DE2112437C3 - Electrophotographic recording material - Google Patents

Description

R, equal to a hydrogen atom. a phenyl. Styryl, ρ - metho.xystyryl-. 3,4 - dimethoxystyryl-, u-phenylsiyryl-, u-phenyl-p -methoxyslyryl,, V-i-uryl- -i '- alkyl- or u -phenyl- ,; - furyl - «'- phenyl group. R ,. R ₄ . R ₆ and R _H equal to a hydrogen atom or a phenyl group, R, and R- equal to a hydrogen atom. a methyl or a phenyl group, R ₅ is a hydrogen atom. a phenyl. Styryl. p-methoxystyryl-. 3,4-dimethoxystyryl-. .i-Pheny lp-nietho. \ ystyryl-. ..'- Fury l-./-ä then vl- or τ- PhctiN I -, .- furyl-ii'-iilhcnyl-Ciruppc. R ₁ , equal to a hydrogen atom or a p-meihoxyphenyl group. A equals a perchlorate huoborate. Chlorferral. t'hlor / inkai or nitrate ion and X is an O- or S-Alom.

The invention achieves that an electrophotographic Recording material with a 2s high sensitivity for a tungsten lamp and a high electrical resistance irr. Dark is made available.

According to one embodiment, the link contains the pholeitlahige layer on IOD parts by weight of Phoiolleiter / wipe 0.01 and 3 (. iewichtieilc sensitizing dye.

This configuration ensures that the dekl ro photographic recording material higher pliotoconductive wedge and a higher electrical vision Has contradiction in the dark.

The l.rliP'Jung is used in the description below explained in more detail with reference to the drawings. The figures in the drawings represent the following:

The Fig. I gives the Graukeilspekti ogramm one clekirophoiographical material, which in Form of an unsensitized 10 weight percentage Solution of brominated poly-N-vinylearba / ol πι Chlorobenzene has been applied as a layer.

The F i g. 2 passes on the gray wedge spectrogram of an electrophotographic material which is described in In the form of a large volume solution of brominated Poly-N-vinylcarba / ol. that with 0.04 percent by weight 2 - (./-Phenyl-p-metho \ yslyryl) -4- [(2-phenyl-4-benzene / opyranylidene (methyl] -benzopyrlium perchlorate) has been sensitized. has been applied as a layer. wherein the brominated poly-N-vinvicarba / ol was dissolved in a solvent. the from 4 parts by weight of chlorobenzene and 1 part by weight ^ s Dichiorethane existed.

The Fi g. 1 represents the (iraukeilspcktrogranim an electrophotographic material again, which is in the form of a 10 weight percent solution of brominated poly-N-vinylearb;> zol. That with 0.04 weight percent 2 - styryl - 3 - phenyl - 4 - [(2 '- styryl-4'-benz.opyranylidenemethyl] -6-methylbene / .opyrylium perchlorate has been sensitized, has been applied as a layer, whereby the brominated poly-N-vinylcarbazole had been dissolved in a solvent, which consists of 4% by weight of chlorobenzene and 1 Part by weight of dichloroalhanum existed.

The F i g. 4 shows the gray-wedge spectrogram of an electrophoresis material which is used in Form of a 10 weight percent solution of brominated Poly-N-vinylearbazole at 0.04 weight percent 2-p-methoxystyryl-4- | (2 '- (i-phenyl-p-methoxystyryl - 4' - benzopyranylidene) methyl] benzopyrylium perchlorate has been sensitized, has been applied as a layer, the brominated poly-N-vinylcarba / ol had been dissolved in a solvent. that from 4 parts by weight of chlorobenzene and 1 Gewiehisil dichiorethane existed.

Fig. 5 gives a gray wedge spectrogram electrophotographic material in the form of a 10% by weight solution of brominated Poly-N-vinyl-carbazole, which is 0.04 percent by weight 2- p-methoxystyryl -4- f (2'-phenyl-4 '-benzothiapyranylidene) -methyl] -benzo-pyrylium perchloral has been sensitized. has been applied as a layer. where the chromed pole \ - N-vin \ Icarbazole was dissolved in a solvent. that from 4 parts by weight of Chlorhenzul and I used dichiorethane.

The I 1 g. Ci gives a gray wedge spectrogram one electrophotographic material that is used in F'onv. a lOgcwichtspio / entigen solution \ on bromieriem Poly-N-vin> l-earbazole. that with 0.04 weight per cent 2- [| 2- phenyl -4 - benzopsrainlidenimeiln I) - λ - phenj Ibenzopy ry liumperehlorat sensihihsierl has been. has been applied as a layer. wherein the brominated poly-N-vinylcarhazole in one Solvent had been dissolved. that is made up of 4 parts by weight of chlorobenzene and 1 part by weight of DichliMäth.in duration.

Fig. 7 is a gray wedge spectra eleklropholographi. see material that is in In the form of a 10% by weight solution of brominated Poly-N-vinyl carba / ol. that with 0.04 percent by weight 2- [(4-Benzolhiapy ran \ lidcn) meth \ i] -. VphenνIbenzopyryliumperehlorat been sensitized isi. has been applied as a layer. where ilabromierle Poly-N-vinylearbaz.ol in a solvent had been resolved. that from 4 iew ilsieilen Chlorobenzene and 1 part by weight dichloroethane.

The F 1 g. X gives a gray wedge spectrogram an electrophotographic Material again, in the form of an iOgcw ichtspro / entigen solution \ on bro rnated poly-N-vmsl-earbazoI. that with 0.04 percent by weight 2 - [| 2 - <(- Phen'vl - ρ - metho \\ si \ r> i 4 '- benzopyranylidenemethyl I - 3 - phenylbeii / opvr> · lii'inperchlorai has been sensihilized. as a layer has been applied. the brominated poly N-vinylcarbaz.ol being dissolved in a solution was. that from 4 parts by weight C'h'orhen / o! around

1 part by weight of dichloroethane consisted.

Fig. ⁽ ) Shows a (jraukeiKpcktrogr.imm an · electrophotographic material again, the π form of a lOycuichLspro / cnliucn solution: u'ii IVh N-vinylcarbazole, which with 0.04 Gcwichlspro / en

2 - f (2 '- phenyl - 4' - bcnzothiapyranylidene) methyl] 3-phenylbenzopyrylium perehlorate sensitized wor that is. when Schi.'hl was applied. where tla brominated poly-N-vinylcarbazole had been dissolved in a solvent. that from 4 Gewichlteilei Chlorobenzene and I part by weight of dichloroalhanum were.

The sensitizers with tier specified above! Formula are produced according to the following chemical) reaction equations A oiler B:

Keaklionsulcichuni! Λ

R ₁

OCII,
(I)

NO,

SO ₁

IR

R, I '

(Ii,

K ₁ (III

, Anion

R ,. I.

K ₁ K,

Anion

OCH,

(I)

NO,

SO,

CIl.

iIY

Anion

R, I R.

R _s ClI anion

(V)

After the reaction mixture A, the 4 - [(4'-Rcn / opyranvlidcnimcllivl] hen / op \ r \ lium derivative Uli) is obtained by an addition reaction of i-methoxyhynzopyrylium-o-nitrobenzenesulfonal (I) with a ben / op \ i> lium salt (II) obtained in an acetic anhydride solution. Flas Benzopyryliumsab has an active Me! ^1. > L- odei methylene residue.

After the reaction solution B, the 2- [14-BenzopyranyHden) melhylJ-benzopyrylium derivative (V) is durcl an addition reaction of 4-methoxybenzopyrylium-o-nitrobenzenesulfonate (I) with a benzopyrylium salt (IV) obtained in an acetic anhydride solution.

The benzopyrylium salt has an active methyl radical.

In both cases, methyl 2,4-dinitrobenzenesulfonate can be used instead of methyl o-nitrobenzenesulfonate. Dimeih) 1 sulfate or methyl iodide can be used.

Typical examples of the benzopyranylidenemethylbenzopyrylium salts and benzothiapyranvlidenemethU Benzopyrylium salts according to the invention are given in Table 1.

Number of
Connection University:

Table I.

Rc / eichnurii! the prevention;

2-phenyl-4 - [(2'-phenyl-4-benzopyranylidene) benzyi] benzopyrylium perchlorate
2,3-Diphenyl-4 - [(2'-phenyl-4'-benzopyranylidene) benzyl] -6-methylbenzopyrylium perchloride
2,3-D'phenyl-4 - [(2'-phenyi-4-benzopyranylidene | methyl] -6-methylene-benzopyrylium perchlorate
2,3-Diphenyl-4 - [(2-phenyl-4'-benzopyranylidene | methyl] -6-phenylbenzopyrylium perchloral

\ UH1U1CI lic \ ei hiinliin /

continuation

Mvliming ilci \ ei huuluiu *

5 --p-Mcth <'Xysiyr \ l-4- [l2'-phcnvl-4'-bcn / (ipyraiivliilciilnicthyl] -bcn / opyr \ iiuniperclik> rat

<> 2 -,; - l-'iiryl (i'lathen \ l-4 - [(2-phenyl-4'-hai / opyranylidene) methyl 1-ben / opyryl ium perchlorate

V 2-1 "-IMiCIi '1-p-metalnmstyryl | -4 - [(2-phen \ i-4-ben / opviaii \ Iiden! Methyl j-bcti / opyrvlium-

perchloiat

H 2-St \ r \ l-3 phenyl-4-j 12-phony! -4'-ben / op \ ran \ liclciilniclhy I l-6-nictliylbcn / .opyrylium-

porclildral
* ί 2-p-Mclli (i \\ st \ iyl-3-plicnyl-4 - [(2 -phony l-4-bcii / opy ran vlidcnlnicthyl l-6-metliylbeii / n-

pyryliimiporchliir.il
lit ^l '. [l2 -PliL'nyl-4'-bcn / opyiaiiylidcn) nn; t! iyl I-Nanthyliunipcrcliloral

11 2 -,; - Ι · 'ιιι · \ Ι | ι / |; it lion \ l-.Vphcn> 1-4 [12-phenyl-4-hL-n / .opyanylHlen! Methyl] -6-m (Mh> Ibcn / opwyliuniporchlorai

12 2.i-I) iphcn \ l-4- [i2 -st \ ry | -4 -bcii / npyraiiylidenlbon / yl l-d-niotliylben / opyryliiiiriporclilorat

13 2-Phcnyl-4 - ((2 -st \ ryl-4'-ben / opyranylidcn) bcn / yl] -bcn / i) pyryli ⁱ .impcrchlorai

14 2.3-Diphony 1-4- [12 -Myryl -4- bon / opy rain I iden! Methyl] -ft-met hy I bcn / opyry II um perohlorat

15 2-1 α-Phon \ I-p-mot how styryl 1-4-1 (2 -sty ι y] -4'-bon / opyranylidcnlmeth \ l] -hcn / opy r \ liumporchlorat

| 6 2-St \ r \ l-3-phen \ l-4 - [(2 -stvr \ l-4 -bon / opuanylideiilmetliylj-e-methylben / npyryliuni-

porchlorate

IT ¹ ) - [| 2-St \ r \ l-4 -bon / tipuanylidonlmothyll-xanthyliunipeichlorate

V 2-p-Motho \\ styrsl-3-plionyl-4- [l2'-styryl-4'-ben / opyraiiylidcnlmeth \ IJ-6-moth \ lbon / (i-

pwylimnperchlorate

19 2.3 - [) iplunyl-4 - [(4 -hon / opy rany liden | bcn / yl l-ben / opyryliumperchKirat

2 <) 2-phon \ l-4 - [(4-bcn / opyran \ lidon | ben / \ r] -bcn / opyryliunipcrohlorat

Jl 2,3-Iiphynyl-4- [14'-bon / (ipyranyhdenlmethyl] -6-methylbene / opy ryliiimporohUirat

J2 2 - ('/ - Phc! Iyl-p-methox \ styryl) -4 - [(4'-hcn / .op \ rain I idcn! Methyl] -ben / opyr vl ium perch I o rat

23 2-St-ryl -. "'- phony l-4- [l4-ben / opyrany I idcn! Methyl] -6-methylbenzopyryliumpcrchli» rai

24 2-p-Metho \ sst \ r \ l-3-phenyl-4-f (4'-bon / i "ipyranylidenemethyl] -6-methylben / opyrNliunipcrchlor; 't

25 ⁽ ) -f (4'-Ben / iipyran \ lidenlmeth \ IJ-xanthvlium perchloiate

2f ·· 2-p-Metlio \ yst \ r \ l-4-f (4-bon / opyraiiylidcn | methylJ-ben / opyrylium perclilorate

2 ~ 2-p-Vlctl'o \ ystyr \ l-4 - ["(2'-p-mctho \> styryl-4'-bcnzopyranylii.lcnliTielhyl"] - r »cn / 'iipy r \ lium-

porchlorate

2S 2- (i / -plicnyl-p-methiixyst \ ryh-4- [l2'-p-metalio. \\ st \ ryl-4 -ben / opyraηvliden! Methyl l-ben / opyrylium perchlorate

2 ¹ J 2'-St ^ ryl · 3-phcnyl-4 - [(2'-p-metho ^ ystyry! -4'-bon / opyranyΊiden) methyl] -6-methylbon / o-

pyrviium perchlorate

3d 2.3-DiphsnYl-4 - [(2'-p-methox \ slyr \ l-4'-beiizop \ ranyliden) mcth \ l] - ⁱ i-mcth \ lbcii / opyryliiiir

perchlorate

31 2.3-Diphenyl-4 - [(2-p-methoxysiyryi-4'-ben / Opyranyliden) benzyl] -6-methylbenzopyiylium ; perchlonu

32! 2-Phenyl-4 - [(2-p-methoNystyryl-4'-benzopyranylidene | benzyl] -benzopyrylium perchlorate

33 9 - [(2'-p-methoxystyry! -4'-bcnzop \ ranylidene! Methyl] -xanthylium perchlorate

? 4 2-p-Methoxystvryl-4 - [(4'-benzothiapyranylidene) methyl] -benzopyryIium perchlorate

35 j 2-1-1-phenyl-p-melhoxystyryl) -4 - [(4'-benzothiapyranylidene) mcthyI] -benzopyrvlium-I perchlorate

36; 2-Styryl-3-phenyl -4 - [(4-benzothiapyranylidene) methyl] -6-methylr) enzopyrylium perchlorate

37 '■ 2.3-Diphenyi-4 - [(4'-benzothiapyranylidene) methyl] -6-methylbenzopyranylium perchlorate

38 j 2,3-Diphenyl-4 - [(4'-benzothiapyranylidene;) benzy!] - 6-methylbenzopyry humperchlurate

39 · 2-Pheny! -4 - [(4-benzothiapyranylidene) benzyl] benzopyrylium perchlorate

40 I 9 - [(4'-Benzothiapyranylidene) methyl] xanthylium perchlorate

41 j 2-p-methoxy.styryl-3-phenyl-4 - [(4'-benzothiapyranylidene) methyl] -6-methylbenzopyryiium ' perchloral

42 i 2-p-Metho.xystyryl-4 - [(2 -S '^' - dimcthoxystyryW-benzopyranylidenlmethylJ-benzo-

pyrviium perchlorate

■ crtsctziinu

10

Number of link

nj iln \ ci

63 64 1) 5 66 67 68 69 70 71 72 73

2-Sl \ ryl-3-phciiyl-4 - [(2'-3 ".4" -i.limcllni \ ystyr \ l-4'-bcn / opsranylidi; ii) meth \ l | -6-pvryliumpcrchlnrat: 9 - [(2'-3 ".4" -ί ') ίΓηοΐΙιοχ_ν.'; Ϊ́_νΓ \ 1-4'-Ιχ ^> η / ΐ) ρ \ Γ; ιηνΙίιΙοΐΊ | ηκΊΐι \ Ι] -simthyliiimpcrchlorat 2-l'hcnyl- 4 - [(2 '-,; - for \ l (a'iälhcii \ l-4'-bcii / iip_ \ r; m \ liilcii | bcn / \ l | -bcn / op \ r \ liumpcrchl "iat 2.3- Diphcnyl-4 - [(2'-; -fiiryl (n); itlien \ 1-4'-hen / ops rain liden) ben / y I l-ii-mcllnlbcn / op \ ryliiimpcrchli> rat 2.3-I) iphL ⁱ nyl-4 - [(2 ⁱ -, i-fiii "\ l | ii ⁱ ) a'lhcn \ i-4'-bcn / np \ ran \ lidi: iiinicth \ l | -6-nicth \ lbcn / npyryliumpcrchlnrat 2 -p-Mctho. \ ystyryl-4- [i2 '-, i'-ruryl ('i'l;iihcinl-4'-bcn / iipyranylidL'ii | nictliyl] -bcn / op_ \ i \ liunipcrchlorate

, 2 - («- Phenyl-p-mctho \ ystyryD-4- [i2 '- ,,; - for \ l |. ('Iäthcnyl-4'-bcn / iip \ raiislidL ⁱ n) not \ l | -bcn / <pyryliiimperchliiral

■ ^c > - [(2 -, .- F-LHyK-; (iit hcn \ l-4-bcti / np \ ran \ liclciilmcl li \ I | - \ anl In I iumpct chloral 2-Phcny! -4- [ l2 '-. i-phcnylstyrvl-4-bcn / (ip \ ran> lidcn | bcn / yl l-hcn / opvixliumpcrchliuai

2-p-methoxystyryl-4- | (2 '-'i-phenylstyryl-4'-hen / iip \ ranyliden | mothyl | -bcn / iipyryIiiim- ^: pcrchlorat 2- (a-Plicn \ lp-mctho. \ Yst \ r> li-4- [(2 -. <- pticn \! st \ r \ 1-4 -hcn / np \ ranylitlcn) mcth \ I | -ben / o-

pyrviium perchlorate 2-Phcnyl-4- [l2'-fi-phen \ ip-nKthoxyst \ r \ l-4'-bciiAipyran \ lidciilbcn / \ l | -ben / op \ r \ liuniperchloral 2,3-Diphcnyl-4 - [(2 '- <- phonyl-p-mcih ^ \\ st \ r>l-4'-hcn / iipyranylidcnlben / y]] - 6-mi: tli \ lbcn / opyryliumpcrchloral 2,3-Diphcnyl-4- [l2'-a- phc! iyl-p-mcllio \ ystyryl-4-bcii / opvranyliden) niclh \ l | -6-inclh \ ibcnziipyr.N liuinperchlorai 2-p-Mctho \ ystyryI-4 - [(2 '-. i-phonyl-p -mctho \ ystyryl-4'-bcn / op \ ran \ lidcn | mi: th \ l Ι-Ινιι / ο-pyryliumperchUirat 2 - (. 1-PhCiIS lp-mctliiwystyryl) -4- | (2 ■ -.i- phcnyl-p-mciluvxystyry 1-4 -bcn / opM-anvlidciiinicih bcnzupyryliumpcrchlnrai 9-fl2- _li -Phcn \ lp-mciho \ ysi.sr \ l-4'-N'n / op \ ran \ lidLMi \) mothyl] - aiuhyliump..rcliK) rai 2-n-Methcnystyryl-4-n2 '- _< -phcnyl- _i .; - fury! {- ₍ ' | ethynyl-4'-bcn / op \ ranylidcn) mcth \ l | -bcM / o pyrylium perchlorate

■ ^ι ^ ["l2 '- i-Pl ^ en \ l- _/ ; -rιιryll · i'); · ithenyΊ-4 · -ncn / Λ) pyran \ Ίidcn | mct! L \ Ί ■] - \ aIlthyliumpcrchl ■> ι ■ al

2-Phcn \ l-4- [| 2'-p-mclht> vystyr \] - 3'-phcnyl-6'-mclliyl-4'-bcn / op \ ran \ lidL ^> n> bcn / \ l] - ben / _l i pyry I ium pc rc hi oral

; 2.3-Diphenyl-4- [| 2'-p-methoxystyryl-3-phcn> l-6-methyl-4-benzene / opyranv] iden) bcn / \ l] -ι 6-nicthyIbcn / opyryiiiiinpcrchlorat 13-Dipheny] -4-ri2'-p-methoxystyryl-3'-phcnyl-6-meth \ l-4 -ben / cpyranylidcnlmctlnl | - 6-methylbenzopyrylium perchlorate

j 2-p-methoxystyryl-4 - [(2'-p-methoxystyryl-3 ^> -phenyl-6'-methyl-4-benzopyran vinyl chloride-4- benzopyrylium perchlorate! 2- (, _i -phenyl-p-methoxystyTyl) -4- [(2'-p-methoxystyryl-3'-phenyl-6-niethvI-4-benzo-: pyranylidenemethyn-benzopyrylium perchlorate j 9- [l2'-p-methoxystyryl-3'-phenyl-6-- _m ethyl-4- benzopyranylidene) methyl] -xanthvlium-ι perchlorate! 2-Phenyl-4 - [(2'-3 ". 4" - dimethoxy _S tyryl-3'-phenyl-6 - methyl-4'-benzopvranylideii | ben / vl] benzopyrylium perchlorate ^J

13-DiphenyI-4 - [(2'-3 ".4" -dinjethoxyMyryl-3'-phenyl-6'-methyl-4'-benzopyranvlidene) ben> j 6-methylbenzopyry] iumperchlorate

2.3-diphenyl ^ NYI-4 - [(2'-3 '''.4' - 3-- _{dirnethoxystyryl-P} henyl-6'-methyl-4'-benzopvranvliden) _m ctl j 6-methylbenzopyryliumperchlorst

j 2-p-Methox _y styryI-4-r (2'-3 - ^ "- dimethoxystvryl-3'-phcnyl-6-- _m ethyI-4'-benzopvranNlide ₁ ! methylj-benzopyrylium perchlorate *

2- _(i phen _y l _P -methox _y st _y r _y l) -4 - [(2'-3 '.4 - di _m ethox _y l _{ys tyr-3'-P} henyI-6' -meth _y l-4'-bcnzc pyranylidenlmetnylj-benzopyrylium perchlorate

r-loc

"ΐ.πια-iler I. \ crnimlniii;

74

184

K7 KX

94 95 96 97 • 98 99 K) O 101 102 103 104 105 106 107 108 109 110 111

Ikv ^ hmm, dc, \. ·, Bnuhin,

Z-Phcnyl ^ -fjZ'-jj-furyllii'jäthcnyl-i'-phcnyl-ö'-nielhyl ^ '- bcnzopyranylidcnJbcn / yl'J-ben / opyrylium perchlorate

2,3-Diplicnyl-4- [12'- _/ ; -furyl ('i') iithcnyl-3'-phenyl-6'-methyl-4'-benzopyranylidium) benzylJ-6-methylbenzopyryiiunipcrchlorate

2,3-Diphenyl-4 - [(2'- _/ ; -furyl ('i') iitheiiyl-.V-phcnyl-6'-mclliyl-4'-bonzopyraiiylidcn) methyl] -fi-methylbenzopyrylium chlorate

2-p-Methoxystyryl-4- [(2 '-,; - furyl (ii') ethyny 1-3'-phonyl-6'-methyl ^ '- benzopyranylidcn (methyl) -benzopyrylium perchlorate

2- (p-phenyl-p-methoxystyryl) -4 - [(2 '-,; - furyl (' i ') ethenyl-3'-phenyl-6'-methyl-4'-benzene / opyranylidin! Methyl j-benzopyrylium perchlorate

9 - [(2 '- / i-i-uryl ((i') ätheriyl-3'-phenyl-6'-methyl-4'-benzopyranylidcn (methyl J-xanthylium-

pcrchlorate

2-Phenyl-4 - [(2'-plien> 1-4'-benzothiapyranylidene) benzyrj-benzopyrylium perchlorate 2,3-niphciiyl-4 - [(2'-phenyl-4'-ben / olhiapyranylidep.) Ben / yl] -6-methylbenzopyrylium-

pcrchlorate

2,3-Diptienyl-4 - [(2'-phenyl-4'-benzothiapyranylidene) methyl] -6-methylbcn / opyryliuiri-

pcrchlorate

2-p-methoxy sty ryl-4 - [(2 '-phony l-4'-benz.i> thiapyranylidene (moth yl] -benzop \ r \ I iuni-

pcrchlorate

2 - ('i-Phenyl-p-methoxystyryl) -4 - [(2'-phenyl-4'-ben / othiapyranylidene) methyl | -bene / .opyrylium perchlorate

2-p-Methoxystyryl-3-phenyl-4- | _ (2'-phenyl-4'-ben / othiapyranylidene) melhyll-fi-inelhylbenzopyry Hum perch lorat

2-styryl-3-phenyl-4 - [(2'-phenyl-4'-ben / othiapyranylidenemeth \ l] -6-niethylbL-n / opyr \ iium-

pcrchlorate

9 - [(2'-Phcnyl-4'-benzothiapyranylidene) mi ⁱ thyr] -xanthylium perchlorate 2- (fi-Phcnyl-p-mclhoxystyryl) -4-r (2'-phenyl-4'-benzopyranylidene) methyr] -benzopyrylium-

tluoborate

2- (fi-Phcnyl-p-methoxystyryl) -4- [(2-phenyl-4'-benzopyranylidene (methyl J-ben / tipyrylium-

chloroferrate

2 - («- Phenyl-p-methoxystyryl) -4 - [(2 ^l -phen \ i-4'-benzopyranylidene) methyl] -ben / opyry! Ium-

chlorozincate

2 - [(2'-Phenyl-4'-benzopyranylidene) methvl] -benzopium perchlorate 2 - [(2'-phenyl-4'-benzopyranylidene) methyl] -3-phenylbenzopyrylium perchlorate 2 - [(2 ' phenyl-4 ^r -bcnzopyranylidcn) methyl-3-phcnylbcnzopyryliunifluoborat 2 - [(2'-Phcnyl-4'-bcnzopyranylidcn) Melh> i] -3- [viicny bcnzopyryliumchloroferrat 2 - [(2'-4'-Plicnyl benzopyranylidene) methyl] -3-phenylbenzopyrylium nitrate 2 - [(2-styryl-4'-benzopyranylidene) methyl] -benzopyrylium perchlorate 2 - [(2'-styryl-4'-benzopyranylidcn) methyl] -3-phenylbenzopyrylium perchloride 2 - [(4 '-Benzopyranylidene) methyl] -benzopyrylium perchlorate 2 - [(4'-Benzopyranylidene) methyl] -3-phenylbenzopyrylium perchlorate 2 - [(2'-p-methoxystyryl-4'-benzopyranylidene) methyl] -benzopyrylium perchlorate 2 - [(2'- p-Methoxystyryl-4'-benzopyranylidene) methyl] -3-phenylbenzopyrylium perchlorate 2 - [(4'-Benzothiapyranylidene) methyl] benzopyrylium perchlorate 2 - [(4'-Benzothiapyranylidene) methyl] -3-phenylbenzopyrylum perchlorate 2 - [(2'- 3 ".4"-Dimethoxystyryl-4'-benzopyranylidene) methyl] -benzopyrylium perchlorate 2 - [(2'- 3 ", 4"-Dimethoxystyryl-4'-henzopyranyl! Den) methyl] -3-phenylbenzopyrylium perchlora 2 - [(2'- _/ i-furyl (fi ') ethenyl-4'-benzopyranylidene) methyl] -benzopyrylium perchlorate 2- [ (2 '- / i'-Furyl (i (') äthenyl-4'-benzopyranylidene) methyl] -3-phenylbenzopyrylium perchlorate 2 - [(2 '- «- phenylstyryl-4'-benzopyranylidene) methyl] -benzopyrylium perchlorate 2- [ (2'-a-phenylstyryl-4'-benzopyranylidene) methyl] -3-phenylbenzopyrylium perchlorate 2 - [(2 '- <i-phenyl-p-methoxystyry! 4'-benzopyranylidene) methyl] benzopyrylium perchlorate 2 - [(2'-f <-phenyl-p-methoxystyryl-4'-benzopyranylidene) methyl] -3-phenylbenzopyrylium perchlorate

13th

continuation

14th

Number animal \ erhinilunu

IWiLhiiim: .- · ilti \ ei hin.l

112 2 - [(2 ¹ - _{f /} - / - furyl (.. 'Phcnyl--|. Iithenyl-4'-bcn / opyranyliden | mcihyl> 3-phcnylbcn / t.pyrylium-

perchlorate ,, -, -,, ,,

113 2 - [(2'-p-Methoxy _S tyryl-3'.6'-diphenyl-4'-benzopyranylidene) methylI-3-phenylbenzo-

pyrylium perchlorate

114 2 - [(2'-3 ", 4" -Dimethoxystyryl-3 ^I .6'-diphenyl-4'-ben / opyranyliden "mcthyll-3-phcnylbcnzo-

pyrylium perchlorate

115 j 2- [| 2'-p-methoxystyryl-3'-pheny! - ^ - methyl-4 ¹ -benzopyranylidene) methyl] -benzopyrylium-

perchlorate

116 ! 2 - [(2'-p-methoxystyryl-3'-phenyl-6'-methyl-4'-benzopyranylidene) methyl] -3-phenylbenzo-

pyrylium perchlorate
IP 2 - [(2'-3 ".4'-nimelhoxvstyryl-3-phenyl-6-methyl-4-ben /. ₁ puainlidenimelhyl | -ben / o-

pyrylium perchlorate
I IX 2 - '[| 2--3'.4 "-Dimethoxystvr>l-3.phenyl-6-methyl-4'-ben / (^ pyranyliden | methvl! -Vphcns |.

ben / opyry hum perch lorat
114 2 - [(2 -,; '- l'uryl | a) äthcn \ l-3-pheny 1-6 -metin 1-4 -hcn / opy rain hden! Methyl] -ben / .opvr> Ii iim -

perchlorate
! 20 2 - [(2 _';; -Turyl (./) athenyl-V-phcnyl-6-mcili> l-4-ben / _(> p \ ran> liden) niethyl] -3-phL'nylbcn / , .-

pyrylium perchlorate

121 2- | l2'-Phenyi.-4'-ben / othiapyran \ liden) methyll-ben / opyryliiimperchl (> rat

122 2 - [(2-phenyl-4-ben / o! Hiapyranylidenimethyl] -3-phenylben / opylium perchlorate

123 2 - [(2'-phenyl-4'-ben / opyiai-.yliden! Methy!] - 4-p-methoxyphenylben / othiapyi '\ liiim-

perchlorate
! 24 2 - [(2'-I ^> henyl-4 ⁱ -hen / op \ ranylidenimernyl] -3-phenyl-4-p-niethoxyphenylben / op \ ryliuin-

perchlorate

125 2- [| 2 '-., - Phen \ lp-methoxy.iyryl-4 ⁱ -ben / opyranylidene! Methyl] -4-p-meihoxyphenyiben / o-

thiapy ryltumperehloral

126 2- [| 2 '-. Il ^> lienyl-p-methoxystyryl-4 ^r -ben / opyranyIiden) methyl] -3-plv.-nyl-4-p-methoxystyryl-4 r -ben / opyranyIiden) methyl] -3-plv.-nyl-4-p-methoxystyryl-4 r -ben

ben / othiapy rylium perch lorat

127 2- [| 2'-phenyl-4'-hen / othiopyranyliilen) methyI | -4-p-methoxyphenylhen / <ithiapyrylium-

perchlorate
12S 2-f (2'-phenyl-4'-beii / otliiopyran \ liclen) niethyl | -3-phenyl-4-p-metho \ yphenylhen / oilia

pyrylium perchlorate

In Table 2 further data on J. ^ \ bsorplioiiMiiaximum in Dichi.irälhan and the ■> chmel / punkl of the new connections after the : ι lindunj; aiiüeiieben.

Tabel

ν , -τ iii-.

I.

135 - 13 ')

I3o - 132

1X2 - ix "

164 - PO

163 - P2

> 300

162-164

1X0 - 1X7

157 - IWi

103-105

120 - 126

P6 - IXO

122 - 126

I> kh I- T.1:! - .: π ■■ ;: ι

41.5 and "IU 430 and "20 410 and

n35

440 and 5 "? 5 and 5 (M) and 44 () and 550 and

610

54

430 and 420 and "3d

14th
15th

l'i

IN

20th
21

23
24
25th

26th

27
X

24

30th
31

163 - H) 160 - IM 166 - IM 1? 5 - 140 Ι ^ς 4 - | ί, 2 PM - IM

140 - 142 165 - Γ2 174 - PX 176 - I74 170 - 175

• 300-300

141-147 201-203 2 (K) - 204 I.X5 - 1X4 PX -! S3

- Ί Γ 'I'
I) klii If It hairdryer 420 and Nile! NlXl and 44 ν .; nd
NXO 7 in 420 * 1 ^v . N
and 'Vi 4M and "III I 410 and 600 5 (K) and 4X5 505 630 ν 60 560 540 NlK) and 710 660 and 650 410 and 640 430 and

Continuation / line

NiiinriKM the
VlM ΙίΠΙιΙΐΙΙΐμ SUu irl / puilkl AtvinrpliMiisniiixinuim 32 ISI - ISS 420 and 700 33 117 - 123 550 and 650 34 185 - 189 35 159 - 164 495 and 600 36 IS5 - 18S 610, 650 and 7i! 0 37 160 - 165 415 and 650 3S 204 - 206 425 and 700 39 166 - 169 415 and 730 40 "300 660 41 173 - ISO 555 42 175 - 1X1 540 and 600 43 167 - 173 660 and 710 44 161 - 164 5X0 and 720 45 145 - 150 415 and 720 46 IXX - 190 425 and 720 47 16X - 175 670 4 X 171 - 176 490 and 5X0 49 179 - 1X6 600 and 720 50 171 - 175 610 and 660 51 151 - 155 4X0 and 740 52 171 - 176 495 and 5X0 173 - 177 590 and 700 54 140 - 147 550 and 750 S S 203 - 207 420 and 6S0 56 13X - 142 555 and 6X0 57 170 - 175 570 5X 154 - 157 5X5 and 690 > 9 I6X - 174 570 60 206 - 209 600 61 ■ 300 65o 62 139 - 146 550 63 202 - 204 425 and 700 64 173 - 177 530 and 690 65 190 - 194 59 () 66 190 - 193 500 and 600 67 192 - 195 620 6 X 1 12 - I IX 570 and "60 69 190 - 192 49 5 70 ! 54 - 159 650 and 700 7 | 177 - 1X2 500 and 7 | 0 - ι 176 - 1X1 5i) 0 7! 195 - 199 495 and 640 74 1X9 - 195 550 75 1X4 - 1X7 415 and 720 76 192 - 196 640 and 700 77 ■ 300 550 Ix 219 ^ 111 550 79 226 - 230 630 MO 127 - 134 410 and 745 Kl 190 - 192 425 and 730 X2 156 - 159 665 83 164 - 169 600 and 6X0 M4 - I7X 600 and 720

112 5 437 Schill Ii Il Number of
Vcihiiultuiu 170 el / puiik S 5 157 - 177 H 6 169 - 166 S7 137 - 172 IO 88 167 - 140 89 160 - 172 90 > - 163 91 12S 300 '5 92 133 - 134 93 152 - 136 94 133 - 158 95 190 - 138 20th 96 156 - 195 97 225 - 15S 9 X 1X3 - 229 99 20S - IS7 25th 100 170 -212 101 225 - 176 102 163 - 22S 103 I7X - I6X 10 104 172 - 1X4 105 167 - 175 106 190 - 171 107 211 - 194 ις K) S 175 - 214 109 I9X - 179 110 I5X - 201 IN THE - 163 40 112 1S5 300 113 199
211 - IXX 1 14
115 177 - 204
- 215 I 16 205 - IXI 4S 117 190 - 207 118 237 - 194 119 - 241 120 207 300 SO 121 155 - 210 122 143 - 1 SS 123 126 - 145 124 144 - 131 55 125 140 - I4X 126 149 - 142 127 141 - 153 12X - 145

lun III-M

550 and 700 650 and 695 635 500 and 610 500 and 610 5 (H) and 610 575 575 and 675 575 and 675 575 and 6 * 75 575 575 620 and 690 565 525 u η d 560 570 630 and 690 610 610 and 690 510 5X0 and 690 565 and 620 560 and 635 570 and 610 570 and 610 570 and 610 5X0 and 630 600 and 645 570 and 620 600 565 and 600 570 and 610 570 590 560 565 and 605 615 and 675 615 619 559 and 657 5X9 around! 663 656 660

In the following description, one embodiment is used of the process for the preparation of benzopyranylidene methylbenzopyrylium salts or Benzothiapyranylidene methylbenzopyrylium salts with reference to the compounds given as examples explained. The details of making other connections are for the Faehmann from the description above and the naelifolp.mden illustrative examples of processes for the preparation of numerous compounds according to the Hrfiniluni can be seen:

17th

18th

al 2-phenyl-l- [i: -phL'n>l-4'-hün / p. \ ran.vlicluMil-lvn /> l | -hen / p. \ i.vliumperLh | ₁ , nii

I connection no. I)

OCH,

NO,

4 "

CH,

CIO ₊

I CK),

5.5 g 2-phenyl-4-melhoxyben / pyryliuni-o-niiroben / (ilsulfon; it. That has been increased from fla \ on and M.;! ...! -. · .Niimben / olsulfonate. And 5 α 2 -Plienyl-4-hen / yl-bi: n / pyryliutnperchlorai are / ur! -. Melting of a solution in 150 ml of acetic anhydrite. The solution is then refluxed for 15 minutes and poured into 900 ml of perchloric acid by weight The solution is filtered to isolate the precipitate. The precipitate is dried and dissolved again in diehlorethane to prepare a solution. For purification, the solution is poured into ether. The precipitated crystals are filtered off, washed with ether and dried, and 4 g | 53 "» of the theoretical yield) of green crystals with a melting point of 135 to 139 C.

b) 2-ia-phenyl-p-melhox_ \ styryl) -4- [i2-phenyl-4-ben / op> ran_ \ liden) meth> l] -ben / op \ riliumperchlorai

(Compound 7)

OCH,

NO;

- SO ₁

C CW

OCH ₁ ^! ClO _a

C! 1,

C \ {

CU):

C CfI

OCII

5.5 g of 2 - ('i-phenyl-p-metho \ yslyryl) -4-nie! Hylhen / opvr> liumperchlorat and 5.5 g of 2-phenyl-p-metho \ yhen / o-

R \ rvlium-o-nitrohen / olsulfonat are dissolved in a solution in 150 ml of aqueous anhydride. the The solution is then refluxed for 15 minutes and dissolved in 900 ml of 10 percent perchloric acid pured. The solution is filtered to isolate the precipitate. The precipitate is then means ) ichlorüthan ether precipitated again. The precipitated crystals are filtered off. washed with ether And dried, and there are 5.5 g (69% of the theoretical yield) of blue crystals with a Melting point of 162-169 ° C obtained.

In the method given above, according to another embodiment, the solution is poured into an ethereal solution of BF, 0 (C ₂ H ₅ ), instead of 10 percent by weight perchloric acid. In this case 2 - ('i-phenyl-p-methoxystyryl) -4-f (2'-phenyl-4'-henzopyranylidene) methyl] -bene / opyrylium fluoroboral! Compound No. SS) is obtained.

If in the above process the solution is dissolved in an aqueous 10 percent by weight zinc chloride solution is poured, 2 - ('[- Phenyl-p-methoxystyryl) -4 - [(2'-phenyl-4'-ben / opyranvliden) methyl] -bcnzopyryliumchloro / inkat (Compound No. 90).

19th

ti Z

I connection no. IS)

20th

- 'i ^f Γ C hl

- C Il

OCH.,

SC),;

CII-CH ~ ' ^/

-OH,

cn /! Γ ι |

CW _x /

/ V CH-CH

Cl!

CIO,

CII CH

OCH,

2-Siyiyl-4-methoxyhenzopyryliuni-i) -niiiobenzolsulk) nat (melting point: 155 to 157 C) becomes liquid for 24 seconds Lime removal of 2-slyrylchromone and methyl-d-niiroben / olsulfonate in dry benzene at 50 ° C. After the same reaction as indicated for procedure a), 2-styryl-4-methoxyhenzopyrylium-o-nitrobenzenesulfonate reacts with 2-p methoxystyryl-3-phenyl-4,6-dimethylbenzopyryluniperchlorate to 2-p-methoxystyryl-3-phenyl-4 - [(2'-styryl-4'-benzopyrany] idenjmethylJ-fi-methylbenzopyrylium perchlorate. that in the form of crystals with a reddish color in dichloride and with a melting point of 159 to 162 C.

The product is produced in a yield of 7%.

d, 2 - (<! - Plien%! - p-melho \ ystyr \ l) -4- | (4'-benzopyranylidai) -meih \ l | -henzop \ ryliumperchlorai

(Connection uni: No. 22)

OCH ₁

NO,

CII.,

C C

OCH ₁ i CK) ₄

(H

ClO ₁

C-CH

OCH,

4-Methoxybenzopyrylium-o-nitrobenzenesuironate reacts with 2- (<< - Phcnyl-p-mclhoxystyryl) -4-methylbenzopyryiium perchlorate using the same procedure as specified under a). to 2 - ("- Phcny! -p-methoxystyryl) -4-f (4'-benzopyranylidcn) methyr] -benzopyrylium perchlorate. The crystals have a violet color in dichloroithane and have a melting point of 174 to IVS C. The product is in a 9% yield

21 22

el 2-p-Metho \ ystyryl-4-f (2'-3 ".4" -dimctho \ ystyryl-4'-ben / opyran \ lidcn | meth \ l] -ben / opsr \ liiimperchlorat

(Compound No. 42)

CH CH

OC H,

ocn,

NO,

! ο

so,.

CII CH

OC II,

CK) ₄

OCH,

CII CII

CII,
OCH,

OCH,

CH

CK) ₄

CII CII

OCH,

MV4-üimethoxystyryl) -4-methoxyben7.opyrylium-o- "it _ri - :. enzolsulfonat (melting point-" ¹ Il bi is made by reacting 2-IV4'-DimcthoxystyryDchromon with methyl-o-nitrobenzenesulfonat, -rl , ^g r " ^ - ⁴ " ^Dimcthox - ^vst - ^vr - ^vlM - ^mclhox > ^{bcn / n} P- ^vr y ^{| illm} - ° -n'trobcnzol.sulfonat and 4 5» "'-p-Methcws 4-methylbenzopyryhumperchlorat are used to produce e.ner Solution in 150 ml acetic acid canhydride The solution is heated for 100 minutes at 100 ° C. After the solution has cooled, it is poured into 10 percent by weight perchloric acid. The precipitates are filtered off and the dry reimping is again precipitated with dichloroethane and ether. 3.2 g of the product The yield corresponds to a yield of 41%. The product has a dark violet color in dichloroethane and a melting point of \ 7> to | S | C

3 C ltcn.

ivrvl · Ä) ml To what

a

Π ^ l · «-Phenylφ-meιh _ι n ^ sι ^ r ^ l | -4 - [(: ■ -p-metho \ ^ st ^ r ^ l-.V-phcn ^ l-6 ■ -mcllnl-4 ■ -ben / op ^ ranvlidL · n) nH · th ^ ί | -

benzopyrilium perchlorate

l \ Eriiulung Nr. 66)

CH-CH

OCH,

CH,

CH

NO.

SC),

C CH

OCII.

(K) ₄

CH,

; -OCH ₃ -,

ClO ₄

C = CH

"■ - OCH ₃

obtain. 2-jvMethoxvstvrvl-3

l3hv] ^ methrAvWthvlten2omrvZr "Methyl-o-nurobenzolsulfona

^, Phenl ^ methxvstrUMmethVltenzopv ^ iurn ^ rchK ^reagierI - ™ '

is described under e ». The product has a 'violeSe ^ color _in nlut- ,? ^ ", ^{Procedure as you} 190 _bjs 593 _c ^{e rarDe ln} iJichlorathan and a melting point of

23

24

j!) 2-p-Melhii \ yst \ ryl-Vplicnyl-4- [12'-plienyl-4-bcn / othiapyranylidcn! methyl '] - (S-inelhylbcnzop \ rylium-

perchloral

(Connection no.X5)

(KTI,

NO,

SO, ι

Cl I,

CII,

CH CII

CH II,

CK) ₄

CII,

ClC) ₄

■ - ' C)

cn cn

C) CH,

2-Phenyl-4-methoxyben / othiapyrylium-n-nitrobene / iilsulfonal is made from thioflavone and methyl-o-nilmbenzenesulfonate obtain. Using the same procedure as described under e). becomes the product produced in 62% yield. The product has a reddish purple color in dichloroethane and one Melting point from 170 to 177 C.

h) 2 - [(2'-phenyl-4'-benzopyranylidene) methyl] -3-phenylbenzopyrylium perchlorate

(Compound no 92)

OCH ₃

NO,

SO, "+

CH ₃

■ v j

CH

ClO ₄

5.5 g of l-PhenyM-methoxybenzopyrylium-o-nitrobenzenesulfonate. that from flavone and methyl o-nitrobenzenesulfonate is obtained, and 4 g of I-methyl-S-phenylbenzopyrylium perchlorate are used to give a solution dissolved in 150 ml of acetic anhydride. The solution is heated at 100 ° C. for 15 minutes. After cooling down the solution is poured into 900 ml of 10 percent strength by weight perchloric acid. Used for cleaning the product is reprecipitated unty the use of dichloroalhanum and ether. The product has a blue color Color in dichloroethane and a melting point of 128 to 134C. 3 g of the product are obtained (46% of the theoretical yield). Compound No. 93 (fluoroborate). the compound No. 94 (chloroferrate) and Compound No. 95 (nitrate) are obtained by using an ethereal solution of boron trifluoride jitherate. an aqueous solution of iron (III) chloride or dilute nitric acid instead of the 10 weight percent Obtain perchloric acid.

25 26

i) 2 - [(2 '- <! - Pheny1-p-methoxystyry1-4 -benzopyranylidene / methyl] -3-phenyl benzo pyryliuniperchlora I.

(Connection no.! I)

Y \ O,

- > -vc cw

I "

(KM,

OCI I,

'NO,

• SC),

O,

cn,

CK) ₁

CH

C C OC H,

ClO ₄

2 - (<i-phenyl- p-methoxvstyryll-4-methmynenzopyryliiim-o-nitrobenzenesulfonate. that from 2- (■ «-phen \ 1-p-methoxvstvryllchromon and methyl - o-nitroben- / olsulfonat is obtained, reacts with 2-methyl-3-phenylbenzoprylium perchlorate using the same procedure as described under h). The reaction product is obtained in 43% yield. The product has a purple color in Dichloroethane and a melting point of 15S to 163 C.

According to the invention it has been found that the compounds listed in Table I sensitizers which are the photoconductivity and the spectral characteristics of polymeric photoconductors, such as poly-N-vinyl carbazole. brominated poly-N-vinylcarbazole. Polyacenaphthylene can improve. These polymers, with the exception of the brominated ones Poly-N-vinyicarbazoles. will be sent to mcIi known processes. The brominated poly-N-vinylearbazole can be made by the following process:

To a solution of 20 g of poly-N-vinylcarbazole in 450 m! Chlorobenzene becomes 18.44 g of N-bromosuccinimide and 0.173 g of benzene peroxide added. The mixture is stirred for 2 hours at 80.degree heated and then poured into methanol, whereby a white polymer is obtained. The polymer is dissolved in chlorobenzene for cleaning and poured again into methanol. The so obtained as a precipitate According to the elemental analysis, pure polymer has a halogen content of 29.87 percent by weight, which is the calculated value of 29.44 weight percent for the monobromo substituted product of the poly-N-vinylcarbazole. This shows that the polymer obtained is a is monobromo-substituted product. The degree of bromination varies depending on the reaction conditions between 50 and 200 mole percent.

The new sensitizing dye containing at least one compound from those listed in Table 1 Group, w ith a small amount of 1 solvent, how /. B. dichloroethane '. Melhylenehlond. Chloroform, or a mixture of these substances this solution becomes the solution of the above Photoconductor added. The preferred added one Amount of the sensitizing color ^ olTs' heti.iui like is given above. 0.01 to 3.0 weightless 100 gauges of the photoconductor. Advantageously is the share in the sensitization 0.1 to 2.0 weight parts on HP weight parts Phoiolleiter.

t f ^'U' u ^Flerstcllun r "Jtr photoconductive insulating layer is a solution of the photoconductor and the sensitizing dye in a solvent üeeimieten on the electrically conductive f rough after customary per se manner / B by Aiif-

spray through by coating with a knife a vortex application process etc .. aufnetrasien and then forming a homogeneous photoconductive insulating layer on the electrically conductive one Trager dried. Usable solvents

so are benzene. Toluene. Chlorobenzene. Dioxane methylene chloride. Dichloroethane and mixtures thereof. Said solution can be used with suitable plasticizers and or organic colloids are added to the flexibility and strength of the

Improve photoconductor. Iced plasticizers are chlorinated diphenyl. Dimethyl phthalate. D. ethyl phthalate and octyl phthalate. Suitable onzamsche Colloids are natural and synthetic

^ RI ^arze - u ^{Vle 2} - ^{B "Phen} olharz modified resin.

Phenolic resin. Polyvinyl acetate polyvinyl butyral. Polyvinyl cinnamate and polycarbonate resin. Suitable materials door the electrically conductive tracers "can are prepared from any substance that the requirements on the device of the electrical

photographs correspond, such as B. metal plates or glass plates with an electrically conductive layer. Had or sheets of electrically conductive resin or with vapor-deposited thin metal layers.

28

-rid.
and
: nen
izie
how
on
egg"
.toil
of

the
of
Loach
Vuf-
: rch
jnd
"conduct-
ittel
len-The

hen
of
igslai.
gache
• tes
, Iyete
3nd the
redden
W.
in

If paper is used as a carrier for the photoconductive layer, a pretreatment of the paper / to prevent penetration of the t ' ^! over / ugslüsuiiü appropriate. A transparent electrophotographic plate, sheet or film can be formed with a transparent support. After an electrostatic charge, ie after the layer has been charged positively or negatively by means of a corona discharge. the layer becomes photosensitive.

The reproduction of images will be carried out after the Electrophotographic process carried out as follows: W; mi the photolcilende layer through a Corona discharge has been charged. the wearer will have the sensitized layer under one Original exposed and then in a known manner with a Har / powder. colored with soot is. ihstiiubt. The image now visible can easily be wiped off. However, it can also be fixed to about 120 ° C. by means of heat. From the positives Positive images are generated from models, which are characterized by good contrast.

The invention is now shown in the following! '. Design examples further explained.

example 1

1 g of polyacnaphthylene and 0.6 g of chlorinated diphenyl as a plasticizer are dissolved in X ml of chlorobenzene. 0.5 ml of dichloroethane is added to the solution given the 0.006 g of a sensitizing dye which consists of a compound with the number given in Table 1. The solution is applied to an aluminum plate using a fluidizing process dried to form a layer 7 microns thick. After the aluminum plalie has been provided with the layer. will do plate by means of a corona discharge with a charger, which maintains a tension of about 6000 full in the dark, negatively charged, under one positive prototype arranged and with a 100 W tungsten lamp exposed with an illuminance of 50 Lu and then with a developer in dusted in a known manner. The developer consists of a toner and a carrier material. The toner is made of low melting point polystyrene. Rosin and carbon black. The toner is mixed with a carrier material, so that the toner then by static electricity with one to charge opposite to the charge generated on the plate. A positive image is created and fixed by gently heating. In Table 3, the optimal exposure values are in units of Lux seconds specified.

Link. number

No

9
15th
16

Tabel ι 3 Optimal exposure
iLuxsekl - i 200,000 320 300 75 180 110

\ ei hinilutiü. number

IX
33
35
41
42
51
52
53
54
S.
60
65
71

103
105
UW
IK)
III
112
113
116

Optimal exposure Il uvsek)

65 135 480 105 320 380 140 2 ¹ X) 140 130 175 140 180

70 150 100 120 130 180

70 170 120

I 15

Example 2

I g Pol \ -N-vin \ lcarha / ol. chlorinated diphenyl uiu: 0.006 g of a sensitizing dye. the one from one Connection with d'T in Table I in each case given Number, are dissolved in 10 ml of dichloroethane to prepare a solution. You The solution is applied to an aluminum plate using the knife application method and dried wherein a layer having a thickness is formed An electrophotographic image is made as described in Example 1. generated. In the table are the optimal exposure values in units specified by lux seconds with which the original images are exactly reproduced.

·] lung. number Table 4 No j Optimal Belichuin
I (lux-sec)
i 1 i
20,000 -) '50 Λ
_ ■> j 220 4th j 60 5 ! 70 6th '' ■ 11 7th i 44 8th I 26 10 i 44 II I 48 ! 160

29

continuation

Wil.iiulii

Nuhiimlm

(iplini.ilc BcliJ

I I IHM'kl

220 90 75 2S 36

115

180

1 44 36 40 60

120 36 50 30 46 90 5 44

4 X 7_ ^

5 X 34 35 70 30 26 28 JS 20 24

44 44

44

74 56 20

τ τ

60 IX 46 50 24 19 17 54

U [IiIiIi, ik-Ik-liL-liiiiii Uli: Νιιπιπκτ ll IIVNL-kl S7 42 8S 25th 89 28 90 30th 91 140 92 18th 93 20th 34 23 95 40 96 66 29 24 98 230 99 460 100 50 ΙΟΙ 36 102 115 103 36 104 6X 105 19th 106 120 07 5 X K) X 76 09 46 ίο ^: 36 I I 20th 112: 42 13th 4X 14th 54 15th 54 16 52 17th 64 IX 50 19th 135 20th 90 21 30th 2X

From table 4 it can be seen that ilii · m Awareness raising the I'liolnleillahiiiiken Pol \ -N- \ inylcarhazole improve.

Example 3

I ti hromierles Poh -N-vinslearba / ol (monohi substituted product). 0.5 g polycarbonates /, t chlorinated diphenyl and 0.002 g of a sensitizing dye identified in Table I. dissolved in a mixed solvent of chlorobin / ol with 2 ml of diehlorethane. the sunu is applied to an aluminum plate using the knife application process and gctrocl being a layer with a thickness of 14 Mi!

is trained. On this document, w is described in Example I. a clcktrnpr graphic image generated. In table 5 sine optimal exposure value in units of

Seconds with which the originals can be accurately reproduced.

31 table

i! Numnii-τ

None 1 2 3 4 5 6 7 8

Il 12 13 14 15 16 17 IS v> 20: i -11

23 24 25 26 27 2S 29 30 31 32 33 34 35 37 38 39 40 41 42 43 44 45 46 47 4S 49 50 51

I tpnm.ile HcIilIiIiiiiu

SOOOO 75 280 67 44 20 26 18 30

4 (1 120 400 I.

75 25

2 X

135

23

410 340 1X0

40! 3d

60 3 (κ ι 100

4S I 320 270

30 26

440

2X 32 75 105 170 42? 2 35 50 4X

45

60

μ. ΝιιιηηκΊ Opiinuik · HcliL-hiunt
ll.iivsckl 53 19th 54 42 55 230 56 26th 57 22nd 58 24 59 23 60 26th 61 36 62 130 63 190 64 44 65 26th 66 20th 67 46 68 75 69 115 70 42 71 IS 72 20th 73 48 74 III) 75 115 76 70 77 44 7S 35 79 75 XO 50 Xl 145 Χ2 35 X 3 20th Χ4 19th X 5 17th X 6 34 Χ7 34 XX 20th 89 20th 90 25th 91 100 92 15th 9 3 17th 94 16 40 96 52 97 26th 98 : 180 99 140 100 j 46 K) I 36 102 ; 58 103 20th 104 '34

continuation I IplMll.lli. ¹
| [u 113! Hein hl in
»• Mil IIU. NlMUMKT 114 ^! KO 106 115 44 107 116 40 108 117 23 109 IIS 26th in the 17th III 26th 112 28 40 44 28 44 36

\ e r h ι π 111111 μ number

120
121
122
123
124
125
126
127
128

34

Oplini.ilu · Mclichliinp Il iivm.1i

105 52 26 21 15 25 17 14 Il 13

From Table 5 and the I-i μ. I to 4 lsi crML-htlirh that the new Sensibilisieruiiüsfarbslolle > o the PhololeJtfiihi-ity and the spectral characteristic values \ mi brnmicrtem Polv-N-vmNlcarba / ol improve.

For this. 3 sheets of drawings

Claims (2)

Patent claims: 1. Electrophotographic recording material with a photoconductive layer containing poly-N-vinylcarbazole, bromicrtcs poly-N-vinylcarbazole or polyacenaphthylene as the photoconductor and a benzopyrylium or benzothiapyrylium salt as the sensitizing dye, characterized in that the photoconductive layer
the formula p a sensitizing dye worm R equals a group of the form! R- R ₁ . Rs R.,
O H, equal to a hydrogen atom, a phenyl. Styryl. p-Vlethoxystyryl-. 3,4-diniethoxystyryl-. ι / - Phenvlstvrvl-. ,, - Phenyl - ρ - methr.v.slyryl-. ₍ ; - For \ 1 ■ - "'- ätlienyl- or ./ - Phenyl - ■' - f'uryl-"'-älhenyl-Gnippe. R,. R _4. R _h and R "equals a hydrogen atom or a Phenyl group. H, and R- equals a hydrogen alom. A methyl or a phenyl group. R, equals a S hydrogen alom. A phenyl- .styryl-. P-Vlelho.xy styryl-. 3,4-dimetlioxvstyryl-. A-phenyl-p- methoxystyryl-., .- l'uryl - Γ-ätlicnyl- or ■ / - I'hcnyl - / .'- füryl - '/' - äthenyl-Ciruppe. R ₁ , equal to a hydrogen atom or a p-metho. \ yphenyl group. equals a perehloral-, Fkioborat-. ("chloroterrate, chlorozincate or nitrate ion and X is equal to a U- or S-Alom. 2. Recording material according to claim I, characterized in that the photoconductive Layer on KX) parts by weight of photoconductor between 0.01 and 3 parts by weight of sensitizing dye contains. Layer that acts as a photoconductor poly-N-vinylcarbazole bromierles poly-N-vinylcarbazole or polyacenaphthylene and contains a benzo · pyrylium or benzothiapyrylium salt as sensitizing dye. It is known that by adding a so-called sensitizing dye, the photoconductive wedge and can improve the spectral characteristics of the above photoconductors, conventional sensitizing dyes are dye compounds such as triarylmethane dyes, xanthene dyes, thiazine dyes or acridine dyes. However, one disadvantage of the conventional sensitizing dyes that they the photoconductivity and the spectral characteristics of available photoconductors are not able to improve to a completely sufficient extent. Except for a strong photoconductivity ;;!: "'' And the Photosensitive wedge to visible light, the electrophotographic technique requires one high electrical. Contradiction of the photoconductive materials in the dark, common sensitizing dyes increase photoconductivity, but disadvantageously increase dark conductivity. t-int high dark conductivity of the photoconductive materials isi not wanted because such a one Loss of electrostatic charge in the dark. The object of the invention is. an electrophotographic Recording material with a high photoconductivity and sensitivity to photography visible light and a high electrical resistance in the dark / ur. The subject of the invention is based on an electrophotographic recording material mil a photoconductive layer that acts as a photoconductor Poly - N - \ inylcarbazole. brominated poly-N-vinyl carbazole or Polyacenaphthvle ;: and as a sensitizing dye contains a Henzopyrvlium or Benzothiapyryliumalz, and is characterized by that the photoconductive layer has a sensi bilisierunusfarbsioff of the l-ormel R, glek Ii R, (irup ( de ι R. MHIC R. R ₁ ic where R jiner r R. R- , X ) The invention relates to an electrophotographic "drawing material having a photo-capable R.,