wavelength longer than 300 nanometers.

Such anions can easily be classified as nonsensitizable Identify anions by> their behavior in combination with photolytically inactive Cations with and without the presence of a spectral sensitizing agent is determined. The in the frame The anions used in the invention have no photographic activity. The photographic Rather, the activity of the compounds used according to the invention is based on the cationic cobalt dll (-complex.

Particularly advantageous for the cationic cobalt (III) complexes suitable non-sensitizable anions are halide anions. ζ. Β chloride, bromide and fluoride anions. also sulfite, sulfate, AIk> 1- and arvlsulfonate, nitrate, nitrite. Perchlorate CarbcmIaK z. B. Haloalkylcarboxylat-, Acetat-, Hexanoatsowie also Hexafliiorphosnhat-. Tetrafiuorhoratijnci anHpre corresponding anions

Though the most varied anicnes in the grain plcxen may exist, it has been shown that

so anions. which are comparatively sour. d. h one Have acid dissociation consonants of 3.5 or less. Cobalt! III! -Complexes that deliver less are easily reducible.

Since the materials used for the production of photographic Mass according to the invention spectral Sensitizers can carry a negative charge, so can spectral sensitizers themselves represent an anionic residue of the cationic CobaltdIIl complex. A spectral scanning

fto sensitizers qualifies as non-sensitive Anion, as its responsiveness at the Exponic This does not depend on the presence of a “usual spectral sensitization means by means of a door SiI Berhalide emulsions Furthermore, cn

(15 or more cations, depending on the charge neutralization rule. in addition to the cationic d> baltlllD complex be present to the connection to να \ oi! ständii; i.ii

advantageous

are those which produce easily soluble compounds No. 17

witness, e.g. B. Alkali and quaternary ammonium

jcations. No. 18

Most cobalt d 11! Complexes are preferred responsive to electromagnetic radiation of 5 No. 19 wavelengths shorter than 300 nanometers. However, it is also a number of Cobaltd 11) - No. 20 complex known that can be photo-reduced directly in solution by electromagnetic No. 21 Radiation with a wavelength longer than 300 nanometers meters. The ability to directly reduce the No. 22-like cobalt (III) complexes, however, decreases markedly from when the complex., in the form of layers or in No. 23 Layers are present. Most Cobaltd 11! Complexes are at wavelengths longer than 300 nanometers ι> No. 24 cannot be reduced directly in photographic layers. No. 25

It is surprising to find that known spectral sensitizers for silver halide are No. 26 photolytic response of cobalt (l11) - 20 complex to electromagnetic radiation No. 27 with a wavelength longer than 300 nanometers can improve. It was even more surprising, No. 28, to find that cobalt) 111! Complexes did not directly through wavelengths longer than 300 nano 25 No. 29 meters are responsive, can be activated photoly table, d. H. can be reduced if they are No. 30 used according to the invention in combination with the described spectral sensitizers No. 31 will. .10

Examples of No. 32 in an advantageous manner according to the invention

CobaIt (III) complexes which can be used are listed in Table I below. No. 33

.15 No. 34

Bis (methylglyoxime) bispyridine-cobaltdll) -trichloroacetate,

N.N'-Ethylene-bis-ualicylidenimine-bisammine-cobalt ( 111) bromide,

Bis (dimethylglyoxime) ethylaquo-cobalt (III) sulfate,

μ-Superoxodeca-am min-dicobal t (IH) -perehlorat.

Sodium dichloro-ethylenediamine diacetocobal K ' 11 l-chloroacetate,

Penta-ammin-carbonato-eobaltdlll-nitrate (-0.440),

trans [bis (ethylenediamine) diazidocobaltlllD sulfate.

cist bisläthyiendiamine azidothiocyanatocoballl 111)] dithionate (- 0.50), cis [bis | ethylenediamine) diazido-cobalt (1H)] - perchlorate (-0.67).

cis [ethylenediamine-nitro-azido-cobalt (III)] -perchlorate (- 0.70).

cis [bis (ether> Ienediamine) dichloro-coball (III)] chloride (- 0.40).

trans [bis (ethylenediamine) dichlorocoballdllljchlorid (-0.40).

trans [bis (ethylenediamine) dibromocobaltdlDjbromid (-0.13).

trans [bis (ethylenediamine) thiocyanatochloro-cobaltl 111)] thiocyanate (- 0.40), Triethylenetetramine dinitro cobalt (III) iodide.

trans [dinitrotetra-ammin-cobalt (III)] nitrate (-0.225).

cisfBisläthylenediaminelamminochlorocobaltdlD chloride (-0.54), transf bis (ethylenediamine) dithiocyanato

cobalt (III)] chloride (-0.150).

Table I.

Examples of suitable cobalt! III! Complexes (Reduction potentials in volts)

No. 1 Hexa-ammin-cobaltdllj-acetate (-0.35). No. 2 Hexa-ammin-cobalt (111l-chloride (0-0.3151. No. 3 Hexa-ammin-cobalt III III trifluoroacctate. No. 4 Chlorpenta-ammin-cobaltilli-bromide. No. 5 Brompenta-ammm-cobaltÜID-bromid. No. 6 Aquopenta-ammin-cobalt (III) -

chlond (- 0.44).
No. 7 bisläthylenediamine-di-ammin-cobalt IIIH) -

perchlorate
No. 8 bis (ethereal diamine) diacetato-cobalt (III) -

chloride
No. 9 triethylenetetramine dichloro-cobalt (III) -

acetate.
No. 10 bis (methylamir) tetra-ammin-eobaltdll) -hexafluorophosphate.

No. 11 AquopentalmethylaminelcobaltdlD-nitrai No. 12 chloropentalethylamine / cobalt dlll-butanoate. No. 13 Trinitrotris-ammin-cobalt / HI-methyl sulfonate.

No. 14 nitrotrislmethylaminelcobaltlllll fluoride, No. 15 aeetatopenta-ammin-cobaltdlll-nitrate

(-0.285).
No. 16 bis (methylenediamine) dichlorocobaltdIII) -tnfluoroacetate.

FiO II. Spectral sensitizers suitable for the production of photographic recording materials according to the invention

To make \ t ™ hluni ^ emnfind! Ieher photcgra Bischer materials according to the invention can be conventionally known spectral sensitizers for use negative working silver halide emulsions provided they have certain properties to have.

First of all, the spectral sensitizers should have an oxidation potential in the ground state, which is unsuitable for the reduction of the CobaltdIIl complex. Because of this property is said to be the spontaneous reduction of the cobalt! III) complex be avoided in the absence of actinic radiation. Advantageously, the "oxidation potential of the spectral sensitizer in the ground state with the reduction potential of the CobaltdIIl complex are related to the fact that in the case of eires electrons from the spectral Sensitizer to the cobalt! III) complex is transmitted, an absolute gain in energy occurs. The reverse energy gradient then protects the Cobalt III (complex in the absence of a external source of energy from reduction.

The spectral sensitizer should also be selected on the basis that it has the energy gradient relationship reversed upon exposure to actinic radiation. This means that the spectral sensitizers used are radiation absorb a wavelength longer than 300 nanometers. The absorbed radiant energy then converts the spectral sensitizer into an excited state that is necessary for reduction of the cobalt (III) complex is favorable. In other words: the energy gradient between the excited spectral sensitizers and the cobalt dlll complex is caused by the action of Radiation reversed, such that. when an electron of the excited spectral sensitizer is transferred to the Cobalt! III! complex absolute energy loss occurs. This creates a favorable energy gradient for reducing the Cobalt! 111! Complex created.

The invention was based on the knowledge that the required energy relationship can be achieved by using a cobalt (III) complex at the same time. which has a reduction potential between the oxidation potential and the reduction potential of the spectral sensitizer is in the ground state, it also applies that in the case of reversibly reducible complexes the reduction potential of the ('obaltllll) complex is more approaches the oxidation potential of the spectral sensitizer in the ground state than that Reduction potential of the spectral sensitizer in the basic state.

The accurate measurement of the oxidation potentials of spectral sensitizers in the excited state is difficult It is known, however, that when excited, the oxidation potential of the spectral Sensitizer approaches the reduction potential in the ground state. This then reverses the energy gradient between the spectral sensitizer and the CobaltIII! complex. Another The advantage of this relationship is that. becomes the potential difference between the reduction potential of the cobalt! IiI! complex and the reduction potential of the spectral sensitizer in the ground state selected large enough in comparison to potential differences? between the Oxidationspeter.tia! of the spectral sensitizer in the ground state and the Redukiiunspoieiiiia! the kaiionic Cobalt! III! Complex, a cheaper one Energy gradient for an electron transition to the CobaltUIl! Complex from the excited spectral Sensitizer is achieved than for retransfer of an electron to the oxidized spectral sensitizer in the ground state. This relationship is particularly important when the cobalt (III) complex reduction reaction is easily reversible is.

Please note. that in the case of a number of cationic Cobalt! Ill! -Complexes a reduction to the Production of cobalt! I'll species under simultaneous Release of ligands leads to a reversal of this reaction is not possible and available standing potential gradient for the regeneration of the cobaltdlD complex is irrelevant

Both the cobalt! 111! Complexes as well as those according to the invention Spectral sensitizers used can contain neutral compounds without be built-in components As it is important.

that the spectral sensitizer and the cobalt (III) complex are in intimate contact with each other are present, cationic cobalt (III) complexes in combination with spectral Sensitizers used with a negative charge. As already explained, it is possible to that negatively charged, spectral sensitizers in the cobalt! I II! Complex as an anionic Rest with the simultaneous use of a cationic

ίο Introduce cobaltlll 1 (complex.

An increased spectral sensitization can be achieved by keeping the negative charge in the Is close to or in close proximity to the chromophore of the spectral sensitizer. the negative charge can be brought into the vicinity of the chromophore either by the fact that it is only a few bond lengths from the chromophore (preferably within 5 bond lengths) or by the fact that the molecule is a has steric configuration. It is known that negative charges can be found in spectral sensitizers introduce by ionizable oxy or sulfur substituents, for example hydroxy, carboxy, Sulfonic acid and mercapto substituents. Any of these charged substituents can can be used to achieve the goal described.

Particularly useful spectral sensitizers for making radiation sensitive photographic ones Materials according to the invention are those with an anodic polarographic half-step potential (also known as the oxidation potential in the ground state), which is below one volt lies. Furthermore, such spectral sensitizers are preferably selected, their Sum of cathodic polarographic half-wave potential (also referred to as the reduction potential in the ground state) and anodic polarographic Half-wave potential is more negative than -0.5OVoIt.

The polarographic measurements are carried out using customary known methods. The cathodic polarographic half-wave potentials can be obtained using an aqueous silver-silver chloride reference electrode for the electrochemical reduction of a test compound using conventional polarographic PntpntialrnpRmethndpn Here, i ■ 10 "" ¹ IHoIaI ciiicihanoiischc solutions of the test compounds. The solvent consists of 100% methanol, provided the compound is soluble in it. In some cases it may be necessary. To use mixtures of methanol and another solvent, for example water. Acetone or dimethylformamide to make a 1 x 10 -4 molar solution of the test compound. Lithium chloride is added to the test solution in a 0.1M concentrator as a supporting electrolyte. Only the most positive (arr least negative! Half-level potentials were

fto determined and here as reduction potentials in the ground state or simply referred to as a reduction potential. The anodic half-wave potentials were by means of an aqueous silver-silver chloride reference electrode for the electrochemical oxidation of the dei

«" I Test connection on a pyrohic graphite electrode determined using solutions that were identical to the solutions used for the determination the cathodic polarographic Huinslufen

Potentials have been used. Only the most negative (least positive) half-height potentials were determined and designated as oxidation potentials in the ground state. In the case of both measurements, the reference electrode, i.e. the aqueous silver-silver chloride electrode at 20 ^c C, was used 1953. More details regarding the measurement of polarographic half-wave potentials, as they were used in the present case, can be found, for example, in the book by Költh off and L i η ga η e "Polarography", 2nd edition, Interscience Publishers, New York (1952). Further details relating to the principles of the electrochemical measuring method using solvents with comparatively low conductivity can also be found, for example, in a work by Kelly, Jones and Fisher. published in »Anal. Chem. «. 31 (1959). S. 1475. Further details of the anodic measuring methods can also be found, for example, in the book by D e 1 ahay "New Instrumental Methods in Electrochemistry". Interscience Publishers. New York (1954). and in the work of Nicholson and Shai η. published in the journal »Annal. Chem ”. 36 (1964). S 706. Further details regarding the graphite electrode used can also be found in a work by Chuang.Fricd and Ii Iv ing. published in »Anal. Chem. «. 36 (1964)

Please note. that for the production of radiation sensitivity photographic recording materials according to the invention also include spectral sensitizers and cobalt (III) complexes can be used which oxidizable ions, e.g. B. Iodide ions. exhibit. For example, the use various compounds, which iodide sal / are. In the presence of oxidizable ions, however, the described polarographic Do not simply take measurements. Consequently such compounds were closed shortly before the polarographic measurements were carried out Compounds with an anion such as a chlorine anion. or a p-toluenesulfonate ion implemented, which do not interfere with the precise polarographic measurements. So this means that the radiation-sensitive photographic materials according to the invention, optionally also compounds with oxidizable ions may contain.

The ones used in the manufacture of radiation-sensitive photographic Materials used in the invention are spectral sensitizers such as already set out, spectral sensitizers of the substance used for sensitizing negative photographic silicon-berhalide emulsions known type. This means that the spectral sensitizers for example customary known, spectral sensitizing dyes, for example acridine, anthrone, Azo, azomethine, cyanine, merocyanine, styryl and styryl base dyes, and also dyes based on polycyclic hydrocarbons, also ketone, nitro and oxonol dyes (also hemioxonol dyes), also sulfur, triphenylmethane dyes, xanthene dyes and corresponding dyes.

Cyanine dyes have proven to be particularly advantageous, spectral sensitizing dyes, with the term cyanine dyes is to be interpreted broadly here d. That is, in an advantageous manner, simple Cyanine dyes, also carbocyanine dyes, dicarbocyanine dyes, Tricarbocyanine dyes, rhodacyanine dyes and the like can be used can.

The cyanine dyes can have customary known basic nuclei, e.g. B. thiazoline, oxazoline, Pyrroline, pyridine, oxazole, thiazole, selenazole and imidazole nuclei. The cores can optionally be substituted in the usual way, for example by alkyl, alkylene, hydroxyalkyl, sulfoalkyl, Carboxyalkyl, aminoalkyl and enamine resles. Furthermore, they can be attached to carbocyclic or heterocyclic ring systems, which in turn can optionally be substituted, z. B. by halogen atoms and or phenyl, alkyl, haloalkyl, cyano and or alkoxy radicals. Both Cyanine dyes can be symmetrical or asymmetrical "dyes with alkyl, phenyl. Enamine or heterocyclic substituents in the methine or polymethine chain. With the cyanine dyes It can also be, for example, complex tri- or tetranuclear cyanines Act.

The merocyanines which can be used according to the invention correspond to the cyanines described or are with comparable to these. This means that the merocyanines have the basic nuclei listed can, as well as acidic nuclei, e.g. B. thiohydantoin, rhodanine, oxazolidendione. Thiazolidenedione, barbituric acid. Thiazolinone and malonitrile cores. The acidic nuclei can also optionally be substituted be, for example by alkyl. Alkylene, phenyl, carboxyalkyl, sulfoalkyl, hydroxyalkyl, Alkoxyalkyl-. Alkylamino and heterocyclic radicals.

As spectral sensitizers, other than sensitizing dyes for negative silver halide emulsions furthermore, for example, conventional optical brighteners are suitable which have the specified Have criteria to spectrally sensitize the cobalt (III) complexes. Examples of suitable categories of known optical brighteners for sensitizing cobalt (III) complexes are stilbenes, triazines, naphthylin or naphthalene sulfonates, oxazoles and coumarins. Particularly advantageous optical brighteners for the production of radiation-sensitive photographic recording materials according to the invention are bistriazinylaminostilbenes, in particular E! is-triazinylaminostilbene disulfonates. Examples of particularly useful sensitizers of this type are des further from US-PS 28 75 058. 30 12 971 and 30 25 242 known.

Furthermore, it has been shown, for example, that an advantageous spectral sensitizer for cobalt (III) complexes which is hematoporphyrin. For example, it has been shown that hexaammine-cobalt (lII) selective spectral to the red part of the visible spectrum when using hematoporphyrin can be sensitized as a spectral sensitizer.

Examples of useful spectral sensitizers for making radiation sensitive photographic ones Recording materials according to the invention are compiled in Table II below.

Table Π

Examples of useful spectral sensitizers 16

Potentials in the ground state (volts)

Oxidation reduction

+ 0.58 -1.11

* = CH - CH = CH

! 1,1 '-Diethyl ^^' - carbocyanin iodide

CH - CH = - ■ CH - CH = CH C ₂ H ₅

!, l'-DiätriyW ^ '- dicarbocyanine iodide

+ 0.27 -0.98

+ 0.40 -1.03

CH

S. /

Br

-ι

l, r, 2,2'-tetrahydro (4H- [1,4] thiazino- [3,4-b] benzothiazolo) cyanine bromide

O ==] - N-CH ₂ -CO ₂ H

Ö ^s \ = CH-CH = I ₅ J = S
--N-QH,
S-carboxymethyl-S-ifS-äthyl ^ -benzothiazolinylidenel-äthylidenjrhodanin

O O ' ¹

H ₅ C ₆ - N ⁷ N == CH - CH = CH - / n - QH ₅

N = L-CH ₃ H ₃ CI = N

Bis [3-methyl-1-phenyl-2-pyrazolin-5-one- (4)] trimethine oxonol

O Ο " ¹

H ₅ C ₆ - N ⁷ N = CH - CH = CH - CH = CH - / n - QH ₅

N = L-CH ₃ H ₁ CJ = N

Bis [3-methyl-1-phenyl-2-pyrazolin-5-one- (4)] pcntamclhinoxonol + 0.5

-1.4

+ 0.37 -1.16

+ 0.27 -1.1

17th

18th

^ Continued

/ \ ⁰ Y- CH = CH - CH == CH - CH = / ° ^N ij N-

CH ₁ -CH ₁ -CO- ¹ CH,

0 CH ₂

CO ₂ H anhydro-S ^ '- diß-carboxyethyO-oxadicarbocyanine hydroxide

CH;

^ = CH - C = f
j

NC ₂ H ₅

N- <T V-SO ₃ H

= N

CH ₃

4 - [(3-Ethyl-2-benzothiazolinylidene) isopropylidene] -3-methyl 1- (p-su] fophenyl) -2-pyrazolin-5-one

--- CH CH = -

N - C ₂ H ₅ H ₃ C -> = N

= CH - CH - = / N-CH ₂ - CO ₂ H

NC ₁ H,

o -> =

3-Carboxymethyl-5 - [(3-ethyl-2-benzoxazolinylidene) ethylidene] -2-thio-2,4-oxazolidendione

Polcnlialc in Grua'izusland (Fully)

Oxidation Rcduktians- + 0.5-1.2

+ 0.6 -1.26

+ 0.48 -1.31

4 - [(1-Ethyl-2-naphtho [1,2-d] thiazolinylidene) isopropylidene] -3-methyll- (p-sulfopheny]) - 2-pyrazolin-5-one

/ \ ⁰ V = CH - CH = / ^N N-CH ₂ - CO ₂ H ^ iNC ₂ H ₅ SJ = S

3-carboxymethyl-5 - [(3-ethyl-2-benzoxazolinylidene) ethylidene] rhodanine

O +0.63

+ 0.56 -1.16

= CH-C = / N-CH ₂ -CO ₂ H

-N-CH ₃ S-1 == S 3-carboxymethyl-5 - [(3-methyl-2-thiazolidinylidene) isopropylidene] rhodanine

-1.48

+ 0.33 -1.47

19th

20th

continuation

NX.

13th

14th

O = CH - CH

^ JUn-C ₂ H ₅ I. _h

N-CH ₂ -CO ₂ H S

1-Carboxymethyl-KB-ethyl-1-benzoxazolinylidene-ethylidene-S-phenyl-2-thiohydantoin

- O ₃ S-CH ₂ -CH ₂ -CH ₂ -CH ₂ -

NC ₂ H ₅

s-l = s

Well " ¹

3-Ethyl-5- [1- (4-sulfobutyl) -4 (1H) -pyridylidene] -rhodanine, sodium salt

N-CH ₂ -CO ₂ H

N-CH, S -> = S

3-carboxymethyl-5- (3-methyl-2-benzoxazolinylidene) rhodanine

Potentials in the Grundy-usiand (Fully)

Oxidation reduction

+ 0.28 -1.50

+ 0.42 -1.70

+ 0.89 -1.76

16

H ₅ Q-NW NC ₂ H ₅

S-L = s 3-ethyl-5- (1-ethyl-4 (1H) -pyridylidene-rhodanine + 0.56-1.68

17th

C ₂ H ₅

hydroxide, sodium salt + 0.60 -1.3

21

continuation

22nd

CH-CH = [N- _{C 2} H _{5 -NC 2} H ₅ SJ = S

3-Ethyl-5- [3-ethyl-2-benzoxazolinylidene) ethylidene] rhodanine

Potentials in the basic / usliind (Volt)

Oxidation Reduction + 0.60-1.37

'Y = CH-CH = / NC ₂ H ₅

¹ X ^ ZNC ₂ H ₅ S.

3-Ethyl-5 - [(3-ethyl-2-benzothiazolinylidene) ethylidene] rhodanine

+ 0.57 -1.27

C ₂ H ₅ C1- / V ^Ν V- CH = CH - CH

C ₂ H ₅

Cl

1 + 1 C ₂ H ₅

H ₅ C ₂ -N

Cl

σ er ¹

5,5 \ 6,6'-tetrachloro-1,1 \ 3,3'-tetraethylbenzimidazolocarbocyanine chloride

CH ₃

I = CH-C = CH

NC ₇ H

₂ n ₅

N-

I- H ₂ CH ₂ C ίτί b O

ί Ι ^!

CH ₃ O anhydro-3-ethyl-9-methyl-3 '- (3-sulfobutyl) thiacarbocyanine hydroxide

+ 0.58 -1.50

+ 0.73 -1.28

CH ₃

CH-C = CH

+

CH ₂ - CH, - CH - S - O '

CH ₂

I CH ₂

i: I '

H, (CHS O, H CH,

Anhydro ^ -methyl ^^ '- difS-sulfobutylHhiacarboxyaninhydroxid

+ 0.72 -1.28

Continued 24

l'oleiituile in the Cirund- / ustarni (VoIiI

Oxidation reduction

23 O = | -NC ₂ H ₅

/ VOn = CH-ChJv _n JS -NC ₂ H ₅ I.

^ G "5 + 0.49 -1.47

3-Ethyl-5 - [(3-ethyl-2-benzoxazolinylidene) ethylidene] -l-phenyl-2-thiohydantoin

° N = CH - CH = CH -ff ^S

I II

-NC ₂ H ₅ H ₅ C ₂ -N-

t-1 Br "

3,3'-Diethyl-4'-methyloxathiazolocarbocyanine bromide

+ 0.63 -1.14

- = CH

C ₂ H ₅ NC ₂ H ₅

+ 0.64 -1.54

2-p-diethylaminostyrylbenzothiazo]

CH ₅

Cl

NpCH-C = CH-j NC ₂ H ₅ H ₅ C ₂ -N

Cl

Br '

SJ'-Dichloro-S.S '^ - tnäthyithiacarbocyaninbromiu

C ₂ H ₅

^S γ = CH - C = CH-T, ^S '

χ ^L- NC ₂ H ₅ ν-i;

^v - 'ι +;

CH, -CH, - CH - S

I ii

C ^- H, + 0.87 -1.06

+ 0.86 -l, running

Anhydro-5.5'-d »chloro-3.9-diethyl-3 '- (3-sulfobutyl) -thiacarbocyanine hydroxide

25th

continuation

26th

—Ν

= CH - CH - ^J - _Q ;> - N - C ₆

J i

NC ₃ H

2 ' ' 5

QH ₅

I'oU'iiliiilt. ' im (irunü- / usliiiul iVolu

(KuUiium- reduction

+ 0.51-1.48

2-Diphenylamino-5 - [(3-ethyl-2-benzoxazoIiny! Idene) ethylidene] -2-thiazolin-4-one

-j-N

- CH

OjN - CH = 4, "JNC ₆ H,

C ₆ H ₅

2-Diphenylamino-5 - [(3-ethyl-2-benzothiazolinylidene) ethylidene] -2-thiazolin-4-one

+ 0.46

0-TNC ₆ H ₅ = CH - CH -NC ₂ H ₅

CO ₂ H

1-p-C \ rboxyphenyl-5 - [(3-ethyl-2-benzoxazolinylidene) ethylidene] -3-phenyl-2-thiohydantoin

NO,

O ₂ Nr ^ -CH = <N -CH ₂ -CH ₂ -CH ₂ -CH ₂ -SO ₃ "Na

4- (2.4-Dinitrobenzylidene) -1, 4-dihydro-1- (4-sulfobutyl) -quinoline, sodium salt

I Λ

Ο =; - N-CH ₂ - CH ₂ - CH ₂ - butyl

^v 'y °> = CH-CH L-.Ji NQ ₈ H ₅

C ₆ H ₅

5 - [(3-Ethylnaphth [2, l-d] oxazolin-2-ylidene) -ethyIidene] -3-heptyl-1-pheriyl-2-thiohydantoin

27

28

continuation

Potentials in the ground state (full)

Oxidation reduction

A / S

- CH - CH = CH - CH

-NC ₃ H ₅

N-CH ₂ -CH ₂ -CH ₂ -BiHyI + 0.21

L c

5- [4- (3-Ethyl-2-benzothiazolinylidene) -2-butenylidene] -3-heplyl-1-phenyl-2-thiohydantoin

QH ₅

^S V = CH - CH = CH - / ^S -N-CH ₃ H ₃ CN

3,3'-dimethyl-9-phenyl-4,5-4 ', 5'-dibenzothiacarbocyanine bromide

NH- ^ ¹ V-NH NN

γ SO ₃ - ¹

HO-CH ₂ -CH ₂ -N-CH ₂ -CH ₂ -Oh

4Na ⁺¹

N, N'-di [2-p-natriumsulfoanilino-4-diethanolamino-1,3,5-triazyinyl (6)] - diaminostilbene-2,2'-disulfonic acid, Sodium salt

SO ₃ "

N N

SO ₃ "

SO ₃ '

H ₅ C ₂ -NC ₂ H ₅

6Na ⁴

N, N'-di [4-diethylamino-6- (2,5-disulfonanilinone-2-s-triazinylamino-2,2'-stilbene disulfonic acid, Hexasodium salt

V-CH-OH

H ₃ C

HO ₂ C-CH ₂ -CH ₂ hematoporphyrin

CH,

CH ₂ -CH ₂ -CO ₂ H

+ 0.8

+ 0.83

-1.22

+ 0.63 -1.29

more negative

as

-1.90

negative

as

-1.90

29 ^! 30th

To produce radiation-sensitive layers tends to selectively use most of the available

all that is required is to absorb sensitizers and standing radiation. Preferably

To combine cobalt (III) complex with one another. That'll be the sensitizers in concentration

Mixture of sensitizer and cobalt! III) - used, which has an absolute optical density of

complex can then deliver 0.5 to 2.0 on a 5 using conventional methods.

Layer support are applied. Advantageously, the binder can contain up to 99% by weight of the

Way, the two reaction components will make up before radiation-sensitive layer. Preferential

However, when applied to a substrate in a solution, the binder is in a concentration

medium or solvent system solved. tration of about 50 to 90 wt .-% of the radiation

The io sensitive layer can be used to prepare such solutions. However, the binding

Usually solvents or combinations of agents from the radiation-sensitive layer too

Miscible solvents used can be omitted entirely. The radiation-sensitive

will. Typical, particularly advantageous solution layer can have a very different thickness, depending on

agents, which alone or in combination with one another according to the desired characteristics of the radiation

can be used are short-chain alkanols, 15 sensitive layer, for example the one to be produced

z. B. methanol, ethanol, isopropanol, t-butanol and low image density, the flexibility of the material and

the like, also ketones, e.g. methyl ethyl ketone, the like. For most photographic applications

Acetone and the like, as well as water, finally for purposes of application, layer thicknesses of 2 to

liquid hydrocarbons, chlorinated hydrocarbons - 20 microns proven to be beneficial,

substances, e.g. B. chloroform. Ethylene chloride. Tetrachloro 20 For the production of the radiation-sensitive material

carbon and the like, as well as ether. 7. B. Materials according to the invention can be conventionally known

ethyl ether. Tetrahydrofuran and the like, closing layer supports are used, for example trans-

Lich acetonitrile. Dimethylsulfoxiü and Dimethylform- parente support, z. B. conventional film base

amide. and glass substrates as well as opaque substrates.

To facilitate the coating and around 25 z. B. made of metals or photographic paper. Reaction components in intimate contact with one another. The support can be rigid or flexible. In order to advance one another, it has generally proven to be advantageous if the layer supports consist of paper or adhesive, and the radiation-sensitive layers are photographic film supports. If necessary, using a photographic material, the support can have one or more photographic materials customary for the production of adhesive layers, in order to produce its surface properties as a binder. As a binder can improve. Typically, those customary known hydrophilic colloids, adhesive layers are used, which are used to adhere the latices and resinous binders to the radiation-sensitive layers. The substrate has been found to be particularly advantageous. Typical suitable layer use of such binders has been shown, 35 carriers are described in more detail, for example, in the magazine "Product Licensing Index" for the production of photographic materials. Vol. 92 of the diazo type. Typical ge December 1971, publication 9232 on p. 108.
Suitable binders which can be used on a layer support for the production of the radiation-sensitive layer can be produced, for example, according to known methods conventionally known according to the invention. Described in a typically advantageous manner in more detail in the journal "Product Licensing, where appropriate, geIndex", Vol. 92 December 1971. Publication 9232 together with the binder in a solution on p. 108. As a particularly advantageous binder medium or solvent system, whereupon the has usually been found to be gelatin. obtained solution in a conventional manner

The concentration of Cobalt Fll! Complex and 45 the layer support is applied, for example spectral sensitizer to each other in the by spin coating, coating with a Radiation-sensitive layer can be very pre-coating knife. by brushing or coating be. Molar ratios of one or about stratification with a coating funnel and the one Match the mole of CobaltUII (complex to one mole. The solvent is then evaporated, Tral sensitizers provide excellent results. Particularly advantageous results can be applied, for example, are known but generally obtained when per mole from the journal "Product Licensing Index", Vol. 92, Sensitizers 0.1 to 10 moles cobalt (IH) - p. 109. Optionally, the coating complex be used. Advantageous results are generally given to conventional, known coating auxiliaries but also obtained if 55 are set per mole, as for example on p. 108 of the Sensitizers 0.01 to 100 moles of cobalt (III) - the references already cited are listed, complex. The concentration of also it is possible to use the photographic materials Sensitizer is a function of that of the invention using anti-density at the maximum absorption wavelength statically effective layers and / or under Verdes Sensitizers above 300 nanofio turn of matting agents to manufacture such as meters. There is also said to be so much sensitizing agent in the literature cited above be applied that an abso- are listed in an advantageous manner.

lute density of 0.1 to 3.0 is obtained. As can be seen from FIG. 1, a lower rating can be used Densification becomes a very high proportion of appropriate photographic material in its disposition standing radiation of the most basic form of a layer carrier 2 and a sensitive layer is not absorbed, whereas radiation-sensitive layer applied to it at higher densities the sensitizer exist on layer 3. In this configuration one the surface of the radiation-sensitive layer of radiation-sensitive material according to the invention

The radiation-sensitive material needs dung! have no ability to record images. Rather, the radiation-sensitive material mainly has only a selective sensitivity to actinic radiation. This selective response can be used in an advantageous manner for recording an image in a special photographic Matena! or exploit element. According to an advantageous embodiment of a radiation-sensitive material of this type, the cobalt (III) complex has one or more ligands which volatilize when the complex is reduced. For example, the cobalt (III!) Complex can have one or more amine ligands which are released in the form of ammonia upon image-wise reduction of the cobalt (III) complex. In such a case, it has been found to be particularly advantageous to use a cobalt (III) -complex to select, which has a comparatively large number of amine or NH _? ligands such complexes are, for example, cobalt-hexamine complexes and cobalt-pentamine complexes.

If the radiation-sensitive layers themselves do not have the ability to record images, they are shared with a special imaging layer used. In its simplest form it can be combined with a radiation-sensitive Material 1 according to FIG. 1 is a special one Use imaging material. In this case are the reaction products involved in imagewise exposure of the radiation-sensitive material are released, transferred imagewise to the image recording layer to produce a copy-out encoder Fading image.

(according to an advantageous embodiment of the invention Ammonia image wise from a radiation-sensitive layer onto a special image recording material transfer. In such a case, the image recording material may be any of usual known material with a layer exist that as a result of the action of ammonia or quite generally capable of generating an image on contact with a base.

In its simplest form, the image recording material can consist of a layer support and a layer thereon applied layer consist of a compound is built up or contains a compound that copies out on contact with ammonia or a base or fades. For example, connections are suitable. such as phthalaldehyde and ninhydrin for manufacture negative images, because of such connections copy out in contact with ammonia. Furthermore, such image recording materials can be used for the production of such a wide variety of dyes are used. z. B. certain types of (vanine dyes, Styryl dye open. Rhodamine dyes, azo dyes and the like, which are changed upon contact with a base. To generate positive In particular, dyes have proven to be advantageous in images which, upon contact with a base, for example ammonia, bleach into a practically transparent form. For this purpose Pyrylium dyes have proven particularly advantageous. Although the image recording layer wholly or practically wholly from a pH-dependent or ammonia-responsive compound can exist, in most cases it has proven to be advantageous to

to produce a bonding agent. Such image recording materials can be based on the described supports and binders described are produced.

When recording an image using separate radiation sensitive and image recording devices Materials will first be the radiation-sensitive layer of the radiation-sensitive Material image-wise with radiation of a wave

\ Srze of preferably 300 to about 900 nanometers, in particular 300 to 700 nm, exposed. This can be done using conventional mercury arc lamps, carbon arc lamps, nitrophot lamps, laser beams and the like. When exposed to

actinic radiation, the sensitizers present in the radiation-sensitive layer become activated by the energy absorption and stimulate the reduction of the cobalt (III) complex. It has proven advantageous to use the recording layer of the image recording material in close contact with the radiation-sensitive layer to hold at the time of exposure. In those cases where it is appropriate. released ammonia ligands expelled by the action of heat, the image recording material can with the radiation-sensitive material before or after exposure. That's the way it is For example, it is possible to first expose the radiation-insensitive material and then to use it to bring the image recording material into contact, for example by the fact that the two materials in contact with each other through the gap formed by two heated rollers. After the radiation sensitive material has been used in the image recording material To generate an image, it can be discarded. To facilitate the transfer of the released ligands on the image recording material it has proven to be advantageous to use the radiation-sensitive Heat layer to a temperature of 80 to 150 C. The heating can optionally be carried out simultaneously take place with the exposure.

If a cobalt (III) complex is used, the amine ligand contains, the ammonia released during the reduction of the complex can with a suitable Choice of reaction components further stimulate the imagewise release of amine ligands. For example μ-Superoxodecammindicobaltd 11! -compounds by contact with free Decompose ammonia. If a radiation-sensitive layer is made using such a cobalt (l! I) complex type is used, it initiates exposure of the spectral sensitizer and of the cobalt (III) complex with amine ligands, the reduction of the complex, with the released ammonia furthermore the μ-superoxadecamminedicobalt (III) compound can further reduce in the irradiated areas.

The use of separate radiation sensors

high sensitive and image recording material is in the fig. 2 to 4 of the drawing are shown in more detail.

In the embodiment shown in FIG

the radiation-sensitive material I consists of the layer substrate 2, which in the present case is a

('5 is a practically transparent substrate, and the radiation-sensitive layer 3. The radiation-sensitive layer is in contact with an image recording material 4. consisting of

609 584/413

a support 5 and an image recording layer 6th

In the case of the illustrated embodiment is the imaging layer initially colored, d. H. ■ has a uniform, visible, optical density but can be bleached. On the other hand, however, an initially colorless image recording layer can be used use that can be colored.

While the recording materials 1 and 4 are in contact with each other, i.e., the image recording layer and the radiation-sensitive layer touch each other and are not through separated from one another by a substrate, the radiation-sensitive material is exposed imagewise with actinic radiation, which is indicated schematically by the arrows 7. The exposure takes place through the layer support 2. Practically all radiation hits the radiation-sensitive Layer 3 on. The radiation activates the spectral sensitizer in layer 3. thereby reducing the cationic cobalt (III) complex promotes. This is shown by the hatched areas 8 and 8. From Ligands released from the cationic cobalt (III) complex migrate into the imaging layer. The ligand transfer can be accelerated by uniform exposure to heat, such as it is shown schematically by the arrows 9 in Fi g.3 is. The released and transferred ligands cause the imaging layer in the Districts 10 and 10 'is bleached. Consequently an image recording material remains when the radiation sensitive material is stripped off. as in Fig. 4 is shown. back which a positive Image of the original artwork.

In contrast, emc initially becomes a colorless image recording layer used by the action of reaction products from the radiation-sensitive Layer can be colored, a negative image of the original is accordingly obtained.

Instead of using separate ones, more sensitive to radiation and image recording materials, a radiation sensitive layer and a Image recording layer can be combined into one material. Line such embodiment of the invention is in F 1 g. 5 shown in more detail.

The material shown in F 1 g .5 consists of the layer support 2, a radiation-sensitive layer 3. those with the substrate 2 and the radiation-sensitive Layer 3 of the material shown in Fig. 1 may be identical, over which there is a radiation-sensitive layer Release layer 4 and an image recording layer thereon 5 '. which may be identical to the image recording layer of a particular one already discussed Image recording files. Possibly can be the order of arrangement of image recording layer and the radiation-sensitive layer are reversed.

The separating layer 4 'does not need to be present to f> o be as in most cases image recording layer and radiation-sensitive layer during longer storage times are chemically compatible with one another. However, to any dismantling or any reduction in properties of the layers due to chemical migration To prevent components from one layer in the other layer, which may be the case with longer storage of the material can happen, a separating layer is preferably arranged.

The separating layer is advantageously equipped in such a way that it is suitable for the reaction product or products which are released from the radiation-sensitive layer upon exposure, are easily permeable. while it is an undesirable migration of initially present components of the two Layers connect. For example, the separating layer can be designed in such a way that the ammonia is easily permeable, but is comparatively impermeable to liquid components. It has It has been shown that the most varied of polymeric layers cause a diffusion of gaseous ammonia from the radiation-sensitive layer into the image recording layer allow, while at the same time the migration of other constituents of the layers inhibit.

Hydrophobic polymers are preferably used to produce the separating layers if the radiation sensitive layer and the image recording layer Contains polar reaction components whose migration is to be prevented. For the production such layers are particularly suitable linear hydrocarbon polymers, e.g. B. polyethylene. Polypropylene and polystyrene. The separating layer preferably has a thickness. those under about 200 microns to ensure that the beneficial Image resolution of the image recording layer is not lost. For most purposes layers 20 microns thick or less have been found to be particularly beneficial.

Although the separate imaging layers, which have been described so far, themselves not sensitive to radiation or need to respond to radiation, image recording layers can also can be used, which are based on the reaction product: that are released from a radiation-sensitive layer, as well on actinic radiation. For example, conventional diazotype materials can be used as image recording materials. hereinafter mostly referred to as diazo recording materials, use.

Typically, I will use such Diazo recording materials do this initially image-wise the influence; exposed to ultraviolet light, to inactivate the areas hit by the radiation, whereupon they are copied out of a positive image can be brought into contact uniformly with ammonia. Diazo recording materials can from the beginning both a diazonium salt, as well as one that can be activated by ammonia Couplers contain, in which case one usually has a 2-component diazo system speaks. However, the diazo recording materials can also initially only contain the diazonium salt and later brought into contact with an appropriate coupler during development in which case one speaks of a one-component diazo system. Both one-component as well as two-component diazo systems can be used in the context of the invention.

The following statements refer primarily to the more common two-component diazo system therefore apply mutatis mutandis to the one-component diazo system.

The photo-responsive image-recording

Layers can be used in special imaging materials be accommodated or also directly in a radiation-sensitive materia ', be accommodated according to the invention, as shown, for example, in FIG. 5 is shown. In this Trap, the separating layer 4 'is preferably designed in such a way that it is impermeable to ultraviolet light is. If an opaque layer support is used, the separating layer is designed in such a way that it is transparent to light of such a wavelength that is sufficient to make it sensitive to radiation Activate layer without activating the imaging layer.

The use of a radiation-sensitive layer and a special photo-responsive one Image recording layer in combination with one another enables a variety of image forming methods for creating both positive and negative images.

The production of a positive image with such a combination results from, for example Fig. 6.

In the case of FIG. 6 became a radiation sensitive Layer 11 and a photo-responsive imaging layer such as a commercially available one Diazo recording layer, brought into contact with each other. The layers can be with a Layer support and optionally a separating layer form a material, for example a material of the in Fig. 5 or on the other hand separate layers are present, in which case a conventional diazo recording material and a radiation sensitive material, for example of the type shown in Figure 1, in contact with one another to be brought.

To create a positive image, the photosensitive image recording layer 12 initially exposed imagewise to ultraviolet light, as shown schematically is indicated by the slide 13 with the image 14. This is done photolytically destroys the diazonium salt in the exposed areas of the imaging layer. The radiation-sensitive Layer 11 is preferably fully exposed to actinic radiation before moving on to the layer 12 is brought together when separate imaging and radiation sensitive materials be used. On the other hand, if a material with layers 11 and 12 is used, the radiation-sensitive layer fully exposed to radiation in the visible range of the spectrum, so as not to destroy the diazonium salt of the picture areas. Exposures through both surfaces can be advantageous if the layers 11 and 12 form one material. It can be transparent or opaque supports having either a single or a plurality of element arrangements are used will.

Heating layers 11 and 12 in contact with one another results in the release of ammonia from the radiation-sensitive layer, which migrates into the diazo layer and there the coupler the diazo layer is activated to produce a colored image 15 which is positive Image of the template 14 is. In contrast, a material with a negative image instead of the slide 13 is used, a negative image is generated in the layer 12.

i iV layer combination of photosensitive

tive image recording layer and separate radiation sensitive Layer as used in FIG. 6 to produce a positive image can also be used to produce a negative

tive image can be used, as shown in FIG. 7 is shown schematically. To create a negative image, the radiation-sensitive layer is first exposed imagewise, which is indicated by the Slide 13 'is illustrated with the image 14'.

ίο Are layers 11 'and 12' in different layers Materials before, so the radiation-sensitive material is preferably before being brought together exposed to the imaging material. If the layers are in one material, the radiation-sensitive layer preferably exposed to visible radiation in order to deactivate the Avoid diazo layer. The assembled layers are heated uniformly. Here is Image-wise ammonia is released from the radiation-sensitive layer, which migrates into the diazo layer and then leads to image-by-image copying. The districts of the diazo layer that have the negative image 16 can then be deactivated by exposure to ultraviolet light, if so

as this is desired, but not required is. The image 16 represents a negative image of the image 14 '. Becomes a material with a negative image used instead of the slide 13 ', the image in the layer 12' is reversed.

Although the above advantageous uses of radiation-sensitive according to the invention Materials being described, it is to be understood that the invention can be modified in a variety of ways enables. For example, the sensitizer can be in the radiation-sensitive layer and the pnoio-responsive image-recording layer are coordinated so that they are opposite sensitive or responsive to different areas of the spectrum. Instead of the sensitizer is responsive to visible light and the diazo layer to ultraviolet A diazonium salt, which is selectively sensitive to light, as described, can also be used Visible light and is a sensitizer that is selectively sensitive to ultraviolet Light with a wavelength longer than 300 nm. Furthermore, it is possible, for example, in the cases in which there is a uniform release of ammonia for the development of the diazo image, a complementary one or to carry out subsequent base treatment in order to further the diazo image produced, if desired improve or strengthen.

In those cases where a radiation-sensitive layer also functions as an image recording layer should exercise, for example, radiation-sensitive materials of the in F ι g. 1 shown Type are used, d. H. Materials with a radiation-sensitive layer that act as active components only a cobalt (lII) complex and a Contains spectral sensitizer. When recording images with radiation-sensitive Materials of this type can be used cobalt (III) complexes, for example oxidizing agents represent leuco dyes which are converted into a colored form by oxidation permit. On the other hand, common fiber-forming components (e.g. oxidizable organic color developing agents and color couplers) are used

which will turn into a colored dye upon oxidation of the organic color developing agent and clutch can be transferred.

In such a case the radiation sensitive Layer initially exposed imagewise, with the cobalt (III) complex in the areas struck by the radiation Districts is reduced imagewise to a cobalt (II) compound. You can do this at the same time be heated or a heating can follow, if this is desired. to ensure that a maximum reduction occurs. Thereupon the radiation-sensitive layer can be brought into contact with a leuco dye or the dye-forming components are within the radiation-sensitive layer brought into contact The cobalt (III) complex. the one in the not irradiated districts still exist. then oxidizes the leuco dye or the organic color developer binding with the generation of a colored image in the unirradiated or unexposed Areas of the radiation-sensitive layer. The organic color developing agent and the color coupler can consequently be introduced jointly or separately into the radiation-sensitive layer will. It is known that both color couplers such as Oxidizable organic developer genes can also be present in a common solution, and at the same time in a radiation-sensitive layer can be introduced. According to an advantageous embodiment of the invention, a coupler is with at least one ballast group is used, which is in the radiation-sensitive layer from the start \ orlianden is. while the organic color developer \ connection will be added later. For the introduction of the image-forming components in the radiation-sensitive layer can be the usual known ones Methods used including bathing di> radiation sensitive material after exposure and heating to form the dyes Components containing solutions for releasing the dye-forming components by the action of pressure-splittable containers, ζ B so-called »pods» or layers with so-called Microcapsules, which can be present in the radiation-sensitive element or in one separate element assigned to this element

A wide variety of Component combinations that form oxidizable leukolars and oxidizable dyes of the prior art can be used. Examples of suitable leuco dyes are amino nars ! methane. Ammoxanthenes. Ammothioxanthenes. Amino- ^ 10-dihydroacndme. Aminophenothiazme. Aminodihydrophenazines. Aminodiphenylmethanes. Ammohydrocinnamic acids (cyanoethanes). Leucol digoid dyes, 1,4-diamino-2,3-dihydroanthraquinones and the like besides these general categories Suitable leuco dyes are, for example, numerous other types of wet nurses, which are to Let colored compounds oxidize, for example wet nurse, as they are for example from the US-PS 3042 515 and 3042 517 are known. ζ. Β 4.4'-eth> lendianilm. Diphenyl lamb. N.N-Dimethv! Aniline. 4,4-methylenedianiline. Triphenylamine and N-vinylcarhalol

For example, hydrazones and Acv Idem ate \ on such Hvdrazonen to diazonium compounds oxidize which with a lot

of couplers capable of coupling to produce aazo dyes. Examples of conn fertilize this type are from US-PS 30 76 72: known. Examples of couplers dealing with such i Hydrazones and acrylic derivatives are Ν, Ν-diethylaninlin, N, N-dimethyl-m-toluidir and N- (2-cyanoethyl) -N-methyl-2-naphthylamine.

The use of primary aromatic amines in combination with couplers can be used

ίο by oxidation azomethine, indoaniline and indo produce phenol dyes.

Examples of usable in an advantageous manner « N.N-dialkylphenylenediamine and p-aminophenok are the N.N - dimethyl - ρ - phenylenediamine. there* N.N - dimethyltoluene-2,5-diamine. 2,6-dibromo-4-aminophenol and the 2-chloro-4-aminophenol. These amines, for example, are suitable for simultaneous Use with conventional couplers, for example open-chain ketomethylene couplers, couplers from Phenol and naphthol types, also 5-pyrazolones and inda ^ olones. More examples of oxidizable Leuco dyes and dye-forming component combinations, which are within the scope of the invention; can be used, for example, from the US-PS 33 83 212 known.

Instead of the after exposure and acquisition / unt To use the remaining cobalt (II I! complex for a colored image reaction, the reaction product, that is generated during image generation and / or during heating, can also be used to around a picture in the radiation-sensitive Schichl if so desired. Such a procedure has the advantage that no additional development stages are required. Any connection can thereby be used, which roughly corresponds to the other connections of the radiation sensitivity Layer is compatible and which can either be bleached or on contact or by further reaction with one or more of the reaction products.

generated in image formation and / or heating darkens. Such a compound or component can, for example, be identical to one of the components which can also be incorporated into separate image recording layers and have been described in this context. For example, ninhydric or o-phthalaldehyde can be used as suitable compounds or components, which lead to color formation on contact with ammonia which is released as a reaction product during image formation and / or heating of the radiation-sensitive layer. On the other hand, for example, bleachable dyes. For example, pyryllium, steel, cyanine, rhodammal and other customary known I dyes can be used, of which is known. that they lead to color changes on contact with a base. Such compounds can be incorporated into the radiation-sensitive layer without difficulty.

If necessary, a cobalt can also be used! Il i connection. those in the reduction of a cationic cobalt (III) complex was generated in the radiation-sensitive layer for recording images can be used so that an image is recorded in

f> 5 of the radiation-sensitive layer can take place, it is only necessary that the cobalt! 11! compound, which has been produced in the exposed areas. is recognizably distinguishable from that

originally existing cobalt (III) complex in the unexposed areas. Typical cobalt (11) compounds which can be generated as reaction products are normally colorless to yellow, so that they are ideally suited for the formation of image background areas. By selecting an optically dense cobalt (III) complex which can be reduced to a colorless to yellow cobalt (III) compound, advantageous positive images can be generated within the radiation-sensitive layer. In a particularly advantageous manner, both the cobalt (111 Y complex and the spectral sensitizer are selected so that they are of lower optical density or have a color which is different from that of the cobalt) 11 (compounds which are generated imagewise .

According to an advantageous embodiment of the invention, For example, a compound can be added to the radiation-sensitive layer which promotes the formation of optically dense cobalt sulfide images upon exposure to actinic radiation and heating.

For this purpose, the radiation-sensitive layer is preferably in intimate contact with added to the cobalt (III) complex and the spectral sensitizer compounds which have a functional thioamide grouping

C N

have or a corresponding tautomeric grouping. Such compounds are selected so that they can be combined with the other components the radiation-sensitive layer are compatible before exposure and heating. Particularly advantageous Thioamide compounds of this type are thiourea and thioacetamide and their substituted ones and or cyclized derivatives. For example, by alkyl. Aryl. Alkaryl and aralkyl and aralkyl radicals substituted thioureas and thioacetamides can be used. The aryl residues and radicals containing aryl groups are preferably phenyl-. Naphthyl and anthryl residues on. The alkyl substituents can be selected from straight-chain or branched chain acyclic and cyclic Acrylic residues with preferably 1 to 20, in particular 1 to 6 carbon atoms. To increase the image densities in the case of using Thioamide compounds are achievable, it has to be proved advantageous, the maximum solubilities of the compounds within the radiation-sensitive Increase layer. This can be done, for example, by using combinations of thioamides or thioamides with other solubilizing compounds. For example Thioacetamide and sulfamide suitable compounds for improving the solubility of thiourea in gelatin. It has been shown that the use a transparent cover layer with one or more thioamide compounds the optical density of the images obtained is increased. The use of such a top layer or coating layer offers the Advantage of using higher concentrations of thioamides. It has also been shown that especially beneficial results in use; of "thioamides can then be obtained if the radiation-sensitive layer is heated simultaneously with the exposure.

It should be noted that the use of a cobalt (III) complex and a spectral sensitizer sizing agent can be used in combination with one another to reduce the sensitivity to radiation and to increase the spectral response of radiation-sensitive systems like them for example from US-PS 18 97 843, 19 62 307

ίο and 20 84 420 are known.

Examples of advantageous thioamides for the production of radiation-sensitive photographic Materials which can be used in accordance with the invention are summarized in Table III below.

Table III

Examples of thioamides for the production of
Cobalt sulfide images

No.
No.
No.
No.
No.
No.
No.
No.
No.

1 N.N-dimethylthioformamide,

2 thioacetamide,

3 thiobutanamide.

4 thiohexanamide.

5 2-phenylthioacetamide.

6 N.N-dimethylthioacetamide,

N.N-Dihexylthioacetamide,

8 4-ethyl-3-thiosemicarbazide.

9 thiourea.

Nr 10 N-methylthiourea.

No. 11 N.N-Diphenylthiourea.

No. 12 ethane dithioamide,

No. 13 propylene thiourea.

No. 14 l-phenyl-2-thiourea,

No. 15 diallylthiourea.

No. 16 3-allyl-1.l-diethyl-2-thiourea,

No. 17 thiobenzamide.

No. 18 thiobenzanilide.

No. 19 thiocarbanilide.

No. 20 thioacetanilide.

No. 21 Dithiobiurea.

According to a further advantageous embodiment of the invention, optically dense cobalt (II) images can be achieved generate by adding a compound to the radiation-sensitive layer which is able to form a visible, colored cbulti! IJ-kornplexes as Li ° and

ίςΐ

possible, optically dense CoGaIt (II! connections to

so generate which are suitable for generating negative images are by incorporating a compound into the radiation-sensitive layer, which is responsible for chelating with the cobalt (II) atom is suitable, which is at Reduction of the cobalt (III) complex is generated.

5 «; The chelating agent is particularly advantageous present from the start and with the CobaltUIIi complex and the spectral sensitizer of the radiation-sensitive layer compatible.

A wide variety of compounds are known.

<Ό the chelates which are optically dense with CobalKIi! Atoms are able to form and can therefore be used in the context of the invention. Particularly advantageous Chelating agents are formazan dyes. Diihiooxamide. Nitrosarole. Azo compounds. Hydra / one

(^ and Schiff's bases formazan dyes are known to form bidenal chelates and can thus be used in the context of the process of the invention for er / cujiuni

advantageous formazan dyes are those with ring-bonded aromatic substituents in the I- and 5 positions. In the case of Fonmazan dyes it is not necessary that one of these be aromatic

Substituents a ligand-forming suitability, so that the dye is suitable for Bidentatelatbildung is, however, can form chelium ligands aromatic substituents can be used to create additional chelating ligands.

A particularly advantageous chelating agent is also the dithiooxamide together with its derivatives in which one or both nitrogen atoms are substituted, for example by alkyl, alkali, aryl or aralkyl resles. Particularly advantageous nitrosarols are those in which the nitroso and hydroxy substituents are adjacent ring substituents. d. H. for example 2-nitrosophenols, i-nitroso-2-naphthols and 2-nitroso-1-naphthols.

Particularly advantageous azo compounds which contribute to the formation of at least Bidcntalchelaten with Cobalt (II) are suitable are those of the following formula:

No. ¹

N = - N -

Particularly beneficial hydrazones, those with cobalt! J11 are at least suitable for the formation of batch chelates are those of the following formula:

Z ³ - C ^- H N - NH Z ⁴

Particularly advantageous Schiff bases that are used for formation of at least batch batch chelates with cobalt (II) are suitable are those of the following formula:

Z * - CH = N - T

where in the given formulas the Z-substituents are ring-bound aromatic substituents and at least Z \ Z \ Z ⁴ . Z ⁵ and Z "are selected such that they are able to form a chelating ligand.

The aromatic substituents forming the ligands Compounds can be either homocyclic or heterocyclic, of one or more Rings existing substituents, for example phenyl. Naphthyl-. Anthryl. Pyridyl. Quinolinyl <~> the A.'oiyhiibsii ücnicii in a hall can do the aromatic substituentsi the ability to form ligands as a result of substitution in the ring position adjacent to the attachment position with a substituent. which door one Ligand formation is suitable. for example a hydroxy. Carboxy or amino radical. In a further case, the aromatic substituent can be selected in this way become that it is an N-heterocyclic aromatic substituent. which is a ring nitrogen atom adjacent to the azo binding position, d. h, for example, a 2-pyridyl, 2-quinoline or 2-azoic substituent. z. B. a 2-thiazoly! -. 2-benzothiazole \ l-. 2-oxazolyl or 2-benzoxazolyl substituent The aromatic ones Substituents, in turn, can have substituents which do not interfere with chelation.? B. short-chain alkyl radicals. especially those with 1 to 6 carbon atoms. Benzyl. Styryl ·. Phenyl-. Biphenyl, naphthyl or alkoxy radicals. e.g. Methoxy or ethoxy radicals or arvloxy radicals. ζ. Β Phenoxy residues or carbon alkoxy residues. ζ B carbomethoxy or carboethoxy radicals or carboaryloxy aryloxyresle, e.g. B. carbophenoxy or carbonaphthoxy radicals or acyloxyresle, e.g. B. acetoxy or benzoxy radicals or acyl radicals. z. B. acetyl or benzoyl radicals or halogen atoms, e.g. B. fluorine, chlorine, bromine or iodine atoms or cyano, azido, nitro or Haloalkyl radicals, ζ. B. Trifluoromethyl- or Trilluoräthylreste or amino residues. z. B. Dimethylamino radicals or amidoresle. z. B. acetamido or benzamido or ammonium residues, e.g. B. Trimethylammonium residues or azo residues. z. B. Phenylazo radicals or sulfonyl radicals. z. B. Melhylsulfonyl or phenylsulfonyl radicals or sulfoxy radicals, e.g. B. Melhylsulfoxy radicals or sulfonium radicals. z. B. Dimethylsulfonium radicals or silyl residues. e.g. trimethylsilyl residues or thioether residues. z. B. methylthio radicals. Preferably the alkyl substituents and substituents with alkyl groups preferably have 1 to 20 carbon atoms, in particular I to 6 carbon atoms. The aryl radicals and aryl groups of the substituents preferably consist of phenyl and naphthyl radicals. Typical suitable chelating agents are in US Pat compiled below Table IV.

Table IV

Examples of suitable chelating agents

1.3.5-triphenylformazan.

l- (4-chlorophen \ l | -3.5-diphen \ lf (> rmazan.

(- (4-iodophenyl) -3.5-diphenylformazane.

1.5-diphen> lformazan.

l.S-Diphenyl-S-methylforma / an.

1,5-diphenyl-3- (3-iodophenyl | formazan.

1.5- (2-carboxyphenyl) -3-cyanoformazan.

l.S-DiphenyM-acetylformazan.

1,3-Diphenyl-5-14-diphenyl) formazan.

I- (2 hydroxyphenyl) -3.5-diphenylforma / an.

1- (2-carboxyphenyl) -3.5-diphenylformazan.

l-phenyl-3- (3.4-dimethoxyphene \ li-

5- (4-nilrophen} l) formazan.

L5-Diphenvl-3- (2-naphth \ llforma / an.

l-Phenyl-3-undecyl-5-l4-nitrcphen \ l) -

formazan.

l- (2-hydroxy-5-sulfophen> ll-3-phen \ I-

5- (2-carboxyphenyl) forma / an.

1.5-ninh _C nj-i-3 carbwi.cAuwformazan.

l- (4-methylthiophene> I) -3- (3-nitrophenyl) -

5- (3.5-dichlorophenyl) formazan.

1- (2-naphthyl) -3- (4-cyanophenyl) -

5- (3-nitro-5-chlorophenyl) formazan.

l- (3-PyridvI) -3- (4-chlorophenyl) -5-phenyl-

formazan.

l- (2.4.5-TrichlorophenyI) -3-phenyI-

5- (4-nitrophenyl) formazan.

H4-pyridyl) -3-phenyl-5- (2-trifluurornethy! -

phenyllformazan.

l- (2-nitro-4-chlorophenyl) -3- | 4-chloro-

phenyl-5- (4-phenyIazophenyl) formazan,

1,3-Diphenyl-5- (2-pyridyl) formazan.

l- (2.5-dimethylphenyl) -3-phenyl-

5- (2-pyridyl) formazan.

l- (2-pyrid> I) -3- (4-cyannphcnyI) -

5-i2-ioly] | forma / an.

l- (2-Benzothiazolvl | -3-phen \ l-

5- (2-pyride} dformazan.

I- (4.4-Dimethylthiazo] -3-yl) -3- (4-bromo

phenylKV (3-! rifluoro-methylphenyl) formazan.

Number 1 No. 2 No. 3 No. 4 No. 5 No. 6 No. 7 No. 8 No. 9 No. 10 No. 11 40 No. 12 No. 13 No. 14 45 No. 15 No. 16 No. 17 50 No. 18 No. 19 No. 20 55 No. 21 No. 22 fiO No. 23 No. 24 No. 25 ⁶ 5 No. 26 No. 27

No. 28 l, 3-diphenyl-5- (benzothiazol-2-yl) formazan, No. 29 l- (Benzoxazol-2-yl) -3-phenyl-5- (4-chloro-

phenyl) formazan,

No. 30 l, 3-Diphenyi-5- (2-quinolinyl) formazan,
No. 31 l-plienylazo-2-phenol,
No. 32 l-Phenylazo ^ -dimethylamino ^ -phenol,
Mr. 33 2-HyCJrOPhCnOIaZO ^ -PhCnOl,
No. 34 l- (2-hydroxyphenylazo) -2-naphthol,
No. 35 l- (2-pyridylazo) -2-naphthol.
No. 36 l- (2-Pyridylazo) -2-phenol.
No. 37 l- (2-pyrid> lazo) -4-rcsurcinol,
No. 38 l- (2-quinolylazo) -2-naphthol,
No. 39 l- (2-Thiazolylazo) -2-naphthol.
No. 40 l- (2-Benzothiazolylazo) -2-naphlhol.
No. 41 l- (4-nitro-2-thiazol> lazo) -2-naphthol,
Nr 42 l- (2-thiazolylazo) -4-resorcinol,
No. 43 2,2-azodiphenol,
No. 44 l- (3,4-Dinitro-2-hydroxyphenylazo) -

2,5-phenylenediamine.

No. 45 l- (2-Benzothiazolylazo) -2-acylnaphlhol,
No. 46 Hl-Isodiinolylazo) -2-acrylnaphthol,
No. 47 2-Pyridincarboxaldehyd-2-pyridylhydΓazon, No. 48 2-PyridincaΓboxaldehyd-2-benzo-

thiazolylhydrazine,
No. 49 2-Thiazolearboxaldeh> d-2-benzoxazolyl-

hydrazone.
No. 50 2-pyridinecarboxaldehyde-2-quinolyl-

hydrazone,

No. 51 l- (2-P>ridylmeth> lcnamino) -2-naphthol,
No. 52 l- (2-quinolylmethyleneamino) -2-naphthol,
No. 53 l- (2-Thiazolylmethyleneamino) -2-naphthol,
No. 54 2-12-Benzoxazülylmethyleneamino) -2-phenol. No. 55 2- (2-P \ ridylmethyleneamino) -2-phenol,
No. 56 2- (2-Pyndlmeth> lenamino) -2-pyridine.
No. 57 2- (2-P \ nd \ lmethyleneamino> -2-quinoline,
No. 58 2- (4-Nitro-2-pyrid \ lmethyleneamino) -

2-thia / ol.
No. 59 2- (2-Ben / o \ a / olylmethyleneamino) -

2-oxazole.

No. 6 (1 i-Nitroso-2-naphthol.
No. 61 2-nitroso-1-naphthol.
No. 62 l-Nitroso ^^ - disulfoO-naphthol.
No. 63 disodium-l-nitroso-2-naphthol-

3.6 disulfonate.
No. 64 4-Nilrosoresorcinol.
No. 65 2-Nitros <i-4-metho \\ phenol.
'No. 66 Dithiooxamide.

No. ti 7 NN -uimeihyidhhiooxamid.
No. 68 NN-Diphenyldithiooxamide.
No. 69 N.N'-Di-n-hexyldithioo \ amide.
No. 70 N.N'-Di-n-tolyldithiooxamide.

The chelating agents can be incorporated into the radiation-sensitive layer in a corresponding manner, for example incorporating the leuco dyes or leuco dye precursor compounds - coupler combinations will. This means that these image-forming compounds may also be used after the imagewise Exposure introduced into the radiation-sensitive layer by customary known methods can be. In order to shorten the development process, it has generally proven to be advantageous proved the image-forming compounds that lead to Are capable of reacting with the reaction products generated upon exposure, the radiation-sensitive Add shift at the time of formation. This can be done in an advantageous manner done by dissolving the image-forming compounds in the coating composition that are used to generate the radiation-sensitive layer is used. Although the relationship of the image-producing Connections within the radiation-sensitive layer can be very different, it has to be but found to be advantageous when the image-forming compound or when the image-forming compounds in a concentration of 0.1 to 10 parts by weight per part by weight of cobalt (lII) complex, which of

ίο Start in the radiation-sensitive layer is available. be used.

in the preceding discussion it has been shown that the radiation-sensitive layers and radiation-sensitive materials apart from their usefulness with particular imaging materials or imaging layers can also be used in an advantageous manner in that one can see images in the layers generating components incorporated. However, it is not essential that there be a visible change takes place in the radiation-sensitive layer in order that the layer is suitable for image recording. Rather, any discernible physical change in the radiation-sensitive layer can occur Exposure and or development can be used to form images.

So it is possible, for example, as a photographic Binder in the radiation-sensitive layer to a polymer with functional groups use which are able to react with the reaction products that result in the reduction of the sensitized CobaltlllU complexes are generated. That Polymer can, for example, have groups which with the reduction of the cobalt (III) complex produced cobalt! 11! Atoms are able to form coordination ligands. In this case the polymer can be selectively modified in the exposed and possibly heat-generated areas and thereby its physical properties

4c ten change. According to an advantageous embodiment of the invention, such a polymer is used, that by the cobalt! 11! Atoms cross-linked thereby selectively rendering the polymer insoluble and oleophilic.

The special advantages offered by the invention can be easily illustrated by referring to the following example:

It is well known that gelatin layers are practically opaque to near-ultraviolet radiation. Furthermore are unsensitized Cobalt! 111 (complexes, if they are in such Layers are incorporated, typically against radiation of a wavelength of longer than 300 nanometers are insensitive and in the vast majority of cases also insensitive to it radiation with a wavelength longer than 400 nanometers. Become cobalt (III) complexes. z. B. Cobalt-hexaamine and cobalt-penta-amine in Gelatin layers without spectral sensitization

f> o medium incorporated, so they do not perform selective physical alteration of the gelatine in the exposed areas. On the other hand, however, if invent> according to a spectral sensitizer in combination with a cobalt (III) complex

h> is applied, its sensitivity in the Region of the visible spectrum extends beyond, so that an exposure of the gelatin layer, one Contains sensitized CobalKIlII complex. ? u one

C J

45 46

physical change of the gelatin leads to the sensitive layer only up to the blue exposure is recognizable and usable. rich of the spectrum, whereas the sensitivities

Since gelatine has carbxy groups, the second radiation-sensitive layer is tarnished

suppose that the cobalt! H) atoms, which in the Ex- only extend to the blue and green areas of the

exposure and / or development are released, extends 5 spectrum. The first radiation-sensitive

Forming ligands with two carboxy groups each, the layer is in contrast to the whole visible

sensitized with cross-linking of the gelatin in the exposed spectrum.

Districts. The gelatin in the exposed areas can be sensitized by using spectral consequently selectively insoluble and comparison means. on different parts of the point of view be made oleophilic. As a result, io can address ble electromagnetic spectrum the gelatin in the unexposed areas and use the same in each of the radiation-selective areas can be removed, for example by washing with sensitive layers, a multi-colored Water, with the oleophilic exposed areas recording image.

lag behind. According to one embodiment of the invention, by arranging a gelatin layer on a support, which comparatively 15 each of the radiation-sensitive layers is a color hydrophile is, can, since the cross-linked gel couplers are incorporated, for the purpose of generating a ink layer on a substrate, the comparative subtractive primary color, soft electromagnetic wise is hydrophilic, since the cross-linked table radiation corresponds to the range of the Spek gelatin selectively absorbs oleophilic printing inks. trums, on the other hand, the shift has been sensitized Make planographic printing plates as it is before the present. absorbed. By developing the radiative Invention was not possible. Will use a comparatively sensitive material after exposure wise thick gelatin layer of, for example, more common color developer solutions can be used as a result about 100 microns are used and a different result is used to produce a multi-colored image that is similar to a negative strong cross-linking, then ti ν of the multicolored template can be. This material Manufacture relief printing plates. If necessary, it is then possible to copy a positive of the original it is also possible to use the gelatin layers uniformly, if desired. harden. Instead of the gelatin, the various embodiments can be used according to a further advantageous embodiment The most other commonly known polymers with the invention become the radiation sensitive cross-linking centers made with cobalt! 11 (-atom layers incorporated chelating agents, which colored Form ligands, use. 30 images in each layer of any color you want

The foregoing has been created for the sake of simplicity. Such chelating agents can be so excellent

Radiation-sensitive and imaging materials are chosen that use subtractive primary colors

rials with a radiation-sensitive or image- each of the radiation-sensitive layers produced

recording layer described, which are used to produce, so that a colored negative of the multicolored

Production of images are suitable by increasing or 35 original artwork can be obtained. To notice

Reduction of the optical density with respect to the is that the choice of the color image that is in the

Background density or by creating a layer sensitive to visual radiation

bar distinguishable discoloration with regard to the outward should, can be independent of the part of the electrical

tergrundbe / irke. According to the invention, the magnetic spectrum, on the other hand, the layer

however, also produce multicolored images, specifically 40 is sensitized. As a result, it is possible. pictures

by using several radiation-sensitive to produce, which are either positive

Layers that each have a different part or negative reproductions of the original

of the visible electromagnetic spectrum or which senses the exposure image in an

are bilized. create a total of different color combinations.

An example of a multicolored sirahlungsemp- 45 The following examples are intended to sew the invention

Sensitive material according to the invention is illustrated schematically

shown in 1 ig K. .

The multicolored radiation-sensitive mate example 1 to 48

rial 1 "consists of the layer carrier 2" with a multitude of spectral sensitivities

Adhesive layer applied thereon or adhesive layer agents of Table II / ur Sensibilisierunj

combination 3 ". a first of the photoreduction of the cobalt! IJI (-complexes No. 1

radiation-sensitive layer 4 ", a first and No. 6 used.

transparent intermediate layer S ". a second of the CobaltUII (complexes and spectral

radiation-sensitive layer 6 ″, another sensitizing agent were each saturated!

transparent intermediate layer 7 ″. a third radiation solution in equal parts by volume of ethanol unc

lungs-sensitive layer 8 "and a protective water, which by the addition of sodium acetate au

the transparent cover layer 9 ″ was adjusted to a pH of 5 above the third

Liquid sensitive layer. After mixing the solutions together, becameei

In the simplest, most advantageous form, these can either be soaked up on filter paper

Intermediate layers, the top layer and the binding 60 or mixed with gelatin, whereupon the Mi

by means of the radiation-sensitive layers made of compounds was applied to a layer support

Gelatin or a combination of gelatin with The materials produced were then little

another synthetic polymer. Seconds with a 100 watt quartz iodine lamp

The intermediate layers and the top layers need to be set up at a distance of 30.5 cm

chcn not to be present, d. that is, they can be removed from the was exposed. Parts of the materials were pan

be left if so desired. chromatically exposed, which showed that di

Advantageously, for example, extends sensitive goods. Other parts of the manufactured

the spectral sensitization of the third radiation materials were furthermore within the sichi

47

spectrum only the light of a wavelength of a third of the visible spectrum, accordingly exposed to the maximum wavelength of absorption of the spectral sensitizer. It was found that all of the materials listed in Table V below are resistant to light of the part of the visible spectrum that is the maximum absorption wavelength of the spectral sensitizer. The spectral sensitizers were chosen so that that they were stable to light in the absence of the cobalt (III) complexes. The spectral Sensitivity was then determined as a function of the level as opposed to the spectral sensitizer faded on exposure. The dye fading was confirmed in several cases by using Chelant No. for printout purposes as an indication of cobalt (II) production. In all cases the materials were found to be panchromatic sensitive Light and light corresponding to the wavelength of maximum absorption of the sensitizer was. The determined spectral results are compiled in Table V below.

Table V

Example no.

Spck-Co (III) layer type

tralcs complex

Sensitivity no security

mean

No.

at Spec CoI HD- Shift type At the..*) game trales complex No. Sensibili No. ization middle No. 28 9 6th gelatin 450-500 IO 29 12th 6th F.P. 492 30th 12th 6th gelatin 492 31 11th 6th F.P. 460 32 11th 6th gelatin 460 15th 33 12th 6th F.P. 490 34 12th 6th gelatin 490 35 13th 6th F.P. 487 36 13th 6th gelatin 487 20th 37 17th 6th F.P. 462 38 17th 6th gelatin 462 39 15th 6th F.P. 410 40 1 6th gelatin 603 41 1 6th F. P. 603 25th 42 3 2 gelatin 635 43 3 2 F.P. 635 44 3 6th gelatin 635 45 3 6th F.P. 635 30th 46 28 6th gelatin 549 and 582 (two tips) 47 28 F. P. 549 48 16 6th gelatin 460

2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25

26th 27

4 4 4 4 17 17 17 17 5 5 5 5 6 6 6 6 7 7 7 7

2 2 6 6 2

2 6 6 2 2 6 6 2 2

6 6

6 6

6 6

F.P **)

gelatin

F.P.

gelatin

F.P.

gelatin

F.P.

gelatin

F.P.

gelatin

F.P.

gelatin

F.P.

gelatin

F.P.

gelatin

F.P.

gelatin

F.P.

gelatin

F.P.

gelatin

F.P.

gelatin

F.P.

Gelatin F.P.

533

533

533

533

578

578

578

578

522

522

522

522

618

618

618

618

584

584

584

584

485

485

485

485

450

(broad tip)

450

45 (1 * |;. = Wavelength of maximum absorption
**) KP = filter paper.

A comparison of Tables II and V shows that spectral sensitizers with a Oxidation potential in the ground state of less than 1.00 volts and a sum of oxidation and Reduction potentials in the ground state of more negative than -0.50 volts are excellent for making Radiation sensitive photographic materials are useful in accordance with the invention.

A particularly useful class of spectral sensitizers for photographic manufacture Materials according to the invention consists

: w from merocyanine dyes with a negative solution with an oxidation potential in the ground state of less than 1.00 volt and a sum of oxidation and ground state reduction potentials more negative than -0.50 volts.

In the above examples, the most effective spectral sensitizers are the merocyanine dyes No. 11, 12, 13 and 18. each have a solubilizing carboxymethyl group in the acidic Ring have and what oxidation potentialc

Ίο in the basic state from 0.5 to 0.89 volts as well as reduction poles from - 1.40 to -1.7OVoIt.

Spectral sensitizers No. 5 and No. 6 composed of oxonol dyes were found

⁽ 15 are only effective when they have been applied in a basic medium, since their reduction potentials are considerably increased in an acidic medium. The oxonol chemical coating solutions

Λ09 584/413

+ 49

The coating masses were replaced by drop CobaIt (III) -comples no. 2 0.5 g

-Also made basic by adding sodium hydroxide. Na ₂ CO, -.U g

_v ^ JThe oxonol dyes in the basic layers H ₂ O ^IUU ™

Proved to be slightly less effective than that. . .

Merocyanine dyes mentioned, but as much cfTek. A blue image comparatively more vigorously than the other low density spectral sensitizers in the third section of the test agent listed in Table V appeared. lings, i.e. the section which without Vo ₁ -

schaltunu had been exposed by the filter. No picture became in the case of exposure with blue, green

Example 49 _{| o or poor} light. The blue picture was

produced by the formazan dye and chelate

i ^Part A formation with cobalt (II), which is produced by the reduction of the

^: V A section of a cobalt »11» complex No. 2 arranged on a layer support with ultraviolet light was produced with 50.0 mc of gelatin per each. The result of this test bestatin ² was treated as follows: ~ 15 takes the well-known natural sensitivity of the

Cobaltd11! Complex to ultraviolet light Step 1 _e j _ner wavelength nm 300th

The specimen was 1 minute in a solution j _ei \ ς
from 0.1 «of the spectral sensitizing agent no. 37.

2.0 g Na ₁ CO ₃ and K) OmI distilled water «e-20 The procedure described in Part A was used

dives. * 'repeats, however, with the exception that the deletion

sun »of the spectral sensitizer No. 37

^btule - in level 1 an additional 0.5 g of the cobalt! IIIl complex

a) A first section of the test line was contained in No. 2.

For 15 seconds with one this case at a distance of 25 m, the density of the blue image was

30.5 cm set up 1000 watt quartz iodine lamp of the third section of the test object (l'V irradiation

due to filters that are commercially available under the trade, without filters) considerably higher than the density

designate Kodak Wratten filters No. 29 and 2A of the comparable section of the test item according to

are available (see »Kodak Filters for Scientific and Part B. Furthermore, a blue image was also formed

Technical Uses «." Kodak Publication No. B-3) such 30 in the first section of the test item, the only red

exposed that only red light had been exposed to the gelatin light. No picture was in the

layer hit. "Sections were made with either green

b) A second section of the specimen has been or has been exposed to blue light. From this it follows With the same light source for 15 seconds, spectral sensitizer No. 37 tet. however, using commercially available filters 35, the photoreduction of the cobalt (III) complex is counteracted (Kodak Wralten filter nos. 98 and 2A). so that it has sensitized about red light and that it is chelediglieh blue light on the gelatin layer mixes up the photoreduction of the cobalt-oil complex met. has sensitized to ultraviolet radiation.

el A third section of the test item was

Irradiated with ultraviolet light for 15 seconds. 40 B eis ρ ie 1 50
emitted by a 1000 watt quartz iodine lamp

at a distance of 30.5 cm from the -r- _e j | ^
Test specimen had been set up. without the interposition of filters. A section of a film placed on a substrate

45 arranged gelatin layer with 40.0 mg gelatin per

^ ^tulc · 'dnr and 15.0 mg of the one blue-green dye

The test specimen was now for 1 minute in the forming coupler 5-f'i- (2,4-di-tert-amyIphenoxy) -

a solution of 0.1 g of 1- (2-hydroxy-5-sodium sulfo-hexanamido] -2-heptafluorobutyramidophenol, dissolved

phenyl) - 3 - phenyl - 5 - (2 - carboxyphenyl) formazan in 15.0 mg dibutyl phthalate, was added for 1 minute in

dye, 2.0 g Na ₂ CO, and 100 ml distilled water 50 a solution of 0.1 g of the spectral sensitization

water immersed. using No. 37, 2.0 g Na ₂ CO, and 100 ml distilled

Immersed in water.

^e4 The examinee was then with for 10 seconds

The test piece was placed at a distance of 30.5 cm for 1 minute with a

0.2% aqueous solution of Na ₂ CO, rinsed. 55 1000 watt quartz iodine lamp through a test object with

graduated density levels, whereupon the test

■ Ling in a color developing solution for 1 minute

The test specimen was developed for 2 minutes with lead with the following composition:
water washed.

In none of the three exposed areas was a 6 ° 4-amino-N-ethyl-N-ß-hydroxy-

Picture emerged. ethyl aniline sulfate 2.0u

Part B ^Na 2 ^C ° 3 ² · ⁰ i.v.

Na ₂ SO ₃ 0.1 g

The procedure described in Part A was H ₂ 0 100 ml

repeated with the exception, however, that in the ⁶ p

Stage 1 the hemaloporphyrin solution through a whereupon the material was washed for an additional 2 minutes

Cobalt hexamine solution of the following composition.

was replaced: No image was recognizable in the test item.

part B

Table VI

Carbon sulfide images on filter paper under 3000 Å

conditions

ίο a) No exposure and no
Heat

b) Exposure to a quartz iodine lamp **) for 30 seconds with simultaneous exposure
Heat to 100 "C

c) As described under b),
however using
a filter that sheds light
3000 Å absorbed (Kodak
Wratten filter No. IA ***))

d) heating for 30 seconds
to 100 C

Behind-picture-3-table density Density")

0.05-0.05 0.9

0.05 0.05

0.05 0.05

A faint image of only one visible step was produced when the procedure described was repeated in a similar manner, but when the solution of spectral sensitizer No. 37 was replaced with a 0.5 si solution of cobalt complex No. 2, 2.0 g Na ₂ CO ₃ and 1bo ^ ml desiliated water.

The image was obviously created by a complex of photolytically generated Co (II) and the coupler.

Part C.

A favorable three-level cyan image was then produced when the one described in Part A. The procedure was repeated in a similar manner, but if the solution of the spectral sensitizing agent No. 37 also contained 0.5 g of the cobalt (III) complex.

Examples 51 to 58

The procedure described in Example 1 was followed

repeated except that this time

as a spectral sensitizer, the spectral one

Sensitizer No. 6 was used, and that this spectral sensitizer with the Cobaltf III (-complex No. 24, 25, 26, 27, 28, 29, 3, and

33 was tested.
The reduction potentials were determined in

Common basic state of every CobalUIII! Complex with the optical density of the test objects in the initial state. The test specimens were then

Panchromatically exposed for a long time, after which the optical densities of the materials were measured again became. A general relationship has been established such that those cobalt (III) complexes with Less negative reduction potentials were more easily sensitized, which was demonstrated by measurements of the bleaching of the spectral sensitizers was detected. This relationship is shown in FIG. 9 shown.

Because they are easier to reduce, cobalt (III) complexes are preferably used with Reduction potentials in the ground state that are more positive than -0.50 volts.

Example 59

A piece of commercially available filter paper (What-.,,

man no 2) was partially in a solution A of the 50 cobalt sulfide images. produced on filter paper by

The composition given below is exposure to radiation with a wavelength of dips and then dried.

*) The density measurements were made using a commercially available Densitometers (Macbeth Quanta Log Reflection).

**) The quartz iodine lamp consisted of a 1000 watt lampc. which are placed approximately 10 inches away had been.

** ') See "Kodak Fillers for Scientific and Technical Uses", Kodak Publication No. B-3, page 57.

From the data obtained, it was found that no images were formed by the action of heat alone

or can be produced by radiation with a wavelength greater than 3000 Å.

In a further series of tests, a corresponding Filter paper in a 4 weight percent aqueous solution of the spectral sensitizer

No. 35, whereupon the paper dried became. The paper was then coated with solution A and dried again. Sections of the paper were then exposed. The results obtained are shown in Table VII below.

Table VII

3000 to 4000 Ä

Solution a

1.0 g CobaltdID complex No. 2 in 10 ml water

ser,

0.13 g of thioamide No. 2 in 10 ml of water.

17 ml of a 12 '/ 2% gelatin solution, 2.5 ml of saponin.

Different by a uniform exposure parts of the paper with the solution absorbed A with radiation having a wavelength of shorter than 3000 A, and subsequent heating at 100 ⁰ C were erhallen cobalt sulfide images. In the following Table VI the background and image densities are given, which were obtained with this procedure and filtered with radiation below 3000 Å.

conditions

a) No exposure and
no heating

b) exposure to a quartz iodine lamp with heating for 20 seconds
100 C

c) As described under b),
however using
a Kodak Wratten No. IA filter

Behind
reason-
density Image-
density 0.05 - 0.05 0.7

0.05

0.6

? f

Hinlcr- Bildgrund- Dichlc
density

0.05 0.2

continuation

conditions

d) As described under b),
but under use!
of filters, soft light
absorbed below 4000 Å
(Kodak Wratten Filters
No. 2A)

From the data of process stage c in Table VI it is found that the spectral response of the radiation-sensitive material in the presence of a optical brightener can be extended beyond 3000 Å. The data of process stage d in Table VII shows that the optical sensitivity of the material extends beyond 4000 Å became, i.e. in the area of the visible spectrum.

Example 60

Solution B

(»5 g
1.0 g
0.1 ε
5 m!
32 ml

CobalUlIIl complex No. 2.

Thioamide No. 9.

Thioamide No. 2.

Water.

a 12 ¹ ₂ % aqueous gelatin solution. 2.5 ml of saponin.
5 mg of spectral sensitizer # 4

in 5 ml of ethanol.
2.5 ml of 5 ° formaldehyde solution.

35

40

The recording material was passed through a test object for 15 seconds with a quartz iodine lamp exposed while it was heated to a temperature of 125 C. A cobalt sulfide image of obtained comparatively lower density.

A section of the special recording material was coated with a solution C of the composition given below. producing a layer of appropriate thickness and air drying. The recording material obtained was then thermally developed again at 125 C for 5 seconds. In this case it was a cobalt sulfide image with a density of over 1.0 is generated, see p

Solution C

0.1 g thioamide # 2.

1.0 g thioamide No. 9.

35 ml of a 12 _'2% aqueous gelatin solution.

2.5 ml of saponin.

Example 61

The procedure described in Example 60 was f-s again. where icdoch this time to generate the Top layer cmc I solution I) of the following anüenen / uvirnim-nsei / uni: \ crwendei was

Solution D

25th

A polyethylene terephthalate film support was used with a solution B of the composition given below in a layer thickness of wet measured 300 microns, coated and dried.

0.1 g thioamide No.

1.0 g thioamide No. 9,

0.5 g cobalt (III) compound x No. 2,

35 ml gelatin solution.

2.5 ml of saponin.

Results similar to those described in Example 60 were obtained.

Example 62

A layer of polyethylene terephthalal film was coated 300 microns thick applied from a coating compound E of the composition given below:

Coating wet E.

0.5 g cobalt dlll complex no.2.

0.5 g thioamide No. 9.

0.1 g thioamide # 2.

2.5 g glycerine.

0.5 ml spectral sensitizer No. 36 32 ml of a copolymer of N-isopropyl acrylamide; 3 - methacryloyloxypropane 1-sulfonic acid. Sodium salt and 2-acetoacetoxyeth} Methacrylate (molar ratio of monomers 7: 2: 1).

A thin, transparent cellulose acetate top layer was applied to the radiation-sensitive layer. The radiation sensitive layer was then imagewise with a at a distance of 16 cm exposed quartz iodine lamp. Because> exposed radiation-sensitive material was then brought into contact with a common two-component diazo recording material and brought into contact heated uniformly to a temperature of 120 ° C. for 25 seconds. In this way became a positive copy of the original in the diazo recording material obtain

Example 63

A radiation-sensitive material was produced using the method described in Example 62. where the active components were used in the following concentrations:

Coating densities

Cobalt! 111 l-complex 20 mg dnr

Thioamide No. 2 4 mg dnr

Thioamide No. 9 20 mg dm ²

Spectral Sensitization

center! No. 36 "20 mg dm ²

A copolymer was also used as a binder from N-isopropyl acrylamide; 3-Acryloylo \ ypropane-1-sulfonic acid. Sodium salt and 2-acetoacetoxyethyl methacrylate (molar ratio of the monomers 7: 2 0.25) is used.

In this case, the radiation-sensitive material and the diazo recording material were before exposure and brought into contact before heating. Fs a negative image was obtained in dem Di.i / o.Hif / cKhiuin ^ sriialerial received

J U

55
Examples 64 to 77

A photographic paper support was used for these experiments, which has a content was marked on Spectral Sensitizer No. 35. Starting from this paper backing various radiation-sensitive materials have been produced in that on the non-gelatin side of the support is coated with radiation-sensitive layers with thiourea as well as thioamides and other solubilizers.

The individual layers were based on a coating composition F of the type indicated below Composition applied without a solubilizer.

Coating compound F

1.37 g thioamide No. 9,
1.0 g CobaltdID complex No. 2,
17 ml of a 12 '/ ₂ weight percent aqueous

Gelatin solution,
2.5 ml of saponin.

Of the solubilizers tested were 200 g each used.

The radiation-sensitive materials produced were in each case with a 1000 watt quartz iodine lamp exposed. The exposure conditions used in detail, the solution mixers and the results obtained are shown in Table VIII below.

I * Table VIII Lnsuti [! S% er! TiitUer l.xponicrung temperature 45 After-l xpomerung l. exposed areas Not exposed t
\ Example no. No in seconds at Time temperature Districts t I-xpnnation Sck C in C \ 1 15th 100 Dark brown Light beige \ 64 14th 15th 100 Light brown Light beige 65 14th 15th 125 Light brown Light beige ί 66 14th 5 150 5 sec. 150 C Light brown Light beige 67 Sulfamide 15th 100 Light brown Light beige 68 Sulfamide 15th 125 Brown Light beige 69 Acetamide 15th 100 Light brown Light beige 70 Acetamide 15th 125 Brown H eil beige 71 Acetamide 5 150 Brown Light beige 72 urea 15th 125 Light brown Light beige 73 Suceinimide 15th 125 Light brown Light beige 74 2 plus sulfamide 15th 100 Dark brown Light beige 75 2 plus sulfamide 15th 100 Dark brown Light beige 76 ' plus urea 15th 100 Brown Light beige 77 example 78 a dye relief image on one transparent

Part of a coating compound, consisting of 64 g of a 12 »5" ounce of aqueous gelatin solution. Ig of the CobaltdIII complex No. 2. 1 g of a 14 ° Oigen aqueous solution of the spectral sensitizer No. 35. 6 ml of a 7.5% solution of Saponin as a spreading agent and 28 ml of water, the pH of which had been adjusted to 8.0 with NaOH. was applied to a transparent hydrophilic film support in such a way that on a support surface of 0.0929 nr 650 mg gelatin, 80 mg of the cobalt complex and 13.5 mg of the spectral sensitizer accounted for.

After the applied layer had dried, a section of the material was passed through a test template For 1 minute with an UltravioleU lamp exposed at a comparatively low output

To make the cross-linked image visible, was removed from the layer of melethylene blue dye aiii allowed to suck. The specimen was then washed with warm water for 1 minute to remove the unexposed and consequently not cross-linked / tcn f ii - '. iiinebc7irke / u remove in the dic-c manner The specimen was tested for planographic printing properties by using as Printing template was used:

First, water and black printing ink were applied to the test specimen in a conventional printing press. The pruning was then brought into contact with printing paper. The cross-linked districts of the test specimen proved to be sufficiently oleophilic. to provide a lithographic reproduction of the original artwork.

Other sections of the material were tested in a similar manner, practically the same Results were obtained. Among the test lines were sections which, according to the Exposure washed, not washed, gelarru and not colored

Were the attempts using the cobali complexc No. 22 and No. 6 (but with a Pcrchlnratunion) repeated, sn practically the same results were obtained

In a further series of experiments, the process was repeated in different use cmc · «Mim.Iv

57 / / 58

Polymer of N -isopropyl acrylamide; 3-methode block was located. The temperature of the block

acryloyloxypropane-1-sulfonic acid, sodium salt and was then increased to 60 C, then 5 minutes

Let 2-acetoacetoxyethyl methacrylate instead of gel and then again reduced to 30.degree. Aul

line. The results were also excellent - the applied layer was then another

received, although they were not quite as cheap as 5 top layer of a 10 weight percent solution

in the case of using gelatin. solution of polymethyl methacrylate in toluene

Wear a wash of the test pieces before coloring, in a layer thickness of wet

Proven to be beneficial but not required- measured 160 microns. The applied layer

Huh Coloring seems to have little effect on heating at 60 ° C for 5 minutes

Ink absorption capacity of the material hardened to io.

to have. The specimens turned out to be particularly The material became recording-sensitive when a small amount of water laminated together in the layer. which was present as the ammonäakemp layer. 2.4-diphen> l-6 - (, (- meth> l-3,4-dilange immersion of the layers in water and by means of alhoxyst) r> l) p \ rvliumiiuoborat contained by a 10 seconds sensitive dye.
Dry wiping is obviously so much 15 Then the cobalt III! Complex dehumidification was introduced. that> a maximum sensitive layer is achieved in one go with the support. Specirograph exposed, the light by means of. of a step wedge with density levels of 0.3 loaE-Ein-Examples / 9 to 9: < _hei , _{en mo} j _u ii _er , _wur d _e . The exposed material

A solution of 10 mg of a spectral Sensi-20 was then added twice at a rate of

bilizing agent in 1 ml of a suitable solution 45 cm per minute through the from 2 to 120 C

by means of 2.5 g of the following standard approach heated gap formed were guided, woraul

given: the laminate was separated. It turned out to be a negative

, 1 \ j 3 0 7 dark image, probably made of cobalt sulfide. in the

μ ⁰ ? 04 a ^2? Cobalt! III! Complex containing layer obtained.

^r """·; whereas a positive picture of the faded

~ became.

The coating compound was then in a die using different spectral

Layer thickness measured wet 160 microns on 30 sensitizers. The results obtained are in

applied to a transparent film support. individually summarized in the following table IX

which is placed on a coating heated to 30 ° C

Table IX Spec
trales
Sensihili Awareness
Beu'tch 540 550 Si-nsihilizing milicl
I osiinjis'nille!
maximum DMi * i example
No sieruniis-
ITUlIfI 620 550 DMl IS 400 550 m > 500 DMF Mcihanoi 79 19th 410 600 520 DMF-methanol 80 20th 480 \ J - \ J 3 sheets 500 1 "\ XU" \ 1 ·
UiMl - VV aSÄLl 81 21 450- 530 530 DMF-methanol 82 —R \ 3 \ J 570 DMF 0 ->
O." 23 4? 0 -500 490 Methanol 84 24 410 640 490 Methanol 85 25th 420 600 470 DMF on water 86 26th 560 520 630 DMF to methanol 87 27 500 570 550 DMF to methanol 88 28 400 550 470 DM"-" 89 29 420 up to 400 4SO DMF 90 30th 450 410 4 " ⁷ O acetone 91 31 400 N / A. acetone 92 32 560 440 Acci on 93 33 * i dimethylformamide.
KA = not recorded: 450 94 34 500 drawings 95 H .

Claims (15)

Patent claims: 1. Photographic recording material composed of a layer support and at least one radiation-sensitive Layer with a cobalt (III) complex, characterized in that the radiation-sensitive layer (a) "is only one photolytic constituent with a cobalt (III) complex free of sensitizable anions at least two unidentical ligands and (b) a sensitizer that radiates one Able to absorb wavelength of longer than 300 nm, where (c) holds that it is a cobalt (III) complex contains, its reduction potential between the oxidation and the reduction potential of the sensitizer is in the ground state. 2. Recording material according to claim 1, characterized in that the radiation-sensitive layer is a cobalt (III) complex with at least one amine. NH ₃ -. Aquo-. Halogen-. Alkylenediamine. Contains azido, thiocyanate and or nitro ligands. 3. Recording material according to claim 2, characterized in that the radiation-sensitive Layer a cobalt (III) complex with a hexa-amine cobalt (III) -. Aquopenta-amine cobalt (III) -. cisfBislathykndiamine) - azidothiocyanato-cobalt (III)] -. cis [bis (ethylenediamine) diazo-cobaltIII10- .cisfBisfäthylenediamineJnitroazidocobaltdIII-. cisf bis-ethylenediamine dichloro-cobalt (III)] -. trans [bis (ethylenediamine) dichloro-cobalt) IH)] -. trans [bis (ethyl, idiamine) dibromocobalt (III)] -. Bisethylene diamine thiocvanate chlorocobalt (IIJ) - or cis- [bis (ethylenediamine) -aminochloro-cobalt (HI)] - cation contains. 4. Recording material according to claim 1, characterized in that the radiation-sensitive Layer contains a Cobaltdll! Complex, the reduction potential of which in the ground state is more positive than - 0.50 volts. 5. Recording material according to claim 1, characterized in that the radiation-sensitive If a sensitizing dye appears as a sensitizer, consisting of a cyanine, merocyanine. Slyryl base or oxonol dye. 6. Recording material according to claim 5, characterized in that the radiation sensitive Layer as cyanine. Merocyanine-. Styryl base or oxonol dye contains: (1) 1.l'-diethyl-2.2'-carbocyanin iodide, (2) l, r-diethyl-2,2'-dicarbocyanin iodide, (3) l, r, 2,2'-tetrahydro (4H- [1,4] thiazino [3,4-bjbenzothiazolo) -cyanine bromide, (4) 3 - carboxymethyl - 5 - [(3 - ethyl - 2 - benzothiazolinylidene) ethylidene] rhodanine, (5) bis [3-methyl-1-phenyl-2-pyrazolin-5-one- (4)] - trimethine oxonol, (6) bis [3-methyl-l-phenyl-2-pyrazolin-5-one (4)] - pentamethine oxonol, (7) anhydro - 3,3 '- di (2 - carboxyethyljoxadicarbocyanine hydroxide, (8) 4 - [(3-Ethyl-2-benzothiazolinylidene) isopropylidene] -3-methyl-1- (p-HuIfophenyl) -2-pyrazoline-5-one, (9) 4 - [(l-Ethyl-2-naphtho [l, 2-d] thiazolinylidene) - isopropylidene] -3-methyl-1 - (p-sulfophenyl) - 2-pyrazolin-5-one,
(10) 3 - carboxymethyl - 5 - [(3 - ethyl - 2 - benzoxazo- linylidene) ethylidene] rhodanine,
jfl 1) 3 - carboxymethyl - 5 - [(3 - ethyl - 2 - benzoxazolinylidene) - ethylidene] - 2 - thio - 2,4 - oxazolidendione, (12) 3 - carboxymethyl - 5 - [(3 - methyl - 2 - thiazolidinylidene) isopropylidene] rhodanine, (13) l-carboxymethyl-5 - [(3-ethyl-2-benzoxazo-iinylidene) ethylidene - 3 - phenyl - 2 - thiohydantoin, (14) 3-Ethyl-5- [1- (4-sulfobutyl) -4 (1H) -pyridylidene] -rhodanine, sodium salt, (15) 3-Carboxymethyl-5- (3-methyl-2-benzoxazolinylidene-rhodanine. (16) 3 - ethyl - 5 - (1 - ethyl - 4 (1 H) - pyridy lidenrhodanine. (17) Anhydro - 9 - ethyl - 3,3 '- (3 - sulfopropyl) -4.5.4'.5' - dibenzothiacarbocyanine hydroxide. Sodium salt, (18) 3 - ethyl - 5 - [(3 - ethyl - 2 - benzoxazolinylidene) ethylidene] rhodanine, (19) 3-Ethyl-5 - [(3-ethyl-2-benzothiazolinylidene) ethy Iidene] rhodanine, (20) 5.5'.6.6'-tetrachloro-1,1.3.3-tetraethylbenzimidazolocarbocyanine chloride, (21) Anhydro - 3 - ethyl 9 - methyl - 3 '- (3 - sulfobutyl) thiacarbocyanine hydroxide. (22) anhydro - 9 - methyl - 3,3 '- di (3 - sulfobutyl) thiacarbocyanine hydroxide, (23) 3-Ethyl-5 - [(3-ethyl-2-benzoxazolinylidene) ethylidene] -l-phenyl-2-thiohydantoin, (24) 3,3 '- diethyl - 4' - methyloxathiazolocarboxyanine bromide, (25) 2-p-diethylaminostyrylbenzothiazole, (26) 5.5'-dichloro-3,3 ', 9-triethylthiacarbocyanine bromide. (27) anhydro-5,5'-dichloro-3,9-diethyl-3 '- (3-sulfobutyl) -thiacarbocyanine hydroxide, (28) 2-Diphenylamino-5 - [(3-ethyl-2-benzoxazolinylidene) ethylidene] -2-thiazolin-4-one, (29) 2 - Diphenylamine - 5 - [(3 - ethyl - 2 - benzothiazolinylidene-ethylidene] -2-thiazolin-4-one. (30) 1 - ρ - carboxyphenyl - 5 - [(3 - ethyl - 2 - benzoxazolinylidene) ethylidene] -3-phenyl-2-thiohydantoin. (31) 4 - (2.4 - Dinitrobenzylidene) - 1,4 - dihydro- 1 - (4 - sulfobutyl) - quinoline, sodium salt, (32) 5 - [(3-Ethylnaphth [2.1 -d] oxazolin-2-ylidene) ethylidene] - 3 -heptyl -1-phenyl-2-thiohydantoin. (33) 5 - [4 - (3 - ethyl - 2 - benzothiazolinylidene) - 2 - butenylidene] - 3 - heptyl -1 - phenyl - 2 - thiohydantoin, (34) 3,3 '- dimethyl - 9 - phenyl - 4,5,4', 5 '- dibenzothiacarbocyanine bromide, (35) 2 - diphenylamine - 5 - [(3 - ethyl - 2 - benzoxazolinylidene) ethylidene-2-thiazolin-4-one, (36) N, N'-di [2-p-sodium sulfoanilino-4-diethanolamino -1,3,5 -lriamyl (6)] -diaminostilbene-2,2'-disulfonic acid, sodium salt, (37) N ₁ N '- di {[4 - diethylamino - 6 - (2,5 - disulfonilino)] - 2 - s - triazinylamino} - 2,2' - stilbene disulfonic acid, hexasodium salt and (38) Hematoporphyrin. 7. Recording material according to claim 1, characterized in that the radiation-sensitive Layer contains a sensitizing agent, the oxidation potential of which in the ground state ' is less than 1.00 volts. 8. Recording material according to claim 1, characterized in that the radiation-sensitive Layer contains a sensitizer whose sum of oxidation and reduction potential in the ground state is more negative than -0.50 volts. 9. Recording material according to claim 1, characterized in that the radiation-sensitive Layer additionally contains a thioamide. 10. Recording material according to claim 9, characterized in that the -> radiation sensitivity Layer than thioamide contains a thiourea or thioacetamide. 11. Recording material according to claims 1 and Z, characterized in that the radiation-sensitive layer additionally contains a compound which reacts with ammonia and that it contains a cobalt OII (complex which has at least one NH ₃ ligand. 12. Photographic recording material from a layer support and at least one radiation-sensitive layer with a cobalt (III) -! -: omplex. characterized in that the radiation-sensitive layer (a) is the only photolytic Part of a cobalt! III! Complex free of sensitizable anions with at least two unidental ligands and (b) a sensitizer that emits one wavelength able to absorb longer than 300 nm, contains, whose reduction potential between the 35; The oxidation and reduction potential of the sensitizer is in the ground state, and that the recording material (d) contains an image-receiving layer. 13. Recording material according to claim 12, 40, characterized in that the image-receiving layer contains a compound which reacts with ammonia and that it contains a cobalt (iII) complex which has at least one NH ₃ ligand. 14. A photographic process for producing images which comprises a photographic recording material imagewise exposed to rays of a wavelength longer than 300 nm and thereafter is brought into contact with an image receiving layer, characterized in that a Photographic recording material according to claims 1 to 13 and an image receiving layer with a compound with at least one of the unidentical ligands of the cobalt (lII) complex to form an optically different compound in the image-receiving layer responds, is used. 15. Photographic positive-positive process for the production of images, in which a photographic recording material in contact with an image-receiving layer is exposed to radiation with a wavelength longer than 300 nm and ^{heated to a temperature of 80 to 150 °} C., characterized in that a photographic material according to claims 1 to 13 and a photosensitive layer of a two-component diazotype material is used as the image-receiving layer and that the photosensitive layer of the two-component diazotype material is exposed imagewise and the photographic material is uniformly exposed to rays having a wavelength longer than 300 nm