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Publication numberUS3373141 A
Publication typeGrant
Publication dateMar 12, 1968
Filing dateOct 8, 1964
Priority dateOct 8, 1964
Also published asDE1570702A1
Publication numberUS 3373141 A, US 3373141A, US-A-3373141, US3373141 A, US3373141A
InventorsAftergut Siegfried
Original AssigneeGen Electric
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Photoconductive copolymers of styrene and acrolein derivatized with aryl amines
US 3373141 A
Abstract  available in
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Claims  available in
Description  (OCR text may contain errors)

United States Patent PHGTGCUNDUCTIVE CGPOLYMERS 0F TYRENE ACROLEIN DEPJVATEZED WiTH ARYL AMENES Siegfried Aftergut, Schenectady, N .Y., assignor to General Electric Company, a corporation of New York No Drawing. Filed Oct. 8, 1964, Ser. No. 402,635 8 'Clairns. (CL-Ztl-SZ) ABSTRACT OF THE DES CLOSURE A copolymerized styrene-acrolein resin is reacted with an aromatic amine or hydrazine to give a photoconductive material.

This invention relates to organic photoconductive materials useful in applications requiring photoconductors such as photoplastic recording. More particularly, this invention relates to photoconductive materials comprising a polyal-dehyde resin modified by the addition of aromatic amines or hydrazines.

The recording of information on a deformable photoconductive medium in the form of minute light-modifying deformations is known. By one such method of information storage, the deformations are formed on the storage medium by first charging the surface to a uniform potential, then exposing to electromagnetic radiation and finally making the effect of the radiation visible by heatsoftening the deformable storage medium. Exposure to electromagnetic radiation produces a latent electrostatic image. On softening the storage medium, the electrostatic forces cause the formation of physical deformations which correspond to the charge pattern of the latent image. Upon cooling the medium, the deformations become permanently fixed on the surface of the recording medium and are thereby permanently stored unless erased by reheating. The information stored in the form of these deformations is retrieved by projecting a beam of light through the medium. The projecting light is diffracted or refracted by the deformations to produce a spatial light image corresponding to the original image.

The information storage medium as known may comprise a multilayer laminate, one of the layers comprising a photoconductive material. The laminate may be prepared in the form of any suitable configuration such as, for example, a tape, disc, or sheet. The recording layer of the laminate may be prepared from a solid thermoplastic polymer or a mixture of such polymers Which are deformable by the application of heat.

Organic photoconductors usually do not have desirable mechanical and film-forming properties; hence, it is the general practice to dissolve or disperse these photoconductors in an inert polymeric media such as polystyrene and polyvinyl chloride. The mixtures of inert media and photoconductors have considerable drawbacks in practical applications including lack of homogeneity, because of the incompatibility of the components, and difliculty of preparing thin films due to the solubility difierences of the components. Further, there maybe a decrease of photoconductor concentration during storage or use due to photoconductor volatility. These disadvantages are eliminated by the use of photoconductor compositions made in accordance with my invention. Such photoconductors are characterized by their homogeneity, stability, and filmforming ability.

It is, therefore, one object of my invention to provide a stable photoconductive material.

It is a further object of my invention to provide a homogeneous photoconductive material.

It is a further object of my invention to provide a ice photoconductive material that has excellent film-forming properties.

Briefly, this invention relates to the chemical tion of a copolymerized styrene-acrolein resin, common- 5 ly known as a polyaldehyde, by co-reacting the resin with aromatic amines or hydrazines to give a photoconductive material having unexpected properties.

Those parts of my invention which are considered to be new are set forth in detail in the claims appended hereto. The invention, however, may be better understood and further objects and advantages thereof appreciated from a consideration of the following description.

The polyaldehyde resins are known in the art. While others may be used, the polyaldehyde resin used in the examples given in this application comprise a photoelectrically inert copolymer of styrene and acroleln having the following formula:

modifica- Formula I I:CH2(IJHEGH2CH I (1H H 0 at The properties of the styrene-acrolein copolymer are listed as follows:

Elemental analysis of the material gave 83.7% carbon and 8.3% hydrogen, leaving 8.0% for oxygen by difference. According to this analysis, values for it and m are about 1.5 and 1, respectively, so that the resin contains 0.47 equivalent of carbonyl per 100 g.

In carrying out my invention the copolymer above referred to was allowed to react with a number of aromatic amines and hydrazines. The reaction took place between the carbonyl group of the resin and amino group of the co-reactant to give Schitf base linkages With the amines and the hydrazones with the hydrazines.

Formula II below is illustrative of a structure when the reacting amine is N,N-dimethyl-p-phenylenediamine. If less than a stoichiometric amount of amine is used or if the reaction is incomplete the resulting product would contain some unreacted acrolein residues.

Formula II CHzCIJH CHMCH H CH3 Formula III oHlon oHloH n N- O2 Jn N02 111 As previously stated, the polyaldehyde resin is reacted with aromatic amines and hydrazines. The amino derivatives correspond to the general formula lTIHa where R is hydrogen, alkyl, alkoxy, alkylamine, nitro, phenylazo, hydroxy, acyl, aldehydo, halogen, cyano, phenylamino, heterocyclic residue and 2,4-dinitrophenylamino and R" may be any of these substituents or identical to R.

V The polyaldehyde resin may also be co-reacted with hydrazine derivatives which correspond to the general formula NHNH2 R! where R is hydrogen, alkyl, alkoxy, akylarnine, nitro, phenylazo, hydroxy, acyl, aldehydo, halogen, eyano, phenylamino, heterocyclic residue, 2,4 dinitrophenylamino and R may be any of these substituents or identical to R.

The following specific examples are given to illustrate the various advantages of the present invention and are not to be taken as limiting in any way. All parts are by weight.

Example 1 A mixture consisting of 7.5 g. of copolymer of styrene and acrolein, 4 g. of N,N-dimethyl-p-phenylenediamine, and 50 ml. of toluene was heated at reflux for 5 hours. The solution was cooled and added dropwise with stirring to 400 ml. of methanol to give 8 g. of a tan-colored precipitate of a copolymer of styrene and acrolein derivatized with N,N-dimethyl-p-phenylenediamine. The melting point of the product was 168-170 C. The analysis was: 84.2% C, 8.5% H, and 7.1% N. Since the percentage of these elements adds to 99.8%, it is inferred that essentially all the carbonyl groups originally present have been converted.

Example 2 melting range of 178195 C. The analysis was 66.6% C,

5.6% H, and 12.9% N. The percentage of oxygen was 14.9 by difference. Since the ratio of nitrogen to oxygen atoms in the product can be shown to be one, it is inferred that all the carbonyl groups in the starting material were derivatized.

Example 3 Using the general method described in Example 1, there was prepared a copolymer of styrene and acrolein derivatized with p-phenylazoaniline, having a melting point of l63-164 C. and containing 83.0% C, 7.5% H, and 4.8% N. 1

Example 4 By the general method described in Example 2 there was prepared a copolymer of styrene and acrolein derivatized with p-nitroaniline having a melting point of 4 187-192" C. and having an analysis of 77.3% C, 7.1% H, and 5.8% N.

Example 5 By the general method of Example 2 there was prepared a copolymer of styrene and acrolein derivatized with 2,4-dinitro-4'-aminodiphenylamine having a melting point of 158-170 C. and having an analysis of 74.2% C, 6.3% H, and 8.7% N.

Example 6 Using the general method described in Example 2 there was prepared a copolymer of styrene and acrolein derivatized with 4-methoxy-2-nitroaniline having an analysis of 82.7% C, 8.3% H, and 0.59% N.

A typical application of the above composition is as follows. A benzene solution was prepared comprising 20% of the copolymer of styrene and acrolein derivatized with p-phenylazoaniline of melting point of 160-165 C., 55% of polystyrene, and 25% of a polystyrene plasticizer. The solution was used for casting a thin film on a glass slide coated with a thin, electrically-conducting layer of tin oxide. The polymeric film was given an electrostatic charge in the dark by means of corona discharge. An ultra-violet image was projected into the charged film layer and the film was quickly heated to the flow point. There was obtained an image on the film in the form of ripplesor grooves which corresponded to the projected image. The ripples could be removed and the film restored to its original conditions by re-melting the polymeric film.

As many widely different embodiments of this invention may be made without departing from the spirit and scope thereof, it is to be understood that this invention is not limited to the specific embodiments thereof except as defined in the appended claims.

What I claim as new and desire to secure by Letters Patent of the United States is:

1. A photoconductive thermoplastic material consisting essentially of the reaction product of a styrene-acrolein resin and a compound having the formula R! where R is hydrogen, alkyl, alkoxy, alkylamine, nitro, phenylazo, hydroxy, acyl, aldehydo, halogen, cyano, phenylamino, heterocyclic residue, 2,4-dinitrophenylamino, and R" is selected from the same group as R.

2. A photoconductive thermoplastic material consisting essentially of the reaction product of a styrene-acrolein resin and N,-N-dirnethylparaphenylenediamine.

3. A photoconductive thermoplastic material consisting essentially of the reaction product of a styrene-acrolein resin and paraphenylazoaniline.

4. A photoconductive thermoplastic material consisting essentially of the reaction product of a styrene-acrolein resin and paranitroaniline.

5. A photoconductive thermoplastic material consisting essentially of the reaction product of a styrene-acrolein resin and 2,4-dinitro-4'-aminodiphenylamine.

6. A photoconductive thermoplastic material consisting essentially of the reaction product of a styrene-acrolein resin and 2-methoxy-2-nitroaniline.

7. A photoconductive thermoplastic material consisting essentially of the reaction product of a styrene-acrolein resin and a compound having the formula ITIHNH:

3,373,141 5 6 Where R is hydrogen, alkyl, alkoxy, alkylamine, nitro, References Cited phenylazo, hydroxy, acyl, aldehydo, halogen, cyano, UNITED STATES PATENTS phenylamino, heterocyclic residue, 2,4-dinitrophenylamino, and R" is selected from the same group as R. 3,163,531 12/1964 Schlesmger 250.725

8. A photoconductive thermoplastic material consisting 5 essentially of the reaction product of a styrene-acrolein WILLIAM SHORT Prlma'y Exammer' resin and 2,4dinitrophenylhydrazine. E. M. WOODBERRY, Assistant Examiner.

Patent Citations
Cited PatentFiling datePublication dateApplicantTitle
US3163531 *May 20, 1960Dec 29, 1964Azoplate CorpPhotoconductive layers for electrophotographic purposes
Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US3503739 *Jan 3, 1966Mar 31, 1970Eastman Kodak CoPhotoconductive layers and their application to electrophotography
US3884689 *Aug 30, 1973May 20, 1975Xerox CorpPolycyclic aromatic polymer as a photoconductor or overlayer
US5623014 *Jun 3, 1993Apr 22, 1997Basf AktiengesellschaftDispersion or solution crosslinkable at room temperature with hydroxylamines or oxime ethers
Classifications
U.S. Classification525/328.7, 430/73, 526/315, 430/50, 525/377, 430/74
International ClassificationC08F8/32, G03G5/07, C08G2/00
Cooperative ClassificationG03G5/071, C08F8/32
European ClassificationC08F8/32, G03G5/07B