DE2229992C3 - Electrophotographic recording material - Google Patents

Description

^{: i} O ^ -gan "s ^g cne ^g fot ^W oleWworthy materials are visible signs of fatigue without any restriction on

I avoid any photole.tfah.gen substances due to their transparency, flexibility, surface smoothness.

• nd selectivity of the charge polarity of large ₃ o Furthermore, the barrier layer according to the invention enables

Advantage. In particular, high-polymer organics can produce a photographic record

«Ical photoconductive materials formed as films. high sensitivity to light

_are excellent film properties such as contingent liabilities

An electrophotographic recording material, like, flexibility, tensile strength and long-term stability

in which an organic photoconductive material has nothing to do with it. .

Bch is applied to a conductive layer support, the proportions of the barrier layer are to be selected so that

For electrophotographic purposes, the specific volume resistance is not certain

Particularly satisfactory, since it has mainly an electro-suitable value for a discharge destruction

Static problems occur. to be avoided completely and fatigue discrepancies.

In particular, electrophotographic exposure of a repeatedly used recording material tends to occur

Sealing material that is made of a common organ- ous to avoid, with the barrier layer in the rest of the

Seeing photoconductor is built up, often to discharge electrophotographic properties such as light sensitivity.

breakthroughs after charging are not adversely affected by means of a corona function.

discharge, and the developed image contains white There are numerous N. trocelluloses with different

Places that reduce the image quality significantly. To 45 üchem Polymerisat.onsgrad and different

Avoidance of this disadvantage has been proposed. These N.trocelluloses can be used for the

a synthetic resin adhesive layer between the layer can be used for purposes of the present invention.

made of photoconductive material and the substrate. The substrate can be <L ·. present

to be provided. So far, however, there have been no artistic purposes.

Resin layers obtained that do not have a sensitivity of 50 den, as is the case with electrophotographic! Record

the light-sensitive layer is reduced and removal material is used. Exemplary

would have adequately prevented charge breakthroughs. Layer supports are metal plates, aluminum, copper

In electrophotographic imaging processes and the like, paper, aluminum-coated paper, art

in which the electrophotographic recording resin film with admixed surface-active agents

If the material is used repeatedly, there are numerous 55 synthetic resin films that have a corternary effect

Disadvantages, in particular symptoms of exhaustion, treated ammonium salt to maintain conductivity

such as reducing the amount of charge, low levels of energy, glass, paper and synthetic resin on the metal,

rise time of the charge, remaining residual images and metal oxide or a metal halide is evaporated

Sensitivity reduction as well as destruction. In general, the specific surface resistance lies

■ cn by discharge. 6 "suitably below 10» ohms, preferably below

There has been no lack of research, an electro- 10 ⁵ ohms. _ _ Photographic recording material with an organic The barrier layer is formed on the layer support in such a way as a photoconductor in an electrophotographic process that a solution of the layer support material, process in which the recording, for example nitrocellulose in a suitable material, is repeated during charging, imagewise 6 _S Weight solvent in a ratio of 2: 8 to 8: 2 exposure, image development and image transfer, the viscosity being set for brushable. So far, no suitable values have been set for the shift success for these investigations. carrier applied according to the usual coating methods.

3 4

will carry, after which a drying process with methyl ethyl ketone was in an amount equal to dsr

If necessary, dry in air and heat, then add half the mixture amount to the mixture

_{to obtain} the barrier layer, add a coating solution for the barrier layer

Since, furthermore, those obtained from a composition. The solution thus obtained was then applied to the

"Made of nitrocellulose and polyvinylpyrrolidone- 5 light-permeable conductive layer with a thickness of

The built barrier has good flexibility, is applied at 3 to 4 microns (after drying)

the preparation of the coating solution per se and dried to get the locking slide. the

Plasticizer necessary, the film formability of the resulting coating (barrier layer) was high

but can be made even better by adding translucent, strong and flexible and adhered

add 10 to 50% of a well-tolerated soft io to the conductive layer

machers, for example trichloroethyl phosphate, tri-barrier layer a photoconductive material made of poly-N-

cresyl phosphate, chlorinated biphenyl and the like vinyl carbazole, crystal violet and benzene-chlorobenzene

The film of the resulting barrier layer is applied and soft zol (1: 1) in an amount of 8 g / m ²

and strong, and has sufficient flexibility. dried to a photosensitive layer

Depending on the purpose of the barrier layer, xs can be obtained. The resulting transparent record

Pigments and other additives in the necessary material was developed by a well-known electrophotographic

Amount of the coating solution to obtain the graphic imaging process subjected, d. H.,

Barrier layer can be added. it was charged, exposed, photographically reduced

The thickness of the barrier layer is expediently smaller and developed when wet, in order to obtain excellent positive images of about 10 micrometers, preferably 3 to 7 micrometers. When the positive images were enlarged by meters, it was found in a recording projector that the film free material for a copier also obtained a good result from the various commonly occurring problems when the thickness of the barrier layer was about electrostatic problems and clear as well 1 micrometer. If the thickness of the barrier layer provided sharply defined images. In contrast, when made larger than 10 micrometers, it has been found that electrophotographic sensitive white spots are produced by charge destruction to a greater extent when an ordinary condition adversely affects them. If the barrier layer is made of smaller photosensitive recording material without a barrier 10 micrometers thick, then the result is that layer was used,
practically no noticeable degradation of the sensation.
chance, and if the barrier layer is greater than 3 micro- 30 Example 2
meter, then discharge destruction on a conductive base made of a polyester film and fatigue phenomena with repeated use (75 micrometers thick), the use of vapor-deposited aluminum on the recording material, can be avoided. nium layer with a light transmission of 60%

The organic photoconductive; Sch.cht is applied to the mixture obtained Barrier layer created according to conventional methods to prevent the 35 by mixing a 5% nitrocellulose solution,

According to the invention, electrophotographic recording degree of nitration 11.5 to 12.2% with a 10% strength

material to receive. Polyvinylpyrrolidone solution in weight ratio

For the organic photoconductive material can be from 1: 1, in both cases the solvent

the known organic photoconductors are used. Ethyl alcohol-methyl alcohol (7: 3) was, and by Particularly preferred materials are organic, 40 adding methyl ethyl ketone and dimethyl

polymeric materials such as poly-N-vinylcarbazole, chi »formamide, each in an amount equal to a quarter

rated poly-N-vinylcarbazole, brominated poly-N-vinyl- of the weight of the above mixture. The mixture

carbazole, cyanated poly-N-vinylcarbazole, poly- has been used to obtain a 3 to 4 micrometer thick

vinylacenaphten and similar barrier layer applied after drying. the

Chlorinated poly-N-vinylcarbazole can be obtained 45 resulting barrier layer showed excellent inheritance by chlorinating poly-N-vinylcarbazole shafts similar to Example 1. A solution with chlorine gas or with sulfuryl chloride or with 3 g of poly-N-vinylcarbazole, 0.1 g of N-vinylcarbazole, 0.2 g Polymerize a chlorinated vinyl carbazole. Be carbon tetrabromide and 45 milliliters of a Lösteiger further details for the production of a solvent mixture of benzene and chlorobenzene (1: 1) to the German Offenlegungsschrift 2 035 679 ver 50 was irradiated with UV light for 20 minutes, im grasslands. in the dark for 6 hours at ambient temperature

The examples below are for the expansion device and applied to the barrier layer,

purposes, they are by no means in the The recording material showed as well as after

restrictive sense. Example 1 excellent transparent positive images,

...... 55 that were free of white spots.

example 1

An aqueous solution of an agent for reducing icepie

of the resistance of poly- (M, N'-dimethyl-3,5-methy- A conductive support made of a polyester film

Lenpiperidiniumchlorid was on a Polyäthylente- (75 micrometers thick) with a vapor-deposited aluminum « rephthalate film applied, which is an underlying 60 minium layer with a light transmission of 60%

Layer (75 micrometers thick) had, and was obtained with a mixture obtained in the following manner

eifies transparent conductive layer dried. Dirt solution coated to after drying

flat was a 10 percent by weight nitrocellulose to get a 4 to 5 micrometer thick barrier layer:

Solution Degree of nitration from 11.5 to 12.2% with a 15% nitrocellulose solution, degree of nitration 10% polyvinylpyrrolidone solution at a ratio of 11.5 to 12.2% in ethyl alcohol-methyl alcohol

mixed with a holding ratio of 2: 8 (parts by weight). The lo- (7: 3) was in the ratio of 8: 2 parts by weight

The external agents in both of the above solutions are ethyl mixed with a 15% polyvinylpyrrolidone

alcohol-methyl alcohol (7: 3). Solution in ethyl alcohol-methyl alcohol (7: 3); then

were methyl ethyl ketone and dimethylformamide per charge image on a ^
took place in an amount equal to the fourth part dps weight of material. If that. J? F ^
added to the above mixture. As in example 1 was in a river
the resulting barrier layer was transparent, strong, excellent images, and the effect was flexible and adhered well to the vapor-deposited aluminum layer. A solution of the barrier layer was then better than with conventional recording media without the barrier layer. The lifespan was the following without chlorinated poly-N-vinylcarbazole and rhodamine B barrier layer, used around a hundred times, with barrier in benzene-chlorobenzene (1: 1) 5 to 6 g / m * thick layered around fifteen hundred times,
wear and dry to the photoconductive layer io Example 6
to obtain. . .

The electrophotographic recording material A recording material which, as in Example 5 was made with a reduced original as in Example 1, was a conventional xerographic exposed to obtain sharp positive images. The process repeatedly subjected, in the course of which a Sensitivity was very good. After enlarging the 15 charge at -7.0 KV, an imagewise exposure resulting positive images with the aid of a projector with about 100 lux sec, a development with liquid one develops projection images free of white spots, a transfer onto ordinary paper and high fidelity. The photoconductive and a cleaning of the recording material instead of layer was strong, flexible and highly adhesive. found. Sensitivity was excellent and that

20 Effect of preventing discharge destruction

Example 4 through the barrier was substantial. The life-barite paper, That of a conductivity treatment duration was as follows

was subjected, a mixed solution was applied - _{without a} barrier layer about 50; eel use,

wear a 15 to 20 micro _mjt barrier layer after drying about 700 times,
meter thick barrier layer. The mixture 25

solution was obtained by mixing a 10% Example 7
Nitrocellulose solution, degree of nitration 11.5 to 12.2%

in ethyl alcohol-methyl alcohol (7: 3) in a mixture on an aluminum foil (31 micrometers thick) as a ratio of 2: 8 parts by weight with a 10 weight-conducting layer support was a solution mixture percent polyvinylpyrrolidone solution in ethyl 3 ° to obtain a Barrier layer in a thickness of alcohol-methyl alcohol (7: 3), then still 1 to 2 micrometers applied after drying. Methyl ethyl ketone in an amount equal to half that. The mixture solution was obtained by adding a mixture amount. 7 percent by weight nitrocellulose solution, Nitrie-Sodann was applied to the resulting barrier layer approx. 11.5 to 12.2% in a ratio of 2: 8. A mixture of poly-N-vinylcarbazole and crystal 35 parts by weight was mixed with a 10% polyviolet in Benzene-chlorobenzene (1: 1) in a starch vinylpyrrolidone solution, in both cases from 4 to 6 g / m ^{2 being} applied and dried. The solvent was ethyl alcohol-methyl alcohol (7: 3). The recording material was then added as usual, methyl ethyl ketone in an amount equal to half the mixture amount by electrophotographic imaging method. This loading, exposed and developed to obtain a clear visible 40 barrier had the same properties as the images free of white spots. according to example 5.

. . The barrier layer was then coated with photosensitive Example 5 substance to give an 8 micrometer thick light-sensitive layer on aluminum foil (31 micrometers thick). The photosensitive support was coated with a mixed solution of 45% composed of 2 grams to obtain a barrier poly-N-vinylcarbazole 1 to 2 micrometers thick and 10 mg of crystal violet, as well as a layer after drying. The Mi- a coumarone resin as a plasticizer in 40 ml of benzene solution was obtained by adding a 10% nitro-chlorobenzene (1: 1). The resulting recording cellulose solution nitration degree 11.5 to 12.2% with material was repeated a process for over 10% polyvinylpyrrolidone solution in a weight transfer of 5 ° of a charge image on an electrophotograph ratio 1: 1 was mixed. The solvent fish paper as in Example 5 subjected. The charge image transferred to both solutions was ethyl alcohol-methyl alcohol was then toner after (7: 3). Then methyl ethyl ketone and the magnetic brush method were developed. The prevention of methylformamide each in an amount equal to the fourth charge destruction effect was pronounced, part by weight of the above mixture was added. The barrier layer obtained at 55 and the fatigue was very small, the barrier layer obtained from this solution was highly trans- The life was as follows
parent, strong and flexible and firmly adhered to the _without " _{barrier layer about 90} times use,
Aluminum Backing The barrier layer was then placed. Barrier layer about 1200 uses,
with a 9 micrometer thick photoconductive layer ^F
coated, it contained 20 mg rhodamine B and ⁶ ° Rpiiniel 8
Diphenylchloride as a plasticizer in 40 ml Benzol- oci » _P ki ο
Chlorobenzene (1: 1). For use as a recording * A photosensitive material prepared as in Example 7 for repeated use in the Itches recording material was subjected to a conventional electrophotography, it was repeatedly subjected to an electro-xerographic production process, subjected to a photographic picture production process, the course of which was charged at -7.0 ^{at 6 S} KV, one with corona charging at -7.0 KV, image-wise image exposure at 100 lux seconds, development exposure with a 500 W tungsten lamp using the cascade method, transfer to ordinary 40 tux see and transfer of the resulting paper and cleaning photosensitive

7 8

lichen recording material took place. It was each in an amount equal to a quarter of the above

found that the preventive effect of a segregation weight was added. The result-

charge destruction was excellent. The end of life barrier was very strong and flexible and

duration was the following stuck firmly to the base. The barrier was

without a barrier layer about SOmalige use, ^{then 5! "L1. e 'ner} photoconductive layer of 15 micro

with barrier layer about 700 uses. ^mc . ^tet . ^{Coated sheets after} drying. the

Layer was composed of 2 g poly-N-vinyl Example 9 carbazole, 3.7 g, 2,4,5,7-tetranitrofluorenone and 0.5 g Diphenyl chloride in 40 ml of tetrahydrofuran.

The support used in Example 5 was coated with. The resulting recording material was a solution mixture to obtain a 1 to 2 micrometer thick barrier layer after drying an electrostatic transfer process is subjected, in the course of which a charging coated. The mixture solution was obtained, -7.0 KV, an imagewise exposure at about by using a 12% nitrocellulose solution, degree of nitration 15 lux sec and a transfer to an image receiving 10.7 to 11.9% in ethyl alcohol-methyl alcohol (7: 3) 15 paper took place. The image receiving paper was then was mixed in a ratio of 7: 3 parts by weight in a liquid electrophotographic developer with a 10% polyvinylpyrrolidone solution developed in the same. The preventing effect of the discharge solvent, taking methylethyl ketone and destroying it, was remarkably improved. The living dimethylformamide each in an amount equal to the duration is the following

Quarter of the above mixture weight was added _{without a barrier layer about 2} 50 times,

the. The resulting junction was highly transparent _{mjt Sperrscnicht about 3} fjoo _ma-celled use,

rent, strong and flexible and adhered well to a ^r e>&

Aluminum support. Example 12 was made on the barrier layer a photoconductive layer 12 micrometers thick

applied after drying. The composition was 0.5 mol (2 g) of chlorinated poly-N-vinylcarbazole, a solution mixture was applied, and 3.2 g of 2,4,7-trinitrofluorenone and diphenylene were used To create a I to 2 micrometer thick barrier layer of chloride as a plasticizer in 40 ml of tetrahydrofuran. to be preserved after drying. The Solution Mixture This electrophotographic recording material was obtained by repeatedly subjecting a 10% nitrocellulose solution to an electrostatic transfer rate of 11.5 to 12.2% in the ethyl alcohol addition process, while a methyl alcohol mixed solvent (7: 3) in one process charge at -7.0 KV, an image exposure at 10 lux see weight ratio of 3: 7 was mixed with and a transfer of the charge image to an image 10% polyvinylpyrrolidone solution in the same solution-receiving material took place. After developing the medium, methyl ethyl ketone being added in an amount equal to that of the image receiving material in liquid developer, half the mixture weight was added. The barrier layer resulting in a good toner image, the preventing effect, had properties as that of discharge / destruction was good. The life given in Example 5. On the barrier layer, the following was ^a photosensitive substance of 0.5 mol (2 g) ..... _5nn , · a "", ",""" chlorinated poly-N-vinylcarbazole and 3.2 g trinitro without a barrier layer about 300 times used, ^^ J g diphenyl chloride as a soft material barrier layer about SOOO times used. _{macher jn} ^ _m] j ^ & ^ n _{plotted to}

_. ■, _in a layer thickness of 12 micro-

^{Be! S} P ' ^{el 10} meters.

Fin recording material as in Example 9 The resulting recording material was repeatedly subjected to an electrostatic transfer process in the course of an electrophotographic process, in the course of which it was subjected to charging, in the course of which a charge was made at 7SKV, an imagewise exposure at about -7, 0 KV, an image exposure at about 5 Iu see and 20 lux sec, a development in the magnetic brush process, a transfer to an electrostatic image pressure, a transfer to normal paper and a fsng paper took place. Because electrostatic image cleaning of the recording material was taking place. The magnetic brush image on the copy was clear and one wound, and good quality images were obtained. The discharge destruction was practically not observed, the discharge destruction preventing effect was also observed. The life was as follows if excellent. The lifespan was the following about 200 uses without a barrier, about 200 uses without a barrier, and about 3000 uses with a barrier. ⁵⁵ with a barrier layer that has been used around 4000 times.

Example Π Example 13 On a sandblasted aluminum foil (100 Mi- A conductive layer support made of a polyester film

micrometer thick) as a conductive layer support, a 60 (75 micrometer thick) and one on top of it was vapor-deposited

Solution mixture applied to after drying aluminum layer with a light transmission of voi

a 1 to 2 micrometer thick barrier layer. 60% a solution mixture was applied, un

The solvents were made by adding a 1 to 2 micrometer dicfc after drying

207 Nitrocellulose solution, degree of nitration 11.5 to obtain a barrier layer. The mixed solution was obtained

12 ^% in ethyl alcohol-methyl alcohol (7: 3) in the 65 one by adding a 6% nitrocellulose solution, nitric

Weight ratio I x 1 was mixed with a 10% degree of 11.5 to 12% in a solvent Polyvinylpyrrolidone solution in the same solvent, mixture of ethyl alcohol-methyl alcohol (7: 3) gf

methyl ethyl ketone and dimethylformamide were then mixed in a weight ratio of 1: 1 with em «

10% polyvinylpyrrolidone solution in the same solvent, with methyl ethyl ketone in an amount equal was added to the quarter of the above mix weight. The barrier layer had film properties similar to Example 5. Further, the barrier layer was coated with a photosensitive substance to obtain a 10 micrometer thick photosensitive layer after drying. The photosensitive substance was composed of 2 g of poly-N-vinylcarbazole, 20 mg of rhodamine B and Diphenyl chloride as a plasticizer in 40 ml benzene-chlorobenzene (1: 1).

The resulting light-sensitive material was subjected to electrostatic repetition Subject to transfer process, in the course of which a charge at -7.0 KV, an image exposure with about 50 lux sec and transfer to an electrostatic recording paper took place. The recording paper was developed in liquid developer. The discharge destruction preventing effect was considerable.

Example 14

A 10% solution of nitrocellulose, degree of nitration 11.5 to 12.7% in methyl ethyl ketone and methyl isobutyl ketone was mixed with a 10% solution of polyvinylpyrrolidone in isopropanol and methanol. The mixing ratio was 3: 7 parts by weight. Of further was a mixed solvent of methyl ethyl ketone and dimethylformamide in an amount equal to half the weight of the above mixture to obtain a transparent, low-viscosity liquid as a solution for the barrier layer. Then TiO _{2 became} this liquid in proportion

S of solid resin to TiO ₂ equal to 6: I added. The whole was then ball milled for two days and filtered to obtain the coating solution. The resultic Solution to obtain a white barrier in a thickness of 5 to 4 microns according to the

Get drying. The resulting applied The film adhered very strongly and had good coverage. A light sensitive was then applied to the barrier layer.

sensitive substance applied in an amount of 5 to 6 g / per m ² after drying to obtain a photosensitive recording material. The photosensitive substance used was composed of poly-N-vinylcarbazole and a trimethine dye

ao a plasticizer such as coumarone and chlorinated Paraffin in a solvent mixture of toluo and monochlorobenzene (1: 1). The resulting light-sensitive material was subjected to charging in a known manner and then subjected to

»5 a usual camera spent taking a picture of the to make the upper half of a human figure in lightning at a distance of 15 m. The up Drawing material was removed from the camera after the end of the recording in the dark and Developed with liquid developer to obtain an excellent positive reflection image.

Claims (1)

An electrophotographic recording material with _otl . a layer carrier and a photoconductive layer Patent claim; au "ZnO and synthetic resin binder as well as a barrier Electrophotographic recording material consisting of a layer support, a barrier layer and a 5 From the d <f see Ausl ^eg Sf _c ^l _bnu ^ _ate ' _r 7 _a , ¹ ^ photoconductive layer with an organic one ^ ψ ^{ο {ο1α} ^ Ζ ^ ίζ ^ Γ ^ οά "ν meh photoconductor, characterized, knows that from ^e X ^ f ^l f ^^ ^l ZoWakS _n that the barrier layer is made of NitroceHulose and Poly- r ^^^^^^ J ^^^ vxnylpyrroltdon consists of complex organic compounds FüiHeitero is a recording material with high photoconductivity with good chemical stability ~ aimed at. .... The invention is based on the object of providing an electrophotographic recording material with £ K "™" ^ ™ "™ * ¹ 15 electrofotg The invention relates to an electrophotogra "bar to make the through £ ^ Fish recording material from a layer carrier 'attacked w, rd and also be. ? wedertioltem use einer.Sperrschicht nd a layer foto.eitTahigen ™ uT ^^ ^ d ^ Smg characterized SSS ^ ^ S ^ SS ^ materials in - ^ Ä gel barrier layer of Nitroce.lulose and ■ ochpolymerer or low molecular weight form are polyvinylpyrrolidone best. known examples of this are poly-N-vinylcarbazole, compared to the known recording material brominated poly-N-vinylcarbazole, polyvinylanthracene, with organic semiconductors st at E « Oxadiazoles and acylhydrazones. If desired, kön- between the Sch.chttrager and the photoconductive .en a _5-ht Schk to obtain the electrophotographic awards provided a barrier layer; ^ehen ' ^and ^ ^{r F} S Ä Ä ^^ Ä emem