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WO1997043696A1 - Procedes pour augmenter la sensibilite d'exposition de matrices photopolymerizables et dispositif utile pour ces procedes - Google Patents

Procedes pour augmenter la sensibilite d'exposition de matrices photopolymerizables et dispositif utile pour ces procedes Download PDF

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Publication number
WO1997043696A1
WO1997043696A1 PCT/US1997/007789 US9707789W WO9743696A1 WO 1997043696 A1 WO1997043696 A1 WO 1997043696A1 US 9707789 W US9707789 W US 9707789W WO 9743696 A1 WO9743696 A1 WO 9743696A1
Authority
WO
WIPO (PCT)
Prior art keywords
exposure
matrix
photopolymerizable
radiation
imaging
Prior art date
Legal status (The legal status 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 status listed.)
Ceased
Application number
PCT/US1997/007789
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English (en)
Inventor
Gregory E. Mueller
Mitch G. Male
David H. Roberts
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Napp Systems Inc
Original Assignee
Napp Systems Inc
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 Napp Systems Inc filed Critical Napp Systems Inc
Priority to AU31193/97A priority Critical patent/AU3119397A/en
Publication of WO1997043696A1 publication Critical patent/WO1997043696A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/20—Exposure; Apparatus therefor
    • G03F7/2022—Multi-step exposure, e.g. hybrid; backside exposure; blanket exposure, e.g. for image reversal; edge exposure, e.g. for edge bead removal; corrective exposure

Definitions

  • the present invention relates to methods for the treatment of photopolymerizable matrices (e.g., printing plates) and related materials to impart an image thereon.
  • the present invention relates to apparatus useful for imparting an image onto photopolymerizable matrices and related materials.
  • Images can be imparted to photosensitive polymeric materials (e.g., materials employed for the production of printing plates) in a variety of ways.
  • a mask typically a negative
  • a mask can be placed over the matrix, which is then exposed to light of sufficient energy to promote the crosslinking of the matrix. This crosslinking occurs only where light is allowed to impact the matrix. Uncured photosensitive polymeric material is then removed (e.g., by washing), leaving the desired image.
  • imaging apparatus useful for carrying out the above-described process.
  • Invention imaging apparatus enable one to increase the effective exposure sensitivity of photopolymerizable materials.
  • the invention method comprises pre-exposing the above-described matrix (i.e., subjecting the matrix to a low fluence of actinic radiation) prior to digitally imaging the matrix.
  • the effective exposure sensitivity of a photopolymerizable material is substantially increased.
  • the energy input required to cause photopolymerization thereof is reduced.
  • actinic radiation refers to electromagnetic radiation capable of initiating photochemical reactions.
  • Ultraviolet and visible wavelength radiation (with wavelengths typically falling in the range of 300-700 nm) is commonly employed for this purpose.
  • Preferred wavelengths are those which correspond to the spectral sensitivity of the photopolymerizable material being imaged.
  • pre-exposure i.e., “exposure to a low fluence of actinic radiation” refers to radiation which imparts less energy to the photopolymerizable matrix than the threshold level required to initiate a substantial level of curing thereof.
  • the "threshold level” required to initiate a substantial level of curing of the photopolymerizable matrix can vary widely, depending on such factors as the particular material being imaged, the processing methodology employed for developing the imaged material, and the like. Radiation levels are said to exceed threshold levels when the pre-exposed photopolymer cannot be completely removed from the support therefor under normal processing conditions.
  • the level of curing of the photopolymerizable matrix imparted by this treatment is generally controlled so as to be insufficient to produce any significant change in the physical properties of the photopolymerizable matrix.
  • Pre-exposure contemplated by the present invention can be imparted either by coherent or non-coherent radiation, and will typically have a wavelength comparable to the wavelength employed for the actual imaging exposure.
  • a variety of methods can be used to achieve the desired pre-exposure employed herein. For example, a lower intensity of radiation than used for the imaging exposure can be employed, or a longer wavelength than used for the imaging exposure can be employed, etc.
  • pre-exposure employed in the practice of the present invention is accomplished employing radiation which imparts energy equal to about 10-99 % of the threshold level required to initiate substantial curing of the photopolymerizable matrix.
  • pre-exposure employed in the practice of the present invention is accomplished employing radiation which imparts energy equal to about 75-96 % of the threshold level required to initiate substantial curing of the photopolymerizable matrix, with radiation which imparts energy equal to about
  • the area of photopolymerizable matrix subjected to pre-exposure is at least as great as the area of the same portion of the matrix as is subjected to digital imaging substantially immediately following the pre-exposure. It is presently preferred that over the entire surface of the photopolymerizable matrix, there is a substantially constant delay between initial pre-exposure of photopolymerizable matrix and the imaging exposure which follows.
  • photopolymerizable matrix is subjected to pre-exposure at least about 0.05 seconds before, but no greater than about 5 minutes before being subjected to digital imaging.
  • the photopolymerizable matrix is subjected to pre-exposure at least about 0.1 seconds, but no greater than about 30 seconds before being subjected to digital imaging.
  • Photopolymerizable matrices contemplated for use in the practice of the present invention include flexographic printing plates, letterpress printing plates, offset printing plates, circuit board resists, stereolithography resins, and the like. Such materials can be prepared from a variety of photopolymerizable resins, such as, for example, (meth)acrylate-based resins (see, for example, U.S. Patent No. 5,348,844, incorporated herein by reference), thiol/ene-based resins (see, for example, U.S. Patent No. 3,783,152, incorporated herein by reference), vinyl ether-based resins (see, for example, U.S. Patent No.
  • Digital imaging contemplated by the present invention is typically accomplished by exposure of the photopolymerizable matrix to coherent (e.g., laser) irradiation.
  • coherent e.g., laser
  • the angle of incidence at which the photopolymerizable matrix is contacted with either the pre-exposure radiation and/or the digital imaging radiation can vary substantially.
  • the angle of incidence is relatively unimportant (and consequently can vary widely, e.g., from 0° up to about 45" or more) .
  • photopolymerizable matrices used for the preparation of circuit boards are relatively insensitive to the angle of incidence.
  • thicker photopolymer matrices i.e., thicknesses of greater than about 5 mils
  • the angle of incidence be substantially perpendicular to the photopolymerizable matrix (i.e., an angle of incidence of about 0°), in order to maximize penetration of the incident radiation into the photopolymerizable matrix, thereby maximizing the effectiveness of the pre-exposure and/or digital imaging.
  • invention apparatus for digitally imaging photopolymerizable surfaces.
  • invention apparatus comprises conventional imaging equipment (having a first exposure means for digitally imaging the photopolymerizable surface) , modified so as to include a second exposure means capable of delivering pre-exposure radiation to the photopolymerizable surface substantially immediately prior to digital imaging thereof.
  • exposure means refers to both a source of radiation, as well as the resulting beam produced by said source.
  • exposure means refers to both a source of radiation, as well as the resulting beam produced by said source.
  • Imaging apparatus contemplated for use in accordance with the present invention include any configuration typically used for exposure of a photopolymerizable matrix to impart an image thereto.
  • Such apparatus include exterior-drum devices (see, for example, European Patent Application No. 491,368, U.S. Patent No. 5,247,883 and U.S. Patent No. 5,385,092, each of which are hereby incorporated by reference herein) ; flatbed devices (see, for example, U.S. Patent No. 5,385,092 and U.S. Patent No. 4,312,590, each of which are hereby incorporated by reference herein) ; interior-arc devices (also known as internal drum devices; see, for example, U.S. Patent No. 5,385,092 and U.S. Patent No. 4,054,928, each of which are hereby incorporated by reference herein) ; and the like.
  • Pre-exposure contemplated by the present invention can be accomplished employing either coherent or non-coherent radiation, and can be provided by a variety of sources, e.g., an ion gas laser (e.g., an argon ion laser, a krypton laser, a helium:cadmium laser, and the like), a solid state laser (e.g., a frequency-doubled Nd:YAG laser), a semiconductor diode laser, an arc lamp (e.g., a medium pressure mercury lamp, a Xenon lamp, a carbon arc lamp, and the like) , and the like.
  • Exposure sources capable of providing ultraviolet and visible wavelength radiation
  • the first exposure means and the second exposure means can be provided by a single source, or by two separate elements. When a single source is employed (in conjunction with a beam splitter) , a portion of the beam is employed for pre- exposure of the photopolymerizable matrix, and the remainder of the beam is employed as the main exposure beam.
  • apparatus comprising: support means for a photopolymerizable matrix, a first exposure means capable of delivering pre-exposure radiation to the surface of said photopolymerizable matrix, wherein said first exposure means is movably positioned with respect to said support means, and a second exposure means capable of digitally imaging said matrix, wherein said second exposure means is movably positioned with respect to said support means, and wherein the positioning of said first exposure means and said second exposure means are interrelated so as to effect a substantially constant delay between pre-exposure of a photopolymerizable matrix mounted on said support means and said digital imaging.
  • Support means contemplated for use in the practice of the present invention include any means suitable to aid in presenting the photopolymerizable matrix to the pre-exposure and the imaging exposure contemplated herein. Examples include the support carriage of an exterior-drum device, the support element of a flatbed device, the support element of an interior-arc device, and the like.
  • the means capable of delivering pre-exposure radiation can deliver either coherent or non-coherent radiation. Such radiation will impart less energy to the photopolymerizable matrix than the threshold level required to initiate substantial curing of the photopolymerizable matrix.
  • pre-exposure contemplated by the present invention can be provided by a separate source, or by the same source as used to generate the main exposure beam.
  • Apparatus according to the invention is designed so that the area of photopolymerizable matrix subjected at any particular point in time to pre-exposure by said first exposure means is at least as great as the area of the same portion of the matrix as is later subjected to exposure by the second exposure means (typically substantially immediately following pre-exposure) .
  • the support means is movably adjustable with respect to the output beam of said first and second exposure means.
  • the output beam of said first and second exposure means are movably adjustable with respect to a relatively stationary support means.
  • both the support means and the output beam of said first and second exposure means are movably adjustable with respect to one another.
  • NAPPflex NF-1 NAPP Systems Inc., San Marcos
  • Plates were exposed employing an external drum device and an ultraviolet argon ion laser delivering wavelengths in the range of 333-364 nm (although wavelengths falling in the range of about 320-550 nm, with wavelengths in the range of about 330-365 nm are also suitable) .
  • the power for pre-exposure was split from the main beam using a beamsplitter, and injected into a fiber optic which guided the beam to the appropriate point.
  • the time delay between the pre-exposure and main beams typically falls in the range of about 30 sec.
  • the pre-exposure threshold fluence was determined by subjecting the material under test to a series of pre-exposures of varying intensities; the material under test was then processed according to the manufacturer's instructions.
  • the threshold fluence is defined as the fluence required to produce a slight scum on the plate after processing (the pre-exposure threshold fluence was thus determined to within a few percent) .
  • the material under test was exposed to the desired pre-exposure, and then a brief (e.g., 5 millisecond) exposure to irradiation by the main laser.
  • the plate was then processed according to the manufacturer's instructions and evaluated.
  • the evaluation comprised measuring the radius, r, of the polymerized area left by the main - exposure with a measuring microscope and finding the main imaging threshold fluence, I(r), using the following equation:
  • I 0 is the peak fluence
  • w is 1/e 2 beam radius
  • the total power requirement i.e., the total of the power requirement for the pre-exposure and imaging exposures
  • the invention process employing a low fluence pre-exposure, followed by an imaging exposure.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Exposure And Positioning Against Photoresist Photosensitive Materials (AREA)

Abstract

Procédés pour augmenter substantiellement la sensibilité d'exposition effective de matériaux photopolymérisables sans modification chimique de ces derniers. Ce résultat est obtenu en soumettant ces matériaux à une pré-exposition avec une énergie relativement faible avant de les soumettre à l'exposition principale formatrice d'images. L'augmentation de la sensibilité d'exposition effective des matériaux photopolymérisables permet d'obtenir une qualité d'image améliorée sur la matrice exposée et autorise l'emploi de plus grandes vitesses d'exposition. L'invention concerne également un appareil pour la formation d'images utile pour appliquer le procédé décrit ci-dessus. Ce dispositif permet d'accroître la sensibilité d'exposition effective de matériaux photopolymérisables.
PCT/US1997/007789 1996-05-16 1997-05-06 Procedes pour augmenter la sensibilite d'exposition de matrices photopolymerizables et dispositif utile pour ces procedes Ceased WO1997043696A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU31193/97A AU3119397A (en) 1996-05-16 1997-05-06 Methods to increase the exposure sensitivity of photopolymerizable matrices and apparatus useful therefor

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US65092096A 1996-05-16 1996-05-16
US08/650,920 1996-05-16

Publications (1)

Publication Number Publication Date
WO1997043696A1 true WO1997043696A1 (fr) 1997-11-20

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AU (1) AU3119397A (fr)
WO (1) WO1997043696A1 (fr)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004021080A1 (fr) * 2002-08-29 2004-03-11 Eudes Dantas Stereoflexographie
WO2006019450A2 (fr) 2004-07-20 2006-02-23 Macdermid Printing Solutions, Llc Procede ameliore d'exposition prealable de plaques d'impression d'image en relief
WO2008145316A2 (fr) 2007-05-25 2008-12-04 Eos Gmbh Electro Optical Systems Procédé de fabrication par couches d'un objet tridimensionnel
EP2176073A4 (fr) * 2007-08-08 2013-07-10 Macdermid Printing Solutions Procédé de pré-exposition de plaque d'impression d'images en relief
EP3944021A1 (fr) * 2020-07-22 2022-01-26 Esko-Graphics Imaging GmbH Procédé et appareil pour le durcissement d'une plaque d'impression

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US3144331A (en) * 1961-01-13 1964-08-11 Du Pont Process for conditioning photopolymerizable elements
GB1136544A (en) * 1966-02-28 1968-12-11 Agfa Gevaert Nv Photochemical cross-linking of polymers
US3832421A (en) * 1972-05-05 1974-08-27 Grace W R & Co Curable compositions containing solid styrene-allyl alcohol copolymer based polyenes and polythiols
US4072524A (en) * 1974-12-06 1978-02-07 Siemens Aktiengesellschaft Mixture yielding thermally stable photo-cross-linkable layers and foils
SU595694A1 (ru) * 1975-10-06 1978-02-28 Предприятие П/Я Х-5476 Негативный фоторезист
US4410562A (en) * 1980-11-29 1983-10-18 Dainippon Ink And Chemicals, Inc. Method for forming a cured resin coating having a desired pattern on the surface of a substrate
US4544627A (en) * 1978-10-31 1985-10-01 Fuji Photo Film Co., Ltd. Negative image forming process in o-quinone diazide layer utilizing laser beam
US4609615A (en) * 1983-03-31 1986-09-02 Oki Electric Industry Co., Ltd. Process for forming pattern with negative resist using quinone diazide compound
US4702994A (en) * 1984-10-01 1987-10-27 W. R. Grace & Co. Projection imaged relief printing plates
US4801477A (en) * 1987-09-29 1989-01-31 Fudim Efrem V Method and apparatus for production of three-dimensional objects by photosolidification
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US4857437A (en) * 1986-12-17 1989-08-15 Ciba-Geigy Corporation Process for the formation of an image
US4868090A (en) * 1985-08-24 1989-09-19 Atsushi Kitamura Methods for the manufacture of cylindrical photosensitive resin structures and cylindrical printing plates
US4910121A (en) * 1983-02-11 1990-03-20 Ciba-Geigy Corporation Photopolymerizable composition containing metallocenes
US4945032A (en) * 1988-03-31 1990-07-31 Desoto, Inc. Stereolithography using repeated exposures to increase strength and reduce distortion
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WO1992015620A1 (fr) * 1991-02-27 1992-09-17 Allied-Signal Inc. Stereolithographie utilisant des polymeres a base d'ether vynilique
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JPH05226211A (ja) * 1992-02-10 1993-09-03 Fujitsu Ltd 露光方法
US5250389A (en) * 1991-02-15 1993-10-05 Asahi Kasei Kogyo Kabushiki Kaisha Photosensitive elastomer composition
CA2101582A1 (fr) * 1992-08-05 1994-02-06 Rudolf Zertani Appareil d'insolation au laser pour la production d'imprimes
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* Cited by examiner, † Cited by third party
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US3144331A (en) * 1961-01-13 1964-08-11 Du Pont Process for conditioning photopolymerizable elements
GB1136544A (en) * 1966-02-28 1968-12-11 Agfa Gevaert Nv Photochemical cross-linking of polymers
US3832421A (en) * 1972-05-05 1974-08-27 Grace W R & Co Curable compositions containing solid styrene-allyl alcohol copolymer based polyenes and polythiols
US4072524A (en) * 1974-12-06 1978-02-07 Siemens Aktiengesellschaft Mixture yielding thermally stable photo-cross-linkable layers and foils
SU595694A1 (ru) * 1975-10-06 1978-02-28 Предприятие П/Я Х-5476 Негативный фоторезист
US4544627A (en) * 1978-10-31 1985-10-01 Fuji Photo Film Co., Ltd. Negative image forming process in o-quinone diazide layer utilizing laser beam
US4410562A (en) * 1980-11-29 1983-10-18 Dainippon Ink And Chemicals, Inc. Method for forming a cured resin coating having a desired pattern on the surface of a substrate
US4816379A (en) * 1982-12-28 1989-03-28 Basf Aktiengesellschaft Production of relief plates and printing plates by a positive-working method
US4910121A (en) * 1983-02-11 1990-03-20 Ciba-Geigy Corporation Photopolymerizable composition containing metallocenes
US4609615A (en) * 1983-03-31 1986-09-02 Oki Electric Industry Co., Ltd. Process for forming pattern with negative resist using quinone diazide compound
US4702994A (en) * 1984-10-01 1987-10-27 W. R. Grace & Co. Projection imaged relief printing plates
US4868090A (en) * 1985-08-24 1989-09-19 Atsushi Kitamura Methods for the manufacture of cylindrical photosensitive resin structures and cylindrical printing plates
US4857437A (en) * 1986-12-17 1989-08-15 Ciba-Geigy Corporation Process for the formation of an image
US4801477A (en) * 1987-09-29 1989-01-31 Fudim Efrem V Method and apparatus for production of three-dimensional objects by photosolidification
US4945032A (en) * 1988-03-31 1990-07-31 Desoto, Inc. Stereolithography using repeated exposures to increase strength and reduce distortion
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WO1992015620A1 (fr) * 1991-02-27 1992-09-17 Allied-Signal Inc. Stereolithographie utilisant des polymeres a base d'ether vynilique
JPH05226211A (ja) * 1992-02-10 1993-09-03 Fujitsu Ltd 露光方法
CA2101582A1 (fr) * 1992-08-05 1994-02-06 Rudolf Zertani Appareil d'insolation au laser pour la production d'imprimes

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Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004021080A1 (fr) * 2002-08-29 2004-03-11 Eudes Dantas Stereoflexographie
WO2006019450A2 (fr) 2004-07-20 2006-02-23 Macdermid Printing Solutions, Llc Procede ameliore d'exposition prealable de plaques d'impression d'image en relief
EP1769285A4 (fr) * 2004-07-20 2011-10-19 Macdermid Printing Solutions Procede ameliore d'exposition prealable de plaques d'impression d'image en relief
WO2008145316A2 (fr) 2007-05-25 2008-12-04 Eos Gmbh Electro Optical Systems Procédé de fabrication par couches d'un objet tridimensionnel
WO2008145316A3 (fr) * 2007-05-25 2009-01-22 Eos Electro Optical Syst Procédé de fabrication par couches d'un objet tridimensionnel
RU2469851C2 (ru) * 2007-05-25 2012-12-20 Эос Гмбх Электро Оптикал Системз Способ послойного производства трехмерного объекта
CN101932429B (zh) * 2007-05-25 2014-07-09 Eos有限公司电镀光纤系统 分层制造三维物体的方法
US9011982B2 (en) 2007-05-25 2015-04-21 Eos Gmbh Electro Optical Systems Method for a layer-wise manufacturing of a three-dimensional object
EP2176073A4 (fr) * 2007-08-08 2013-07-10 Macdermid Printing Solutions Procédé de pré-exposition de plaque d'impression d'images en relief
EP3944021A1 (fr) * 2020-07-22 2022-01-26 Esko-Graphics Imaging GmbH Procédé et appareil pour le durcissement d'une plaque d'impression
WO2022017632A1 (fr) * 2020-07-22 2022-01-27 Esko-Graphics Imaging Gmbh Procédé et appareil de durcissement d'une plaque d'impression
EP4418047A3 (fr) * 2020-07-22 2025-06-04 Esko-Graphics Imaging GmbH Procédé et appareil pour durcir une plaque d'impression

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