DE1522542A1 - Process for the optical sensitization of inorganic photoconductors - Google Patents

Description

Process for the optical sensitization of inorganic

Photoconductor

The invention relates to a recording and reproducing material containing a spectrally sensitized inorganic Contains photoconductor substance, and a method for sensitizing this substance.

Inorganic photoconductor substances are, for example, the oxides, sulfides and selenides of zinc, cadmium, mercury, Known as antimony, bismuth, and lead.

Both inorganic and organic compounds are suitable as sensitizers for inorganic photoconductor substances. For example, for the sensitization of photoconductive zinc oxide, mercury sulfide, lead oxide and lead iodide or organic dyes such as triphenylmethane derivatives, sulfonphthalein and cyanine dyes of various structures has been proposed.

909837/12 01 AG 118

It has now been found that organic compounds which can form a colored chelate complex with the metal ion of an inorganic photoconductor, optisoh sensitize the inorganic photoconductor.

In particular, it has been found that certain classes of ohelate-forming compounds optically sensitize photoconductive zinc oxide in the absorption region of the chelate formed. line entered · Htsao eelcher connections is duroh dl · allf «n» iae form ·! (I) described t

* C-

£ -NH-H-C-

This formula says

£ for a hydrogen atom and an alkyl atom, e.g. one Alkyl radical with 1 to 5 carbon atoms »

2 or 2 · the missing links, necessary to form a 5- or 6-glledrigen nitrogen-containing ring ·· notwan dif are mean. This 5- or 6-ring can contain one or more heteroatoms in addition to the nitrogen atom, for example oxygen, nitrogen, selenium or sulfur and thus form a heterocyclic ring, for example from the ihiazole series (e.g. thiazole, 4-methylthiazole, 4-methyl-5 -carbethpxythiazole, 4-phenylthiazole, 5-methylthiazole, 5-phenylthiazole, 4- (p-tolyl) -thiaz <bl, 4- (p-bromophenyl) thiazole, 4,5-dimethylthiazole, 4,5-diphenylthiazole, 4- (2-Ihienylthiazole, 4- (m-nitrophenyl) -thiazole) or from the benzothiazole series (e.g. benzthiazole, 4-chlorobenzothiazole, 5-chlorobenzothiazole, 6-chlorobenzothiazole, 7-chlorobenzthiazole, 4-methylbenzthiazole, 5-methylbenzthiazole, 6-methylbenzthiazole -

thiaeol, 5-bromobenzthiazoi, 6-bromobenzothiazole, benzthia- _{A fl 1ia} 909837/1201 ₉

AII - 2 - _BATH

«Ol-6-8ulfonic acid, 4-phenylbenzthiazole, 5-phenylbenzothiazole, 4-methoxybenzthiazole, 5-methoxybenzthiazole, 6-methoxybenzthiazole, 5-iodobenzothiazole, 6-iodobenzothiazole , 4-i.thoxybenzotniazole, 5-ethoxybenz , 5,6,7- ffttrahydrobenzthiazole, 5,6-dimethpxybenzthiazole, 5,6-dioxyaethylenebenzthiazole, 5-hydroxybenzthiazole , 6- hydroxybenzthiazole, 5,6-dimethylbenzthiazole) or from the laphthothiazole series (e.g. haphtho [^ , 1 - d] thiazole, naphtho [Γ, 2-3] thiazole, 5 -Me thoxynaphtho pt 2-d] thiazole, 5- Xthoxynaphtho [j, 2-d] thiazole, Θ-Μβ thoxy naphtho \ 2 , 1 -cQ thiazole, 7-methoxynaphtheno [7,6-d] thiazole from the thionaphtheno U, 6-d | thiazole series (e.g. 7-methoxy thionaphtheno [7,6 -d] thiazole), from the thiadiazole series (e.g. 4-phenylthiaiia-sol), Mt der Oxazolrtih · (iB 4-lUthyloxaiol, 5-Mtthyloxa- nol , 4-Ph "nyloxaeol, 4,5-Diph * nyloxazole, 4-Ithyloxaeol, 4,5-DlJithtyloxaeol, 5-Ph" nyloxa "ol), also the benzoxazole (eg benzoxazole, 5-chlorobenzoxazole, 5-methylbenzoxazole, 5- phenylbenzoxazole, 6-methylbenzoxazole zol, 5,6-dimethylbenzoxazol , 4,6-dimethylbenzoxazol, 5- ¹ ^ e thoxybenzoxazol, 6-methoxybenzoxazol, 5-hydroxybenzoxazol, 6-hydroxybenzoxazol ), except for the naphthoxazol series (e.g. naphtho [?, 1- d] oxazole, Haphtho Q, 2-d} oxazole), the 8elenazolreihe (eg aue 4-methylselenazole, 4-Phenylaelenazol) from which Benzaelenasolreihe (eg Benzaelenazol, 5-Chlorbenzeele- Nazole, 5-Hethoxybenz8elenazol, 5-Hydroxybenzselenazol, 4 , 5,6,7-tetrahydrobenzeelenazole) , from the naphthosele- nazole series (e.g. naphtho [5,1 -dj selenazole, naphtho Q, 2-

AQ 118 - 3 -

909837/1201

eefenazole), from the 2-quinoline series (e.g. quinoline, 3-methylquinoline, 5-methylquinoline, 7-methylquinoline, 8-methylquinoline, 6-chloroquinoline, 8-chloroquinoline, 6-methoxyquinoline, 6-lthoxyquinoline, 6-hydroxyquinoline, 8-hydroxyquinoline etc.), from the pyridine series or from the quinoxalineine, from the quinazoline series or from the 1-phthalazine series, from the 2-pyridine series (e.g. Pyridine, 5-methylpyridine, 3-nitropyridine), from the benziaidazole series (e.g. 1-ethylbenzimidazole, 1-phenylbenzimidazole, 1-ethyl-5,6-dichlorobenzimidazole, 1-hydroxyethyl-5,6-dichlorobenzimidazole, 1-ethyl-5- chlorobenzimidazole, i-ethyl- ^ iö-dibromobenzimidazole, 1-ethyl-5-dhlor-6-aminobenzimidazole, 1-ethyl-5-chloro-6-bromobenzimidazole, 1-ethyl-5-phenylbenzimidazole, 1-ethyl-5-fluorobenzimidazole, 1-ethyl-5,6-difluorobenzimidazole, 1-ethyl-5-cyano-benzimidazole, 1 - (^ - acetoxyethyl) -5-cyano-benzimidazole, 1-ethyl-5-chloro-6-cyano-azimidazole, 1-ethyl-5-fluoro 6-cyanobenzimidazole, 1-ethyl-5-ebetylbenzimidazole, 1-ethyl-S-chloro-e-f luorbenzimidacol, i-ethyl-5-carboxybenzimidazole, 1-ithyl-7-oarboxybenzimidazole, 1-ithyl-5-carbethoxybenzimidazole, i-Ithyl-7-carbethoxybenzimidazole, 1-ethyl-5-eulphamylbenzimidazole or 1-ethyl-5-N-ethyleu] pkanylbenzimidazole.

The following list contains a division of Hydraeon compounds referred to in the examples.

AO 118 - 4 - BATH C

909837/1201

.- ¹ ^ ₁ -NH-N

NH-N = HC-

C "

-CH = N-NH-

0 "" "TI *

⁴ ' ²

. ZnSO

HC ' ^x C-NH-N = CH- ^ SC N

C-NH-N = CH-

-NH-N = CH-

NH-N = CH-

si ti — Si — On—

A-O 909837/1201 - 5 -

12th

13th

H.

15th 16.

17th

18th

19th

20th

C-NH-N = CH-

HC-C N

-NH-N = CH-

H ₃ C- C__ N

L_N -NH-N = CH-

HO ₃ S- -C-NH-N = CH- ^ ^N >

S.

O -CH = N-NH-CI

NH-N = CH-

NH-N = CH-

-NH-N = CH-

NO,

A-G 909837/1201 - 6 -

21st

Ν0 _Λ -NH-N = CH- f * ^N -ι-CH

Li

Li

22nd

NO,

23 CH

24. ' ^Y N

0-NH ₁ -N = Cj ^ "> |

-NH-N = CH-

H, C-

26th 27 26th 29 30th

O-

^ i.

.-NH-N = CH-

^ ^S > -NH-N = CH- f ^ ^N > -

0-NH-N = CH- ^ X

909837/1201 7 -

31.

32. 33. 34

35. 36. 37.

NH-N = CH-

Ö-CHoN 7

Br-

_V mi CO

Vj-NH-N = CH- ^> -C -N [^ J

-N = CH- < ^N ^,

NH-N = CH-f * ^N - ^ - CH

Ü "

▲ -a ns

909837/1201 - 8 -

• ν

The preparation of hydrazones 1, 2 and 5 is ταη

In 3.1. Geldard, F. Lions, / J.Am. Chem. Soc. 84, 2262-3 (1962)

described. rs * The manufacture of the Hydrazone 23 is described by »■ Λ ϊ. Linons, K.V. Martin in J. Am. Chem. Soc. 80: 3858-65 (1958).

¹⁰ The hydrazone 4 can be prepared as follows werdeni

0.145 moles of Hydrazone 1 are boiled in 350 ecm acetone dissolved. 0.15 mol of zinc sulfate-i-water are dissolved in the resulting solution and poured into 100 ecm barrels with stirring added.

The solution is cooled. The Hiederschlag formed is abgenutsoht, once with cold Lasser and twice gewasohen with ethanol and then dried at 10O ⁰ C. Analysis ι

calculated ι C 34.2 found! C 33.92

H 3.37 H 3.70

N 14.52 N 14.11

S 8.31 S 8.87

The hydrazone compound 5 is formed by heating the compound in an oil bath at 220 ⁰ C for 3 hours.

The other hydrazones can be produced according to the following common procedure!

One dissolves or disperses 0.025 lol of the corresponding hydrazine derivatives in ethanol and mixes this solution with a solution of 0.025 mol of the corresponding aldehyde derivatives in 25 qcm of ethanol. The reaction mixture is now AG 118 - 9 -

BATHROOM 0RK5INAL

909837/1201

CM

LO (N (N UO

Ir.

Refluxed on the water bath for 30 minutes. After cooling, the precipitate formed is filtered off with suction, washed with ethanol and dried. In most cases it is the product is so pure that further purification is superfluous. Only connections 20 and 22 become recrystallized from ethylene glycol monomethyl ether. The following table contains the starting products that Melting points and the analytical results of the hydrazones prepared according to the above Torschrift.

Aldehyde ! Melting

Hydrazine derivatives

| point

Ueaente

reotw found

net

the

10

NHRH,

H ₉ N-NH-C- ^ N

" AROUND

ο

H ₀ N-NH-C 1 -C H 2 h ti

N C-CgH

NH J-NHNH,

γΎί

L · JL -J-NHNH

NHNH,

t J-CHO N

195

IL J-CHO N

I ^ J-CHO N

Q-CHO

266

210

260

t J-

> 26O

CHO

CH.-

220

CQ-

244

-q

909837/1201

- 10 -

H
3

C.
H
3

C.
H

C.
H

C. H

67.53 4.45

59.80 3.92

11.46

.25

4.28 11.42

65.80 4.64

67.50 4.42

68.50 4.94

72.30 4.35

67.49 4.25

60.02

4.16

11.11

64.18

4.44

11.13

65.56 4.82

67.66 4.60

68.25 4.89

72.07 4.64

BAD ORK) INAL

12th

13th

14th

15th

H ₉ N-NH- w ^ ^S >

° 6 ^H 5

H ₂ N-NH- j < ³ ^ - COOC ₂ H ₅

N.-CK,

HgN-NH-

-OH

rf ¹ - ¹⁸ -Γ γ

N i-

17th

19th

20th

ί N

H ₂ N -NH- ^ -N

ϊϊ Ϊ-SCH "- <* - >>

co

NHNHj

NH-NH,

H ₂ N-

NH-

NO, CHO

CHO

CO

C-

CH, -Ϊ J-CHO ^J N

CO- OHO

Cl

-CHO

-CHG

F J-CHO

240 C. 69.10 H 4.24 3 9.70 260 C. 53.60 H 4.63 3 04/11 229 C. 55.25 II 5.26 S. 10.52 257 C. 60.00 H 4.70 3 9.40 > 260 C. 46.70 H 3.00 S. 19.16 210 C. 55.50 H 3.98 S. 19.60 210 C. 67.50 H 4.42 215 C. 72.30 H 4.38 250

69.46 4.27

10.09

53.96 5.08

10.63

55 * 71 5.45 10.61

59.63 4.66 9.19

46.56

3.25 19.38

54.92 4.01 19.28

67.69 4.36

72.15 4.48

A-G - 11 -

909837/1201

²¹

Ui-

UO,

^r * ^J 2

ΠΛ

25, - .r

ο 5

27

H ₁ -

ET TTTT ^ - * "

As

i - <* 2

Π 230

-CHC

260

210

, J-CHO

233

IT

CK, -IL -i-CHO

• i

H
3

C.
H
3

C.
H
S.

ί ³ '

^fie:

56 .60 3 .64 9 .45 60 •? 0 3 .47 8th .53 69 .80 4th .65 9- .30 70 , 80 4th 50 8th, 97 71. 40 4th 55 8th. SS

53.93

3.86

T-T

i C! 74.00

H
3

236

H
S.

U _ _,

j ϊ ΐ!

; {s ij

! 205

4.43

7-8

65.30

4.76

10.89

G (66.20

5.20
1C.40

59.63 3.51 8.85

67.82 5.62 8.46

71.09 4.51 9.25

71 .62 8.32 "

74.07.451 8.00

65.60.

4.58

10.88

66.24

5.20

10.37

J

909837/1201 BAD

HHHH.

MB- f

/ J. 33 i _{HF m} ^ S

Γ ² " ^l " 3

37

hi j

TT

ν »

O-

260

.J-GKO

> 26O

CH, - i!

230

250

i ^H

54.37 54.40

3.73

13.17

65.80
4.06

j C 55.70

50.10
3.06
8.92

51.50
3-49
8.58

3.35 13.25

65.72 4.39

208

-CHOi

IT 174

-CHOi

H
S.

C.
H
S.

3.18
7.82

65.30

4.76

10.90

64

5.34

50.32 3.15 9.16

51 ^], 3.67 8.60

55.90 3.40 7.68

65.56

5.06.

11.32

$ 63 - 6 5.39

A-G- 118

- 13 -

SO 983 7/1 20

ί ί,

uiTxo second group constituted by the following general Porael (II)

describedί

Ό - NH - N = CH

r ⁱⁱ⁰ 2

Z 'has in this formula the ^ spawning soda as in iPormsl (Γ)

3u the allsomainöß Jormol (II) oaion Followondo Bsijpiai 3orianrit *

Yerbindun ^ 3Qi

ndur ^ 39 3

-ITO,

i i:

Schinelapunlc-t 225 C

lcc 254

Connection 40s

Yerbindu: i3 41 3

\ - ^ - '^ - HH-IT = C H-

.D

UlWj,

, -CII ^ -S- ^ ¹ X -2IH = Ii-GH- .- / ^ -30 - '

3cxus8lzpunkt 239 ° C

j.i-

222 ⁰ G

.Door dl3 rijdracono to dar all ^ saolnen Morsel (XI)

• u .ij.Acr.!, Oaunj of 0.1 LIoI ΰίηοα

- W C3 0 O / / ί Γ. Ü i

the allrjoaoinon

BAD OR] -GIMAL '

¹ ■ is-

u - G - 3H - HHo

in üor 3 * dio glaiclio meaning τ »1β obon beochriobon, in 50 qQzi abaol ^ riasa alcohol ^ _{ird its solution of O f} 1 mol

in -50 q.c.m aooolutom ethanol

rsciilas · 2ao Rcaktionageni30; i Tiird Ώ-αη 15 liinuton long aa ^ aaaerbade Im RUckfluQ oriii't.r; ? λζιΙ aaaCiilio.'Sojid goliüiilt. 2cr arhal ^ ano Hiedarochlag

siiQl. ^ - 'ibil.Io ^ .urr connections is through ίίηα 2οκ: βΙ (III)

- -J

- / S-UQ ₀

SJ ^: i. ; ^- 5 1: 3. üIdijOZ ΓαΙΙο dia ~ Iciche meaning «la in dar

Λ1.Ί D3ir; pialQ for aio allgasoiiie Pormsl (III) aoion following

! .; Melting point> 260 ° C

~ Q

: ~ "2 narrow spur; > 260 ° G

3 0 3 3 3 7/1201 lad orksimal

The following production process applies to the compounds corresponding to the general formula (III)

0.1 mol of a hydrazine of the general formula is added to 0.1 mol of S-nitrothiophene ^ -carboxyaldehyde (Dokl. Akad. Lauk. SSSR 83 (1952) 85-8) dissolved in 160 qcm of ethanol

- NH - NH ₂

added.

In this formula, Z ^{1 has} the meaning described above. The hydrazine is used dissolved in 100 qcm ethanol. Hachdem the reaction mixture was heated for 1 hour on a water bath e at reflux, is cooled, the resulting fiederschlag filtered with suction and washed successively with ethanol and Ät.htr.

the general formula (IV) t applies to a fourth group

JH _n -C

f JT-NH-CrS • CH ₀ -CH ' ^ ^

^l 2

Z ¹ has the same meaning here as in the general formula (I).

A typical example of the general formula (IV) is the following compound!
Connection 44t

-NH-N-CH-CH ₂ -B-Ch ₂ -CH ₂ -S-CH ₂ -CH-N-NH-

A manufacturing specification for this connection gives

_i4Q 909837/1201

118 - 16 -

θΑϋ OnKi ■; ·

F. Lions, K.V. Martin in J. Am. Chem. Soc. 80 (1958) 3860.

A fifth class of suitable compounds has the general formula (V) t

The compounds 4-5 »46 and 47 _f in which R ^ can be hydrogen, methoxy and methylthio, are according to that of FA Snavely, WS Trahanovsky and FH Suydam, Inorg. Chem 3 (1964) 123 described procedures.

A sixth class of suitable compounds is described by the general formula (VI)!

R ₀ M - N - / V

R ^ Ni -N-. ³ H.

Mean therein

R ₂ and R, is hydrogen or alkyl, for example methyl or they are required together for a Atomydas is to close a homocyclic ring, for example a (GHP) group;

Z ¹ has the same meaning as in general formula (I) I.

Examples of compounds according to the general formula (VI) ^are 909837/1201

AS 118 -17-

Compound 481

Melting point 216 ^° C

manufactured according to F. Lions, K.V. Martin, J. Am.Ohem.Soc, 80 (1958) 3858.

Connection 49 *

H.

, CrNi-NH-

Melting point> 260 ° C

manufactured according to B. Chiswell, F. Lions, Inorg. Chem. 3 (1964) 490.

A seventh group describes the general formula (VII) ι

^ C = N-NH-

C = O
^R 5
in which R- and R ^ for alkyl, for example methyl, aryl,

for example phenyl and Z 'has the same meaning as in general Formula (I) has.

A-G 118

- 18 -

bad c ~ yy: .- i _: \\.

909837/1201

Connection 50 i Compound 511

.-C = N-NH-

“V

Connection 52t Compound 551

C = N - HH-

CeO H ₇ O-

Compound 541

link 55 1

C = Ji-NH-

Connection 56ι

<Τ ~ *> - O = Jf-NH-

A-G 118

Melting point HO C

Melting point 178 ° C

Melting point 166 ° C

Melting point 169 ° C

Melting point 182 ° C

Melting point 190 ° C

Melting point 222 ° C

- 19 -

909837/1201

Compounds 50-55 are prepared according to the given example of Ohiswell, F. Lions, MI Tomlinson provision. The connection 56 can be established analogously to the connections 50-55 .

An eighth group has the general formula (VIII) t

The compounds 57, 58, 59 and 60, in which Rg stands for hydrogen, methyl, carbethoxy and benzoyl, are based on B. Eistert, H. Selzer, Ohem Ber. 96 (1963) 3U-319.

In addition, compounds which form chelates with zinc ions and contain an aromatic nucleus which, in the o-position to a hydroxyl group, contain a -CB> N ~ grouping, a -CO-NH-NsCH grouping, an -N = N- Carry aryl group or a -CH = NN = CH-aryl group, as well as ( chtlat-forming compounds which carry tine azo group in the o-position to a carboxyl group.

Examples of such azo compounds can be found in the German patent application entitled "Process for Electrostatic Image Development ", filed concurrently with the present application.

AG 118 - 20 -

909837/1201

Connection 61 ι

Melting point> 260 ° G

is made as follows!

0.1 mol of salicylaidazole is added to 0.1 mol of 2 (o-aminophenyl) benzimidazole (Ber. 32,1465) dissolved in 10 ecm of ethanol. The reaction mixture is refluxed on the water bath for 2 hours. The resulting precipitate is filtered off with suction and washed with ether. Melting point τ 26O ⁰ G,

Connection 62 «

3-GH ₀ -CO-NH-N = CH-

2 |

^ ^H melting point 213 ° 0

HG ^{ά X} S-CH ₂

-GO-NH-N = GH-AA

The sensitizing compounds are preferably used in dissolved form used for the sensitization of the inorganic photoconductor, the photoconductor in the normal case is used in the form of a solution or a dispersion in a binder. The sensitizing compounds can be mixed with the photoconductor, e.g. zinc oxide, before processing, for example dissolved in dimethylformamide will. The compound is then absorbed on the photoconductor grain and can be used with those offered by the photoconductor Metal ions form a complex. The photoconductor treated in this way is then coated with a suitable binder

mixed, after which the mixture produced in this way is transferred to an AG 1 18 21 -

909837 * 71201

suitable support can be applied.

The sensitizing compound can also be used as in Beiapiel 2 described in a complex form. The treatment of the photoconductive substance with the sensitizing Connection in the non-complex form is not a condition, but should be considered a preferred embodiment.

The sensitizing compounds according to the present invention are preferably used in conjunction with an acid applied to ensure the presence of metal ions. According to a preferred embodiment, the acidic ones described in Belgian patent 612,102 Compounds used that increase the dark resistance of the photoconductive zinc oxide. Otherwise the spectral

Sensitization of the photoconductive layers according to of the present invention is also modified by sensitizing compounds other than those described herein will.

Such combinations with other optical sensitizers Connections will be of interest if the photoconductor layer covers the entire area of the visible Spectrum should be sensitive, for example in the case of a photoconductor layer that is used for the production of multicolor products is determined.

The ratio of the photoconductor and the sensitizing agent Compound can vary within wide limits and is dependent on the desired effect. The sensitizing ones

AG 118 - 22 -

909837/1201

Yerbin

Applications can, for example, in a range from 0.001 to 0.5 wt .- ^, based on the photoconductor, used herds. Particularly suitable for described herein dae method eeneibilisierende compounds are listed in the Example 3 given in Table 2 below. The majority of these compounds have a sensitizing effect in the range of 440-5-5 mn.

In a known application of xerography, photoconductor binder combinations are used which exhibit a specific electrical resistance of at least 10 ohm.cm.

The quantitative ratio of photoconductor substance and binder can vary within wide limits. A weight ratio of binder and photoconductor of 111 to 110 is preferred here. The bead of the photoconductor layer can be matched within wide limits to the intended use of the recording material. Bit photoconductor layers with a bead of 1 - 20 ^ and preferably 3 - 10 / * are obtained. Too thin layers have inadequate insulation properties, while layers that are too thick require longer exposure times.

Suitable binders for inorganic photoconductors are described, for example, in Belgian patent 612 102 and British patent 964 885. You photoconductive layer that contains photoconductors, embodying the present invention
AQ 118 - 23 -

909837/1201

can be suitably sensitized, photoconductive Contain substances with the erfindungegemäflen Compounds cannot be sensitized. These include, for example, monomeric organic photoconductors, as described in Belgian patents 585 507, 585 555, 587 301, 585 450, 587 794, 589 239, 594 794, 595 696, 597 616 and 625 683 are described. This also includes those in the Belgian patent 599 627 and in British patents 964 871, 964 877 and 964 875 organic polymeric photoconductors described. In addition, dt Photoconductor layer also contain additives that are suitable for certain coating techniques have proven effective. E.g. pigments (see Belgian patent application 609 056) or also compounds that affect gloss and / or viscosity, compounds that affect aging and / or the Prevent oxidation of the layer or compounds that improve its thermal stability. When choosing, the Preferred compounds which reduce the dark resistance of the photoconductor layer the least.

The sensitized photoconductor material according to the invention can be produced by one of the known processes. So can the photoconductor mixture with a suitable Apply solvent or dispersant for the binder to a base using one of the known techniques. Of the It can be applied, for example, by spraying on, by spinning, in the immersion process or with the aid of a doctor blade take place. The support is in view of the technology of exposure, recording, development and / or

AG 118 909837 / Jfcpl

of the transfer printing selected, after which the recording material should be processed.

for xerographic use, a support is preferred which has an electrical volume resistance which is lower than that of the layer material. For example, the Belgian patent documents 602 794, 612 102 and 610 060 and US Pat. No. 3,008,825 describe suitable substrates.

Purely the charging of the electrophotographic material, according to the invention, the usual methods can be used. The recording material according to the invention is suitable in addition, methods according to which the exposure takes place before charging. Such a way of working is described in Belgian patent 625,335, for example.

example 1

120 g of a copolymer of vinyl acetate and vinyl laurate

(80/20) would appear in »■

500 cm toluene dissolved. To this solution one adds

20 ecm of the above ethanolic solution of Üono-Jktyl-

phosphate and

300 g of photoconductive zinc oxide, which has ^{been dried for 30 minutes at 12O 0} C, to.

After the mixture has been ground in a ball mill for 15 hours, it is mixed with it

AG 118 - 25 -

909837/1201

20 qcm of a 53% ethanolic solution of succinic acid

and with
6 qcm of a 1 above solution of one of the following

Table listed hydrazones in dimethylformamide. The dispersion obtained in this way is then applied to a toluene-tight glassine paper. The dried layer has a weight of 25 g / m ² .

According to this process, a number of listing countries are produced. One of these materials does not contain a sensitizing compound, while the remaining materials one of the compounds listed in the table below is incorporated.

Recording materials produced in this way are charged under the same conditions with a corotron which has a potential difference of 6000 V between the earth and the sprayed wires. The spray wires of the Corotrone are connected to the negative fol of a direct current source. The charged materials are then exposed to an incandescent lamp through a gray filter with a factor of 0.1

You develop the materials with a 2-coapone

ten developer consisting of a resinous toner and Consists of an iron file. The toner image is fixed by heating.

The sensitometric values compiled in Table 1 below Measured values represent relative values. The non-sensitized material has the value 1 here.

BATH

909837/1201
AG 118 - 26 -

Table 1

Desensitizing compounds according to color page 5

Relative
Overall sensation
liohigkeit Awareness
maximum 1
5 445 nm 8th . 505 nm 10 4-45-505 nm 12th 505 nm 10 505 nm

2 3 4 5 6

Example 2

250 qca of a 20 pound solution of silicone resin in toluene 750 qoB toluene 20 qoa of a 1 above ethanolic solution of monobotyl

phoaphat 500 g photoconductivea zinc oxide and

6g of equalizing compound no. 4

Diapered in a ball mill for 16 hours. Dft »material is made according to the instructions given in Example 1 further processed. The material produced in this way does not show a sensitivity four times higher than the corresponding one ■ qualified material.

Beiepitl 3

640 g «In ·· Miachoopolymers of vinyl acetate and yinyl laurate

(80/20) are in

8 1 toluene dissolved. This solution is then 64 ecm of a 1Obigen ethanolic solution of Monotrldecyl-

A-G 118

phoaphat and

909837/1201

- 27 -

BAD Cf ^ .tfAL.

2.4 leg photoconductive zinc oxide added, whereupon the Mixture dispersed in a ball mill.

To the dispersion obtained in this way, 320 qcm of a 5% ethanolic solution of succinic acid and one of the sensitizing compounds from the table below are added in the amount specified there. In this way, a series of sensitized materials and an unsensitized material which is further processed according to the method described in Example 1 are obtained .

The results of the sensitometric measurements are in Table 2 below. The numbers given are relative values with the value 1 for the non-sensitized Material.

Table 2

No. of percent by weight Relative sensitizers sens. Connection Total sensation connection related to maximum sensitivity

- A-G 118 - 1 mm 6th 0.5 20th 445 7th 0.5 64 445-505 7th 0.05 16 445-505 8th 0.5 20th 445 9 0.5 16 505 10 0.5 16 475 " 11 0.2 20th 505 12th 0.5 12th 515 13th 0.5 20th 505 14th 0.5 16 515 15th 0.5 20th 515-555 16 0.5 50 475 909837/1201 - 28 - BAD OR ^ NM

17th 0.5 16 445 18th 0.5 20th 475 19th 0.5 25th 505 20th 0.5 10 505 21 0.5 5 505-515 22nd 0.5 16 515 23 0.5 64 505 24 0.5 16 515 25th 0.5 64 505 26th 0.5 40 515 21 0.5 32 575 28 0.05 12th 505 29 0.2 16 515 30th 0.2 40 505 31 0.2 25th 505 36 0.2 25th 38 0.5 8th 39 0.05 6th 505-515 40 0.5 6th 41 0.5 16 505-515 42 0.2 '64 605 43 0.05 40 515 44 0.2 8th 605 49 0.05 16 515 56 0.5 5 515 57 0.2 25th 605 61 0.2 8th 62 0.5 6th

AG 118 - 29 -

909837/1201

Example 4

The following table contains the composition of different types Photoconductor reports and their aenaitometriac: he data. In all cases, the support is made of glassine paper. The relative sensitivity was determined after comparing the The sensitized layers are numbered with the non-sensitized layer, the non-sensitized layer has the value 1. Observation and processing of the material a were carried out in accordance with the precautionary measure given in Example 1.

AG 118 '- 3C ■ -

909837/1201

ÄD ö ^ 2

binder

lionobutyl phosphate based on ZnO

Ratio of solvent-binding agent / medium ZnO

Mr. the 3e *, -) i sens. Relative sea iron. Connections Sensitivity binding related to flexibility

Zno max

Polyvinyl butyral

0.6 0.6 0.6

Mixed polyester of 2,2- (4,4 • -dihydroxy diphenyl) -propane, isophthalic acid and terephthalic acid (75/25)

co

O
CO

°°
CO

Mixed polymer ron C, 6 (Methyl methacrylate and n-butyl methacrylate)

(60/40)

Polycarbonate of 0.6 2.2- (4.4'-dihydro-0.6 xydiphenyl) propane 0.6

ro

Aliphatic
Ketone resin

0.6 0.6 0.6

Mixed polymer of (vinyl chloride, vinyl acetate and vinyl alcohol) (91/3/6)

Mixed polymer of (n-butyl methacrylate and ieobutyl methacrylate (40/60 )

Mixed polymer το »ίί (η <* qc Yinylmcetat und Vinyl ο.6 ■ tearat (85/15) 0 _t 6

HTsch polymer of (n- o, 6 Butyl ethacrylate and υ, 6 Leobutyl methacrylate

2 t 20

^ tnanol

6th 7th 8th

0.2

0.2 0.2

4 ι 15

10 ί 30

acetone

10

0.1

4 ι 15 methylene 8

chloride 9

11

0.2 0.2 0.2

6 ι 15

Ethanol

9
4th
3

.0.2 2
2

4 t 15

acetone

11

0.2

4 t 15

toluene

10

11

0.2 0.2 0.2

4 t 22.5

Etnylene Glycoliono

10
11

0.2 0.2 0.2

4:15

toluene

2
3

0.5

3 8 4

12 3 '3

16 16

2.5 10

20 32 16

16

445 505 475

Methylene 11 0 , 2 6th 505 ahlorid 9 · 0 ■ 2 12th 505

475

505 475 505

5P5 555 505

474

475 505 505-515

475 ^ 505 cn 505 N)

Example 5

To 1 liter of a toluene-free solution of β ine β copolymers of vinyl acetate and vinyl laurate (80/20) are added Stirring added ι 8 com of a 10% ethanolic solution of monobutyl

phosphate and

300 g of photoconductive zinc oxide.

The mixture is then dispersed in a ball mill for 16 hours and then with a 5 # ethanol Solution of succinic acid added. The whole is stirred for another 4 hours and finally with a solution optically sensitizing compounds of the following composition mixed.

15 ecm of a 10bigen solution of hydrazone no. 9 in dimethylformamide and

3.3 ocm of a 1 # solution of Eriocyanin A (CI. 42,561) in dimethylformamide.

A glassine paper is coated with this mixture. The application is 30 g solids / m ² .

The recording material produced in this way is in one Multi-stage process each negatively charged and through one Color slide exposed using the appropriate blue, green and red large extractable filters. The charge images produced in the individual stages of the process become made visible with dispersion developers. The developer liquids contained dispersed in an insulating Liquid (hexane), a developer pigment, whose color

AS 118 - 32 -

909837/1201

BATH ORIGINAL

is complementary to the filter color used for exposure. In this way, a positive copy of the 1 color template.

Example 6

In the procedure given in Example 2, compound 4 is replaced by compound 44 in the same concentration replaced.

The sensitivity of the material produced according to this is

Times higher than that of the non-sensitized reference sterile.

Example 7

The sensitizer used for example 3 is replaced by the compounds recorded and characterized in the table below .

No. of Wt. - ^ Relative Sensibilisens. Connection sens. Connection overall sensation-

based on ZnO likelihood maximum

- 1

44 0.2 8 605

57 0.2 25 605

62

- 1 0.2 8th 0.2 25th 0.2 8th 0.9 6th

AG 118 - 33 -

909837/1201 ^ AD oa.G; NAL

Claims (1)

Claimsι Μ7) Process for sensitizing inorganic photoconductive substances »characterized in that the Inorganic photoconductive substance is treated with an organic substance that forms colored chelates with the metal ions of the inorganic Photoconductor substances is capable. 2. The method according to claim 1, characterized in that the inorganic photoconductive substance contains zinc ions and is treated with an organic compound which is capable of forming colored chelates with these zinc ions. 3 * Method according to claims 1 and 2, characterized in that the inorganic photoconductive substance treated with an acidic substance prior to treatment with the organic chelating compound. 4. Electrophotographic material containing an inorganic, Contains photoconductive substance, characterized by a sensitizing content of a chelate complex of an organic compound capable of chelating and the metal ions of the inorganic photoconductive substance. 5. Elektrophotographisehes material according to claim 4 »thereby characterized in that the inorganic photoconductive substance is a compound capable of supplying zinc ions. AS 118 - 34 - 909837/1201 6. Electrophotographic material according to claim 5 »thereby acknowledged that the inorganic photoconductive compound is photoconductive zinc oxide. 7 "Xlectrophotographic material according to claim 4, characterized in that know that organic chelating! Connect formula corresponds to the general formula (I) » No. ^{1 1} C-NR-N = C- In the Z and Z ¹ mean an atom that is necessary for completion a 5- or 6-membered ring is necessary and R represents hydrogen or alkyl. Θ. A sheet metal photographic material according to claim 4, characterized known that the organic chelating compound corresponds to the general formula (II), / P-NH-N in the Z * means an atom that is necessary to complete a 5- or 6-membered ring. 9 · Electrophotographic material according to claim 4, characterized known that the organic chelating compound corresponds to the general formula (III), AQ 118 - 35 - 909837/120 1 &quot; ^ ^c - ^v - V Ρ- ^ΝΗ - ^Ν - ^0Η -ιΓν ^ΝΟ 2 in the Z ^{1 represents} an atom necessary to complete a 5- or 6-membered ring. Electrophotographic material according to Claim 4, characterized in that the organic chelating compound corresponds to the general formula (IV), ^ά Tf-NH-O Z ¹ CH ₂ OH I ^ά Tf-NH-O CH ₅ yy / Ν-ΝΗ- / Z ' τι n-as ' ^Η 2 ~ ^ ^Η in the Z 'represents an atom necessary to complete a 5- or 6-membered ring. Electrophotographic material according to claim 4, characterized in that the organic chelating compound corresponds to the general formula (V), -N-N-HC! C-GH, I \ ³ R ₁ in the R _{1 represents} hydrogen, an alkoxy or alkylthio group, AG 118 - 36 - 909837/1201 12. Electrophotographic material according to claim 4-, characterized in that the organic chelating de compound corresponds to the general formula (VI), ^E 3 in the Rp and R, hydrogen or alkyl mean or together for an atom s ^ ttien that is necessary, one close homocyclic ring and Z ¹ denotes an atom which is necessary to close a 5- or 6-membered ring. 13. Electrophotographic material according to claim 4, characterized in that the organic chelating compound of the general formula (VIl). is equivalent to, G = O in the R. and Rc stand for alkyl or aryl and Z ^{1 stands for} an atom which is necessary to close a 5- or 6-membered ring. AG 118 - 37 - 909837/120 1 14. Electrophotographic material according to claim 4, characterized in that the organic chelating compound corresponds to the general formula (VIII), OH in the R _{6 represents} hydrogen, alkyl, alkoxy or acyl. 15 * Electrophotographic material according to claim 4, characterized characterized in that the organic chelating compound contains an aromatic nucleus which is in the o-position to a hydroxyl group a ~ CH »N group, a CQ-NH-N = CH group, an -N = N-aryl group or a -CH = N-N = O H-aryl group or that the organic chelating compound contains an aromatic nucleus in the o-position carries an azo group to a carboxyl group. AG 118 - 38 - 909837/1201