SU289648A1 - PHOTO-CONDUCTING MATERIALj "sesoyuznd '.- <' '' '' '-: P ..' t" ^ "E1: GID1 ^ •. .., ..ki. .-., • "../.:,tffl"l.wjWf1 'g - ^,; .. g: -': c7;: kA - Google Patents

Description

The invention relates to a photographic material that can be used to record and reproduce information. A photoconductive material is known, consisting of a substrate and a photoconductive 5 layer containing a semiconductor, zinc oxide, a polymeric binder, and an organic phosphorus compound, such as monobutyl phosphate. The introduction of organic phosphorus compounds connects the research institute to improve the photoresistance of zinc oxide grains, as a result of which a large number of binders and even those types of binders that do not have very low electrical conductivity can be used. In addition, the photoconductive recording layer becomes less sensitive to changes in relative humidity and may contain very large amounts of photoconductive zinc oxide, so that an optimum 20 sensitivity is achieved. However, the introduction of organic phosphorus compounds leads to a sufficiently large memory effect, i.e., to significant asthumic conductivity after exposure. 25 The purpose of the invention is to increase the dark resistance of the photoradiating layer, reduce the memory effect, improve the charge ability of the photoconductive layer to the negative corona and the possibility of charging the photoconductive layer to a positive corona size. This goal is achieved by that, as an organic compound, the combination of the general formula / -G Z-N - R o is used where RI and R2 is a hydrogen atom, an unsubstituted or substituted alknl. unsubstituted or substituted aryl, unsubstituted) 1 or substituted acyl, unsubstituted 1 or substituted heterocyclic ring or RI and Ro together are aTONraMH, 15 is necessary for closing the ring system; Z is the atoms required for the closure of a 5nly 6-membered unsubstantiated or substituted hetero ring; X is a hydrogen atom or an imine group, with rtrir rf-i -rinO T-IT this is more than one of the ring nitrogen atoms enclosed by Z. contains a hydrogen atom that can be replaced with a compound by using a salt compound.

Due to the fact that such recording material can be charged both positively and negatively, it is possible with the use of the same product to reproduce the same original in both positive and negative form depending on the sign of electrostatic charge. Yes, and applying to the recording layer. The same effects are observed in the case of the use of mixtures of photoconductive oxidation 10 with other photoactive substances, for example, with photoradiating cadmium chalcogenides. Additives may be added to these chalcogenides, for example, to increase their photosensitivity. 15

For the practical determination of the memory effect, the recording material under investigation is fixed on a rotating disk on which it is successively subjected to a corona discharge and is iodine by a probe or electrode on which a charge, an irrational charge, which is on the recording Cassiers layer (J. Phot. Sci. 10/1962/58).

Urazol, guanazole and derivatives can be 25 and obtained by known methods described in the literature.

In order to achieve an optimal effect, it is desirable to use a feeding agent. The molten state with photoconductive 30 zinc oxide.

The invention can be applied in iro,: extracting electrophotographic materials by contacting zinc oxide with the indicated substance at any stage of production. In order to obtain the desired effects, it is not necessary to contact the organic compound with the zinc oxide particles over their entire surface. The electrophotographic recording materials 40 according to the invention may contain not only impregnated zinc oxide particles, but also a mixture of impregnated and non-impregnated zinc oxide particles.

It was established experimentally that the onti- mal dark resistance is obtained by adding to: photoconductive zinc oxide (depending on the activity of the chosen impregnating agent, which in this case does not contain cations and does not use — 50 seconds in complex form) from 0.01 to 10% of the impregnating agent, but relative to the weight of the photo-zinc oxide, preferably from 0.01 to 3%. If salt or complex bonding is used as an impregnating agent, usually a larger amount of them is required, i.e., more than 0.5% but relative to the weight of photoconductive zinc oxide, for example 0.5-40%.

In the case of a photoconductive layer containing 60 impregnated zinc oxide in the binder, the ratio of the binding agent to the photoconductor affects its photonic properties, mechanical strength, and insulating properties. Preferably iso-65

The binding agent and photoconductor in a weight ratio of from 1: 3 to 1: 9. In the case of using layers with a higher ratio of binding agent, the image sharpness decreases. If the layer contains much less binding agent than the minimum required, then the mechanical strength of the coating may be insufficient for many purposes.

The photoconductive recording materials obtained according to the invention can be used for a variety of reproduction methods, to obtain contrasting images that are formed even under different conditions, for example, under conditions of drastically changing air humidity.

Preferably, binders containing acidic groups or acid-forming groups are used.

The proposed impregnating agents do not preclude an increase in the photosensitivity of the photoconductive material by, for example, spectral sensing of a photogeneous zinc oxide.

Photoconductive layers comprising an impregnating agent for photoconductive zinc oxide may additionally contain a compound that increases the dark resistance or sensitivity, for example, organic phosphoric hydroxyacid.

Example 1. 2309 g of a 20% strength solution in dichloroethane of HYPALONE 30 (ethylene ethylene: viii sulfonyl chloride: vinyl chloride in a ratio of 26.1: 6.9: 67% by weight of EJ. Du Pout de Petoise Co) diluted 535 ml of dichloroethane, 560 ml of methylethylketone and 112 ml of ethanol. During mixing, 1820 from photoconductive zinc oxide (marketed by Vieille Moptagne S. A. Belgi, as type A) are added.

880 g of the resulting dispersion is diluted with 508 g of dichloroethane, 17 g of ethanol, and 85 g of methyl ethyl ketone and sensitizing dyes of the following formulas:

c-CH CH-CH (f y

Sbn

(CHASO NHCOCHs (CHjliSOgNHCOCHj

To reduce the memory effect of the recording layer containing this mixture, 9 ml of a 10% urazole solution in dimethylformamide is added. A mixture containing urazol (or without it), under the same conditions, is applied to a vitrified paper substrate. Negative corona charge without

pre-exposure

recording layer

Ku and maintained after the substance at 20 ° C and a relative humidity of 50%.

When measured by a rotating disk, the results shown in the table were obtained.

Negative corona charge,

next 15 seconds, 500 lux

pre-exposure

Example 2. Example 1 is repeated, but instead of 9 ml of a 10% solution of urazol in dimethylformamide, 9 ml of a 10% solution in the same solvent of a compound of the formula NC II, O C - NH O is used. Since the memory effect turned out to be comparable with the one shown in the table of irimer 1, the following results were obtained: a) without preliminary exposure 310 e / 17-lO-i sec, b) after preliminary exposure 300 S / 17-10-1 ce / s. . Example 3. 101 g of HIPALONE 30 is dissolved in a mixture of 575 ml of dichloroethane, 156 ml of methyl ethyl ketone and 31 ml of ethanol. To this .1 solution, 19.5 ml of a 80% toluene solution of cellolip 95 (an acid alkyd resin from The Negsz Powder Comp. Jnc.) Was added as a disrupting agent. Then, when transferring, 447 g of photoconductive zinc oxide, 61 g of KADMOPUR GLDGELB n (Farbenfabriken Bayer), cadmium sulfide pigment containing 76% cadmium, 22% sulfur, 2% of a mixture of barium sulfate and silicon dioxide and traces of zinc and selenium are added . 4 ml of a 10% solution of urazole in dimethylformamide are added to the pigment dispersion. Then the pigment mixture is passed once through the mill at a speed of 24 l1h. The dispersion is applied on vitrified paper in the amount of 33 g of solid particles per 1 m. The coating is present in a laminar flow dryer at 30–40 ° C (air velocity 7 m / min). A smooth surface is obtained. The squeezed material is charged with a double crown, with the crown wires before the recording layer and below the substrate having a potential difference of -5000 b and + 5000 v. A material is exposed through a stepped wedge with a constant 0.1 by means of glowing plates. The exposed material exhibits an electrophoretic hydrocarbon carbon-dispersing dispersion. The images are produced with a sharp gradation, so that the originals in the form of texts were reproduced with very sharp letters on a clean background. Images have a high density, and recording materials have a low memory effect and high sensitivity. Example 4. 884 ml of a 57.5% solution in toluene of a copolymer of vinyl acetate: methyl acrylate: acrylic acid- ( 87; 12: 1% by weight) diluted with 3316 ml of toluene.The following ingredients are added during placement: Photoconductive zinc oxide (average particle size 0.5 micron, kg 2400 10% solution of urazole in dimethylformamide, ml19.2 1% solution of bromophenol blue in methanol, ml 18 0.5% solution of the compound of the formula Okhl / s-sr-sr-sr (at BrN (CH, MO, KHCOCH3 1, in methanol, nl36) Dyyersy is treated in a sand mill to obtain grains of an average size of 0.15 micron, after which it is applied on vitrified paper 80 g / m - in the amount of 30 g of solid particles per 1 m. The applied layer is present in a la.minary flow dryer. The deposited material is negatively charged to -500 volts using a double crown, with the corona wires and the recording layer and under the substrate having a difference

-5000 0

accordingly

potentials

- | -5000 8 in relation to the so-called floating earth.

The charged recording layer is projected on a 3-second projection by means of a lamp with a tungsten filament of 100 Vg / 12 V, placed at a distance of 30 cm, through a transparency and developed with the help of a topper. Get a positive sevenfold increased reproduction of the slide. The manufacturer is prepared by diluting the concentrated developing mixture below, and 1M Isopar P (trade name for isoparaffin hydrocarbon mixture having a boiling range of 177-188 ° C, ESSO Belgium N. V) in a volume ratio of 15: 1000: Soot ( average particle size

20 nm, g30

Zinc monotridecyl phosphate as dispersing agent, g1,5 Isopar H, ml 750 Binder solution, prepared as described below, g 150 Binder solution is prepared by heating 500 g Alkidal 67 trade name Farbenfabriken A.J. for modified flax oil (67 % by weight of alcd salt and 500 ml of white spirit containing 11% by weight of aromatics at 60 ° C until a clear solution is obtained, followed by cooling.

The layer is charged up to 4-500 positons in the same element with a double crown.

A positively charged recording layer is exposed in an enlarger described above, but with a negative multi-image display as the original. Thanks to the use of EO pro vptel, indicated viiii, get a sevenfold enlarged reproduction, having a reversed image but with respect to the negative image of the microfilm.

Example 5. 360 g of a vinyl acetate: crotonic sonolymer (95.7: 4.3% by weight) is dissolved in a mixture of 21.4 L of dichloroethane and 1.6 g of ethanol. 12 kg of zinc oxide with particles of an average size of 0.15 microns in 8 liters of methyl isobutyl ketone are added to the binder solution. The resulting mixture is homogenized and, with stirring, the following mixture is added to 43280 kg of the resulting dispersion:

10% solution of urazol in dimethylformamide, ml88.8

HYPALON 30 dissolved in

8325 l of dichloroethane, g1665

0.5% compound solution

0

J-CH CH-CH (.r V

Bfn

(CH2) 4S02NH (; oCH: 3

in dimethylformamide, ml 162

1% bromofeiol solution

blue in methanol, ml 45,5

The resulting dispersion is applied with a knife to a conducting paper base of 67 g / lg2 in an amount of 25 g of solid particles per 1 - 2, then it is formed at 80 ° C. The thin layer is negatively charged to -600 in a double crown.

The charged layer is projected and exposed to a 10-second lamp with a 400-watt tungsten filament, placed at a distance of 40 cm, through a transparency and is shown by an electrophoretic promoter described in Example 4. A positive, sevenfoldly increased reproduction of the positive radiation is obtained.

The same sizing layer is charged with a positive to - | -500 in the same element with a double corona. A positively charged recording layer is exposed in an optical magnifier, indicated above, but with a negative image on the microfilm as an original.

Through the use of the developer described in Example 4, a sevenfold enlarged reproduction is obtained, having a reversed image in relation to the negative image of the microfilm. Example 6 525 g of vinyl chloride copolymer: viii acetate: maleic anhydride (85: 14: 1% by weight) is dissolved in 39.5 l of dichloroethane. The following mixture is added to this solution: 10% monobutyl phosphate solution

in ethanol, ml280

Ethanol, l2720

Zinc oxide with medium particles

size 0.17 micron, kg21

 The following mixture is added to disnergy: Dichloroethane, L2550

Ethanol, ml600

Pzonar N, l3,1

10% solution of urazol in dimethylformamide, ml90

Soiolimer viyl chloride: vinyl acetate: vinyl alcohol (91: 3: 6% by weight) dissolved in 2 l of dichloroethene,.

0 Ethanol, ml2-1

Vinyl acetate copolymer: vinyl laurate (80: 20% by weight), g 1548

1% -1nd solution of bro. M.phenol o

crap in methanol, ml47

0.5% compound solution

-CH CH-CH cf

 BfK-H SbN5

60 HjC,

(mon, 5o, gasosnz, d

The resulting dispersion is applied in the amount of 27 g of solid particles per 1 m on vitrified paper of 60 g / m, the layer is dried in a laminar flow dryer at nrn 80 ° C.

Charging, exposure and development are carried out according to Example 5.

Subject invention

Claims (9)

1. Photoconductive. A material consisting of a substrate and a photoconductive layer comprising semiconductor zinc oxide, a polymer binder and an organic compound, characterized in that, in order to increase the dark resistance of the photoconductive layer, reduce the memory effect, improvement of the charge capacity of the photoconductive layer to the negative corona and the possibility of charging the photoconductive layer with a positive corona discharge; an organic compound of the general formula II / -N-R, Z - N-RO where RI and Kr are a hydrogen atom, unsubstituted or substituted alkyl, unsubstituted or substituted aryl, unsubstituted or substituted acyl, unsubstituted or substituted heterocyclic ring, or RI and R2 are all atoms necessary to close the ring system; Z is the atoms required for the closure of a 5 or 6-membered unsubstituted or substituted heterocyclic ring; X is an oxygen atom or an imino group, with not less than one of the nitrogen atoms of the ring, closed by Z, contains a hydrogen atom, which can be replaced by a cation when using the compound in the form of a salt. 2. The material according to claim 1, characterized in that a substrate is used having a bulk the resistance is lower than the bulk resistance of the unexposed photoconductive layer. 3. The material of claim 2, wherein the paper substrate is applied. 4.Material on PP. 1-3, characterized in that a spectral sensitizer is introduced into the photoconductive layer. 5.Material on PP. 1-4, characterized in that applied as a semiconductor a mixture of zinc oxide with another semiconductor, for example cadmium chalcogenide in an amount of 0.01 -10% by weight of zinc oxide. 6.Material on PP. 1-5, characterized in that zinc oxide and polymeric binder are taken in a ratio from 1: 3 to 1: 9. 7.Material on PP. 1-6, characterized in that a polymeric binder containing acid groups is used. 8. Material on PP. 1-7, characterized in that, in order to increase the dark resistance of zinc oxide, an organic phosphoric hydroxy acid is introduced into the photoconductive layer. 9. Material on PP. 1-8, characterized in that urazol or its derivatives are used as an organic compound.