DE1814678A1 - New small molecule photoconductors - Google Patents

Description

PATENT ADVOCATE

TELEGRAMS = WESPATENT .6 ^^^ «l POST CHECK: MUNICH 1 41 B 94 J« u ~ «n,

BANK H. AUFHÄUSER 379B04, TELEPHONE: 673203

Docket SA 967 042

INTERNATIONAL, BUSINESS MACHINES CORPORATION

Armonk, NY $ 10 *, USA

New small molecule photoconductors

SSSgBBB ■ It JCC »■■■ ι Ii ι ■■ imZÜm ι ^ iiai StES .SS SSSlS - ■■■ ί—

The present invention relates to electrophotographic photoconductive materials »which have a photoconductor of the formula

included in the

R ₁ denotes a radical -N ^ * * or a morpholino, thiomorpholine, piperidino or julolidinyl radical, R ₀ denotes a radical of the formula _{n o}

η / 7

Cf * f * in the Q

4 * »lV \ ß ^ * fj

^ C a N "^ C N ^

0 rq

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O O

η η

or C 0 R ₁₀

represents

R-, R ^, Rc * Bg * R ^ ¹ ^ d% ' ^which S ^{leiön cd} ®r can be different from one another, mean lower alkyl radicals »

Rq denotes the radical of a mononuclear or binuclear or trinuclear condensed aryl group, so that the ring shown is a five-membered ring, with CgH ^ being preferred, and R ₁₀ denoting an aryl or substituted aryl radical, with phenyl being the most preferred radical.

The invention also relates to a reproduction method in which an electrostatic charge image is applied to these materials is applied and the image is developed.

In electrophotographic reproduction processes, im generally an electrostatic charge image is applied to a photoconductive material, and the image is then developed, usually by contacting an electroscopy Powder. These methods are based on the phenomenon that certain photoconductive substances are electrostatic Be able to retain charge in the absence of light * However, when the photoconductive material is exposed, a discharge occurs on.

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As the photoconductive materials, various inorganic ones have hitherto been used Substances «such as selenium * sulfur and Zinc oxide, and organic substances «such as anthracene» Anthraquinones Benzidine or various heterocyclic compounds are used. The previous photo guides ·? . however, the materials have many disadvantages. Many known photoconductors show poor sensitivity when they used alone »and require awareness raising with various dyes and / or activators. These additions often increase the electrophotographic sensitivity or speed of the systems in which it is used will. Many of the commonly used Dye® are missing it is, however, in terms of stability "which leads to color fading and the like." In addition, the solubility of the previous photoconductors is Dyes and activators in organic solvents quite low "which is the amount of material" that is on an electrophotographic pad for use in them Systems can be applied as a layer »limited.

An object of the present invention is to provide one electrophotographic photoconductive material free from the disadvantages of the previous materials.

Another object of the invention is to provide a new one electrophotographic reproduction process.

The present invention relates to a new electrophoto-

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graphic photoconductive material comprising a backing layer and has a photoconductive insulating layer, the one photoconductor of the formula

contains * in the

R .. a residue -N "* or a Morphollno-, Thiomorpho ·

^{1 X} % ■ *

lino- «means piperidino or julolidinyir radical,

from the group of the following residues

0 .R ₇

/ SH ^. C - N _K

C, ■ C C »S,

■ N ^^ c - ν '

0 0

H M

W ^ * V

Il 9

^{0 R} 10

is chosen «

R, "Rj ^ * Rc» * Hj Rg and Rg may be the same or different, # mean lower alkyl groups,

the rest of a single-core or - ^ *! core or drel-

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nuclear condensed aryl group means, so that the ring shown is a five-membered ring, where C ^ H ^ is preferably,

R ₁₀ denotes an aryl or substituted aryl residue, with phenyl being the most preferred radical.

The invention also relates to a new electrophotographic vision Reproduction process in which an electrostatic charge image applied to photoconductive materials which contain the photoconductors, which are very flat above, and the image is being developed.

The novel photoconductors of the present invention have various types extraordinarily advantageous and desirable properties. It was found to be highly electrophotographic Possess sensitivity or speed. These photoconductors will be used with many of the known ones Activators activated so becomes their electrophotographic Sensitivity increases and is in the range of that of Selenium, a commercially used inorganic photoconductor " In addition, the photoconductors according to the invention are strongly colored, what the requirement of the addition of sensitizing agents Turns off dyes. In addition, due to their strong coloring, these materials can also be used as sensitizing Dyes can be used for other photoconductive materials. As many of the known sensitizing dyes are very unstable, it represents a significant advantage of the present invention * that their presence in the elec-

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trophotographic materials is unnecessary. Furthermore, 'j inventive photoconductor in a wide range of organic solvents atark soluble, waa ;, these photoconductors in large quantities on suitable substrates, as To apply layer

The inventive electrophotographic photoconductive » Some materials generally have a suitable base or carrier layer with a photoconductive layer Layer / which contains the photoconductor material described above * is coated «

Any suitable support material can be used as a base sheet ». For example, metal plates can be made from Aluminum «zinc» copper «tin« bis »lead and the like are used will. Glass plates and other ceramic materials can also be used. Paper is also a suitable underlay material. Also from films made of synthetic po- ' polymer materials »such as polystyrene« polyethylene » Films produced by cellulose esters and the like can be used. Although it is not necessary to carry out the invention It is sometimes two-dimensional, the high-resistance underlayers with a conductive one To cover material «to make the base conductive =. For example, the sheets of paper and polymer fills used as substrates can be printed with a transparent SoM oht to be coated with silver "QoId or stannous oxide" around them

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to make conductive "

The invention. Photoconductors are placed on the pad » material by any of the known conventional methods Applied as a layer, the photoconductors are generally used dissolved in a suitable organic solvent or dispersed and uniformly on a surface of the base by centrifugation, spraying, brushing or coating applied «The formed layer is then dried * um a uniform photoconductive slate on the backing surface su form »Suitable organic solvents are Benzene "Acetone" Methyl anehlorid, Kthyleneglykolmonometh ^ iether, Dichloroethane * Dlox & n «BiagfcliylfOFmamid or mixtures of this «

In general, it is desirable to use the photoconductive materials to be introduced into a polymer matrix on the base layer. This can be achieved by soaking in the photoconductive material solution a quantity of polymer material is introduced into the organic solvents described above, that. after coating and drying, one layer delivers «in that the photoconductive material is uniformly distributed throughout the polymer matrix.

As polymer materials can be many of the natural and synthetic Resins can be used. Suitable natural resins include balsam resins "rosin" shellac "gum arabic and manila resin · microscrystalline waxes «as well as modifl-

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Ornate natural substances, such as cellulose diacetate, cellulose triacetate, oilulose acetate butyrate * ethyl cellulose, ethyl cellulose stearate and the like can also be used be used. Also synthetic polymers »such as vinyl polymers» e.g. polyvinyl chloride * polyvinylidene chloride, polyvinyl acetate, polyvinyl acetals, polyvinyl ether and the like. " are suitable. Other synthetic resinous materials include polyacrylic * and polymethacrylic acid esters, polystyrene * polyisobutylene * chlorinated rubber * Polyester * such as phthalate resins, alkyd resins * Halelnresinate * maleic resin rosin, mixed Beter of higher alcohols * phenol-formaldehyde resins, aldehyde resins * Ketone resins * Polyamides, polyurethanes »Polyolefins, such as polyethylene». Polypropylene * and the like «and silicone resins»

In addition, the photoconductors according to the invention can be used as sensitizing dyes together with other photoconductive resins such as poly-4-vinyldibenzofuran, Pcly-ot-methylstyrene, polydimethylaminostyrene, polystyrene, poly-1-vinylnaphthalene, polyvinylcarbazole and the like.

When the photoconductors of the present invention are used together with resins are used »so the proportion of resin to photo« conductor can vary over a wide range. In general

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can be the ratio of photoconductor to resinous material in the final coated electrophotographic product vary from about 0.2 to about 1.0 * The resinous material and the photoconductor may be mixed or mixed in any suitable manner prior to being dissolved in the organic solvent separately from the organic solvent prior to application can be added to the underlay material. If necessary, the photoconductor can also be applied to the base material first applied as a layer and a layer of the resinous material applied over it to form a protective layer to build"

It should also be noted "that each of the usual additives" such as pigments »luster agents and stabilizers», can be added to the photoconductive layer · bines . the advantageous features of the invention, however, is » that the photoconductors according to the invention are highly colored and have high photoconductivity sensitivities. As a result, it is not necessary »to these materials the sensitizers »to add activators and pigments» which are normally required for the previous photoconductors was. As a result, instability becomes common The dyes and sensitizers used are inherently »avoided.

It has been found that the photoconductors according to the invention have a sensitivity »that of selenium»

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a commonly used inorganic photo filter .. is comparable. Although the Smpfindliahk © iten öi ^ sar Khotolaiter are sufficiently high "to allow their sole use in electrophotographic materials * the susceptibility to can be increased even further by adding" gas laser activators or Slek'tronenakasep.toren ® & τά®η. It should be pointed out «that these activators are not to be confused with the sanaibilislsrendan dyes normally required in connection with the previous fhotolaiters. llig * even if the sensitivity of the photo conductor is increased. The activators "which can be used together with the photoconductors according to the invention" do not lead to any instability of the system and are relatively simple compounds compared to the previous dye sensitizers. Suitable activators include those described in U.S. Patent 2,2 ^ 2,755. Specific activators include 2,2 * "4 _Λ 4 *, 6.6" -Hexanitrodiphenylamin, 3,5-dinitro benzoic acid, Tetrabromphthalsäu »anhydride, 2,6-diphenol-p-benzoquinone, 2,4,7 ~ trinitro-9 -fluorenone * 4,4 ', 6,6 ^I- tetranitrodiphenic acid and 3 * 5-dihitriD-benzoic acid. These activators can be mixed with the photoconductor and the polymer matrix material "if one is used" before coating the base material.

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Activation tones used by DI® are not particularly critical lind is limited by the dark conductivity. I.e. « High concentration of certain activators increase the darkness in-siaaai such, Auaraass, that the photolei T © nde material not very useful in the art of photography * Mormiarwsis © are Msngan'to about .20 $ satisfied -

The Biok® of the electrophotographic and photoleltendan layer is not critical »Guta Irgsbnissa? Jard © n obtained when ·: the thickness of the layer varies from about 2 to about 20 ^ t * it can be seen that the soles are too thin , ur chendss laolaticnsvsrsögsn bssitzsn _ä while too diok © shifts require too long handling time.

The inventive reproduction process using the electrophotographic photoconductive ones described above Materials can be done in various forms. According to the first working method, a conductive base material can be used that with the electrophotographisohen according to the invention Materials is coated, by friction with a soft material, by corona discharge, by contact charging and the like. Electrostatically charged. The electrophotographic The layer is subsequently formed with exposed to electromagnetic radiation of suitable wavelength, so that the exposed parts of the layer are discharged and obtain an electrophotographic latent image

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ifIz ¹ Cl. This latent image can be developed according to various methods: "According to one procedure, an electroscopic developing powder is" brought into contact "with the layer that carries the latent image, whereby the powder is attracted to the charged parts of the layer and repelled from the uncharged areas leads to a visible image.

The electroscopic powder usually consists of a carrier material and a toner. The carriers can be small (Jlaskügelohen, Bisenpulver, small plastic balls and the like. contain. The toner can consist of a pigmented polymer powder such as a resin-carbon black Gemisoh.

Optionally, the developer may comprise a solution of a resin or pigment and a liquid which is similarly removed from the charged parts of the exposed Layer is attracted. After developing the picture can be fixed by any of the known methods. For example, the developed image can be heated or it can be transferred to another underlay material before fixing «

Instead of the photoconductive schipht before exposure first To charge, one can also project an episcopic or translucent image onto the photoconductive layer using any of the known projection devices and the

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electrostatic charge © nasSaliasssnd elegant® ». Baa (obtained electrostatic image is then like © & © ώ

working method ® & n @ I®kts »Qpa © togjmphIaol5 @ .s llatsrial VSBrU ^ n ₃ bei« ielshsai <Si @ Unterlage®shiohfc niishtisitand is «Di @ s @ M @ thod @ is in the sinssln ^ n in d © r US- F © t © ntsehrift 2 9 ^ 2 883 b®aohriefe @ n _a course said ^ ird] ii <arb © i das aufTila »dend © elsktrophotographiSGhe material between two corona *? Discharge device ^ carried out. A © dar * corona device creates a negative corona discharge _s bombarding a surface of the material with negative ions. The other device bombarded the opposite surface with positive ions. This system creates opposing charges on opposite sides of the material, thereby eliminating the need for a conductive reverse. Obviously, this method can also be used if no support pad is used. The present invention therefore also provides photoconductive insulating layers without a support.

It was unexpectedly found, however, that the inventions photoconductive materials give unusually good results in the electrophotographic method called "persistent mode of operation" Deliver process. This procedure is

COPY

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la individual In u & r US Bafcei & aehrlft S 84g 348

a @ sa LiohtMld © usgaaetetSs tos aas fShigkaitebild in least material results in MM remains for a © IMsaggs »© Säritspaona .voySiai ^ enn as long as the mattrial ¥ o ^- ^ Idoht g @ esktISst is · Di © s @ ® ist ^ nfs® picture wijpd by electric Äiafladen ö @ s llstardal.® W wodui »sh an ele &trostafcisehss; BUS gsbildat wl LaitiJOiigleeitebild sprioht “The elektrosfcafciaoft® BiM can then be developed after a d © r obaxi bgaohrisbenaii Apbaits waisan, baispial3weis @ durall cascade development with pigmented toner particles.

Surprisingly _{, it was found} that the photoconductive materials according to the invention provide particularly advantageous results when using the method described above.

Yet another method is * the photoleitonda Sohioht to charge and at the same time through transparent © To expose electrodes · The image obtained can be developed according to one of the procedures described above *

The final fixed electrophotographic "images" can be used according to a well-known technique «

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For example, the image can be transferred to printing plates and Can be used as a measure for making further copies.

The following examples illustrate the invention without limiting it impress.

0 »S5 β 10-piSthyl-S-iS-CSi ^^. T-tsfcrahydro-IH. ^ I-teengo-fi, 43-quinolisinoö-yi) -1,3-neopantjlen-S "4-p @ sitadienyliden3 -2-fchio-

-ψ ■ · "■■■■■: .- ■: -.- · ·

barb! tursätire were dissolved in 5 ml of DlohlorUthane and added to 1 g a 25% polystyrene solution was added. This solution was placed on an aluminum plate using an aesauf-, tragapalta of 0.127 nai (5 mil)? J, a layer applied, the material obtained was dried? whereby an electrophotographic film having a thickness of 7 - Su would be obtained.

The electrophotographic material formed was on its electrophoresis sensitivity using a Drehsoheibenelektrouieters «often for the investigation of the photoelectrisohen waste of photoconductors is used » checked. The unit consists of a disk "dl" with ^ 600 RPM is driven by a motor and on which a sample holder is mounted. The sample size is 12.7 mm (1/2 inch) in diameter · The charging station consists of a Two-wire! Corotron, in which the voltage ranges from 4 to 8 kV varies and the polarity can be set positive or negative. The next stop on the way. Sample,

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which is offset by 180 ° is the detector or sensor. This consists of a micrometer with a copper tip (for Setting the distance to the sample), which is isolated from the earth and connected to an oscilloscope via a series resistor eats. When the charged sample moves past the probe, a current is induced in the probe, known as voltage is taken from the resistor on the oscilloscope. the The last station is an exposure slit with an electronic shutter through which a tungsten projection lamp can flash. When actually testing a sample disc, the corotron is turned on and the sample is turned on carried out under this as often as it is necessary to reach the charge equilibrium. Then she will turn on Turned past the transparent probe, where the signal is monitored and the sample is exposed. The cargo drop on the sample is recorded by the oscilloscope.

Bs was found to be the electrophotographic photoconductive Film had an electrophotographic sensitivity 1/20 that of selenium "

Example 2

The procedure described above was used with the exception that 10 mg of the activator 2.2 ', 4.4 ⁸ 6.6 ^G -hexanitrodiphehylamine were added to the polymer solution before application to the aluminum plate ο

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The material obtained was found to have a. photographic sensitivity equal to that of Selenium ^1. .

Example ?

The procedure was as in Example 2 with the exception that as photoconductor 1,3-diethyl-5 "ip-diethylamino * phenyl-1,> - neopentylene-2,4-pentadienylideneJ-2-thiobarbituric acid was used. The obtained electrophotographic plate had As was found to have an electrophotographic sensitivity 1/0 that of selenium.

Example 4

The procedure of Example 2 was repeated with the exception that as a photoconductor 1,3 ~ diethyl-5-ip-dirnethylamino phenyl-1,3-neopentylen-2,4-pentadienylidene] -2-thiobarfeiturr acid was used. The plate obtained was found to have became, i /> the electrophotographic sensitivity voa selenium.

Example 5

The procedure was as in Example 1 with the exception that j3 # 5-dinitrobenzoic acid was used as the activator. The received photographic plate showed a sensitivity 1/3 that of selenium »

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Example 6

It was worked as in example t with the exception that tetrabromophthalic anhydride was added as an activator. The obtained plate showed a sensitivity equivalent to T / 4 that of selenium.

Example 7

It was worked as in Example 1 with the exception «that the photoconductor was activated with 2,6-diphenol-p-benzoquinone. The plate obtained, when tested by the method of Example 1, showed a sensitivity 1/4 that of that deceived by selenium.

example d

A solution containing 3 g of 7 # -lgem polyvinylcarbazole in dichloroethane, 0.2 g of 1,> diethyl-5- [5- (2,3,6,7-tetrahydro-1H, 5H-benzo- [i, J] -ohinolizin-9-yl) -1 > ji-neopentylen-2,4-pentadienylden] -2-thiobarblturic acid and 10 mg of hexanitrodiphenylamine were coated onto an aluminum plate using a 0.173 mm (7 mil) gap for wet application and dried to obtain an electrophotographic photoconductive film having a thickness of 7 Ai.

To test the electrophotographic sensitivity of the The procedure of Example 1 was followed. It was found that the material doubled

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- 19 possessed sensitivity of selenium.

Example 9

A solution of 0.25 g of polyvinyldibenzofuran, 0.25 g of i5- (2, j5-6,7-tetrahydro-1H * 5H-benzo- [iJJ-quinolizin-9-yl) -1 * J5- neopentylene-2,4-pentadienylidene] malonitrile and 20% hexanitrodiphenylamine and 4 ml of bichloroethane were coated onto an aluminum plate using a 0.170 mm (7 mil) gap for spot application, resulting in a dried film 7 to β thick J * ledο The material was tested according to the method of Example 1 and showed the sensitivity of selenium. .

Example 10

A mixture containing 0 × 25 g of the photoconductor from Example 9 and 10 mg of hexanitrodiphenylamine and 1 g of a 25% solution of polystyrene in diehlorethane was applied to an aluminum sheet using a 0.127 mm (5 mil) gap for wet application as a layer upset. The photoconductive film obtained had a thickness of 1 to 8 j * and, when tested by the method described in Example 1, showed a sensitivity which corresponded to 1/2 that of selenium,

The following example explains the "persistence mode of operation" described above said electrophotographic processes using the photoconductors according to the invention.

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Example 11

A PiIm produced according to the procedure of Example 2 gave an image when he was exposed to a 40 W Wqlfram lamp for 2 seconds exposed at a distance of about 30.5 ora (.12 inches) through a transparent positive and then exposed to a corona discharge was charged with a voltage of 6 kV.

The resulting image was cascaded with Xerox 914 toner tinted. The image thus developed was fixed by heating.

Example 12 .

A composition containing 0 * 25 g of 1,3 ~ diethyl-5-C 5- (2,3,6, / - tetrahydro-1H, 5H-benzo ~ L i, j 3-ohinollzin-9-yl) -1 »3-neopentylen-2,4-pentadienylidene] -2-thiobarburic acid and 1.0 g of a 25% polystyrene solution in 5 ml of dioloroethane was applied as a layer on aluminum foil using a 0.127 mm (5 mil) gap for hatred application * The sample was positively charged with a Xerox Model D Processor at a voltage of 7 kV * The exposure conditions were 0.1 seconds using a 40 W tungsten lamp at a distance of 50.8 cm (20 ineh) through a transparent positive. The images were toned with Xerox 914 toner using a cascade method transferred to paper. The images had a good density without any background.

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Example 13

The procedure of Example 12 was repeated with the exception that 0.01 g 2.2 ^t , 4.4 ^} , 6.6 ^L -hexanitrodiphenylamine was added to the composition prior to coating. The exposure conditions were 0.1 seconds at one Distance of 76.2 cm (150 inches) using a 15 W tungsten lamp. The copy had good image density, good contrast and no background.

Example 14

A composition with a content of 0.2 g of 1,3-diethyl-5-ί ρ-dläthylaminopheny1-1,3-neopentylen-2,4-pentadieny1iden 3 2-thiobarbituric acid ,. 1.0 g of a 25 # styrene solution and 5 ml of dichloroethane was coated onto an aluminum panel using a 0.127 mm (5 mil) gap for wet application. The procedure of Example 12 was repeated using the exposure conditions 0.1 seconds at a distance of 16 ₃ 2 cm (50 inches) using a 40 W tungsten glow lamp. The copy had good image density with no background whatsoever.

Example 15

The procedure was as in Example 14 except that 0.01 g of hexanitrodiphenylamine was added to the composition and the exposure conditions were 0.1 seconds at a

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Distance of 76 * 2 ora (30 inches) using a 15 W. WolframglUhlampe were · The picture had no background and had a good image density »

Example 16

A composition of 0.25 g of 1,3-diethyl ~ 5- [p-dimethylaminopheny1-1,3 ~ neopentylene ~ 2,4-pentadienylidene ~ 2-thioebarbituric acid, 1.0 g of a 25 # strength polystyrene solution and 5 ml of dichloroethane was coated onto an aluminum panel using a 0.127 mm (5 mil) gap for wet application. The procedure was as in Example 12, with the exposure b @ ± 0.5 seconds at a distance of 76.2 cm (30 inches) using a 15 W incandescent lamp. The copy was free from a background and had excellent image density. - «...

Example 17

The procedure of Example 12 was followed with the exception that 0.01 g of 3 »5- dinitro cenzoic acid was added to the composition. The exposure conditions were 0.2 seconds at a distance of 76 _ß 2 cm (30 inches) using a 15 W incandescent lamp. The copy had good images and no background.

Example 18

It was according to the work cycle of Example 5 with the exception

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The method used to add 0.013 g of 2,6-diphenyl-p-benzoquinone to the Composition were added. The exposure conditions was 0.3 seconds at a distance of 76.2 om (30 inches) using a 15 W incandescent lamp. The copy had no background and had good image density.

Example 19 .

A composition of 0.25 g of [5- (2,3,6,7 ~ tetrahydro-1H, 5H-benzo-egg, j 3 ~ öhinolizin-9 ** yl) -1 ^ -neopentylene ^^ - pentadienyli-, den] -malonitrli, 1.0 g of a 25% polystyrene solution and 2.5 ml of diohlorethane was applied to an aluminum sheet using a 0.127 mm (5 mil) gap for wet application as Layer applied. The exposure conditions were 1 1/2 seconds at a distance of 76.2 cm (30 inches) with a 15W Tungsten light bulb. The picture had essentially no background and had good image density.

Example 20

A composition of 0.12 g of the compound of the formula

CH, Ä,. *

If 8 ^ 5

■ C - N CH = CH ^ j. . j / \

^ = ä: C C = S

CN η i

0.005g hexanitrodiphenylamine, 1.0 g Polyviny! Formal and 1 ml Diehlorethane was applied as a layer on an aluminum sheet with a

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A squeegee at a 0.127 mm (5 mil) gap for wet application upset. The procedure of Example 12 was used with the exposure baths for 2.0 seconds a distance of 76.2 cm (j50 inch) with a 15 W incandescent lamp was. The copy formed had no background and was good Image density up.

Example 21

The composition of Example 1 was used with the exception that 0.015 g of tetrabromophthalic anhydride was added to the composition. The exposure conditions were 0.1 seconds at a distance of 6.2 cm (20 inches) with a 15 W incandescent lamp. The copy formed had good image density and no background.

The following examples illustrate the invention, with the above photoconductors described can be used as paraffin sensitizers for other photoconductor substances.

Example 22

A composition of a 5 % solution of poly-4-vinyldibenzofuran in benzene containing 10% by weight of trinitrofluorenone and 2% by weight of the compound used in Example 12 was applied to an aluminum sheet using a gap of 0.127 mm '(5 mil) applied as a layer for wet application * Exposure was for 0.5 seconds at

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a distance of 76.2 cm (30 inches) using a 40 W incandescent lamp. The copy had no background and had good image density.

Example 23

A composition of a 5 # solution of polyvinylnaphthalene in benzene containing 14 # 2,4, Γ-trinitro-9-fluorenone and 2 % of the compound from Example 1 was applied as a layer on an aluminum foil using a gap for wet application 0.076 mm (3 mil) was applied. The exposure conditions were 0.1 seconds at a distance of 76.2 cm (30 inches) with a 40 W incandescent lamp. The copy formed had a good image density with no background.

Example 24

A composition of 3 g of a 7% solution of poly-N-vinylearbazole in dichloroethane, 0.2 g of the compound used in the composition of Example 1, 2 ml of dichloroethylene and 0.01 g of hexanitrodiphenylamine was coated onto an aluminum plate using a gap of 0.173 mm (7 mil) applied for wet application. The exposure conditions were 0.05 seconds at a distance 76.2 cm (30 inch) with a 15 W incandescent lamp. The copy good density and little subsoil.

The following examples illustrate methods of making the photoconductive materials according to the present invention.

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Example 25

1, ^ - diethyl-S- ί 5- (2,3,6,7-tetrahydro-IH.SH-benzo-ί i, J J-ohlnolizln-9-yl) -1,3-neopentylene> 2.4 ° pentadienylidene].> 2-thiobarbituric acid was made according to the following equation:

CHO +

CH,

? a »5

- N

O-S

^c sp5]

- N

C = S

A mixture of 12 g (0.05 mol) 9-FomiyljulolIdin and 9.6 g (0.03 mol) 1,3-diethyl-5- (3 * 5 »5-trimethyl-2-oyolöhexen-1-ylidene) ~ 2-thiobarbituric acid in 75 ml of ethanol containing 6 ml of piperidine was refluxed for 20 minutes, after which 200 ml of methanol and 12 ml of acetic acid were added. The reaction mixture was cooled overnight. A black-green solid substance (5 g) was filtered off and crystallized from methyloyclohexane, dark green crystals with a golden reflex of F *> 225 ⁹ C being obtained. The floodplain

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The yield was 33 %. A further yield of $ 40> was obtained from the original solution, which was left to stand for 72 hours.

The 1 * 3-diethyl-5- (3 »5 # 5-trimethyl-2-cyolohexen-1-ylden) ~ 2-thiobarbi door acid can be produced by reacting isophorone and 1,3-diethyl-2-thiobarbituric acid are produced »9-ForsaylJulolidin can according to the in the Journal of Organic Chemistry4 Volume 21, Page 1470 (1956), described method.

Example 26

ί 5- (2, 3 # 6, 7-tetrahydro-1H, 5H-benzo-ί i, j 3-quinolizin-9-yl) -1,3 ~ neopentylen-2,4-pentadienylden] -malonitrile can according to the the following qualifications:

1 * 86 g ^ iSiS-Trifflethyl ^ -cyclohexen-i-yliden-maloni-feril and 4 g 9-Formyljulolidin were in 25 ml of ethanol and 2 al piperidine

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18H678

Heated under reflux for 20 minutes «/ 0 ml of methanol and 4 ml Acetic acid was then added and the whole mixture was placed in a cabinet. The reaction product became filtered off as a pest substance and recrystallized from methyloyclohexah. The recrystallized product exhibited a melt point of 223 - 226 * C on «Bs was obtained in a yield of 35 obtain·

Analysis:

Calculated C 81.74 Found: 81.73

H 6.81 6,

N 11.45 % 11.22 %

The 3,5,5-dimethyl-2-cyclohexen-1-ylidene ~ malonitrile can by reaction of isophorone with Malonitrll according to the in the U.S. Patent 2,882,158.

Example 27

2-15- (2,3> 6,7-tetrahydro-1H, 5H-benzo- [i, jJ-quinolizin-9-yl) -1,3-neopentylen-2,4-pentadlenylidene] -1,3- indandion was after produced by the following equation:

CH

CHO

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CH-CH

1 g of JjSiS-trimethyl ^ -cyelohexen-i-yliden-ii ^ -indandione and 1.8 g of 9-pormyljulolidine were refluxed in 25 ml of ethanol with 1 ml of piperidine for 15 minutes. The mixture was cooled and 2 ml of acetic acid and 50 ml of methanol were added. The reaction mixture was placed in a refrigerator, whereupon a precipitate formed. The precipitate was filtered off, dried and recrystallized from methylcyclohexane. It has been prepared by P β 197, a yield of 18% of the product - obtained 200 ⁰ C.

The 2- (3,5,5, -trimethyl-2-cyclohexen-1-ylidene) -1, ^ - indandione can be produced by reacting isophorone with indandione will.

Example 28

4- [5- (2,5 »6,7-tetrahydro-1H, 5H-benzo-U, j] -quinolizin-9-yl) -1, j> -; neopentylen-2,4-pentadienylidene) -JJ-phenyl ^ -isoxazolin-5-one was established according to the following equation.

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Ί-.814678

CHO

CH,

CH = CH

2.81 g ^ -

Isoxazolin-5-one and 4 g of 9-formyljulolidine are in 25 Ethanol containing 2 ml of piperidine was refluxed for 15 minutes. 4 ml of acetic acid were added to the cooled reaction vessel with stirring. The solution then became Put in a refrigerator for several hours until a precipitate was formed. The precipitate was filtered off, dried and recrystallized from methyloyclohexane. A £ 29 yield was obtained.

909834/1561
SAO ORIGINAL

18U678

Example 29

1, ^ - Diethyl-5- (p-dioethylaminophenyl-1, J-tadienylideneV - ^ - thiobarbituric acid was made according to the following Equation made:

CHO

(CH ₃ ) ₂ N

CH = CH

CH

c «s -

O C-Hr- N η σ - N _x C ₂ H ₅ \ / C - It O

3 # 2 g!, J

2-thiobarbituric acid and 2.3 g of p-dimethylaminobenzaldehyde were mixed in 25 ml of absolute ethanol. 2 ml piperidine were added and the mixture was refluxed with stirring for about 15 minutes. Then the mixture was in Poured a beaker »and 100 ml of methanol was added. The reaction mixture was placed in a 250 ml Erlenniäyer flask brought. 4 ml of acetic acid were added to the reaction mixture. Then the mixture was placed in a refrigerator.

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brought * noxuuf eich a precipitate formed »The precipitate titrated off, dried and made from methyloyolohe xan urDkristallisleg "!; · 2 g of product from P · 203 205 * 0 obtain".

Example 30

tadie »ylldeii) -> 2« * tMobax * bitursäur @ murde according to the following Connection established:

j5 # 2 g 1 j3-diethyl ~ 5 - (^, SfS-trimethyl ^ -cyclohexen-i-ylidene) 2-thiobarbituric acid and 3 * 54 g of p-diethylamlnobenzaldehyde were in 25 ml of absolute ethyl alcohol »containing 2 ml of piperidine» mixed." The mixture was stirred for about 15 minutes. partly heated under rickfluff and then-in.a 250 ml alder

"..- ■ 903834 / .1-58 1"

BADORIGIHAL

18U-678

meyer flask brought. 100 ml of methanol and 4 ml of glacial acetic acid were added and the mixture was placed in a refrigerator, whereupon a precipitate formed. The precipitate was filtered off, dried and recrystallized from methylcyolohexane. 1 g of product from P “85-87 ^P C” was obtained in this way.

Example 51

1 »3-Diethyl-S- (p-morpholinophenyl-1 j.3-neopentylen-2» 4-pentadienylidene) -2-thiobarbituric acid was made according to the following equation:

CHO

CHp - CH ₂

1 * 91 g of morpholinobenzaldohyd and 1.6 g of 1,3-diethyl "-5- (5.5 * 5 · -" - ■ trimethyl-2-cyclohe? cen-1-ylidene) -2-thiobarbituric acid mixed with stirring in 25 ml of ethyl alcohol. 2 ml of piperidine were added and the mixture was stirred for 20 minutes heated under reflux. 100 ml of ethyl alcohol and 4 ml of glacial acetic acid were added, and the mixture was poured into a KUhI-

'909834/1561

-Ä; Hr '> C / -:,; BATH ORIGINAL

18-H678

cabinet placed »whereupon a precipitate formed · The precipitate was filtered off, washed with methanol, dried and recrystallized from Mathyloyolohexane. The product was obtained in a yield of 40 % . Ss had a melting point of 153 - 15 ^ ^e C

909834/156 1

Claims (1)

18U67 0p r- 'S @ : gekenhseiohnet '* 4ocafa a salary from «isiem photo leader de? a © the one morpholino-3 thiomorpho line, piperidino or rJulolMinylrest denotes, from the öruppe iron best C - 0 “ S. G " H η t (R ₀₁ ) and ^R 3 * ^R 4 * ^R 5 *% * ¹ V ⁰ ^ ³ % * ^aie be separated from germination * low © Alkflraat® from each other? ver SO98 3 4 / 15S 8ADOR1GH4AL 18U678 the rest of a single or double or trinuclear condensed ary! group means so that the depicted Ring is a five-membered ring, and R _{10 represents} an aryl or substituted aryl radical. 2. Composition according to claim 1, characterized in that that the photoconductor is the only photoconductive substance. 3. Composition according to claim 1, characterized in that that the photoconductive substance senslbilieiert through this photoconductor is* 4. Composition according to claim 1, characterized by a Backing and a photoconductive insulating layer containing the photoconductor. 5 »Composition according to claim 1, characterized in that that the photoconductor is distributed in a polymer matrix. 6. Composition according to Claim 1, characterized in that that it also contains an activator. 7. Electrophotographic composition according to claim 1, characterized in that the photoconductor has the formula 909834/156 1 CHaCH owns. 8. The electrophotographic composition according to claim 1, characterized «that the photoconductor is the forael CH «CH owns. 9 electrophotographic composition according to claim 1, characterized «that the photoconductor has the formula H-CH owns. 09834/1561 IJ ι J 18H678 ' - 3a - 10. Electrophotographic composition according to claim 1, characterized «that the photoconductor has the formula CH CH-CH owns. 11. The electrophotographic composition according to claim 1, characterized »that the photoconductor has the formula GH »CH S WS OS C ₂ H ₅ owns. 12. Electrophotographic composition according to claim 1 * characterized »that the photoconductor has the formula CH-CH C-3 owns. 909834/1561 13 · Electrophotographic composition according to claim 1 » characterized by «that the photo head the formula CH, owns. 14 «Electrophotography, rough reproduction process» characterized * that an electrostatic charge image is applied to the photoconductor composition according to claim 1 and < the charge pattern is developed, 15 · The method according to claim 14, characterized in that. That the charge pattern is formed by exposing the photoconductive composition to light and electrically charging the photoconductive composition from the bottom. 16. The method according to claim 14 *, characterized in that the charge image duroh electrical charging of the photoconductive Composition and subsequent exposure of the charged Composition is formed. ■ 17. The method according to claim 15, characterized * that the developed image is fixed. 18. Compounds of the formula 9098 34 / IS 61 18U678 CH = CH in the R ₃ I a ResJ? -N * or yes , or Piperidinoresfc means, from the group iron remnants of the OR ₇ ^ C sn I - if is chosen R ₂ -ri Tllioinorpholino- 0 ir J | g _f IU jind Rg * which can be the same or different yojieiniifider, represent lower alkyl radicals, the remainder of a single or double core or three core gen condensed aryl group means, so d§§§ jfgj ?. Ring is a five-membered ring, and RjQ denotes an aryl or substituted aryl radical 19. Connection of the P <> r # e | BATH CEaCH CS N 20. Connector. formula CH-CH Il - C C. η 21. Compound of Formula CH-CH ι » C η ? 2 »5 22. Compound of Formula CH-CH 909834/1 561 " 18U678 23 · Compound of the formula CK-CH CH ₂ - 24. Elektrophotographisohe photoconductive Zuaaonwneet.zung naoh one of claims 1 - 6, characterized marked »that and Rg Hethylreate are * . Compound according to claim 18, characterized »that R ^, R ^, R ₅ , Rg, R, and Hq are methyl radicals · 90983A / 15S1