DE2105199A1 - Photosensitive material and process for its manufacture - Google Patents

Description

Liciiterrrpfinalich.es Haterial "una procedure. Zvl his Jie

The invention "relates to a light-sensitive material and a process for its production. In particular, the invention relates to a light-sensitive material. Katerisl, which contains an organic, photoconductive material or at least one organic, photoconductor.de compound as its essential main component, as well as a process for the production of such a light-sensitive material

As electrostatic, photographic, light-sensitive materials, metallic selenium alloys for indirect electrostatic photography, like zinc oxide, for direct electrostatic photography have been used up to now, especially with these electrophotographic materials widespread for re-production bans

109633/1809

• AD ORIGINAL

Have found application. Organic, phatoleitonde Katc-x ·: · --Jiv are far better than selenium and zinc oxide in terms of transparency, flexibility, low weight, processability into films, selectivity in terms of charging polarity and surface smoothness, but they have in contrast for the last-mentioned photoconductive materials so far no practical use for electrostatic photography has been found, which is due to the fact that the photosensitivity of organic, photoconductive llmaterialien is significantly lower than that of selenium and zinco-jcja, so that for imagewise exposure after charging strong light source is required. As organic, photoconductive materials, for example, condensed polynuclear "aromatic compounds such as anthracea, pyrene, perylene and the like, heterocyclic compounds such as ir-iphsnylpyrazoline derivatives, acylhydrazone derivatives and high-polymer compounds such as poly-N-vinyl carca.20l." Recently v.arii; considered the photosensitivity of the above: ii conventional photoconductive materials with low erinr.cr Er.Vj-.i'v ... · .'.- sensitivity through the application of organic oynthenopiocuiico or with the help organic synthesis method. A1.-J As a result of these efforts, several valuable photoconductive materials have been found -N-vinylcarbazole, in Japanese Patent Publication No. 7592/1968 Poly-3,6-d iodine-9-vin.y icaj / V ^ zo in Japanese Patent Publication Kr. 9639 / 19o7.; · .. - .. Poly-N-vinyl-3-aminocarbas ol tmd in the Japanese i'at & nsy publication No. 2629/1968 Polyvinylanhracon besehri eauii . «

109833/1809.

IAD ORIGINAL

suggested. This photoleite ^ -or; Does not have a particularly high photosensitivity ar ¹ : on its own and is therefore used in practice together with a spectral bilizing dye. For example, bromier <* ■: ..; 'Polyvinyl carbazole is a certain triaryl carbonium dye *, ■; ■. combined to achieve a photosensitivity comparable to "that of dye-sensitized zinc oxide.

As can be seen from the above example, the organic photoconductive materials and the sensitizing dyes usually combined therewith obtained by means of special and complicated organic syntheses and subsequent purification. It therefore remains even if a high sensitivity is achieved, unresolved economic and practical problems.

In a known printing recording material, which is known as a system containing free radicals, radical formers are used, ie substances which can generate free radicals when excited by radiant energy. Recording material only has poor stability. This is due to the radical generator used. Venn as a radical example, a Polyhalοgenverbindung, such as: - is used ,,, .. · Teträbronkohlenstoif, so in the photosensitive layer of such material or lichteiipfindlichen Aufzeichmmgssaterials is substantially non umgesetztsr or free £ ^ etrabromkohlenstof present, - the scr .flüchtig, iryitabi ^ is toxic that such a photosensitive material or

IAD ORIGINAL

Aufzeiehnungsmotcrial not used in practice we can.

The invention is therefore based on the aim of creating a highly sensitive, chemically stable, organic photoconductive material, in particular for electrostatic photographic purposes, and of providing an economical method for producing such a photosensitive material, since none requires complicated organic syntheses and no complicated purification steps and makes it possible to obtain the light-sensitive material through a simple sensitization treatment.

It has now been found that Orange photoconductive materials through a simple S-erislbilisiernngsbehan-dlurj-rr to a photleitenden Material can be sensitized, its identity sensitivity with that of conventional SeIeb odor (dye-sensitized) 2inkoxjd is comparable or this is known photosensitive materials even surpasses in this regard.

It was found that an organic photosensitive material with the properties explained above can be obtained by simply adding a mixture of at least one substance capable of forming free radicals when excited with radiation energy ζην (radical generator) and at least one photoconductive, organic ?! Connect -: - · in the presence of at least one iaetallorgani, see connection kit. Radiant energy under chemisekei ¹ reaction be-h & h & felt .. With JLl.1Ge

ORIGINAL

one containing such a mixture as an essential ingredient Photosensitive material can have the disadvantages known organic, photoleiteη - η described above Overcome materials and can be a highly sensitive, we · ο obtained economical and chemically stable, light-sensitive material for electrophotography.

The subject of the "invention is thus a photosensitive material, containing a mixture of at least one in the presence of at least an organometallic compound treated with radiant energy under (chemical) reaction, when excited with radiant energy substance capable of forming free radicals (radical generator) and at least one organic, 'photoconductive compound, as an integral part.

According to a preferred embodiment, the photosensitive Material additionally a dye base compound and / or an organic one Color component included.

According to a further preferred embodiment of the invention can produce the above-mentioned photosensitive material by applying radiant energy to a mixture, optionally with the simultaneous application of heat leaves that contains the ingredients listed above.

According to a further embodiment of the invention, ira . ^ 4, -, ... ,, light-sensitive elements can be called by using rayui. lets act on "in on a carrier" applied mixture of the above.,.,. mentioned constituents.

109833/1809

PAD ORK3INAL

The organic to be used for the purposes of the invention, Photoconductive materials can be any of the following organic. V3rbindurigen or groups of substances from ^ c; .- an It will be:

A) Examples of vinyl carbazole are:

Vinylcarbazole, poly-9-vinylcarbazole, 9 ~ vinyicarbazole copolymers, 3-nitro ~ 9-vinylcarba3olcopolymers, ^ - ^ - i'ethylaiQino- ^ vinylcarbazole, nitrated poly-9-vinylcarbazoles, bromine-substituted 3-vinylcarbazoles, such as 3-bromo-vinylcarbazoles 9-vinylcarbazole copolymers, brominated g-vinylcarbazole copolymers and 3} 6-dibromo-9-vinylcarbazole copolymers, poly-II-vinyl-3-ailinocarbazole, brora-substituted poly-9-vinylcarbazoles, such as poly »3-brOD-9-carbazole, 71 , Boly-3 "6-dibromo-9-vinyl carbazole and broraierte IT Yinylcarbazole, jodsubstituier be poly-vinyl carbazole 9 as J-Jew-g-vir ^. 'lcarDazolcopolymere and poly-3 ₁ 6-diiodo-9-vin ; / lcarbazolG, iodsui; -;: - ti f.uierte 9-vinylcarbazole copolymers, such as 3-iodo-9-vinylcarbasolcopol / .rere, poly-3-benzylideneamino-9-vinylcarbazole ^ - , ^ -Bis-Cli-carbazole) alkane derivatives, vinyl anthracene-N-vinylcarbazole copolymers unl 2- (or 3-) vinyl-9-alkylcarbazole homo- or copolymers with primary alkyl radicals, such as methyl, ethyl and propyl radicals. . -

B) Examples of aromatic amino derivatives are:

Aminopolyphenyl, allylidenazine, Ii, N'-diallyl-N, N'-dibenzylphej :; Ίλ-ιι- diamine, H, H ¹ , lI'-tetrabenzyl-p-phenylenediamine, lijN'-diplienyl-p-phenylenediamine, NjN'-dinaphthyl-p-phenylenediamine and 4,4'-bisdimethylaminobenzophonone.

C) As biphenymethane and triphenyliaei; ha: v. t-. ⁵ nd example leuco bases of diphenyl- and trxphenyl ^ ·: tn-mfarbstof fen. to neixuai.

D) As compounds with heterocyclic yci i? Ing's are, for example, · ^ ·; ö Qxadiazole-, 5-Affinothia s'ol-, A- , 1,2-Tri'n χ oil-; 'Imiciazolön-, 0x "a ... ο 1 -, imidazole, pyrazoline, imidazolidiii _-«% toly r hcnyleHthiazol -,' 1,6- "- '

1 09 833/1 8.0 9, ...,

iAD ORIGINAL

«Ι. 7 -

i1ethO5: .yphenazin ~ and pyrazolinopyrasoline derivatives should be mentioned;

E) As Verbincjuripen with condensed rings are be pie is Is ve is'2 benzothiazole, benzimidazoles Benzor-ra ^ olderivate such as 2- (4 '-DiaT.Jr ₁ o ~ phenyl) -benoxaKol and 2- (4'-Dimethylaminopheyl ) -benzoxazöl _t Aminoacridine, quinoxaline, Biphenrflenhydrazcnverbindungen _# pyrrocoline and 9 ^ 10 -dihydroanthracenderivatei

As Verbindiinpeii with at least one double bond, for example, Ac ^ hydrazone, Äthylcnderivate _t 1,1,6,6-Tetrapheiiylhexatrien and 1.1 ^ -Triphenylpent-i cn - ^ - to name in-3-ol.

G) Condensation products include, for example, condensate! products of aldehydes with aromatic amines, reaction product « secondary aromatic amines with aromatic halides and pyrömethanimidopoly-p-phenylene-1,3,4-oxadiazole for hens,

H) As yinyl polymers (with the exception of polyvinyl carbazole) are wise -v-alkylacrylic acid amide polymers ^ polyvinylacridines ,, poly- \ _Λ , 5-diphenyl-3- (4-viny! Phenyl) -2-pyrazolines, pyrazolines, polyacenaphthalenes _t ring-substituted polyacene ₅ phiäiiä # $ Polyviriylanthracene and Poly-2-vinyldibenzthiophenes to be mentioned «

I) As organic photoconductive oligomers are, for example Connections of the lOrmel

Ji \ / y

to be mentioned, in which l, m and η each mean 0 or 1 and dei Relationship 1- τη2: η suffice, e.g. p-bis (2-phenyi-4-thiazolyl.) - ' benzene as a pinpoint ring compound, 2-4 bis £ 4- (2-phe23 phenylj-thiazole as a seven-membered ring compound and 1,4- ' 4-thia.2; olyl) -phenyl i-thiasolylT -benzene as letaa

109833/1809

OBK3INAL

Vota of the organic, pliotolei tendon materials listed above are preferably Yiirj Ic orb azo 1 and. Viny derivatives, aromatic amino derivatives and di- and Trlp metaanderivate used »The radical formers used for the purposes of the JEG are substances that form free radicals when excited by radiation energy kep: ·. Radical formers can for the purposes of the invention au π follow ·; ·. wide range of different substances or substance classes can be selected:

A) As polyhalogen compounds, one can, for example, Y er of the general formula

use ,, in the H a hydrogen, chlorine, bromine or Jodafcom, an alkyl radical © of a group of the formula

-C- II K "-S- III

O 0

or E- -S- IV

* H

■ ο ■

is wherein R- is a substituted or unsubstituted alkyl, aryl or he trocyclic group, X, T and. Z equals or

109 * 33/1889

“AD

are different and each a hydrogen, chlorine, bromine or Iodators or an alkyl radical, with the proviso that at least one of the Eeste X, Y and Z is an Ilalogenatom is. Examples of such connections are:

CBr ₄ , CJ ₄ , CHJ ₃ , C ₂ Cl ₆ , CBrCl ₅ , CCl ₄ , CHBr ₅₁ C ₃ Br ₆ , C ₃ HBr, C ₆ H ₅ CBr ₅₁ CJBr ₅ , CJCl.- ,, CHJBr ₂ , CBrCl ₅ , CHBrCl ₂ , 2,2,2-trichlorotoluene, 2,2,2-tribronacetopheriOii, 1,1, i-tribromo - ^ - methyl ^ -propanol, 1,1,2,2-tetrabromoethane, 2,2,2 - ^f fribromäthanol, CH ₂ Cl _2, CH ₂ Br _2, OEpJ _2, "ClCHojCHgCl, BrCH ₂ CH ₂ Br, CH ₅ CHCl _2, CII ₅ CHBr _2, CHCl ₀ CHCl _5, ClCH = CHCl ₁ CHCl-CCIP, Br (Clip), Br, Br (CHp), Br, '\ Br (CH ₂ ) t-Br and Br (CH ₂ ^ Br ₁ halogenated organic sulfoxides, v; ie pentabromodimenthyl sulfox3 ^r d and hexabromodimethyl sulfoxide and halogenated organic sulfones, such as hexabromodimethyl sulfone , Trichloromethylphenylsulphone, tribromomethylphenylsulphone, trichloromethylp-chlorophenylsulphon., Tribromethyl-p-nitrophenylsulphone, 2-trichloromethyl-benzoxathiazolylsulphone, 4, D-dimethylpyrimidyl ^ -din 2-dinine-sulfone, 4-methyl-2-dichloro-tri-methyl-2,4-dichloromethyl-tri-methyl-trichlorophenyl-trichlorophenyl-tri chlorophenyltrichloroethylsulphone, 2,5-dimethyl- ^z i-chloro-phenyltric hloriiiethylsulphone, 2, ^ - dichlorophenyltribroEimethylEulphone and bromomethyIdibromomethylsulphone.

B) As carbonyl compounds, for example, vicinal rol.yVictaldonyl compounds, ^ - carbonyl alcohols, Acryloin ether, - ^ -hydrocarbon substituted acryloins and polynuclear quinones 2U

C) As Sehwefelverbindungen are, for example Alkyldis.ulfidc, aralkyl disulfides, aryl disulfides, Aroyldisulfide, AcryldiLuifide, cyclic alkyl disulfides, mercaptans, thiols, Hetc "Liniere", ... ■:;, dithiocarbamates, O-Alkylzanthogenate and Thiuranderivatt. : -; u i '.'n'i

10 9833/1809 BADOBIGINAt

- ίο -

D; Examples of peroxides are. · Vreise './-^.■^cTstoiVCncror-ry-'i, dialkyl peroxides, diacrylperocyao and ■ -l-ij / oyipeio-ide zn ^ οΐΐΐνοϊ. Examples of azo and diazo compounds are Aaon. Tril Lr diazo compounds, such as p-nitrobenzoldiaonium-p-chlorberiz-o Ir. ul .'.- ■ .- ;. to call.

Particularly excellent results are obtained if κ?: Λ. for the purposes of the invention, the above-vn ;; _o rif cfüh'üca-radical formers, a polyhalogen compound verv / eu.ot.

Representative examples of organometallic compounds which can be used for the purposes of the invention are i-ritallrd Λ, / Ie, metal aryls, alkylaryl-ietJallverbindungen and cyclopentadiene / 1-metal compounds. As metal ο, the Al.:;/!-, aryl and alkylaryline compounds contain metals from groups TVb and Vb of the periodic table of elements. These compounds preferably contain the metals Ge, Sn, Pb, P, As, Sb and Bi. The cyclopentadiene / metal compounds contain transition metals from groups IHa, IVa, Va, Via, VIIa and UIa of the periodic table as HotalLe. As transition metals the Gru; ir; o 1IJx- :. \ Ϊ́ιά Sc, Y, La, Ce, Pr, Nd, Sai, Gd, Dy, Er and Ib, as all ran t'v? Group IVa of the periodic table the elements Ti, Zv and h: \ as metals of group Va the elements V, Hb and 'la, as>I.;;. R.3 _; 2e of group VIa the elements Cr, Mo, V and Ii, as transition elements of group VIIa the elements I-ia, Te and Re as well as Mots 1-1.-. eier Group Villa to name the Elctac ^ te Fe, Co, IJi, and Ru.

109833/1809

Examples of those suitable for the purposes of the invention organometallic compounds are listed below.

- and alkylnrylmetallverbiridungen are, for example, tryphenyl metal compounds, such as triphenyl bismut in, 'friphe-pylstibin, triphersylarsine and triphynylphosphine, tetrapnylr; t. all compounds, such as tetraphenyldistibine, tetraphenyl lead,! tetraphenyltin, tetraphenylarain and tetrapaenylgermanlum, B tripfrenyl lead, Iriinethyltripheriyldizinn,] i.cxa.methyldizin2i vr.u name phenyldizinn zn .

In d "n compounds _f the alkyl aryl or alkylaryl groups are bound to the metals that they to form absattigen- whose valences Ketall-carbon bonds

As a metal of group III A containing metallic compounds, for example cyclopentadienyl-erbiamingeri of scandium, yttrium, lanthanum, _{gers, praseodymium 4} neodymium, samarium, gadolinium, dysprosium, erbium and ytterbium are to be mentioned. Examples of suitable organometallic compounds with a transition metal from group IV are bis-cyclopenta titanium, dihalogenated bis (cyclopentadienyl) -titanium di-vB.te _i bi-clopentadienyl) -titanium diaryle and bis (cycloprntadienyl) zirkcdibi " to name aBij! S. Examples of suitable organometallic compounds of transition metals of group VA are bis-CcyelDpenta & iecyl) -

109833/1809

vanadindihalogenide "Bi s- (cyclopentadiene; / J) -niobtribramid, bis (cyclopentadienyl) -taiitaltr2broniid, bis (cyclopentadiene j ~ vanadium and Cyclopentadienylvanadintetraearbon.

Examples of suitable organometallic compounds of transition elements of group VA A sirri bis (cyclop 'ntadierr; i.) - · chromium, bis (cyelopentadienyl) - u -pentakohlenmonoxydblmolybden, bis-cyclopentadienyl) - η -hexakohlejimonoxydbiwolfrain, Triu- (c. vclopentadienyD uranium chloride.

Examples of suitable organometallic compounds of ferrous metals from group VII A are bis-cyclopentadienyl) manganese waä hydrogenated bis-cyclopentadienyl) rhenium.

Examples of dietal organic compounds of transition metals of group VIII A which can be used for the purposes of the invention are bis (cyclopentadienyl) eicene / Forrocr.?:, Bis (cyelopentadienyl) iron dicarbonyl, cyclopentadicnyloi: .. ■ '. carbonyl chloride, cyclopentadienyl carbonyl cyanate ^ Bie- (cyclopentadienyl) cobalt bromide, bis (cyelopentadienyl; ~ cobalt [eobaltocene}, cyclopentadienyl ^ .obalt diearbon.yl, bis (cyelopentadienyl) -nicadicnyl, cyclo-cyclo-cenyl

* - J

nekelltrosyl, bis (cyclopentadienyl) ruthenium and bira (cyclopentadienyl) ruthenate.

109831 / $ 180

«AD ORIGINAL

One or more organometallic compounds can be used. Of the above-mentioned organometallic compounds, triphylbisinu.tin, l'riphenylphosphine, tetraphenylallene, ferrocene and cobaltocene are preferably used. _; ..._ ₍ ... "■ -

The radiation sources used in the process of the invention are selected as a function of the organometallic compounds, radical formers, organic photoconductive compounds or substances and / or solvents used in each case. Any type of light source can be used as long as it can generate free radicals from a radical generator in the sensitization system. Light sources are preferably used which emit a high proportion of ultraviolet rays or rays in the national UV range, such as mercury (low pressure, high pressure or super high pressure), metal halide and xenon lamps. If necessary, the otv? -Jhlyngr "energy, eg UV radiation, can be combined with heat ^ .. ij-ov / oi; :::. In order to prevent the decomposition of radical formers; iu beach] ΐ.α-ni gen that the 'i' temperature at which the structural energy is "applied" i.} it,:; proch> .iiid we selected !. ', ^r oboj_ ■ ■■ i-'"'^; - in time for you: Be.st-r ^ alurigüdaucr so chosen, di / i di _t · ■ -1 - ..'. ο '. <■' ■ Senoibi J i eiervu-, and the thereby occurring a secondsUi ¹ CiTe) CIt-,:;. Ss. Noticeable

1 0 9 8 3 3/1 a 0 9

Discoloration and gelling of the Ht; uk υ ions ^ j er. Lichen, Ir a balanced relationship can be brought, ./eiternin Irözinen, of course, the Zers et van ^; des K ^ uilcalbi idners uriu the occurring chc, <; i :: che iic ^: Hon dr.auron;.; / · ΐ.-, -.- ^ t that one has the Z; jit of the »Ji. .-ii.ViIun ^ T.cr-orjio.-.- nv / t ^ -. taf ^, adjusts accordingly. i »ie v; j rr ^ r- ^ en ..'-- li ^ rilun ^ Vi- the radiant energy are explained below for the sake of sake:

- · ΊΟΟ m / rev

Carbonyl compounds 3 & O - 3öf ^; πι / u Organic sulfur compounds 2bü - 'I-OO ia, u Peroxides 3 ^ 0 - 400 m, u

Azo compounds 3 ^ 0 - 400 m ^ a

Of the above on ^ uiiihrteu v / irksa / ner .. V / ellenläi. _o s are the nachstehcna & uf some 6Γ · _{Γΐΐιααη} ο α ^^: ^1: .ώ 7i; X'Wer bare Halogenverbiridunij'vri anv / enabaren wellenlfic _u eu on _d e type:

CBr. below 400 m / rev

CH ₂ Br ₂ "330 irya

₅ "400 Ly u

CHJ, "400 ir./a

3 /

The SensibilisieruntjSLun ^ ridlimt, iionri v / i- fol ^ L by; /: to be carried out: Under /tr./ondunt; a ^ ^ eu-i.Tieten Lü-u: .. .. mitteis v; ird an aor ^ o _t vuü Lo ^ uu ^ au.'j a oi ^ uiijc:. ·.;. ^ lo toi ext ending material, a liadikalbilduer and eJ.ncr organometallic compound 'ndur :. _o her ^ t ^ ^ eIIt, on aie ι: .- .: α zur Durchführungun _t ; aer ov.-ioibiii
can act. , Venn i:.:. Lne lüc-L

1 O a 8 3 3/1 8 ü 3

■ AD ORIGINAL

I iU3

is used, i; .o leaves iiicii only ronwor oi:, / jL-i ^ ut. ■ ■ Löü.u.ri (j £.; KiLtel select b; .v /. I'inu ·.;. ·, Da u .;. · Vcrvcu ·. '. ·· ■ · Loaun ^ uiittel üowohi with regard to Gc .-r. or ^ arii;: ·.. -n, ph οι head ::, lint '.;! ·] οΐΰ r1: j; -. uc): Lr ^' Jich uf; ; ouika.'l · .. ·.;. ^; . ■ -ners a auürv; ici-oau.e ^ Lci ^ un ^ üVi - ^{r #;} . "·, On beti t.;, En ilujJ ..- ία also Löiiun _t ; sjr.iu1; el vernaeat;:, because. ·; J üolltf ι-, the ac ■ Sensibili.iiieruUj_, ij-e ± ' f ect decrease. iJo germinate, beisp.ic j i _.- when using van lolj-. ·., -vinylcarbazole aJ.b i-; chc- ^, pJi j uolcitbiideü I-üL%, - vi: .J. aiiu. ΪΌ ι, γι. urcLuio; .χ ■ ..- staXi "al :: - xuiaijcalbilaner, iiwiaol uaci KoriochJ orbenaol ·: .ΐ öensibl3 ir.icruii ^ rc-XXekt increase, v.'änrerid i'ct.rahydrcl <■> ■ <i: and HioÄ? ■ · aen oen ^ ibi.liyierurit, 3cij «urt heraawühlen.

The rfina.ui: _{tJ is} based, among other things, on the knowledge, α, - ,, Ζ the verriutjerui.it caused by lazurite, the sensitization ei'fect aurch üusat ^: a small amount of an organometallic YerbiriG-aum liQsitioüi; -syatem considerably a: .., _. € can be weakened- ijo , for example, with Vc-rfείΐΓ '/ η aer .trfinduuc ethylene chloride, chlorofuran, toluene and xylene, which are usually not particularly suitable, so .'ie autßerdei ·. , Vorv.'ariden are as LÖGunysEiittel with beXüieal ^ endeia ürl'olg ^":;: füraii and Dioxau that otherwise extremely un _a u - Tetrahyuro * :: zi. Through the Ilri'inäung soiniu the freedom freedom:. ".. züh dec Losuri ^ sniittelG selir strongly egg-wide;. Pie use dun ^ of organometallic ye r bin fertilize leads to a high sensitivity to light. Hex iiensibilization effect. the erXinaungsgeaäS used meballor ^ anisehen compounds is further below in the hüiüpiele it in detail according to sr t "If eii: e a liadikalbildner u.a. an organic, photoconductive material -containing solution - v: .irä., which is colored or Additionally

109833/1809

“AD

a dye base compound or an organic dye contains, the sensitization can be followed visually, since the coloration of the solution is noticeably accelerated will.

The sensitization treatment can be carried out by various methods, for example, by applying radiation energy to a solution which is an organometallic Compound and contains a radical generator and then this solution with a solution of a organic, photoconductive compound, or by adding a solution that contains a radical generator and a organic, photoconductive material and a second solution that contains a radical generator and an organometallic Contains compound, each irradiated individually and then mixes the two solutions together, εον / ie finally, by irradiating a solution applied to a support which contains an organic, 'photoconductive material, contains a radical generator and an organometallic compound. You can also use a photosensitive Material with even higher photosensitivity can be obtained by adding the photosensitive material a dye base compound or an organic dye incorporated. Especially when irradiating a solution applied to a carrier that contains an organic, photoconductive material, a radical generator, an organometallic compound and, if desired, a Contains dye base and / or an organic, coloring component, any solvent can be selected, as long as it is only able to dissolve the organic, photoconductive material. This freedom of choice regarding of the solvent is very valuable.

109833/1809

• AD

-v-

It is believed that the effects of Radiant energy to an organic, photoconductive Material, a radical generator and an organometallic compound evolved into does not perform any of the following:

Assume the radical generator is a polyhalogen compound the formula

R - OX, V,

in which R is a hydrogen or halogen atom or an alkyl or aryl radical (substituted or unsubstituted) and the radicals X are identical or different to one another and each represent a chlorine, bromine or iodine atom, so takes place when the polyhalogen compound is exposed exposed to a sufficient amount of radiation energy the following reaction takes place:

1) R-GX, - »R-GX ₂ + X.

The halogen free radical formed in this way "X ·" snatches a hydrogen atom from the surrounding medium, whereby a hydrohalic acid of the formula HX is formed after the following secondary reaction:

2) X -? - H> HX

The free organic radical "R-GX ^""is to be regarded as a chain number:, (-. R , which allows the reactions 1) and 2) given above to proceed as chain reactions.

109833/1809

If in the Reaktior-srsyctc. :::: there is an inorganic pre-bond (M), then the x-wTfcki / iviv: 't der Radikalbilduni, * by SoraiL.l., R _; sener-lo in the by the following Reaiit'iousgleJ.oi-u: ^: wiecür.ogebenen. Way increased /. ·

3) R-CX ₃ ——--> R-CZ ₂ + X ·

It is assumed that the organic compound acts as a reaction accelerator or catalyst.

Those given in reaction equations 1) and 2) Reactions can therefore be triggered effectively and one can be inorganic through the action of the set Shorten the reaction time and at the same time this will reduce the applicable range of reaction conditions, v / ie selectivity of the solvent, too tolerable pollution levels and the applicable temperature range broadened for the reactions proceeding according to equations 1) and 2). It also leads the addition of an organometallic compound to a Improvement of photosensitivity.

In the present invention, the above-mentioned organometallic compound and the halogen compound become a solution an organic, photoconductive material added, in front of the resulting solution of a radiation energy which is sufficient to carry out the reactions represented by reaction equations 1) and 2) to trigger and thereby to sensitize the organinche photoconductive material considerably.

1 09833/1809

Eg it was found that through ^. "Ie vorr > ■ · ■■. End er. V πte Sensibilifn er'inrsbehonälung OJ =: Lichi.» -? ¹ ^ fi ndli ohi.ti t of light-sensitive Matorialieη for din Elektro-Pnotography can be improved, but de ^ JlechaniF.mns this R ^ nsibilisi pninf is not yet completely: re ¹ "l." rt. Di f- ϊ '<ΐτ the purposes of the invention to be used "Rfoikolbildrer ^ .enre \' ίτά depending on the photoconductive material used and the applied ften-Te an F. Tn the Reecel beta ^ ä ^ t; the Iienpre of radical formers pre-lashing about 1-30 percent by weight. The amount of metallurgical compound to be used is selected in a pure kneading manner depending on the photoconductive material used, the radical generator and the amount of radiation energy used. Tn the Hee; el the Yienre used is an me tailor p; ani shear Verbindimfr preferably between about 10 - 10 percent by weight.

If the traktorra African, rhotoleitende material used pelbrt the EiprenFchaft has to make movies, or mxr to _films: - to be malleable, so it does not iet erforder] me, a binding "i '/ resin or to use a plasticizer if!. the organic "photoconductive mater-la!" ... but no film re-image. He recommends using a binder resin based on the photoconductive material. " ¹ .. Use about 30-100 percent by weight of a binder resin. To improve the properties of the films obtained, use 5 Add 100 weight percent V.'oichrnachei *. Representative examples of suitable bonding agent resins are polystyrene, polyvinyl chloride, phenol, polyvinyl acetate, polyvinyl acetal, Ευο: "· ™, xylene, alkyd, polycarbonate - xmd acrylonitrile-styrene resino.

109833 / 1S09

Representative examples of suitable plasticizers are Dioctyl phthalate, tricresylphonphate, diphenyl chloride, Methylnaphthalene, p-terphenyl and

In order to increase the photosensitivity of obtained according to the invention, light-sensitive material for the EleVtrophoton-rq-nhie to increase further and the spectral sensitivity sc ^ qfter. set, the addition of one in the ElektroDhotogra-ohie commonly used dye sensitizers and / ocior one Lewis acid is an effective agent.

Furthermore, one can check the photosensitivity of the photosensitive Material can also be effectively increased by adding a dye base compound, which is produced by the »radiation energy caused reaction with a radical generator can form a dye. You can also do this for this purpose too add an organic coloring component, the reaction caused by radiation energy with a radical generator can form a dye. These color rabbit compounds imd organic coloring components can be a far stronger one or generate higher sensitivity than usual Dye sensitizers is achieved.

Below are representative examples of suitable dye compounds, listed:

Leuco bases or carbino bases suitable for the purposes of the invention are, for example, leuco bases from Trit) heny1. ⁱ⁾ -et> nnfarbstoffen as Leukomalachi tgrün, Leukokristallviolet, T.erkomethylviolet and Leukoopalblau and Garbinolbanen of Trn piifnylmethanfarbstoffen as Carbino crystal violet and carbinol .-: .- htylviolet and leuco bases or carbinol bases of Diphenyle- ^"1M ?? r> -

109833/1809

SAD

dyes of the formula

in which E ^, E ₂ , E, and E ^ each represent a hydrogen atom or a (substituted or unsubstituted) alkyl, aralkyl or aryl radical, a leuco base being present when X is a hydrogen atom and a carbinol base, such as "Michler's Hydrol" when X is a hydroxyl group as well. Styryl dyes such as 4- (4-dimethylaminophenyl-1, 3-butadienyl) quinoline, 4-p-dimethylaminostyrylquinoline, 2-p-dimethylaminostyrylquinoline and 2-p-dimethylaminostyrylquinoline, a cyanine dye such as 2- / 3-ethyl-2 ( 1H) -quinolylidenepenyl7- quinoline, 2- / 2-methyl-3- (3-ethyl-2 (3H) -benzthiazolylidene) -propenyl7-benzthiazole, 4- / 2- (3-ethyl-2 (3H) -benzthiazolylideneamino) -vinyl7-quinoline, 4- (1-ethyl-2 (1H) -quinolylideneamino) -quinone, 2- (p-dimethylaminobenzylidene) -aminoquinoline and 4- (p-dimethylaminophenylimino) -cyanomethylquinoline, a merocyamine color base such as 3-A ^ hyl-5 ~ / 3-ethyl-2 (3H) -benzoxazolylidene-7-rhodanine, 1-ethyl-3- (3-ethyl-2 (3H) -benzoxazolylidene) -oxyindole and 4 - / 'C3-ethyl-2- ( 3H) -benzoxazolylidene) -äthylinden7-3 ~ phenyl ~ 5 ( ^z '-H) -isooxazolone, a leuco-dihydroanthracene compound, such as 2,7-bis- (dimethylamino) -10-p-dimethylaminophenyl-9,10-dihydro-9, 9-Ä.imethylanthracene and 2,7-bis (dimethylamino) -9,10-dihydro-9,9-c-limethylantracene.

As coloring components usable for the purpose of the invention the following connections are to be mentioned, for example:

A) Arylamines, e.g. compounds of the general formula

EKR ₂

109833/1809

in dor Ii a Wasse.rstoffatoia or a (substituted or unsubs "substituted) alkyl, aryl or aralkyl group, R ^ a phenyl, ^ -ITaphtyl- or β-ITaphtylrest and R ₀ a (substituted or unsubstituted ) Alkyl, aryl or aralkyls; l; means, 2; .B. Diphenylamine, IT-He thyl anil in, IJ, IT-Dirne th; /.! Aniline, H-Ätliylanilin, Ν, ϊϊ-Diethylanilin, Phenyl - ^ - naphtylar ^ in, phenyl-ß-naphtylamiri, triphenylanine and N-methyldiphenylamine.

B) Carbazoles of the general formula

VIII,

in which R is a hydrogen atom or a (substituted or unsubstituted) alkyl, alkenyl, aralkyl or aryl radical and R ^ and Rp are the same or different and are each one Mean hydrogen or halogen atom or an alkyl, alkenyl, aralkyl, alkoxy or dialkylamino radical, e.g. carbazole, N-ethylcarbazole, N-methylcarbazole, N-phenylcarbazole, N-benzylcarbazole, N- vinyl carba ζ oil, 3,6, dibromo-IT- vinyl carbazole, 3-Ch.lor-N-ethylcarbazole, 3-chloro-N-vinylcarbazole, 3-iodine-iT-vinylcarba: <Ol and 3-dimethylamino-N-ethylcarbazole.

C) indoles of the general formula

IX,

in which R is a hydrogen atom or a (substituted ode

109833/1809

substituted) alkyl, aralkyl or aryl radical i «t and the Ko.stο R-, are the same or different from one another and each have a Vci.ner-stoff- or halogen atom or an alkyl, alkoxy or Malkylar.ri no group ", e.g. indole, 2-methylindole, 1,2-dimethyliridol, 1-phenylindole, 4-chloroindole and H-vinyldndole. "

D) 1,3,4-oxathiazoles, e.g. 2,5-oxadiazole, 2,5-bis-p » ^l -diethylaminophenyl-1 ¹ J -1,5, ^ - oxa <3ia7.ol, S ^ -Bis- . ^ A'-n-propylaminophenyl-i ¹ J
\ '-cyclohexylarainophenyl ~ 1 ¹ I -1,3,4-oxadiazole

¹ J -1,3,4-oxadiazole and 2,5-bis-

E) 1,3,4-triazoles, e.g. 1-methyl-2,5-bis-L "^ ^l -N, N-diethylamine0T _J heuyl '1 C -1,3 ·, ^ - triazole, 2,5- BiS-O '-Ν, Ν-diethylarainophenyl-i'] -1,3,4-triazole, 2-5-bis [3'-ainophenyl-1 | j -1,3,4-triazole and 2,5 -Bis- ^ '-N-ethylaininophenyl-1 ¹ J -1,3 * 4-triazole.

P) imidazoles, for example 4- (4'-Mmethy] aminophenyl) -5- (4 ^l -chlorophenyl) -imidazole, 1-methyl-2- (diethylaminophenyl) -4,5-diphenylimidazole, 4- (4'-dimethylaminoT > henyl) -5-phenylimida7.ol and 2- (4 · -dimethylaminophenyl) -4,4-diphenyliiaida3ol.

G) pyrazolines, e.g. -1,3,5-triphenylpyrazoline, 1,5-diphenyl-3-atyrylpyrazoline, 1 ^ -Diphenyl ^ -p-oxyphenylpyrasoline and 1-phenyl-3-p-dimethylaminostyryl-5-p-dimethylaminophenylpyrazoline.

H) aminophenyl-substituted oxazoles, e.g. 2- (4'-dimethylaminophenyl) -4- (4'-dimethylaminophenyl) -5- (2'-chlorophenyl) -oxazole, 2- (4'-dimethyl aminophenyl) -4- (4 · -dimethylaniinophenyl) -5-phenyloxasol and 2- (2'-chlorophenyl) -4- (4 ■ -dimethylaminopheryi) -5- (2'-chlorophenyl) -oxazole.

I) Benzidine compounds, e.g. ortho-tridine, N ^ '- diphenylbeniridine, naphthidine and benzidine.

J) Λ, ~ 3 ^{D: i} te trahydroimidazole phenyl, for example ^1,3-D iphenyl-2- (4'-dimethylaminophenyl) -tetrahydroimidazol, 1,3-diphenyl-2-styrvltetrahydroiinidazol and Λ, 3 ~ diphenyl-2- styryl-tetrahydroimidi? 3ol.

109833/1809

K) Phenazine compounds, e.g. Λ, G-Qixi
Diiaethylphenaz in ..

L) acridine compounds, example sv / e ι ze 3) G-Bi r> ~ (dian: '/} ο) acridine, 3j6-bis (dimethylamino) -ac: r \ idin and acridine «

M) Acylliydrazone derivatives, e.g. compounds of the formula

OCO-WH-Ki-CiI

-CO-NH-H-CH

/ ^H 3

CH.

CO-NH-N = CiI

N) Quinoxaline compounds, for example 2,3-bite- (4'methoxyp] aenyl) - 6-aminoquinoxaline, 2-phenyl-3- (4 ^l -dimethylaminophenyl) -6-chloroquinoxaline and 2-phenyl-3 ~ (4'dimethylaminophenyl) -6,7-benzquinoxaline.

0) Arylidenazine compounds with R-dicubstituted amino groups, e.g. bis-4,4-diallylaminobenzylidenazine, bis-4,4-diethylamino-2,2-dimethylbenzylidenazine, Bis-4,4-dibenzylamino-benzylidenazine and bis-4,4-arylmethylamino-benzylidenazine.

109833/1809

BAD ORIGINAL,

- 25 -

P) pyridine and quinoline compounds, e.g.? - / ΐ, 3 - Γ> 1οχο-hydrindenyl- (2) 7-quinoline, 2- /
-quinoline, 2- / Ϊ, 3-dioxohydrindenyl- (2) 7-py.riciin and 4-kethyl-2/ ⁷ 1,3-cLioxohydriiidenyl- (2) 7-pyri <iin.

Q) Ethylene derivatives, e.g. compounds of the formula

HC ^^

\ - <> - C-C-CN

HC ^v ' H II

^N0 2, CH,

NC V> Μ ^> \ ^

CH ₃

CN H H CN

CLH-OOC-CC - ^ - \ _ ^{C = C} "^COÖC;

R) spiropyrans, e.g.

1, 3 _i 3-1 ¹ rimethyiindolinoben7; pyrylspiran _i 1,3,3-trircethylindolino-6'-nitrobonzpyrylspiran, 1,3,3-trimethylindolino ~ 6'-nitro-8'-msthoxybenzpyrylspiran and 1 ^, ^ - trimethylindolino- G'-metboxy-ß ¹ - nitrobenzpy_rylspiran ..

According to the invention, a photosensitive material can be produced by applying radiation energy and heat at the same time a radical generator and an organic photoconductive material in the form of an organometallic compound: can act or by letting "rahliin ^ s energy act on a solution, ImIJt, a radical generator, an organic, photoconductive man and contains a metallorfranische connection or else by

109833/1809

“AD

Radiant energy can act on a solution that contains a radical generator and an organometallic compound ■ -. ·. ■ - / * the po treated solution with another Tömmg inirohh, you? at least? an organic, photoconductive material pnl, or finally by the fact that a solution containing a radical generator, an organic?, photoconductive * material] and electrical "organometallic compound" was exposed to the action of radiation ·. "energy , mixed with a solution irradiated with stranium energy, which contains a radical generator · - '· - ·' ■, if desired, an organometallic compound.

With the manufacturing methods described above, your System, if desired, a color base connection and / or an organic coloring component is added.

According to a preferred embodiment of the method for producing a photosensitive element according to the invention, a solution containing an organic photoconductive material, a radical generator and an organometallic compound, which is sensitized before or after application by the action of radiation energy, is applied according to conventional application or application methods. Pchinhtung methods such as Valzbeschicbten, wire knife coating, air knife coating and the like. Applied to a transparent or opaque 'embossing. As already mentioned, the solution can be irradiated before or after it has been applied to the carrier. For example, the solution can be irradiated while it is continuously applied and then dried. Furthermore, a '? Farbba. ^ Envr.rhi ικΐυηκ or an organic coloring component can be added.

109833/1809

iAD ORIGINAL

There? Inventive method for producing a light-sensitive Elements is simple and very effective and economical.

Some examples of making photosensitive are given below Items reproduced using this procedure.

1) A mainly organometallic compound, a organic photoconductive material and a solution containing a radical generator is applied to a support and then irradiated with radiant energy sufficiently to cause considerable sensitization in the resulting coating layer achieve.

2) A beam is assembled with one as specified under 1) Solution coated, whereupon the applied solution is sufficiently exposed to the action of radiant energy, to cause significant sensitization in the resulting coating which is dried, the The sensitization taking place in it is accelerated.

3) A beam is assembled with one as specified under 1) Solution coated, allowing photons and thermal energy to act simultaneously on the applied layer.

M) A solution composed as specified under 1) is applied to a carrier and the applied layer is gelled and subjected to the action of light energy and thermal energy, before the layer is dried by thermal energy.

109833/1809 _iA D ORIGINAL

The strength of the resulting, u pb.c te-lc.it ends ocoicht on the carrier can be in a Berci:; ii vpn c. ^: ? d.gon HiJ-; ron bii .; on a few tens of micron eggs. I '-' r. ^For common uses, the thickness of the layer is a few but less than 10 microns.

Metal sheets, such as aluminum, copper, Ziuk and silver sheets or foils, paper that has been treated so that it is not penetrated by a solvent, aluminum-laminated paper, synthetic resin films in which a wetting agent is incorporated, glass, the surface of which is provided with a metal, metal oxide or metal halide layer by vacuum vapor deposition, paper and synthetic resin films, ζ. B. polyethylene, polypropylene, polyethylene terephthalate, polystyrene, polyvinyl chloride, ethyl cellulose, cellulose acetate and polyester films can be used. Any support whose surface resistance is lower than that of the photoconductive layer can be used in the crucible. In other words, you can use any material with a

Q "

state
use

the amount of less than 10- ^ X1, preferably less than

All known techniques of conventional electrophotographic processes can be applied to the photosensitive material or photosensitive elements according to the invention. You can usually get a so-called. Use the Carlson process, which includes the steps of charging, exposing, developing and fixing.

10 9 8 3 3/1809

• AD ORIGINAL

105199

The light-sensitive element is positively charged, for example, up to a potential of about 150 to 60μ volts by carrying out it in the dark several times under a corona discharge device charged with + 6 KV. Then it is illuminated with light from any suitable light source, e.g. B. a V / olfraralainpe exposed by a corresponding I-ositiv ^ UoLGr or -bild, \ .- orauf the electrical charge disappears at the exposed areas.

The latent image created in this way is then coated with a negatively charged image powder (toner), e.g. 5. after the magnetic brush, the cascade or the PeI :: - brush method developed into a positive image. This Image can be fixed by heating it or by passing it through an appropriate solvent vapor atmosphere. Ilan can also develop using a liquid developer. The liquid developer must be used as a necessary Constituents in each case contain a coloring component and a carrier liquid. You can do it too a means of regulation or control and a means of improvement add to the adhesive or fixing properties.

It should also be mentioned that the photosensitive material charges positively or negatively by means of the corona discharge can be.

The examples illustrate the invention, but are not to be understood as a restriction.

example 1

Poly-y-vinyl carbazole

(Luvican M-I70, trade name, product of the

Baden aniline and soda factory) 8g

Carbon tetrabromide 400: n :.

Triphenyl bismuthine δη ;; ·;

Benzene 200inL.

^109833/1809 , ADW.G.NAL

- 30 ~

A solution of the above ingredients is available below Using a photochemical, with a 100 Wafcu High pressure mercury lamp by Ushio Denki Kabushihi Kaisha irradiated with light for 5 minutes. (If a solution without Triphenylbsiinutin is used, then this is exposure time 15 minutes required to achieve the same light sensitivity). The treated in this way Solution is then in a solids amount of about

ρ ρ

5 g / m 2 is applied to a carrier paper (70 g / m 2) that has been previously inhibited against the penetration of solvents by coating with polyvinyl in an amount of about 2 g / m 2. The coated paper is then dried for 5 minutes to obtain a photosensitive paper. This photosensitive paper is then provided with a uniform negative charge of about 30 V by means of a corona discharge using a charging device with about 5 »5 -KV , brought into contact with an original positive film , exposed to 100 lux · sec using a 150 watt tungsten lamp and finally soaked in a liquid developer for positive images, whereby a positive image of high fidelity to the original is obtained.

If you compare a solution without triphenyl bismuthine is used, the required amount of exposure light is about 250 lux. sec.

When a solution of the ingredients listed above is applied to the above-mentioned backing paper and arm for 5 seconds with one spaced 150 mm apart High-pressure mercury lamp is exposed to a power of 100 watts, so the resulting photosensitive results Paper under the reproduction conditions given above

109833/1809

21D5T99

- 31 -

also a positive image with high original fidelity would be ο ο in.:. Irradiation before 30 sec. Duration is required to remove the gloii / .hu Achieve photosensitivity when comparing oiij.c Lo Solution used without triphenyl bismuthine.

In the present example, the triphenyl bismuthine Sensitization effects achieved measured by means of the degree of coloration generated by the light irradiation in the solution will. This means that in the presence of triphenyl bismuthine, the light exposure causes the solution to dissolve in about 5 minutes bluish in color, while in the absence of triphenylbismutine 15 Must be irradiated minutes to achieve the bluish discoloration.

If you get one by falling or falling over in the foregoing specified poly-9 ~ "vinylcarbazole or one by polymerizing Poly-9 ~ vinylcarbazole made from vinyl carbazole instead of polyvinyl varbazole (Luvican 11-170) is used, a bluish coloration of the solution can be achieved by exposure to radiation for 5 minutes in the absence of triphenyl bismuthine at a 5 minute Irradiation, a blue coloration of the solution can hardly be detected and a lower sensitivity to light is observed.

If you add 80 mg of leuco malachite green to the above-mentioned approach added and the solution irradiated for 2 minutes, so is the amount required to produce clear positive images Amount of exposure light in a photosensitive paper made from such a solution 95 lux · sec. If one uses a solution from the initially listed ingredients 200 mg R-vinylcarbazole additive and Solution irradiated for 5 minutes, it is necessary to achieve kl-; c-r Positive images with the sensitive paper made from such a solution 90 lux sec.

109833 / T80 9

it should be stated that by coating ι-Λν. a solution of the aforementioned poly-9-vinylCi ;; r-oa2.ü]; ^; : Preserved light-sensitive paper reit elr ^ r Bell cn iv.-leslie- .: ■■ ', - amount of about 60,000 lux · sec. exposed υ he must in order to get good positive images. With a commercially available light rpfi /.- soft paper with dye-sensitized zinc oxide requires about 95 lux · sec. to produce good positive images.

Example 2

Poly-9-vinyl carbazole

(Luvican M-170, product of the "BASI ¹ ")

Acrylonitrile-styrene copolymer

(Estylen AS-6INT, trade name, product

the Yahata Kagaku) 4g

Carbon tetrabromide 400mg

Triphenyl bismuthine 16mg

Methylene chloride 200ml

Using a mixture of the constituents listed above, a photosensitive one is produced analogously to Example 1 Paper produced, with an irradiation time of 5 min. is applied. The photosensitive paper obtained in this way is charged and exposed analogously to Example 1 and developed with the exposure light amount being 200 lux. sec. amounts to. Clear positive images with a high degree of fidelity to the original are obtained.

The above example is repeated, but in deviation therefrom, instead of carbon tetrabromide, 400 mg of “tribrcraotbylsulfone and, as the dye base compound, 50 mg of leuco crystal violet be used. The amount of exposure light required to achieve clear positive images is 190 lux · sec. V / oim instead des Leukochristallviolett 80 mg K-MethyIdiphenylamin as organic Coloring component are used, so is the amount to achieve Required amount of exposure light for clearer images 180 lux · see.

10 9833/18 09:

■ AD ORfQINAL

Example 3

Poly-y-vinyl carbazole

(Luvican M-I70, product of BASF). 8 g

Carbon tetrabromide 400mg

Bis (cyclopentadienyl) -

t itandiphenyl 8mg

Benzene 200ml

A mixture of the constituents listed above is irradiated analogously to example <t ". 5 ml of a solution of 80 mg 1 ₎ 3,5- ^/ erinitrobenzene (Lewis acid) in benzene is then added. Using this mixture, analogous to example Λ A photosensitive paper is produced. Using this photosensitive paper, positive images are then produced in the same way as in Example 1, with a deviation from Example -I having a negative charge of volts and an amount of exposure light of 120 lux ". sec. can be used. Clear positive images with a high degree of fidelity to the original are obtained.

Example 4-

Poly-y-vinyl carbazole

(PO-098, trade name, product of

Schuchardt) 2 g

Tribromomethylphenylsulfoc, 100 mg

Triphenyibismutine 2mg

Dioctyl phthalate 0.5g

Chlorobenzene. . 70ml

A carrier paper with a weight of 79 g / m, which is pretreated with a hydrophilic polymer, uia the inclusion Solvents are prevented by means of a "jppelwalzenbeSchichtungverfahren" with a solution of voro.c; ond listed ingredients in an amount of about 5G / ^ "

109833/18 09

ORIGINAL

coated, whereupon the applied layer immediately 5 see. with a spaced about 10 cm 500 V / att xenon lamp is exposed to a light-sensitive To produce paper. Will no triphsn: /! - bisumtin is used, the required irradiation time is The photosensitive paper obtained in this way is produced analogously to Example 1 of a _positive image used, deviating from this a charge of about 280 volts and an exposure light amount of 150 lux · sec. was applied will. A positive image is obtained that is very faithful to the original.

In Examples 5 to 39 below, the procedure is analogous to Example 1, i.e. one by mixing the respective Listed components obtained solution is each with a 100 watt high pressure Queeksilberlanpe 5 min. Irradiated, after which a carrier paper is coated with the irradiated solution, which is then dries to a photosensitive paper. The photosensitive paper thus obtained becomes each charged analogously to Example 1, brought into contact with an original positive film and by means of exposed to a 150 watt tungsten lamp.

In Examples 5 to 39, the recipe is in each case the solution, as well as the amount of exposure light required to achieve a clear positive image and, for comparison, the amount of exposure light required to produce a clear positive image to be achieved if no organometallic compound is used. The latter value is in each case given in brackets.

109833/1809

Example 5

Poly ~ 3-broia- ⁱ j-vinylcarbazole 8g

Di-tert-butyl _r P-oxide. 4-OQmg 2,7-Eis- ^ diEiöthylauiiiio) -10-Pc.Liae tlxylaminophenyl-y, 10-dihydro-9 »9-dimethyl-

anthracene 100mg

Triphenylphosphine 8mg

Monochlorobenzene 200ml

Required exposure light level: 170 lux sec. (without triphenylphosphine 350 lux.

Example 6

Copolymer

3-iodo-9-vinylcarbazole and

9-vinylcarbazole (in the ratio

4-0: 60)

Bromoform · 4-OOmg

1,2-dimethylindole 100mg

Triphenylphosphine 8mg

Benzene 200ml

Required amount of exposure light: 160 lux sec. (without triphenylphosphine 390 lux sec /

Example 7

Poly-9-vinyl carbazole
PC-098, Schuchardt Go.)

Carbon tetrabromide. 4-OOmg

Triphenyl bismuthine 8mg

Benzene 200ml

Oriental rose 20mg

Required exposure light meter: 90 lux. s ^ ec *. (without triphenyl bismuthine 300 lux sec.) ^x

109833/1809

Example 8

Poly-3-bromo-9-vinylcarbazole tribroethylphenylsulfone
2- · 1, 3-dioxo-hydrindenyl - (2) * - quinoliii "
Cobaltocene
Monochlorobenzene
Methyl violet

Pr-

20OmI 20mg

Required amount of exposure light: 80 lux (without cobaltocene 280 lux * "sec.)

Example 9

9-vinylcarbazole graft copolymer 8g and ethyl acrylate 4-OOing Bromoform 80mg Leucomethyl violet 0.5mg Cobaltocene 200ml toluene 2g Diphenyl chloride 50mg 2,4,7-trinitro-9-fluorenone : 140 lux Required amount of exposure light; (without cobaltocene 325 lux s§c. _t ) Example 10

sec,

• see.

Poly-3-bromo-9-vinylcarbazole 8g

Carbon tetrabromide 400mg

Triphenyl bismuthine 8mg

Benzene - 200ml

p-terphenyl - · ^ g

Required amount of exposure light: 95 lux sec, (without triphenyl bismuthine 280 lux «sec.)

109833/1809

- 37 Example 11

Poly-y-vinylcart azο1 (Luvican M-170, product of BASI ¹ ) carbon tetrabromide 4- (P-Mmethylaminostyryl) -iiti.noliii totraphenyl lead

benzene

400mg 80mg

200ml

Required amount of exposure light: 90 lux (without tetraphenyl lead 255 lux .see.)

Example 12

Block copolymer made from 9-vinyl carbazole 8g and ethyl acrylate (in a ratio of y0: 10) 200mg Carbon tetrabrocarbon 800 mg ^ -Vinylcarbazole Bis (cyclopentadienyl) - 8mg - zirconium dibromide 200ml benzene 2g Diphenyl chloride 50mg 2.4-. 7-trinitro-9-fluorenone

Required amount of exposure light: 185 lux · sec. (Without bis (cyclopentadienyl) zirconium dibromide 395 lux sec.J "

Example 13

Copolymer of 3-iodo-9-vinylcarbazole and ^ -Vinylcarbazole (in a molar ratio of 40:60) 8g iodoform "400mg

Triphenyl bismuthine. ' 4mg

Benzene · 200ml

Required amount of exposure light: 70 lux * sec. (without 2riphenylbismuthine 250 lux sec.)

109833/1809

EXAMPLE 14

Bis- 4, 4'-dialkylaminofren ^ ylidenaZin 4 g copolymer of acrylonitrile and styrene

(Estylene AS-61NT, product of 4 g Yahata Kagaku) 400 mg Pentabromodiraethylsulfoxide 4-C 2- (3-ethyl-2 (3H) - benaothiazolydenamino) vinyl3 - 80 mg quinoline 0.1 mg Ferrocene 200 ml Methylene chloride 20 mg Acridingelt » 70 mg Cliloranil

Required amount of exposure light: 140 lux. sec, (without ferrocene 380 lux ·. sec).

Example 15

Nitrated poly-9-vinylcarbazole (with 0.06 nitro groups per carbazole unit mainly in the 3-position of the carbazole ring) Iodoform

2,5-bis- t 4'-dimethylaminophenyl-1. '.] -1, 3, 4-oxadiazole triphenylars in
benzene

8th S. 100 mg 100 mg 8th mg 200 ml

109833/1809

Required exposure ichtr. 01 ·. ^ ': ^Λ : 2? ^ .Lux · sec (without Trdphenylarsin 560 1½>: · sec).

Example Ί6

Poly-2 ~ l3roia-9-vinylcarba- "ol 8 g

Iodoform '400 mg

Triphenylphosphine 8 mg

Nitrofensol 200 ml

Methyl violet 20 mg

Required exposure light amount: 155 1 "^ x · see (without triphenylphosphine 335 liuc Bee)

Example 17

Poly-9-vinyl carbazole
(Luvican 11-170,
BASF product)
Carbon tetrabron

diethylaminophenyl-1 ¹ J -1, 3 ■>

triazole

Nickelocene

benzene

Required amount of exposure light: 105 lux sec. (Without nickelocene 210 lux sec)

8th 6th 400 ng 80 mg 0 .5 mg 200 ml

109833/1809

• AD ORIGINAL

Example 18

Bis-4,4-diallylaminobenzylidenazine 4 g Modified phenolic resin

(Beckacite 1100

Product of Japan Reichhold Chemical

Ind. Go.) 4g

Iodoform "400 mg

1-ethyl ~ 3- L3-ethyl-

2- (3H) -benzoxazolylideneJ -

oxyindole 80 mg

Bis (cyclopentadienyl) niobium

tribromide 8 mg

Chlorobenzene 200 ml

Tetrachlorophthalic anhydride. 80 mg

Required amount of exposure light: 830 lux .. sec (without bis (cyclopentadienyl) niobium tribromide 15 ^ 0 lux: sec)

Example 19

Poly-9-vinyl carbazoI
(Luvican M-I70

BASF product). 8 g

Iodoform '400 mg

Triphenyl bismuthine 4 mg

2, 4, 7-trinitro ~ 9-fluorenone 50 mg

Benzene 200 ml

Diphenyl chloride 2 g

109833/1809

Required amount of exposure light: 55 lux. sec (without triphenylbisimrthin 170 lux. sec).

Example 20

Ν, Ν, Ν ', N'-tetrabenzyl-P-phenylenediamine 4 g

Polyvinyl butyral resin

(S-lec ELS, trade name

Product of the Sekisui Kagaku)

Hexabr omdiine thyl sul foxy d

3-ethyl-5-D-ethyl-2 (3H) -

benzthiazolylidene ^] rhodanine

Bis (cyclopentadienyl) chromium

toluene

Required amount of exposure light: 1170 lux. sec (without bis (cyclopentadienyl) chromium 1920 lux. sec).

Example 21

4th S. 400 mg 60 mg 4th mg 200 ml

Bis-4,4'-dialkylaminobenzylidenazine 4 g of copolymer resin
-Acrylonitrile and styrene
(Estylene AS-61NT,

Product of Yahata Kagaku) 4 g

Di-tert-butyl peroxide 400 mg

4- (4'-dirnethylaminophenyl) -

5- (4 "-chlorophenyl) -imidazole 80 mg

Bis (cyclopentadienyl) tantalum

tribromide 16 mg

Methylene chloride 200 ml

109833/1809

Required exposure level: 870 lux. sec. (without bis (cyclopentadienyl) tantalum tribromide Ια 80 lu>: sec.).

Example 22

Nitrated poly-9-vinylcarbazole (with 0.OG nitrogroups pro

Carbazole unit, mainly

in the 3-position of the carbazole ring) 8 g

Bromoform 400 ing

Triphenyl bismuthine 16 mg

Benzene 200 ml

Required exposure light amount: 270 lux. sec. (without l'riphenylbismuthin 530 lux. sec).

Example 23

Leuco crystal violet 4 g

Epoxy resin

(Epikote 1004, trade name,

Shell Oil product) 4 g

2-azo-bis-isobutyronitrile 400 mg

4- / 4- (P-dimethylaminophenyl) -

1,3-butadienyj7 -quinoline 80 mg

Bis (cyclopentadienyl) vanadium 4 mg

Benzene 200 ml

109833/18 09

Required exposure levels: 2060 lux. acc (olme ice (cyclopentadienyl) vanadium 3750 lux.gcc)

Example 24

Bis-4,4-diallylaminobenzylidene

azin 4 g

Modified phenolic resin

(Beckacite 1100,

Product of Japan Reichholö Chemical Co.) 4g

TrxbroiEEiethylphenylsulfone 400 mg

1,3? 5-triphenylpyrazoline 80 mg

Tetraphenyltin 16 mg

Chlorobenzene 200 ml

Required amount of exposure light: · 640 lux. sec (without tetraphenyltin 1770 lux. sec).

Example 25

Poly-9-vinyl carbazole

(I / uvican M-1? 0, product of BASl? 8 g

Tribromomethyl sulfone 400 mg

Tetraphenyl lead 16 mg

Benzene 200 ml

Required amount of exposure light: 440 lux. sec, (without tetraphenyrl lead 1280 lux. sec).

109833/1809

Example 26

Leuco malachite green '4 f "

Polystyrene resin

(Piccolastic D-1OO, trade name

Product of the ESSO) 4 g

Diphenylthiocarbazone 400 mg

2- (p-Dimethylaminostyryl) -chii) olin Ί ^ Ο ^κ ίϊ

Bis- (cyclopentadienyl) -P-penta cool-

monoxide-bimolybdenum 4 inpj

Benzene 100 ml

Methylene chloride 100 ml

Required amount of exposure light: 2 ^ 00 lux. sec (without bis- (cyclopentadienyl) -P-pentacarbonirionoxide- "bimolybdenum 4150 lux. sec)

109833/1809

Example 27

LeukomalachiL-green - 4 g

Polycarbonate resin

(Panlite C, trade name,

Product of leijin) 4 g

2-azo-bis-isobutyronitrile 4-00 mg

2- (4 ¹ -diethylaminophenyl) -4-

(4'-dimethylaminophenyl) -5-

(2'-ch.lorplieiiyl) -oxazole 80 mg

Bi s- (eye lop ent adieny I) -P-

liexac ar b ο ny 1 -

biotungsten 4 mg

Methylene chloride 200 ml

Required amount of exposure light: 920 lux.see. (without Bis- (cyclopentadienyl) -P-hexacartonyl-biwungfram 1650 lux.see)

Example 28

4,4'-bis-dimethylamino-benzo-phenone 4 g • Polycarbonate resin
(Iupilon S, trade name

Product of Mitsubishi Edogawa Kagaku) 4 g

Carbon tetrabromide 400 mg

Triphenyl bismuthine x 4 m £;

Methylene chloride 200 ml

Required exposure light menu: 100 lux.see. (without Triphenyl bismuthine 290 lux.see).

109833/1809

Example 29

Leuco Crystal Violet £ 4 Acrylonitrile-Styrene Copolyxier
(Estylene AS-61HT,

Product of Xahata Kagaku) 4 g

2-azobisisobutyronitrile 400 3 ~ ethyl-5- _i / 3-ethyl-2 (JH) -

benzoxazolyliden_7-rhodanine 200 n.; j

Mckelocen 4 γ ;; _ο

Methylene chloride 200 ΐ 1

Required amount of exposure light: 1590 lux. sec. (without Nickelocene 493 ° lux.sec).

Example 50

Leuco Crystal Violet "4 g

Epoxy resin

(Epikote 1004,

Shell Petroleum Co. product) 4g

Hexabromodiniethylsulfoxide 400 rr.g

o-0? oluidine 100 mg

Hydrogenated bis (cyclopenta-

dienyl) rhenium 2 mg

Benzene 200

Required amount of exposure light: 750 lux.see. (without hydrogenated bis (cyclopentadienyl) rhenium, 1> 10 lux.see).

109833/1809

»47 -

Example 31

Bi s-4,4'-Gi ally1aaino-

benzyl enazine 4

Acrylitrile-ßyrene-CopolyK.er

(Estylene AS-61NT, product

the Y ah at ei Ka ^ aku) 4

Iodoform '400

Bis (cyclox3entadicnyl) -iron-dicarbonyl 2

Kethylene ciloride 200 ml

Acridine ^ elb 20 js _b -

Chloranil 70 mc

Required exposure level: 520 lux.sec. (without Bis (cyclopentadienyl) iron dicarbonyl 950 lux.sec).

Example 32

Leuco malachite green 4 g

PoIys tyrolhar ζ
- (Piccolastic D-100, product

the ESSO) '4 e

-J) iphenylthiocarbozone 400 eg

Vinylcarbozole 50 n ^

Brominated bis (cyclopentadienyl) -

cobalt 4 mg

Benzene. 100 nl

Methylene chloride '100 r.l

Required amount of exposure light: 2400 lux.sec. (oL;: e brominated bis (cyclopentadienyl) cobalt 90,400 lux.sec.)

109833/1809

“AD ORlQtNAU

Example 33

N ₁ H, N ¹ , N'-Ietrabenzyl-p-

phenylenediamine 4 g

Modified phenolic resin

(Beckacite 1100, product

from Japan Reichhold Chemical Co.) 4g

Bromoform 400 mg

letraphenyltin 4 iag

Benzene 200 ml

Required amount of exposure light: 1550 lux.see. (Without (fetraphenyltin 2250 lux.see.).

Example 34

Bis-4,4-diallylaminobenzylidene in 4 g

Modified phenolic resin

(Beckacite 1100, product

from Japan Beichhold Chemical Co.) 4g

Tribromomethylphenylsulfone 400 mg

Hexaphenyl tin 4 mg

Chlorobenzene 200 ml

Required amount of exposure light: 720 lux.see. (without Hexaphenyl tin 1120 lux.see).

Example 35

Leuco malachite green 4 g

Po Iys tyrοlhar ζ

(Piccolastic D-100, product

the ESSO) 4 g

109833/1809

Dipheylthiocarbazone 400 mg

Hexaphenyl tin 2 mg

Benzene 100 ml

Methyienciilorid 100 ml

Required amount of exposure light: 2300 lux.sec. (onne Hexapnenyl tin 3750 lux.sec).

Example 36

Leuco crystal violet 4 g

Acrylonitrile-styrene copolymer

(Estylene AS-61NT, product

the Xahata Kagaku) ■ ■ 4g

2-Azobisisole-Dutyroiiitrile 400 mg

Perrocene 0.5 mg

Meth.ylene chloride 200 ml

Required amount of exposure: 600 lux.sec. (without Ferrocene 23OO lux.sec).

Example 37

Leuco crystal violet 4 g
Acrylonitrile-styrene copolymer
(Estylene AS-61N! ??, product

the lahata kogaku) 4 g

Bipheriylthiocarbozone 200 mg

Tetraphenylgermanium ^Λ 8 mg

2-azobisisobutyronitrile 200 mg

Methylene chloride 200 ml

Orient-Girosa OP 20 mg (Orierri; oil pink OP)

109833/1809

Required amount of exposure light: 7oO lax, see. (Without Tetraphenylgeraanium 14 ^ 0 lux.see).

Poly-9-vinylcarbozene

(Luvican M-17O, product

from BASF) 8 g

Carbon tetrabromide 400 mg

Bis (cyclopentadienyl) cerium 8 mg

Dioxane 200 ml

Required amount of illumination light: 100 lux.see. (without Bis (cyclopentadienyl) cerium 315 lux.see).

Example 59

Example 33 is made using bis (cyclopentadienyl) titanium, Bis (cyclopentadienyl) chromium, bis (cyclopentadienyl) manganese or dihalogenated. Bis (cyclopentadienyl) vanadium instead of bis- (cyclopentadienyl) -cer repeated, whereby the required amount of exposure light in each case about 200 lux.see. amounts to.

Example 40

Iodoform 100 mg

Triphenylphosphine 4 mg

Benzene · 25 ml

A solution of the components listed above is poured into a 50 ml Erlenineyer quartz flask tit / za 20 minutes with a 100 \ h-.tt

109833/1809

5199

High pressure mercury lamp irradiated, (uine no tripheuylpho: containing otherwise equals solution will be 30 ilinutes bes cre

Then a solution is made up of the following ingredients

Poly-3-nitro-9-vinylcarbazole 2 g

Diphenyl chloride ο, 5

Benzene 25 ml

This solution is poured into the Erlenmeyer flask and its contents mixed, whereupon the flask is left in the dark for 3 days. Then a 50 , \ x thick aluminum-laminated paper about 5 / U- thick is coated with the solution, whereupon the layer is allowed to dry by itself to a photosensitive paper. This photosensitive paper is using a corona discharge device of about 5> 5 K \ ^r equilibrium; Negatively charged to about $ 50 V, brought into contact with a positive ornate film , using a 150 watt tungsten lamp with an exposure light amount of Λ ^> 0 lux.sec. exposed and finally soaked in a liquid positive developer, whereby a positive image of high fidelity to the original is obtained.

Example 41

Carbon tetrabromide 100 mg

Vinyl carbazole 50 mg

TriphenyIbismutine x 2 mg

Benzene · 25 ml

"A solution made up of the ingredients listed above is approx. in a 50 ml Erlenmeyer quartz flask

109833/1809

BAD OWQtNAL

-52-

5 minutes with a ^ uO v / att at a distance of 10 cm Xenon lamp irradiated. In the case of a solution that does not contain 1'riphenylbismutine contains is an irradiation duration of 30 minutes necessary.

Then immediately a solution of 2 g of poly-9-vinylcarbazole (PO-098, trade name, product from Schuchardt) in 25 ml Benzene poured into the Erlenmeyer flask, whereupon the resulting mixture was left in a dark place for 3 days leaves. Then a 0.8 mm thick aluminum sheet is coated with the mixture in such a way that a 5 / U thick PiIm is formed, which is allowed to dry under ambient conditions, whereby a photosensitive plate is obtained. This photosensitive plate is subjected to the electrophotographic process of Example 40, with an exposure light amount from 110 lux.see. is required to obtain positive images with high fidelity to the original.

Example 42

Pentabromodimethylsulfoxy.d 100 mg

iCriphenyl bismuthine 1 mg

Xylene 25 itl

A solution of the above ingredients is placed in a 50 ml Erlenmeyer quartz flask with a 500 watt xenon lamp arranged at a distance of 20 cm Exposed for 10 minutes. In the case of a solution that does not contain triphenyl bismuthine an irradiation time of 30 minutes is required.

Then a solution of 1 g of leuco malachite green and 1 g of an epoxy resin (Epikote 1004, trade name, product egg

109833/1809

- 53 -

Shell Petroleum Co.) in 25 ml MEK immediately into the Evlenmeye: = poured flask, whereupon the flask is left in a dark place for 2 days. Thereupon the contents of the flask with 5 ml of a ΓΙΕΚ solution containing 5 mg rose bengal as Sensitizing dye and 10 mg of piric acid as Contains Lewis acid, added.

With the solution contained in this way, a 80 j \ x thick, treated to increase the electrical conductivity of baryta paper or barium oxide paper is coated so that an approximately 5 / U. a strong film is formed which is allowed to dry on its own, whereby a photosensitive paper is obtained. This photosensitive paper was subjected to the electrophotographic process of Example 40, whereby positive images with high fidelity to the original were obtained. The required amount of lighting light is 350 lux.see.

Example 45

(I) poly-9-vinylcarbazole Carbon tetrabromide Sriphenyl bismuthine Benzene

(II) iodoform
benzene

A solution from the above under I) as well as a supplementary solution from the above under II) is in each case irradiated with a 100 watt high pressure mercury lamp arranged in about 10 cm above;. · .-. J> minutes. (Without Triphenylbismutine is d ... ·.

109833/1809

“AD

2 S. 50 mg 2 atg 25th ml 50 mg 25th ml

Exposure time 10 minutes). The two Lc.iaitJön are then immediately v'crnischt together v.'crauf the mixture 10 Scunden to eineiu dark Ox * is allowed to stand fc, then with the mixture a 75 Ai star! -: -: · lolyesterfilm with an aluminum It is described in such a way that an approximately 5 / U thick coating layer is obtained by allowing it to dry under ambient conditions. The photosensitive film thus produced is subjected to the electrophotographic process of Example 4-0, with an exposure light amount of 12G lux is required to obtain positive images with high fidelity to the original.

If a photosensitive film is prepared using a poly-9-vinylcarbazole solution in the manner described above, the amount of exposure light required to obtain good positive images with this film is about 58,000 lux.

Example 44

I) Poly-3-bromo-9-vinylcarbazole Bromoform chlorobenzene

II) hexachloroethane

! Pr ipheny lbi smut in chlorobenzene

Two of those listed above under I) and II) Solutions that already exist in components are used for 10 minutes at a distance of 100 i / au at a distance of about 10 cm High pressure mercury lamp irradiated. (If no triphenvl-

2 G 50 mg 25th ml 50 mg 2 mg 25th ml

109833/1809

BAD ORIGINM.

bismutin is used, the required amount applies Irradiation duration 15 minutes).

Immediately after irradiation. v. ^r eraen the solutions are mixed together, and then allowed to stand for about 10 hours, the mixture Ilan in Israel in a dark place. Then the mixture is mixed with 10 ml of a solution of 0.5 g of p-terphenyl in chlorobenzene as // eichinacher, whereupon a> 0 λχ thick aluminum laminate paper is coated with the mixture in such a way that a layer about 5 / U thick is obtained, whereupon the coated paper is allowed to dry by aileine under natural conditions. The photosensitive paper thus obtained was subjected to the electrophotographic process of Example 40. Kit with an exposure light amount of 150 lux. sec. one obtains fositiv bileans of high fidelity to the original.

Example 45

I) poly-9-vinylcarbazole (Luvican M-17O, product of BASP), hexabromodimethyl sulfoxide Triphenyl bismuthine benzene

¹ ) Pentabromodimethylsulfoxide 1,6-Dimethoxyphenazine Triphenylbismuthine Benzene

Solutions from the above under I) baw. II) on _o ei! .Ij'.rten

2 fa 50 Eg 1 mg 25th ni 50 mg 20th mg 1 25th ml

^109833/1809

Components are each included about 5 minutes. ■■ ,: ^ 00 v / att xenon!; .. ' arranged at a distance of about 20 cm. _x > q irradiated (if no triphenylbicinutine is used ν; 1ι · ο, the required irradiation time is $ 0 Vü.u \ iir: ri.). Immediately after the irradiation, the two lo :; : v gen mixed together, whereupon you get the mixture

under a Flu ore η sen ζ lamp about 24 Lets stand for hours. Then 5 ml of a solution are added of 5mg Ülrosa (Oil pink) in Benaol as a sensitizing dye and uses the mixture analogously to produce a photosensitive PiIm, which is similar to the electrophotographic Process of Example 40 is subjected. There is an exposure light amount of 120 lux.see. necessary, to obtain positive images with high fidelity to the original.

Example 46

Poly-9-vinyl carbazoI

(PO-098, product of

Schuchardt) 170 g

Carbon tetrabromide 10 g

iriphenyl bismuthine 340 mg

Diphenyl chloride 30 g

Benzene 5 ml

ELn backing paper weighing 60 g / m 2, the surface to be coated of which is treated with a hydrophilic polymer in order to prevent the penetration of solvents, is coated with a solution of the above-mentioned constituents in an amount of about 6 g / m 2 by a roll coating process, whereupon man ec immediately 10 see. with a spaced about 15 cm

■ AD ORIGINAL 109833/18 09

High-pressure mercury lamp (100 watt) irradiated- 'Jena no triphenylbisinutin is used, the required irradiation time is JO see. The coating is then applied at 70 ^° C. and a wind speed of 1.5 m / sec. dried with hot air, whereby a photosensitive paper is obtained. This photosensitive paper was subjected to the electrophotographic process of Example 40, using an exposure light amount of 11:? lux.see. is required to obtain positive images with high fidelity to the original.

The only figure in the accompanying drawing shows a cross section through a photosensitive according to the invention Element with a carrier layer 1 and a photosensitive Layer 2 represents.

- patent claims -

109833/1809

Claims (1)

1 y light-sensitive material, containing a mixture of at least one substance treated in the presence of at least one organometallic compound with radiation energy under chemical reaction, capable of forming free radicals when excited with radiation energy (radical generator) and at least one organic, photoconductive compound as essential components. 2. Photosensitive material according to claim 1, characterized in that it is anische as inetallor ^ Compound of at least one metal alkyl, -aryl and / or -alkylaryl of at least one metallic element group IV B or V B of the Periodic Table of the Elements. 3 · Photosensitive material according to claim 2, characterized characterized as being organometallic Connection at least one tailor ganic connection contains, as a metallic element of group IV B or V B germanium, tin, lead, phosphorus, Contains arsenic, antimony or bismuth. 109833/1809 5199 - 39 - 4. Photosensitive material according to claim 2 or 3, characterized in that os as Kot all aryl at least one iron and oil tetraphenyl metal compound contains. 5. Photosensitive material according to claim 1, characterized in that it is as met inorganic compound r _; Contains at least one cyciopentadienyl metal compound of at least one transition metal from the group III A, IV A, VA, VI A, VII A and / or VIII A of the periodic table of elements. 6. Photosensitive material according to claim 5, characterized in that there is at least one Cyclopentadienylmetallverbindungen at least one of the metals Sc, Ϊ, La, Ge, Pr, l \ ^T d, Sm, Gd, Dy, Er, Ib, Ti, Zr, Hf , V, Nb ₁ Ta, Cr, Mo, W ₁ U _x Mn, Tc ₁ Re, Fc, Co, Ni and Ru. 7. Photosensitive material, according to at least one of the Claims 1 to 6, characterized f that it, based on the weight of the organic, photoconductive compounds) 10 10 Contains% by weight of at least one organometallic compound. 8. Photosensitive material according to at least one of claims 1 to 7, characterized in that it, based on the organic ⁰ , OhOtOIeIt 0 T ¹ ^ rC compound (s), 1-? 0 wt. Vo "contains radical formers. 10 9 8 3 3/1809 - 60 - 9. Photosensitive material nech at least ρπ? einr ^ der Claims 1 to 8, d a d u r c h characterized that dp πι rait "trahlunp'.soiK'rfrie υ nt ^ r Reaction treated mixture of radical generator and organic, photoconductive material a .Sensibilisiwi'm.:.; - medium is incorporated. 10. Photosensitive material according to claim 9i, characterized in that he rAr. Sensibilisierunccsmittel contains at least one Lewis acid and / or at least one sensitizing dye. 11. Photosensitive material according to at least one of claims 1 to 10, characterized in that it contains as me taH.l organic Yerbinduni-r triphenylbismutine, "" triphen, ylphosphine ₅ tetra-phenylarsine, ferrocene and / or cobaltocene. 12. Photosensitive material according to at least piner rio? · Claims 1 to 11, characterized in that it is an organic, photo] r> i ter ^ io.? Material or ^r . organic photoconductive compounds: i: j or more vinyl carbazoles, aromatic diphenylinethane compounds uno / odfr contains. 15. Photosensitive material according to claim 12, characterized in that it al? Vinylcarbazole at least one poly-vinylcarbazole 9, bromo-substituted poly-9-vinyl carbazole and / or zolcopolymere jodi tuiertes poly-9-vinyl carbazole Urid / or one or more 9-Vinylcarbazolcopolymere, bromine-substituted 9-Vinylc and / or 9-iodine substituted ViQylcai- ⁱ b.'i: ..: copolymers contained 8 3 3/1809 S - 105199 - 61 - ' LichteTUT) sensitive material according to at least eir-f-: ⁿ of claims 1 "to 13, thereby k e η η ζ e rejects, d ^ ß it as ^T jndikiO.bn a · '· one or more PolyhaloFcri ^ erbindun ^ nn.Oarb ^ nyl -verbindimr-en, orp: arri pche Scnv / pfelverhinrinns-en. Peroxides, Λ ^ compounds and / or '"' diazo compounds contains. TdchtrpiTipfindlichos Hnterial according to claim 14, d p. characterized in that there is at least one polyhydric compound of the formula E-C - Y (I) \ Z contains, in which R is a hydrogen, chlorine, bromine or Iodine atom, an alkyl radical or a radical of the general formula ^R 1 " ?, - Cn), ^R 1" 5 "(in) O O Il or R "- S - (IV) • It ipt, where IL · is a substituted or not sv.br- - · t.nated APcyl radical, aryl radical or heteroz ^Tr }: li see means Pe ^ t, ΎΛ and Z are identical or different from one another and;] e is a water atom f -.Chl or-, Brom- ode ^, 7o ---: - o "or an alkyl radical, with the Nn β ^ q be. *"'■> ^rii iride · one of the radicals X, Y and 7. , a halor »ir-» tn.n '. 109833/1809 PAD - 62- 16. Photosensitive Y \ r. \ R;? \ Ial vc.h. Claim 1 ^: 5, d η by reke η η ζ eich η ο f: that fr ^ ¹ - Pol.yhalogenverbindimr Tetrabror-'ohlen ^ tof t , Bromc f οττ · _; , Iodoform, a haloererd ρτ-fcep or Iranian sulfoxide iTc / n a halogenated organic SiH fonverlxi ndunfc In that it contains 17 · A photosensitive material according mindestem- eineir- d- ¹¹ entitlement to benefits 1 to 16, characterized in that as radical least "a Polyhaloprenverbindunc and a3 s organic material phofoleitendes mindeistens a vinylcarbazole 18. Photosensitive material after at least one dor Claims 1 to 17, characterized that it also contains a color base. 19 · The light-sensitive material according to claim 18, characterized by that, that ER- n ~ la Farbbase_ (s) containing at least one leuco base, Cs.rbinolba "^, Styrylfarbbase, Cyaninfarbbase, Merocyaninfarbbase IMD / or Leukodihydroanthraoe η. 20. Photosensitive material according to AnsDruch 19j in that it g e k e η η ζ e i c h η e t that it contains at least one leuco base of a tri- and / or a diphenylmethane dye as the leuco base. 21. Light sensitive material according to claim 19, d - ·· characterized in that it ·· ' . ·. 109833/1 809 “ORIGINAL Carbinolbasc at least one Cnrbinolb?: ^ A Tr'Ä- uiv.V 'or- one]) jpher: ylr: cthanfarbsüoffs cr, 1;} ;; ^; according to 22. The light-sensitive material is still less r / '.. ons on a eggs claims 1 bi-.s 21, dadurc} igeke η η ζ eic hn ct, d's eat in addition at least one organic lf: lr-exercise component. 23 · Light-sensitive material according to claim 22, d a el u;, · ·, Ii labeled, doΠ it as an organic training component at least one arylamine, garbazole, indo]., 1,3,4-oxadiazole, 1 ^, 'l-triazole, imidazole, pyrasoliii, aminophenyl-substituted Oxazole, benzidine, Ί, 3-uiphenyltetrahydroimidazole, Phenazine, acridine, acylhydrazone derivative, quinoxaline, H-disubstituted aminoarylidinazine, pyridine, quinoline, Contains ethylene derivative and / or spiropyran. 24. Photosensitive material according to claim 231 thereby characterized in that there is at least one arylaiuin the formula R-IT-R ₂ (VII), •, ^R 1 in which R is a 'hydrogen atom or an, optionally substituted, Is alkyl, aryl or aralkyl radical, R ^ is a phenyl, '-I-taphthyl or β-ITaphthyl radical and Rg is, optionally substituted, alkyl, aryl or aralkyl radical is wrong. 25 · Photosensitive material according to claim 25, characterized marked that there is at least one carbasol the general formula (viii; 10 9833/1809 IAD ORIGINAL contains, in which E is a hydrogen atom; t or a, ger: even-: r - if substituted, alkyl, alkenyl, arallryl or / · -yl radical and R ^ and Rp are the same or different; are and ever denote a hydrogen or halogen atom or an alkyl, alkenyl, aralkyl, alkoxy or dialkylamino group. 26. Photosensitive material according to claim 23, d a d u r c h marked that there is at least one indole the general formula contains, in which S is a hydrogen atom or, optionally substituted alkyl, aralkyl or aryl radical and the best R ^ are mutually identical or different and each a hydrogen or halogen atom or an alkyl, alkoxy or represent the alkylamino group. 27. Process for the production of photosensitive material, in particular according to at least one of claims 1 to 26, characterized in that at least one radical generator with at least one organic, photoconductive material and at least one organometallic compound mixed, wherein at least a part of the Radik & lLiViners or the radical generator in the presence of the "organometallic compound (s) the action of radiant energy is subject to. 28. The method according to claim 27, characterized in that radiation and energy are allowed to act simultaneously on the at least one radical generator and Gc ::.: Rien containing an organometallic compound. 109833/1809. - ■ AD ORIGINAL 29. The method according to claim 27 or 28, dad υ ν ch characterized in that nnn dera G-nri.sch from radical formers, organic, photoconductive material and organometallic compound on a hol iebicen ring] ^ dep manufacturing plants. - one and / or at least one organic coloration incorporated. 30. Method according to at least one of the claims 27 b 29, characterized that the radiation energy is reduced to a minimum !? Free radical generator, at least one organic, jihotolcitcr-des Material and at least one metal lorpjanische connection st The solution containing it is allowed to soak. 31. The method according to at least one of claims 27 to 29, thereby r e k e η η ζ e i c h η e t, that one lets the radiation energy act on a solution that contains at least one radical generator and at least one? contains an organometallic compound and the solution thus treated is then incorporated into a solution which contains at least one organic, photoconductive material. 32. The method according to claim 31, characterized that one of the or di ^ radical formers and organometallic (ii) compounds) and / or the solution containing at least one organic photoconductive material has at least one color base and / or at least one organic dye component? incorporated. 109833/1809 33 · Method according to mirn ^ stens finer · dev / ^ 'rprüch ^ 27 to 29, dad ii rch ρ ek ρ η η ζ ο i - · net that a « ^{T ;:} sum' :, äi ^ nindc-N ^ : cln-τ ^: ^ / l;>? <I · ■ bildner, at least '· f-in OT " ^: -? Tii'.cnr-F, ^ notoloit' -. r'ic" material and at least ^c : t- "n ^c : eino metal or · -'-- nt. see ve ^T -;: I /. as well as a second solution ·;, dip contains at least one ^ n TVid-i ¹ - ■■ ; -generator, irradiated and the two solutions are then mixed together. A method according to claim 33, characterized in that indicates that the second "," solution containing a radical generator is at least Gtor · " me tall or ftp η is ehe Ver ^ indun ^; contains. 35 · The method according to claim 33 or 34-, dad υ ν r ·. ν-, in d »ß · the first, prevented ⁰ a radical generator, at least .a-orr ^ nic, NBO oüeitendes material and reduces ^ ns ^ a metallorp aniscb" compound-containing solution · and / or ζ '- ^ ΐΐ ^ η, r-iiri.bestens a radical generator containing Töcunf "■■? ndesten: -? a color base and / or at least one organic coloring component is or will be added. 36. The method according to at least one of claims 27 M- "30 for the production of a photosensitive EIc -" - ^ r · characterized in that df.i-an at least one radical generator, r organic, photoconductive material and nietalloriTanj peb e verb in η ν η ν ^ '^ ^hi ? "· T ^ n ^ri f; Tö ^ applied in the carrier and, Terrebe ^ 'onfal 1 s after TJT> vrr _{.; I} .- ·' in a solid over-prasohicht, irradiated there wi-n-- ·. 109833/1809 ORfGJNAL