JPH0695367A - Electrophotographic peeling type color proofing system - Google Patents

Abstract

(57) [Summary] (Correction) [Purpose] To provide an electrophotographic peelable color proofing film capable of accurately reproducing an image when exposed to an actinic radiation source through a screen image, and a color proofing system using the same. The structure is useful as a color proofing film that can be used to accurately predict image quality from lithographic printing methods. The image is prepared by forming a complex of an image receiving base, an adhesive layer, a photosensitive diazo, diazide or photopolymerizable layer, a conductive layer and a photoconductor layer.
During charging, laser exposure, toning, fixing and actinic exposure, the image appears on the image receiving base after dry strip development.

Description

Detailed Description of the Invention

[0001]

This invention relates to a color proofing film (colo).
r proofing film). In particular, the invention relates to electrophotographic color proofing systems in which color images are produced by peel development.

[0002]

BACKGROUND OF THE INVENTION In the field of multicolor printing, multicolor proofs are made prior to making lithographic plates and printing with them.
It is desirable to manufacture and help the printer. The proof should reproduce the color quality that would be obtained during the printing process. The proof must be a coherent copy of the desired halftone image. Visual inspection of the color proof should show the expected color rendering and press defects in the image from press printing, which may need to be modified before making the printing plate.

Color proofing sheets for multicolor printing can be made by using a printing machine or a proofing machine. This requires performing all of the actual printing process. However, this conventional color proofing method is expensive and time consuming.

Photoimaging methods can also be used to produce color proofs. There are two general types of photoimaging methods: overlay and single sheet.

In the overlay color proofing method, separate images are produced on separate transparent plastic supports. A plurality of such supports bearing images of corresponding colors are then overlaid on one another on a white sheet to produce a color proofing composite. The main advantages of the overlay method are:
The proof can be made quickly and can serve as a color separation proof by combining two or more colors in register. However, this type of color proofing method has the disadvantage that the overlaid plastic support tends to darken the color proofing sheet. As a result, the impression of the color proofing composite thus produced differs significantly from the impression of a copy actually obtained on a conventional printing machine. An example of such an overlay approach is U.S. Pat. No. 3,136,637, 3,2.
11,553 and 3,326,682.

In the single sheet color proofing method, color proofing sheets are prepared by sequentially producing images of different colors on a single image receiving sheet without an overlaid plastic support. This can be accomplished by sequentially applying the colorant or colored photosensitive layer to a single opaque support. This method approximates the actual printing method and eliminates the color distortion inherent in overlay systems. An example of such a single sheet approach is U.S. Pat. No. 3,671,236, 4,260,67.
No. 3, No. 4,656,114, No. 4,6
59,642 and 4,808,508.

The photoimaging methods used for color proofing generally require an aqueous development step as given in the previous example. However, the dry peel apart method can be used instead of the wet development step. An example of such a peel-away approach for over proofing is contained in US Pat. No. 4,316,951. An example of such a dry development approach for single sheet proofs is
U.S. Pat. Nos. 4,356,253 and 4,8
95,787.

The peel-developable element is based on a photopolymerizable layer. Discrimination is
Obtained after exposure. Other peel developable imaging systems are also known. Some are in U.S. Pat. No. 4,334,00
No. 6, based on o-quinonediazide, and as illustrated in US Pat. No. 4,520,094, based on diazonium salt.

Color separation in the form of screen or non-screen negative or positive films is commonly used to expose the light-sensitive layers in proofing elements and in printing plates. However, the image can also be scanned with information stored as digital data. This information can be edited on the cathode ray tube display device as needed and then used to directly expose the proof element and printing plate without the use of negative or positive films.

Electrophotography is suitable for exposure using digital information. It is US Pat. No. 4,680,24
It can be used to make a printing plate as shown in No. 4. This method can also be used to make color proofs as shown in US Pat. Nos. 4,358,195 and 4,686,163. The material consists of at least one photoconductive layer and a conductive layer. They are charged, exposed with a modulated laser light beam, developed with liquid or solid toner, and heat-fixed. The electrophotographic color proofing system described in the patent requires different color toners: cyan, yellow, magenta, and black. Also, the consistency of toner concentration on the proof changes with changes in charge density, temperature, and humidity. These special toners and toner inconsistencies are the two major disadvantages of these color proofing systems.

In the present invention, electrophotographic color proofing articles are manufactured. The element comprises a sequential photoconductive layer, a conductive layer,
It has a transparent support and a colored photosensitive layer. In one aspect of the invention, the photosensitive layer is divided into two parts. In another aspect, the adhesive layer is in contact with the photosensitive layer. The element is electrophotographically formed by laminating the element to an image receiving base, electrophotographically forming a toner mask on the photoconductive surface, blanket exposing the photosensitive layer through the mask and support, and the non-image areas to the support, photoconductive surface. Processed by removing together with the conductive layer and the conductive layer. The toned mask gives good final dot reproduction. The process is repeated for all cases of colored layers. This method results in full colored reproduction on a single sheet.

The advantages of the present invention are: (1) Both conventional actinic radiation and digitally generated light can be used to expose the article, and (2) imaging is accomplished by a convenient peel-type method. (3) only one toner is needed for different colored articles, and (4) the color density is consistent due to the pre-coated colored layer. Traditional color proofing films have been used to check the quality of the color separation films that will last be used to make printing plates. The present invention is suitable for digital color proofing, where a proof can be made directly from digital information using a laser to write image data directly to film. Color separation films do not have to be made, so an object of the present invention would be to calibrate digital data and data output devices directly. Traditional color proofing systems cannot calibrate digital data.

[0013]

The present invention comprises (i) a transparent support, (ii) a transparent conductive layer on one surface of the support, and (iii) a transparent light layer on the conductive layer. A conductive layer, and (i
v) a colored photosensitive layer on the other side of the support, the colored photosensitive layer comprising at least one colorant, at least one photosensitive component, and at least one binder resin; The component is selected from the group consisting of a polymeric diazonium salt, o-quinonediazide, and a photopolymerizable composition; said photopolymerizable composition being a photoinitiator and a free radical polymerizable having at least one ethylenically unsaturated group. Including both components and;
The photosensitive component is present in an amount sufficient to provide image discrimination when the composition is imagewise exposed to actinic radiation (actinic radiation) through the photoconductive layer, the conductive layer, and the support; The colorant is present in an amount sufficient to evenly color the layer; the binder resin is present in an amount sufficient to bind the composition components into a uniform film), and (v) An optional adhesive layer directly bonded to the colored photosensitive layer, the adhesive layer comprising a thermoplastic resin having a Tg in the range of about 25 ° C to about 100 ° C. An electrophotographic color proof article is provided.

The present invention also includes (i) a transparent support,
(Ii) a transparent conductive layer on one surface of the support, and (iii)
A transparent photoconductive layer on the conductive layer, and (iv) a photopolymerizable composition layer on the other surface of the support (wherein the photopolymerizable layer is a photoinitiator, at least one ethylenically unsaturated A free radical polymerizable component having a group, and a binder resin; the photoinitiator is a free radical of the polymerizable component upon exposure to actinic radiation through the photoconductive layer, the conductive layer, and the support. The polymerizable component is present in an amount sufficient to initiate polymerization; the polymerizable component is present in an amount sufficient to provide image discrimination when imagewise exposing the composition layer to actinic radiation; And (v) the colored photosensitive layer on the photopolymerizable composition layer (wherein the colored photosensitive layer is at least one colored). An agent, at least one photosensitive component, and at least one binder resin; Gender component of the polymer diazonium salt, o
-A quinonediazide, and a photopolymerizable composition; said photopolymerizable composition comprising both a photoinitiator and a free radical polymerizable component having at least one ethylenically unsaturated group; The photosensitive component is present in an amount sufficient to provide image discrimination when the composition is imagewise exposed to actinic radiation through the photoconductive layer, the conductive layer, and the support; and the colorant is a layer. Is present in an amount sufficient to uniformly color the composition; said binder resin is present in an amount sufficient to bind the composition components into a uniform film), and (vi)
An optional adhesive layer directly bonded to the colored photosensitive layer, the adhesive layer comprising a thermoplastic resin having a Tg in the range of about 25 ° C to about 100 ° C. An electrophotographic color proof article is provided.

Furthermore, the present invention provides: (A) preparing one of the electrophotographic color proofing articles; and (B) (i) receiving the electrophotographic article via a colored photosensitive layer or an optional adhesive layer. Laminate on sheets at high temperature and high pressure;
Charging the photoconductive layer of the electrophotographic article; exposing the charged photoconductive layer to radiation that the colored photosensitive layer and any photopolymerizable layer are not sensitive to; the photoconductive layer to the colored photosensitive layer. Toning the layer and any of the photopolymerizable layers described above with a toner that is substantially opaque to the actinic radiation used to expose it; optionally fixing the imaging toner onto the photoconductive layer at elevated temperature; Exposing the colored photosensitive layer and any of the photopolymerizable layers described above to actinic radiation through the toned photoconductive layer, the conductive layer and the support, or (ii) the photoconductive layer of the electrophotographic article. Charge; imagewise exposing the charged photoconductive layer to radiation to which the colored photosensitive layer and any photopolymerizable layer are not sensitive; the photoconductive layer to the colored photosensitive layer and any light described above. Substantially opaque to the actinic radiation used to expose the polymerizable layer Toner, optionally fixing the imaging toner onto the photoconductive layer at elevated temperature; the colored photosensitive layer and any of the photopolymerizable layers toned photoconductive layer, conductive Exposure to actinic radiation through the layer and support, laminating the imaged electrophotographic article to the image-receiving sheet at high temperature and pressure through the exposed colored photosensitive layer or optional adhesive layer, and (C) toning the support. The photoconductive layer, the conductive layer, the optional photopolymerizable layer and the non-image area of the colored photosensitive layer are peeled off, and the image area of the colored photosensitive layer and any adhesive are applied on the image receiving sheet. An image manufacturing method is provided, which is characterized by being left on.

In the most preferred embodiment, the process comprises repeating steps (A)-(C) at least once and preforming another electrophotographic article of step (A) having at least one different colorant. Laminating an image produced from the electrophotographic article of.

In a typical full color proofing guide, four distinct colored images are formed: magenta, cyan, yellow, and blurry. Simulated perfect color reproduction occurs when the images are overlaid on top of each other. As mentioned above, the method of the present invention begins by producing an electrophotographic article having a transparent support. The conductive layer is on one side of the support and the photoconductive layer is on the conductive layer. A colored photosensitive layer containing a photosensitive component and a binder resin is on the other side of the support. There is an optional adhesive layer on the colored photosensitive layer. In one aspect of the invention, two photosensitive layers are used instead of one photosensitive layer. In this case, the photopolymerizable layer is located adjacent to the support and the colored photosensitive layer is on the photopolymerizable layer.

In the preferred embodiment, the support may be comprised of any suitable flexible sheet material that is transparent to the actinic radiation for the colored photosensitive layer and any photopolymerizable layers. Also, it should preferably be dimensionally stable when undergoing the lamination and debonding processes specified herein. That is, it is about 60 ° C to 120 ° C when laminated.
It should have substantially no dimensional change upon heating within the range. One preferred material is polyethylene terephthalate. In a preferred embodiment, it is
It has a thickness of about 25 μm to about 250 μm, a more preferred thickness is about 50 μm to about 125 μm, and a most preferred thickness is about 50 μm to about 75 μm. Suitable films are not exclusive, Meline available from ICI
x 054, 504, 505 and 582, and Host available from Hoechst Celanese Corporation
aphan 4400, 4500 and 4540. The surface of the support may be smooth, and Melinex 4
A matte texture may be provided as in the case of No. 75.
A smooth surface is preferred because the rough surface reduces the resolution of the element by scattering actinic radiation. Other supports may be other types of polyesters, polycarbonates, polystyrenes, cellulose acetates, polyvinyl acetates, polyethylenes, polyamides, etc., provided they are substantially transparent. One or both sides of the support can be modified for proper bonding of the conductive layer and the colored photosensitive layer and optional photopolymerizable layer.

One surface of the support must have a transparent electrically conductive material thereon. Among these are, inter alia, evaporated metals such as aluminum,
Copper, zinc, silver, nickel, chromium, SnO ₂ or In
₂ O ₃ may be mentioned. Vapor deposition techniques are well known in the art.
The conductive surface is used to selectively dissipate electrostatic charges applied to the photoconductive layer when grounded. Such a conductive material can be vacuum deposited on the transparent film support as an ultrathin transparent layer, and the underlying photosensitive layer can be exposed to light rays through the conductive layer and the transparent film support. A particularly useful electrically conductive support is a conductive layer prepared by dispersing an electrically conductive compound (eg, SnO ₂ and In ₂ O ₃ ) or metal powder in a solvent onto a support material such as polyethylene terephthalate. It can be manufactured by These conductive layers are described in US Pat. Nos. 2,901,348 and 3,245,83.
No. 3 specification.

Another useful conductive layer is a composition comprising substantially at least one protective inorganic oxide and about 30 to 70% by weight of at least one conductive metal, based on the weight of the conductive layer. And those manufactured by vacuum vapor deposition. For example, conductive layers produced by vacuum evaporation are disclosed in US Pat. No. 3,880,657. Similarly, suitable conductive coated products can be prepared using the sodium salt of the carboxyester lactone of maleic anhydride and vinyl acetate polymers. Conductive layers of this type, and their preparation and use are described in US Pat. Nos. 3,007,901 and 3,262,80.
No. 7 specification.

The photoconductor itself is well known in the art.
Organic photoconductors are preferred for the present invention. The photoconductive composition for use in the electrophotographic light-sensitive material of the present invention preferably contains a photoconductive substance and an electrically insulating film-forming binder substance. Such photoconductive materials include various organic and inorganic photoconductive materials including organometallic compounds. The photoconductive composition can contain various sensitizers, such as spectral sensitizers and chemical sensitizers. Generally, a typical photoconductive composition of the present invention contains a photoconductive material in an amount of at least 1% by weight based on the total weight of the photoconductive composition when dried. Preferably, the photoconductive material is included in an amount of at least about 15% by weight, based on the total weight of the photoconductive composition.

The upper limit of the amount of photoconductive material in a given photoconductive composition varies widely depending on the compatibility of the sensitivity of the photoconductor with the particular binder component. When a polymeric photoconductive material is used as the photoconductor, the photoconductive composition can consist of the polymeric photoconductive material alone. The reason is that the polymeric photoconductive substance functions as a binder because of its polymeric properties. However, in many cases
Even when a polymeric photoconductive material is used in the photoconductive composition for electrophotographic conductive photosensitive materials of the present invention, a binder specifically selected to provide useful electrical insulation and film forming properties. Is preferably added to the photoconductor composition. The amount of polymeric binder component used is in the range of about 10-85% by weight, based on the total dry weight of the photoconductive composition.

Various photoconductors, including inorganic, organic and polymeric photoconductive materials, including organometallic compounds, can be used in the photoconductive compositions of the present invention. These compounds are well known in the art and include, by way of example, and not exclusively, zinc oxide, lead oxide, selenium oxide, particulate organic pigments such as indigo and phthalocyanine pigments, and organic compounds such as polymeric organic light. An organometallic compound as a conductor may be used.

Such a photoconductive material is described in Research Disclosure, Vol. 109, page 61 (5, 1973).
"Electrophotographic Elements, Materials and Methods"
Processes)) ”.

Preferably the photoconductive material used in the present invention is a polymeric organic photoconductive material containing a polycyclic or heterocyclic aromatic ring. The polymer organic photoconductor containing a polycyclic or heterocyclic aromatic ring is a vinyl polymer type polymer containing an electronic system in its main chain or side chain.

Typical p contained in high molecular organic photoconductors
The i-electron system includes naphthalene, anthracene, pyrene, perylene, acenaphthene, phenylanthracene,
Polycyclic aromatic hydrocarbons such as diphenylanthracene,
Heterocyclic aromatic compounds such as carbazole, indole, acridine, 2-phenylindole, N-phenylcarbazole, and their halogen or carbon number 1
-5 lower alkyl-substituted derivatives. A representative example is given below. Polymers or copolymers, for example vinyl polymers, for example polyvinylnaphthalene, polyvinylanthracene, polyvinylpyrene, polyvinylperylene,
Polyacenaphthenes, polystyrylanthracenes, polyvinylcarbazoles, polyvinylindoles and polyvinylacridines; vinyl copolymers, such as those obtained by reacting methyl methacrylate, methyl acrylate or acrylamide with at least one of said vinyl compounds. Vinyl ether polymers such as polyanthryl methyl vinyl ether, polypyrenyl methyl vinyl ether, polycarbazolyl ethyl vinyl ether, and polyindolyl ethyl vinyl ether; epoxy resins such as polyglycidyl carbazole polyglycidyl indole, and poly-p-glycidyl ann Tolylbenzene; a polyacrylate or polymethacrylate containing a pi electronic system as described above as a substituent; and i Electronic compound and condensation polymers with formaldehyde.

Among these compounds, poly-N-vinylcarbazole and a carbazole ring have, for example, 6 carbon atoms.
To C12 aryl group, C7 to C20 alkaryl group, amino group, C1 to C10 alkylamino group, C2 to C10 dialkylamino group, C6 to C12 arylamino group, carbon Number 12-18 diarylamino group, N-alkyl-N-arylamino group having 1-10 carbon atoms and aryl group having 6-12 carbon atoms, nitro group, and poly-N substituted by halogen atom -Vinylcarbazole (these poly-N-vinylcarbazoles are referred to herein as substituted poly-N-vinylcarbazoles), and N-vinylcarbazole copolymers are preferred.

The N-vinylcarbazole copolymer which can be used has the general formula

[0029]

[Chemical 1] (In the formula, Z represents the same substituent as described in the case of the substituted poly-N-vinylcarbazole).
It contains at least 50 mol% of ethylene carbazole component repeating units.

Other than the N-vinylcarbazole component repeating unit, the component repeating unit forming the N-vinylcarbazole copolymer includes 1-phenylethylene, 1-cyanoethylene, 1-cyano-1-methylethylene, 1-chloro. Included are ethylene, 1- (alkoxycarbonyl) ethylene, and 1-alkoxycarbonyl-1-methylethylene, which are derived from styrene, acrylonitrile, methacrylonitrile, vinyl chloride, alkyl acrylate, and alkyl methacrylate, respectively and alkoxycarbonyl. The alkyl group for a group has 1 to 1 carbon atoms
Eighteen alkyl groups such as methyl, ethyl, hexyl, dodecyl, octadecyl, and 4-methylcyclohexyl groups can be used.

The photoconductive composition of the present invention can be used in a conventional manner. It is as a dispersion or solution of photoconductive material mixed with a binder and coated on the conductive layer.

The photoconductive compositions of this invention can be sensitized by adding conventional sensitizers in amounts effective to provide improved electrophotographic sensitivity. Sensitizing compounds useful for various photoconductive compositions can be selected from the following compounds, for example. Various pyrylium dye salts as described in U.S. Pat. No. 3,250,615, such as pyrylium, bispyrylium, thiapyrylium and selenapyrylium dye salts, Japanese Patent Application (OPI) 55-129.
283, 56-12560, 54-105.
2,6-di-t-butylthiapyrylium dye salts as described in JP 547 and 55-114259.
Fluorene, for example 7,12-dioxo-13-dibenzo (ah) -fluorene, US Pat. No. 2,610,
Aromatic nitro compounds as described in US Pat. No. 120, anthrone as described in US Pat. No. 2,670,284, quinones as described in US Pat. No. 2,670,286, Benzophenones, such as those described in US Pat. No. 2,670,287, thiazoles, such as those described in US Pat. No. 3,732,301, cyanines (including carbocyanines). ), Merocyanine, diarylmethane, thiazine, azine, oxazine, xanthene, phthalein, acridine, and azoanthraquinone dyes, and mixtures thereof.

When such sensitizing compounds are added to the photoconductive composition of the present invention, they are usually mixed with other coating ingredients. According to this method, the sensitizing compound is
It is evenly distributed in the resulting coating layer. Other methods of adding sensitizing compounds can be used in the practice of this invention. Of course,
It is not necessary that the particular photoconductive material used sensitize a layer that is sufficiently sensitive in a given spectral region without a sensitizer. The optimum concentration varies depending on the type of photoconductive compound and sensitizing compound used, but is about 0.001 to 30% by weight, preferably about 0.005 to 10% by weight based on the dry weight of the photoconductive composition. Addition of sensitizing compounds within the concentration range of wt% increases sensitivity.

Of the various binders that can be used in the photoconductive composition of the present invention, film-forming hydrophobic polymeric materials having high dielectric strength and good electrical insulation are preferred for use.

Typical examples of such substances are natural resins, polystyrenes, polymethacrylates, polyolefins, polyvinyl acetals, polyvinyl alcohols, polyamides, phenol-formaldehyde resins, paraffins and mineral waxes.

Various known solvents can be used as a solvent or a dispersion medium for preparing the photoconductive composition of the present invention. Volatile organic solvents are very effective. Typical of such solvents are aromatic hydrocarbons such as benzene, substituted aromatic hydrocarbons such as toluene, xylene, and mesitylene, ketones such as acetone, and 2-
Butanone, halogenated aliphatic hydrocarbons such as methylene chloride, chloroform, and ethylene chloride, ethers and cyclic ethers such as tetrahydrofuran, methyl ethyl ether, and ethyl ether, and mixtures thereof.

In a particularly preferred embodiment of the present invention, the photoconductive composition for use in the electrophotographic article of the present invention comprises an electrically insulating film-forming polymeric binder and organic light in the binder in the form of a solid solution. It is a uniform organic photoconductive composition containing a conductor. One or more sensitizing compounds can be added, for example one of pyrylium, bispyrylium, thiapyrylium and selenapyrylium. The photoconductive composition can be easily coated using an organic solvent.

On the other side of the transparent support there are one or two photosensitive layers. In one aspect, a monochromatic photosensitive layer is used that contains a colorant, a photosensitive component that may be a photopolymerizable composition, a diazonium salt or an o-quinonediazide compound, and a polymeric binder. In another embodiment, two photosensitive layers are used, in which case the photopolymerizable composition is first applied to the support. The photopolymerizable composition contains a photoinitiator, a free radical polymerizable compound, and a binder resin. To this photopolymerizable layer is applied a colored photosensitive layer containing a colorant, a photosensitive compound and a binder resin.

The photopolymerizable layer, when used, is applied to the support from a solvent coating composition. Organic solvents are preferred for photopolymerizable coatings due to the different solubility characteristics of the various components. Typical solvents include, but are not limited to, methyl ethyl ketone, 2-methoxyethanol, 1
-Methoxy-2-propanol, 4-hydroxy-4-
Methyl-2-pentanone, tetrahydrofuran, and γ-butyrolactone are mentioned.

A typical photopolymerizable layer is a photopolymerizable monomer,
It includes a photoinitiator, a binder resin, and any other ingredients known in the art.

The photopolymerizable material preferably contains at least one, preferably at least two terminal unsaturated groups and is a non-gas capable of producing high molecular weight polymers by free radical initiated chain growth addition polymerization. State (1 at standard atmospheric pressure
Boiling temperature higher than 00 ° C.) consisting of ethylenically unsaturated compounds. The most preferred compounds are acrylate or methacrylate monomers as are well known in the art. Suitable polymerizable substances include, but are not limited to, triethylene glycol dimethacrylate, tripropylene glycol diacrylate, tetraethylene glycol dimethacrylate, diethylene glycol dimethacrylate, 1,
4-butanediol diacrylate, 1,6-hexanediol dimethacrylate, pentaerythritol tetraacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, di-pentaerythritol monohydroxypentaacrylate, pentaerythritol triacrylate, bisphenol A ethoxy Included are rate dimethacrylate, trimethylolpropane ethoxylate triacrylate, and trimethylolpropane propoxylate triacrylate.

Free-radical free photoinitiators include any compound that releases free radicals upon stimulation with actinic radiation. Preferred photoinitiators are not exclusive, but include quinoxaline compounds as described in US Pat. No. 3,765,898, vic polyketals as described in US Pat. No. 2,367,660. Donyl compounds, US Pat. Nos. 2,367,661 and 2,36
.Alpha.-carbonyl as described in US Pat. No. 7,670, acyloin ether as described in US Pat. No. 2,448,828, as described in US Pat. No. 3,479,185. Triaryl imidazolyl dimer,
Α-Hydrocarbon-substituted aromatic acyloins as described in US Pat. No. 2,722,512, US Pat.
51,758 and 3,046,127 and polynuclear quinones as described in U.S. Pat. No. 4,6.
S-triazines such as those described in 56,272. The most preferable photoinitiator is 2,3-
Examples include di (4-methoxyphenyl) quinoxaline, 9-phenylacridine, bis (2,4,5-triphenyl) imidazole, bis-trichloromethyl-s-triazine and their derivatives.

The photopolymerizable layer also contains a binder resin which is used not only to determine the hardness and / or flexibility of the coating, but also to control dry development. Binder resins found to be suitable for the layers are polyvinyl acetate, styrene / maleic anhydride copolymers and their half-esters; acrylic polymers and copolymers; polyamides; polyvinylpyrrolidone; cellulose and its Derivatives: phenolic resins and the like. The most preferred binder resins are polyvinyl acetate, polyvinyl acetals such as UCARS from Union Carbide, and polyvinyl butyral and polyvinyl propional.

Dyes, eg US Pat. No. 4,282,3
Nos. 09 and 4,454,218 and European Patent Applications 0,179,448 and 0,211,615 describe the photoinitiators spectrally. You may mix | blend in order to sensitize.

Other ingredients that may be present in the photopolymerizable layer are:
Thermal polymerization inhibitors, plasticizers, oligomers, residual solvents, surfactants, inert fillers, antihalation agents, hydrogen atom donors, photoactive agents and optical brighteners.

In a preferred embodiment, the dry photopolymerizable layer has a laydown range of about 0.1 to about 5 g / m ² . A more preferable coating amount is about 0.4 to about 2 g / m ² .

In the practice of the present invention, the photopolymerizable monomer component is preferably present in the photosensitive layer in an amount of about 10-60% based on the weight of solids in the layer. A more preferred range is about 15% -40%.

In the practice of the present invention, the photoinitiator component is preferably present in the photosensitive layer in an amount of about 2 to 30% based on the weight of solids in the layer. A more preferred range is about 6% -20%.

In the practice of this invention, the binder resin component is preferably present in the photosensitive layer in an amount of from about 10% to 75%, based on the weight of solids in the layer. A more preferred range is about 20% -50%.

The photosensitive layer is flexibly bonded to the surface of the transparent support or the photopolymerizable layer. Photosensitive layers broadly include photosensitizers, colorants, binder resins, and other optional ingredients such as plasticizers, stabilizers, surfactants, antistatic compositions, UV absorbers, optical brighteners. Agents, inert fillers, photoactive agents, spectral sensitizers, antihalation agents, hydrogen atom donors, exposure indicators, polymerization inhibitors and residual coating solvents.

In one embodiment, the photosensitizer is preferably a photosensitive negative-working polymeric diazonium salt. The most preferred photosensitizers are 3-methoxy-4-diazo-diphenylamine sulphate and 4,4'-bis-methoxymethyl which are precipitated as mesitylene sulfonates as taught in U.S. Pat. No. 3,849,392. A polycondensation product with diphenyl ether. Other suitable photosensitizers are described in US Pat.
No. 804. The particular diazo compound is preferably soluble in organic solvents.

In another embodiment, the photosensitizer is preferably a photosensitive positive-working o-naphthoquinonediazide. The most preferred photosensitizers are bis- (3-benzoyl-4,5,6-trihydroxyphenyl) -methane and 2-diazo-1- as taught in U.S. Pat. No. 4,407,926. Naphthol-5
It is an ester with sulfonic acid. Other suitable photosensitizers are described in US Pat. No. 3,106,365, 3,1.
48,983, 3,201,239 and 4,266,001. The special grade diazide compound is preferably soluble in an organic solvent.

In a preferred embodiment, the photosensitizer is a combination of a photoinitiator and a photopolymerizable monomer. Photoinitiators are compounds that liberate free radicals upon exposure to actinic radiation as described in the description of the photopolymerizable layer. The monomer is a non-gaseous ethylene containing at least two terminal unsaturated groups as described in the description of the photopolymerizable layer and capable of producing a high molecular weight polymer by free radical initiated chain growth addition polymerization. It is an unsaturated compound. Dyes and / or pigments are
Incorporated in the photosensitive layer to impart color to the image area. The preferred colorants for the present invention are pigments rather than dyes. Lightfast colorants are preferred. The pigment is typically dispersed in an organic solvent or mixture of organic solvents with an organic binder. The pigment may be organic or inorganic. The pigment is ground to a particle size that is small enough to reproduce a uniform ink particle size and color. The median diameter is generally less than 1 μm.

Non-exclusive examples of colorants that can be used in the present invention are: Permanent Yellow G (C.I.
I. 21095), permanent yellow GR (C.I.
I. 21100), permanent yellow DHG (C.I.
I. 21090), permanent rubin L6B (C.
I. 15850: 1), Permanent Pink F3B
(C.I. 12433), Hosta Palm Pink E (73
915), Hosta Palm Red Violet ER (C.
I. 46500), permanent carmine FBB (12
485), Hosta Palm Blue B2G (CI.741)
60), Hosta Palm Blue A2R (C.I. 7416)
0), and Printex 25. Most of these are
It is a product of Hoechst AG. They can be used separately or blended for the desired color.

Binders found to be suitable for the colored photosensitive layers are styrene / maleic anhydride copolymers and their half-esters; acrylic polymers and copolymers;
Polyamides; polyvinylpyrrolidone; cellulose and its derivatives; phenolic resins; and polyvinyl acetals, such as polyvinyl formal, polyvinyl butyral and polyvinyl propional.

Other components that may be present in the colored photosensitive layer are acid stabilizers, thermal polymerization inhibitors, plasticizers, oligomers, residual solvents, surfactants, inert fillers, antihalation agents, hydrogen sources. Children's donors, photoactive agents and optical brighteners.

In the practice of the present invention, the binder component is
Preferably, the composition components are present in the photosensitive layer in an amount sufficient to combine into a uniform mixture and a uniform film when coated on a substrate. It is preferably present in an amount of about 10% to about 80% by weight of solids in the layer. A more preferred range is about 20% to about 70%.
When the diazonium salt or diazide compound is the photosensitizer component, it is present in the photosensitive layer in an amount of from about 5 to about 70 weight percent, more preferably from about 10 to about 50 weight percent.

In the practice of the present invention, the colorant component is
Preferably, it is present in an amount sufficient to evenly color the photosensitive layer. It is preferably present in an amount of about 5% to about 50% based on the weight of solids in the layer. A more preferred range is from about 10% to about 40%.

Suitable acid stabilizers useful in the photosensitive composition layer include phosphoric acid, citric acid, benzoic acid, m-nitrobenzoic acid, p (p-anilinophenylazo) benzenesulfonic acid, 4,4. Included are'-dinitro-2,2'-stilbene disulfonic acid, itaconic acid, tartaric acid, p-toluene sulfonic acid, and mixtures thereof. Preferably,
The acid stabilizer is phosphoric acid.

A plasticizer may also be included in the photosensitive composition layer of the present invention to prevent coating embrittlement and to keep the composition soft if desired. Suitable plasticizers include dibutyl phthalate, triaryl phosphates and their substituted analogs, and preferably dioctyl phthalate.

To form the photosensitive composition layer, the composition components are dissolved in a solvent or mixture of solvents to facilitate application of the composition to a support or any photopolymerizable layer. Good.

Suitable solvents for this purpose include water, tetrahydrofuran, γ-butyrolactone; glycol ethers such as propylene glycol monomethyl ether and methyl cellosolve; alcohols such as ethanol and n-propanol; ketones such as methyl ethyl ketone. Generally, the solvent system evaporates from the coating composition once applied. However, some non-significant amount of solvent may remain as a residue.

In a preferred embodiment, the photosensitive layer has a laydown range of about 0.1 to 5.0 g / m ² . The most preferable coating amount is about 0.5 to 2.0 g / m ² .

The adhesive layer, when used, is then applied to the colored photosensitive layer. The purpose of the adhesive layer on the photosensitive layer is to facilitate transfer of the photosensitive layer to the image receiving sheet and to provide integrity of the preformed image provided thereunder during dry development of one or more subsequent layers. To protect. It may be applied to the photosensitive layer in several different ways. It can be coated directly onto the photosensitive layer from organic or aqueous based solvent mixtures or can be applied by hot melt extrusion, lamination or coating. The adhesive layer preferably comprises a major amount of one or more thermoplastic polymers and optionally other desired additives such as UV absorbers, antistatic compositions, optical brighteners, inert fillers, plasticizers and the like. May be included. Suitable polymers include, but are not limited to, vinyl acetal resins such as Butvar B-79 available from Monsanto; acrylic resins such as Elvacite 2044 available from DuPont; Elvax 210 available from DuPont.
Ethylene resins such as; and vinyl chloride resins such as Hostaflex CM133 available from Hoechst AG. Preferably the polymer is a vinyl acetate polymer or copolymer. Useful polyvinyl acetate is not exclusive but Mowilith DM available from Hoechst AG
-6, DM-22, 3060 and mixtures thereof. These are usually dispersed in water or dissolved in methyl isobutyl ketone or n-butyl acetate or other solvent compositions for coating on the photosensitive layer. Then
It is from about 2 to about 30 g / m ² , more preferably about 4 to.
Dry to a coating weight of about 20 g / m ² . The layer may optionally contain a UV absorber such as Uvinul D-50 available from GAF. It may also contain a plasticizer such as Resoflex R-296 available from Cambridge Industries. It may also contain antistatic agents such as Gafac, Gafstat available from GAF. It is Nitrocellulo available from Hercules
Other resins such as seRS1 / 2 may also be included. The adhesive layer should not be tacky to the touch when stored.
The layers are about 60 ° C to about 180 ° C, preferably about 60 ° C to about 120 ° C, more preferably 60 ° C when laminated by hot pressing.
It should be transferable to the image receiving sheet within a temperature range of -100 ° C. In a preferred embodiment, the one or more thermoplastic polymers are present in the adhesive layer in an amount greater than about 50% by weight. The plasticizer may be present in an amount up to about 30% by weight, the UV absorber may be present in an amount up to about 20% by weight, the other resin may be present in an amount up to about 50% by weight. Good.

In practice, the electrophotographic article formed as described above is laminated on an image receiving sheet via an adhesive layer. The image-receiving sheet can be composed of virtually any material that can withstand the laminating and dry development processes. White plastic sheets, such as the adhesive pretreated polyester Melinex 3020 from ICI, are useful for this purpose. Plastic coated paper sheets, such as polyethylene coated paper from Scheller, may also be used. Other bases include wood, glass, metal, paper and the like.

When the optional adhesive layer is not used, the image-receiving sheet can be pretreated with the adhesive layer. This adhesive layer is
It can be coated directly on the image-receiving sheet or on a carrier having a release surface and then transferred to the image-receiving sheet.

Lamination may be carried out by contacting the adhesive layer of the electrophotographic article with the image receiving base and then introducing the material into the nip of a pair of heated laminating rollers under suitable pressure. Suitable lamination temperatures typically range from about 60 ° C to 120 ° C.
C, preferably 70 to 100 ° C. The photoconductive layer is then fully charged and imagewise exposed, preferably via a laser such as an argon laser. Essentially any known technique of conventional electrophotography may be used. They are generally charged, exposed,
A method consisting of a developing step and a fixing step is used. The production of images by electrophotographic means may be carried out as follows.

First, the conductive layer is grounded. The photoconductive surface is brought in the vicinity of the electrostatic charge imparting device to provide an overall uniform electrostatic charge. The electrostatic charge imparting device may consist of a number of point electrodes mounted on a movable insulating device so that it can pass back and forth over a grounded coated metal film. A high voltage DC source connects to the charge application device to provide the required charge on the film. The voltage should be sufficient to produce a corona discharge adjacent the electrodes. The device and method can produce an overall negative or positive charge depending on the polarity of the electrode with respect to the metal.
The choice of polarity depends on the toner developer used in this method. When the photoconductive layer is provided with an electrostatic charge by corona discharge in a charge applying device maintained at, for example, 6000 to 7000 V, the photoconductive layer has an area of the photoconductive layer which is attacked by the light beam. Exposure to actinic radiation by projection or through a master to create an electrostatic pattern corresponding to the desired image applied by leaking over or through a laser. Whatever the light beam strikes the surface of the photoconductive coating, the electrostatic charge on it is reduced in direct proportion to the light beam received. This leaves an electrostatic image or pattern of charges corresponding to the light rays and the dark areas of the original image. In one example, the positive charge is accumulated and its potential reaches 150-600V by passing through the photosensitive member several times in the dark below a corona discharge device charged at + 6KV. The actinic radiation is then patternwise projected onto the charged surface from a suitable light source such as a laser, tungsten lamp or the like. The charges in the exposed areas are thus neutralized. The latent image thus formed is developed with charged toner by magnetic brush or cascade development to produce the image. The image may be fixed by heating or passing through a suitable solvent vapor. Liquid development methods may also be used. The toned image is used as an exposure photomask for an underlying colored photosensitive layer or a combination of a photopolymerizable layer and a colored photosensitive layer provided below. Therefore, the toner should be substantially opaque to the actinic radiation to be used in the second exposure step. The colored photosensitive layer or combination of the colored photosensitive layer and the photopolymerizable layer is then simultaneously exposed through the formed toner mask conductive layer and the transparent support by means well known in the art. This second exposure may be performed by exposure to actinic radiation from a light source such as a mercury vapor discharge lamp or a metal halide lamp. Other sources such as carbon arc, pulsed xenon, and lasers may also be used.

After the second exposure, a positive image is formed on the image-receiving sheet by removing the transparent support from the image-receiving sheet in a constant continuous motion at room temperature. No device is required to hold the image receiving base upon removal as it requires only moderate manual peel force to separate the material. The preferred peel angle relative to the peel direction is greater than 90 °. Delamination is
Leave the non-image areas of the colored photosensitive layer attached to the transparent support or photopolymerizable layer. The toned photoconductive layer and conductive layer are also removed along with the transparent support. The image area of the colored photosensitive layer and the optional adhesive layer remain on the image-receiving sheet.
In this way, the colored image is formed on the image receiving sheet. At the same time, the image may be post-exposed to destroy any residual unexposed photosensitizer present in the image.

To obtain a multicolor image, another electrophotographic element is laminated to the first image on the same image-receiving sheet.
The second element preferably has a different color than the first element. After stacking on the same receiver, charging, exposure,
Toning, development, exposure and stripping are carried out again as for the first article. The second image and optional adhesive layer are
Remains with the first image. The third and fourth images may be added in a manner similar to that used to make the second image. In the usual case, four color layers are used to produce the perfect color reproduction of the desired image.

The matte finish of the final image may be obtained by embossing the glossy top side of the image with a matte material such as Melinex 377 from ICI. This is done by laminating the final image and matte material together. The matte material is then generally removed after lamination.
The advantage of this method is that the finish of the final proof can be determined by careful selection of the matte material.

The final four color proof may be subjected to a uniform blanket exposure to photoharden the unexposed colored areas on the image receiving base. The protective layer may also be laminated on top of the last dry development layer.

[0073]

The following non-limiting examples will be useful in illustrating the present invention.

Example 1 A series of electrophotographic articles is prepared as shown schematically in FIG. 2 with the adhesive layer on the heterochromatic photosensitive layer.

Kodak Ektavolt SO101 is an electrophotographic composite available from Kodak. It consists of four layers: a photoconductive layer, a conductive layer, a transparent support, and an adhesion promoting base layer. The base layer is rinsed with methyl ethyl ketone for the present invention. The support of the composite without the base layer is coated with the colored sensitizing solution.

The four different color photosensitive solution formulations contain the following components in the following parts by weight.

Cyan yellow magenta black tetrahydrofuran 200 200 200 200 200 4-hydroxy-4-methyl-2-150 150 150 150 150 pentanone 1-methoxy-2-propanol 444 465 489 490 γ-butyrolactone 44 65 89 90 90 Formvar 12/856 13 18 9 Di-pentaerythritol mono-hi 8 12 8 12 12 droxypentaacrylate 2,3-di (4-methoxyphenyl) 4 4 4 4 quinoxaline Hostaperm B2G 7 --- Permanent yellow GR-7 --- Permanent red FBB- -12-Printex 25 ---- 11 Disperse the pigment in some of the binder resin and solvent. Grind them to the proper particle size for accurate clarity. The median diameter is less than 0.2 μm. The ingredients are thoroughly mixed before coating on the support of the Ektavolt composite. The coatings are dried at 93 ° C. to give optical densities of 1.3, 0.
Gives 9, 1.3, and 1.6.

The adhesive layer formulation contains the following components in the following parts by weight.

N-Butyl Acetate 78 Resoflex R-296 1 Butvar B76 1 Mowilith30 20 Adhesive components are mixed well and coated onto a 67 μm thick film of Melinex 516, a slip treated film available from ICI. The coating is dried at 93 ° C. to a coating weight of 12 g / m ² . The adhesive layer is then 2
The different materials are applied to four different photosensitive layers by laminating them together at 85 ° C. The adhesive film carrier is removed, leaving an adhesive layer on each photosensitive layer.

The cyan electrophotographic article was placed at 85 ° C. via an adhesive layer to form a white image receiving sheet, that is, 145 μm thick Meline.
Laminate to x 3020. The transferred electrophotographic article is then charged. The photoconductive layer is exposed to visible light that the photosensitive layer is not sensitive to. The electrostatic latent image is then made visible by toning the photoconductive layer with carbon black. The photosensitive layer is then exposed to UV light which is attenuated by the carbon black image but which passes through the support to areas free of carbon black. The toned photoconductive layer, the conductive layer and the support together with the exposed colored portion of the photosensitive layer are peeled off from the image-receiving sheet after the second exposure. Only the unexposed parts of the adhesive layer and the photosensitive layer remain on the image-receiving sheet. In this way, a cyan positive image is obtained.

The yellow electrophotographic article is laminated via its adhesive layer to the cyan image on the image receiving sheet. The yellow article is then charged, imagewise exposed to visible light, toned with carbon black, blanket exposed to UV through a carbon black mask and stripped. The unexposed areas of the adhesive layer and the yellow photosensitive layer remain on the cyan image. In this way, a yellow image and a cyan image are obtained on the same image receiving sheet.

The process is repeated for magenta photographic articles, then for black articles. Full four-color reproduction occurs, which gives an accurate representation of the original colored image. Equivalent line and space resolution using these electrophotographic articles is 25 μm. Dot reproduction is 4-96 for 60 lines / cm of screen.

Example 2 A series of electrophotographic articles is prepared as shown schematically in FIG. Here, first, the different color photosensitive layer is exposed, and then,
Laminate on the adhesive layer. Remove the base layer on the Kodak Ektavolt S0101. The composite support without this layer is coated with a colored sensitizing solution. The four different color photosensitive liquid formulations contain the following components in the following parts by weight.

Cyan yellow magenta black 2-methoxyethanol 4100 4100 4650 4100 2-butanone 4100 4099 4648 4100 γ-butyrolactone 1000 1000-1000 dimethyl phthalate 75 75 75 88 75 dibutyl phthalate 25 25-25 25 p-toluenesulfonic acid --- 18 35 Scripset 540 333 260 360 315 371 Scripset 550 117 --- Hydrolysis Scripset 540-67-SMA2625-202-US Patent No. 3,849,392 No. 133 135 70 200 Diazo Hostaperm B2G 117-G-104 --- -Permanent Red FBB-144-Printex 25 --- 94 Scripset resin is available from Monsanto, SMA tree It is available from Arco. The pigment is dispersed in some of the binder resin and solvent. Grind them to the proper particle size for accurate clarity. The median diameter is less than 0.2 μm. The ingredients are thoroughly mixed before coating on the support of the Ektavolt composite. The coating is dried at 93 ° C. to give optical densities 1.1, 0.9, 1.2 and 1.5 for cyan, yellow, magenta and black, respectively. The coating weights are 1.3, 0.9, 1.8 and 1.2 g / m ² , respectively.

The adhesive layer formulation contains the following components in the following parts by weight.

N-Butyl Acetate 78 Resoflex R-296 1 Mowilith 60 21 Adhesive components are mixed thoroughly and coated onto Melinex 516. The coating is dried at 93 ℃ and the coating weight is 12g / m
^Set to ² . The adhesive layer is then applied at 85 ° C. to Melinex 302
0 Applies to image receiving sheet. The adhesive film carrier is removed, leaving the adhesive layer on the receiver.

Charge the cyan electrophotographic article. Then
The photoconductive layer is exposed to visible light that the photosensitive layer is not sensitive to. The electrostatic latent image is then made visible by toning the photoconductive layer with carbon black. Then
The photosensitive layer is exposed to UV light through a carbon black mask. The toned photoconductive layer, conductive layer, transparent support and exposed photosensitive layer are laminated at 85 ° C. through the photosensitive layer to the adhesive layer on the image-receiving sheet. Toned layers,
The conductive layer and the support are laminated together with the unexposed colored portion of the photosensitive layer and then peeled off from the image-receiving sheet. Only the exposed parts of the adhesive layer and the photosensitive layer remain on the image-receiving sheet. In this way, a cyan negative image is obtained.

Another layer of adhesive is laminated to the cyan image on the image receiving sheet. The film carrier is removed. The yellow electrophotographic article is charged, imagewise exposed to visible light, toned with carbon black, blanket exposed to UV through a carbon black mask, laminated to the adhesive on the cyan image and peel developed. The exposed areas of the second adhesive layer and the yellow photosensitive layer remain on the cyan image. In this way, a yellow image and a cyan image are obtained on the same image receiving sheet.

The process is repeated for the magenta electrophotographic article, then the black article. Full four-color reproduction occurs, which gives an accurate representation of the original colored image.

Example 3 A series of electrophotographic articles is prepared as shown in FIG. 3 in which the photopolymerizable layer is in contact with the different color photosensitive layer. Kodak Ektavolt
The base layer on S0101 is removed. The support of this layerless composite is coated with a photopolymerizable solution. The photopolymerizable solution formulation includes the following components in the following parts by weight. Tetrahydrofuran 200 4-hydroxy-4-methyl-2-pentanone 150 1-methoxy-2-propanol 400 γ-butyrolactone 50 Mowilith30 12 trimethylpropanetriacrylate 8 2,3-di (4-methoxyphenyl) quinoxaline 4 photopolymerizable solution Is coated on four base layer removed Ektavolt supports and dried. The dry coating amount is 2 g / m ² . The four different color photosensitive liquid formulations contain the following components in the following parts by weight.

Cyan Yellow Magenta Black Tetrahydrofuran 200 200 200 200 200 4-Hydroxy-4-methyl-2-150 150 150 150 150 Pentanone 1-Methoxy-2-propanol 400 400 400 400 400 γ-butyrolactone 50 50 50 50 50 2-Butanone 84 89 90 90 Scripset 540 11 6 5 4 Diazo Hostaperm B2G 5 − − − Permanent Yellow GR − 5 − − Permanent Red FBB − − 5 − Printex 25 − − − 6 Melinex 516 sheets from U.S. Pat. No. 3,849,392 4 2 22 2. The ingredients are thoroughly mixed before being overcoated. The coating is dried at 93 ° C. to give optical densities of 1.3, 0.9, 1.3, and 1.6 for cyan, yellow, magenta, and black, respectively. The dry coating is then separately laminated to the four photopolymerizable layers via the colored photosensitive layers. The film carrier for the photosensitive layer is removed.

The adhesive layer formulation includes the following components in the following parts by weight.

N-Butyl Acetate 78 Resoflex R-296 1 Mowilith 30 21 Adhesive components are mixed well and coated directly onto the transferred photosensitive layer. The adhesive coating is dried at 93 ° C. to a coating weight of 12 g / m ² . 85 magenta electrophotographic articles
White image-receiving sheet, namely Champi, at ℃ through the adhesive layer
Laminate on Kromekote1S coated paper. The transferred electrophotographic article is then charged. The photoconductive layer is exposed to visible light which the photopolymerizable layer and the colored photosensitive layer are not sensitive to. The electrostatic latent image is then made visible by toning the photoconductive layer with carbon black. The photopolymerizable layer and the photosensitive layer are then simultaneously exposed to ultraviolet light using a carbon black mask. The toned photoconductive layer, conductive layer, transparent support and photopolymerizable layer together with the exposed colored portion of the colored photosensitive layer are peeled off from the image-receiving sheet after the second exposure. Only the unexposed areas of the adhesive layer and the colored photosensitive layer remain on the image-receiving sheet. In this way, a magenta positive image is obtained.

The cyan electrophotographic article is laminated to the magenta image on the image receiving sheet via the adhesive layer. The cyan article is then charged, imagewise exposed to visible light, toned with carbon black, blanket exposed to UV through a carbon black mask, and peel developed. The unexposed areas of the adhesive layer and the cyan photosensitive layer remain on the magenta image. In this way, a magenta image and a cyan image are obtained on the same image receiving sheet.

The process is repeated for a yellow electrophotographic article, then a black article. Complete 4-color reproduction occurs.

Example 4 Polyethylene terephthalate film (PET) (adhesion-promoted on one side and untreated on the other side) (Me from ICI
linex 504) is aluminized on the untreated surface to such a level that a light transmission of about 50% is obtained. An organic photoconductor solution is prepared as follows (parts by weight): toluene 8.00 2-butanone 4.00 γ-butyrolactone 2.40 poly (9-vinylcarbazole) 1.60 Eosin Y dye (alcohol soluble) 0 .1 This solution is coated on the aluminized surface of the metallized PET film with a # 24 wire wound rod and dried. The following sensitizer is coated on the opposite adhesion promoting side of the PET film: di-pentaerythritol monohydroxypentaacrylate 8 tetrahydrofuran 200 4-hydroxy-4-methyl-2-pentanone 150 1-methoxy-2-propanol 444 γ- Butyrolactone 44 Formvar 12/85 6.25 2,3-di (4-methoxyphenyl) -quinoxaline 4 Hostaperm Blue B2G pigment 6.75 Blue pigment is dispersed in some of Formvar 12/85 binder resin and solvent. Grind them to the proper particle size for accurate clarity. The median diameter is less than 0.2 μm. Prior to coating onto the metallized PET film, the ingredients are mixed thoroughly to give an optical density of 1.3.

The adhesive layer is prepared by thoroughly mixing the following components: n-Butyl acetate 79 Resoflex R-296 1 Mowilith30 20 An adhesive solution is coated on a 67 μm thick Melinex 516 film and dried at 93 ° C. The coating amount is 12 g / m ² .
Adhesive layer from ICI to Melinex 939 using hot pressure
As a white polyester image receptor. The Melinex 516 carrier film is then peeled from the adhesive layer. The colored photosensitive coated surface of the electrophotographic article is laminated to the adhesive layer. The electrophotographic coating is charged and then imagewise exposed with a scanning argon ion laser beam having a wavelength of 488 nm. The electrostatic latent image is developed using dry black toner (Elfasol EL07 from Hoechst AG). The photosensitive pigmented coating is exposed to actinic radiation through a PET film, photoconductive coating and toned image. Toned image, photoconductive layer, PET
The support and the unexposed colored portions of the photosensitive layer are peeled off from the image receiving sheet. Only the unexposed parts of the adhesive layer and the photosensitive layer are
Remains on the image receptor.

Example 5 A metallized polyester film having a visible light transmission of about 50% and which has been adhesively treated on the nonmetallized surface is coated on the metallized surface with the following solution: parts by weight toluene 49.50 methyl ethyl ketone 25.00 Butyrolactone 15.00 Poly (9-vinylcarbazole) 10.00 Eosin Y Dye (Alcohol Soluble) 0.50 This solution # 32 on the metallized side of the polyester film.
Withdraw with a wire-wound rod. A colored sensitizing solution is prepared as follows: parts by weight di-pentaerythritol monohydroxypentaacrylate 0.93 tetrahydrofuran 23.17 4-hydroxy-4-methyl-2-pentanone 17.38 1-methoxy-2-propanol 51. 45 Formvar 12/85 0.70 2,3-di (4-methoxyphenyl) quinoxaline 0.46 Hostaperm B2G 0.70 γ-butyrolactone 5.10 This solution was applied to the adhesion-promoting non-metallized surface of a polyester film # 12. Withdraw with a wire-wound rod. Me as described in Example 2
Mowilith 30 and Resofl coated on linex 516
Adhesive film of exR-296 as an image receiving sheet (Pressmatch Standard Receiver Bas from Hoechst Celanese
Laminate on e) and peel the carrier sheet. The film is laminated to Mowilith adhesive with the photosensitive color coat down.
The polyvinylcarbazole photoconductor side of the film is charged and then exposed with an argon ion laser operating at 488 nm. Dry toner (Elfaso from Hoechst AG
The latent image is developed by toning with EL07 developer. Berk film with multi-spectral valve
Exposure to actinic radiation through a toned image in an ey-Ascor exposure system. After exposure, the metallized polyester film and toner are stripped off leaving a cyan image similar to the toned image.

[Brief description of drawings]

FIG. 1 is a cross-sectional view showing an electrophotographic color proofing article of the present invention that includes a photoconductive layer, a conductive layer, a transparent support, and a colored photosensitive layer.

FIG. 2 is a cross-sectional view showing an embodiment of the present invention including a photoconductive layer, a conductive layer, a transparent support, a colored photosensitive layer, and an adhesive layer.

FIG. 3 is a cross-sectional view showing another embodiment of the present invention including a photoconductive layer, a conductive layer, a transparent support, a photopolymerizable layer, a colored photosensitive layer, and an adhesive.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification number Reference number within the agency FI Technical indication location G03F 7/34 7124-2H G03G 13/01 (72) Inventor Robert, Jae, Fon, Trebra United States New Jersey State, Flemington, Spruce, Court, 207 (72) Inventor Tugras, A, Sealy New Jersey, USA High, Bridge, Church, Street, 63 (72) Inventor Sonia, Ibet, Show New Jersey, Whitehouse, USA , Station, teasel, court, 198

Claims (43)

[Claims] 1. (i) a transparent support; (ii) a transparent conductive layer on one surface of the support; (iii) a transparent photoconductive layer on the conductive layer; (iv) A colored photosensitive layer on the other side of said support, wherein said colored photosensitive layer comprises at least one colorant, at least one photosensitive component, and at least one binder resin; Is selected from the group consisting of polymeric diazonium salts, o-quinonediazides, and photopolymerizable compositions; said photopolymerizable composition being a photoinitiator and a free radical polymerizable component having at least one ethylenically unsaturated group. And the photosensitive component is present in an amount sufficient to provide image discrimination when imagewise exposed to actinic radiation through the composition through the photoconductive layer, the conductive layer, and the support. The colorant is present in an amount sufficient to evenly color the layer. The binder resin is present in an amount sufficient to bind the composition components into a uniform film), and (v) any adhesive layer directly bonded to the colored photosensitive layer (provided that The adhesive layer comprises a thermoplastic resin having a Tg in the range of about 25 ° C. to about 100 ° C.). 2. The element of claim 1, wherein the photoconductive layer comprises polyvinylcarbazole. 3. The element according to claim 1, wherein the transparent support contains a substance selected from the group consisting of polyester, polycarbonate, polystyrene, cellulose acetate, polyvinyl acetate, polyethylene and polyamide. 4. The conductive layer comprises aluminum, copper, zinc, silver, nickel, chromium, SnO ₂ and In ₂ O _3.
The element of claim 1, comprising a vapor deposition component selected from: 5. A polymeric diazonium wherein the colored photosensitive layer is a polycondensate of 3-methoxy-4-diazo-diphenylamine sulphate precipitated as mesitylene sulfonate and 4,4'-bis-methoxymethyl-diphenyl ether. The element of claim 1 comprising a salt. 6. A diazide in which the colored photosensitive layer is an ester of bis- (3-benzoyl-4,5,6-trihydroxyphenyl) -methane with 2-diazo-1-naphthol-5-sulfonic acid. The element of claim 1, comprising: 7. The colored photosensitive layer comprises triethylene glycol dimethacrylate, tripropylene glycol diacrylate, tetraethylene glycol dimethacrylate, diethylene glycol dimethacrylate, 1,4-
Butanediol diacrylate, 1,6-hexanediol dimethacrylate, pentaerythritol tetraacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, di-
Includes at least one monomer selected from the group consisting of pentaerythritol monohydroxy pentaacrylate, pentaerythritol triacrylate, bisphenol A ethoxylate dimethacrylate, trimethylolpropane ethoxylate triacrylate, and trimethylolpropane propoxylate triacrylate. The element of claim 1 comprising a photopolymerizable composition. 8. The colored photosensitive layer comprises 2,3-di (4-methoxyphenyl) quinoxaline, 9-phenylacridine, bis (2,4,5-triphenyl) imidazole,
The element according to claim 1, comprising a photopolymerizable composition comprising one or more photoinitiators selected from the group consisting of bis-trichloromethyl-s-triazine and derivatives thereof. 9. The colored photosensitive layer comprises a styrene / maleic anhydride copolymer and a half ester thereof; an acrylic polymer and a copolymer; a polyamide; a polyvinylpyrrolidone; a cellulose resin; a phenol resin; a polyvinyl acetal; a polyacetic acid. The element according to claim 1, comprising one or more binder resins selected from the group consisting of vinyl; and copolymers thereof. 10. The photosensitive layer comprises a plasticizer, a stabilizer, an antistatic composition, an ultraviolet absorber, a spectral sensitizer, an optical brightener, an inert filler, a polymerization inhibitor, an oligomer and a surfactant. Further comprising one or more components selected from the group consisting of a hydrogen atom donor, an antihalation agent and a photoactive agent,
The element according to claim 1. 11. The adhesive layer according to claim 1, wherein the adhesive layer contains at least one polymer selected from the group consisting of vinyl acetate, vinyl chloride, vinyl acetal, acrylic and ethylene polymers and copolymers. element. 12. The adhesive layer contains at least one component selected from the group consisting of a plasticizer, an ultraviolet absorber, an antistatic composition, an inert filler, an antihalation agent and an optical brightener. The element according to claim 1. 13. (i) a transparent support; (ii) a transparent conductive layer on one surface of the support; (iii) a transparent photoconductive layer on the conductive layer; (iv) A photopolymerizable composition layer on the other side of the support, the photopolymerizable layer comprising a photoinitiator, a free radical polymerizable component having at least one ethylenically unsaturated group, and a binder resin; The photoinitiator is present in an amount sufficient to initiate free radical polymerization of the polymerizable component upon exposure to actinic radiation through the photoconductive layer, the conductive layer, and the support; Is present in an amount sufficient to provide image discrimination when imagewise exposing the composition layer to actinic radiation; said binder resin is present in an amount sufficient to combine the composition components into a uniform film. Present), and (v) a colored photosensitive layer on the photopolymerizable composition layer (at least one colored photosensitive layer is present). A colorant, at least one photosensitive component, and at least one binder resin; the photosensitive component selected from the group consisting of polymeric diazonium salts, o-quinonediazides, and photopolymerizable compositions; The photopolymerizable composition includes both a photoinitiator and a free radical polymerizable component having at least one ethylenically unsaturated group; the photosensitive component includes the composition as the photoconductive layer, the conductive layer. , And the colorant is present in an amount sufficient to provide image discrimination when imagewise exposed to actinic radiation through the support; the colorant is present in an amount sufficient to uniformly color the layer; The resin is present in an amount sufficient to combine the composition components into a uniform film), and (vi) any adhesive layer directly attached to the colored photosensitive layer (wherein the adhesive layer is about Tg in the range of 25 ° C to about 100 ° C
And a thermoplastic resin having a). 14. The element of claim 13, wherein the photoconductive layer comprises polyvinylcarbazole. 15. The element according to claim 13, wherein the transparent support contains a substance selected from the group consisting of polyester, polycarbonate, polystyrene, cellulose acetate, polyvinyl acetate, polyethylene and polyamide. 16. The conductive layer comprises aluminum, copper, zinc, silver, nickel, chromium, SnO ₂ and In ₂ O _3.
14. The element of claim 13, comprising a vapor deposition component selected from 17. A polymeric diazonium wherein the colored photosensitive layer is a polycondensate of 3-methoxy-4-diazo-diphenylamine sulphate and 4,4'-bis-methoxymethyl-diphenyl ether precipitated as mesitylene sulfonate. 14. The element of claim 13, comprising salt. 18. A diazide in which the colored photosensitive layer is an ester of bis- (3-benzoyl-4,5,6-trihydroxyphenyl) -methane with 2-diazo-1-naphthol-5-sulfonic acid. 14. The element of claim 13, comprising: 19. The colored photosensitive layer comprises triethylene glycol dimethacrylate, tripropylene glycol diacrylate, tetraethylene glycol dimethacrylate, diethylene glycol dimethacrylate, 1,4.
-Butanediol diacrylate, 1,6-hexanediol dimethacrylate, pentaerythritol tetraacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, di-
Includes at least one monomer selected from the group consisting of pentaerythritol monohydroxy pentaacrylate, pentaerythritol triacrylate, bisphenol A ethoxylate dimethacrylate, trimethylolpropane ethoxylate triacrylate, and trimethylolpropane propoxylate triacrylate. 14. The element of claim 13, which comprises a photopolymerizable composition. 20. The colored photosensitive layer comprises 2,3-di (4-
Methoxyphenyl) quinoxaline, 9-phenylacridine, bis (2,4,5-triphenyl) imidazole, bis-trichloromethyl-s-triazine, and one or more photoinitiators selected from the group consisting of derivatives thereof. 14. The element of claim 13, which comprises a photopolymerizable composition. 21. A styrene / maleic anhydride copolymer and a half ester thereof; an acrylic polymer and a copolymer; a polyamide; a polyvinylpyrrolidone; a cellulose resin; a phenolic resin; a polyvinyl acetal; a polyacetic acid. 14. The element according to claim 13, comprising one or more binder resins selected from the group consisting of vinyl; and their copolymers. 22. The colored photosensitive layer comprises a plasticizer, a stabilizer,
Group consisting of antistatic composition, ultraviolet absorber, spectral sensitizer, optical brightener, inert filler, polymerization inhibitor, oligomer, surfactant, hydrogen atom donor, antihalation agent and photoactive agent 14. The element of claim 13, further comprising one or more components selected from 23. The photopolymerizable composition layer, triethylene glycol dimethacrylate, tripropylene glycol diacrylate, tetraethylene glycol dimethacrylate, diethylene glycol dimethacrylate,
1,4-butanediol diacrylate, 1,6-hexanediol dimethacrylate, pentaerythritol tetraacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, di-pentaerythritol monohydroxypentaacrylate, pentaerythritol triacrylate,
14. The element of claim 13, comprising one or more monomers selected from the group consisting of bisphenol A ethoxylate dimethacrylate, trimethylolpropane ethoxylate triacrylate, and trimethylolpropane propoxylate triacrylate. 24. The photopolymerizable composition layer comprises 2,3-di (4-methoxyphenyl) quinoxaline, 9-phenylacridine, bis (2,4,5-triphenyl) imidazole, bis-trichloromethyl-. 14. The element of claim 13, comprising one or more photoinitiators selected from the group consisting of s-triazines and their derivatives. 25. The photopolymerizable composition layer comprises a styrene / maleic anhydride copolymer and a half ester thereof; an acrylic polymer and a copolymer; a polyamide; a polyvinylpyrrolidone; a cellulose resin; a phenol resin; a polyvinyl acetal; 14. The element of claim 13, comprising one or more binder resins selected from the group consisting of polyvinyl acetate; and copolymers thereof. 26. The adhesive layer according to claim 13, wherein the adhesive layer contains one or more polymers selected from the group consisting of vinyl acetate, vinyl chloride, vinyl acetal, acrylic and ethylene polymers and copolymers. element. 27. The adhesive layer contains one or more components selected from the group consisting of a plasticizer, an ultraviolet absorber, an antistatic composition, an inert filler, an antihalation agent and an optical brightener. The element according to claim 13. 28. (A) (i) a transparent support, (ii) a transparent conductive layer on one surface of the support, (iii) a transparent photoconductive layer on the conductive layer, (Iv) a colored photosensitive layer on the other surface of the support (the colored photosensitive layer contains at least one colorant, at least one photosensitive component, and at least one binder resin; The polymeric component is selected from the group consisting of polymeric diazonium salts, o-quinonediazides, and photopolymerizable compositions; said photopolymerizable composition being a photoinitiator and free radical polymerization having at least one ethylenically unsaturated group. A photosensitive component and an amount sufficient to provide image discrimination when the composition is imagewise exposed to actinic radiation through the photoconductive layer, the conductive layer, and the support. The colorant is present in an amount sufficient to evenly color the layer. The binder resin is present in an amount sufficient to bind the composition components into a uniform film) and (v) any adhesive layer directly attached to the colored photosensitive layer (the adhesion An agent layer including a thermoplastic resin having a Tg in the range of about 25 ° C. to about 100 ° C.), and (B) (i) coloring the electrophotographic element Laminating at high temperature and pressure to the image-receiving sheet through a layer or optional adhesive layer; charging the photoconductive layer of said electrophotographic element;
A toner imagewise exposing said charged photoconductive layer to radiation to which the colored photosensitive layer is not sensitive; a toner which is substantially opaque to the actinic radiation used to expose said colored photosensitive layer. And optionally fixing the imaging toner onto the photoconductive layer at elevated temperature; exposing the colored photosensitive layer to actinic radiation through the toned photoconductive layer, the conductive layer and the support. Or (ii) charging the photoconductive layer of the electrophotographic element; imagewise exposing the charged photoconductive layer to radiation to which the colored photosensitive layer is not sensitive;
Toning the colored photosensitive layer with a toner that is substantially opaque to the actinic radiation used to expose the colored photosensitive layer; optionally fixing the imaging toner onto the photoconductive layer at elevated temperature; Exposed to actinic radiation through the toned photoconductive layer, the conductive layer and the support to expose the imaging electrophotographic element to the image receiving sheet through the exposed colored photosensitive layer or optional adhesive layer at high temperature and high pressure. Laminating, and (C) peeling the support together with the toned photoconductive layer, the conductive layer and the non-image area of the colored photosensitive layer, and the image area of the colored photosensitive layer and any adhesive. A method for producing an image, characterized in that the image is left on the image receiving sheet. 29. Another electrophotographic element of step (A), wherein steps (A)-(C) are optionally repeated at least once and having at least one different colorant,
29. The method of claim 28, further comprising laminating to an image produced from the previous electrophotographic element. 30. The method of claim 28, wherein exposing the photoconductive layer is with a laser. 31. The method of claim 28, wherein the exposing step of the photoconductive layer is performed with visible light. 32. The step of exposing the photoconductive layer is performed with ultraviolet light,
The method of claim 28. 33. The method according to claim 28, wherein the image-receiving sheet comprises paper, coated paper, or polymer film. 34. The method of claim 28, wherein each lamination is conducted at a temperature of about 60 ° C to about 120 ° C. 35. The method according to claim 28, further comprising the step of providing a protective image cover on the image receiving sheet. 36. (A) (i) a transparent support, (ii) a transparent conductive layer on one surface of the support, (iii) a transparent photoconductive layer on the conductive layer, (Iv) a photopolymerizable layer on the other surface of the support (wherein the photopolymerizable layer is a photoinitiator, at least 1
A free radically polymerizable component having ethylenically unsaturated groups, and a binder resin; the photoinitiator being the photoconductive layer, the conductive layer, and the support upon exposure to actinic radiation through the support. Is present in an amount sufficient to initiate free radical polymerization of the polymerizable component; said polymerizable component being present in an amount sufficient to provide image discrimination when imagewise exposing the composition layer to actinic radiation; The binder resin is present in an amount sufficient to combine the composition components into a uniform film), and (v)
A colored photosensitive layer on the photopolymerizable composition layer, the colored photosensitive layer comprising at least one colorant, at least one photosensitive component, and at least one binder resin; Is selected from the group consisting of polymeric diazonium salts, o-quinonediazides, and photopolymerizable compositions; said photopolymerizable composition being a photoinitiator and a free radical polymerizable component having at least one ethylenically unsaturated group. Including both;
The photosensitive component is present in an amount sufficient to provide image discrimination when the composition is imagewise exposed to actinic radiation through the photoconductive layer, the conductive layer, and the support; and the colorant is The binder resin is present in an amount sufficient to evenly color the layer; the binder resin is present in an amount sufficient to combine the composition components into a uniform film), and (vi) the colored photosensitivity. Any adhesive layer directly adhered to the layer (the adhesive layer is about 2
(Including a thermoplastic resin having a Tg in the range of 5 ° C. to about 100 ° C.), (B) (i) the electrophotographic element being a colored photosensitive layer or an optional Laminating to an image-receiving sheet at high temperature and pressure via an adhesive layer; charging the photoconductive layer of said electrophotographic element;
Imagewise exposing the charged photoconductive layer to radiation to which the colored photosensitive layer and the photopolymerizable layer are not sensitive; for exposing the photoconductive layer to the colored photosensitive layer and the photopolymerizable layer. Toning with a toner that is substantially opaque to the actinic radiation used; optionally fixing the imaging toner onto the photoconductive layer at elevated temperature; toning the colored photosensitive layer and the photopolymerizable layer Exposure to actinic radiation through the photoconductive layer, the conductive layer and the support, or (ii) charging the photoconductive layer of the electrophotographic element; coloring the charged photoconductive layer with a photosensitive layer and photopolymerizable Imagewise exposing the layer to insensitive radiation; toning the photoconductive layer with a toner that is substantially opaque to the actinic radiation used to expose the colored photosensitive layer and the photopolymerizable layer. Optionally with imaging toner on said photoconductive layer Fixing at elevated temperature; exposing the colored photosensitive layer and the photopolymerizable layer to actinic radiation through the toned photoconductive layer, conductive layer and support to expose the imaging electrophotographic element to the exposed colored photosensitive material. Of a photoconductive layer, a conductive layer, a photopolymerizable layer, and a colored photosensitive layer, which are toned with a (C) support, which is laminated on an image-receiving sheet at high temperature and high pressure via a photosensitive layer or an optional adhesive layer. A method for producing an image, which comprises peeling together with a non-image area and leaving the image area of the colored photosensitive layer and an optional adhesive on the image-receiving sheet. 37. Another electrophotographic element of step (A), wherein steps (A) to (C) are optionally repeated at least once and having at least one different colorant,
37. The method of claim 36, further comprising laminating to an image on the same image receiving sheet made from the previous electrophotographic element. 38. The method according to claim 36, wherein the step of exposing the photoconductive layer is performed with a laser. 39. The method according to claim 36, wherein the exposing step of the photoconductive layer is performed with visible light. 40. The method according to claim 36, wherein the exposing step of the photopolymerizable layer and the photosensitive layer is performed with ultraviolet light. 41. The method according to claim 36, wherein the image receiving sheet is made of paper, coated paper, or polymer film. 42. The method of claim 36, wherein each lamination is conducted at a temperature of about 60 ° C to about 120 ° C. 43. The method according to claim 36, further comprising a subsequent step of providing an image protective cover on the image receiving sheet.