DE1956667A1 - Silver halide-free photographic recording material - Google Patents

Description

Silver halide free photographic Recording material

The invention relates to a light-sensitive, direct-positive silver halide-free photographic recording material, that consists of a layer support and a light-sensitive layer with metallic nuclei for the physical Development and possibly a binding agent "

It is already known that when exposing silver halide-free photosensitive recording materials which are disclosed in Their photosensitive layer germinates physical development together with a photosensitive substance contain, which forms a desensitizer when exposed to actinic light, which forms the exposed development nuclei insensitive, direct-positive images are obtained. The direct-positive image is created through physical development of the unexposed germs. For example, US Pat. No. 3,320,064 discloses a photosensitive recording material known its photosensitive layer

009823/1687

from a photosensitive organic azide compound, Silver germs and a thioether color coupler. When exposed to light, the organic azide reacts with the thioether color coupler with the formation of a substance which deactivates the germs in the exposed areas. In the physical Development creates a direct positive image. Although this system has been found to be quite useful for producing direct positive images through physical development, efforts were made to find a simpler and more effective physical development system. In the USA patent 3 320 064 it has already been pointed out that in some cases the use of silver halide-free seeds for the physical development, e.g. B. in recording materials in which a high image resolution is desired, expedient were.

The object of the invention was therefore to provide a photosensitive, direct-positive, silver halide-free photographic recording material to provide available that does not have the disadvantages described above and images with high resolution supplies. .

ψ It has now been found that light-sensitive direct-positive photographic recording materials can be obtained when coating a substrate with a photosensitive composition, the adsorbed one on nuclei for physical development, contains electron-accepting organic dye.

The invention relates to a light-sensitive, direct-positive, silver halide-free photographic recording material, consisting of a layer support and a light

0 0 9823/1667

sensitive layer with metallic nuclei for physical development and, if necessary, a binding agent, which is characterized in that the photosensitive layer has at least one on the metallic nuclei adsorbed, electron accepting cyanine dye with at least one methine group whose hydrogen atom is through a halogen atom is replaced, and / or contains at least one dye of the following general formula:

I R ₁

C «L (-L« L) _n _ _r CI

or

II. R _x -NC-CH-CH), -C-LC-LL), -j g-ι ni

or

III. 0-C -

or

0 09823/1667

VIII.

L-L-C (-CH-CH). Ar

or

IX, R ₁₀ -N (-CH-CH) _{h- 1} -CL (-LL) _{k- 1} -C (-CH-CH) _{g- 1} -NR _l

or

X. R ₁₂ -NC-CH-CH). ., - CLLC - CO

or

XI. Ar ^f -LC - CO

or

XII.

d and k

g, h, j and ρ

1, 2, 3 or 4; each 1, 2 or 3; each 1 or 2;

009823/1667

a methine group optionally substituted by an alkyl or aryl radical, e.g. B. -CH-, * C (CH,) - or -C (C _n H _1. ) -;

J »8 * 9 *

and Rj- each independently of one another

optionally by a hydroxy, alkoxy, aryl, carboxy, acyloxy, Carboalkoxy, carboxyalkoxy or sulfo group substituted by alkyl radical 1-18, preferably 1-4 carbon atoms, ζ. B. a methyl, ethyl, propyl, Isopropyl, butyl, sec-butyl, hexyl, cyclohexyl, dodecyl or octadecyl radical, a hydroxyalkyl radical, e.g. B. a 2-hydroxyethyl or 3-hydroxypropyl radical, an alkoxyalkyl radical, e.g. B. a 2-methoxyethyl or 2-ethoxyethyl radical, an aralkyl radical, e.g. B. a 2-phenylethyl or benzyl radical, a 2-carboxyalkyl radical, e.g. B. a 2-carboxyethyl, Carboxymethyl or 3-carboxypropyl radical, an acyloxyalkyl radical, e.g. B. a 2-acetoxyethyl or 3-acetoxypropyl radical, carbomethoxyalkyl, e.g. B. a carbomethoxymethyl radical, a carboxyalkoxyalkyl radical, e.g. B. a Carboxyäthoxyäthylrest, a 3-sulfopropyl- or 4-sulfobutyl radical, an alkenyl radical, e.g. B. an allyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl or 3-butenyl radical,

009823/1667

an aryl radical optionally substituted by alkyl groups or halogen atoms, z. B. a phenyl, p-tolyl, o-tolyl or 3,4-dichlorophenyl radical;

A is an oxygen, sulfur or selenium

atom;

R ', R " and R" ¹ each optionally replaced by one

Aryl group-substituted alkyl radical with 1-12, preferably 1-4 carbon atoms, ζ. Β. a methyl, ethyl, propyl, isopropyl, butyl, hexyl, Cyclohexyl, decyl, dodecyl, benzyl or phenetyl radical,

a styryl radical optionally substituted by an alkoxy or styryl group, z. B. a styryl, ο-, ρ- or m-methoxystyryl, ο-, ρ- or m-styrylstyryl radical,

an N-phenylacridanylidenemethyl radical, an alkoxy group, preferably a short-chain alkoxy group, e.g. B. a methoxy, ethoxy, propoxy, isopropoxy or butoxy radical,

an aryl radical optionally substituted by an alkyl group, e.g. B. a phenyl, ο-, ρ- or m-tolyl, ο-, ρ- or m-Äthylphenylrest, an alkoxyphenylrest, z. B. an o-, p- or m-anisyl radical, an o-, p- or m-ethoxyphenyl radical,

009823/1667

an Ilydroxyalkoxyphenylrest, ζ. Β.

a ß-IIydroxyäthoxyphenyl-, oO-hydroxy-

amyloxyphenyl- or ^ O-hydroxybutoxy-

phenyl radical,

a carboxyalkoxyaryl radical, e.g. B. a

Carboxymethoxyphenyl-, ß-carboxyethoxy-

phenyl or u) -carboxybutoxyphenyl radical,

a biphenyl radical,.

an azidophenyl radical, e.g. B. an ο-,

p- or m-azidophenyl radical,

an acylamidophenyl radical, e.g. B. a

o-, p- or m-acetamidophenyl or p-

Propionamidophenyl radical,

an alkoxycarbonylphenyl radical, e.g. B.

a methoxycarbonylphenyl-, co-butoxy-

carbonylphenyl, chloromethoxycarbonyl

phenyl or bromomethoxycarbonylphenyl

rest,

a naphthyl radical, e.g. B. a 1- or

2-naphthyl radical,

an arylalkenyl radical with preferably

1-20 carbon atoms, ζ. Β. a

4-phenylbutadienyl- or 3-methyl-4-

phenylbutadienyl radical;

Ar given as defined above

if substituted aromatic radical, in particular a phenyl radical;

Ar ^{1 is} substituted by a nitro group

th aryl radical, e.g. B. a m-nitrophenyl, p-nitrophenyl or nitronaphthyl radical;

009823/1667

X, X-, Χ ~ and X,

• 1 ' 2 * 3' 4 and Zr

an acid anion in each case that does not have any adverse effect on the emulsion, z. B. a chloride, bromide, iodide, thiocyanate, sulfamate, perchlorate, p-toluene sulfonate, methyl sulfate, ethyl sulfate, Fluoroborate, sulfoacetate, boron fluoride, or trifluoroacetate anion;

in each case those to complete a customary for cyanine dyes, if necessary substituted 5- to 6-membered heterocyclic containing a nitrogen atom Ring, which can contain an oxygen, sulfur, selenium or nitrogen atom as a second hetero atom Number of non-metal atoms, in particular to complete one optionally with alkyl and / or Aryl groups substituted thiazole ring, e.g. B. a thiazole, 4-methylthiazole, 4-phenylthiazole, 5-methylthiazole, 5-phenylthiazole, 4,5-dimethylthiazole, 4,5-diphenylthiazole, 4- (2-thionyl) thiazole, Benzothiazole, 4-chlorobenzothiazole, 5-chlorobenzothiazole, 6-chlorobenzothiazole, 7-chlorobenzothiazole, 4-methylbenzothiazole, 5-methylbenzothiazole, 6-methylbenzothiazole, 5-bromobenzothiazole, 6-bromobenzothiazole, 5-phenylbenzothiazole, 6-phenylbenzothiazole, 4-methoxybenzothiazole, 5-methoxybenzothiazole, 6-methoxy-

009823/1667

benzothiazole, S-iodobenzothiazole, 6-iodobenzothiazole, 4-ethoxybenzothiazole, 5-ethoxybenzothiazole, tetrahydrobenzothiazole, 5,6-dimethoxybenzothiazole, 5,6-dioxymethylene benzothiazole, 5-hydroxybenzothiazole, 5-hydroxybenzothiazole, Naphtho [2,1-dJthiazole-, naphtho (j, 2-d] thiazole-, 5-methoxynaphtho £ 2,3-d] thiazole-, 5-ethoxynaphtho [2,3-dJ thiazole-, 8-methoxynaphtho JJ2, 3-d] thiazole, 7-methoxynaphtho [] 2,3-d] thiazole or 4'-methoxythianaphtheno-7 ¹ , 6 ', 4,5-thiazole ring; an oxazole ring optionally substituted by alkyl and / or aryl groups, e.g., 4-methyloxazole, 5-methyloxazole, 4-phenyloxazole, 4,5-diphenyloxazole, 4-ethyloxazole, 4,5-dimethyloxazole, 5-phenyloxazole, benzoxazole, 5-chlorobenzoxazole -, 5-methylbenzoxazole, 5-phenylbenzoxazole, 6-methylbenzoxazole, 5,6-dimethylbenzoxazole, 4,6-dimethylbenzoxazole, 5-methoxybenzoxazole, 5-ethoxybenzoxazole, 5-chlorobenzoxazole, 6-methoxybenzoxazole, 5-hydroxybenzoxazole, 6-hydroxybenzoxazole, naphtho | ^ 2,1-d | oxazole- or naphtho- [1,2-dj oxazole ring,

a selenazole ring optionally substituted by alkyl and / or aryl groups, e.g. B. a 4-methylselenazole, 4-phenyl selenazole, benzoselenazole 5-chlorobenzo

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selenazole, 5-methoxybenzoselenazole, 5-hydroxybenzoselenazole, tetrahydrobenzoselenazole, naphtho ζζ , 1-dJselenazole

or naphtho [j »2-dJ selenazole ring, one optionally through an alkyl group substituted thiazoline ring,

z. B. a thiazoline or 4-methyl

thiazoline ring,

one optionally through an alkyl group substituted pyridine ring,

z. B. a 2-pyridine, 5-methyl-2-pyridine, 4-pyridine or 3-methyl-4-

pyridine ring,

one optionally by a chlorine atom, a hydroxy, alkyl or alkoxy group substituted quinoline ring, e.g. B. a 2-quinoline, 3-methyl-2-quinoline, 5-ethyl-2-quinoline, 6-chloro-2-quinoline, 8-chloro-2-quinoline, 6-methoxy-2-quinoline, 8-ethoxy-2-quinoline, 8-hydroxy-2-quinoline, 4-quinoline, 6-methoxy-4-quinoline, 7-methyl-4-quinoline, 8-chloro-4-quinoline, 1-isoquinoline, 3,4-dihydro-1-isoquinoline or 3-isochino

linringes,

a 3,3-dialkylindolenin ring, e.g. B.

a 3,3-dimethylindolenine or 3,3,5-trimethylindolenine ring or an imidazole ring optionally substituted by alkyl, alkoxy and / or aryl groups, z. B. an imidazole, 1-

009823/1657

Alkylimidazole, i-alkyl-4-phenylimidazole, i-alkyl ^ jS-dimethylimidazole, benzimidazole, 1-alkylbenzimidazole, 1-aryl-5,6-dichlorobenzimidazole, 1-alkyl-1H -naphth- [1,2-djimidazole-, 1-aryl-3H-naphth | j, 2-dj imidazole- or i-alkyl-5-methoxy-IH-naphth-Γΐ , 2-dJ imidazole ring; and

Q, Q ₁ and Q- each used to complete a

optionally substituted 5- to 6-membered heterocyclic keto-methylene ring, which preferably contains a nitrogen atom and a nitrogen, sulfur or oxygen atom as the second hetero atom, the number of non-metal atoms required, in particular to complete an optionally with an alkyl and / or aryl group-substituted pyrazolin-5-one ring, e.g. B. a 3-methyl-1-phenyl-Z-pyrazolin-S-one-, i-phenyl-2-pyrazolin-S-one- or 1- (2-benzothiazolyl) -3-methy1-2-pyrazoline-5 -on ring, an isoxazolone ring optionally substituted by an alkyl or aryl group, e.g. B. a 3-phenyl-5 (4H) -isoxazolone or 3-methyl-5- (4H) -isoxazolone ring, an optionally substituted by an alkyl group oxindole ring, e.g. B. a 1-alkyl-2,3-dihydro-2-oxindole ring, a 2,4,6-triketohexahydropyrimidine ring, e.g. B. of barbituric acid or 2-thiobarbituric acid and their 1-alkyl derivatives with 1 to

009823/1667

7 carbon atoms in the alkyl group, e.g. B. the 1-methyl, 1-ethyl, 1-propyl or 1-heptyl derivatives, their 1,3-Pialkylderivate with preferably 1 to 6 carbon atoms in the alkyl group, e.g. B. the 1,3-dimethyl, 1,3-diethyl, 1,3-dipropyl, 1,3-diisopropyl, 1, S-dicyclohexyl or 1,3-di (ß-methoxyethyl) derivatives, their 1,3-diaryl derivatives, e.g. B. the 1,3-niphenyl, 1,3-di (p-chlorophenyl) - or 1,3-Di (p-ethoxycarbonylphenyl) derivatives, their 1-aryl derivatives, e.g. B. the 1-phenyl, 1-p-chlorophenyl or 1-p-ethoxycarbonylphenyl derivatives or their 1-alkyl-3-aryl derivatives, z. B. the 1-ethyl-3-phenyl- or 1-n-heptyl-3-phenyl derivatives,

one optionally by alkyl, carboxyalkyl, Sulfoalkyl or aryl groups substituted rhodanine ring of the 2-thio-2,4-thiazolidinedione series, z. B. a rhodanine, 3-alkylrhodanine ring, e.g. B. a 3-Äthylrhodanin- or 3-allyl rhodanine ring, a 3-carboxyalkyl rhodanine ring, e.g. B. one 3- (2-carboxyethyl) rhodanine or 3- (4-carboxybutyl) rhodanine ring, a 3-sulfoalkylrhodanine ring, e.g. B. a 3- (2-sulfoethyl) rhodanine, 3- (3-sulfopropyl) rhodanine or 3- (4-sulfobutyl) rhodanine ring or a 3-arylrhodanine ring, e.g. B. a 3-phenylrhodanine ring,

a 2- (3H) imidazo Jj, 2-a] pyridone ring, a 5,7-dioxo-6,7-dihydro-5-thiazolo [3,2-a] pyrimidine ring optionally substituted by an aryl group, e.g. B. one

009823/1667

5,7-nioxo-3-phenyl-6, y-dihydro'-S-thiazolojJS, 2-a] pyrimidine ring,

a 2-thio-2,4-oxazolidinedione ring optionally substituted by an alkyl group the 2-thio-2,4 (3H, 5H) oxazoldione series, e.g. B. a 3-ethyl-2-thio-2,4-oxazolidinedione, 3- (2-sulfoethyl) -2-thio-2,4-oxazolidinedione-, 3- (4-sulfobutyl) -2-thio-2, 4-oxazolidinedione- or 3- (3-carboxypropyl) -2-thio-2,4-oxazolidinedione ring, a thianaphthene ring, e.g. B. a 3- (2H) -thianaphthenone ring,

a 2-thio-2,5-thiazolidinedione ring optionally substituted by an alkyl group the 2-thio-2,5 (3H, 4H) -thiazoldione series, e.g. B. a 3-ethyl-2-thio-2,5-thiazolidinedione ring,

a 2,4-thiazolidinedione ring optionally substituted by an alkyl or aryl group, z. B. a 2,4-thiazolidinedione, 3-ethyl-2,4-thiazolidinedione-, 3-phenyl-2,4-thiazolidinedione- or 3-o ^ -naphthyl-2, 4-thiazolidinedione ring,

a 4-thiazolidinone ring optionally substituted by an alkyl or aryl group, z. B, a 4-thiazolidinone, 3-ethyl-4-thiazolidinone, 3-phenyl-4-thiazolidinone or S-oC-naphthyl-i-thiazolidinone ring,

a thiazolinone ring optionally substituted by mercapto or amino groups the 2-thiazolin ~ 4-one series, e.g. B- ". of a 2-ethylmercapto-2-thiazolin-4 * "On-,

009823 / 1S67

Z-Alkylphenylamino-Z-thiazolin - ^ - on- or 2-diphenylamino-2-thiazolin-4-one ring, a 2-imino-4-oxazolidinone (pseudohydantoin) ring,

a 2,4-imidazolidinedione (hydantoin) ring optionally substituted by alkyl and / or aryl groups, z. B. a 2,4-imidazolidinedione, 3-ethy1-2,4-imidazolidinedione, 3-phenyl-2,4-imidazolidinedione, 3-o <'- naphthyl-2,4-imidazolidinedione, 1,3-diethyl-2,4-imidazolidinedione, 1-ethyl-3-phenyl-2,4-imidazolidinedione-, 1-ethyl-3-o ^ -naphthyl-2,4-imidazolidinedione- or 1,3-diphenyl-2,4-imidazolidinedione ring, a 2-thio-2,4-imidazolidinedione (a 2-thiohydantoin) ring, e.g. B. a 2-thio-2,4-imidazolidinedione, 3-Ethy1-2-thio-2,4-imidazolidinedione-, 3- (4-sulfobutyl) -2-thio-2,4-imidazolidinedione-, 3- (2-carboxyethyl) -2-thio-2,4-imidazolidinedione-, 3-phenyl-2-thio-2,4- imidazolidinedione, 3-o (-Naphthyl-2-thio-2,4-imidazolidinedione-, 1,3-diethyl-2-thio-2,4-imidazolidinedione-, 1-ethyl-3-phenyl-2-thio-2,4-imidazolidinedione-, 1-ethyl-3-c ^ -naphthyl-2-thio-2,4-imidazolidinedione- or 1,3-diphenyl-2-thio-2,4-imidazolidinedione ring, one optionally through an alkyl mercapto group substituted 2-imidazolin-5-one ring, z. B. a 2-propylmercapto-2-imidazolin-5-one ring,

00 982 3/166 7

especially to complete a 5-membered heterocyclic ring, which consists of three carbon atoms, one nitrogen atom and one nitrogen, oxygen or sulfur atom,

wherein at least one of the substituents Z- and Z. or Zr and QJ is substituted by a nitro group.

The seeds used for the preparation of the silver halide-free photographic material of the invention for the physical developments are already known; these are often dispersed particles that act as development centers serve for physical development. The term "seeds for physical development" as used herein denotes those substances that act as active centers for the formation of metal ions, for example metal complexes, ζ. Β. Silver complexes.

In practical use of the silver halide-free photographic Recording material of the invention apparently destroys the electron-accepting organic dye in the photosensitive Layer the ability of the developmental nuclei to promote physical development, especially in those parts of the world Recording material in which the dye with actinic Light has been irradiated.

In the silver halide-free photographic material According to the invention, all known seeds can be used for physical development. Forming such development nuclei Agents can be composed of particles of any of the heavy metals, e.g. B. gold, palladium, platinum or silver, from colloidal sulfides or selenides of the metals of groups Ib, lib, IVb and VIII des Periodic Table of the Elements, e.g. B. zinc, cadmium or

009823/1 667

Nickel sulfides or selenides exist. Particularly good results are made with titanium particles, e.g. B. in the form of titanium dioxide, palladium particles and silver particles, e.g. B. Particles made of Carey Lea silver.

The physical development nuclei preferably have an average particle size of up to about 0.5, especially from about 0.001 to 0.25 microns. The seeds for physical development can be used to produce the silver halide-free photographic recording material of the invention in extremely thin layers on the support applied, with concentrations of about 10 "mol" *

2 of the seeds for physical development per cm of substrate excellent results can be achieved. But it can also be concentrations within the range of about 5.4 · 10 to

-2 -5

1.1x10 mg, preferably from about 2.1x10 to about 5.4

-4 2

10 mg of germs for physical development per cm of substrate be used.

As the electron-accepting organic dye in the light-sensitive layer of the photographic material of the invention, e.g. B. a desensitizing nucleus containing cyanine, merocyanine or benzylidene dyes or desensitizing dyes, such as. B. Pyrylium, Thiapyrylium or Selenapyrylium dyes can be used. These dyes desensitize when incorporated into a gelatin silver bromoiodide negative test emulsion in which the silver halide consists of 99.35 mols of bromide and 0.65 mols of iodide, in a concentration of 0.2 millimoles of dye per mole of silver halide one produced from this emulsion by application to a layer support and exposed to light with a wavelength of 365 _{nm by means of a graduated gray wedge in a sensitometer (for measuring I> max} ) for three minutes

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1356667

20 ° C in a developer with the following composition:

Developer A
N-methyl-p-aminophenol sulfate 2.0 g

Dehydrated sodium sulfite 90.0 g

Hydroquinone 8.0g

Sodium carbonate monohydrate 52.5 g

Potassium bromide 5.0 g

Water ad 1.0 liter

developed and then fixed, washed and dried photographic recording material by more than 0.4 x log E. The silver bromoiodide negative test emulsion used was made as follows:

In a temperature controlled vessel, a solution of the following was added Composition filled:

(a) Potassium bromide 165 g potassium iodide 5 g gelatin 65 g Water 1700 ecm

A filtered solution of the following composition was introduced into another vessel:

(b) silver nitrate 200 g water 2000 ecm

Solution (a) was kept at 54 ° C during precipitation and ripening, while solution (b) was placed in a separatory funnel at a temperature of 54 ° C. The silver nitrate solution ran from the separating funnel through a measuring nozzle into the vessel containing the solutionCa), its contents

009823/1667

with the help of a mechanical stirrer during the precipitation and ripening and later kept in constant motion during post-processing. The precipitation was within a Period of JO minutes.

As already mentioned above, they desensitize for production of the photographic material of the invention were used Dyes are the usual negative emulsions containing silver halide, which are themselves sensitive to blue. This sensitivity is reduced by the above-mentioned dyes. In addition, these dyes do not impart such emulsions useful spectral sensitization. It was therefore completely surprising when it was found that photographic recording materials could be used therewith spectrally sensitized with a photosensitive layer containing seeds for photographic development can be.

Dyes useful in making the photographic material of the invention are electron accepting Dyes which have an anodic polarographic half-wave potential and a cathodic polarographic half-wave potential which result in a positive sum in the algebraic addition. The polarographic measurements were carried out as follows:

The cathodic polarographic half-wave values for the electrochemical reduction of the dye under investigation were measured using polarographic voltage regulation methods against an aqueous silver / silver chloride reference electrode. A 10 molar methanolic solution of the dye under investigation was prepared, the solvent being 100 % methanol if the dye was soluble therein . In some cases, however, had to produce the 1O ^-

009823/166 7

molar dye solution mixtures of methanol and another solvent, e.g. B. acetone can be used. the Test solution contained 0.1 mol of lithium chloride as the auxiliary electrolyte served. There were only the highest positive values (or the lowest negative values) of the half-wave potential considered; they are referred to below as E values.

The electropositive (anodic) half-wave values given in volts for the electrochemical oxidation of the dyes on a pyrolyzed graphite electrode were measured against an aqueous silver / silver chloride reference electrode and by control voltage voltammetry using solutions that matched the for determination the solutions used for cathodic polarographic values were identical. Only the highest negative value (the lowest positive value) of the observed half-wave potential was taken into account; this is referred to below as E_. The reference electrode (aqueous silver / silver chloride) was kept at a temperature of 20 ° C. for both measurements. The signs correspond to the international recommendation of the Stockholm Convention of 1953 (IUPAC). The well-known basic principles for polarographic measurements were applied,> Eq. Kolthoff and Lingane, "Polarography", 2nd Edition, Interscience Publishers, New York (1952). The principles of voltage-controlled electrochemical measuring devices, which allow very precise measurements in solvents with low conductivity, are by Kelly, Jones and Fisher in Anal. Chem., 3}., 1475 (1959). The theory of deflection voltammetry, such as that used to measure anode values, is described in Delahay's publications, New Instrumental Methods

009823/16 67

in Electrochemistry "Interscience Publishers, New York (1954) and by Nicholson and Shain, Anal. Chem., J36_, 706 (1964). Further details on the usability and properties of the pyrolyzed graphite electrode are from Publication of Chuang, Fried and Elving in Anal. Chem., 36, (1964) can be found. It should also be noted that to those in the photographic recording materials of Spectral sensitizing dyes which can be used in the invention also include those dyes which have oxidizable ions, e.g. B. Iodide ions. For example, many iodide salts ™ of dyes are very suitable. The polarographic ones described above However, measurements cannot be made in the presence of oxidizable ions. For this reason such Dyes before carrying out polarographic measurements in dyes with a chloride or p-toluenesulfonate anion transferred, which does not interfere with precise polarographic measurements. However, it should be expressly pointed out again, that also dyes with oxidizable ions are used in the manufacture of the photographic recording materials of the invention can be.

As already mentioned above, the invention is used for spectral sensitivity bilization of photographic recording materials with light-sensitive, Coatings or layers containing germs for photographic development with certain cyanine, Merocyanine, benzylidene and pyrylium dyes, also known as Electron acceptors act. The term "cyanine dye" used here is to be understood in its broadest sense; it includes z. B. simple cyanines, carbocyanines, dicarbocyanines and tricarbocyanines, which contain a desensitizing core. It also includes symmetrical and asymmetrical cyanine dyes as well as those dyes which are linked by a methine chain are substituted. This also includes the implementation products

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V 195666?

of bromine with certain simple cyanine sensitizing dyes. The cyanine dyes which can be used according to the invention contain an amidinium ion as a chromophoric system, see Mees and James, "The Theory of the Photographic Process", MacMillan Company (1966), 201.

The term "merocyanine dye" used here is also understood in its broadest sense and includes dyes, which are characterized by the chromophoric amide system, See Mees and James, ibid.V "pp. 201 and 218. ™

As used herein, the term "pyrylium dye" generally includes pyrylium salts, thiapyrylium salts and selenapyrylium salts.

The term "desensitizing nucleus" as used herein means those nuclei which, after conversion into a "symmetrical cyanine dye and addition to a silver chlorobromide gelatin emulsion, the 4Ö MoI-I chloride and 60 Mol-'P /

- Ί Β γ

Bromide contains, in a concentration of about 0.01 to 0 "? 2 -g dye per mole of silver, after the sensitometric exposure and three-minute development at 20 ° C. of a photographic recording material produced therefrom in the developer A given above, a reduction in the blue sensitivity cause of the examined recording material of at least 80%. Among desensitizing nuclei such are preferably to be understood, 'the .hervorrufen a practically complete desensitization of the inspected photographic material to blue light, after conversion into a symmetrical carbocyanine dye at the above described test "Here, the term "Practically complete desensitization" means that the sensitivity to blue is at least

009823/1667

- 22 -

90 \, preferably 95%, decreases. Particularly effective desensitizing nuclei are the 5- to 6-membered heterocyclic rings which are customary for cyanine dyes and contain a nitrogen atom with a nitro group as a substituent, the imidazo [4,5-bJ quinoxaline rings and those substituted in the 2-position by an aromatic group Indole rings. Other desensitizing nuclei are the aryl rings substituted by a nitro group which are customary for benzylidene dyes.

A preferred class of dyes used in the preparation of the photographic material of the invention comprises the cyanine and merocyanine dyes which contain a desensitizing imidazo [4,5-b-quinoxaline ring. Particularly suitable cyanine dye salts of this class are those in which both rings are linked to one another via a methine group, one ring being an imidazo [4,5-b] quinoxaline ring, the methine group attaching to its carbon atom in the 2-position, and a second ring completes the cyanine dye. The second ring of these dyes preferably contains a nitrogen atom as a hetero atom and the methine group is part of a polyene chain which contains an equal number of alternating single and double bonds, one terminal carbon atom of the polyene chain being the 2-carbon atom of an imidazo jjl, 5-bJ is quinoxaline ring and the other terminal carbon atom of the polyene chain belongs to the second ring and is linked to a nitrogen heteroatom. The second ring in these dyes is preferably also a desensitizing nucleus. The merocyanine dyes which can also be used for the production of the photographic recording material of the invention consist of two rings which are linked to one another via an acyclic methine group which forms part of a

009823/1667

Polychain with an equal number of alternating single and represents double bonds, one terminal atom of the polyene chain being the 2-carbon atom of an imidazo [4,5-b] quinoxaline ring and the other terminal carbon atom of the polyene chain to the heterocycle of the second ring and with an extra-cyclic carbonyl oxygen atom is linked.

For the production of the photographic recording material of the invention are also cyanine dyes are suitable, which consist of two imidazo [4,5-b] quinoxaline rings which have a Polyenkette are linked to one another with an equal number of alternating single and double bonds, the terminal carbon atoms of the polyene chain in each case Represent 2 carbon atoms of the imidazo j * 4,5-b] quinoxaline rings. The polyene chain of these dyes preferably contains five carbon atoms.

The dyes of the general formulas I to III given above which have an imidazo [4,5-b] quinoxaline ring are particularly preferred exhibit.

The dyes containing an imidazoj_4,5-bj quinoxalinium salt can be made from intermediates of the following general formula:

009823/166 7

wherein R, R- and X have the meanings given above and R2 is one optionally substituted by an aryl group Alkyl radical with 1 to 4 carbon atoms, e.g. B. a methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, benzyl or Mean phenylethyl radical.

These dyes are generally produced upon heating a mixture of a quaternary salt of the above Formula IV and the appropriate intermediate. The reaction mixtures are expediently in one for the Dye synthesis used suitable solvents, e.g. B. ethanol, propanol, dioxane, pyridine or quinoline, to temperatures heated to the reflux temperature of the mixture. The reaction is preferably carried out in the presence of a basic condensing agent, for example in the presence of pyridine or a tertiary amine, e.g. B. trimethylamine, triethylamine, Tri-n-propylamine, tri-n-butylamine, N-methylpiperidine, N-ethylpiperidine, Ν, Ν-dimethylaniline or N, N-diethylaniline.

The symmetrical cyanine dyes of the formula I given above are prepared by adding a mixture of a compound of the formula IV (in which R £ is a methyl radical) with, for example Diethoxymethyl acetate (with formation of carbocyanine), Trimethoxypropene (with formation of dicarbocyanine) or 1-anilino-5-phenylimino-1,3-pentadiene hydrochloride (with formation of tricarbocyanine (preferably in a solvent and, if desired, in the presence of one of the above-mentioned basic Condensing agent · heated.

The unsymmetrical cyanine dyes given above

0098 2 3/166

Formula II are prepared by adding a mixture of a compound of the formula IV (in which R, denotes a methyl radical) heated with a compound of the following general formula:

COR,

where R ₃ »L» X and Z have the meanings given above, g and q each have 1 or 2, R ^ an aryl radical with 6-7 carbon atoms optionally substituted by an alkyl group, Z. B, a phenyl or p-tolyl radical, and R- is an optionally substituted alkyl group having 1-12 carbon atoms.

The reaction is preferably carried out in a suitable solvent and in the presence of a basic condensing _agent

The mercyanine dyes of the formula III given above are produced »by m ^ n a mixture of a compound of the formula IV (in which R2 means a methyl radical) with a compound de? rims general formula heated!

in which Q has the meaning given above and W is a radical of the following formula:

in which ρ 1 or 2 and L, R _ß and R, have the meanings given above.

Those dyes which contain an imidazo £ 4,5-b] quinoxalinium ring are particularly suitable for the production of the photographic recording material of the invention. B. 1,1 ', - 3,3'-Tetraethylimidazo [4,5-b] quinoxaline carbocyanine chloride, 1, 1 ·, 3,3' -Tetraäthylimidazo \ a, 5-b] quinoxalinodicarbocyanine chloride, 1,3,3'- Triethylimidazo pt, 5-bj quinoxalinooxacarbocyanine iodide, 1,3,3'-triethylimidazo [4,5-b] quinoxalinothiacarbocyanine iodide, 1, 3-diethyl-1 ·, 3 ', 3'-trimethylimidazo [4,5-b] quinoxalinoindocarbocyanine iodide, 1,3-diethyl-3 ^! -methylimidazQ Γ4,5-bl quinoxalino-thiazolinocarbocyaninjodide; 1,1 ', 3-triethylimidazo-UjS-b ^ quinoxalino-Z'-carbocyanin iodide, 5- Γ (1, 3-diethylimi.dazoj £, 5-b] quinoxalin-2-ylidene) -äthylidenj -3-ethylrhodanine, 5 - [(1 _f 3-diethylimidazo | 4,5-b] quinoxalin-2-ylidene) ethylidene) -1, 3-diethyl-2-thiobarbituric acid, 1.1 * _l 3 _l 3'-tetra (2-hydroxyethyl ) -imidazo £ 4,5-bJ quinoxalinocarbocyanine iodide, 1,3-di (2-hydroxyethyl) -1 ·, 3 ', 3'-trimethylimidazP | j _? 5-b] quinoxalinoindocarboeyaninjodid, 1,1 ', S ^' - Tetraallylimidazo [4,5-bJ quinoxalinocarbo cyanine-p_-toluenesulfonat, 1, S ^ piallyp quinoxalinooxaearbocyaninjpdiiii 1, S-

1 ', 3 », 3'-

trimethylimidazo j_4,5-bj quinoxalinoindocarbocyanine iodide, 1,3-diallyl-3'-ethyl-4 ', 5'-benzoimidazo [4,5-b] quinoxalinothiacarbocyanine-p-toluenesulfonate, 1,3-diallyl-1'-ethylimidazo - | jl, 5-b] quinoxalino ^ '- carbocyanine iodide, 5- [(1, 3-diallylimidazo [4,5-b] quinoxaline-2 (3H) -ylidene) ethylidene] -3-ethylrhodanine, 1,1 ', 3,3'-Tetraphenylimidazo [4,5-b] quinoxalinocarbocyanine- ε-toluenesulfonate, 3'-ethyl-1,3-diphenylimidazo [4,5-bJ quinoxalinothiacyanine iodide, 3' -ethyl-1,3-diphenylimidazo [4, 5-bJ quinoxalinooxacarbocyanine iodide, 3'-ethyl-1,3-diphenylimidazo- [4,5-bJ quinoxalinothiacarbocyanine iodide, 1 ', 3', 3'-trimethyl-1,3-diphenylimidazo [4,5-b] quinoxalinoindocarbocyanine iodide, 1 * -] ethyl-1,3-diphenylimidazo [4,5-b] quinoxalino-2'-carbocyanine iodide, 5- Γ (1,3-diphenylimidazo [4,5-b] quinoxaline-2 (3H) - ylidene) ethylidene] -3-ethylrhodanine, 6-chloro-2- [(i-methyl-2-phenyl-3-indolylj -1,3-diphenylimidazo [4,5-bJ quinoxalinium-p-toluenesulfonate, 6.6 '-Dinitro-1,1', 3,3'-tetraphenylimidazo [4,5-b] quin oxalino-p_-toluenesulfonate and 9 - {^ 2- (1-methyl-2-phenyl-3-indolyl) vinyl3 -8,10-diphenyl-8H-benzo jf / imidazo [4,5-b] quinoxalinium bromide.

A more detailed description of the manufacturing process Belgian patents 660 253, 695 368 and 660 253 contain the above-mentioned classes of dyes,

In the dyes described above, the imidazo J ~ 4,5-bjquinoxaline ring for example by halogen atoms, e.g. B. 1 or 2 chlorine or bromine atoms, a nitro group or by one be substituted on fused ring.

3- / 466

Another class of dyes used in the manufacture of the photographic material of the invention The cyanine dyes can be used for the spectral sensitization of the organic photoconductor layer which have an indole ring which is substituted in the 2-position by an aromatic group and which has the 3-carbon atom of the indole ring is linked to the methine chain of the cyanine dye. Dyes of this type are from the U.S. Patent 2,930,694, British Patent

and
970 601 / Belgian patent 695 365

known.

Dyes of this type include the trimethine cyanine dyes with two in the 2-position through an aromatic group substituted indole rings, each via its 3-carbon atom are linked to the respective terminal carbon atoms of the trimethine chain. An example of one The dye is bis (1-methyl-2-phenyl-indole-3) trimethine cyanine bromide. The unsymmetrical dyes, the first ring of which is a substituted in the 2-position by an aromatic group Indole ring and its second ring is a heterocyclic ring to complete the dye, both rings linked by a methine group are also suitable. The indole ring of these dyes is about that 3-carbon atom of the indole ring linked to the methine chain of the dye. The second ring of these dyes is preferably a desensitizing core. For use with Particularly useful in the preparation of the photographic material of the invention are dyes of the following general formula

VII. D-L-L-Y

0098 23/1667

in the D an indole ring which is substituted in the 2-position by an aromatic group and which has the 3-carbon atom of the Indole ring is linked to the methine chain, L is a methine group and Y is a desensitizing nucleus.

A preferred desensitizing nucleus is, for example, an imidazo j ~ 4,5-bJ quinoxaline ring, which has its 2-carbon atom associated with the methine group.

Spectral sensitizing dyes of this type can be prepared by known methods. A convenient method is to reflux a carboxaldehyde derivative of an aromatic group substituted indole in a suitable solvent with an alkyl group substituted quaternary salt of a compound containing the desired desensitizing nucleus. For example, an indole-3-carboxaldehyde substituted in the 2-position by an aromatic group can be used in z. B. acetic anhydride as a solvent with a 2-alkylimidazoj ^ 4,5-b] quinoxalinium salt or a 2-alkylene-pyrrolo jjJ »3-bj pyridine compound can be heated under reflux to form the desired dye. The substituent at the 2-position of the indole ring can be any suitable aromatic group, e.g. B. a phenyl ring, which in turn may contain various substituents, for example alkyl radicals having 1 to 4 carbon atoms, e.g. B. a methyl, ethyl, propyl or butyl radical, alkoxy radicals with 1 - 4 carbon atoms, z. B. methoxy, ethoxy, propoxy or butoxy, halogen atoms, e.g. B. bromine, fluorine or chlorine atoms, and aryl radicals, e.g. B «is a naphthyl or phenyl radical. Valuable dyes of this class include those of the general formula VIII given above. Examples of particularly preferred representatives of these dyes

009823/1667

Material class are:

1,3-Diethyl-1'-methyl-2'-phenylimidazo (4,5-b] quinoxalino-3
indolocarbocyanine iodide

6-chloro-i'-methyl-1,2 ', 3-triphenylimidazo [4,5-b] quinoxalino- 3' -indolocarbocyanine p-toluenesulfonate ___ ^

CH-CH-C

Ph

Cl

Ph

P-CH ₃ -C ₆ H ₄ -SOj

1,1 ·, 3 ', 3 ^L -Tetramethyl-2-phenyl-3-indolopyrrolo [2,3-b] pyrido carbocyanine iodide

Me.

CH-CH-C 'IJ

ι ^h I I Me

Me

1,1 ', 3,3-tetramethyl-5-nitro-2'-phenylindo-3 ¹ -indolocarbocyanine · iodide

Me

3'-Ethyl-1-methy1-2-pheny1-6'-nitro-3-indolothiacarbocyanine iodide

CH-CH-C

5'-chloro-1,3'-dimethyl-Z-phenyl-6'-nitro-S-indolothiacarbo cyanine-p-toluenesulfonate

CH-CH-C

Me

Cl

009823/1667

ORIGINAL INSPECTS)

Another class of in the photographic recording material The dyes which can be used according to the invention are the cyanine and merocyanine dyes, in which at least one ring, preferably two rings, a desensitizing substituent, z. B. contain a nitro group. These cyanine salt ζ dyes of the formula IX given above consist of two 5- to 6-membered ones customary for cyanine dyes, one nitrogen atom containing heterocyclic rings which have a methine group to de «! each 2-carbon atom linked together are, with at least one of these rings through a nitro group is substituted.

The MiiTCCTsaiiirarbstoffe the above formula X consist of _two} übet a methine interconnected S-membered to 6-rigan "a Stickstoffatoiu containing heterocyclic RiSgSK ₉ in which the first ring is a Merocyaiiir dyes for" usual Xetomethylenring is "the via one of its

tcffeieffic is linked to the methine group; the second ring is the usual ring to complete the cyanine dye with a nitro group as a substituent which is linked to the methine group via one of its carbon atoms. A typical representative of this class of dyes is the Z _f Z " ^Ja - diethyl-öj ^ -dinitrüthiacarbocyaninsaiz.

An x iZ * T} - Eiass © dyes, aia 2UR manufacture · d; a photograpkiscfeeii recording material -: ier T: ^ ^f:; .-, you :: -ι. vsrr ^^ dst be k "im © s- represent the cyanine color? tcffe air, dis e-ΓΚ ^ 'ΐ?

in the ring oclisr ia - chain exercises a triflui-ruiethyl ^ rüpps snthaiiv ^ Bo öiü \ 1 ^] : j ^ dyes of this Kiassü £> xtia solt-he üöi 'cfee ..-. a: i ^

Ui '.VJ

ze * ter ^ .z ^ it®? of this class are ^ cl.jhe _f ii: -J.sneii iiu. Ivas

009 8 23/1667

hydrogen atom in the methine chain of the cyanine dye a trifluoromethyl group is replaced. The cyanine dye can be a simple cyanine, a dicarbocyanine or a tricarbocyanine. Those in the meso position are particularly suitable carbocyanines substituted by a trifluoromethyl group. The dyes in this class preferably contain one for example, nucleus derived from benzimidazole, benzoxazole, benzothiazole, benzoselenazole or indole.

Also useful are the benzylidene dyes of the general formula IX given above, in which a ring represents Merocyanine dyes is a common ketomethylene ring which has a methine group with one substituted by a nitro group Aryl ring is linked.

Another valuable class of dyes used in manufacture of the photographic material of the invention can be used, represent those from the Belgian Patent specification 695 354 and the Belgian patent specification 695 140-

known, electron accepting cyanine dyes that contain at least one methine group in which the hydrogen atom is replaced by a halogen atom, e.g. B. a chlorine, bromine or iodine atom is replaced. The best results are achieved with the monomethine cyanine dyes, for example the reaction product of bromine with a 1,1'-diethyl-Z.Z'-cyanine dye salt or a 1 ', 3-diethylthia-2'-cyanine dye salt.

Another class of dyes which can be used for the production of the photographic recording material of the invention are the pyrylium, thiapyrylium and selenapyrylium compounds, in particular those of the above-mentioned general

003823/1667

mean formula XII. The dyes of the above formula XII in which the substituents R ¹ , R "and R"'each represent an optionally substituted aryl group have proven to be particularly effective. They are therefore particularly preferred.

Typical representatives of these dyes of the formula XII given above are, for. B. 2,6-di-p-methoxyphenyl-4-phenylpyrylium fluoroborate, 2,6-bis (£ -anisyl) -4- (£ -n-amyloxyphenyl) pyrylium-

™ perchlorate, 2- (p_-n-amyloxyphenyl) 4,6-diphenylpyrylium fluoroborate,

2- (4-phenylbutadienyl) -4,6-diphenylpyrylium perchlorate, 6- (4-phenylbutadienyl) -2,4-diphenylthiapyrylium perchlorate, 2,6-bis- (£ -ethylphenyl) -4- (£ -anisyl) pyrylium perchlorate, 2,6-bis- (p-ethylphenyl) -4- (£ -anisyl) thiapyrylium perchlorate, 2,6-Diphenyl-4- (£ -anisyl) -thiapyryliumchlorid, 2,6-Bis- (p-ethylphenyl) 4- (£ -n-amyloxyphenyl) pyrylium fluoroborate, 2,6-bis- (£ -anisyl) -4- (p-n-amyloxyphenyl) thiapyrylium perchlorate, 2,4-diphenyl-6-styrylpyrylium perchlorate, 2,6-bis (£ -anisyl) -4-phenylthiapyrylium fluoroborate, 2,6-bis (£ -ethylphenyl) -4- (£ -n-amyloxyphenyl) -pyrylium perchlorate, 2,4,6-tris (£ -anisyl) pyrylium fluoroborate, 2-j] p _- (ß-hydroxyethoxy) phenyi] -4,6-diphenylpyrylium perchlorate,

L 2,4,6-triphenylselenapyrylium fluoroborate, 2,4,6-tris- (£ -anisyl) -

thiapyrylium £ -toluenesulfonate, 2,4,6-tris (£ -anisyl) thiapyrylium sulfoacetate, 2,6-bis (£ -chloromethoxycarbonylphenyl) -4-phenylpyrylium fluoroborate, 2,6-bis- (£ -ethylphenyl) -4 - (£ -n-amyloxyphenyl) thiapyrylium fluoroborate, 2,4,6-tris (p-anisyl) pyrylium perchlorate, 2,4,6-tris- (p-anisyl) thiapyrylium perchlorate, 2,6-diphenylr4- (£ -acetaminophenyl) pyrylium perchlorate, 2- [j> ~ (β-hydroxyethoxy) phenyl] -4-phenyl-6- (ε-anisyl) pyryliuraperchlorate, ■; 2- (2-naphthyl) -4,6-diphenylthiapyrylium perchlorate, 2,6-bis (£ -tolyl) -4- (£ -anisyl) pyrylium fluoroborate, 2,4,6-tris- (£ -anisyl) -thiapyrylium trifluoroacetate , 2-methyl-4,6-bi3- (p-anisyl) pyrylium7 sulfoacetate and 2,6-bis- (£ - * ni »yl) -4-C6-n-amyloxypheny1thi * - pyrylium fluoroborate.

009823/1667

The organic, electron-accepting dyes can be adsorbed onto the nuclei for physical development in a known manner. For example, a dispersion of the nuclei for physical development can be produced in a suitable hydrophilic colloid, the organic dye can then be mixed with it, and a suitable carrier can be coated with the resulting mass and dried. If desired, a dispersion of the germs for physical development can be dispersed in a hydrophilic colloid and applied to a suitable layer support: this can then be dipped into a suitable solution of the dye or a solution of the dye can be dabbed, brushed or sprayed onto the coated support . If the seeds for physical development do not contain any binder

Layers in vacuum on the Sc is it expedient dep_ beschic

light carriers are deposited, ιteten carrier with the. Germinate

immerse -marriage development into a suitable dye solution or the dye solution to the binder-free ski el · ΐ illite the germs for the physical development o f to tup;; for physiVaIi. he aufzubürsten or aufsusprohen _s

The term "physical developer" referred to here means substances that are a compound that provides a self-releasing metal! ng mid eir reducing agent SEtksltem "causes that the '-eci ^ ierb-nr ^ metal se a b © Sti.! iEttm point is deposited.

The physical er.tv'fckliir.g can be filled with any metal suitable for metal. Production of pictures after -, he, physi ^^ lisclii ™. Biitwicklüiigs-ifeTfaliTen particularly suitable, Ai; sCs! Ie vr-: i Silver Maiiea & ϊτ äie pliysi

009823/1667

see development but other metals are also used, which are known to be suitable for this. For the physical development, metals are mostly used, which are in the Electronegativity table to the right (below) of hydrogen, e.g. B. copper, arsenic, antimony, platinum, gold, mercury or silver.

A wide variety of physical development techniques can be used. For example, an image-wise exposed photographic recording material with the W emulsion side of a previously treated with a conventional, by adding a silver halide solvent, e.g. B. sodium thiosulfate, modified photographic developer moistened conventional photographic negative silver halide emulsion are brought into contact. After a short contact time, the two layers are separated from one another and a positive silver image is created in the unexposed areas of the layer containing the cores for physical development. The exposed areas of the layer are practically free of a silver image.

Another physical development process is that containing the cores for physical development exposed recording material is immersed in a physical developer solution consisting of a silver halide, a conventional silver halide developer and a solvent for the silver halide. After the to achieve a sufficient Density required time, usually after a few minutes, the recording material is removed, whereby a direct-positive silver image is created.

The process used to manufacture the cores for physical development

009823/166 7

winding-containing photosensitive layer used Binder is not essential because virtually any water permeable material is essential for use colloid known in silver halide photography can be used e.g. B. gelatin, carboxymethyl cellulose, corn protein, albumin, various synthetic resins, e.g. B. polyvinyl alcohol, polyvinyl pyrrolidone or acrylic resins. Although the concentration of the binder within a wide range can be varied, it has proven expedient to produce photosensitive layers in which the binder in an amount of up to about 10 wt .- t of the total Coating compound is present.

The wet thickness of the layers can range from about 0.00254 cm to about 0.0254 cm (0.001 to 0.01 inches), preferably 0.0076 to 0.0153 cm (0.03 to 0.006 inches). It can easily but thicker layers can also be applied.

Suitable supports for the production of photographic recording materials of the invention are e.g. B. such from Cellulose acetate, cellulose acetate propionate, cellulose nitrate, polyethylene, polypropylene, polystyrene, polyvinyl chloride, polyalkylene terephthalate, paper, metal and glass.

In physical development by diffusion transfer, any known silver halide emulsion can be in contact with the light-sensitive, exposed silver-dye complex emulsion be used, e.g. B. a silver chlorobromide, silver chloroiodide, silver chlorobromide, silver bromide or silver bromoiodide emulsion.

The usual developers,

009823/1667

ζ. B. N-monomethyl-p-aminophenol sulfate, dihydroxybenzenes Hydroquinone or p-phenylenediamine developers, hydroquinone compounds e.g. B. Chlorhydrochinai, dichlorohydroquinone or Bromohydroquinone; 1-phenyl-3-pyrazolidone and its derivatives and triaminophenols can be used.

Examples of the solvents used in physical development for the silver halide are alkali metal thiosulphates, ammonium / sulxate, alkali metal thiocyanate, Ammonium thiocyanate and sodium sulfite.

The following examples are intended to explain the invention in more detail. example 1

In a physical diffusion transfer developer system a direct positive silver image was generated using the following procedure:

Preparation of the photographic recording material containing seeds for photographic development:

100 ml of 5 liter gelatine were added

a) 4 ml of a 7.5% saponin solution and

b) 3 ml of a 10% formaldehyde solution

admitted. To 10 ml of this solution, 0.10 ml of a 0.10 molar silver nitrate solution added.

On a support made of a * cellulose triacetate film was the dispersion described above was applied in layers 0.0102 cm (0.004 inch) wet thick so that the dabti obtained photographic material about

009823/1667

0.0028 mg AgNO ₃ (2.6 mg / ft ² ), 0.431 mg gelatin (400 mg / ft ² ) and 0.00007 mg dye (0.065 mg / ft ² ) per cm ^{2 of} support.

The recording material was exposed for 15 seconds through a graduated gray wedge with a 100 watt tungsten lamp at a distance of 91.5 cm. The recording material was then immersed for two minutes in a solution of the dye 1,1'-diethyl-2.2 ^t -cyanine sulfate, which had previously been reacted with a bromine-pyrrolidone complex. forming a photosensitive, blue colored solution. The dyed recording material was then dried and exposed in stages perpendicular to the first exposure and developed by covering it with an unexposed fine-grain silver chlorobromide film which had previously been in a developer solution of the following composition for three seconds:

Developer B

Methylaminoethanol-sulfur dioxide 190 g

(18.9 % sulfur dioxide)

Hydroquinone 11.6 g

1-phenyl-4,4-dimethylpyrazolidone 1 g

Sodium thiosulfate · 5H ₂ O 60 g

Potassium iodide 0.42 g

Water ad 1 liter

1 * ige methanolic solution of
S-methyl-S-piperidinylmethyl ^ -
thiooxazolidine 10 ml

was immersed, brought into contact,

009823/166 7

The moist, fine-grain silver chlorobromide film was in contact with the colored and re-exposed recording material rolled out. After two minutes of contact at about 20 ° C, the two layers were separated from one another. On the second exposure, the effect of the first exposure became proportional to the intensity of the second exposure canceled.

The above-described procedure was repeated, but this time in a previous stepped gray-wedge exposure a line art was used. It turned out to be good reverse line art obtain.

When you consider the one containing the cores for photographic processing light-sensitive layer of the photographic material of the invention for four seconds Exposure with a 100 watt lamp at a distance of 91.5 cm evenly veiled and then in the blue dye solution was found to be on a second imagewise exposure following the physical diffusion transfer development process described above a high density direct positive line image was obtained. The quality of the Silver reversal image was excellent.

Preparation of the dye solution

To 40 ml of a solution of 5 x 10 g of the sensitizing dye 1,1'-diethyl-2,2'-cyanine sulfate in ethyl alcohol was added 20 ml of an aqueous solution of 2 x 10 -4 g of a commercially available bromine-pyrrolidone complex (General Aniline and Film Corporation) admitted,

009823/1667

When these two solutions were mixed, the previously red colored dye solution (absorption maximum at 540 m, u) converted into a blue colored solution (absorption maximum at 590 m, u). The blue form of the dye was photosensitive and could only be manufactured and used in a completely dark room in order to avoid immediate decomposition.

Example 2

The process described in Example 1 was repeated, but this time using the reaction product of 1 ', 3-diethylthia-2'-cyano iodide with the bromine-pyrrolidone complex as a dye solution was used. The results obtained in general corresponded to those of Example 1, for example a direct positive line image of high density and excellent quality was also obtained.

Example 3

This example illustrates the production of a direct positive silver image by generating latent metal nuclei beforehand in a layer containing titanium dioxide and subsequent incorporation of an electron acceptor, for example of a brominated dye, into the system, subsequent exposure and development in a physical developer solution. It became the following photographic material made in the light:

A dispersion of finely divided titanium dioxide in 50 ml of water was stirred with .50 ml of a 10 Ugen gelatin solution at 40.degree. 0.1 ml of a 0.1 η AgNO solution, 5 ml of water and 0.3 ml of a 10 % formaldehyde solution were added to 10 ml of this dispersion

3/1667

was added, and with it a polyethylene-coated paper in a moist layer thickness of 0.0051 cm (0.002 cm) was applied inch) coated. In the titanium dioxide formed under the action of light during the production of the recording material a latent metal seed.

The composition applied to the substrate had the following composition:

Silver (AgNO,) 0.0032 mg / cm ²

³ (3 mg / ft. ² )

Gelatin 0.162 mg / cm

(150 mg / ft. ² )

TiO- 0.324 mg / cm ²

^L (300 mg / ft. ² )

The paper coated with this mass was then immersed under the light of a red darkroom lamp in a brominated dye which was obtained by adding 98 mg of N-bromosuccinimide in 50 ml of methanol to 100 ml of 1,1'-diethyl-2,2 ^f -cyanine chloride in 50 ml of methanol. The colored light-sensitive photographic recording material was then dried in the dark, exposed for 5 to 10 seconds through a negative line image with a photo lamp and immersed directly in a physical developer solution of the following composition for two minutes at 20 ° C:

Developer C
Part A

water 800 ecm Sodium sulfite 20th G Sodium salt of isoascorbic acid 26th G Sodium carbonate monohydrate 50 G ++ wetting agents 20th ecm (1 Water ad 1 liter pH - 11.0

in H ₂ O) ♦♦ Octylphenoxy-ethoxyethyl-dimethyl-p-chlorobenzyl-ammonium chloride

009823/1667

Part B

Water sodium thiosulphate · silver chloride water 5-methylbenzotriazole

- 43 -

5 H ₂ O

+ Production of the silver chloride:

800 ecm 30 g

Mol (2 bottles)

5 10 to 960 ecm

40 ecm (1 % in diluted KOH)

1) 42.4 g of AgNO ₃ in 900 ecm of water,

2) 42.4 g of KCl in 900 ecm of water

3) Mixture of 90 ecm of solution 1) and 90 ecm of solution 2) in a 170 g bottle,

4) Let stand overnight »then pour off the liquid for use.

Each bottle contained 2.5 together made 5

10 ~ ² moles.

10 moles, i.e. H. both bottles

Before use, parts a and b above were mixed in a ratio of 1: 1.

After the development, the recording material was washed with water. A direct-positive silver image was obtained, which after 20 seconds appeared in the developer. It was clear and sharp. In the procedure described above, the titanium dioxide be replaced by zinc oxide, a corresponding direct-positive silver image generally being obtained.

Example 4

In this example the sensitizing dye was used in the mass containing the seeds for physical development was incorporated and the resulting mixture was

009823/1667

applied to a suitable substrate. The photographic material thus obtained was then exposed and developed into a positive image with a physical developer solution. All operations were carried out in Light carried out by a darkroom lamp.

150 ml of a 10% gelatine solution and 30 ml of a 1.0% silver nitrate solution were added to 15.0 g of finely divided titanium dioxide dispersed in 200 ml of water in a bath at 40 ° C. The pH was adjusted to 9.0, the temperature was increased to 55 ° C. and 6.0 ml of a 5% formaldehyde solution were added. The stirred mixture was held at 55 ° C for 16 minutes, after which the pH was lowered to 5.8. A 20 ml portion of this melt was mixed with 13 ml of the brominated dye solution described in Example 3 and the mixture was applied to polyethylene-coated paper to a thickness of 0.00506 ml / cm ² (4.7 ml / ft. ² ) applied, ^N so that the recording material obtained was 0.0017 mg of silver (1.6 mg / ft. ² ), 0.0029 mg of dye in the form of the dibromide (2.7 mg / ft. ² ) and 0.1 Contained <785 mg titanium dioxide (110 mg / ft. ² ) per cm of support.

A sample of the colored light-sensitive material prepared above was exposed to one for two minutes Slit width of 10 mm was spectrographically exposed with a monochromator and then exposed for two minutes at room temperature in the developer C given in Example 3 developed. It was found that the recording material was excellent had direct-positive spectral sensitivity.

0 0 9823/1667

Example 5

This example corresponds in general to Example 4 above, but this time the titanium dioxide is omitted became. In this example, too, all operations were carried out in the light of a red darkroom lamp.

A dispersion was prepared from 30 ml of an aqueous 1.0 L silver nitrate solution and 350 ml of an aqueous 4.3 Hgen gelatin solution in a bath at 40.degree. The melting temperature of this dispersion was increased from 40 ° C. to 55 ° C. at a rate of 1.7 ° C. per minute and then held at 55 ° C. for two minutes before the pH value increased to 4.75 and the temperature increased to 40 ° ° C. A 20 ml portion of this melt was mixed with 13 ml of the brominated dye solution described in Example 3 and the mixture was applied to polyethylene-coated paper in an amount equivalent to 0.00506 ml per cm ^{2 of} substrate (4.7 ml / ft ² ) was applied to form a recording material containing 0.0017 mg silver (1.6 mg / ft. ² ) and 0.002.9 mg of the brominated dye (2.7 mg / ft. ² ) per cm ^{2 of} support .

A sample of the photosensitive prepared as described above The recording material was spectrographed for two minutes with a slot width of 10 mm in a monochromator exposed and then developed at room temperature in developer C given in Example 3 Recording material with an excellent direct-positive

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Preserve spectral sensitivity.
Example 6

This example illustrates the use of silver nuclei produced by vapor deposition as centers for the physical Development.

Under the light of a red darkroom lamp, a sample of a recording material containing 0.00016 mg of evaporated silver (0.15 mg / ft. ² ) per cm ^{2 of} polyethylene-coated paper with a particle size of 20 Å or less was placed in immersed the brominated dye solution described in Example 3, then dehydrated and dried. The sample was exposed (in contact with a line negative) for 30 seconds to a photolamp at a distance of 30.5 cm and then developed for three minutes in the developer C given in Example 3 at room temperature. An excellent direct positive image was obtained.

Example 7

According to the process described in Example 6, a direct-positive image was obtained on a photographic recording material, the substrate of which consisted of a paper coated with polyethylene and which contained palladium vapor-deposited instead of the vapor-deposited silver. The photosensitive layer of the recording material of this example contained about 0.00016 mg palladium (0.15 mg / ft. ² ) per cm of support with an average particle diameter of about 20 Ά or less *

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Example 8

The procedure of Example 7 was repeated, but this time a recording material containing palladium nuclei was used, which was manufactured as follows:

A mass containing palladium nuclei, which had been prepared by reducing palladium chlorate with hyposulfite in a polymer of acrylic acid, acrylonitrile and vinylidene chloride in gelatin (25 % monomer in the gelatin), was applied to a support made of polyethylene-coated paper.

The photographic recording material obtained in this way was exposed for four minutes to a photolamp at a distance of 15.24 cm, then developed in developer C given in Example 3 at 20 ° C. for one minute. An excellent direct positive image was obtained. The photosensitive layer of the photographic material used in this example contained about 0.000043 mg palladium (0.04 mg / ft. ² ) per cm ^{2 of} support having an average particle diameter of about 50 Å or less.

The brominated dye solution used in Examples 4-8 above can be replaced by an appropriate amount of a solution of other dyes, for example 5-m-nitrobenzylidene rhodanine, 1,3-diethyi-1'-methyl-2'-pheny-imidazo [4 , 5-bJ quinoxolino-S'-indolocarbocyanine iodide or 3'-ethyl-1-methyl-2-phenyl-6 ^f -nitro-3-indolothiacarbocyanine iodide are replaced. The abovementioned carbocyanine dyes can of course also be used in the form of their salts, for example in the form of chloride, bromide, perchlorates or p-toluenesulphonate

0 0 9823/1667

those in the systems described in the preceding examples are also effective electron acceptors and spectral sensitizers works. The development nuclei can be combined with the electron accepting dye by

Mix either solution / both together and ^{add them to a 6} / man

Applying the layer support, or by / the development nuclei, alone applied to a substrate and then this with the dye soaks.

Example 9

In this example, a pyrylium dye of the general formula VIII was used as an electron acceptor and spectral sensitizer used to produce a Carey Lea silver £ CLS) emulsion for physical diffusion transfer development.

The colloidal silver with an average diameter of 50-70 Å was produced using a modified CLS process, v &. M. Carey Lea, Kali. Journal, VS ₁ , ¹⁸ ° O91 ³ ) ·

A gelatin emulsion was made from the above Carey Lea silver (CLS) manufactured. This was over a gelatin pad,

2 2 containing 0.512 mg gelatin (475 mg / ft.) Per cm, applied to a layer support in such a layer that the recording material obtained was 0.027 mg gel (25 mg / ft. ² ) and about 0.00043 mg silver ( 0.4 mg / ft. ² ) per cm ² .

This CLS recording material was sensitized by it was immersed for 30 seconds in a solution containing 0.1 g of the thiapyrylium dye 2,6-bis (p-methoxyphenyl) -4- (p-pentyloxyphenyl) thiapyrylium perchlorate of the following formula per liter of solution.

009823/1667

2,6-bis (p-methoxyphenyl) -4- (p-pentyloxyphenyl) thiapyrylium perchlorate

(CH ₂ ) ₄ CH _:

OCH,

ClO,

The dye was dissolved in a 1-term potassium chloride solution, wherein the solvent consisted in equal parts of water, acetone and dimethylformamide.

After immersing the CLS recording material for 30 seconds In this dye bath, it was then dried without washing exposed through a line image with a conventional photolamp for 10 seconds at a distance of 61.0 cm.

The exposed CLS recording material was immersed for one minute at 20 ° C. in the physical developer C described in Example 3; a direct positive image was obtained with physically developed silver in the unexposed areas, while the exposed areas remained relatively clear.

Of course, in the examples described above

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instead of the dyes mentioned therein, any other sensitizing dyes of the above general formulas I - III and VIII - XII are used, corresponding high quality direct positive images are generally obtained.

Although in the examples described above, the images were formed by physical development Always silver or palladium-silver images, but other metals, which are known for the physical Development are suitable to be used in the form of suitable metal salts. The metals most commonly used for this purpose include those to the right of hydrogen in the electronegativity table, e.g. B. copper, Mercury, platinum and gold. Excellent images can also be obtained with these metals.

009823/1667

Claims (8)

Claims i.) Photosensitive, direct positive silver halide free Photographic recording material, consisting of a support and a photosensitive layer with metallic Germs for physical development and optionally a binder, characterized in that the photosensitive layer has at least one electron-accepting cyanine dye adsorbed on the metallic nuclei with at least one methine group whose hydrogen atom has been replaced by a halogen atom, and / or at least contains a dye of the following general formulas: R. R.
I. I. ^L) nr ^C ^, _N I. ^R 1 R. (II.) R ₃ -N (-CH «CH) _g . _l -CL (-LL) _n _ ₁ (III.) 0 «C - C (-L-L), 009823/1667 (VIII.) LLC (-CH-CH) ₁ -NR ^ or (IX.) R ₁₀ -N (-CH * CH) _h _ _t -CL (-LL) _k . ₁ -C (-CH-CH). (X.) R ₁₂ -Ni-CH-CH) -JCLLC-CO or (XI.) Ar'-L-C-C-O R ⁿ (XII.) _R h, where mean: d and k g, h, j and ρ
L. or -1,2,3 or 4; each 1, 2 or 3; each 1 or 2; an optionally substituted methine group; 009823/1667 R * Rj * Rjt Rg »Rg R-Q, R-- and R-- independently of one another, each one optionally substituted alkyl, alkenyl or aryl radical; A is an oxygen, sulfur or selenium atom; R ¹ , R "and R"'each have an optionally substituted one Alkyl, alkoxy, alkenyl or aryl radical; Ar is an optionally substituted aryl rest; Ar ^{1 is} one substituted by a nitro group Aryl radical; X, X ₁ , X ₂ and X ₃ each represent an acid anion; Z »Zj, Z2» Zj, Z ^ and Zg each to complete a for Cyanine dyes customary, optionally substituted, 5- to 6-membered heterocyclic Ring's required number of non-metal atoms; and Q, Q ₁ and Q, each available for a Optionally substituted, 5- to 6-membered merocyanine dyes customary Ketomethylene ring required number of non-metal atoms; where at least one of the substituents Z and Z * or Z ₅ and Q- is substituted by a nitro group. 2. A photographic recording material according to claim 1 _t wherein the photosensitive layer as an electron 009823/1667 absorbing dye contains: a) a methine dye that acts as a desensitizing core an optionally substituted one customary for cyanine dyes, a nitrogen atom-containing 5- to 6-membered heterocyclic ring with a nitro group on contains a ring carbon atom, an optionally substituted imidazo £ 4,5-bjquinoxaline ring or an optionally substituted 2-arylindole ring, b) a benzylidene dye, the one for merocyanine dyes contains conventional, optionally substituted 5- to 6-membered ketomethylene ring which has a methine group is connected to an aryl radical substituted by a nitro group, c) a cyanine dye with at least one methine group, in which the hydrogen atom is replaced by a halogen atom, e.g. B. a Chlorine, bromine or iodine atom, or d) a pyrylium, thiapyryliura or selenapyrylium dye. 3. Photographic recording material according to Claims 1 and 2, characterized in that the light-sensitive layer contains heavy metal germs as metallic germs. 4. Photographic recording material according to claim 3, characterized characterized in that the photosensitive layer contains silver, titanium and / or palladium nuclei as metallic nuclei. 5. Photographic recording material according to claim 4, characterized , characterized in that the light-sensitive layer contains germs from Carey Lea silver as metallic germs., 009823/1667 195666? 6. Photographic recording material according to claim 5, characterized in that the light-sensitive layer as Electron-accepting dye containing 2,6-bis (p-methoxyphenyl) -4- (p-pentyloxyphenyl) thiapyrylium perchlorate adsorbed on the Carey Lea silver nuclei. 7. Photographic recording material according to claims 1 to 6, characterized in that the photosensitive layer contains metallic nuclei with a particle diameter of up to about 0.5 , u * ' 8. Photographic recording material according to claim 7, characterized in that the photosensitive layer contains metallic nuclei with a particle diameter of about 0.001 to about 0.25 μ * 009823/1667