DE1907617A1 - Electrophotographic recording material - Google Patents

Description

Electrophotographic 'recording material

The invention relates to an electrophotographic recording material, consisting of a conductive layer support and a photoconductor and a spectrally sensitizing one Photoconductor layer containing dye "

The usual known recording materials which are used in the context of electrophotographic processes are known to consist of an electrically conductive support and a photoconductive insulating layer applied to it, the specific electrical resistance of which is considerably greater in the dark than after exposure to actinic light * In the known electrophotographic processes daptation subject to the ups calibration drying materials usually first a so-called * Dunkei & that has the Zwack "in d @ r photoconductive layer isolate · to a uniformly high electrical resistance forth vorzurufen ·", after which the AüfseichnunßSGiaterial in the dark electro-

is statically charged, with the aim of generating a relatively high potential, which can have either a negative or positive polarity. If the recording material is then exposed appropriately, the electrical resistance and the charge density of the photoconductor layer are reduced in accordance with the intensity of the amount of light irradiated * In this way a latent electrostatic image is obtained. Of the latent electrostatic ßildern then visible JJiIder can be generated in verschiedenster manner, for example by sputtering aufschinelzbarer pigment particles "dio have an electrostatic tadung to that charging of the photoconductor layer opposite. After the pigment particles have been applied, they can be melted onto the surface, giving a permanent image »

A wide variety of compounds have already been used as photoconductors for the production of electrophotographic recording materials. Typical inorganically known photoconductors are, for example, selenium and zinc oxide. Such inorganic photoconductors have the disadvantage that they are not suitable for the production of electrophoretographic recording materials for reflex copier systems and that no images can be produced on transparent film carriers when they are used -, except through indirect measures. ...

1907817

Such secondary oils are inherent in the known inorganic photoconductors "can" be eliminated by using organic photoconductors. However, the previously known organic photoconductors have the disadvantage that they have only a relatively low sensitivity to visible radiation. It is therefore b.ekannt "ζ" as of "fen to use US-Patentsehrlften 3 ITA" 85 ^ and 3 Oki 165 and from the British Patent 961,873 "organic to increase the spectral sensitivity photoconductor cyanine and merocyanine dyes, such as those as listed in the following Table D. However, the spectral sensitivity of the photoconductors caused by such dyes is very low.

The object of the invention was therefore to provide spectral sensitization for organic photoconductors to find soft the photoconductor capable of sensitizing spectrally to a high degree effectively.

The invention was based on the knowledge that certain polymethine dyes with two 5- or 6-membered, nitrogen-containing heterocyclic rings which are connected to one another via a dimethine group and whose first ring consists of an imidazole ring which is connected via the carbon atom in the 5-position ( which is not necessarily the 5-position in the numbering of the compound) is bound to the dimethine group and whose imidazole ring has at least one fused 5- or 6-membered ring on the / ~ a_7 side, and whose second ring has an electron accepting or electrons accepting ring is of the type common in cyanine dyes and that of 909845/1393

1907117

one of its carbon atoms is bonded to the dimethine group ₀ excellent spectral sensitizationÄe dyes for organic photoconductors are *

The invention relates to an electrophotographic recording material, consisting of a conductive layer support and a photoconductor and a photobiter layer containing this spectrally sensitizing dye, which is characterized in that the photoconductor layer contains a methine dye of one of the fine formulas as the spectrally sensitizing dye; ^:

CiI-CH). "^ N.- R, η - Ji

/ \ ■ / ■ .-. ■ ■ - ■■■■■ «

R ₉ -K * S CL ⁸ ^ L-CC-CII-CU) ,, T = N ^ vj [, 'η-1

ir

R -. '.. ■■■■■■ .-. "■'" ■■■ '. . ■

SÖ984S / 139

in which btjjdeutejvi

R a hydrogen atom, a gel Venezuelan substitute »

th alkyl radical with I to 12 C ^ atoms or an «optionally substituted arylrosti

Rj and EL ₂ optionally substituted alfcyl groups with 1 to 12 carbon atoms, alkenyl groups with 3 to 4 carbon atoms or optionally substituted aryl groups;

L öine gQgöbon «n £ all & durcli einöii alkyl» or aryl radical

substituted methine group of formula --CiI = V

η * 1 or 2;

Q the request for completion, if necessary substituted 5- or 6-membered * .- "■" "lieteTocyclischeit.Ringes ^ e ^ required atoms;

Z the atoms necessary to complete a d ^ sensitizing effecti optionally: substituted S or 6-membered ring and

X is an acid anion

Preferably the electrophotographic recording material contains according to the invention a hethine dye of the specified Formulas in which Q is the optionally pure to complete substituted::

Pyridine-, ThiasoX-, Öxazol-, Selenazoi-jl: - _K .5v4 »Thiai.diäzQ'l" _Y -Pyridazine- or Quinoliiiros necessary atorai gives »

1907S17

According to this, the el.ektrophoto.gr aphis before recording material according to the invention can thus contain, for example, a methyl dye of the formulas given, in which -Q is the one to complete an optionally substituted imxilAZp ^ Y ^ Z ^ & Jvy ^^^^ ' * Iiaidazo ^ "2 _> i-b7selenazol- _i imidazo £ ~ 2» 1 * b? OxazOl-, imidazo / "? $ 1 ^ bJ thiazole-, imidazo ^" 2 _l 1-b7-t _t 3,4-thiadiazole- or Imidazo ^ "!, 2 ^ b? - pyridazinringes represents required aetony»

The second residue is an electron accepting odey receiving ring of the type ^ as known in is common '. ; ",; --_-

Preferably the electrophotographic recording medium contains _; According to the invention, a methine dye of the formulas given, in which Z is the nitrobenzot / uazol * ^ Hitrobeiizoxa? oil *> selenazole, iinidazo ^ '^ jS ^ bJquinoxaline,], 3 quinoxaline, 1,3-diarylimidazo / ~ 4 _f 5- * b7chiiiöxalin.-, 3,3-dialkyl * Sli-pyrrolo / 'ZjS- ^ pyridin'-,!, S-dialkyl-Sii ^ nitroindol-s, thiazolo ^ ^ "4 _> 5-b7cJiinolin -, Nitrochinolin-, Mtronaphthotniazol * · ^ Miter »· naphthoxazole, Nitroselenazöl-, _# Nitronaphthoselenazol- or nitro> pyridine ringes represented the atoms required ^ _i:

For example, in the structural formulas given, t can be a Methine group of formulas:

^ 09848/1393

- 1 - "- ■ ..- ■■ .-. ■. ■ ■ .:

Il has the meaning of an alkyl radical, it may be that ali * phatischer and cycloalphötisclier Nature, DVH * R can be for example a methyl, ethyl _-6 propyl, isopropyl, butyl, hexyl, cyclohexyl -, "or decyl R is preferably an aryl radical, preferably of the phenyl or naphthyl series, d * h · R can be, for example, a -phenyl-, ToIyI: - _p XyIyI-, bromophenyl-, chlorophenyl-, nitrophenyl-, -methoxyphenyl · - , Naplithyl or thenylazophenyl radical.

if U- and U ₂ mean optionally substituted alkyl radicals _5, they have preferably 1 to 4 "carbon atoms. The alkyl radicals represented by It. and U- can be aliphatic and cycloaliphatic in nature ₉ that can be R and R for example its methyl, ethyl, propyl, isopropyl, uutyl, ilexyl, cyclohexyl, DeCyI or dodecyl radicals ; liydroxyalkyl radicals, e.g. ß-liydroxyäthyl or ω-ίiydroxybutyl radicals; carboxyalkyl radicals, e.g. ß-carboxyethyl or ω-carboxybutyl radicals, e.g. B-sulfoethyl, z. sulfobutyl, ω-sulfobutyl or ω-sulfobutyl radicals; B. ß-Sulfatoäthyl- or ^ -Sulfatobutyirestej Acyloxyalkylreste, "z. B. ß-Acetoxyäthyl-, γ-Propionyloxypropyl- or ω-Butyryloxybutylreste; Alkoxycarbonylalkyl radicals _p e.g. B ß-Ilethoxycarbonylethyl- or ω-Metlioxycarbönylbutylreste and the like.

9.0984S / 13Ö-3

1907517

■ '.- ■■■ -. ■■ - ■■■■ - 8 - ■ ..' ■■ - "■ '■" ■ -: - ■ ■■■; ■ - ■ - ■■ - ■ -

If R ₁ and It- have the meaning of alkenyl radicals, these can be ordered, for example, from allyl, 1-propenyl or 2-butenyl radicals,

If R * and R, have the meaning of optionally substituted aryl radicals, then these preferably consist of radicals from the phenyl or naphthyl series, i.e. Ii. R ^ and R ₂ can be, for example, phenyl, tolyl, xylyl, chlorophenyl, methoxyphenyl or naphthyl radicals.

X can be a common acid anion, as it is in known cyanine dyes usually present, i.e. for example a Chloriä-, Browid-iJpdid-iTliiiocyanat-, Sulphamat-, Perchlorat-, p-Toluene sulfonate * !, methyl sulfate or ethyl sulfate anion.

The ring completed by Z can be, for example, an S-nitrobenzothiazole, 6-nitrobenzothiazole or S-chloro-6-nitrobenzothiazole ring; an S-nitrobenzoxazole, 6-nitrobenzoxazole or S-chloro-ö-nitrÖttenzoxazolfingi a 5-nitrobenzoselenazole, 6 " nitrobenzoselenazole or S-chloro-o-nitrobenzoxazole ring; a 1 _f 3-di äthylimidÄzo ^ i ^ S ^ b / quinoxaline or 6-chloro-3-i _# diäthyliinida2o- ^ '4, S'b7chin0xalinring; a 1,3-diallylijnidazo ^ "4, S-b7quinoxaline or 6 * chloro-1 _# 3-diallyliniida2ioY *" 4,5-b7quinoxaline ring in 1 # 3-. piphenyiiraidazo ^^ iS- ^ quinoxaline or ö-chloro-IS-diphenylimida2o £ ~ 4,5-b7quinoxaline ring; a 3,3-diinethyl-3H-pyrrolo ^ 5,3-b7

909ÖA5 / 1393

pyridine or 3,3-diethyl-3H-i:) yrrolo £ ~ 2j3-h7pyridine ring; a 3,3-dimethyl-S-nitro ^ SU-indole-, S ^ -Diethyl-S-nitro-SH-indole- or 3,3-Dimothyl-6-nitro-3H-indole ring or a 5-nitroquinoline or 6-nitroquinoline ring.

Q can for. -the "non-metallic atoms are used to complete at least one fused heterocyclic Ring with 5 to 6 ring atoms are, such heterocyclic Rings other than the pre-existing nitrogen atom also have a second or third heteroatom, such as an oxygen, sulfur, selenium or nitrogen atom can. ,

In particular, the heterocyclic ring completed by Q can be, for example, a pyridine ring; an alkylpyridine ring, e.g. a methylpyridine or ethylpyridine ring, a chloropyridine, methoxypyridine, nitropyridine or a phenylpyridine ringj a thiazole, 4-methylthiazole, 5-methylthiia? ol- ₈ 4,5-üiniethylthiazol-, 4- Phenylthiazole, 5-phenylthiazole or a 4, S-diphenylthiazole ring; an oxazole, 4-methyloxazole, 5-methyloxazole, 4,5-dimethyloxazoi, 4-phenyloxazole or 5-phenyloxazole ring; a selenazole, 4 * Metllylselenazol-, 5-Metliylselenazol- ₁ 4, S-Dimethylselenazol '·, · 4-phenyl selenazole or 5-Phenylselenazolring; a -1. »3 _f 4V]% i8ä £ 9« Ql · -, 2-alkyl * 1 _f 3,4-thiadiazole * »eg 2-methyl · |, 3 _f 4-thiadiasol ring or a 2"
a 2 ^

or 2-nitro-1,3,4-thiadiazole ring; a pyridazirring, e.g. B. a Alkylpyridazine ring, 2nd β. a 3-methylpyridazine or 3-butylpyridazine ring or a chloropyridazine ring, ζ. B. a 3-chloro ο pyridazine ring or an aryl pyridazine ring, e.g. B. a 3-phenylpyridazine or 3,6-Üiphenylpyridazinrins, or an alkoxypyridazine ring, z. B, a 4-kthoxypyridazine ring.

As particularly advantageous spectral sensitizers for organic The monosalt dyes of the formula I have become photoconductors proven. .

The electron-accepting or electron-accepting rings of the methine dyes used according to the invention are those rings which, after conversion into a symmetrical carbocyanine dye and addition to a customary gelatine ^ silver chlorobromide emulsion with 40 mol-I chloride and & o mol% bromide in a concentration of 0.01 to 0.2 g dye per mole of silver by electron trapping or receiving electrons result in at least about SOIigea loss of the blue sensitivity of the emulsion when it is sensitometrically exposed and processed at 20 ⁰ C in a developer having the following "composition 3 minutes:

N-methyl-p-amine phenol sulfate 2.0 g

Sodium sulphate (drained) 90.0 g

Hydroquinone 8.0 g

Sodium carbonate, monohydrate 5-2 «.5. G

^ aiium bromide 5.0 g /

iftit Wasiser made up to 1.0 liters

1907517

Particularly advantageous electron acceptors or electrons c in catching rings are those which, after being transferred into a symmetrical carbocyanine dye and testing in the described Way to a practically complete desensitization the tcsteinulsion against blue radiation lead · A tactical complete desensitization leads to a min- » at least 9OVigen, preferably at least 9Siigen loss of Sensitivity to blue radiation *.

The spectral sensitizing dyes used according to the invention for the production of electrophotographic recording materials desensitize a negative gelatin-silver bromo-iodide emulsion, the halide of which consists of 99.35 mol of chromide and 0.65 of HoI-S of iodide, if it is in one concentration 0.2 Ifillimolen dye per mole of silver halide can be added by more than 0.4 log Ε units, if the test * emulsion is applied to a conventional layer support, through a step wedge in a sensitometer (to achieve D _x ) with light a trowel length of 365 nm exposed for 3 minutes at 20 ⁰ C in a developer of the composition indicated developed * fixed, washed and dried * the negative Silberbromojodidtestemulsion was thereby prepared as follows:

A solution consisting of was placed in a temperature controlled container filled with the following components:

S09Ö4S / 1393

- ί2 -

(A) potassium bromide; 165 g "potassium iodide 5 8 Gelatin 65 g

Water 1700 ml ^;

A filtered solution of:

(B) silver nitrate 200 g

Water 2000ml -

filled.

The solution A was kept at a temperature of 54 ^° C. The solution B was brought into a separating funnel and likewise heated ^{to a temperature of 54 ° C.} The silver nitrate solution was then passed through the separating funnel through a calibrated nozzle into the container with solution A, the contents of the container being kept in constant motion during precipitation and ripening and later during the final preparation of the emulsion by means of a mechanical stirrer Precipitation of the silver halide took place over a period of 10 minutes.

The developer used to develop the material possessed the already specified composition.

According to the invention for the production of the electrophotographic Recording material used polymethine dyes desensi-

909845/1393

thus form common negative silver halide emulsions. Such Emulsions have their own sensitivity to blue radiation. The dyes used according to the invention reduce this sensitivity. In addition, these dyes cause practically no spectral sensitization in such dyes Emulsions. In view of this, it was not to be expected that these dyes spectrally sensitize organic photoconductors capital.

Another peculiarity or characteristic of the dyes used in accordance with the invention for the preparation of the electrophotographic recording materials is that they are practically non-photoconductive. Practically not photo-bitable means that no image is produced if a solution of 0.002 g of dye and 0.5 g of polyester binder (as described later in Examples 1 to 14) is dissolved in 5.0 ml of methylene chloride and the mixture is placed on a support is applied and tested in the absence of a photoconductor in de ^x r in Examples 1 to 14 described manner. .

The dyes used according to the invention increase the sensitivity the organic photoconductor by expanding or increasing the responsiveness of the photoconductor to more visible Radiation, d. H. Radiation in the range from about 400 nm to 700 nm.

Applied in the usual concentrations, they act according to the invention used dyes as spectral sensitizers. Are

. ■ '■■■■. '"■■ · 9QdfriS.l1.3d3.:, -

the organic ones used to produce the recording material Photoconductors hardly or only slightly effective, this is how they work the dyes used according to the invention as well as the Sensitivity increasing compound as well as a spectral sensitizer.

The polymethine dyes of the formula I are easy to prepare, e.g. ß. by heating a mixture of a heterocyclic Compound of formula III; , ".

R ₁ -NC "" CII -CH) _n * C -R

in which n, R ₁₉ R ₉ , X and Z have the meanings already given and R. is, for example, a methyl, ethyl or benzyl radical and a heterocyclic compound of the formula IV:

where R and Q have the meanings already given. Appropriate v / ground the two connections in practically equiraolar ones

Quantities together in a suitable solvent, for example Hssetic anhydride, implemented. The raw dye can be isolate in the usual manner from the reaction mixture and then recrystallize one or more times from suitable solvents, e.g. B. ethanol, methanol, cresol / methanol Mixtures and the like, recrystallization.

The preparation of dyes of the formula II is expedient Durcli implementation of a compound of the formula III with a compound of the formula Vi

VQ * v

β 9 .-: ■■ -.-

■ = ■ ■ - c «ssr N- ■■ '". ■ ■' - -

R ₂ -NC-CHO

where R, R ₂ and Q have the meaning already given * Isolation and purification of the dyes can be carried out as described for the dyes of the formula I.

Compounds of the formula IV can be easily prepared by Formylation of compounds of the formula VIi

t mammm I. c - -N · / ■ Λ N GH N I ' R.

90S84S / 1393

1997617

wherein II and Q have the meaning already given, through a so-called. Vilsmeier reaction, which is based on the reaction of a compound of formula VI with a complex of phosphoryl chloride and dimethylformamide in excess dimethylformamide as solvent and hydrolysis with aqueous sodium hydroxide. After the reaction mixture has cooled, they can precipitate Crystals filtered off, washed with water and, if necessary, by one or more recrystallizations from solvents such as acetone, ethanol or chloroform-ethanol * Mixtures and the like, are cleaned.

Compounds of formula V may be prepared by quaternization of compounds of the formula IV with usual known Quaternärisierungsmitteln, for example methyl iodide, "dimethyl sulfate, diethyl sulfate, methyl-p-tolüolsulfonat and the like easily. _A

The preparation of 3-ethyl-6-nitro-2 - / "2- (2 * phenylimidazö / T _# 2-a7-pyrid-3-yl) vinyl7benzothiazoliurajodid of the following structural formula:

can be done, for example, according to the following procedure:

909845/1393

1.11 g of 3-Foriiiyl-2-phenylimidazo ^ 1, 2-a7pyridine and 1.98 g of 3-ethyl-Z-methyl-δ-nitrobenzothiazolium-p-tQluolSulfonat in 10 ml of acetic anhydride v / earth for 5 minutes at the reflux temperature heated. The cooled reaction mixture is then diluted with ether. The ethereal layer is decanted off and the sticky residue is dissolved in 25 ml of hot methanol. Then a solution of 2.0 g of sodium iodide in a little water is added, whereupon the mixture is chilled. The precipitated dye is filtered off, after recrystallization from zweir.ialig-er v ilc.than.ol ground about -. ¹ J, (3υ -g dye, corresponding to 21% of theory nit, a bchuelzpunkt obtained from about 179 ° C.

For the production of electrophotographic records nacii the lirfindun ?; suitable icthin dyes are, for example the substances listed in the following TaDcIIe Λ. .

Γ a 1) e 1 1 e

dye λ'γ. Dye-Cf

pyrid-3-yl) vinyl7hen2otiiia2oliumiodid;

II 1, 3-i) 'iphenyl-2 - ^ "2.-C2-phenyliriiiJazo ^ 1,2-a7-pyrid-3-yl) viayl7ii "id-azo ^" - 4, "5-t> 7quinaxaliniuinjodid; - '

III 3- ^v Ethyl-2 - / "" 2- CI-raiothyl-2-phenyl-hi-imidazo- I "I » 2-a7pyridiiiiuni «3-yl} viiiy ^ -6-nitrob

BATH ORIQiMAL

- ΛΒ -

IV 2 - ^ "'2- (i-Methyl-2-paenyi-1M-.i: aidazo / ~' l- _t 2-a7- · - pyridinium-3-yL) vinyl7-113-dipheii: yliriidazo l ~ <\ , S-bJquinoxaLiniundijodid;

V 3-ethyl-2- {2- / "8-] r-ethyl-2-C4-nitrophynyl) ii; sidazol ~] _t 2-a7pyrid-3-yl7vinyl} -6-nitrobenzothiazolium iodide;

VI 1,3-Diethyl-2- {2 - / "o-riethyl-2-C4-rLitrophGnyl) -imide £ i20 ^ ~ 1 , 2-a7pyrid-3-yl7vin '/ l} -inidazp / T, S-b7 ^ quinoxaliuiuia-r-toluenesulfonate;

VII 6-Caloro-2- {2 - / "" :: - iaet'iyl-2- (4-uitrophenyl) -iinidazo ^ 1, 2-a7ryrid-3-yl7v ^r iny L> -1, 3-di ' picnrli.aidazo / 4,5-b7ciiinoxaliniu », tjodId;

VIII. 1,3,3-Tri: et:; yL-2- {2- / ^"I _5-; ict.il-2-C4-nitro: jhen7l) imidazo ^ 1 _s 2-A7R>^'r id -3-yl7viuyl} -S-nitro-Siindoliun-M-toluene3i: 1 conate;

IX I _> 3 _l 3-Trir! Ethyl-2-t2- / ~ i; - :: uthyl-2-C4-pIiön / lazopiicr.yL) iridazo / "l, 2- £ ΐ7 · Ρ7ΓίίΙ-3->' 1 · 7.νία>'. Ί} -5-! Ϊ́ίίΓο-3L-iiuloliur: -n-toluolsulfpn-at;.

X 3-Xtiiyl-2-i2 - / "ß-aetiLyl-2-C4-pheTiylazopionyl) -inidazo ^" 1,2-a7pyrid ~ 3-> ^r i7vin.yl 1-6-nItrobenzothiazoiiuni-p-toluoisulfonati.

XI 1,3-I> iät] iyl-2- {2 - ^ "S-niethyl-2-C4-pheiiylazopIienyl)» iαidazo ^ ~ ^ _l 2 · -a7pyΓiΛ ~ 3 ^ yl7viftyl _: } iί quinoxaliniuK-p-toluo .ls.ul.fona.t;

XII 1,3-diethyl-2- [2- / "7-red} iyl-2-C4-ni imidazo / "!» Z-a

BADORfGtNAL

-.19-

XIII 6-Chloro-2- {2 - ^ "7-methyl-2-C4-nitrophenyl> imidazo ^" ° 1, 2-b7pyrid-3-yl7vinyl} -t, 3-diphenylimidazo ^ "4,5-b7quinoxalinium iodide;

XIV 1,3,3-trimethyl-2- {2 - ^ "7-methyl-2- (4-nitrophenyl) imidazo £ ~ 1,2-a7pyrid-3-yl7vinyl} -5-nitro-3H-indolium-p -toluenesulfonate;

XV 1 _f 3,3-trimethyl-5-nitro-2 - {. 2 - ^ "6- (4-nitrophenyl) -imidazo ^" 2,1-b7tl

p-toluenesulfonate

Κ CH-
3n
J J ^^> - CM « * CH— ^ NO- > V% _r N0 ₂ «I I ti ■> - ^ .- I. CH ₃

⁹ OSO ₂ C ₇ H ₇

XVI 1,3-Dietliyl-2- {2 - ^ "6'-C4-nitrophenyl) imidazo * ^ "2,1-b7thiazol-5-y l7vinyl} iniidazo ^" 4,5-b7-quinoxalinium-p-toluenesulfonate;

XVII 6-Chloro-2- {2- ^ 6 * (4-nitrophenyliinidazo ^ "2, T-b7-thiazol-5-yl7vinyl} -Ί, 3 * diphenylimidazo ^" 4, S-b7-quinoxalinium-p-toluenesul £ onat;

XVIII t, 3,3-trimethyl-2- {2 - / "2-methyl-6- (4-nitroph6nyl) · nitro-SH-indolium ^ p-toiuolsulfonat:

90984S / 1393

- 2Q -

-NO.

NO.

3-Ethyl-2- {2 - ^ "2-methyl-6- (4.-nitrophenyl) imidazo ^" 2,1-b7-1,3,4-thiadiazol-5-ylJvinyl} -G * nitro benzothiazolium p-toluenesulfonate;

1,3-Diethyl-2- {2 - ^ "2-methyl-6- (4-nitropheayl) -iraidazo ^" 2,1-b7-1, '3,4-thiadiazol-5-yl7vinyl} -imidazo ^ "4 _i S-b7quinoxalinium p-toluenesulfonate;

2- {2- / ~ 2- (4-bromophenyl) -6-chloroimidazo ^ T _r 2-b7r pyridazin-3-yl7vinyl} -3-ethyl-6-nitrobenzöthia * zolium-p-töluenesulfonate:

Br

90 9845/1393

2- {2- ^ ~ .2- (4-ßromophenyl-6-chloroiinidazo £ "i, 2-b7-

quinoxaliniuin p-toluenesulfonate;

2- {2 - ^ "2- (4-broinophenyl-6-methaxyimidazo ^ ~ l ·, 2-b7 pyridazin-3-yl7tfinyi} -1, SjS-tri

2- {2- / ~ 2- (4-bromophenyl) -6- * chloroimidazo ^ ~ 1,2-b7-pyridazin-3-yl7vinyl} -1 ₈ 3,3 - trimethyl '* 5-n.itrQ- 3II «· indoliuiii-p-toluene sulfonate;

2- {2- ^ ~ 2- (4-bromophenyl) "G-methoxyimidazo / 1,2-b7 * pyridazin-3-yl7vinyl} -3'ätiiyl-6-nitrobenzotliiazole ium p-toluenesulfonate;

2- { 2 ~ l ~ 2- ■ (4 ij.iromoph.eayl) -6 -iac thoxyiinidazo ^ ~ T, 2-b7 "

pyridazin-3-yl7vinyl} -l ₍ , 3-diatliyliinidazo / "4 ₍ 5 - b7- '

cliinoxaliniuin p-toluenesulfonate.

Others for making the electrophatographic recording material according to the invention, suitable, the dyes Dyes similar to the formula I to XIV are for example 1-alkyl * (2 ... Ii. Methyl, ethyl, propyl, isopropyl, Butyl- or decyl-) -ö-nitrσ ~ 2 - / '"2- (2-phenylimidazQ £" 1, 2-a7 " pyrid-3-yl) vinyl7benz, oxa2ioliiiiTisaIze; t-alkyl (e.g. methyl, Ethyl-, propyl-, isopropyl-, eatyl- or decyl--) -ö-nitro-2-

Butyl or

Ethyl _for propyl, isQpropyl. _t l) -2- {2 «^?" »for S-) methjrl-2- (4.-Ritroj.ih.eayl>

salts; ί, 3-diallyl-2- {2- / ~ 8-Γιΐethyl-2- (4-nitrophenyl) iIaidazo « / "1, 2-a7pyrid-3-yl7vinyl} imidazo /" 4,5-b7cliinoxaliniurisalze or 1,3-dialkyl (with alkyl = methyl, ethyl, propyl, isopropyl, Butyl or decyl) -6-chloro-2- {2 - / "7- (or 3-) methyl-2- (4-nitrophenyl) imidazo ^" 1, ^ -a ^ p

The salts can be used, for example, as chloride, broraide, Iodide perchlorate or p-toluenesulfonate are present.

Others, for the production of the electrophotographic recording material according to the invention? Suitable dyes which are very similar to the dyes of the formulas XV to XVIl are, for. B .; 3-alkyl- (e.g. methyl-, - ethyl-, .. propyl-, isopropyl-, butyl- or decyl-) -2- {2 - ^ * 6- (4-nitrophenyl) inidazo £ "* 2 _{l (} 1 -h7-thiazol-S-yl7vinyl} -6-nitrobenzot] iiazoliunalze; 3-alkyl- (e.g. methyl-, xthyl-, propyl-, isopronyl-, butyl- or decyl-} -2- {2 - ^ ''.. 6 - (4-nitrophenyl) iniidazq ^ 2 _J-b7thiazol .1 - 5-y "l7vin-Y_l-i"'6-nitrohenzoxazoliunsalze; 3-alkyl (eg, methyl, ethyl · ", Propyl, isopropyl, butyl or decyl") -2- (2- / "6-C ^ -nitrophenyl) imidazo /" 2, i-b7selenazole- £ -yl7vinyl> -6-nitro "eji2; oselerL * Azoliuni salts and 2 - / ^ 2- (6-Phenylint
vinyl7-1,3-diph

These salts can, for example, in the farm of € ki bromides, iodides, perchlorates, p-Tol-ualsulföreatea "üiicü ..diergl are present" _ ■■ ■ =

803045 / 13Sa - -. "■ ': ■."' -

BAD0RI31WAL

Further dyes which are suitable for producing the electrophotographic recording material of the invention and which are structurally similar to the dyes of the formulas XVII to XX are, for example, ^ -Allcyi- (e.g. methyl, ethyl, propyl, isopropyl, butyl) . or decyl) -2 - {2 "" / "2-methyl-l-6 --- {4-nitrophenyl) imidazo ^ '2, _l-t B7-1 3,4-thi.adiazol-5 -yl7vinyl} -6-nitTO - benzothazolium salts; 3-alkyl (e.g. methyl, ethyl, propyl, isopropyl, butyl, or decyl) -2- {2 - ^ "2-methyl-6- (4-nitroplienyl) iinidazo ^" 2 , 1-b7 ~ 1, S ^ -thiadiasol-Sy ^ vinyiJ-ö-nitrobenzoxazoliumsalzc and 2 - ^ "2- (6-phenylimidazo / ~ 2,1-b7-1» 3 »4-thiadiazol-5-yl) vinyl7-1,3rdiphenyliinidazo ^ "4,5-b7quinoxalinium salts.

These dyes can also be used, for example, as chlorides, bromides, Iodides, perchlorates and p-toluene sulfonates are present.

Others for making the electrophotographic recording material According to the invention suitable dyes which structurally very similar to the dyes of the formulas XXl to XXVI are, for example; 2- {2- ^ ~ 2-C4-chlorophenyl) -6-chloroimidazo ^ "i , 2-b7pyridazin-3-yl7vinyl} -3-alkyl (ζ. Β »-methyl * ·, ethyl, propyl, isopropyl, butyl or decyl) - 6-nitrobenzothiazolium salts; 2-C2 - ^ "2- (4-broniophenyl) -6-nietlioxyimidazo ^" i, 2-b7pyridazin-3-yl7vinyl} -3-allcyl (z * B »-methyl'-, -ethyl-, propyl, isopropyl, butyl or decyl)> 6> nitrobenzoxazolium salts as well as 2- {2 - ^ "2- (4-BrQmophenyi) -6-chloroimidazo-

90984S / 1393

_; 19Ö7617

l ~ 1, 2-b7pyridazin-3-yl7vinyl} -1,3 diphenylimidazo * ^ "4, Sb / r chinoxaliniumsalze.

• These salts can also be used, for example, in the form of chlorides, Bromides, iodides, perchlorates and p-toluenesulfonates are present.

The photoconductor layer of the olectrophotographic recording material of the invention may contain a methine dye of the formulas given or several methine dyes of the formulas given.

The organic photoconductor of the recording material of the invention can consist of any of the commonly known organic photoconductors, .d. H. a so-called monomeric as well as a so-called polymeric organic photoconductors.

A particular advantage of the invention is that the invention used methine dyes to increase sensitivity of organic photoconductors that are practically insensitive or have only a low sensitivity to it Have radiation from 400 to 700 nm / i.e. a sensitivity of less than 25 and generally less than 10 when tested according to the method described in Examples 1 to 14 below.

909845/139 3

A particularly advantageous class of organic photoconductors, those for making the recording material of the invention can be used are composed of organic amines "» de photoconductor. Such photoconductors have as gladly ins ame s Feature at least one amino group,

The photoconductor of the photoconductor layer of the electrophotographic recording material of the invention can thus consist, for example, of an arylamine, for example (1) diarylamine, e.g. Dinaphthylamine; Ν, Ν'-diphenyl benzidine; N-phenyl-t-naphthylamine; N-phenyl-2-naphthylamine; Ν, Ν ¹ «diphenyl-p-phenylenediaminej 2-carboxy-5-chloro-4 · -methoxydiphenylamine; p-anilinophenol; NjN'-di - ^ - naphthyl-p-phenylenediamine; 4,4'-benzylidene-bisCNjN-diethyl-m-toluidine), the photoconductors known from US Pat. No. 3,240,597 and the like; and (2) triarylamines, namely (a) non-polymeric trarylamines, e.g. B. triplienylamine; N, W, N ', N'-tetraphenyl-m-phenylenediamine;4-acetytriphenylamine; 4-Hexanoyltriphenylaminej 4-Lauroy1.triphenylaminej 4-IIexyltriphertylamine; 4-dodecyl triphenylamine; 4,4'-bis (diphenylainino) benzal; 4,4 ^l -bisCdiphenylariiino) benzophenone and (b) polymeric triarylamines, e.g. B. Poly £ ° N, 4 "-CM _s N ', N'-triphenyIbenzidinX?«. Polyadipyltripkenylaminej Polysebacyltriphenylamin; PolydecaräethyleneentriphenylamiK; Poly ~ N- (4-vinylphenyl) -diphenylainin and Poly-N ^ (vinylpheiiyl) * * '-dinaphthylamine »

Other very suitable photoconductors from Äntintyii wordöii, for example hi uet ÜSÄ patent specification S 130? 3O besckriebeii *

The photoconductor of the photoconductor layer of the recording material the invention can further comprise, for example, a photoconductor of the type known from U.S. Patent 3,265,496. Such photoconductors can be defined by the following general Represent structural formula:

Herein mean:

a mononuclear or polynuclear, divalent aromatic, condensed or linear Rest, e.g. B. ehen phenylene, naphthylene, biphenylene, Binaphthylene radical or a substituted divalent one aromatic radical of this type, it being possible for the substituents to consist, for example, of Acy! Residues of 1 to about 6 carbon atoms, e.g. Acetyl, propionyl or dutyryl radicals or alkyl radicals with 1 to about for carbon atoms, z, -.- B- .. Methyl, ethyl, propyl or butyl, or Alkoxy radicals up to about 6 carbon atoms, ζ-. B, methoxy-, ethoxy *,? Ropoxy- or pentöxy * - resten or Nitrorcstenj

a mononuclear or polyrtulclearea.,. monovalent aromatic ^ lioadefisiert or lin <istctt radical, z. B * a flienyl-jlaphthyl or bi

5/1393

BADORfQiNAL

phenyl radical or a subs ti tuieTte.ii monovalent aromatic radical of this type, with the substituents for example best dim can from acyl residues With .1 to 6 carbon atoms, ζ, B. acetyl, propionyl or butyryl radicals, or alkyl radicals having 1 to about 6 carbon atoms, e.g. B. Methyl, ethyl, propyl or butyl radicals, or Alkoxy radicals with .V "up to: 6 carbon atoms, e.g. Methoxy ^, pro-oxy or pentoxy radicals * or nitro radicals;

Q ^{1 is} a hydrogen or halogen atom or an aro-

matischon amino radical, e.g. B * is a radical of the formula A'NH-, where A * has the meaning already given owns;

b * a number from T to about 12 and

G is a hydrogen atom or a mononuclear or

polynuclear aromatishen ₉ kohdensierten either linear or radical, for example, "a phenyl or naphthyl _# Biphenylrestg or a substituted aro · ^ matisJien rest of the specified type, the substituents thereof may for example consist of alkyl *, alkoxy, acyl barren nitro radicals or poly ( 4'-vinyl · phenyl) tests ₈ which are bonded to the nitrogen atom through a carbon atom of the phenyl radical.

S0984S / 1393

- 23 -

The photoconductor of the recording material of the invention Rann also consist of a nitrogen-containing heterocyclic compound, e.g. B. 1,3,5-triphenyl-2-pyrazoline and 2,3 ^ 4,5-tetraphenylpyrrole.

Particularly advantageous organic photoconductor is polyarylalkane have proved, as described for example in US Patent 3,274,000 and French Patent Γ 383 and Belgian Patent 696,114

to be discribed.

Such photoconductors consist, for example, of leuco bases Diaryl and triarylraethane dye salts, 1,1,1-triarylalkanes, in which the alkane radical has at least 2 carbon atoms, and tetraaryl methanes. At least one of the aryl radicals attached to the alkane or methane test are bound by an amino residue substituted. The compounds listed last are not leuco bases.

Particularly advantageous polyarylalkane photoconductors have been found to be those of the formula

R "

- "I '- ■' ■■ ■", .. .λ

Rt ___ _C RItI

R ""

proven, in which mean:

909845/1393

R »is a hydrogen atom or an alkyl or

Aryl radical and

R ", R ¹ " and R " ¹¹ each represent an aryl radical, with the proviso that

at least one of these aryl radicals through a secondary or tertiary amino radical is substituted.

The aryl radicals attached to the central carbon atom are preferably composed of phenyl radicals, although they are e.g. B. can also consist of naphthyl residues. These aryl radicals can be in be substituted in various ways, for example by Alkyl and / or alkoxy radicals with 1 to 3 carbon atoms, hydroxyl radicals, Halogen atoms and the like, namely in the ortho-, meta or para position. As particularly advantageous compounds those with ortho-substituted phenyl radicals have been found. The aryl radicals can furthermore be connected to one another or be cyclized to form, for example, a fluorene radical.

The axno substituents can be expressed by the formula

represent, wherein R ^ can be an alkyl radical with preferably 1 to 8 carbon atoms, a hydrogen atom, an aryl radical j preferably of the phenyl or naphthylene series, or both Radicals R ^ together a heterocyclic amino radical with typical-

90984S / 1392

may form 5 to 6 ring atoms, for example one ^; Morpholino, pyridyl or pyrryl ring. At least one of the radicals iV \ R " ¹ " and R "" preferably consists of a p-dialhylaminophenyl radical.

If R ^{1 has} the meaning of an alkyl radical, this alkyl radical has approximately 1 to 7 carbon atoms.

Typical ones used in making the recording materials of the invention suitable polyarylalkane photoconductors are as follows Table B compiled:

T a b e 1 1 e B

Photoconductor No.

4.4 ^l -bis (diethylamino) -2,2'-dimethyltriphenylniethane;

4 ', 4 ^lt diamino-4-dimethylamino-2 ^l _t 2 "-dimethyltriphenylnethan;

4 ^t _t 4 ⁿ -ßis- (diethylaniino) -2,6-dichloro-2 ' _l 2 "-dimethyltriphenylinethane;

4 ^l »4 ^ll -Bis- (diethylamino) -2 '_>2' ^I -diinethyldiphenylnaphthy lnie th an;

845/1393

BATH ORIGINAL

2 ¹ , 2 "-; jimethyl-4,4 ', ^" - tri triphenyl methane;

1 ', 4 "-bis- (diätuylamino) -4-'dinethylamino ^l-2, 2"-dinethyltriphenylmethan;

4 ', 4 "-bis (diethylamino) -2-ClIlOrO-Z', 2" -di-

methy1-4-dimethylaminotriphenylmethane;

ί? 4 ', 4 "-üis (diatliylanino) -4-dimethyla;: vino-2,

2 *, 2 "-trivyltriphenylmethane; 4 ·, 4 "-liis (dimethylamino) -2-chloro-2 ', 2" -

dimethyl triphenyl methane;

4 ¹ 4 _f ^ll-bis (dimethylamino) -2 ^l, 2 "-dincthyl-4-methoxytriphenylmethan;

4,4'-bis (benzylethylamino) -2,2'-dimethyltriphenylnethan;

4,4 '' -Uis Cdiethylamino) -2, 2'-diethoxytriphenylriethane;

4,4 '-Ris (dirie thy lamino) -1, 1, 1-triphenylathane;

1 - (4-N, N-methylaminophenyl) -1 _s 1-diphenylethane; -

4-dimethylaminotetraphenylmethane and 4-l) iäthylaminotetraphenylmethane.

909845/1393

Further photoconductors suitable for the production of the electrophotographic recording material of the invention are, for example described in the following U.S. patents:

3,122,435; 3,127,266; 3,130,046; 3,131,060; 3,139,338; 3,139,339;

3,140,946; 3,141,770; 3,148,982; 3,155,503; 3,158,475; 3,161,505;

3,163,530; 3,163,531; 3,163,532; 3,169,060; 3,174,854; 3 ISO 729;

3,180,730; 3,139,447; 3,206,306; 3,141,770; 3,037,861; 3,041,165;

3,066,023; 3,072,479; 3,047,095; 3,112,197; 3,113,022; 3,114,633; 3,265,497 and 3,274,000.

The photoconductor layer of the electrophotographic recording material according to the invention can consist of the photoconductor and the
Dye or the photoconductor, the dye and a binder. The use of a binder for manufacture
the photoconductor layer is not absolutely necessary as the
Photoconductor itself can have film-forming properties, what z. B. in the known as a photoconductor poly (vinyl carbazole) the
Case is. Usually, however, a conventional binder is used to produce the photoconductor layer. One such
Binder should have high dielectric strength and good insulating properties, at least in the absence of
possess actinic radiation and ultimately be a good film former. Particularly advantageous binders for production
the photoconductor layer are, for example, polymers such as polystyrene; Polymethylstyrene; Styrene-butadiene polymers; Polyvinyl chloride; Poly-

909845/1393

vinylidene chloride; Polyvinyl acetate; Vinyl acetate-vinyl chloride copolymers; Polyvinyl acetate; Polyacrylic acid and polymethacrylic acid esters; Polyester, e.g. > i. Poly (ethylene alkaryloxy alkylene entcrep-htlialate); Phenol-formaldehyde resins; Polyamides and polycarbonates.

The support of the electrophotographic recording material according to the invention can consist of eggs of the usual known electrically conductive layer support, which is usually for the production of electrophotographic recording materials used tverden, e.g. B. from a metal plate or metal foil or from a sheet of paper laminated with a metal foil or made of a plastic polie laminated with a metal foil, made of electrically conductive papers and foils as well as papers and foils coated with transparent electrically conductive resin <pi are coated. The conductive layers can also through Deposition of nickel can be generated in a high vacuum on layer substrates. Layer supports with cuproiodide layers can also be used are used, for example, in the USA patent 3,245,833.

The layer supports can be transparent and translucent or opaque Carrier materials are used »Should a reflex exposure are carried out, a layer support is required for this, which allows light to pass through, whereas such a requirement does not exist when a projection exposure

9098Λ.5 / 1393

should take place. Likewise, the substrate must be made of a transparent one Layer supports exist when the reproduced recording is to be projected later. Translucent base are preferably used when reflex copies are to be made. Opaque or opaque substrates can be can then be used if the image produced is later transferred to another layer support, if the one on the support The record obtained initially satisfies the requirements or when the record or reproduction is used as a printing plate for manufacture of prints or copies of the original is to be used.

The concentration of the electrophotographic f Methine dyes used for recording materials according to the invention can be very different. It usually depends on the results you want and the specific case used organic photoconductor. It has proven to be useful to add 0.1 to 50% by weight of dye, preferably 1 to 10% by weight Dye based on the weight of the photoconductor to be used. To produce the photoconductor layer, for. B. 0.01 to 10 parts by weight of dye per 1 to 75 parts by weight of organic Photoconductors are used. Will be used to manufacture If binders are used in the photoconductor layer, this can make up 25 to 99 parts by weight of the photoconductor layer.

Furthermore, the photoconductor layer can contain customary, known additives included, e.g. B. other sensitizers, namely

90 9 84 5 / -1 3 9 3

neither spectral sensitizers nor sensitizers Connections or both types of connections.

The terms "insulating" and "electrical" used here conductive "means that layers of the binders which are used to produce position of the recording materials are used, surface Have resistances that are greater than 10 ohms per Square unit j ζ. B. per 0.09 m (1 sq.ft.), or that the oil-capable Substrate of the recording materials Surface resistances have that are less than 10 ohms per square unit, e.g. B. 0.09 m (1 sq.ft.).

The photoconductor layer of the electrophotographic recording material according to the invention can be that for electrophetographic Recording materials of the type described, usual strength exhibit. It is advisable to measure layer thicknesses from - dry about 1 to 200 microns. Preferably the photoconductor layer has of the recording material of the invention have a thickness of about 3 to 50 microns.

Before using the electrophotographic recording material according to the invention, it is preferably subjected to a dark adaptation, whereupon it is charged either negatively or positively. For this purpose, for example, a corona discharge device can be used, which is kept at a potential of 6000 to 7000 volts. The charged material is then exposed through an original or subjected to a reflex exposure in contact with an original, in which way an electrostatic image corresponding to the original is generated. This invisible image is then made visible in the usual way by contact with a developer composed of carrier and toner. The 9098 AS / 1393

Carriers can, for example, be made of small glass or plastic balls or iron powder. The toner can be, for example, a pigmented thermoplastic synthetic resin with a Particle size of about 1 to 100 μ, which can be applied to the recording material Can be melted, and the image permanent, too do. On the other hand, a developer can also be used of a dispersed in an insulating liquid Pigment or pigmented liarζ can consist of the liquid may still contain a dissolved resin «Is the polarity of the charge on the toner particles the polarity of the opposite to the electrostatic image, a copy of the original is obtained. However, the polarity of the toner charge is that same as the polarity of the electrostatic latent image, a reverse image or negative image of the original is obtained.

Although the development process described is a visible one Image on the electrophotographic recording material of the invention, it is also possible to either to transfer the electrostatic latent image or the already developed image to a second support, in which Case the transferred image becomes the final copy. Such development methods are known and are in a Described in a large number of patents. V

The following examples are intended to illustrate the invention in more detail.

90 9 8 45/1393

The following examples show the large increase in sensitivity organic photoconductor, if this by the invention The dyes used are sensitized. The examples show Furthermore, that the Ümpf iiullichkeitsmaxima ("Abs. max.") in most Fall at wavelengths from around 350 to 6 25 nm. Poisons number the dyes used according to the invention also lead to several Sensitivity minimums or maximum sensitivity peaks, such as themselves from the / Table Ϊ below.

Examples 1 to 14

Various solutions were prepared from 5.0 ml of riethylene chloride as the solvent; 0.15 g of 4 _{t of} 4'-bis (diethylamino) -2.2 ^t -diniethyltriphenylr.ietliane as an organic photoconductor; 0.50 g of polyester made from terephthalic acid and a glycol mixture of 2,2-oleis-4-hydroxyethoxy) phenyl7propane and ethylene glycol in a weight ratio of 9: 1 as a binder and 0.0065 g of those listed in Table I below Dyes,

The solution produced in each case was applied to a layer substrate of an aluminum> ä >> which was kept at 25 ^° C. It was then dried. All procedural operations were carried out in a dark room. The individual recording materials were then uniformly charged with a corona discharge to a potential of about 600 volts and then exposed ^{to a tungsten light source of 300 ° K through a transparent original with optically dense characters.}

909845/1393

The electrostatic images obtained were then developed by cascade development. Finely divided, colored thermoplastic, electrostatically responsive toner particles were used for development used on glass beads. i) the individual generated electrostatic Images were made this way by 'precipitation of the toner developed in a way that is fair to the picture. ■

Others for developing the recording material of the invention suitable development processes are described, for example in UbA patents 2,786,439; 2 7S6 440; 2,736,441; 2,311,465; 2,874,063; 2,934,163; 3,040,704; 3 117;? Ά #; Re 25,779; 2,297,691; 2 55t 582 as well as in "RCA Review", Hand 15 (1954) :, pages 469 - 484 ... ".:

In all cases, images were obtained.

Other samples of the recording materials produced were on their electrical sensitivity and the maximum sensitivity. " _ tested. For this, the recording materials became positive or negative, as indicated in Table I, with a Gorona discharge charged until the surface potential, as if by a " Electrometer sample was measured, had reached 600 volts

The recording materials were then exposed to 215 lux by means of a tungsten light source of 3000 ^{° K.} The exposure was made through a gray scale. The exposure caused a reduction in the surface potential of the recording material

909845/1393

under each level of the gray scale from the original potential Vo to a lower potential V, the exact Kert of which depends on the LiciitnenjV-i aiming on the area of the recording material occurred.

The results of the measurements were plotted in a diagram. For this purpose, the surface potential V was plotted against the logarithm the exposure of each level. The real sensitivity every recording material can be expressed in lorm of the reciprocal., crtc of the exposure that is required, to reduce the surface potential by IJO volts.

The sensitivities given in Table I below represent the numerical values of 10 divided by the jixposition in 1cter-candlc-seconds, which is required to the surface of a recording material charged to 600 volts to decrease 100 volts. The results obtained are summarized in Table I below.

Tabel! '

Schulter- limp find! i i t

positive negative

Example dye iVilder- charged charged (Abs.max.) No. No. Generation surface upper flat nm

Comparison
example without Yes 8th 7th __ - 1 II Yes 60 50 400 2 V ) * \ 1400 720 540 3 VI Yes 125
345/139 3-. 630 510

4th IX. Yes 320 1 00 550 5 X Yes 250 120 550 6th XI Yes' 200 280 530 7th XIII - 200 60 8th XVII Yes 80 50 9 XVIII Yes 50 1 00 380 10 XIX Yes 250 230 470 11th XX Yes 250 200 460 12th XXIII Yes 25th 30th 370 13th X-XV Yes 150 250 490 14th XXVI Yes 320 800 470

As can be seen from Table I, when using the; not sensitized photoconductor only sensitivities "of- and 7 obtained, whereas those obtained with sensitization of the photoconductors the sensitivity values achieved are significantly higher. Particularly high sensitivity is achieved when using the dye Mr. V (Example 2). From the specified values it is found that there is an increase in sensitivity over the comparative material by a factor of about 175 for the positively charged material and by a factor of 103 for the negatively charged material.

The expansion of the absolute sensitivity is also of great importance, z. B. in some cases up to 550 nm. The comparatively somewhat less effective dye XXIII (Example 12) leads

90 9 845/1393

still increasing the sensitivity by the factor 3 or 4 for the positively charged recording material or * negatively charged recording material.

Corresponding results were obtained when instead of the dyes listed in table I have approximately the same concentrations of dyes I, III, IV, VII, VIII, XII, XIV-XVI, XXI, XXII and XXIV were used.

Results corresponding to those given in Table I would also be obtained if ^{0.15 g triphenylamine was used as the organic photoconductor instead of 4.4 l} -bis (diethylanvino) -2.2 ^l -dimethyltriphenylniethane (in which case the dyes are each as p-toluenesulfonate salt were used) or 1.3 _M 5-triphenyl-2-pyrazoline or 2,3,4,5-tetraphenylpyrrole or 4,4 • -üis-diethylaminobenzophenon were used. This clearly shows that the dyes used according to the invention are capable of spectrally sensitizing a wide variety of known organic photoconductors (

The dyes used according to the invention are not themselves photoconductive.

Furthermore, the photoconductors described have if they used alone, has very little sensitivity to visible light.

909845/139

Example 15 (comparative example)

Following the procedure given in Examples 1 to 14 were further recording materials under Verv / endim :; of the dyes listed in Table i) below. P. at this-dyes it is typical spectral sensitization means of the state of the art.

T a be 1 1 e D,

dye

Λ pinacyanol; B cryptocyanine; C.

yyy thiacarboxyanine hydroxide;

D S ^ '- diethyl-O-ynethyltliocarbocyanine bromide;

ü 3-Carboxymet] iyl-5 - / "(3-methyl-2-thiiazolidinylidene)

1-methylethylidene-rhodanine; ^: \

F anhydro-S.S'-dichloro ^ Sg-diethyl-J'-CS-sulfobutyl) thiacarbocyanine hydroxide) ;

G 1'-Xthyl-S-'methylt.hia-Z't-cyanine chloride and

H 1,1 • -Diethyl-Z ^ '- cyanine chloride.

In all cases it was found that the organic Photoconductors were only very weakly spectrally sensitive.

9Ö984S / 1393

Claims (1)

Claims <\ J hleltrophoto ^ raphisches recording material, consisting of ■, a conductive support and a photoconductor and a this spectrally sensitizing dye containing photoconductor layer, characterized in that the photoconductor layer as a spectral sensitizing dye is a methine dye of one of the following formulas contains: c N S R.
and c- * äL_N SC-LS = LC (= ClI-CH) ^ = ⁵ N- R ₂ - NS * C - Las L - C (β CH _{- CII)] χ} = γ = N - where mean: 909845/139 3 - 44 - ■■. ".-; R is an hydrogen atom, an optionally substituted one Alkyl radical with 1 to 12 carbon atoms or one optionally substituted aryl radical; U-. and R? optionally substituted alkyl res-te- with 1 to 12 carbon atoms, alkenyl radicals with 3 to 4 carbon atoms or optionally substituted aryl radicals; L - one optionally by an alkyl or aryl radical substituted methine group of the formula -CII =; η = 1 or 2; Q to complete a condensed, optionally substituted 5- or 6-membered heterocyclic ring required atoms; Z the completion of a clesensitizing acting, optionally substituted 5- or G-membered ring required atoms and θ
X is an acid anion. 2. Electrophotographic recording material according to Claim 1, characterized in that it is a methine dye of the specified type Contains formulas in which Z includes the ones to complete an optionally substituted: Nitrobenzothiazole,
Nitrobenzoxazole, 909845/1393 Τ 9 07 Nitrobenzosolenazole, Inii dazol ~ \ , 5-b7quinoxal in-, 1,3-Dialkenylimidazo ^ ~ 4, S-b T, 3-I) iarylimidazo ^ "4,5-b7quinoxaline-, 3,3-dialkyl-3H-pyrrolo ^ ~ 2,3-b7pyridin-, 3, S-DialkyL-SH-nitroindole-, Thiazolo ^ ~ 4, S-t ^ quinoline-, Nitroquinoline, Nitronaphthothiazole, nitronaphthoxazole, Nitroselenazole, Nitronaphthoselenazole or Nitropyridine ring represents required atoms. 3. Hlektrophoto ^ raphisiies recording material according to claims and 2, characterized in that it is a methine dye of the formulas given, in which Q contains those to complete an optionally substituted: Py r id i Ii-, Thiazole, Oxazole, Selenazole, 1,3,4-thiediazole, Pyridazine or Quinoline ring represents the required atoms, Q Π Q A A R / Ϊ393 19Ό7617 4. iilektrophötographic recording material according to claim 3, denoted by the fact that there is a thin color 5; to ff the specified Fornein contains, in which · 'the for the preliminary completeuiu; an optionally substituted: Imidazo ^ 1, 2 - &] χ> γτϊάϊτ \ - ₁
Iriidazo / "2, l-bjselenazol-,
Imidazo ^ "* 2,1 -b ^ oxazole-,
Imidazo ^ "2 _f 'T-b7thiazol- _l
L * 'iidazo ^ "2, 1-b7" 1 »3»' i-rthiadiazol- ojor i, 2-b7pyridazi.nrin; it required Atonc represents 5. Llektrophotonrarhisches Aufzichnüiifysnaterliil according to claims and 2, dadurcii gekennzeiclinet that it contains a methine dye of the formulas given, uorin Z. the for. Completion of a. . , ^ ■ '■ """-, ii'itrobenzoxazole,
nitrobenzoselenazole, - or Iraidazo / ~ 4, S-required Represents atoms. 909845/1 393 ORfQfNAL 6. L.lcktrop'ioto'.u'a] hisciics Auf zeicimun "snaterial according to claims 1 to 5, characterized in that the photoliter layer from .. one. ". ischun ^ from 1 to 7 5 (lev; .- parts photoconductor and 25 to 99 f.cv; - parts i-indene and 0.01 to 1C part by weight There is dye. 7. niektrophotojraivhisclies AufzeichnUHi; sHiaterial according to claims 1 to 6, characterized in that the photoconductor layer an organic Thoto conductor of the Pormula: R " 1\ till contains, where mean: W ^ - a hydrogen atom or an alkyl or aryl radical and R ", R" ¹ and R "" each represent an aryl radical, with the proviso that at least one of these aryl radicals through a secondary or tertiary amino radical is substituted. 3. «Blectrophotographic recording material according to claims Γ to 6, characterized in that the photoconductor layer 909845/139 3 ρ *. ■■■■■■■■■ triphenylamine as a photoconductor; 1,3 _# 5-triphenyl.-2-pyrazoline ^{:; / 4.4 l} -bis (diethylamino) -2.2 ^l -dimethyltriphenylamine; Contains 2,3,4,5-tetraphenylpyrrole or 4,4 ^I -bis «» diethylaminobenzophenone. _4th 9. Elektrophotographischcs recording material according to claims 1 to 8, characterized in that the photoconductor layer ils a polyester of terephthalic acid and a binder Glycol mixture, consisting of 9 parts by weight of 2.2 to £ 4- (2-hydroxyethoxy) phenyl7propane and 1 part by weight of ethylene glycol. 909845/139 3