JPH04264449A - Acid additive for back transfer in positive light sensitive electrostatic master - Google Patents

Abstract

PURPOSE: To improve offset characteristics by adding a specific acidic additive into a photosensitive composition for a single exposure photosensitive electrostatic master. CONSTITUTION: In the master consisting of an electrical conductive substrate carrying a layer of the photosensitive composition, the composition is composed of an organic polymer, a hexa-aryl bi-imidazol photo-oxidizing agent, a leuco dyestuff oxidized and stabilized by the photo-oxidizing agent, a nonionic halogen compound, a plasticizer and the acidic additive, and the acidic additive is selected from the group consisting of (1) a compound expressed by formula I, (2) phosphonic acid expressed by formula II, (3) a carboxylic acid having an acidity stronger than that of acetic acid, (4) a sulfonic acid expressed by formula III, (5) an inorganic acid and (6) a Lewise acid. In formula I-III, R expresses R<1> -SO2 -, R<1> -CO- or the like, R<1> expresses H, a 1-12 alkyl, a 6-30C aryl, a halogen or the like, R<1> expresses a 1-12C alkyl, a 6-30C aryl, acyl or the like, each of R<4> and R<5> expresses a 1-12C alkyl, a 6-30C aryl, a heterocyclic group or the like.

Description

Description: [0001] The present invention relates to a photosensitive electrostatic master, and more particularly to a photosensitive electrostatic master that can create a positive image from a single imagewise exposure. be. More particularly, the present invention relates to a photosensitive positive electrostatic master with improved back transfer properties. BACKGROUND OF THE INVENTION Photopolymerizable compositions and films or materials containing binders, monomers, initiators, chain transfer agents, and the like are available commercially. One of the important applications of such photopolymerizable elements is in the field of graphic arts. Materials containing such photopolymerizable layers are used today as electrostatic masters for analog color proofing and are considered promising future materials to be developed for digital color proofing applications. For analog color proofing, a photopolymerizable layer is coated onto an electrically conductive substrate and contact exposed with an ultraviolet (UV) light source through a halftone color separation negative. The photopolymerizable composition hardens by polymerization in areas exposed to ultraviolet light and remains in a liquid-like state elsewhere unexposed. This difference in viscosity between the exposed and unexposed areas manifests itself in the transport properties, ie, the unexposed photopolymerizable areas conduct electrostatic charge while the exposed areas are non-conductive. [0004] By subjecting an imagewise exposed photopolymerizable material to a corona discharge, an electrostatic latent image is obtained consisting of an electrostatic charge that remains only in the exposed or non-conductive areas of the material. This latent image is then developed by applying electrostatic toner to the surface. When the toner is countercharged with a corona charge, it selectively adheres to exposed or polymerized areas of the photopolymerizable material. Photocurable electrostatic masters are necessary to reproduce the imaging characteristics of printing devices. The conductivity of both exposed and unexposed areas can be adjusted by incorporating into the photopolymerizable composition an electron donor or acceptor that changes the electrical properties of the composition and is achieved by a printing device. Electrostatic masters are known that provide dot gain similar to that of The use of photopolymerizable compositions in electrostatic photography has been proven and many formulations can be considered, but it is difficult to create a photopolymerizable electrostatic master that can produce both positive and negative images. I didn't think it was possible. These results demonstrate that photocurable materials having a conductive support carrying a photocurable layer consisting of a polymeric binder, at least one ethylenically unsaturated group, an initiator, a photoinhibitor, and at least one sensitizer compound This was achieved using the following materials. Positive and negative images are achieved through a relationship between the order of exposure and the wavelength of exposure. Such materials are extremely useful because one material satisfies the proofing requirements of all printers, regardless of whether the printer is running negative or positive color separations. A disadvantage of these materials is that they require two exposures to provide a positive working electrostatic master. In electrostatography, a photoconductive layer is electrically charged and upon imagewise exposure to light produces a local charge decay, with applied toner or developer being attracted to the unexposed areas. Electrostatographic devices are generally designed to locally discharge the conductive layer following exposure to light and then apply toner. After toner transfer, the photoconductive layer is cleaned. For multiple copies, the charging, exposing, toning and transfer steps are repeated. Since image quality is affected by changes in charging and exposure levels, virtually each resulting print will vary at least slightly from the others. A photosensitive electrostatic master comprising a conductive substrate and a photosensitive layer, wherein the composition of the photosensitive layer is (A) at least one organic polymer binder;
(B) Hexaarylbiimidazole photooxidant (p
(C) leuco dyes that can be oxidized to ionic species by photooxidants; (D) nonionic halogenated compounds; and (E
) It is known to be composed of compatible plasticizers and to provide a positive working electrostatic master with a single exposure. [0010] The material also provides a printout image that can be visually determined for exposure and prevents double exposure of the material that might otherwise occur. This photosensitive electrostatic master can be charged, toned, charged and toned multiple times after a single exposure to reproduce a permanent image. However, these masters were found to have problems associated with back transfer during multilayer transfer. It has been found that the above-mentioned disadvantages can be overcome by adding to the photosensitive composition of the single exposure photosensitive electrostatic master described above an acidic additive as defined below. The photosensitive electrostatic master of the present invention has improved back transfer properties,
Also, a positive image can be created with one exposure. SUMMARY OF THE INVENTION In accordance with the present invention, there is provided a photosensitive electrostatic master for forming conductive exposed image areas upon imagewise exposure, the master comprising an electrically conductive material carrying a layer of a photosensitive composition. the composition comprises (A) at least one organic polymeric binder; (B) a hexaarylbiimidazole photooxidant;
(C) leuco dyes that can be oxidized to ionic species by photooxidizing agents; (D) nonionic halogenated compounds; (E)
at least one plasticizer, and (F) at least one acidic additive selected from the group consisting of: (1) a compound of the following general formula R-NH-R', where R is R1-SO2- , R1-CO-,
R1-SO2-NH-CO-, or [Formula 4]; R' is H, C1-C12 alkyl, C6-C
30 aryl, C1-C12 substituted alkyl, C6-
C30 substituted aryl, R3-CO-, halogen or heterocyclic group; R and R' together can also form a 5- to 6-membered heterocycle; R1, R2 and R3 are the same or different; (2) Phosphonic acid of the following general formula , R4-PO[OH]2 where R4 is C1-C12 alkyl, C6-C30 aryl, C1-C12 substituted alkyl, C6-C30
is a substituted aryl, halogen or heterocyclic group; (3) A carboxylic acid with stronger acidity than acetic acid; (4
) Sulfonic acid of the following general formula, R5-SO3H where R5 is C1-C12 alkyl, C6-C30 aryl, C1-C12 substituted alkyl, C6-C30
(5) an inorganic acid; and (6) a Lewis acid. . According to one embodiment of the invention, there is provided a xeroprinting method for producing a positive image in a single imagewise exposure, comprising: (a) at least one organic polymeric binder; (B) Hexaarylbiimidazole photooxidizer, (
C) leuco dyes that can be oxidized to ionic species by photooxidizing agents; (D) nonionic halogenated compounds; (E)
at least one plasticizer, and (F) at least one acidic additive selected from the group consisting of: (1) a compound of the following general formula R-NH-R', where R is R1-SO2- , R1-CO-,
R1-SO2-NH-CO-, or [Formula 5]; R' is H, C1-C12 alkyl, C6-C
30 aryl, C1-C12 substituted alkyl, C6-
C30 substituted aryl, R3-CO-, halogen or heterocyclic group; R and R' together can also form a 5- to 6-membered heterocycle; R1, R2 and R3 are the same or different; (2) Phosphonic acid of the following general formula; R4-PO[OH]2 Here, R4 is C1-C12 alkyl, C6-C30 aryl, C1-C12 substituted alkyl, C6-C30
is a substituted aryl, halogen or heterocyclic group; (3
) Carboxylic acid with stronger acidity than acetic acid; (4) Sulfonic acid of the following general formula, R5-SO3H where R5 is C1-C12 alkyl, C6-C30 aryl, C1-C12 substituted alkyl, C6-C30
(5) an inorganic acid; and (6) an electrically conductive substrate carrying a layer of a photosensitive composition consisting essentially of a Lewis acid; (b) electrostatically charging the master to form a latent image of electrostatic charge in the unexposed areas; (c) conversely; (d) developing this latent image by applying a charged electrostatic toner or developer; and (d) depositing this toned image on a receiver surface.
ed) or transferring the developed image. [Detailed Description of the Invention] Throughout this specification, the following terms have the following meanings. [0015] "Essentially consisting of" in the claims means
This does not mean that unspecified components that do not interfere with the recognized features of the photosensitive electrostatic master are not excluded from the composition of the photosensitive layer of the electrostatic master. For example, in addition to the main ingredients, co-initiators, visible light sensitizers, heat stabilizers or thermal inhibitors, ultraviolet light absorbers, coating aids, electrical property modifiers, such as electron acceptors, electron donors, etc. etc. can exist. [0016] The present invention provides a method in which a photosensitive layer on a conductive substrate consisting essentially of each of the components (A) to (F) described above can be exposed to a single exposure, that is, a visible printout image, to produce a positive image. It is based on the knowledge that electrostatic images can be created and further have improved back transfer properties. This photosensitive layer is not photopolymerizable. Suitable binders (A) include acrylate and methacrylate polymers and co- or terpolymers such as poly(methyl methacrylate), poly(ethyl methacrylate), poly(isobutyl methacrylate); vinyl polymers and copolymer,
For example, poly(styrene (70)/methyl methacrylate (30)), acrylonitrile/butadiene/styrene, polystyrene, etc.; polyvinyl acetals, such as poly(vinyl acetal), poly(vinyl formal), etc.; polyesters, such as poly( Condensation polymers, such as polycarbonate, polysulfone, polyetherimide, polyphenylene oxide, poly(1,4-cyclohexanedimethanol terephthalate), etc.; Butadiene copolymers, such as styrene-butadiene copolymer;
Included are cellulose esters and ethers, such as ethyl cellulose; and polyurethanes. The selection of a polymeric binder for formulations with improved environmental acceptability is related to its Tg. The Tg of a polymer is influenced by the chemical structure of the main chain and side groups. Polymers with rigid structures exhibit high Tg's, while more flexible polymers exhibit low Tg's. Desired Tg
Polymers of high value can be obtained by copolymerization of suitable combinations of rigid and flexible monomers. The following publications, J. Brandrup, E. H. Imme
rgut: "POLYMER HANDBOOK" published by John Wiley and Son, 1975, which contains a collection of glass transition temperatures of homopolymers known in the literature, and is listed in Chapter III, 140 of this publication.
Pages 192 to 192 display Tg values for most known polymers. Preferred binders have a Tg value of 1
Since it is in the range of 5℃ to 105℃, Elvaci
teR resins are included. Low Tg resins include poly(
ethyl methacrylate) (Tg 70°C), Elva
citeR 2045 or 2042 and poly(methyl methacrylate), a high Tg resin (Tg 110°C
) or poly(styrene/methyl methacrylate) (
Tg 95°C) is particularly preferred. Broadening the Tg with a combination of high Tg and low Tg binders will provide improved environmental stability. The mixed binder should have a resistivity in the range 1014-1020 Ohm-cm, preferably 1014-1016 Ohm-cm. Hexaarylbiimidazole photooxidizing agent (
An example of B) is 2,2',4,4',5,5'-hexaarylbiimidazole, sometimes referred to as 2,4,5-triarylimidazolyl dimer, and HABI
When exposed to actinic radiation, it dissociates to form the corresponding triarylimidazolyl free radical. Any 2-o-substituted HABI is useful in the photosensitive compositions of the present invention, including those disclosed in the US patents listed below. HABI can be represented by the following general formula: where R is an aryl group, such as phenyl, naphthyl, etc., preferably a phenyl group, and it is a Cescon
No. 3,784,557, column 2, line 20 to column 3, line 67 and column 23, lines 53 to 74, The description is hereby incorporated by reference. 2-o-substituted HABI is one in which the aryl groups at the 2 and 2' positions are ortho-substituted. Other positions of the aryl group are unsubstituted or have substituents that do not interfere with the dissociation of HABI during exposure or have no adverse effect on the electrical or other properties of the photosensitive system. Can be done. Mixtures of HABIs are also useful. Preferred HABIs are 2-o-chloro substituted hexaphenylbiimidazoles, with the other positions of the phenyl group being unsubstituted or substituted by chloro, methyl or methoxy. Most preferred HA
BI is 2,2'-bis(o-chlorophenyl)-4,
4',5,5'-tetraphenylbiimidazole. A preferred hexaarylbiimidazole photooxidant (B) is described by Chambers, US Pat.
No. 79,185, Chang's No. 3,549,36
No. 7, Baum et al. 3,652,2
No. 75, Cescon No. 3,784,557;
Dueber No. 4,162,162, Dess.
auer No. 4,252,887, Chambe
rs et al. No. 4,264,708, T
Anaka et al. No. 4,459,349 of
No. 4,622,286 of Sheets.
It is disclosed in the issue, and joins here by listing these descriptions as a reference. The leuco dye (C) useful in the present invention is Ce
scon, US Pat. No. 3,598,592, the disclosure of which is hereby incorporated by reference. The leuco dyes mentioned in column 9, lines 4-18 of this patent are preferably stable in the form of leuco dyes when present in the photosensitive composition. Leuco dyes that are less stable than those mentioned herein can also be used if a heat stabilizer or heat inhibitor is present in the composition. The leuco form of the dye which constitutes one component of the photosensitive composition of the present invention is a reduced form of the dye having one hydrogen atom and in some cases an additional electron. When a hydrogen atom is removed together with a hydrogen atom, dyes, compounds with different colors, are produced. Such dyes are, for example,
U.S. Pat. No. 3,445,234, column 2, 49-6
It is stated in line 3, column 3, line 39 to column 7, and line 55, and this description is listed here for reference. These include: (a) aminotriarylmethane, (b) aminoxanthene, (c) aminothioxanthene, (d
) Amino-9,10-dihydroacridine, (e)
Aminophenoxazine, (f) Aminophenothiazine, (g) Aminodihydrophenazine, (h
) aminodiphenylmethane. Aminotriarylmethane is preferred. Generally preferred aminotriarylmethanes are phenyl groups having an R1R2N-substituent (A) at the para position to the point where at least two aryl groups are bonded to the methane carbon atom, where R1 and R2 and respectively hydrogen, C1-C10 alkyl, 2-hydroxyethyl,
A group selected from 2-cyanoethyl or benzyl, and a group located ortho to the carbon atom of methane (
B) is selected from C1-C4 lower alkyl, C1-C4 lower alkoxy, fluorine, chlorine, or bromine; and the third aryl group is the same as or different from the previous two; (1) Lower alkyl, lower alkoxy, chloro, dialkylamino, diarylamino, cyano,
Phenyl, which can be substituted with nitro, hydroxy, fluoro or bromo, etc.; (2) Naphthyl, which can be substituted with amino, di-lower alkylamino, or alkylamino, etc.;
(3) pyridyl which can be substituted with alkyl; (4) quinolyl; (5) indolinylidene which can be substituted with alkyl. R1 and R2 are preferably hydrogen or a C1-C4 alkyl group. Particularly preferred leuco dyes in (a) above, because they are stabilized, are the Class I compounds described in Cescon, US Pat. No. 3,598,592, column 9, lines 4-18. It is. The preferred stabilized leuco dye compound (b) is 9-diethylamino-1
2-(2-methoxycarbonyl-phenyl)-benzaxanthene. [Halogenated Compounds] Useful halogenated compounds (D) include halogenated hydrocarbons, which can be aromatic, aliphatic, alicyclic, heterocyclic, and combinations thereof. can. The halogenated compound is preferably non-ionic. Besides halogens, these compounds can be substituted with oxygen, amines, amides, hydroxyls, nitriles, or phosphates, and the like. The hydrocarbyl ring or chain is an ether (-O-),
Ester (-CO-O-), carbonyl (-CO-),
Alternatively, it can be interrupted with amide (-CO-NH-) or the like. Halogenated aliphatic compounds include halogenated alkanes and alkenes of 1 to about 8 carbon atoms, such as carbon tetrachloride; carbon tetrabromide; bromoform; iodoform;
Iodoethane; 1,2-diiodoethane; 2-bromo-
1-iodoethane; 1,2-dibromoethane; 1-bromo-1-chloroethane; 1,1,2,2-tetrabromoethane; hexachloroethane; 1,1,1-trichloroethane; 1,1-bis-(p -chlorophenyl)-2,
Illustrated by alkanes such as 2,2-trichloroethane and substituted 1,2-dibromoethane compounds. This substituted 1,2-dibromoethane compound is described in Holman, U.S. Pat. For reference, this substituted 1,2-dibromoethane compound has 1,2-dibromo-
1,1,2-trichloroethane; 1,2-dibromotetrachloroethane; 1,2-dibromo-1,1-dichloroethane; 1,2-dibromo-1,1-dichloro-2,2
-difluoroethane, etc.; 1-bromo-3-
Chloropropane; 1,2-dibromo-3-chloropropane; 1,2,3-tribromopropane; 1-bromobutane; 2-bromobutane; 1,4-dibromobutane; 1-
Bromo-4-chlorobutane; 1,4-diiodobutane;
1,2,3,4-tetrabromobutane; pentamethylene bromide; hexamethylene bromide, etc.; 2 to about 8
halogenated alkanols of carbon atoms, e.g. 2-
Bromoethanol; 2,2,2-trichloroethanol; tribromoethanol; 2,3-dibromopropanol; 1,3-dichloro-2-propanol; 1,3-diiodo-2-propanol; 1,1,1-trichloro −
2-propanol; di(iodohexamethylene)aminoisopropanol; 1,1,1-trichloro-2-methyl-2-propanol; tribromo-t-butyl alcohol; 2,2,3-trichlorobutane-1,4-diol ; halogenated alicyclic compounds, such as tetrachlorocyclopropene; dibromocyclopentane; hexachlorocyclopentadiene; dibromocyclohexane; chlorendic anhydride; compounds containing halogenated aliphatic carbonyls of 2 to about 8 carbon atoms, etc. So, this is 1,1-dichloroacetone; 1,3-dichloroacetone; hexachloroacetone; hexabromoacetone; pentachloroacetone; 1,1,3,3-tetrachloroacetone; 1,1,1-trichloroacetone; 3,4-dibromobutanone-2; 1,4-dichlorobutanone-2; 1
, 2,5-trichloropentanone-2; exemplified by dibromocyclohexanone; halogenated ethers of 3 to about 8 carbon atoms such as 2-bromoethyl methyl ether; 2-bromoethyl ethyl ether; di( 2
-bromoethyl) ether; di(2-chloroethyl) ether; 1,2-dichloroethyl ethyl ether, and the like. Halogenated amide and ester compounds are conveniently described as esters and amides thereof in relation to halogenated mono- or dicarboxylic acids of 2 to 8 carbon atoms. These compounds have the following general formula: Xa-(A)-(CO-G)b where X is Cl, Br or I, a is an integer from 1 to 4 A is an Alkyl or alkenyl G is -OA' or -NH-A'', where A' is C1-C15 alkyl or haloalkyl, and halogen is Cl, Br
or I; A″ is hydrogen, C1-C4 alkyl or haloalkyl, and halogen is Cl, Br or I; b is 1 or 2; a is an integer from 1 to 4; Under the conditions,
It is noted that clearly chemically impossible structures are excluded, such as tetrachloroacetamide and β,β,β-trichlorobutyramide. That is, a is 1
The condition of an integer of ~4 means that no carbon atom bonded to two other carbon atoms contains more than two halogen atoms, and that no carbon atom bonded to one carbon atom contains more than three halogen atoms. When A has 1 carbon atom, a is an integer from 1 to 3, and when A has 2 to 7 carbon atoms, a is an integer from 1 to
This is intended as a simple way to indicate that it is an integer of 4. A is methyl, ethyl, propyl, butyl,
Amyl, hexyl, heptyl, their isomers; vinyl, allyl, isopropenyl, butenyl, isobutenyl,
Or it can be pentenyl, etc. The ester can be an ester of a halogenated carboxylic acid, a halogenated carboxylic acid ester, or a halogenated halogenated carboxylic ester, as exemplified below. Chloroacetic acid; Bromoacetic acid; Iodoacetic acid; Dichloroacetic acid; Trichloroacetic acid; Tribromoacetic acid; 2-chloropropionic acid; 3-bromopropionic acid; 2-bromoisopropionic acid; 2,3-dibromopropionic acid; 3-iodopropionic acid ; α-bromobutyric acid; α-bromoisobutyric acid; 3,4-dibromobutyric acid, etc.; bromosuccinic acid; bromomaleic acid and dibromomaleic acid, etc.; bromoethyl acetate; ethyl trichloroacetate; trichloroethyl trichloroacetate; isooctyl trichloroacetate; Tridecyl trichloroacetate;
Homopolymers and copolymers of 2,3-dibromopropyl acrylate; trichloroethyl dibromopropionate; iodoethyl dibromobutyrate; ethyl α,β-
Dichloroacrylate; ethyl 3,4-dibromovinyl acetate, etc. Amides and imides include chloroacetamide; bromoacetamide; iodoacetamide; dichloroacetamide; trichloroacetamide; tribromoacetamide; trichloroethyltrichloroacetamide; 3-bromopropionamide; 2-bromoisopropionamide; 2,3-dibromo Propionamide; 2
, 2,2-trichloropropionamide; 2-bromobutyroamide; 2-bromoisobutyroamide and N-chlorosuccinimide, N-bromosuccinimide, 2,
3-dibromosuccinimide, N-[1,1-bis-(
Examples include p-chlorophenyl)-2,2,2-trichloroethyl]acetamide. Preferred amides are those with melting points ranging from 90° to 150°C, such as the following compounds:
Compound
Melting point (℃)
BrCH2CONH2
91 ClCH2CONH
2 121
Cl2CHCONH2
99.4 ICH
2CONH2
95 Br3CCONH2
121.5
Cl3CCONH2
142 BrCH2
CH2CONH2 111
(CH3)2CBrCONH2
148 CH3CH
2CHBrCONH2 112.5
(CH3)2CHCHBrCONH2
Other halogenated aliphatic hydrocarbon compounds include chlorinated rubbers such as Parlons® (Hercules); poly(vinyl chloride); Vinoflex® MP-400 (BASF Dye and Chemicals Company); Copolymer of vinyl chloride and vinyl isobutyl ether; Chlorowox
Chlorinated aliphatic waxes such as R 70 (Occidental Electrochemical Company); Perchlorocyclodecane; Clo
rafinR40 (Hercules) and Unichl
chlorinated paraffins such as orR 70B (Dover Chemical Co.); and 2,3-bis-(bromoethyl)-1,
Includes 4-dibromo-2-butene and the like. The halogenated aromatic hydrocarbon compounds include polyhalobenzenes such as di-, tri-, tetra-, penta-, and hexachlorobenzenes and bromobenzenes; di-, tri-, and tetra-chloroxylenes and bromobenzenes; xylenes; di- and trichloroanilines and bromoanilines; generally polychlorinated diphenyls, polychlorinated triphenyls and mixtures thereof, Araclor®
Polyhalogenated polyphenyl compounds such as plasticizers (Monsanto); hexabromobiphenyl, tetrabromobisphenol A, and the like. The halogenated heterocyclic compound includes 2,3,4
, 5-tetraiodopyrrole, 2-tribromoquinoline, 2-trichlorooxazole, and the like. Although it is clear that both aliphatic and aromatic halides can be used effectively, aliphatic halides are preferred and generally contain two or more halides bonded to the same carbon atom. Preference is given to using halides, such as those having halogen atoms, and particular preference to using halogenated aliphatic compounds, in which three halogen atoms are bonded to one carbon atom. The halogen-containing material can be present as a single compound or it can be a mixture of halogen-containing compounds. Stability is a factor when a composition is prepared and stored for a period of time. For this reason, carbon tetrabromide, iodoform, ethyl iodide and 2,2,
Volatile materials such as 2-trichloroethanol usually work quite well, but are not preferred in electrostatic masters that are stored for significant periods of time. These compounds are generally not used due to their odor and/or high volatility. Therefore, non-volatile liquid or solid halogenated compounds are preferred. A wide range of non-polymerizable plasticizers (E) are useful in achieving reasonable exposure times and good printout images. When a polymeric binder is present in the photosensitive layer, the selected plasticizer is miscible with the binder as well as with each of the other components of the composition. for example,
Useful plasticizers for acrylic binders include dibutyl phthalate, dioctyl phthalate, and other esters of aromatic acids; esters of aliphatic polyacids and nitrates such as diisooctyl adipate; glycols, polyalkylene glycols , aromatic or aliphatic acid esters of aliphatic polyols; alkyl and aryl phosphates; low molecular weight polyesters; and chlorinated paraffins. In general, water-insoluble plasticizers are preferred, but not required, to enhance high humidity storage stability and environmental handling acceptability. Other useful plasticizers are: triethylene glycol, triethylene glycol diacetate, triethylene glycol dipropionate, triethylene glycol dicaprylate, triethylene glycol dimethyl ether, triethylene glycol bis(2-ethyl- hexanoate), tetraethylene glycol diheptanoate, poly(ethylene glycol), poly(ethylene glycol) methyl ether, diethylene glycol dibenzoate, glyceryl tribenzoate, isopropylnaphthalene, diisopropylnaphthalene, poly(propylene glycol), glyceryl tributyrate, Diethyl adipate, diethyl sebacate, dibutyl suberate, tributyl phosphate, tris(2-
ethylhexyl) phosphate, t-butylphenyldiphenyl phosphate (SanticizerR 1
54), triacetin, triisooctyl trimellitate, BrijR 30 [C12H25(OCH2CH2
)4OH], and BrijR 35[C12H25
(OCH2CH2)20OH], BrijR is ICI
Tris(2-butoxyethyl) phosphate, dicyclohexyl phthalate, dioctyl phthalate, diphenyl phthalate, diundecyl phthalate, butylbenzyl phthalate (S
anticizerR 160), 2-ethylhexylbenzyl phthalate (SanticizerR 261
), alkyl benzyl phthalate (Santicize
phthalates such as rR 278). Sa
nticizer® is a registered trademark of Monsanto Company. Many of the plasticizers can be represented by the following general formula: ##STR7## where R1 and R2 are each a C1-C10 alkyl group; R3 is H or a C8-C16 alkyl group, and R4 is a C8-C16 alkyl group. H or CH3; x is 1-4; y is 2-10 and z is 1-20. Particularly preferred plasticizers are triethylene glycol dicaprylate, tetraethylene glycol diheptanoate, diethyl adipate, 2-ethylhexylbenzyl phthalate and tris-(2-ethylhexyl) phosphate. Other plasticizers useful in photosensitive compositions will be apparent to those skilled in the art and can be used in accordance with the present invention. Preferred plasticizers are those that are insensitive to humidity and are not extractable by non-polar liquids such as Isopar R-L. The combination of organic polymeric binder and plasticizer is important for achieving a useful contrast potential, ie, voltage difference between exposed and unexposed areas. Binders with different resistivity and Tg values and plasticizers with different viscosities are chosen to achieve some degree of migration of groups and/or ions within the film matrix. A glassy film matrix would not work because the active species generated during exposure would not be able to diffuse through the matrix and react with each other. Similarly, a film matrix with very low viscosity may not be able to maintain a high enough charge in the unexposed areas to attract enough toner or developer to achieve adequate toner or developer concentration. Probably. At least one of the acidic additives (F) present in the photosensitive master is selected from the group consisting of: (1) a compound of the general formula R-NH-R', where R is R1-SO2-, R1-CO-,
R1-SO2-NH-CO-, or [Formula 8] R1 is H, C1-C12 alkyl, C6-C30 aryl, C1-C12 substituted alkyl, C6-C30 substituted aryl, R3-CO-, halogen or a heterocyclic group; R and R' together can also form a 5- to 6-membered heterocycle; R1, R2 and R3 may be the same or different, and C1-C12 alkyl, C6- C30
aryl, C1-C12 substituted alkyl, C6-C3
0 substituted aryl, acyl, halogen or heterocyclic group. Group 1 compounds include sulfonamides and imides, sulfonylureas, carboximides, and phosphonamides. Sulfonamides and imides are represented by the formula: R1-SO2-NH-R' where R1 is C1-C12 alkyl, C6-C30 aryl, substituted alkyl or substituted aryl, such as C1-C12 alkyl, C6-C30 aryl, substituted alkyl or substituted aryl. C10 alkyl, C1 to C6 alkoxy,
For example, those substituted with halogen such as Cl, Br, I, amino, carboxyl ester, etc.; R' is H, acyl, C1-C12 alkyl, C6-C30 aryl, as described above for R1. is substituted alkyl or substituted aryl substituted with . Sulfonamides are exemplified by A6 in the examples. Other examples include o-, p-toluenesulfonamide, α-toluenesulfonamide, p-(p-toluenesulfonamide)-diphenylamine, and benzoic sulfonimide. Sulfonamides and imides useful in the present invention are as follows. Mentioned in the publication: E. H. Nor
They “Sulfonamides and Al
Lied Compounds”, Reinhold Publishers, 1948, and Kirk-Othmer, ed., Encyclopedia of Chemical
Technology, Volume 2, “Sul
fonamides", pp. 795-808, published by Wiley-Interscience, 1978. Sulfonylurea is represented by the following formula:
R1-SO2-NH-CO-NH-R' where R1 and R
' may be the same or different and are C1-C12 alkyl, C6-C30 aryl, substituted alkyl or substituted aryl, such as C1-C10 alkyl, C1-C10 alkyl,
1 to C6 alkoxy, such as Cl, Br, I, substituted with halogen; amino, carboxyl ester, etc.; or N, O, S, Se, P, As in the ring
It is a 5- to 6-membered heterocyclic group including the following. Suitable sulfonylureas and methods for their preparation are described in U.S. Pat. No. 4,127,4.
No. 05, No. 4,383,113, No. 4,394,
No. 506, No. 4,420,325, No. 4,435
, No. 206, No. 4,478,635, No. 4,47
No. 9,821, No. 4,481,029, No. 4,5
No. 14,212, No. 4,789,393, No. 4,
No. 810,282, and EP-A-87,780, the descriptions relating to these compounds are hereby incorporated by reference. Carboximide is represented by the following formula:
R1-CO-NH-CO-R' Here, R1 and R' may be the same or different, and C
1-C12 alkyl, C6-C30 aryl, substituted alkyl or substituted aryl, for example C1-C10
alkyl, C1-C6 alkoxy, e.g. Cl,
Halogens such as Br and I; those substituted with amino, carboxyl ester, etc.; or those substituted with N, O,
It is a 5- to 6-membered heterocyclic group containing S, Se, P, As, etc. R1 and R' together can also form a 5- to 6-membered heterocycle or a fused ring. Other useful carboxamide compounds other than phthalimide, diacetamide, parabanic acid (exemplified by A15) include:
[0048] Phosphonamide is represented by the following formula: [
Here, R1, R' and R2 may be the same or different, and are C1-C12 alkyl, C6-C30 aryl, substituted alkyl and substituted aryl, for example, C1-C12 alkyl, C6-C30 aryl, substituted alkyl and substituted aryl.
12 alkyl, C1-C6 alkoxy, e.g.
Halogens such as l, Br, I; those substituted with amino, carboxy esters, etc.; halogens, or 5- to 6-membered heterocyclic groups containing N, O, S, Se, P, As, etc. in the ring be. The phosphonamide is exemplified in the examples by A13 as phenyl N-phenylphosphonamide chloridate. Other phosphonamide compounds are derived from the phosphonic acids described in the next section. The phosphonic acid (2) is represented by the following formula: R4-PO[OH]2 where R4 is C1-C12 alkyl, C6-C30 aryl, substituted alkyl or substituted aryl, for example C1 ~C10 alkyl, C1 to C6 alkoxy,
For example, those substituted with halogen such as Cl, Br, I; amino, carboxy ester, etc.; or 5- to 6-membered heterocyclic group containing N, O, S, Se, P, As, etc. in the ring It is. Phosphonic acid is exemplified by A3 in the examples as benzenephosphonic acid. Other phosphonic acids are described in the following publications: G. M. Ko
solapoff's “Organophosphor”
US Compounds”, pp. 148-170
, published by John Wiley and Son, 1950 and “Organophosphorus Chemist
ry”, Expert Periodic Reports Volumes 1-19, Chemical Society, London, published 1970-1988. The carboxylic acid in (3), which is more acidic than acetic acid, is represented by the following formula: R- (COOH)n=1-4 where R is C1-C12 alkyl or alkylene,
C6-C30 aryl, N, O, S, Se, P, As
a 5- to 6-membered heterocycle including C1-C6 alkoxy, an alkylalkylene, aryl or heterocycle substituted with a halogen such as Cl, Br, I; amino and alkylated amino, and the like. In addition to this,
Carboxylic acids can be partially esterified. Suitable carboxylic acids include oxalic acid, malonic acid, citric acid, tartaric acid, benzoic acid, fumaric acid, maleic acid, trichloroacetic acid, dichloroacetic acid, perfluorooctanoic acid, phthalic acid, diphenic acid, trimellitic acid, Contains pyromellitic acid, naphthalene dicarboxylic acid, etc. Carboxylic acids are A1, A2, A7, A8, A9 in the examples.
, A10 and A14. Other carboxylic acids are described in the following publications: A. I.
Vogel’s “Practical Organic
Chemistry” pp. 489-495 and 751-779, John Wiley & Son, Inc., 195
7 issue, and C. R. Noller's “Chemi”
Try of Organic Compounds
", pp. 173, 594, 870-891, published by W B Sounders, 1965. The sulfonic acid (4) has the following general formula: R5-SO3H where R5 is C1-C12. Alkyl, C6-C30 aryl, C1-C12 substituted alkyl, C6-C30
Substituted aryl, halogen or N, O, S, Se, P
, a 5- to 6-membered heterocyclic group containing As. Useful sulfonic acids include p-toluenesulfonic acid, naphthalenesulfonic acid, benzenesulfonic acid, 2,5-dimethylbenzenesulfonic acid, 2,4-dinitrobenzenesulfonic acid, o-sulfobenzoic acid, 5-sulfosalicylic acid, 5- Dimethylamino-1-naphthalenesulfonic acid, trichlorobenzenesulfonic acid, 5-nitro-o-toluenesulfonic acid, 1
-butanesulfonic acid, 10-camphorsulfonic acid, 4
-(2-hydroxyethyl)-1-piperidine-ethanesulfonic acid, 8-hydroxy-5-quinolinesulfonic acid, and the like. Preferred sulfonic acids are p-toluenesulfonic acid and naphthalenesulfonic acid.
5 is exemplified. The inorganic acid in (5) is selected from the group consisting of: hydrochloric acid, hydrobromic acid, hydroiodic acid, sulfurous acid, sulfuric acid, nitrous acid, nitric acid, phosphorous acid. , phosphoric acid, selenite, selenate and chromic acid. The inorganic acid is exemplified by A11 in the examples. The Lewis acid (6) is an electron-deficient molecule or ion that can be coordinated with another molecule using a lone pair of electrons. Lewis acids are electrophilic (electrophilic) reagents or agents commonly used as catalysts in electron transfer type chemical reactions and cationic polymerizations. Lewis acids useful in the present invention are selected from the group consisting of boron fluoride, aluminum chloride, aluminum bromide, zinc chloride, stannous chloride, titanium chloride, and the like. Lewis acids are exemplified as A12 in the examples. Lewis acids are described in the following literature: E. S. Gould's “Mechanism and Structure”
in Organic Chemistry”, pp.
115-119, H. Holt Publishing, 1959, and J. Hine's “Physical Organ”
ic Chemistry, Chapter 2, published by McGraw-Hill Publishers, 1962. Additional useful components that may be present in the photosensitive layer include co-initiators, visible light sensitizers, thermal stabilizers or These include thermal inhibitors, brighteners, UV light absorbers, coating aids, electrical property modifiers such as electron acceptors, electron donors, etc. Useful co-initiators include benzophenone,
These include alkylarylketones and mixtures thereof. Visible light sensitizers may also be present in the photosensitive layer, eg, Dueber, US Pat.
62,162, the description of which is incorporated herein by reference. This sensitizer absorbs radiation in a broad spectral range from 300 to 700 nm. Maximum absorption (λmax) is 350
~550 nm, preferably 400-500 nm. Useful thermal stabilizers or inhibitors include hydroquinone, 1,4,4-trimethyl-diazobicyclo-(3.2.2)-non-2-ene-2,3-dioxide, 1 -Phenyl-3-pyrazolidinone, 4-(hydroxymethyl)-4-methyl-1-phenyl-3-pyrazolidinone, p-methoxyphenol, alkyl and aryl substituted hydroquinones and quinones, t-butylcatechol, pyrogallol, copper resinate, naphthylamine , β-naphthol, cuprous chloride, 2,6-di-t-butyl p-cresol, phenothiazine, pyridine, nitrobenzene, dinitrobenzene, p-torquinone, and chloranil. Also useful are the dinitrosodimers described in Pazos, US Pat. No. 4,168,982, which is incorporated by reference. In order to increase the storage stability of the photosensitive composition, it is preferred to have a thermal stabilizer or inhibitor present in the photosensitive composition. Useful UV light absorbers and coating aids are well known to those skilled in the art. Useful electron donors and acceptors are Bla
nchet-Fincher et al. No. 4,849,314, the disclosure of which is incorporated by reference. Examples of such compounds include: aromatic amines, e.g. triphenylamine, methyldiphenylamine, N-dimethylaniline; aromatic phosphines, e.g. triphenylphosphine; triphenylarsine; triphenylantimony; carbazole compounds, e.g. 9-ethylcarbazole, poly(9-vinylcarbazole); polycyclic aromatic compounds such as naphthalene, benzophenone, trinitrofluorenone, p-
Includes biphenyl, etc. Triphenylamine is a preferred electron donor and biphenyl is a preferred electron acceptor, as disclosed in the aforementioned US patents, and the descriptions of these compounds are included for reference. Other additives that can modify electrical properties and final image quality include N-phenylglycine,
1,1-dimethyl-3,5-diketocyclohexane, and 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, pentaerythritol tetrakis-(mercaptoacetate), 4-acetamidothiophenol, dodecanethiol , and organic thiols such as β-mercaptoethanol. Other compounds that can be used include 1-phenyl-4H-tetrazole-5
-thiol, 6-mercaptopurine monohydrate, bis-(5-mercapto-1,3,4-thiodiazole-
2-yl), 2-mercapto-5-nitrobenzimidazole, and 2-mercapto-4-sulfo-6-chlorobenzoxazole. Generally, the main components of the photosensitive composition are used in the following approximate proportions: (A) binder 40-8
5%, preferably 50-70%; (B) hexaarylbiimidazole photooxidant 1-20%, preferably 2-6%;
(C) Leuco dye 0.5-40%, preferably 0.5-6
%; (D) halogenated compound 0.25-10%, preferably 0.25-5%; (E) plasticizer 2-50%, preferably 10-40%, and (F) acidic additive 0.1-5%. 10%
, preferably 0.4 to 4%. These are weight percentages based on the total weight of the photosensitive composition. The preferred ratios depend on the particular compounds selected for each component. For example, the amount of component (B) is related to the required film sensitivity. Component (B) of 10% by weight or more
Compositions with a content of 10% give highly sensitive (high speed) films and can be used in laser imaging to record digitized information, such as digital color proofing. Film sensitivity for analog applications, eg, exposure through a separation plate or master plate, is related to the mode of exposure. The photosensitive electrostatic master is prepared by mixing the photosensitive components in a solvent such as methylene chloride or other solvent that dissolves all of the components of the photosensitive composition. High boiling co-solvents such as methanol, isopropanol and the like are also useful to aid in coating and drying. The photosensitive coating solution is then coated onto a conductive substrate by means known to those skilled in the art and the solvent evaporated. The dry coverage should be about 40-250 mg/dm2, preferably 80-150 mg/dm2. The conductive substrate can be a metal plate such as aluminum, copper, zinc, silver, etc., a conductive polymer film,
For example, a support such as polyethylene terephthalate, etc., or coated with a metal, electrically conductive metal oxide or metal halide by vapor or chemical deposition on one or both sides of a support such as paper, glass, synthetic resin, etc. thing;
Substrates coated with conductive polymers; substrates coated with polymeric binders containing metals, conductive metal oxides, conductive metal halides, conductive polymers, carbon, or other conductive fillers, etc. can. Positive images are conveniently prepared by a single image exposure followed by charging and toning. The photosensitive layer has a wavelength ranging from 200 to 550 nm, preferably from about 310 to about 4
Exposure to radiation with a wavelength of 00 nm. Any convenient source of ultraviolet/visible light can be used to activate the photosensitive composition and induce image formation. in general,
Light sources that provide radiation in the range between about 200 nm and about 550 nm are useful for creating images. Light sources that can be used are solar lamps, electronic flash guns, germicidal lamps, mercury vapor arcs, fluorescent lamps with ultraviolet light-emitting phosphors, argon and xenon glow lamps, electronic flash devices, photographic light sources, especially short An ultraviolet lamp that emits light at a wavelength (253.7 nm), a lamp that emits light at a long wavelength (450 nm), etc. can be used. The exposure time depends on the intensity of the light source, the distance from the photosensitive composition, the opacity of the original plate, the nature and amount of the photosensitive composition,
and varies from a fraction of a second to several minutes depending on the intensity of color in the desired image. A coherent light beam, such as an electron beam, a pulsed nitrogen laser, an argon ion laser, and an ionized neon II laser, such that the emitted light is within or overlaps the ultraviolet absorption band of component (B). You can also use Visible light emitting lasers such as argon ion, krypton ion, helium-neon, and frequency doubled YAG lasers can be used for the visible light sensitized photosensitive layer. Ultraviolet light emitting cathode ray tubes, commonly used in printout systems for writing on photosensitive materials, are also useful for imaging the compositions of this invention. These generally have an internal coating of UV-emitting phosphor as a means for converting electrical energy into optical energy, and a fiber optic faceplate as a means for directing this radiation to the photoreceptor surface. ing. For purposes of the present invention, the phosphor must emit strongly below 420 nm so as to substantially overlap the near-UV absorption characteristics of the photosensitive compositions of the present invention. P4B is a typical fluorescent substance.
(Emits from 300 to 550 nm, maximum at 410 nm), P
16 (330-460 nm, maximum at 380 nm) and P22B (390-510 nm, maximum at 450 nm) types. The Electronic Industries Association of New York has established the P standard and provides information on the characteristics of each phosphor;
Phosphors with the same P number have substantially identical properties. Images are formed in the photosensitive layer by exposing selective areas to light with a light beam or under a positive resolution plate, stencil or other relatively opaque pattern. The positive resolving plate may also have opacity arising from a collection of locations of different refractive index. Image formation can be carried out in conventional diazo printing equipment, or even in thermographic equipment if the equipment emits light in the ultraviolet range. As a master pattern for copying, for example, onion paper with typed characters or writing paper of light to medium quality can also be used. When using an artificial light source, the distance between the photosensitive layer and the light source can be varied depending on the nature and radiation sensitivity of the photosensitive composition. Usually the mercury vapor lamp is placed 1.5 to 60 inches (3.8 to 152.4 cm) from the photosensitive layer.
Use at a distance of A luminous flux of 10 to 10,000 μw/cm 2 is generally suitable for use. The length of time that the photosensitive composition is exposed to radiation varies from a fraction of a second or more. Exposure times will vary depending on the nature and concentration of the stabilized leuco dye, halogenated compound, miscible plasticizer, photooxidant, etc., and the type of radiation. Exposure is over a wide temperature range,
For example, it can be carried out at temperatures from about 0°C to about +40°C depending on the composition. Preferred exposure temperatures range from about 10°C to about +35°C. This has clear economic advantages for operation at room temperature. For example, the imagewise exposure in preparing an electrostatic master consists exclusively of regions of the process master, ie regions that are substantially opaque to the radiation used and regions that are substantially transparent, with the opaque regions being substantially This is carried out by exposing the photosensitive composition layer to radiation through an image-bearing original, such as a so-called line or halftone negative or positive, which has the same optical density as . The process blank is constructed from any suitable coated material, including cellulose acetate film and polyethylene terephthalate film. Charging and toning of this exposed master results in a positive working master suitable for use such as color proofing. A preferred charging means is corona discharge. Other charging means may also be used, such as discharges from condensers, shielded corotrons, scorotrons, etc. Any electrostatic liquid toner or dry powder toner and any method of toner application can be used. Preferred liquid toners consist essentially of a dispersion of colored resin toner particles in a non-polar liquid, the toner particles being charged with an ionic or zwitterionic compound. A commonly used non-polar liquid is the branched aliphatic hydrocarbon Isopar® (registered trademark of Exxon Corporation), which has a cowry-butanol value of less than 30. These are narrow distillate ranges of high purity isoparaffinic hydrocarbons,
It has the following boiling point range: IsoparR-G 1
57-176°C, IsoparR-H 176-191
°C, IsoparR-K 177-197 °C, Isop
arR-L 188-206℃, IsoparR-M
207-254°C, IsoparR-V 254-32
9℃. Preferred resins have an average particle size of 10 μm or less, preferably 5 μm or less, and contain ethylene (8 μm or less).
0-99.9%)/acrylic or methacrylic acid (2
0-0%)/C1-C of acrylic or methacrylic acid
Copolymers of 5 alkyl esters (0-20%), e.g. ethylene (89%) and methacrylic acid (11%)
It is a copolymer with a methol index value of 100 at 190°C. Useful ionic or zwitterionic charge control agent compounds that are soluble in nonpolar liquids are lecithin and basic barium Petronate® oil-soluble petroleum sulfonate, available from Witco. Optionally present in the non-polar liquid is at least one adjuvant compound as shown in the following patents: Mitchell U.S. Pat. No. 4,631,244;
No. 4, U.S. Pat. No. 4,734,352, Taggi U.S. Pat. No. 4,670,370, Larson U.S. Pat. No. 4,702,985, Larson and Trout.
No. 4,681,831, El-Saye
d and Taggi U.S. Pat. No. 4,702,9
No. 84 and Trout U.S. Pat. No. 4,707,4
No. 29, etc., the descriptions of each of these patents are listed for reference. Typical useful dry electrostatic toners include Ko
dak EktaprintRK, Hitachi Hitone
r HMT-414, Canon NP-350F toner,
Includes Toshiba T-50P toner, etc. The present invention is not limited to these toners. After toning or development, the toned or developed image is transferred to a receiver surface, such as paper, to make a proof. It is also possible to transfer from the latter to another receiver in order to obtain a normal image. Other image receptors are not limited to polymeric films or cloth. To produce integrated circuit boards, the transfer surface can be an insulating plate coated with a conductor, for example a fiberglass plate covered with a layer of copper, onto which the resist is printed in this way. Transfer is effected electrostatically or by other means, such as by contacting an adhesive receiver surface. Electrostatic transfer is carried out by known methods, for example by bringing the transfer surface into contact with the toned image, pressing a conductive rubber roller against the surface to ensure sufficient contact, and immediately applying a corona discharge to the back side of the transfer material. , etc. [Industrial Applicability] Photosensitive electrostatic masters with improved environmental tolerance to changes in humidity and temperature are used in the field of graphic arts, especially as color proofs for making reproductions of images achieved by printing. It is useful in the following areas. Very high resolution is achieved due to the molecular structure of the dye image. A photosensitive electrostatic master with improved environmental tolerance and capable of forming a printout image (POI) has the following additional advantages: (1)
The user can immediately determine that the master has been exposed; (2) Overprinting or overlapping images can be performed and the position of the image can be easily determined; (3) Visual correction can be facilitated;
This is very important when removing cut lines from a positive photosensitive master; (4) you can write in the unexposed areas with a light pen, and this writing becomes part of the information on the master; and (5) Since POIs of different colors can be generated, it is possible to color code the master; for example, a master from a cyan separation original plate can be given a cyan POI, a master from a magenta separation original plate can be given a magenta POI, etc. Possible; this is for a system that prints sequentially.
You can avoid mistakes caused by the master's mistakes. Photosensitive electrostatic masters can also be used to transfer etch-resistant inks to make printed circuit boards. Examples [0080] Examples are shown below, but they do not limit the present invention. Parts and percentages are by weight. [Abbreviation] [Binder] B1 Poly(styrene/methyl methacrylate) 7
0/30 copolymer, Tg=95°C; Tg is glass transition temperature B2 Poly(ethyl methacrylate), n=1
．． 5, n is intrinsic viscosity, Tg = 70°C B3 poly(methyl methacrylate), n = 0.1
8, Tg=105°C B4 poly(methyl methacrylate), n=1.2
5, Tg=110°C 0082] [Plasticizer] P1 2-ethylhexylbenzyl phthalate 0083] [Initiator/Photooxidant] IN1 2,2'-bis(o-chlorophenyl)-4
,4',5,5'-tetraphenylbiimidazole IN
2 2,2',4,4'-tetrakis(o-chlorophenyl)-5,5'-bis(m,p-dimethoxyphenyl)biimidazole [Leuco dye] LD1 Tris-(4-diethylamino-o -tolyl)methane [halogenated compound] H1 1,2-dibromotetrachloroethane 008
5] [Acidic additive] A1 Phthalic acid A2 Oxalic acid A3 Benzenesulfonic acid A4 p-Toluenesulfonic acid A5 Naphthalenesulfonic acid A6 p-Toluenesulfonamide A7
Diphenic acid A8 Benzoic acid A9 2-chlorobenzoic acid A10 Perfluorooctanoic acid A11 Phosphoric acid A12 Zinc chloride A13 Phenyl N-phenylphosphonamide chloridate A14 Citric acid A15 Parabanic acid [0086] [Others] M1 1-phenyl-3- Pyrazolidinone (phenidone) M2 4,4'-bis-(diethylamino)benzophenone M3 2-mercaptobenzoxazole M4 P
luronic® 31R, ethylene oxide/propylene oxide block copolymer, surfactant, sold by BASF. Unless otherwise indicated, the following method was used in all examples. Approximately 80 parts of methylene chloride and 20 parts of solids
A solution containing 0.004 inch (0.010
It was coated on a polyethylene terephthalate substrate processed with aluminum (2 cm). 6 to remove methylene chloride
After drying the film at 0-85°C, a 0.00075 inch (0.0019 cm) thick polypropylene cover sheet was laminated to the dried layer. The amount of application is 8
It is 0 to 150 mg/dm2. The film was then rolled up until it was exposed and developed. To test the image quality of each photosensitive composition, the photosensitive layer was exposed, charged, toned with magenta toner, and image transferred to paper as described below. In either case, “magenta toner” is described in 4 below.
Color refers to the standard magenta toner used to make color proofs. Image quality was evaluated based on dot range and dot gain on paper. The standard paper is Plainwell Paper Company's 60 1bs Solitai.
reR paper and offset enamel text. However, the various papers tested included 60 1bs plainwell offset enamel text, 70 1b
s plainwell offset enamel text, 15
0 1bs White Regal TufwiteR Wet Strength Tag, 60 1bs White Cover, 70 1bs White FlokoteR Text, 60 1bs White All Purpose Squirrel, 11
0 1bs White Scott Index, 70 1
bs white nekusa vellum offset and 80
1bs White SovR Text etc. are included. The results showed that this method can be used with any paper, but the ink penetration varies depending on the quality of the fiber fibrils of the paper used. Dot gain or dot growth relative to dot size is a standard measure of how much difference there is between a proof and a printed proof. Dot gain was measured using a set pattern called a Brunner target available from System Brunner. Dot gains typically desired for graphic arts applications range from 15 to 22% in the midtone range. Dot range is easily measured using the Institute of Graphic Arts Technology's UGRA target, which includes 0.5% highlight dots to 95% shadow dots on a 150 lines/inch screen, and 4.
Contains ~70 μm highlight and shadow microlines. The typically desired dot range for graphic arts applications is 2-98%. The photosensitive electrostatic master is model TU64V.
ioluxR 5002 light source device (Exposure Systems) and model no. Using a Dosit Option x Exposure Unit (Dosit Co., Ltd.) equipped with a 5027 photopolymer lamp, exposure was first carried out through a positive decomposition original plate. Exposure time was varied from 1 to 100 seconds depending on the prescription. This exposed master was then mounted on the drum surface. The SWOP density (Web Offset Publication Standard) of the solid area is defined as the unexposed area of the photosensitive layer of the electrostatic master.
It was obtained by charging to 00 to 500V. This charged latent image was developed with a liquid electrostatic developer or toner using a two roll toning station and an appropriately regulated developer layer. The developing and regulating sections are located at 5 o'clock and 6 o'clock positions, respectively, on the drum. This toner image is 2
．． At a speed of 2 inches/second (5.59 cm/second), 4.3
A transfer corona of 5 to 4.88 kV and 10 to 150 μA;
Corona transfer onto paper using a tackdown roll voltage of -2.5 to -8.0 kV and welding in an oven at 100°C for 15 seconds. A four color proof was obtained according to the procedure described below. First, alignment marks were cut into the photosensitive layer of each electrostatic master before exposure. A master for each of the four color separations was created by exposing four photosensitive elements with cover sheets to one of the four color separation negatives corresponding to cyan, yellow, magenta and black. Each of the four photosensitive layers was exposed using the Douthitt Optionx exposure unit described above. Visible light emitted from a light source transmits UV light and absorbs visible light Kokomo
R Glass filter (manufactured by Kokomo Opalescent Glass Co., Ltd., No.
400). Remove the cover sheet and
Each master is mounted on the drum of the corresponding color module in a position that will correct the registration of the four images sequentially transferred from each master to the receiver paper. Use the tip clamp to ground the aluminized back side of the photosensitive master to the drum. In order to attach each master flat to the drum, it is stretched by a spring attached to the tip. Each module has a charging scorotron at the 3 o'clock position, a developing station at the 5 o'clock position, a regulating station at the 6 o'clock position, and a cleaning section at the 9 o'clock position. The methods of charging, developing, and regulating are the same as described above. The transfer station includes a tuck-down roll, a transfer corona, a paper feed, and a positioning device for determining the relative position of the paper and the master through four transfer operations. In preparing a four-color proof, the four developers, or toners, have the following compositions:
Growth
minutes
Quantity (g) Copolymer of black ethylene (89%) and methacrylic acid (11%) Melt index at 190°C 100, acid value 66 2,193.04St
erling NF carbon black

527.44 Heucophthal Blue, G
XBT-583D, Heubach
27.76 Basic Bariu
m Petronate, Witco Co., Ltd.
97.16
Aluminum tristearate, Witco 132, Witco 27.76 IsoparR
-L, a non-polar liquid with a cowry-butanol value of 27;
Exxon

188,670.0 Copolymer of cyanethylene (89%) and methacrylic acid (11%) Melt index at 190°C 100, acid number 66 3,444.5Cib
a-Geigy Monarch Blue X362
7
616.75DalamarR Y
yellow YT-858, Heubach
6.2
25 aluminum tristearate, as mentioned in black developer 83.0 basic Bar
ium PetronateR, Witco Co., Ltd.
311.
25IsoparR-L, as described for black developer
292,
987.0 Copolymer of magenta ethylene (89%) and methacrylic acid (11%) Melt index at 190°C 100, acid value 66 3,973.47 Mo
bay RV-6700, Mobay Chemical Company
1,
156.66Mobay RV-6713, Mobay Chemical Company
204.12 Aluminum Tristearate S, Witco Co., Ltd.
108.86 Basic Barium Pet
ronateR, UITCO Co., Ltd.
326.58Isopa
rR-L, as mentioned in black developer
378,876.0 0
Copolymer of yellow ethylene (89%) and methacrylic acid (11%) Melt index at 190°C 100, acid value 66 1,824.75Ye
llow 14 Polyethylene Flash, Sun Chemical Co., Ltd. 508.32 Aluminum Tristearate, as described for black developer
46.88 Basic Barium
PetronateR, Witco Co., Ltd.
59.5Iso
parR-L, as mentioned in black developer
160,191.0
First, the cyan master is charged, developed and calibrated. A transfer station is provided and the toned cyan image is transferred onto the paper. After the cyan transfer is complete, the magenta master is corona charged, developed and calibrated, and the magenta image is transferred onto the cyan image under registration. The yellow master is then corona charged, developed, and calibrated, and this yellow image is transferred onto the previous two images. Finally, the black master is corona charged, developed, calibrated, and this black image is transferred over the three previously transferred images under registration. After the operation is complete, carefully remove the paper from the transfer station and store the image at approximately 100°C for 15 minutes.
Weld for seconds. The conditions used for proof preparation were: drum speed 2.2 inches/second (5.588 cm/second); Scotron grid voltage 100-400V; Scotron current 200-1000 μA (5.11-6.04 kV). ); Regulation roll voltage 20-200V; Tuck-down roll voltage -0.5--8.0kV; Transfer corona current 10-150
μA (4.35~4.88kV); Standard roll speed 4~
8 inches/second (10.16-20.32 cm/second); normal roll gap 0.002-0.005 inch (0.
0051-0.0127cm); developer electrical conductivity 12
~30 picomo/cm; developer concentration 1-2% solids. To test back transfer, the exposed element was mounted on the surface of a drum. The charged latent image is 4
Developed with magenta toner used to create color proofs. The charging corona voltage and current are SWOP on the solid part.
Adjusted to give concentration. Standard conditions are scorotron grid voltage 200-300V, charging corona current 5
It is 50μA. After completion of the first image transfer, the photosensitive element (electrostatic master) was tested for degree of back transfer with three subsequent cycles of charging, development and transfer as follows: The paper with the wet image was carefully placed in the transfer position. The leading edge of the photosensitive element and the wet image on the paper are spaced 1 inch (2.54 cm) apart, and both the leading edge and the trailing edge of the paper are aligned such that they are held apart from the photosensitive element. Clean the electrostatic master and start a second charge, develop and transfer cycle. A second toner layer is thus obtained on top of the original image. The transfer efficiency of the second image and the degree of back transfer of the previous image are evaluated by an operator standing near the exit of the transfer zone. After the second transfer is completed, this method is repeated a third and fourth time, and the back transfer is checked each time. This four-pass process replicates the creation of an actual four-color proof, where the initially developed image passes through the transfer station three more times before the proof is completed. [0103] The above method can be carried out under at least two transfer conditions,
The transfer corona current was changed to 10 and 50 μA, and the tackdown roll voltage was changed to −0.5 and −8.0 kV (standard conditions: 30 μA and −3.5 kV). As shown in the Examples below, the presence of acidic additives in the photosensitive layer reduces back transfer under a wide range of operating conditions. A photosensitive layer without back transfer under these conditions is suitable as an electrostatic master in a multicolor system. [Examples 1 to 5] Methylene chloride 80
Each solution of the photosensitive composition was made up to contain 20 parts solids. The solid content is a binder or combination binder,
It consists of plasticizers, initiators, halogenated compounds, leuco dyes, acidic additives, etc. This liquid has a thickness of 0.
0.004 inch (0.0102 cm) aluminized polyethylene terephthalate conductive substrate and laminated with a 0.00075 inch (0.001905 cm) thick polypropylene cover sheet. The coating amount was 80 to 150 mg/dm2 or the film thickness was about 7 to 12 μm. The photosensitive layer of each element has the composition shown in Table 1, where amounts are in parts by weight. Each photosensitive element was tested for back transfer using magenta toner and the method described above. The results are summarized in Table 2 below. [Table 2] [0109] The abbreviations are as follows. 1st time is the transferred second image 2nd time is the transferred 3rd image 3rd time is the transferred 4th image P has poor transfer efficiency N: virtually no back transfer L: slightly The back transfer Y shows a considerable amount of back transfer.This table shows that back transfer can be reduced by using an acidic additive. [Examples 6 to 12] In addition to the fact that the photosensitive layer of each element had the composition shown in Table 3 below, Example 1
Eight types of photosensitive elements were prepared and evaluated as described in . The back transfer results are summarized in Table 4 below. Table 3 Table 4 This table shows the effect of acidic additives on Control Example 2. [Examples 13 to 17] The photosensitive layer of each element had the composition shown in Table 5 below, and in addition to using a black toner for evaluation, as described in Example 1. Six types of photosensitive elements were prepared and evaluated. The results are summarized in Table 6 below. [Table 5] [Table 6] [Examples 18 to 23] The photosensitive layer of each element had the composition shown in Table 7 below, and the evaluation was carried out using black toner. In addition to those used, six types of photosensitive elements were prepared and evaluated as described in Example 1. The results are summarized in Table 8 below. [Table 7] [Table 8] [Examples 24 to 26] The photosensitive layer of each element had the composition shown in Table 9 below, and black toner was used for evaluation. In addition to those used, four types of photosensitive elements were prepared and evaluated as described in Example 1. The results are summarized in Table 10 below. Example 27 This example demonstrates the use of a photosensitive electrostatic master in preparing a four-color proof. The following compositions were made from each component indicated in parts by weight:
B1 B2 P1
IN2 LD1 H1 M1
M2 M3 A4 47.01
17.44 27.3 4.0 2.
0 0.5 0.02 0.6 0.1
1.0 After stirring the solution for 24 hours to properly dissolve all the ingredients, it was divided into 0.0
The coating was applied to a 0.04 inch (0.0102 cm) aluminized polyethylene terephthalate film base at a coating speed of 100 feet (30.48 m)/min. The coating amount was 120 mg/dm2. A 0.00075 inch (0.001905 cm) thick polypropylene cover sheet was laminated onto the photosensitive layer immediately after drying. The material thus made is approximately 30 x 40 inches (76.2 x 101.6 cm) to make a four-color color proof.
It was cut into four sheets of size m). Four color proofs were obtained using photosensitive electrostatic masters exposed through the cyan, magenta, yellow and black color separation positives, respectively, according to the general method for making color proofs described above. Ta. Dot range and midrange (50%) from a typical print
) is shown below. [0126]

Claims (69)

[Claims] 1. A photosensitive electrostatic master which forms conductive exposed image areas upon imagewise exposure, said master comprising an electrically conductive substrate carrying a layer of a photosensitive composition, said composition comprising: (A) at least one organic polymeric binder;
(B) hexaarylbiimidazole photooxidant, (
C) leuco dyes that can be oxidized to ionic species by photooxidizing agents; (D) nonionic halogenated compounds; (E)
at least one plasticizer, and (F) at least one acidic additive selected from the group consisting of: (1) a compound of the general formula R-NH-R', where R is R1-SO2-; R1-CO-,
R1-SO2-NH-CO-, or [Formula 1]; R' is H, C1-C12 alkyl, C6-C
30 aryl, C1-C12 substituted alkyl, C6-
C30 substituted aryl, R3-CO-, halogen or heterocyclic group; R and R' together can also form a 5- to 6-membered heterocycle; R1, R2 and R3 may be the same or different; Good, and C1-C12 alkyl, C6
~C30 aryl, C1-C12 substituted alkyl, C
6-C30 substituted aryl, acyl, halogen or heterocyclic group; (2) phosphonic acid of the following general formula, R4-PO[OH]2, where R4 is C1-C12 alkyl, C6-C30 aryl, C1-C12 substituted alkyl, C6-C30
is a substituted aryl, halogen or heterocyclic group; (3) a carboxylic acid with stronger acidity than acetic acid; (4
) Sulfonic acid of the following general formula, R5-SO3H where R5 is C1-C12 alkyl, C6-C30 aryl, C1-C12 substituted alkyl, C6-C30
a substituted aryl, halogen or heterocyclic group; (5) an inorganic acid; and (6) a Lewis acid. [Claim 2] The acidic additive (1) has the formula R1-SO
2-NH-R', where R1 is C
1 to C12 alkyl, C6 to C30 aryl, substituted alkyl or substituted aryl; R' is H, acyl, C1 to C12 alkyl, C6 to C30 aryl;
The photosensitive electrostatic master according to claim 1, which is substituted alkyl and substituted aryl. 3. The photosensitive electrostatic master according to claim 2, wherein the acidic additive represented by the above formula is a sulfonamide. 4. A photosensitive electrostatic master according to claim 3, wherein the acidic additive is a mixture of o- and p-toluenesulfonamide. 5. The photosensitive electrostatic master of claim 3, wherein the acidic additive is alpha-toluenesulfonamide. 6. The photosensitive electrostatic master according to claim 3, wherein the acidic additive is p-(p-toluenesulfonamido)-diphenylamine. 7. The photosensitive electrostatic master according to claim 2, wherein the acidic additive represented by the above formula is a sulfonimide. 8. The photosensitive electrostatic master according to claim 7, wherein the acidic additive is benzoic sulfonimide. 9. The acidic additive is a sulfonylurea of the formula R1-SO2-NH-CO-NH-R', where R1 and R' may be the same or different, and C1-C12 alkyl , C
The photosensitive electrostatic master according to claim 1, which is a substituted alkyl or substituted aryl substituted with 6-C30 aryl, alkyl, alkoxy, halogen, amino, carboxy ester, etc.; or a 5-6 membered heterocyclic group. 10. Acidic additive (1) has the formula R1-CO-
NH-CO-R', where R1 and R' may be the same or different, and C1-C12 alkyl,
C6 to C30 aryl, substituted alkyl, substituted aryl, 5 to 6 membered heterocyclic group, and both R1 and R' are 5 to
The photosensitive electrostatic master according to claim 1, which is capable of forming a 6-membered heterocycle or a fused ring. Claim 11: The acidic additive is phthalimide.
The photosensitive electrostatic master according to claim 10. 12. The photosensitive electrostatic master according to claim 10, wherein the acidic additive is diacetamide. 13. The photosensitive electrostatic master according to claim 10, wherein the acidic additive is a 5- to 6-membered heterocyclic ring or a fused ring. 14. The photosensitive electrostatic master according to claim 13, wherein the acidic additive is parabanic acid. 15. The acidic additive (1) has the formula: where R1, R' and R2 may be the same or different and are C1-C12 alkyl, C6-C30 alkyl; The photosensitive electrostatic master according to claim 1, which is aryl, substituted alkyl, substituted aryl, halogen, or a 5- to 6-membered heterocyclic group. 16. The photosensitive electrostatic master of claim 15, wherein the acidic additive is phenyl N-phenylphosphonamide chloridate. [Claim 17] The acidic additive (2) has the formula R4-PO
[OH]2, where R4 is C1-C1
2. The photosensitive electrostatic master according to claim 1, which is a C6-C30 aryl, a substituted alkyl, a substituted aryl, a halogen, or a 5- to 6-membered heterocyclic group. 18. The photosensitive electrostatic master according to claim 17, wherein the acidic additive is benzenephosphonic acid. [Claim 19] The acidic additive (3) has the formula R(COO
H) n=1-4, where R is C1-C
12 alkyl or alkylene, C6-C30 aryl, 5-6 membered heterocycle containing N, O, S, Se, P, As, etc., and partial esters, substituted alkyl, substituted alkylene or substituted heterocycle of the above-mentioned acids The photosensitive electrostatic master according to claim 1, which is a compound. 20. The photosensitive electrostatic master of claim 19, wherein the acidic additive is phthalic acid. 21. The photosensitive electrostatic master of claim 19, wherein the acidic additive is maleic acid. 22. The photosensitive electrostatic master according to claim 19, wherein the acidic additive is diphenic acid. 23. The acidic additive (4) has the formula R5-SO
3H, where R5 is C1-C12 alkyl, C6-C30 aryl, C1-C12 substituted alkyl, C6-C30 substituted aryl, halogen or N, O, S, Se, P, As. The photosensitive electrostatic master according to claim 1, which is a 5- to 6-membered heterocyclic group including the following. 24. The photosensitive electrostatic master of claim 23, wherein the acidic additive is p-toluenesulfonic acid. 25. The photosensitive electrostatic master of claim 23, wherein the acidic additive is naphthalene sulfonic acid. 26. The acidic additive (5) is hydrochloric acid, hydrobromic acid, hydroiodic acid, sulfurous acid, sulfuric acid, nitrous acid, nitric acid, phosphorous acid, phosphoric acid, selenite acid, selenite and chromium. The photosensitive electrostatic master according to claim 1, wherein the photosensitive electrostatic master is selected from the group consisting of acids. 27. The photosensitive electrostatic master of claim 26, wherein the acidic additive is phosphoric acid. 28. The acidic additive (6) is boron fluoride,
2. The photosensitive electrostatic master of claim 1, wherein the master is selected from the group consisting of aluminum chloride, aluminum bromide, zinc chloride, stannic chloride, and titanium chloride. 29. The photosensitive electrostatic master of claim 28, wherein the acidic additive is zinc chloride. Claim 30: The photo-oxidizing agent is 2,2',4,4',5
, 5'-hexaarylbiimidazole. The photosensitive electrostatic master according to claim 1, which is 5'-hexaarylbiimidazole. 31. The photooxidizing agent is 2,2',4,4'-tetrakis(o-chlorophenyl)-5,5'-bis(m
, p-dimethoxyphenyl)biimidazole. 31. The photosensitive electrostatic master of claim 30. 32. The photosensitive electrostatic master of claim 30, wherein the photooxidizing agent is 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole. 33. The photosensitive electrostatic master of claim 1, wherein the polymeric binder is poly(methyl methacrylate). 34. The photosensitive electrostatic master of claim 1, wherein the polymeric binder is a poly(styrene/methyl methacrylate) copolymer. 35. The photosensitive electrostatic master of claim 1, wherein the polymeric binder is polystyrene. 36. The photosensitive electrostatic master of claim 1, wherein the leuco dye is stabilized. 37. The stabilized leuco dye is tris-
37. The photosensitive electrostatic master of claim 36, which is (4-diethylamino-o-tolyl)methane. 38. The photosensitive electrostatic master of claim 36, wherein the stabilized leuco dye is 9-diethylamino-12-(2-methoxycarbonyl-phenyl)-benzaxanthene. 39. The photosensitive electrostatic master of claim 1, wherein the halogenated compound is a halogenated hydrocarbon selected from the group consisting of aromatic, aliphatic, cycloaliphatic, and combinations thereof. 40. The photosensitive electrostatic master of claim 39, wherein the halogenated hydrocarbon is substituted with a member selected from the group consisting of oxygen, amine, amide, hydroxyl, nitrile, and phosphate. 41. The photosensitive electrostatic master of claim 39, wherein the halogenated hydrocarbon is 1,2-dibromotetrachloroethane. 42. The photosensitive electrostatic master of claim 39, wherein the halogenated hydrocarbon is trichloroacetamide. 43. The photosensitive electrostatic master of claim 1, wherein the plasticizer is selected from the group consisting of dioctyl phthalate, triacetin, t-butylphenyl diphenyl phosphate, diethylene glycol dibenzoate, and 2-ethylhexylbenzyl phthalate. . 44. The photosensitive electrostatic master of claim 43, wherein the plasticizer is 2-ethylhexylbenzyl phthalate. 45. The photosensitive electrostatic master of claim 1, wherein the conductive substrate is aluminized polyethylene terephthalate. 46. The binder (A) is 40 to 85%, the photooxidizing agent (B) is 1 to 20%, and the leuco dye (C) is 0.5% by weight based on the total weight of the photosensitive composition. 5-40
%, halogenated compound (D) 0.25-10%, plasticizer (E) 2-50% and acidic additive (F) 0.1%.
2. The photosensitive electrostatic master of claim 1, wherein ˜10% of each is present. 47. Claim 1, wherein a visible light sensitizer is present.
Photosensitive electrostatic master as described. 48. The photosensitive electrostatic master of claim 47, wherein the visible light sensitizer is an arylidene aryl ketone. 49. The photosensitive electrostatic master of claim 1, wherein a heat stabilizer is present. 50. The photosensitive electrostatic master of claim 49, wherein the thermal stabilizer is 1-phenyl-3-pyrazolidinone. 51. The layer of the photosensitive composition comprises (A) poly(methyl methacrylate), (B) 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetraphenylvinylate. imidazole, (C) tris-(4-diethylamino-o-tolyl)methane, (D) 1,2-dibromotetrachloroethane, (E
2.) 2-ethylhexylbenzyl phthalate; and (F) p-toluenesulfonic acid. 52. The photosensitive electrostatic master of claim 1, wherein there is a protective cover sheet over the photosensitive layer. 53. A zero printing method for creating a positive image by a single imagewise exposure, comprising: (a
) (A) at least one organic polymeric binder, (B) a hexaarylbiimidazole photooxidant, (
C) leuco dyes that can be oxidized to ionic species by photooxidizing agents; (D) nonionic halogenated compounds; (E)
at least one plasticizer, and (F) at least one acidic additive selected from the group consisting of: (1) a compound of the following general formula R-NH-R', where R is R1-SO2- , R1-CO-,
R1-SO2-NH-CO-, or [Formula 3]; R' is H, C1-C12 alkyl, C6-C
30 aryl, C1-C12 substituted alkyl, C6-
C30 substituted aryl, R3-CO-, halogen or heterocyclic group; R and R' together can also form a 5- to 6-membered heterocycle; R1, R2 and R3 are the same or different; Also, C1-C12 alkyl, C6-
C30 aryl, C1-C12 substituted alkyl, C6
-C30 substituted aryl, acyl, halogen or heterocyclic group; (2) Phosphonic acid of the following general formula, R4
-PO[OH]2 where R4 is C1-C12 alkyl, C6-C30 aryl, C1-C12 substituted alkyl, C6-C30 substituted aryl, halogen or heterocyclic group; (3) than acetic acid Carboxylic acid with strong acidity; (4
) A sulfonic acid of the following general formula, R5-SO3H, where R5 is a C1-C12 alkyl, a C6-C30 aryl, a C1-C12 substituted alkyl, a C6-C30 substituted aryl, halogen or a heterocyclic group; 5) an inorganic acid; and (6) a photosensitive electrostatic master comprising an electrically conductive substrate carrying a layer of a photosensitive composition consisting essentially of a Lewis acid; (b) electrostatically charging the master to form an electrostatically charged latent image in the unexposed areas; and (c) applying oppositely charged electrostatic toner or developer. A method as described above comprising the steps of developing the latent image by applying and (d) transferring the toned or developed image to a receiver surface. 54. The method of claim 53, wherein the actinic radiation is in the spectral range from 200 to 550 nm. 55. The method of claim 53, wherein the source of actinic radiation is ultraviolet/visible light. 56. The method of claim 53, wherein the source of actinic radiation is an ultraviolet light emitting cathode ray tube. 57. The active radiation source is ultraviolet or visible light.
54. The method of claim 53, wherein the method is an emitting laser. 58. The active radiation source is an electron beam.
54. The method of claim 53. 59. The method of claim 53, wherein the master is electrostatically charged by corona discharge. 60. The method of claim 53, wherein the image is developed with a liquid electrostatic developer. 61. A liquid electrostatic developer is present in a predominant amount, a carrier liquid having a Cowrie-butanol value of less than 30, thermoplastic particles having an average particle size of less than 10 μm, and a carrier liquid soluble in the carrier liquid. 61. The method of claim 60, consisting essentially of an ionic or zwitterionic charge control agent compound. 62. The method of claim 53, wherein the image is developed with dry electrostatic toner. 63. The method of claim 53, wherein the toned image is transferred to a paper receiver. 64. The method of claim 53, wherein the toned image is transferred to an insulating plate having a conductive surface. 65. The layer of the photosensitive composition comprises (A) poly(methyl methacrylate), (B) 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetraphenylvinylate. imidazole, (C) tris-(4-diethylamino-o-tolyl)methane, (D) 1,2-dibromotetrachloroethane, (E) 2-ethylhexylbenzyl phthalate, and (F) p-toluenesulfonic acid, 54. The method of claim 53, wherein the method is configured to: 66. A liquid electrostatic developer is present in a predominant amount of a carrier liquid having a Cowrie-butanol value of less than 30, thermoplastic resin particles having an average particle size of less than 10 μm, and a carrier liquid soluble in the carrier liquid. 54. The method of claim 53, consisting essentially of an ionic or zwitterionic charge control agent compound. 67. A liquid electrostatic developer is present in a predominant amount of a carrier liquid with a Cowrie-butanol value of less than 30, thermoplastic particles having an average particle size of less than 10 μm, and a carrier liquid soluble in the carrier liquid. 66. The method of claim 65, consisting essentially of an ionic or zwitterionic charge control agent compound. 68. The method of claim 53, wherein the image is developed with powdered electrostatic toner. 69. Above the photosensitive layer is a protective cover sheet, which is removed prior to imagewise exposure.
The method described in 3.