DE2522778A1 - PHOTOSENSITIZED, LIGHT SENSITIVE MATERIAL - Google Patents

Description

^ ATENYAN> / VÄLTE A. GRÜNECKER

ι * λ .. ι. \: α

H. KINKELDEY W. STOCKMAIR

2522778 ^{κ Schumann}

N ^ DH. ΠΕΗ WAT -DlPU-PHVS

DH. ΠΕΗ WAT -DlPU-PHVS

P. H. JAKOB

ÖPL-ING

G. BEZOLD

DFl RKR NAT OHL.

MUNICH E. K. WEIL

OR HtR OEC INCj

LINDAU

8 MUNICH 22

MAXlMiUANSTRASSE 43

May 22, 1975 P 9214-

Fuji Photo Film Co., Ltd.

No. 210, Nakanuma, Minami Ashigara-Shi, Kanagawa, Japan

Photosensitized, light-sensitive material

The invention relates to a photosensitive material and, more particularly, to a photosensitive material comprising a complex of a tellurium halide or selenium halide and an organic base as a light-sensitive material and contains a photosensitizer.

In the known photosensitive materials, metal halides are used such as silver halides, diazo compounds, and high molecular weight photosensitive compounds as photosensitive materials used. For special purposes, combinations of polyhalogenated hydrocarbons are also used with amines of N-vinylcarbazole in photography with free radicals, in photochromic materials used among others. Photographic processes in which the above-mentioned photosensitive compounds are used in detail, for example, in the following

References Described: Silver Halide Photographic Process by CEK Mees and TH James, in The Theory of the Photographic Process, Macmillan Co., New York (1966), etc .; photographic processes employing metal halides other than silver halides, diazo compounds, high molecular weight light-sensitive compounds, or photochromic materials, by J. Kosar in Light-Sensitive Systems, John Wiley & Sons, New York (1965); and free radical photography in Photographic Science & Engineering, 5, 298; ibid 8, 91 and 95; ibid 9, 133, and in U.S. Patents 3,042,517 and 3,042,519.

Many of those used in the known photographic processes However, photosensitive materials have disadvantages, although they also have certain advantageous features exhibit. For example, silver halide light-sensitive materials are very suitable photographic materials, because they have high sensitivity. However, they have the disadvantages of being difficult and very specialized Process steps have to be carried out which sometimes take a lot of time because they are complicated Post exposure bath developments are required to form photographic images therefrom. The photosensitive Silver halide materials are also expensive because silver is used as a raw material. Photosensitive Materials for so-called diazo photography using diazo compounds generally require an alkaline solution development treatment, although they themselves are less expensive compared to the silver halide light-sensitive materials. In dry heat diazo photography where none Solution treatment is necessary, there is the difficulty that the light-sensitive material must contain an alkaline forming agent. Vesicular or vesicular photographic processes using diazo compounds

509849/0912

cannot be used to produce color images, although they can be made using the Dry development can be carried out, and they are therefore only used for the production of photographic films Suitable for projection purposes. Photographic, photosensitive Materials using high molecular weight photosensitive compounds require one Solution development, and they can be used to produce colored photographic images are not used as is the case with vesicle photography. Free radical photography gives, though generally Dry development processes are used, often many disadvantages in terms of sublimation, toxicity or stability of the raw materials used. In addition, it is generally difficult to control the formed images fix, and they are unstable in most cases.

Photosensitive materials have recently been developed which have fewer disadvantages than the known photographic, Possess photosensitive materials. For example, a photosensitive material has been developed that is commercially available under the trademark "Dry Silver" (3M Co.) and in which a metal salt of an organic acid such as Salt of behenic acid is present as an image-providing material and in which also a reducing agent and a silver halide are present as photocatalyst. One such photosensitive material can be obtained according to the methods as detailed in U.S. Patents 3,152,903; 3,152,904; and 3,457,075. Photographic, light-sensitive materials which uses a basic organic compound which has such a chemical structure that the carbon atoms in the organic compound are directly bound to chalcogen elements are disclosed in the Japanese patent application (OPI) 29438/73 (corresponding to the German Auslegeschrift 2 233 868) »Although the above-described

509849/0912

Since light-sensitive materials can very easily be dry-developed to produce colored images simply by heating them after exposure, they have various disadvantages. The former photosensitive materials are expensive because silver is used therein as a raw material for the image providing material, and the photosensitive layer in the photosensitive material is semi-transparent due to the way the crystals are dispersed therein, and therefore the material is not suitable for the projection of photographic films. With the latter photosensitive materials, it is difficult to fix the formed images; The same is true of the light-sensitive materials for free radical photography, and the covalent bonded compounds used therein, such as organic compounds to which other elements are bonded, hydrolyze and are therefore not stable. In addition, these compounds hardly show photosensitivity unless a sensitizer is used at the same time, and the kinds of these compounds that can be used are very limited. The compounds can also be synthesized only in low yield and their synthesis is difficult. In addition, photosensitive materials using these compounds must be heated to significantly higher temperatures for development after exposure.

The present invention is therefore based on the object of the disadvantages of the known photosensitive materials, used in various photographic processes were to be eliminated.

The invention relates to a photosensitive material, characterized in that it contains a carrier, which has a layer thereon which contains at least one complex

509849/0912

(A) at least one tellurium halide and / or selenium halide and

(b) at least one organic base,

wherein the layer or a layer adjacent to it, contains at least one of the following compounds as a sensitizer; a quinone compound, an aryl ketone compound, a Te tracyanoquinone dimethane, / benzene or naphthalene, substituted with one or more hydroxyl groups or Alkoxy groups with 1 to 7 carbon atoms, an arylamine compound, a diazonium salt, a metal acetylacetonate or an inorganic salt or mixtures of these compounds.

The invention thus relates to a photosensitive material which contains a support which contains a layer thereon, the at least one complex of (a) at least one tellurium halide or selenium halide and (b) at least one organic base, the layer or a layer adjacent thereto containing a photosensitizer.

Surprisingly, it has been found that complexes of tellurium halide or selenium halide and an organic base in the presence of a photosensitizer. Photosensitivity show and that a layer containing the complex and the photosensitizer, together in a suitable binder dispersed, contains, can be used to form stable images by exposure and development by heating.

The components of the photosensitive materials used in the photosensitive material of the present invention i.e., (a) tellurium halide or selenium halide and (b) organic bases are explained in more detail below.

(a) Tellurium halides or selenium halides

These halides are, for example, compounds represented by the following general formula:

509849/0912

"Vm

M is a tellurium atom or a selenium atom, X and Y are each a halogen atom such as fluorine, chlorine,

Bromine or iodine atom,

η and m each mean 0 or an integer and

η + m mean 2 or 4, depending on the valence of M.

Specific examples of these halides are Tellurdichlorid, Tellurdibromid, tellurium, tellurium _t tellurium tetrabromide, Tellurtetrajodid, Tellurdibroiaid-diiodide, Tellurdibromid dichloride, selenium tetrachloride, selenium tetrabromide, Selentetrajodid and Selendibromid-diiodide. These tellurium halides and selenium halide are described by KW Bagnall in The Chemistry of Selenium, Tellurium and Polonium, Elsevier Publishing Co. (1966), and these compounds can be used individually or in combination with one another.

(b) Organic bases

The organic bases that can be used in the present invention are aliphatic amine compounds, Aralkylamine compounds, aromatic amine compounds, Nitrogen-containing heterocyclic compounds, etc. For example, suitable organic bases are represented by the the following general formulas (I) to (XII) are shown.

(D

^A 1 -

R ₂

(II) R ₁ ^

.N-B-

R ₂ R ₄

509 8 49/0912

A ₂

^Λ 2% β

-Ν-

- Λ

(VII)

Λ-

Γ

Ii -. y.

-A.

5098 ^ 9/0 9-12

ORIGINAL INSPECTED

(VIII)

A ..

A-,

A,

jfl.-.

A-,

A.

A,

R-,

(XII)

Ar - N ₂ Cl

In the above formulas, Α. ,, A ₂ , A ₇₅ and Αλ each represent a hydrogen atom, an alkyl group (which may be straight-chain or branched-chain or cyclic and including a substituted alkyl group) or an aryl group (including a substituted aryl group. Preferred alkyl groups for A ^, A ₂ , A, and Αλ are alkyl groups with 1 to 25 carbon atoms. The alkyl groups can be substituents such as alcohol, cy, aryl, aryloxy, aminoalkyl, aminoaryl, suIfoalkyl, sulfoaryl, carboxyalkyl, carboxyaryl Suitable aryl groups for A ^, A ₂ , A ^ and Αλ are phenyl, naphthyl, anthryl and phenanthryl groups and the aryl groups can contain substituents such as alkyl, aryl, alkoxy -, aryloxy, acetyl, sulfoalkyl, sulfoaryl, haloalkyl, haloaryl, aralkyjL-nitro, aralkyl, nitro or hydroxyl groups or halogen atoms.

Specific examples of groups for A ^, A ₂ , A ^ and A ^ are methyl, ethyl, propyl, isopropyl, cyclopropyl, butyl, sec-butyl, tert-butyl, pentyl, Isopentyl, neopentyl, tert-pentyl, hexyl, isohexyl, tert-hexyl, cyclohexyl, heptyl, isoheptyl, tert-heptyl, methyl, cyclohexyl, octyl, isooctyl, tert-octyl, dimethylcyclohexyl, nonyl, tert-nonyl, decyl, tert-decyl, undecyl, tert-undecyl, dodecyl, tert-dodecyl, tridecyl, tert. -Tridecyl-, tetradecyl-, tert-tetradecyl-, pentadecyl-, sec-pentadecyl-, tert-pentadecyl-, hexadecyl-, tert-hexadecyl-, octadecyl-, sec.u. tert-octadecyl, nonadecyl, sec-nonadecyl, tert-nonadecyl, eicosyl, sec-eicosyl, tert-eicosyl, heneicosyl, sec-heneicosyl, tert-heneicosyl , Docosyl, sec-docosyl, tert-docosyl, tricosyl, sec-tricosyl, tert-tricosyl, tetracosyl, sec-tetracosyl, tert-tetracosyl, pentacosyl, sec .-Pentacosyl, tert-pentacosyl, ethoxyethyl, ethoxy

509849/0912

propyl, ethoxybutyl, ethoxypentyl, ethoxyhexyl, methoxyhexyl, Methoxyheptyl-, ethoxyheptyl-, methoxyoctyl-, Ätlioxyoctyl-, Benzyl-, Tripheriy-imethyl-, Phenyl-, Naphthyl-, ToIyI-, Xylyl, mesityl, oxyphenyl, dioxyphenyl, acetyl phenyl, Benzophenonyl, methoxyphenyl, ethoxyphenyl, nitrophenyl, Dinitrophenyl, chlorophenyl, bromophenyl, trifluoromethylphenyl, Biphenylylphenoxyphenyl-, Viny! Phenyl-, SuIfophenyl-, Naphthyl, acetonaphthyl, chloronaphthyl, dichloronaphthyl, oxynaphthyl, methylnaphthyl, methoxynaphthyl, ethoxynaphthyl, Anthryl, acetanthryl, chloranthryl, oxyanthryl, dioxyanthryl, methoxynaphthyl, phenanthryl, acetylphenanthryl, Methoxyphenanthryl, dimethoxyphenanthryl and sulfophenanthryl groups.

Of the substituents for A ₁ , Ap »A ^ and A /, particularly preferred substituents are a hydrogen atom; Alkyl groups having 2 to 25 carbon atoms, unsubstituted or substituted with an alkoxy group having 1 to 2 carbon atoms or a phenyl group; a phenyl group unsubstituted or substituted with an alkyl group having 1 to 2 carbon atoms, an alkoxy group having 1 to 2 carbon atoms, an acetyl group, a halogen atom, a trifluoromethyl group, a nitro group, a hydroxyl group, an acetophenonyl group, a phenoxy group or a phenyl group; an anthryl group; · A phenanthryl group and a naphthyl group.

B represents a divalent aliphatic hydrocarbon group (which can be straight chain or branched chain, inclusive a substituted aliphatic hydrocarbon group and additionally those that have an unsubstituted or substituted phenylene group or a double bond in of the straight chain) or an arylene group (including a substituted arylene group). Preferred Divalent aliphatic hydrocarbon groups for B are those groups containing 1 to 10 carbon atoms

509849/0 9 12

and the further substituents can contain tan such as alkoxy, aryl, aryloxy, nitro, amino, aminoaryl, arylalkyl and acetyl groups or halogenatorae and the groups in the chain thereof such as phenylene, substituted phenylene, naphthylene -, substituted naphthylene, biphenylene, substituted biphanylene, carbonyldiarylene or thiocarbonyldiarylon group. Preferred arylene groups for B are phenylene, naphthylene, anthrylene and phenanthrylene groups, and these can have substituents such as alkyl, aryl, alkoxy, aryloxy, nitro, amino, aminoaryl, arylalkylene, aralkyl, halogen , Acetyl, acetylaryl or hydroxyl groups. Specific examples of groups for B are ethylene, propylene, butylene, pentamethylene, heptamethylene, Qctamethylene, nonamethylene, decane, ethylene, dimethy! Propylene, methylbutylene, dimethylbutylene, ethylbutylene, methylpentainethylene , Damn thy lpentanisthylen-, ethylpentamethylene, diethylhexamethylene, phany! Propylene, chloropheny! Propylene, oxy'pentamethylene, oxylioptamethylene, methoxyheptamethylene, methoxyoctamethylene, »ethoxynonamethylene, chloropentamethylene, chloro-decamethyl-gnene, Benzylbutylen-, Benzylpropylen-, Tolylpeivtarnethylen-, Xylylbutylen-, xylyl-heptamathylen-, A, h '-Methylendiphenylen-, 4,4'-Phenylmethylendiphenylen-, 4, k' -Carbonyldiphenylen-, 4,4'-Aminophenylmethylendiphenylen-, oxydiphenylene -, propenylene, butenylene, pentenylene, heptene ^ / len, octenylene, Nonenylen-, decadienylene, Nonadic-nylon, octadienylene _r heptadienylene, phenylene, chlorophenylene, Aminophenylen-, Nitrophenj ^ IEn- , Methoxyphenylene, phenylphen ylene, phenoxyphenylene, aminophenylphenylene, styry! phenylene, acetylphenylene, acetylphenyIphenylene, aminophenacylphenylene, bromophenylene, oxyphenylphenylene, biphenylene, methylbiplienylene, dimethylbiphenylon, oxybetonaphthylene, methylbiphenyl, oxybetonaphthylene, Dinethylnaphthylene, oxynaphthylene, phenanthrylene, acetylphenanthrylene, methylphenanthryl and methoxyx) henanthrylene groups. Of the groups for B, particularly preferred groups are alkylene groups with 2 to 6 carbon

9/0912

substance atoms and those groups that are linked to an alkoxy group with 1 "to 2 carbon atoms, a phenyl group, an aminoxylieny group, a halogen atom, an alkyl group with

1 to 2 carbon atoms or a hydroxyl group are substituted, and those groups with a Mo no en, a Diene or a triene with a hydrocarbon group with

2 to 6 carbon atoms are interrupted, an arylene group, a 4,4'-methylenediphenylene group, a 4,4'-carbonyldiphenylene group, an oxydiphenylene group or a diphenylene group; a phenylene group; a phenylene group, the with an alkyl group with 1 to 2 carbon atoms, an alkoxy group with 1 to 2 carbon atoms, an acetyl group, a halogen atom, a trifluoromethyl group, a nitro group, a hydroxyl group, an acetophenonyl group, a phenoxy group, an amino group, an aminophenyl group, a nitrophenyl group, a halophenyl group, substituted by an oxyphenyl group or a phenyl group; a naphthylene group; an anthrylene group and a Phenanthrylene group.

Ar represents an aryl group, the aryl group including phenyl, naphthyl, anthryl and phenanthryl groups, and unsubstituted or substituted with an alkyl group, a hydroxyl group, an alkoxy group, an aryloxy group, an amino alkyl group, an amino aryl group, a cyano group, a nitro group, a carboxy group, a sulfo group or a halogen atom.

R ₁ , Rr ,, Rz and R ^ can be the same or different and each represent a hydrogen atom, an alkyl group or an aryl group. The alkyl groups can be straight-chain, branched-chain or cyclic. Preferred alkyl groups are those alkyl groups containing 1 to 6 carbon atoms, and preferred aryl groups are a phenyl group and a naphthyl group. The alkyl groups and aryl groups can be further

509849/0912

may be substituted with an alkyl group, an aminoalkyl group, an aminoaryl group, an alkoxy group, a halogen atom and the like groups. Specific examples of R ₁ , R ₂ , Rz and R ^ include methyl, ethyl, propyl, butyl, hexyl, octyl, pentyl, cyclopentyl, cyclohexyl, chloroethyl, phenyl, styryl, p-methoxyphenyl, p-chlorophenyl, p-nitrophenyl, naphthyl, p-aminophenyl, aminonaphthyl groups, a tolyl group and a hydrogen atom. Particularly preferred for R ₁ , R ₂ , R ₅ and R 1 are alkyl groups having 1 to 2 carbon atoms which can be unsubstituted or substituted by a chlorine atom or a phenyl group; Phenyl groups, which may be unsubstituted or substituted with an alkoxy group, a nitro group or an amino group, and a hydrogen atom.

The substituents A ₁ , A ₂ , A ^, A ^, Ar, B, R ₁ , R ₂ , R ^ and R ^ in the compounds represented by the above-described formulas (I) to (Xl) and (XII) are not limited to the substituents specifically described above and may contain any substitutes as long as the compound can form a complex salt with a selenium halide or tellurium halide.

Specific examples of compounds produced by the above-described Formulas (I) to (Xl) and (XII) are ethylamine, propylamine, butylamine, tert-butylamine, Pentylamine, isopentylamine, hexylamine, heptylamine, octylamine, Nonylamine, decylamine, tert-decylamine, undecylamine, dodecylamine, Tetradecylamine, pentadecylamine, octadecylamine, nonadecylamine, eicosylamine, docosylamine, tricosylamine, tetracosylamine, Pentacosylamine, ethoxyethylamine, ethoxypropylamine, ethoxybutylamine, Ethoxypentylamine, ethoxyhexylamine, methoxyhexylamine, Methoxyoctylamine, methoxyeicosylamine, methoxytricosylamine, benzylamine, tritylamine, phenethylamine, vanillylamine, Veratrylamine, poly (p-aminostyrene), N-methyleth'ylamine,

5098A9 / 0912

N-methylpropylamine, N-methylbutylamine, N-methyl-tert-butylamine, N-methylheptylamine, N-kethyloctylamine, N-methylnonylamine, N-methyl-tert-decylamine, N-methyl-octadecylamine, N-methylde-cylamine, N-methylethoxybutylamine , N-Methylmethoxjrhaxylamin, N-Methylmethoxyeicosylamin, N-MathyIbenzylainin, H-Methyltrimethylamin, N-Methylphenäthylamin, N-Methylvanillylaiain, N-MethyIveratrylaain, N-Äthylbutylarain, N-Äthylpentyldecylamin, N-Ethylpentyldecylthyl, N-Ethylpentyldecylamin N-Äthyleicοsylamin, N-Äthyldocosylamin, N-Äthyltetracosylarain, N-Äthylpentacosylarain, N-Athyläthoxyhexylarnin, N-Äthylmethoxyhexylamin, N-Äthylbenzylamin, N, N-Diraethyläthylamin, N, N-Diraethyläthylamin, N, N -la Dlmethylamin Ν-dimethyl-tert-butylamine, N, N-dimethy lheptylamine, Ν, Ν-dimethyloctylamine, N, N-dimethyinonylamine, N _? N ~ Diinethylmethoxyhexylamin, N, N-Dimethylmethoxyeico sylamin, N, N-Dimethylphenäthylamin, N, N-Dimethylvanillylarain, N, N-Dimathylveratrylamin, N, N-Diä bhylvanillylamine, N, N-Diethylpropylamin ₇ Ν, ϊ-1-Diethylbenzylamin, Ν, Ν-dimethylbenzylamine, aniline, nitroaniline, trifluoromethylaniline, toluidine, ethylaniline, chloroaniline, bromaniline, methylaminobenzoate, butylaniline, phenylaniline, naphthylaniline, dinitroaniline, naphthylamine, ac, methoxyaniline, naphthylamine, diminitroaniline, naphthylamine, methoxyaniline, naphthylamine, dimethylaniline, naphthylamine, dimethylaniline, naphthylamine, dimethylaniline, naphthylamine, dimethylaniline, naphthylamine, dimethylaniline, Ν, Ν-diethylaniline, N-methylnitroaniline, N, N-dimethylnitroaniline, Ν, Ν-diethylnitroaniline, N, N-dimethyltoluidine, Ν, Ν-dimethylacetylaniline, Ν, Ν-dimethylmethoxyaniline, Ν, N-dimethylamine, Ν, N-dimethylamine Dimethyltrifluoroaniline, pn-dodecylaniline, ethylenediamine, propylenediamine, butylenediamine, ethylethylenediamine, methyl triethylenediamine, propenylenediamine, hexadienylenediamine, phenyltriiaethylenediamine, diaminodipheriylmethane, diaminobenzophenidiphenylenediamine, phenylenediamine, phenylenediamine amine, methylphenylenediamine, ethyj-phenylenediamine, N, N, N ·, N '-tetramethyj-phenylenediamine, N, N, N ·, N · -tetramethyloxydiphenylenediamine, 4,4'-tetramethyldiaminodiphenylmethane, N, N, N', N ' -Tetramethyidiaminobenzophenon, N, N, N ¹ , N'-Tetramethylbenzidine, N, N, N ^T , N'-TetraExethyl-

5098A9 / 0912

ethylenediaain, N, IJ, N ', N' -Tetrame thy! hexamethylenediamine, Ν, Ν, Ν ', rrrTetrariistliylpropandlamine, N, N, N ¹ , N'-Tetramethylt rime thy lendianiln, pyridinediamine, methylpyridine, dimethylpyridine-, pyridincarbinol, Pyridinethanol, Pyridincarbonsäurerae thy! Ester, Pyrazine, Hetliylpyraxin, Ethylpyrazine, Pyrazinedicarbonsäure-methyl ester, Trimethylpyrazine, Pyrimidine, 5-Methylpyrimidin, Methoxypyriraidin, 5-Hydroxypyrimidin ,y, Methylpyridazin, Methoxypyridyridy , Dinitropyrrole, tetramethylpyrrole, dipyrrymethane, N-methylacetylpyrrole, indole, ß-aminoethylindole, methylindole, methoxyindole, N-methylindole, N-methylmathylindole, dimethylindole, carbazole, N-methylcarbazole, N-ethylcarbazole, N-ethylcarbazole , N-MethyInitrocarbazol, N ~ Propylcarbazol, Aninocarbazol, quinoline, Chinolinraethanol, Chlorchiiiolin, methoxyquinoline nitroquinoline, aminoquinoline Benzol-iiiazoniuinchlor.id, p-nitrobenzene-dia zoniurachlorid, methylbenzene-diazoiiiunichlorid, chlorobenzene-diazoniumchlorid, Cyaaobcnzol-uiazoniiixnchlorid, Acetylbenzoldiazoniumchlorid and ρ-N, N-Dimethylaminobenzol-diazoniumchlorid.

These organic base components can be desired to fail with each other mixed, i.e. used in combination.

The complexes used according to the invention generally contain complexes of 1 to 6 moles of an organic base with 1 mole of tellurium or gel halide and they can be synthesized, for example, as described by A. Lowy & PF Dunbrook in Journal of the American Chemical Society, 44, 614 (1922), by S. Prasad and BL Khandelwal in Journal of the Indian Chemical Society, j5§, ⁸ 37 (1961), by R. Korewa in Roczniki Cliemistiy, 37., 1565 (1963), by EA Boudreaux in Journal of the American Chemical Society, 85, 2039 (1963) and others.

509843/0 312

Examples of the synthesis of typical complexes used in of the present invention are given below. Unless otherwise stated, all are Parts, percentages, ratios, etc., expressed by weight.

Synthesis example (1)

Complex of ethylenediarain with tellurium tetrachloride:

6.75 g (0.025 mol) of tellurium tetrachloride and 50 ml of chloroform are placed in a 200 ml flask equipped with a stirrer and a dropping funnel. A solution of 1.65 g (0.0275 mol) of ethylenediamine in 50 ml of chloroform is added dropwise to this mixture with stirring. After the addition, the mixture is stirred for a further hour and then the resulting precipitate is filtered off, washed with chloroform until no complex with tellurium tetrachloride can be found in the filtrate, and then it is dried. This gives 7.8 g of compound (yield 9k%, light yellow powder, which decomposes over 150 ⁰ C).

Synthesis example (2)

Complex of p-nitrobenzene-diazonium chloride with tellurium tetrachloride: (O ₂ NC ₆ H ^ N ₂ ) ₂ -TeCl ₆ .

A solution of p-nitrobenzene-diazonium chloride in ethyl alcohol, which is obtained from p-nitroaniline in absolute ethanol accordingly produced by the Koenig process (as described in Ann., 509, 149 [1934]) becomes a suspension given from tellurium tetrachloride in ethyl alcohol in a molar ratio of 2: 1 diazonium salt to tellurium tetrachloride. The mixture is stirred for about 1 hour. The resulting precipitate is filtered off, washed with diethyl ether and then dried under reduced pressure, taking p-nitrobenzene diazonium-chlorotellur complex obtained in quantitative yield, melting point 121.degree.

509849/0912

Different mechanisms can be responsible for the effects of the sensitizers in increasing the photosensitivity of the complexes described above, which is an essential component of the photosensitive material according to the invention, apply or the reaction of the complexes in the formation of the Create and activate images. Although no commitment to one of these mechanisms should be made, for example the sensitizer absorb the energy of visible light or ultraviolet light and thus stimulate it will. The sensitizer then reacts with a hydrogen-containing compound (possibly e.g. the Binder or residual organic solvent) and is converted into a reduction product thereof. The reduction product reduces the complex, with tellurium or selenium being released and deposited from the complex and Images emerge. According to another mechanism, the sensitizer absorbs the energy of visible light or ultraviolet light and is excited and the excitation energy is transferred to the complex, and thereby the Complex excited to the excited state. The complex then decomposes, releasing tellurium or selenium and separated, and pictures emerge.

The sensitizers described above include quinone compounds, Aryl ketone compounds, tetracyanoquinone dimethane, Benzene or naphthalenes substituted with a hydroxyl group or an alkoxy group with 1 to 7 carbon atoms, Arylamine compounds, diazonium salts, metal acetylacetonates and inorganic metal salts. At least one connection selected from the above classes of compounds, is used for the production of the photosensitive material according to the invention used. Specific examples of sensitizers for each of these classes are given below.

509849/0912

(1) Quinone compounds of the following general formulas:

(XIII)

-fr ^x

(XV)

5G9B49 / O912

UVl)

- 19 -

Il

(XVIl)

i, j, k and ζ positive integers, less than 4, "mean and

D, E, F and G can be the same or different and each represents a hydrogen atom, an alkyl group- (e.g. a straight or branched chain, unsubstituted or substituted alkyl group of up to 10 and inclusive 10 carbon atoms, the substituents being one

509849/0912

ORIGINAL INSPECTED

Hydroxy group, a halogenator, an alkoxy group such as methoxy and ethoxy group and an aryl group such as phenyl and naphthyl group, etc.); an aryl group (e.g. an unsubstituted aryl group such as a phenyl group or a substituted aryl group such as a phenyl group substituted by an alkyl group having 5 or fewer carbon atoms, a halogen atom, a hydroxyl group, an alkoxy group such as a methoxy group or an ethoxy group, a cyano group, a Acetyl group, a nitro group, an amino group, etc.); a halogen atom such as F, Cl, Br and J; a hydroxyl group, an alkoxy group of up to 10 carbon atoms; a cyano group; a nitro group; an amino group; a monoalkylamino or dialkylamino group such as a methylamine * ethylamino, dirnethylamino, diethylamino group; a -SO, R ^ ~ group; a -COOR ^ group; a -NHCOR ₅ group and an R ^ -CO group, wherein R ₁ - represents a hydrogen atom or an alkyl group having up to 5 and including 5 carbon atoms.

Specific examples of the quinone compounds of the above general Formulas (XIIl) to (XVIII) are unsubstituted quinone compounds such as 9,10-phenanthrenequinone, acetnaphthenquinone, 9,10-anthraquinone, α-naphthoquinone, β-naphthoquinone, p-benzoquinone etc. and substituted quinone compounds such as 2-methyl-9,10-phenanthrenequinone, 3-chloroacetnaphthenquinone, 2-bromoanthraquinone, 1-nitroanthraquinone, 1-chloro-2-aminoanthraquinone, 2-tert-butylanthraquinone, 3-methylnaphthoquinone, 3,6-dimethyl-2-naphthoquinone, 2,5-dimethyl-1,4-naphthoquinone, 4-Benzyl-1,2-naphthoquinone, 3-chloro-1,2-naphthoquinone, Duroquinone, Trimethyl-p-benzoquinone, p-toluquinone, p-xyloquinone, Chloranil, bromanil, tetracyano-p-benzoquinone and 2,3-dicyano-p-b enzo quinone.

(2) Aryl ketones of the following general formulas:

S09849 / 0912

(XX)

(XXI)

D.

; λ

/ 7

(XXII)

(XXlII)

Ej-

609843/0912

ORIGINAL INSPECTED

(XXIV)

where i, j, k and ζ and D, E, F and G depending on the general Formulas (XIII) to (XVIII) for the above quinone compounds have the meanings described, R, an alkyl group (including a substituted alkyl group) such as described above for D, E, F and G means.

Specific examples of aryl ketones of the general formulas (XIX) to (XXIV) above are unsubstituted aryl ketone compounds such as benzophenone, phenyl naphthyl ketone, acetophenone, cn- or ß-acetone naphthone, benzil, fluorenone, etc., and substituted aryl ketone compounds such as p-acetylbenzophenone, 3- Michler Nitrobenzophenone, 4-cyanophenyl naphthyl ketone, p-diacetylbenzene, Ct ^ -tribromoacetophenone, dibenzoylmethane, 4,4'-cyclobenzil and 2,4,7-trinitrofluorenone.

(3) tetracyanoquinodiinethane.

(4) Substituted benzenes and substituted naphthalenes.

Benzenes or naphthalenes with one or more substituents are substituted which may be the same or different such as a hydroxyl group and an alkoxy group with 1 to 7 carbon atoms. Specific examples of these compounds are hydroquinone, resorcinol, catechol, pyrogallol, α-naphthol, anisole and p-methoxyphenol.

(5) arylamine compounds.

Arylamine compounds are, for example, diphenylamine triphenylamine and phenylnaphthylamine and such compounds,

509849/09 1 2

wherein the aromatic ring with one or more substituents, which can be the same or different, such as with Alkyl groups with 1 to 5 carbon atoms, haloalkyl groups with 1 to 5 carbon atoms, halogen atoms or Is substituted hydroxyl groups. Specific examples of substituted compounds are 4,4 "-chlorodiphenylamine» 4,4'-dimethyl diphenylarain and 4-hydroxydiphenylamine.

(6) diazonium salts

Diazonium salts are discussed in detail by Jaromir Kosar in Light-Sensitive Systems: Chemistry and Application of Nonsilver Halide Photographic Processes.

Typical examples of diazonium salts are as follows:

In the following formulas, X denotes an anion such as Cl, Br, SO ^ ", NO ₃ ", ClO ^ "or BF ^", to which ZnCl ₂ , CdCl ₂ or SnCl ^ can be bonded.

(1) Compounds represented by the following general formula:

Y ¹

ζ ¹ - ⁿ i

(iCXV)

Y and Z each represent an alkoxy group with 1 to 5 carbon atoms (e.g. methoxy, ethoxy, propoxy, butoxy, isopentyloxy etc.), a halogen atom (e.g. fluorine, chlorine, bromine or iodine) or an aryl group (e.g. phenyl, alkoxyphenyl, wherein the alkoxy part contains 1 to 5 carbon atoms, Halophenyl, in which the halogen atoms have the meaning described above) and

809849/0912

m. and M ₁ each represent 0 or a positive integer from 1 to 5.

Typical examples of compounds made by the above Formula (XXV) are 4-ethoxybenzenediazonium chloride and 2,5-bimethoxybenzene diazonium chloride.

(2) Compounds represented by the following general formula:

(XXVIJ

R 'and R each represent an alkyl group having 1 to 5 carbon atoms (e.g. methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, isopentyl, 2-methylbutyl, etc.), an alkoxy group with 1 to 5 carbon atoms (e.g. methoxy, ethoxy, propoxy, Butoxy, isopentyloxy, etc.), a hydroxyalkyl group with 1 to 5 carbon atoms (e.g. 2-hydroxyethyl, 3-hydroxypropyl, 4-hydroxypropyl, etc.), a benzyl group, a substituted benzyl group (e.g. substituted with alkyl groups with 1 to 5 carbon atoms such as methyl, ethyl, n-bropyl, isopropyl, n-butyl, isobutyl, isopentyl, 2-methylbutyl, etc. or halogen atoms such as fluorine, chlorine, bromine or iodine), a phenyl group, a substituted phenyl group (e.g. substituted with alkyl groups with 1 to 5 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, isopentyl, 2-methylbutyl etc. or halogen atoms such as fluorine, chlorine, bromine or iodine) or a hydrogen atom.

S09849 / 0912

2 2 1

Y and Z each represent a halogen atom (e.g. as above for Y

and Z), an alkyl group with 1 to 5 carbon

7 8

substance atoms (e.g. as described above for R and R), a Carboxyl group, an alkoxy group having 1 to 5 carbon atoms (e.g. as described above for R and R), a nitro group or an acetoxy group and

nip and n ₂ each represent 0 or a positive integer from 1 to 4.

Typical examples of compounds represented by the above formula (XXVI) are 4-N, N-dimethylaminobenzene-diazonium chloride, 3-chloro-4-N, N-dimethylaminobenzene diazonium chloride, 4-N, N-diethylaminobenzo1-diazonium chloride, 1, ö-diethoxy ^ -NjN-diethylaminobenzene-diazonium chloride, 4-N-Ethyl-N-hydroxyethylaminobenzene-diazonium chloride, 4-N, N-diethoxyaminobenzene-diazonium chloride, 4-phenylaminobenzene diazonium chloride and 4-N- (p-methoxyphenyl) aminobenzene diazonium chloride.

(3) Compounds represented by the following general formula:

(XXVII)

wherein R ⁹ denotes a -CH ₂ CH ₂ OCH ₂ CH ₂ - or -CH ₂ OCH ₂ CH ₂ group and Y, Z, m ₂ and n _{2 have} the same meanings as in formula (XXVI). Typical examples of compounds represented by the above formula (XXVII) are

509849/0912

4-morpholinobenzene-diazonium chloride, 2,5-diethoxy-4-morpholino-diazonium chloride and 4-oxazolidinobenzene diazoniuin chloride.

(4) Compounds represented by the following general formula:

(XXVIII)

10 11

R and R each have a hydrogen atom or an alkyl

7 group with 1 to 5 carbon atoms (e.g. as for R 'and

R described) mean

Y ^ and Z ^ each have an alkyl group with 1 to 5 carbon

substance atoms (e.g. as described for Y and Z), an AIk-

7 oxy group with 1 to 5 carbon atoms (e.g. as for R and

R), a carboxy group, an acetoxy group or

1 ■ 1 is an aryl group (e.g. as described for Y and Z)

nw and η- * each denote 0 or an integer from 1 to 4.

Typical examples of compounds represented by the above formula (XXVIII) include 4,5-dimethyl-2-dimethylaminobenzene-diazonium chloride.

(5) Compounds represented by the following general formula:

509849/0912

-, ι

ΊΟ 11 " ⁵ S ^ 5
where R, R »Y, Z, eu and n ^ have the same meanings

as in the oMgen formula (XXVIII) ". Typical examples of compounds represented by the above formula (XXIX) include 3-dimethylaminobenzene-diazonium chloride.

(6) Compounds represented by the following general formula i

J ₂ X ¹ (XXX)

, 12

12 '

R is an alkyl group having 1 to 5 carbon atoms

7 R

(e.g. as described for R 'and R), an alkoxy group with 1 to 5 carbon atoms (e.g. as described for R and R)

1 1

or an aryl group (e.g. as described for Y and Z) ,

13th
R ^ represents a hydrogen atom or an alkyl group

7 fi

1 to 5 carbon atoms (e.g. as described for R and R) means,

S09849 / 0912

it . r \

Y * ■ and Z each have a halogen atom (e.g. as for Y and Z), an alkyl group having 1 to 5 carbon atoms (e.g. as described for Y and Z) or an alkoxy

2 is a group with 1 to 5 carbon atoms (e.g. as described for Y and Z) and

m ^ and n ^ each represent 0 or an integer from 1 to 4.

Typical examples of compounds represented by the above formula (XXX) include 2,5-diethoxybenzoylaminobenzene-diazonium chloride and 2,5-dibutoxybenzoylaminobenzene diazonium chloride.

(7) Compounds represented by the following general formula:

ι \

an alkyl group (e.g. as described for Y ¹ and Y ²

Λ 2

written) or an aryl group (e.g. as described for Y and Y) means.

Typical examples of compounds represented by the above formula (XXXI) include 4-ethylmercapto-2,5-diethoxybenzene diazonium chloride, 4-tolylmercapto-2,5-diethoxybenzene diazonium chloride and 4-benzylmercapto-2,5-dimethoxybenzene diazonium chloride.

(7) metal acetylacetonates

Specific examples of metal acetylacetonates are molybdenum oxide acetylacetonate, zirconium acetylacetonate, titanium acetylacetonate and vanadium acetylacetonate.

509849/0912

(8) Inorganic metal salts

Specific examples of inorganic metal salts are Iron (II) chloride, iron (III) chloride, iron (II) bromide, iron (III) bromide, iron oxalate, iron ferrocyanide, iron ferricyanide, Vanadium trichloride, manganese chloride, manganese bromide, cobalt chloride, cobalt bromide, cobalt acetate, tin (II) chloride, Tin (IV) chloride, tin (II) oxalate, mercury chloride, lead iodide, nickel chloride and cerium chloride and the hydrates of that.

The photosensitive layer of the present invention can be prepared by placing both components of the complex described above and the sensitizer in a binder solution dissolves, applies it to a carrier and then dries the coating. Alternatively, the photosensitive layer be prepared by an agent containing the complex, dissolved in a solution of the binder, on a Applies carrier, then dries and then the photosensitizer, dissolved in a binder solution, applies and then the coating dries. You can also put the photosensitizer layer on a support apply and apply a complex layer on top. When the respective components are consecutively as two layers applied, as is the case with the latter two cases, can be the same in the two layers or different binders and solvents can be used. The coating can be carried out using a bar coater, a roll coating device, a "curtain" coater, a dip coater etc. take place.

Various natural or synthetic high molecular weight materials can be used as binders. Particularly preferred binders are those which are stable to light, oxygen and moisture and which are used during can be stored for a long time and the opposite

509849/0912

are sufficiently stable when heated during development, are easily soluble in solvents and can form a film. Suitable binders are described by J. Brandrup and EH Immergut in Polymer Handbook, Interscience Publishers (1967). In general, the molecular weights of the high molecular weight materials used as binders are preferably in the range of about 1,000 to 500,000. Suitable high molecular weight materials which can be used as binders in the present invention are synthetic high molecular weight materials , for example various vinyl polymers such as polyvinyl chloride, polyvinylidene chloride, copolymers of vinylidene chloride and acrylonitrile (containing up to 50 KoX% acrylonitrile), polyvinyl acetate, polyvinyl alcohol, polyvinyl formal, polyvinyl butyral, polystyrene, polymethyl methacrylate or polyvinyl pyrrolidone, as well as nylon and polyester, which are condensation polymers; semi-synthetic high molecular weight materials such as acetyl cellulose and natural high molecular weight materials such as gelatin.

In general, the appropriate solvents are for the preparation the coating mass polar solvents. In order to achieve a suitable drying speed, Solvents with too high a vapor pressure or too low a vapor pressure are avoided, and are preferred solvents those which have a boiling point in the range of about 40 to 200 ° C. For example, Ν, Ν-dimethylformamide, Dimethyl sulfoxide, aliphatic ketones such as acetone or methyl ethyl ketone, lower monohydric alcohols such as methanol or ethanol, cyclic ethers such as tetrahydrofuran or dioxane, Esters such as ethyl acetate or ethylene glycol monomethyl ether, halogenated hydrocarbons such as chloroform, carbon tetrachloride, Methylene chloride or trichlorethylene, aromatic hydrocarbons such as benzene, toluene or xylene and halogenated aromatic hydrocarbons, etc. are used.

509849/0912

The carrier can be any carrier that is photosensitive Wear layer and show good adhesion to the binder, in the present invention use. The supports can be transparent or cloudy and also glossy. For example, transparent synthetic or semi-synthetic materials with high Molecular weight such as polyester, polyimide or triacetyl cellulose, opaque high molecular weight materials such as Paper, synthetic paper, cellulose fibers, synthetic fibers, leather sheets or foils or wood sheets or - Foils or inorganic materials such as metal foils or glass plates can be used, depending on the use of the photosensitive material of the present invention. Support in the form of a thin film, for example films of materials high molecular weight such as polyester or paper are preferred in the preparation of the light-sensitive material used in roll form. In this case, a suitable thickness of the support is generally about 10 / U. to 1 ram, although it depends on the use of the light-sensitive material. The photosensitive material can can also be produced without a carrier. That is, the photosensitive layer can be applied to a support such as a glass plate or a metal foil can be applied, dried and then removed from the support, and the thus produced Layer aus.dem binder can be used as a photosensitive Material to be used.

A suitable thickness for the photosensitive layer provided on a support is in the range of about 0.5 to 50 / u, in particular from 1 to 50 / u, based on Dry basis. The binder concentration in the coating composition and the coating conditions are preferred adjusted to obtain a layer having such a thickness. The binder concentration in a coating agent depends on the type or molecular weight of the

509849/0912

rejected binder, but the concentration is preferably in the range of about 1 to 50% by weight based on the solvent used. Drying is generally done at a temperature
admitted from about 40 to 80 ⁰ C.

generally at a temperature below about 100 C, preferably

The amount of complex used may vary within a wide range depending on the use of the light-sensitive material, the desired sensitivity thereof, etc., but the amount is preferably in the range of about 3% up to about 60% by weight. %, based on the amount of binder used to produce a stable, photosensitive layer that does not crack and does not lose its transparency.

The amount of sensitizer that is used can also vary widely, depending on the desired sensitivity and image density, but the amount of sensitizer, which is present in the same layer or in an adjacent layer is preferably in the range of about 0.1 up to 100 parts by weight, particularly preferably 1 to 80 parts by weight / 100 Parts by weight of the complex used.

For recording the images, the one produced according to the invention is used photosensitive material exposed through an original image and then heated / heated to a suitable temperature. A latent image is generally formed upon exposure, and this is then formed upon subsequent heating developed. In general, the images formed are negative in relation to the original and colored black or red. Man assumes that the images are formed by crystals or amorphous solids caused by the aggregation of tellurium or selenium, which are formed during the decomposition of the complex.

509849/0912

The electromagnetic radiation that is generally used for The exposure used can range from ultraviolet to visible and from light sources such as come from a xenon lamp, a mercury lamp, a tungsten lamp, a carbon arc, etc. Irradiation can also be used with shorter wavelengths such as X-rays or γ-rays according to the invention for the formation of the images be used. The selection of a suitable light source, i.e. the selection of the suitable wavelength of the electromagnetic Exposure for image formation depends on the spectral sensitivity properties of the photosensitive material away. With regard to exposure, a suitable guideline is that when using a 1 kW xenon lamp Exposure of the photosensitive material at a distance from 30 cm to the light source a suitable exposure time generally in the range of about 1 second to about 200 seconds, preferably from 5 to 60 seconds.

-The photosensitive material is heated for development by closely touching it with a hot plate which is heated uniformly or by using radiant heat rays from an infrared irradiation lamp. The material can also be heated by immersing it in a hot, inert liquid. The temperature during heating is generally in the range of about 50 to 200 ° C, preferably 80 to 150 ⁰ C. The heating time is generally in the range from about 0.1 seconds to 3 minutes, preferably from 10 seconds to 1 minute.

Some of the surprising effects are explained below. obtained in the present invention.

(1) A completely new photosensitive material containing no silver can be made and exposed to light can to form latent images by heating

509849/0912

can be developed, forming very stable black or red images.

(2) The photosensitive material of the present invention can be developed at lower temperatures as compared with photosensitive materials in which organic compounds to which other elements are bound are used will.

(3) Since various kinds of organic bases are used to prepare the photosensitive complexes can, the organic parts in such complexes can be varied much more than in the usual organic Compounds that contain other elements. It is of great advantage that, according to the invention, the various Properties such as sensitivity, compatibility with a sensitizer or temperature and time, required for development can be varied within a wide range depending on the use of the photosensitive material.

(4) The complexes as the photosensitive material can be quantitatively and easily synthesized, and that The photosensitive material of the present invention can thus be manufactured at a lower cost compared with that of the present invention Use of organic compounds that contain other elements.

The following examples illustrate the invention.

example 1

50 mg of aniline-tellurium tetrachloride complex (light-sensitive material), 20 mg of 9,10-phenanthrenequinone and 250 mg of polyvinyl formal (binder) are dissolved in 3 ml of Ν, Ν-dimethylformamide. The composition so prepared is applied to a polyester film (support) in a thickness of 100 / u, where one uses a bar coater, and then at 50 ⁰ C for 1 hour dried. A transparent, photosensitive layer with a thickness of 10 / U is obtained. The light-

509849/0912

sensitive layer is 1 minute using a xenon lamp with 1 kW as a light source at a distance of 30 cm exposed, in close contact with a gray wedge made using silver halide photosensitive material was produced. No visible changes appear in the photosensitive layer. The shift was then with a hot plate at 150 ° C during Brought into close contact for 30 seconds, resulting in a black image with a continuous tone, the opposite the wedge image was negative.

Example 2

30 mg p-acetylaniline tellurium tetrachloride complex, 10 mg tetracyanoquinone dimethane and 30 mg of polyvinyl butyral are dissolved in 3 nil of N, N-dimethylformamide. The mass produced in this way is used for coating in the same way as described in Example 1, then it is exposed and dev / iled, and a black image as described in Example 1 is obtained.

Example 3

40 mg o-phenylenediamine tellurium tetrabromide complex, 15 mg Iron (III) chloride and 300 mg polyvinyl butyral are in 3 ml of tetrahydrofuran dissolved. The agent thus prepared is used in the same manner as described in Example 1 for coating is used, then it is exposed and developed, and a dark brown image with a continuous tint is obtained, which, compared to the wedge image, is negative.

Example 4

50 mg ethylenediamine selenium tetrachloride complex, 30 mg catechol and 250 mg of polyvinyl form are dissolved in 3 ml of tetrahydrofuran. The agent prepared in this way is used for coating in the same manner as described in Example 1, then is exposed and developed, and a red image is obtained which is negative compared to the wedge image.

509849/0912

Example 5

20 mg stearylamine-tellurium tetrachloride complex, 20 mg 9,10-phenanthrenequinone and 300 mg polyvinylbutyral are in
2.5 ml Ν, ΙΙ-dimethylformamide dissolved. The agent prepared in this way is used for coating in the same way as described in Example 1, is then exposed and developed, and a blue-black image is obtained, compared with that
Wedge image, is negative. The photosensitivity is about 30 times higher than that of Example 1. The image produced in this way shows hardly any changes after exposure to.
Sunlight for 7 days, and it is so stable that no fixation is required unless it has been further heated,

Example 6

15 mg of laurylamine-tellurium tetrachloride complex and 250 mg of polyvinylbutyral are dissolved in 2.5 ml of N, N-dimethylformamide.
The agent produced in this way is applied to a polyester base material.

rial with a thickness of 100 / u using a rod

coating device applied and then at 50 C

Dried for 2 hours. Subsequently, an agent is applied to the layer thus formed, which is prepared by adding 50 mg of acetnaphthenehinone and 20 mg of polyvinyl butyral in 2 ml
Tetrahydrofuran dissolves, and then it is ^{dried at 50 °} C. for 1 hour; a transparent film is obtained. The film is exposed in the same way as described in Example 1
and developed and a blue and black image was obtained
as in example 5.

509849/0912

Claims (12)

Claims Photosensitive material characterized in that it contains a support thereon has a layer which contains at least one complex of (a) at least one tellurium halide and / or selenium halide and (b) at least one organic base, wherein the layer or a layer which is adjacent thereto is at least one of the following compounds as a sensitizer contains: a quinone compound, an aryl ketone compound, ex η a tetracyanoquinone dimethane »/ benzene or naphthalene substituted with one or more hydroxyl groups or alkoxy groups with 1 to 7 carbon atoms, an arylamine compound, a diazoniunis salt, a metal acetylacetonate or a inorganic salt or mixtures of these compounds. 2. Photosensitive material according to claim 1, characterized in that it is used as a tellurium halide Tellurium dichloride, tellurium dibromide, tellurium tetrafluoride, tellurium tetrachloride, Tellurium bromide, tellurium tetraiodide, tellurium dibromide iodide or tellurium dibromide dichloride and, as selenium halide, selenium tetrachloride, selenium tetrabromide, selenium tetraiodide or Contains selenium dibromide diiodide. 3. Photosensitive material according to at least one of claims 1 and 2, characterized in that that it is an aliphatic amine compound, an aralkylamine compound, an aromatic amine compound as the organic base or contains a nitrogen-containing heterocyclic compound. 4. Photosensitive material according to at least one of claims 1 to 3, characterized in that 509849/0912 that it contains a compound of the following general formulas (I) to (XII) as the organic base: (D Α., -Ι : (II) (III) ^A l (V) Λ-, (IV) A. 509849/0912 (VJlI) fV- ₂ Κ · ,. Ν f - if ^Α 1 -κ- 509849/0912 -κ (XX) (XII) A ^, A ₂ , A- * and A ^ each represent a hydrogen atom, an alkyl group or an aryl group, B is an aliphatic hydrocarbon group is two or more valences or an arylene group, Ar is an aryl group and R., R ₂ , R * and R ^ can be the same or different and each represent a hydrogen atom, an alkyl group or an aryl group. 5. Photosensitive material according to at least one of claims 1 to 4, characterized in that the alkyl groups for A ^, A ₂ »A ^ and A ^ are straight-chain, branched-chain or cyclic alkyl groups which can be unsubstituted or substituted and one or more alkoxy groups , Aryl groups, aryloxy groups, aminoalkyl groups, aminoaryl groups, sulfoaryl groups, carboxyalkyl groups, carboxyaryl groups, haloalkyl groups, haloaryl groups or aralkyl groups as substituents, the Arylfüruppen for A ^, A ₉ , A ^ and Ai an unsubstituted aryl group or an aryl group with one or more 508849/0912 Alkyl groups, aryl groups, alkoxy groups, aryloxy groups, Acetyl groups, sulfoalkyl groups, sulfoaryl groups, haloalkyl groups, Haloaryl groups, aralkyl groups, nitro groups, Hydroxyl groups or halogen atoms as substituents is substituted, are, the aliphatic hydrocarbon group for B is a straight chain or branched chain aliphatic. Is group that contain one or more arylene groups or double bonds which interrupt the straight chain and which can be unsubstituted or substituted with an alkoxy group, an aryl group, an aryloxy group, a nitro group, an amino group, an aminoaryl group, an arylalkyl group, an acetyl group or a halogen atom as a substituent, and wherein the arylene group for B and the arylene group which is the straight chain of the aliphatic hydrocarbon group for B interrupts, an unsubstituted arylene group or a substituted arylene group, by one or more Alkyl groups, aryl groups, alkoxy groups, aryloxy groups, nitro groups, amino groups, amino aryl groups, arylalkylene groups, Aralkyl groups, acetyl groups, acetylaryl groups, Hydroxyl groups or halogen atoms can be substituted as substituents, mean and wherein the alkyl group for R ^, Rp, R ^ and R- is a straight chain, branched chain or cyclic alkyl group and wherein the alkyl group and the aryl group for R ^, R ₂ , R ^ and R ^ are unsubstituted alkyl or aryl groups or alkyl or Aryl groups which are substituted with one or more alkyl groups, aminoalkyl groups, aminoary groups, alkoxy groups or halogen atoms as substituents. 6. Photosensitive material according to at least one of claims 1 to 5, characterized in that that the photosensitive layer contains a binder. 509849/0912 7 · Photosensitive material after at least one of claims 1 to 6, characterized in that that the photosensitive layer has a thickness in the range of approximately 0.5 to 50 microns. 8. 'Photosensitive material after at least one of claims 1 to 7, characterized in that the complex is present in the light sensitive layer in an amount of from about 3% by weight to about 60 % by weight, based on the weight of the binder. 9 · Photosensitive material after at least one of claims 1 to 8, characterized in that it contains a quinone compound as the quinone compound, which is represented by the general formulas (XIII) to (XVIIl): (XIiI) (XIV) 0 · ff-F 509 849 ■ ii 9 12 ^E 3 ^D i • fr -G (XVIl) (XVIII) 9849/0912 vro r in i, j, k - and ζ positive integers, less than 4, mean and D, Ξ, F and G can be the same or different and each have a hydrogen atom, an alkyl group with up to 10 and including 10 carbon atoms, an aryl group, a halogen atom, a hydroxy group, an alkoxy group with up to 10 and including 10 carbon atoms, a cyano group, a nitro group, an amino group, a monoalkyxainino group, a dialkylamino group, a -SO ^ R ^ group, a -COORp group, a -NHCOR ^ group or an Rc-CO group mean,. v / orin Rp- a hydrogen atom or a Represents an alkyl group of up to 5 and including 5 carbon atoms, and that it is an aryl ketone compound as the aryl ketone compound which is represented by the general formulas (XIX) to (XXIV): (XiX) (XX) r ·. ρ ν j. {η / fi ο (XXI) (XXlI) (XXIIl) (XXIV) F, where i, j, k and ζ and D, E, F and G are each used in the general Formulas (XIIl) to (XVIII) have the meanings described for the quinones and R ^ denotes an alkyl group, as described for D, E, F and G in the general formulas (XIII) to (XVIII), and that it contains, as the diazonium salt, a compound which
represented by the general formulas (XXV) to (XXXI)
will: 509849/0912 r / l is I./L ¹ (XZV) 1 1 Y and Z each represent an alkoxy group having 1 to 5 carbon atoms, a halogen atom or an aryl group and m ,, and n ^ each 0 or a positive integer of Are 1 to 5; (XXVl) R 'and R each represent an alkyl group with 1 to 5 carbon atoms, an alkoxy group with 1 to 5 carbon atoms, denote a hydroxyalkyl group having 1 to 5 carbon atoms, a benzyl group, a phenyl group or a hydrogen atom, 2 2 Y and Z each have a halogen atom, an alkyl group with 1 to 5 carbon atoms, a carboxyl group, an alkoxy group having 1 to 5 carbon atoms, a nitro group or mean an acetoxy group and nip and np each 0 or a positive integer of 1 to 4; BATH ORIGINAL α K '' - 47 - (ZXVIl) R ^{y is} a -CH ₂ CH ₂ OCH ₂ CH ₂ group or a CH ₉ OCH ₉ CH ₉ group means and ? ρ Y, Ζ ~, m ₂ and η _{2 have} the same meanings as in Have formula (XXVI); (X / LVJI1) 10 11
R and R each have a hydrogen atom or an alkyl mean a group with 1 to 5 carbon atoms, Y ^ and Z ^ each represent an alkyl group with 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a carboxy group, an acetoxy group or an aryl group mean, and and
interpret; U and n, each 0 or an integer from 1 to 4 be , -3 (X) JX) S- - - BATH ORIGINAL 10 11 3 " ² I. where R, R, Y and Z, nu and η, each have the same meanings as in formula (XXVIII) above; (XXX) 12th
R is an alkyl group with 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms or a Aryl group means R ^ represents a hydrogen atom or an alkyl group Means 1 to 5 carbon atoms, a 4
Y and Z each have a halogen atom, an alkyl group with 1 to 5 carbon atoms or an alkoxy group of 1 to 5 mean carbon atoms and m ^ and n ^ each represent 0 or an integer from 1 to 4;
and Bf '' 2 ^A (XXXI) 14th
R represents an alkyl group or an aryl group; X ¹ in any of the above formulas (XXV) to (XXXI) Anion means 509849/0912 and that there is molybdenum oxide acetylacetonate as metal acetylacetonate, Contains zirconium acetylacetonate, titanium acetylacetonate and / or vanadium acetylacetonate and that it is iron (H) chloride as an inorganic metal salt, Iron (III) chloride, iron (II) bromide, iron (III) bromide, Iron oxalate, iron ferrocyanide, vanadium trichloride, manganese chloride, Manganese bromide, cobalt chloride, cobalt bromide, cobalt acetate, Tin (II) chloride, tin (IV) chloride, tin (II) oxalate, Contains mercury chloride, lead chloride, nickel chloride and / or cerium chloride and / or the hydrates thereof. 10. Photosensitive material according to at least one of claims 1 to 9, characterized in that that the optical sensitizer is in an amount ranging from about 0.1 to 100 parts by weight per 100 parts by weight of the complex is available. 11. A method for producing an image, characterized in that the photosensitive Material according to at least one of claims 1 to 10 exposed imagewise and the photosensitive material heated. 12. The method according to claim 11, characterized in that the heating takes place at a temperature in the range from about 50 to 200 ⁰ C for about 0.1 seconds to 3 minutes. 509849/0912