DE1497145A1 - Photoelectrically conductive insulating layer applied to a carrier and method for its production - Google Patents

Description

DR. E. WIEGAND DIPUNG. W. NIEMANN DR. M. KÖHLER DIPUNG. C. GERNHARDT

MONKS HAMBURO

sis *? «8000 Munich 15 ^ 8 * October 1968

TELEOIAMME: KARPATENT NUSSBAUMSTRASSE 10

W. 12402/65 13 / Ko, P 14 97 145.0.

Fuji Shashin Film Kabushiki Kaisha Kanagawa (Japan)

Electrically conductive, applied to a carrier Insulating layer and method for its

Manufacturing

The invention relates to a novel photosensitive layer for electrophotographic purposes, where zinc oxide is used as a photoelectric material, and in particular on a photoelectrically conductive, An insulating layer applied to a carrier and made of an intimate mixture of a photoelectrically conductive Zinc oxide powder and an organic film-forming material and a method for their production.

The characteristics of a photosensitive layer for the Electrophotography, the aas the light or photoelectric Zinc oxide and an electrically insulating film-forming material are made noticeable by that change of the film-forming material, hereinafter referred to as the binder, is affected. '

Essential items required for electrophotographic properties are dia given below:

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I, The initial surface potential (a potential immediately near the surface due to a corona discharge in a dark place) is high »

II · The dark attenuation is suitably slow «

III. The light attenuation is quick and the ileut potential is low ». '

IV »No veil is formed during development

Investigations have been carried out on a number of binding agent additions and it has been established that a considerable number of them can be put to general use with light before charging 'is changed considerably by the special liindeiuittelzuaai: iraen3oti2uns, and that therefore the following © condition (V) was added

V «The influence of the pre-exposure hardly occurs on or can be switched off permanently »

A state in which the influence of the preboliohtung remains is called "Lichtangogilchen"("li ^ ht · adapted"), rolling a state in which such an influence is avoided by storage in a dark place for a long period of time , ale "DunkelangeglichGii ¹ * (" dark-adapted ") is called»

If a layer is subjected to corona discharge in a light-adjusted state (fatigue-dungöjsuatand), that is

Potential low and the dark attenuation speed

• '. , high·

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•. ■ BAD OFJGiN

In order to bring this material to the dark-blended state, it is effective to put it in a dark place for a Let it stand for a long time, heat it in a dark place or subject it to a negative corona discharge.

Since the corona discharge itself allows the layer to recover from the light-adjusted state to the dark one. brings about an equalized state, it is safer to correctly assess the degree of fatigue to observe and record a development time-surface potential curve instead of measuring an initial surface potential. In a . dark-blended layer that occurs during a prolonged tent was left in a dark place, the gradient of the charge curve is particularly high and the value of the saturation potential is high, while in a light-adjusted layer the gradient X is weak and the value of the saturation potential is low.

The rate of recovery from fatigue varies greatly depending on that with the zinc oxide associated binders. Research has shown that silicone resin is most beneficial in this insight, with many other resins, such as alkyd, epoxy, epoxy ester resins, copolymers of vinyl chloride and acetate, acrylic esters, methacrylic esters, polyvinyl butyral, copolymers of

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Styrene and butadiene, sulfonamide and polyketone and their miscible combinations are unfavorable compared to silicone resin , i.e. the recovery speed is much slower. In the case of hardening or solidifying resins the recovery rate after hardening is slower than before »A new method has been found in which use has been made of this phenomenon (see Japanese Patent Application 39 ^ 89/63) · According to the invention Effective additives have now been determined which can considerably increase the speed of recovery with any binder composition

It has been found that the fatigue recovery feature can be substantially improved by a combination of zinc oxide and a finely divided water-insoluble compound containing " ¹ " cupric ions. This method according to the invention is more effective and convenient compared to the procedures of treating zinc oxide with an aqueous solution of an inorganic salt.

The light-electrically conductive coated on a support insulating layer made of an intimate mixture of a light electrically conductive Zinkoxydpulvers and an organic film-forming material according to the invention is characterized in that the insulating layer at least one water-insoluble copper (II) compound in an amount of 0.002 to 20 wt.% Copper , based on zinc oxide.

The ■ method for producing a photoelectrically conductive an insulating layer applied to a carrier

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intimate mixture of a photoelectrically conductive zinc oxide powder and an organic film-forming material is characterized in that one is a photoelectrically conductive Zinc oxide powder and a finely divided! Copper (II) compound, consisting made of copper (II) sulfide, copper (II) selenide, copper (II) hydroxide, Copper (II) oxide, copper (II) carbonate, basic copper (II) carbonate, Copper (II) phosphate, copper (II) arsenite, copper (II) oxalate, Copper (II) oleate or copper (II) stearate mixed with a solution of an organic film-forming material and then applying the resulting mixture as a coating on a carrier, the mixing ratio of the copper (II) compound to ZnO is in the range between 0.002: 100 to 20: 100.

In a light-sensitive layer of zinc oxide in the light-adjusted State, the adsorption of oxygen on the surface of zinc oxide is prevented by certain factors; that recovery is delayed by a binder is probably due to the mechanism by which the functional Group in which the binder on the surface is absorbed by zinc oxide instead of oxygen or which is scavenged by oxygen «

It is believed that the copper (II) compound is the Promotes the progress of absorption according to a certain mechanism. Although it is not yet clear whether part of the copper (II) ions Partially present in the surface of zinc oxide or not, partial penetration or uptake of it may occur Copper (II) ions take place with a view to the fact that the Mixing zinc oxide and a binding agent with copper (II) ions in an amount of only 0.002% by weight, based on the zinc oxide, a considerable effect 'is produced.

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Knowing about Eupfor (II) salt can help achieve this of a clear effect more than 0.002 Gow .-% copper ions, Especially on zinc oxide, the resistance against Exposure to a higher radiation intensity is achieved by increasing the amount of zinc oxide added Achieved · Even if a large amount of these is added water-insoluble copper compound, other electrophotographic properties are hardly affected · About up to 20% by weight of copper (II) ions can be added to the zinc oxide will.

As is already known, the phenomenon of fatigue depends on the surface layer of a light-sensitive Layer from 5 it is possible according to the invention to adapt the photosensitive layer only to the surface layer, the lower layer being free of the copper compound a pick of about 20 microns if only the surface layer is 2 to 5 microns thick or above it consists of a layer with a bucketful of fatigue recovery, the sharp character of the light-sensitive ' Layer represented by that of the surface layer.

In the case of a binder with a calibration hardening Will hate the 'exhaustion recovery' by curing or Solidification delayed in the usual way. Through the

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■ \ '' ■,, ■ V-- rv-iu:? TMAL "

However, presence of copper salt can cause this error or Disadvantage can be improved somewhat

Among the copper (XI) compounds, the copper (II) stearate has, in addition to the advantages described above, the particularly advantageous feature that when it is the • coating liquid for the electrophotographically sensitive layer containing zinc oxide particles is added, it remarkably prevents the precipitation of zinc oxide particles and also easily causes a back dispersion of zinc oxide particles precipitated in the coating liquid, thereby increasing the stability and durability of the coating-forming ! fluid is improved; d »h. a large amount of copper (II) stearate causes the liquefaction or the flowable behavior of the thixotropic liquid, which some overlay work is associated with difficulties, however, when used appropriately, the sedimentation of inorganic pigments, such as zinc oxide, is prevented the shelf life of the coating liquid is improved · Therefore, preferably the stearate is put together; used with another copper salt to t achieve two or more improvements at the same time Combinations of two or more other copper (X1) salts can also be used advantageously.

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Since the ifcupfer connection has such an effect, that they have the dark attenuation character), eats, moreover, possible to add a material, which has a worsening effect exerts on the darkening property, β.B. a Sen * sibilieator, the addition of which is undesirable for this reason * '

This is inclined in Examples 4 and 5 below, the presence of the copper compound having the disadvantage associated with the use of aluminum stearate alone, an increase in the dispersibility of a pigment causes, however, the dark dampening character soothed, Improved · A similar effect can be found in the joint '

Use with an een8ibill «usually observe the dye,

be switched. · '.,'.

Another advantage of lieht sensitive ptftoelektriflohleitenden layer according to the invention is that it can be not only common to copy ζ wake in the office, but also door Prägunga- or Merkierungssweokt (marking) used · \. ,,

'The invention will now be described ti * "Vh ^g T? Examples Nuhar. ■ · ',; - '. ^'\' \, ^'V'; '' ...- 'V ■'

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1497 t «

Zuoainroenaetaung A.

light-permeable zinc acid powder ■

Soy type alkyd varnish

(Soda bean oil modification, oil length · 40%), ■ ·.

Silicone resin varnish with a low degree of polymerisation.

Cobalt naphthenate '» Ethyl ethyl ketone peroxide

toluene

Gew.-Tolle

"■ - 100 '. ·'

30 (non-volatile

50%)

-30 (non-volatile

1 _f 0

0.5 ' 20th

The composition given above was in a ball mill made of 'porcelain eJnc ^ br ^ cht and appropriately ground ·'

The composition was 0.02 parts of Eupfera sulfide . introduced to obtain Composition B · Both of you.

Masses were expediently diluted with toluene and on a 'Welohstahlplattt coated with a Seoklaok (wash primer) applied by spraying in order to create a Überzusaeotilch.t vnn

20 microns to get

After standing for 2 days at room temperature, the plates were left in a dark place for more than 10 hours left standing, whereupon they corona discharge on one

90.9823 / 0920

• ι

dark place subjected · The olektrophotographischen properties were determined _t whereby the following results were obtained »were Moreover, after issuing a Vorbeliohtung examines the recovery features ·

Initial surface potential, 450-500 V 450-500 volts

'·' - ·. ■ *. ,. Half-time £ Ür dark dampening 6-8 min 6-9 niJ \

Belative I & sensitivity for - Xenon light, 100 70

Initial potential when loading after pre-exposure to light

of 5000 Liuc from a Fluoressseng-

lamp on for 5 minutes and standing

a dark place for 2 min « '

(5000 livuc from a glow lamp) 70-80 volts 250-300 volts

In Composition 2, the sensitivity is somewhat lower ι wae, however, in practical use without Downside is · you recovery or recovery from the Fatigue is faster than with composition A.

Example 2

Similarly, the following were given Compositions or masses 0 and S mixed uniformly and ground and applied to an original paper on which polyvinylpyrrolidone is applied as an underlayer has been) the haters C and Z) were each in one Layer thickness From 15 to 18 microns (based on a frog) applied and dried. . . <

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Qow »parts

ZnO photoelectric powder 100

Silioonharelaok (non-volatile

liatorial 60%) 18

styrene-modified alkyd hard

paint (non-unnecessary material 50%) 32

Toluene 10

Methyl ethyl ketone 10 Composition Dt

Composition of 0 with a further addition of the following components

f, -geile

JIupfer (II) stearate, 0 _t 2

Kupfor (II) oxalate 0.2

the following egg £ CHij ο were found to adhere!

Initial surface potential 450-500 volts 450-500 volts "Half time for dark elimination approx. 5 min approx. 7 min '

Relative sensitivity to Xenon light 100

Initial potential after exposure to light of 500 üuc · ■ by a Glimmlanpe while 100-150 volts 400-460 volts for 5 min and Stehon in a dark place for 5 ^mi &

Example 3 '

Similarly, the two are given below Compositions on an aluminum sheet in a layer thickness of 20 microns (based on drywall) applied; '

X & eichromat 15 parts by weight. ·· '_'. '·,

Composition E:. . Parts by weight PhotoelektriEches Zinkoayd ^100:

Polyvinyl butyral 45 ^ ._ '

Toluene "; /. '60,

Ethyl acetate; 120 _; ^l

Ioopropyl alcohol 20 '

Composite unia; Q: ■

Composition E with a further addition of 0.015 part by weight of copper (II) o3cyd · · '.

The following SL properties were found:

Initial surface potential /

220-250 volts 250-280 volts

Half time for dark attenuation approx. 3 min approx. 4 min «

Relative sensitivity for Ke-. *

nonlicut .100. 109

Initial potential after past

with an output of 500 lux from one

Glow lamp for 5 min and standing 120-150 volts 200-220 volts

in a dark place for 5 min

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In this pall the & upfer (II) oxide became like »a sensitizer implemented to a certain extent.

Example 4

A similar effect of promoting relaxation recovery by the addition of copper salt became as with the Both compositions according to Example 2 are observed if 8 ml of 0.5 # solution of Eose Bengal were added to this was.-Here the recovery or recovery was at the composition of C more quickly through the addition of Pants Bengal · ■.

Example 5

The & ι angegebecMi below k * L compositions were applied to einrf genuine paper 80 microns in a layer thickness of 15 microns
Composition Cr weight-horny

Light electric? Zinc acid 100

Polybutyl methacrylate 0 Aluminum stearate ■ ',' ■ ° »® ι. · Silicone resin varnish (non-mandatory Material 6OJ6) \ 21 '

Sulphonamide resin varnish (non-volatile fl '\ material 50%) W

Ethyl acetate 20

Toluene 20

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• Composition Ht

ZuBammonsätz G- mixed with 2 Gowl parts of Kupfor (II) sulfide,. ₍ ""

The following properties were found: Initial area potential.

300 - 520 volts 280 - 300 full half-time for duration damping 1 min '2 min

Relative sensitivity for Ee-

nonlight. -100. 120

Initial potential according to, pre-lighting with light of 1000 lux from
a glow lamp for 5 min
and standing in a dark place

for 5 min 150-160 volts 240-260 '

volt

. '... . '■■' Example 6 · · _ '.'.

The following compositions were made. Mix j

and grinding the ingredients listed below in each case j

. ''. ■ ■. ■ ■ I made ». · I

Composition I (control) 'Λ
< ^J
ι ■
\ . Part by weight Photoelectric zinc oxide ■ * ·. ■■ '. ¹ 100 Silicone resin varnish (non-volatile
Material 60%) '. ■ Styrene modified »alkyd resin varnish
(non-volatile material 50%) ■ "; .- ■ ■ '. 32 -." "; ■. toluene : .- ·; ■ ' Ί io. .. ': ■ ■ Methyl ethyl ketone ■. 10

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■ ■■ ■ ■■ ι. · ... '■ ■ ... "... · .. · ■■■ · ■■■. ·· · · -'

". ν

14 971 AS · ■■ '■: ·

Zusainmenetsunr; Jt

Composition I with a further addition of 0.4% by weight, ' Share to Xupfor (II) atearate. .

The above-mentioned, coating-forming, liquid compositions I and J were each applied as a coating to a steel plate treated with a sandblasting blower, ';^; around a photoelectric layer with a dry thickness of. 15 to 18 microns to form. The properties of the layers are summarized in the table below, "where the;

^ results listed under 1, 2 and 3 by determination • after placing in a dark room for more than '■,', '10 hours'. Ss3tabilität, the $ i ^ Uberzu sflussigkeit that is being expressed in '· Table below 5 dao "a symbol ^tt the case welohom almost no caking of digestion;; nach'Stehenlassen of ■ Zinltoxyd beTwahrung - In addition, during the up means the upper ^ ugsflüeeigkeit in one. sealed vessel for more than two-week observed ■■ / 'vmrde and fillings formed could be easily converted back into die'V dispersion · the symbol "b" Working ■, records the case , in which caking was observed - and the back-dispersion of the filling

rig was

1. Starting surface potential 450-500 volts 450-500 volts

2nd half for dark dampening 5 »i» ■ 7 bin

3. Relative sensitivity for

Xenon light .100. 90

4 · Initial soborfiachon potential

after pre-exposure to light - ■■>. '.

of 500 lux of a glow lamp "during 5 am and standing during 5 ntin in a darkroom 100-150 volts -420-480 volts

5. Storage stability "b ^M. " A "

As shown in the table above,

the composition Σ difficulties or disadvantages

and (5)

the properties listed under (4) /, while the composition J proved to be excellent in the properties listed under (4) and (5) as well as in other properties «, -, ■ ^! . .

Example 7

The following compositions were prepared « Composition K (control)

photoelectric 2inkO2yd 100

Silicone resin varnish (non-volatile. ' Material 60%); 35

Phenol-modified alkyd resin varnish

(non-volatile material 50 #) ·, > ■ '20 18

toluene 20

90982.3 / 092 0

ΓΑΓ

-V- · '■■■ .. *

Tensile etching L;

Composition K with a further addition of 1 part by weight Copper (II) stearate. '

Each of these compositions vaurde alö coating a high quality paper with an intermediate or lower layer (Substrate) of polyvinyl alcohol with a thickness of 60 milcron in a layer thickness of 12 microns, based on dry basis, upset. The results of the determination of the storage \ 7ahrun? Stability of the coating compositions and the properties> the light-sensitive layers are in after drying the following! table compiled ι

. KL

1. Initial surface potential 320-260 volts 940-380 volts' 2 Half time for dark dampening 5-6 min 6-8 min, '

3. Relative sensitivity

for xenon light 100 100

4 Initial surface potential. -

after pre-exposure with light.
■ from 2000 lux of a glow lamp

for 5 min and after standing

while in a darkroom
'5 min,, 100-120 volts 370-410 volts

5 · Storage stability of the liquid ' _f

Composition (excluding cobalt naphthenate). '/ VV .. ^m ä ^m

• ■ ■ ■■. ··. ■■ ·· ■ ... \ ·. ' - ■ v ·· ■■■. / ■. . "·

90 982 3/0920

Boinpiol 8 ■.

The following ^ uaammonsotzunson were made:

Λ-

Composition ; M (Kont & olle) Part by weight Light- sensitive zinc oxide. . 100 'epoxy modified alkyd resin

(non-volatile material 50%) 55

Toluene / 30

Methyl ethyl ketone peroxide 0.5

Composition N:. '.

Composition M mixed with 0.7 parts by weight of Eupfer (II) -etearate.

Each of the masses M and K was provided with 10 parts by weight of a 10% strength solution of cobalt naplithenate in toluene immediately before the coating and then applied to a steel plate as a coating to form a dry pilm with a layer thickness of 30 to 35 microns · the '' drying was carried out in that was allowed to stand, the material on Sachtleben at room temperature "

The results given below were obtained,, get'eni,, ■.

• "·. ■ ■■. ■■ -" "- ■. ■■■ '.' ··" ■ · ■ Ν ",. '■ -

•.;. '"-, · ^ν ■' ·. ^Ν *. VB, * D ORIGINAL ·

9 09 8 23V 0920 ''.

M N

1. Initial note? Surface potential -450-500 volts 450-500 volts

2nd half for dark dampening 5-6 min, 6-8 min

3. Relative sensitivity ■

for xenon light, 100.

4 ·· initial surface potential after. Pre-lighting with light of 2000 lux of a glow lamp \ <

for 5 min and standing in a darkroom for 5 min x 100 * 120 volts 370-410 volts

5 · Storage resistance of the liquid · ■ * composition (without addition of cobalt naphthenate). ₍ ^M b " ⁿ a ^w

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Claims (2)

Claims (! ■ *) Photoelectrically conductive insulating layer applied to a carrier made of an intimate mixture of photoelectrically conductive zinc oxide powder and an organic film-forming material, characterized in that the insulating layer contains at least one water-insoluble copper (II) compound in an amount of 0.002-20 wt. % Copper ion, based on the zinc oxide. 2. Insulating layer according to claim 1, characterized in that the copper (II) compound copper (II) sulfide, copper (II) selenide, copper (II) hydroxide, copper (II) oxide, copper (II) carbonate, basic copper ( II) carbonate, copper (II) phosphate, copper (II) arsenite, copper (II) oxalate, copper (II) oleate or copper (II) stearate is _t 3 · Process for the production of a photoelectrically conductive insulating layer applied to a carrier from an intimate mixture of a photoelectrically conductive Zinc oxide powder and an organic film-forming material according to one of Claims 1 or 2, characterized in that that a photoelectrically conductive zinc oxide powder and a finely divided copper (II) compound, consisting of copper (II) sulfide, Copper (II) selenide, copper (II) hydroxide, copper (II) oxide, copper (II) carbonate, basic copper (II) carbonate, Copper (II) phosphate, copper (II) arsenite, copper (II) ox / alate, Copper (II) oleate or copper (II) stearate with a solution of a 909823/0920 EAD ORiGINAL i \ v. ij-s.-. :. ' i '-' i.'iOPli fA ··! > §). <»BE L - ', r. i'Sut? 3 des andf- runq ^ ges, v. 4. 9.1967i Ή 9 7.1 A 5 organic film-forming material mixed and then
the resulting mixture as a coating on a carrier
applies, the mixing ratio of the copper (II) compound to ZnO in the range between 0.002: 100 to 20: 100. k% A method according to claim 3, characterized in that the organic film-forming material is selected from alkyd resin or a epoxymodif! ed alkyd resin consists · 909823/0920