WO1992011581A1 - Imagerie photo-electrographique au moyen de colorants de sensibilisation a l'infrarouge proche - Google Patents

Imagerie photo-electrographique au moyen de colorants de sensibilisation a l'infrarouge proche Download PDF

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Publication number
WO1992011581A1
WO1992011581A1 PCT/US1991/009078 US9109078W WO9211581A1 WO 1992011581 A1 WO1992011581 A1 WO 1992011581A1 US 9109078 W US9109078 W US 9109078W WO 9211581 A1 WO9211581 A1 WO 9211581A1
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WO
WIPO (PCT)
Prior art keywords
acid
photoelectrographic
group
copper
dye
Prior art date
Application number
PCT/US1991/009078
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English (en)
Inventor
Douglas Eugene Bugner
William Mey
Dennis Reed Kamp
Original Assignee
Eastman Kodak Company
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Eastman Kodak Company filed Critical Eastman Kodak Company
Publication of WO1992011581A1 publication Critical patent/WO1992011581A1/fr

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Classifications

    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
    • G03G5/02—Charge-receiving layers
    • G03G5/026—Layers in which during the irradiation a chemical reaction occurs whereby electrically conductive patterns are formed in the layers, e.g. for chemixerography

Definitions

  • This invention relates to new
  • photoelectrographic elements and an imaging method of exposing such elements with near-infrared radiation.
  • Acid photogenerators are known for use in photoresist imaging elements. In imaging processes utilizing such elements, the acid photogenerator is coated on a support and imagewise exposed to actinic radiation. The layer containing the acid photogenerator is then contacted with a photopolymerizable or curable composition such as epoxy and epoxy-containing resins. In the exposed areas, the acid photogenerator generates protons which catalyze polymerization or curing of the photopolymerizable composition. Acid photogenerators are disclosed, for example, in U.S. Patent Nos.
  • Acid photogenerators have been employed in photoelectrographic elements to be exposed with actinic or undefined radiation as shown, for example, in U.S. Patent No. 3,316,088. Photoelectrographic elements have been found useful where multiple copies from a single exposure are desired. See e.g., U.S. Patent No. 3,316,088. Photoelectrographic elements have been found useful where multiple copies from a single exposure are desired. See e.g., U.S. Patent
  • Sensitizer dyes have been disclosed with regard to such elements, but not for sensitization in the near-IR portion of the spectrum. See, for example, in U.S. Patent No. 3,525,612 and Japanese Patent
  • the present invention relates to a
  • photoelectrographic element comprising a conductive layer in electrical contact with an acid photogenerating layer.
  • the acid photogenerating layer is free of photopolymerizable materials and includes an
  • the photoelectrographic element which absorbs near-infrared radiation.
  • the element can be sensitized with such radiation.
  • the present invention also provides a photoelectrographic imaging method which utilizes the above-described photoelectrographic element. This process comprises the steps of: exposing the acid photogenerating layer imagewise to near-infrared
  • the imaging method and elements of the present invention use acid photogenerators in thin layers coated over a conductive layer to form images. This imaging technigue or method takes advantage of the discovery that exposure of the acid generator significantly
  • the charged toner may have the same sign as the electrographic latent image or the opposite sign. In the former case, a negative image is developed, while a positive image is developed in the latter.
  • decomposition of iodonium salts especially when used in conjunction with compounds containing secondary hydroxyl groups, may also be included in the acid photogenerating layer.
  • the present invention relates to a photoelectrographic element comprising a conductive layer in electrical contact with an acid photogenerating layer which is free of photopolymerizable materials and includes an electrically insulating binder and an acid photogenerator.
  • the improvement resides in the use of a dye which absorbs near-infrared radiation so that the element can be exposed with such radiation during electrostatic imaging or printing processes.
  • the acid photogenerator, the electrically insulating binder, and the dye are co-dissolved in a suitable solvent, and the resulting solution is coated over the electrically conductive support.
  • Solvents of choice for preparing acid photogenerator coatings include a number of solvents including aromatic hydrocarbons such as toluene;
  • ketones such as acetone or 2-butanone
  • esters such as ethyl acetate or methyl acetate, chlorinated
  • hydrocarbons such as ethylene dichloride
  • the acid photogenerating layers are coated on a conducting support in any well-known manner such as by doctor-blade coating, swirling, dip-coating, and the like.
  • the acid photogenerating materials should be selected to impart little or no conductivity before irradiation with the conductivity increasing after exposure. Useful results are obtained when the coated layer contains at least about 1 weight percent of the acid photogenerator. The upper limit of acid
  • a preferred weight range for the acid photogenerator in the coated and dried composition is from 15 weight percent to about 30 weight percent.
  • the thicknesses of the acid photogenerator layer can vary widely with dry coating thicknesses ranging from about 0.1 ⁇ m to about 50 ⁇ m. Coating thicknesses outside these ranges may also be useful.
  • aromatic onium salts include Group Va, Group Via, and Group Vila elements.
  • triarylselenonium salts, aryldiazonium salts, and triarylsulfonium salts to produce protons upon exposure to ultraviolet and visible light is also described in detail in "UV Curing, Science and Technology",
  • a representative portion of useful Group Va onium salts are:
  • a representative portion of useful Group VIa onium salts including sulfonium and selenonium salts, are:
  • a representative portion of the useful Group VIIa onium salts, including iodonium salts, are the following:
  • Also useful as acid photogenerating compounds are:
  • Aryldiazonium salts such as disclosed in U.S. Patent Nos. 3,205,157; 3,711,396; 3,816,281;
  • a particularly preferred class of acid photogenerators are the diaryliodonium salts, especially di-(4-t-butylphenyl)iodonium trifluoromethanesulfonate ("ITF").
  • Useful electrically insulating binders for the acid photogenerating layers include polycarbonates, polyesters, polyolefins, phenolic resins, and the like. Desirably, the binders are film forming. Such polymers should be capable of supporting an electric field in excess of 1 ⁇ 10 5 V/cm and exhibit a low dark decay of electrical charge.
  • Preferred binders are styrene-butadiene copolymers; silicone resins; styrene-alkyd resins;
  • soya-alkyd resins poly(vinyl chloride); poly(vinylidene chloride); vinylidene chloride, acrylonitrile
  • copolymers poly(vinyl acetate); vinyl acetate, vinyl chloride copolymers; poly(vinyl acetals), such as poly(vinyl butyral); polyacrylic and methacrylic esters, such as poly(methyl methacrylate), poly(n-butyl
  • polystyrene polystyrene
  • nitrated polystyrene polystyrene
  • styrene-alkyd resins can be prepared according to the method described in U.S. Patent Nos. 2,361,019 and 2,258,423. Suitable resins of the type contemplated for use in the
  • photoactive layers of this invention are sold under such tradenames as Vitel PE 101-X, Cymac, Piccopale 100, Saran F-220.
  • Other types of binders which can be used include such materials as paraffin, mineral waxes, etc.
  • Particularly preferred binders are aromatic esters of polyvinyl alcohol polymers and copolymers, as disclosed in pending U.S. Patent Application Serial No. 509,119, entitled "Photoelectrographic Elements".
  • the binder is present in the element in a concentration of 30 to 98 weight %, preferably 55 to 80 weight %.
  • Useful conducting layers include any of the electrically conducting layers and supports used in electrophotography. These include, for example, paper (at a relative humidity above about 20 percent);
  • metal foils such as aluminum foil, zinc foil, etc.
  • metal plates such as aluminum, copper, zinc, brass, and galvanized plates
  • regenerated cellulose and cellulose derivatives certain polyesters, especially polyesters having a thin electroconductive layer (e.g., cuprous iodide) coated thereon; etc.
  • the acid photogenerating layers of the present invention can be affixed, if desired, directly to a conducting substrate or support, it may be desirable to use one or more intermediate subbing layers between the conducting layer or substrate and the acid photogenerating layer to improve adhesion to the conducting substrate and/or to act as an electrical and/or chemical barrier between the acid
  • subbing layers typically have a dry thickness in the range of about 0.1 to about 5 ⁇ m.
  • Useful subbing layer materials include film-forming polymers such as cellulose nitrate, polyesters, copolymers or poly(vinyl pyrrolidone) and vinylacetate, and various vinylidene chloride-containing polymers including two, three and four component polymers prepared from a polymerizable blend of monomers or prepolymers containing at least 60 percent by weight of vinylidene chloride.
  • Other useful subbing materials include the so-called tergels which are described in Nadeau et al, U.S. Patent No. 3,501,301.
  • Optional overcoat layers are useful with the present invention, if desired.
  • the surface layer of the photoelectrographic element of the invention may be coated with one ore more organic polymer coatings or inorganic coatings.
  • organic polymer coatings or inorganic coatings are well known in the art and accordingly an extended discussion thereof is unnecessary.
  • overcoats are described, for example, in Research Disclosure. "Electrophotographic Elements, Materials, and Processes", Vol. 109, page 63, Paragraph V, May 1973, which is incorporated herein by reference.
  • the dye which absorbs near-infrared radiation can be any such material possessing this property but must not adversely interfere with the operation of the acid photogenerating layer.
  • Suitable dyes include those selected from the cyanine dye family.
  • a particularly preferred dye is 1,3,3-trimethyl-2-[7-(l,3,3-trimethyl-5-nitroindolenin-2-yl)-4-chloro-3,5-trimethylene-1,3,5-heptatrienylidene]-5-nitroindolium hexafluorophosphate ("TTNTHNH”) having the following formula:
  • This dye when included in the photoelectrographic element of the present invention at concentrations between 0.1 and 2.0% by weight of the element, gives rise to an absorption between about 600-900 nm, with a maximum near 820 nm.
  • a typical element containing 1 wt% of this dye and measuring 10 ⁇ m in thickness exhibits an optical density ("OD") of about 3.54 at 818 nm.
  • the acid generating layer contains iodonium salts
  • a copper (II) salt which, when used together, are known to catalyze thermal decomposition of iodonium salts.
  • Suitable copper (II) salts are disclosed by J. V.
  • a particularly preferred example of a copper (II) salt useful for this invention is copper (II) ethyl acetoacetate.
  • This salt is soluble in organic solvents such as dichloromethane and can be homogeneously
  • the compound with secondary hydroxyl groups include those which contain dialkyl-, diaryl-,
  • a particularly preferred compound with secondary hydroxyl groups is the binder polymer having the following formula:
  • the dye can either be included in the acid photogenerating layer or in an adjacent separate layer.
  • the acid generating layer contains .1 to 30, preferably 1-15, weight percent of dye. If a copper (II) salt and a compound with
  • the copper (II) salt is present in an amount of 1 to 20, preferably 10-15, weight percent and, except when
  • PHENOXY RESIN the compound with secondary hydroxyl groups is present in an amount of 1 to 10, preferably 2-4, weight percent.
  • PHENOXY RESIN is also functioning as the binder and then is used in a concentration of 30-98 weight %, preferably 55 to 80 weight %.
  • the thickness of the acid generating layer ranges from 1 to 30 ⁇ m, preferably 5 to 10 ⁇ m.
  • the dye is utilized as a separate layer, that layer is positioned adjacent to the acid
  • the photogenerating layer preferably between the conductive layer and the acid photogenerating layer.
  • the dye containing layer has a thickness of .05 to 5, preferably .5 to 2.0, ⁇ m.
  • a near-ultraviolet radiation (250 to 450 nm) sensitizer in the photoelectrographic element. This gives the element the capability of being exposed either with traditional near-ultraviolet radiation or with near-infrared radiation from a laser diode.
  • the amount of near-ultraviolet radiation sensitizer used varies widely, depending upon the type and thickness of the acid photogenerator used as well as the particular sensitizer used. Generally, the near-ultraviolet
  • Iodonium salt acid photogenerators may be sensitized for near-ultraviolet radiation with ketones such as xanthones, indandiones, indanones,
  • thioxanthones acetophenones, benzophenones, or other aromatic compounds such as anthracenes,
  • dialkoxyanthracenes dialkoxyanthracenes, perylenes, phenothiazines, etc.
  • Triarylsulfonium salt acid photogenerators may be sensitized for near-ultraviolet radiation by aromatic hydrocarbons, anthracenes, perylenes, pyrenes, and phenothiazines.
  • the photoelectrographic elements of the present invention are employed in the photoelectrographic process summarized above. This process involves a
  • 2-step sequence ⁇ i.e. an exposing phase followed by a printing phase.
  • the acid photogenerating layer is exposed imagewise to near-infrared radiation without prior charging to create a latent conductivity pattern.
  • a persistent latent conductivity pattern exists on the element, and no further exposure is needed.
  • the element can then be subjected to the printing phase either immediately or after some period of time has passed.
  • the element is given a blanket electrostatic charge, for example, by passing it under a corona discharge device, which uniformly charges the surface of the acid photogenerator layer.
  • the charge is dissipated by the layer in the exposed areas, creating an electrostatic latent image.
  • electrostatic latent image is developed with charged toner particles, and the toned image is transferred to a suitable receiver (e.g., paper).
  • the toner particles can be fused either to a material (e.g., paper) on which prints are actually made or to an element to create an optical master or a transparency for overhead
  • the toner particles are in the form of a dust, a powder, a pigment in a resinous carrier, or a liquid developer in which the toner particles are carried in an electrically insulating liquid carrier.
  • multiple prints from a single exposure can be prepared by subjecting the photoelectrographic element only once to the exposing phase and then subjecting the element to the printing phase once for each print made.
  • the photoelectrographic layer can be developed with a charged toner having the same polarity as the latent electrostatic image or with a charged toner having a different polarity from the latent
  • the photoelectrographic layer can be charged either positively or negatively, and the
  • resulting electrostatic latent images can be developed with a toner of given polarity to yield either a
  • the photoelectrographic element of the present invention can be imaged with a laser which emits
  • 200mW peak power output at 827 nm and a spot size of about 40 ⁇ m can be used to image the photoelectrographic element.
  • the element is mounted on a rotating drum, and the laser is stepped across the length of the drum in lines about 25 ⁇ m from center to center. The image is written by modulating the output of the laser in an imagewise manner.
  • photoelectrographic elements of the present invention are imaged in this manner, an imagewise conductivity pattern is formed from which toned images can be produced, as described above.
  • a polyester support was coated successively with solutions of (i) cuprous iodide (3.4 wt%) and poly(vinyl formal) (0.32 wt%) in acetonitrile (96.3 wt%), and (ii) cellulose nitrate (6 wt%) in 2-butanone (94 wt%), such that the layer formed from solution (i) is about 0.5 ⁇ m thick, and the layer formed by solution (ii) is about 1.5 ⁇ m thick.
  • the resulting photoelectrographic element was dried in a convection oven for 20 min at 60oC.
  • Cross-section and optical microscopy of a sample of this element show it to be approx. 7.4 ⁇ m thick.
  • Optical spectroscopy reveals an absorption maximum at 816 nm with an OD of 1.08.
  • a sample of this film was evaluated for sensitivity to near-IR irradiation in the following manner.
  • the film was exposed on a breadboard equipped with a 200 mW IR laser diode (827 nm output), and the output beam focused to a 40 ⁇ m spot.
  • the breadboard consists of a rotating drum, upon which the film is mounted, and a translation stage which moves the laser beam along the drum length.
  • the drum rotation, the laser beam location, and the laser beam intensity are all controlled by an IBM-AT computer.
  • the drum was rotated at a speed of 120 rpm, and the film was exposed to an electronically generated graduated exposure consisting of 11 exposure steps.
  • the line spacing (distance between scan lines in the continuous tone step-wedge) was 25 ⁇ m, and the maximum intensity was about 100 mW with an exposure time of about
  • the sample was mounted and tested on a separate linear breadboard.
  • the sample was corona charged with a grid controlled charger set at a grid potential of +500 V.
  • the surface potential was then measured at 1 sec and 15 sec after charging.
  • Example 4 An element was prepared in the same manner as that described in Example 1, except that no TTNTHNH was added and 7.59 wt% of PHENOXY RESIN was used. This photoelectrographic element was found to be 7.8 ⁇ m thick and did not exhibit any absorption at wavelengths greater than 450 nm. Data for this element is listed in Table 1. This element displayed no photoelectrographic activity. It is thus apparent that a near-IR absorbing species must be present in the element.
  • Example 4 An element was prepared in the same manner as that described in Example 1, except that no TTNTHNH was added and 7.59 wt% of PHENOXY RESIN was used. This photoelectrographic element was found to be 7.8 ⁇ m thick and did not exhibit any absorption at wavelengths greater than 450 nm. Data for this element is listed in Table 1. This element displayed no photoelectrographic activity. It is thus apparent that a near-IR absorbing species must be present in the element.
  • Example 4 Example 4
  • a photoelectrographic element was prepared as described in Example 2, except that 2.50 wt% of ITF, 1.52 wt% of the copper (II) salt, and 5.78 wt% of
  • the photoelectrographic element was subsequently charged and toned, and the toned image was transferred to paper.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Photoreceptors In Electrophotography (AREA)

Abstract

L'invention se rapporte à un élément photo-électrographique comportant une couche conductrice en contact électrique avec une couche photogénératrice acide qui est exempte de substances photopolymérisables et qui contient un liant électro-isolant et un photogénérateur acide. Un colorant qui absorbe les rayonnements dans l'infrarouge proche est inclus dans l'élément photo-électrographique pour que, utilisé dans des techniques de copiage électrostatique, il puisse être exposé à des rayonnements dans l'infrarouge proche. Un procédé de formation d'images au moyen de cet élément est également décrit.
PCT/US1991/009078 1990-12-21 1991-12-10 Imagerie photo-electrographique au moyen de colorants de sensibilisation a l'infrarouge proche WO1992011581A1 (fr)

Applications Claiming Priority (2)

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US63230490A 1990-12-21 1990-12-21
US632,304 1990-12-21

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WO1992011581A1 true WO1992011581A1 (fr) 1992-07-09

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1993003426A1 (fr) * 1991-07-29 1993-02-18 Eastman Kodak Company Contretype negatif photoelectrographique sensible au rayonnement infrarouge proche
US5401607A (en) * 1991-04-17 1995-03-28 Polaroid Corporation Processes and compositions for photogeneration of acid
US5582956A (en) * 1994-04-25 1996-12-10 Polaroid Corporation Process for fixing an image, and medium for use therein

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0201725A2 (fr) * 1985-04-17 1986-11-20 Hoechst Aktiengesellschaft Matériel d'enregistrement pour l'électrophotographie
US4661429A (en) * 1986-04-28 1987-04-28 Eastman Kodak Company Photoelectrographic elements and imaging method
EP0401782A2 (fr) * 1989-06-06 1990-12-12 Nec Corporation Titanylphthalocyanine cristalline, procédé pour sa fabrication et son utilisation pour des matériaux électrophotographiques photosensibles

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0201725A2 (fr) * 1985-04-17 1986-11-20 Hoechst Aktiengesellschaft Matériel d'enregistrement pour l'électrophotographie
US4661429A (en) * 1986-04-28 1987-04-28 Eastman Kodak Company Photoelectrographic elements and imaging method
EP0401782A2 (fr) * 1989-06-06 1990-12-12 Nec Corporation Titanylphthalocyanine cristalline, procédé pour sa fabrication et son utilisation pour des matériaux électrophotographiques photosensibles

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5401607A (en) * 1991-04-17 1995-03-28 Polaroid Corporation Processes and compositions for photogeneration of acid
WO1993003426A1 (fr) * 1991-07-29 1993-02-18 Eastman Kodak Company Contretype negatif photoelectrographique sensible au rayonnement infrarouge proche
US5240800A (en) * 1991-07-29 1993-08-31 Eastman Kodak Company Near-infrared radiation sensitive photoelectrographic master and imaging method
US5582956A (en) * 1994-04-25 1996-12-10 Polaroid Corporation Process for fixing an image, and medium for use therein
US5741630A (en) * 1994-04-25 1998-04-21 Polaroid Corporation Process for fixing an image, and medium for use therein

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JPH05504214A (ja) 1993-07-01
EP0516794A1 (fr) 1992-12-09

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