Галерея 3250615

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Галерея 3250615
y 1966 J. A. VAN ALLAN ETAL 3,250,615
LIGHT-SENSITIVE LAYERS CONTAINING PYRYLIUM AND THIA'PYRYLIUM SALTS Flled Oct. 23, 1961 2 Sheets$heet 1 Fig.1
In 11mm mml III! In: llll 300 4 00 500mg POLY (V/N YL CINNAMYLI DE NEA CE TATE Figz 3 0O 4 00 5O 0 my POLY(VINYL CINNAMYLIDENEA CETATE) +COMPOUND 44 Fig: 3
Hill IIHTIN Ill] MI I!!! IlH-HIHIH 300 400 500 mp POLY(VINYL CINNA MATE) 3 O0 4 O0 500 m1! POLY (VINYL C/NNA MATE) COMPOUND 28 JizmesAUanAllan @orneliaflNalale Frederick JRauner IN V EN TORS ATTORNBYG AGENT y 0, 1966 J. A. VAN ALLAN ETAL 3,
LIGHT-SENSITIVE LAYERS CONTAINING PYRYLIUM AND THIAPYRYLIUM SALTS Filed Oct. 23. 1961 2 Sheets-Sheet 2 ill! IHI TTINIII Hll Hll III! III! Fig.5
300 400 500mu POLY(BUTYLENE CINNAMALMALONATE) FigzG POLY (BUTYLENE CINNA MA LMALONATE)+COMPOUND 44 1 1| WWW! 1m 1m 1m 1m O O 400 500 mu PO LY VINYL ACETATE C0 AZIDOBENZOATE) ill! mgwwmm H w! llll O O 4 0 0 5 O 0 m u POLY (VINYL ACETATE-CO-AZIDOBENZOATE) +COMPOUND 44 Fig&
James AVanAl lan CorneliaGNaiale Frederick J. Rauner INVENTORS' K; CM'ZZW ATTORNEY AGENT United States Patent LIGHT-SENSITIVE LAYERS CONTAlNlNG PYRYLIUM AND THIAPYRYLIUM SALTS James A. Van Allan, Cornelia C. Natale, and Frederick J. Ranner, Rochester, N.Y., assignors to Eastman Kodak Company, Rochester, N.Y., a corporation of New Jersey Filed Oct. 23, 1961, Ser. No. 146,743
11 Claims. (Cl. 96-1) This invention is related to novel light-sensitive polymer layers and more particularly to light-sensitive polymer layers containing a pyrylium or a thiapyrylium salt as a novel class of sensitizers or as a novel class of photoconductors.
Various light-sensitive layers not containing silver halide compounds are well known in the art of making copies of documents, drawings, microfilm images, printed circuits, metal engraving, etc.
For example, various polymer layers, such as albumen, glue, and certain synthetic polymers, such as poly(vinyl alcohol), poly(vinyl cinnamate), etc., are used in making photoresists for metal engraving, the preparation of lithographic plates, printed circuits, etc.
These colloid layers are either inherently light-sensitive or are sensitized by the addition of certain sensitizing compounds. The exposure of these layers to activating radiation alters their physical properties, such as solvent solubility, so that by development with the appropriate solvent a relief image is obtained for printing, for metal etching, etc.
Another type of light-sensitive polymer layer is used in electrophotography. These layers contain a photoconducting material, such as zinc oxide, polyvinyl carbazole, etc., that are nonconductors of electricity before exposure and become electrical conductors upon exposure. Such elements are used in photoconductography where the passage of an electrical current through the conducting areas of the image exposed material produces a visible image, or in xerography where the conducting image produced by exposure to a light image allows an electrostatic charge on the layer to leak-off in an imageWise manner to produce an invisible electrostatic image that can be made visible by applying a xerographic developing composition which has color contrasting with the color of the ele ment. Usually, these developing agents are finely powdered materials.
Although some of the polymers comprising the materials described are inherently light sensitive, their degree of sensitivity is usually low and in the short wave length portion of the spectrum so that it is common practice to add materials to increase sensitivity and to shift the sensitivity toward the longer wave length portion of the visible spectrum. Increasing the sensitivity of such systems into the visible regions of the spectrum has several advantages: it makes available inexpensive and convenient light sources such as incandescent lamps; it reduces exposure time; it makes possible the recording of a wide range of colors in proper tonal relationship, and allows projection printing through various optical systems.
Many of the sensitizers available heretofore have not produced the desired speed increase or shifted the range of sensitivity as far into the longer wave lengths as is desired. Many of the sensitizers are very specific, being effective in one type of photosensitive system and completely ineffective in others.
There is a never ceasing search for new organic photoconductors for use in electrophoto graphic elements. Many of the prior art sensitizers used in electrophotographic elements that have absorption in the infrared region of the spectrum cannot be used effectively because they greatly increase the dark conductivity, causing them to lose their applied electrostatic charge rapidly in the dark.
3,25il-,6l5 Patented May 10, 1966 It is, therefore, an objectof our invention to provide a novel class of sensitizers for photosensitive systems which produces an unusual increase in sensitivity and extends the range of sensitivity into the longer wave lengths of the visible spectrum. Another object is to provide a novel class of sensitizers which are remarkably versatile and produce unusual increases in sensitivity and unusual increases in the range of spectral sensitivity in a number of dilferent photosensitive layers, including a variety of photosensitive polymer coatings as Well as organic photoconductor layers and coatings of inorganic semiconductor pigments.
Another object is to provide a new class of sensitizers for electrophotographic elements which absorb in the infrared region of the spectrum and yet which do not substantially increase the dark conductivity causing them to lose their applied electrostatic charge in the dark.
Another object is to provide a novel class of organic photoconductors for incorporation in binder coatings of electrophot-ographic elements.
Another object is to provide photosensitive layers containing our compounds as novel sensitizers, or novel photoconductors. I
Still other objects will be apparent from the following specification and claims.
These and other objects are accomplished by the use of light-sensitive film-forming compositions comprising a polymer and a pyrylium or a thiapyrylium salt compound represented advantageously by the following formula:
propoxy, butoxy, amyloxy, hexoxy, octoxy, etc.; aryl, such as phenyl, 4-biphenyl, a lkphenyl, such as 4-ethylphenyl, 4-propylphenyl, etc., alkoxyphenyl, e.g., 4-ethoxyphenyl, 4-methoxyphenyl, 4-amyloxyphenyl, 2-hexoxyphenyl, 2- m-ethoxyphenyl, 2-amyl-oxyphenyl, 3,4-dimethoxyphenyl, etc., w-hydroxy alkoxyphenyl, e.g., 2-hydroxyethoxyphenyl, 3-hydroxyethoxyphenyl, etc., 4-hydroxyphenyl, halophenyl, e.g., 3,4-dichlorophenyl, 3,4-dibromophenyl, 4-chlorophenyl, 2,4-dichlorophenyl, etc., azidophenyl, nitrophenyl, etc., aminophenyl, e.g., 4-diethylaminophenyl, 4-dimethylaminophenyl, etc.; X is a hetero atom, such as oxygen, sulfur and selenium; and Y is an anionic function.
In addition to the pyrylium and thiapyrylium salts described above, various other modifications can be made suchas 2,3,4,6-tetra substituted derivatives, bis pyrylium and thiapyrylium salts such as octamethylene-2,2'-bis[4, 6-di(4-methoxyphenyl) pyrylium fluoborate] and derivatives formed from a methyl substituted pyrylium salt and a cyclic ketone such as 2,6-dimethyl-4-pyrone.
The preferred pyrylium and thiapyrylium salts are prepared generally from the reaction of an aromatic aldehyde with a methyl aryl ketone in the presence of an acidic agent, such as boron trifiuoride or phosphoryl chloride. The pyrylium salt compounds thus obtained are converted to thiapyrylium salt compounds by treatment with sodium sulfide and an acid.
A wide variety of these salts have been made representing different solubility characteristics and optical absorptions to accommodate various photosensitive systerns.
Various photosensitive polymers examined in the past have differed widely in their response to sensitizers. For instance, polymers containing the cinnamic ester function can be readily sensitized by a number of ditferent classes of organic compounds. On the other hand, polymers containing the styryl ketone group (which is very similar in structure to the cinnamic ester group) show little or no response to these sensitizers. It was, there- .ffore, quite surprising that pyrylium and thjapyrylium salts would sensitize all the above-mentioned polymers and, in addition, sensitize elastomers and vinyl polymers. In addition, pyrylium and thiapyrylium salt sensitized coatings of organic and inorganic photoconductors used in electrophotography show high sensitivities when exposed to light. A number of our pyrylium and thiapyrylium salts also have been used to advantage as novel photoconductors in electrophotographic elements.
Among the pyrylium and thiapyrylium salts used ac cording to our invention are the representative examples listed in the table below:
TABLE I Compound Name of compound number 2,4,6-triphenylpyrylium perchlorate. 4-(4-methoxyphenyl)-2,6-diphenylpyrylium perchlo- 4-igdlchlorophenyl)-2,6-dlphenylpyrylium perchlo- 4-gigdichlorophenyl)-2,6-diphenylpyry]ium perchlo- 2,t;-i:-(4methoxyphenyl)-4-phenylpyrylium perchlo- 6-g lgnethoxyphenyl)-2A-diphenylpyry1ium perchloe. 2-(3,4 dichlorophenyl)-4-(-methoxyphenyl)-6-phenylpyrylium perchlorate. A 4- (4-amyloxyphenyl)-2,6-b1s (4-ethylphenyl) pyrylium perchlorate. 4-(4amy1oxyphenyl)-2,6-bis(4-methoxyphenyl)pyrylium perchlorate. 2,4,6-triphenylpyrylium fluoborate.
2,6-bis(4-ethylphenyl)-4-(4-methoxyphenybpyrylium perchlorate. 2,6-bis(4-ethy1phenyD-4-(4-methoxyphenyDpyrylium fluobora 6-(3,4-diethoxystyryl)-2,4-diphenylpyrylium perchlor 2,6 bls(*t-rnethoxyphenyl)-4-phenylthiapyrylium perchlorate. 4-(2,4-dichlorophenyl)-2,6-d1pheny1thiapyrylium perchlorate. 2,4,6-tri(4-methoxyphenyllthiapyrylium perchlorate. 2,6-bis(Mthylphenyl)-4-phenylthiapyrylium per chlorate. 4-(4-arnyloxyphenyl)-2,6bis(tethylphenybthiapyrylium perchlorate. 6-(4-dimethylamtnostyryl)'ZA-diphenyIthiapyryIium perchlorate. 2,4,6-triphenylthiapyrylium fiuoborate; 2,4,6-triphenylthiapyrylium sulfate.
4 TABLE L-Continued rylium perchlorate. 2-(3,4-diethosystyryl)-4,6-diphenylth1apyryliurn perchlorate. 2,4,6-trianisylthlapyrylium perchlorate. 6-ethyl-2,a-diphenylpyrylium fiuoborate. 2,6-bis(4ethylphenyl)-4-(4-methoxyphenyl) thlapyrylium chloride. 6-[AH-bis(-i'dlmethylaminophenyl)vinylene]-2,4-di(4- ethylphenyl) pyrylium perchlorate. 2,6-bis(4-amyloxyphenyl)-4- (4-methoxyphenyl).
thiapyrylium perchlorate; 6-(3,4-diethoxy-fi ethylstyryl)-2,4-diphenylpyryllum fluoborate. 6-(4-methoxy-fi-ethylstyryl)-2,4diphenylpyryliun1 fluoborate.
Our compounds are valuable as sensitizing agents for enhancing the sensitivity and extending the spectral range of sensitivity of a wide range of film-forming radiationtransparent polymers which may or may not be inherently light sensitive.
These polymers include the polyvinvyl resins, such as the poly(vinyl cinnamate) polymers described by Minsk et a1. U.S. 2,610,120, issue-d September 9, 1952, the polymers having recurring alkapolyenoate groups, e.g., the homopolymers and copolymers of copending Leubner and Unruh U.S. patent application entitled Novel Light- Sensitive Polymers" filed simultaneously with the immediate application, the polymeric chalcones, e.g., the polymeric chalcones of Allen and Van Allan, U.S. Patent 2,566,302, issued September 4, 1951, the azido polymers, e.g., poly (vinyl acetate-co-azidobenzoate) and many others described in the following paragraphs, the unsat urated esters, e.g., poly(vinyl cinnamalmalonate), poly- (acrylic acid ethyl acrylate), poly(tetramethylene cinnamalmalonate), etc., the esters and amides of the maleic anhydride copolymers of styrene described in Leubner, Williams and Unruh, U.S. Patent 2,816,091, issued December 10, 1957, and Smith, Smith and Unruh, U.S. Patent-2,811,509, issued October 29, 1957, e.g., styrene maleic anhydride copolyrner ester of 4-(2-hydroxyethyl)- fi-nitrostyrene, etc., polystyrene-co-butadiene, poly(vinyl butyral), poly(vinyl acetophenone), etc., the polyesters, such as those described in Michiels et al., U.S. Patent 2,956,878, issued October 18, 1960, etc.
Especially valuable polymers are those which contain recurring units containing one or more azido groups. Among those azide polymers are those described in Merrill et al., U.S. patent applications, Serial Nos. 525,271 and 525,368, filed July 29, 1955, now Patent Nos. 2,948,- 670 and 3,096,311 and in Rauner et al., U.S. patent application, Serial No. 18,745, filed March 30, 1960, now Patent No. 3,100,702. Representative azide polymers illustrating those advantageously sensitized according to our invention are described as follows.
Light-sensitive, film-forming azidostyrene homopolymers containing the following recurring structural unit:
or copolymers of said azidostyrenes consisting of the following recurring structural units in random combination:
wherein the ratio of III(a) units to III(b) units in each resin molecule can vary from 1:19 to 19:1, i.e., III(b) are present from 5 to 95 mole percent, and wherein m represents in each instance a digit 1 or 2, n represents a digit of from 0 to 2, X represents a hydrogen atom, a chlorine atom, an alkyl group containing from 1 to 4 carbon atoms, e. g., methyl, ethyl, propyl, butyl, etc., an alkoxy group containing from 1 to 4 carbon atoms, e.g., methoxy, ethoxy, propoxy, butoxy, etc., and a nitro group, and -R represents a unit such as ethylene, isobutylene, a 1,3-butadiene, styrene and substituted styrenes, etc., an a,f3-unsaturated monoor di-carboxylic acid unit such as acrylic acid, an a-alkylacrylic acid, maleic acid, c-itraconic acid, itaconic acid, etc., and the anhydrides, alkyl esters, imides, N-a-l-kyl imides, nitriles, amides, and N-alkyl and N, N-dialkyl substituted amides of these acids, fum aric and mesaconic acids and their alkyl esters, nitriles, amides and N- alkyl and N,N-dialkyl substituted amides, vinyl alkyl ketones such as vinyl methyl ketone, vinyl halides, such as vinyl chloride, vinylidene halides, such as vinylidene chloride, and the like units, and wherein in each instance in the above the alkyl and alkoxy groups contain from 1 to 4 carbon atoms, by diazotizing a polyaminostyrene or a copolymer-of aminostyrene and reacting the resulting diazonium salt with sodium azide, followed by separation of the azido derivative from the reaction mixture. The intermediate aminostyrene polymers can be prepared by ni-trating the styrene nucleus of the appropriate styrene polymer and then reducing the nitro derivative to the corresponding amine derivative. Where R in the above structure III is an B-unsaturated di-carboxylic acid unit, e.g., a 1:1 copolymer of an azidostyrene and maleic acid, the copolymer can be treated with acetic anhydride to give the maleic anhydride derivative and this can then be reacted with a variety of hydroxyland amino-containing components, including hydroxylated azide-containing components which greatly increase the azide content of the polymer molecule, to give the corresponding ester and amide derivatives. In place of the maleic acid-azidostyrene copolymer, there can be employed citraconic or itaconic acid copolymers with the azidostyrene.
To obtain the film-forming, light-sensitive polymers of the invention, wherein the azido grouping is contained in an ester type side chain of the polymer, as in the azidobenzoates of vinyl alcohol polymers represented, for example, by the homopolymers consisting essentially of the following recurring structural unit:
or by copolymers consisting essentially of the following recurring structural units in random combination:
(N3) in wherein the ratio of V(a) units to V(b) in each resin molecule can vary from 1:19 to 19: 1, and wherein m, n and X are as previously defined, and R represents a unit such as ethylene, isobuty lene, 1,3-butadiene, etc., a vinyl or isopropenyl carboxylic ester, ether, ketone, carbamate or acetal, and the like units, an o, m or p-azidobenzoyl chloride represented by the general formula:
-COCl wherein m, n and X are as above defined, is condensed with a polyvinyl alcohol, a partially hydrolyzed polyvinyl or a polyisopropenyl ester, e.g., partially hydrolyzed polyvinyl acetate, polyvinyl butyrate, polyvinyl benzoate, polyvinyl carbamate, polyvinyl cinnamate, polyvinyl cyanoacetate, polyvinyl azidobenzoate, etc., or with a partially hydrolyzed copolymer of vinyl and isopropenyl esters, or with partial alkyl ethers of polyvinyl alcohol, or with partial polyvinyl acetals. The free hydroxyl groups in each instance can be partially or substantially completely esterified, as desired, with the azidobenzoyl chloride reactant. Where the esterification of a partially hydrolyzed polyvinyl acetate with azidobenzoyl chloride is incomplete, the final light-sensitive polymer product may contain more than two different units making up the structure such as vinylazidobenzoate units, vinyl acetate units and vinyl alcohol units.
In place of the azidobenzoyl chloride, there may be employed an azidonaphthoyl chloride, azidophenylacyl chlorides, such as 0-, mor p-azidophenylacetyl chloride,
etc., an azidocinnamoyl chloride, and the like, to give the corresponding polymeric derivatives of the above-mentioned hydroxyl-containing polymers. The mentioned azido-group-containing acid chlorides are also capable of condensing with other hydroxylic polymeric materials,-
for example, with naturally occurring materials, such as cellulose, starch, guar, alginic acid or with their partially esterified or ethen'fied derivatives to give other operable light-sensitive polymers. The said acid chlorides are capable of condensing also with polymeric materials containing amino groups having free hydrogen atoms, for
example, with synthetic polymers, such as polyvinylamine,
or by copolymers consisting essentially of the following recurring structural units in random combination:
o o coon wherein the ratio of VII(a) units to V1105) units in each resin molecule can vary from 1:19 to 19:1, and wherein m, n, X and R are as previously defined, an mor pvazidophthalic anhydride is condensed with a hydroxylic polymer such as mentioned in the process for preparing the light-sensitive polymers of structures IV and V. The azidophthalic anhydride can be substituted by various azidonaphthalic anhydrides. Also; the azidophthalic and azidonaphthalic anhydrides may be condensed with aminogroup-containing synthetic polymers, such as polyvinylamines, polyvinyl anthranilates, polymeric: aminotriazoles, etc., and proteins, such as gelatin, casein, etc., to give the corresponding light-sensitive amide derivatives.
To obtain the film-forming, light-sensitive polymers of the invention wherein the azido grouping is contained in a still different ester type of side chain of the polymer as in the esters of azidophenylalkanols with maleic anhydride copolymers consisting essentially of the following recurring structural unit:
VIII. (R)m CH C H- an alkylimino group and p represents a digit 0 or 1, a
hydroxylated azido-group-containing compound, such as an o-, mor p-azidophenylallcanol, such as represented by the general formula:
I I D wherein m, n, X, R D and p are as previously defined, is condensed with a maleic anhydride copolymer, preferably With a 1:1 styrene-maleic anhydride copolymer. As typical azidobenzylalkanols, there may be employed, for example, p-azidobenzyl alcohol, o-azidobenzyl alcohol, m-azidobenzyl alcohol, 2-(azidophenyl)ethanol, an azidophenoxyethanol, an aliphatic hydroxylated azido compound, such as 2-azidoethanol or 2-azido-2-phenylethanol to give the corresponding light-sensitive esters. maleic anhydride copolymer can be replaced by polyacrylic or polymethacrylic anhydrides to give generally similar light-sensitive polymers with the said hydroxylated azido group containing compounds.
To obtain
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