Photoconductive polymer and photoconductive compositions and elements containing same

• US 4,025,341 A
• Filed: 12/20/1974
• Issued: 05/24/1977
• Est. Priority Date: 12/20/1974
• Status: Expired due to Term

• Current Assignee: Eastman Kodak Company
• Original Assignee: Eastman Kodak Company
• Inventors: Rule, Norman G.
• Primary Examiner(s): Weinblatt, Mayer
• Application Number:
  US05/534,980
• Time in Patent Office: 886 Days
• Field of Search: 96/1.6, 96/1.5, 260/65
• US Class Current: 430/58.6
• CPC Class Codes: G03G 5/0614 Amines
• CPC Class Codes: G03G 5/0618 containing oxygen and nitrogen
• CPC Class Codes: G03G 5/076 having a photoconductive moiety in the polymer backbone

Abstract

A photoconductive polymer, and photoconductive insulating compositions and elements containing the same, are disclosed. The aforementioned polymer is a condensation product, preferably of relatively low molecular weight, of certain tertiary aromatic amines and certain carbonyl-containing compounds.

Claims

1. In a photoconductive insulating element comprising:

(a) a conductive support,

(b) a charge-generation layer coated on said support and

(c) a charge-transport layer in electrical contact with said charge-generation layer,

(i) said charge-generation layer having a thickness of about 0.1 to about 15 microns comprising a continuous, electrically insulating, polymer phase and dispersed in said continuous phase a discontinuous phase comprising a finely divided, particulate, co-crystalline complex of (1) at least one polymer having an alkylidene diarylene group in a recurring unit and (2) at least one pyrylium-type dye salt, said co-crystalline complex, upon exposure to activating radiation for said complex, capable of generating and injecting charge carriers into said charge-transport layer, and

(ii) said charge-transport layer comprising an organic composition in electrical contact with said charge-transport layer, said organic composition comprising as a p-type, charge-transport material an organic photoconductive material capable of accepting and transporting injected charge carriers from said charge-generation layer,

the improvement wherein said p-type, charge-transport material is a photoconductive polymer having the formula;

##STR12## wherein;

n represents an integer of from 0 to about 20;

each of R² and R³ represents hydrogen or, when taken together, R² and R³ represent a chemical bond which completes a carbazole nucleus;

Each of R⁴, R⁵ and R⁶, which may be the same or different, represents a member selected from the group consisting of a substituted or unsubstituted alkyl or aryl group, said substituted alkyl group having a substituent selected from the group consisting of an alkoxy, aryloxy, amino, hydroxy, alkylamino, aryl arylamino, nitro, cyano or a halogen group, said substituted aryl group having a substituent selected from the group consisting of an alkoxy, aryloxy, amino, hydroxy, alkylamino, arylamino, nitro, cyano, halogen or alkyl group;

each of R⁷, R⁸, R⁹, R¹⁰, R¹¹ and R¹², which may be the same or different, represents a member selected from the group consisting of hydrogen, the substituted and unsubstituted alkyl and aryl groups as defined for R⁴, R⁵ and R⁶, an alkoxy group, aryloxy group, halogen, nitro group, cyano group, amino group or an acyl group;

each of R¹ and R¹⁴, which may be the same or different, represents a member selected from the group consisting of hydrogen and the substituted and unsubstituted alkyl and aryl groups defined for R⁴, R⁵ and R⁶ ; and

each of R and R¹⁶, which may be the same or different, represents a member selected from the substituted and unsubstituted alkyl and aryl groups defined for R⁴, R⁵ and R⁶ ;

with the proviso that, when taken together, R¹ and R or R¹⁴ and R¹⁶ represent the carbon atoms necessary to complete a cycloalkyl group containing 3 to about 21 carbon atoms in the cycloalkyl ring.

2. In a photoconductive insulating element having at least two layers comprising a charge-generation layer in electrical contact with a charge-transport layer,

(a) said charge-generation layer having a thickness of from about 0.1 to about 15 microns comprising a continuous, electrically insulating, polymer phase and dispersed in said continuous phase a discontinuous phase comprising a finely-divided, particulate, co-crystalline complex of (i) at least one polymer having an alkylidene diarylene group in a recurring unit and (ii) at least one pyrylium-type dye salt, said co-crystalline complex, upon exposure to activating radiation for said complex, capable of generating and injecting charge carriers into said charge-transport layer,

(b) said charge-transport layer comprising an organic composition containing as a p-type, charge-transport material an organic photoconductive material capable of accepting and transporting injected charge carriers from said charge-generation layer,

the improvement wherein said p-type, charge-transport material is a photoconductive polymer having the formula ##STR13## wherein n represents an integer of from 0 to about 20;

R² and R³ each represent hydrogen or, when taken together, R² and R³ represent a chemical bond which completes a carbazole nucleus;

R⁴, r⁵ and R⁶, which may be the same or different, each represent a member selected from the group consisting of a substituted or unsubstituted alkyl or aryl group, said substituted alkyl group having a substituent selected from the group consisting of an alkoxy, aryloxy, amino, hydroxy, alkylamino, aryl, arylamino, nitro, cyano, or a halogen group, said substituted aryl group having a substituent selected from the group consisting of an alkoxy, aryloxy, amino, hydroxy, alkylamino, arylamino, nitro, cyano, halogen, or an alkyl group;

R⁷, r⁸, r⁹, r¹⁰, r¹¹ and R¹², which may be the same or different, each represent a member selected from the group consisting of hydrogen, the substituted and unsubstituted alkyl and aryl groups as defined for R⁴, R⁵ and R⁶, an alkoxy group, aryloxy group, halogen, nitro group, cyano group, amino group, or an acyl group;

R¹ and R¹⁴, which may be the same or different, each represent a member selected from the group consisting of hydrogen and the substituted and unsubstituted alkyl and aryl groups defined for R⁴, R⁵ and R⁶ ;

R and R¹⁶, which may be the same or different, each represent a member selected from the substituted and unsubstituted alkyl and aryl groups defined for R⁴, R⁵ and R⁶ ;

with the proviso that, when taken together, R¹ and R or R¹⁴ and R¹⁶ represent the carbon atoms necessary to complete a cycloalkyl group containing 3 to about 21 carbon atoms in the cycloalkyl ring.

3. A photoconductive insulating element as defined in claim 2 wherein R and R¹⁶ each represent an unsubstituted alkyl group having 1 to about 8 carbon atoms;

R⁴, R⁵ and R⁶ each represent a member selected from the group consisting of an unsubstituted phenyl group, an alkyl-substituted phenyl group having 1 to about 3 carbon atoms in the alkyl substituent, or an unsubstituted alkyl group having 1 to 4 carbon atoms in the alkyl group;

R¹, R², R³, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹² and R¹⁴ represent hydrogen; and

n is an integer of from 0 to about 12.

4. A photoconductive insulating element as defined in claim 2 wherein said photoconductive polymer is selected from the group consisting of ##STR14## wherein n is an integer of from 0 to about 12.

5. A photoconductor insulating composition comprising a condensation polymer of (a) a tertiary amine having at least 2 phenyl groups bonded to the amine atom, (b) an amount of sensitizer effective to sensitize said composition and (c) a carbonyl-containing compound having the formula:

##STR15## wherein R¹ represents a member selected from the group consisting of hydrogen, alkyl group or an aryl group;

R represents an alkyl or aryl group; and

R¹ and R, when taken together, represent the carbon atoms necessary to complete a cycloalkyl group containing 4 to about 8 carbon atoms in the cycloalkyl ring.

6. In an electrophotographic element comprising a conductive support and a photoconductive layer coated over said support, the improvement wherein said photoconductive layer comprises the photoconductive insulating composition of claim 5.

7. In an electrophotographic process wherein an electrostatic charge pattern is formed by a photoconductive element comprised of an electrically conducting support having coated thereover a layer of a photoconductive insulating composition, the improvement wherein said photoconductive insulating composition is as described in claim 5.

8. A photoconductive insulating composition comprising an electrically insulating, film forming polymeric binder, a photoconductive polymer, and an amount of sensitizer effective to sensitive said composition, said photoconductive polymer having the formula ##STR16## wherein n represents an integer of from 0 to about 20;

R² and R³ each represent hydrogen or, when taken together, R² and R³ represent a chemical bond which completes a carbazole nucleus;

R⁴, r⁵ and R⁶, which may be the same or different, each represent a member selected from the group consisting of a substituted or unsubstituted alkyl or aryl group, said substituted alkyl group having a substituent selected from the group consisting of an alkoxy, aryloxy, amino, hydroxy, alkylamino, aryl, arylamino, nitro, cyano, or a halogen group, said substituted aryl group having a substituent selected from the group consisting of an alkoxy, aryloxy, amino, hydroxy, alkylamino, arylamino, nitro, cyano, halogen, or an alkyl group;

R⁷, r⁸, r⁹, r¹⁰, r¹¹ and R¹², which may be the same or different, each represent a member selected from the group consisting of hydrogen, the substituted and unsubstituted alkyl and aryl groups as defined for R⁴, R⁵ and R⁶, an alkoxy group, aryloxy group, halogen, nitro group, cyano group, amino group, or an acyl group;

R¹ and R¹⁴, which may be the same or different, each represent a member selected from the group consisting of hydrogen of the substituted and unsubstituted alkyl and aryl groups as defined for R⁴, R⁵ and R⁶ ;

R and R¹⁶, which may be the same or different, each represent a member selected from the substituted and unsubstituted alkyl and aryl groups defined for R⁴ R⁵ and R⁶ ;

with the proviso that, when taken together, R¹ and R or R¹⁴ and R¹⁶ represent the carbon atoms necessary to complete a cycloalkyl group containing 3 to about 21 carbon atoms in the cycloalkyl ring.

9. A photoconductive insulating composition as defined in claim 8 wherein R and R¹⁶ each represent an usubstituted alkyl group having 1 to about 8 carbon atoms;

R⁴, R⁵ and R⁶ each represent a member selected from the group consisting of an unsubstituted phenyl group, an alkylsubstituted phenyl group having 1 to about 3 carbon atoms in the alkyl substituent, or an unsubstituted alkyl group having 1 to 4 carbon atoms in the alkyl group;

R¹, R², R³, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹² and R¹⁴ represent hydrogen; and

n is an integer of from 0 to about 12.

10. A photoconductive insulating composition as defined in claim 8 wherein said sensitizer is present in an amount of from about 0.005 to about 10 percent by weight of said composition and said photoconductive polymer is present in an amount of from about 15 to about 90 percent by weight of said composition.

11. A photoconductive insulating composition as defined in claim 8 wherein said composition is a homogeneous composition having said photoconductive polymer in solid solution with said polymeric binder.

12. In an electrophotographic element comprising a conductive support and a photoconductive layer coated over said support, the improvement wherein said photoconductive layer comprises the photoconductive insulating composition of claim 8.

13. A homogeneous photoconductive insulating composition comprising an electrically insulating, film forming polymeric binder, a photoconductive polymer in an amount equal to at least about 15 percent by weight of said composition, and a sensitizer for said composition in an amount within the range of from about 0.005 to about 10 percent by weight of said composition, said photoconductive polymer in solid solution with said binder and having the formula ##STR17## wherein n represents an integer of from 0 to about 20;

R² and R³ each represent hydrogen or, when taken together, R² and R³ represent a chemical bond which completes a carbazole nucleus;

R⁴, r⁵ and R⁶, which may be the same or different, each represent a member selected from the group consisting of a substituted or unsubstituted alkyl or aryl group, said substituted alkyl group having a substituent selected from the group consisting of an alkoxy, aryloxy, amino, hydroxy, alkylamino, aryl, arylamino, nitro, cyano or a halogen group, said substituted aryl group having a substituent selected from the group consisting of an alkoxy, aryloxy, amino, hydroxy, alkylamino, arylamino, nitro, cyano, halogen, or an alkyl group;

R⁷, r⁸, r⁹, r¹⁰, r¹¹ and R¹², which may be the same or different, each represent a member selected from the group consisting of hydrogen, the substituted and unsubstituted alkyl and aryl groups as defined for R⁴, R⁵ and R⁶, an alkoxy group, an aryloxy group, a halogen, a nitro group, a cyano group, an amino group, or an acyl group;

R¹ and R¹⁴, which may be the same or different, each represent a member selected from the group consisting of hydrogen and the substituted and unsubstituted alkyl and aryl groups defined for R⁴, R⁵ and R⁶ ;

R and R¹⁶, which may be the same or different, each represent a member selected from the substituted and unsubstituted alkyl and aryl groups defined for R⁴, R⁵ and R⁶ ;

with the proviso that, when taken together, R¹ and R or R¹⁴ and R¹⁶ represent the carbon atoms necessary to complete a cycloalkyl group containing 3 to about 21 carbon atoms in the cycloalkyl ring.

14. A homogeneous photoconductive insulating composition as defined in claim 13 wherein said photoconductive polymer is selected from the group consisting of ##STR18## wherein n is an integer of from 0 to about 12.

15. An aggregate photoconductive insulating composition comprising a continuous, electrically insulating binder phase containing (a) dissolved therein one or more photoconductive polymers and (b) dispersed therein a particulate, cocrystalline complex of (1) a pyrylium-type dye salt and (2) a polymer having an alkylidene diarylene group in a recurring unit thereof, at least one of said photoconductive polymers having the formula:

##STR19## wherein;

n represents an integer of from 0 to about 20;

each of R² and R³ represents hydrogen or, when taken together, R² and R³ represent a chemical bond which completes a carbazole nucleus;

each of R⁴, R⁵ and R⁶, which may be the same or different, represents a member selected from the group consisting of a substituted or unsubstituted alkyl or aryl group, said substituted alkyl group having a substituent selected from the group consisting of an alkoxy, aryloxy, amino, hydroxy, alkylamino, aryl, arylamino, nitro, cyano or a halogen group, said substituted aryl group having a substituent selected from the group consisting of an alkoxy, aryloxy, amino, hydroxy, alkylamino, arylamino, nitro, cyano, halogen or an alkyl group;

each of R⁷, R⁸, R⁹, R¹⁰, R¹¹ and R¹², which may be the same or different, represents a member selected from the group consisting of hydrogen, the substituted and unsubstituted alkyl and aryl groups as defined for R⁴, R⁵ and R⁶, an alkoxy group, aryloxy groups, halogen, nitro group, cyano group, amino group or an acyl group;

each of R¹ and R¹⁴, which may be the same or different, represents a member selected from the group consisting of hydrogen and the substituted and unsubstituted alkyl and aryl groups defined for R⁴, R⁵ and R⁶ ; and

each of R and R¹⁶, which may be the same or different, represents a member selected from the substituted and unsubstituted alkyl and aryl groups defined for R⁴, R⁵ and R⁶ ;

with the proviso that, when taken together, R¹ and R or R¹⁴ and R¹⁶ represent the carbon atoms necessary to complete a cycloalkyl group containing 3 to about 21 carbon atoms in the cycloalkyl ring.

16. An aggregate photoconductive insulating composition as defined in claim 15 wherein said dye salt is a 2,4,6-substituted thiapyrylium dye salt, R and R¹⁶ each represent an unsubstituted alkyl group having 1 to about 8 carbon atoms;

R⁴, R⁵ and R⁶ each represent a member selected from the group consisting of an unsubstituted phenyl group, an alkyl-substituted phenyl group having 1 to about 3 carbon atoms in the alkyl substituent, or an unsubstituted alkyl group having 1 to 4 carbon atoms in the alkyl group;

R¹, R², R³, R⁷, R⁸, R⁹, R¹⁰ R¹¹, R¹² and R¹⁴ represent hydrogen; and

n is an integer of from 0 to about 12.

17. In an electrophotographic element comprising a conductive support and a photoconductive layer coated over said support, the improvement wherein said photoconductive layer comprises the photoconductive insulating composition of claim 15.

18. An aggregate photoconductive insulating composition comprising a continuous, electrically insulating binder phase containing (a) dissolved therein one or more photoconductive polymers and (b) dispersed therein a particulate, co-crystalline complex of (1) a thiapyrylium dye salt and (2) a polycarbonate containing an alkylidene diarylene group in the recurring unit thereof, at least one of said photoconductive polymers having the formula:

##STR20## wherein;

n represents an integer of from 0 to about 20;

each of R² and R³ represents hydrogen or, when taken together, R² and R³ represent a chemical bond which completes a carbazole nucleus;

each of R⁴, R⁵ and R⁶, which may be the same or different, represents a member selected from the group consisting of a substituted or unsubstituted alkyl or aryl group, said substituted alkyl group having a substituent selected from the group consisting of an alkoxy, aryloxy, amino, hydroxy, alkylamino, aryl, arylamino, nitro, cyano or a halogen group, said substituted aryl group having a substituent selected from the group consisting of an alkoxy, aryloxy, amino, hydroxy, alkylamino, arylamino, nitro, cyano, halogen or alkyl group;

each of R⁷, R⁸, R⁹, R¹⁰, R¹¹ and R¹², which may be the same or different, represents a member selected from the group consisting of hydrogen, the substituted and unsubstituted alkyl and aryl groups as defined for R⁴, R⁵ and R⁶, an alkoxy group, an aryloxy group, a halogen, a nitro group, a cyano group, an amino group or an acyl group;

each of R¹ and R¹⁴, which may be the same or different, represents a member selected from the group consisting of hydrogen and the substituted and unsubstituted alkyl and aryl groups defined for R⁴, R⁵ and R⁶ ; and

each of R and R¹⁶, which may be the same or different, represents a member selected from the substituted and unsubstituted alkyl and aryl groups defined for R⁴, R⁵ and R⁶ ;

with the proviso that, when taken together, R¹ and R or R¹⁴ and R¹⁶ represent the carbon atoms necessary to complete a cycloalkyl group containing 3 to about 21 carbon atoms in the cycloalkyl ring.

19. An aggregate photoconductive insulating composition as defined in claim 18 wherein R and R¹⁶ represent a member selected from the group consisting of an unsubstituted alkyl group having 1 to about 8 carbon atoms;

R⁴, R⁵ and R⁶ each represent a member selected from the group consisting of an unsubstituted phenyl group, an alkyl-substituted phenyl group having 1 to about 3 carbon atoms in the alkyl substituent, or an unsubstituted alkyl group having 1 to 4 carbon atoms in the alkyl group;

R¹, R², R³, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹² and R¹⁴ represent hydrogen; and

n is an integer of from 0 to about 12.

20. An aggregate photoconductive insulating composition as defined in claim 18 wherein at least one of said photoconductive polymers is selected from the group consisting of ##STR21## wherein n is an integer of from 0 to about 12.