DE2504652A1 - LIGHT SENSITIVE MATERIAL - Google Patents

Description

PATENT ANWXtTE

OR. E. WIEGAND DIPL-ING. V /. NO MAN DR. M. KÖHLER DIPL-ING. C GERNHARDf

MÖNCHEN HAMBURG TELEPHONE: 555 * 7 «8000 MONKS 2,

TELEGRAMS! KARPATENT MATHILDENSTRASSE

TELEX: 529068 KARP D

¥ 42 251/75 - Ko / Ja 4th February 1975

Fujji Photo Film Co. Ltd., Minami Ashigara-Shi, Kanagawa (Japan)

Photosensitive material

The invention relates to a photosensitive material, and more particularly to a photosensitive material using a complex of (a) a tellurium or selenium halide and (b) an organic base as a photosensitive substance.

According to the invention, a photosensitive material is specified which has a support with a photosensitive layer located thereon, which has little-

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at least one complex

(a) a tellurium halide or a selenium halide and

(b) contains at least one organic base.

The light-sensitive substances contained in known light-sensitive materials include metal halides, such as silver halide, as well as diazo compounds and light-sensitive substances of high Molecular weight known. Furthermore, a combination of a polyhalogenated one is also suitable for special uses Hydrocarbon with an amine or an N-vinylcarbazole in the so-called free radical image systems and photochromic substances and the like are known. Photographic processes using the above photosensitive Substances are detailed in the following References Described: For example, the silver halide photographic process is described in C.E.K. Mees and T.H. James, "The Theory of the Photographic Process", Macmillan (1966), and the like; the .photographic Process using metal halides other than silver halide, diazo compounds, photosensitive High molecular weight substances or photochromic substances are described in J. Kosar, "Lightsensivite Systems ", John Wiley & Sons (I965) and the radical photography is in "Photographic Science & Engineering", j5, 298, ibid., 8, 91 and 95 and ibid., 9,133 and U.S. Patents 3,042,517 and 3,042,519.

However, many light-sensitive materials used in these conventional photographic processes have Disadvantages, although they have their respective advantageous features. Silver halide photosensitive materials For example, highly desirable photographic materials because of their high sensitivity are they however, have the disadvantages that laborious and high-quality

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fied measures are necessary, which are time consuming, since complicated solution treatments for the formation of a photographic Image thereon are required and, in addition, they are expensive because silver is used therein as a raw material will. Photosensitive materials for so-called diazo photography using diazo compounds, although less expensive per se compared to silver halide photosensitive materials, generally require Development processes with an alkali solution or require the incorporation of an alkali-forming agent, even if such a treating solution as in, for example, dry-type wännediazo photography is not is required. Vesicular photographic processes using diazo compounds, albeit using Performed by dry processes, can not produce substances by absorption of light Form images and are therefore only suitable for the production of photographic films for projection purposes. Photographic photosensitive materials using photosensitive substances of high molecular weight require solution treatments and cannot produce color photographic images like the one described above Vesicular photography. Radical photography, although dry treatment is generally used, can often due to sublimation, toxicity, or stability be disadvantageous with regard to the material used. In addition, the images generated are general difficult to fix and in most cases unstable.

Photosensitive materials, which have the disadvantage of these common photographic light-sensitive materials have recently been developed, for example, photosensitive materials commercially available are available under the trade name "Dry Silver" (3M Co.), wherein a metal salt of an organic acid

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re, such as a salt of behenic acid, as an image forming agent Substance is incorporated and also a reducing agent and silver halide are incorporated as a photocatalyst. The products are obtained according to techniques specifically described in U.S. Patents 3,152,903, 3,152,904, and 3,457,075. Furthermore, photographic photosensitive materials using a compound of an organic element with a chemical Structure in which the carbon atoms in the organic compound are directly linked to chalcogen elements, for example in Japanese Patent Laid-Open 29 438/73 (corresponding to DT-OS 2 233 868). While the above two photosensitive materials can be treated in an extremely simple dry treatment, with image-forming substances through Absorption of visible light can only be generated by heating after exposure, have these photosensitive Materials various disadvantages. The former photosensitive materials are expensive, since silver is used therein as a raw material as an image-forming substance and that on the photosensitive material The photosensitive layer formed is translucent because its structure is a dispersion of crystals and thus cannot be suitable for projecting photographic films. With reference to the latter In photosensitive materials, the images produced are difficult to fix because they are in photosensitive materials for radical photography, the covalent bonded compounds such as those used therein Element-organo-compounds are easily subject to hydrolysis and are therefore not stable and beyond these compounds hardly produce any photosensitivity

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freedom, if not used in conjunction with a sensitizer, regarding the selection of these compounds there are significant limitations, these compounds are generally in low yield and produced with difficulty and require photosensitive materials using these compounds heating to considerably higher temperatures for post-exposure development.

Considerable studies have been made in view of the above disadvantages of conventional light-sensitive materials in various photographic processes carried out and as a result the present invention developed. That is, the invention provides a photosensitive material comprising a support having thereon light-sensitive layer containing at least one complex of (a) a tellurium halide or a selenium halide and (b) contains at least one organic base.

The invention is based on a completely new finding that the above complex of (a) a Tellurium halide or a selenium halide and (b) one organic base is photosensitive and a layer dispersing such a photosensitive complex in a suitable binder, produce stable images by developing with post-exposure heating can. -

The components of the photosensitive substance used in the photosensitive material of the invention (a) a tellurium halide or a selenium halide and (b) an organic base are explained in detail in the following description.
(a) Tellurium halide or selenium halide The tellurium halide and selenium halide are both

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for example compounds of the following general formula:

"Vm

■ where M is a tellurium or selenium atom; X and Y _f, which can be the same or different, each represent a halogen atom such as fluorine, chlorine, bromine and iodine; η and m are each 0 or an integer and η + m is the value 2 or 4 according to the valency of M.

Specific examples of tellurium halides and selenium halides are tellurium dichloride, tellurium dibromide, tellurium tetrafluoride, tellurium tetrachloride, tellurium tetrabromide, tellurium tetraiodide, tellurium dibromide iodide, tellurium dibromide dichloride, selenium tetrachloride, selenium tetrabromide, selenium tetraendumide. These tellurium halides and selenium halides are described in KW Bagnall, "The Chemistry of Selenium, Tellurium and Polonium ¹ , ¹ Elsevier Publishing Co. (1966), and they can be used individually or in admixture.
(b) Organic base

Organic bases include aliphatic amine compounds, aralkylamine compounds, aromatic amine compounds, nitrogen-containing heterocyclic compounds, diazonium compounds or the like., For example those of following general formulas (I) to (XII).

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(III)

(IV)

A ₂

(VI)

A ₂

(VII)

A ₁

A ₂

N «ν .Ν (VIII)

A ₂

A,

• Ν-

Ri

(IX)

■ Ν>

(X)

(XI) (XII)

Ar-N ₂ CA

Α «,

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In the above formulas, A ₁ , A ₂ , A, and A ^, each a hydrogen atom, represent an alkyl group which may be a straight chain, branched chain or cyclic alkyl group including a substituted alkyl group or an aryl group including a substituted aryl group. Suitable alkyl groups for A ₁ , A ₂ , A, and Aa are those having 1 to 25 carbon atoms. The alkyl groups can be substituted with substituents such as, for example, alkoxy, aryl, aryloxy, aminoalkyl, aminoaryl, suIfoalkyl, sulfoaryl, carboxyalkyl, carboxyaryl, haloalkyl, haloaryl or aralkyl groups. Suitable aryl groups for A ₁ , A ₂ , A ^ and A ^ include phenyl, naphthyl, anthryl and phenanthryl groups, and they can be substituted with substituents such as alkyl, aryl, alkoxy, aryloxy, acetyl, sulfoalkyl -, sulfoaryl, haloalkyl, haloaryl, aralkyl, nitro or hydroxyl groups or halogen atoms may be substituted. Specific examples of groups for A ₁ , 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, isohepty, tert-heptyl, methylcyclohexyl, octyl, isooctyl, tert. -Octyl-, dimethylcyclohexyl-, nonyl-, tert-nonyl-, decyl-, tert-decyl-, dimethylcyclohexyl-, undecyl-, tert-undecyl-, dodecyl-, tert-dodecyl-, tridecyl-, tert , Tridecyl, tetradecyl, tert, tetradecyl, pentadecyl, sec. Pentadecyl, tert. -Pentade'cyl-, hexadecyl-, tert. Hexadecyl-, octadecyl-, sec-octydecyl *, tert-octadecyl-, nonadecyl-, sec-nonadecyl-, tert-nonadecyl-, licosyl-, / 'sec-eicosyl-, heneicosyl-, sec.- Heneicosyl, tert-heneicosyl, docosyl, sec-docosyl, tert-docosyl, tricosyl, sec-tricosyl, tert-tricosyl, tetracosyl, sec-tetracosyl, tert. -Tetracosy-, pentacosyl-, sec-pentacosyl-,

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tert-pentacosyl, ethoxyethyl, ethoxypropyl, ethoxybutyl, Ethoxypentyl, ethoxyhexyl, methoxyhexyl, methoxyheptyl, Ethoxyheptyl, methoxyoctyl, ethoxyoctyl, benzyl, triphenylmethyl, phenyl, naphthyl, ToIy1-, Xylyl, mesityl, oxyphenyl, dioxyphenyl, acetylphenyl, Benzophenyl, methoxyphenyl, ethoxyphenyl, nitrophenyl, dinitrophenyl, chlorophenyl, bromophenyl, trifluoromethylphenyl, Biphenyl, phenoxyphenyl, vinylphenyl, carboxymethyl, carboxyethyl, carboxypropyl, carboxybutyl, Carboxyhexyl, carboxynonyl, carboxyphenyl, carboxynaphthyl, sulfoethyl, sulfopropyl, sulfobutyl, sulfopentyl, Sulfophenyl, sulfonaphthyl, naphthyl, aceto-r naphthyl, chloronaphthyl, dichloronaphthyl, oxynaphthyl, methylnaphthyl, methoxynaphthyl, ethoxynaphthyl, Änthryl, Acetoanthryl, chloranthryl, Öxyanthryl, dioxyanthryl, Methoxynaphthyl, phenanthryl, acetylphenanthryl, methoxyphenanthryl, Dimethyloxyphenanthryl and. Sulfophenanthryl groups.

Of these substituents for A ^, A ₂ , A, and A ^ are hydrogen atomsj alkyl groups having 2 to 25 carbon atoms which are unsubstituted or substituted by an alkoxy group having 1 to 2 carbon atoms or a phenyl group; Phenyl groups which are unsubstituted or substituted with an alkyl group having 1 to 2 carbon atoms, an alkoxy group having 1 to 2 carbon atoms, acetyl groups, trifluoromethyl groups, nitro groups, hydroxyl groups, acetophenonyl groups, phenoxy groups or phenyl groups or halogen atoms; Naphthyl groups; Anthryl groups and phenanthryl groups are particularly suitable.

B means one equipped with 2 or more valences aliphatic hydrocarbon group, the straight chain or can be branched chain and inclusive

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substituted groups and also those with unsubstituted or substituted arylene groups, such as, for example Phenylene groups or double bonds that interrupt the straight chain; or arylene groups including -substituted arylene groups. Suitable aliphatic hydrocarbon groups with 2 or more valences for B are those with 1 to 10 carbon atoms, and they can be mixed with alkoxy, aryl, aryloxy, nitro, amino, aminoaryl, Arylalkyl or acetyl groups or halogen atoms and the like. Be substituted and by groups such as Phenylene, substituted phenylene, naphthylene, substituted naphthylene, biphenylene, substituted biphenylene , Carbonyldiarylene or thiocarbonyldiarylene groups be interrupted. Suitable arylene groups for B are Phenylene, naphthylene, anthrylene and phenanthrylene groups, and they can, for example, with alkyl, aryl, alkoxy, aryloxy, nitro, amino, aminoaryl, aryalkylene, Aralkyl, acetyl, acetylaryl or hydroxyl groups or halogen atoms may be substituted.

Specific examples of the groups for B include ethylene, propylene, butylene, methylene, tetramethylene, pentamethylene, heptamethylene, octamethylene, nonamethylene, decamethylene, ethylethylene, dimethylpropylene, methylbutylene, dimethylbutylene, Ethylbutylene, methylpentamethylene, dimethylpentamethylene, ethylpentamethylene, diethylhexamethylene, phenylpropylene, chlorophenylpropy. len-, oxypentamethylene, oxyheptamethylene, methoxyheptamethylene, methoxyoctamethylene, ethoxynonamethylene, ethoxydecamethylene, chloropentamethylene, chlorooctamethylene, benzylbutylene, benzylpropylene, toylheptamethylene, 4,4'-butylene, tolylpentamethylene, x '- (methylene) -diphenylene-, 4,4' - (phenylmethy len ) -diphenylene-, 4,4 ^f -Carbonyldiphenylen-, 4,4 '- [(amino-

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phenyl) -methylene] -diphenylene-, oxydiphenyreii-, propenylene-, Butenylene, pentylene, heptenylene, octenylene, Nonenylene, decadienylene, nonadienylene, octadienylene, heptadienylene, phenylene, chlorophenylene, aminophenylene, Nitrophenylene, methoxyphenylene, phenylphenylene, phen-.oxyphenylene, Aminophenylphenylene, styrylphenylene, acetylphenylene, acetylphenylphenylene, aminophenacylphenylene, Bromophenylene, oxyphenylphenylene, biphenylene, methylbiphenylene, dimethylbiphenylene, oxybiphenylene, Naphthylene, acetonaphthylene, methylnaphthylene, dimethylnaphthylene, oxynaphthylene, phenanthrylene, acetylphenanthrylene, Methylphenanthrylene and methoxyphenanthrylene "groups. Of the groups for B are particularly suitable Groups alkylene groups with 2 to 6 carbon atoms which are unsubstituted or with alkoxy groups with 1 to 2 carbon atoms, Phenyl groups, aminophenyl groups, alkyl groups are substituted with 1 to 2 carbon atoms or hydroxyl groups or halogen atoms or those which with monoene, diene or triene hydrocarbon groups with 2 to 6 carbon atoms, arylene groups, 4,4 * -Methylendiphenylen-, 4,4'-carbonyldiphenylene, oxydiphenylene or diphenylene groups are interrupted; Phenylene groups; Phenylene groups with, alkyl groups with 1 to 2 carbon atoms, Alkoxy groups with 1 to 2 carbon atoms, Acetyl groups, trifluoromethyl groups, nitro groups, hydroxyl groups, acetophenonyl groups, phenoxy groups, amino groups, Aminophenyl groups, nitrophenyl groups, halophenyl groups, Oxyphenyl groups or phenyl groups or halogen atoms are substituted; Naphthylene groups; Anthrylene groups and phenanthrylene groups,

Ar means an aryl group which is unsubstituted or with alkyl, hydroxyl, alkoxy, aryloxy, aminoalkyl, aminoaryl, cyano, nitro, carboxy, sulfo groups or

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Halogen atoms can be substituted. Examples of aryl groups include phenyl, naphthyl, anthryl, and phenanthryl groups.

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. The alkyl groups can be straight-chain, branched-chain or cyclic groups. Suitable alkyl groups are those having 1 to 6 carbon atoms and suitable aryl groups are phenyl and naphthyl groups. The alkyl groups and aryl groups may further be substituted with alkyl, aminoalkyl, aminoaryl or alkoxy groups or halogen atoms and the like. Specific examples of the groups for R ₁ , R ₂ , R ^ and R ^ include methyl, ethyl, propyl, butyl, hexyl, octyl, pentyl, cyclopentyl, cyclohexyl, chloroethyl, phenyl , Styryl, p-methoxyphenyl, p-chlorophenyl, p-nitrophenyl, naphthyl, p-aminophenyl, p-aminonaphthyl or tolyl groups and a hydrogen atom. Of the groups for R *, R ₂ , R, and R », particularly suitable groups are alkyl groups having 1 to 2 carbon atoms, which can be unsubstituted or substituted by a chlorine atom or a phenyl group; a phenyl group, which can be unsubstituted or substituted by alkoxy, nitro or amino groups, and a hydrogen atom.

The substituents Aj, A ₂ , A 1, A ^, Ar, B, R ^, R ₂ , R, and R ^ in the compounds of the above-described formulas (I) to (XII) are not limited only to those described above and may contain any other substituents so long as the compounds can complex with selenium halide or tellurium halide.

Specific examples of compounds of the formulas (I) to (XII) described above are ethylamine, propylamine, Butylamine, tert-butylamine, pentylamine, isopentyl

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amine, hexylamine, heptylamine, octylamine, nohylamine, decylamine, tert-decylamine, undecylamine, dodecylamine, tetradecylamine, Pentadecylamine, octadecylamine, nonadecylamine, elcosylamine, Docosylamine, tricosylamine, tetracosylamine, pentacosylamine, Ethoxyethylamine, ethoxypropylamine, ethoxybutylamine, ethoxypentylamine, ethoxyhexylamine, methoxyhexylamine, methoxyoctylamine, Methoxyeicosylamine, methoxytric ο sylamine, benzylamine, tritylamine, phenethylamine, vanillylamine, veratrylamine, Poly (p-aminostyrene), N-methylethylamine, N-methylpropylamine, N-methylbutylamine, N-methyl-tert. -butylamine, N-methylheptylamine, N-methyloctylamine, N-methylnonylamine, N-methyl-tert-decylamine, N-methyloctadecylamine, N-methyldecylamine, N-methylethoxybutylamine, N-methylmethoxyhexyl-'amine, N-methylmethoxyeicosylamine, N-methylbenzylamine, N-methyltrimethylamine, N-methylphenethylamine, N-methylvanillylamine, N-methylveratrylamine, N-ethylbutylamine, N-ethylpentylamine, N-Ethyldecylamine, N-Ethyldodecylamine, N-Ethyloctadecylamine, N-Ethyleicosylamine, N-Ethyldocosyamine, N-Ethyltetrac ο sylamine, N-Äthylpentaco sylamin, N-Äthyläthoxyhexylamin, N-ethylmethoxyhexylamine, N-ethylbenzylamine, N, N-dimethylethylamine, Ν, Ν-dimethylpropylamine, N, N-dimethylbutylamine, N, N-dimethyl-tert-butylamine, N, N-dimethylheptylamine, Ν, Ν-dimethyloctylamine, N, N-dimethylnonylamine, Ν, Ν-dimethylmethoxyhexylamine, Ν, Ν-Dimethylmethoxyeicosylamin, N, N-Dimethylphenäthylamin, Ν, Ν-Dimethylvanillylamine, N, N-Dimethylveratrylamin, N, N-diethylvanillylamine, N, N-diethylpropylamine, N, N-diethylbenzylamine, Ν, Ν-dimethyl benzylamine, Aniline, nitroaniline, trifluoromethylaniline, toluidine, ethyl, aniline, chloroaniline, bromaniline, methylaminobenzoate, butylaniline, Phenylaniline, naphthylaniline, dinitroaniline, naphthylamine, methoxyaniline, acetylaniline, N-methylaniline, N-ethylaniline, Ν, Ν-dimethylaniline, N, N-diethylaniline, N-methylnitroaniline, N, N-dimethylnitroaniline, N, N-diethyl

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nitroaniline, Ν, Ν-dimethyltoluidine, Ν, Ν-Dimethylacetylanilin, Ν, Ν-Dimethylmethoxyanilin, N, N-dimethylnaphthylamine, Ν, Ν-Dimethyltrifluoranilin, pn-dodecyl aniline, ethylenediamine, propylenediamine, butylenediamine, Äthyläthylendi-.amin, Methyltrimethylendiamin, Propenylendiamin , Hexadienylenamine, phenyltr imethylenediamine, diaminodiphenylmethane, diaminobenzophenone, naphthylenediamine, benzidine, oxydiphenylenediamine, phenylenediamine, methylphenylenediamine, ethylphenylenediamine, N, N, N ^! , N · -Tetramethylphenylendiamin, N, N, N *, N * -Tetramethyloxydiphenylendiamin, 4,4 '-Tetramethyldiaminodiphenylmethan, Ν, Ν, Ν ^1, N'-tetramethyldiaminobenzophenone, Ν, Ν, Ν ^1, N ^f tetramethylbenzidine, Ν , Ν, Ν *, Ν · - Tetramethylbenediamine, N, N, N *, N'-tetramethy! Hexamethylenediamine, NjNjN'jN'-tetramethylpropanediamine, Ν, Ν, Ν *, N'-tetramethyltrimethylenediamine, pyridinediamine, methylpyridine, Pyridine carbinol, pyridine ethanol, pyridine carboxylic acid methyl ester, pyrzine, methyl pyrazine, ethyl pyrazine, pyrazine dicarboxylic acid methyl ester, trimethyl pyrazine, pyrimidine, 5-methylpyrimidine, methoxypyrimidine, 5-hydroxypyrimidine, 5-hydroxypyrimidine, methylpyridine, pyrroline pyrimidine, pyrrole pyridazine, pyrrole, pyrrole pyridazine, pyrrole, pyrrole, pyrrole pyridazine, pyrrole, pyrroline pyridazine, pyrroline, pyrrole pyridazine, pyrrole, tri-pyridyridazine, methoxypyridyridazine, methyl pyrazine, methyl pyrazine, ethyl pyrazine, methyl pyrazine, pyrazine, methyl pyrazine, tr Tetramethylpyrrole, dipyrrylmethane, N-methylacetylpyrrole, indole, ß-aminoethylindole, methylindole, methoxyindole, - N-methylindole, N-methylmethylindole, dimethylindole ,. Carbazole, N-methylcarbazole, N-ethylcarbazole, N-Methylacetylcarbazol, N-Methyldiacetylcarbazol, N-Methylnitrocarbazol, N-Propylcarbazol, aminocarbazole, quinoline, quinolinemethanol, chloroquinoline, methoxyquinoline nitroquinoline, aminoquinoline, benzenediazonium, p-nitrobenzenediazonium chloride, Methylbenzoldiazoniumchlorid, Chlorbenzoldiazoniumchlorid, Cyanobenzene diazonium chloride, acetylbenzene diazonium chloride and ρ-Ν, Ν-dimethaminobenzene diazonium chloride ..

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These organic bases can be used as constituents individually or, if appropriate, in a mixture with one another will.

The complexes used according to the invention include generally complexes of 1 to 6 moles of an organic base to 1 mole of the tellurium or selenium halide, you can be found with reference to the literature, for example A. Lowy and P.F. Dunbrook, J. Am. Chem. Soc, 44, 614 (1922); S. Prased and B.L. Khandelwall, J. Indian Che. Soc, 58. 837 (1961); R. Korewa, Roczniki Chemistry, £ 2, 1565 (1963); E.A. Boudreaux, J. Am. Chem. Soc, 8j5, 2039 (1963).

Examples are given below which illustrate the preparation of the typical compounds used according to the invention explain.

Production example 1 complex of ethylenediamine with tellurium tetrachloride:

Into a 200 ml flask equipped with a stirrer and a dropping funnel were placed 6.75 g (0.025 mol) of tellurium tetrachloride and 50 ml of chloroform. To this, a solution of 1.65 g (0.0275 mol) of ethylenediamine and 50 ml of chloroform was added dropwise with stirring. After the addition, stirring was continued for a further 1 hour. The resulting precipitate was filtered off, washed with chloroform to remove the diamine until the piltrate no longer gave a complex with tellurium tetrachloride when tellurium tetrachloride was added to the washing solution and then dried. The amount obtained was 7.8 g (yield: 94% _t pale yellow powder with him

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a temperature above 15CK! decomposed). ■

Production example 2

Complex of p-nitrobenzenediazonium chloride with tellurium tetrachloride: (O ₂ NC ₆ H ₄ N ₂ ) ₂ · TeCl ₆

A solution of p-nitrobenzenediazonium chloride in ethyl alcohol, which is made from p-nitroaniline in absolute ethanol according to Koenigs, Ann., 509 . 149 (1934) was added to a suspension of tellurium tetrachloride in ethyl alcohol in a molar ratio of 2.1 of the diazonium salt to tellurium tetrachloride. The mixture was then stirred for about 1 hour. The resulting precipitate was filtered, washed with ether and then dried under reduced pressure to give a p-nitrobenzenediazonium chlortellurkomplex was obtained in quantitative yield, having a melting point of 121 ⁰ C. This reaction took place in a dark room.

A layer containing the complexes described above inherently contains, is sensitive to visible light or ultraviolet light and produced by exposure and Heating pictures. Furthermore, by incorporating a sensitizer in such a layer, the absolute sensitivity can be increased or the photosensitive wavelength range can be extended, i.e. the layer can to be spectrally sensitized »

The photosensitive layer of the invention can be prepared by making the above-described complex and optionally a sensitizer are dissolved or dispersed in a solution of a binder, the solution or dispersion onto a carrier using a cover

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device such as a bar coating device, a roll coating device, a curtain coating device or a dip coating device is applied and then dried.

Various natural or synthetic high molecular weight substances can be used as the binder. Particularly preferred binders are those which are resistant to light, oxygen and moisture, can be stored for a long period of time and are sufficiently stable to heating during development, are easily soluble in solvents and are capable of forming a film. The molecular weight of the high molecular weight substances used as binders is therefore preferably in the range from about 1000 to 500,000. Suitable binders are described in J. Brandrup and EH Immergut, Polymer Handbook, Interscience Publishers, (1967). The high molecular weight substances which can meet the above requirements which can be used as binders according to the invention include synthetic high molecular weight substances, for example various vinyl polymers such as polyvinyl chloride, polyvinylidene chloride, copolymers of vinylidene chloride and acrylonitrile (which can be up to 50 Mo contain 1% acrylonitrile), polyvinyl acetate, polyvinyl alcohol, polyvinyl formal, polyvinyl butyral, polystyrene, polymethyl methacrylate or polyvinylpyrrolidone as well as types of nylon (e.g. 6-nylon, 6,6-nylon, 6,10-nylon, 7-nylon, 9-nylon, 11 -Wylon ■ and the like.) And polyesters such as polyethylene terephthalate, polyethylene isophthalate and the like. Which are condensation polymers; semi-synthetic substances of high molecular weight, such as acetyl cellulose and natural substances of high molecular weight, both

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for example gelatin. ·

Polar solvents are generally suitable as solvents for use in the preparation of a coating composition. In order to keep the drying speed moderate, the use of solvents that have too high or too low a vapor pressure should be avoided, and the use of solvents with a boiling point in the range from about 40 to 20O ⁰ 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, Methylene chloride or trichlorethylene or aromatic hydrocarbons such as benzene, toluene or xylene or halogenated aromatic hydrocarbons and the like are preferred.

Any carrier which can carry a thin photosensitive layer and has good adhesive properties can be used as the carrier with reference to a binder can be used in accordance with the invention. The porters can be transparent or opaque and can also be glossy. For example, they can be transparent synthetic or semi-synthetic Substances of high molecular weight, such as polyesters, polyimides or triacetyl cellulose, opaque substances with a high molecular weight, such as papers, synthetic papers, cellulose fibers ^ synthetic Fibers, leather sheets or wooden sheets or inorganic materials such as sheet metal or Glass sheets Depending on the end use of the photosensitive Materials of the invention can be used. The use of thin film supports, for example

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- 19 -

Filming of high molecular weight substances such as polyester or papers is useful for enabling the light-sensitive material to be manufactured in a roll form. In this case there is a suitable one Thickness of the carrier generally around 10 / u to 1 mm, although the strength of the end use of the photosensitive Material depends. In addition, it is not essential that the photosensitive material be a support contains. That is, a layer of a binder can also per se can be used as a photosensitive material formed by mounting the photosensitive material on any Support such as a glass plate or metal plate, drying the same and then removing the layer of the carrier is made.

A suitable thickness of the photosensitive layer formed on the support is in the range of about 0.5 to 50 / u, preferably 1 to 50 / u, on a dry basis. It is appropriate to adjust the concentration of the binder in the coating composition and the coating conditions so that the photosensitive layer has such a thickness. The concentration of the binder solution depends on the type and molecular weight of the binder used, but is preferably in the range from about 1 to 50 % by weight of the solvent used. The drying is generally carried out at a temperature below about 10 ° 0, preferably at 40 to 8OPG.

The amount of the complex can vary over a wide range depending on the end use of the photosensitive material, the desired sensitivity and vary the like., But preferably the amount is about 3% to about 60 Gev,% of the amount of the binder of preparing a stable light-sensitive layer in which no cracks form and no loss of permeability occurs. ■ - '■'

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The amount of the sensitizer can also vary widely The amount will vary depending on the sensitivity and image density desired, but the amount is preferably within Range from about 0.1 to 100 parts by weight per 100 parts by weight of the complex used.

The photosensitive material obtained according to the invention can be used for recording images by exposure the photosensitive material by an original image and then heating the exposed photosensitive Material to be used at a suitable temperature. That is, after exposure, generally creates a latent image which is then developed by heating. In general, the image produced is negative to the original and black vein red. The image is believed to be formed by crystals or amorphous solids that are produced by the aggregation of tellurium or selenium resulting from the decomposition of the complex result.

Electromagnetic waves that are generally used for exposure are ultraviolet light or visible light, for example from a xenon lamp, a mercury lamp, a tungsten lamp, a Carbon arcs and the like. In addition, waves of shorter wavelengths, such as X-rays, for example or γ-rays can be used to form images according to the invention. The spectral sensitivity properties of the photosensitive material determine which light source is expediently used or which wavelength of electromagnetic waves is suitable for forming the images. In terms of exposure there is a suitable instruction therein if a 1 kw xenon lamp is used to expose the photosensitive material at a Distance of 30 cm from the light source is used, where-

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"with a suitable exposure time generally about 0.01 sec to about 300 sec," preferably 0.1 sec to 50 sec lies.

The photosensitive material can be heated for development by closely bringing the photosensitive material into contact with a uniformly heated hot plate or by applying radiant heat rays from an infrared lamp. In addition, the photosensitive material can be heated by immersing the material in a hot inert liquid. A suitable heating temperature is generally in the range of about 50 to 20O ⁰ C, especially 80 to 15O ⁰ C. A suitable heating time is generally in the range of about 0.1 sec to 3 min, particularly 10 sec to 1 min.

Excellent effects can be obtained due to the invention can be achieved and some are listed below.

A completely new non-silver photosensitive material can be obtained which is very stable black or red images by exposure to produce latent images and forms development by heating.

. The photosensitive material of the invention can operate at lower temperatures compared to photosensitive Materials using element organic compounds to be developed.

As a wide variety of organic bases for production of complexes that are photosensitive can be used, the organic components in these Complexes compared to element-organo-compounds in Can be varied to a greater extent and therefore one of the advantages achievable according to the invention is that several Properties such as sensitivity, compatibility with a sensitizer

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or the temperature and time necessary for development to a large extent depending on the end use of the photosensitive Materials can be varied.

The complex as a photosensitive substance can be quantitatively and easily synthesized and thus photosensitive materials can be used at lower Costs can be obtained compared to the use of element organo compounds.

The invention is further described in detail with reference to the following examples. If nothing else is indicated, all parts, percentages, ratios and the like relate to the weight.

example 1

50 mg of aniline tellurium tetrachloride complex (light-sensitive material) and 250 mg of polyvinylforraal (binder) were dissolved in 3 ml of Ν, Ν-dimethylformamide. The mass was drawn onto a polyester film (carrier) with a thickness of 100 / u using a coating rod and drawn down at 50 ^° C. for 1 hour to form a transparent photosensitive layer with a thickness of 10 / u Using a xenon lamp of 500 W as a light source exposed at a distance of 10 cm while the layer is in close contact with a wedge stand made using a silver halide photosensitive material. There were * no visible changes in the photosensitive layer. The layer was then brought into contact with a hot plate at 150 ^° C. for 30 seconds, as a result of which a black image appeared in the exposed parts.

The formed image was stable for a long period of time and because the light sensitive layer was not images generated only by exposure, was a fixing treatment

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Treatment is not particularly required so long as the photosensitive layer has not been heated.

Example 2

50 mg p-acetylaniline-tellurium tetrachloride complex and 250 mg of polyvinyl butyral were dissolved in 3 ml of tetrahydrofuran. A photosensitive layer was made on a polyester film provided in the same manner as in Example 1. The photosensitive layer was exposed and then obtained in the same manner as in Example 1 to obtain a black image of a continuous tone, that was negative to the original.

Example 3

30 mg of p-phenylenediamine tellurium tetrachloride complex and 300 mg of a copolymer of vinylidene chloride and acrylonitrile (in a monomeric molar ratio of 85; 15) were dissolved in 2.5 ml of 1,3-dioxane. The mass was drawn up on an art paper having a thickness of 300 / u in the same manner as in Example 1. The photosensitive layer was exposed in the same manner as in Example 1 and then 30 sec by close contact of the film with a hot plate, which was heated to 13O ⁰ G to obtain a black image of a continuous tone, which was negative to the original, heated .

Example 4

40 mg ethylenediamine tellurium tetrachloride complex and 250 mg polyvinyl formal were in 2.5 ml Ν, Ν-dimethylform-

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amide dissolved. The composition was applied to a polyester film in the same manner as in Example 1 to form a photosensitive Layer raised. The layer was exposed and heated in the same way as in Example 1, whereby a continuous tone black image negative to the original was obtained.

Example 5

50 mg of N-ethylcarbazole-tellurium tetrachloride complex and 250 mg of polyvinyl formal were in 2.5 ml of Ν, Ν-dimethylformamide solved. A photosensitive layer was produced on a polyester film, exposed and then in the Heated in the same manner as in Example 1, leaving a black image of continuous tint negative to the original was received.

Example 6

60 mg of pyridine-tellurium tetrachloride complex and 250 mg of polyvinyl formal were dissolved in 3 ml of tetrahydrofuran. One photosensitive layer was prepared on a polyester film, exposed and then exposed in the same manner as in Example 1 to give a continuous tone black image negative to the original.

Example 7

30 mg benzene diazonium chloride tellurium tetrachloride complex and 250 mg of polyvinyl butyral were dissolved in 2.5 ml of N, N-dimethylformamide. A photosensitive layer was prepared on a polyester film, exposed and then heated in the same manner as in Example 1, wherein

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a black image of continuous tint was obtained, that was negative to the original. ·.

The invention has been preferred by way of above Embodiments are described without being limited to be.

Claims (12)

Claims Photosensitive material that has a support thereon located photosensitive layer having at least one complex of (a) a tellurium halide or a selenium halide and (b) contains at least one organic base. 2. Photosensitive material according to claim 1,. characterized in that the tellurium halide from tellurium dichloride, tellurium dibromide, tellurium tetrafluoride, tellurium tetrachloride, tellurium bromide, tellurium tetraiodide, Tellurium dibromide iodide or tellurium dibromide dichloride and the selenium halide consists of selenium tetrachloride, selenium tetrabromide, Selenium tetraiodide or selenium dibromide iodide. 3. Photosensitive material according to claim 1 or 2, characterized in that the organic Base of an aliphatic amine compound, an aralkylamine compound, an aromatic amine compound, a nitrogen-containing heterocyclic compound or a diazonium compound. 4. Photosensitive material according to claim 3, characterized in that the organic Base is represented by the following general formulas: (ID A ₁ -N. "R ₂ NBN (III) (IV) A ₂ (VI) • Ν (VII) Αχ (VIII) A ₂ Ai R ₁ (IX) • (X) S098 3 2/0953 (χι) (Xu) Ar-N ₂ CA where A ^, A «, A, land A ^ each represent a hydrogen atom, an alkyl group or an aryl group, B an aliphatic hydrocarbon group with 2 or more valences or an arylene group, Ar an aryl group and R ^, R ₂ , R- * and R ^. which can be the same or different, each represent a hydrogen atom, an alkyl group or an aryl group. 5. Photosensitive material according to claim 4, characterized in that the alkyl group for A ^, A ₂ , A, and A, represents a straight-chain, branched-chain or cyclic alkyl group which is unsubstituted or with one or more alkoxy groups, aryl groups, aryloxy groups, aminoalkyl! groups, Aminoarylgrupne, sulfoalkyl groups, sulfoaryl groups, carboxyalkyl groups, carboxyaryl groups, haloalkyl groups, haloaryl groups or aralkyl groups can be substituted as substituents that the aryl group for A ^, A ₂ , A, and A ^. represents an im * substituted aryl group or an aryl group which is bound with one or more alkyl groups, ary groups, alkoxy groups, aryloxy groups, acetyl groups, sulfoalkyl groups, sulfoaryl groups, haloalkyl groups, haloaryl groups, aralkyl groups, nitro groups, hydroxyl groups or 509832/0953 Halogen atoms can be substituted as substituents. that the aliphatic hydrocarbon group for B represents a straight-chain or branched-chain aliphatic group which can contain one or more arylene groups or double bonds which interrupt the straight chain and which are unsubstituted or with an alkoxy group, an aryl group, an aryloxy group, a nitro group, an amino group, an aminoaryl group, an aryl group, an arylalkyl group, an acetyl group or a halogen atom can be substituted as substituents and in which the arylene group for B and the arylene group interrupting the straight chain of the aliphatic hydrocarbon group for B is an unsubstituted arylene group or one with one or more alkyl groups, aryl groups , Alkoxy groups, aryloxy groups, nitro groups, amino groups, aminoaryl groups, arylalkylene groups, aralkyl groups, acetyl groups, acetylaryl groups, hydroxyl groups or halogen atoms represents arylene group substituted as substituents that the alkyl group pe for R ₁ , R ₂ , R ^ and R ^ represents 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 ^ represent an unsubstituted alkyl group or aryl group or one with one or represents a plurality of alkyl groups, aminoalkyl groups, aminoaryl groups, alkoxy groups or halogen atoms as substituents substituted alkyl or aryl group. 6. Photosensitive material according to claim 1 to 5, characterized in that the light-sensitive layer contains a binder. 7. Photosensitive material according to claim 1 to 6, characterized in that the photosensitive layer has a thickness in the range of about 0.5 to 50 microns. S09B327Ö9S3 8. Photosensitive material according to claim 1 to 7, characterized in that the complex is present in the photosensitive layer in an amount from about 3 to about 60 percent by weight based on the weight of the binder. 9. Photosensitive material according to claim 1 to 8, characterized in that the light-sensitive layer contains at least one optical sensitizer. 10. Photosensitive material according to claim 9 _f, characterized in that the optical sensitizer is present in an amount of about 0.1 to 100 parts by weight per 100 parts by weight of the complex. 11. A method for producing an image, thereby characterized in that the photosensitive material according to claims 1 to 10 is exposed imagewise and heating the photosensitive material. 12. The method according to claim 11, characterized in that the heating takes place at a temperature in the range of about 50 to 200 ³ C for about 0.1 sec to 3 min.